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We use lasers to produce the intense light needed fitr speetrtt- scopic studies of geochemical solutions and materials. We tune lasers to a variety of wavelengths to examine different types of samples. By measuring fluorescence, absorption, or Human scattered light, we determine such characteristics as structure and concentration of the species present. The blue beam from this argon ion laser is used to pump a titanium-dopi'ti saphire rml (glowing red at center); it protluces another beam that can be tuned throughout the near infrared sftectral rcgittn but cannot be seen. We have developed a unique instrument based on this tunable near-infrared laser to da resonance Human and laser-induced Puorescence spectroscopy in
Cover Located in volcanic luff on the edge of the Xevuda lest Site, Yucca Mountain is the proposed site for radionuclides such as plutonium could move through the grounduater system into the surrounding environment. To predict their behavior in such a situation, we are studying the specifiiion of this and other radionuctides. In the inset photograph, it is easy to identify the four oxidation states ofplutonium in noneomplexing perchloric Isotope and Nuclear Chemistry Division Annual Report FY 1988 October 1987—September 1988 Donald W. Barr, Division Leader Loc Aianos Na!'Oi;ai Laboratory Abstract This report describes some of the major research and development programs of the Isotope and Nuclear Chemistry Division during FY 1988. The report includes articles on weapons chemistry, biochemistry and nuclear medicine, geochemistry and environmental chemistry, actinide and transition metal chemistry, materials chemistry, nuclear structure and reactions, and the INC Division facilities and laboratories. iv teotope and Nuclear Chemistry Division Annual Report FY 1988 LA—11620-PR Contents DE89 014361 Point of View 2 Weapons Chemistry Overview 12 Radiochemistry for Weapons Diagnostics 14 Thermal Ionization Mass Spectrometry 16 Mass Spectrometers and Isotope Separatoi-s—Why Both? 18 Biochemistry and Nuclear Medicine Overview 22 Biosynthesis of the Coenzyme Pyrroloquinoline Quinone 24 Lanthanide Schiff Base Complexes as Contrast Agents for Magnetic Resonance Imaging 26 Biomedical Applications for Radioisotope Generators 28 Geochemistry and Environmental Chemistry Overview 32 Thermodynamic Properties of Aqueous Solutions at High Temperatures and Pressures 34 Geochemical Measurements Suggest Widespread Circulation of Ocean Ridge Material 36 Trace-Element Variations in the Fumes of Kilauea and Mauna Loa Volcanoes 38 Actinide and Transition Metal Chemistry Overview 42 Determining the Redox Reactivity of Plutonium(IV) Colloid 44 Synthesis and Properties of a New Class of Synthetically Useful Precursors 46 Molecular Hydrogen Coordination to Transition Metals 48 Materials Chemistry Overview 52 Solution Routes to High-Temperature Ceramic Superconductors 54 ,t Chemistry of Nitroalkanes and Related Molecules at High Pressure 56 Synthesis of New Quasi-One-Dimensional Mixed Valence Solids 58 Nuclear Structure and Reactions Overview 62 Molybdenum-Technetium Solar Neutrino Experiment 64 Using the TOFI Spectrometer to Measure Half-Lives of Exotic Nuclei 66 Fission and Multifragmentation from Niobium Beam/Gold Target Collisions 68 Division Facilities and Laboratories 72 Omega West Reactor 74 ICON Facility 76 Appendix Division Personnel 80 Advisory Committee 83 Program Funding 84 Publications 87 Presentations 99 Division Meetings and Seminars 111 References 113 Acknowledgments Production Team: Editor: Jody Heiken Designer/Illustrator: Garth Tietjen (INC-DO/IS-12) Assistants: Janey Headstream Octavio Ramos Technical Reviewers: Sec. 1 Allan Ogard Sec. 2 Janet Mercer-Smith and Pat Unkefer Sec. 3 Robert Charles Sec. 4 Alfred Sattelberger Sec. 5 Basil Swanson Sec. 7 Merle Bunker Contributors: Marty Akin Joann Brown Ruth Capron Lillian Hinsley Carla Lowe Lia Mitchell Valerie Oritz Elaine Roybal Cathy Schuch Photographer: Henry Ortega (IS-9) Printing Coordinator: Guadalupe Archuleta (IS-9) ii '• Isotope and Nuclear Chemistry Division Annual Report FY 1988 Overview Point of View myriad audits, inventories, and compliance; issues as well as safety, security, training, and quality assurance requirements. Donald W. Barr We welcomed David Clark to the Division The Isotope and Nuclear Chemistry Division's as he began his appointment as a J. Robert increased involvement in environmental and Oppenheimer Fellow in January 1988. geochemistry programs reflects our growing commitment to these 2'esearch efforts. National This year, I particularly wish to cite our concern about diminishing resourses, basic staff for their valued contributions to the Joint energy shortages, atmosphere and aquifer Verification Experiment with the USSR con- pollution, and the demand for waste disposal ducted at the Nevada Test Site August 17,1988. has challenged us to find successful, efficient, and cost-effective methods to solve these On a nostalgic note—in November 1988, problems. The multidisciplinary scientific and Group INC-11 organized a 40th Anniversary engineering approaches essential for dealing reunion of the formal Radiochemistry Group with these important issues emphasize a (known in previous years by such labels as vigorous campaign to understand the processes CNC-11 and J-ll). Held at Fuller Lodge, it was that have created these problems. Many of the an opportunity for of current staff to meet former technical challenges represented by these issues group members and leaders of the radiochemistiy require basic research on the complex chemistry organization here at Los Alamos. Our special of ecosystems—an area in which INC Division is guests were Rod and Louise Spence, George and well qualified to make major contributions. The Satch Cowan, Jim Sattizahn, Darleane and Marvin research efforts represented by photos and Hoffman, Carson and Kay Mark, and Bob and illustrations on the cover and inside front cover Nancy Thorn. There were many familiar faces of this annual report are an indication of our and the usual tall tales of scientific—and Division's commitment to these programs. nonscientific—events of years past. Readers familiar with our annual report will Despite the current, rather tight fiscal notice the new, streamlined format. We hope to situation, the vitality and vision of our showcase a selection of the Division's programs Division's staff are a souixe of strength upon and technical accomplishments each year. which to build our future. The research efforts described in this report reflect well on their This year we occupied major new laboratory skills and expertise. space. The 15,000-ft2 Advanced Radiochemistry Weapons Diagnostics Facility was completed and dedicated in May 1988. We also were able to occupy the new 4000-ft2 Weapons Diagnostic Instrument Development Building, and con- struction began on a new wing for weapons radiochemical diagnostics data storage and interpretation. Another major step came when Laboratory Senior Management assigned high priority to a new research reactor that will replace our aging Omega West Reactor. With the new fiscal year, we saw changes in Division and Group Office staff. Bruce Crowe left Group INC-7 for an assignment to the Yucca Mountain Project in Las Vegas, Nevada. We wish him well and welcome Dave Curtis and Bob Charles as Group Leader and Deputy of the Isotope Geochemistry Group. Gary Eller succeeded "Woody" Woodruff as Deputy Group Leader in Group INC-4. Basil Swanson and Gene Peterson joined Bruce Erdal as half-time Technical Coordinators for the Division; this change reflects the current need for increased efforts in program development. Sara Helmick also came to the Division Office Staff as Compliance and Accountability Officer. In this capacity, she will use her considerable Donald W. Barr experience to guide the Division through Division Leader Isotope and Nuclear Chemistry Division Annual Report FY 1988 Overvwu LOS ALAMOS NATIONAL LABORATORY ISOTOPE AND NUCLEAR CHEMISTRY (INC) DIVISION TECHNICAL DIVISION LEADER INC-DOT COORDINATORS D w. Ban a «. irdal J. R. Bralnard OEPUTV OIWSION LEADER E. J Peterson P. J. Unkeler S. L Susnson uI AJ. Gincarz INC-4 INC-5 ISOTOPE AND STRUCTURAL RESEARCH REACTOR CHEMISTRY Group LeaOer-U. £. Bunker Group Leaaer-R. R. Ryan Deputy Group LeaftrM M. Minor Deputy Group Levter-P. G. Bier INC-11 INC-7 NUCLEAR AND RADIOCHEMISTRY ISOTOPE GEOCHEMISTRV Group Leaoer-W. R. Daniels Deputy Group Leader-G. F. Grisham Group Leader-D. B. Curtis Deputy Group Leader tor Medical Deputy Group Leader P.. W. Charles PMimsolopes Researcti-D. C. Moody INC Division's mission is to develop, maintain, and supply capabilities in chemistry, nuclear chemistry, geochemistry, and stable and radioactive isotopes for solution of national Alexander J. Gancarz security, energy, health, and environmental Deputy Division Leader problems. The Division's four groups foster excellence in fundamental research. potential sponsors; and, in some cases, encourage INC Technical Coordinators entirely new efforts. Environmental programs The INC Technical Coordinators help Division offer myriad opportunities, particularly in and Group leaders develop new programs and problems related to waste minimization, global directions for research. They are knowledgeable change, and restoration of the weapons complex. about cui-rent programs, areas of emphsis, and Materials chemistry for advanced processing and the policies of both the Laboratory and external production of high-temperature superconductors agencies. The Coordinators must also stay also shows significant potential. The Technical abreast of the Division's current capabilities and Coordinators devote substantial effort to smaller the new areas being developed. They attempt to initiatives as well because these frequently have couple INC's skills, facilities, and interests with great potential for growth and represent some of program needs; facilitate interactions with the most intriguing scientific frontiers. Bruce Erdal, Gene Peterson, and Basil Swanson provide assistance as the Division's Ti-chnival Coordinators. Isotope and Xmlear Chemistry Usrimnn Aimuul Il< /;<;/•' !•')' 7!ts Overview Robert R. Ryan David B. Curtis INC-4 Group Leader INC-7 Group Leader INC-4 Isotope and Structural Chemistry INC-7 Isotope Geochemistry addresses performs and communicates fundamental important national scientific problems in and supporting research in chemistry to bring the fields of nuclear chemistry and geochem- together the areas of synthesis, separation, istry by employing radiochemical and mass and use of isotopic and physical methods for spectrometric techniques. There is particular studies of structure and dynamics. emphasis on nuclear weapons diagnostics and related nuclear research, atmospheric and geochemical processes, and development of enhanced analytical and modeling capabilities. Merle E. Bunker INC-5 Group Leader INC-5 Research Reactor provides reactor- based facilities and services in support of Laboratory programs and conducts applied William R. Daniels and basic research in nuclear chemistry. INC-11 Group Leader Isotope and Nuclear Chemistry Division Annual Report FY 1988 Overview INC-11 Nuclear and Radiochemistry applies expertise in nuclear and radiochemistry to support national needs and Laboratory programs, including weapons test diagnostics, radioactive waste management, nuclear medicine research, radioisotope production, and basic research in nuclear phenomena. The Group expands and improves our human and facilities resources to support Laboratory goals and to seek new applications of nuclear and radiochemistry for scientific and technological development. Laboratory Fellows Laboratory Fellows are appointed in recognition of their scientific excellence as well as sustained outstanding contributions and exceptional promise for continued professional achievement within their area of competence. They play a key Jerry B. Wilhelmy role in stimulating new research initiatives. Alvarez asteroid-impact hypothesis, which Carl Orth's principal research involves the was based on a discovery of excess iridium at use of nuclear and radiochemical techniques to a similar boundary in marine rocks. Almost all study extinction boundaries in the fossil record. the extinction boundaries recorded in the last The objective is to determine if the biological 600 Myr are currently being examined in crises were caused by hypothesized swarms of collaboration with about 50 paleontologists from comets periodically entering the inner Solar around the globe. To complement this work and System—some striking the Earth—or by less provide a better database of terrestrial impact exotic terrestrial processes. In earlier work, events, melt and target rocks from suspected he and his coworkers in INC Division found impact structures are being examined to the iridium anomaly at the Cretaceous/Tertiary determine if they resulted from impacts or boundary in nearby fluvial sediments; this volcanism. Carl also is interested in meson/ discovery provided strong support for the nucleus interactions and stimulation of nuclear isomers to release their stored energy. Jerry Wilhelmy's primary research has been focused on the study of nuclear fission and the investigation of heavy ion reactions. These efforts attempt to determine the limiting conditions for the existence of nuclear matter. He will continue research in the fission process by addressing the heaviest element fission properties and will study the effect of nuclear dissipation on the time scale of fission. One of Jerry's new major areas of interest is the field of weak interaction studies, in which he measures total solar neutrino fluences to determine possible neutrino flavor oscillations and their consequences on neutrino masses. He continues to be interested in applied efforts within the Division—especially those associated with nuclear reactions and atomic and nuclear laser possibilities. Charles J. Orth Isotope and Nudear Chemistry Division Annual tiept>r-t ^Y Qverviciv exhibited exceptional scientific merit and creatively sought new outlets for Division capabilities. The Division provides financial and resource support for the appointees during their tenure and contributes to their career development through increased exposure to the Laboratory, Directorate, Division, and Groups. The appointees serve as Division spokespersons and assist the Division by contributing their expertise and ideas to new technical initiatives and program development. These processes particularly encourage frequent communication and interaction with Division staff. DOT appointments follow regularly scheduled calls for applications. In the DOT's fourth year, Pat Unkefer and James Brainard, both of INC-4, share the DOT appointment. Their half-time DOT Gregory J. Kubas research projects are summarized here. Pat Unkefer's half-time appointment has Greg Kubas' research centers on the been devoted to the first phase of developing an activation of small energy-related molecules environmental initiative within the Division. such as SO and H2 on transition metal 2 This initiative is composed of two separate complexes. His long-term goal is to reduce technical efforts. The first project is to develop SO2 to sulfur or sulfur-containing species by cost-effective technology for bioremediation of employing metal hydride complexes, hydrogen, explosives contamination. The technical basis and other reducing agents as a possible means for this effort involves identifying and charac- of controlling emissions that produce acid rain. terizing soil microorganisms that can completely Greg and his coworkers developed the first degrade high explosives. It may be possible to homogeneous (solution) catalytic process for use these microbes for in situ reclamation of clean and rapid conversion of SO to sulfur 2 soils that are contaminated with high explosives and water through the use of hydrogen and or for on site degradation of these explosives in an organometallic molybdenum sulfide catalyst. Originally a spinoff of these studies, Greg's discovery of molecular hydrogen coordination to metals several years ago is now recognized as one of the major advances of the decade in inorganic chemistry; his work has stimulated much new research worldwide. The ability of metals and metal complexes to bind H2 intact rather than as atomic H" represents a new type of chemical bonding and has profound impact in energy-related areas such as hydrogen storage and catalysis. INC Division'*! DOT Program The Division Office Technical (DOT) program provides INC staff members with the oppor- tunity for an internal sabbatical; the concept stresses mutual benefits to the chosen individuals and to the Division. The DOT program seeks to reward those who have Pat J. Unkefer Isotope and Nuclear Chemistry Division Annual Report FY1988 Overview a biological reactor. Pat's second project is to Because these signal peptides are involved develop cost-effective remediation schemes for in transporting and targeting many proteins actinide contamination or for process modifi- to their proper locations in cells, they play a cation by using biological chelators of the central role in the compartmentation and actinindes. The initial technical work for this organization of eukaryotic cells. The labeling effort explores two strategies: (1) identification techniques developed are expected to and characterization of biological binding agents significantly contribute to new Laboratory that can be used either to sequester actinides efforts in the area of structural biology. Jim from solutions such as process streams, or also is working to increase the contributions to form barriers that would halt actinide high- resolution NMR can make to Division and movement in the environment; (2) the use of Laboratory research programs in actinide and bacterial siderophores—biochelators with high lanthanide coordination chemistry—particularly affinity for iron—to increase the solubility and to problems in waste management and chemical hence, the extraction and removal, of actinides processing and the development of improved from contaminated soils. Both projects include MRI contrast agents. developing a base for the technology, which is a necessary prelude to obtaining outside funding for these initiatives. The startup phase also INC Division Accomplishments in FY1968 involves identifying users who need this INC Division comprises 228 employees. This technology and can help fund its development. total includes 91 member scientists (76 with This last phase, conducted in collaboration with PhD degrees), 7 administrative staff members, the Laboratory's Energy Technology and 49 technicians, and 15 general support staff. Weapons Technology program managers, has In 1987, we hosted 34 postdoctoral employees already identified US Air Force, Army, and Navy (4 from foreign countries), 4 J. R. Oppenheimer Research programs and several bioremediation fellows, 1 summer teacher, 20 undergraduate companies. students, and 29 graduate research assistants. In addition, there were 195 affiliates, of whom During his INC-DOT appointment, Jim 34 were scientists from foreign countries. An Brainard is working on understanding important group of these visitors composes structure/function relationships in small INC Division's Advisory Committee, which' is peptides. This effort emphasizes the use of high- assembled from eminent scientists in our fields resolution NMR and stable isotope labeling to of interest. This committee serves the very characterize the structures of signal peptides in important function of reviewing our plans, aqueous and hydrophobic environments. progress, and priorities and bringing to our scientific staff a different perspective on the new and most significant developments in many areas. Membership of our Advisory Committee for FY 1989 is listed in the Appendix of this report. Division seminars, also listed in the Appendix, serve as a valuable additional and complementary window on interesting recent progress and ideas from both within and outside the Division. Awards and Recognition When Laboratory Director Sig Hecker presented plaques for the 1988 Distinguished Service Awards, he recognized the efforts of two INC-4 members. John Hanners pioneered biochemical methods to obtain labied sugars and ammo acids from living organisms. He also established James R. Brainard Isotope and Nuclear Chemistry Division lit port 198S Overview widely used methods for separating complete program for the next 10 years. He helped plan mixtures of carbohydrates. John's influence and supervise construction of the extensive extends to the lives of young scientists as nuclear chemistry facilities at the LAMPF well. Over the years, he has been active in accelerator, where he initiated and led the Laboratory outreach programs and has LAMPF Nuclear Chemistry Program. For over supervised numerous undergrad co-op students. a decade, he and colleagues from Group INC-11 and universities made significant contributions As a tech supervisor at INC-4's ICON Facility, to medium-energy meson and particle physics. Charles Lehman is known for having "a feel" He realized the importance of an isotope for production processes to improve that production facility at the LAMPF beam stop for facility's operation. When Laboratory and nuclear medicine applications and is credited other scientific community users' demand for with the inception of this important program. high-purity isotopes increased substantially, Bruce is remembered for his dedication to Charlie's dedication helped overcome equipment science and his sincere and caring personality. failures, personnel shortages, and nature's inconsistencies. Francine Lawrence retired from the Laboratory in September 1988 after more David Clark, an Oppenheimer Fellow in than 30 years as a chemist in INC-11 and its INC-4, was the recipient of the 1988 Nobel predecessors. She came to Los Alamos in 1953; Laureate Signature Award for Graduate joining Group J-ll as a chemical technician, Education in Chemistiy. Sponsored by the she worked with Charles Browne, Louise Smith, American Chemical Society, the award is the and Darleane Hoffman on the actinides, highest honor given for graduate research in including the exciting products of the Mike shot. chemistry in the US. David's current work After a few years away from the Laboratory involves the chemistry of uranium(III) and is while her husband completed his doctoral represented by an article in Sec. 4 of this report. studies at Vanderbilt University, she rejoined the group (then J-ll) in 1960. Francine As the foundling father of INC-Division's new completed her own B.S. and later an M.S. in Advanced Radiochemical Weapons Diagnostics chemistry to become a staff member. In her long Building, James Sattizahn was honored at the collaboration with Darleane Hoffman, she dedication of that new facility in May. Many worked on a variety of problems, ranging from years were dovoted to planning and ensuring weapons diagnostics and the production of support for the building, which is designed to heavy elements to the development of nuclear allow extremely sensitive measurements on engines for rocket propulsion, underground minute quantities of elements. Retired now, radionuclide migration, and nuclear waste Jim was INC-11 Group Leader for 14 years, management. This work led to coauthorship on INC Deputy Division Leader, and a 40-year many journal publications reporting discoveries member of the Division and its precursors. In in areas of actinides and fission products, speaking of the $3.7 million, 14 500 ft2 building, including the discovery of 244Pu in nature. he said, "A building Jike this is a resource not only for the Lab, but for the nation—it's unique." Shari Lermuseaux came to Group INC-11 in 1978. As an experimental equipment/ facilities operator, she was responsible for Retirements the radioactive samples chemists brought to In 1953, Bruce J. Dropesky joined the the counting room. Shari did the scheduling, Radiochemistry Group (J-ll). Throughout entered sample identification into the computer, most of his career he contributed his talents used the appropriate counter to process samples, to the weapons program, but he also was active and returned the computer-analyzed data to in basic research. To advance his early research the chemists. This was far from an easy job in nuclear structure and reaction mechanisms, because we have more than 40 different he constructed a state-of-the-art solenoidal beta- counters/spectrometers and their electronic ray spectrometer. In 1964, Bruce acquired from appurtenances in the counting room. Shari Sweden this Laboratory's first electromagnetic thoroughly enjoyed her work and her cheerful mass separator, which was used for the weapons personality will be missed. 8 Isotope and Nuclear Chemistry Division Annual Report FY ]988 Overview Petrita Oliver, a much travelled lady, retired from INC-11 in December 1987. She began working in the Laboratory's Project Y as a Junior Technician in 1945. After matei-nity leave, she picked up again in CMR-3, then moved to CMR-4 and to J-2; following a second maternity leave, she returned to J-2; then she went to J-11, J-12, and CMR-1. Pat returned to J-11 in 1953 and then moved to the new CNC-11 (subsequently renamed INC-11) in 1971, where she remained until her retirement. Most of her work involved weapons radiochemistry and waste isolation. Over the years she held positions, variously titled "counting technician," "microanalyst," "radiochemist," and "chem tech II." As a Senior Technologist, she spent her last 2 years in Group INC-11 helping to develop biomedical generators in the Medical Radio- isotopes Research Program. Pat has many secret stories that would reveal interesting facts about some of her coworkers in the group—if only she would talk! Ramon Romero joined the Laboratory in 1968 after 8 years with Zia Company, the Laboratory's chief contractor at that time. He went to work in Group CMF-4—later known as CNC-4 and then JNC-4. His major responsibility there was fol fabricating the ICON program's first large carbon monoxide distillation column, which was used to produce carbon monoxide highly enriched in 13C. For the next 20 years, Ramon continued as a fabricator with the ICON Facility, constructing many and ever-larger columns for separating different isotopes. He contributed much to this program's successful effort to reduce—by orders of magnitude—the cost of light stable istopes. Ramon was always known for the high quality of his work and his dedication to the project; he is sorely missed. We were saddened this year by the death of long-time Los Alamos resident Helen Bruington. She had worked at the Laboratory since 1960 and was a member of (then) Group CNC-11 from 1974 to 1980. Isotope and Nuclear Chemistry Division Report 1988 9 Wetipons Chemistry Overview Radiochemistry for Weapons Diagnostics Thermal Ionization Mass Spectrometry Mass Spectrometers and Isotope Separators—Why Both? Wer Dons C/iem istrv Weapons Chemistry Overview products from the device. Personnel from Group INC-11 and/or Group INC-7 direct the sampling Allen E. Ogard efforts in the field to ensure that samples are of the desired quantity and composition. A side- The Radiochemical Test Diagnostics Program wall sampler collects and retrieves the samples requires a significant fraction of INC-Division from depth. Properly packaged to contain the funding and resource commitments. We not only radioactive debris, these samples are sealed in contribute to yield determinations for all Los appropriately shielded shipping containers and Alamos Nevada tests but also provide details of transported to Los Alanos. the physics and chemistry of nuclear explosions. Radiochemical testing of a nuclear device can be Samples Prepared from Test Debris separated into the following six activities: Samples obtained from the postshot hole are a mixtm-e of drilling mud, melted tuff Detector development and use containing radioactive elements, and natural Drillback for samples tuff. We manually separate the melted and Sample preparation from test debris radioactive pieces from the drilling muds and Separation of chemical elements unmelted tuffs and process them into solutions Analysis of isotopes suitable for separation chemistry. Because Interpretation of results these raw samples are highly radioactive, most of the dissolution operations are carried Detectors out behind shielding. Conventional wet Detectors, either as chemical elements or chemistry techniques that involve heating chemical compounds, are added to a nuclear samples for relatively long periods in strong device being tested. When the detector material acids such as hydrofluoric and perchloric yield is activated by reaction with neutrons produced completely dissolved and homogeneous samples. during the test, it yields isotopes that are different from those of the original element. Recently, we have found that microwave Determining the quantity of an isotope produced heating the acid solutions during dissolution gives a measure of the integral neutron fluence results in shorter dissolution times and smaller (neutrons per square centimeter) over the volumes of acids being used. neutron range to which the reaction is sensitive. A combination of results from various detector reactions is used to interpret test results, Useful detectors have reaction products that are separable from the bulk of the soil sample and extraneous activated materials; they also have levels of activation that are detectable above background production, and they can be quantified by measurement of either their nuclear decay properties or their isotopic mass ratios. However, the detector must not affect the performance of the device. Americium-241 has been used as a detector since 1966, and we continue to research other possible detectors.1 Drillback Operation Following an event at the Nevada Test Site, an angled postshot hole is drilled using oil-field drilling techniques (Fig. 1.1). The postshot hole is drilled into and through the cavity formed by the explosion; at the base of the cavity is a puddle of solidified melted-rock that contains Fig. 1.1. The same techniques used to drill oil most of the fission products and activation wells are employed at the Nevada lest Site. 12 Isotope and Nuclear Chemistry Division Annual Report FY19S8 Weapons Clwniiatiy Separation Chemistry the Experimental Review Group (ERG) The products that result from reaction of the and the Weapons Working Group (VVWG). neutrons with the detectors during a test are In addition, twice a year we hold an generally far less abundent than fission and Intel-laboratory Working Group (ILWOG) other activation products. Although we use meeting with Lawrence Livermore National extremely sensitive measuring techniques such Laboratory and other organizations to review as mass spectrometry and low-level gamma-ray current procedures and new techniques in counting to determine their production, these radiochemical test diagnostics. reaction products first must be concentrated and separated from elements that could interfere The classified summai-ies of these activities with their analysis. A comprehensive document, can be made available to properly cleared "Collected Radiochemical and Geochemical individuals who contact Charles Miller. Group Procedures," contains descriptions of chemical INC-7. processes that we use t< purify the reaction products of interest before we measure them.2 After the chemical processes, the sample is sometimes subjected to mass separator analysis, which separates an element into its individual isotopes, before the element is counted. Selected separation processes are discussed in more detail in the three articles that follow this overview. Analysis Radioactive isotopes decay at specific rates (half-lives) through the emission of specific radiations (tx, p1", P+, etc.). By measuring these radiations as a function of time and energy, we can identify the isotope and measure its concentration quantitatively or relative to other isotopes in the chemically separated samples. INC Division has a large number of radiation "counters" that can measure the energy and quantity of gamma rays and particles (a, p', P+) being emitted during the decay of the radio- active species. More specific information about these counters can be found in Sec. 7 of this report. Another technique used to measure the relative concentrations of isotopes in test debris samples involves mass spectrometers, which are discussed in an article within this section. Interpretation of Data Radiochemical diagnostics of weapons tests provide the final word on certain aspects of a device's performance. From this information LANL designers can infer whether the device worked as expected or if changes should be made in its design. The planning and results of weapons test diagnostics are reported at two internal classified forums, both of which meet monthly: Isotope and Nuclear Chemistry Division Ann ual Report FY 19SS IS Weapons Chemistry Radiochemistry for Weapons The first example is mass separation Diagnostics of the isotopes of silver for counting and determination. The process requires (1) radiochemical separation and purification Moses Attrep, Jr. of silver from debris, (2) mass separation of the isotopes, and (3) counting the individual isotopes INC Division has developed a level of of silver. This preparation differs from that of radiochemical expertise that is matched rhodium in that the silver isotopes are nowhere else in the world. This achievement physically separated and counted, whereas is the result of INC's pioneering endeavors and the rhodium analysis relies upon counting its leadership in developing radiochemistry as techniques alone to determine the isotopes. an essential tool for nuclear weapons tests By using mass separation techniques, the diagnostics. As instrumental sophistication analyst is able to obtain the data more quickly improved our ability to detect radioactive and with less ambiguity. In this process, we emission, radiochemical separation processes chemically separate silver from the debris by were put to severe tests and changes. In earlier removing it from all interfering radionuclides days, most radioactive samples were counted and then we carefully prepare the metal for the with traditional beta and/or sodium iodide separation of its isotopes on the mass separator. counting systems. Our stringent chemistry requirements allowed for little or no interfering The key in this procedure is the preparation radioactive substances in the final counting of a pure sample that is suitable for the mass samples. These standards and the concomitant separation. Using a combination of radio- skills necessary to carry out the techniques of chemistry and instrumentation technology, radiochemical separations are maintained in we have adopted a unique process that allows present day diagnostic activities. us to excell in isotope determination for nuclear weapon diagnostics. Other elements that we One example of our technological development mass separate routinely are zirconium, thulium, is the radiochemical separation and purification europium, and lutecium. of rhodium from nuclear bomb debris. This procedure was developed to ensure that the As demands increased on the diagnostic team final sample, prepared for counting in a low- to determine fewer atoms with greater precision level well-type Ge(Li) counter, was free from and accuracy, it became evident that mass all radioactive contaminants. The radiochemical spectrometers would play a larger role in demands in the rhodium analysis do not differ nuclear weapons radiochemical diagnostics. significantly from the requirements of the This could not be done, however, without the earlier radiochemical analyses done here. skillful preparation of ultrapure samples for Radiochemical purity is vital: extremely small mass spectrometric analysis. In our analysis amounts of long-lived rhodium nuclides must be of plutonium, for example, totally new concepts determined, and we can tolerate no interfering of sample preparation had to be developed, substances that might compromise that deter- demanding analytical chemistry skills that mination. The Isotope and Nuclear Chemistry were normally thought unattainable, so that Division's "Collected Radiochemical Procedures" 2 the analyst could make the determination at volume describes our procedures in detail. the levels required. When developing and The side bar on the next page shows the various implementing this type of work, the radio- chemical steps required to produce high-quality chemist must keep in mind several points: samples for the radiochemical determination of rhodium isotopes. (1) A unique chemical separation procedure is needed to provide very high As more sensitive and sophisticated instru- separation factors; mental techniques become available and are (2) Labware must be specially cleaned to used to detect radionuclides, more demanding remove "background" levels of the and varied radiochemistry is required to prepare element being determined; these samples for analysis. The cases described (3) The work must be conducted in an here illustrate how different radiochemical environmental".., controlled area where demands affect sample preparation. the air is carefully filtered; 14 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Weapons Chemistry (4) The analyst must wear clean outer garments; and Radiochemical Analysis for Rhodium in Debris (5) Special reagents must be obtained and checked for any level of the element 10-80 g Dissolved Dirt being determined. Volume taken to 20 ml/g. Add Rh carrier and make 6H HC1. A sample being analyzed for plutonium Heat to boiling and add 1-2 g Nal. content is treated under the conditions described Continue heating 1 b; centrifuge. above, and we use an established radiochemical Wash Rhl3 precipitate with 3M HC1. procedure. This procedure, requiring several days, produces an ultrapure sample that is delivered to the mass spectrometrists who load Rhodium Chloride the sample for instrumental analysis. If the Add 35f NaCN; heat until solution occurs; radiochemistry has been done well, the isotopic add Te(IV) holdback carrier and HC1; destroy composition can be determined properly. iodine by adding NaNO2. Dilute and scavenge with ferric hydroxide by making Because we might be analyzing extremely basic with ammonia. small quantities of plutonium, it is imperative that these strict procedures be followed conscientiously and deliberately. Both 3 Solution of [Rh(CN)6] - plutonium and uranium are routinely analyzed Add bariuim and precipitate with sodium in this manner. Although the radiochemical carbonate; centrifuge. demands are higher, determinations in the lower detection levels allow INC Division to lead the field in isotopic analyses. Solution of [Rh(CN)6]3- Acidify and add Te(III) and SbdII) holdback carriers; precipitate sulfides with H S; filter. In his Nobel Prize acceptance speech, 2 W. F. Libby referred to low-level radiochemical separation science as 3 Solution of [Rh(CN)6] " Remove H2S by boiling; acidify and add "something like the discipline of Cu(II) to form precipitate. surgery—cleanliness, care, seriousness, and practice." Cu3[Rh (CN)6]2 Precipitate The skills required and developed in INC's Put rhodocyano complex into solution by weapons diagnostics program have served as adding strong NaOH. a basis for pioneer work in the areas of environ- mental radiochemistry, isotope geology, and nuclear medicine. Solution of [Rh(CN)6]3- Evaporate to near dryness; add cone H2SO.