Search results for: deuterium

Authors: Farzad Doostishoar, Abdolreza Hasanzadeh, Seyed Amin Ayatolahi Mousavi

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Introduction and Goals: Deuterium has different action from its isotopes hydrogen in chemical reactions and biochemical processes. It is not a significant difference in heavier atoms between the behavior of heavier isotope and the lighter One but for very lighter atoms it is significant . According to that most of the weight of all creatures body is water natural rate can be significant. In this article we want to study the effect of reduced deuterium on the fungus cell. If we saw the dependence of deuterium concentration of environment on the cells growth we can test this in invivo models too. Methods: First we measured deuterium concentration of the distillated water this analyze was operated by Arak’s heavy water company. Then the deuterium was diluted to ½ ¼ 1/8 1/16 by adding water free of deuterium for making media. In tree of samples the deuterium concentration was increased by adding D2O up to 10,50,100 times more concentrated. For candida albicans growth we used sabor medium and for aspergillus fomigatis growth we used sabor medium containing chloramphenicol. After culturing the funguses species we put the mediums for each species in the shaker incubator for 10 days in 25 centigrade. In different days and times the plates were studied morphologically and some microscopic characteristics were studied too. This experiments and cultures were repeated 3 times. Results: Statistical analyzes by paired-sample T test showed that aspergilus fomigatoos growth was decreased in concentration of 72 ppm( half deuterium concentration of negative control) significantly. In deuterium concentration reduction the growth reduce into the negative control significantly. The project results showed that candida albicans was sensitive to reduce and decrease of the deuterium in all concentrations.

Keywords: deuterium, cancer cell, growth, candida albicans

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Authors: Alexey Yu. Postnikov, Nikolay T. Kazakovskiy, Valery V. Mokrushin, Irina A. Tsareva, Andrey A. Potekhin, Valentina N. Golubeva, Yuliya V. Potekhina, Maxim V. Tsarev

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The development of tritium and deuterium targets for neutron tubes and generators is a part of the activities in All-Russia Research Institute of Experimental Physics (RFNC-VNIIEF). These items contain a metal substrate (for example, copper) with a titanium film with a few microns thickness deposited on it. Then these metal films are saturated with tritium, deuterium or their mixtures. The significant problem in neutron tubes and neutron generators is the characterization of substrate surface before a deposition of titanium film on it, and analysis of the deposited titanium film’s surface before hydrogenation and after a saturation of the film with hydrogen isotopes. The performance effectiveness of neutron tube and generator also depends on upon the quality parameters of the surface of the initial substrate, deposited metal film and hydrogenated target. The objective of our work is to study the target prototype samples, that have differ by various approaches to the preliminary chemical processing of a copper substrate, and to analyze the integrity of titanium film after its saturation with deuterium. The research results of copper substrate and the surface of deposited titanium film with the use of electron microscopy, X-ray spectral microanalysis and laser-spark methods of analyses are presented. The causes of surface defects appearance have been identified. The distribution of deuterium and some impurities (oxygen and nitrogen) along the surface and across the height of the hydrogenated film in the target has been established. This allows us to evaluate the composition homogeneity of the samples and consequently to estimate the quality of hydrogenated samples. As the result of this work the propositions on the advancement of production technology and characterization of target’s surface have been presented.

Keywords: tritium and deuterium targets, titanium film, laser-spark methods, electron microscopy

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Authors: Kaouther Bergaui, Nafaa Reguigui, Charles Gary

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Characterization and the applications of deuterium-deuterium (DD) neutron generator developed by Adelphie technology and acquired by the National Centre of Nuclear Science and Technology (NCNST) were presented in this work. We study the performance of the neutron generator in terms of neutron yield, production efficiency, and the ionic current as a function of the acceleration voltage at various RF powers. We provide the design and optimization of the PGNAA chamber and thus give insight into the capabilities of the planned PGNAA facility. Additional non-destructive techniques were studied employing the DD neutron generator, such as PGNAA and neutron radiography: The PGNAA is used for determining the concentration of 10B in Si and SiO2 matrices by using a germanium detector HPGe and the results obtained are compared with PGNAA system using a Sodium Iodide detector (NaI (Tl)); Neutron radiography facility was tested and simulated, using a camera device CCD and simulated by the Monte Carlo code; and the explosive detection system (EDS) also simulated using the Monte Carlo code. The study allows us to show that the new models of DD neutron generators are feasible and that superior-quality neutron beams could be produced and used for various applications. The feasibility of Boron neutron capture therapy (BNCT) for cancer treatment using a neutron generator was assessed by optimizing Beam Shaping Assembly (BSA) on a phantom using Monte-Carlo (MCNP6) simulations.

