Low-level Liquid Scintillation Research Articles

Application of the CIEMAT/NIST method to 14C low-level measurements

Radiocarbon dating of samples from benzene synthesis by low-level Liquid Scintillation Counting (LSC) method requires the availability of 14C standards in benzene, which are difficult to obtain, or the use of an absolute measurement which is out of reach for most analytical laboratories. This paper describes how the CIEMAT/NIST method can help to solve this issue and presents the measurements of low activity concentrations performed in the LRI-D using two different benzene base scintillator cocktails.

Radiostrontium determination by combination of automated Sr isolation and “on-column” Cherenkov detection using chromatographic model

A novel analytical solution of non-linear chromatography in case of parabolic isotherm for frontal analysis was obtained by combination of Cole-Hopf and Laplace transform. It was used for simulation of strontium capturing on chromatographic column with aim to improve quantitative determination of low-level 90Sr activities. From the experimentally determined breakthrough curves, the retention factor and the number of theoretical plates were calculated using the Glueckauf and Wenzel relations and by fitting the breakthrough curves for the linear isotherm using MatLab. These were used to simulate the breakthrough curves using a parabolic isotherm solution where the non-linear term of the isotherm was taken as a small negative deviation of the retention factor. On the base of theoretical prediction and experimental data, procedure for automated capturing of strontium on chromatographic column with specific dimension and off line „on-column“ Cherenkov detection on commercial ultra low-level liquid scintillation counter was developed. It was shown that analytical solution for parabolic isotherm in comparison with solution for linear isotherm gives better prediction of mass of captured Sr on column filled with small amount of Sr resin and SuperLig®620 in case of elevated Sr concentration, even when non-linear effect is not obvious. The solution also makes it possible to predict the mass of resin required for strontium isolation at 100% yield under given conditions. Considering the limited dimensions of the column, and consequently small mass of the resin in them, it resulted in the low efficiency of the columns, which, however, did not affect the yield in real conditions of isolation. The results have shown that the yields achieved after isolation on SuperLig®620 from real samples are 100%. In addition, it is shown that captured 90Sr can be detected through 90Y ingrowth, on column filled with strontium specific resin, with Cherenkov detection efficiency of at least 50%. The efficiency may be enhanced to 60%, depending on parameters which can affect detection efficiency change (type of column, resin type, surrounding solution, etc.). The developed procedures enable quantitative determination of 90Sr in natural water samples with MDAC below 12 mBq l−1 and solid (soil and vegetation) samples with MDAC below 6 Bq kg−1 within 2–3 days. The proposed solution may easily be implemented in radiochemical laboratories where this type of analysis is routinely done within environmental monitoring or other purposes.

Measuring the half-life of 215Po by low-level liquid scintillation counting

The half-life of short-lived 215Po was studied in a new experimental setup by means of liquid scintillation counting. The new value of 1.781 (5) ms was obtained by offline data analysis using the delayed coincidence method. Along with the half-life determination, a careful assessment of uncertainties was carried out. The result was compared with data available from the literature.

Assessment of natural radioactivity in bottled mineral water from Brazil

The approach taken in the WHO Guidelines for controlling radiological hazards in public water supplies has two stages. The first is an initial screening for gross alpha and beta activity to determine whether the activity concentrations are below levels at which no further action is required; and if these screening levels are exceeded, investigation of the concentration of individual radionuclides and comparison with specific guidance levels. Mineral water is obtained directly from natural sources or by extracting groundwater, it is characterized by the quantity of mineral salts, trace elements and other constituents. The bottled water industry is present in the major regions of the world, and the population consumption has increased every year in Brazil and world, also increasing new mineral water mining sites, so it is necessary to constantly check the amount of radioactivity in mineral water. The aim of this study is to quantify the concentration of the natural radionuclides in the bottled mineral water consumed in São Paulo city. The bottled mineral water samples were purchased in a supermarket in São Paulo, with 23 different brands. The determination of gross alpha and beta activity concentration in bottled mineral water by Liquid Scintillation Counting measurement was performed using a 1220 Quantulus™ Ultra Low-Level Liquid Scintillation Spectrometer. The natural radionuclides (226Ra, 228Ra, 210Pb and 40K) were measured by gamma spectrometry, using an HPGe detector. The results obtained in this study can be used for a database on bottled mineral water radioactivity from Brazil.

Radiological risk associated with 222Rn occurrence in groundwater sources of rural communities in the semiarid region of Paraíba, Brazil.

