Scintillation and structural properties of copolymers and mixtures of styrene, 9-vinylcarbazole and 4-vinylbenzyl chloride based plastic scintillators.

The research team has developed new plastic scintillators in the form of microspheres, called PSm, by combining styrene, 9-vinylcarbazole (VK), and 4-vinylbenzyl chloride (VBC). The primary objective of this study was to explore the feasibility of incorporating the fluorescent solute (VK) into the polymer structure to prevent its leaching out when PSm are utilized in liquid flow through detection systems or organic solvents. The secondary aim was to examine the impact of adding the chlorine functional group to the scintillation polymer, with the intention of replacing it with an extractant in the future to create covalently linked PSresins. The findings of the study reveal that the homopolymer of polyvinylcarbazole (PVK) performs poorly while used as a unitary scintillator system for plastic scintillation measurements. However, the incorporation of monomers in the form of copolymers with styrene has a more significant impact on scintillation properties compared to the mixture of homopolymers. In the case of 9-vinylcarbazole (VK), its presence at a weight proportion of 10% leads to an increase in scintillation efficiencies, although it is still inferior to the classical PS. Conversely, the situation is different for 4-vinylbenzyl chloride (VBC), where the chlorine in the copolymer results in higher quenching, and the polymer is also less resistant to organic solvents due to the formation of short polymer chains. For VBC, the mixture of polymers yields better results and enables the production of covalently linked PSresins.

Fast analysis of gross alpha with a new plastic scintillation resin.

Radionuclides analysis is a complex task, with high time and economic costs. In decommissioning activities and environmental monitoring, it is very evident, in which, to obtain an appropriate information, it is necessary to perform as many analyses as possible. The number of these analyses can be reduced using screening gross alpha or gross beta parameters. However, the currently used methods cannot give an answer as fast as it would be desired and, moreover, more than 50% of the results reported in the interlaboratory exercises fall outside the acceptance range. This work presents the development of a new material and method to gross alpha activity determination using a plastic scintillation resin (PSresin) in drinking and river water samples. A specific procedure was developed involving a new PSresin (using bis-(3-trimethylsilyl-1-propyl)-methanediphosphonic acid as an extractant) that is selective for all actinides, radium and polonium. Quantitative retention and 100% detection efficiencies were obtained at pH 2 with nitric acid. PSA value of 135 was used for α/ß discrimination. Eu was used to determine or estimate retention in sample analyses. The method developed can measure, in less than 5 h from the reception of the sample, the gross alpha parameter with quantification errors comparable or even lower to those obtained with conventional methods.

A new method based on selective fluorescent polymers (PSresin) for the analysis of 90Sr in presence of 210Pb in environmental samples.

90Sr is of major concern in emergency and environmental control plans. It is one of the main fission products in nuclear facilities and is a high-energy beta emitter that presents chemical properties similar to those of calcium. 90Sr is commonly detected using methods based on liquid scintillation counting (LSC) following a chemical separation to remove potential interferences. However, these methods generate mixed wastes (hazardous and radioactive). In recent years, an alternative strategy using PSresins has been developed. For 90Sr analysis with PSresins, 210Pb is the main interferent that should be considered, as it is also strongly retained in the PSresin. In this study, a procedure was developed involving a precipitation with iodates to separate lead from strontium before the PSresin separation. Moreover, the method developed was compared with well-established and routinely used methods based on LSC, revealing that the new method produced equivalent results in less time and with less waste generation.

Investigation of a new approach for 36Cl determination in solid samples using plastic scintillators.

This work reports a new approach for the determination of 36Cl in radioactive waste samples from nuclear decommissioning, wherein novel plastic scintillator (PS) materials were used for the concentration of 36Cl prior to the detection with scintillation counting. Different plastic scintillator (PS) materials were tested for their selective absorption and detection of 36Cl activity in solid samples. PS microspheres (PSm), cross-linked PSm (CPSm) and PS resin have been investigated. PS resin was identified as the most suitable material for 36Cl analysis. Pyrolysis and subsequent trapping of the volatile elements in a bubbler was used. The trapping solution was finally loaded onto a cartridge of the PS resin. Scintillation counting and ion chromatography were used to determine the activity concentration and the chemical recovery, respectively.

