LA12143-PR Progren Report

Isotope dnd Nuclecqr Chemistry Division Ann vial Report FY 1990^

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? L«>Alaa^Natkif^'ljri>oratoryk operated by the UnhrcnUy of Colitbr^ Geologists inspect the Devil's Thumb Sinkhole, which is located in travertine at the base of the Mammoth Hot Springs Terraces, before injecting multiple tracers to determine flow paths, transit times, and chemical Water from Boiling River (Mammoth Hot reaction processes in a natural aquifer. Hot Springs) was sampled at many intervals during a water from pools on top of this terrace flows multicomponent tracer experiment. Analysis of over the orange travertine and down into the data from this major outflow of the Mammoth sinkhole. Inactive travertine is grey; the oldest system (-40°C and 27 f&ls flow rate) provides deposits support several types of trees. information about the flow path, transit titles, and chemical reaction processes of a natural aquifer. This information is used to test hypotheses and field approaches for characterizing geothermal, petroleum, and environmental reservoirs.

A team of geologists collected more than 250 samples over an 18-hr at Boiling River —one of many remote field sample processing sites—during the multicomponent tracer experiment. In this wilderness area, team members used the environmentally benign transport system (shown in red) to move equipment and samples. Closeup of the Devil's Thumb Sinkhole shows wet, actively depositing travertine in orange and old, degrading travertine in white.

These moths caught in the hot springs were fossilized as hydrothermal solutions flowed across the ground surface at Mammoth Hot Springs in Yellowstone National Park. The mini-cascade and trapped bubble features, as well as the coating on the moths, formed during precipitation of travertine and exsolution of dissolved gases. Subtle purple and yellow tints on raised features are indicative of algae, which control the structure formation. (Photos on cover and this page: Dale E. Spall) and Nuclear Chemistry Division Annual Report FY 1990

October 1, 1989—September 30, 1990 .

i Alexander J. Gancarz, Division Leader

'•<*• Abstract This report describes some of the major research and development programs of the Isotope and Nuclear Chemistry Division during FY 1990. The report includes articles on weapons chemistry, environmental chemistry, actinide and transition metal chemistry, geochemistry, nuclear structure and reactions, biochemistry and , materials chemistry, and INC Division facilities and laboratories.

iv Isotope and Nuclear Chemistry Division Annual Report FY 1990 Contents

Point of View 2 Overview 4 1. Weapons Chemistry Overview 14 Radiochemistry of the Rare-Earth Elements 16 Isotope Separators: Three Steps Forward 18 Instrumentation for High Dynamic Range Isotopic Analysis 20 2. Environmental Chemistry Overview 24 Isotopic Analysis of Environmental Samples 26 Determining Co-Contaminant Speciation on Environmental Substrates 28 Biodegradation of TNT 30 3. Actinide and Transition Metal Chemistry Overview 34 Convenient Entry into the Inorganic and Organometallic Chemistry of 36 Stereochemical Consequences of Electronic Structure 38 Synthesis of the First (VII) Imido Complexes 40 4. Geochemistry Overview 44 Multicomponent Tracer Experiments at Mammoth Hot Springs in Yellowstone 46 Using Surface Ages to Understand Geological Processes 48 Geochemical Studies Using Long-Lived Members of the Decay Series 50 5. Nuclear Structure and Reactions Overview 54 Direct Mass Measurements of the Neutron-Rich of through 56 SNOing in Los Alamos—Neutrinos in the Nineties 58 The Exotic-Beam Facility—A New Initiative 60 6. Biochemistry and Nuclear Medicine Overview 64 Metabolism of Methylotrophic Bacteria 66 Structure of Cytochrome £ Oxidases: Sequence and Analysis oftheSubunit lie Gene 68 Labeled Biologically Active Peptides for Myasthenia Gravis Research 70 7. Materials Chemistry Overview 74 Synthesis and Characterization of Novel Low-Dimensional Materials 76 Radioisotope Research and Development: Materials Issues in Targetry 78 Conductivity of Polystyrene Film When Exposed to Dioxide: A Novel NO2 Sensor 80 8. Division Facilities and Laboratories INC-Division Facilities and Laboratories 84 Omega West Reactor 88 Radioisotope Research Facility and Applications 92 Mass Spectrometry Facilities 94 Appendix Division Personnel 98 Advisory Committee 101 Program Funding 102 Publications 106 Presentations 114 Division Meetings and Seminars 124 References 126 Acknowledgements