|; fume. Solution of Rh(III) Repeat Rhl3 precipitation; form cyanide complex; perform Fe(OH)3 scavenge, BaCO3 precipitate, H2S cavenge and Cu precipitation/dissolution; Repeat BaCo3 precipitate, H2S scavenge, Cu precipitation, dissolution, and cyanide destruction. Solution of Rh(III) Fume with HC1O4 and HNO3; neutralise with NaOH to form Rh(OH)3; centrifuge, wash, dissolve with minimum HC1, evaporate to dryness, dissolve in water and transfer to counting vial. | Isotope and Nuclear Chemistry Division Annual. Report FY 19SS 15 Weapons Chemistry Thermal-Ionization Mass Spectrometry separations chemistry must produce an isotope in high yield while eliminating all other components that might interfere by (1) reducing Richard E. Perrin, Donald J. Rokop, ionization efficiency or (2) producing isobaric John H. Cappis, Michael T. Murrell, interferences in the mass range of interest. Joseph C. Banar, Eddie L. Rios, We require separation factors as high as 1012; Ruben D. Aguilar, and Jose A. Olivares for details of our progress in separations chemistry, see Chamberlin's article "Mass During the past 11 years, thermal-ionization Spectrometers and Isotope Separation—Why mass spectrometry has become an increasingly Both?" in this section. important technique for the radiochemical diagnostics program. This technique is used in The second improvement was reduction of the several ways. chemical blank, which has been accomplished by three primary efforts. We now conduct chemical • Pre- and postshot isotopic analysis of processing in class 100 clean room facilities to uranium and plutonium provides the reduce pai*ticulate blanks. We have developed isotopic inventory data that allows us suppliers and/or in-house techniques for to calculate fission yields. producing ultrapure acids and selecting process containers. Microprocessing techniques have • Postshot analysis for specific isotopes been applied to all separations processes to incorporated into the test device reduce the total exposure of the sample to provides valuable information on contamination sources. With this combined geometric and chemical fractionation. approach we have reduced the actinide blank to below 1 x lO12 g for routine processing and 5 • Analysis of long-lived isotopes formed to as low as 5 x 10 atoms in some special by the interaction of neutrons with applications. elemental tracers, which arc added to the test device, provides additional The final area that required major information concerning neutron fluence improvement was mass spectrometer and energy. performance, where three components of instrument performance have been enhanced At this time, we routinely performed high- substantially. These are the detector systems, accuracy, high-sensitivity isotopic analyses ionization processes, and abundance sensitivity. for uranium, plutonium, americium, and neptunium. Other actinides such as Initially, we added pulse-counting detectors to protactinium and curium are analyzed give us the capability of detecting individual when necessary. We can accomplish precise ions. Combination detectors were then added that allow us to measure dynamic ranges as isotopic analysis (better than 0.1% at the 95% 12 confidence limit) for major ratios by using as high as 10 . We now are investigating very little as 1 x 10"9 g of the element. In addition, low noise detector systems to further increase for elements added as neutron monitors, we detection limits. can detect the neutron induced isotopes in concentrations as low as 1 in 108 (relative to Ionization efficiency has improved through soil background). the development of several procedures. To achieve the results described above, (1) An electrodeposition system permits a number of new techniques and special high-yield deposition of the sample, instrumental modifications have been necessary. and we have successfully used further These developments improve one or more of electrodeposition of a diffusion barrier three critical performance factors: accuracy, of platinum for all actinide analyses. sensitivity, and dynamic measurement range. This process increases the ionization efficiency for actinides by a factor of 10. The first area that required significant improvement was separations chemistry. (2) A procedure we developed for lead, To achieve the sensitivity and accuracy required, bismuth, ruthenium, and technetium 16 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Weapons Chemistry incorporates the sample to be analyzed into a small bead of borosilicate glass. This procedure, which virtually eliminates interferences from impurities in the filament material, is being investigated for other elements. (3) Negative ionization from a lanthanum oxide substrate provides even greater ionization efficiency for technetium. Although this process was not developed specifically for weapons diagnostics, it shows great promise for solving problems in that area. We also have under way a series of instrumental developments to increase abundance sensitivity (the ability to measure a very small isotopic abundance adjacent to an isotope of very large abundance). Our standard single-stage instruments have an abundance sensitivity of approximately 1 x 105. We have built two dual-magnetic sector instruments that have demonstrated abundance sensitivities of 5 x 107. We now plan to add an electrostatic sector that should increase the abundance sensitivity to 2 x 109. As a result of the developments in chemistry, ionization processes, blank control, and instrumentation, we can achieve very low detection limits for the suite of elements shown here. Element Detection Limit Uranium 5xl06atoms Plutonium 5 x 105 atoms Americium 2xl05atoms Neptunium 2 x 105 atoms Bismuth 5 x 107 atoms Technetium 2 x 106 atoms Our ability to measure isotopes at these very low levels has led to a number of important spin-off studies, including the measurement of actinide retention in human tissues; migration of plutonium, technetium, and americium in either uranium ore deposits or waste repository soil samples; studies of solar neutron flux; and examinations of the double-beta decay processes. In addition, our precise measure- ments of uranium and plutonium in very small samples has resulted in a program to safeguard these materials in the nuclear processing cycle. Isotope and Nuclear Chemistry Division Annual Report FY1988 17 Weapons Chemistry Mass Spectrometers and Isotope the isotopic ratio of the sample loaded into tha Separators—Why Both? ion source, This ratio will be measured several times to attain the desired confidence in the Edwin P. Chamberlin measurement. On the isotope separator, no slit is used and Two types of instruments at INC-Division the magnet is run at a constant field value. can be used to measure the relative abundances A long foil is placed at the focal plane and ions of isotopes (isotopic ratio) within any given of various masses are collected on it until the element: mass spectrometers and isotope sample in the ion source is exhausted. Because separators. Although these two instruments are each isotope hits the foil at a specific location, similar in many respects, they differ in others. isotopic separation is achieved. The collection foil is then cut midway between each of the Both instruments use an ion source to remove isotopes. Each section of foil, which contains electrons (or add, in the case of negative ions) a single isotope, is loaded into a calibrated from atoms of the sample material. The ions detector to determine the number of radioactive are then allowed to fall through an electrical atoms present—and thus, the isotopic ratios of potential to reach the desired energy—10 kV the sample. for spectrometers and 50 kV for separators. Further details on mass spectrometer analyses In both instruments, the ions then enter a may be found in a companion article in this transverse magnetic field, where they are section. The discussion below describes isotope deflected along a radius of curvature that is separator operation. proportional to the square root of their mass. This magnet effects the separation of ions Separation and Collection of different mass. The magnet for a mass When a nuclear device is to be tested, chemical spectrometer may weigh as little as 500 kg, detectors are loaded into the device so that we whereas the magnet for an isotope separator can determine the neutron spectrum and flux at may weigh as much as 10 000 kg. the time of detonation. Neutrons from the device produce a wide range of radioactive isotopes The ion current levels are also significantly from the originally nonradioactive detector. 9 different: ~10' A in a mass spectrometer vs Measuring the relative abundances of these 10"5 A in an isotope separator. radioactive isotopes (isotopic ratios) is one of the purposes of the weapons diagnostic program. These instruments have optical properties like We use the isotope separators to isolate specific a camera or telescope. If properly designed, they isotopes from each other and from any fission will provide an image of the ion source at a focal products that may be present in abundance. point downstream of the magnet. When ions of Separators must perform well in two areas if we various masses are emitted from the ion source, are to make these measurements accurately. each mass will be brought to a focus at a different position downstream of the magnet. The locus After isotopic separation, the samples are of focal points is called the focal plane. It is at sent to the counting room, where the number this focal plane that mass spectrometers and of radioactive atoms on each foil segment is isotope separators employ significantly different determined. A large number of radioactive techniques to measure isotopic ratios. atoms makes this determination easier; therefore, the efficiency of ionization in the ion The mass spectrometer usually has, at the source is important. Raising this efficiency from focal plane, a slit that is narrow enough to 1 to 10% can reduce the counter time required, permit ions of only one mass to pass. A detector reduce the magnitude of background correction, behind the slit determines how many ions per and provide greater overall statistical accuracy. second pass through. The field of the magnet is then changed so that ions of a different mass There is no single solution to the problem of can pass, and the detector determines how many ionization efficiency. Each element behaves ions per second of that mass are present. The differently because of its vapor pressure and ratio of the two detector count rates determines ionization potential. The chemical compound 18 Isotope and Nuclear Chemistry Division Annual Report FY1988 Weapon* Chemistry (and its purity) chosen by the chemist preparing In 1985, tailings were commonly at a ratio of the sample can affect ionization efficiency. For 10-3 to the main isotope. Today, tailings can example, rare-earth elements are ionized by usually be limited to the 10"* levei. Our goal is surface ionization techniques in which the to consistently hold tailings to 10'5. sample atoms ^re vaporized and then contact a 3000 K tungsten surface. This method requires Not all samples are run for weapons loading the rare-earth sample as an oxide so analysis. The laboratory has many other uses that it does not vaporize and escape before the for separated isotopes; for example, if a pure ionizing surface reaches the desired tempera- "spike" isotope is loaded with a test sample, ture. But the preparation of oxides must be it can sometimes reduce the running time done carefully to ensure that excessive alkali required on the mass spectrometers. Figure 1.2 or alkaline earth compounds are not included. shows the periodic table from an ion source If such compounds are present, ionization user's point of view. For each element, this efficiency can be reduced by a factor of 10 to table gives data that are useful in deciding 100 times. which ion source will provide the best efficiency. The second area of desired improvement is Any element that has a first ionization that of separation purity. Not all ions of mass M potential of 6.5 eV or less can be run with 10% end up at the mass M position on the collection or higher efficiency in the surface ionization foil; some will be at the M+I position and some source. Any element with a listed temperature will be at the M-l position—this phenomenon of 1100 K or less can be run in the plasma source is called tailing. If the available quantity of with 3% efficiency. Any gaseous element can be mass M atoms greatly exceeds that of mass M+l run in the microwave ion source.3 atoms, a small amount of tailing might mean more mass M atoms will be in the M+l position than mass M+l atoms themselves. H Element He 5.4 K IK 13.6 eV 24.5 eV -0.75 eV Temperature ooetf Li Be B N I- Ne 670 K 1275 K 1975 K c 32 K o 37 K 10 K 5.4 eV S.3 eV 1st lonization Potential 8.3 CV 2400 K 14.5 eV 37 K 17.4eV 21.6 eV -0 62 eV •0.2B eV 11.3 eV 13.6 eV -3.40 eV -1.26 eV Na M e- Affinity Al Si -1.46eV C! Ar 465 K 1250 K 1615 K 400 K 330 K 110K 36K 5.1 eV 6.0 eV 6.2 eV 10.5 CV 10.4 eV 13.0 K 15.eeV •0.55 eV -0.44 eV •1.39 eV •0.75 eV -2.08 eV -3.62 K Ca Sc Ti Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 395 K 730 K 1375 K 1710K 1820K 1430 K 1020K 1500K 1530K 1530K 1300 K 520 K 1175 K 475 K 435 K 162 K 49 K 4.3 eV 6.1 eV 6.6 eV 6.633 V S.7eV 7.4 eV 7.9 eV 7.9 eV 7.6 eV 7.7 eV 9.4 eV 6.0 eV 9.8 sV 9.8 ev li.BeV 14.0 eV -0.50 eV -0.04 -0.19 eV •0.05 eV •0.S3 6V •0.16';V -0.66 eV •1.16 eV •1.23 eV -0.3 eV VS.0 0.80 eV •2.02 eV •3.37 eV •1.2 eV Rb' 3r Y Zr Nb Mo Tc Ru Rh Pd Ap Cd In Sn Sb Te Xe 1600 K 2275 K 2550 K 2400 K 2350 K 2250 K 1975 K 1450 K 11CWK 1000 K 1275 K 700 K 550 K 225 K f.3K 6.2 eV 6.8 eV 6.9 eV 7.1 eV 7.3 eV 7.4 eV 7.5 eV 8.3 eV 7.6 eV 9.0 eV 5.3 eV 7.3 eV 8.6 eV 9.0 eV 10.5 eV 12.1 eV -0.49 e •0.31 eV •0 43eV •0.89 eV 0.75 eV •0.6 eV • 1.1 eV I.UeV 0.56 eV 1.30 eV •0.3 ev •1.2eV •1.1 eV S7V •3.56 ev Cs Ba La Hf Ta Re Os Ir Pt Au Hg TI Pb Bi Po At Rn 350 K 730 K 1700K 2275 T 2850 K w 2e50K 2750 K S380K 2010 K 1400 K 26?K 740 K 790 K 495 K 3.9 eV 5.2 eV 5.3 eV 6.8 eV 7.9 eV 3000K 7.9 eV 8.7 eV 9.1 eV 9.0 eV 9.2 eV 10.4 ev 6.1 eV 7.3 eV 8.4 eV 0 47 eV •0.5 eV 8.0 eV 0.15 eV •1.4 eV •1.57eV •2.13 eV •2.31 dV •0.3 eV •1 9eV •2 9eV -0.32 eV 0.82 eV •0.95 eV Fr Ra Ac 690 K 5.3 eV Ce" Pr ' Nd" Pm Sm"1 Eu Gd "I Tfa " Ho" Er TrrT Yb ' Lu " 1650 K 1420 K 1325 K 1050 K 850 K 730 K 1350 S 1425 K 1125K 1225 K 1225 K 950 K 690 K 1550K 5.5 eV 5.5 eV 5.5 eV 5.6 eV 5.6 eV 5.7 eV 6.2 eV | 5.8 eV 5.9 eV 6.0 eV 6.1 eV 6.2 eV S3 eV 5.4 eV Th Pa Np Pu Am 2250 K u 1475 K 1130 K 6.1 eV 1850 K 6.1 eV 6.0oV 6 2eV Fig. 1.2. This chart shows the temperature required to reach 10'4-7brr pressure, the first ionization potential, and the electron affinity. A slash in the upper-right-hand corner indicates that we have run that element within the past 3 yr and have some confidence in our ion source operating parameters. Isotope and Nuclear Chemistry Division Annual Report FY 1988 19 :-.. O L / Biochemistry amd Nuclear Medicime Overview ,•-.-•• „••••—. =;;-w=-=^^ \ If Biosynthesis of the Coenzyme Pyrroloquinoline Quinone Lanthanide Schiff Base Complexes as Contrast Agents for Magnetic Resonance Imaging BiomedicaT Applications for Radioisbtope Generators Biochemistry and Nuclear Medicine Biochemistry and Nuclear Medicine used to probe the complex relationships by Overview which metabolites influence gene expression of the very systems generating them. Another Pat Unkefer and Janet Mercer-Smith research effort seeks to understand the regulation of nitrogen assimilation by cells; this process is a working example of metabolism Biomedical and nuclear medicine efforts in influencing gene expression and is carried out in INC Division are centered in INC-4 and INC-11. mammals, higher plants, and microorganisms. The variety of projects under way in each area are outlined here, and three specific projects Other investigations include a character- are discussed in detail in articles that follow. ization of the detailed structure of the iron sulfur proteins that carry out the electron Biochemistry transfer process of cellular respiration. We The Division's biochemistry activities include are examining these proteins, whose gene research in several subcatagories of this expression is controlled by the ferrous iron discipline: protein structure, metabolic studies, uptake system, as a complementary project in and synthesis and application of improved our characterization of the structure/biological magnetic resonance imaging agents. These role of superoxide dismutase. studies are technically supported and comple- mented by the Division's expertise in producing Studies of metabolism and protein structure and employing radionuclides as well as the are complemented by the function of the separation and use of stable isotopes. National Stable Isotopes Resource. This resource is funded by the National Institutes Stable isotopes of carbon, nitrogen, and oxygen of Health to help provide stable, isotopically are routinely produced in large quantities in the labeled, biologically important compounds to Division. These isotopes are powerful research the basic research community. The resource tools for answering fundamental questions assists this community by developing efficient, about the way living systems function and steriospecific syntheses for specific-position specific questions about the biosynthesis of isotopic labeling of biological compounds not important components in biological systems. available from other sources. In this way, the One class of essential biological components is Resource supports the best and most significant the cofactors used by enzymes to catalyze biological research—work at the cutting edge of certain steps in metabolism. These cofactors are science. often the commonly recognized vitamins. Recent efforts use 13C combined with nuclear magnetic Nuclear Medicine resonance detection to study the route of We conduct nuclear medicine research using biosynthesis for a newly recognized cofactor, radioisotopes produced at the Los Alamos Meson pyrroloquinoline quinone. These studies readily Physics Facility (LAMPF). During FY 1988, indemnified the biological precursors of this the Medical Radioisotopes Research Program material, providing yet another excellent shipped 30.1 Ci of radioisotopes (in 177 example of the accuracy and efficiency of this shipments) to research institutions, industry, experimental approach. For the identification of extramural collaborators, and intralaboratory biological precursors and their biosynthesis, this researchers. Future radioisotope production experimental approach is without equal. New research and development will continue to applications of this method can be expected; for emphasize beamstop processing for ^Ti, 26A1, example, recent studies have shown that and 32Si. These long-lived radioisotopes are important regulatory actions are exerted by produced through the long irradiations that metabolism upon gene expresssion in higher are available at the LAMPF beamstop. One of organisms, but these systems are poorly our current efforts is to expand the applications understood. The systems are clearly important of electrochemistry in radioisotope separations in such processes as development and growth in to obtain high-purity radioisotopes for medical normal and abnormal cell types like cancer cells. and biological research. Stable-isotope-assisted studies will be an exceptionally powerful tool as we examine the In other applications research, we have focused metabolically perturbed systems that will be on three areas: (1; development of biomedical 22 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Biochemistry and Nuclear Medicine generators to make short-lived radioisotopes cancer therapy modality, and (4) determine the available to the nuclear medicine community, physical extent of infections. A diagnostic (2) development of methods to radiolabel small imaging agent for inflammatory lesions would molecules and monoclonal antibodies, and also locate abscesses. Our immediate goal is (3) biological investigations of radiolabeled to determine the mechanism of porphyrin porphyrins as agents to image tumors. localization both in inflamed and neoplastic lymph nodes and in inflammatory lesions. 67 Biomedical generators are used to separate The Cu porphyrin reaches a maximum long-lived parent radioisotopes from their concentration in the inflamed lymph nodes; short-lived daughters. These separation this concentration is 4 times greater than in methods make available isotopes whose half- surrounding muscle and 8 times greater than lives are too brief to make overnight shipping in fat. Initial mechanism studies suggest that feasible. Biomedical generators are also macrophages and T cells may be responsible designed to ensure a continuous, readily usable for the enhanced uptake in inflamed lymph nodes. Preliminary studies indicate that the supply of the daughter radioisotopes for clinical 67 personnel. Our current research is directed to Cu-labeled porphyrin is taken up by sterile the development of three particular generators: abscesses and the surrounding inflamed tissue (1) the lOgcd/^'nAg generator for ^™-Ag, an far more than by normal tissue. An under- ultrashort-lived isotope that is potentially useful standing of this mechanism of porphyrin for gamma-camera imaging with pediatric localization will help us determine the applications, (2) the 8sZr/88Y generator for 8SY, optimum conditions for localization. a gamma-emitting isotope that can be used to develop chemical and biological applications Another related area of nuclear medicine for 90Y (Yttrium-90 is a beta emitter useful for research is the development of 67Cu porphyrins internal radiation therapy; however, investi- to image early, treatable stages of lung cancer. gating the biodistribution of beta-emitting In a collaborative research project with compounds is much more difficult than studying physicians at St. Mary's Hospital in Colorado, gamma-emitting analogs); (3) the72Se/72As we are using porphyrins to analyze the sputum generator for 72As, a radioisotope with potential of uranium miners who have radon-induced for positron emission tomography imaging of lung cancer. We have found that the porphyrins pathological processes and tumors. give us excellent recognition of tumor cells in sputum. We hope to de^Telop radiolabeled Because 67Cu has nuclear decay properties porphyrins that can be used to image lung that are suitable for tumor imaging and internal tumors at an early stage of cancer development, radiation therapy, we are investigating "cold kit" when the cancer is most susceptible to methods to radiolabel antibodies with 67Cu. treatment. The specificity of the antibodies for tumors carries the radioisotope to the tumor site for Researchers in INC-4 and INC-11 are internal radiation therapy or gamma-camera collaborating on a project to design chelating imaging. Our cold kit method consists of an agents for paramagnetic metal ions, which N-benzyl porphyrin covalently attached to an can be used as paramagnetic contrast agents antibody; the porphyrin can be radiolabeled for magnetic resonance imaging (MRI), with 67Cu under mild reaction conditions. a noninvasive method of in vivo imaging. This method of preparing the 67Cu-labeled Because the paramagnetic metal ions are toxic, antibody yields antibodies that have high chelating agents that form extremely stable immunoreactivity and good localization in complexes with paramagnetic retaliations mouse tumors. are needed for paramagnetic contrast MRI technology. We are currently developing We are developing 67Cu labeled porphyrins to chelating agents for gadolinium(III), the detect inflamed and neoplastic lymph nodes as paramagnetic metal ion with the highest well as inflammatory lesions that cause fever paramagnetic contrast effect for MRI. We've of unknown origin. The ability to image diseased had some success with macrocydic chelating lymph nodes gives us the ability to (1) detect agents that completely encircle the gadolinium. nodal involvement in metastatic cancer and in lymphatic tumors, <2) stage cancer, (3) determine Isotope and Nuclear Chemistry Division Annual Report FY 1988 23 Biochemistry and Nuclear Medicine Biosynthesis of the Coenzyme a vitamin. None of the biosynthetic precursors Pyrroloquinoline Quinone or intermediates had been identified until recently. Using specific 13C-labeling and NMR Clifford J. Unkefer, David R. Houck, and spectroscopy, we examined the biosynthesis John L. Hanners of PQQ in the methylotrophic bacterium Methylobacterium AMI.8-9 We demonstrated We are attempting to understand the physiology that PQQ is biosynthesized from the two and biochemistry of methylotrophic bacteria; common amino acids L-glutamate and L-tyrosine (Fig. 2.2). these soil-borne bacteria are unique because of their ability to grow by using simple one-carbon compounds such as methane or methanol as To determine the biosynthetic origin PQQ, their sole source of carbon and energy. An we isolated PQQ from cultures of Methylo- bacterium AMI that were grown from either important component of this process is the 13 13 oxidation of methanol to formaldehyde by [1- C] or [2- C]ethanol as a carbon source. methanol dehydrogenase, which requires the The labeling patterns in PQQ were compared coenzyme pyrroloquinoline quinone (PQQ). with those obtained in amino acids purified from protein hydrolysates. The [1-13C] and [2- This enzyme was first recognized as a cofactor 13 for the pyridine nucleotide-independent C]ethanol labeling experiments, coupled with methanol dehydrogenase from methylotrophs.4 the obvious structural homologies, provide a These quinoproteins represent a novel class of working hypothesis for the biosynthetic origins dehydrogenases that is distinct from the well- of PQQ (Fig. 2.2). We believe that glutamate known pyridine nucleotide and flavoprotein provides N-6 and carbons 7', 7, 8,9, and 9'; the dehydrogenases.5 In these quino-dehydro- remaining portion is derived from a symmetric genases, PQQ serves as a 2e72H+ redox carrier product (C2 axis through C-l' and C-4') of the that donates electrons from the oxidation of shikimate pathway, likely tyrosine. The phenol methanol through an electron transport chain side chain provides the six carbons of the ring to O (Fig. 2.1). that contain the orthoquinone, whereas the 2 amino acid backbone forms the pyrrole-2- Recent studies indicate that PQQ is also carboxylic acid moiety. a cofactor for several well-known copper- To demonstrate directly that tyrosine is a containing amine-oxidases, including bovine 13 serum amine oxidase, porcine kidney diamine precursor of PQQ, we added [3'5'- C2]tyrosine oxidase, and human placental lysyl oxidase.6'7 to Methylobacterium AMI cultures growing on methanol.10 PQQ isolated from this culture was This class of enzymes serves to cross-link 13 collagen, which makes up the connective tissue examined by ^H and C NMR spectroscopy. The 13C spectrum indicates that L-[3',5'- of animals. The presence of PQQ in higher 13 organisms raises the question of how this C2]tyrosine labels PQQ at C-5 and C-9a as novel compound is biosynthesized and whether predicted by the biosynthetic model (Fig. 2.2). or not this compound or a related analogue is coo- COO' coo- N—i Gluiamate I COO" COO' COO' j^" COO" 1 ( 'OOC^^N»H 'OOC + ",2H ? 0 oocr -QOC -O-H PQQ o O-H COO" COO" POQ PQQH2 ^"N ^\ Tyrosine m + oo. FIG. 2.1. PQQ acts as a 2e , 2H carrier in quino- 0 dehydrogenases and cycles between the quinone (PQQ) and quinol (PQQH^ forms. FIG. 2.2. Proposed biosyntketic precursors ofPtfQ. 24 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Biochemistry and Nuclear Medicine Because C-9a is spin-spin coupled to H-8, !H As demonstrated from the results obtained in NMR analysis can be used to determine the experiments on Methylobacterium AMI, PQQ 13C enrichment at C-9a. Under these culture arises from the condensation of glutamate and conditions, PQQ was labeled at C-9a (and C-5) tyrosine. A possible route for the biosynthesis to an enrichment of 63%. The resonances for of PQQ is diagrammed in Fig. 2.3. In this route, C-5 and C-9a are doublets as a result of 13C-13C tyrosine or some derivative of tyrosine is coupling, which proves that the phenol group oxidized to dopachrome in a reaction catalyzed of tyrosine is incorporated intact into the ring of by a monophenol monooxygenase-like enzyme. PQQ containing the orthoquinone. Glutamate could form a Schiff base with dopaquinone. The cyclization of the tyrosine The results outlined above show that tyrosine backbone to form the pyrrole ring could occur by provides the six carbons of the orthoquinone- a Michael-type addition analogous to the known containing ring. To examine the possibility that nonenzymatic cyclization of dopaquinone to form 11 internal cyclization of the tyrosyl backbone dopachrome. Alternatively, dopachrome may forms the pyrrole-2-carboxylic acid moiety, we be an intermediate in the biosynthesis of PQQ. cultured Methylobacterium AMI on a mixture We are now identifying possible intermediates in 13 13 of [3',5'- C2]tyrosine (50%) and [3- C]tyrosine the biosynthetic pathway to PQQ. This research (5&%). The 13C NMR spectrum of PQQ isolated project contributes to our overall understanding from the culture filtrate contained only three of the physiology of methylotrophic bacteria. The 13 resonances corresponding to C-5, C-9a, and C-3. samples of C-labeled PQQ generated during The 13C enrichments were determined by *£[ this research project are being used to examine NMR. The equal incorporation of 13C at C-3 and the chemical mechanism of methanol C-9a (41 and 42%, respectively) indicates that dehydrogenase. This enzyme plays the central tyrosine is incorporated intact (Fig. 2.2). role in the energy metabolism of methylotrophs. COO' ,000" + H3 N —C COO' PQQ FIG. 2.3. Possible route of PQQ biosynthesis. Isotope and Nuclear Chemistry Division Annual Report FY 1BS8 25 Biochemistry and Nuclear Medicine Lanthanide Schiff Base Complexes as the toxic free metal ion.1- Present NMR contrast Contrast Agents for Magnetic Resonance agents such as GdDPTA rely on the thermo- dynamic stability of multidentate complexes to Imaging reduce the toxicity of the free metal. Unfortunately, the first coordination sphere of the paramagnetic James R. Brainard, Paul H. Smith, metal is primarily occupied by coordinating David E. Morris, John H. Hall, groups from the ligand and efficient relaxation Gordon D. Jarvinen, Robert R. Ryan, of water protons is limited. Our approach to Dean A. Cole, Joanna Norman, designing stable paramagnetic complexes with Karen Bullington, Timothy Burns, multiple water coordination sites *s to use Janet Mercer-Smith, Richard Griffey,* macrocyclic ligands with high kinetic stability. Mark Brown,* and Nick A. Matwiyoff* The lanthanide Schiff base maerocycles synthe- Magnetic resonance imaging (MRI), a non- sized by Vallerino and coworkers13 (illustrated invasive method for obtaining images of objects, below) appeared to be good candidates for MRI has many applications in medical diagnosis and contrast agents. We refer to these complexes as research. MRI uses magnetic fields and radio- LnHAM, for lanthanide HexaAzaMacrocycles. frequency radiation to localize the position of A particular advantage of these systems is that atomic nuclei in space. Protons are the most the synthesis can be accomplished in one step abundant and sensitive nuclei in biological tissues; by using a template approach. The ease and therefore, most medical applications of MRI versatility of synthesis make Schiff base macro- have imaged protons. The protons in biological cycles an especially attractive system in which tissue are present primarily as water; conse- to examine structure-activity relationships. quently, MRI images primarily reflect the distri- bution and properties of water in the body. Because water is centrally involved in many biological processes, and because the method does not use ionizing radiation, MRI is rapidly >< J = LnHAM becoming a preferred imaging method for Ln = La Ihrobgn Lu diagnosis of many diseases, including multiple sclerosis, stroke, and cancer. This project focuses on designing, synthesizing, and evaluating paramagnetic complexes that can be used to The first step in evaluating the potential of improve the differences (contrast) in MRI images. these complexes as MRI contrast agents was to measure their effectiveness as relaxation agents. The properties reflected most directly in MRI Relaxivity is defined as the change in solvent images are the amount of water contained in the relaxation rate per concentration unit of the relaxation agent. The relaxivity of GdHAM in tissue (proton density) and the rates at which 1 1 the water protons return to their ground state aqueous solution was 9.7 s* mM at 0.47T; by comparison, the relaxivities of gadolinium energy levels (relaxation rates). Although many 1 tissues and disease states naturally exhibit aquo ion and GdDTPA are 9.1 aud 4.1 s^mM" , differences in proton density and relaxation rates, respectively. The relaxivity of the GdHAM MRI contrast agents could be developed to enhance complex is significantly greater than that for the differences in MRI intensity between various GdDTPA and slightly greater than that for the tissues and between healthy and diseased tissue. gadolinium aquo ion, which suggests that the One way to increase relaxation rates of water expectation of increased relaxivity in complexes is by adding paramagnetic metal ions. If para- with multiple open coordination sites is realized. magnetic metals are differentially taken up by To more completely understand the effects of the tissues, relaxation rates of water in those tissues ligand structure on the relaxivity of paramag- are increased, and they appear light in MRI images. netic complexes, we investigated the solid state and solution properties of the europium and One problem with using paramagnetic metal gadolinium complexes by x-ray diffraction, ions in living organisms is that the metals are fre- electron and nuclear magnetic resonance, cyclic voltametry, and luminescence lifetime quently toxic. To reduce toxicity, researchers use 14 complexes of paramagnetic metals with organic measurements. A ball and stick representation ligands, thereby lowering the concentration of of the single-crystal x-ray structure of the [GdHAM(Acetate)2]+ is shown in Fig. 2.4. ^'Center for Non-Invasive Diagnosis, University of The gadolinium atom sits in the cavity of the New Mexico, Albuquerque, New Mexico. macrocycle, and two acetate anions occupy the 26 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Biochemistry and Nuclear Meditina coordination sites above and below the macro- Fid cycle, making the complex 10-coordinate. This OU observation and luminescence lifetime measure- *»• 60DTPA / o 50 "•• GdHAM / ments suggest that the complex has 3 to 4 ••» Contr! im e / coordinated waters in solution. 