Rapid method for determination of radiostrontium in emergency milk samples

A new rapid separation method for radiostrontium in emergency milk samples was developed at the Savannah River Site (SRS) Environmental Bioassay Laboratory (Aiken, SC, USA) that will allow rapid separation and measurement of radiostrontium within 8 hours. The new method uses calcium phosphate precipitation, nitric acid dissolution of the precipitate to coagulate residual fat/proteins and a rapid strontium separation using Sr Resin (Eichrom Technologies, Darien, IL, USA) with vacuum-assisted flow rates. The method is much faster than the previous method that use calcination or cation-exchange pretreatment, has excellent chemical recovery, and effectively removes beta-interferences. When a 100 mL sample aliquot is used with a 20 minute count time, the method has a detection limit of 0.5 Bq·L⁻¹, well below generic emergency action levels.     

Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry

An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric tecniques, is less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of⁹⁹Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method one liter samples of water are spiked with⁹⁷Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with, dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the⁹⁹Tc/⁹⁷Tc ratio in the eluant is measured with an ICP-MS. The⁹⁹Tc concentration in the original sample is calculated from the⁹⁹Tc/⁹⁷Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts atm/z=99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/l.     

Determination of hydrogen peroxide in reactor moderator solutions by flow injection analysis

A flow injection analysis (FIA) method for the determination of hydrogen peroxide in reactor moderator water has been developed and installed at the Savannah River Site (SRS) Water Quality Laboratory. The mode of detection is amperometric and the technique has an analytical range of 0.10-2.50 mug/ml with a sampling rate of 40 samples/hour. The calibration curve is linear with a correlation coefficient of 0.999 and the relative standard deviation is at the 0.50% level for both 0.10- and 2.50-mug/ml standards. When the FIA procedure is compared to the manual method previously used at the SRS Water Quality Laboratory for hydrogen peroxide analysis, it demonstrates a minimum twenty minute reduction in analysis time per sample and the total liquid waste generated per sample analyzed is reduced by 95%.     

Determination of tritium enrichment parameters of a commercially available PEM electrolyzer: a comparison with conventional enrichment electrolysis

The combination of an Ir/Pt PEM electrolyzer with a 1 L flow-through gas proportional counter was characterized for the quantification of tritium in water. The goal of the detection system is to quantify at concentrations below the Environmental Protection Agency (EPA) primary drinking water standard (740 Bq/L) with minimal expendables. The detector operating voltage, efficiency, background count rate of the passively shielded counter were measured in order to calculate the minimum detectable concentration of the detection system. The electrolyzer fractionation factor β _e value deduced from the measurement of gas phase activity concentrations generated from tritium aqueous standards was found in good agreement with literature values.     

Proportional counting of tritium gas generated by polymer electrolyte membrane (PEM) electrolysis

The combination of an Ir/Pt PEM electrolyzer with a 1 L flow-through gas proportional counter was characterized for the quantification of tritium in water. The goal of the detection system is to quantify at concentrations below the Environmental Protection Agency (EPA) primary drinking water standard (740 Bq/L) with minimal expendables. The detector operating voltage, efficiency, background count rate of the passively shielded counter were measured in order to calculate the minimum detectable concentration of the detection system. The electrolyzer fractionation factor β _e value deduced from the measurement of gas phase activity concentrations generated from tritium aqueous standards was found in good agreement with literature values.     

In-Situ Sample Preparation for Radiochemical Analyses of Surface Water

A new method for radionuclide sample analysis of surface water has been demonstrated at the Savannah River Site, an U.S. Department of Energy manufacturing facility, currently in standby. The method makes use of selective solid phase extraction (SPE) disks being placed in a modified portable aqueous sampler. The analytes currently measured by this in-situ preparation are ⁹⁹Tc, ⁹⁰Sr, ¹³⁷Cs and ^58,60Co. The SPE disks are placed singly or in series in an automatic sampler; water is passed through the SPE disks at the time of collection. The disks are then returned to the laboratory for counting; no additional chemical separation is performed prior to analysis. The modified automatic samplers have been placed at several different locations around the Savannah River Site along side traditional samplers. The traditional samplers were used to collect water that was analyzed for the same analytes using standard laboratory methods. Most of the sample results were less than five times the method detection limit, thus a mean difference statistic was used to compare the data. Within the uncertainties of the methods, there was no statistical difference in the ⁹⁹Tc results, although a slight negative bias was observed for the in-situ ⁹⁰Sr results versus the laboratory method. The in-situ method produces a dissolved (<0.45µm) and particulate ¹³⁷Cs result, whereas the traditional laboratory method measures total activity in the sample. As expected, a negative bias was found between the dissolved in-situ result and the laboratory total ¹³⁷Cs result, and a positive bias between the in-situ total (dissolved plus particulate) and laboratory total ¹³⁷Cs result.     

