Application of new covalently-bound diglycolamide sorbent in sequential injection analysis flow system for sample pretreatment in ICP-MS determination of 239Pu at ppt level.

Diglycolamide ligands are widely applied in the analysis of radionuclides, especially lanthanides and actinides. They are used in liquid-liquid extraction procedures or in solid-phase extraction sorbents where they are adsorbed on the surface of hydrophobic polymers. The main objective of this study was to synthesize the N,N,N'N'-tetrahexyl diglycolamide with one vinyl terminating group (vTHDGA) for further covalent immobilization on the polystyrene-divinylbenzene polymeric support. The obtained complexing resin (THDGA) was employed for the mechanized sample pretreatment in the Sequential Injection Analysis - Lab-on-Valve (SIA-LOV) flow system for the determination of 239Pu using ICP-MS detection. The analytical procedure was optimized in terms of selectivity towards several other radionuclides and elements forming potentially isobaric interferences in mass spectrometry. For 100 mL volume of sample to be analyzed, the method detection limit (MDL) was 96 mBq L-1 (42 pg L-1). The developed method was employed for the determination of 239Pu in real samples of a nuclear reactor coolant and spent fuel pool water from a nuclear reactor.

Evaluation of Shiryaev-Roberts procedure for on-line environmental radiation monitoring.

Water can become contaminated as a result of a leak from a nuclear facility, such as a waste facility, or from clandestine nuclear activity. Low-level on-line radiation monitoring is needed to detect these events in real time. A Bayesian control chart method, Shiryaev-Roberts (SR) procedure, was compared with classical methods, 3-σ and cumulative sum (CUSUM), for quantifying an accumulating signal from an extractive scintillating resin flow-cell detection system. Solutions containing 0.10-5.0 Bq/L of 99Tc, as T99cO4- were pumped through a flow cell packed with extractive scintillating resin used in conjunction with a Beta-RAM Model 5 HPLC detector. While T99cO4- accumulated on the resin, time series data were collected. Control chart methods were applied to the data using statistical algorithms developed in MATLAB. SR charts were constructed using Poisson (Poisson SR) and Gaussian (Gaussian SR) probability distributions of count data to estimate the likelihood ratio. Poisson and Gaussian SR charts required less volume of radioactive solution at a fixed concentration to exceed the control limit in most cases than 3-σ and CUSUM control charts, particularly solutions with lower activity. SR is thus the ideal control chart for low-level on-line radiation monitoring. Once the control limit was exceeded, activity concentrations were estimated from the SR control chart using the control chart slope on a semi-logarithmic plot. A linear regression fit was applied to averaged slope data for five activity concentration groupings for Poisson and Gaussian SR control charts. A correlation coefficient (R2) of 0.77 for Poisson SR and 0.90 for Gaussian SR suggest this method will adequately estimate activity concentration for an unknown solution.

New Efficient Organic Scintillators Derived from Pyrazoline.

We report on the synthesis, spectroscopic and scintillation properties of three new pyrazoline core based fluorophores. Fluorescence properties of the fluorophores have been studied both in a solution state and in a solid polyvinyltoluene (PVT) resin matrix of different porosity. The synthesized fluorophores were found to be promising candidates for application in plastic scintillators for detection of ionizing radiation (alpha, beta particles, γ rays and neutrons) and demonstrated superior efficiency in comparison to the existing commercially used fluorophores (2-(1-naphthyl)-5-phenyloxazole (αNPO), 9,10-diphenylanthracene, etc.). Moreover, the suggested synthetic route allows functionalization of the fluorophores with a vinyl group for further covalent bound to the PVT or other vinyl polymer matrices, which dramatically improves chemical stability of the system simultaneously improving the photoluminescence quantum yield. Possible mechanisms of the enhanced scintillation properties are discussed based on preliminary quantum mechanical calculations and spectroscopic characteristics of the fluorophores under study.

Evaluation of silica/ferrocyanide composite as a dual-function material for simultaneous removal of ¹³7Cs⁺ and 99TcO4⁻ from aqueous solutions.

A novel mesoporous silica-coated ferrocyanide (MSCFC) composite was successfully synthesized and evaluated as a dual-function material for simultaneous removal of (137)Cs(+) cations and (99)TcO4(-) anions from aqueous solutions. Sorption behavior of both radionuclides on MSCFC under different experimental conditions has been studied using a batch technique. Results revealed that about 100% of (137)Cs(+) and 97% of (99)TcO4(-) were removed by MSCFC in the pH ranges of 2.2-12.4 and 4.1-9.5, respectively. Sorption kinetic data were analyzed by pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models, while Langmuir and Freundlich models were applied for the sorption isotherms. The maximum sorption capacity of MSCFC for radiocesium was determined and compared with other reported sorbents. Applicability of the coated ferrocyanide for simultaneous removal of (137)Cs(+) and (99)TcO4(-) from low-level liquid radioactive waste (LLLW) was also tested, and the data revealed that 99.91% and 98.34% were removed from (137)Cs(+) and (99)TcO4(-), respectively. It is concluded that MSCFC exhibits excellent efficiency for simultaneous removal of the mixed radionuclides with different charge from LLLW.

