The Separation of Beryllium from Selected Elements Using the Dipex® Extraction Chromatographic Resin

Abstract

An extraction chromatographic resin containing the acidic chelating organophosphorus extractant, Dipex^®, sorbed onto an inert polymeric substrate has been evaluated for the separation of beryllium from a wide range of elements. The elements selected comprise those which can interfere with the determination of beryllium by inductively coupled plasma‐atomic emission spectroscopy (ICP‐AES) and matrix elements which commonly occur in environmental and industrial samples. Based on batch uptake measurements, a method that separates beryllium from all potential ICP‐AES spectral interfering elements using a single extraction chromatographic column is outlined. The chromatographic parameters of the separation method have been optimized using simulated samples generated using the digestion process employed in beryllium analyses by the Y‐12 National Security Complex and simulated ground water samples.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 1: ACID DEPENDENCIES OF ACTINIDE IONS*

ABSTRACT

The uptake of several actinide ions [U(VI), Pu(IV), Np(IV), Th(IV] and Am(DI)) from nitric and hydrochloric acid solutions, and of U(VI) from near-neutral solutions by the new chelating ion-exchange resin, Diphonix^TM, has been investigated. Diphonix is a polyfunctional resin containing sulfonic and gem-diphosphonic acid groups chemically bonded in a styrene-divinylbenzene polymeric network. Comparison of the acid dependencies of the actinide ions uptake measured with Diphonix with those obtained using a commercial sulfonic -type resin and a resin containing both sulfonic and monophosphonic aCid groups, hat Shown that Diphonix binds the actinides via a different kind of chemical interaction, involving the.formation of chelate complexes through the phosphoryl groups of the gem-diphosphonic acids. As a consequence, Diphonix is superior to other resins in extracting actinide ions from very acidic solutions. A better performance of Diphonix is also observed with the uptake of uranium from neutral solutions. Conditions for efficient stripping of actinide species from the resin have been found.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 2: ACID DEPENDENCIES OF TRANSITION AND POST-TRANSITION METAL IONS*

ABSTRACT

Diphonix^(tm)is a new dual-mechanism polyfunctional resin containing sulfonic and gem-diphosphonic acid groups. In Part 1 of this series the effectiveness of Diphonix in removing actinide ions from very acidic solutions was demonstrated. In this paper we report on the uptake of various transition and post-transition metal ions with Diphonix and two other resins for comparison. The results show that Diphonix has a very high affinity for Fe(III) and Cr(III) in very acidic solutions. From neutral solutions Diphonix exhibits a high selectivity for lead and transition metals over calcium. Conditions for efficient stripping of the investigated ions have been found.     

DIPHONIX-CS : A NOVEL COMBINED CESIUM AND STRONTIUM SELECTIVE ION EXCHANGE RESIN*

ABSTRACT

The recently developed Diphonix® resin contains the geminally substituted diphosphonic acid ligand chemically bonded to a styrene-divinylbenzene copolymer. The resin exhibits an extraordinarily strong affinity for actinides, especially in the terra- and hexavalent oxidation states. Therefore the resin has potential for application in TRU removal from nuclear wastes. The Diphonix-CS resin is a Diphonix-type resin that contains also phenolic groups chemically attached to the polymeric matrix. The phenolic groups exhibit high affinity for Cs⁺ ions from highly alkaline media. Thanks to the combined action of the diphosphonic acid and the phenolic groups, the Diphonix-CS resin can simultaneously remove actinide species, Cs and Sr from alkaline media. In this paper the results obtained in the characterization of the new resin are reported, with regard to the uptake equilibrium and kinetics of Cs⁺ and Sr⁺² removal from NaOH solutions and from synthetic alkaline wastes. The chemical and radiolytic stability of the resin has been investigated. The results have indicated that the Diphonix-CS resin is remarkably stable under the experimental conditions of this work (up to 35 days in I to 4 M NaOH, and up to 200 MRad gamma ray absorbed dose). The possibility of stripping the Cs⁺ and Sr⁺² from the resin has been investigated in column experiments by using 1 M HNO₃ as the stripping agent. Some problems encountered in the stripping of Sr⁺² and possible ways to improve the stripping performance are discussed.     

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT

A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.     

SECONDARY CLEANUP OF TRUEX PROCESS SOLVENT

Several secondary cleanup procedures have been tested for hydrolytically and radiolytically degraded TRUEX process solvent (0.2 M. n-octyl(phenyl)N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO)-1.2 M tributylphosphate (TBP) in n-dodecane). Sodium carbonate scrub was used as primary cleanup. For the secondary cleanup macroporous anion exchange resins and other solid adsorbents, such as goethite (a-FeOOH), alumina and activated charcoal were used. The effectiveness of a cleanup procedure was established by its capability to restore the original americium(III) distribution ratio from low HNO₃ concentration, that is characteristic of pristine process solvent. Further information was obtained from the measurement of up to seven successive AmfJIT) distribution ratios with the regenerated solvent, using the stripping conditions of the TRUEX process. Although all the procedures tested proved to be effective in removing most of the unwanted acidic products from the degraded solvent, the use of a strong base macroporous anion exchange resin, acid washed activated charcoal and acid washed alumina were particularly successful.     

