Electron paramagnetic resonance radiation dosimetry in fingernails

There is now an increased need for accident dosimetry due to the increased risk of significant exposure to ionizing radiation from terrorism or accidents. In such scenarios, dose measurements should be made in individuals rapidly and with sufficient accuracy to enable effective triage. Electron paramagnetic resonance (EPR) is a physical method of high potential for meeting this need, providing direct measurements of the radiation-induced radicals, which are unambiguous signatures of exposure to ionizing radiation. For individual retrospective dosimetry, EPR in tooth enamel is a proven and effective technique when isolated teeth can be obtained. There are some promising developments that may make these measurements feasible without the need to remove the teeth, but their field applicability remains to be demonstrated. However, currently it is difficult under emergency conditions to obtain tooth enamel in sufficient amounts for accurate dose measurements. Since fingernails are much easier to sample, they can be used in potentially exposed populations to determine if they were exposed to life-threatening radiation doses. Unfortunately, only a few studies have been carried out on EPR radiation-induced signals in fingernails, and, while there are some promising aspects, the reported results were generally inconclusive. In this present paper, we report the results of a systematic investigation of the potential use of fingernails as retrospective radiation dosimeters.     

Advances towards using finger/toenail dosimetry to triage a large population after potential exposure to ionizing radiation

Rapid and accurate retrospective dosimetry is of critical importance and strategic value for the emergency medical response to a large-scale radiological/nuclear event. One technique that has the potential for rapid and accurate dosimetry measurements is electron paramagnetic resonance (EPR) spectroscopy of relatively stable radiation-induced signals (RIS) in fingernails and toenails. Two approaches are being developed for EPR nail dosimetry. In the approach using ex vivo measurements on nail clippings, accurate estimation of the dose-dependent amplitude of the RIS is complicated by the presence of mechanically-induced signals (MIS) that are generated during the nail clipping. Recent developments in ex vivo nail dosimetry, including a thorough characterization of the MIS and an appreciation of the role of hydration and the development of effective analytic techniques, have led to improvements in the accuracy and precision of this approach. An in vivo nail dosimetry approach is also very promising, as it eliminates the problems of MIS from the clipping and it has the potential to be an effective and efficient approach for field deployment. Two types of EPR resonators are being developed for in vivo measurements of fingernails and toenails.     

Protocol for emergency EPR dosimetry in fingernails

There is an increased need for after-the-fact dosimetry because of the high risk of radiation exposures due to terrorism or accidents. In case of such an event, a method is needed to make measurements of dose in a large number of individuals rapidly and with sufficient accuracy to facilitate effective medical triage. Dosimetry based on EPR measurements of fingernails potentially could be an effective tool for this purpose. This paper presents the first operational protocols for EPR fingernail dosimetry, including guidelines for collection and storage of samples, parameters for EPR measurements, and the method of dose assessment. In a blinded test of this protocol application was carried out on nails freshly sampled and irradiated to 4 and 20 Gy; this protocol gave dose estimates with an error of less than 30%.     

Effect of spectrum processing procedure on the linearity of EPR dose reconstruction in tooth enamel