Stable and selective scintillating anion-exchange sensors for quantification of 99TcO4- in natural freshwaters.

New dual functionality scintillating anion-exchange resins were developed for selective determination of (99)TcO4(-) in various natural freshwater samples. Stable scintillating particles were formed by preparing the vinyl monomer 2-[4-(4'-vinylbiphenylyl)]-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (vPBD), starting with the commercial organic flour TBut-PBD and its subsequent copolymerization with styrene, divinylbenzene, and p-chloromethylstyrene mixture. To integrate the radiochemical separation and radiometric detection steps within the same bead, the chloromethyl groups of the scintillating resins were subjected to amination reactions with dioctylamine (DOA) and trioctylamine (TOA). On-line quantification of (99)TcO4(-) was achieved by packing the scintillating anion-exchange resin into Teflon tubing for quantification by a flow scintillation analyzer (FSA). The two functionalized resins were selective for pertechnetate over the common anions in natural freshwaters, especially Cl(-) and SO4(2-) with up to 1000 ppm and with up to 10 ppm I(-) and Cr2O7(2-). The uptake efficiency of the TOA sensor decreased from 97.88% to 85.08% in well water and river water, respectively, while the counting efficiency was almost constant (69.50%). The DOA performance showed lower efficiency in the two water types relative to TOA. On the other hand, the DOA sensor could be regenerated by 5 M HNO3 for reuse at least four times without losing its chemical or optical performance. The detection limit was 1.45 Bq which could be achieved by loading 45 mL from well and tap water containing the maximum contaminant level (MCL) of (99)Tc (33 Bq/L).

Preparation of polymer-coated, scintillating ion-exchange resins for monitoring of 99Tc in groundwater.

The present study was oriented to prepare new scintillating anion-exchange resins for measurement of (99)TcO(4)(-) in natural waters. The organic fluor 2-(1-naphthyl)-5-phenyloxazole was diffused into (chloromethyl)polystyrene resin. Thereafter, a thin layer of poly[[2-(methacryloyloxy)ethyl]trimethylammonium chloride] was grafted from the resin surface by surface-initiated atom transfer radical polymerization as an attempt to overcome potential problems related to the leaching of fluor molecules during usage. The residual chloromethyl groups of the polymer-coated resin were aminated by reaction with two different tertiary amines, triethylamine (TEA) and methyldioctylamine (MDOA). Off- and on-line quantification of (99)Tc was achieved with high detection efficiencies of 60.72 ± 1.93% and 72.83 ± 0.81% for resin with TEA and MDOA functional groups, respectively. The detection limit was determined to be less than the maximum contaminant level (33 Bq L(-1)) established under the Safe Drinking Water Act. The two functionalized resins were demonstrated to be selective for pertechnetate from synthetic groundwater containing up to 1000 ppm Cl(-), SO(4)(2-), and HCO(3)(-) and up to 1200 ppb Cr(2)O(7)(2-) in an acidic medium.

Utilization of natural chabazite and mordenite as a reactive barrier for immobilization of hazardous heavy metals.

INTRODUCTION: Understanding the sorption process in natural geomedia is necessary for effective utilization of these materials as low-cost adsorbents and consequently as controlled release hazardous elements. This research was oriented to investigate the affinity of two natural zeolite minerals towards cobalt, zinc, and nickel mixture as an important industrial and radioactive waste. METHOD: The uptake of metal ions as a function of different parameters has been studied using a batch equilibrium technique. RESULTS: The results revealed that the affinity and adsorption capacity of chabazite and mordenite follow the order: Zn(2+) > Co(2+) > Ni(2+), with good fits being obtained using Langmuir and Freundlich adsorption isotherms. The metal uptake was found to be concentration-dependent and independent of the pH over 3.0 to 8.0 range; this reveals that the adsorption mechanism is controlled mainly by a pure ion-exchange reaction at the experimental conditions used. Kinetic curves showed a rather fast exchange reaction for three cations, as equilibrium was mostly reached within 20 min. CONCLUSION: These materials especially chabazite are recommended to be used as a reactive barrier for hazardous heavy metals control.

Simultaneous measurement of (226)Ra and (228)Ra in natural water by liquid scintillation counting.

Several types of bottled drinking water originating from three different areas in Egypt are studied through measurement of radium activity, assessment of related annual dose for adults and finally to define the role of water quality on radium levels. The mean levels of (226)Ra activity range from 0.44 to 0.92 Bq/L and the mean levels of (228)Ra from 0.30 to 0.78 Bq/L, with related (226)Ra/(228)Ra ratios ranging from 2.61 to 0.56. Water types originating from the Eastern Nile Delta area are characterized by low (226)Ra levels and relatively high (228)Ra activity, presumably due to the muddy agricultural nature of this area, which is subject to water from several surface resources for irrigation. In general, the mean activity levels for both (226)Ra and (228)Ra are within those in drinking water in several other countries and the annual ingested dose is comparable with the typical range reported by UNSCEAR. Also, the effect of TDS, pH, calcium, bicarbonate, sulphate and chloride ion concentrations on radium levels is studied and discussed.