A new technology is under development to selectively recover regulated metal ions from electroplating rinse waters. The electroplating metal ions are recovered in a concentrated form with the appropriate counter ions ready for return to the original electroplating bath. The technology is based on the use of specially designed water-soluble polymers that selectively bind with the metal ions in the rinse bath. The polymers have such a large molecular weight that they can be physically separated using available ultrafiltration technology. The advantages of this technology are high metal selectivity with no sludge formation, rapid processing, low energy, low capital costs, and small size. We have tested and demonstrated the recovery of zinc and nickel (using a new alloy electroplating bath designed to replace cadmium) from rinse waters. The metal-ion concentrate was returned to the original electroplating bath. Impurity metals such as iron and copper were removed from the zinc/nickel concentrate and were not returned to the electroplating bath. Test panels were electroplated as a baseline and compared with new test panels electroplated after the addition of the recovered zinc and nickel. No adverse effects on the bath integrity were observed. The rinse water was depleted of the electroplating metals to less than 0.1 ppm zinc and nickel, and the water was satisfactory for discharge to the sewer system.

Powdered samples of the high-temperature superconductors A Ba2Cu3O7−δ (A = Gd,Y) were treated with fluorine gas (100 Torr) at room temperature and 400 °C for varying times (12–64 h). Magnetic shielding measurements on fluorinated products showed that the superconducting volume fraction in treated samples was greatly reduced or even completely eradicated. All samples were structurally characterized by x-ray powder diffraction. Two yttrium samples, one fluorinated at 25 °C and one at 400 °, were also examined by neutron powder diffraction. For samples treated at room temperature, no change in the structure or composition of the products was apparent by either technique. However, samples fluorinated at 400 °C are tetragonal, with a = 3.8641 (3), c = 11.704(1) Å, and bulk composition corresponding to the formula YBa2Cu3F3.5O4.5. Nuclear activation analysis, nuclear reaction analysis, and Auger spectroscopy were used to determine fluorine concentration and distribution in the fluorinated materials. For samples treated at room temperature, fluorine was found primarily within approximately 1 μm of the surface of the product particles. No evidence for a fluorinecontaining superconducting phase was found in any sample; fluorine was found to be detrimental to superconductivity in all cases. These results suggest that the 123 oxides are sensitive to surface effects.

Defense program use of beryllium has resulted in the need for a wide variety of sampling methods to assess the potential for airborne beryllium particulates. One technique employed in field sampling uses large (8 x 10 in.) mixed cellulose ester (MCE) filters in high volume air samplers. Standard methods for the acid digestion and analysis of the large MCE filters cannot be utilized as the increase in filter mass leads to an uncontrolled exothermic reaction (open flames). As this compromises data quality and presents a significant safety hazard, we propose here an alternative method for digesting these large filters to ensure a solution compatible with ICP-AES (inductively coupled plasma-atomic emission spectroscopy) analysis. The method is a modification of well accepted hot plate digestion methods, which avoids the use of the most hazardous acids such as perchloric or hydrofluoric. While only beryllium was investigated, it is likely that other metals on filters could be digested by this method Filter media were spiked with a variety of beryllium sources to test the digestion, including beryllium solution spikes, beryllium metal, beryllium oxide and beryllium in soil. Recovery of beryllium metal (103%), beryllium in soil (96%) and beryllium solution spikes (93%) were excellent. Published by Elsevier B.V.

Be is a toxic metal used in both aerospace and defense industries. Lung exposure to Be can lead to a specific immune response called chronic beryllium disease (CBD). CBD has the unique characteristics that it can be triggered by very low level exposures, yet the onset of systems can be delayed from one to over 20 years. This variable delay in the onset of systems implies that a change in the local environment leads to dissolution and bio-availability of the particulate Be. We report here on the dissolution of the highly insoluble BeO in the presence of known Be ligands including the iron transport protein, transferrin, and the ubiquitous citric acid. The presence of ligands even at the 100 mu M level led to dissolution of Be to levels that have been shown to cause immune response in both the blood and the lung. Dissolution occurred at pH 7 and was significantly enhanced in a 10 mM phosphate buffer. (c) 2008 Elsevier B.V. All rights reserved.