Rural and isolated communities traditionally lack adequate water treatment and distribution systems, and water quality assessment often does not include radioactivity measurement. Here we present, for the first time, the results of Rn measurements and the evaluation of the associated dose in groundwaters of rural communities in a semiarid area in Paraiba State, Brazil. Water samples were analysed using a low-level liquid scintillation spectrometer (LSS). Radon concentrations were higher than EPA and WHO recommended levels in water for most of the wells (range of 5.5-1107.0Bq/L, average 252.8Bq/L). Higher Rn concentration was measured in deeper wells and located in area rich in granite and diorite rocks. The annual effective doses varied between 0.021 and 4.317mSv/y for infants, 0.016-3.182mSv/y for children, and 0.015-3.022mSv/y for adults, exceeding, in some cases, the 1mSv/y reference level recommended by the WHO and UNSCEAR for the public. Thus, water consumption from half of the wells should be avoided unless adequate treatment is provided. Results highlight the need to perform actions to supply water with appropriate quality to the local population.

226Ra and natural uranium in Bulgarian mineral waters

A complex investigation on Bulgarian mineral waters from certain frequently used sources have been carried out. Specific activities of 226Ra and concentration levels of natural uranium in mineral waters samples were analyzed using nuclear and analytical methods. 226Ra is a naturally occurring radioisotope with a period of half live 1 600 years, which specific activity in water was determined through analysis of the daughter 222Rn. The measurements were carried out using a low-level liquid scintillation counting in a Packard Tri-Carb 2770 TR/SL liquid scintillation spectrometer. Uranium concentration was measured in water samples using a luminescent method. In addition to 226Ra and natural uranium, determination of gross alpha and beta activities of waters was made by means of the same liquid scintillation spectrometer. The concentrations values obtained were compared with data reported by other authors in different countries and with reference values accepted for drinking water. The expected annual effective doses for ingestion of natural uranium and 226Ra in the analysed waters were calculated.

Investigation of fast screening LSC method for monitoring 14C activity in wastewater samples

This paper explores the possibility of a direct measurement of 14C activity concentration in wastewater without chemical pretreatment of samples, which would provide the advantages such as rapidity, low-cost, and simplicity of radioanalysis that is desirable in the case of nuclear emergencies. A method via Liquid Scintillation Counting (LSC) technique has been implemented and optimized. The method assumes mixing of the water sample with a scintillation cocktail (Permafluor E+ and Ultima Gold AB cocktails were tested). Measurements were performed on Ultra Low Level Liquid Scintillation Spectrometer Wallac 1220 Quantulus. Optimization of the method included optimal water:cocktail volume ratio, optimal counting window selection, PAC (Pulse Amplitude Comparator) parameter adjustment, based on the highest FOM (Figure of Merit) value achieved, as well as detection efficiency and detection limit evaluation. The main problem in such an approach, interference with other beta emitters that are often present in wastewater samples, has been discussed. The possibility to eliminate low-energy counts that would be generated from 3H, and to estimate the contribution of other high-energy beta emitters to obtained results of 14C content is presented as well. Method's constraints, its accuracy, and precision have been considered from the obtained results of measurements of wastewater samples. Its application is limited only to 14C screening of samples with much higher 14C activities than those of the environmental (surface and ground) waters. Presented results could be used as guiding principles of development, optimization, and implementation of the fast 14C screening method in other laboratories.

Nuclear and analytical methods for investigation of high quality wines

Nuclear and analytical methods can help to determine the year of production – vintage and the geographical provenance of high quality wines. A complex analytical investigation of Melnik fine wines from “Artarkata” vineyards, Vinogradi village near Melnik in Southwest Bulgaria using different methods and equipment were performed. Nuclear methods, based on measured gamma-ray activity of 137Cs and specific activity of 3H can be used to determine the year of wine production. The specific activity of 137Cs was measured in wines from different vintages using Low-Background High-Resolution Gamma-Spectrometry. Tritium measurements in wine samples were carried out by using a low level liquid scintillation counting in a Packard Tri-Carb 2770 TR/SL liquid scintillation analyzer. The identification of the origin of wines using their chemical fingerprints is of great interest for wine consumers and producers. Determination of 16 chemical elements in samples from soil, wine stems, wine leaves and fine wine from the type Shiroka Melnishka, which are grown in typical Melnik vineyard was made, using Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES).

A low level liquid scintillation spectrometer with five counting modules for 14C, 222Rn and delayed coincidence measurements

This paper presents a low-level liquid scintillation counting spectrometer with five identical counting units that allow simultaneous measurements to be performed. The counting chambers are enclosed in high purity copper and lead shielding which significantly decreases the background count rate. Each of the five counting chambers is equipped with a high stability software-controllable power supply, and each counting module contains a signal analyzer that measures the pulse height, pulse shape and the time between subsequent pulses, returning all the data as a time-stamped sequence which enables the identification of pulse pairs. Such pulse pairs, arising from the decay of 214Bi/214Po, provides a sensitive tool for 222Rn contamination determination in low-level 14C measurements. This enables radiocarbon dating or bio-component determination to be performed directly after liquid scintillator production without the risk of 222Rn interfering with the measurement of 14C.