Production Team: Editor: Jody Heiken Illustrators: Ward Zaelke (INC-DO/IS-12), Garth Tietjen (INC-DO/IS-12), and Janey Heads tream Designer: Garth Tietjen (INC-DO/IS-12) Editorial Assistant: Molly Minahan Production Assistant: Janey Headstream Technical Reviewers: Sec. 1 Mary Anne Yates Sec. 2 Eugene J. Peterson Sec. 3 Carol J. Sec. 4 R. Janecky Sec. 5 Gilbert W. Butler Sec. 6 Dennis Phillips and Clifford J. Unkefer Sec. 7 Alfred P. Sattelberger Sec. 8 Jose A. Olivares Contributors: Joann Brown Carla Lowe Lori Abney Elaine Roybal Cathy Schuch Photographers: Cover and inside front cover: Dale Spall (CLS-1); articles: Henry Ortega (IS-9) Printing Coordinator: Guadalupe Archuleta (IS-9)

vi Isotope and Nuclear Chemistry Division Annual Report FY 1990 OVERVIEW

J-* -*• Overview

Point of View production, and education. We have also been asked to consider the possibility of using the Omega West Reactor to produce "mTc, the Alexander J. Gancarz most widely used medical isotope.

The second arena in which we are 1990 was a year of transition for INC aggressively pursuing new opportunities is Division. We made significant shifts in our environmental chemistry. We have helped to strategic focus, particularly in the Biochemistry- staff the newly created Los Alamos Technology Nuclear Medicine and Environmental Chemistry Office at Rocky Flats, whose mission is to find arenas. We developed a new perspective and matches between the needs at Rocky Flats and approach to environment, safety, and health the technological expertise at Los Alamos. issues. We also underwent major leadership We have successfully participated in several changes in the Division. From my point of view, initiatives, and we are optimistic about the these transitions were made quite successfully. future of this program. We are also developing new programs with the DOE Office of INC Division first identified strategic Environmental Restoration and Waste opportunities in the Biochemistry-Nuclear Management. These efforts range from basic Medicine arena in 1985; Environmental technology development to local Los Alamos Chemistry was targeted in 1988. Over the site characterization and remediation past several years, we have continued to activities. build our capabilities in both of these areas. Another area of transition was in our Our efforts in biochemistry have resulted approach to and execution of the Division's in several new programs. A particularly environment, safety, and health (ES&H) interesting example is the project to identify responsibilities. We have always taken very microbes that degrade TNT and to optimize the seriously our charge to ensure the safest process for large-scale use. Sites contaminated possible working conditions and to minimize the with TNT and other explosives are a large impact of our operations on the environment. national problem and, consequently, this However, the increased emphasis on ES&H initiative offers significant potential for nationally and within the DOE requires that we growth. In the nuclear medicine field, we have be even more scrupulous in these areas and that made substantial programmatic advances and we implement a much more formal approach to see major opportunities. This year, the INC- our operations. This effort—as well as the developed 82Sr/82Rb medical radioisotope challenge of solving the Laboratory's legacy generator was approved by the US Food of environmental problems—has been a major and Drug Administration. The generator, task for the Division, in both time and dollars. successfully marketed to the medical I deeply appreciate the effort made by each and community, is being used for in vivo imaging every INC Division employee to address the past in hospitals and clinics throughout the US. and to change our way of conducting business in In the research portion of the nuclear medicine accordance with the new ES&H culture. program, there have been significant advances in the early detection of lung cancer. This This has also been a year of transition in progress was achieved by using the 67 leadership for the Division. I was selected to radioisotope Cu produced at the LAMPF head the Division following Donald Barr's Medical Radioisotope Production Facility. retirement in January 1990. It was an honor The future in this area looks both exciting to be chosen for this position. Al Sattelberger and promising. The US DOE has invited us to joined the Division Office in September to be participate in the development of a National the Deputy Division Leader. We both look Biomedical Tracer Facility for research, isotope forward to leading INC Division into the 1990s.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

Merle Bunker, whose association with the Laboratory covers 40 years and who has been the Leader of the Research Reactor Group since 1974, also retired in January 1990. We will certainly miss his leadership. Don Hull, who has many years of reactor experience, was selected to fill Merle's vacated position.

