Thermoluminescence and ATR-FTIR study of UVC-irradiated low-density polyethylene (LDPE) food packaging.

This research aims to study the effects of ultraviolet C (UVC) radiation on low-density polyethylene (LDPE) food packaging. Main objectives include evaluating LDPE degradation and detecting UVC radiation using thermoluminescent dosimeters (TLDs) placed under LDPE samples. Results confirm accurate UVC detection after one hour of exposure, providing a useful tool for optimize food treatment procedures. ATR-FTIR spectroscopy analysis revealed subtle alterations (<8 % transmittance relative) in UVC-irradiated LDPE samples, including possible CH breakage (2910 and 2848 cm-1) and potential CC bond vibrations (1470 cm-1), among others. However, observed variations may stem from LDPE properties rather than entirely from UVC radiation. A comparative study of UVC-induced thermoluminescence (TL) emissions provided insights into various TLDs materials. TL kinetic analysis, using computerised glow curve deconvolution (CGCD) method, unveiled trap charge activation due to UVC exposure, including partial ionization, bleaching effect and photo-transfer (PTTL) processes. LDPE samples amplified UVC-TL responses, revealing intensity differences between the TLDs attributed to the PTTL process, accentuated by the lack of an annealing treatment. Additionally, chemical composition of the TL detectors such as, type, concentration, number, oxidation states and ionic radii of their dopants may influence UVC-TL response. Consequently, TL intensity ratios follow as: GR-200 (LiF: Mg, Cu, P) > TLD-100 (LiF: Ti, Mg) > TLD-400 (CaF2: Mn) > TLD-200 (CaF2: Dy). Thus, GR-200 detects ionizing radiation but cannot distinguish between ionizing and non-ionizing UVC radiation, while TLD-100 has limited effectiveness as a UVC radiation detector. In contrast, TLD-400 is suitable for detecting UVC radiation and TLD-200 emerges as the most favorable UVC detector, showing consistent response levels and minimal PTTL effect placed under the LDPE samples without the need of a thermal annealing treatment that makes the TLD-200 to be reusable in a low-cost measurement protocol.

Comparing the effect of electron beam, beta and ultraviolet C exposure on the luminescence emission of commercial dosimeters.

This paper reports on the luminescence characterization of TLD-100 (LiF: Ti, Mg), TLD-200 (CaF2: Dy), TLD-400 (CaF2: Mn) and GR-200 (LiF: Mg, Cu, P) dosimeters exposed to electro beam, beta and ultraviolet C radiation -UVC-. All of them show high sensitivity to radiation regardless of whether it is ionizing or partially ionizing radiation based on their luminescence properties (cathodoluminescence -CL- or thermoluminescence -TL-). CL emission differs significantly among them in shape and intensity due to their chemical compositions. LiF samples display three maxima at: (i) 300-450 nm linked to intrinsic and structural defects, (ii) a green waveband probably due to F3+ centres or the presence of hydroxyl groups and (iii) the red-infrared emission band associated with F2 centres. However, CL spectra from the CaF2 dosimeters display meaningful differences due to the dopant. TLD-200 is characterized by an emission with four sharp individual peaks in the green-IR spectral region (due to the Dy3+), whilst TLD-400 exhibits a broad maximum peaked at Ì´500 nm (linked to the Mn2+). On the other hand, the variation in the TL glow curves allows to discriminate the TLDs exposed to beta and UVC radiation since they give rise to different chemical-physical processes and that have been studied from the estimation of the kinetic parameters by means of the Computerised Glow Curve Deconvolution (CGCD) method.

Preliminary study on the thermally stimulated luminescence characterization of UVC and beta irradiated tridymite.