卟啉类L—B膜分子间相互作用的光谱研究

以无取代的meso-四-(4-N)-吡啶基卟啉及其过渡族金属(主要Cu~(2+)、Zn~(2+))络合物制备L-B膜,以近紫外-可见吸收光谱和荧光光谱为手段,研究叶啉类分子在氯仿溶液中,L-B膜状态下以及固态状态下的相互作用。探讨分子聚集体的存在对光谱性质的影响。 为了研究叶咻类分子间的相互作用及其对光谱性质的影响,我们首先分析了叶啉在CHCl_3溶液中及固态状态下的近紫外-可见吸收光谱和荧光光谱。并将其与叶啉类分子的L-B膜作比较。结果表明,卟啉类的Soret吸收带带宽及峰位置在三种状态下均不相同,L-B膜的情况介于溶液中的和固体下的情况之间,说明了在L-B膜中,卟啉分子存在着某种形式的聚集体,且在这种聚集体中分子间的相互作用程度比固体弱,可以认为L-B膜上的分子呈准晶体状态。     

On the non-approximability of points-to analysis

Determining points-to sets is an important static-analysis problem. Most of the classic static analyses (used e.g., by compilers or in programming environments) rely on knowing which variables might be used or defined by each expression in a program. In the presence of pointers, the use/def set of an expression like *p = *q can only be determined given (safe) points-to sets for p and q. Previous work has shown that both precise flow-sensitive and precise flow-insensitive pointer analysis is NP-Hard, even when restricted to single-procedure programs with no dynamic memory allocation. In this paper, we show that it is not even possible to compute good approximations to the precise solutions (i.e., to compute points-to sets whose sizes are within a constant factor of the sizes of the precise points-to sets) unless P=NP. Received: 1 November 2001 / 4 February 2002     

Enhancement of the surface expression of tumor necrosis factor alpha (TNFalpha) but not the p55 TNFalpha receptor in the THP-1 monocytic cell line by matrix metalloprotease inhibitors

The monocytic cell line THP-1 can be induced to express and release tumor necrosis factor alpha (TNFalpha) and both TNFalpha receptors (p55 and p75) upon exposure to bacterial lipopolysaccharide (LPS). The broad-spectrum matrix metalloprotease (MMP) inhibitors [4-(N-hydroxyamino)-2R-isobutyl-3S-(phenylthiomethyl)succinyl]-L-p henylalanine-N-methylamide (GI-129471) and marimastat [2S-[N4(R*),2R*,3S*]]-N4[2,2-dimethyl-1-[(methylamino)carbonyl]propyl]-N 1,2-dihydroxy-3-(2-methylpropyl)butanediamide (BB-2516) were effective inhibitors of LPS-induced TNFalpha (soluble) release with IC50 values of 0.2 and 4.0 microM, respectively. Upon LPS stimulation, the expression of pro-TNFalpha (membrane associated) on the cell surface (FACS analysis) could not be observed. However, in the presence of GI-129471, a concentration-dependent increase in TNFalpha surface expression was observed. Peak expression (percentage of cells expressing pro-TNFalpha and mean fluorescence units) in the presence of GI-129471 was at 2 hr, and steadily declined to return to near control levels by 8 hr. This time course was similar to TNFalpha release, which also peaked at 2-4 hr after LPS exposure and then declined. Stimulation of THP-1 cells with LPS + phorbol myristate acetate increased the percentage of cells expressing pro-TNFalpha by 10-fold. In the presence of GI-129471, these increases were augmented further and peaked between 2 and 4 hr, but also returned to near control levels of expression by 24 hr. This was in contrast to the release of soluble TNFalpha, which continued to accumulate over a 24-hr time course. TNFalpha receptor I (p55, TNFRI) and II (p75, TNFRII) shedding was also inhibited by GI-129471 (IC50 = 1.5 and 3.1 microM, respectively) and BB-2516 (IC50 = 14 and 15 microM, respectively). Unlike pro-TNFalpha surface expression, surface expression of both TNFalpha receptors steadily increased over 72 hr. In contrast to pro-TNFalpha surface expression, TNFRI surface expression was not augmented by these MMP inhibitors in THP-1 cells after LPS stimulation. Surface expression of TNFRII was augmented by these MMP inhibitors. These results suggest that even in the continued presence of LPS stimulation and an inhibitor of TNFalpha processing, the augmented surface expression of TNFalpha is transient. The potential "deleterious" implications of high levels of surface pro-TNFalpha expression in the presence of these inhibitors may be lessened by its transient nature.     

Disposition of 14C-eptifibatide after intravenous administration to healthy men

Eptifibatide, a synthetic peptide inhibitor of the platelet glycoprotein IIb/IIIa receptor, has been studied as an antithrombotic agent in a variety of acute ischemic coronary syndromes. The purpose of the present study was to characterize the disposition of 14C-eptifibatide in man after a single intravenous (i.v.) bolus dose. 14C-Eptifibatide (approximately 50 microCi) was administered to eight healthy men as a single 135-microgram/kg i.v. bolus. Blood, breath carbon dioxide, urine, and fecal samples were collected for up to 72 hours postdose and analyzed for radioactivity by liquid scintillation spectrometry. Plasma and urine samples were also assayed by liquid chromatography with mass spectrometry for eptifibatide and deamidated eptifibatide (DE). Mean (+/- SD) peak plasma eptifibatide concentrations of 879 +/- 251 ng/mL were achieved at the first sampling time (5 minutes), and concentrations then generally declined biexponentially, with a mean distribution half-life of 5 +/- 2.5 minutes and a mean terminal elimination half-life of 1.13 +/- 0.17 hours. Plasma eptifibatide concentrations and radioactivity declined in parallel, with most of the radioactivity (82.4%) attributed to eptifibatide. A total of approximately 73% of administered radioactivity was recovered in the 72-hour period following 14C-eptifibatide dosing. The primary route of elimination was urinary (98% of the total recovered radioactivity), whereas fecal (1.5%) and breath (0.8%) excretion was small. Eptifibatide is cleared by both renal and nonrenal mechanisms, with renal clearance accounting for approximately 40% of total body clearance. Within the first 24 hours, the drug is primarily excreted in the urine as unmodified eptifibatide (34%), DE (19%), and more polar metabolites (13%).