Epithermal neutron activation analysis of blue-green algae Spirulina platensis as a matrix for selenium-containing pharmaceuticals

To evaluate the potentiality of the blue-green algae Spirulina platensis as a matrix for the production of Se-containing pharmaceuticals, the background levels of 31 major, minor and trace elements (Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni using (n,p) reaction), As, Br, Zn, Rb, Mo, Ag, Sb, I, Ba, Sm, Tb, Tm, Hf, Ta, W, Au, Hg, Th were determined in Spirulina platensis biomass by means of epithermal neutron activation analysis. The possibility of the purpose-oriented incorporation of Se into Spirulina platensis biomass was demonstrated. The polynomial dependence of the Se accumulation on nutritional medium loading was revealed. The analytical technique used allows to control the amount of toxic elements in algae Spirulina platensis. Based on this study, a conclusion of the possibility to use Spirulina platensisas a matrix for the production of Se-containing pharmaceutical was drawn.     

Epithermal neutron activation analysis

Different modes of epithermal neutron activation analysis are described. The principles and examples are given for each.     

Epithermal neutron activation analysis of food

Food samples were irradiated with thermal and epithermal neutrons. The average ratios of thermal to epithermal activity were determined for⁸⁰Br,⁴⁹Ca,³⁸Cl,^60mCo,⁴²K,²⁷Mg,⁵⁶Mn,²⁴Na, and^86mRB. They were equal to 2.1, 26, 24, 6.6, 19, 16, 11, 23 and 1.9, respectively. Then, 57 food samples were analyzed by epithermal neutron activation analysis for Br and Rb. The concentrations (in ppm) of Br and Rb were in asparagus (2) 2.3, 11.5; beets (3) 0.5, 0.8; beef (3) 1.7, 3.6; cabbage (5) 0.5, 10.8; carrot (3) 0.2, 3.7; chicken (3) 0.6, 4.4; chocolate (7) 11.1, 18.7; egg (3) 0.9, 1.9; french bean (3) 0.3, 1.0; goose (2) 1.3, 9.3; lettuce (2) 0.9, 1.7; pork (1) 1.5, 4.4; potato (7) 1.0, 1.2; sausage (3) 0.6, 4.0; strawberry jam (3) 0.4, 1.4; tomato (1) 13.5, 14.6; turkey (3) 1.2, 4.9. respectively. The number of samples analyzed is indicated in parentheses.     

Epithermal neutron activation analysis in applied microbiology

Some results from applying epithermal neutron activation analysis at FLNP JINR, Dubna, Russia, in medical biotechnology, environmental biotechnology and industrial biotechnology are reviewed. In the biomedical experiments biomass from the blue-green alga Spirulina platensis (S. platensis) has been used as a matrix for the development of pharmaceutical substances containing such essential trace elements as selenium, chromium and iodine. The feasibility of target-oriented introduction of these elements into S. platensis biocomplexes retaining its protein composition and natural beneficial properties was shown. The absorption of mercury on growth dynamics of S. platensis and other bacterial strains was observed. Detoxification of Cr and Hg by Arthrobacter globiformis 151B was demonstrated. Microbial synthesis of technologically important silver nanoparticles by the novel actinomycete strain Streptomyces glaucus 71 MD and blue-green alga S. platensis were characterized by a combined use of transmission electron microscopy, scanning electron microscopy and energy-dispersive analysis of X-rays. It was established that the tested actinomycete S. glaucus 71 MD produces silver nanoparticles extracellularly when acted upon by the silver nitrate solution, which offers a great advantage over an intracellular process of synthesis from the point of view of applications. The synthesis of silver nanoparticles by S. platensis proceeded differently under the short-term and long-term silver action.     

Epithermal neutron activation analysis using the monostandard method

A method is described for epithermal neutron activation analysis of 17 elements in granite rock samples using a single standard. Gold has been used as a single comparator due to its relatively high resonance integral value (I₀=400 barn). In addition, it is preferable to Co in order to obtain a large epithermal activation in a short irradiation. The method of calculation is simple and rapid and can be done using a small calculator. Epithermal activation is able to overcome the difficulty arising from changing irradiation position as well as increasing the number of determinable elements by eliminating the interference from undesired isotopes which have relatively high thermal cross section values (₀), when reactor neutron flux is used. The coupling of epithermal activation with the monostandard method has the advantage of using a small Cd-cover which overcomes most of the difficulties arising in the relative method with large volume cadmium filters.     

Epithermal neutron activation analysis of short-lived nuclides in geological material

The cadmium ratios of 52 short-lived nuclides have been measured. Epithermal neutron irradiation reduces the activities of²⁰F,²⁷Mg,²⁸Al,³⁸Cl,⁴⁹Ca,^46mSc,⁵¹Ti,⁵⁶Mn and⁶⁶Cu by factors of 20–30. The calculated improvements in detection limits for Ga, Br, Rb, Y, Mo, Rh, Pd, Ag, In, Sn, Sb, I, Ba, Nd, Sm, Gd, Dy, Er, Yb, Hf, W, Re, Pt, Au, Th and U are in the range 1–6. Hafnium was measured in USGS rocks: AGV-1 (4.9 μg g⁻¹), G-2 (7.5 μg g⁻¹) and GSP-1 (14.7 μg g⁻¹) and IAEA standards: SOIL-5 (6.3 μg g⁻¹ and SL-1 (4.6 μg g⁻¹). CCRMP reference concentrates PTC and PTM were analysed for rhodium (1.1 and 0.75 μg g⁻¹, respectively) and silver (69 and 5.8 μg g⁻¹, respectively).     