Thermoluminescence (TL) emission of tridymite, a quartz-like mineral, could be used for a variety purposes, including basic research, ceramic technology, traditional/medical industry, and dating. The current study focused on the investigation of the thermal effects on both the luminescence emission and structural properties of natural tridymite. Thermally stimulated luminescence of beta and UVC irradiated samples exhibits complex glow curves indicating simultaneous physical-chemistry processes such as phase transitions, dehydration, dehydroxylation or redox reactions involving intrinsic defects (O vacancies giving rise to F+ and F-type centers, Schottky and Frenkel defects), extrinsic defects (dopants) and structural defects (stacking fault defects, linear and planar defects or dislocations). TL glow curves can be analyzed despite the complexity by assuming that photon emission can be fitted to 1st order kinetics. The structural changes observed using thermal X-ray diffraction up to 200 °C indicate that the Miller indices (204) and (321) have only a reversible behavior in the range of 26-29° 2θ. Tests based on the TL also corroborate such reversibility.

A kinetic model for the thermoluminescent high dose response of LiF:Mg,Cu,P (MCP-N).

This contribution describes a kinetic model attempting to reproduce the response of the thermoluminescent material LiF:Mg,Cu,P when it is irradiated to absorbed dose values in the kGy range. The modelling is based on the hypothesis of a relationship between the irradiation time (i.e. the absorbed dose) and the density of trapping/recombination centres. X-ray diffraction and thermal X-ray diffraction measurements have been performed to investigate the potential radiation and thermal damage on the structure of the material, including the possibility of partial phases. The proposed kinetic model qualitatively reproduces the observed changes in the TL glow curve for temperatures above the main peak as well as the two observed regions of absorbed dose response: linear and sub-linear.

UV effect on the cathodo- and thermoluminescence properties of a gem-quality Cr-rich diaspore (α-AlOOH).

This work reports on the cathodoluminescence (CL) and thermoluminescence (TL) properties of gem-quality diaspore samples from Milas/Mugla (Turkey) after 100 h of ultraviolet-C (UVC) exposure. The UVC exposure induces significant changes in the intensity of the CL emission in the range of 400-800 nm that would be mainly associated with photo-oxidation processes of the impurities (Cr3+, Ti3+, Fe2+) that substitute for Al3+ in the diaspore (α-AlOOH) lattice. The UVC effect on the 400 nm-TL behavior of beta irradiated samples in the range of 0.1-8 Gy modifies the TL glow curves probably due to both photo-transfer process where electrons release from deeper to shallower traps and redox reactions involving, also, breakages-linkages of chemical bonds. Meanwhile, the 'as received' samples consist of three maxima centered at about 120, 180, and 234 °C, the 100 h UVC-irradiated samples display three maxima at 122, 220 and 270 °C. The physical trapping parameters (intensity and peak position, trap depth and pre-exponential factor) for each TL curve were estimated by using a computerized glow curve analysis program.

Simple methods to analyse thermoluminescence glow curves assuming arbitrary recombination-retrapping rates.

Numerical solutions of the differential equations system describing the transitions between energy levels can help in the understanding of the physical mechanisms governing thermoluminescence (TL) emission but they are not suitable for the analysis of complex experimental TL glow curves. On the other hand, simplified descriptions, as mixed or general order kinetics, require many additional assumptions that may limit the validity of the results or are mostly empirical. In this paper, the accuracy of such approximations has been evaluated for different retrapping-recombination ratios and it has been found that differences between the fitted and the simulated parameters arise from the simplification of the models because quasi-equilibrium condition seems to be valid in all the considered cases.

Evolution of the trapped charge distribution due to trap emptying processes in a natural aluminosilicate.

The evolution of the thermoluminescence glow curve of a natural Ca-Be rich aluminosilicate after annealing treatments at different temperatures has been studied in order to evaluate the changes in the trapped charge distribution. The glow curve consists of a single broad peak that continuously shifts toward higher temperatures when the sample is preheated up to increasing temperatures, thus indicating the presence of a continuous trap distribution. The glow curve fitting assuming different distribution functions shows how a gaussian distribution becomes a nearly exponential distribution owing to the thermal leakage of charge carriers from trapping centres.

Thermal stability of the thermoluminescence trap structure of bentonite.