Polyethylenimine (PEI) was modified with ligands containing sulfur donors to give soluble polymers for binding toxic metal ions. Reaction of purified PEI with mercaptosuccinic anhydride, ethylene sulfide, or methylthiocyanate gave PEI-MSA (25% functionalization), PEI-ET (100% functionalization), and PEI-TU (25% functionalization), respectively. Purification of the polymers was accomplished by diafiltration. The capacities for toxic metal ions (Hg, Cd, and Pb) and transition metal ions (Cu and Ni) were measured for each of the polymers. PEI-ET and PEI-TU showed high affinity for the softer metal ions, Hg and Cd, with loading capacities substantially higher than those for the base polymer PEI. Both polymers had high capacities for Cu. Release of the metal ions from the polymers was accomplished by lowering pH; however, small amounts of metal remained bound to the polymers at pH 1. Competition studies showed that PEI-TU and PEI-ET bound Hg and Cu more strongly than Cd and Pb.

Exposure to beryllium (Be) induces a delayed-type hypersensitivity immune reaction in the lungs of susceptible individuals, which leads to the onset of Be sensitivity and Chronic Beryllium Disease (CBD). Although some mechanistic aspects of CBD have begun to be characterized, very little is known about the molecular mechanisms by which Be activates the host immune response. To gain insight into the cellular response to Be exposure, we have performed global microarray analysis using a mixture of peripheral blood mononuclear and dendritic cells (PBMC/DCs) from a non-CBD source to identify genes that are specifically upregulated in response to BeSO4 stimulation, compared to a control metal salt, Al2(SO4)3. We identified a number of upregulated immunomodulatory genes, including several chemokines in the MIP-1 and GRO families. Using PBMC/DCs from three different donors, we demonstrate that BeSO4 stimulation generally exhibits an increased rate of both chemokine mRNA transcription and release compared to Al2(SO4)3 exposure, although variations among the individual donors do exist. We show that MIP-1α and MIP-1β neutralizing antibodies can partially inhibit the ability of BeSO4 to stimulate cell migration of PBMC/DCs in vitro. Finally, incubation of PBMC/DCs with BeSO4 altered the binding of the transcription factor RUNX to the MIP-1α promoter consensus sequence, indicating that Be can regulate chemokine gene activation. Taken together, these results suggest a model in which Be stimulation of PBMC/DCs can modulate the expression and release of different chemokines, leading to the migration of lymphocytes to the lung and the formation of a localized environment for development of Be disease in susceptible individuals.

The effect of beryllium (Be) exposure has been extensively studied in patients with chronic beryllium disease (CBD). CBD patients carry mutated MHC class II alleles and show a hyperproliferation of T cells upon Be exposure. The exact mechanism of Be-induced T-cell proliferation in these patients is not clearly understood. It is also not known how the inflammatory and suppressive cytokines maintain a balance in healthy individuals and how this balance is lost in CBD patients. To address these issues, we have initiated cellular and biochemical studies to identify Be-responsive cytokines and other cellular markers that help maintain a balance in healthy individuals. We have established an immune cell model derived from a mixture of peripheral blood mononuclear cells (PBMCs) and dendritic cells (DCs). In this article, we demonstrate that pro-inflammatory cytokine IL6 shows decreased release whereas suppressive cytokine IL10 shows enhanced release after 5–10 h of Be treatment. Furthermore, the Be-specific pattern of IL6 and IL10 release is dependent upon induction of threonine phosphorylation of a 45 kDa cytosolic protein (p45), as early as 90 min after Be treatment. Pharmacological inhibition of phosphatidylinositol 3′ kinase (PI3′K) by wortmannin and p38 mitogen-activated protein kinase (MAPK) by SB203580 reveal that PI3′K mediates Be-specific p45 phosphorylation and IL6 release, whereas p38 MAPK regulates the release of IL6 and IL10 and the phosphorylation of p45 independent of metal-salt treatment. While the IL10 and IL6 release pathways are uncoupled in these cells, they are linked to phosphorylation of p45. These findings suggest that the balance between IL10 and IL6 release and the correlated p45 phosphorylation are important components of the Be-mediated immune response in healthy individuals.

