Volumen 60 (2015): Edición 3 (July 2015)

The interface between optical spectroscopy, electron magnetic resonance (EMR), and magnetism of transition ions forms the intricate web of interrelated notions. Major notions are the physical Hamiltonians, which include the crystal field (CF) (or equivalently ligand field (LF)) Hamiltonians, and the effective spin Hamiltonians (SH), which include the zero-field splitting (ZFS) Hamiltonians as well as to a certain extent also the notion of magnetic anisotropy (MA). Survey of recent literature has revealed that this interface, denoted CF (LF) ↔ SH (ZFS), has become dangerously entangled over the years. The same notion is referred to by three names that are not synonymous: CF (LF), SH (ZFS), and MA. In view of the strong need for systematization of nomenclature aimed at bringing order to the multitude of different Hamiltonians and the associated quantities, we have embarked on this systematization. In this article, we do an overview of our efforts aimed at providing a deeper understanding of the major intricacies occurring at the CF (LF) ↔ SH (ZFS) interface with the focus on the EMR-related problems for transition ions.

The difficulty in determining the electron paramagnetic resonance (EPR) line parameters of ferromagnetic semiconductors has been addressed. For these materials, the resonance line is very broad and lies at low resonance field, so that only a part of the line can be detected experimentally. Moreover, the line is of asymmetric (Dysonian) shape as described by the line shape parameter α. We have compared values of line parameters derived by computer fitting of the whole experimental EPR line to the Dyson function (or modified Dyson function) with the values obtained by applying this procedure to the left and the right half of the line.

Two-temperature electron paramagnetic resonance (EPR) measurements, applied to determine the relative contributions of paramagnetic centers – fulfilling and not-fulfilling the Curie law, were carried out. The measurements were made on the macerals – exinite and vitrinite, separated from clarain of the Polish medium-rank coal (85.6 wt% C). The two-temperature EPR measurements, presented in this work, were performed respectively, at temperatures: T₁ = 293 K and T₂ = 173 K for exinite, and T₁ = 293 K and T₂ = 153 K for vitrinite. The relative contributions X of spins not-fulfilling the Curie law present in the studied macerals were calculated. A comparison of different methods of calculating the relative contributions of paramagnetic centers – fulfilling and not-fulfilling the Curie law, present in exinite and vitrinite studied by EPR was made.

Penetration of the liposome membranes doped with vanadium complex formed in the liquid-crystalline phase from egg yolk lecithin (EYL) by the TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) spin probes has been investigated. The penetration process was followed by 360 hours at 24°C, using the electron spin resonance (EPR) method. The spectroscopic parameter of the partition (F) of this probe indicated that a maximum rigidity of the membrane was at 3% concentration of the vanadium complex. Computer simulations showed that the increase in the rigidity of the membrane corresponds to the closure of gaps in the surface layer of the membrane, and indicates the essential role of the membrane surface in transport processes.

In this work, the electron magnetic resonance (EMR) spectra of the mullites powders were measured for different grain sizes (0.07 and 0.12 mm). We have used EMR spectroscopy at X-band, combined with superposition model (SPM) calculations to reveal electronic structure and establish correlations between structure, and surroundings of these complexes.

Single crystals of ErVO₄ were grown by the Czochralski method under ambient pressure in a nitrogen atmosphere. Obtained crystals were transparent with strong pink coloring. Electron paramagnetic resonance (EPR) spectra were recorded as a function of the applied magnetic field. Temperature and angular dependences of the EPR spectra of the samples in the 3–300 K temperature range were analyzed applying both Lorentzian––Gauss approximation for diluted medium and Dyson for dense magnetic medium. EPR-NMR program was done to find local symmetry and spin Hamiltonian parameters of erbium ions.

Three nCo,N-TiO₂ nanocomposites (where cobalt concentration index n = 1, 5 and 10 wt %) were prepared and investigated by magnetic resonance spectroscopy at room temperature. Ferromagnetic resonance (FMR) lines of magnetic cobalt agglomerated nanoparticle were dominant in all registered spectra. The relaxation processes and magnetic anisotropy of the investigated spin system essentially depended on the concentration of cobalt ions. It is suggested that the samples contained two magnetic types of sublattices forming a strongly correlated spin system. It is suggested that the existence of strongly correlated magnetic system has an essential influence of the photocatalytic properties of the studied nanocomposites.

An ²⁷Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) study of nominally pure and Cr-doped yttrium-aluminum garnet (Y₃Al₅O₁₂ and Y₃Al₅O₁₂:Cr) crystals is reported. It has been shown that the doping by Cr of the Y₃Al₅O₁₂ crystals leads to the variation of the occupation by Al atoms both octahedrally and tetrahedrally coordinated sites of the garnet lattice.

The aim of this study is the application of electron magnetic resonance (EMR) spectroscopy to determine the interactions between NaY and HY zeolites and Cu-Mn-Zn spinels loaded onto the zeolite surfaces. The materials were characterized using XRD and IR spectroscopies. Four types of EMR lines were observed for Cu-Mn-Zn/NaY, Cu-Mn-Zn/HY samples. The difference between the EMR spectra recorded at 77 and 293 K has been shown. The spectra recorded at 77 K allowed us to distinguish between the species formed on NaY and HY zeolites. The EMR spectrum of Cu-Mn-Zn/NaY recorded at 77 K showed only one line attributed to antiferromagnetic spinels Cu_1.4Mn_1.6O₄ and ZnMn₂O₄ or/and Cu_0.5Zn_0.5Mn₂O₄. The spinels appeared to be more stable (more strongly attached) on HY zeolite than on NaY one. It was proved that different strength of interactions between the zeolites and Cu-Mn-Zn spinels was caused by differences in the acidity of NaY and HY zeolites.