MnO2 NPs-AgX zeolite composite as adsorbent for removal of strontium-90 (90Sr) from water samples: Kinetics and thermodynamic reactions study

In this research, the MnO2NPs-AgX zeolite as a novel composite adsorbent was synthesized and identified via Scanning electron microscopy (SEM), Atomic adsorption spectrometry (AAS), X-ray diffraction (XRD) and Fourier transform infrared (FTIR) techniques. Furthermore, the removal of radioactive strontium-90 (90Sr) from drinking tap water of Ramsar city was investigated via the synthesized MnO2NPs-AgX zeolite composite. A single radiometric technique, Ultra Low-Level Liquid Scintillation Counting (LSC), was also exerted to monitor the reaction progress. The obtained results revealed that the 90Sr was perfectly removed after 8 h by the MnO2NPs-AgX zeolite composite. Also, the reaction kinetic information was studied applying pseudo first and second order kinetic Elovich and Intra particle diffusion kinetic models. The adsorption kinetics of 90Sr was matched appropriately to the pseudo second order kinetic model. Further, the evaluation of the thermodynamic parameters such as ΔG0, ΔH0 and ΔS0, specified that the adsorption procedure of 90Sr was spontaneous and illustrates physical adsorption properties and exothermic nature of the adsorption. It is emphasized that the MnO2NPs-AgX zeolite as a novel composite represents a high capacity and potential for the removal of radioactive 90Sr from drinking water samples.

Simple Method for High-Sensitivity Determination of Cosmogenic 35S in Snow and Water Samples Collected from Remote Regions.

Cosmogenic 35S is useful in understanding a wide variety of chemical and physical processes in the atmosphere, the hydrosphere, and the cryosphere. The 87.4-day half-life and the ubiquity of sulfur in natural environments renders it an ideal tracer of many phenomena. Measurements of 35S in snow and water samples are scarce as existing analytical methods require a large volume of sample (>20 L) due to their high analytical activity background and low counting efficiency. Here, we present a new set of snow/water sample collecting and handling procedures for high-sensitivity determination of cosmogenic 35S using a low-level liquid scintillation spectrometer. Laboratory experiments using diluted 35S standards (with activities of <5 disintegrations per minute) showed a 35S recovery percentage of ∼95%, demonstrating a relatively small deviation from the true value. Using this method, we successfully measured 35S in ∼1 L of fresh snow sample collected from a glacier on the Tibetan Plateau to be 47 ± 7 mBq/L. On the basis of 35S activities in 9 natural samples measured in this study, a first proof-of-concept approximation for age determinations and source attributions was presented. This new method will provide a powerful tool in studying 35S in small volumes of snow and water samples, especially those from remote but climatically important regions such as the polar regions and the Tibetan Plateau and Himalayas. The measurements are particularly important as the radioactive sulfur provides an actual clock of glacial melting processes. With the growing rate of glacial loss, the need for measurements from remote locations becomes all the more important.

A sequential determination of 90Sr and 210Po in food samples.

The latest EU Council Regulation 2016/52/Euratom updates the emergency limits on radionuclides in foods including 210Po and 90Sr, two of the most important radionuclides for radiological dose from the ingestion pathway. A novel and straightforward method has been developed for sequential determination of 90Sr and 210Po in food samples using ultra low-level liquid scintillation counting and alpha-particle spectrometry. For 90Sr analysis, the method makes use of stable strontium as yield tracer, and 210Po is determined through self-deposition using 209Po as a yield tracer. The quantification limit for this method is 25.0 and 2.0Bqkg-1 for 90Sr and 210Po, respectively. The proposed radiochemical separation can be completed within 2days for a batch of 12 samples. The radiochemical procedure was validated by its application for the measurement of IAEA certified reference materials, and through participation in a national intercomparison exercise. Results are also presented in seafood from the Mediterranean coast.