This work reports about the thermal stability of the blue thermoluminescence (TL) of a well-characterised natural bentonite from Almeria (Spain). The main interest of this clay, mainly composed of montmorillonite, is because of its application in the field of high-level radioactive waste (HLW) repository in deep-lying rocks. As observed in other aluminosilicates, bentonite exhibits a very complex structure of the emission spectra based on a wide broad maximum peaked at approximately 265 degrees C that can be associated to physico-chemical processes such as dehydroxylation processes, consecutive breaking linking of bonds, formation of hydrolysed ions and redox reactions. The thermal stability tests performed at different temperatures confirm a continuum in the distribution of traps. Hence, the glow curve analysis methods commonly used for synthetic materials based on single discrete traps cannot be applied for this material and the kinetic parameters were fitted assuming an exponential distribution of trapped electrons.

Retrospective luminescence dosimetry: development of approaches to application in populated areas downwind of the Chernobyl NPP.

The cumulative absorbed dose in fired-clay bricks collected from ten buildings in the populated contaminated settlement (137Cs, 1,470 kBq m(-2)) of Stary Vishkov, located 175 km downwind of the Chernobyl Nuclear Power Plant (NPP) in the Bryansk administrative region of Russia, was determined using luminescence techniques by five laboratories. At each location, the cumulative dose, after subtraction of the natural background dose, was translated to absorbed dose in air using conversion factors derived from Monte Carlo simulations. The simulations employed source distributions inferred from contemporary soil contamination data and also took into account heterogeneity of fallout deposition. At four locations the cumulative dose at a reference location was calculated, enabling the luminescence determinations to be compared directly with values of cumulative absorbed dose in air obtained using deterministic models. A "local" conversion factor was also derived from the Monte Carlo simulations for locations where the disturbance of soil was significant. Values of the "local" cumulative dose in air calculated using this factor were compared with those predicted using the deterministic models at each sampled location, allowing location factors to be calculated. The methodology developed is generally applicable to populated areas contaminated by radioactive fallout in which brick buildings are found. The sensitivity of the luminescence techniques for bricks from this region of Russia was sufficient to evaluate cumulative absorbed dose in brick due to fallout of less than 20 mGy.

Effect of heating rate on the thermoluminescence and thermal properties of natural ulexite.

Boron-rich compounds are of interest in the nuclear industry because they exhibit a high neutron absorption cross section. The manufacture of these materials involves the application of thermal and chemical treatments. This paper focuses on the study of the effect of the heating rate (HR) in two thermal techniques, differential thermal analysis (DTA) and thermoluminescence (TL), performed on natural ulexite from Bigadiç-Balikesir (Turkey). The TL measurements were performed at six different heating rates in the range of 25-240°Cmin-1. The UV-blue TL emission of natural ulexite shifted toward higher temperatures with increasing heating rate, whereas the intensity decreased. The kinetic parameters of the ulexite (Ea=0.65(9) eV and s=1.22×1012s-1) were calculated using the variable heating rate method. DTA measurements performed in the range of 0.5-10°Cmin-1 displayed similar behavior to that of the TL response, despite the differences in technique and HR values. The DTA results indicated that natural ulexite exhibits two endothermic peaks originating from different processes: (i) a phase transition between the pentahydrated ulexite phase and a triple-hydrated phase and (ii) dehydration, dehydroxylation and alkali and earth-alkali self-diffusion processes in the ulexite lattice. The main endothermic peak shifted from 160°C to 250°C as the heating rate was increased.

Luminescence emission spectra in the temperature range of the structural phase transitions of Na2SO4.

