Michael D. Kaminski

Extractant-coated magnetic particles for cobalt and nickel recovery from acidic solution

Waste minimization and recycling practices can often constitute a significant fraction of industrial operating costs. Magnetically assisted chemical separation (MACS) is a simple, cost-effective process that utilizes micrometer-sized magnetic composite materials containing a sorbed layer of chelating or ion exchange material. This paper presents the use of MACS particles for recovering cobalt and nickel from acidic solution.

Transuranic separation using organophosphorus extractants adsorbed onto superparamagnetic carriers

Polymeric coated ferromagnetic carriers with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted by tributyl phosphate (TBP) are being evaluated for application in the separation and the recovery of low concentrations of americium, plutonium, and uranium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles and the complexed particles can be recovered from the solution using a magnet. Physical and chemical characterization of the extractant-absorbed particles were performed by gamma and liquid scintillation counting, scanning electron microscopic (SEM) micrograph, and other physical measurements. Plutonium, americium, and uranium separations have been performed at various HNO{sub 3} and HCl concentrations. Parameters were studied to determine the limitations and capacity of the process. The status of the chemistry and application of the process to Department of Energy (DOE) remediation efforts for actinide decontamination are discussed.

Encapsulation and release of plasminogen activator from biodegradable magnetic microcarriers.

There are a number of therapies available to recanalize occluded arteries. However, even though proven beneficial, these approaches are not without significant shortcomings. Previous research showed that by encapsulating therapeutic thrombolytic enzymes in liposomic formulations, the reperfusion times in vivo were significantly lower than for administration of free thrombolytic. Like liposomes, biodegradable, diblock polymers of poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) have been shown to have therapeutic benefit as delivery vehicles for a variety of drug delivery concepts. We report on new formulations based on tissue plasminogen activator (tPA) encapsulated in magnetic, PLA-PEG microcarriers. We studied the tPA encapsulation efficiency, loading, and release after varying the molecular weight of polymer, carrier size, tPA solution composition, and use of ultrasound to enhance release. We loaded 3.3-9.4wt% tPA and 12-17wt% magnetite into the carriers, depending on the exact formulation. The release of tPA was complete 20min after reconstitution. Ultrasound insonation failed to enhance tPA release rates in smaller carriers but significantly enhanced release in larger carriers. With these formulations, we should be able to achieve lytic concentrations if we can magnetically concentrate 5mg of carrier within about 11ml of blood volume near the clot.

Actinide Separation of High-Level Waste Using Solvent Extractants on Magnetic Microparticles

Abstract Polymeric-coated ferromagnetic particles with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide diluted by tributyl phosphate are being evaluated for application in the separation and the recovery of low concentrations of americium and plutonium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles, which can be recovered from the waste solution using a magnet. The effectiveness of the extractant-absorbed particles at removing transuranics (TRU) from simulated solutions and various nitric acid solutions was measured by gamma and liquid scintillation counting of plutonium and americium. The HNO3 concentration range was 0.01 to 6 M. The partition coefficients (K d) for various actinides at 2 M HNO3 were determined to be between 3000 and 30,000. These values are larger than those projected for TRU recovery by traditional liquid/liquid extraction. Results from transmission...

Optimizing the coating process of organic actinide extractants on magnetically assisted chemical separation particles

Abstract The coatings of ferromagnetic-charcoal-polymer microparticles (1–25 gm) with organic extractants specific for actinides were optimized for use in the magnetically assisted chemical separation (MACS) process. The organic extractants, octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in tributyl phosphate (TBP), coated the particles when a carrier organic solvent was evaporated. Coated particles were heated in an oven overnight to drive off any remaining carrier solvent and fix the extractants on the particles. Partitioning coefficients for americium obtained with the coated particles routinely reached 3000–4000 ml g−1, approximately 10 times the separation efficiency observed with the conventional solvent extraction system using CMPO and TBP.

Capture of magnetic carriers within large arteries using external magnetic fields

Our overall research goal is to advance the safety and effectiveness of acute ischemic stroke therapy by improving the benefit/risk ratio of thrombolysis and hence, the long-term outcome of acute ischemic stroke victims. Our approach is the development of a novel tissue plasminogen activator (t-PA) delivery system based on t-PA-loaded magnetic nano- and microcarriers guided directly to the site of vascular occlusion by external magnetic fields. Such a t-PA delivery system would conveniently combine the advantages of both intravenous (systemic) and intraarterial (catheter-facilitated) thrombolysis: non-invasiveness—the magnetic t-PA carriers can be injected intravenously and targeted, as drug delivery is magnetically guided to and t-PA focally released at and within the vascular clot to induce lysis. The focus of our discussion are the two necessary, fundamental and interrelated bioengineering steps: the research and development of well-characterized, biocompatible, functionally active and t-PA-loaded (encapsulated) magnetic nano- and microcarriers able to induce effective thrombolysis, and the design of magnetic guidance systems for targeted tPA-delivery allowing also the triggered release of the thrombolytic agent at the clot site. In this paper, we theoretically demonstrated magnetic trapping of blood borne magnetic nano- and microcarriers from human large vessels, especially arteries. Then, some preliminary experiments using primate models (monkeys) were done to identify successful in vivo sequestration of magnetic carriers in large and smaller arterial branches after arterial upstream and systemic venous injection. Histology (hematoxylin–eosin stain) verified intraarterial carrier concentration (identified as black carrier agglomerates on H and E staining) at the arterial region above the surface magnet. The results revealed the feasibility of magnetic drug-targeting at arteries and solidified the proposed t-PA delivery system.