90Sr determination in water samples using Čerenkov radiation

A procedure for the determination of 90Sr in environmental water samples using Čerenkov radiation and low–level liquid scintillation counter Quantulus 1220 was applied and optimized. Low diffusion polyethylene vials, high performance glass counting vials and low potassium borosilicate glass vilas of 20 ml volume (all from PerkinElmer) were used in order to examine their potential effect on counting process. The derived efficiencies were 45.86(9)%, and a minimum detectable activity of 0.32 Bq l−1 in a 20 ml polyethylene vial (20 ml water sample) has been achieved during 300 min of measurement. Environmental water samples might be colored and this will lead to color quenching, which one of the most important problems that affect Čerenkov is counting (Mosqueda et al., 2005). The sample channel ratio (SCR) method has been applied to correct this effect. The analytical procedures and measurement techniques were tested by participating in the IAEA-TEL-2015-03 world-wide proficiency test on determination of 90Sr in water sample.

Bio-ETBE determination in a mixture of gasoline using low level liquid scintillation counting

There is a growing interest in Korean government to add bio-ethyl tert-butyl ether (bio-ETBE) in sub-octane gasoline to reduce dependence on fossil fuel based transportation gasoline. The development of bio-ETBE analysis method is an urgent issue to protect illegal circulation of synthetic ETBE because synthetic ETBE and bio-ETBE are chemically indistinguishable even by using chromatography and conventional spectroscopy. This paper communicates the results of bio-ETBE determination from gasoline cocktail using low level liquid scintillation counting (LSC). The counts per minute (CPM) value increased linearly with the concentration of bio-ETBE, showing the correlation coefficient of 0.984.

Radioecological investigation of 3H, 14C, and 129I in natural waters from Fuhrberger Feld catchment, Northern Germany

Ongoing radionuclide releases from nuclear facilities, e.g. from reprocessing plants, but also from nuclear reactors require monitoring of the environment. Particularly drinking water reservoirs are prone to possible radionuclide accumulation fostering the need for routine surveillance. In this work, we investigated tritium (3H), radiocarbon (14C), and iodine-129 (129I) activity levels in natural aquatic samples at the water protection area of Fuhrberger Feld near Hannover city, Northern Germany. For that aim, a low-level liquid scintillation counting (LSC) technique was used to measure 3H in the water samples based on a distillation process after alkaline permanganate treatment. Isotopic ratios for both 14C and 129I were measured by accelerator mass spectrometry (AMS) after chemical separation and purification of the samples. Mean 3H levels in precipitation (8.8 ± 3.4 TU) were found to be comparable to its levels in precipitation data in Germany. Rivers and small streams revealed similar mean 3H value (11.0 ± 3.3 TU) as in lake water (10.6 ± 3.4 TU). Variations in 3H concentrations in groundwater samples were observed and discussed. 14C levels in all groundwater samples were below the atmospheric natural level of 100 pMC indicating no anthropogenic input of radiocarbon. The 129I/127I isotopic ratios in all investigated water samples were in the order of 10−8 to 10−7, which is significantly higher than the pre-nuclear natural equilibrium isotopic ratio (∼1.5 × 10−12). In strong contrast to all other regional groundwaters, the Fuhrberger Feld groundwater has much higher values of 129I concentration and 129I/127I isotopic ratio close to the ones of surface water. The overall annual effective dose via ingestion for all nuclides in the investigated groundwater remains substantially below the reference dose level of 0.1 mSv a−1.

Rapid determination of 210Pb and 210Po in water and application to marine samples

Measurement of radionuclides in marine samples, specifically radioactive pairs disequilibrium, has gained interest lately due to their ability to trace cutting edge biogeochemical processes. In this context, we developed a fast, direct method for determining 210Pb and 210Po water through the use of ultra low-level liquid scintillation counting and alpha-particle spectrometry respectively and through Eichrom Sr resins for the Po-Pb separation. For 210Pb analysis, the method uses stable lead as a yield tracer measured by a robust ICP-MS technique, and 210Po is determined through self-deposition using the conventional 209Po yield tracer. The improvements of the method over other techniques are: a) the analysis can be completed within 6 days, simplifying other methods, b) very low limits of detection have been achieved −0.12 and 0.005mBqL−1 for 210Pb and 210Po, respectively – and c) most of the method could be carried out in on-board analysis. We applied the method to different aqueous samples and specifically to marine samples. We determined 210Pb and 210Po in the dissolved fraction of Mediterranean Sea water and an estuary at the South-West of Spain. We found that it can be successfully employed to marine samples but we recommend to i) use a minimum of 20L water to measure the 210Pb in the dissolved phase by LSC and lower volumes to measure total concentrations; ii) wait for 210Pb and 210Bi in secular equilibrium and measure the total spectrum to minimise the limit of detection and improve accuracy.

Beta Emitter Radionuclides (90Sr) Contamination in Animal Feed: Validation and Application of a Radiochemical Method by Ultra Low Level Liquid Scintillation Counting.