Epithermal neutron activation analysis using a boron carbide irradiation filter

The use of boron carbide as a thermal neutron filter in epithermal neutron activation (ENAA) analysis has been investigated. As compared to the use of a cadmium filter, boron provides a greater reduction of activities from elements relatively abundant in terrestrial rocks and fossil fuels, such as Na, La, Sc and Fe. These elements have excitation functions which follow the 1/v law in the 1 to 10 eV lower epithermal region. This enhances the sensitivity of ENAA for elements such as U, Th, Ba and etc. which have strong resonances in the higher epithermal region above 10 eV. In addition, a boron carbide filter has the advantages over cadmium of acquiring a relatively low level of induced activity which poses minimal radiation safety problems, when used for ENAA.     

Epithermal instrumental neutron activation analysis of biological reference materials for iodine

Epithermal instrumental neutron activation analysis (EINAA) methods have been optimized and applied to several biological reference materials and selected food items for the determination of iodine. The method involves irradiation of the samples for different periods in epi-cadmium and/or epi-boron flux of the Dalhousie University SLOWPOKE-2 reactor and direct counting without any pre-treatment on a 25-cm³ hyperpure Ge detector. The 443 keV photopeak of ¹²⁸I is used for assaying the iodine content. Precision of measurements, expressed as the relative standard deviation, is 10–15% at 200–500 ppb and 3–12% at 500–6000 ppb levels of iodine. Accuracy of iodine measurements is within 5%. The detection limits for iodine in several biological materials with cadmium and boron, either alone or a combination of the two, as thermal neutron shields have been found to vary between 0.1 and 0.4 mg · kg^–1 for different periods of irradiation, decay and counting. The results suggest that the EINAA methods can be successfully applied to biological materials for routine analysis of iodine at levels higher than 200 ppb.     

Epithermal neutron activation analysis using (n,n′) reaction

The (n, n′) reaction with the epithermal and fast neutrons of a nuclear reactor has been studied for activation analysis of Sr, Cd, In, Ba, Hf, Os, Au, Hg and Pb. For some elements (In, Os, Au, Hg and Pb) the use of a cadmium sheet reduced the activity by less than a factor of two, while the interferences from the most abundant elements have been reduced by more than two orders of magnitude.     

Chemical composition and selenium distribution in selenium enriched Spirulina platensis biomass

Conditions for cultivating selenium enriched Spirulina platensis were developed. The protein, carbohydrate, lipids, and pigments were determined. The organic selenium and its distribution were analyzed. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 519–522, November–December, 2006.     

Epithermal neutron activation analysis and its application in the Miniature Neutron Source Reactor

The cadmium and boron ratios from 44 elements, totally 66 nuclides, were determined in the inner and outer irradiation sites of the Miniature Neutron Source Reactor (MNSR). China Institute of Atomic Energy. A permanent Cd-shielded epithermal neutron irradiation site has been designed and installed in the outer of the beryllium reflector of this reactor. Elements e.g., I, Br, Sr, Si, Th and U in biological samples, such as foodstuff, water and blood, geological and environmental samples, such as soil, rock, sediment and vegetable leaves were analyzed by BN-shielded epithermal neutron activation analysis (ENAA), and Au, As, Sb, Th and U by Cd-shielded ENAA. The results show that the detection limits of these elements by ENAA are better by a factor of 1.5–7 than those with conventional NAA.     

Biosorption of copper ions from aqueous solutions by Spirulina platensis biomass

In this study, the economically important micro-alga (cyanobacterium) Spirulina platensis was used as biosorbent for the removal of copper from aqueous solutions. The cyanobacterium was exposed to various concentrations of copper and adsorption of copper by the biomass was evaluated under different conditions that included pH, contact time, temperature, concentration of adsorbate and the concentration of dry biomass. Increased adsorption of copper by the non-living biomass was recorded with gradually increasing pH, and a maximal uptake by the biomass was observed at pH 7. The adsorption of copper was found to increase gradually along with decrease in biomass concentration. Biosorption was found to be at a maximum (90.6%), in a solution containing 100 mg copper/L, at pH 7, with 0.050 g dry biomass and at 37 °C with 90 min of contact time. Analysis of the spectrum obtained with atomic absorption spectrophotometer (AAS), indicated that the adsorbent has a great potential to remove copper from aqueous media contributing to an eco-friendly technology for efficient bioremediation in the natural environment.     