Electron Paramagnetic Resonance (EPR) spectroscopy with tooth enamel is a widely used method of dosimetry. The accuracy of EPR tooth dosimetry depends on the spectrum processing procedure, the quality of which, in its turn, relies on instrumental noise and the signals from impurities. This is especially important in low-dose evaluation. The current paper suggests a method to estimate the accuracy of a specific spectrum processing procedure. The method is based on reconstruction of the radiation-induced signal (RIS) from a simulated spectrum with known RIS intensity. The Monte Carlo method was used for the simulations. The model of impurity and noise signals represents a composite residual spectrum (CRS) obtained by subtraction of the reconstructed RIS and the native background signal (BGS) from enamel spectra measured in HMGU (Neuherberg, Germany) and IMP (Yekaterinburg, Russia). The simulated spectra were deconvoluted using a standard procedure. The method provides an opportunity to compare the simulated “true” RIS with reconstructed values. Two modifications of the EPR method were considered: namely, with and without the use of the reference Mn²⁺ signals. It was observed that the spectrum processing procedure induces a nonlinear dose response of the reconstructed EPR amplitude when the height of the true RIS is comparable with the amplitudes of noise-like random splashes of CRS. The area of nonlinearity is below the limit of detection (DL). The use of reference Mn²⁺ signals can reduce the range of nonlinearity. However, the impact of the intensities of CRS random signals on nonlinearity is two times higher than the one observed when the reference signals were not used. The reproducibility of the software response is also dependent on both the amplitude of the CRS and the use of a reference signal, and it is also two times more sensitive to the amplitude of the CRS. In most EPR studies, all of the data are used, even those for which the dose value is lower than the DL. This study shows that low doses evaluated with the help of linear dose–response can be significantly overestimated. It is recommended that linear dose response calibration curves be constructed using only data above the DL. Data below the DL should be interpreted cautiously.     

Feasibility of Q-Band EPR Dosimetry in Biopsy Samples of Dental Enamel, Dentine and Bone

Electron paramagnetic resonance (EPR) dosimetry of tooth enamel in X-band has been established as a suitable method for individual reconstruction of doses 0.1 Gy and higher. The objective was to demonstrate the feasibility of using Q-band EPR in small biopsy tooth enamel samples to provide accurate measurements of radiation doses. Q-band spectra of small (<10 mg) irradiated samples of dentine and bone were studied to investigate the possibility of using Q-band EPR for dose measurements in those materials if there are limited amounts of enamel available, and there is no time for the chemical sample preparation required for accurate X-band measurements in dental enamel. Our results have shown that Q-band provides accurate measurements of radiation doses higher than 0.5 Gy in tooth enamel biopsy samples as small as 2 mg. Q-band EPR spectra in powdered dentine and bone demonstrated significantly higher resolution and sensitivity than in conventional X-band measurements.     

Radiation Dosimetry Using Alanine and Electron Paramagnetic Resonance (EPR) Spectroscopy: A New Look at an Old Topic

The detection and quantification by electron paramagnetic resonance (EPR) spectroscopy of stable radicals formed in alanine by exposure to γ-radiation is used as a secondary standard for radiation dosimetry measurements, even though the EPR signal is actually derived from >1 radical with different spectral properties. For high radiation doses, microwave power saturation and spectral linewidths are both dependent on the received dose, and result in non-linear calibration curves. Furthermore, using a high-sensitivity microwave cavity, the power at which EPR signal saturation commences is ~0.3–0.4 mW for samples with irradiation doses ≤10 kGy; these values are an order of magnitude lower than those normally used in alanine dosimetry. In addition, the central peak of the first derivative spectrum, the height of which is commonly used in dosimetry measurements, is the most susceptible to microwave power saturation. Therefore, for high-level dosimetry we now recommend that analyses be performed under non-saturating conditions, and that the spectral acquisition parameters should be determined with a standard irradiated to ≤10 kGy to eliminate any intensity problems associated with variable saturation characteristics. At low radiation doses, variations in spectral saturation characteristics are negligible, and partially saturating conditions along with modulation amplitudes much higher than those normally used can reliably produce improved signal-to-noise ratios and allow extension of the methodology to practical working limits of ~0.1–0.2 Gy.     

Spectral analysis of paramagnetic centers induced in human tooth enamel by x-rays and gamma radiation

Based on study of spectral and relaxation characteristics, we have established that paramagnetic centers induced in tooth enamel by x-rays and gamma radiation are identical in nature. We show that for the same exposure dose, the intensity of the electron paramagnetic resonance (EPR) signal induced by x-radiation with effective energy 34 keV is about an order of magnitude higher than the amplitude of the signal induced by gamma radiation. We have identified a three-fold attenuation of the EPR signal along the path of the x-radiation from the buccal to the lingual side of a tooth, which is evidence that the individual had undergone diagnostic x-ray examination of the dentition or skull. We have shown that the x-ray exposure doses reconstructed from the EPR spectra are an order of magnitude higher than the applied doses, while the dose loads due to gamma radiation are equal to the applied doses. The data obtained indicate that for adequate reconstruction of individual absorbed doses from EPR spectra of tooth enamel in the population subjected to the combined effect of x-radiation and accidental external gamma radiation as a result of the disaster at the Chernobyl nuclear power plant, we need to take into account the contribution to the dose load from diagnostic x-rays in examination of the teeth, jaw, or skull.     