In addition to these changes in leadership, we have had significant personnel changes. We added 10 new staff members, 14 new structured series personnel, and 25 new postdoctoral fellows and graduate research associates.

I would particularly like to congratulate Woody Woodruff on being named a Laboratory Fellow; this year he joins three other distinguished INC Division fellows. I also commend Al Ogard for his major contributions to the Protocol to the Treaty Between the United States of America and the Union of Soviet Socialist Republics on the Limitation of Underground Nuclear Weapon Tests.

In closing, I would like to reiterate how extremely proud I am to be associated with INC Division. I look forward to working with Alexander J. Gancarz our excellent staff on the opportunities, Division Leader challenges, and successes that are on the horizon for this vital organization.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

Division Leader A.J. Gancarz Technical INC-DOT Deputy Division Leader Coordinator R.E. Gritzo A.P. Satteiberger B.R. Erda! D.R. Janecky

INC-4 INC-5 Isotope and Structural Research Reactor Chemistry Group Leader—D.L. Hull Group Leader—R.R. Ryan Deputy Group Leader—P.J. Unkefer

INC-11 INC-7 Nuclear and Radiochemistry Isotope Geochemistry Group Leader—W.R. Daniels Group Leader—D.B. Curtis Deputy Group Leader—EJ. Peterson Deputy Group Leader—R.W. Charles Deputy Group Leader—K.W. Thomas

The INC Division's mission is to develop, chemistry, technetium chemistry, multiple metal- maintain, and supply capabilities in chemistry, metal bonding, low-valent early transition metal nuclear chemistry, geochemistry, and stable chemistry, and organometallic chemical vapor and radioactive isotopes for solution of national deposition. security, energy, health, and environmental problems. The Division's four groups foster excellence in fundamental research. INC Division is divided into four groups that represent its four major areas of interest, expertise, and achievement over the past 30 years: INC-4 Isotope and Structural Chemistry, INC-5 The Research Reactor, INC-7 Isotope Geochemistry, and INC-11 Nuclear and Radiochemistry. The Division Leader, Deputy Division Leader, Technical Coordinator, Group Leaders, Laboratory Fellows, and Division Office Technical staff members provide leadership, stimulation, and stable management as the Laboratory shifts emphases to reflect the needs of national l'esearch efforts.

INC Deputy Division Leader Alfred Satteiberger came to the Division Office from the Isotope and Structural Chemistry Group (INC-4), where his research focused on Alfreds. Satteiberger actinide coordination and organometallic Deputy Division Leader

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

INC Division Groups

INC-4 Isotope and Structural Chemistry performs and communicates fundamental and supporting research in chemistry to bring together the areas of synthesis, separation, and use of isotopic and physical methods for studies of structure and dynamics.

Robert R. Ryan INC-4 Group Leader

INC-5 Research Reactor provides reactor- based facilities and services in support of Laboratory programs and conducts applied and basic research in nuclear chemistry.

Donald L. Hull INC-5 Group Leader

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

INC-7 Isotope Geochemistry addresses national scientific problems in the fields of nuclear chemistry and the earth sciences by employing radiochemical and mass spectrometric techniques. There is an emphasis on nuclear weapons diagnostics and related nuclear research, atmospheric and geochemical processes, and measurement science.

David B. Curtis INC-7 Group Leader

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 research and distribution, and basic research in nuclear phenomena. Group resources support Laboratory goals and new applications of nuclear and radiochemistry for scientific and technological development.