40 / ni tn > f A very important requirement for a successful 30 Ce l y clinical MRI contrast agent is low toxicity. Using d / a sensitive cell growth inhibition method, we 20 Is / performed a preliminary toxicity study on CD GdHAM compared to GdDTPA. Figure 2.5 o 10 No . shows that both GdHAM and GdDTPA inhibit r\ - » U growth compared to the control; however, the ) 24 48 72 toxic effect of GdHAM was considerably less. Time (h) The specificity of GdHAM for tumors was demon- FIG. 2.5. Growth inhibition toxicity assay of GdHAM strated by MRI of a canine glioma tumor model and GdDTPA. in a rat. Tumors were implanted into the flanks of two rats 7 days before MRI. One rat was imaged difficult to obtain high-contrast MR images on using GdHAM as a contrast agent and the other many low-field MRI instruments in only 5 min. using GdDTPA at the Center for Non-Invasive Diagnosis (Fig. 2.6). The tumors appear as areas The GdHAM complex shows significant of white intensity in the right flank of each rat. promise as an MRI contrast agent because of its These images, taken at various times after injec- high relaxivity and kinetic stability. In addition, tion of the contrast agent, show that GdHAM our preliminary in vitro toxicity data and in and GdDPTA give similar contrast to the tumor vivo MR images of a tumor model in rats suggest 5 min after injection. However, in the second, that it may be more efficacious than GdDTPA. third, and fourth images, the tumor image in the Although we need to more completely define the GdHAM-treated rat is significantly brighter. The structural and dynamic properties responsible slower washout exhibited by GdHAM is a poten- for the high relaxivity and stability of this tial advantage for clinical imaging because it is complex, the concept of designing macrocyclic ligands for gadolinium (III) clearly shows potential for improved MRI contrast agents. By performing structure-activity studies in these systems to identify the key factors that determine relaxivity, stability, tissue specificity, and toxicity, we hope to develop a rational basis for contrast agent design. FIG. 2.4. This side view of the GdHAMiAcetate)2 complex shows the acetates coordinated above and below the gadolinium metal as well as the FIG. 2.6. In them: MRI experiments with tumor* m two bending of the macrocycle in the solid state at rats, the rat on the right was given GdHAM and the the diamine hinges. (Yellow = gadolinium, blue rat on the left was given GdDTPA. The images K*n> = nitrogen, white = hydrogen, black = carbon, obtained (from upper left) 5,20,35, and 50 min after and red = oxygen.) injection. Isotope and Nuclear Chemistry Division Annual Itvport FY 1388 Biochemistry and Nuclear Medicine Biomedical Applications for half-life requires physiologically compatible Radioisotope Generators eluents to permit direct injection into patients. Dosimetry calculations indicate that we must minimize 109Cd in the eluate—"breakthrough"— Dennis R. Phillips, Frederick J. to reduce the patient's radiation exposure. Steinkruger, and Wayne A. Taylor Breakthrough is reported as the ratio of 109Cd in the eluate to that loaded on the generator. Nuclear medicine owes its existence to the Anger camera and the development of the Using a sodium-thiosulfate eluent, we 99Mo/99mTc biomedical generator system. surveyed commercially available inorganic A generator is a system in which a short-lived exchanger materials and discarded many daughter isotope is quantitatively separated because of mechanical problems in making a from its longer lived parent. Depending upon the column. We investigated Photi D, a form of generator and application, the daughter might titanium phosphate, because initial results be used directly for diagnosis or therapy or showed a high silver yield with a moderate converted to an appropriate chemical form cadmium breakthrough. After extensive for medical procedures. For daughters with experimentation, we also discarded Photi-D ultrashort half-lives, this is the only wa3r to because we were not able to reduce cadmium efficiently and economically provide the isotope breakthrough to an acceptable level. We finally to the nuclear medicine community. With the returned to Phostain, a form of tin phosphate appropriate parent/daughter combinations, it that had exhibited reasonable silver yield with is possible to provide isotopes for positron low cadmium breakthrough (Fig. 2.7). emission tomography, single-photon-emission computed tomography imaging, and therapy. We investigated the possibility of operating the column at elevated temperatures to enhance It was the99 Mo/99mTc generator that the lO9mAg yield. Raising the column temperature permitted routine clinical applications of nuclear increased the daughter yield to a maximum of medicine imaging techniques, and it is still the 71%; however, if the temperature exceeded 36'C, mainstay of nuclear medicine. However, this there was an unacceptable increase in cadmium generator has a number of shortcomings, breakthrough (Fig. 2.8). When we installed a including a brief parent half-life and lack of small filter containing ~50 mg of cation daughter emissions suitable for therapeutic exchange resin on the outlet of the column, applications. Therefore, the development of there was no statistically significant change in other generators with appropriate parent/ the silver yield, but there was a substantial drop daughter combinations may be very beneficial in cadmium breakthrough (Fig. 2.8). It was not to nuclear medicine in the future. clear whether this drop was the result of ion exchange or filtration of submicron shards of Since its inception, the Medical Radioisotopes Phostain. When we used scanning electron Research Program in Group INC-11 has worked microscopy to examine the surface of the to develop new biomedical generators. The 68Ge/68Ga and 82Sr/82Rb generators investigated here are now being used in the nuclear medicine community. We are presently investigating iO9Cd/iO9mAg, 72ge/72AS) ^d 88Zr/88y generators. The lOSCd/^nAg Generator g> In this generator, the daughter 109mAg, m which decays with a 39.6-s half-life to stable 109Ag, is suitable for first-pass angiography with multiple repeat studies. The short half-life permits higher doses that result in sharper images but also reduces the radiation exposure to the patient. Because of the parents long half- life, we must use inorganic ion exchange Silver Recovery i%) material to avoid possible radiolysLs of organic- FIG. 2.7. Silver yield and cadmium breakthrough based exchangers. The daughter's ultrashort profiles from a cadmium/silver generator. 28 Isotope and Xuclenr Chemistry Division Annual Report FY 1U88 Biochemistry and Nuclear Medicine decay. Using this process we have obtained a 99% radiochemically pure 72As traction. 88 o The Zr/88Y Generator 4 Yttrium-90 shows promise as a tool for internal I radiation therapy because of its beta emission; 3 S however, research in labeling monoclonal anti- 90 2 1 bodies with Y has been hampered by the lack of suitable gamma emission by which the isotope can be traced. Yttrium-88, with its long half-life (106 days) and several gamma rays, is a good 26 32 36 substitute for developmental applications. For Temperature (°C) labeling applications, we need an isotope that is •Results with a cation stripper on generator available in very high specific activity (the ratio of radioactivity to mass of the element). We FIG. 2.8. Yield and breakthrough vs operating 88 temperature. developed a procedure to recover Y from the decay of88 Zr with a specific activity near the 4 88 inorganic ion exchanger particles, we observed theroetical maximum (lx 10 Ci/g). The Zr was submicron shards on the surface of the sieved produced by irradiating a molybdenum target at particles (Fig. 2.9). We can remove these shards LAMPF. The molybdenum was dissolved with by wet sieving techniques. This may help the hydrogen peroxide and the resulting solution breakthrough problem. was passed through a cation exchange resin column. The zirconium was retained, and we An Electrochemical 72Se/72As Generator washed the molybdate through the column with Radioarsenic could prove to be a versatile hydrogen peroxide. We stripped the zirconium and powerful agent in nuclear medicine. We from this column in SM HC1 and purified it by could use some arsenic-containing compounds to loading it onto an anion column and washing image and study metabolic activity in most organ with 12M HC1. The zirconium sticks, and the contaminants are eluted. We removed a pure systems—the brain and skeletal systems are 88 two proven examples. Monoclonal antibodies fraction of Zr from the anion column in 2M HC1. labeled with radioactive arsenic could be employed 88 for imaging and possibly therapy in cancer Yttrium-88 was allowed to grow in as the Zr studies. Arsenic-72 is a particularly promising decayed and was separated by a repetition of the anion column procedure. This method produced isotope: a positron emitter, it is potentially 88 valuable in positron emission tomography. Its Y that has no observable radioactive contam- 26-h half-life is long enough to allow synthesis inants and minimal stable isotope contamination; of radiopharmaceuticals, but short enough to it is suitable for development of labeling minimize radiation doses in patients. The procedures and for biodistribution studies. development of applications will depend upon a reliable supply of the isotope. Probably the best approach for 72As production is through a 72Se/72As radiochemical generator system. We have developed a dependable method for producing 72Se in a rubidium/bromide target irradiated at the LAMPF 800-MeV linear accel- erator.15 We dissolve the target in water, acidify the solution, add copper(II) ion and selenious acid carrier, and electrochemically deposit selenium isotopes as Cu2Se at a platinum gauze working electrode. This deposition leaves arsenic in solution, which suggests that electro- chemical separation can serve as the basis of a radiochemical generator. We are developing a process to strip the selenium into an appropriate 72 FIG. 2.9. Scanning electron micrographs of Phoxtain electrolyte, allowing the As to grow in by nuclear (top) and Photi-D (bottom). hotope and Nuclear Chemistry Division Annual Report FY GeochemUtry and Environmental Chemistry Overview Thermodynamic Properties of Aqueous Solutions at High Temperatures and Pressures Geochemical Measurements Suggest Widespread Circulation of Ocean Ridge Material Trace-Element Variations in the Fumes of Kilauea and Mauna Loa Volcanoes Geochemistry and Environmental Chemistry Geochemistry and Environmental geochemical environments. We developed a high- Chemistry Overview temperature Raman cell to stud3r aqueous brines up to 400°C and 1 kbar. We've examined zinc Robert W. Charles bromide and chloride in our initial .studies of elemental transport in geothermal systems. By investigating silica-organic acid complexing, INC Division's increased involvement in we can determine the extent of silica transport, geochemical and environmental programs in, for example, hydrocarbon reservoirs, where reflects the Laboratory's growing commitment organic complexation is dominant. Metal to these research efforts. National concern about speciation in organic systems such as the diminishing resources, basic energy shortages, transport of elements in acetate- and polymaleic- and atmospheric and aquifer pollution, as well acid-bearing systems will help us model fulvic as an increasing demand for waste disposal has and humic acid movement in natural waters. challenged us to find successful, efficient, and cost-effective methods to solve these problems. The technetium geochemistry program developed "Tc as a natural tracer for some Basic Energy Sciences aqueous environments. Technetium, formed by Investigation of rock-water interactions and natural fission of uranium, decays with a half- element migration includes experimental and life of 2.13 x 105 yr and comes to nuclear computational modeling of rock-fluid reactions equilibrium with the parent in ~1 x 106 yr in hydrothermal systems. These models are if there is no geochemical fractionation in the applicable to environments that are appropriate natural environment. Technetium geochemistry for the discovery and recovery of energy—whether has practical relevance in our plans to store high- geothermal or fossil. For the Continental Scientific level nuclear waste underground and as a chrono- Drilling Program, we collect samples and investi- meter for physical and chemical processes in the gate experimental/computational hydrothermal sub-surface. The ultratrace-element abundance reactions of various natural hydrothermal of technetium required that we develop chemical systems such as Sulphur Springs, VC-2a and and mass spectrometric techniques to detect VC-2b in the Jemez Mountains, and the deep concentrations of l(r12 g/g uranium. Salton Sea well in California. Using a recently developed nuclear microprobe, we analyze major-, We use solid source mass spectrometry minor-, and trace elements in rocks and fluids to measurements of 238U-230Th disequilibrium in determine the state of equilibrium in these geo- geologic systems to examine the geochemistry of thermal systems. We use experimental hydro- such systems on the million-year time scale. Mass thermal systems that consist of flexible reaction spectrometer techniques greatly reduce sample cells (gold and titanium) to study reaction size and increase precision. When the technique relations of phase assemblages in concentrated was applied to "zero aged" dredged basalt brines. Solubility measurements are then samples from the Juan de Fuca Ridge axis, initial employed to improve mathematical models of results showed fractionation effects caused by the natural systems. magmatic processes; this same method will be applied to the young (<350 000-yr) flows sampled We use flow calorimetry to measure thermo- in VC-1, in the Jemez Mountains. dynamic properties of aqueous solutions at high temperatures and pressures. These measurements Two articles in this section describe other are ideal because the data can be integrated as trace-element studies: one of volcanic gases and a function of temperature to determine solution particles and the other of samples from asteroid- enthalpies and total free energies. We have heat impact-induced extinction boundaries around the capacity data for a number of aqueous chloride world. and sulfate bearing systems. Our goal is to provide data to 400°C so that we can study the When many of our field investigations required behavior of electrolyte solutions in the region a technologically advanced fluid and gas sampler, very near the critical point of water. Integrated we developed a slick-line-based tool to collect heat capacities also can be used in modeling. uncontaminated fluid in the difficult environ- ments encountered in the Continental Scientific Laser Raman investigations of mineral/organic Drilling Project. We tested a gas-tight,l-/ capacity interactions in aqueous systems focus on aqueous prototype sampler made of titanium Beta-C speciation, which is important in a number of suitable for brine salinities above 300°C. 32 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Geochemistry and Environmental Chemistry Atmospheric Sciences will develop and demonstrate drilling, instru- We are a part of the Winter Haze Intensive mentation, and analytical techniques to be used Tracer Experiment, a consortium of public in the exploratory shaft diffusion test. utilities and governmental agencies examining the origins of visible haze in the southwestern US. We also are using hydrothermal geochemistry Los Alamos provides expertise in complex-terrain to create a model of past and future mineral meteorology (ESS Division) and atmospheric alteration in Yucca Mountain. The model will tracer technology (INC Division) for conducting explain (1) natural mineral evolution resulting an atmospheric tracer experiment. Heavy in stable phase assemblages and (2) the effects methane (CD4) was released from the stack of of a repository placed there. A model of mineral the Navajo Generating Station for 6 weeks in alteration in Yucca Mountain suggests that winter 19S7. Preliminary indications are that mineral transformations observed there are the tracer-tagged emissions from the power plant primarily controlled by aqueous silica activity. were generally confined to the immediate vicinity, The rate of these reactions is related to the but haze events were detected from Canyonlands evolution rate of metastable silica polymorphs, National Park to Grand Canyon National Park. assuming that SiC^aq) is controlled at the We infer that there are other, unidentified equilibrium solubility of the most soluble silica sources that contribute to winter haze in the polymorph present. Rate equations accurately southwestern US. predict the present depths at which these polymorphs disappear; rate equations are also The DNA dust characterization project attempts used to predict future mineral alteration in the to (1) determine the quantities of dust lofted by presence of a high-level nuclear waste repository. pre-1962 atmospheric nuclear tests and contem- porary high-explosive events and (2) characterize We are determining the concentrations and its particle-size distribution and mineralogy. speciation of important nuclear waste elements We obtain details of the dust's source by placing that could be released to Yucca Mountain's elemental and organic tracers in the test bed and far-field environment if the repository were sampling with both airplane- and truck-mounted breached; the critical elements are neptunium, samplers; the data are used to assess operational plutonium, and americium. We study reactions and environmental impacts of such explosions. of ligands that are strong complexers of actinide elements, which are common in the groundwater Nevada Nuclear Waste Isolation at the proposed site. This work is made more In one of this program's many related tasks, difficult because the pH regime of typical groundwaters (near 7) implies that most we measure the distributions of cosmogenic and 7 fallout radionuclides at Yucca Mountain, Nevada, actinide elements have solubilities of >10" lf. to characterize the infiltration of precipitation To measure these low levels,we are developing and the velocity of water movement through ?. state-of-the-art photo-acoustic spectrometer the unsaturated zone at this potential high-level facility. nuclear waste repository. The US Geological Survey provided cuttings to a depth of 1270 ft We must be able to predict radionuclide into the unsaturated zone. Multikilogram samples movement from a potential repository to the of the cuttings are ground and leached to obtain environment. Using crushed-tuif, intact-tuff, chloride samplers for 36C1 analyses performed at and fractured-tuff columns, we investigate the the University of Rochester's tandem accelerator effect of kinetics, dispersion, diffusion, speciation, mass spectrometer. We will use 36Cl's 3 x 105 yr and nitration on the transport of radionuclides. half-life to time the water-borne transport of We also are studying the variability of pore chloride through the unsaturated zone. tortuosity and constrictivity to determine the rate of movement of radionuclides through tuff We are measuring effective diffusivity coeffi- in the absence of an advective flux, the diffusivity cients under in situ conditions in two tuffs that of radionuclides as a function of saturation in will be penetrated by the exploratory shaft at blocks of intact tuff, and the time-dependence the potential Yucca Mountain repository. Data of radionuclide uptake in solid tuff. from this test will be compared with data from laboratoiy measurements and computer models to help vp'^date nuclear waste transport calculations. A prototype diffusion, test being performed at the Nevada Test Site's G-Tunnel Isotope and Nuclear Chemistry Division Annual Report h'Y 1888 33 leochcinistrv and Environmental Chemistry Thermodynamic Properties of Aqueous disturbing the thermal stability (and hence, the Solutions at High Temperatures calibration) of the calorimeter. and Pressures Generally, the calibration of flow calorimeters Pamela S. Z. Rogers has been complicated by experimental difficulties; researchers report that two different methods of calibration give different results. It is important that we understand However, we have shown that the two methods thermodynamic properties of electrolyte give the same results if corrections are made solutions at high temperatures when we are for differences in experimental conditions. studying geothermal systems, hydrothermal In addition, we have obtained calibration results alteration processes, and elemental transport that are an order of magnitude more precise in deep brines such as those encountered in than those previously available. This is the Continental Scientific Drilling Program. important, because previous calibration To model cementation, mineral digenesis, methods introduced an absolute error up to and element transport in sedimentary basin 25 times as large as the precision of a heat evolution, we need to know the properties capacity measurement for high-temperature, of carbonates, hydroxy species, and organic concentrated solutions Our results reduce complexes to at least 473 K. Our investigation the error introduced from calibration until it is will determine the total free energies of about equal to the precision of a heat capacity geochemically important ionic species in measurement. This improvement stems aqueous solutions over a wide range of primarily from the complete automation of composition and temperature. Because the our flow calorimeter, which allows us to measure number of different electrolyte solutions of more precise, time averaged values of many interest at high temperatures is large, we experimental parameters. Results from heat want to find a method of obtaining thermo- capacity measurements of the system Na2SO4- dynamic properties from a minimum amount NaCl-H2O are shown in Fig. 3.1, where the of experimental data. Heat-capacity measure- ments are ideal for this purpose because we can integrate the data to yield enthalpy and free-energy information by using literature data available (for room temperature) to evaluate the integration constants. High- 5.0 temperature free energies determined in this manner can be used directly in calculations of mineral/solution equilibria. acit y (J - 4.5 8 w \ ^^ ^© 548 K We have constructed an automated, flew c5 JV \ calorimeter to measure the heat capacities of X I l"^L \ u *. \ Tv. \ - single and mixed electrolyte solutions over a Ci l 4.0 CD temperature range of 298 to 673 K and at Q. CO \»\ \ \ pressures from saturation to 50 MPa. The heat capacity is determined by measuring the power 3.5 required to raise the temperature of a fluid ©4 0.5m NaCI ~ by a precisely measured amount. The experi- s^ " > -2m NaCI mental fluid is pumped through 4-mm, •4m NaCI ^*S J corrosion resistant, capillary tubing; the necessary heaters and temperature sensors 0 0.5 1.0 are placed on the outside of the tubing. MolaliiyNa2 S04 Long lengths of tubing are wrapped around FIG. 3.1. Specific heat capacities of mixtures in the temperature controlled blocks to ensure that system. Na2SO4-Na.Cl-H.jO have been superimposed the fluid inside reaches a constant, known by plotting the difference of the heat capacity of temperature before the heat capacity is the mixture and that of the appropriate amount of added NaCl(aq). The properties of the mixtures to introduce samples, and even change the are not predicted by simple addition of the twrect pressure of the fluid inside the tubing, without proportions of the two end members' properties. 34 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Geochemistry and Environmental Chemistry specific heat capacities of NaoSO4(aq) with constants needed in the morld so that they various amounts of added NaCl(aq) have been reflect the new free-energy values yet remain overlaid by subtracting the appropriate internally consistent. Such a recalculation is contribution of NaCl(aq) to the mixture. prohibitive for any but the smallest modeling The divergence of the heat capacities of the projects. mixtures from the curves for pure Na2SO4 shows that the properties of the mixtures are We are in the uncomfortable position of not simply additive. Instead, the C1-SO4 having excellent quality data available to very interaction also must be taken into account high temperatures, yet no really good way to when modeling the mixtures. use it. Our future work in this area will necessarily involve developing appropriate Heat capacity data can be integrated directly estimation methods for determining the much to provide total free energies that can be used needed infinite dilution properties. to calculate mineral/solution equilibria. However, many commonly used computer modeling codes require activities, rather than total free energies, as input parameters. The two quantities are closely related; the activity is a function of the difference between the free energy of the real solution and that of an ideal solution under the same conditions. The calculation of activities is usually done by extrapolating the heat capacity data to infinite dilution and then calculating the excess properties as the difference between the total heat capacities and the infinite dilution value. The excess heat capacities can then be integrated to obtain activity values. Unfortunately, at temperatures above 523 K, the extrapolation to infinite dilution required to calculate activities from the total free energies can not be done from the heat capacity Na2SO^573 K. 20 MPa- data alone. Additional thermodynamic data are needed, such as heat of solution measurements (which are extremely difficult to obtain at high temperatures) or ion-paring constants from L • conductance or spectroscopic studies. In turn, j the interpretation of these results is often CD *"Pi!2er" Extrapolation ambiguous and information on many electrolytes is not available. Figure 3.2 illustrates the difficulties encountered in the 2 x NaCI Value extrapolation to infinite dilution for Na2SO4. The "best guess" value for the infinite dilution "Best guess" from heat heat capacity derived from one heat of solution of Solution datum measurement is very different than other •3.47 Value from Helgeson's "SCPCRT extrapolated values, especially that chosen Data Base in a widely used solution modeling program. 0.? 0.4 0.6 O.B 1.0 The difference in the latter two values, when (molalily)12 integrated, would lead to an order of magnitude difference in an equilibrium constant for a FIG. 3.2. In this comparison of various methods of extrapolating to infinite dilution, the Pitzer reaction involving Na2SO4. extrapolation accounts for possible ion-pair formation only in an indirect manner. The Alternatively, the use of the total free energies extrapolation based on NaCI properties is requires a recalculation of the equilibrium based solely on electrostatic arguments. Isotope and Nuclear Chemistry Division Annual livport F}' 7.W.S' ,V.5 Geochemistry and Environmental Chemistry Geochemical Measurements Across the chromium) was some form of deep-source 'upper Late Cenomanian Extinction Interval: mantle) volcanism; however, numerous Evidence Suggests Widespread eruptions at that time by continental During much of the Cretaceous Period, a shallow sea covered the western interior of North America from what is now the Arctic shore of Alaska to the Gulf of Mexico. Maximum eustatic flooding of our planet during the Cretaceous began just before the C-T boundary and peaked in the Early Turonian. Erosion and tectonic uplift of these marine rock sequences have left many excellent exposures on outcrops and in roadcuts in western North America. Last year we reported the results of our study of the classic C-T exposure just west of Pueblo, Colorado, and gave some preliminary data for other localities in Kansas, Nebraska, and Manitoba. In particular, we discovered two iridium abundance peaks that coincided with foraminiferal and molluscan extinctions in the Latest Cenomanian marine rocks.20 The concentration of iridium is 1000 to 10 000 times larger in meteorites than it is in average Earth crustal rocks, so an iridium concentration spike (anomaly; in sedimentary strata has been used Carbonate - Tree basis to indicate fallout from a large-body impact. FIG. 3.3. Abundances find ratios are shown for Although large-body impacts with Earth could some selected elements across the Cenomanian- have provided the excess iridium we observed, Turonian extinction horizon that is exposed on such a scenario does not account for the excess outcrop at Chispa Summit, south of Van Horn, scandium, titanium, vanadium, and manganese Texas. The extinction of the foraminifer genus that accompany the iridium anomalies. We Rotalipora precisely coincides with the lower iridium peak. Some molluscs and other suggested that a more plausible source of the foraminifers disappear at the upper iridium excess iridium and other elements (especially peak. 36 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Geochemistry and Environmental Chemistry We cannot completely preclude large-body impact sources for the elemental abundance anomalies; however, the abundance patterns and ratios are better compared with those from ocean ridge basalts and mid-ocean tholeiitic lavas. We suspect the anomalies are the result of increased spreading center activity in the Late Cenomanian North Atlantic/Caribbean regions and/or the deep-water opening of the Atlantic (separation of South America from Africa) and the beginning of the North Atlantic gyre (clockwise circulation of the ocean currents). The circulation scenario fits the extinction problem because it would result in upwelling of deep anoxic water onto the outer shelf and continental margin communities that thrived on FIG. 3.4. This map indicates relative deposition of oxygenated water conditions. The depositional iridium. in the Late Cenomanian extinction interval patterns we observed further suggest that the across the western interior of North America. The enhanced elements were deposited in the form of approximate shoreline of the Late Cretaceous (~92 Myr) microscopic particles carried by ocean currents, Epeiric Seaway is shown. rather than by absorption from solution (as ions) on and in clay particles in the local sediments. interfering radioactive nuclides. The results Thus our evidence from the C-T extinction of measurements on a section near Van Horn, interval does not support the cyclic comet swarm West Texas (Chispa Summit section) are shown hypotheses discussed above. in Fig. 3.3. Although we measured abundances over a stratigraphic span of 47 m (equivalent Much more work must be done before firm to ~3 Myr of deposition), only the crucial extinc- conclusions and models can be drawn. Planned tion interval is shown here because abundances work on Deep Sea Drilling Project cores from the of the significant elements are very low and Atlantic and Pacific Oceans and further work on constant in the rest of the section. However, European localities should provide the necessary strong hafnium and thorium peaks, which are clues. associated with ash beds from continental volcanic eruptions, occur throughout the entire 47-m interval. To determine the distribution of iridium in the western interior, we integrated the amounts above background level at each of our 16 measured localities (the pattern is shown in Fig. 3.4). Similar results were obtained for the other enriched elements. The pattern shown in Fig. 3.4 suggests that the excess of iridium (and other elements) might have come from the proto-Caribbean/Atlantic region, so we obtained samples from a deep- water carbonate section in southern England. The results of these measurements from Beachy Head are shown in Fig. 3.5. Once again, two peaks are observed, but at about 10% the intensity found at the strongest North American localities. Recent measurements on a platform carbonate section in southern France failed to FIG. 3.5. Abundances and ratios for some locate the anomalies. Perhaps the sediments selected elements are shown for the Late were eroded by wave action. Cenomanian extinction interval exposed at Beachy Head (near Eastbourne), on the southeast coast of England. Isotope and Nuclear Chemistry Division Ann ual Report FY 1988 37 Geochemistry and Environmental Chemistry Trace-Element Variations in the Fumes days) of intense lava fbuntaining called episodes. of Kilauea and Mauna Loa Volcanos Our first sampling mission to Kilauea was in November 1983 after episode 11. The next two David L. Finnegan, Bruce M. Crowe, and sampling missions were conducted during and Theresa L. Miller after episodes 13 and 15 in January and March of 1984 (Kef. 22). In July and August 1985, Volcanos have long captured the imagination we tried to collect samples during a complete of man. Whether the powerful, pyroclastic eruption cycle. We began sampling several days explosion of a Mt. St. Helens or the fire-fountain after episode 33 and continued until the end of of lava from a Kilauea, volcanic eruptions are episode 35. The sampling was interrupted just fearful and wondrous events. In addition to before and during episode 34 when a hurricane their obvious dramatic and aesthetic fascination, threatened the island. To complete our sampling these massive events pi'ovide opportunities to of Kilauea, we returned in October 1985 to study chemical and physical processes occurring sample during lava fountaining in episode 38. beneath the earth's surface. To further this research, we collected fumes from volcanos Mauna Loa began its first major eruption before, during, and after eruptions to determine in 35 yr by erupting in March 1984. The 2-day the trace metals and acidic gas chemistry of eruption was characterized by low-level lava volcanic fumes and their relationships to fountaining (<50 m). We sampled from 2 days volcanic eruptions. after the eruption began through the end of the eruption and for several days after it ceased.23 Our project has been limited to studies of the Hawaiian volcanos Mauna Loa and Kilauea, Three different types of samples were taken both located on the island of Hawaii. These from Mauna Loa and Kilauea: aircraft, active volcanos were chosen because (1) these volcanos vent, and cooling vent gases. We used a are fairly active and erupt so frequently that we sampling device attached to the wing of the can sample them as necessary, (2) we have plane to collect gases from the plume during convenient access to these volcanos through the fountaining activity. Active vent samples were Hawaiian Volcanic Observatory, and (3) the collected on the ground during lava fountaining basaltic magma of Hawaiian volcanos has a low or spattering. These samples were collected as viscosity, and eruptions usually occur as easily close to the vent as the activity would permit sampled lava fountains (volcanos with viscous (usually <100 m). After the eruption ceased at magmas erupt explosively and dangerously.). Mauna Loa and between episodes at Kilauea, we took cooling vent samples from fumes coming To sample volcanic fumes, we modified the directly off cooling magmas. treated filter pack sampling method used in atmospheric chemistry.21 The sampling system The samples were analyzed by INAA at the consists of a filter pack, a small 12-V DC pump, Los Alamos Omega West reactor. Each filter and a 12-V battery—all connected by flexible underwent a 30-s, 5-min., and 4-h irradiation, tubing. The filter packs contain a series of five and element concentrations were determined filters, one of which is a Teflon particle filter by Ge(Li) detectors from the resulting gamma that collects 0.01-um-diam. particles very activity. Approximately 40 elements were efficiently. The remaining four are all base- determined in each sample. treated filters designed to collect the acidic gases in volcanic fumes. We chose 7LiOH as the base After obtaining elemental data from our because it is strong enough to collect a weak acid samples, we determine whether the acidic gases such as SO2, is available in a relatively pure in the fumes were quantitatively collected. form to keep blank values down, and provides We examine the concentrations of the elements minimal interferences for instrumental neutron from the major gases, sulfur (from SO2), and activation analysis (INAA). chlorine (from HCI), on the treated filters. If they have been quantitatively collected, the Kilauea volcano has been extremely active amounts of sulfer and chlorine will be highest over the past century; its most recent eruption on the first treated filter and progressively began in January 1983 and continues today. lower on the following filters. In general, the The first several years of this eruption we re- filters quantitatively collected acidic compounds characterized by short periods chours to a few of chlorine, fluorine, bromine, arsenic, and 38 Isotope and Nuclear Chemistry Division Annual Kepor/ FY HitiS Geochemistry and Environmental Cliemisiry selenium. Sulfur dioxide was not always quantitatively collected, especially on samples collected for longer than 30 min. 11 /•—•** ACT my 10 Because samples were gathered at various distances from the vent, in fumes of varying S • / ._ 1 density, durir.g periods of differing eruptive rS~~ 7 J • AC"! .'?. ifTJT 'E •/ + AIRCRAFT activity, absolute elemental concentrations in O € the samples are of limited value. Therefore, we 3. use ratios to look at changes in the composition 3 " A : / .„,„.