We report the rational design of ligands that selectively bind beryllium. We selected two ligands to design Be based on binding polynulear species with a Be-O-Be motif: 2-hydroxyisophthalic acid (HIPA) and 2,3-dihydroxybenzoic acid (DHBA). All previous work has focused on BeL or BeL2 species. The HIPA and DHBA have extremely high binding constants of 17.5 and 18.4, respectively. These ligands outcompete chromotropic acid, which has one the highest binding constants for Be reported in the literature for a simple BeL species. The binding of the second Be to form the Be-O-Be motif is so strong that polynuclear species predominates in solution down to micromolar concentrations. Both ligands show a fluorescence response in the presence of beryllium, making them promising candidates for fluorescence-based sensors. In the case of HIPA, there is a fluorescence shift, and in the case of DHBA, the presence of beryllium turns on the fluorescence by removing two OH bonds that otherwise lead to nonradiative decay. The most dramatic result is that DHBA selectively binds Be in the presence of a metal cocktail containing a 50-fold excess of Al, Fe, Cr, Cu, Zn, Cd, and Pb. This is the first time that such selectivity for beryllium has been demonstrated.

Beryllium is an important industrial metal because of its unusual material properties: it is lighter than aluminum and six times stronger than steel. Often alloyed with other metals such as copper, beryllium is a key component of materials used in the aerospace and electronics industries. Beryllium has a small neutron cross-section, which makes it useful in the production of nuclear weapons and in sealed neutron sources. Unfortunately, beryllium is one of the most toxic elements in the periodic table. It is responsible for the often-fatal lung disease, Chronic Beryllium Disease (CBD) or berylliosis, and is listed as a Class A EPA carcinogen. Coal-fired power plants, industrial manufacturing and nuclear weapons production and disposal operations have released beryllium to the environment. This contamination has the potential to expose workers and the public to beryllium. Despite the increasing use of beryllium in industry, there is surprisingly little published information about beryllium fate and transport in the environment. This information is crucial for the development of strategies that limit worker and public exposure. This review summarizes the current understanding of beryllium health hazards, current regulatory mandates, environmental chemistry, geochemistry and environmental contamination.

The health consequences of beryllium (Be2+) exposure can be severe. Beryllium is responsible for a debilitating and potentially fatal lung disease, chronic beryllium disease (CBD) resulting from inhalation of beryllium particles. The US Code of Federal Register (CFR), 10 CFR 850, has established a limit of 0.2 microg beryllium/100 cm(2) as the maximum amount of beryllium allowable on surfaces to be released from beryllium work areas in Department of Energy (DOE) facilities. The analytical technique described herein reduces the time and cost of detecting beryllium on laboratory working surfaces substantially. The technique provides a positive colorimetric response to the presence of beryllium on a 30.5 cm x 30.5 cm (1 ft(2)) surface at a minimum detection of 0.2 microg/100 cm(2). The method has been validated to provide positive results for beryllium in the presence of excess iron, calcium, magnesium, copper, nickel, chromium and lead at concentrations 100 times that of beryllium and aluminum and uranium (UO2(2+)) at lesser concentrations. The colorimetric detection technique has also been validated to effectively detect solid forms of beryllium including Be(OH)2, BeCl2, BeSO4, beryllium metal and BeO.

ADVERTISEMENT RETURN TO ISSUEPREVBook ReviewNEXTGreen Chemistry: Frontiers in Benign Chemical Syntheses and Processes Edited by Paul T. Anastas and Tracy C. Williamson (U. S. Environmental Protection Agency). Oxford University Press: New York, NY. 1999. 360 pp. $115.00. ISBN 0-19-850170-6.Nancy N. SauerView Author Information Los Alamos National LaboratoryCite this: J. Am. Chem. Soc. 2000, 122, 22, 5419–5420Publication Date (Web):April 19, 2000Publication History Published online19 April 2000Published inissue 1 June 2000https://doi.org/10.1021/ja995756gCopyright © 2000 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views525Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (17 KB) Get e-AlertsSUBJECTS:Biocatalysis,Green chemistry,Inorganic carbon compounds,Phase transitions,Solvents Get e-Alerts