Diverse active well neutron coincidence counter utility at the Savannah River National Laboratory

In this paper we describe use of the Aquila active well neutron coincidence counter for nuclear material assays of ²³⁵U in multiple analytical techniques at Savannah River Site (SRS), at the Savannah River National Laboratory (SRNL), and at Argonne West National Laboratory (AWNL). The uses include as a portable passive neutron counter for field measurements searching for evidence of ²⁵²Cf deposits and storage; as a portable active neutron counter using an external activation source for field measurements searching for trace ²³⁵U deposits and holdup; for verification measurements of U-Al reactor fuel elements; for verification measurements of uranium metal; and for verification measurements of process waste of impure uranium in a challenging cement matrix. The wide variety of uses described demonstrate utility of the technique for neutron coincidence verification measurements over the dynamic ranges of 100–5000 g for U metal, 200–1300 g for U-Al, and 8–35 g for process waste. In addition to demonstrating use of the instrument in both the passive and active modes, we also demonstrate its use in both the fast and thermal neutron modes.     

Method for rapid tritiated water extraction from environmental samples

We have developed a thermal vacuum desorption process to rapidly extract water from environmental samples for tritium analysis. Thermal vacuum desorption allows for extraction of the moisture from the sample within a few hours in a form and quantity suitable for liquid scintillation counting and allows detection of tritium at the levels of <2 Bq/l of milk, <0.5 Bq/g of vegetation, and <0.5 Bq/g of soil. We developed a prototype unit that can process batches of twenty or more samples within 24 hours. Early data shows that a high percentage of water is extracted reproducibly without enrichment or depletion of the tritium content. The quench coefficient of the extracted water is low allowing for accurate, direct liquid scintillation counting. In most samples, good comparison has been observed with results using freeze-dry lyophilization as the water extraction method     

Development of field portable sampling and analysis systems

A portable, field rugged, sampling and analysis system has been developed for the rapid screening of aqueous samples during scoping and remediation studies. Using field portable equipment, water is pumped through ion selective solid phase extraction (SPE) disks, at a flow rate of 150-250 ml/min, and counted for the radionuclide of interest in the field using portable detectors. SPE disks are currently available to selectively concentrate ⁹⁹Tc, ⁹⁰Sr, radiocesium (¹³⁴Cs and ¹³⁷Cs) and radium isotopes. In the field the radiocesium concentration is determined by gamma-spectrometry, ⁹⁰Sr and ⁹⁹Tc are determined by beta-counting. A one-liter sample can be processed and ready for counting within ten minutes. Using a 5-minute counting time, a detection limit of <50 pCi/l for ⁹⁹Tc or ⁹⁰Sr and ~50 pCi/l for ¹³⁷Cs has been achieved. Up to 10 liters of water have been processed for the analysis of ⁹⁹Tc and ¹³⁷Cs when lower limits of detection were required. The sampling and analysis system has been field tested at the Savannah River Site (SRS), Aiken SC, and the Hanford Site, Richland WA. The SRS H-area tank farm storm water runoff system was analyzed for ⁹⁰Sr and ¹³⁷Cs. Groundwater from the SX tank farm at the Hanford Site was analyzed for ¹³⁷Cs and ⁹⁹Tc. Groundwater from seeps below the 100-H area at Hanford was analyzed for ⁹⁰Sr and ⁹⁹Tc.     

Measurement of tritium with plastic scintillators in large vials of a low background liquid scintillation counter: an organic waste-less method

The tritium compounds, tritiated water as a volatile compound and ³H-methionine as a non-volatile compound, were measured with two types of plastic scintillators (PSs) using a low background liquid scintillation counter (LSC). It is advantage that minimal organic waste is generated when a plastic scintillator is used for LSC measurement. The effect of large vials on counting efficiency, plasma effects with three types of plasma devices for PS-sheets, the effect of UV-light on PS-pellets, the relationship between the activity and the count rate, and the detection limits of tritium were studied with respect to the development of large-scale measurement systems.

     

Gamma-pulse-height evaluation of a USA Savannah River Site Burial Ground special configuration waste item

The Savannah River Site (SRS) Burial Ground had a container labeled as Box 33 for which they had no reliable solid waste stream designation. The container consisted of an outer box of dimensions 48″ × 46″×66″ and an inner box that contained high density and high radiation dose material. From the outer box Radiation Control measured an extremity dose rate of 22 mrem/h. With the lid removed from the outer box, the maximum dose rate measured from the inner box was 100 mrem/h extremity and 80 mrem/h whole body. From the outer box the material was sufficiently high in density that the Solid Waste Management operators were unable to obtain a Co-60 radiograph of the contents. Solid Waste Management requested that the Analytical Development Section of Savannah River National Laboratory perform a γ-ray assay of the item to evaluate the radioactive content and possibly to designate a solid waste stream. This paper contains the results of three models used to analyze the measured γ-ray data acquired in an unusual configuration.     