„„ of the volcanic fumes with time and calculate an enrichment factor (EF). The EF is a measure of / QLs'y' An£R ERUPTION an element's fractionation between the fumes 2 1 and the magma relative to a reference element. '/ .J* P03T-CRUPTIOW A fi i 7 and noneruptive activity. By using trace mftals 10 : • • Aaive Ver-:t 1 to distinguish between types of activity, we may «« - , . Cooling Venl be able to predict changes in volcanic activity. s p This is only a preliminary study of two volcanos; 10 Aircraft we plan to sample other basaltic and silicic 10* JZ*4 volcanos to discover if trace metals behave 103 similarly in their fumes. A. i To understand the chemistry of volcanic 10' fumes, we characterized emissions by their elemental composition. Next we will examine 0 V /^ Enriched Metals „ 7 and Voiatiies the speciation of these elements to discover Ash »- why changes in composition occur with eruptive A- C* U; T U V *' ** "F activity. When we know the chemical species being released in the fumes, we can say more FIG. 3.6. Average EF by sample type for samples from Mauna Loa. Elements are ordered by increasing EF about the conditions under which the species for active vent samples. were released. Isotope awl Nuclear Chemistry Division Annual livport FY J9S8 39 AcHnide and Transition Metal Chemistry : Overview Determining the Redox Reactivity of Plutonium(IV> Colloid Synthesis and Properties of a New Class of Synthetically Useful Precursors Molecular Hydrogen Coordination to Transition Metals Actinide and lYatwition Metal Chemistry Actinide and Transition Metal Chemistry • Development of low-temperature routes to Overview known and new solid-state actinide materials from solution or the vapor Alfred P. Sattelberger phase. : Sevei'al INC Division programs in synthetic Recent results from * .aic research inorganic chemistry make important contri- program include (1) structural character- butions to the Laboratory's missions and basic ization of the first thermalty stable uranium research and development programs. Our alkyl complex, U[CH(SiMe3)2]3, (2) synthesis research efforts include actinide coordination and structural characterization of UI3(THF).j— and organometallic chemistry, ligand design, a valuable starting material for further superoxidizer/superacid chemistry, transition explorations of uranium(III) chemistry (see metal-mediated reactions of small molecules, article by Clark and Sattelberger in this molecular hydrogen complexes, and materials section), and (3) preparation and x-ray structure chemistry. of Me3SiNsU[N(SiMe3)2]3F, which is the first uranium(VI) complex with a multiple bond to Actinide chemistry is the cornerstone of a main group element other than oxygen. the overall chemistry effort at Los Alamos and our programs in actinide chemistry provide Actinide separations chemistry is a vital fundamental data on the synthesis, reactivity, component of many INC-, MST-, and CLS- and structure of actinide organometallic and Division operations that support national coordination complexes, ceramics, actinide security and other programs such as plutonium separations chemistry, and the behavior of processing, nuclear weapons diagnostics, special actinides under environmental conditions nuclear materials safeguards technology, and and in nuclear waste isolation and storage. nuclear waste disposal. Major advances in We have state-of-the-art facilities for synthe- separations chemistry require a molecular-level sizing, handling, and characterizing a wide understanding of the way substrates selectively bind to a receptor. The recent National Research variety of actinide systems, including volatile 24 early actinide hexafluorides, aqueous phase Council report identifies six generic research plutonium colloids, and air- and moisture- frontiers where, "focused efforts could lead to sensitive organometallic complexes. much clearer insights into fundamental principles and major opportunities for techno- In the actinide organometallic program, logical innovation." The committee states: our current research focuses on the following areas: "The most important generic research goal is to develop highly selective agents that can discriminate among • Synthesis and characterization of new chemically similar species in a readily classes of early actinide complexes that reversible process. Research relevant contain nonclassical ligands such as to this goal focuses on understanding alkyls, silyls, amides, phosphides, and and generating separating agents with specific chemical, physical, or biological thiolates; interactions at the molecular level." • Investigation of actinide-mediated small The second-highest ranked area emphasizes molecule chemistry, such as the insertion the development of agents to selectively remove of carbon dioxide into actinide-alkyl, solutes from dilute solutions. Our research -amide, and -phosphide bonds; yields fundamental knowledge that is impoitant in both of these areas—especially when the • Synthesis and characterization of solutes of concern are actinide and lanthanide actinide alkoxide and oxo/alkoxide ions. In recent work we have (1) developed cluster compounds that will be useful extraction systems, based on soft donor atoms, models for aqueous-phase actinide that give a remarkable group separation of the oxo/hydroxide complexes relevant to trivalent actinides from the trivalent environmental speciation; lanthanides, (2) synthesized and characterized new multidentate ligands with phosphoryl 42 Isotope and Nuclear Chemistry Division Annual Report FY Actinide and Transition Metal Clutiiishy and N-oxide functionality to bind actinides in the hexafluorides of uranium, neptunium, and high-acid media, (3) devised a template plutonium at temperatures < 25'C No other synthesis for and studied the coordination known practical agents can carry out these properties for a new octadentate Schiff base transformations at appreciable rates at cryptand, and (4) examined macrocyclic temperatures < 300°C! complexes of transition metals and lanthanides as electrochemical fluoride sensors. In another major discovery, we found that superacid media such as SbF5/HF and AsF5/HF We anticipate that Los Alamos will play a are powerful complexing agents for virtually any major role in the multibillion dollar moderni- actinide substrate. Our results have demon- zation and clean-up of nuclear production strated that the ability of superacids to convert facilities throughout the country. Our research actinide substrates that are normally highly provides information that will be needed to intractable, such as high fired oxides, metals, develop improved systems not only for actinide and high-impurity mixed oxides, is unmatched analysis and processing, but also for remedia- by any other known class of compound. tion of environmental actinide contamination. We are designing new ligand systems to enhance Our experience with superoxidizers and separation processes used for recovery and reuse supersolvents leads us to believe that there of waste materials and to provide crucial is tremendous potential for their use in information on actinide-ligand interactions. synthesizing many new actinide compounds The economic advantage of reducing hazardous that have been unattainable because we lacked waste is particularly apparent in the area of proper fluorinating or complexing agents. nuclear materials processing. Because there are Our work with superacid media, particularly many types of actinide-contaminated wastes and in conjunction with superoxidzers, has opened sites in the DOE complex, it will be necessary to up a new area of actinide fluorine chemistry tailor separations chemistry to widely varying that has not only fundamental significance conditions. INC Division will use its diverse but also important technological ramifications. experience and expertise to respond to these challenges. The Division's research in transition metal chemistry has focused on the basic chemistry Another coordination chemistry project in of energy-related small molecules—primarily INC Division is the study of plutonium oxides, SO2 and H2—mediated by transition metal hydroxides, and related compounds in near- complexes. A fundamental understanding neutral aqueous solution as a function of pH, of.the cleavage of S=O and H-H bonds has Eh, ionic strength, and complexing ligand ramifications in SO2 emissions control and concentration. This important information will provide new directions in catalysis. is used to assess the potential for nuclide We have achieved the first example of homo- migration in the environment and to separate geneous catalytic reduction of SO2 to sulfur and heavy actinides. Solubility information may be H2O by hydrogen on the organometallic the determining factor in setting upper limits molybdenum sulfide complex Cp'2Mo2S,|. (Cp = on the concentrations of actinides in natural CsMes), and are investigating the mechanisms groundwater systems. Therefore, it is extremely of this important reaction. In research related to important in designing studies of speciation H2 activation, our discovery of side-on banding effects and radionuclide sorption by geologic media. of H2 molecules to metals represents the first stable o-bond complex and serves as a prototype Much of our basic knowledge of actinide for other c-bond activations, such as C-H bonds chemistry was established through studies in hydrocarbons (see article by Kubas et al. in of actinide fluorine complexes. Recent this section). These complexes may be important breakthroughs in research by INC and MST in catalysis, and we are studying the reactivity Divisions will have significant impact in this of M-H2 complexes toward protonation and area and will stimulate further progress. In isotopic exchange as well as the thermo- part, these advances stem from our observations dynamics and kinetics of H2 reactions. that dioxygen difluoride (FOOF) and krypton difluoride ^KrF2J are capable of generating, from a wide variety of lower valent substrates, Isotope and Nuclear Chemistry Division Annual Report FY WHS 43 Actinide and Transition Metal Chemistry Determining the Redox Reactivity of of redox reactivity research in heterogeneous Plutonium(IV) Colloid media such as colloidal suspensions. Despite the anticipated complexity in the David E. Morris, David E. Hobart, redox reactions of plutonium(IV) colloid, we Thomas W. Newton* and P. D. Palmer expect that the dominant electrochemical pi'ocesses are reduction to a dissolved For many years we have known that aqueous plutonium(III) species and oxidation to a 2+ plutonium(IV) converts to a colloidal species dissolved Pu(VI)O2 species, which may also under appropriate chemical conditions.25 This involve a plutonium(V) species as an plutonium(IV) colloid is particularly important intermediate. Our initial experiments tested in nuclear waste management and environ- these hypotheses. To determine the product of mental contaminant arenas because we expect it the reduction of plutonium(IV) colloid, we chose will be one of the dominant forms of plutonium Zn(Hg) amalgam, with a potential of-0.76 V vs under chemical conditions similar to those found the normal hydrogen electrode (NHE), as a in typical groundwaters. However, despite the reducing agent. We stirred a solution of significance of this species, little is known about plutonium(IV) colloidal suspension in dilute its chemical reactivity or its physical properties. perchloric acid in the presence of excess Zn(Hg) As part of our ongoing programs with the US and monitored the course of the reaction Department of Energy's Yucca Mountain Project spectrophotometrically. We readily identified the and the Office of Basic Energy Sciences, we are product spectrum as that of dissolved aquated investigating the formation and stability of this plutonium(III). This reduction reaction followed species as a function of solution conditions.26"27 simple first-order kinetics with a half-time of Here we discuss preliminary results from our ~40 min. In a related experiment, we used a most recent studies of the chemical reactivity of potentiostatically controlled mercury cathode plutonium(IV) colloid toward oxidation and and monitored the rate of reduction of the reduction processes. colloid as a function of applied potential. In this Information on the redox reactivity of case, we determined that a significant reduction plutonium(IV) colloid (the potentials at which rate occurs even at -0.46 V. The reaction oxidation and reduction occur and the rates and appears to reach a maximum rate at —0.76 V, mechanisms of these processes) is important as which is maintained at more negative we characterize this species. Redox reactions potentials. To determine the product of may represent viable mechanisms of colloid plutonium(IV) colloid oxidation, we studied the degradation that produce dissolved ionic species reaction of a stirred solution of colloid in contact with enhanced environmental mobility. Our with a platinum gauze anode. In this case, we results will also be valuable in defining found no significant colloid oxidation takes place general reactivity patterns for the colloid and until the potential reaches ~+1.6 V. The product of the oxidation was Pu(VI)O22+. We detected no interpreting other chemical kinetic phenomena. + We may be able to use voltammetric redox Pu(V)O2 but cannot exclude its existence as a techniques to study the colloid's physical short-lived intermediate in this reaction because properties; these data would be useful for the time scale of the assay was rather long. corroborating results from other techniques. Several years ago we investigated the Investigations of the electrochemical oxidation of plutonium(IV) colloid by cerium(IV) properties of plutonium(IV) colloid (or any in perchloric acid and found the reaction was quite complicated. A recent report of similar colloidal material) present a keen challenge. 2 The electrochemical behavior of dissolved studies in nitric acid ** prompted us to revisit plutonium in its four readily accessible oxidation these studies. We have now conducted states is well characterized28 and can be experiments in both nitric and perchloric acids interpreted within the framework of existing for several colloid preparations that differ in theories of solution-phase thermodynamics and particle size. The potential of the cerium(IWIII) kinetics. In contrast, very few reports discuss couple is —hi .6 V in nitric acid and —1-1.7 V in the application of electrochemical methods to perchloric acid vs NHE. We monitored the plutonium(IV) colloid studies. Presumably, this oxidation reaction by measuring the spectro- paucity of data can be attributed to complexity photometric absorbance of the product Pu(VI)O22+ peak near 830 nm. The initial colloid *Guest scientist with the Isotope and Nuclear Chemistry oxidation, quite fast in all cases, is faster in Division. 44 Isotope and Nuclear Chemistry Division Annual Report FY1988 Actinide and Transition Metal Chemistry nitric acid than in perchloric acid, and the experiments were done in dilute hydrochloric reaction goes to completion only in nitric acid. acid without stirring, diffusion and migration In perchloric acid, the reaction is quenched after were the only means of delivering the colloid to 30 to 70% of the plutonium(IV) has reacted. This the electrode. We detected no oxidative vai'iation in completion appears to depend on voltammetric activity for plutonium(IV) colloid particle size, acid concentration, and cerium(IV) by either technique. This suggests that the concentration, but we have not yet found any colloid oxidation rate—even at potentials at obvious trends. Figure 4.1 shows representative which water is oxidized—is quite slow. We kinetic data for these experiments. Data for observed reductive voltammetric activity for nitric acid appear to follow theoretical second- plutonium(IV) colloid by both techniques; order kinetic behavior. This is very surprising; potentials ranged from -0.9 to 1.2 V. This it suggests that the rate law is second-order in voltammetric behavior is distinctly different plutoniumdV) colloid concentration because the from the usual behavior exhibited by dissolved oxidant is present in large excess. We cannot species. Figure 4.2 shows a series ofchrono- formulate a simple mechanism that is consistent amperograms as a function of potential. with this finding. Data from experiments in These curves exhibit a current peak at times perchloric acid do not appear to follow any greater than t = 0 instead of the usual t"1/2 simple rate law. Our results are dramatically decay for t>0. We believe this novel behavior different from those of others who found a first- may be attributable to the diffusion of a order dependence on colloid concentration in partially reduced colloid particle back to nitric acid.29 We also note that small particle- the electrode surface for further reduction. size colloid samples react more rapidly than the Our preliminary results for redox reactivity of large-particle size samples in nitric acid. We plutonium(IV) colloid reveal the anticipated hope to unravel these puzzling kinetic phenomena. complexity in reactions for this species. The Our voltammetric studies used two standard potentials at which the colloid is oxidized and techniques: cyclic voltammetry and chrono- reduced are well removed from those for amperometry, both of which provide a much dissolved plutonium(IV) and reflect the stability shorter time-scale interrogation of the redox of the colloidal form of plutonium(IV). Although reactions than the methods discussed above. these potentials are outside the range expected We varied the potential of the indicator under normal environmental conditions, electrode (platinum for oxidation and mercury oxidation state stabilities of dissolved plutonium for reduction) and monitored the current flow, species are strongly influenced by coordination which is proportional to the rate of oxidation or to environmentally ubiquitous complexants reduction of the colloid. Because these (such as carbonate ion), and similar effects may exist for colloidal plutonium(IV). Our research -o ' 0) has merely scratched the surface of this o to challenging problem, and much additional work cr T3 is needed before we can understand this system. \\ 3 v »» v V . *. g 0.5 » \ • 1 V % cr o « V ». 3 0_ c ,g » K o \ X Fr a o0 0.5 1 1.5 2 2.5 3 3.5 Log [Time (min.)J FIG. 4.1. In these Powell plots for the oxidation reaction of cerium(JV) with plutonium(FV) colloid, open circles are data for a small-particle plutoniumdV) colloid sample in dilute nitric acid; filled circles are for a FIG. 4.2. Chronoamperograms for the small-partMe large-particle sample in dilute perchloric acid. The plutoniumdV) colloid in reduced dilute hydrochloric dashed line is the theoretical curve for a first-order acid at a mercury vatho>ie. Potentials for curves I reaction; the solid line is the theoretical curve for a through 4 are -1.20, -.".2o, -1.30, «nrf 1.35 V vs a Ag/AgCl second-order reaction. reference electrode. Isotope and Nuclear Chemistry Division Annual iiepurt FY 19SS 45 Actinidc and 'lYansition Metal Chemistry Syntheses and Properties of Lewis Base It is well established that the stability of Adducts of Uranium Triiodide: A New higher oxidation state transition metal and Class of Synthetically Useful Precursors actinide halides decreases in the order: fluorine > chloi"ine > bromine > iodine. In the David L. Clark and Alfred P. Sattelberger case of uranium, all the tetrahalides are known, but the tetraiodide is thermally unstable and decomposes slowly to uranium triiodide and It is interesting, from an historical perspective, iodine at room temperature. This tendency of that after some 50 years of synthetic actinide iodide ligands to favor the trivalent oxidation research, very little is known about the non- state prompted us to search for a soluble form 30 aqueous chemistry of tzivalent uz'anium. of uranium triiodide. We have discovered a The paucity of molecular uranium(III) series of organic-solvent-soluble Lewis base compounds is undoubtedly due to a lack of adducts of uranium triiodide that are easy to suitable starting materials. The binary uranium prepare; they serve as excellent precursors to trihalides, UX3 (X = fluorine, chlorine, bromine, a variety of new and known trivalent uranium iodine), are polymeric solids that are insoluble compounds. in common organic solvents and quite unreactive. Uranium tetrachloride, UC14, A slight excess of clean uranium turnings dissolved in tetrahydrofuran (THF) can be reacts with freshly sublimed elemental iodine reduced (with sodium amalgam, for example) in THF solution at 0°C to yield royal blue to produce a sparingly soluble material UI3(THF)4 (1) in -70% yield after 24 h formulated as {UC13(THF))X (Ref. 31). [Eq. (3)]. Compound 1 can easily be prepared The exact identity of the latter material is on a 100-g scale! This solution reaction is not unknown, and its utility as a precursor to specific to THF solvent alone. uranium(III) compounds is limited. THF Ten years ago, Andersen reported that U +1.5 I2 > UI3(THF)4 (3) monomeric U[N(SiMe3)2]3 could be synthe- 0°C sized from !UC13(THF)X] and sodium bis(trimethylsilyl)amide [Eq. (1)]. More than A slight excess of oxide-free uranium one product is present in the reaction solution, turnings also reacts with iodine at 0°C in however, and the yield of U[N(SiMe3)2]3 is 1,2-dimethoxyethane (dme) solution to give only about 60%, based on UC14 (Ref. 31). More UI3(dme)2 (2) as a light-purple microcrystalline recently, we have prepared the first examples powder in 80% yield [Eq. (4)]. This reaction is, of trivalent uranium aryloxide complexes from however, slower than the THF reaction and reactions of 2,6-disubstituted phenols (HO-2,6- requires 3 days for completion. In a similar Me2C6H3, for example) with U[N(SiMe3)2]3 manner, with pyridine as solvent, we obtain [Eq. (2)] (Ref. 32). Similar experiments black microcrystalline Ul3(py)4 (3) in 80% yield employing aliphatic alcohols provide a mixture [Eq. (5)] after 2 days of stirring. of uranium(IV) products, which indicates that simple alcoholysis reactions can promote dme oxidation of the uranium(III) center. This U + 1.5 I2 > UI3(dme)2 (4i suggests that the best routes into uranium(III) 0cC chemistry will require reducing conditions and ligand metathesis. Unfortunately, there are no py well-defined soluble uranium trihalide starting U + 1.5L, -> Ul3(py)4 1.0) materials for the metathetical procedures. o°c THF Compounds 1-3 are exceedingly air- and UC13(THF)X + 3NaN(SiMe3)2 moisture-sensitive, and all are soluble in THF. U[N(SiMe3)233 + 3NaCl Adducts 1 and 3 are also slightly soluble in toluene. Only one type of THF or pyridine ligand Hexane is observed in the 1H NMR spectra of 1 and o at U[N(SiMe3)2l3 + 3ArOH room temperature. The infrared spectra of 1 -3 U(OAr)3 + 3HN(SiMe3j2 show absorption bands characteristic of the 46 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Actinide and Transition Metal Chemistry coordinated ligands. For example, infrared provided there is a rapid interconversion of absorption bands at 1011, 853, and 833 cnv1 seven-coordinate structures (pentagonal were observed for 1—indicative of coordinated bipyramid <—> capped trigonal prism, for THF—whereas 3 displayed the expected shift example) on the NMR time scale that time- for the in-plane ring deformation of pyridine averages THF environments. from 604 to 621 cm*1, which is consistent with coordinated pyridine. The UI3(THF)4 reacts cleanly at or below room temperature with sodium or potassium Single crystals of UI3(THF)4 were grown from alkoxides, amides, phosphides, cyclopent- a concentrated THF solution at -40°C, and the adienides, etc., to give high yields of spectro- structure was determined from x-ray diffraction scopically pure trivalent uranium products data collected at 23°C. In the solid state, with concomitant loss of THF-insoluble Nal Ul3(THF)4 exhibits a pentagonal bipyramidal or KI (Fig. 4.4). Some of these compounds— coordination geometry about the uranium atom, U[N(SiMe3)2]3, (C6H5)3U(THF), and as shown in Fig. 4.3. Two iodide ligands occupy U(OAr)3(THF), for example—have been apical coordination sites with an avei*age U-I reported in earlier work but never in the distance of 3.111(2) A; the third iodide ligand yields (essentially quantitative) observed in our lies in the equatorial plane with U-I = 3.167(2) A. laboratory. Others, such as (C5H5)Ul2(THF)3, All four THF ligands lie in the equatorial plane are new and offer exciting opportunities for with an average U-0 distance of 2.52(1) A. The further explorations of uranium(III) chemistry. I-U-I angles between equatorial and axial iodide We anticipate that UI3(THF)4 will be an ligands average 94.25(5)°, forcing the the axial excellent precursor to a host of other iodide ligands to bend away from the equatorial uranium(III) complexes. iodide ligand. The resulting Iax-U-Iax angle is 171.30(5)°. Note that there are two types of THF ligands in the equatorial plane: those proximal to the unique iodide ligand and those distal to it. This result is consistent with the proton NMR (nuclear magnetic resonance) spectrum, FIG. 4.3. This ORTEP drawing of the UI^(THF)^ molecule emphasizes the pentagonal plane. Selected bond distances and angles: U-I(l) = 3.103(2) A; U-K2) = 3.167(2) A; U-I(3) = 3.119(2) A; U-O(l) = 2.48(1) A; U-O(2) = 2.51(1) A; UO(3) = 2.54(1) A; UO(4) = 2.56(1) A; I(l)-U-I(2) = 95.01(5) °; I(1)-V.I(3) = 171.30(5) °; FIG. 4.4. Some reactions ofUI3(THF>4. Abbreviations: O(l)-U-O(4) = 68.9(4)c; O(3)-U-O(4) = 71.4(5)°; Ar = 2,6-R2C6H3; tmeda = Me2NCH3CH2NMeg; dmpe = O(3)-U-O(2) = 70.2(4)°; l(2)-U-Q<2) = 76.1(3)'; Me2PCH2CH2PMe2; Cp = CSH5; Pd = 2,-t-dimetkyl- I(2)-U-O(l) = 73.9(3) °. pentadienyl. Isotope and Nuclear Chemistry Division Annual Report FY 1988 47 Actinidc and 'transition Metal Chanistrv Molecular Hydrogen Coordination to H2 bond energy, and collaboration with Carl Transition Metals Hoff at the University of Miami resulted in the first measurements of this important value. Gregory J. Kubas, Robert R. Ryan, The heat of reaction of H2 with the coordina- G. Rattan, K. Khalsa, and Juergen Eckert' tively unsaturated precursor W(CO)3(PCy;.{)2 to form W(CO)3(PCy3)2(H2) (Cy = cyclohexyl) measured by solution calorimetry, is -10 kcal/mole. The coordination, or binding, of atoms or Because the precursor already had an intra- molecules (ligands) to transition metals is molecularly bound "agostic" C-H from a perhaps the most important chemical reaction cyclohexyl group,3*5 this energy represents to life on earth. Photosynthesis, respiration, and the additional energy of the metal-H2 bond. most catalytic and enzymatic processes would Assuming the tungsten-C-H interaction is at not be possible without the unique bonding least 10 kcal/mole, the heat of reaction of H2 features of the d-orbitals of the transition with the metal center would be ~20 kcal/mole. metals. The dynamic nature of metal-ligand If we compare this result with 30 to 40 kcal/mole binding facilitates chemical transformations for "normal" strong donor or it acceptor ligands that otherwise either would not occur or would such as carbon monoxide, dihydrogen appears be too slow to support life or industrial to be one of the most weakly bonded ligands. processes. Until recently, metals were known Nonetheless, the mtermolecular metal-H2 to coordinate ligands in essentially two ways: o-bond interaction is 10 kcal/mole stronger than (1) interaction of a metal orbital with either a the m^ramolecular C-H c-bond interaction. "lone" electron pair or an empty orbital of one ligand atom (as in iron-oxygen binding in We found the H2 bonding to tungsten is hemoglobin) or (2) interaction with the pi (K) stronger than to molybdenum, which is also a orbitals of groups of ligand atoms such as those Group 6 metal. It is useful to make correlations in ethylene (Fig. 4.5). In the latter case, the within a particular group because the metals double bond of Cr^CHg is side-on bound to the have the same electronic configurations. metal, and the metal "back donates" electrons However, we could not initially synthesize into empty antibonding n orbitals on carbon. analogous H2 complexes of the first row Group 6 metal chromium by the route we Our discovery of side-on coordination of an H2 had used for the molybdenum and tungsten molecule to tungsten complexes (Fig. 4.6) was species. Hoff s modification37 in the precursor startling, therefore, because dihydrogen does did lead to the synthesis of Cr(CO)3(PCy3)2; not have it orbitals or lone pairs available for 33 34 we showed by x-ray crystallography that it binding. - Hence, we have established a new contained the same agostic metal C-H inter- class of stable metal-ligand binding, that of action found for the tungsten complex. This sigma-bond coordination. In this interaction, species did bind H2 but only under high two electrons are shared by three atoms (the metal and two hydrogen atoms), and the bonding is somewhat like that in n coordination: the H2 donates to an empty metal orbital and M - olefin M-H2 the metal back donates to sigma-antibonding orbitals (a*) of H2 (Fig. 4.5). Intramolecular interaction of C-H sigma bonds of ligands already bound to metals through other atoms was already known (as "agostic" binding35), but ; H2 binding is significant because it is strictly >c<;) inter molecular. No one had believed that such bonding could be stable at room temperature. M - K - bond The H2 ligand is reversibly bound; that is, it is M-a - bond not tightly held and freely dissociates if the complex is exposed to vacuum. Therefore, we FIG. 4.5. Bonding models are shown here comparing the were quite interested in determining the metal- interactions between n orbitals of an olefin (for example, ethylene) and metal orbitals to those for U2 -ainter- actions with a metal. Shaded lobes represent electron- P-LANSCE. filled orbifatsandarrotvsdepict 'backdonation." 48 Isotope and Nuclear Chemistry Division Annual Report FY1988 Ar/inido and 'J)-ausitio/i Meial Chvmiairy pressure (300 psi 1%). Thus, we know the both Los Alamos and the Institute Lauc- chromium complex binds H2 even more weakly, Langevin in Grenoble, France. The spectra which is consistent with lower basicity of first- obtained on LANL's Filter Difference row metals (weaker M —» \\~> donation). Spectrometer are similar to vibrational spectra and show torsional (rotational) frequencies The dihydrogen complexes can be viewed at 300 to 400 im"1. Using these data,we found as arrested intermediates in the formation of the calculated rotational barriers for several hydride complexes, which contain atomically different tungsten, molybdenum, and iron bound hydrogen. Our dihydrogen complexes complexes were 1.1 to 2.4 kcal/mole, which is exist in dynamic equilibrium with their generally much smaller than those calculated dihydride forms (-20%) in solution: for metal-olefin rotation. For identical ligand systems, the barrier depends on the metal, W(CO)3(P-;-Pr3)2(H2)« WH2(CO)3(P-/-Pr3)2. implying that the barrier is determined principally by electronic interaction between We have carried out nuclear magnetic metal and H2. These bamers do have steric resonance (NMR) studies of this process and components; that is, nonbonding interactions determined that the thermodynamic parameters of the H2 with other ligand atoms in close AH", AS", and AG° are 2, 3, and 1 kcal/mole, proximity (Fig. 4.6). Molecular mechanics respectively. The activation energy was calculations showed that these interactions are 10 kcal/mole and the first-order rate constant smaller—0.6 to 1.4 kcal/mole for the tungsten was 20 S"1. These values show tha'J there is little complexes. New theoretical calculations on the energy difference between dihydrogen and model complex W(CO)3(PH3)2(H2) show that the dihydride bonding—a surprising finding because electronic component of the barrier should be it has been thought that metal-dihydrogen- ~1.6 kal/mole. If we add the steric component interaction was only an unstable transient along to the latter, we get values close to those from the reaction coordinate towards hydride neutron scattering, which lends experimental formation. support for-metal-to-H2 back donation in the bonding model. Therefore, cr-bond coordination Metal-H2 binding is probably the most is somewhat similar to rc-bond coordination, structurally dynamic metal-ligand system except it is weaker because of the energies of known. In addition to the above equilibrium, the orbitals involved. the bound H2 rapidly exchanges with free H2 and also undergoes isotopic exchange with deuterium to give HD by an as yet undeter- mined mechanism that necessarily must invoke H-H bond cleavage. Because the H2 complex is already coordinatively saturated, it is difficult to envision how the D2 interacts with it to produce HD. The HD formation occurs even in solid-gas phases, and we are planning kinetic and mechanistic studies to determine whether we can obtain evidence for intermediates. Another important dynamic aspect is rapid hindered rotation of the H2 about the metal-H2 axis. We have carried out extensive neutron scattering studies of this phenomenon because by determining the energy barrier to rotation FIG. 4.6. This'ball and stick" model depicts we will obtain direct experimental information the crystallographically determined molecular about the nature of metal-H2 bonding. H d structure of W(CO)^P(isoCsH7)3]2( 2> <** Inelastic neutron scattering is an excellent shows H2 (blue) bound to the tungsten center technique here because the interaction of (yellow). The proximity of the atoms of the neutrons with hydrogen nuclei is very sensitive phosphine group to the H-j is evident father atoms: carbon (black), hydrogen (white), to large-angle motion of hydrogen. Experi- oxygen (red), and phosphorus (yellow-orange)!. mental measurements were carried out at A CO ligand is obscured by the tungsten. Isotope, and Nuclear Chemistry Division Annual liepvrt FY WSti 4{J Materials Chemistry Overview Solution Routes to High-Temperature Ceramic Superconductors Chemistry of Nitroalkanes and Related Molecules at High Pressure Synthesis of New Quasi-One-Dimensional Mixed-Valence Solids Materials Chemistn1 Materials Chemistry Overview spectroscopic methods to probe spociation behind a shock wave. It is only through Basil I. Swanson complementary studies of this type that we can develop an understanding of the chemistry that occurs under shock loading. The lack of suitable materials often limits The article by Agnew et al. in this section provides the implementation of new, more sophisticated an overview of one aspect of our research with approaches designed to address problems in materials under extreme conditions. defense, energy, environment, communications, space, and other technology areas. To overcome In response to the Laboratory's call for these limitations, it has become increasingly enhanced research on the new class of ceramic important to synthesize and characterize high-Tc superconductors (HTS), some INC substances tailored for particular applications. Division scientists have redirected their efforts Chemistry provides an essential component to address problems in characterization and in our fundamental understanding of the synthesis of these materials. One of the relationship between microscopic and macro- important unresolved issues associated with scopic properties—vital information as we ceramic HTS is the control of composition, develop advanced materials with optimal structure, and material homogeneity. Our properties for specific purposes. Division's approach has been to develop solution routes to HTS films and bulk materials; these Materials chemistry research continues to, routes include sol-gel methods that use metal grow rapidly in INC Division as our capabilities alkoxides and the synthesis of precursor in this area become more widely known ands molecules with idealized metal stoichiometries. our knowledge of probems and applications ! Our researchers also have employed diffraction increases. At present, the materials chemistry (x-ray and neutron) methods, optical effort is chiefly in Group INC-4, where scientists spectroscopy, and neutron activation analysis employ their capabilities in novel materials to characterize HTS materials. In particular, synthesis and characterization to study an structural studies have been quite important increasing number of materials problems. • in helping to establish phase stabilities and Materials research activities in other INC to gain a better understanding of the solid state groups are expected to grow as their expertise structures of these materials. The article by in analytical chemistry, process chemistry, Sauer et. al. in this section describes our efforts chemical diagnostics, and isotopes is focused on to investigate HTS materials preparation. problems associated with advanced materials.1 Over the past three years,we have developed For several years we have studied chemistry a research program in novel, electronically and materials behavior under extreme pressure active, low-dimensional materials. This and temperature conditions. One of our highly multidisciplinary effort began with a principal motivations for this type of work collaboration between spectroscopists in Group is the need to develop a microscopic-level INC-4 and theorists in Group T-ll who were understanding of how energetic materials interested in nonlinear materials; it now function. For example, we must understand involves scientists from Groups INC-4, T-12, and control the initiation of detonation of high T-ll, P-10, and MEE-11. The materials of explosives and propellants so that we can use ] immediate interest are quasi-one-dimensional, these energetic materials more safely in a mixed-valence solids for which a competition variety of defense and nondefense applications. between electron-electron forces and electron- A wide range of stimuli, including the impulsive phonon coupling controls the ground and local pressure and temperature rise associated with state properties as well as macroscopic a shock wave can initiate the detonation of properties such as conductance. These complex energetic materials. Group INC-4's program materials present new theoretical challenges centers on the use of diamond anvil cells and a that require a combination of quantum wide variety of optical and structural probes to chemistry, band theory, and many-body study molecular systems at high static pressure modeling to span from isolated metal and temperature. Complementing this effort is complexes—which are the building blocks a joint Group INC-4/M-9 collaboration that uses of these low-dimensional materials—to the 52 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Materials Chemistry extended interactions present in the solid Other areas of growth within materials state. One of the program's objectives is to chemistry include traditional solid state characterize and model these materials as chemistry, materials diagnostics and we chemically tune the competition between characterization, materials processing, and electron-electron forces and electron-phonon investigations of ways to use our traditional coupling to optimize materials properties. strengths in isotope chemistry for materials We hope to develop a theoretical understanding modification. Our materials chemistry programs of charge instabilities in these crystalline low- must begin to combine all these elements into dimensional materials that we can also apply an integrated approach that includes both to many other important solids, including the research and technology development. For new ceramic HTS systems. Another objective example, frontier areas such as the new ceramic is to synthesize new low-dimensional nonlinear HTS require the input of solid state chemistry materials for applications such as microscopic for both materials synthesis and an switches, sensors, and nonlinear optical understanding of structure/function materials. The article by Clark et al. in this relationships that are essential for correlating section presents recent results on the synthesis composition and properties. In this area, of an entirely new class of low-dimensional materials characterization and new efforts in materials that show great potential for tuning materials processing research are emerging as materials properties. important activities for INC Division and the Laboratory. Characterization continues to be an The future of materials chemistry research important aspect of materials research as does in INC Division is exciting as new opportunities INC Division's capability to address materials continue to emerge in novel materials synthesis, problems by using EXAFS, neutron activation modification, and characterization. An analysis, mass spectrometry, ion-microprobe, important frontier in materials science is the diffraction methods, and optical spectroscopy. determination of reaction pathways required to turn individual inorganic, organometallic, The Division's capabilities in the production and organic molecules into new materials that and use of stable and radioisotopes may also we will use to address specific applications. find several applications in materials research. One promising area is the synthesis of precursor Many materials use impurity doping of host molecules for chemical vapor deposition (CVD) lattices or matrices to achieve desired and chemical vapor impregnation (CVI) methods structural, electronic, or optical properties. that will be used to prepare thin film metals and Solid state lasers, for example, rely on descrete ceramics. For example, new precursor molecules states of impurities to achieve population used in CVD processes can lead to applications inversion in gain media. Doping with radioactive such as the preparation of noncorrosive metal isotopes could lead to molecular modification of films for use as coatings for structural ceramics. materials by radiation damage or annealing We will also investigate new routes to ceramic- with concomitant improvement in materials ceramic composites that employ volatile properties. The use of pure materials with precursor infiltration (CVI) into structural selected isotopes also is important, as we have ceramics. These approaches to CVD and CVI shown by employing 12C in diamond films for rely on the synthesis of new molecules with enhanced heat transfer properties and 16O in appropriate physical properties and chemical PuO2 for application as a heat source. stoichiometries that mimic the final product material. We will examine solution routes to We anticipate that the role of chemistry metal-matrix composites and structural in materials research and development will ceramics for conventional defense applications. expand as requirements for new materials and Synthetic studies to create new precursor characterization of materials behavior become molecules must be complemented by studies to more complex. INC Division will participate in determine reaction chemistries that will lead to materials design, synthesis, fabrication, and other advanced materials. Materials processing processing efforts that are directed toward a chemistry also is required to take advanced better understanding and predictive capability materials from the research stage to the for materials behavior in programmatic technology development stage. applications. Isotope arid Nuclear Chemistry Division Annual Report FY 1988 53 Materials Chemistry Solution Routes to High-Temperature After removing the insoluble copper alkoxide Ceramic Superconductors by filtration, we hydrolyze and add yttrium alkoxide to the resultant blue solution; this Nancy N. Sauer, Eduardo Garcia, solution is used for thin film deposition. Kenneth V. Salazar, and Robert R. Ryan Presumably, hydrolysis results in a soluble, condensed copper-barium alkoxide species, A wide range of technical applications require to which we add the yttrium alkoxide. These thin films of the new high-temperature super- precursor solutions have been used to deposit 3 conductor YBa2Cu3O7. Although several YBa2Cu307 on Pt (Ref. 40). methods, such as laser deposition or electron beam evaporation, are available for depositing For film preparation, we spin several coats these ceramic materials as thin films, they of precursor solution onto 0.25-in. SrTiO3 substrates. require specialized equipment or facilities.38 After each set of coats, we heat the films at In contrast, routes based on soluble precursors 250°C for 5 min to decompose the precursor and that can be spun or dipped into films appear remove organic residues before additional coats attractive for a variety of reasons, including low are deposited. To achieve complete coverage of expense, the ability to coat large, unusually the substrate, we apply multiple coats (30 to 50) shaped objects, and increased film homogeneity of the precursor solution. We heat the films and purity. We are exploring two solution- based rapidly to 920°C in argon or nitrogen and hold routes to superconducting films: sol-gel at 920°C in an O2 atmosphere for 15 min to processing and synthesis of molecular precursors convert the deposited material to the 1-2-3 with the desired 1:2:3 metal stoichiometry. phase. A final oxygen anneal (2 h at 420°C) is In the sol-gel process, the controlled solution necessary to convert the insulating tetragonal hydrolysis of metal alkoxide compounds results phase, YBa2Cu3O6, to the orthorhombic in condensation of soluble polymeric species, superconducting phase YBa2Cu3O7. which can then be spun to films or formed into bulk materials. Thermal degradation of the We analyzed films prepared with this method films or formed materials drives off organic by resistivity, powder x-ray diffraction, Ruther- Iigands and produces the desired ceramic ford backscattering (for metal stoichiometry), oxides.39 This method's versatility made it an and nuclear reaction analysis (to determine excellent choice for our investigations of solution carbon residue levels). Four-point-probe resist- routes to YBa2Cu3C>7 thin film preparation. ivity measurements show that the films undergo a superconducting transition at 85 K and have The following paragraphs describe synthetic zero resistance at 65 K Figure 5.1 shows a and mechanistic studies we initiated for this typical plot of resistivity vs temperature for route to thin films of YBa2Cu3O7, the physical films prepared by this method. Both the width characterization of resultant thin films, and our of the superconducting transition (15 K) and the preliminary efforts to adapt this method for small slope of the resistance at temperatures films of bismuth-based superconductors. higher than Tc suggest that the sample may be oxygen deficient, a problem we can alleviate by To prepare precursor solutions for spinning thin increasing the annealing time at 420^. X-ray films, we react a copper dimer, [(acac)Cu(OR)]2, powder diffraction found only small amounts of with barium metal in 2-methoxyethanol in an impurity phases. inert atmosphere drybox. A redistribution reaction occurs in which the acac ligand is transferred to X-ray diffraction also gives us an under- barium, producing (acac)Ba(OR) and forms standing of epitaxy, another key feature of copper alkoxide as an insoluble blue precipitate. superconducting films. Aligning the super- conducting grains on the films substrate greatly enhances the current carrying capacity of the o 2.5 (acac) Cu • 2Ba'«* 2 (acac)Ba (OR) +2 CJ(OR)2 film; thus it is very desirable to have methods that produce a high degree of alignment. 