EPR dosimeter material properties of potassium tartrate hemihydrate

The ability of potassium tartrate hemihydrate as a radiation sensitive material for electron paramagnetic resonance (EPR) dosimetry was investigated. The samples were subjected to different doses, in the range of 1–9 Gy of ⁶⁰Co gamma rays at room temperature. The EPR spectra were investigated through variation of signal intensity with respect to absorbed dose, magnetic field modulation amplitude, microwave power and time stability. The results indicate that the sensitivity of potassium tartrate hemihydrate is about 30% higher than that of alanine. However, the EPR signal is timely less stable within the first two weeks after irradiation.     

Analysis of EPR tooth enamel spectra exposed to combined radiation and mechanical effects

In the EPR spectra of tooth enamel samples exposed to sequential radiation and mechanical effect, the intensity of the signal in the spectra of tooth enamel samples exposed to sequential mechanical and radiation effects exceeded the amplitude of a signal in enamel samples that were only exposed to radiation. The increased dosimetric signal can be explained by superposition of mechanically and radiation-induced signals. The contribution of the mechanically induced component to the individual dose load reconstructed by EPR-spectra of tooth enamel has been evaluated.     

In Vivo EPR For Dosimetry

As a result of terrorism, accident, or war, populations potentially can be exposed to doses of ionizing radiation that could cause direct clinical effects within days or weeks. There is a critical need to determine the magnitude of the exposure to individuals so that those with significant risk have appropriate procedures initiated immediately, while those without a significant probability of acute effects can be reassured and removed from the need for further consideration in the medical/emergency system. In many of the plausible scenarios there is an urgent need to make the determination very soon after the event and while the subject is still present. In vivo EPR measurements of radiation-induced changes in the enamel of teeth is a method, perhaps the only such method, which can differentiate among doses sufficiently for classifying individuals into categories for treatment with sufficient accuracy to facilitate decisions on medical treatment. In its current state, the in vivo EPR dosimeter can provide estimates of absorbed dose with an error approximately +/- 50 cGy over the range of interest for acute biological effects of radiation, assuming repeated measurements of the tooth in the mouth of the subject. The time required for acquisition, the lower limit, and the precision are expected to improve, with improvements in the resonator and the algorithm for acquiring and calculating the dose. The magnet system that is currently used, while potentially deployable, is somewhat large and heavy, requiring that it be mounted on a small truck or trailer. Several smaller magnets, including an intraoral magnet are under development, which would extend the ease of use of this technique.     

Potential use of wallboard (drywall) for EPR retrospective dosimetry

Concern regarding the possibility of criminal or terrorist use of nuclear materials has led to an interest in developing the capability to measure radiation dose in a variety of natural and manufactured materials. Electron paramagnetic resonance (EPR) measurements of radiation dose following a radiological incident may aid in screening affected populations (triage) and in reconstruction of doses following accidents. One such EPR dosimeter is wallboard (drywall), a common construction material composed largely of gypsum (calcium sulphate dihydrate). We have identified the CO₃⁻ and SO₃⁻ dose-sensitive lines in drywall and developed a measurement protocol using the intensity of CO₃⁻ line. Proper background subtraction is a major difficulty, and we demonstrate a procedure based on alignment of a contaminant Mn²⁺ line. As a proof-of-concept, a wallboard panel was irradiated with a ⁶⁰Co source, and a two-dimensional map of the absorbed dose was measured. While most aliquots yielded reasonably accurate doses, a spatially contiguous region of apparent dose-insensitivity in one panel was identified.     