Keywords: neutron generator deuterium-deuterium, Monte Carlo method, radiation, neutron flux, neutron activation analysis, born, neutron radiography, explosive detection, BNCT

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Authors: Xiangxu Chai, Bin Feng, Ping Li, Deyan Zhu, Liquan Wang, Guanzhong Wang, Yukun Jing

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In high power large-aperture laser systems, such as the inertial confinement fusion project, the Nd: glass laser (1053nm) is usually needed to be converted to ultraviolet (UV) light and the fourth harmonic generation (FHG) is one of the most favorite candidates to achieve UV light. Deuterated potassium dihydrogen phosphate (DKDP) crystal is an optimal choice for converting the Nd: glass radiation to the fourth harmonic laser by noncritical phase matching (NCPM). To reduce the damage probability of focusing lens, the DKDP crystal is suggested to be set before the focusing lens. And a converging beam enters the FHG crystal consequently. In this paper, we simulate the process of FHG in the scheme and the dependence of FHG efficiency on the lens’ F is derived. Besides, DKDP crystal with gradient deuterium is proposed to realize the NCPM FHG of the converging beam. At every position, the phase matching is achieved by adjusting the deuterium level, and the FHG efficiency increases as a result. The relation of the lens’ F with the deuterium gradient is investigated as well.

Keywords: fourth harmonic generation, laser induced damage, converging beam, DKDP crystal

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Authors: Tahreem Yousaf, Michael P. Bradley, Jerzy A. Szpunar

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Currently, nuclear fusion is considered one of the most favorable options for future energy generation, due both to its abundant fuel and lack of emissions. For fusion power reactors, a major problem will be a suitable material choice for the Plasma Facing Components (PFCs) which will constitute the reactor first wall. Tungsten (W) has advantages as a PFC material because of its high melting point, low vapour pressure, high thermal conductivity and low retention of hydrogen isotopes. However, several adverse effects such as embrittlement, melting and morphological evolution have been observed in W when it is bombarded by low-energy and high-fluence helium (He) and deuterium (D) ions, as a simulation conditions adjacent to a fusion plasma. Recently, tantalum (Ta) also investigate as PFC and show better reluctance to nanostructure fuzz as compared to W under simulated fusion plasma conditions. But retention of D ions found high in Ta than W. Preparatory to plasma-based ion implantation studies, the effect of D and He ion impact on W and Ta is predicted by using the stopping and range of ions in the matter (SRIM) code. SRIM provided some theoretical results regarding projected range, ion concentration (at. %) and displacement damage (dpa) in W and Ta. The projected range for W under Irradiation of He and D ions with an energy of 3-keV and 1×fluence is determined 75Å and 135 Å and for Ta 85Å and 155Å, respectively. For both W and Ta samples, the maximum implanted peak for helium is predicted ~ 5.3 at. % at 12 nm and for De ions concentration peak is located near 3.1 at. % at 25 nm. For the same parameters, the displacement damage for He ions is observed in W ~ 0.65 dpa and Ta ~ 0.35 dpa at 5 nm. For D ions the displacement damage for W ~ 0.20 dpa at 8 nm and Ta ~ 0.175 dpa at 7 nm. The mean implantation depth is same for W and Ta, i.e. for He ions ~ 40 nm and D ions ~ 70 nm. From these results, we conclude that retention of D is high than He ions, but damage is low for Ta as compared to W. Further investigation still in progress regarding W and T.