0 Diffraction studies on our films indicate at least 1.5 (acac) Cus ^Cu(acas) 50% alignment of superconducting grains. We 0 have yet to complete studies designed to assess acac- 2,4 pentanedione R^ CH2CH2OCH3 the current carrying capacity of these films. 54 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Materials Chemistry The formation of this Ba2Cu2 cluster from a solution that contains a 2:3 ratio of barium to copper suggests this compound is an inherently stable unit. It may be suitable as a template for building a molecular precursor cluster with the desired 1:2:3 yttrium:barium:copper metal stoichiometry through reactions with yttrium and barium alkoxides. The final segment of work on high- temperature superconductors involves our recent efforts in the area of bismuth alkoxide chemistry. We have just begun to explore this chemistry; if we are able to use bismuth FIG. 5.1. Resistivity vs temperature plot for thin films of YBa Cu O . alkoxides as molecular precursors to 2 3 7 superconducting thin films, we must first Because this is a metal-organic route to the examine the synthesis and structural chemistry superconductor, we also were concerned about of bismuth alkoxides. We will then be able to carbon contamination of the films. Nuclear identify appropriate precursors for a sol-gel reaction analysis, however, found that only route to films of the bismuth superconductors. small amounts of carbon (>0.1 at.%) were present. It is not clear what level of carbon In addition to our studies on bismuth these films will tolerate before film quality alkoxides, we will continue to investigate the deteriorates; therefore, we will investigate mechanism of the solution process. Firing other alkoxides as synthetic precursors to films. conditions will be varied to optimize the super- In general, preliminary diagnostics on these conducting transition as well as to increase the films did not identify any significant problems epitaxial growth of the superconducting grains. with this sol-gel route. We have concluded that The Ba2Cu2 cluster will be used as a starting the low superconducting transition temperature material for cluster expansion reactions. and the broad transition are manifestations of Clusters resulting from these reactions, with the the films' thermal processing: we believe that target YBa2Cu3 stoichiometry, will be used as optimizing the firing conditions will substan- molecular precursor for films. tially improve the quality of these thin films. To achieve a better understanding of the chemistry occurring in this process, we have begun to isolate the intermediates at each stage of this process and characterize them structurally. In the initial reaction of [(acac)Cu(2-methoxyethoxide)]2 and barium metal, we found that slow evaporation of 2-methoxyethanol solutions [obtained after separation of the precipitated Cu(OR)2 (rxn 1)] produced large, dark-blue crystals suitable for x-ray crystal structure analysis. Figure 5.2 shows the molecular structure for the isolated compound Ba2Cu2(acac)4(OR)4»2 HOR, where R = CH2CH2OCH3. The metals are arranged in a diamond shape, in which two triply bridging alkoxide ligands cap each face of the metal plane. Each of these alkoxides is further bound to a barium through the methoxy unit of the FIG. 5.2. Molecular tincture of Ba^Cw methoxymethanol. (OR)4*2 HOR, h RCHCHOH BMtCwt s: 0XygCH and white * carbon. Isotope and Nuclear Chemistry Division Annual Report FY 1988 55 Materials Chemistry Chemistry of Nitroalkanes and Related volume changes. Such reactions are disfavored Molecules at High Pressure at high pressure because the solvent cage must expand around the reactant center as the Stephen F. Agnew, Basil I. Swanson, reaction proceeds. This expansion is like a David Pinnick, Patrick Killough, and piston compressing a gas—it takes work or Douglas Eckhart energy to accomplish the task. That work is the energy the reaction must expand as it proceeds, thereby changing the amount of activation The chemistry that occurs under extreme energy and slowing the reaction down. For pressure (1 to 10 GPa or 10 000 to 100 000 times associative reactions, the converse is true and atmospheric) is of interest to many diverse reactions are accelerated with increasing disciplines, including energetic materials, pressure. Another reaction type involves a geochemistry, planetary physics, and novel negative volume change that creates ions. materials development. Our research in Ionic materials are more dense than molecular materials at high pressure is primarily linked materials; the long-range order of molecules to our need to understand the chemistry surrounding an ion-pair (electrostriction) leads associated with sensitivity and ignition of to -AV for solutions and, therefore, ionic energetic materials. reactions are expected to become strongly favored with increasing pressure. Finally there We use diamond-anvil cells to generate very are concerted bond-making, bond-breaking high pressure (0.1 to 25 GPa) in a very small reactions that do not involve change in volume amount of material (5 to 10 ug). Of course, and should not be pressure-dependent. it is difficult to obtain quantitative information on such a small amount of material, and we We studied the reaction of the NO dimer N2O2 have needed to adapt our various spectroscopic at high pressure and low temperature because it techniques to analysze microscopic quantities. is a model for a simple high-explosive material. The techniques that we have used for the This molecule, a high explosive in the condensed materials described here are infrared absorp- phase, is expected to show reactions that are tion, fluorescence (for the ruby emission used characteristic for the -NO group in the absence as a pressure calibrant), and spontaneous of either hydrogen or carbon. The products of the Raman scattering. reaction of N2O2 under static loading at 2.0 GPa and 160 K are N2O and N2O3. The reaction What Have We Learned about High- proceeds as a solid-solid reaction and is Pressure Chemistry? apparently nondisruptive. The implication is Our studies have included several materials, that an intermediate is formed as including nitric oxide, dinitrogen tetroxide, C= Us nitrosyl chloride, and nitromethane, that have \ the common chemical feature of nitrogen oxide o functionality, which is ubiquitous among energetic materials. By determining the kinds of chemical transformations that occur at high pressure in these nitrogen oxides, we will gain This intermediate results from an associative a better understanding of the chemistry of step (-AV), even though the overall reaction has energetic materials under similar conditions. no change in molecularity. Therefore, with We already know, for example, that reactions increasing pressure, the overall reaction is involving negative volume changes are accelerated, provided the second step releases accelerated with increasing pressure; whereas sufficient energy. Even though this reaction reactions that involve positive volume changes releases about one-half of the thermal energy are disfavored with increasing pressure. It expected from N9O2 —> N2 + O2, the overall follows that statements can be made about the lack of change in molecularity suggests this is effect of pressure on the rates of general classes not the initiation reaction for detonation, but of reactions. Dissociative reactions, on the rather a competing reaction. However, it is one hand, are reactions that directly trade possible that the intermediate is common to intramolecular bonds for intermolecular another reaction branch leading more directly interactions and therefore involve positive to N2 and O2. We are trying to understand the 56 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Materials Chemistry stabilization of this intermediate by studying at slightly lower pressure precludes the actual the reaction of NaO2 in liquid and solid krypton production of HNO, and therefore the solutions at high pressure. mechanism must be concerted bimolecular. We have also studied the decomposition of What general principles have we uncovered nitromethane at moderate temperature. This thus far in our investigations of chemistry at decomposition ma3- produce both COQ and H2O, very high pressure? The expected increasing thereby evolving substantial thermal energy. importance of concerted and intermolecular Nitromethane is another simple high explosive, reactions vs dissociative pathways is very albeit an extremely insensitive one, and has evident, and we have noted differences with been used as a model for insensitive energetic gas phase decomposition mechanisms. At even material. Under low pressure, nitromethane higher pressure, the increased stability of only decomposes at very high temperatures ionic moieties is a further extension of this (250 to 350°C). At high pressure, nitromethane phenomenon because ionic solids have much decomposes at more moderate temperatures higher densities than their molecular counter- (120 to 150°C) to produce three different volatile parts. Thus, in both N2O4 and ONC1 we have products—N2O, CO2, and H2O—as well as a found that only self-ionization chemistry occurs solid residue that has been identified as either at high pressure. For nitromethane, different ammonium formate (NH^HCOO") or kinds of chemistry can and do occur, but an ionic ammonium oxalate. Figure 5.3 shows the channel nevertheless does appear at high relative amounts of volatile products as a pressure and is strongly favored. function of reaction pressure, and we propose the following general reaction scheme. Future Work A better understanding of the chemistry of 1 + H CO + 1/2H O -21.0 kcal A H3C-NO2 —> 1/2N2O 2 2 energetic materials at high density will greatly increase our knowledge of the chemistry that ! B H3C-NO2 —> C02 + NH3 -83.8 kcal 1 occurs in important applications of propulsion c H2CO + NH3 + H20 --> NH4+ + HCOO- HHH2 -12.7 kcal and detonation. Our new knowledge is a direct result of incorporating novel high-pressure D N20 + NH3 —> 3/2 N2 + H2O + 1/2H2 -76.8 kcal devices—diamond-anvil cells—with state-of- the-art instrumentation involving microscopic E N20 + H2CO —> N2 + CO2 + H2 -85.9 kcal analyses from fast-fourier-transform infrared absorption spectrometers, laser Raman The branching reflected by reactions A and B spectrometers, and UV-visible absorption is presumably indicative of a common inter- and laser-induced emission spectrometers. mediate or transition state, which we suggest is By studying the chemistry that occurs under unusual and extreme conditions, we will gain a better understanding of the processes that H2C-N H2C o sometimes dominate these capricious materials. XN/ H This is the 2+2 adduct of formaldehyde and HNO. The HNO dimer fl7 , OH O \ N 0 P 0 ! O I E reacte d II Z 0.4 I I N N 0 O \ § 0.3 OH I 02 is suspected as an intermediate in the well- -5 0.1 known overall reaction that produces N2O and 0.0 water under gas phase and matrix isolated 0 2 4 6 B 10 Pressure (GPa) conditions; we believe it is implicated in the N2O production we also observe with nitromethane FIG. 5.3. Relative amount* of volatile products m* decomposition. The lack of reaction in the liquid a function of reaction pressure. Isotope and Nuclear Chemistry Division Annual Report FY 1988 57 Afaterials Chemistry The Synthesis of New Quasi-One- electronic structure of the constituent bimetallic Dimensional Mixed Valence Solids complexes and the extent of valence deloca!i- Containing Diruthenium zation, we initiated a synthetic program to "fine tune" the electronic properties of one- Tetracarboxylate Subunits dimensional materials through systematic variation in the electronic properties of the David L. Clark, Carol J. Burns, metal and ligand units within a linear chain Alex J. Zozulin, Alfred P. Sattelberger, system. We anticipate that in a mixed-valence and Basil I. Swanson system, the corresponding band gap between occupied (M2+-M2+) and unoccupied (M3+-M3+j For many years chemists have been intrigued re* bands would be significantly smaller than by quasi-one-dimensional mixed-valence solids the a* band gap (because of decreased overlap;; n+ with either alternating mononuclear (ML4 ) therefore, the electronic properties of the rnixed- n+ or binuclear (L4M-ML4 ) metal complexes and valence linear chain material would be altered halide ions (X-) because they exhibit unusual (see the left side of Fig. 5 A). electronic properties Cfor example, see Ref. 41). These materials have recently been recognized In our exploratory program to prepare one- as prototypical, low-dimensional charge-density- dimensional linear chain materials, we used wave (CDW) systems that provide models for Ru2(O2CR)4 complexes as the bimetallic linear charge transfer instabilities in solids such as chain subunit. We expected Ru2(O2CR;4 com- the new class of ceramic high-temperature plexes would be uniquely suited for preparing superconductor. Over the past few years, mixed-valence linear chain materials with a Group LNC-4 has performed extensive spectro- band gap between occupied and unoccupied scopic studies on platinum linear chain bands of it* symmetry like the o* gap in the 44 complexes, including [Pten2][Pten2X2](C104)4 platinum chains. and K4[Pt2(P2O5H2)4X;]nH2O (whereX = Cl or Br). These studies were invaluable as we We prepared Ru2(O2CR)4 complexes by reflux- developed an understanding of ground and ing hydrogen-reduced methanolic "ruthenium local state structures and their relation to blue" solutions with a stoichiometric amount of materials properties in low-dimensional CDW carboxylate anion [Eq. (1)], slightly modifying systems.42-43 Our work is part of a coordinated the procedure described in Ref. 45. By heating experimental and theoretical program to study the bis(methanolatej adduct under vacuum at low-dimensional solids as they are tuned away 80°C [Eq. (2)], we easily removed the axial from the trapped-valence CDW limit and toward methanol ligand. This process allows us to a valence-delocalized structure. prepare nonligated Ru2(O2CR)4 complexes for Our detailed electronic structure calculations 4- performed on [Pt2(P2OgH2)4Cl] model com- ;t* band o*band pounds agree with our previous spectroscopic results- they indicate that the unusual optical SomaMM properties of these mixed-valence bimetallic chains are the result of a low-energy electronic transition, which corresponds to an electron IVCT f transfer between neighboring Pt2+ and Pt3+ IVCT sites along the chain axis.' In the terminology of modern chemical band theory, this represents an optical transition between an occupied metal- •• ••I metal a* band on Pt2+-Pt2+ centers and an unoccupied metal-metal c* band on Pt3+-Pt3+ centers—referred to as an intervalence charge transfer (see the right side of Fig. 5.4). To under- FIG. 5.4. This qualitative drawing shows filled (solid stand the fundamental relationship between the blocks) and empty (shaded blocks) electronic bands of a and it* symmetry in one-dimensional linear chain materials. Corresponding c* and n* band orbitals appear 'Information provided by D. L. Clark, C. M. Boyle, and below each band, and the arrwv between the filled and P. J. Hay, Los Alamos National Laboratory (1989j. empty bands depicts the IVf IT optical transition. 53 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Materials Chemistry a series of R .where R = H, Me, Et, CF3, But, subunits). The expected chain structure of and Ph. The Ru2(O2CR)4 complexes undergo Ru2(O2CR)4L compounds is illustrated reversible one-electron oxidation in solution, qualitatively in Fig. 5.5. and the oxidation potential varies as a function of R. The facile oxidation of Ru2+ to Ru3+ is an important aspect of generating a mixed- Ru2(O2CR)4(THF)2 + PZ -> RU2IO2CR)4(PZJ <3j valence linear chain material that is based on diruthenium units. We now have a convenient Ru2(O2CCF3j4(THF)2 + PHZ -»Ru2(O2CCF3)4'PHZ) <4) method of "fine tuning" the electronic properties The different reactivity observed for pyrazine of new linear chain materials based on the and phenazine bases towards Ru^CC^CR^ Ru2(O2CR)4 core. compounds strongly suggests that using intermediate Lewis bases such as quinoxaline "RuC!2" + 2 NaO2CR -> Ru2(O2CR)4(MeOH)2 + 2 NaCl (1) (QN) and 4,4-bipyridine (BPY) would allow us to isolate single crystals of a variety of Ru2(02CR)4(Me0H)2 -* Ru2(O2CRj4 + 2 MeOH (2) RugtOgCR^L linear chain complexes for spectroscopic and structural study. After To provide a continuous bonding framework the chain assembly, we plan to oxidize the between diruthenium centers, we chose a series material through vapor-phase transport of aromatic bifunctional nitrogen donor ligands doping—a technique used successfully to such as phenazine (PHZj, pyrazine (PZ), dope organic conducting materials. quinoxaline (QN), and 4,4'-bipyridine (BPY), which are illustrated in the lower portion of The complexes discussed above represent Fig. 5.5. These ligands not only possess an the first of a new class of materials that rely aromatic xc system with vacant n* orbitals, but on jc* orbitals to establish the extended overlap are effective in mediating electron-exchange that controls valence-delocalization in low- interactions between metal centers. To prepare dimensional mixed-valence solids. We will be 1:1 pyrazine adducts, we stir, ed one equivalent employing crystal structures and electronic absorption spectra to identify new materials of Ru2(O2CR)4 and pyrazine in methanol or THF solution and isolated the resulting dark that show promise of optimal valence delocali- purple microcrystalline powder by vacuum zation and electronic conduction. We will then filtration [Eq. (3)]. Using this method, we further characterize and use this information to help develop new theoretical models of charge have prepared a series of Ru2(O2CR)4'PZ) compounds, where R = H, Me, Et, CCF , CMe , transfer instabilities in low-dimensional 3 3 materials. and Ph. In the case of pyrazine, Ru2(O2CR)4 compounds are sufficiently Lewis acidic, but the acid-base reaction occurs so rapidly that we have been unable to isolate single crystals suitable for x-ray diffraction analysis, even when we used diffusion techniques. We found phenazine is a significantly weaker Lewis base towards these systems—so weak that only in the case of the very Lewis acidic Ru2(O2CCF3J4 could a 1:1 adduct be prepared [Eq. (4)]. R R This reaction produces purple crystals of R = H, Me, Et, Cf3, CMe3, Ph Ru2(O2CCF3)4(PHZ) when a saturated diethyl ether solution is cooled slowly. N N We have planned a single-crystal x-ray \ 7 diffraction study, and we expect that the molecular structure of the pyrazine and PZ PHZ ON BPY phenazine adducts will be a simple extension of the structure obs.-rved for disubstituted FIG. 5.5. A qualitative drawing represents the molecular structure of new one-dimensional linear chain materials Lewis base adducts Ru2^O2CRj4L2 (as observed of formula RugfOvCIDfiL), where R and L are as listed for linear chains based on dichromium below the chain. Isvtope and Nuclear Clwmislry l)n ision Annual Report FY JUHfi Nuclear Structure and Reaction* Overview Molybdenum-Technetium Solar Neutrino Experiment Using the TOFI Spectrometer to Measure Half-Lives of Exotic Nuclei Fission and Multifragmentation from Niobium Beam/Gold Target Collisions Nuclear Structure and Reactions Nuclear Structure and Reactions heavy ion reactions, which are probing Overview the limiting excitation energy regime of conventional nuclear matter; and studies of Jerry B. Wilhelmy solar neutrino emission through the use of a time-integrating geological probe associated with the inverse beta-decay process of neutrino Nuclear studies continue to be a major aspect capture on molybdenum ore samples to produce of both the applied and research components technetium isotopes. of INC Division. The role of nuclear chemistry (and, for that matter, low-energy nuclear physics Though these articles represent major efforts in general) is rapidly changing. Traditional within INC, they by no means constitute an areas of low-energy studies dealing with exhaustive description of our Division's detailed questions of nuclear structure activities in this field. In low-energy studies, phenomena are being deemphasized; emerging we have continued to develop helium jet is a general attack on the more fundamental transport systems that will produce copious aspects of the nucleus. This trend is evident yelds of isotopes far from stability through in the increasing world-wide emphasis placed spallation and fission reactions at LAMPF; in such areas as relativistic heavy-ion reactions, we have produced targets of229 Th for studies a field in which one goal is that of identifying of fission product dynamics; and we have and studying the thermodynamics of quark studied the systematics of neutron-capture deconfinement. The trend is also evident in gamma rays on separated calcium isotopes the construction of new facilities like the and thereby accurately determined reduced Continuing Electron Beam Accelerator Facility decay probabilities for the important super- and, possibly, the Kaon Accelerator and the allowed transition in 42Sc. In the area of Advanced Hadron Facility to address limiting medium-energy theory, we are studying the questions associated with definitive tests of role played by meson exchange for pion the "Standard" model. There is also increasing annihilation in low-energy double-charge emphasis on expanded electro-weak studies, exchange reactions, and we are continuing especially those relevant to tests of neutrino to investigate the properties of nuclear matter properties and other cosmological issues. containing bound eta mesons. In the heavy-ion reaction field, we have continued Monte-Carlo This is truly an exciting time for nuclear intranuclear cascade studies to simulate our science and one in which INC Division can be a measured reactions, and we have worked to major contributor. Many of the experiments, in understand and improve our large gas-detector an operational sense, require very sophisticated, arrays for both medium-energy reaction studies ultrasensitive analysis techniques. At INC, and possible application to accurate low-energy we are blessed with unsurpassed capabilities fission product determination. In fundamental in ultrapure chemical processing of radioactive physics studies, we have developed the requisite and nonradioactive species, thermal and procedures for the mass spectrographic resonance ion mass spectrometry at determination from molybdenite ores of demonstrated sensitivity levels in the the double-beta decay of 10oMo to 100Ru; 106 atom range, and extensive, automated we are attempting to establish theoretical counting facilities for all types of radioactivity. links between pion double-charge exchange An organization with a traditionally strong and the double-beta decay process; and we multidisciplinary flavor, we are able to use our have joined a collaboration to perform real- broad nuclear capabilities to attack a wide range time physical measurements on all flavor solar of problems, from weapons diagnostics and neutrinos. In support of other programmatic nuclear waste storage to geological impact efforts, we are investigating the enhanced studies. The emphasis of nuclear science within release of stored isomer energy in crystalline INC is also rapidly changing. To provide some materials and have begun a program to study insight into the range of our efforts, this year we nuclear isomer production in laser produced have chosen to highlight three diverse areas: high-thermal environments. TOFI spectrometer studies of the nuclear mass surface for low-Z isotopes far removed from From this description, it is obvious that we are stability; ongoing efforts in medium-energy involved in very diverse efforts in the nuclear 62 Isotope and Nuclear Chemistry Division Annual Report FY1988 Nucloav Structure and Jicwiions science field. To a point, this is a strength and a The INC Division has certainly made natural consequence of the evolving interests of substantial contributions to a wide range the staff. However, we are a small number of of nuclear studies and has served as a focal practitioners, and too much diversity could point of expertise for programmatic result in isolation from overall Division requirements. We believe that the field is interests. Funding is always a concern. rapidly changing and that by taking innovative We have partial direct support from the steps into emerging areas we can continue our Office of High Energy and Nuclear Physics, high-visibility contributions. some support from the internal Institutional Supporting Research and Development program, and some support from the Weapons Supporting Research efforts; we are, to some degree, subsidized by available INC discretionary funding. To help ameliorate both the funding and diversity concerns, we have collectively tri^d to identify and develop new research areas where we can make forefront contributions to science in general and our organization in particular. After considering several alternatives, we felt our organizational operational strengths lay in the areas of ultra- sensitive analysis. This is certainly fortuitous, because many of the most challenging areas of modern nuclear science require such expertise. In a recent major embarcation, we formally joined (with others from Group P-3) the Sudbury Neutrino Observatory collaboration. This second-generation solar neutrino detection facility will provide information on both the flavor and spectra of the neutrino distribution. This study represents a major advance beyond current experiments that determine only the integral yields of electron neutrino fluencies as sampled by inverse beta-decay reactions. Over the next few years, we expect that the TOFI effort will continue to emphasize high- precision measurements in the A ~40 region, and there will be a coupling of spectroscopic capabilities to identify and study beta-delayed particle emission of far off stability species. The technetium solar neutrino experiment is nearing completion and should provide insight into the long-term stability of the solar neutrino spectrum. We will attempt reconfirmation of any extracted number through follow-on experiments of technetium extraction from the Henderson molybdenum ore body. We also hope to increase the level of support that our nuclear science endeavors provide to programmatic efforts. Stimulated emission of isomeric nuclear energy has great scientific and practical importance, and initial steps in that direction—through isomeric implantation in crystalline matrices—should be investigated. Isotope and Nuclear Chemistry Division Annual Report FY 1988 €3 Xuch'ar Structure and Reactio, Molybdenum-Technetium more energetic neutrinos, highly excited states Solar Neutrino Experiment of the daughter nucleus can be produced to allow neutron emission. Neutrinos produced Kurt Wolfsberg, Donald J. Rokop, and by galactic collapses may be energetic enough Norman C. Schroeder to induce significant reactions of the latter type. The first requirement for a geochemical experiment is a suitable parent-daughter The chlorine solar neutrino experiment of Ray 46 pair. Because neutrino capture rates are Davis and co-workers in the Homestake Mine ~10"35 captures/target atom/s, a number of is one of the more famous experiments of recent very stringent conditions must be satisfied. times. Its objective is to measure the flux of The daughter nuclide should be sufficiently high-energy neutrinos produced by thermo- long-lived to integrate over the long time period nuclear reactions in the core of the sun. This of interest. An ultrasensitive detection method task is accomplished by measuring the 36Ar 6 s 37 is essential because only 10 to 10 daughter produced through neutrino capture on C1 in atoms will be assayed. Detection of product a large underground tank of perchloroethylene. atoms would be very difficult in the presence of The result of 2.07 SNU (solar neutrino units) 36 1 1 any stable nuclides of the same element. (For (lO captures s" atom- ), agrees with initial example, a 1-ppt abundance of a different and limits from the Kamiokande II detector but stable isotope of the product element in 1000 kg seriousfy conflicts with the standard solar of target in the above case represents 6 x 1018 model's prediction of 7.9-SNU (Ref. 47). The atoms that must be discriminated against in discrepancy, known as the "solar neutrino measurements of a few million atoms.) Thus, it problem," has prompted numerous theoretical is desirable to chose an element that has no studies and several experiments—proposed, stable isotopes. planned, or in progress—designed to explain production of neutrinos in the sun, their proper- Background effects from other nuclides ties, propagation to the earth, and detection. through natural radioactivities and cosmic radiation must be tolerable. This means that the Explanations for the discrepancy generally ore deposit must be at sufficient depth, uranium focus either on transformation of electron and thorium concentrations must be low, and neutrinos to another type of neutrino (vacuum concentrations of nearby elements that can be or matter-enhanced oscillations) or nonstandard transformed into the nuclides of interest must solar models that reduce the central temper- also be low. The target element and the product ature of the sun and the high-energy (principally nuclide must have remained geologically 8 the B) neutrino flux. Some nonstandard models immobile. We must know the age of the deposit predict periodic mixing of the sun's core with and the product nuclide. It is also necessary to cooler adjacent regions about every 200 Myr; know or infer the cross section for neutrino these events stem from gravity-mode instability capture. Calculations involving Gamow-Teller and result in decreased nuclear reaction rates strength distributions are model-dependent; the for periods of ~3 Myr. It is suggested that such distributions are measured by forward-angle phenomena account for glacial epoches and the (p,n) reaction. Finally, we must be able to 8 48 present-day low B-neutrino flux. Thus, separate submicrogram quantities of the a possible solution to the neutrino problem is element from the ore material: chemical a mixing episode that occurred within the last separation factors of >1020 are required. several million years; this possibility leads to the question of long-term flux. Our molybdenum-technetium solar neutrino experiment, conceived by Cowan and The answer must lie in a long-term history of Haxton,48'49 is the only such geochemical study the sun, and evidence can most likely be found today. In samples of deeply buried molybdenum in the earth's geological record. Neutrinos ore, we will measure technetium isotopes that induce rare nuclear reactions, similar to those are produced by38 Mo(v,e-)98Tc, 97Mo(v,e M97Tc, in the Davis experiment, on all nuclides in the and 98Mo(v,e-n)97Tc reactions. The first reaction earth. For low-to-moderate energies, the has an effective threshold of 1.74 MeV, which reactions are simple inverse beta decays to means that it is effectively sensitive to only8 B ground state or low-lying excited states of the neutrinos from the sun. The second reaction has daughter nucleus; these inactions simply a lower threshold and can be induced by "Be increase the nuclear charge by one unit. For 64 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Nuclear Structure and Heart ions neutrinos as well. The third reaction is sensitive high efficiency and no isobaric molybdenum to both higher energy neutrinos from the sun beams. (One of our filaments is shown in 8 ( B and hep) and high-energy neutrinos from Fig. 6.2.) Molybdenum is produced as the MoO;j" galactic collapses. Haxton and Johnson50 calcu- ion. Isobaric impurities contributed by the lated that, for a rate of 0.09 supernovae per ionization technique are measured at 6 x 105 year, 40% of the 97Tc signal may be caused by atom equivalents of 96Tc, 97Tc, and 99Tc. galactic stellar collapses. The half-lives of 98Tc Measurement limits on pure samples of 98Tc and 97Tc are 4.2 and 2.6 Myr, respectively; the and 97Tc are ~106 atoms. abundances of 98Mo and 97Mo are 24 and 9.6%. We expect ~108 atoms of 98Tc in ~50 tons of the Using the material produced from roasting mineral molybdenite, MoS2, at equilibrium. -10 tons of molybdenite, we chemically purified the technicium and measured 99Tc in the The only deep molybdenite deposit mined sample. We are now attempting to make the commercially is the Henderson ore body, located first measurements of 98Tc and 97Tc. at a depth of 1130 to 1500 m in Red Mountain, Colorado (see Fig. 6.1). The AIvlAX corporation mines this ore, which is -0.5% molybdenite. Fortunately, the uranium concentration in the molybdenite mineral is only '.. .3 ppm, which makes background reactions tolerable for the production of 98Tc and perhaps for 97Tc. Our tasks are to (1) chemically separate technetium from thousands of tons of ore and (2) measure 106 to 108 atoms of 98Tc and 97Tc, by mass spectrometry. The abundance of "Tc, produced by n,y reaction on 98Mo, should be orders of magnitude greater than that of 98Tc. The absolute concentration of 99Tc in molybdenite can be measured on a laboratory sample that is spiked with 97Tc tracer during dissolution. The known concentration of 99Tc is an internal yield monitor as we determine 98Tc and 97Tc. FIG. 6.1. The Henderson ore body is buried 4260 to 5000 m below the turnout of Red Mountain in The AMAX corporation has been extremely Colorado. (Reproduced by permission of helpful in initial chemical separations— Economic Geology.,* a process we could not do with our own resources. We perform the rest of the chemistry at Los Alamos; details are provided in Ref. 51. After a number of chemical purification steps, we produce an essentially massless sample that contains the technetium isotopes. Mass spectro- metric isotopic measurements of technetium are difficult to achieve because thermal ionization requires low-volatility compounds and relatively low ionization potentials. In most forms, techne- tium is very volatile, and its ionization potential, 7.3 eV, is too high to achieve efficient ionization by standard positive thermal ionization pro- cesses. There is an additional complication because the most ubiquitous isobaric impurity is molybdenum, which has similar ionization characteristics and atomic masses. To overcome these difficulties, we developed a negative FIG. 6.2. Chemical processing by the AMAX thermal ionization technique in which TCO4 Corporation and by Los Alamos produces a ions are produced by L^C^ ion enhancers with massless sample that contains th* techneemm isotopes on a rhenium filament. Isotope and Nuclear Chemiatry Division Annual Report FY 1U88 .Xuclcar Structure and Reaction.