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 <Superscript>99</Superscript>Tc in Savannah River Site high activity waste

Summary Waste cleanup efforts currently underway at the Savannah River Site have created a need to characterize ⁹⁹Tc in the various high activity waste matrices currently in Site inventories. The traditional method our laboratory used for analyzing ⁹⁹Tc in higher activity matrices was a solvent-solvent extraction method using Aliquat-336 in xylene. In an effort to eliminate the resulting generation of mixed wastes, a variety of different separation methodologies have been studied. Eichrom TEVA solid phase extractions using column technology have been employed in a case by case basis over the last several years. More recently, applications using Eichrom TEVA extraction discs and 3M Empore Tc extraction discs have also been explored.     

Recovery and determination of adsorbed technetium on Savannah River Site charcoal stack samples

Experimental results are provided for the sample analyses for technetium in charcoal samples placed in-line with a Savannah River Site (SRS) processing stack effluent stream as a part of an environmental surveillance program. The method for Tc removal from charcoal was based on that originally developed with high purity charcoal. Presented is the process that allowed for the quantitative analysis of ⁹⁹Tc in SRS charcoal stack samples with and without ⁹⁷Tc as a tracer. The results obtained with the method using the ⁹⁷Tc tracer quantitatively confirm the results obtained with no tracer added. All samples contain ⁹⁹Tc at the pg·g⁻¹ level.     

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.     

An in situ method for remediating 137Cs-contaminated wetlands using naturally occurring minerals

Cesium's enhanced bioavailability in contaminated wetlands onthe U.S. Department of Energy's Savannah River Site (SRS) is thoughtto be due to the low clay fraction of SRS soils, and that the clay mineralogyis dominated by kaolinites. Remediation of the wetlands is problematic becausecurrent technologies are destructive to the sensitive ecosystems. We tested11 clay minerals (two micas, a vermiculite, six illites, a kaolinite, anda smectite) for their propensity to sorb and retain ¹³⁷Cs. Twominerals were subsequently chosen as candidates for in situ remediation amendmentmaterials because they had ¹³⁷Cs distribution coefficients (K d) well in excess of 10,000 ml . g –1 , and desorbed less than 20% ofthe Cs when mixed in a 0.1M NH 4 Cl solution. Incremental additions of thecandidate minerals to ¹³⁷Cs-contaminated sediments appreciablyintercepted and retained desorbed ¹³⁷Cs in the presence of highlevels of NH₄ . Implications for using the minerals as a nondestructive,in situ remediation technique are discussed.     

Analysis of high-level waste for tetraphenylborate using HPLC

Summary One waste remediation process used at the Savannah River Site was the in-tank precipitation of the beta-emitting ¹³⁷Cs from high-level waste (HLW) using sodium tetraphenylborate (NaTPB) followed by processing the resulting decontaminated filtrate into grout at the Saltstone Production Facility (SPF). A simple method was developed for the monitoring of tetraphenylborate (TPB) in high-level waste (HLW) containing up to 0.38 Ci/gal of ¹³⁷Cs. Separation was achieved by extraction of the high sodium-bearing waste with acetonitrile followed by analysis using reversed-phase high performance liquid chromatography (HPLC). The sample preparation method allowed for the handling of an organic extraction layer that had 94% less acitivity than the HLW sample. The subsequent HPLC analysis of the extraction layer determined the TPB concentration in HLW waste to 0.8 mg/l with a %rsd of 8.     

Calibration of an automated high resolution gamma-ray spectroscopy system for in-situ real-time monitoring of a processed waste effluent stream

A pilot plant is being designed at the U. S. Department of Energy's Savannah River Site (SRS) to demonstrate the removal of ⁹⁰Sr, ¹³⁷Cs, and transuranics from a high-level liquid waste stream prior to encapsulation in a Saltstone Facility. In-line monitors are required to determine the concentration of all radionuclides on this processed waste stream. Calibration standards containing ⁶⁰Co, ¹³⁷Cs, and ⁹⁰Sr were prepared and counted. Efficiency curves were generated. Strontium-90 is readily observable above the system background in the calibration standard count, and is observable at less than 3 nCi/ml in a mixed solution having the maximum allowable concentration of all other activities present in the proposed SRS effluent stream.     

Organic Analyses of Highly Radioactive Solutions Requiring Pretreatment by 137Cs Removal

The beta-emitting radionuclide ¹³⁷Cs is precipitated from the Savannah River Site (SRS) high-level waste by adding sodium tetraphenylborate (TPB). The concentrated and washed precipitate slurry containing CsTPB is transferred to Defense Waste Processing Facility (DWPF) Salt Processing Cell and hydrolyzed to yield an aqueous product (PHA) free of benzene. The PHA is highly radioactive (1E+11 dpm) and contains some water-soluble organic compounds that need to be analyzed for process control and process history. High performance liquid chromatography (HPLC) methods were developed to analyze these compounds with instruments contained in unshielded fume hoods. Removing ¹³⁷Cs from PHA in a shielded cell prior to HPLC analyses is essential to minimize personnel radiation exposure. In this study ammonium molybdophosphate (Bio-Rad AMP-1) was used for removing ¹³⁷Cs in PHA (pH 3.8). With a two-step application of AMP slurry, a decontamination factor of 1E+4 was achieved for Cs removal. Two separate HPLC methods were used to analyze four polar organic compounds. The recovery of all the organic compounds were above 85%.     