William A. Daniels INC-11 Group Leader

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

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 role in stimulating new research initiatives. Greg Kubas' research centers on the activation of small energy-related molecules such as SO2 and H2 on transition metal complexes. His long-term goal is to catalytically convert SO2 to or sulfur-containing species by employing metal complexes as a possible means of controlling emissions that produce acid rain. Greg and his coworkers developed the first homogeneous (solution) catalytic process for clean and rapid conversion of SO2 to sulfur and water through the use of and an organometallic sulfide catalyst. Originally a spinoff of these studies, Greg's Bruce R. Erdal discovery of molecular hydrogen coordination Technical Coordinator to complexes 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. INC Technical Coordinator The ability of metals and metal complexes to bind H2 intact rather than as atomic H" The INC Technical Coordinator helps Division represents a new type of chemical bonding and Group leaders develop new programs and and has profound impact in energy-related directions for research. He attempts to couple areas such as hydrogen storage and catalysis. INC's skills, facilities, and interests with program needs; facilitate interactions with potential sponsors; and, in some cases, encourage entirely new efforts. Environmental programs offer myriad opportunities, particularly in problems related to waste minimization, global change, and restoration of the weapons complex. Materials chemistry for advanced processing and production of high-temperature superconductors also shows significant potential. Environmental programs continue to be the primary area of emphasis for Bruce Erdal in his role of Technical Coordinator. In addition to his efforts within the INC Division, Bruce works in the Laboratory's Energy, Environment, and Technology Applications Office, which is the principal organization responsible for developing environmental R&D programs in the Laboratory. His primary responsibility there is to coordinate efforts in waste management and environmental remediation at the Rocky Flats Plant of the DOE. Bruce also works with the Chemistry and Materials directorate to coordinate environmental research development. Gregory J. Kubat

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

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 on the fission process by addressing the heaviest element fission properties and studying the effect of nuclear dissipation on the time scale of fission. One of Jerry's new major areas of interest is the field of we^k 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.

Woody Woodruffs research interests include Charles J. Orth energy conversion in inorganic and bioinorganic chemistry, and novel applications of lasers to problems in solution chemistry and dynamics. He is particularly interested in inorganic photochemistry and the conversion of light into Carl Orth's principal research involves the chemical energy by inorganic photosystems— use of nuclear and radiochemical techniques to a process that involves the study of the structure study extinction boundaries in the fossil record. and dynamics of electronically excited transition The objective is to determine if the biological metal complexes and strategies for extracting crises were caused by hypothesized swarms of comets periodically entering the inner Solar System—some striking the Earth—or by less exotic terrestrial processes. In earlier work, he and his coworkers in INC Division found the anomaly at the Cretaceous/Tertiary boundary in nearby fluvial sediments; this discovery provided strong support for the Alvarez -impact hypothesis, which was based on a discovery of excess iridium at a similar boundary in marine rocks. Almost all the extinction boundaries recorded in the last 600 Myr are currently being examined in collaboration with about 50 paleontologists from around the globe. To complement this work and provide a better database of terrestrial impact events, melt and target rocks from suspected impact structures are being examined to determine if they resulted from impacts or volcanism. Carl also is interested in meson/ nucleus interactions and stimulation of nuclear isomers to release their stored energy.

Jerry B. Wilhelmy

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

The INC Division's 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 indivi- duals and to the Division. The DOT program seeks to reward those who have 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 ievelopment through increased exposure to the Laboratory, Directorate, Division, and Groups. 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 inter- action with Division staff. The DOT appoint- ments follow regularly scheduled calls for William "Woody" Woodruff applications.

Russ Gritzo (INC-11) will concentrate their energy of photoexcitation; for example, on studies of neural networks and their the energy of a (II) complex of applications during his DOT appointment. His acetonitrile is retained long enough to be research on various neural network paradigms harvested by conventional approaches such and simulation tools is directed toward as electrochemistry. Another research focus developing the Division's ability to evaluate the is the biophysics of transition metals in proteins suitability of neural networks to a variety of that perform biological energy transduction and storage functions. Understanding these phenomena requires examining the extremely complex structural and dynamical transformations in proteins such as an oxidase that catalyzes the reduction of in all animals, plants, and many lower organisms and which transforms the energy of this reaction into a transmembrane proton gradient. Such studies have led to new insights into the mechanisms of bioconversion of energy. Because of his interest in both solution dynamics and laser spectroscopy, Woody was one of the early developers of time-resolved resonance Raman techniques, and he continues to develop advanced techniques in time-resolved laser spectroscopy.

Russell E. Gritzo

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

In tandem with these modeling efforts, he is using recent advances in chemical tracer technology to develop external funding opportunities. Dave and coworkers are proposing projects that involve the use of these tracers both in laboratory experiments combined with new modeling approaches and in field tests as a part of collaborative efforts with petroleum, geothermal, and environmental industrial partners.