Three-dimensional modeling of a portable medical device for magnetic separation of particles from biological fluids

A portable separator has been developed to quantitatively separate blood-borne magnetic spheres in potentially high-flow regimes for the human detoxification purpose. In the separator design, an array of biocompatible capillary tubing and magnetizable wires is immersed in an external magnetic field that is generated by two permanent magnets. The wires are magnetized and the high magnetic field gradient from the magnetized wires helps to collect blood-borne magnetic nano/micro-spheres from the blood flow. In this study, a 3D numerical model was created and the effect of tubing-wire configurations on the capture efficiency of the system was analyzed using COMSOL Multiphysics 3.3(R). The results showed that the configuration characterized by bi-directionally alternating wires and tubes was the best design with respect to the four starting configurations. Preliminary in vitro experiments verified the numerical predictions. The results helped us to optimize a prototype portable magnetic separator that is suitable for rapid sequestration of magnetic nano/micro-spheres from the human blood stream while accommodating necessary clinical boundary conditions.

Evaluation of solid-supported room-temperature ionic liquids containing crown ethers as media for metal ion separation and preconcentration

Extraction chromatographic (EXC) resins incorporating an appropriate crown ether in an oxygenated organic solvent such as 1-octanol are well established as sorbents for the analytical-scale separation and preconcentration of radiostrontium from a variety of sample types. Recent solvent extraction studies employing crown ethers in various 1-alkyl-3-methylimidazolium-based (CnC1im(+)) room-temperature ionic liquids (RTILs) indicate that under certain conditions, distribution ratios (DSr) for strontium far in excess of those observed with conventional organic solvents are observed. To determine if this increase in liquid-liquid extraction efficiency will lead to improved strontium sorbents, several EXC resins and sol-gel glasses incorporating di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6) in either 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C10C1imTf2N) or the related hydroxyalkyl-functionalized IL 1-(12-hydroxydodecyl)-3-butylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C12OHC4im Tf2N) were prepared and characterized. Unexpectedly the performance of these materials was not uniformly better than that of a conventional EXC resin, an apparent result of the greater viscosity of the ionic liquids and the lower solubility of the crown ether in ILs versus conventional organic solvents.

Wide-area decontamination in an urban environment after radiological dispersion: A review and perspectives

Nuclear or radiological terrorism in the form of uncontrolled radioactive contamination presents a unique challenge in the field of nuclear decontamination. Potential targets require an immediate decontamination response, or mitigation plan to limit the social and economic impact. To date, experience with urban decontamination of building materials - specifically hard, porous, external surfaces - is limited to nuclear weapon fallout and nuclear reactor accidents. Methods are lacking for performing wide-area decontamination in an urban environment so that in all release scenarios the area may be re-occupied without evaluation and/or restriction. Also lacking is experience in developing mitigation strategies, that is, methods of mitigating contamination and its resultant radiation dose in key areas during the immediate aftermath of an event and after lifesaving operations. To date, the tremendous strategy development effort primarily by the European community has focused on the recovery phase, which extends years beyond the release event. In this review, we summarize the methods and data collected over the past 70 years in the field of hard, external surface decontamination of radionuclide contaminations, with emphasis on methods suitable for response to radiological dispersal devices and their potentially unique physico-chemical characteristics. This review concludes that although a tremendous amount of work has been completed primarily by the European Community (EU) and the United Kingdom (UK), the few studies existing on each technique permit only very preliminary estimates of decontamination factors for various building materials and methods and extrapolation of those values for use in environments outside the EU and UK. This data shortage prevents us from developing an effective and detailed mitigation response plan and remediation effort. Perhaps most importantly, while the data available does include valuable information on the practical aspects of performing the various remediation methods including costs, coverage rates, manpower, pitfalls, etc., it lacks the details on lessons learned, best practices, and standard procedures, for instance, that would be required to develop a mitigation strategy. While the urban decontamination problem is difficult and there is much more research to do, the existing literature provides a framework for a response plan. Using this framework, in conjunction with computer modeling and relevant data collection, can lead to development of appropriate plans and exercises that would permit development of a mitigation and remediation response.

Separation of Uranium from Nitric- and Hydrochloric-Acid Solutions with Extractant-Coated Magnetic Microparticles

The magnetically assisted chemical separation (MACS) process utilizes selective magnetic microparticle composites to separate dissolved metals from solution. In this study, MACS particles were coated with neutral and acidic organophosphorus extractants,octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO), tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), and bis(2-ethyl-hexyl)phosphoric acid (D2EHPA or HDEHP) and were evaluated for the separation of uranyl ions from nitric- and hydrochloric-acid solutions. The results suggest that a synergistic interaction between the particle surface and solvent coating may explain why the particles display, in some cases, orders of magnitude of higher partitioning coefficients than are estimated from solvent-extraction measurements. Particles coated with TBP and those coated with a combination of TOPO and D2EHPA displayed the most desirable characteristics for removing uranium from dilute acid environments typical of contaminated groundwater. Uranium separation from moderate to highly acidic waste streams typical of Department of Energy (DOE) nuclear wastes is best accomplished using particles coated with a combination of CMPO and TBP. The submitted manuscript has been created by the University of Chicago as Operator of Argonne National Laboratory (“Argonne”) under Contract No. W-31-109-ENG-38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.