Keywords: helium and deuterium ion impact, plasma facing components, SRIM simulation, tungsten, tantalum

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Authors: Chunduru Amareswara Prasad

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The main aim of this proposal it to reveal the secrets of the universe by accelerating neutrons. The proposal idea in its abridged version speaks about the possibility of making neutrons accelerate with help of thermal energy and magnetic energy under controlled conditions. Which is helpful in revealing the hidden secrets of the universe namely dark energy and in finding properties of Higgs boson. The paper mainly speaks about accelerating neutrons to near velocity of light in a LINAC, using magnetic energy by magnetic pressurizers. The center of mass energy of two colliding neutron beams is 94 GeV (~0.5c) can be achieved using this method. The conventional ways to accelerate neutrons has some constraints in accelerating them electromagnetically as they need to be separated from the Tritium or Deuterium nuclei. This magnetic gradient method provides efficient and simple way to accelerate neutrons.

Keywords: neutron, acceleration, thermal energy, magnetic energy, Higgs boson

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Authors: Morteza Habibi, Reza Amrollahi

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The Aluminum made targets were placed at the central part of a Fillipov type (90KJ) plasma focus cathode. These targets were exposed to perpendicular dense plasma stream incidence. Melt layer erosion by melt motion, surface smoothing, and bubble formation were some of different effects caused by diverse working conditions. Micro hardness of surface layer tends to decrease particularly in the central region of the sample where destruction is more intense. The most pronouced melt motion is registered in the region of the maximum gradient of pressure and the etching of aluminium surface is noticeable in the central part of target. The crater with a maximum depth of 200µm, and the diameter of about 8.5mm is observed close to the mountains. Adding Krypton admixture to the Deuterium gas lead to collapsing bubbles and greater surface damage.

Keywords: fillipov type plasma focus, al target interaction, bubbling effect, melt layer motion, surface smoothing

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Authors: Hossam Shalabi, George Hadjisophocleous

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The Canadian Nuclear Power Plants (NPPs) use some portions of NUREG/CR-6850 in carrying out Fire Probabilistic Risk Assessment (PRA). An assessment for the applicability of NUREG/CR-6850 to CANDU reactors was performed and a CANDU Fire PRA was introduced. There are 19 operating CANDU reactors in Canada at five sites (Bruce A, Bruce B, Darlington, Pickering and Point Lepreau). A fire load density survey was done for all Fire Safe Shutdown Analysis (FSSA) fire zones in all CANDU sites in Canada. National Fire Protection Association (NFPA) Standard 557 proposes that a fire load survey must be conducted by either the weighing method or the inventory method or a combination of both. The combination method results in the most accurate values for fire loads. An updated CANDU Fire PRA model is demonstrated in this paper that includes the fuel survey in all Canadian CANDU stations. A qualitative screening step for the CANDU fire PRA is illustrated in this paper to include any fire events that can damage any part of the emergency power supply in addition to FSSA cables.

Keywords: fire safety, CANDU, nuclear, fuel densities, FDS, qualitative analysis, fire probabilistic risk assessment

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Authors: Bharat Kumar, Deepak Kumar, Vijay Chaudhry

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Zirconium alloys are widely used for the core components of a pressurized heavy water reactor (PHWR) or Canada deuterium (CANDU) reactor due to their low neutron absorption cross-section and excellent mechanical properties. The components made of Zirconium alloys are subjected to flow-induced vibrations, resulting in fretting wear at the interface of; pressure tubes and bearing pads, pressure tubes and calandria tubes, and calandria tubes and Liquid injection shutdown system (LISS) nozzles. There is a need to explore the tribological response under such conditions. Present work simulates the contact between calandria tube and LISS nozzle of PHWR/CANDU reactor as cylinder-on-cylinder contact configuration. Reciprocating tribo-tests were conducted on Zircaloy-4 (Zr-4) under the self-mated condition at varying amplitude, frequency, and sliding time. To understand the active wear mechanism, worn surfaces were analyzed using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The change in amplitude severely affects the wear than other factors. The wear mechanism transits from adhesion to abrasion with increasing test amplitude. The dominant wear mechanisms are micro-cutting and micro-plowing followed by delamination in some areas. However, the coefficient of friction has indifferent behaviors.