Division Accomplishments in FY 1989 The INC Division comprises 236 employees, including 87 member scientists (72 with PhD degrees), 8 administrative staff members, 46 technicians, and 15 general support staff. This year we hosted 20 postdoctoral employees, 1 summer teacher, 28 undergraduate students, 17 graduate research assistants, and 14 Laboratory associates. In addition, there were David R. Janecky 227 affiliates, 79 of whom were scientists from foreign countries. An important group of these visitors composes INC Division's Advisory Committee, which is assembled from eminent scientists in our fields of interest. This problems. Recent development of a new committee serves the very important function of generation of automated radionuclide assay reviewing our plans, progress, and priorities as systems in INC-ll's counting room has provided well as bringing to our scientific staff a different several opportunities to explore neural network perspective on the new and most significant applications issues. Russ has developed a developments in many areas. Membership of neural-network-based event scheduler for real- our FY 1989 Advisory Committee is listed in time scheduling of automated sample counting the Appendix of this report. Division seminars, and is currently developing pulse processing also listed in the Appendix, serve as a valuable applications. In collaboration with scientists in additional and complementary window on the Center for Nonlinear Studies, Russ is interesting recent progress and ideas from exploring a wide variety of other applications. both within and outside the Division. Dave Janecky (INC-7) has chosen to focus his DOT appointment on developing models and tracer techniques that can be used to investigate Awards and Recognition coupled chemical reaction and fluid flow in rocks. In collaboration with scientists in CNLS Division INC-4's Stephen Agnew was among those and Group EES-5, Dave is applying recent who received the prestigious R&D 100 Awards advances in lattice-phase automata computer this year for his research on the solid-state algorithms and massively parallel computer nitrogen dioxide sensor, which detects nitrogen architectures to examine chemical reactions in dioxide in seconds by monitoring the electrical pore networks. Mutiphase flow, temperature/ conductivity change of a thin polystyrene film. pressure variations, and simple two-component Los Alamos won seven of the 100 awards given chemical reactions involving kinetic/catalytic by R&D magazine for 1990—the most awards interactions have been developed by tagging and given to any single laboratory for the year. tracking the automata. Dave has been investigating the applicability of a new type of Clifford J. Unkefer and Robert R. Ryan of model to geochemical processes—which could be INC-4 are among the recipients of the combined with visualization capabilities such as Laboratory's Inventor Awards for 1990. Cliff, video animations of time-dependent processes. with four other staff members, holds a patent for a process for the "Removal of Metal Ions from

10 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Overview

Aqueous Solution" and Bob's award stemmed 30 years from his work with two other Laboratory Sixto Maestas INC-11 chemists in developing an "Extractant Composition." 25 years Gilbert. W. Butler INC-11 Robert Ryan and Gordon Jarvinen Martin A. Ott INC-11 (INC-4) were two of a three-member team that 15 years received a Distinguished Patent Award for Fred R. Roensch INC-11 "Separation of Actinides from Lathanides." Thomas A. Myers INC-11 P. Gary Eller (INC-4), Robert Penneman Zita V. Svitra INC-11 Pamela Z. Rogers INC-7 (INC affiliate), and a third Los Alamos staff Edwin P. Chamberlin INC-11 member were presented a Laboratory Gregory K. Bayhurst INC-7 Distinguished Patent Award for their "Method David B. Curtis INC-7 for Fluorination of Actinide Fluorides and Joy Drake INC-11 Oxyfluorides Thereof Using O2F2." 10 years Two INC staff members were honored with Barbara J. Anderson INC-DO Laboratory Distinguished Performance Awards Michael T. Murrell INC-7 for 1990. Phillip Chamberlin (INC-11) was Joann W. Brown INC-DO recognized for his technical contributions to the Michael R. Cisneros INC-11 weapons isotope separations program and his Arend Meijer INC-7 leadership of the Medical Radioisotope Jose G. Garcia INC-11 Production Program. Phil used his technical and Charles M. Miller INC-7 organizational skills to improve techniques and Carla E. Lowe INC-11 to maintain production schedules, thus providing Timothy M. Benjamin INC-7 a steady supply of radioisotopes to universities, Early in 1990, appointments were made to hospitals, industrial laboratories and other the Laboratory's middle Management Council national laboratories. Alfred Sattelberger to replace members whose terms had expired. (INC-4) received his award for leadership and INC-Division Leader Alexander Gancarz technical contributions that helped build a was named to the organization, which involves world-class research program in actinide middle-level managers in Laboratory-wide organometallic chemistry at Los Alamos—a feat issues. The council was chartered in January made possible by both his own research 1987 by Director Sig Hecker, who selected its accomplishments and his ability to attract first 14 members. New members are now outstanding inorganic chemistry postdoctoral appointed by the existing membership and students to Los Alamos during the past 5 years. serve 1- to 2-year terms. The North Central New Mexican Technician As a member of the Laboratory's outreach Affiliate of the American Chemical Society has program, chemical technician Kenneth Salazar awarded Alan Mitchell (INC-11) the "1990 (INC-4) made the news with his "magic show." Technician of the Year Award." This award was The story of this chemical show-and-tell, which presented to Alan for his sustained contributions has played to local area schools since 1984, was in the field of waste management and his recent a feature article in an issue of Hispanic achievements in environmental remediation. Magazine, a national publication. Alan is responsible for the development of many procedures used to study the transport of The Laboratory's decommissioned Water Boiler radionuclides in the environment. Reactor, built during the Manhatten Project and operated by personnel now a part of (or recently The Laboratory presents service awards to its retired from) INC Division, was designated a personnel at 5-year intervals. The INC Division nuclear historic landmark by the American has a number of long-time employees who were Nuclear Society. A commemorative plaque will be recipients this year. placed at a site in Los Alamos Canyon where the reactor once stood. The Water Boiler used enriched uranium to produce the first man-made, self-sustaining nuclear chain reaction.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 11 Overview