In calcite and aragonite, γ-irradiated at 77 K, several paramagnetic centers were generated and detected by EPR spectroscopy; in calcite, CO₃⁻ (orthorhombic symmetry, bulk and bonded to surface), CO₃³⁻, NO₃²⁻, O₃⁻, and in aragonite CO₂⁻ (isotropic and orthorhombic symmetry) depending on the type of calcium carbonate used. For calcium carbonates enriched with ¹³C more detailed information about the formed radicals was possible to be obtained. In both natural (white coral) and synthetic aragonite the same radicals were identified with main differences in the properties of CO₂⁻ radicals. An application of Q-band EPR allowed to avoid the signals overlap giving the characteristics of radical anisotropy.

Magnetic properties of a Ni₅₀Mn_35.5In_14.5 Heusler ribbon were studied by ferromagnetic resonance (FMR) in the temperature range of 335–100 K. In the temperature region of 265–170 K, the FMR signal disappeared, in spite of the fact that this region comprised the main crystal transformation temperatures: M_s, M_f, A_s, A_f. In the austenite crystal state, a weak antiferromagnetic interaction was observed, whereas ferromagnetism was detected in the low temperature martensitic state.

Free radicals formed during thermal sterilization of eucerinum anhydricum – the pharmaceutical base were examined by an X-band (9.3 GHz) spectrometer. Eucerinum anhydricum was sterilized at different physical conditions according to the Polish Pharmacopeia norms. The samples were heated at temperatures: 160°C (120 min), 170°C (60 min), and 180°C (30 min). The aim of this study is to compare free radical concentration and effect of microwave power on EPR spectra of eucerinum anhydricum base thermally sterilized at different temperatures and periods of time. The effect of time storage on the free radicals in the heated samples was tested. Free radical concentrations in the sample stored 15 min strongly decreased with the increasing of sterilization temperature, probably as the result of recombination. Storage caused strong decrease of free radical concentrations in the samples, probably as the result of interactions with oxygen. It was observed to be independent of sterilization conditions from 2 days of storage and longer. Because of the lowest free radical concentration, for eucerinum anhydricum thermal sterilization at 180°C for 30 min is recommended. The sterilized samples should be stored at inert atmosphere without oxygen molecules. Fast spin-lattice relaxation processes existed in sterilized eucerinum anhydricum. The character of changes of amplitudes and linewidths of EPR lines with increasing of microwave power was the same for different storage times. The parameters of thermal sterilization and storage time influenced free radical concentration in eucerinum anhydricum, but magnetic spin-lattice interactions were unchanged. The usefulness of EPR spectroscopy in optimization of thermal sterilization process of eucerinum anhydricum was confirmed.

The popular pharmaceutical base used in pharmacy – vaselinum flavum – was studied by an X-band (9.3 GHz) EPR spectrometer in the range of microwave power of 2.2–70 mW. The samples were sterilized in hot air oven at temperatures: 160°C (120 min), 170°C (60 min), and 180°C (30 min). The aim of this work was to determine properties and free radical concentrations in vaselinum flavum thermally sterilized at different conditions. The changes in free radical system in vaselinum flavum during storage were analyzed. Free radicals were found in all the heated samples. The lowest free radical concentration was obtained for vaselinum flavum heated at 180°C for 30 min; so these parameters are proposed for the thermal sterilization of this pharmaceutical base. Interactions with oxygen decreased free radical concentration in vaselinum flavum during storage. Strong quenching of free radicals in vaselinum flavum was observed after 2 days for the samples sterilized at temperatures 160 and 180°C. Such an effect for vaselinum flavum heated at temperature 170°C was observed later, 13 days after sterilization. Fast spin-lattice relaxation processes exist in thermally sterilized vaselinum flavum. The EPR lines of heated vaselinum flavum were homogeneously broadened. EPR spectroscopy and its use for examining the thermal sterilization process in pharmacy was confirmed.

Paramagnetic centers in the two exemplary synthetic and natural dental biocompatible materials applied in implantology were examined by the use of an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra were measured in the range of microwave power 2.2–70 mW. The aims of this work were to compare paramagnetic centers concentrations in different dental biocompatible materials and to determine the effect of microwave power on parameters of their EPR spectra. It is the very first and innovatory examination of paramagnetic centers in these materials. It was pointed out that paramagnetic centers existed in both natural (~10¹⁸ spin/g) and synthetic (~10¹⁹ spin/g) dental biocompatible materials, but the lower free radical concentration characterized the natural sample. Continuous microwave saturation of EPR spectra indicated that faster spin-lattice relaxation processes existed in synthetic dental biocompatible materials than in natural material. Linewidths (ΔB_pp) of the EPR spectra of the natural dental material slightly increased for the higher microwave powers. Such effect was not observed for the synthetic material. The broad EPR lines (ΔB_pp): 2.4 mT, 3.9 mT, were measured for the natural and synthetic dental materials, respectively. Probably strong dipolar interactions between paramagnetic centers in the studied samples may be responsible for their line broadening. EPR spectroscopy is the useful experimental method in the examination of paramagnetic centers in dental biocompatible materials.

In this paper, the effects of model (commercial) and natural (extracted from peat) humic substances on the membrane of liposomes formed with egg yolk lecithin (EYL) are presented. In our research, mass concentrations of fulvic and humic acids were used, which in relation to lecithin varied from 0% to 13%. To study membrane fluidity, electron spin resonance (EPR) was used with two spin probes, penetrating various regions of the lipid bilayer. The effects of model and natural humic substances (humic acids – HAs and fulvic acids – FAs) on the lipid membrane in different regions were researched: the lipid-water interphase, and in the middle of the lipid bilayer. It was shown that FA and HA impact the fluidity of liposome membranes in different ways. Increased mass concentrations of HAs decreased membrane fluidity in both acids: extracted from peat and the model. However, increased mass concentration of FAs extracted from peat, decreased membrane fluidity in the surface region, at the same time stiffening the central part of the bilayer. Increasing the concentration of FAs extracted from peat had the opposite effect when compared to model FA. This effect may be related to the complexation of xenobiotics present in the soil environment and their impact on biological membranes.