Keywords: zircaloy-4, tribology, calandria tube, LISS nozzle, PHWR

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Authors: Massimo Zucchetti

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In the US, the SPARC-ARC projects of compact tokamaks are being developed: both are aimed at the technological demonstration of fusion power reactors with cutting-edge technology but following different design approaches. However, they show more similarities than differences in the fuel cycle, safety, radiation protection, environmental, waste and decommissioning aspects: all reactors, either experimental or demonstration ones, have to fulfill certain "essential" requirements to pass from virtual to real machines, to be built in the real world. The paper will discuss these "essential" requirements. Some of the relevant activities in these fields, carried out by our research group (ESSENTIAL group), will be briefly reported, with the aim of showing some methodology aspects that have been developed and might be of wider interest. Also, a non-competitive comparison between our results for different projects will be included when useful. The question of advanced D-He3 fuel cycles to be used for those machines will be addressed briefly. In the past, the IGNITOR project of a compact high-magnetic field D-T ignition experiment was found to be able to sustain limited D-He3 plasmas, while the Candor project was a more decisive step toward D-He3 fusion reactors. The following topics will be treated: Waste management and radioactive safety studies for advanced fusion power plants; development of compact high-field advanced fusion reactors; behavior of nuclear materials under irradiation: neutron-induced radioactivity due to side DT reactions, radiation damage; accident analysis; reactor siting.

Keywords: advanced fuel fusion reactors, deuterium-helium3, high-field tokamaks, fusion safety

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Authors: Long Wang, Yongjin Feng, Xiaofang Luo

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Tritium permeation through structural materials is a significant issue for fusion demonstration (DEMO) reactor blankets in terms of fuel cycle efficiency and radiological safety. Reduced activation ferritic (RAFM) steel CLF-1 is a prime candidate for the China’s CFETR blanket structural material, facing high permeability of hydrogen isotopes at reactor operational temperature. To confine tritium as much as possible in the reactor, surface modification of the steels including fabrication of tritium permeation barrier (TPB) attracts much attention. As a new alloy system, high entropy alloy (HEA) contains at least five principal elements, each of which ranges from 5 at% to 35 at%. This high mixing effect entitles HEA extraordinary comprehensive performance. So it is attractive to lead HEA into surface alloying for protective use. At present, studies on the hydrogen isotope permeability of HEA coatings is still insufficient and corresponding mechanism isn’t clear. In our study, we prepared three kinds of HEA coatings, including AlCrTaTiZr, (AlCrTaTiZr)N and (AlCrTaTiZr)O. After comprehensive characterization of SEM, XPS, AFM, XRD and TEM, the structure and composition of the HEA coatings were obtained. Deuterium permeation tests were conducted to evaluate the hydrogen isotope permeability of AlCrTaTiZr, (AlCrTaTiZr)N and (AlCrTaTiZr)O HEA coatings. Results proved that the (AlCrTaTiZr)N and (AlCrTaTiZr)O HEA coatings had better hydrogen isotope permeation resistance. Through analyzing and characterizing the hydrogen isotope permeation results of the corroded samples, an internal link between hydrogen isotope permeation behavior and structure of HEA coatings was established. The results provide valuable reference in engineering design of structural and TPB materials for future fusion device.

Keywords: high entropy alloy, hydrogen isotope permeability, tritium permeation barrier, fusion demonstration reactor

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Authors: Gheorghe Ionita, Sebastian Brad, Ioan Stefanescu

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In any fusion device, tritium plays a key role both as a fuel component and, due to its radioactivity and easy incorporation, as tritiated water (HTO). As for the ITER project, to reduce the constant potential of tritium emission, there will be implemented a Water Detritiation System (WDS) and an Isotopic Separation System (ISS). In the same time, during operation of fission CANDU reactors, the tritium content increases in the heavy water used as moderator and cooling agent (due to neutron activation) and it has to be reduced, too. In Romania, at the National Institute for Cryogenics and Isotopic Technologies (ICIT Rm-Valcea), there is an Experimental Pilot Plant for Tritium Removal (Exp. TRF), with the aim of providing technical data on the design and operation of an industrial plant for heavy water depreciation of CANDU reactors from Cernavoda NPP. The selected technology is based on the catalyzed isotopic exchange process between deuterium and liquid water (LPCE) combined with the cryogenic distillation process (CD). This paper presents an updated review of activities in the field carried out in Romania after the year 2000 and in particular those related to the development and operation of Tritium Removal Experimental Pilot Plant. It is also presented a comparison between the experimental pilot plant and industrial plant to be implemented at Cernavoda NPP. The similarities between the experimental pilot plant from ICIT Rm-Valcea and water depreciation and isotopic separation systems from ITER are also presented and discussed. Many aspects or 'opened issues' relating to WDS and ISS could be checked and clarified by a special research program, developed within ExpTRF. By these achievements and results, ICIT Rm - Valcea has proved its expertise and capability concerning tritium management therefore its competence may be used within ITER project.