The Dependence of IRSL Intensity on Radiation Dose for Samples of Chlorides Contained in Feldspars

The intensity of the luminescence generally increases with radiation dose and measurement of these phenomena can be used to characterise the degree of dependence on beta doses. In this study, in order to test whether this is a significant problem on the optically stimulated luminescence (OSL) studies, the radiation dose response of the OSL signal from samples of chlorides contained in feldspars have been investigated by irradiating the samples with beta doses. The infrared-emitting diodes were used with a wavelength of (880±80) nm, and an IRSL (infrared stimulated luminescence) intensity parametres, m, was described and found m = 1±0.03.     

Investigation of metabolic changes in blood and tissue of mice γ-irradiated with sublethal doses by direct observation of EPR signals from Hb-NO complexes

The metabolic changes in probes of blood and tissue (spleen, liver and kidney) of mice under total γ-irradiation with the doses varied in the interval of 1–10 Gy at the dose rate of 0.073 Gy/min were studied in the early postirradiation period by ex vivo electron paramagnetic resonance (EPR). It was established that the impact with the lower dose rate leads to more intensive nitric monoxide biosynthesis in comparison with higher dose rates. In the early postirradiation period (from 2 up to 6 h), irradiation with doses higher than 2 Gy brings about an increase of the NO concentration and, hence, the appearance of nitrosyl complexes which were registered directly by EPR in blood and spleen. The observed line is identified as the signal from α-(Fe²⁺-NO)₂β(Fe³⁺)₂ or α-(Fe²⁺-NO) α(Fe²⁺)β(Fe³⁺)₂ complexes since the methemoglobin concentration also increases in comparison with the control level. The concentration of Hb-NO complexes in blood and spleen depends on the dose and individual radiosensitivity of the organism. Therefore, the intensity of the Hb-NO signal may serve as a criterion of the radiation injury level during the first hours after the irradiation. 30 h after the impact, the Hb-NO complexes were no longer detected. For the first day, the concentration of Fe³⁺-transferrin in blood increases with the dose and time passed after the irradiation. The intensity of the EPR signal from Fe³⁺-transferrin in blood may also serve as a measure of the radiation injury level.     

Radiation-dose dependence of E′1 centers in samples of quartz containing uncharged oxygen vacancies

EPR is used to study the generation of E′₁ centers (oxygen vacancies that have trapped one electron) in quartz samples containing uncharged oxygen vacancies as a function of irradiation dose. It is found experimentally that an irradiation dose of order 400 Gy is sufficient to allow every oxygen vacancy to trap two electrons apiece in essentially all such quartz samples. The linear segment of the dose dependences of E′₁ centers in samples annealed at 300 °C for 15 minutes can be used to reconstruct prior radiation doses up to 60–70 Gy. If the concentration of oxygen vacancies in the original sample is larger than 10¹⁸ cm⁻³, the signal intensity from E′₁ centers in the sample can be used to detect radiation doses as low as 1–3 Gy, which is significantly lower than the minimum radiation dose detectable by other paramagnetic centers in quartz. Fiz. Tverd. Tela (St. Petersburg) 40, 651–652 (April 1998)     

Room-temperature ferromagnetism in EDTA capped Cr-doped ZnS nanoparticles

Cr-doped ZnS nanoparticles with Cr concentrations of 0.5, 1, 2 and 3 atm.% were successfully synthesized by the chemical co-precipitation method using ethylenediaminetetraacetic acid (EDTA) as the capping agent. The structural, optical and magnetic properties of the prepared samples were studied. Energy dispersive spectroscopy (EDS) measurements showed the presence of Cr in the Cr-doped ZnS. No mixed phase was observed from X-ray diffraction (XRD) studies and all the peaks were indexed to the cubic phase of ZnS. The average diameter of the particles was in the range of 6–10 nm, and it was confirmed by TEM studies. The magnetic behavior of the nanoparticles for different chromium concentrations was investigated by magnetism measurements using a vibrating sample magnetometer (VSM). The nanoparticles with lower Cr concentration exhibited strong ferromagnetism, where as in samples of higher Cr concentrations the ferromagnetism suppressed. The electron paramagnetic resonance (EPR) spectra of the nanocrystals showed the resonance of electron centers with a g-value of 1.989. The signal intensity and linewidth of the EPR signal increased with increasing Cr content. FTIR studies indicated that the nanoparticles were sterically stabilized by EDTA.     