In the present work, we report the results of a spin trapping ESR study of four essential oils widely used for skin care products such as creams and bath salts. The studied essential oils are Rosmarini aetheroleum (rosemary), Menthae piperitae aetheroleum (mint), Lavandulae aetheroleum (lavender), and Thymi aetheroleum (thyme). Fenton reaction in the presence of ethanol was used to generate free radicals. The N-tert-butyl-α-phenylnitrone (PBN) was used as a spin trap. In the Fenton reaction, the rosemary oil had the lowest effect on radical adduct formation as compared to the reference Fenton system. Since essential oils are known to be lipid soluble, we also conducted studies of essential oils in Fenton reaction in the presence of lipids. Two model lipids were used, namely 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The obtained results suggested that in the presence of DOPC lipids, the ^•OH and PBN/^•CHCH₃(OH) radicals are formed in both phases, that is, water and lipids, and all the studied essential oils affected the Fenton reaction in a similar way. Whereas, in the DPPC system, the additional type of PBN/X (a_N = 16.1 G, a_H = 2.9 G) radical adduct was generated. DFT calculations of hyperfine splittings were performed at B3LYP/6-311+G(d,p)/EPR-II level of theory for the set of c-centered PBN adducts in order to identify PBN/X radical.

Cookies are a group of convenient food products that are popular among consumers. They may contain high amounts of fats, which can be prone to oxidation. To retard the oxidative deterioration, synthetic and natural antioxidants may be added. Herb and spice extracts can be sources of natural biologically active substances with antioxidant activity. In this work, electron paramagnetic resonance spectroscopy was used to monitor the lipid oxidation in cookies with rosemary and thyme extracts subjected to the storage in elevated temperature. It was shown that thyme extract can be used as a natural antioxidant source for the preparation of bakery products, while the rosemary extract should be used with care in fat-rich products exposed to high temperatures.

The interaction of synthetic dihydroxyphenylalanine (DOPA) melanin (DM) with nitrite ions, NO₂⁻, in the pH 3.6–7.0 range, has been investigated using electron paramagnetic resonance (EPR). We found that especially at pH <5.5 (from ca. 5.5 to 3.6) the reaction of DM with nitrite generated large quantities of new melanin radicals, which implies the involvement of nitrous acid, HNO₂, in the radical formation process. Measurements carried out at constant pH of 3.6 showed that the melanin signal increased together with nitrite concentration, reaching a plateau level which was more than fourfold larger compared to the initial signal amplitude observed in a nitrite-free buffer of the same pH. The effects of nitrite and DM concentrations on the melanin-free radical content were also investigated. It is proposed that the radicals are generated by one electron oxidation of melanin ortho-hydroquinone groups to ortho-semiquinones by HNO₂ or related nitrogen oxides such as NO₂^• radicals. The possible involvement of nitric oxide (^•NO) and peroxynitrite (ONOO⁻) in DM oxidation was also examined. In air-free solutions, nitric oxide per se did not generate melanin radicals; however, in the presence of oxygen a marked increase in the melanin EPR signal intensity was observed. This result is interpreted in terms of the generation of radicals via the oxidation of DM by peroxynitrite. Our findings suggest that melanin can function as a natural scavenger of nitrous acid and some nitrous acid-derived species. This property may be relevant to physiological functions of melanin pigments in vivo.

Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR) spectroscopy. The effect of time of ultraviolet (UV) irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz) in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~10²¹–10²² spin/g) of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.

The aim of this study is the evaluation of electron dose enhancement and photon contamination production by various nanoparticles in the electron mode of a medical linac. MCNPX Monte Carlo code was used for simulation of Siemens Primus linac as well as a phantom and a tumor loaded with nanoparticles. Electron dose enhancement by Au, Ag, I and Fe₂O₃ nanoparticles of 7, 18 and 30 mg/ml concentrations for 8, 12 and 14 MeV electrons was calculated. The increase in photon contamination due to the presence of the nanoparticles was evaluated as well. The above effects were evaluated for 500 keV and 10 keV energy cut-offs defined for electrons and photons. For 500 keV energy cut-off, there was no significant electron dose enhancement. However, for 10 keV energy cut-off, a maximum electron dose enhancement factor of 1.08 was observed for 30 mg/ml of gold nanoparticles with 8 MeV electrons. An increase in photon contamination due to nanoparticles was also observed which existed mainly inside the tumor. A maximum photon dose increase factor of 1.07 was observed inside the tumor with Au nanoparticles. Nanoparticles can be used for the enhancement of electron dose in the electron mode of a linac. Lower energy electron beams, and nanoparticles with higher atomic number, can be of greater benefit in this field. Photons originating from nanoparticles will increase the photon dose inside the tumor, and will be an additional advantage of the use of nanoparticles in radiotherapy with electron beams.