Simultaneous determination of 210Pb and 90Sr and 210Po isolation in sludge samples using a plastic scintillation resin.

This study describes a new and fast method for separating 210Po from 210Pb and 90Sr, before simultaneously measuring the individual activities of the latter two radionuclides using a plastic scintillation resin (PSresin) in sludge samples taken from a drinking water treatment plant. This method speeds up the analysis process significantly by simultaneously measuring 210Pb and 90Sr in a single step. The method is reproducible and has a relative standard deviation of less than 25% for 210Pb, 210Po and 90Sr. The method was satisfactorily validated with an intercomparison sample and applied to sludge samples from a drinking water treatment plant. The minimum detectable activities for 0.9 g of sludge are 5.5 Bq/kg and 8 Bq/kg for 210Pb and 90Sr respectively when measured for 180 min, and 0.5 Bq/kg for 210Po when measured for 5000 min.

A comparison of different approaches for the analysis of 36Cl in graphite samples.

This study compares different approaches for the quantification of the massic activity of 36Cl in graphite samples. All approaches consisted of a combustion step in combination with a trapping solution to collect the volatile elements. Two different resins were used to separate 36Cl from the matrix (CL resin and PS resin). Liquid scintillation counting (LSC), scintillation counting (SC) and tandem inductively coupled plasma mass spectrometry (ICP-MS/MS) were used to quantify 36Cl activity. The chemical yield in all approaches was determined by means of ion chromatography (IC). In addition, the methods were applied to a real activated graphite sample.

Analysis of isotopes of plutonium in water samples with a PSresin based on aliquat·336.

There is a necessity to have techniques capable to perform rapid determinations of specific radionuclides with the aim to provide fast response in emergency situations where a large number of samples need to be measured in a short time. Plastic Scintillation Resins (PSresins) raises as an adequate tool to achieve this purpose and in the present study a methodology to determine plutonium using a PSresin based on Aliquat·336 was developed. Different sample treatments have been studied under acidic conditions with an emphasis on valence adjustment treatment to achieve an effective retention within the PSresin. Under 3 M nitric acid conditions and an iron sulphamate (II) + nitrite valence adjustment, quantitative retention and 100% detection efficiency were achieved. The retention of the different interferences evaluated (238U, 230Th, 241Am, 210Pb and 99Tc) was low and therefore they do not interfere significantly in the determination of plutonium, except for 99Tc. Finally, a stable tracer to calculate the PSresin separation yield was studied, revealing that gold is suitable for this purpose. This procedure was applied to the analysis of spiked sea and river water samples, obtaining errors lower than 10% in their quantification.

Capability of Far-Infrared for the selective identification of red and black pigments in paint layers.

Artworks are complex objects that merit study and preservation. Far-infrared spectroscopy in ATR mode appears to be a suitable technique for this purpose because it enables information to be obtained regarding the material's composition in a non-destructive way. The use of Far-infrared is especially interesting because most organic compounds do not absorb in this energy range, suggesting the possibility of identifying inorganic pigments. Based on works performed by two research groups from the University of Bologna and the University of Tartu, this study attempts to obtain additional information regarding the capabilities and limitations of Far-infrared spectroscopy when it is applied to objects as complex as artworks. This article first studies the capability of the technique for identifying pigments by following the stability of the position of their absorption bands when mixed with linseed oil, the minimum amount of pigment necessary to be detected and how this amount changes when it is part of a paint layer. The consequences of the pigment: linseed oil interaction and the ageing process are also studied through changes in the linseed oil signal absorptions related to the acid carboxylic and carboxylate bands. The entire study leads to the conclusion that Far-Infrared in ATR mode is an interesting option for the selective identification of some inorganic pigments, but their potential application depends on each case considered.

PSresin for the analysis of alpha-emitting radionuclides: Comparison of diphosphonic acid-based extractants.