Aspects of detection of irradiated foods by EPR spectroscopy

Some methodological aspects important for the detection of irradiated foods by the EPR spectroscopy are discussed. These are: specificity and stability of the EPR signals produced by ionizing radiation in foods, complexity of radiation induced EPR signals and their detection at different doses, the dose dependence of the intensities of the EPR signals involved. The importance of the native EPR signals observed in foods for the detection of irradiation and the role of quantitative measurements in the development of detection methods are shown.     

EPR and UV spectrometry investigation of sucrose irradiated with carbon particles

Solid state/EPR (SS/EPR) dosimeters of carbon ions irradiated sucrose are studied with EPR, and their water solutions – with UV spectroscopy. Doses between 20 and 200 Gy are used with linear energy transfer (LET) values for carbon ions of 63, 77, 96 and 230 keV μm^?1. After irradiation all samples show typical for irradiated sucrose EPR and UV spectra. The obtained data are compared with those previously reported for nitrogen particles and gamma rays irradiated sucrose. The identical shape of both the EPR and UV spectra of irradiated with various type radiation samples suggests that generated free radicals are not influenced by the nature of radiation. The lack of difference in the line width of the separate lines or the whole EPR spectrum, obtained for gamma and heavy particles irradiation, suggests negligible spin–spin interaction among the radiation-generated free radicals in the samples. The linear dependence of the EPR response on the absorbed dose radiation is found to be higher when generated by gamma rays, than by the same absorbed dose of heavy particles. In addition, the EPR response for carbon ions is higher than that for nitrogen ions. Water solutions of irradiated sucrose exhibit UV spectrum with absorption maximum at 267 nm, attributed to the recombination products of free radicals. The UV band intensity depends on the absorbed dose radiation. The UV spectra obtained for carbon, nitrogen and gamma rays irradiated sucrose are also compared.     

Post-annealing effects on EPR response of irradiated nano-structure hydroxyapatite

In this work, the nano-structure hydroxyapatite was synthesized via the hydrolysis method. The produced powders were thermally treatment at different temperatures from 400 to 1200°C. The morphological and chemical analyses were carried out using the Fourier transmission infrared spectroscopy, transmission electron microscopy, and X-ray diffraction system. Then, the samples were irradiated at different absorbed doses from 1 to 80 kGy using ⁶⁰Co γ -ray. Electron paramagnetic resonance (EPR) responses of the samples were measured at room temperature in air. Subsequently, the variations of EPR signal intensities were constructed as the peak-to-peak signal amplitude and results were compared with those of non-annealed samples. The results show that the EPR responses of non-annealed samples are higher rather than other samples and also are saturated at higher doses in comparison with the others.     

Egyptian limestone for gamma dosimetry: an electron paramagnetic resonance study

The electron paramagnetic resonance (EPR) properties of limestone from a certain Egyptian site were investigated in order to propose an efficient and low-cost gamma dosimeter. Radiation-induced free radicals were of one type which was produced in the limestone samples at g=2.0066 after exposure to gamma radiation (⁶⁰Co). EPR spectrum was recorded and analyzed. The microwave power saturation curve and the effect of changing modulation amplitude on peak-to- peak signal height were investigated. The response of limestone to different radiation doses (0.5–20 kGy) was studied. Except for the decrease in signal intensities during the first five hours following irradiation, over the period of two months fair stabilities of signal intensities were noticed. From the current results, it is possible to conclude that natural limestone may be a suitable material for radiation dosimetry in the range of irradiation processing.