Retirements Merle Bunker began working with weapons research in 1944 as a GI assigned to the Special Engineer Detachment at the Manhattan Project in Decatur, Illinois, where the diffusion barrier for the K-25 was made. After the war, Merle earned his PhD in nuclear physics at Indiana University, and in 1950, he hired on in Group P-2, the "Water Boiler" Group. His first job there was helping design and assemble the recombiner system of the SUPO version of the Water Boiler. Merle supervised that program for a number of years until the Water Boiler was shut down in 1973. In 1959, Merle was named a Fellow of the American Physical Society as a result of his work in nuclear spectroscopy. He received a National Science Foundation Senior Fellowship in 1964, which allowed him to spend a year at the Niels Bohr Institute in Copenhagen. Following his return to the Laboratory, he was made Deputy Group Leader of P-2 (now INC-5) and was named Group Leader in 1974. For many of us, Merle's name has been synonymous with the Omega West Reactor for years; his historical perspective as well as his quiet good humor will be sadly missed. Marjorie Lark came to Los Alamos in 1948 to work as a telephone operator for the Atomic Energy Commission. After raising a family, she joined the Lab in 1965 as a computer operator in T-Division before moving to C-Division's computer program library. She joined INC-11 in 1974 to work in the counting room, where she counted radioactive samples for the chemists. Marj worked the swing shift; she was so dependable and willing to help that she was given a great variety of tasks, such as checking safes and large copying machine jobs, which she always carried out reliably. Marj's friendly disposition has already been missed, but she still works part time in the counting room whenever the work load becomes too heavy.

12 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Weapons Chemistry

Overview

Radiochemistry of the Rare-Earth Elements

Isotope Separators: Three Steps Forward

Instrumentation for High Dynamic Range Isotopic Analysis '