The analysis of radionuclides is complex, with high economic and time costs. For this reason, there is a need to develop new methods and strategies to reduce these costs. One important group in the analysis of radionuclides is the actinides, which are the main constituents assessed in the total gross alpha together with radium and radon test used to measure radioactivity in drinking water. Moreover, in nuclear dismantling processes, the possible spread of the released radionuclides has to be controlled, which is measured by many techniques, depending on the radionuclides, through scintillation. This work presents a new method to analyse actinides using plastic scintillation resins (PSresins) packed in a solid-phase extraction cartridge. The proposed method combines chemical separation and sample measurement into a single step, reducing the effort, time and reagents required for analysis as well as decreasing the amount of waste generated. The PSresins compared in this study contained three selective extractants based on methylenediphosphonic acid with different radicals, which has a high affinity for tri-, tetra-, and hexavalent actinides in dilute acids. These extractants were immobilised on plastic scintillation microspheres at a ratio of 1/1:6, producing a retention and detection efficiency of 100% for 241Am, 230Th, Uranium and 238Pu. The retention and detection efficiency were 20% and 100%, respectively, for 210Po and low for 226Ra.

A new plastic scintillation resin for single-step separation, concentration and measurement of technetium-99.

Technetium is a synthetic element with no stable isotopes, produced as waste in nuclear power plants and in cyclotrons used for nuclear medicine. The element has high mobility, in the form of TcO4(-); its determination is therefore important for environmental protection. Technetium is found in low concentrations and therefore common methods for its analysis include long treatments in several steps and require large amounts of reagents for its purification and preconcentration. Plastic scintillation resins (PSresin) are novel materials used to separate, preconcentrate and measure radionuclides in a single step. The objective of this study is to prepare and characterise a PSresin for the preconcentration and measurement of (99)Tc. The study first evaluates the reproducibility of the production of PSresins between batches and over time; showing good reproducibility and storage stability. Next, we studied the effect of some common non-radioactive interferences, showing small influences on measurement, and radioactive interferences ((36)Cl and (238)U/(234)U). (36)Cl can be removed by a simple treatment with 0.5 M HCl and (238)U/(234)U can be removed from the column by cleaning with a mixture of 0.1 M HNO3 and 0.1 M HF. In the latter case, a slight change in the morphology of the PSresin caused an increase in detection efficiency. Finally, the PSresin was applied to the measurement of real spiked samples (sea water and urine) with deviations lower than 10% in all cases.

Analysis of (210)Pb in water samples with plastic scintillation resins.

(210)Pb is a radioactive lead isotope present in the environment as member of the (238)U decay chain. Since it is a relatively long-lived radionuclide (T1/2 = 22.2 years), its analysis is of interest in radiation protection and the geochronology of sediments and artwork. Here, we present a method for analysing (210)Pb using plastic scintillation resins (PSresins) packaged in solid-phase extraction columns (SPE cartridge). The advantages of this method are its selectivity, the low limit of detection, as well as reductions in the amount of time and reagents required for analysis and the quantity of waste generated. The PSresins used in this study were composed of a selective extractant (4',4″(5″)-Di-tert-butyldicyclohexano-18-crown-6 in 1-octanol) covering the surface of plastic scintillation microspheres. Once the amount of extractant (1:1/4) and medium of separation (2 M HNO3) were optimised, PSresins in SPE cartridges were calibrated with a standard solution of (210)Pb. (210)Pb could be fully separated from its daughters, (210)Bi and (210)Po, with a recovery value of 91(3)% and detection efficiency of 44(3)%. Three spiked water samples (one underground and two river water samples) were analysed in triplicates with deviations lower than 10%, demonstrating the validity of the PS resin method for (210)Pb analysis.

Application of the CIEMAT-NIST method to plastic scintillation microspheres.

An adaptation of the MICELLE2 code was used to apply the CIEMAT-NIST tracing method to the activity calculation for radioactive solutions of pure beta emitters of different energies using plastic scintillation microspheres (PSm) and (3)H as a tracing radionuclide. Particle quenching, very important in measurements with PSm, was computed with PENELOPE using geometries formed by a heterogeneous mixture of polystyrene microspheres and water. The results obtained with PENELOPE were adapted to be included in MICELLE2, which is capable of including the energy losses due to particle quenching in the computation of the detection efficiency. The activity calculation of (63)Ni, (14)C, (36)Cl and (90)Sr/(90)Y solutions was performed with deviations of 8.8%, 1.9%, 1.4% and 2.1%, respectively. Of the different parameters evaluated, those with the greatest impact on the activity calculation are, in order of importance, the energy of the radionuclide, the degree of quenching of the sample and the packing fraction of the geometry used in the computation.