The spectral properties of Na2SO4 have been studied by means of infrared stimulated luminescence (IRSL), thermoluminescence (TL) and radioluminescence (RL) in the range of 200-800 nm. The observed changes in the RL emission spectra after an annealing treatment (400 degrees C for 1 h) could be linked to thermal phase transformations and alkali self-diffusion through the lattice of this salt. Despite the complexity of the luminescence spectra structure, five emission bands peaked at 330, 345, 385, 460 and 630 nm could be distinguished. The UV-blue TL emission of this material exhibits a maximum peaked at 230 degrees C which is well correlated with the differential thermal analysis (DTA) and can be associated with the thermal transformation of the orthorhombic sodium sulphate (Na2SO4) V (thenardite) phase into Na2SO4 III, II and I phases. Taking into account the observed changes on the structural phase transition by X-ray diffraction (XRD) from 16 degrees C onwards, this material does not show satisfactory features for radiation dosimetry, but could be employed for temperature calibration of TL readers.

Comparison of retrospective luminescence dosimetry with computational modeling in two highly contaminated settlements downwind of the Chernobyl NPP.

The cumulative absorbed dose in bricks collected from six buildings in two heavily contaminated settlements (137Cs > 2,000 kBq m(-2)) located downwind of the Chernobyl Nuclear Power Plant was determined using luminescence techniques by six laboratories. The settlements, Vesnianoje in Ukraine and Zaborie in Russia, are located in, respectively, proximal and distal locations relative to the Chernobyl Nuclear Power Plant. The luminescence determinations of cumulative dose in brick, after subtraction of the natural background dose, were translated to absorbed dose in air at a Reference Location using conversion factors derived from Monte Carlo simulations of photon transport. The simulations employed source distributions inferred from contemporary soil contamination data and also took into account heterogeneity of fallout deposition. This translation enables the luminescence determinations to be compared directly with values of cumulative absorbed dose obtained by computational modeling and also other dose reconstruction methods. For each sampled location the cumulative dose was calculated using three deterministic models, two of which are based on the attenuation of dose-rate with migration of radionuclides in soil and the third on historic instrumental gamma dose-rate data. The results of the comparison of the two methods indicate overall agreement within margins of +/-25%. The methodology developed is generally applicable and adaptable to areas contaminated by much lower levels of radioactive fallout in which brick buildings are found.

Luminescence characteristics of dental ceramics for retrospective dosimetry: a preliminary study.

Ceramic materials that are widely employed in dental prosthetics and repairs exhibit luminescent properties. Because of their use in the body, these materials are potentially of interest in situations where retrospective dosimetry for individuals is required but where monitoring was not planned. The luminescent properties of dental ceramics obtained from Germany, Spain and the UK were examined. Linear dose-response characteristics were obtained in the range < 100 mGy to 10 Gy using thermoluminescence (TL), optically stimulated luminescence (OSL) and infrared-stimulated luminescence (IRSL) measurement techniques. Measurements of time-resolved luminescence were also performed to examine the nature of the luminescence recombination under visible (470 nm) and IR (855 nm) stimulation. The results obtained by TL and optically stimulated techniques suggest that there may be deeper traps than previously observed in certain types of dental ceramic. Such traps may be less susceptible to optical and athermal fading than was reported in earlier studies.

Kinetic parameters of lithium and aluminium doped quartz from thermoluminescence glow curves.

The thermoluminescence (TL) glow curves of irradiated annealed and non-annealed synthetic beta-quartz (Li0.73Al0.73Si1.27O4) synthesised using the ceramic method have been studied. Annealed samples (1200 degrees C for 12 h) exhibit some changes of shape and intensity in the TL glow curves when compared to non-annealed samples in the range of 0.1-5 Gy. These changes can be attributed mainly to thermal alkali self-diffusion through the lattice interfaces involving modifications in the components of the luminescent traps. In non-annealed samples six groups of components at about 100 degrees C, 130 degrees C, 160 degrees C, 210 degrees C, 330 degrees C and 450 degrees C can be found, whereas annealed samples only display one very intense peak at a lower temperature (deconvoluted into three peaks at 90 degrees C, 105 degrees C and 130 degrees C) and a lower intensity second wide broad emission at approximately 240 degrees C. In this paper, a computerised curve-fitting based on general order kinetics has been used to characterise the glow curve structure resolving trapping parameters for each glow peak: trap depth (E), frequency factor (s) and the order of the kinetics (b). The dose dependence of the individual components of the glow curve has been also studied. These data allow us to select the most stable component for use in dosimetric purposes.