* Using the TOFI Spectrometer to different atomic number), we determine the Measure the Half-lives of Exotic Nuclei atomic number (Z) of each recoiling ion from its rate of energy loss, dE/dx. In this experiment, we have employed a passive uniform degrader David J. Vieira, Yi-Kyung. Kim, ^ 2 Paul L. Reeder,** Ray A. Warner,** (a stack of six 0.4-mg/cm nitrocellulose foils) Walter K. Hensley,'**Jail M. Wouters, placed at an intermediate focus position in the K. E. Gunther Lobner," Zong-Yuan Zhou,"1 transport line. By combining measurements of and V. Gordon Lind" the ion's velocity before and after the degrader with its mass as determined in TOFI, we can calculate the energy lost in the degrader. We use The oiiginal goal of the Time-of-Flight Isochronous a plot of this calculated energy loss us the (TOFI) spectrometer was to perform systematic average velocity (as shown in Fig. 6.4,), to obtain direct mass measurements for the wide variety the characteristic Z ridge lines indicative of the of neutron-rich nuclei produced at the Los ion's dE/dx. In this way, we determine the Alamos Meson Physics Facility (LAMPF). TOFI 52 53 atomic number of each ion, mass independently; has achieved this goal ' and continues to help Z resolutions range from 1.4 to 2.0% (fwhm). us understand the nuclear mass surface through These results are consistent with the fact that additional mass measurements. This article our measurements are limited by fluctuations in describes developments that allow us to use TOFI the energy loss process.54 as a recoil tagging device to measure the half- life of several p-delayed neutron-emitting nuclei. Because Z identification was performed ahead of the spectrometer itself, we were able to place Figure 6.3 shows the experimental arrangement a large high-efficiency neutron counter, which for this new work. Neutron-rich nuclei are pro- consisted of 40 3He proportional tubes in a duced by a high-intensity (1-mA) SOO-MeV polyethylene moderated housing, around a proton beam when it strikes the 1.0-mg/cm2 nat single silicon detector at the exit of TOFI. This Th target located in the thin target/switchyard detector provides both the stop time for the area of the LAMPF accelerator. Many of these mass-to-charge measurement and the total reaction products recoil out of the target with energy needed to determine the charge state. energies of ~3 MeV/amu and with little angular We use the neutron counter to detect the pi-eference. Some of these recoils are transported subsequent P-delayed neutron emission of to the entrance of the spectrometer by four identified neutron-rich reaction products. quadrupole triplets and a crude mass-to-charge Because P-delayed neutron emission occurs only (M/Q) prefilter. The TOFI spectrometer, which in the most neutron-rich nuclei accessible by consists of four 81 integrated-function dipole TOFI, this decay signature proved valuable in magnets, ii designed to be isochronous—the selecting the exotic species from among the more time-of-flight for an ion passing through the abundant but less neutron-rich species that spectrometer is independent of its velocity and were also implanted in the silicon detector. depends only on the M/Q ratio. Measurements We measure the half-lives of these p-delayed of the ion's energy and velocity uniquely define the charge state. Several additional features of TOFI make this system suitable for studying CP Degrader TOFI exotic reaction products: (1) the transit times / and CPV are short (typically 1 us); (2) the acceptance is reasonably large (Q = 2.5 msr, 8(p/Q)/(p/Q) = 4%); ION and (3) the system is nondispersive overall, which means that all transmitted ions (both vi- ; M/Q unknown and known species) are concentrated Neutron in a small focal spot (20-mm <>). Delecior To discriminate between isobaric members FIG. 6.3. The experimental setup to tag each recoil (that is, nuclei with the same mass number but according to its M, Z, and Q and to measure its half- life by delayed coincidence. CP = secondary-electron, micro-channel plate, fast-timing detectors. Time of "Utah Slate University. Logan, Utah. flight is a measurement of the ion's velocity before the "Pacific Northwest Laboratory, Richland, Washington. degrader (vl), velocity after the degrader (v2), and the 1"University of Munich, Munich, Federal Republic of Germany. mass-to-charge ratio. ttNanjing University, Nanjing, People's Republic of China. 66 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Nuclear Structure and detector, such as neutrons produced directly by the prittiary beam. We use 1:3B, which has a 7_ 6 Z=8 Z=10 Z=12 2.8 negligible delayed neutron emission probability 4 * (Pn = 0.3%), to determine the time-dependent 2.6 - shape of the background. The absolute magni- 'ns ) 11 ^ tude of this background is determined from the 2.4 s 125-s integrated count rate measured tor each j i particular species of interest. We subtract this ocit y (c i t 2.2 1 normalized background point by point to obtain * the net decay curve data from which we are able •1. g e Ve l 1 t I to extract the half-life of the nuclide of interest. 2 2.0 4 > "•. i. S H I During a proof-of-principle experiment, we 1.8 determined the half-lives of 11 nuclei ranging 9 1:l 25 i ! '• \ 1 from > Li to F (Ref. 56). Our measurements 10 30 50 70 agreed well with those reported in the literature in degrader (MeV) for nine nuclei. We are reporting the half-lives of Energy loss 25 21N (T1/2 = 170 (±33) ms) and F (T1/2 = 60 FIG. 6.4. A plot of the calculated energy loss in the 2 2 (±30) ms) here for the first time. When we examine degrader [AE - M(vl -v2 )/2J vs the average velocity the shell model calculations of Wildenthal57 and [vave = (vl+v2)/2] yields the characteristic Z ridge lines indicative of the ion's stopping power. Brown* and the gross theory of (i-decay predictions of Tachibana,58 our results show neutron-emitting nuclei by a delayed that the half-life of 25F was well predicted, but coincidence technique in which both the ion the half-life of 21N is 3 to 4 times longer than arrival times and the delayed neutron times are expected from theory. Further studies of 21N are recorded by a free-running, common clock. needed to explain this discrepancy. Decay curves, such as those in Fig. 6.5, are This work represents the first use of the TOFI obtained by producing time difference histograms spectrometer as a recoil tagging device to between M-, Z-, and Q-gated ion start events facilitate the decay characterization of exotic and all subsequent neutron stop events that nuclei. We have suggested a passive degrader/ 55 occur within 1 s after the ion arrival time.* All velocity difference approach to determine the decay curve data can be decomposed into an expo- atomic number of the recoil and have measured nential decay component and a chance coinci- the half-lives of several P-delayed neutron- dence background component that is slightly emitting nuclei. We are planning other experi- time dependent. This fairly large background ments with TOFI in this mode to measure arises because (1) other delayed neutron emitters additional half-lives and to search for unknown are continuously implanted in the stop detector, isomeric states that could complicate the or (2) neutrons arise from sources outside the extraction of ground-state masses. a) b) c) 10000 100i 100 9Li T(V2)=17l tnms 21N 7(1.21 = 170 JS3i 25F 21 TO tr i 200 400 600 800 0 200 400 600 800 1000 0 200 400 600 800 1000 Time (ms) Time (ms) Time (ms) FIG. 6.5. Time difference histograms for (a) 9U, (b) *'N, and (c) 2SF. Open squares = total counts; filled squares = normalized 'Information received from B. A. Brown, background counts (based on '"%>. Points with error bars = net Michigan State University (December 1988). counts. Solid line = half-life determined from fit to net coMHfx. Isotope and Nuclear Chemistry Dhision Annual Report FY J988 Fission and Multifragmentation from position-sensitive multiwire planes used to Niobium Beam/Gold Target Collisions define the time-of-flight region. The proportional detector gives a linear signal that is dependent Marieluise Begemann-Blaich, on the energy loss of the transversing particle. Thomas Blaich, Malcolm Fowler, Thus each gas detector gives us three signals for and Jerry Wilhelmy* particle identification: the time of flight between the two multiwires, the dE signal from the front proportional region, and an energy signal from Heavy-ion collisions with incident energies the back ion chamber. In a plot of the front-ion between 20 and 200 MeV/A are considered to chamber signal vs the time-of-flight, data are be in a transition region between (1) collisions clearly separable into three generic classes of at low energies, which are dominated by the mean fragments: heavy target-like residues, fission nuclear field of all nucleons, and (2) collisions at fragments, and IMF, in which the separated Z high energies, which are dominated by the inter- lines between Z = 2toZ = 10 can easily be action of individual nucleons. Therefore, this identified. region should be marked by changes in the mechanism for momentum transfer and energy One of our most important projects this year deposition; it may show new decay modes—like was the calibration of the front proportional multifragmentation—and give us insight into chamber. This effort has resulted in an algorithm the defining conditions when a nucleus goes to extract che element number and primordial from a composite, cooperative, collective body fragment velocity of all detected particles. Our to a mere spatially correlated ensemble of first plan was to calculate the energy loss in individual nucleons. We can obtain information different parts of the detector and the time of about such an excited system from the relative flight by using the DONNA or ZIEGLER dE/dx probabilities for fission and particle evaporation computer codes. To compare these calculations and from the production probability for particles with experimental data, we used the Los Alamos with element number Z between 2 and 15—the Ion Beam Facility to scatter a variety of heavy so called intermediate-mass fragments (IMF). ion beams (from carbon up to iodine) at energies To investigate in detail, we studied, with high geometrical detection efficiency, the reaction products formed in the collision between 50-, 75-, and 100-MeV/A niobium beams and gold targets. Scale (in.) 0 5 10 1520 Using the "Pagoda" detector system,59 we performed the experiment at the low-energy beam line of the Lawrence Berkeley Laboratory BeValac accelerator. The system consists of an eight-fold array of gas detectors, which are backed by 54 fast-slow plastic phoswhich scintillators, and has, at forward angles, a 34-element hodoscope (Fig. 6.6a). This combi- nation of detectors has a wide dynamic range response—it allows us to detect particles ranging from 200-MeV protons to slowly moving target residues. In earlier work we showed that the relative production probability for IMF is rather high, but at that time, our experimental setup was not optimized to study this mass region.60 We have since improved our gas Pressure detectors by adding a low-pressure dE Proptoponwnai A E-E Ptiosmctl proportional counter between the two existing Telescope Array MtVPC lonza'ton IBctTtKiecm) Chamber *In a consortium with staff members from Lawrence Livermore National Laboratory, Lawrence Berkeley FIG. 6.6. (a) Ibp schematic view of the "Pagoda"detector Laboratory* Argonne National Laboratory, and the system; (b) side representation of one of the eight detector Weizmann Institute, Israel. array elements. 68 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Nuclear Structure and Reactions between 0.5 and 5 MeV/A on different targets chamber and/or the phoswhich detectors, we (from titanium up to gold). At these energies, should be able to identify the fast particles, the scattering process is Rutherford, and which represent a significant portion of therefore we obtained energy and time-of-flight total fragment yield. For heavier nuclei, we calibrations for both the beam particles and the distinguish only between fission fragments and target recoils. Comparisons with the energy loss residues, but we have velocity information calculations showed a large discrepancy—which over a very wide range from 0.02 to 2.0 MeV/A. is not understood—for both dE/dx codes used in our analysis. The detector response for two We tested the new algorithm by analyzing different particles depositing the same amount fission fragments from a 252Cf calibration of energy is not independent of the element source and were able to accurately reproduce number, and this means we must use an ion- the known mean values for both Z and velocity dependent calibration procedure. We have distributions. We applied this method to the been able to couple these extensive empirical experimental data to extract Z and velocity calibration measurements and the easily distributions for fragments produced in the identified Z lines in the niobium/gold run to 50-, 75-, and 100- MeV/A niobium/gold collisions. produce an algorithm that extracts the physical We have concentrated on the low-energy portion quantities Z and velocity from the measured of the fragment distribution; that is, on incident time of flight and energy-loss signals indepen- energies smaller than 2.7 MeV/A. The Z distri- dent of any theoretical dE/dx code (Fig. 6.7). bution of all detected single events as a function of the beam energy is shown in Fig. 6.8. For all The Z identification is possible for particles three energies, the production probability for with incident energies between 0.5 and 2.7 MeV/A IMF, compared with the production probability and for Z smaller than 48. For light particles for fission or fission-like fragments, is fairly high with incident energies higher than 2.7 MeV/A, and increases with increasing beam energy. In the resolution of the front-ion chamber is not, by the next step, we will study the coincidence of a itself, sufficient to extract the element number gas detector module with any other detector. from these signals. However, by combining these Because our geometric coverage is reasonably data with information from the back-ion high, we have a large yield of correlated events and expect that studies of the emission correlations will provide both new insight into the IMF production mechanism and information on the multifragmentation process. _. its ) 10000 —* rar y u n I '""I-' (arbi t N •a 1000 400 0 10 20 30 40 Z FIG. 6.7. Two-dimensional correlated data between the fragment time of flight and the signal FIG.6.8. Observed yields of element* for the three amplitude in the front proportional region. experimental energies studied: SO (solid line), 75 (dmshed HR = heavy-element target-like residues; FF = line), and 100 (dotted line) MeV/A niobimm projectiles. The fission fragments; and IMF = intermediate-mass data have been normalized in the fission product region fragments. Signal intensity increases from blue to and show a relative enhancement of IMF «ur the remction green to yellow to red data points, as shown here. energy is increased. Isotope and Xuctsar Chemistry Division Annual Report FY 1988 €9 Division Facilities and Laboratories Division Facilities and Laboratories Omega West Reactor ICON Facility Facilities and Laboratories INC-Division Facilities and Laboratories nuclides. These detector systems include alpha, beta, gamma-ray, x-ray, and fission detectors as Merle E. Bunker well as a computer-based data acquisition system and software for the collection and analysis of the resulting data. We are currently In addition to the Omega West Reactor and involved in an extensive upgrade and the ICONS Facility, which are described in the automation effort to increase the overall articles immediately following, INC Division is reliability of the various detector systems. pro i ofthese state-of-the-art laboratories and We are also conducting research on background facilities. reduction, gas-filled proportional counter improvements, and new detector systems. Advanced Radiochemical Weapons Diagnostics Facility Medical Radioisotope Production Facility This facility, which occupies a new 10 000-ft2 at LAMPF and Hot Cells at Technical building, was designed to minimize limitations Area 48 that environmental factors impose on the The Medical Radioisotopes Research section of accuracy, precision, and sensitivity of isotope Group INC-11 operates the Isotope Production ratio measurements used in weapons test Facility at the Los Alamos Meson Physics Facility diagnostics. The facility includes 11 chemistry (LAMPF), where up to 9 targets are simultan- and 7 instrument laboratories that are designed eously irradiated in one of the most intense and operated to provide a particulate-free accelerator beams in the world (800 MeV, environment in which to prepare samples and 1.1 mA). These targets are highly radioactive measure isotope ratios by mass spectrometry. (>100 000 Rem) when removed from the LAMPF The clean laboratories are constructed of beam and therefore are processed in the particulate-free, corrosion-resistant materials. extensive hot cell facilitiesat Technical Area 48. Critical work spaces are bathed in class-100 The latter facilities consist of 13 cells, each with filtered air, and the air flow is designed to 18-in. lead glass windows and high-density minimize cross contamination between work concrete walls for shielding. These facilities areas. The instrument labs are shielded from make it possible for the program to serve as a external electrical interferences, and the national resource for radioisotopes that are used instruments themselves are powered by isolated in nuclear medicine and biomedical research. Of motor generators. The building currently houses the more than 30 radioisotopes in current use by four single-stage, one double-stage, and one the medical profession, -15 are produced only triple-stage thermal-ionization mass here at Los Alamos. spectrometers. Another section of the facility contains a laboratory for measuring isotope Single-Crystal X-Ray Diffraction Facility ratios in noble gases. In a separate building, Group INC-4 maintains and operates a single- we also have in operation two large 1.5-m radius crystal x-raj' diffraction capability that is unique magnetic-sector isotope separators: one of 55° = within the Laboratory. The facility currently and one of 90 . These separators can be operated consists of three automated single-crystal at beam currents up to 50 mA. An additional diffractometers with the capability of data 126°, 1.46-m radius instrument is under collection at temperatures between -160 and construction. 1000°C. Data collection capabilities at high pressures (to 300 kbar) are also available. In addition to work associated with nuclear A variety of structure solution packages are weapons tests, the above laboratories are maintained, including the LANL system used for experiments in solar physics, the TEXRAY and another package developed at geosciences, biology, and atmospheric science. the University of California, Los Angeles. Both precession and Weissenberg cameras Counting Room Laboratory are used. An effort has been made to develop The Data Acquisition Section of Group INC-11 a facility that is user friendly to knowledgeable maintains a large counting laboratory that but nonexpert structural chemists. Current contains a wide variety of calibrated detector output is 50 to 60 crystal structures/yr; systems for quantitatively determining the maximum capability is -150. We provide absolute abundance of selected radioactive support for basic and appjicd research programs 72 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Facilities and Laboratories in the areas of high explosives, small-molecule Division-Wide Computer Networks activation, actinide and fluorine chemistry, and Group INC-11 sponsors a Division-wide several other molecular design projects. computing system in the open environment and a smaller secure network for classified Condensed Matter Spectroscopy Facility computations, data base management, and Group INC-4 operates and maintains an document preparation and control. extensive optical spectroscopy facility in open The extensive open system is a distributed laboratories at Technical Area 21. The processor on the Laboratory Integrated instrumentation includes several spectro- Computer Network (ICN) and permits meters for spontaneous and resonance authorized users to access more than 500 Raman scattering, FT-Raman studies, infrared other nodes on the ICN as well as all major absorption, electronic absorption and emission open computing facilities at LANL's Central measurements, photoaccoustic spectroscopy, and Computer Facility. The most recent addition transient Raman and electronic absorption to our system, a VAX 8700 computer, networks spectroscopy on the nanosecond time scale. most of the Division's computing resources Specialized equipment is also available for into a cluster named MAGIC. This cluster now variable temperature (4 to 600 K) and pressure allows user access from nearly 200 terminals to (0 to 30.0 GPa), ultraviolet and near-IR 5 VAX computers of various sizes, a disk cluster resonance Raman, and ultrahigh resolution totaling 10.8 gigabytes of memory for program FTIR studies. The facility supports basic and and data storage, and 10 laser printers. applied research programs in energetic In FY 1989, most of MAGIC's components materials, photophysics and photodynamics, will be consolidated in one location in Building materials research, bioinorganic chemistry, RC-1 at Technical Area 48; the secure system geochemistry, and environmental chemistry. will be relocated to the vault in the new RC-1 The condensed matter spectroscopy facility is Data Wing addition. currently used by scientists throughout the Laboratory and at several universities. Time-of-Flight Isochronous (TOFI) Spectrometer Classified Radiochemistry Document The TOFI spectrometer and its associated Repository transport line is a facility designed to measure The Division's 40-yr accumulation of classified the masses of energetic, recoiling nuclear documents is held in a repository maintained reaction products. The TOFI facility is sited by Group INC-11. The current estimate of at the Los Alamos Meson Physics Facility accountable items is in excess of 50 000. (LAMPF) to take advantage of the high yields In FY 1989, these documents will be moved of exotic light nuclei that are produced in to a newly constructed 1200-ft2 vault at interactions of the intense 800-MeV proton Technical Area 48 that will house a high- beam with heavy- and medium-mass targets. density mobile storage system with nearly From measurements of the recoil's transit time 450 linear feet of storage shelves, a computer through the spectrometer, we can make direct room for the Group INC-11 classified VAX mass measurements with precisions of 100 to 11/780 (INCDP2) computer system, two 1000 keV—depending on production rates. workrooms, and an office area for the document To date, we have measured the masses of 28 custodian. To track the 50 000 documents, the neutron-rich nuclei that range from uLi to 37P. -100 monthly send/receive transactions, and the Recent improvements in the detection system thousands of other document control actions, have also allowed us to use TOFI as a fast-recoil we maintain a bar-code enhanced DATATRIEVE tagging device that facilitates the gross decay- VAX/VMS data base on the INCDP2 system. property characterization for many of these This vault facility is the LANL historic resource exotic species. for all weapons radiochemical diagnostics data and associated test performance evaluations. Isotope and Nuclear Chemistry Division Annual Report FY 1S88 73 Facilities and Laboratories Omega West Reactor experiments, and neutron-activation trace- element assay measurements. Data on experi- Terry W. Smith, Gerald F. Ramsey, ments other than irradiations performed at the Michael M. Minor, Sammy R. Garcia, OWR during FY 1988 are shown in Table 7.1. Keith H. Abel, and Merle E. Bunker The total number of experiment hours (3649) exceeds by a factor of 2 the average value recorded over the 5 previous years. This large The Omega West Reactor (OWR), operated by increase resulted mainly from expansion of Group INC-5, is the only research reactor at Los work on thermal cross sections by the Subatomic Alamos. Its main purpose is to provide Los and Research Applications Group (P-3), studies Alamos experimenters and scientists from other of tritium storage devices by the Weapon laboratories with an intense steady-state flux of Subsystems Group (WX-5), capture gamma- thermal and epithermal neutrons. The reactor is ray measurements by the Research Reactor normally operated at a thermal power level of Group (INC-5), and high-level gamma-ray 8 MW, 7,5 h per day, 5 days per week. At 8 MW, 13 irradiation of explosives for the Explosives the thermal-neutron flux in the core is 9 x 10 Technology Group (M-l). A large fraction of neutrons/cm2-s, and the "fast" flux (> 0.1 MeV) 13 2 the experimental work done at the OWR is is 5.6 x 10 neutrons/cm s. Extending away in support of the weapons program. from the core is a 5 by 5 by 7.5-ft graphite region (see Fig. 7.1), known as a thermal The largest single use of the reactor is for column, which slows the fast fission neutrons neutron irradiation of materials, which is from the core to thermal energies. Most sample usually done to induce radioactivity in the irradiations are carried out in this thermal samples but, in some cases, is done to cause column. Numerous beam tubes, pneumatic physical changes in the materials. In the latter rabbit systems, and removable graphite category, recent examples include fast-neutron "stringers" provide access to the OWR's irradiations of both low- and high-temperature neutron flux and allow several experiments superconductors by the Physical Metallurgy and irradiations to proceed simultaneously. Group (MST-5) to determine the effect such bombardment has on the conduction properties The reactor facilities are used for a wide of these materials. During FY 1988,20 LANL variety of research activities, including groups and 14 outside laboratories irradiated radioisotope production, neutron-diffraction materials at the OWR, for a total of 13 838 and neutron-transmission experiments, in-core samples. This value is typical of the annual irradiation of instrumented devices, neutron number of OWR irradiations over the past radiography of assemblies, neutron-capture 8 yr. As a designated DOE User Facility, the prompt-gamma-ray studies, neutron cross- OWR is available to non-DOE organizations section measurements, radiation damage such as universities. Harvard University, Brigham Young University, University of New Mexico, University of Alaska, and the 6" Through 12" Square Ports Ports University of Washington have all made use 6" Beam Ports of the reactor facilities in the past year. with Shutten Roughly two-thirds of the above samples are submitted to OWR personnel for neutron activation analysis (NAA), which is a highly 6" Beam sensitive and accurate method of assaying Ports bulk materials nondestructively for trace levels of a large number of elements. The main NAA method used at the OWR involves irradiation of the sample material with slow neutrons, followed by high-resolution detection of the Heavy Concrete, Shield gamma rays emitted from the sample by radioactive isotopes formed through capture of neutrons by the sample elements. The FIG. 7.1. Horizontal cross section of the OWR. individual gamma rays can be uniquely 74 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Facilities and Laboratories identified with specific elements, and the A formal proposal to replace the 32-yr-old intensity of each gamma ray gives a direct OWR with a new facility by the mid 1990s has measure of the element abundance. been submitted to senior management for their Approximately 50 elements can be observed consideration. The suggested plan is to operate by this method (some at the part-per-billion the OWR until the new reactor is operational level) by recording spectra at 20 min, 3 days, so that experimenters will experience no and 3 weeks after irradiation. interruption in their local access to an intense neutron flux. The proposal recommends that the The automated NAA facilities at the OWR new reactor be designed and built by an external are reputed to be the best in the US. A wide contractor as a turnkey facility, have a thermal variety of sample types was assayed in FY 1988, power of ~10 MW, and be inherently safe. Its including human urine, soil, water, oils (for PCB experimental capabilities would be at least as content), biological samples, air filters, lunar extensive as those now available at the OWR. and meteoric materials, geologic materials, The replacement reactor would likely be sited organic foams, plastics, superconductors, and near Technical Area 48 rather than Los Alamos "pure" metals and chemicals such as beryllium, canyon, partly because of lack of space in the palladium, and boron carbide. During the year, canyon and partly to place the reactor closer to we developed a successful method of assaying the major users. for silicon in geologic and biologic materials; the method involves fast neutron irradiation of the samples in a newly installed, boron-shielded epithermal-neutron facility, which makes silicon detectable through the 29Si(n,p)29Al reaction. Table 1. Experiments Performed at the OWR in FY 1988 fapmimt Organization Experiment Hour* Los Alamos National Laboratory P-3 (n,p) and (n,a) cross-section measurements 1021 P-8 Position-sensitive neutron detector tests 5 P-15 Filtered beam resonance capture studies 239 ESS-11 Neutron radiography 2 WX-3 Neutron radiography 23 WX-5 Retention of 3He in tritides 506 WX-5 Neutron diffraction studies 265 MST-3 Neutron diffraction studies 19 INC-5 Development tests of new (n,y) facility 44 INC-5/P-DO Neutron capture gamma-ray measurements 711 INC-7 Neutron capture gamma-ray measurements 97 M-1 Radiation damage to explosives 375 N-1 Spent fuel element measurements 126 Battelle Northwest Radiation damage to CTR-type metals 214 TOTAL Isotope and Nuclear Chemistry Division Annual Report FY 1988 75 Facilities and Laboratories The ICON Facility The repaired first-stage column will be restarted early in FY 1989. For FY 1989, Lee F. Brown, John R. FitzPatrick, we have scheduled lower production rates Thomas R. Mills, Charles A. Lehman, because of a decrease in demand. As soon as Michael G. Garcia, Troy A. Nothwang, the principal first-stage column is restarted, Glenda E. Oakley, Robert £. Baran, the three smaller first-stage columns will be Kathryn D. Elsberry, Shirley R. Roybal, shut down and put on standby. Hong Bach, B. B. Mclnteer, and Joe G. Montoya Process Improvement Production of 17O this year barely met demand, and need for 17O could increase in The function of the ICON facility located at coming years. Consequently, we are developing TA-46 is to isolate large quantities of individual plans to incorporate an unused column into isotopes of certain light elements, such as the NO distillation process to separate the carbon, oxygen, and nitrogen (hence, the 1 kg/yr of 17O that is fed to the system but facility name). The separations are carried out not recovered. We will implement these plans by cryogenic distillation in vertical distillation when need for additional 17O is apparent. columns, some of which are more than 200 ft long. The separated isotopes, or compounds This year we made system changes to containing these isotopes, are used in research improve the facility's safety and impact on the activities at Los Alamos and at many other environment. An acid storage and containment institutions. For example, separated nitrogen system was constructed for fresh acid feeding isotopes are widely used as tracer materials in and storage of waste acids, vent systems were field studies of the nitrogen cycle in agricultural improved for better plant air quality, and a research. The isotopic materials are sold at cost liquid-nitrogen vent system was changed so to Los Alamos investigators or are available to that ground fog would not develop in the area the general research community through EG&G around the building. Mound. New Processes for Stable Isotope During FY1988, the ICON program's Separation objectives included production of stable isotopes Positron-emission tomography's use of of nitrogen, oxygen, and neon; improving the 18O water may exceed presen* international processes for separating these isotopes; production capability in the mid-1990s. developing new processes for separating stable Therefore, we have developed plans to isotopes; and providing chemical support to the convert our CO distillation complex to handle separation processes. O2 distillation. When it is necessary, we will be able to implement these plans and increase Stable Isotopes Production the ICON Facility's 18O separation. We obtain nitrogen and oxygen isotopes by cryogenic distillation of nitric oxide and produce This year we built a new experimental still a neon isotope by cryogenic distillation of neon. to explore the possibility of separating stable Table 7.2 shows our production for FY 1988. isotopes of other light elements by distillation. The column complex for distilling CO to obtain 13 12 The new column, 1.5 m long by 1.4-cm i.d., CO and CO was on cold standby this year is filled with wire helix packing (Heli-Pak) and because US requirements for stable carbon is temperature controlled by thermal balance isotopes could be met from other sources. between a helium cryogenic refrigerator and 15 18 column heaters. Preflooding the column The amounts of N and O produced were improves the separation factors markedly. less than our 9-kg/yr capacity for each. When a We distilled CO, which has known separation hole developed near the bottom of the principal factors, to determine how many stages are first-stage nitric-oxide distillation column in needed in the column. By measuring the early July, we shut down the 200-ft first-stage i2CA3C separation, we concluded 75 plates are column for removal and repair. adequate for CO distillation. 