To design a potent agent for positron emission tomography/magnetic resonance imaging (PET/MRI) imaging and targeted magnetic hyperthermia-radioisotope cancer therapy radiolabeled surface modified superparamagnetic iron oxide nanoparticles (SPIONs) were used as nanocarriers. Folic acid was conjugated for increasing selective cellular binding and internalization through receptor-mediated endocytosis. SPIONs were synthesized by the thermal decomposition of tris (acetylacetonato) iron (III) to achieve narrow and uniform nanoparticles. To increase the biocompatibility of SPIONs, they were coated with (3-aminopropyl) triethoxysilane (APTES), and then conjugated with synthesized folic acid-polyethylene glycol (FA-PEG) through amine group of (3-aminopropyl) triethoxysilane. Finally, the particles were labeled with ⁶⁴Cu (t_1/2 = 12.7 h) using 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono (N-hydroxy succinimide ester) DOTA-NHS chelator. After the characterization of SPIONs, their cellular internalization was evaluated in folate receptor (FR) overexpressing KB (established from a HeLa cell contamination) and mouse fibroblast cell (MFB) lines. Eventually, active and passive targeting effects of complex were assessed in KB tumor-bearing Balb/C mice through biodistribution studies. Synthesized bare SPIONs had low toxicity effect on healthy cells, but surface modification increased their biocompatibility. Moreover, KB cells viability was reduced when using folate conjugated SPIONs due to FR-mediated endocytosis, while having little effect on healthy cells (MFB). Moreover, this radiotracer had tolerable in vivo characteristics and tumor uptake. In the receptor blocked case, tumor uptake was decreased, indicating FR-specific uptake in tumor tissue while enhanced permeability and retention effect was major mechanism for tumor uptake.

With gamma spectrometric method 23 samples of mineral and thermal waters of Bosnia and Herzegovina were analyzed. Activity concentrations of the investigated radionuclides were in the range 12–346 mBq·L⁻¹ for ⁴⁰K, 1.1–791 mBq·L⁻¹ for ²²⁶Ra, 0.2–221 mBq·L⁻¹ for ²²⁸Ra, 13–367 mBq·L⁻¹ for ²³⁸U, and 0.6–17 mBq·L⁻¹ for ²³⁵U. For all investigated radionuclides annual effective dose was estimated. The estimated total annual committed effective dose received by population as a result of ingestion of water was in the range 0.11–2.51 μSv·y⁻¹ for thermal water and in the range 0.11–38.8 μSv·y⁻¹ for mineral water. Measurement of activity concentrations of natural radionuclides in the examined samples was carried out with a gamma-spectrometer with high-purity germanium (HPGe) detector, having a relative efficiency of 70%.

The main objective of the present study was an assessment of the possibility of uranium recovery from domestic resources in Poland. In the first stage uranium was leached from the ground uranium ore by using acidic (sulfuric acid or hydrochloric acid) or alkaline (carbonate) solutions. The leaching efficiencies of uranium were dependent on the type of ore and it reached 81% for Dictyonemic shales and almost 100% for sandstones. The novel leaching routes, with the application of the helical membrane contactor equipped with rotating part were tested. The obtained postleaching solutions were concentrated and purified using solvent extraction or ion exchange chromatography. New methods of solvent extraction, as well as hybrid processes for separation and purification of the product, were studied. Extraction with the use of membrane capillary contactors that has many advantages above conventional methods was also proposed as an alternative purification method. The final product U₃O₈ could be obtained by the precipitation of ‘yellow cake’, followed by calcination step. The results of precipitation of ammonium diuranate and uranium peroxide from diluted uranium solution were presented

In this paper, we compare the methodology of different time-step models in the context of Monte Carlo burnup calculations for nuclear reactors. We discuss the differences between staircase step model, slope model, bridge scheme and stochastic implicit Euler method proposed in literature. We focus on the spatial stability of depletion procedure and put additional emphasis on the problem of normalization of neutron source strength. Considered methodology has been implemented in our continuous energy Monte Carlo burnup code (MCB5). The burnup simulations have been performed using the simplified high temperature gas-cooled reactor (HTGR) system with and without modeling of control rod withdrawal. Useful conclusions have been formulated on the basis of results.

Three-dimensional simulations of neutronics and thermal hydraulics of nuclear reactors are a tool used to design nuclear reactors. The coupling of MCB and FLUENT is presented, MCB allows to simulate neutronics, whereas FLUENT is computational fluid dynamics (CFD) code. The main purpose of the coupling is to exchange data such as temperature and power profile between both codes. Temperature required as an input parameter for neutronics is significant since cross sections of nuclear reactions depend on temperature. Temperature may be calculated in thermal hydraulics, but this analysis needs as an input the power profile, which is a result from neutronic simulations. Exchange of data between both analyses is required to solve this problem. The coupling is a better solution compared to the assumption of estimated values of the temperatures or the power profiles; therefore the coupled analysis was created. This analysis includes single transient neutronic simulation and several steady-state thermal simulations. The power profile is generated in defined points in time during the neutronic simulation for the thermal analysis to calculate temperature. The coupled simulation gives information about thermal behavior of the reactor, nuclear reactions in the core, and the fuel evolution in time. Results show that there is strong influence of neutronics on thermal hydraulics. This impact is stronger than the impact of thermal hydraulics on neutronics. Influence of the coupling on temperature and neutron multiplication factor is presented. The analysis has been performed for the ELECTRA reactor, which is lead-cooled fast reactor concept, where the coolant fl ow is generated only by natural convection

The main object of interest was a typical fuel assembly, which constitutes a core of the nuclear reactor. The aim of the paper is to describe the phenomena and calculate thermal-hydraulic characteristic parameters in the fuel assembly for a European Pressurized Reactor (EPR). To perform thermal-hydraulic calculations, the RELAP5 code was used. This code allows to simulate steady and transient states for reactor applications. It is also an appropriate calculation tool in the event of a loss-of-coolant accident in light water reactors. The fuel assembly model with nodalization in the RELAP5 (Reactor Excursion and Leak Analysis Program) code was presented. The calculations of two steady states for the fuel assembly were performed: the nominal steady-state conditions and the coolant flow rate decreased to 60% of the nominal EPR flow rate. The calculation for one transient state for a linearly decreasing flow rate of coolant was simulated until a new level was stabilized and SCRAM occurred. To check the correctness of the obtained results, the authors compared them against the reactor technical documentation available in the bibliography. The obtained results concerning steady states nearly match the design data. The hypothetical transient showed the importance of the need for correct cooling in the reactor during occurrences exceeding normal operation. The performed analysis indicated consequences of the coolant flow rate limitations during the reactor operation.