Methodologies for the practical determination and use of method detection limits

Underwater NaI(T1) and HPGe detectors are used in the environmental measurements programs at the Savannah River Site (SRS). A 22.9 cm × 10.2 cm NaI(T1) detector on the Savannah River continuously monitors effluent releases from both SRS (DOE) and Plant Vogtle (Georgia Power). Correlations with known releases indicate a sensitivity of 4 mBq/l for⁵⁸Co with 1500 min spectra; such levels are well below those of hazardous or legal concern. A 30%-efficient HPGe detector has appraised radionuclides in SRS cooling pond sediments; the dominant gamma-emitting radionuclide detected was¹³⁷Cs, at levels ranging up to 2.0 MBq/m². The pond activities were adequately quantified by 1 min counts with the HPGe detector; resulting contour maps of sediment¹³⁷Cs provided guidance for partially draining the ponds for dam repairs.     

Advances in <Superscript>79</Superscript>Se analyses on Savannah river site radioactive waste matrices

Waste cleanup efforts underway at the United States Department of Energy’s (DOE) Savannah River Site (SRS) in South Carolina, as well as other DOE nuclear sites, have created a need to characterize ⁷⁹Se in radioactive waste inventories. Successful analysis of ⁷⁹Se in high activity waste matrices is challenging for a variety of reasons. As a result of these unique challenges, the successful quantification of ⁷⁹Se in the types of matrices present at SRS requires an extremely efficient and selective separation of ⁷⁹Se from high levels of interfering radionuclides. A robust ⁷⁹Se radiochemical separation method has been developed at the Savannah River National Laboratory (SRNL) which is routinely capable of successfully purifying ⁷⁹Se from a wide range of interfering radioactive species. In addition to dramatic improvements in the K_d, ease, and reproducibility of the analysis, the laboratory time has been reduced from several days to only 6 h.     

Tritium activity concentration along the Western shore of the Black Sea

The Black Sea tritium level was investigated in 33 places southward the Danube Delta covering about 360 km of the Black Sea Western Shore. Both surface (10 cm depth) and bottom (up to 20 m depth) water samples were collected. In the close vicinity of Danube Delta, the tritium activity concentration in the surface water was around 28 TU, which is almost the same as that of the Danube River waters, but it decreased to about 5 TU in the bottom water. This discrepancy slowly diminished wherein at about 120 km southward, the tritium content in both surface and bottom water reached almost the same constant value of 6.5 ± 2.3 TU. This value, about two and a half times smaller than that reported 17 years ago, remained almost unchanged for the last 240 km of shore up to the Turkish border.     

Rapid separation method for emergency water and urine samples

The Savannah River Site Environmental Bioassay Lab participated in the 2008 NRIP Emergency Response program administered by the National Institute for Standards and Technology (NIST) in May, 2008. A new rapid column separation method was used for analysis of actinides and ⁹⁰Sr in the NRIP 2008 emergency water and urine samples. Significant method improvements were applied to reduce analytical times. As a result, much faster analysis times were achieved, less than 3 hours for determination of ⁹⁰Sr and 3–4 hours for actinides. This represents a 25%–33% improvement in analysis times from NRIP 2007 and a ∼100% improvement compared to NRIP 2006 report times. Column flow rates were increased by a factor of two, with no significant adverse impact on the method performance. Larger sample aliquots, shorter count times, faster cerium fluoride microprecipitation and streamlined calcium phosphate precipitation were also employed. Based on initial feedback from NIST, the SRS Environmental Bioassay Lab had the most rapid analysis times for actinides and ⁹⁰Sr analyses for NRIP 2008 emergency urine samples. High levels of potential matrix interferences may be present in emergency samples and rugged methods are essential. Extremely high levels of ²¹⁰Po were found to have an adverse effect on the uranium results for the NRIP-08 urine samples, while uranium results for NRIP-08 water samples were not affected. This problem, which was not observed for NRIP-06 or NRIP-07 urine samples, was resolved by using an enhanced ²¹⁰Po removal step, which will be described.     