Synthesis of plastic scintillation microspheres: alpha/beta discrimination.

Plastic scintillation microspheres (PSm) have been developed as an alternative for liquid scintillation cocktails due to their ability to avoid the mixed waste, besides other strengths in which the possibility for alpha/beta discrimination is included. The aim of this work was to evaluate the capability of PSm containing two combinations of fluorescence solutes (PPO/POPOP and pT/Bis-MSB) and variable amounts of a second organic solvent (naphthalene) to enhance the alpha/beta discrimination. Two commercial detectors with different Pulse Shape Discrimination performances (Quantulus and Triathler) were used to evaluate the alpha/beta discrimination. An optimal discrimination of alpha/beta particles was reached, with very low misclassification values (2% for beta particles and 0.5% for alpha particles), when PSm containing PPO/POPOP and between 0.6 and 2.0 g of naphthalene were evaluated using Triathler and the appropriate programme for data processing.

Determination of oil reservoir radiotracer (S14CN-) in a single step using a plastic scintillator extractive resin.

The analysis of radiotracers is important in the study of oil reservoir dynamics. One of the most widely used radiotracer is S(14)CN(-). Prior to activity measurements by Liquid Scintillation (LS), routine determinations require the pretreatment steps of purification and concentration of the samples using anion exchange columns. The final elution media produces samples with high salt concentration that may lead to problems with phase separation during the LS measurement. Plastic Scintillation (PS) is an alternative technique that provides a solid surface that can be used as a platform for the immobilisation of selective extractants to obtain a PS resin. The proposed procedure unifies chemical separation and sample measurement preparation in a single step, serving to reduce the number of reagents needed and manpower required for the analysis while also avoiding mixed waste production by LS. The objective of this study is to develop a PS resin for the determination of (14)C-labelled thiocyanate radiotracer in water samples. For this purpose, the immobilisation procedure was optimised, including optimisation of the proportion of PS microspheres:extractant and the use of a control blank to monitor the PS resin immobilisation process. The breakthrough volume was studied and the detection and quantification limits for 100 mL of sample were determined to be 0.08 Bq L(-1) and 0.31 Bq L(-1), respectively. The established procedure was applied to active samples from oil reservoirs and errors lower than 5% in the sample determinations were obtained.

Mixture quantification using PLS in plastic scintillation measurements.

This article reports the capability of plastic scintillation (PS) combined with multivariate calibration (Partial least squares; PLS) to detect and quantify alpha and beta emitters in mixtures. While several attempts have been made with this purpose in mind using liquid scintillation (LS), no attempt was done using PS that has the great advantage of not producing mixed waste after the measurements are performed. Following this objective, ternary mixtures of alpha and beta emitters ((241)Am, (137)Cs and (90)Sr/(90)Y) have been quantified. Procedure optimisation has evaluated the use of the net spectra or the sample spectra, the inclusion of different spectra obtained at different values of the Pulse Shape Analysis parameter and the application of the PLS1 or PLS2 algorithms. The conclusions show that the use of PS+PLS2 applied to the sample spectra, without the use of any pulse shape discrimination, allows quantification of the activities with relative errors less than 10% in most of the cases. This procedure not only allows quantification of mixtures but also reduces measurement time (no blanks are required) and the application of this procedure does not require detectors that include the pulse shape analysis parameter.

Radiostrontium separation and measurement in a single step using plastic scintillators plus selective extractants. Application to aqueous sample analysis.

This study describes a new protocol for (90)Sr determination in water samples based on the use of a selective extractant (DtBuCH18C6) and plastic scintillator microspheres. The proposed procedure unifies chemical separation and sample measurement preparation in a single step to reduce the effort, time and reagents required for analysis. In addition, the final measurement does not produce mixed waste. The minimum activity detectable for 10 mL of sample solution is 0.46 Bq L(-1). Relative errors for the determination of (90)Sr activity in drinking, sea and river waters are less than 4%.