Following the accident at the Daiichi Fukushima nuclear power plant in 2011, a vast number of Pacific seawater samples from many locations far from Fukushima have been collected by Japanese investigators. Due to dilution, the activities of radionuclides from North Pacific seawater samples are very low, which calls for extraordinary measures when being measured. This study focuses on the metrological aspects of the gamma-ray spectrometry measurements performed on such samples in two underground laboratories; at HADES (by JRC-IRMM in Belgium), and at Ogoya (by Kanazawa University in Japan). Due to many samples and long measurement times, all available HPGe detectors needed to be employed. In addition to single coaxial detectors, this involved multidetector systems and well detectors. Optimization of detection limits for different radionuclides and detectors was performed using Monte Carlo simulations.

A closed near-surface radioactive waste repository is the source of various radionuclides causing the human exposure. Recent investigations confirm an effectiveness of the engineering barriers installed in 2006 to prevent the penetration of radionuclides to the environment. The tritium activity concentration in groundwater decreased from tens of kBq/l to below hundreds of Bq/l. The monitoring and groundwater level data suggest the leaching of tritium from previously contaminated layers of unsaturated zone by rising groundwater while ²¹⁰Pb may disperse as a decay product of ²²⁶Ra daughters.

Safety of radioactive waste repositories operation is associated with a multibarrier system designed and constructed to isolate and contain the waste from the biosphere. Each of radioactive waste repositories is equipped with system of barriers, which reduces the possibility of release of radionuclides from the storage site. Safety systems may differ from each other depending on the type of repository. They consist of the natural geological barrier provided by host rocks of the repository and its surroundings, and an engineered barrier system (EBS). The EBS may itself comprise a variety of sub-systems or components, such as waste forms, canisters, buffers, backfills, seals and plugs. The EBS plays a major role in providing the required disposal system performance. It is assumed that the metal canisters and system of barriers adequately isolate waste from the biosphere. The evaluation of the multibarrier system is carried out after detailed tests to determine its parameters, and after analysis including mathematical modeling of migration of contaminants. To provide an assurance of safety of radioactive waste repository multibarrier system, detailed long term safety assessments are developed. Usually they comprise modeling of EBS stability, corrosion rate and radionuclide migration in near field in geosphere and biosphere. The principal goal of radionuclide migration modeling is assessment of the radionuclides release paths and rate from the repository, radionuclides concentration in geosphere in time and human exposure to ionizing radiation

Although a disk-type fly ash filter has shown a good performance in trapping gaseous cesium, it has difficulty in charging filters into a filter container and discharging waste filters containing radioactive cesium from a container by remote action. To solve the difficulty of the disk-type fly ash filter, five types of granule filters, including a ball type, tube type, and sponge-structure type have been made. Among them, the best filter type was chosen through simple crucible tests. The five types of granule filters packed into containers were loaded into five alumina crucibles of 50 cc. Five grams of CsNO₃ was used as a gaseous cesium source. They were then placed in a muffle furnace and heated to 900°C and maintained for 2 hours. After the experiment, the weights of the cesium trapped filters were measured. Among the five types of granule filters, the sponge-structure type granule filter was the best, which has the highest trapping capacity of cesium. Its capacity is 0.42 g-Cs/g-filter. The chosen sponge-structure type granule filters and disk-type filters have been tested using a two-zone tube furnace. Cs volatilization and Cs trapping zones were maintained at 900 and 1000°C, respectively. Sixteen grams of CsNO₃ was used as a gaseous cesium source. The cesium trapping profile of the sponge-structure type granule filters was almost similar to that of the disk-type fly ash filters. For both cases, cesium was successfully trapped within the third filter.

In the paper, we assess the accuracy of the Monte Carlo continuous energy burnup code (MCB) in predicting final concentrations of major actinides in the spent nuclear fuel from commercial PWR. The Ohi-2 PWR irradiation experiment was chosen for the numerical reconstruction due to the availability of the final concentrations for eleven major actinides including five uranium isotopes (U-232, U-234, U-235, U-236, U-238) and six plutonium isotopes (Pu-236, Pu-238, Pu-239, Pu-240, Pu-241, Pu-242). The main results were presented as a calculated-to-experimental ratio (C/E) for measured and calculated final actinide concentrations. The good agreement in the range of ±5% was obtained for 78% C/E factors (43 out of 55). The MCB modeling shows significant improvement compared with the results of previous studies conducted on the Ohi-2 experiment, which proves the reliability and accuracy of the developed methodology.

The concept of closed nuclear fuel cycle seems to be the most promising options for the efficient usage of the nuclear energy resources. However, it can be implemented only in fast breeder reactors of the IVth generation, which are characterized by the fast neutron spectrum. The lead-cooled fast reactor (LFR) was defined and studied on the level of technical design in order to demonstrate its performance and reliability within the European collaboration on ELSY (European Lead-cooled System) and LEADER (Lead-cooled European Advanced Demonstration Reactor) projects. It has been demonstrated that LFR meets the requirements of the closed nuclear fuel cycle, where plutonium and minor actinides (MA) are recycled for reuse, thereby producing no MA waste. In this study, the most promising option was realized when entire Pu + MA material is fully recycled to produce a new batch of fuel without partitioning. This is the concept of a fuel cycle which asymptotically tends to the adiabatic equilibrium, where the concentrations of plutonium and MA at the beginning of the cycle are restored in the subsequent cycle in the combined process of fuel transmutation and cooling, removal of fission products (FPs), and admixture of depleted uranium. In this way, generation of nuclear waste containing radioactive plutonium and MA can be eliminated. The paper shows methodology applied to the LFR equilibrium fuel cycle assessment, which was developed for the Monte Carlo continuous energy burnup (MCB) code, equipped with enhanced modules for material processing and fuel handling. The numerical analysis of the reactor core concerns multiple recycling and recovery of long-lived nuclides and their influence on safety parameters. The paper also presents a general concept of the novel IVth generation breeder reactor with equilibrium fuel and its future role in the management of MA.