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.     

Low-level measurement of alpha-particle emitting nuclei in ceramics and lead

The operationally defined bioavailable fraction from a commonly used sequential extraction (SE) procedure was compared to biological availability represented by plant uptake of¹³⁷Cs and⁹⁰Sr. Experiments were conducted at two locations in the Ukraine and at several field locations on the Savannah River Site, South Carolina. A significant regression existed between plant uptake and the ammonium acetate fraction (r ²=0.65), however, ratios of predicted uptake from the SE procedure to observed plant uptake ranged from 0.03 to 5.2 Data suggest that SE procedure was useful for qualitative interpretations of biological availability but lacked sufficient rigor to be useful for quantitative predictions.     

A neutron monitor for in-situ real-time determination of transuranics in a processed waste effluent stream

A pilot plant operation at the Savannah River Site will remove ⁹⁰Sr, ¹³⁷Cs, and transuranics from a high-level liquid waste stream prior to encapsulation in a Saltstone Facility. Monitors are required to determine the concentrations of all radionuclides, including transuranics, in real-time on this processed waste stream. A neutron counter used to measure the concentration of each actinide isotope present in the stream is described. The neutron counter assembly consists of nested annular layers of shielding, reflectors, detectors, and moderators. On-line, live-time system control and calibration is provided by a time-tagged neutron source embedded in the moderator assembly.     

Observation and Measurement of 79Se in Savannah River Site High Level Waste Tank Fission Product Waste

We report the first observation of confirmed ⁷⁹Se activity in Savannah River Site high level fission product waste. ⁷⁹Se was measured after a seven step chemical treatment to remove interfering activity from ¹³⁷Cs, ⁹⁰Sr, and plutonium at levels 10⁵ times higher than the observed ⁷⁹Se content and to remove ⁹⁹Tc at levels 300 times higher than observed ⁷⁹Se. ⁷⁹Se was measured by liquid scintillation -decay counting after specific tests to eliminate uncertainties from possible contributions from ⁹⁹Tc, ¹⁴⁷Pm, ¹⁵¹Sm, ⁹³Zr, or ²⁴¹Pu, whose -decay spectra could appear similar to that of ⁷⁹Se, and whose content would be expected at levels near or greater than ⁷⁹Se.     

Polydimethylsiloxane-based permeation passive air sampler. Part I: Calibration constants and their relation to retention indices of the analytes

A simple and cost effective permeation passive sampler equipped with a polydimethylsiloxane (PDMS) membrane was designed for the determination of time-weighted average (TWA) concentrations of volatile organic compounds (VOCs) in air. Permeation passive samplers have significant advantages over diffusive passive samplers, including insensitivity to moisture and high face velocities of air across the surface of the sampler. Calibration constants of the sampler towards 41 analytes belonging to alkane, aromatic hydrocarbon, chlorinated hydrocarbon, ester and alcohol groups were determined. The calibration constants allowed for the determination of the permeability of PDMS towards the selected analytes. They ranged from 0.026 cm² min⁻¹ for 1,1-dichloroethylene to 0.605 cm² min⁻¹ for n-octanol. Further, the mechanism of analyte transport across PDMS membranes allowed for the calibration constants of the sampler to be estimated from the linear temperature programmed retention indices (LTPRI) of the analytes, determined using GC columns coated with pure PDMS stationary phases. Statistical analysis using Student's t test indicated that there was no significant difference at the 95% probability level between the experimentally obtained calibration constants and those estimated using LTPRI for most analyte groups studied. This correlation allows the estimation of the calibration constants of compounds not known to be present at the time of sampler deployment, which makes it possible to determine parameters like total petroleum hydrocarbons in the vapor phase.     

Determination and lebels of99Tc in environmental and biological samples

In this paper, the physical and chemical methods used in our laboratory for the measurement of⁹⁹Tc in natural samples are reviewed. Levels of⁹⁹Tc in rainwater, algae, and freshwater samples are given. In addition, and estimation of the radiological impact of⁹⁹Tc to the population, derived from our earliear atmospheric⁹⁹Tc measurements, is presented. For rainwater, levels of¹³⁷Cs are also given for comparison.Work partially supported by the contract PB86-0207 of the Spanish CICYT.     

In-situ spectrometry of137Cs in the soil by an unfolding method

The approach is based on in-situ measurements performed with a portable high-resolution germanium -spectrometer and on calculations of the depth distribution by an unfolding method. To unfold the depht distribution of¹³⁷Cs concentration in soil four detector responses and the iterative procedure SAND II were used. The detector responses consist of the responses to primary 662 keV photons and to photons scattered in soil with the rest energies of 620–655 keV. The detector is used with and without collimator. The method is sufficiently sensitive for measurements of¹³⁷Cs concentration in soil 10 years after the Chernobyl accident. The results are compared to laboratory analyses of collected soil samples and with a standard method of in-situ spectrometry.     