The objectives of this project were to understand the molecular-level mechanisms that govern transport of ions and molecules through a semipermeable membrane and to develop a new class of robust molecular recognition membranes. The approach used recent advances in nanotechnology to fabricate thin membrane assemblies with specific receptors for molecular recognition incorporated into the pore structure. The new membrane technology will strengthen the Laboratory’s core competencies in separation science and technology, nuclear and advanced materials, and advanced manufacturing by providing new methods to minimize wastes and increase safety and efficiency of nuclear materials operations. Significant progress toward the objectives was made during the lifetime of the project, and a solid foundation for progress toward important new separation technology was laid. Background and Research Objectives A membrane is a semi-permeable structure separating two phases that can operate as an active or passive barrier to the transport of matter between the phases. The membrane can discriminate between the components of the phases based on differences in one or more properties of the components such as size, shape, electrical charge, volubility, and diffusion rate. The resulting separation achieved by a membrane system is a function of both thermodynamic partitioning and kinetics. Control of the interaction of these features provides a wide range of separation possibilities with membranes, but is difficult to achieve in practical applications. The wide spectrum of separation possibilities encompassed by membranes can be illustrated by the contrast between the gravity-driven filtration of ground coffee beans from fresh-brewed coffee to the selective transport of sodium ions through cell membranes driven by the cell’s metabolic machinery. Filtration in all its forms is a very important separation technology with industrial spending of about $75 billion per year. Molecular recognition membranes that accomplish precise separations based on chemical properties would allow membrane separation systems to reduce separation costs for a much wider range of industrial needs, including many separation challenges faced by the U.S. Department of Energy. *Principal Investigator, e-mail: gjarvinen @lanl.gov . . .. . .,, ,...=T .j..,. -. ,-’.. =-, ,,/ ,; ;.. .. .=:. ~.LeJ; .ti, & ,: -J cc-f 3 ‘: ::3 ~~~~ Our focus in this project was on membranes for selective separation of metal io from solution. Supported liquid membranes (SLMS) have been investigated for many years to selectively separate metal-ions and other species from aqueous solutions. The preparation of an SLM essentially involves placing a liquid-liquid extraction system into the pores of a thin membrane support. A carrier molecule dissolved in the organic layer contained in the pores acts as a shuttle for metal ions between an aqueous feed solution on one side of the membrane and an aqueous receiving solution on the other side. The SLM systems have illustrated that the selective chemistry developed for liquid-liquid extraction of metal ions could be applied in a membrane format, but the poor long-term stability of the SLMS has inhibited their industrial application. A number of approaches to mitigate the stability problem have been attempted, but none have yet been a significant commercial success. Our grand challenge in this project was to develop very stable thin membrane structures containing ionic recognition sites that facilitate the selective transport of target metal ions. The objective of our efforts was to understand the molecular-level mechanisms that control transport of ions and molecules through membrane pores and use this knowledge to develop a new class of molecular recognition membranes. Importance to LANL’s Science and Technology Base and National R&D Needs The Department of Energy faces many challenges in the 21s’ Century that require advances in separation technology. The continuing defense mission will require purification and processing of nuclear materials with increased safety and reduced wastes. Cleaning up the legacy of over 50 years of defense nuclear material production operations will be much less costly with improved separation technologies. This legacy cleanup also extends to aiding efforts in the former Soviet Union where the impacts of nuclear operations have often been more severe than in the U.S. Nuclear energy is likely to grow in importance because of the negative global environmental impact of fossil fuels and the increasing worldwide energy demand. Major improvements in the nuclear power fuel cycle are possible with new approaches to separating the components of spent fuel. Thus the Laboratory needs to maintain a strong core competency in separation science and technology. Membrane separation technology can be a significant contributor to meeting these challenges, Industry also faces significant separation challenges. Separation processes are often a significant part of the cost of industrial production operations.

Large quantities (thousands of drums) of waste uranium metal or alloyed metals as scrap or chips and turnings are generated annually in the DOE complex. The high surface areas of this waste renders it highly reactive with both air and moisture. Storage of the materials is hazardous and expensive, but most DOE sites are forced to store the waste, because no adequate treatment or recycle technology is available. Los Alamos National Laboratory (LANL) currently has over 200 55-gal drums of reactive uranium awaiting treatment or recovery. To address this problem, LANL has developed a process for the low-temperature conversion of waste uranium metal to uranium oxide. The basis of our technology is a mild solution oxidation using sodium hypochlorite (bleach). Divided uranium metal or alloys are excellent candidates for this type of oxidation because of their high chemical reactivity. uranium turnings react rapidly with dilute solutions of sodium hypochlorite to form an insoluble uranium (VI) oxide, UO{sub 2}(OH){sub 2}, as a finely divided yellow powder. The resulting powder is suitable for disposal after solidification or for recycle. Designs for a suitable reactor system for this process have been completed in the Waste Management Group at LANL. The skid-mounted mobile unitmore » will be capable of treating up to 100 kg of metal or alloy per batch. This paper summarizes the details of the process, including formation and characterization of the uranium product, identification of process operating conditions, and reactor design. Included is a description of the steps for permitting the process.« less