To use effectively any radiation detector in high-temperature plasma experiments, it must have a lot of benefits and fulfill a number of requirements. The most important are: a high energy resolution, linearity over a wide range of recorded particle energy, high detection efficiency for these particles, a long lifetime and resistance to harsh conditions existing in plasma experiments and so on. Solid-state nuclear track detectors have been used in our laboratory in plasma experiments for many years, but recently we have made an attempt to use these detectors in spectroscopic measurements performed on some plasma facilities. This paper presents a method that we used to elaborate etched track diameters to evaluate the incident projectile energy magnitude. The method is based on the data obtained from a semiautomatic track scanning system that selects tracks according to two parameters, track diameter and its mean gray level.

Anthropogenic activities, such as high-altitude flights and living in buildings, have enhanced the public exposure to natural radiation. In particular, ⁴⁰K and radionuclides belonging to ²³²Th and ²³⁸U decay chains are present even in building materials, and they may be considered as partially responsible for the effective dose coming from natural radioactivity. Scientists and governments have devoted great attention to the evaluation of the effects produced on the public by naturally occurring radionuclides. In this context, to evaluate the building materials acceptability, accurate and reliable methods for the measurement of the specific activity of natural radioactive isotopes in building materials have been developed. This paper aims to provide a clear and exhaustive review on natural radionuclide measurement procedures. Several standard national normatives (Dutch NEN 5697, Italian UNI 10797, Polish ITB 455), based on gamma spectrometry, have been considered and some critical issues were identified regarding the preparation and the radiometric measuring of the samples. Therefore, the direct measurement of ²³⁸U and ²³²Th by ICP-MS spectrometry as well as the extrapolation of the specific activities without waiting for secular equilibrium have been considered as two promising alternative approaches.

The Fricke xylenol orange (FX) gel system is a chemical dosimeter characterized by good sensitivity, linear dose response, tissue equivalence, no toxicity, easy preparation, reproducibility and low cost. Thanks to the presence of the gelatinous matrix, the system is particularly suitable to perform reliable 3D mapping of the absorbed dose spatial distribution via magnetic resonance imaging (MRI) or optical techniques. The aim of this work is to study in a systematic way the influence of the pre-irradiation storage procedure upon sensitivity, dose response stability and lifetime of use of a FX gel system made with gelatin from porcine skin subjected to homogeneous irradiation. For this purpose, different pre-irradiation storage procedures, in terms of temperature and duration of each storage step, were investigated. In order to evaluate the dose response stability, the optical analyses of the samples were performed up to 6 hours after irradiation. Moreover, the samples were irradiated at time intervals of 24 hours for up to 7 days after preparation in order to evaluate the system lifetime of use. Regardless of their thermal and temporal life, the samples show linear dose responses in the investigated dose range (3-24 Gy) and an increase of sensitivity with the time elapsed between preparation and irradiation. Among the three pre-irradiation storage procedures considered here, a procedure that provides the best dose response stability and lifetime of use was identified and recommended for further use. The analyzed dosimetric system possesses good properties that make it promising for medical application, particularly concerning the evaluation of pre-treatment plan quality assurance within the conformational external beam radiotherapy

Basing on alanine solid state/electron paramagnetic resonance (EPR) dosimetry, a supplementary method of cumulatively recording the therapeutic dose received by ocular cancer patients undergoing fractionated proton radiotherapy is proposed. By applying alanine dosimetry during the delivery of consecutive fractions, the dose received within each fraction can be read out by EPR spectrometry and a final permanent cumulative record of the total dose delivered obtained. The dose response of the alanine detector was found to be practically independent on its position within the extended proton Bragg peak region. Dose measurements based on entrance dose recorded in proton beams individually formed for each patient are presented. The described method will be applied as a complementary Quality Assurance procedure for patients undergoing proton radiotherapy at the Institute of Nuclear Physics, Polish Academy of Sciences, Krakow, Poland (IFJ PAN).

Characterization of nuclear materials is an important topic within the context of nuclear safeguards, homeland security and nuclear forensics. This paper deals with the performance of multigroup gamma-ray analysis (MGA) method using the X- and γ-rays in the 80-130 keV region and enrichment meter principle (EMP) based on the analysis of 185.7 keV peak for a certain geometry using different absorbers and collimators. The results from MGA and those of EMP are compared. In particular, the effect of aluminum/lead absorbers and lead collimator on the enrichment determination of ²³⁵U in natural and low enriched samples is investigated in a given source-detector geometry. The optimum diameter/height ratio for the Pb-collimator is found to be D_c/H_c = 1.4-1.6 in the chosen geometry. In order to simulate the container walls, ten different thicknesses of Al-absorbers of 141 to 840 mg·cm^-2 and six different thicknesses of Pb-absorbers of 1120-7367 mg·cm^-2 are interposed between sample and detector. The calibration coefficients (% enrichment/cps) are calculated for each geometry. The comparison of the MGA and EMP methods shows that the enrichment meter principle provides more accurate and precise results for ²³⁵U abundance than those of MGA method at the chosen geometrical conditions. The present results suggest that a two-step procedure should be used in analyses of uranium enrichment. Firstly MGA method can be applied in situ and then EMP method can be used at a defined geometry in laboratory.