Effect of the chemical impurities on the luminescence emission of natural apatites.

This paper reports on both cathodoluminescence (CL) and blue thermoluminescence (TL) emission of well-characterized natural Spanish and Brazilian apatites [Ca5(PO4)3(OH, F, Cl)]. Chemical analyses performed by means of Electron Microprobe Analysis (EMPA) have shown the presence of trace elements that can induce CL bands. In this sense, the apatites shown emission bands peaked at 3.26, 2.86, 2.62, 2.14, 2.02 and 1.94eV are respectively linked to substitutional Ce(3+), Tb(3+), Dy(3+), Pr(3+), Sm(3+) and Mn(2+) in structural Ca(2+) positions. The 3.18eV emission band can be associated with intrinsic electron defects on oxygen of the phosphate group (PO4)(3-). The presence of (UO2)(2+) gives rise to an emission at 2.14eV. All the studied aliquots exhibit one single UV-blue TL peak that modifies the position from one sample to another (370, 256 and 268°C) probably due to (i) the variation in the crystallinity index (from 0.88 to 1.34) and (ii) successive chemical processes such as oxidation, dehydration, dehydroxylation, and fluorine ions losses due to the thermal readout.

Thermal and electron stimulated luminescence of natural bones, commercial hydroxyapatite and collagen.

The luminescence (cathodoluminescence and thermoluminescence) properties of natural bones (Siberian mammoth and adult elephant), commercial hydroxyapatite and collagen were analyzed. Chemical analyses of the natural bones were determined using by Electron Probe Micro-Analysis (EMPA). Structural, molecular and thermal characteristics were determined by X-ray Diffraction (XRD), Raman spectroscopy and Differential Thermal and Thermogravimetric analysis (DTA-TG). Cathodoluminescence (CL) spectra of natural bones and collagen showed similar intense broad bands at 440 and 490 nm related to luminescence of the tetrahedral anion [Formula: see text] or structural defects. A weaker luminescence exhibited at 310 nm could be attributed to small amount of rare earth elements (REEs). Four luminescent bands at 378, 424, 468 and 576 nm were observed in the commercial hydroxyapatite (HAP). Both natural bones and collagen samples exhibited natural thermoluminescence (NTL) with well-defined glow curves whereas that the induced thermoluminescence (ITL) only appears in the samples of commercial hydroxyapatite and collagen. Additional explanations for the TL anomalous fading of apatite, as a crucial difficulty performing dosimetry and dating, are also considered.

Thermo- and cathodoluminescence properties of lepidolite.

Lepidolite, K(Li,Al)3(Si,Al)4O10(F,OH)2, and many of the related phyllosilicate mineral of the mica group have been well studied from the chemical and structural point of view; however, to the best of our knowledge, studies on their luminescence properties have been scarcely reported. This work focuses on the thermoluminescence (TL) and cathodoluminescence (CL) response of a natural lepidolite from Portugal previously characterized by means of environmental scanning electron microscope (ESEM) and X-ray fluorescence (XRF) and atomic absorption spectroscopy (AAS) techniques. The complexity of the thermoluminescence glow curves of non-irradiated and 1 Gy irradiated samples suggests a structure of a continuous trap distribution involving multiorder kinetics. UV-IR CL spectral emission shows seven peaks centered at 330, 397, 441, 489, 563, 700, and 769 nm. Such emission bands could be due to (i) structural defects, i.e., [AlO4] or non-bridging oxygen hole centers and (ii) the presence of point defects associated with Mn(2+) and Fe(3+).

Comparison of thermoluminescence (TL) and cathodoluminescence (ESEM-CL) properties between hydrothermal and metamorphic quartzes.