Keywords: ITER project, heavy water detritiation, tritium removal, isotopic exchange

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Authors: Naziha Mokadem, Rainier Dennis, Ingrid Dennis

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In South Africa, Karst aquifers are receiving greater attention since they provide large supplies of water which is used for domestic and agricultural purposes as well as for industry. Accordingly, a better insight into the origin of water mineralization and the geochemical processes controlling the recharge of the aquifer is crucial. Analyses of geochemical and environmental isotopes could lead to relevant information regarding karstification and infiltration processes, groundwater chemistry and isotopy. A study was conducted in a typical karst landscape of Wonderfonteinspruit catchment, also known as Wonderfonteinspruit Valley in North-western -South Africa. Furthermore, fifty-two samples were collected from (35 boreholes, 5 surface waters, 4 Dams, 4 springs, 1 canal, 2 pipelines, 1 cave) within the study area for hydrochemistry and 2H and 18O analysis. The determination of the anions (Cl-, SO42-, NO2, NO3-) were performed using Metrohm ion chromatography, model: 761 compact IC, with a precision of ± 0.001 mg/l. While, the cations (Na+, Mg2+, K+, Ca2+) were determined using Metrohm ion chromatography, Model: ICP-MS 7500 series. The alkalinity (Alk) was determined by pH meter with volumetric titration using HCL to pH 4.5; 4.2; and 8.2. In addition, 18O and 2H relative to the Vienna-Standard Mean Ocean Water (RVSMOW), were determined by picarro L2130-I Isotopic H2O (Cavity Ringdown laser spectrometer, Picarro Ltd). The hydrochemical analysis of Wonderfonteinspruit groundwater showed a dominance of the cations Ca-Mg and the anion HCO3. Piper diagram shows that the groundwater sample of study area is characterized by four hydrochemical facies: Two main groups: (1) Ca–Mg–Cl–SO4; (2) Ca–Mg–HCO3 and two minor groups: (3) Ca–Mg–Cl; (4) Na–K–HCO3. The majority of boreholes of Malmani (Transvaal Supergroup) aquifer are plotted in Ca–Mg–HCO3.Oxygen-18 (18O‰SMOW) and deuterium (D‰SMOW) isotopic data indicate that the aquifer’s recharge is influenced by two phenomena; precipitation rates for most of the samples and river flow (Wonderfonteinspruit, Middelvieinspruit, Renfonteinspruit) for some samples.

Keywords: South Africa, Wonderfonteinspruit Valley, isotopic, hydrochemical, carbonate aquifers

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Authors: Belhaj Mohamed, M. Saidi, N. Boucherab, N. Ouertani, I. Bouazizi, M. Ben Jrad

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Natural hydrocarbon seepage has helped petroleum exploration as a direct indicator of gas and/or oil subsurface accumulations. Surface macro-seeps are generally an indication of a fault in an active Petroleum Seepage System belonging to a Total Petroleum System. This paper describes a case study in which multiple analytical techniques were used to identify and characterize trace petroleum-related hydrocarbons and other volatile organic compounds in groundwater samples collected from Sousse aquifer (Central Tunisia). The analytical techniques used for analyses of water samples included gas chromatography-mass spectrometry (GC-MS), capillary GC with flame-ionization detection, Compund Specific Isotope Analysis, Rock Eval Pyrolysis. The objective of the study was to confirm the presence of gasoline and other petroleum products or other volatile organic pollutants in those samples in order to assess the respective implication of each of the potentially responsible parties to the contamination of the aquifer. In addition, the degree of contamination at different depths in the aquifer was also of interest. The oil and gas seeps have been investigated using biomarker and stable carbon isotope analyses to perform oil-oil and oil-source rock correlations. The seepage gases are characterized by high CH4 content, very low δ13CCH4 values (-71,9 ‰) and high C1/C1–5 ratios (0.95–1.0), light deuterium–hydrogen isotope ratios (-198 ‰) and light δ13CC2 and δ13CCO2 values (-23,8‰ and-23,8‰ respectively) indicating a thermogenic origin with the contribution of the biogenic gas. An organic geochemistry study was carried out on the more ten oil seep samples. This study includes light hydrocarbon and biomarkers analyses (hopanes, steranes, n-alkanes, acyclic isoprenoids, and aromatic steroids) using GC and GC-MS. The studied samples show at least two distinct families, suggesting two different types of crude oil origins: the first oil seeps appears to be highly mature, showing evidence of chemical and/or biological degradation and was derived from a clay-rich source rock deposited in suboxic conditions. It has been sourced mainly by the lower Fahdene (Albian) source rocks. The second oil seeps was derived from a carbonate-rich source rock deposited in anoxic conditions, well correlated with the Bahloul (Cenomanian-Turonian) source rock.