The scientific interest in air pollution comes from its influence on human health, the condition of cultural heritage and climate. The PM2.5 fraction (particles of a diameter of 2.5 mm or below), indirectly, has a significant impact on health which is associated with respiratory tract and blood vessel related diseases. However, not only the size, but also the content of the particles has a significant meaning. To determine the particulate matter contents, elemental analysis can be performed using numerous techniques, the most important of which is X-ray fluorescence. In this study, samples of PM2.5 fraction collected in Krakow, Poland were analyzed. The X-ray fluorescence method was used to perform elemental analysis. The gravimetric method was applied to determine the concentration of the PM2.5 fraction. Low detection limits of individual elements and precision of the X-ray fluorescence method were determined. The concentrations of the following elements: Cl, K, Ca, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr and Pb in the PM2.5 fraction samples collected in Krakow were evaluated. The homogeneity of the samples was also estimated. The concentrations of PM2.5 fraction collected in the summer of 2013 were in the range of 6-23 ng/m³. The concentrations of PM2.5 fraction collected in the winter of 2013 were in the range of 26-171 ng/m³. The precision of the method was found to be below 1% for elements with high concentration in the sample and 6-8 % for trace elements.

The dominating carbohydrates in fruits are monosaccharides like fructose, glucose, sorbose and mannose. In dehydrated fruits, concentration of monosaccharides is higher than in fresh fruits resulting in the formation of sugar crystallites. In most of dried fruits, crystalline fructose, and glucose dominate and appear in proportion near to 1:1. Irradiation of dried fruits stimulates radiation chemical processes resulting in the formation of new chemical products and free radicals giving rise to multicomponent EPR signal which can be detected for a long period of time. For that reason, it is used as a marker for the detection of radiation treatment of dried fruits. It has been found that EPR spectra recorded in dried banana, pineapple, papaya, and fig samples resemble the EPR spectrum obtained by computer addition of fructose and glucose spectra taken in proportion 1:1. The decay of radiation induced EPR signals proceeds in dried fruits fast during the first month of observation and becomes much slower and almost negligible after prolonged storage. However, it remains intense enough for EPR detection even one year after processing. The radiation induced EPR signal is easily detected in dried fruits exposed to 0.5 kGy of gamma rays. Thus, the EPR method of the detection of irradiated fruits can be used for the control of dried fruits undergoing quarantine treatment with 200-300 Gy of ionizing radiation.

During the operation of large industrial installations, a very important task is to maintain the proper technical state. In the event of an emergency, it is vital to locate the place of occurrence as soon as possible. In solving this type of problem, it often helps to apply the methods of measurement associated with ionizing radiation. One of these methods is the gamma scanning. The purpose of this type of measurement is the detection and localization of disturbance of technological processes which may result in incorrect decomposition the fl owing medium and workpiece (sediments, congestion) as well as damage to the internal constructions. A particularly: (i) preventive diagnosis - early detection of installation failure; (ii) rationalization of repairs and renovations - to determine the need to take or not to take remedial action; (iii) quick and precise installation inspections - to gain knowledge of the technical condition and technological installations; (iv) indication of worn parts and posing a threat - diagnostics of the technical condition installation; (v) forecasting the useful lifetime of equipment.

In this study, after the pulse shape calibration of a liquid scintillation counting (LSC) spectrometer (Quantulus 1220), the effi ciency was determined depending on sample quenching parameters. Then, gross alpha and beta activities in two spiked water samples obtained from International Atomic Energy Agency (IAEA) were used for the validation of the ASTM D7283-06 method, which is a standard test method for alpha and beta activity in water by LSC. Later, the drinking water samples (35 tap water and 9 bottled water) obtained from different districts of Ankara, Turkey, were measured. The maximum gross alpha activities are measured to be 0.08 Bq/L for tap waters and 0.13 Bq/L for bottled waters, whereas the maximum gross beta activities are found to be 0.18 Bq/L for tap waters and 0.16 Bq/L for bottled waters. These results indicate that these drinking water samples are below the required limits, which are 0.1 Bq/L for alpha emitting radionuclides and 1 Bq/L for beta emitting radionuclides. As a result, gross alpha and beta activities in drinking water of Ankara were determined accurately by this validated LSC method. It is also worth noting that LSC is a rapid and accurate method for the determination of gross alpha and beta activities without requiring a tedious sample preparation.

Mass casualty scenarios of radiation exposure require high throughput biological dosimetry techniques for population triage, in order to rapidly identify individuals, who require clinical treatment. Accurate dose estimates can be made by biological dosimetry, to predict the acute radiation syndrome (ARS) within days after a radiation accident or a malicious act involving radiation. Timely information on dose is important for the medical management of acutely irradiated persons [1]. The aim of the study was to evaluate the usefulness of the micronuclei (MNi) scoring procedure in an experimental mode, where 500 binucleated cells were analyzed in different exposure dose ranges. Whole-body exposure was simulated in an in vitro experiment by irradiating whole blood collected from one healthy donor with 60 MeV protons and 250 keV X-rays, in the dose range of 0.3-4.0 Gy. For achieving meaningful results, sample scoring was performed by three independent persons, who followed guidelines described in detail by Fenech et al. [2, 3]. Compared results revealed no significant differences between scorers, which has important meaning in reducing the analysis time. Moreover, presented data based on 500 cells distribution, show that there are significant differences between MNi yields after 1.0 Gy exposure of blood for both protons and X-rays, implicating this experimental mode as appropriate for the distinction between high and low dose-exposed individuals, which allows early classification of exposed victims into clinically relevant subgroups.

Measurements of α-particle sources require corrections to the counting rate due to scattering and self-absorption in the source and the backing material. In this study, we describe a simple procedure to estimate these corrections using the new Monte Carlo code AlfaMC to consider the effects of scattering and self-absorption conjointly, and so to determine the activity of α emitters. The procedure proposed was applied to ²³⁵UO₂ sources deposited on highly polished platinum backings. In general, the dependence of the efficiency with source thickness was in good agreement with a simple model considering a linear and a hyperbolic behavior for thin and thick sources, respectively, although significant deviations from this model were found for very thin sources. For these very thin sources, the Monte Carlo simulation revealed to be as a required method in the primary calibration of α-particle sources. The efficiency results obtained by simulation with AlfaMC were in agreement with available efficiency data.