This paper reports on the Thermoluminescence (TL) and Cathodoluminescence (CL) emission of well-characterized hydrothermal milky quartz specimens from Hakkari in Turkey, labeled THQ, and Madrid in Spain, labeled SHQ, and metamorphic quartz from Madrid, in Spain, labeled SMQ. Both hydrothermal and metamorphic quartz samples display similar UV-IR CL spectra consisting of five groups of components centered at 330 nm and 380 nm linked to [AlO(4)]° centers, 420 nm due to intrinsic defects such as oxygen vacancies, lattice defects, and impurities which modify the crystal structure, 480 nm associated with [AlO(4)]° centers of substitutional Al(3+), and a red broad band related to the hydroxyl defects in the quartz lattice as precursors of non-bridging oxygen hole centers (NBOHC) and substitutional point defects. The Turkish quartz specimen exhibits higher CL intensity in the UV region (up to 330 nm) than the Spanish specimens probably linked to the presence of Ca (0.95% in THQ and less than 0.1% in SHQ and SMQ). At wavelengths greater than 330 nm, SMQ (formed at high pressure 6000 bars and temperatures over 500-600°C) shows higher intensity than the hydrothermal (growth at 2000 bars and temperatures 200-300°C) samples associated with the formation process. The natural blue TL glow curves of both THQ and SHQ display a weaker TL intensity than the SMQ, attributable to the Al (0.32%), Ti (0.14%), K (0.01%) and Zr (76 ppm) content. It is shown that mineralogical formation, crystallinity index and the content of the impurities seem to be the main parameters of influence in the shape intensity of the CL and TL glow curve emission.

Review of retrospective dosimetry techniques for external ionising radiation exposures.

The current focus on networking and mutual assistance in the management of radiation accidents or incidents has demonstrated the importance of a joined-up approach in physical and biological dosimetry. To this end, the European Radiation Dosimetry Working Group 10 on 'Retrospective Dosimetry' has been set up by individuals from a wide range of disciplines across Europe. Here, established and emerging dosimetry methods are reviewed, which can be used immediately and retrospectively following external ionising radiation exposure. Endpoints and assays include dicentrics, translocations, premature chromosome condensation, micronuclei, somatic mutations, gene expression, electron paramagnetic resonance, thermoluminescence, optically stimulated luminescence, neutron activation, haematology, protein biomarkers and analytical dose reconstruction. Individual characteristics of these techniques, their limitations and potential for further development are reviewed, and their usefulness in specific exposure scenarios is discussed. Whilst no single technique fulfils the criteria of an ideal dosemeter, an integrated approach using multiple techniques tailored to the exposure scenario can cover most requirements.

The role of rare earth elements and Mn(2+) point defects on the luminescence of bavenite.

Natural fibrous crystals of bavenite (Ca(4)Be(2)Al(2)Si(9)O(26)(OH)(2)) collected in intra-granitic pegmatite bodies of Bustarviejo (Madrid, Spain) have been examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), electron microprobe (EMPA) and inductively coupled plasma-mass spectrometry (ICP-MS). The strong luminescence emissions of bavenite using thermoluminescence (TL), cathodoluminescence (CL) and its thermal stability have been recorded, looking for new physical properties and new phosphor or dosimetric uses. The bavenite luminescence takes place in the 5d electron shell that interacts strongly with the crystal field; the spectra bands assignment are Gd(3+) (319nm), Sm(3+) (562 and 594nm), Dy(3+) (572nm) and Tb(3+) (495nm). A Mn(2+) band at about 578nm in Ca(2+) sites is present as a broad band that overlaps with the Dy(3+), Sm(3+) and Tb(3+) bands. Mn(2+) is a transition metal ion that has an electron configuration of 3d(5) and interacts strongly with the crystal field (d --> d) transition. Stability tests at different temperatures show clearly that the TL glow curves at 400nm in both irradiated and non-irradiated bavenite samples track the typical pattern of a system produced by a continuous trap distribution. The ICP-MS analyses show concentrations of Yb = 29.7ppm, Dy = 22.7ppm, Sm = 9.45ppm, Nd = 8.95ppm and Gd = 8.15ppm in the bavenite lattice.