Keywords: biomarkers, oil and gas seeps, organic geochemistry, source rock

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Authors: Ajit Singh, Waliur Rahaman, Parmanand Sharma, Laluraj C. M., Lavkush Patel, Bhanu Pratap, Vinay Kumar Gaddam, Meloth Thamban

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The Himalayan glaciers are the potential source of perennial water supply to Asia’s major river systems like the Ganga, Brahmaputra and the Indus. In order to improve our understanding about the source of precipitation and hydrograph components in the interior Himalayan glaciers, it is important to decipher the sources of moisture and their contribution to the glaciers in this river system. In doing so, we conducted an extensive pilot study in a Sutri Dhaka glacier, western Himalaya during 2014-15. To determine the moisture sources, rain, surface snow, ice, and stream meltwater samples were collected and analyzed for stable oxygen (δ¹⁸O) and hydrogen (δD) isotopes. A two-component hydrograph separation was performed for the glacier stream using these isotopes assuming the contribution of rain, groundwater and spring water contribution is negligible based on field studies and available literature. To validate the results obtained from hydrograph separation using above method, snow and ice melt ablation were measured using a network of bamboo stakes and snow pits. The δ¹⁸O and δD in rain samples range from -5.3% to -20.8% and -31.7% to -148.4% respectively. It is noteworthy to observe that the rain samples showed enriched values in the early season (July-August) and progressively get depleted at the end of the season (September). This could be due to the ‘amount effect’. Similarly, old snow samples have shown enriched isotopic values compared to fresh snow. This could because of the sublimation processes operating over the old surface snow. The δ¹⁸O and δD values in glacier ice samples range from -11.6% to -15.7% and -31.7% to -148.4%, whereas in a Sutri Dhaka meltwater stream, it ranges from -12.7% to -16.2% and -82.9% to -112.7% respectively. The mean deuterium excess (d-excess) value in all collected samples exceeds more than 16% which suggests the predominant moisture source of precipitation is from the Western Disturbances. Our detailed estimates of the hydrograph separation of Sutri Dhaka meltwater using isotope hydrograph separation and glaciological field methods agree within their uncertainty; stream meltwater budget is dominated by glaciers ice melt over snowmelt. The present study provides insights into the sources of moisture, controlling mechanism of the isotopic characteristics of Sutri Dhaka glacier water and helps in understanding the snow and ice melt components in Chandra basin, Western Himalaya.

Keywords: D-excess, hydrograph separation, Sutri Dhaka, stable water isotope, western Himalaya

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Authors: Engy Shokry, Giancarlo La Marca, Maria Luisa Della Bona