Epithermal neutron activation analysis of uranium by neptunium-239 using high resolution gamma-spectrometry

The possibility to use the most intensive gamma-peak of²³⁹Np for INAA of uranium with epithermal neutrons and high resolution Ge(Li)-spectrometry is evaluated. A way for calculation of the peak area of overlapping peaks of¹⁵³Sm and²³⁹Np is proposed. This can be used in other similar cases in the practice of NAA. On this basis a scheme for NAA of uranium in geological objects is proposed. Lower detection limit is 8·10⁻⁸ g U the precision 5–10% (relative standard deviation). The accuracy is demonstrated by the analysis of some geological standard reference materials.     

Epithermal instrumental neutron activation analysis with Compton suppression spectrometry for the determination of iodine in food samples

Epithermal instrumental neutron activation analysis (EINAA) together with Compton suppression system were optimized and used to analyze several food samples for the determination of low levels of iodine. The method involved the irradiation of samples in the outer epi-cadmium site of the Dalhousie University Slowpoke-2 reactor facility. The samples were then counted directly without any chemical treatment on an anticoincidence counting system. This system comprised a 25 cm³ hyperpure Ge detector, a guard detector consisting of a 10"×10" NaI(Tl) annulus with five photomultiplier tubes (PMTs) and a 3"×3" NaI(Tl) plug with one PMT. Iodine was quantitatively analyzed using the 443 keV photopeak of ¹²⁸I. The precision and accuracy of the method were evaluated using real samples and biological reference materials, respectively. The precision of the method was calculated as percent relative standard deviation and in all cases was within ±5%. The agreement between our iodine values and those of the certified values was generally within ±10%, suggesting an excellent accuracy of the method. The detection limits of the various samples calculated, with the lowest value of 20 ppb. The values of iodine determined ranged between 24 to 3080 ppb. The methods and results are presented.     

Epithermal instrumental neutron activation analysis in conjunction with anti-coincidence gamma-ray spectrometry for investigating iodine levels in Canadian foods

In order to reduce interferences from high activities of ²⁴Na, ⁵⁶Mn, ⁸²Br, and ³⁸Cl as well as to improve detection limits, precision, and accuracy of measuring iodine levels in biological materials, foods and diets in particular, an epithermal instrumental neutron activation analysis (EINAA) method in conjunction with anti-coincidence (EINAA-AC) gamma-ray spectrometry was employed. The Compton scattering background in the region of the 442.9-keV photopeak of ¹²⁸I was significantly suppressed by anti-coincidence counting. In order to validate the EINAA-AC method as well as to evaluate its broad applicability to diverse types of biological material, 17 NIST and IAEA reference materials containing very low to high levels of iodine as well as interfering elements were analyzed by the EINAA-AC method. The samples were irradiated in the cadmium-lined pneumatic site at a neutron flux of 2 × 10¹¹ cm^?2 s^?1 of the Dalhousie University SLOWPOKE-2 Reactor (DUSR) facility for 10 or 20 min followed by 1-min decay and 30-min counting. The detection limit for iodine by EINAA-AC was improved by a factor of 2–5 compared to EINAA depending on the sample matrix and other factors, and a limit of 3–5 μg kg^?1 was achieved for low-salt foods. We found the RSD to be about ±5 % above 200, increasing to ±10 % at 20, and then to greater than ±30 % at about 5 μg kg^?1 iodine levels.     

Epithermal instrumental neutron activation analysis for the determination of gold and arsenic in Ghanaian gold tailings using conventional and anti-coincidence counting

Epithermal instrumental neutron activation analysis (EINAA) together with both conventional and anti-coincidence counting techniques were used to analyze six different gold tailing samples from Ghana for Au and As. The method involves the use of the epi-cadmium site of the Dalhousie University Slowpoke-2 reactor facility for the irradiation of the samples. After irradiation, the samples were counted directly on the detectors. The identification and quantification of the elements were done using 411 keV photopeak of ¹⁹⁸Au and both 559 keV and 657 keV photopeaks of ⁷⁶As. The precision and accuracy of the method were evaluated. Values for Au in the samples ranged from 2.48 ppm and 6.76 ppm and for As between 1,550 ppm and 3,460 ppm. The values obtained using the two counting systems were in good agreement while the anti-coincidence counting system gave values of higher precision and accuracy. The detection limit for Au were 20 and 10 ppb for the conventional and anti-coincidence spectrometric systems, respectively, and 50 ppb for As in both cases. Details of the method and results are presented.     

Continuous neutron activation analysis

A review on the uses of neutron activation techniques for on-stream analysis.     

Chemical Composition of Spirulina platensis Cultivated in Uzbekistan

Conditions for growing spirulina (Spirulina platensis) were developed. The amino-acid and carbohydrate compositions were determined. Lipids and vitamins of the culture biomass were studied.     

Multiparameter neutron activation analysis

An advanced neutron activation technique has been developed for the accurate analysis of elemental and isotopic fissile material required in nuclear safeguards, nuclear material standardization and other applications. It is based on reactor neutron flux spectrum differentiation by cadmium screening and multistandard calibration, including the solution of a second order equation system or of computerized calibration curve fitting, taking into account the thermal neutron flux depression. Some discrepancies at high enrichments have still to be eliminated in order to achieve the required measurement accuracy.