76 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Facilities and Laboratories We successfully used this column to separate silicon, sulfur, and chlorine isotopes through distillation of SiF4, SF4, COS, HCi, and CI2. The observed separation factors in SiF4 and SF4 are sufficient to indicate that these compounds can be employed to produce silicon and sulfur isotopes. From previous work, we know that H2S is an alternative to SF4 for sulfur separation. The chlorine separation factor of 1.0010 to 1.0012 we obtained with HC2 is large enough to show that we can use HC7 distillation to enrich chlorine isotopes. Chemistry Support The chemistry subsection of the ICON Facility conducts chemistry research to support the processing and conversion of isotopically enriched nitric oxide. Among other efforts, we have developed a program to reconcile results from direct mass spectrometric analysis of NO with those obtained when NO is "sparked" or placed in an RF discharge and converted to N2 and O2. "Sparking" is used where mercury is employed to reduce a nitrate salt or nitric acid to NO. In such situations, the oxygen is typically of natural isotopic abundance, and the nitrogen isotopic distribution is determined from the m/z peaks of 28, 29, and 30. We are developing a small-sample electrolysis apparatus that will convert labeled water samples to oxygen. Using sodium bromide or potassium bromide as a source of ions does not appear as successful as using a sodium amalgam. Our goal is to find a reliable method to back up the CO2 exchange method we currently use for oxygen isotopic analysis. Table 7.2. Stable Isotope Production by the ICON FaciUty During FY 1988 Quantity Produced EnrichaMttt Isotope («*> (%) 15N 2.12 10+ 15N 1.08 60-85 15N 2.82 96+ 16O 205.8 99.96+ 170 0.083 20-35 170 0.257 36-50 ISO 3.10 10+ ISO 3.88 95+ 2.78 90+ Isotope and Nuclear Chemistry Division Anhual Report FY 1988 77 TDTE Appendix: Personnel List of Division Personnel by Group INC-DO (667-4457) Michael G. Garcia Buildings RC-29 and 34, TA-48 John L. Hanners Judith C. Hutson Gordon D. Jarvenin * Donald W. Barr Scott Kinkead Division Leader Richard J. Kissane * Alexander J. Gancarz, Jr. Gregory J. Kubas Deputy Division Leader Laboratory Fellow Jiri Kubicek * Bruce R. Erdal Judith A. Landaiche Technical Coordinator Charles A. Lehman, Jr. * Eugene J. Peterson Michael W. Mather Technical Coordinator Raymond C. Medina * Basil I. Swanson Thomas R. Mills Technical Coordinator Cleo M. Naranjo Barbara J. Anderson Troy A. Nothwang Joann W. Brown Glenda E. Oakley Audrey L. Giger Valerie D. Ortiz Janey Headstream John D. Purson Jody H. Heiken Shirley R. Roybal S. Kathleen Kelly Kenneth V. Salazar Alfred P. Sattelberger Section Leader INC-4 (667-6045) Penelope A. Springer Buildings 3 and 150, TA-21; Clifford J. Unkefer Building 88, TA-46 Pat J. Unkefer William E. Wageman * Robert R. Ryan William H. Woodruff Group Leader Tatsuro Yoshida * Phillip G. Eller Deputy Group Leader * Stephen F. Agnew INC-5 (667-4151) f Robert E. Baran Omega Site, TA-2 * James R. Brainard * Lee F. Brown * Merle E. Bunker Section Leader Group Leader * Stephen D. Conrad son * Michael M. Minor Douglas G. Eckhart Deborah S. Ehler Deputy Group Leader Scott A. Ekberg f Glen E. Barber * Phillip G. Eller * Michael M. Denton Section Leader * Sammy R. Garcia Kathryn D. Elsberry Michael D. Kaufman * James A. Fee Janet S. Newlin Section Leader * Gerald F. Ramsey Marielle Fenstermacher Thomas C. Robinson * John R. FitzPatrick Cathy Schuch * Terry W. Smith Staff Member. Section Leader No longer working in INC Division. * John W. Starner SO Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appendix: Person nel INC-7 (667-4498) INC-U (667-4546) Radiochemistry Building, TA-48 Radiochemistry Building, TA-48; LAMPF Building, TA-53 * David B. Curtis Group Leader * William R. Daniels * Robert W. Charles Group Leader Deputy Group Leader * Genevieve F. Grisham Deputy Group Leader Ruben D. Aguilar * David C. Moody, III *~ Mohammed Alei Deputy Group Leader Phyllis L. Baca Hong T. Bach * Moses Attrep Joseph C. Banar M. Romayne Betts Gregory K. Bayhurst Roland A. Bibeau * Timothy M. Benjamin * Scott M. Bowen * Ernest A. Bryant * Gilbert W. Butler * John H. Cappis Section Leader * Clarence J. Duffy * Edwin P. Chamberlin ~ Suzanne Dye Section Leader * Bryan L. Fearey Michael R. Cisneros * David L Finnegan * David D. Clinton *t Jeffrey S. Gaffney * Dean A. Cole * David R. Janecky Joe Cortez * AllenS. Mason Samia Davis * Arend Meijer Joy Drake * Charles M. Miller * Deward W. Efurd Project Leader Section Leader f Lia M. Mitchell Maureen A. Flynn * Eugene J. Mroz * Malcolm M. Fowler * Michael T. Murrell * Russell E. Gritzo * A. Edward Norris * Sara B. Helmick * Allen E. Ogard Allen N. Herring II * Jose A. Olivares * David E. Hobart * Richard E. Perrin Gregory M. Kelley * Jane Poths * Sylvia D. Knight Eddie L Rios Marcella L. Kramer * Pamela Z. Rogers Marjorie E. Lark * Donald J. Rokop * Francine 0 Lawrence Technical Coordinator * Lon-Chang Liu C. Elaine Roybal Calvin C. Longmire * Norman C. Schroeder Robert M. Lopez Henrietta Tixier Carla E. Lowe * Kurt Wolfsberg Patrick S. Lysaght Section Leader * Michael R, Maclnnes Sixto Maestas i! Janet Mercer-Smith * Geoffrey G. Miller Alan J. Mitchell * David E. Morris Thomas A. Myers * Charles J. Orth Laboratory Fellow Martin A. Ott Isotope and Nuclear Chemistry Division Annual Report FY19SS 81 Appendix: Personnel Charles P. Padilla JRO Fellows Phillip D. Palmer Dennis R. Phillips Carol Burns, INC-4 Frederick R. Roensch David L. Clark, INC-4 Robert S. Rundberg t Jeanette C. Roberts, INC-11 Lisa M. Schneider Raymond G. Schofield Summer Teacher Franklin H. Seurer Richard C. Staroski Leonard R. Quintana, INC-11 Frederick J. Steinkruger Zita V. Svitra Wayne A. Taylor Graduate Research Assistants Kimberly W. Thomas Section Leader Marieluise Begemann-Blaich, INC-11 Joseph L. Thompson Katherine Bradley, INC-4 Inez R. Triay Peter Dorhout, INC-4 Larry S. Ulibarri t Marci D. Ferrell, INC-4 Frank O. Valdez Janet Griego, INC-4 David J. Vieira Monica Hilliard, INC-4 Section Leader John A. Keightley, INC-4 Jerry B. Wilhelmy Dawn Lewis, INC-11 Laboratory Fellow Theresa A. Miller, INC-7 Jan M. Wouters Cheryl L. Peach, INC-7 Mary Anne Yates Julia A. Peck, INC-4 Eric W. Prestbo, INC-7 Laboratory Associates William B. Sanborn, INC-4 Hardy Siefert, INC-11 Ruth Capron, INC-4 Bradley E. Sturgeon, INC-4 * Bruce J. Dropesky, INC-DO i Daniel VanGent, INC-5 Frank Newcom, INC-5 Lori VanderSluys, INC-4 Raymond Vandervoort, INC-4 John Wilson, INC-11 * Herbert Williams, INC-5 Jonathan J. Zieman, INC-7 David Yarnell, INC-11 Undergraduate Assistants Postdoctoral Appointees William J. Caperton, INC-11 Kent D. Abney, INC-4 Jason N. Ceballes, INC-4 Thomas Blaich, INC-11 Lynda S. Halloran, INC-DO Timothy P. Burns, INC-11 Michael Y. Han, INC-4 Rajeev Chemburkar, INC-4 Lillian Hinsley, INC-DO Robert J. Donohoe, INC-4 Lily Hsu, INC-4 Olof Einarsdottir, INC-4 Kermit Lopez, INC-11 Eduardo Garcia, INC-4 Sherri Newmyer, INC-11 Steven J. Goldstein, INC-7 David A. Nix, INC-11 David Houck, INC-4 Joanna K. Norman, INC-11 f Patrick M. Killough, INC-4 Debra E. Smith, INC-4 Juan Lopez-Garriga, INC-4 f NancyA. Marley, INC-7 Undergraduate Interns 1 Kimberly A. Martin, INC-4 Eric Neiderhoffer, INC-4 I Allyn Bates, INC-7 Jon B. Nielsen, INC-4 ~ Jonathan Briggs, INC-4 David Pinnick, INC-4 Octavio Ramos, Jr., INC-11/DO Nancy Sauer, INC-4 Jean Y. Yang, INC-11 Louis D. Schulte, INC-11 Paul H. Smith, INC-4 Co-op Students Carleton D. Tait, INC-4 William VanderSluys, INC-4 William H. Straight, INC-7 (DIR) Jeffrey B. Weinrach, INC-4 John R. VanMarter, INC-11 82 Isotope and Nuclear Chemistry Division Report 1988 Appendix: Advisory Committee Isotope and Nuclear Chemistry Division Advisory Committee Committee Chairman (1985-1989) Harry B. Gray Chemistry 127-72 California Institute of Technology Pasadena, CA 91125 Committee Members (1988-90) Gordon E. Brown, Jr. Department of Geology Stanford University Stanford, CA 94305 (1989-91) Gary M. Hieftje Department of Chemistry A169 Chemistry Building Indiana University Bloomington, IN 47401 (1986-89) Heinrich D. Holland Department of Geological Sciences Hoffman Laboratory Harvard University Cambridge, MA 02138 (1987-89) Anthony Turkevich Enrico Fermi Institute The University of Chicago 5630 Ellis Avenue Chicago, IL 60637 (1988-90) Henry N. Wagner Division of Radiation Health Science and Nuclear Medicine Johns Hopkins University 615 N. Wolfe Street Baltimore, MD 21205 (1984-89) George E. Walker Department of Physics Swain West 233 Indiana University Bloomington, IN 47405 Isotope and Nuclear Chemistry Division Atinual Report FYI9SS 83 Appendix: Program Funding Funding Sources FY 1988 Funding Profile Operating $26.8 M Capital $ 1.7 M Total $28.5 M Defense Programs Energy Research Laboratory R&D OBES 6% OHER 6% OHENP 4% Work for Others Nuclear Energy DOE 9% NIH 4% DOD 2% OTHER 1% 84 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appi'ndix: Program Funding Project Title Principal Investigator $K Weapons Chemistry (DOE/OMA) D.W. Barr 11178 (DoD.) D.W. Barr 411 Isotope Separator Construction E.P. Chamberlin 40 Other D.W. Barr 1610 13239 Biochemistry and Nuclear Medicine Medical Radioisotopes Research (DOE/OHERj D.C. Moody 900 National Stable Isotopes Research (NIHj J.A. Fee 544 Imaging Agents for Lymph Nodes i DOE/OHER) J.A. Mercer-Smith 300 Radiopharmaceuticals (ISR) J.A. Mercer-Smith 276 Mechanisms of Respiration (NIH,) J.A. Fee 218 C13 NMR and Metabolism (DOE/OHER) J.A. Fee 209 Bacterial Toxins (ISRJ P.J. Unkefer 187 Methylotrophic Bacteria Metabolism (DOE/OBES) C.J. Unkefer 115 Signal Peptides (ISR) J.R. Brainard 103 Red Blood Cell Modeling (ISRj J.A. Fee 103 Superoxide Dismutase (NIH) J.A. Fee 96 Vibrational Spectroscopy (NIH) W.H. Woodruff 84 Biomedical Research Support (NIH) 21 3156 Environmental and Geochemistry Yucca Mountain Project (DOE/NV) E.S. Patera 2786 Geochemistry Research (DOE/OBES) R.W. Charles 740 Radionuclide Migration Project (DOE/NV) J.L. Thompson 336 Data Base Review (DNAj A.S. Mason 263 Atmospheric Chemistry of Organic Oxidants J.S. Gaffney 147 (DOE/OHER) Continental Scientific Drilling Project (ISR) R.W. Charles 98 Natural Plutonium Geochemistry (DOE/ANL) D.B. Curtis 95 Biotechnology (ISR) P.J. Unkefer 75 Iridium Anomaly (ISR) C.J. Orth 50 Geochemistry: Advanced Concepts (DOE/OBES) R.W. Charles 50 Instrumentation (ISR) J.S. Gaffney 35 Advanced Mass Spectrometry (IGPP) M.M. Fowler 35 Iridium Mini-Grant (IGPP) C.J. Orth 27 INAA Analysis fEPRIj E.J. Mroz 17 Alligator Rivers Analogue (ANST) D.B. Curtis 12 Nuclear Microprobe Mini-Grant (IGPP) D.R. Janecky 8 White Garnets on Navajo Nation (LANL) R.W. Charles 6 Elemental Abundances (NASA) C.J. Orth 5 4785 Actinide and Transition Metal Chemistry Transition Metal Mediated Reactions (DOE/OBES) G.J. Kubas 356 Stereoselective Ligands HSR) G.D. Jarvinen 310 Actinide Organometallic Chemistry i DOE/OBES J A. P. Sattelberger 225 Actinide Chemistry (ISR) A.R Sattelberger 197 Actinides in Near-Neutral Solution 'DOE/OBES) D.E. Hobart 148 Structure-Function Relationships 'ISRj R.R. Rvan 128 Hydrogen Uptake G.J. Kubas 118 Photodynamics CISR) W.H. Woodruff 1580 Isotope and Xuclear Chemistry Division Annual RrpoH FY lfiSS .So Appendix: Program Funding Project Title Principal Investigator SK Materials Chemistry Synchrotron Radiation/Neutron Scattering (ISR) S.D. Conradson 235 Chemistry of Shocked Energetic Materials (ISR) B.I. Swanson 190 Materials Under Extreme Conditions (ISR) B.I. Swanson 158 Chemical Modification and Structure (ISR) R.R. Ryan 100 Mixed Valence Solids (ISR) B.I. Swanson 99 Optical Spectroscopy (ISR) B.I. Svvanson 98 Carbon Disulfide/Molecule Studies (ONR) B.I. Swanson 61 Chemistry of Reacting HEs (DoD) S.F. Agnew 58 Structural Studies (ISR) R.R. Ryan 50 Fuel Cells (Conserv. Renew. Energy) S.D. Conradson 20 Synchrotron Radiation Research (ISR) S.D. Conradson 20 High Reflectance Mirrors (DOE/OBES) S.D. Conradson 15 CMS Research (ISR) B.I. Swanson 13 1117 Nuclear Structure and Reactions Nuclear Chemistry Research—LAMPF (DOE/OHENP) D.J. Vieira 630 Solar Neutrino Flux (DOE/OHENP) K. Wolfsberg 229 Double Beta Decay (ISR) R.S. Rundberg 167 Fission and Reaction Studies (DOE/OHENP) J.B. Wilhelmy 139 1165 Major Facilities ICONS Production (MOUND) L.F. Brown 1086 Omega West Reactor (LAND M.E. Bunker 352 ICON Facility (DOE/OHER) L.F. Brown 125 Other OWR Services M.E. Bunker 44 User Facility Agreement (WTC) M.E. Bunker 40 Contaminated Solid Waste Burial (DOE) M.E. Bunker 20 Ne22 Sales (LLNL) L.F. Brown 20 Neutron Irradiations (DOE) M.E. Bunker 13 Irradiation of Minerals (NTT) M.E. Bunker 10 1710 Division Total 26752 86 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appendix: Puh!iif)tionn Publications poxyphosphinojpyridine AT,P-Dioxide. Crystal and Molecular Structure of Bi.s[2-(diisoprop L. R. Avens, P. G. Eller, L. B. Asprey, S. D. Conradson, M. A. Stroud, M. H. Zietlow, K. D. Abney, and S. A. Kinkead, "Analytical B. I. Swanson, D. Baeriswyl, and A. R. Bishop, Applications of Superacid Dissolution of "Charge Density Waves and Local States in Actinide and Lanthanide Substrates," J. Quasi-One-Dimensional Mixed Valence Radioanal. Nucl. Chem. 123(2), 707-712 (1988). Inorganic Complexes," IAEA IC/87/315 (Miramare-Trieste, 1987), and Solid State N. R. Bastian, G. Diekert, E. C. Niederhoffer, Commun. 65(7), 1405-1409 (1988). B-K Teo, C. T. Walsh, and W. H. Orme-Johnson, "Nickel and Iron EXAFS of Carbon Monoxide S. D. Cope, D. K. Russell, H. A. Fry, L. H. Jones, Dehydrogenase from Clostridium and J. E. Barefield, "Analysis of the n: thermoaceticum Strain DSM," J. Am. Chem. Fundamental Mode of HTO," -J. Mol. Spectrosc. Soc. 110(16), 5581-5582 (1988). 127, 464-471 (1988). D. B. Bush, and P. J. Langston-Unkefer, D. T. Cromer, H. L. Ammon, and J. R. Holden, "Tabtoxinine-b-lactam Transport into Cultured "A Procedure for Estimating the Crystal Corn Cells: Uptake Via an Amino Acid Densities of Organic Explosives," Los Alamos Transport System," Plant Physiol. 85, 845-849 National Laboratory report LA-11142-MS (1987). ^November 1987). L. G. Butler, M. H. Zietlow, C-M Che, D. T. Cromer, J. H. Hall, K-Y. Lee, and R. R. W. P. Schaefer, S. Sridhar, P. J. Grunthaner, Ryan, "The Structure of the Ethylene- B. I. Swanson, R. J. H. Clark, and H. B. Gray, diammonium Salt of 3-Nitro-l,2,4-triazol-5-one, "Translational Symmetries in the Linear-Chain C9H4( NH3)2-2C2N4O3H, Ada Cryst C 44, 1144-1147 (1988"). Semiconductors K4[Pt2(P2O5H2)4X]*reH2O (X=C1, Br, I;," J.Am. Chem. Soc. 110'4), 1155- 1162 (1988). D.T. Cromer, K-Y Lee, and R. R. Ryan, Structures of Two Polymorphs of 1,1 -Dinitro- A. Campion and W. H. Woodruff, "Multichannel 3,3-azo-l,2,4-triazole,' Acta Cryst. C44'9.u Raman Spectroscopy,' Anal. Chem. 59(2), 1673-1674 (1988). 1299A-1308A(1987). D. T. Cromer, R. R. Ryan, and M. D. Coburn. G. S. Conary, A. A. Russell, R. T. Paine, The Structure of 3,5-Dinitroisoxazole, Acta J. H. Hall, and R. R. Ryan, "Synthesis and Crvst. C43<10.;, 2011-2013 '1987'. Coordination Chemistry of 2-(Diisopro- Isotope and Xuclear Chemistry Division Annual Rvpnrt b~Y Appendix: Pu blications W. L. Earl, R. L. Wershaw, and K. A. Thorn, P. J. Jackson, C. J. Unkefer, K. Watt, "The Use of Variable Temperature and Magic- J. A. Doolen, and N. J. Robinson, "Poly—ig- Angle Sample Spinning in Studies of Fulvic glutamylcysteine) Glycine: A Functional Acids," J. Magn. Reson. 74, 264-274 (1987). Analogue of Metallothionein in Angiosperms," Proc. Nat. Acad. Sci., USA 84,6619-6623 (1987). J. Eckert, G. J. Kubas, and A. J. Dianoux, "Rotational Tunneling of Bound H2 in a L. H. Jones, and S. A. Ekberg, "Hindered Tungsten Complex," J. Chem. Phys. 88(1), Rotation and Site Structure of CD4 Trapped in 466-468 (1988). Rare Gas Solids," J. Chem. Phys. 87(8), 4368-4370(1987). D. D. Ensor, G. D. Jarvinen, and B. F. Smith, "The Use of Soft Donor Ligands, 4-Benzoyl-2,4- B. S. Jorgensen, M. Aldissi, R. Liepins, and dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione S. F. Agnew, "Highly Oriented Unsubstituted and 4,7-Diphenyl-l,10-phenanthroline, for Polydiacetylene," Proc. Symposium on Improved Separation of Trivalent Americium Nonlinear Optical Properties of Polymers, 1987 and Europium," Solvent Extraction and Ion (Materials Research Society, 1988), pp. 379-384. Exchange 6(3), 439-445 (1988). T. J. Knight and P. J. Langston-Unkefer, J. A. Fee, B. H. Zimmerman, C. I. Nitsche, "Adenine Nucleotides as Allosteric Effectors of F. Rusnak, and E. Miinck, "The Cytochrome Pea Seed Glutamine Synthetase," J. Biological caa% from Thermus thermophilus," Chemica Chem. 263(23), 11084-11089 (1988). Scipta 28A, 75-78 (1988). T. J. Knight and P. J. Langston-Unkefer, E. Garcia, N. N. Sauer, R. R. Ryan, A. Williams, "Enhancement of Symbiotic Dinitrogen Fixation and P. G. Eller, "Neutron Powder Diffraction by a Toxin-Releasing Plant Pathogen," Science Study of the Products from Fluorinating 241,951-954(1988). YBa2Cu3O7_,j at Room Temperature and at 400°e," J. Mat. Res. 3(5), 819-824 (1988). G. J. Kubas, "Molecular Hydrogen Complexes of the Transition Metals," Accts. Chem. Res. 21(3), E. Garcia, R. R. Ryan, N. N. Sauer, Z. Fisk, 120-128 (1988). B. Pierce, M. Fluss, and L. Bernadez, "Synthesis and Superconducting Critical G. J. Kubas, "Molecular Hydrogen Coordination 18 1 Temperature of YBa2Cu3 07-d,' Phys. Rev. B to Transition Metals," Comments Inorg. Chem. 38(4), 2900-2902 (1988). 7(1X17-40(1988). Invited. L. Hedberg, K. Hedberg, P. G. Eller, and G. J. Kubas, R. R. Ryan, and C. J. Unkefer, R. R. Ryan, "Dioxygen Difluoride: Electron "Molecular Hydrogen Complexes. 5. 2 Diffraction Investigation of the Molecular Electronic Control of h -H2 vs. Dihydride Structure in the Gas," Inorg. Chem. 27(2), Coordination. Dihydride Structure of 2 232-235 (1988). MoH2(COXR2PC2H4PR2)2 for R=Et, i-Bu vs. h - H2 for R=Ph," J. Am. Chem. Soc. 109(26), 8113- D. E. Hoekenga, J. R. Brainard, and 8115 (1987). J. Y. Hutson, "Rates of Giycolysis and Glycogenolysis During Ischemia in Glucose, K. A. Kubat-Martin, G. J. Kubas, and Insulin and Potassium (GIK) Treated Guinea R. R. Ryan, "Reaction of Sulfur Dioxide with (h5- 13 31 Pig Hearts: A C, P Nuclear Magnetic C5Me5)Ru(CO)2H: Insertion of SO2 into the Ru- Resonance Study," Circulation Res. 62(6), H Bond and Oxygen Transfer to Form (h5- 1065-1074(1988). C5Me5)Ru(CO)2SO3H," Organometallics 7(7), 1657-1659 (1988). D. R. Houck, J. L. Hanners, and C. J. Unkefer, "Biosynthesis of Pyrroloquinoline Quinone. I. E. M. Larson, P. G. Eller, J. D. Purson, Identification of Biosynthetic Precursors Using C. F. Pace, M. P. Eastman, R. B. Greegor, and 13C Labeling and NMR Spectroscopy," J. Am. F. W. Lytle, "Synthesis and Structural Chem. Soc. 110(20), 6920-6921 (1988). Characterization of CaTiO3 Doped with 88 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appendix: Publications 0.05-7.5 Mole% Gadolinium(III)," J. Solid State B. F. Smith, D. Jarvinen, G. G. Miller, Chem. 73, 480-487 (1988). R. R. Ryan, and E. J. Peterson, "Synergistic Extraction Studies of Am(III) and Eu(III) from M. W. Mather, "Base Compostion-Independent Perchloric Acid with 4-Benzoyl-2,4-dihydro-5- Hybridization in Dried Agarose Gels: Screening methyl-2-phenyl-3H-pyrazol-3-thione(BMMPT) and Recovery for Cloning of Genomic DNA and Tri-n-octylphosphine Oxide (TOPO) in Fragments," BioTechniques 6(5), 444-447 (1988). Benzene," Solvent Extraction and Ion Exchange 5(5), 895-908 (1987). B. H. Meier, and W. L. Earl, "A Double-Quantum Filter for Rotating Solids," J. Am. Chem. Soc. B. I. Swanson, M. A. Stroud, S. D. Conradson, 109(26), 7937-7942 (1987). and M. H. Zietlow, "Observation of a Pressure Induced Reverse Peierls Instability in the H. L. Nekimken, B. F. Smith, G. D. Jarvinen, Quasi-One-Dimensional Mixed Valence Solid E. J. Peterson, and M. M. Jones, "Computer- K4[Pt2(P2O5H2)4Br]-3H2O," Solid State Controlled Flow Injection Analysis System for Commun. 65(11), 1405-1409 (1988). On-Line Determination of Distribution Ratios," Analytical Chem. 60(14), 1390-1393 (1988). B. I. Swanson, S. F. Agnew, and N. R. Greiner, "Static High Pressure Study of Nitric Oxide D. W. Reagor, A. Migliori, Z. Fisk, R. D. Taylor, Chemistry: Proposed Mechanism for Nitric K A. Martin, and R. R. Ryan, "Microwave Oxide Detonation," in Proc. Eighth Symposium Collective Transport in Single-crystal (International) on Detonation, Albuquerque, Eu2Cu04," Phys. Rev. B 38(7), 5106-5109 New Mexico, July 15-19,1985 (April 1988), (1988). pp. 715-724. B. A. Robinson, J.W. Tester, and L.F. Brown, W. G. Van Der Sluys, C. J. Burns, J. C. Huffman, "Reservoir Sizing Using Inert and Chemically and A. P. Sattelberger, "Uranium Alkoxide Reacting Tracers," SPE Formation Evaluation, Chemistry. 1. Synthesis and the Novel Dimeric 227-234 (March, 1988). Structure of the First Homoleptic Uranium(III) Aryloxide Complex," J. Am. Chem. Soc. 110(17), F. M. Rusnak, E. Munck, C. I. Nitsche, 5924-5925 (1988). B. H. Zimmermann, and J. A. Fee, "Evidence for Structural Heterogeneities and a Study of T. E. Walker, C. J. Unkefer, and D. S. Ehler, Exchange Coupling: Mossbauer Studies of "The Synthesis of Carbon-13 Enriched Cytochrome 0^83 from Thermus thermophilus," Monosaccharides Derived from Glucose and J. Biological Chem. 263(34), 16328-16332 Mannose," J. Carbokydr. Chem. 7(1), 115-132 U987). (1988). J. M. Saber, KB. Kester, J.L. Falconer, and K. H. Whitmire, J. M. Cassidy, A. L. Rheingold, L.F. Brown, "A Mechanism for the Sodium Oxide and R. R. Ryan, "A Series of Thallium-Iron Catalyzed CO2 Gasification of Carbon, Carbonyl Cluster Molecules: Structural J. Catalysis, 109, 329-346 (1988). Comparisons of [Et4N]2 {Tl2Fe4(CO)16 j, [Et4]4[Ti4Fe8(CO)30] and N. N Sauer, E. Garcia, J. A. Martin, R. R. Ryan, [Et4N]6[Tl6Fe10(CO)36]," Inorg. Chem. 27(8), P. G. Eller, J. R. Tesmer, and C. J. Maggiore, 1347-1353(1988). "Fluorination of the High Tc Superconductors YBa2Cu307.d and GdBa2Cu3O7.d," J. Mat. Res. W. H. Woodruff, R. B. Dyer, and 3(5), 813-818(1988). J. R. Schoonover, "Resonance Raman Spectroscopy of Blue Copper Proteins," in J. R. Schoonover, R. B. Dyer, W. H. Woodruff, Biological Applications of Raman Spectroscopy, G. M.Baker, M. Noguchi, and G. Palmer, Vol. 3, Resonance Raman Spectra of Heine and "A Comparison of the Resonance Raman Metalloproteins, T. G. Spiro, Ed. (Wiley- Properties of the Fast and Slow Forms of Interscience, New York, 1988),Chap. 9, Cytochrome Oxidase," Biochem. 27, 5433 (1988). pp. 413-438. Isotope and Nuclear Chemistry Division Report 1988 89 Appendix: Publications C. S. Yoo, J. J. Furrer, G. E. Duvall, S. F. Agnew, D. A. Wrobleski, K. H. Abel, A. J. Gray, and and B. I. Swanson, "Effects of Dilution on the J. M. Williams, "Potential Foams and Metal Ultraviolet and Visible Absorptivity of CS2 Foils for Cosmic Dust Capture," Los Alamos under Static and Shock Compression," J. Phys. National Laboratory report LA-11271-MS Chem. 91(27), 6577-6578 (1987). (July 1988). Patents J. Stix, F. E. Goff, M. P. Gorton, G. Heiken, and S. R. Garcia, "Restoration of Compositional L.B. Asprey and P. G. Eller, "Method for Zonation in the Bandelier Silicic Magma Recovery of Actinides from Refractory Oxides Chamber Between Two Caldera-Forming thereof Using O2F2," U.S. Patent #4,724,127, Eruptions: Geochemistry and Origin of the issued February 9,1988. Cerro Toledo Rhyolite, Jemez Mountains, New Mexico," J. Geophys. Res. B6,6129 (1988). J.R. FitzPatrick, J. G. Dunn, and L. R. Avens, "Method for Removal of Plutonium Impurity from Americium Oxides and Fluorides," U.S. INC-7 Patent #4,710,222, issued December 1,1987. S. F. Agnew, T. Miller, S. Eckberg, and E. Fukushima, A. R. Rath, and S.B.W. Roeder, B. I. Swanson, "Analysis of Diamond-Anvil "Apparatus for Unilateral Generation of a Cell Reaction Products: High-Pressure Homogeneous Magnetic Field," U.S. Patent Decomposition of Nitromethane," in "Isotope #4,721,914, issued January 26,1988. and Nuclear Chemistry Division Annual Report FY 1987, October 1986-September 1987," Los Alamos National Laboratory report INC-5 LA-11291-PR (May 1988), pp. 42-46. W. L. Talbert, Jr., M. E. Bunker, and J. W. K H. Birdsell, P. G. Stringer, L. F. Brown, Starner, "Optimization of a He-Jet Activity G. A. Cederberg, B. J. Travis, and A. E. Norris, Transport System to Use at LAMPF," Nucl. "Modeling the Exploratory Shaft Diffusion Test," Instr. Methods B26, 345 (1987). Los Alamos National Laboratory document LA-UR-87-307 (January 1S88). W. L. Talbert, Jr., J. W. Starner, R. J. Estep, S. J. Balestrini, M. Attrep, Jr., D. W. Efurd, R. W. Charles, "State of Geochemical and F. R. Roensch, Phys. Rev. C 36,1896 (1987). Equilibrium in California State Well 2-14: The Salton Sea Scientific Drilling Project," R. G. Helmer, C. W. Reich, M. E. Bunker, and in "Isotope and Nuclear Chemistry Division J. W. Stamer, "Decay of 150Tb," Idaho National Annual Report FY 1987, October 1986- Engineering Laboratory report EGG-PHY-7569 September 1987,' Los Alamos National (October 1987). Laboratory report LA-11291-PR (May 1988), pp. 116-120. D. E. Robertson, M. P. Bergeron, D. A. Myers, K. H. Abel, C. W. Thomas, D. R. Champ, R. W. Charles, C. Navarro, D. R. Janecky, and R. W. Killey, G. L. Moltyaner, and J. L. Young, C. Wells, "Advanced Downhole Sampler "Demonstration of Performance Modeling of a Prototype," in Proceedings of the Wellbore Low-Level Waste Shallow-Land Burial Site," Sampling Workshop, November 1987, Sandia Pacific Northwest Laboratory report PNL-6175, National Laboratories report SAND87-1918 Vol. 1, NUREG/CR-4879 (November 1987). (1987), pp. 72-73. P. E. Koehler, C. D. Bowman, F. J. Steinkruger, B. M. Crowe, D. L. Finnegan, W. H. Zoller, and D. C. Moody, G. M. Hale, J. W. Starner, S. A. W. V. Boynton, "Trace Element Geochemistry of Wender, R. C. Haight, P. W. Lisowski, and W. L. Volcanic Gases and Particles from 1983-1984 Talbert, "7Be(n,p)7Li total cross section from 25 Eruptive Episodes of Kilauea Volcano," meV to 13.5 keV," Phys. Rev. C 37, 917 (1988). J. Geophys. Res. 92 (B13), 13,708-13,714 (December 1987). 90 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appendix: Publications C. J. Duffy, "Control of Low- Temperature F. A. Gifford, S. Barr, R. C. Malone, and Mineral Alteration by Aqueous Silica Activity," E. J. Mroz, "Tropospheric Relative Diffusion in "Isotope and Nuclear Chemistry Division to Hemispheric Scales," Atmos. Environ. 22 (9;, Annual Report FY1987, October 1986- 1871 (1988). September 1987," Los Alamos National Laboratory report LA-11291-PR (May 1988), S. J. Goldstein and S. B. Jacobsen, "Rare Earth pp. 114-116. Elements in River Waters," Earth Planet. Sci. Lett. 88, 35-47 (1988). B. L. Fearey, C. M. Miller, M. W. Rowe, J. E. Anderson, and N. S. Nogar, "Pulsed Laser S. J. Goldstein and S. B. Jacobsen, "Nd and Sr Resonance Ionization Mass Spectrometry Isotopic Systematics of River Water Suspended (RIMS) for Elementally Selective Detection of Material: Implications for Crustal Evolution," Lead and Bismuth Mixtures," Anal. Chem. 60, Earth Planet. Sci. Lett. 87, 249-265 (1988). 1786-1791 (1988). S. J. Goldstein and S. B. Jacobsen, "REE in the B. L. Fearey, D. C. Parent, R. A. Keller, and Great Whale River Estuary, Northwest Quebec," C. M. Miller, "Progress Toward the Analytical Earth Planet. Sci. Lett 88, 241-252 (1988). Viability of Resonance Ionization Mass Spectrometry," in "Isotope and Nuclear D. R. Janecky, R. W. Charles, F. E. Goff, and Chemistry Division Annual Report FY 1987, J. Hulen, "Geochemistry of Molybdenum- October 1986-September 1987," Los Alamos Bearing Assemblages in CSDP Well VC-2a, National Laboratory report LA-11291-PR Valles Caldera, New Mexico," Trans. Am. (May 1988), pp. 210-213. Geophys. Union 68 (44), 469 (1987). B. L. Fearey, M. W. Rowe, J. E. Anderson, D. R. Janecky, R. M. Haymon, and C. M. Miller, and N. S. Nogar, "Elementally T. M. Benjamin, "Trace-Element Analysis Selective Detection of Lead and Bismuth Applied to Seafloor Hydrothermal Systems Mixtures by Pulsed Laser Resonance Ionization and Processes: Using the Los Alamos Nuclear Mass Spectrometry," in "Isotope and Nuclear Microprobe," in "Isotope and Nuclear Chemistry Chemistry Division Annual Report FY 1987, Division Annual Report FY 1987, October 1986- October 1986-September 1987," Los Alamos September 1987," Los Alamos National National Laboratory report LA-11291-PR Laboratory report LA-11291-PR (May 1988), (May 1988), pp. 214-218. pp. 106-109. D. L. Finnegan and E. A. Bryant, "Methods for D. R. Janecky and W. E. Seyfried, Jr., Obtaining Sorption Data from Uranium-Series "Transition Metal Mobility in Oceanic Ridge Disequilibria," Los Alamos National Laboratory Crest Hydrothermal Systems at 350oC-425"C,' report LA-11162-MS (December 1987). in Chemical Transport in Metasomatic Processes, H. C. Helgeson, ed. (D. Reidel J. S. Gaffney, N. A. Marley, and I. R. Triay, Publishing Company, 1987), pp. 657-688. "Looking Past Nuclear Winter," in "Isotope and Nuclear Chemistry Division Annual Report N. Kaffrell, P. Hill, J. Rogowski, H. Tetzlaff, FY 1987, October 1986-September 1987," Los N. Trautmann, E. Jacobs, P. De Gelder, Alamos National Laboratory report LA-11291- D. De Frenne, K. Heyde, G. Skarnemark, PR (May 1988), pp. 232-233. J. Alstad, N. Blasi, M. N. Harakeh, W. A. Sterrenburg, and K. Wolfsberg, J. S. Gaffney, E. W. Prestbo, J. Zieman, "Levels in 109Rh,' Nucl. Phys. A470,141-160 W. H. Zoller, E. Franzblau, and C. J. Popp, (1987). "Monoterpene Moderation of Surface Ozone Concentrations in the Troposphere," in "Isotope R. D. Loss, J. R. De Laeter, K. J. R. Rosman, and Nuclear Chemistry Division Annual Report T. M. Benjamin, D. B. Curtis, A. J. Gancarz, FY 1987, October 1986-September 1987," J. E. Delmore, and W. J. Maeck, The Oklo Los Alamos National Laboratory report LA- Natural Reactors: Cumulative Fission Yields 11291-PR (May 1988), pp. 233-235. and Nuclear Characteristics of Reactor Zone 9," Earth Planet. Sci. Lett. 89,193-206 Isotope and Nuclear Chemistry Division Report 1988 91 Appendix: Publications N. A. Marley, P. S. Z. Rogers, T. M. Benjamin, Alamos National Laboratory report and D. R. Janecky, "The Study of Metal LA-11291-PR (May 1988), pp. 121-124. Speciation at High Temperatures and Pressures via Laser Raman Spectroscopy," Trans. Am. F. V. Perry, W. Scott Baldridge, and D. J. Geophys. Union 68 (44), 1538 (1987). DePaolo, "Chemical and Isotopic Evidence for Lithospheric Thinning Beneath the Rio Grande N. A. Marley, P. S. Z. Rogers, T. M. Benjamin, Rift," Nature 332 (6163), 432-434 (March 1988). and D. R. Janecky, "Raman Spectroscopic Study of Metal Speciation Under High Temperatures J. Rogowski, N. Kaffrell, H. Tetzlaff, and Pressures: Zinc Bromide and Zinc Chloride N. Trautmann, D. De Frenne, K. Heyde, Systems," in "Isotope and Nuclear Chemistry E. Jacobs, G. Skarnemark, J. Alstad, Division Annual Report FY 1987, October 1986- M. N. Harakeh, J. M. Schippers, S. Y. van September 1987," Los Alamos National der Werf, W. R. Daniels, and K. Wolfsberg, Laboratory report LA-11291-PR (May 1988), "Evidence for Shape Coexistence in Neutron- pp. 110-113. Rich Rh and Ag Nuclei," in Proceedings of the International Workshop on Nuclear Structure A. S. Mason, D. L. Finnegan, R. C. Hagan, of the Zirconium Region," Bad Honnef, R. Raymond, Jr., .K. Bayhurst, J. Mroz, Germany, April 24-28,1988. C. L. Peach, and K. H. Wohletz, "Misty Picture Atmospheric Test," in "Isotope and Nuclear R. L. Tanner, A. H. Miguel, J. B. de Andrade, Chemistry Division Annual Report FY 1987, J. S. Gaffney, and G. E. Streit, 'Atmospheric October 1986-September 1987," Los Alamos Chemistry of Aldehydes: Enhanced Peroxyacetyl National Laboratory report LA-11291-PR Nitrate Formation from Ethanol-Fueled (May 1988), pp. 227-230. Vehicular Emissions," Environ. Sci. Tech. 22, 1026-1034 (1988). A. Meijer, S. T. Kwon, and G. R. Tilton, "Pb-Sr- Nd Isotopic Studies on Ultramafic Nodules," J. L. Thompson, Comp., and Ed., "Laboratory in Trans. Am. Geophys. Union 69, 502 (1988). and Field Studies Related to the Radionuclide Migration Project, October 1,1986-September E. J. Mroz, M. Alei, A. S. Mason, and C. Cone, 30,1987," Los Alamos National Laboratory "Winter Haze Intensive Tracer Experiment," report LA-11223-PR (February 1988). in "Isotope and Nuclear Chemistry Division Annual Report FY 1987, October 1986- September 1987," Los Alamos National INCH Laboratory report LA-11291-PR (May 1988), pp. 230-231. FY1986 A. E. Norris, K. Wolfsberg, S. K. Gifford, W. B. N. Berry, P. Wilde, M. S. Quinby-Hunt H. W. Bentley, and D. Elmore, "Infiltration and C. J. Orth, "Trace Element Signatures in at Yucca Mountain, Nevada, Traced by 36C1," Dictyonema Shales and their Geochemical and Nucl. Instr. and Methods B29, 376-379 (1987). Stratigraphic Significance," Norsk Geologist: Tidsskrift 66, 45-51 (1986). A. E. Ogard, J. L. Thompson, R. S. Rundberg, K. Wolfsberg, and H. W. Bentley, "Migration of R. R. Brooks, C. P. Strong, J. Lee, C. J. Orth, 36C1 from an Underground Nuclear Test," in J. S. Gilmore, D. E. Ryan, and J. 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Wouters, and the TOFI Collaboration, "Direct Mass Measurements of R. S. Rundberg, A. J. Mitchell, I. R. Triay, Light Neutron-Rich Nuclei Using Fast Recoil and B. J. Torstenfelt, "Size and Density of a Spectrometers," AIPConf. Proc. 164,1 (1988). 242Pu Colloid," In "Scientific Basis for Nuclear Waste Management XI;" M. J. Apted and W. S. Wolbach, I. Gilmour, E. Anders, C. J. Orth, R. E. Westerman, Eds.; Material Research and R. R. Brooks, "Global Fire at the Society Symposium Proceedings: Pittsburgh, Cretaceous-Tertiary Boundary," Nature 334, 1988; Vol. 112, p. 243-248. 665 (1988). C. P. Strong, R. R. Brooks, C. J. Orth, and Patents X.-Y. Mao, "An Iridium-Rich Calcareous Claystone (Cretaceous-Tertiary Boundary) P. M. Wanek, F. J. Steinkruger, and D. C. Moody, from Wharanui, Marlborough, New Zealand," "Biomedical Silver-109m Isotope Generator," New Zealand J. of Geology andGeophys. 31, United States Patent, Number 4,664, 892, 191 (1988). May 12,1987. Thompson, J. L., Comp. and Ed., "Laboratory and Field Studies Related to the Radionuclide Migration Project, October 1.1986 - September 30,1987," Los Alamos National Laboratory report LA-11223-PR (February 1988). I. R. Triay and R. S. Rundberg, "Deconvolution of Ion-Exchange Isotherms," Los Alamos National Laboratory YMP Milestone Report R720 (September/1988). A. Turler, F. Wegmuller, H. R. Von Gunten, K. E. Gregorich, D. Lee, D. C. Hoffman, and M. M. Fowler, "Fast Radiochemical Separation of Am, Pu, Np, U, Pa, Th, Ac and Ra in Heavy Ion Reactions with Actinide Targets," Radiochimica Acta 43,149-152,1988. L. E. Ussery, D. J. Vieira, J. J. H. Berlijn, G. W. Butler, B. J. Dropesky, G. C. Giesler, N. Imanishi, M. J. Leitch, and R. S. Rundberg, "Excitation Function for the Pion Single-Charge- 98 Isotope and Nuclear Chemistry Division Annual Report FY 198S ,\f>]H'rtri>\; Presentations Spectroscopy, Asilomar, Pacific Crow. California, January 20-22. 1988. Poster. INC-4 S. F. Agnew, "Seismosauras of San Vsidro: II. K. D. Abney, "Reaction Chemistry of the Dinosaur Fossils as Experiments in Long-term Actinido Metals, Oxides, and Fluorides Mineral Migration," l"SV Division Colloquium. in Superacid Media," seminar, Lawrence November 19.1987. Livermore National Laboratory, Livermore, California, July 19,1988. Invited. S. F. Agnew, "Spcctroscopy at High Pressure: Model for Predicting Density Dependence of K .D. Abney, "Reaction Chemistry of the Electronic Absorption Bands," Physics Actinide Metals, Oxides, and Fluorides in Department, Washington State University. Superacid Media," seminar, Savannah Pullman, Washington, October 13,1987. River Laboratory, Aiken, South Carolina, Invited colloquium. April 19,1988. Invited. S. F. Agnew and M. Aldissi, "Resonance Raman K. D. Abney, P. G. Eller, L. B. Asprey, Excitation Profiles of Polyacetylene/Polyisoprene S. A. Kinkead, E. M. Larson, L R. Avens, Block Co-Polymers in Toluene," International C. F. Pace, and W. H. Woodruff, "Reaction Conference on Science and Technology of Chemistry of Uranium and Thorium Metals, Synthetic Metals, Santa Fe, New Mexico Oxides and Fluorides in Superacid Media," June 26-July 2,1988. ACS Spring Meeting, Toronto, Canada, June 5-10,1988. S. F. Agnew and B. I. Swanson, "FTIR Spectroscopy and High Pressure: (a) SF6 in K. D. Abney, P. G. Eller, M. P. Eastman, Xenon at High Pressure, (b) Analysis of High W. H. Woodruff, C. F. Pace, and S. A. Kinkead, Pressure/High Temperature Nitromethane "Kinetic Investigation of Dioxygendifluoride Reaction Products," Symposium on FT-IR (FOOF)," 12th International Symposium on Spectroscopy, 9th Rocky Mountain Regional Fluorine Chemistry, Santa Cruz, California, Meeting, ACS, Las Vegas, Nevada, March 27-30, August 7-12,1988. 1988. Invited. S. F. Agnew and B. I. Swanson "Vibrational S. F. Agnew and B. I. Swanson, "FTIR Spectroscopy at Extreme Pressure," Gordon Spectroscopy and High Pressure: SF6 in Conference on Vibrational Spectroscopy, Xenon at High Pressure, (b) Analysis of High Brewster Academy, Wolfeboro, New Hampshire, Pressure / High Temperature Nitromethane August 15-19,1988. Invited. Reaction Products," Digilab Workshop on New Techniques, Albuquerque, New Mexico, S. F. Agnew and B. I. Swanson, "Reactions April 8,1988. Invited. under Extreme Conditions: Decompo-sition of Nitromethane and Nitric Oxide at Very High S. F. Agnew, B. I. Swanson, D. Pettit, and Pressure," Gordon Conference on Energetic J. Dick, "Conversion of N2O4 to NO+NO3- Materials, New Hampton, New Hampshire, with Shock Loading and Static Loading," June 24,1988. Invited. Shock Wave Symposium to honor George Duvall, Washington State University, S. F. Agnew, "FTIR Spectroscopy and High Pullman, Washington, September 1,1988. Pressure: (aj SF6 in Xe at High Pressure; (b) Analysis of High Pressure and High S. P. Armes, M. Aldissi, and S. F. Agnew, Temperature CH3NO2 Reaction Products," "Poly(vinyl-pyridine)-based Stabilizers for Technical Discussions at CLS-4 Group Aqueous Polypyrrole Latices," International Meetings, December 3,1987. Conference on Science and Technology of Synthetic Metals, Santa Fe, New Mexico, S. F. Agnew, "Pressure Dependence of Electronic June 26-July 2,1988, Absorption Spectra," Western Spectroscopy Association, 35th Annual Conference on Modern 1 and Nuclear VkamisWv Dii isi L. R. Avens, K. D. Abney, E. M. Larson, and P. K. Dorhnut. P. f>. Kller. A. li. K11R P. G. Eller, "Chemistry, Thermal Decomposition, H. J. Ki.-sanc. and W. H. Woodruff. and Crystal Structure of Hydronium "Intercalation of Acliny] Jons into Hydrogen Hexafluoroantimonate," ACS Spring Actinyl Phosphate Host Lattices: Uranyl and Meeting, Toronto, Canada, June 5-10,1988. Neptunyl Compounds," Eighteenth Rare- Earth Research Conference, Lake Geneva, Wisconsin, L. R. Avens and P. G. Eller, "Low Temperature September 12-16, 1988. Fluorination of Actinides," 1987 Winter Meeting, American Nuclear Society, Los Angeles, M. P. Eastman, P. G. Eller, K. D. Abney. California, November 15-19,1987. W. H. Woodruff, C. F. Pace. S. A. Kinkead. R. C. Kennedy, and R. J. Kissane, Gas Phase J. R. Brainard and S. Edmondson, "Structure of Stability of Dioxygendiiluoride.' ACS Spring the Signal Sequence from Yeast Mitochondrial Meeting, Toronto. Canada, June 5-10,1988. Superoxide Dismutase," American Society for Biochemistry and Molecular Biology, Las Vegas, P. G. Eller, "Superoxidizer/superacid Nevada, May 1-5,1988. Chemistry," Chemistry Department, University of Wisconsin, Madison, C. J. Burns, R. R. Ryan, and A. P. Sattelberger, Wisconsin, October 12,1987. "Disproportionation of Uranyl Alkoxides," Eighteenth Rare Earth Research Conference, P. G. Eller, "Superoxidizer/superacid Chemistry," Lake Geneva, Wisconsin, September 12-16, Department of Chemistry, University of Hawaii 1988. Invited seminar. C. J. Burns, W. H. Smith, R. R. Ryan, and P. G. Eller, "Superoxidizer/Superacid P. Sattelberger, "High Valent Organouranium Chemistry," Monash University, Clayton, Complexes: Synthesis, Characterization and Victoria, Australia, March 11,1988. Reactivity," ACS Spring Meeting, Toronto, Canada, June 5-10,1988. P. G. Eller, "Superoxidizer/superacid Chemistry," University of Melbourne. Melbourne. Australia, S. D. Conradson, "Recent Developments in April 27,1988. X-Ray Absorption Spectroscopy at Los Alamos," INC Division Colloquium, Los Alamos, April 21, L. Esserman and S. D. Conradson, 1988. "Potential Medical Applications of UV Free-Electron Lasers," Optical Society of S. D. Conradson, "X-ray Absorption America topical meeting on Free-Electron I Spectroscopy of Elements of Z < 10 Using a Laser Applications in the Ultraviolet, Free-Electron Laser Source," Optical Society Cloudcroft, New Mexico, March 2-5,1988. of America topical meeting on Free-Electron Laser Applications in the Ultraviolet, J.A. Fee, "Some Old Problems in Bio-Inorganic Cloudcroft, New Mexico, March 2-5,1988. Chemistry" Revelations from the Study of Thermophilic Bacteria," Spring Seminars, S. D. Conradson, "XAS Studies of 1-2-3 Chemistry Department, University of Materials as a Function of Temperature New Mexico, Albuquerque, New Mexico, and Chemical Modifications," FORUM on February 26,1988. High Temperature Superconductivity, CMS Division, September 14,1988. P. J. Hay and E. M. Kober, "Ab Initio Studies of Transition-Metal Dihydrogea Chemistry," S. D. Conradson, M. A. Stroud, and Symposium on the Interplay of Theory and B. I. Swanson, "Pressure Tuning of the 1-D Experiment in Organometallic Chemistry, Mixed-Valence Solid March 28,1988. K4[Pt2(P2O5H2)4Br].nH2O from a Charge- Density-Wave to a Valence-Delocalized Ground P. J. Hay and E. M. Kober, Ab Initio Studio State," American Physical Society General of Transition-Metal Dihydrogen Chemistry," Meeting, New Orleans, Louisiana, March 21-25, ACS Spring Meeting, Toronto, Canada, 1988. June 5-10,1988. Isotope and Nuclear Chemistry Division Annual Report FY ]988 D. R. Houck, J. L. Hanners, C. J. Unkefer. G. J. Kubas, "Coordination of Hydrogen M.A.G. van Kleef, and J. A. Duine, "PQQ: Molecules to Metal Centers: Prototype for Biosynthetic Studies in Methylbacterium Non-Classical Chemical Bonding," INC AMI and Hyphomicrobium X Using Specific Division colloquium, January 21,1988. 