90Sr is considered as a dangerous contaminant of agri-food supply chains due to its chemical affinity with Calcium, which makes its absorption in bones easy. 90Sr accumulation in raw materials and then in final products is particularly significant in relationship to its ability to transfer into animal source products. The radionuclides transfer (137Cs and 90Sr) from environment to forages and then to products of animal origin (milk, cow and pork meats) was studied and evaluated in different studies, which were carried out in contaminated areas, from Chernobyl disaster until today. In the present work, the development and validation of a radiochemical method for the detection of 90Sr in different types of animal feed, and the application of this technique for routinely control activities, are presented. Liquid scintillation counting was the employed analytical technique, since it is able to determine very low activity concentrations of 90Sr (<0.01 Bq Kg–1). All samples analysed showed a 90Sr contamination much higher than method detection limit (0.008 Bq kg–1). In particular, the highest mean activity concentration was registered in hay samples (2.93 Bq kg–1), followed by silage samples (2.07 Bq kg–1) and animal feeds (0.77 Bq kg–1). In fact, all samples were characterized by 90Sr activity concentrations much lower than reference limits. This notwithstanding, the necessity to monitor these levels was confirmed, especially considering that 90Sr is a possible carcinogen for human.

An analytical method for 14C in environmental water based on a wet-oxidation process

An analytical method for 14C in environmental water based on a wet-oxidation process was developed. The method can be used to determine the activity concentrations of organic and inorganic 14C in environmental water, or total 14C, including in drinking water, surface water, rainwater and seawater. The wet-oxidation of the organic component allows the conversion of organic carbon to an inorganic form, and the extraction of the inorganic 14C can be achieved by acidification and nitrogen purging. Environmental water with a volume of 20 L can be used for the wet-oxidation and extraction, and a detection limit of about 0.02 Bq/g(C) can be achieved for water with carbon content above 15 mg(C)/L, obviously lower than the natural level of 14C in the environment. The collected carbon is sufficient for measurement with a low level liquid scintillation counter (LSC) for typical samples. Extraction or recovery experiments for inorganic carbon and organic carbon from typical materials, including analytical reagents of organic benzoquinone, sucrose, glutamic acid, nicotinic acid, humic acid, ethane diol, et cetera., were conducted with excellent results based on measurement on a total organic carbon analyzer and LSC. The recovery rate for inorganic carbon ranged tween 98.7%–99.0% with a mean of 98.9(±0.1)%, for organic carbon recovery ranged between 93.8% and 100.0% with a mean of 97.1(±2.6)%. Verification and an uncertainty budget of the method are also presented for a representative environmental water. The method is appropriate for 14C analysis in environmental water, and can be applied also to the analysis of liquid effluent from nuclear facilities.

Digital liquid-scintillation counting and effective pulse-shape discrimination with artificial neural networks

Abstract A typical problem in low-level liquid scintillation (LS) counting is the identification of α particles in the presence of a high background of β and γ particles. Especially the occurrence of β-β and β-γ pile-ups may prevent the unambiguous identification of an α signal by commonly used analog electronics. In this case, pulse-shape discrimination (PSD) and pile-up rejection (PUR) units show an insufficient performance. This problem was also observed in own earlier experiments on the chemical behaviour of transactinide elements using the liquid-liquid extraction system SISAK in combination with LS counting. α-particle signals from the decay of the transactinides could not be unambiguously assigned. However, the availability of instruments for the digital recording of LS pulses changes the situation and provides possibilities for new approaches in the treatment of LS pulse shapes. In a SISAK experiment performed at PSI, Villigen, a fast transient recorder, a PC card with oscilloscope characteristics and a sampling rate of 1 giga samples s−1 (1 ns per point), was used for the first time to record LS signals. It turned out, that the recorded signals were predominantly α, β-β and β-γ pile up, and fission events. This paper describes the subsequent development and use of artificial neural networks (ANN) based on the method of “back-propagation of errors” to automatically distinguish between different pulse shapes. Such networks can “learn” pulse shapes and classify hitherto unknown pulses correctly after a learning period. The results show that ANN in combination with fast digital recording of pulse shapes can be a powerful tool in LS spectrometry even at high background count rates.

Establishment of a method for ²²²Rn determination in water by low-level liquid scintillation counter.

A procedure for the determination of (222)Rn in environmental water samples using liquid scintillation counting (LSC) was performed. The (226)Ra content in the water was determined by gamma-ray spectroscopy. An application of this procedure to drinking water collected from a public drinking fountain in Vojvodina (Serbia) is presented, including calculations of the annual effective dose for ingestion and inhalation for adults.