Medieval Central Europe coins - the Saxon coins, also called as the Otto and Adelheid denarii, as well as the Polish ones, the Władysław Herman and Bolesław Śmiały coins - were examined to determine their provenance and dating. Their attribution and chronology often constitute a serious problem for historians and numismatists. For hundreds of years, coins were in uncontrolled conditions and in variable environment. Destructed and inhomogeneous surface were the effect of corrosion processes. Electron microscopy with energy dispersive X-ray analysis (scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS)), X-ray fluorescence (XRF) analysis (energy dispersive X-ray fluorescence (EDXRF) and total reflection X-ray fluorescence (TXRF)), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were applied. The results of these investigations are significant for our knowledge of the history of Central European coinage, especially of Polish coinage

Radiation preservation of objects of historical significance is an interesting proposition for museums, archives, libraries and private collectors. In this paper, we have limited ourselves to studying the effects of ionizing radiation on the paper. The radiation resistance of various grades of paper was examined in INCT. Irradiations were done by electron beam (10 MeV, 10 kW) and by gamma radiation (7 kG/h), for the purpose of comparison. Yields of hydrogen and absorption of oxygen were determined by gas chromatography (GC). For this purpose, the first time in an original way was used diffuse reflection spectroscopy (DRS). Described as the dose, dose rate, and lignin were found to affect degradation processes of cellulose. Examined the protective effect of lignin in the process of radiation degradation of paper. Proposed research methodology can be successfully applied to study other materials relevant to the conservation of works of art.

The cornstarch: poly(vinyl alcohol) (PVA) films characterized by the alternating ratio of starch:PVA (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100) and containing 30% of glycerol were prepared by solution casting. The films were irradiated with an absorbed dose of 25 kGy with gamma rays in a vacuum and with fast electrons in the air. The films characterized by a high content of starch appeared stiff, while the films characterized by a high content of PVA were highly flexible. The tensile strength and flexibility, as well as swelling and hydrophilicity, increased with the increase in the PVA content in the films. However, the tensile strength and wetting angle values achieved a minimum at an intermediate composition. It was found that irradiation enables to reduce hydrophilicity of the films accompanied by a decrease in their flexibility. No general conclusion concerning the effect of irradiation on tensile strength and swelling behavior can be derived. An increase in the homogeneity of the films and an increase in the compatibility of their components was found by scanning electron microscopy (SEM). Strong interactions of the starch and the PVA components were discovered by diffuse reflectance spectroscopy. Degradation was found to be the prevailing process occurring in the films under the influence of irradiation. The possible accompanying crosslinking is discussed in terms of the gel content in the samples. Creation of various oxidation products in the films characterized by the modified composition was observed under the influence of irradiation carried out in the air. Basing on the obtained results it can be supposed that the selected starch-PVA compositions might appear useful as packagings of the products predicted for radiation decontamination.

Effectiveness of electron beam irradiation was evaluated against Phytophthora nicotianae var. nicotianae, the causal agent of stem base and root rot of tomato. In laboratory trials, irradiation of 7-day-old Phytophthora cultures growing on potato-dextrose-agar (PDA) medium with 1 kGy resulted in the disintegration of the pathogen’s hyphae. Increasing the irradiation dose to 3 kGy caused decay of the hyphae. Irradiation of infested stonewool with 5 kGy caused decrease of the pathogen population about 5 times. Application of 20 kGy completely eliminated the pathogen from stonewool. Irradiation of substratum resulted in significant increase of tomato seedlings healthiness, especially when the dose 20 kGy was applied.

A Proton Beam Imaging System (ProBImS) is under development at the Institute of Nuclear Physics, Polish Academy of Sciences (IFJ PAN). The ProBImS will be used to optimize beam delivery at IFJ PAN proton therapy facilities, delivering two-dimensional distributions of beam profiles. The system consists of a scintillator, optical tract and a sensitive CCD camera which digitally records the light emitted from the proton-irradiated scintillator. The optical system, imaging data transfer and control software have already been developed. Here, we report preliminary results of an evaluation of the DuPont Hi-speed thick back screen EJ 000128 scintillator to determine its applicability in our imaging system. In order to optimize the light conversion with respect to the dose locally deposited by the proton beam in the scintillation detector, we have studied the response of the DuPont scintillator in terms of linearity of dose response, uniformity of light emission and decay rate of background light after deposition of a high dose in the scintillator. We found a linear dependence of scintillator light output vs. beam intensity by showing the intensity of the recorded images to be proportional to the dose deposited in the scintillator volume.

The exhaust gases from marine diesel engines contain high SO₂ and NO_x concentration. The applicability of the electron beam flue gas treatment technology for purification of marine diesel exhaust gases containing high SO₂ and NO_x concentration gases was the main goal of this paper. The study was performed in the laboratory plant with NO_x concentration up to 1700 ppmv and SO₂ concentration up to 1000 ppmv. Such high NO_x and SO₂ concentrations were observed in the exhaust gases from marine high-power diesel engines fuelled with different heavy fuel oils. In the first part of study the simulated exhaust gases were irradiated by the electron beam from accelerator. The simultaneous removal of SO₂ and NO_x were obtained and their removal efficiencies strongly depend on irradiation dose and inlet NO_x concentration. For NOx concentrations above 800 ppmv low removal efficiencies were obtained even if applied high doses. In the second part of study the irradiated gases were directed to the seawater scrubber for further purification. The scrubbing process enhances removal efficiencies of both pollutants. The SO₂ removal efficiencies above 98.5% were obtained with irradiation dose greater than 5.3 kGy. For inlet NO_x concentrations of 1700 ppmv the NO_x removal efficiency about 51% was obtained with dose greater than 8.8 kGy. Methods for further increase of NO_x removal efficiency are presented in the paper.