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Newborn screening for Congenital Adrenal Hyperplasia (CAH) relies on quantification of 17α-hydroxyprogesterone using enzyme immunoassays. These assays, in spite of being rapid, readily available and easy to perform, its reliability was found questionable due to lack of selectivity and specificity resulting in large number of false-positives, consequently family anxiety and associated hospitalization costs. To improve specificity of conventional 17α-hydroxyprogesterone screening which may experience false transient elevation in preterm, low birth weight or acutely ill neonates, steroid profiling by LC-MS/MS as a second-tier test was implemented. Unlike the previously applied LC-MS/MS methods, with the disadvantage of requiring a relatively high number of blood drops. Since newborn screening tests are increasing, it is necessary to minimize the sample volume requirement to make the maximum use of blood samples collected on filter paper. The proposed new method requires just one 3.2 mm dried blood spot (DBS) punch. Extraction was done using methanol: water: formic acid (90:10:0.1, v/v/v) containing deuterium labelled internal standards. Extracts were evaporated and reconstituted in 10 % acetone in water. Column switching strategy for on-line sample clean-up was applied to improve the chromatographic run. The first separative step retained the investigated steroids and passed through the majority of high molecular weight impurities. After the valve switching, the investigated steroids are back flushed from the POROS® column onto the analytical column and separated using gradient elution. Found quantitation limits were 5, 10 and 50 nmol/L for 17α-hydroxyprogesterone, androstenedione and cortisol respectively with mean recoveries of between 98.31-103.24 % and intra-/ inter-assay CV% < 10 % except at LLOQ. The method was validated using standard addition calibration and isotope dilution strategies. Reference ranges were determined by analysing samples from 896 infants of various ages at the time of sample collection. The method was also applied on patients with confirmed CAH. Our method represents an attractive combination of low sample volume requirement, minimal sample preparation time without derivatization and quick chromatography (5 min). The three steroid profile and the concentration ratios (17OHP + androstenedione/cortisol) allowed better screening outcomes of CAH reducing false positives, associated costs and anxiety.

Keywords: congenital adrenal hyperplasia (CAH), 17α-hydroxyprogesterone, androstenedione, cortisol, LC-MS/MS

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Authors: Seema Kothari, Dinesh Panday

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An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

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Authors: Yury S. Shpanskiy, Boris V. Kuteev

Abstract:

Development of a fusion-fission hybrid facility based on superconducting conventional tokamak DEMO-FNS runs in Russia since 2013. The main design goal is to reach the technical feasibility and outline prospects of industrial hybrid technologies providing the production of neutrons, fuel nuclides, tritium, high-temperature heat, electricity and subcritical transmutation in Fusion-Fission Hybrid Systems. The facility should operate in a steady-state mode at the fusion power of 40 MW and fission reactions of 400 MW. Major tokamak parameters are the following: major radius R=3.2 m, minor radius a=1.0 m, elongation 2.1, triangularity 0.5. The design provides the neutron wall loading of ~0.2 MW/m², the lifetime neutron fluence of ~2 MWa/m², with the surface area of the active cores and tritium breeding blanket ~100 m². Core plasma modelling showed that the neutron yield ~10¹⁹ n/s is maximal if the tritium/deuterium density ratio is 1.5-2.3. The design of the electromagnetic system (EMS) defined its basic parameters, accounting for the coils strength and stability, and identified the most problematic nodes in the toroidal field coils and the central solenoid. The EMS generates toroidal, poloidal and correcting magnetic fields necessary for the plasma shaping and confinement inside the vacuum vessel. EMC consists of eighteen superconducting toroidal field coils, eight poloidal field coils, five sections of a central solenoid, correction coils, in-vessel coils for vertical plasma control. Supporting structures, the thermal shield, and the cryostat maintain its operation. EMS operates with the pulse duration of up to 5000 hours at the plasma current up to 5 MA. The vacuum vessel (VV) is an all-welded two-layer toroidal shell placed inside the EMS. The free space between the vessel shells is filled with water and boron steel plates, which form the neutron protection of the EMS. The VV-volume is 265 m³, its mass with manifolds is 1800 tons. The nuclear blanket of DEMO-FNS facility was designed to provide functions of minor actinides transmutation, tritium production and enrichment of spent nuclear fuel. The vertical overloading of the subcritical active cores with MA was chosen as prospective. Analysis of the device neutronics and the hybrid blanket thermal-hydraulic characteristics has been performed for the system with functions covering transmutation of minor actinides, production of tritium and enrichment of spent nuclear fuel. A study of FNS facilities role in the Russian closed nuclear fuel cycle was performed. It showed that during ~100 years of operation three FNS facilities with fission power of 3 GW controlled by fusion neutron source with power of 40 MW can burn 98 tons of minor actinides and 198 tons of Pu-239 can be produced for startup loading of 20 fast reactors. Instead of Pu-239, up to 25 kg of tritium per year may be produced for startup of fusion reactors using blocks with lithium orthosilicate instead of fissile breeder blankets.

Keywords: fusion-fission hybrid system, conventional tokamak, superconducting electromagnetic system, two-layer vacuum vessel, subcritical active cores, nuclear fuel cycle

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