Quality assessment of hydrosphere in the vicinity of Czech nuclear power plants by radioanalytical methods

Summary The paper deals with the impact of nuclear plants and radioactive waste disposal on surface and ground water quality in their vicinity using various radiometric and radioanalytical methods. The impact of nuclear power plant Temelin on activation concentrations and fission products in hydrosphere, including tritium, was detected. The annual average tritium concentrations in Vltava River correspond to the previously calculated estimates for average and minimal quaranteed flow rates. The concentrations histories of ⁹⁰Sr and ¹³⁷Cs in surface water show a decreasing trend. This trend was not influenced by the nuclear power plant pilot operation. In the case of tritium, a concentration increase trend has been already observed since the startup of pilot operation. An attempt has made interpreting the sorption and diffusion data for radionuclides of cesium, strontium and tritium and technetium as representatives of multivalent elements. Sorption and diffusion data of ¹³⁷Cs and ⁹⁰Sr in contact with natural sorbent bentonite lead to the conclusion that both diffusion and batch sorption experiments can be simulated by an exchange model. Sorption of technetium on various bentonites plus additives materials is described. Retention of technetium on these solid phases is driven by sorption of reduced form of technetium Tc(IV).     

Levels of tritium concentration in the environmental samples around JAERI TOKAI

By the operation of research reactors, tritium-handling facilities, nuclear power plants, and a reprocessing facility around JAERI TOKAI, tritium is released into the environment in compliance with the regulatory standards.To investigate the levels of tritium concentration in environmental samples around JAERI, rain, air (vapor and hydrogen gas), and tissue-free water of pine needles were measured and analyzed from 1984 to 1993. Sampling locations were determined by taking into consideration wind direction, distance from nuclear facilities, and population distribution. The NAKA site (about 6 km west-northwest from the TOKAI site) was also selected as a reference point.Rain and tissue-free water of pine needles were sampled monthly. For air samples, sampling was carried out for two weeks by using the continuous tritium sampler. After the pretreatment of samples, tritium concentrations were measured by a low background liquid scintillation counter (detection limit is 0.8 Bq/l).Annual mean tritium concentrations in rain observed at six points for 10 years was 0.8 to 8.9 Bq/l, which decreased with distance from the nuclear facilities. Tritium concentrations in rain obtained at Chiba City were around 0.8 Bq/l (1987–1988) and those at the NAKA site were 0.8 to 3.8 Bq/l.Annual mean HTO concentrations in air at three points for 10 years were 9.2×10^–2 to 1.1 Bq/m³, although HT concentrations in air, ranging from 1.7×10^–2 to 5.8×10^–2 Bq/m³, were not influenced by the operation of the nuclear facilities.Annual mean tritium concentrations in tissue-free water of pine needles at four points for 10 years were 1.4 to 31 Bq/l. Those at the NAKA site ranging from 1.4 to 6.2 Bq/l were in good agreement with the reported value by Takashima of 0.78 to 3.0 Bq/l at twenty-one locations in Japan.Monthly mean HTO concentrations in air for 10 years showed a good correlation with absolute humidity, while other samples showed no seasonal variation.Higher level tritium concentrations in rain, in air (vapor), and in tissue-free water of pine needles at the TOKAI site were caused by the tritium released from the nuclear facilities.The committed effective dose equivalent to the member of general public, estimated using the maximum tritium concentration in air (1.1 Bq/m³), was 0.23 Sv, which was about 1/4000 of dose limit for general public.     

Efficiency of tritium enrichment by electrolytic cell with multi-nickel-plates electrode and its application to the determination of tritium in environmental water

For the purpose of speeding up the tritium enrichment by electrolysis, we have produced an electrolytic cell with the multi-plate-electrode system instead of the commonly used single-plate-electrode, and examined the efficiencies for the tritium enrichment under the conditions of different current densities and electrode gaps. From the results, the tritium recovery and the separation factor beta were found to be maximized under the condition of 70 mA/cm2 of current density and 1.6 mm of electrode gap, and they were 90 percent and 23, respectively. Using this cell, it took 28 hours to reduce 100 ml of a sample water to 10 ml, and took 2 days, including the time required for other operations, to determine the tritium concentration of 1.85 Bq/l (50 pCi/l) with the counting error of within +/- 10 percent. This method has been applied to determining the tritium concentrations of environmental samples from Yamato River region during July 1981-February 1983. They were in the range of 1.11-9.48 Bq/l (30-256 pCi/l).     

Development of continuous inflow tritium measurement in water technology using electrolysis and a plastic scintillator

Our goal was to develop a mobile tritium monitor for continuous inflow system for water sample. The system is based on electrolysis and a plastic scintillator detection system. The minimum detectable activity (MDA) of the prototype system is 431 kBq L^?1, while the MDA of a commercially available product is 740 kBq L^?1. We expected to achieve a 5.73-times lower MDA by optimizing detection geometry using a multi-hydrogen-gas-channel. The system can be applied either as a mobile leakage surveying method or as a fixed-type monitor for detecting tritium in drinking water by adapting conventional background reduction technologies.