Sources of 137Cs fluvial export from a forest catchment evaluated by stable carbon and nitrogen isotopic characterization of organic matter

Fluvial export of particulate and dissolved ¹³⁷Cs was investigated to reveal its sources and transfer mechanisms in a broadleaved forest catchment using a continuous collection system. The finest size fraction (<75 µm), consisting of decomposed litter and surface mineral soil, was the dominant fraction in the particulate ¹³⁷Cs load, although the contribution of coarser size fractions increased during high water discharge in 2014. The dissolved ¹³⁷Cs originated from the decomposition of ¹³⁷Cs-contaminated litter. Temporal changes in ¹³⁷Cs distribution in the litter–mineral soil system indicated that the dissolved ¹³⁷Cs load will be moderated in several years, while particulate ¹³⁷Cs load has the potential to continue for a long time.

     

EB-radiolysis of carbamazepine: in pure-water with different ions and in surface water

A method for the rapid and simultaneous monitoring of particulate and dissolved ¹³⁷Cs concentration in water was developed. This method uses pleated polypropylene nonwoven fabric filter to collect particulate radiocesium, and nonwoven fabric impregnated with Prussian blue (PB) to absorb dissolved radiocesium. The fabric was placed into cylindrical plastic cartridges (SS-cartridge and PB-cartridge). Traditional monitoring methods, such as evaporative concentration, often require time for pre-processing. However, this method described requires much less pre-processing time before the detection. Experiments conducted with simulated river water demonstrated that almost all of the suspended solids weight was collected in the SS-cartridge, and that more than 92 % of dissolved ¹³⁷Cs was absorbed onto the two PB-cartridges by 2.5 L/min flow rate when the range of the pH was 6–8. This device was applied to monitor Abukuma River water at two locations and the results were compared with those obtained using the filtrating and evaporative concentration method. The suspended solids concentration in river water, calculated by weight gain of the SS-cartridge and by sediment weight after filtration with a 0.45-μm membrane filter, agreed well. The radioactivity of the particulate and dissolved ¹³⁷Cs also agreed well in one of the two replications of this method. In addition, the required time for pre-processing was reduced by 60 times that by filtrating and evaporative concentration method. This method can separately collect and concentrate particulate and dissolved radiocesium rapidly and simultaneously in the field.     

Radiochemical analyses for the defense waste processing facility startup at the Savannah River Site

Highly radioactive waste from defense-related activities at the Savannah River Site in South Carolina are to be incorporated into a borosilicate glass in the Defense Waste Processing Facility (DWPF) for long-tem geological isolation. Processing and repository safety considerations require the determination of 24 radioisotopes that meet the reporting criteria. These isotopes include fission products, activation products, and daughter nuclei that grow into the waste. Four isotopes,¹³⁷Cs,⁹⁰Sr,²³⁸Pu and²³⁸U will be routinely measured in the DWPF operation for process control. This work shows that the concentrations of the other 20 reportable radioisotopes in the final glass product can be predicted from a thorough characterization of the high level waste (HLW) tanks and a knowledge of the concentrations of the major non-radioactive components in the vitrification process.     

Global fallout levels of <Superscript>99</Superscript>Tc and activity ratio of <Superscript>99</Superscript>Tc/<Superscript>137</Superscript>Cs in the Pacific Ocean

Summary Global fallout levels of ⁹⁹Tc and ¹³⁷Cs of surface seawater in the Pacific Ocean were measured. The ⁹⁹Tc concentrations ranged from 0.62 to 3.33 mBq^. m^-3and 5 of 6 samples showed less than 1 mBq^. m^-3except one sample taken in the Great Barrier Reef, Australia. The ¹³⁷Cs concentrations ranged from 2.13 to 3.14 Bq^. m^-3, showing a gradual decrease in the North Pacific toward the equator and a constant level in the South Pacific. The ⁹⁹Tc/¹³⁷Cs activity ratios ranged from 2.5^. 10^-4to 2.9^. 10^-4, which is very close to that calculated theoretically from the fission yield.     

Simultaneous determination of some long-lived semivolatile radionuclides in environmental samples

A radiochemical method is presented to determine simultaneously the long-lived semivolatile radionuclides⁷⁹Se,⁹⁹Tc,¹⁰⁶Ru,¹²⁵Sb,^125mTe,^127mTe,¹³⁴Cs and¹³⁷Cs in environmental samples. The pure -emitters⁷⁹Se and⁹⁹Tc are counted in a low-level gas flow counter, the -emitters in a -spectrometer with a high purity well-type Ge detector. The procedure was tested using environmental samples with known concentrations of⁹⁹Tc,¹⁰⁶Ru,¹²⁵Sb,¹³⁴Cs and¹³⁷Cs.