Alpha/beta pulse shape discrimination in plastic scintillation using commercial scintillation detectors.

Activity determination in different types of samples is a current need in many different fields. Simultaneously analysing alpha and beta emitters is now a routine option when using liquid scintillation (LS) and pulse shape discrimination. However, LS has an important drawback, the generation of mixed waste. Recently, several studies have shown the capability of plastic scintillation (PS) as an alternative to LS, but no research has been carried out to determine its capability for alpha/beta discrimination. The objective of this study was to evaluate the capability of PS to discriminate alpha/beta emitters on the basis of pulse shape analysis (PSA). The results obtained show that PS pulses had lower energy than LS pulses. As a consequence, a lower detection efficiency, a shift to lower energies and a better discrimination of beta and a worst discrimination of alpha disintegrations was observed for PS. Colour quenching also produced a decrease in the energy of the particles, as well as the effects described above. It is clear that in PS, the discrimination capability was correlated with the energy of the particles detected. Taking into account the discrimination capabilities of PS, a protocol for the measurement and the calculation of alpha and beta activities in mixtures using PS and commercial scintillation detectors has been proposed. The new protocol was applied to the quantification of spiked river water samples containing a pair of radionuclides ((3)H-(241)Am or (90)Sr/(90)Y-(241)Am) in different activity proportions. The relative errors in all determinations were lower than 7%. These results demonstrate the capability of PS to discriminate alpha/beta emitters on the basis of pulse shape and to quantify mixtures without generating mixed waste.

Comparative study of pre-treatment procedures for (3)H monitoring in water samples from environmental protection programs.

The determination of tritium activity in water samples is included in most environmental protection programs, and the recommended procedure consists of sample distillation and further measurement by liquid scintillation. Distillation is a simple but time consuming pre-treatment, especially in routine analysis. Here we evaluate alternative pre-treatments for tritium activity determination, such as filtration or the use of multiple selective ion exchange columns. 52 samples from different water sources (rain, surface, underground, sea and drinking water) in Spanish environmental protection programs, together with an IAEA reference material were analyzed. Results show that both pre-treatments can be applied as a preliminary tool to discriminate between tritium active and non active waters in environmental monitoring programs. In addition, filtration and multiple selective ion exchange column pre-treatments can be used as alternative procedures for tritium activity determination in the routine analyses of water samples with known and reproducible chemical and isotopic composition. Both methods are less time consuming than distillation and, in the case of filtration, extremely cheap. For waters with complex matrices, especially sea water, distillation is the recommended procedure due to the interference from salts contained in the sample.

Plastic vs. liquid scintillation for 14C radiotracers determination in high salt matrices.

The use of radiotracers is a common procedure for better understanding of the dynamics of oil reservoirs. Several molecules and radionuclides are implemented for this purpose; one of these is (14)C labelled thiocyanate. Samples taken from fluids in production wells require a pre-treatment step in order to purify and concentrate the activity of the radiotracer before measurement. Pre-treatment is based on ionic exchange and the solution eluted includes a high concentration of salt that can be a serious drawback for the development of a stable emulsion when the liquid sample and the scintillation cocktail are mixed for Liquid Scintillation (LS). The objective of this study is to evaluate the capability of Plastic Scintillation (PS) to determine the activity of radiotracers in salt matrices. For this purpose, an initial comparative study of the influence of salt and coloured matrices on the detection efficiency for PS and LS was performed. Results indicate that in both techniques colour quenching produces the same effects: efficiency decrease and spectra shift, whereas salt quenching produces different effects for PS and LS, ionization quenching for PS and chemical quenching for LS. As a result of this divergence, the calibration required for each counting method is different: two steps for PS and a single step for LS. After system study and procedure optimization, radiotracer activities in real samples taken from oil reservoirs have been determined. The results indicated that PS shows similar capability to the classical LS to determine the activity in these salt matrix samples with the additional advantages that no separation of the phase can appear and no mixed waste is produced after measurement.