13C Labeling and NMR," 1st International Symposium on PQQ and Quinoproteins, Delft, G. J. Kubas, "Molecular Hydrogen Coordination The Netherlands, September 5-7,1988. to Transition Metals," Department* s) of Chemistry at Northwestern University, D. R. Houck and C. J. Unkefer, "13C and 1H Evanston, Illinois, November 5,1987, and NMR studies of PQQ and Selected Derivatives," University of Chicago, Chicago, Illinois, 1 st International Symposium on PQQ and November 6,1987. Invited seminars. Quinoproteins, Delft. The Netherlands, September 5-7, 1988. G. J. Kubas, C. J. Unkefer, and G.R.K. Khalsa. "Molecular Hydrogen Coordination to Ti'ansition G. D. Jarvinen, R. R. Ryan B. F. Smith, Metal Complexes," Symposium on the Interplay W. H. Smith, and D. D. Ensor, "Complexation of Theory and Experiment in Organometallic Studies of Soft Donor Ligands," 12th Actinide Chemistry, March 28,1988. Separations Conference, Naperville, Illinois, May 8-11. 1988. Invited. G. J. Kubas, J. Eckert, L. S. Van Der Sluys, P. J. Vergamini, R. R. Ryan, and G.R.K. Khalsa, B. S. Jorgensen, M. Aldissi, R. Liepins, and " Dynamics in Binding of Molecular Hydrogen S. F. Agnew, "Highly Oriented Unsubstituted Ligands," ACS Spring Meeting, Toronto, Polydiacetylene," The Materials Research Canada, June 5-10,1988. Society 1987 Fall Meeting, Boston, Massachusetts, November 30-December 5,1987. P. J. Langston-Unkefer, "A Microbe-Mediated Enhancement of Symbiotic Nitrogen Fixation," G.R.K Khalsa, C. J. Unkefer,G. J. Kubas, and Department of Plant Pathology, Michigan State R. R. Ryan, "Investigation of the Dihydrogen- University, East Lansing, Michigan, December Dihydride Equilibrium, W(CO)3(PR3)2(h2-H2) 21,1987. <--> WH2(CO)3(PR3)2," ACS Spring Meeting, Toronto, Canada, June 5-10,1988. P. J. Langston-Unkefer, "A Microbe-Mediated Enhancement of Symbiotic Nitrogen Fixation," R. J. Kissane, P. G. Eller, S. A. Kinkead, Division of Biology and Biomedical Sciences, T. R. Mills, J. D. Purson, and R. C. Kennedy, Plant Biology Program, Washington University, "Synthesis and Handling of Dixoygen St. Louis, Missouri, October 28,1987. Difluoride," Technicians Session, 9th Rocky Mountain Regional Meeting, ACS, Las Vegas, P. J. Langston-Unkefer, "Assimilation Nevada, March 27-30,1988. ofNitrogen," Guest Lecturer in the Biology Department, Visiting Seminar Series on T. J. Knight, C. Sengupta-Gopalan, and Nitrogen Metabolism, Washington University, P. J. Unkefer, "Oats Tolerant of Pseudomonas St. Louis, Missouri, October 27,1987. syi'ingae pv. tabaci Contain TbL-insensitive Leaf Glutamine Synthetases," Annual Meeting, P. J. Langston-Unkefer, "Molecular Basis of a Southwest Consortium on Plant Genetics, Microbe-Mediated Enhancement of Symbiotic Las Cruces, New Mexico, April 17-20,1988. Nitrogen Fixation," Plant Biochemistry Colloquium speaker, University of Missouri, T. J. Knight, R. Dickstein, C. Sengupta-Gopalan, Columbia, Missouri, October 15,1987. and P. J. Langston-Unkefer, "Enhancement of Symbiotic N2 Fixation," International P. J. Langston-Unkefer, T. J. Knight, and Symposium on Plant Nirtrogen Metabolism, C. Sengupta-Gopalan, "A Microbe-Mediated Annual Meeting of the Phytochemical Society Enhancement of Symbiotic N2-Fixation in of North America, Iowa City, Iowa, June 26-30, Legumes," Annual Meeting, Southwest 1988. Consortium on Plant Genetics, Las Cruces, New Mexico, April 17-20,1988. Isotope and Nuclear Chemistry Division Report 19SS 101 Appendix: Presentations T. R. Mills, "FOOF Production and Process Dismutase Regulation by the fur Locus in Development," FOOF'Superaeids Project Escherichia coli." 1988 UCLA Colloquium on Midyear Review, Los Alamos National Metal Ion Homeo.stasi.s: Molecular Biology and Laboratory. April 8. 1988. Chemistry, Frisco, Colorado, April 10-16. 1988. T. R. Mills, B. B. Mclnteer, and J. G. Montoya, D. R. Pettit, S. A. Sheffield, J. C. Dallman, "Sulfur and Selenium Isotope Separation by R. L. Rabie, S. F. Agnew, and J. J. Dick, Distillation," Third International Symposium on "Absorption Spectroscopy on Shocked N2O4,' the Synthesis and Applications of Isotopically American Physical Society General Meeting, Labelled Compounds, Innsbruck, Austria, New Orleans, Louisiana, March 21-25, 1988. July 17-21,1988. J. D. Purson, S. A. Kinkead, and J. R. T. R Mills, B. B. Mclnteer, and J. G. Montoya, FitzPatrick, "Synthesis of Krypton Difluoride," "Sulfer and Selenium Isotope Separation by 12th International Symposium on Fluorine Distillation," Third International Symposium Chemistry, Santa Cruz, California, August 7-12, on the Synthesis and Applications of Isotopically 1988. Labeled compounds, Innsbruck, Austria, July 17-21,1988. G. E. Oakley and R. E. Baran, "Identification of Impurities in Enriched Nitric Oxide," American H. L. Nekimken, B. F. Smith, G. D. Jarvinen, Chemical Society 196th National Meeting, and C. S. Bartholdi, "Separation of Yttrium Los Angeles. California, September 25-28,1988. (Y(III)) and Lanthanide (Ln(III)) Ions with the "Soft" Donor, 4-benzoyl-2,4-dihydro-5-methyl-2- A. P. Sattelberger, "Organo-f-Element phenyl-3H-pyrazo-3-thione (BMPPT) and Chemistry: Balancing Theory and Experiment," Neutral Adducts Using an Automated Symposium on the Interplay of Theory and Extraction System," ACS Spring Meeting, Experiment in Organometallic Chemistry, Toronto, Canada, June 5-10,1988. March 28,1988. E. C. Niederhoffer, C. M. Naranjo, and J. A. Fee, A. P. Sattelberger, "Niobium and Tantalum "Iron Superoxide Dismutase and Iron Uptake in Hydride Complexes," ACS Spring Meeting, Escherichia coli," seminar(s), Department of Toronto, Canada, June 5-10,1988. Symposium Pharmaceutical Chemistry, University of on the Nobel Laureate Signature Award, invited. California, San Francisco, California, August 10, 1988, and Department of Biochemistry, A. P. Sattelberger, J. C. Huffman, and W. G. Van University of California, Berkeley, California, Der Sluys, "Uranium(III) Aryloxide Complexes," August 11, 1988. Eighteenth Rare Earth Research Conference, Lake Geneva, Wisconsin, September 12-16, E. C. Niederhoffer, "Evidence for the 1988. Involvement of Superoxide Dismutases in the fur Operon in Escherichia coli K-12: B. F. Smith, G. D. Jarvinen, and C. S. Bartholdi, Is There a Physiological Role for SOD?" "Extraction Properties of Soft Donor Ligand Occasional Seminars in Biochemistry Series, Systems," 12th Actinide Separations INC-4, Los Alamos, April 7,1988. Conference, Naperville, Illinois, May 8-11,1988. Invited. E. C. Niederhoffer, C. M. Naranjo, and J. A. Fee, "Regulation of the Iron Superoxide Dismutate B. F. Smith, G. D. Jarvinen, H. L. Nekimken, Gene (sodB) by the fur Locus in Escherichia M. Jones, and C. S. Bartholdi, "Comparison coli K-12," 3rd Internationa] Conference on of Several Monothio-b-dicarbonyl Ligands for Archaebacteria: Genome Structure, the Separation of Actinide (An(IID) and Transcription, Translation, and Gene Lanthanide (Lndll))," ACS Spring Meeting, Expression, Vancouver Island, B. C, Canada, Toronto, Canada, June 5-10,1988. July 31- August 5, 1988. M. A. Stroud, "The Effects of Pressure on the E. C. Niederhoffer, C. Naranjo, and J. A. Fee, Electronic and Resonance Raman Specira of "Iron (sodB) and Manganese fsodA) Superoxide Quasi-One-Dimensional Mixed Valence 102 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Semiconductors." .seminar at Group OLS-4. Los Technology of Synthetic Metals. Santa Fe, Alamos National Laboratory, November 1.6, New Mexico, June 26-July 2, 1988. 1987. B. I. Swanson, S. D. Conradson, J. Weinrach, M. A. Stroud. B. I. Swanson, M. H. Zietlow, and A. P. Sattelberger, "Structural Studies H. B. Gray, and H. G. Drickamer, "Pressure of the Valence-Delocalized and Metastable Tuning of the Electronic and Resonance Trapped-Valent Forms of the 1-D Mixed-Valence Raman Spectra of Quasi-One-Dimensional Solid K4[Pt2 B. I. Swanson, "Spectroscopic Studies of P. J. Unkefer: see also Langston-Unkefer. Materials Under Extreme Conditions," Selected Topics in Explosive Research W. G. Van Der Sluys, C. J. Burns, Featuring the ISRD Program Chemistry, A. P. Sattelberger, and J. C. Huffman, M Division seminar, December 9,1987. "Synthesis and Characterization of U(IV) Phenoxide Complexes," American Chemical B. I. Swanson, "Static High Pressure and Society National Meeting, Los Angeles, Shock Studies of Nitrogen Oxides," California, September 25-30,1988. Symposium on the Characterization and Diagnostics of Energetic Materials, L. S. Van Der Sluys, K. A. Kubat-Martin, Los Angeles, California, August 9-10,1988. G. J. Kubas, and R. R. Ryan, "Reactions of Invited. Metal-Dihydrogen Complexes: Studies of Fe, Ru, and W," American Chemical Society National B. I. Swanson and S. D. Conradson, Meeting, Los Angeles, California, September 25- "Spectroscopic and Structural Studies of 30,1988. Low-Dimensional Mixed-Valence Solids," International Conference on Science and Isotope and Xuch'ar Clu'inistrx l)n ISIUH Rium! V.W-s 1<):1 Appendix: Presentations W. G. Van Dor Sluys, R. K. Ryan, and INC-7 A. P. Sattelborger, "Lanthanidc and Actinide Phosphido Complexes. Versatile Reagents in J. C. Banar, R. K. Pen-in, and R. A. Ostrengu. Inorganic and Organic Chemistry," ACS Spring "Multiple Filament Analyzing Turret," Thirty- Meeting, Toronto, Canada, June 5-10, 1988. Six Allied Topics, San Francisco, California, June 5-10,1988. W. G. Van Der Sluys, A. P. Sattelberger, and J. C. Huffman, "Uranium AJkoxide Chemistry: G. K. Bayhurst, D. L. Finnegan, R. C. Hagan, Synthesis and Characterization of Novel A. S. Mason, E. J. Mroz, C. L. Peach, Aryloxide Complexes," ACS Spring Meeting, R. Raymond, Jr., and K. H. Wohletz, Misty Toronto, Canada, June 5-10,1988. Picture Dust and Fallout Characterization (Draft),' MISTY PICTURE Results Symposium, W. E. Wageman, "A Simple User Upgrade to Harry Diamond Laboratories, Adclphi, Replace the CDC CMD Disk Drives on Bruker Maryland, December 7-10, 19S7. Spectrometers," Bruker User's Group meeting, Lowell, Massachusetts, October 18-24,1987. B. M. Crowe, F. V. Perry, B. Turrin, S. G. Wells, and L. D. McFadden, "Volcanic Hazard T. Yoshida, "A Biochemical Model of Human Assessment for Storage of High-Level Erythrocytes," INC-4 Group Meeting, September Radioactive Waste at Yucca Mountain, 9,1988. Nevada," Geological Society of America Meeting, Las Vegas, Nevada, March 27-30,1988. T. Yoshida, M. Dembo, and J. A. Fee, "A Biochemical Model of Human Eryihrocytes," R. C. Estler, N. S. Nogar, B. L. Fearey, American Society for Biochemistry and C. M. Miller, and M. W. Rowe, "Laser Molecular Biology, Las Vegas, Nevada, Desorption/Ablation Studies by Resonance May 1-5,1988. Ionization Mass Spectrometry," Resonance Ionization Spectroscopy (RIS-88) Conference, B. H. Zimmerman, C. I. Nitsche, J. A. Fee, Gaithersburg, Maryland, April 1988. F. Rusnak, and E. Munck, "Properties of a Copper Containing Cytochrome ba3. A Second B. L. Fearey, J. E. Anderson, C. M. Miller, Terminal Oxidase from Thermus thermophilus N. S. Nogard, and M. W. Rowe, "Resonance (Tt)," American Society for Biochemistry and Ionization Mass Spectrometry of Lead and Molecular Biology, Las Vegas, Nevada, Bismuth Mixtures," Resonance Ionization May 1-5,1988. Mass Spectroscopy (RIS-88) Conference, Gaithersburg, Maryland, April 1988. INC-5 B. L. Fearey, D. C. Parent, R. A. Keller, and C. M. Miller, "Isotopically Selective, Doppler- M. M. Minor and E. B. Shera, "Real-Time Data Free, Saturation Spectroscopy of Lutetium Acquisition and Control Using Xinu in a Isotopes Via Resonance Ionization Mass VMEbus Environment," Symposium on Real- Spectrometry," Resonance Ionization Mass Time Software and Operating Systems Spectroscopy (RIS-88) Conference, (sponsored by the IEEE Computer Society Gaithersburg, Man'land, April 1988. and the Usenix Assoc), Washington, D.C., May 12-13,1988. B. L. Fearey, D. C. Parent, R. A. Keller, and C. M. Miller, "Secondary, Non-Resonant M. E. Bunker, "The Omega West Reactor as CW Laser Ionization Efficiency Enhancement a Chemistry Resource," Chemistry Review for Resonance Ionization Mass Spectrometry," Committee, LANL, May 16,1988. Resonance Ionization Spectroscopy (RIS-88) Conference, Gaithersburg, Maryland, M. E. Bunker, "Review of OWR and Plans for April 1988. a Replacement Reactor," LANL Management meeting chaired by ADR, Los Alamos, August B. L. Fearey, D. C. Parent, R. A. Keller, and 26,1988. C. M. Miller, "Very High Resolution Saturation Spectroscopy of Lutetium Isotopes Via CW Isotope and Nuclear Chemistry Division Annual Report FY 1988 Appendix: Pre Single Frequency Laser Resonance by Proton Microprobe J. S. Gaffney, J. H. Hall, N. A. Marley, N. A. Marley, D. R. Janecky, and J. S. Gaffney, G. E. Streit, and I. R. Triay, "Modeling "Laser Raman and Fourier Transform Infra-Red Carbonaceous Atmospheric Chemical Spectroscopic Studies of Organic Acid/Silicic Processes," Third International Conference Acid Complexation," 1988 Spring American on Carbonaceous Particles in the Atmosphere, Geophysical Union Meeting, Baltimore, Berkeley, California, October 6-8,1987. Maryland, May 16-20,1988. J. S. Gaffney, E. W. Prestbo, E. Franzblau, N. A. Marley, P. S. Z. Rogers, T. M. Benjamin, and C. J. Popp, "NO2 and Peroxyacetyl Nitrate and D. R. Janecky , "The Study of Metal Measurements in Albuquerque, New Mexico," Speciation at High Temperatures and Pressures 1988 American Chemical Society Annual Via Laser Raman Spectroscopy," 1987 American Meeting, Los Angeles, California, September 18- Geophysical Union Fall Meeting, San Francisco, 23,1988. California, December 6-11,1987. J. S. Gaffney and R. L. Tanner, "Alcohol Fuel A. S. Mason, "Long Range Atmospheric Tracer Use: Implications for Atmospheric Levels of Experiments in the Antarctic," University Aldehydes, Organic Nitrates, Pans, and of Miami, Rosenstiel School of Marine and Peroxides. Separating Sources Using Carbon Atmospheric Science, Miami, Florida, Isotopes," CRC-APRAC Methanol Fuel Vehicle January 15, 1988. Workshop, Orange, California, April 19-21, 1988. A. S. Mason and E. J. Mroz, "Atmospheric Methane," INCOR Meeting, Los Alamos, D. R. Janecky, "Coupled Sulfur Isotopic and New Mexico, September 15-16,1988. Chemical Mass Transfer Modeling: Approach and Application to Dynamic Hydrothermal A. Meijer, "Evaluation of Sorption Approach," Processes," 1988 American Chemical Society Sorption Informational Exchange Meeting with Annual Meeting, Los Angeles, California, Lawrence Livermore EQ3/6 Group, Livermore, September 18-23,1988. California, February 10, 1988. D. R. Janecky, R. S. Rundberg, M. A. Ott, and A. Meijer, S. T. Kwon, and G. R. Tilton, Pb-Sr- A. J. Mitchell, "Dynamic Transport of Dissolved Nd Isotopic Studies on Ultramafic Nodules," Tracers (Tritiated Water, Pertechnetate, and 1988 Spring American Geophysical Union Sulforhodamine/Thru Fractured Tuff," 1987 Meeting, Baltimore, Maryland, May 16-20,1988. Geological Society of America Annual Meeting, Phoenix, Arizona, October 26-29,1987. C. M. Miller, B. L. Fearey, B. A. Palmer, and N. S. Nogar, "High-Fidelity in Isotope Ratio A. Kracher, T. M. Benjamin, C. J. Duffy, and Measurements by Resonance lonization Mass P. S. Z. Rogers, Analysis of Meteoritic Minerals Spectrometry," Resonance lonization Mass Isoto/teafid Xuckar Chemistry Division Report 1HHS Appendix: Presentations Spectroscopy (RIS-88) Conference, D. J. Rokop, "Mass Spectrometry at 2.2 km," Gaithersburg, Maryland, April 1988. University of Mainz, Institute of Nuclear Chemistry, Mainz, Germany, September 7, E. J. Mroz, M. Alei, and A. S. Mason, "Injection 1988. of Deuterated Methane into the Stack of a Coal- Fired Power Plant," Air Pollution Control D. J. Rokop, "Mass Spectrometry at 2.2 km," Association Meeting, Eighty-First Annual University of Regensburg, Regensburg, Meeting and Exhibition, Dallas, Texas, Germany, September 8,1988. June 20-24,1988. D. J. Rokop, N. C. Schroeder, and K. Wolfsberg, M. T. Murrell, "238U-230Th Disequilibrium "High Sensitivity Technetium Analysis Utilizing Measurements Using Solid Source Mass Negative Thermal Ionization Mass Spectrometry," JOI Workshop on Dating Spectrometry," Eleventh International Mass MORB, Northwestern University, Evanston, Spectrometry Conference, Bordeaux, France, Illinois, November 1987. August 29-September 2,1988. A. E. Norris, "Scientific Needs of the Los Alamos F. R. Roensch, R. E. Perrin, J. H. Cappis, National Laboratory Geochemistry Program," M. Attrep, Jr., and D, W. Efurd, "Quantification U.S. DOE Workshop on Dry Drilling and Coring of Actinides by Isotope Dilution Mass Technology, Las Vegas, Nevada, July 26-27, Spectrometry," South West Regional American 1988. Chemical Society Meeting, Cosmochemistry Symposium, Little Rock, Arkansas, December 2- A. E. Norris, "Diffusion Test," Yucca Mountain 4,1987. Project Briefing for Los Alamos National Laboratory Deputy Directory W. F. Miller, J. Rogowski, N. Kaffrell, H. Tetzlaff, Los Alamos, New Mexico, September 13,1988. N. Trautmann, D. De Frenne, K. Heyde, E. Jacobs, G. Skarnemark, J. Alstad, R. E. Perrin and M. T. Muurell, "Evaluation of M. N. Harakeh, J. M. Schippers, S. Y. van der the Boric Acid-Silica Gel System for Production Werf, W. R. Daniels, and K Wolfsberg, of Thermal Ions," Thirty-Sixth ASMS "Evidence for Shape Coexistence in Neutron- Conference on Mass Spectrometry and Allied Rich Rh and Ag Nuclei," International Workshop Topics, San Francisco, California, June 5-10, on Nuclear Structure of the Zirconium Region, 1988. Bad Honnef, Germany, April 24-28,1988. F. V. Perry, W. S. Baldridge, and D. J. DePaolo, R. L. Tanner, J. M. Roberts, J. S. Gafihey, and "Lithospheric Thinning Inferred from D. L. Sisterson, "Evaluation of Springtime Geochemical and Nd and Sr Isotopic Studies of Nitrogen Oxide and Oxidant Data from a Basalts from the Rio Grande Rift Region," 1987 Suburban/Rural Northeast USA Surface Site," Geological Society of America Annual Meeting, 1988 American Chemical Society Annual Phoenix, Arizona, October 26-29,1987. Meeting, Los Angeles, California. September 18-23,1988. E. W. Prestbo and J. S. Gaffhey, "Peroxyacetyl Nitrate (PAN) Measurements at a Remote Site in New Mexico," 1988 American Chemical INC-11 Society Annual Meeting, Los Angeles, California, September 18-23,1988. FY1986 E. W. Prestbo, W. H. Zoller, R. Dizon, J. Zieman, M. M. Fowler, P. Lysaght, J. B. Wilhelmy, J. S. Gaffney, E. Franzblau, and C J. Popp, W. B. Ingalls, and J. R. Tesmer, "Accelerator "PAN and Ozone Measurements at Remote Based Mass Spectrometry of Molecules," and Rural Oceanic and Continental Influenced American Chem. Society, Chicago, Illinois, Field Stations," 1987 American Geophysical September 8-13,1985. Union Fall Meeting, San Francisco, California, December 6-11,1987. 106 Isotope and Nuclear Chemistry Division Annual Report FY1988 dtx: I'tvst 'ft 1a tion ,s J. A. Mercer-Smith, D. A. Cole, S. D. Figard, R. L. Ferguson, A. Guessou.s, B. V. Jacak, A. H. Herring, R. M. Lopez, D. C. Moody, P. Lysaght, G. Mamone, F. E. Obenshain, P. Q. Oliver, F. H. Seurer, R. C. Staroski, F. Plasil, C. Ristori, R. Schmidt, R. G. Stokstad, F. J. Steinkruger, W. A. Taylor, and S. Wald, M. M. Fowler, A. Gavron, A. Gayer, and D. K. Lavallee, "Applications of Medical S. Gazes, "Saddle to Scission: Time Scales and Radioisotopes," invited paper, Metals in Dissipative Mechanisms," American Chemical Medicine Symposium, Abstract INOR-45, Society, Chicago, Illinois, September 8-13,1985. American Chemical Society National Meeting, Anaheim, California, September 7-12,1986. P. Wilde, W. B. N. Berry, M. S. Quinby-Hunt, K. Rice, C. J. Orth, J. S. Gilmore, and J. A. Mercer-Smith and D. A. Cole, L. R. Quintana, "Chemostratigraphic Analysis "Copper-67 Research," Dimensions in Science across a Jurassic Extinction Event in the (Radio Program #1365), Science Chronicles Yorkshire Toarcian," 99th Annual Meeting of and Science Log (Radio Program #223), the Geological Society of America, San Antonio, American Chemical Society Radio Interviews. Texas, November 10-13,1986. D. J. Nichols, G. A. Izett, and C. J. Orth, W. S. Wolbach, E. Anders, M. M. Grady, "Cretaceous-Tertiary Event: vidence from C. T. Pillinger, R. R. Brooks, C. J. Orth, and Southern Canada," Society of Economic J. S. Gilmore, "Carbon Isotopes and Iridium at Paleontologists, Raleigh, North Carolina, Two Cretaceous-Tertiary Boundary Sites in September 26-28,1986. New Zealand," 49th Meteoritical Society Meeting, New York, September 22-25,1986. C. J. Orth, J. S. Gilmore, X.-Y. Mao, and J. E. Barrick, "Pt-Group Element Anomalies H. Wollnik, J. M. Wouters, and D. J. Vieira, in the Lower Mississippian of Oklahoma," 99th "TOFI: An Isochronous Time-of-Flight Mass Annual Meeting of the Geological Society of Spectrometer," 2nd Int. Conf. on Charged America, San Antonio, Texas, November 10-13, Particle Optics," Albuquerque, NM, May 19-23, 1986. 1988. R. D. Rieke, T. P. Burns, R. Wehmeyer, B. Kahn, J. M. Wouters, D. J. Vieira, H. Wollnik, "Preparation of Highly Reactive Metal Powders: G. W. Butler, R. H. Kraus, Jr., and K. Vaziri, Some of Their Uses in Organic and "The Time-of-Flight Isochronous (TOFI) Organometallic Chemistry," Symposium on Spectrometer for Direct Mass Measurements High Energy Processes in Organometallic of Exotic Light Nuclei," Proc. 11th Int. Conf. Chemistry, 192nd Meeting of the American on Electromagnetic Isotope Separators and Chemical Society, September 1986, Anaheim, Techniques Related to Their Application, CA, (invited paper). Los Alamos, NM, August 1986. F. J. Steinkruger, P. M. Wanek, A. Cui, FY1987 D. R. Phillips, W. A. Taylor, and D. C. Moody, "Biomedical Generator Development at Los J. Boissevain, H. C. Britt, M. M. Fowler, Alamos National Laboratory," IAEA Seminar A. Gavron, B. Jacak, P. Lysaght, G. Mamane, on Radionuclide Generator Technology, Vienna, and J. B. Wilhelmy, "Composite Charged Austria, October 13-17,1986. Particle Detectors with Logarithmic Energy Response for Large Dynamic Range Energy K. Vaziri, F. K. Wohn, D. J. Vieira, H. Wollnik, Measurements," National Meeting of the and J. M. Wouters, "Performance of the American Chemical Society, Denver, Colorado, Reaction-Product Transport Line Associated April 5-10,1987. with the TOFI Spectrometer," Proc. 11th Int. Conf. on Electromagnetic Isotope Separators J. S. GaRhey, J. H. Hall, N. A. Madey, and Techniques Related to Their Application, G. E. Streit, and I. R. Triay, "Modeling Los Alamos, New Mexico, August 1986. Carbonaceous Atmospheric Chemical Processes," 3rd International Conference on J. B. Wilhelmy, C. Albiston, J. P. Bocquet, Carbonaceous Particles in the Atmosphere, J. Boissevain, H. C. Britt, Y. D. Chan, Berkeley, California, October 6-8,1987. IsotojM! and Nuclear Chemistry Division Report 1988 U>7 Apfh'n dix: Pn-si'ii in tions I. Gilmour, C. J. Orth, and R. R. Brooks, A. E. Ogard, K. Wolfsberg, J. L. Thompson "Carbon at a New K-T Boundary Site in New R. S. Rundberg, P. W. Kubik, D. Elmore, and Zealand," 50th Meeting of the Meteoritical H. W. Bentley, "Migration in Alluvium of Society, Newcastle, England, July 27-30,1987. Chlorine-36 and Tritium from an Underground Nuclear Test," International Conference on B. V. Jacak, H. C. Britt, A. I. Gavron, Chemistry and Migration Behavior of Actinides J. Wilhelmy, J. W. Harris, G. Claesson, and Fission Products in the Geosphere, Munich, K. G. R. Doss, R. Ferguson, H.-A. Gustaffson, Germany, September 14-19,1987. H. Gutbrod, K.-H. Kampert, B. Kolb, F. Lefebvres, A. M. Poskanzer, H.-G. Riter, C. J. Orth, "Mass Extinctions of Life: H. R. Schmidt, L. Teitelbaum, M. Tincknell, A Geochemical Search for Causes," INC S. Weiss, and H. Wieman, "Fragmentation Division Colloquium, October 22,1987. and Flow in Central Collisions," ACS Spring Meeting, Denver, Colorado, April 5-10,1987. R. S. Rundberg and I. R. Triay, "Modeling of Multivalent Ion-Exchange Isotherms, National D. R. Janecky, R. S. Rundberg, M. A. Ott, and Meeting of the American Chemical Society, A. J. Mitchell, "Dynamic Transport of Dissolved New Orleans, Louisiana, August 30-September Tracers (Tritiated Water, Pertechnetate, and 4,1987. Sulforhodamine) Thru Fractured Tuff," 1987 Geological Society of America Annual Meeting, R. S. Rundberg, K. Wolfsberg, D. J. Rokop, Phoenix, Arizona, October 26-29,1$87. R. E. Perrin, M. T. MurrelL D. B. Curtis, G. A. Cowan, E. A. Bryant, and M. Attrep, N. Kaffrell, J. Rogowski, H. Tetzlaff, "Mass Spectrometric Measurement of '""Mo N. Trautmann, D. DeFrenne, K. Heyde, Double Beta Decay Experiment," National E. Jacobs, G. Skarnemark, J. Alstad, Meeting of the American Chemical Society, M. N. Harakeh, J. M. Schippers, S. Y. van New Orleans, Louisiana, August 30-September der Werf, W. R. Daniels, and K. Wolfsberg, 4,1987. "Evidence for Shape Coexistence in Neutron- Rich Rh and Ag Isotopes," Fifth International R. S. Rundberg, A. J. Mitchell, and Conference on Nuclei Far from Stability, B. J. Torstenfelt, "Size and Density of a 242Pu Rosseau Lake, Ontario, Canada, September Colloid," Material Research Society Meeting, 14-19,1987. Boston MA, November 30 - December 5,1987. T. D. Kunkle, F. N. App, W. L. Hawkins, R. R. Ryan, J. H. Hall, I. O. Bohachevsky, and A. Ogard, J. L. Thompson, W. M. Brunish, I. R. Triay, "Conformation Optimization Using "The Aleman Radionuclide Migration Study," Generalized Simulated Annealing," National The Fourth Containment Symposium, Colorado Meeting of the American Chemical Society, Springs, Colorado, September 21-24,1987. Denver, Colorado, April 5-10 1987. L. C. Liu, "Eta Mesons in Nuclei," Conf. on K. Thomas, "Careers in Chemistry," Physics with Light Mesons, Los Alamos, New presentation and demonstration to Santa Mexico,Aug. 1987. Fe Indian School, October 1987. L. C. Liu, "Nuclear Dynamics of Bound and N. Trautmann, T. Altzitzoglou, G. Herrmann, Unbound Eta Mesons: Eta-Mesic Nuclei and N. Kaffrell, J. Rogowski, N. Tetzlaff, Eta-Mesic Compound Nuclear Resonances," G. Skarnemark, M. Skaalberg, J. Alstad, Int. Symposium on Medium Energy Physics, W. R. Daniels, and W. L. Talbert, "Investigation Beijing, People's Republic of China, June 1987. of Short-Lived Fission Products in the Mass Region a ) 110 After Fast Chemical J. A. Mercer-Smith and F. J. Steinkruger, Separations," 2nd International Conference on "Chemistry and Biochemistry of Nuclear and Radiochemistry," Brighton, Radiopharmaceuticals," External Biosciences England. ISRD Review, Los Alamos National Laboratory, Los Alamos,, November 3-5,1987. 108 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Ap/h'n(iix: I''v'si'Titatiotin I. R. Triay and R. S. Rundbcrg, "Deconvolution FY1988 of Ion-Exchange Isotherms," National Meeting of the American Chemical Society, Denver, CO, M. Attrep, Jr. and C. J. Orth, Radiochemical April 5-10,1987. Study of Biological Crisis Zones in the Fossil Record," 196th National Meeting of the I. R. Triay and R. S. Rundberg, "Application of American Chemical Society, Los Angeles, the Numerical Deconvolving Technique of California, September 25-30,1988. Regularization to the Analysis of Ion-Exchange Isotherms," 36th Annual Clay Minerals T. P. Burns and J. A. Mercer-Smith, Conference. Socorro, New Mexico, October 18- "Paramagnetic Contrast Imaging Agent 22,1987. Research at Los Alamos Medical Radioisotope Research Program," INC-1.1 Seminar Series, A. L. Turkevich, G. A. Cowan, F. 0. Lawrence, July 28,1988. S. D. Knight, T. Economou, W. C. Haxton, " 238u Double Beta Decay Experiment;" D. A. Cole, J. A. Mercer-Smith, J. K. Norman, American Chemical Society National Meeting, K. P. Williams, M. J. Behr, and D. K. Lavallee, August 30 - September 4,1987, New Orleans, "Localization of Water-Soluble Porphyrins in Louisiana. Inflamed Lymph Nodes," American Society for Photobiology 16th Annual Meeting, Colorado D. J. Vieira, J. M. Wouters, and the TOFI Springs, Colorado, March 13-17,1988. Collaboration, "Direct Mass Measurements of Light Neutron-Rich Nuclei Using Fast Recoil D. A. Cole, J. A. Mercer-Smith, K. P. Bullingtcn, Spectrometers,',' 5th Int. Conf. on Nuclei Far J. K. Norman, M. J. Behr, and D. K. Lavallee, From Stability^ Rosseau Lake, Ontario, "The Uptake of a Copper-67 Labeled Porphyrin Canada, September 14-19,1987. by Inflamed Lymphatic and Nonlymphatic Tissues," Federation of American Societies for J. M. Wouters, "TOFI: Not Just Another Experimental Biology (FASEB), 72nd Annual Candy," Nuclear Science Division Seminar Meeting, Las Vegas, Nevada, May 1-5,1988. Lawrence Berkeley Laboratory, May 1987. M. M. Fowler, "The Development of the The following four papers were presented at PAGODA Detector System and Some the 1987 Annual Meeting of the Geological Preliminary Results from Nb + Au at 100 Society of America, Phoenix, Arizona. Mev/Nucleon," Univ. of Mainz, April 7,1988. October 26-29,1987: B. M. French, C. J. Orth, and L. R. Quintana, W. B. N. Berry, M. S. Quinby-Hunt, P, Wilde, "Iridium in Vredefort Bronzite Granophyre: and C. J. Orth, "Use of the Cerium Anomaly in Impact Melting and Limits on a Possible Black Shales: Climatic Interpretation in the Extraterrestrial Component," 19th Lunar and Ordovician-Silurian Boundary Interval, Dob's Planetary Science Conference, Houston, Texas, Linn, Scotland." March 14-18,1988. K. R. Johnson, C. J. Orth, and D. J. Nichols, T>. K. Lavallee, J. A. Mercer-Smith, D, Ai Cole, "Fossil Leaf and Palynomorph Changes J. C. Roberts, and R. Fawwaz, "Gamma Imaging Associated with an Iridium Anomaly at the with Metalloporphyrins," Abstract INOR-13, Cretaceous-Tertiary Boundary in North Dakota" Metalloporphyrin Symposium, 196th American Chemical Society National Meeting, Los C. J. Orth, M. Attrep, Jr., X.-Y. Mao, Angeles, CA, September 25-30,1988. E. G. Kauffman, and R. Diner, "Iridium Abundance Peaks at L^pper Cenomanian D. K. Lavallee, J. A. Mercer-Smith, Stepwise Extinction Horizons." J. C. Roberts, D. A. Cole, and R. A. Fawwaz, "Novel Porphyrins: Stable Chelators for P. Wilde, M. S. Quinby-Hunt, W. B. N. Berry, Imaging Applications," Florida Conference and C. J. Orth, "Southern New Brunswick - on Chemistry in Biotechnology, 1988: A Balto-Scandian Terranein the Tremadoc Biomedica) Applications of Metals, Palm (Ordovician) Iapetus Ocean." Coast, Florida, April 26-29,1988. Isotope and Nuclear Chemistry Division Report 1988 JG9 Appendix: Publications C. J. Orth and M. Attrep, Jr., "Elemental Derived Acetaldehyde," 21st National Medicinal Abundance Patterns Across Bio-Event Chemistry Symposium, Minneapolis, Minnesota, Horizons," Spring Meeting of the American June 16-23,1988. Geophysical Union, Baltimore, Maryland, May 16-20,1988. F. J. Steinkruger, "New Generators for Diagnostic and Therapeutic Nuclides," 35th C. J. Orth and M. Attrep, Jr., "Iridium Society of Nuclear Medicine Annual Meeting, Anomalies and Mass Extinctions~A Search San Francisco, Calif., June 14-17,1988. for Periodicity," Albuquerque Geological (Continuing Education Course - Society, September 20,1988. Radiopharmaceuticals from Parent/Daughter Generator Systems). •; C. J. Orth, M. Attrep, Jr., L. R. Quintana, R. Diner, and W. P. Elder, "Siderophile K. Thomas, "High School Requirements for an Abundance Maxima at Upper Cenomanian Advanced Technical Degree," Mathematics Marine Invertebrate Extinction Horizon: Institute for Teacher Enhancement, Los Alamos Western Interior of North America," National Laboratory, June 17,1988. 19th Lunar and Planetary Science Conference, Houston, Texas, March K. Thomas, 'Chemistry is Fun," presentation 14-18,1988. and demonstration to Pinon Elementary School- 1/88, Kachina Preschool-4/88, and the YMCA P. D. Palmer, "Preparation and Characterization Afterschool Program-4/88. of Pure Oxidation States of the Actinide Elements," presented to the Central New Mexico Thompson, J. L., "The Los Alamos Program," Section of the Technicians Affiliate Association Hydrology/Radionuclide Migration Program of the ACS at Sandia National Laboratories, Steering Committee Meeting, Las Vegas, March 10,1988. Nevada, September 15-16,1988. J. C. Roberts, J. A. Mercer-Smith, S. A. Schreyer, D. A. Cole, S. D. Figard, and D. K. Lavallee, "Labeling Proteins with Copper-67," Florida Conference on Chemistry in Biotechnology, 1988: Biomedical Applications of Metals, Palm Coast, Florida, April 26-29, 1988. J. Roberts, J. Mercer-Smith, D. Cole, S. Schreyer, S. Figard, and D. Lavallee, "Site- Directed Imaging and Therapy of Cancer Using Copper-67 Labeled Monoclonal Antibodies," Third Santa Fe Graduate Medicinal Chemistry Conference, Santa Fe, New Mexico, August 7-9, 1988. J. C. Roberts, S. A. Schreyer, D. A. Cole, J. A. Mercer-Smith, S. D. Figard, and D. K. Lavallee, "Porphyrins as Chelating Agents for Labeling Antibodies with Copper Radioisotopes," Metalloporphyrin Symposium, 196th American Chemical Society National Meeting, Los Angeles, California, September 25-30,1988. J. C. Roberts, H. T. Nagasawa, J. A. Elberling, and E. G. DeMaster, "Prodrugs of D- Penicillamine in the Sequestration of Ethanol- 110 Isotope and Nuclear Chemistry Division Annual Report FY 1988 Afi/M'ii(f(x: Oil in/t/tt Xh'fttni's rind Sr Division Meetings and Seminars Advisory Committee for Isotope and Nuclear Chemistry Division, July 19-22,1988 Donald W. Barr, "Response to 1987 Committee Michael Minor, "The Integrated Omega West Report and Summary of Division Activities" Reactor (OWR) Laboratory" Robert Ryan, "Isotope and Structural Chemistry James Fee, "The Stable Isotope Resource and Overview, INC-4" an Overview of the Biochemistry Section of Group INC-4" Merle Bunker, "Research Reactor Overview, INC-5" Michael Mather, "Cloning Cytochrome Oxidase Genes from Thermus" Bruce Crowe, "Isotope Geochemistry Overview, INC-7" Clifford Unkefer, "Biosynthesis of the Coenzyme PQQ in Methylobacterium AM1" William Daniels, "Nuclear and Radiochemistry Overview, INC-11" Pat Unkefer, "New Insights into the Control of Symbiotic N2-Fixation" Robert Charles, "Sleuthing the Geochemistry at Salton Sea" Gordon Jarvinen, "New Directions in Actinide Separation Chemistry" Michael Murrell, "238(j.230jn Disequilibrium Measurements Using Solid Source Mass Inez Triay and Robert Rundberg, "Development Spectrometry" of an Innovative Technique for the Study of Cation Exchange in Synthetic and Natural Exchangers" Jeff Gaffney, "Tropospheric Chemistry of Organics" David Hobart and David Morris, "The Chemistry Nancy Marley, "Laser Raman Investigations of of Actinides Under Environmental Conditions" Aqueous Geochemical Complexation" Moses Attrep and Wes Efurd, "Requirements, Merle Bunker, "Low-Energy Nuclear Structure Techniques and Capabilities for Low Abundance, Research" High Purity Radiochemical Determination" Phil Chamberlin, "Electromagnetic Isotope Separation: Progress and Plans" Isotope and Xucltar Chi'rm-:tr\ ])nis;i>n Annual R<]»>rt FY 111 Appendix: Division Meetings and Seminars Division Seminars "Immunization with Rat Osteosarcoma Cells "Recent Development in X-Ray Absorption Yield Monoclonal Antibodies that Recognize Spectroscopy at Los Alamos," Steven Conradson, Two Distinct Cell-Associated Proteoglycans," INC-4, April 21, 1988. Jeffrey P. Gorski. University of Missouri, October 29, 1987. "Humics and Radionuclide Migration," Gregory R. Choppin, Florida State University, April 22,1988. "Mass Extinctions of Life: A Geochemical Search for Causes," C. J. Orth, INC-11, October 22, 1987. "A Fortran Precompiler and System for Automating the Implementation of Forward "Seismosauras of San Ysidro," Steve Agnew, and Adjoint Deterministic Sensitivity Methods INC-4, November 19, 1987. into Existing Fortran Computer Codes," Brian A. Worley, Oak Ridge National Laboratory, "Technetium Chemistry and Its Relevance to April 27, 1988. Nuclear Medicine," Alan Davison, Department of Chemistry, Massachusetts institute of Technology, "Stripa Project," Edward S. Patera, US Department December 3, 1987. of Energy, Argonne, Illinois, July 6,1988. "Coordination of Hydrogen Molecules to Metal "Kinetics of Crystal Growth in Igneous Systems: Centers: Prototype for Nonclassical Chemical Experiments and a Simple Model," Gregory E. Bonding," Gregory J. Kubas, INC-4, January 21, Muncill, Carnegie Institution of Washington, July 1988. 26, 1988. "Accelerator 14C Dating of Amino Acids: "The Speciation of Transuranic Ions in Natural Applications in Quaternary Geology and Aquifer Systems by Laser Induced Photoacoustic Paleontology," T. W. Stafford, University of Spectroscopy (LPAS)," Professor Jae-il Kim, New Mexico, March 11, 1988. University of Munchen, September 9, 1988. 112 Isotope and Nuclear Chemistry Division Report FY 1988 Appendix: References 14. P. H. Smith, J. R Brainard,. G. D. Jarvinen, D. E. Morris, and R. R. Ryan, Am. Chem. 1. R. E. Perrin, P. Q. Oliver, T. L. Norris, G. F. Soc. Pz-oc. A341 (1988). Grisham, A. J. Gancarz, D. W. Efurd.W. R. 15. Phillips et al., Appl, Radial. IsoL 38, No. 1, Daniels, and D. W. Barr, "A New Radio- 521-525, (1987). chemical Detector: 243Am," in "The Isotope 16. M. R. Rampino and R. B. Stothers, Nature and Nuclear Chemistry Division Annual 308, 707 (1984). Report FY 1982," Los Alamos National Laboratory report LA-9797-PR (June 1983), 17. D. P. Whitmire and A. A. Jackson, Nature p. 24. 308, 713 (1984). 18. W. Alvarez and R. A. Muller, Nature 308, 2. Jacob Kleinberg and Merlyn E. Holmes, 718 (1984). Comps. and Eds., "Collected Radiochemical 19. D. M. Raup and J. J. Sepkoski, Jr., Proc. and Geochemical Procedures, 5th Edition," Natl. Acad. Sci. 81, 801 (1984). Los Alamos National Laboratory report LA-1721, 5th ed. (July 1989). 20. C . J. Orth, M. Attrep, Jr., X.-Y. Mao, E. G. Kauffman, R. Diner, and W. P. Elder, 3. E. P. Chamberlin, K. N. Leung, S. Walthers, Geophys. Res. Lett. 15, 346 (1988). R. A. Bibeau, R. L. Stice, G. M. Kelley, and 21. B. M. Crowe, D. L. Finnegan, W. H. Zoller, J. Wilson, Nucl. lustrum. Meth. Phys. Res. B26, 227 (1987). and W. V. Boynton, J. Geophys. Res. 92, B13,13708-13714 (1987). 4. J. A. Duine, and J.Frank Jzn., Trends 22. D L. Finnegan, J. P. Kotra, D. M. Hermann, Biochem. Sci. 6, 278-280(1981). and W. H. Zoller, Bull. Volcanol. 51, 83-87 5. J.A. Duine, Jzn. J. Frank, and J.A. (1988). Jongejan, FEMS Microbiol Rev. 32, 23. D. L. Finnegan, B. M. Crowe, W. H. Zoller, 165-1781986. and D. M. Hermann, "Trace Element 6. C. L. Lobenstein-Verbeck, J. A. Jongejan, Composition of Mauna Loa Gases and Jzn. J. Frank, and J. A. Duine, FEBS Lett. Particles During the Spring, 1984 170, 305-309 (1984). Eruption," Submitted to J. Geophys. Res., 7. R. A. van der Meer and J. A. Duine, 1989. Biochem. J. 23 9, 789-791 (1986). 24. King, Separation and Purification: 8. D. R. Houck, J.L. Banners, and C. J. Critical Needs and Opportunities (US Unkefer, J. Am. Chem. Soc. 110, 6920-6921 National Research Council, Washngton, (1988). DC, 1987). 25. B. B. Cunningham, in The Transuranium 9. D. R. Houck, J.L. Hanners, C.J. Unkefer, Elements, J. J. Katz and G. T. Seaborg, M. A. G. van Kleef, and J.A. 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