»><* - Weapons Chemistry

Overview Experimental Design Very early in the planning stages of an experiment, INC personnel work with Mary Anne Yates the design physicist to determine which detectors and tracers will best diagnose The Weapons Radiochemical Diagnostics the test. In addition, our chemists and Program in INC Division has a long and proud spectroscopists work with the fabrication history. By consistently providing the highest groups to analyze specific characteristics of quality data and detailed analyses, we have materials to be used. Cooperation with the established device yields measured by prompt diagnosticians and rack engineers radiochemical means as the standard to also is extensive, to ensure compatibility which all other yield determinations are between our requirements. calibrated. In addition, by using our analyses of various detector and tracer elements, NTS Drillback Operations we are able to evaluate the time-integrated nuclear behavior of many parts of a device When a nuclear device is exploded in the during the underground explosion. All of this geologic formations at the Nevada Test Site, information helps the design physicist better the material of the device, the prompt- understand the impact of various features as measurement instruments, and some of well as the overall device performance. the surrounding rock are vaporized. This material rapidly condenses into a black glassy puddle that also contains fission As is the case in all scientific research products and activation products. Once programs, the technical requirements of an event has occurred, our first responsibility the experiments are constantly evolving. is to obtain representative samples of this Therefore, we are continually assessing the glassy debris for radiochemical analysis. need to add different detector elements, refine The techniques used for sampling were our chemical separations, and/or alter our developed for drilling and logging oil wells counting techniques to meet changing demands. and involve the use of directional drilling Another factor that us to review our and a side-wall sampler. The entire sampling procedures is our concern for the safety of our operation is locally directed by INC-Division personnel. We strongly subscribe to the recently chemists, who monitor the debris. These articulated DOE policy regarding exposure to samples are then packaged in appropriate radiation—namely, that exposure should be containers and shipped to Los Alamos for kept as low as reasonably achievable. One very processing. straightforward way to achieve this effect is to reduce the size of the radioactive samples to be processed. To maintain the quality of Test Debris Sample Preparation our data while using less material, we must The highly radioactive samples are increase the efficiency of our chemical and processed in a well-shielded facility. First the isotopic separations and the sensitivity of our drilling mud and extraneous dirt are washed measurement systems. Examples of some of from the debris of interest. This "high-graded" our advances in these areas are described in residue is then dried and ground into a powder, the following three articles. which is dissolved in strong acid and then heated by either conventional methods or INC Division's participation in the weapons microwave oven. Use of the latter is part of a testing program can be divided into the developmental program to reduce both the following categories: amount of acid required and the exposure of personnel. For each event, several portions of • Experimental Design debris (varying from 2 to 100 g) are processed • NTS Drillback Operations for different analyses. Care is taken with each • Test Debris Sample Preparation sample to ensure that the relative amounts of the elements in the debris are not altered during • Chemical and Isotopic Separations dissolution. • Isotopic Measurements • Interpretation and Documentation

14 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Weapons Chemistry

Chemical and Isotopic Separation The data, analyses, and analytical tools The dissolved debris is treated chemically used in this research effort ''models, computer to separate the many individual elements of codes, etc.) are archived in the INC-Division interest. One hundred twenty-l• .ur detailed vault and in the developing Radiochemistry procedures have been developed and Data Base, which is maintained on our classified documented. Some recent improvements in computer system. these procedures are described in the following article by Svitra and Bowen. Most of the highly Cleared personnel may obtain more details purified elements can be directly assayed for on our classified work by contacting Charles M. isotopic content by radiation counting or mass Miller, Technical Coordinator for Weapons spectrometric analysis. There are exceptions Radiochemistry. however. If an element has isotopes that (1) have mutually interfering gamma radiation, (2) decay only by beta emission with no gamma rays, or (3) are overwhelmed by the presence of a fission product, the element must be isotopically separated before all its isotopes can be detected. Improvements to this system are described in Chamberlin's article in this section.

Isotopic Measurement The relatively short-lived (half-life < 100 yr) fission and activation products are detected by the radiation they emit: a, p", p+, x-ray, or y rays. Our extensive counting facilities are maintained in strict calibration to standards from the National Bureau of Standards and undergo continual assessment to reduce background and increase sensitivities. We also use automation to allow maximum availability.

Products that are long-lived or stable are detected by means of our highly advanced mass spectrometric capabilities. We can detect isotopic amounts as low as 107 atoms in specific cases. The article by Olivares in this section describes recent improvements in this area.

Interpretation and Documentation Interpretive specialists analyze the isotopic data and use it to determine device yield and other information of interest to the design physicist. The results are reported internally at weekly weapons program meetings fJid externally at experimental review groups and monthly weapons working groups. Twice each year, the results undergo peer review at Interlaboratory Working Group meetings held in conjunction with radiochemists from Lawrence Livermore National Laboratory.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 15 Weapons Chemistry

Radiochemistry of the Rare-Earth Elements Separation of Rare Earths and

Zita V. Svitra and Scott M. Bowen Add carriers and fume with HCIO4

INC Division's chief responsibility in the nuclear testing program is to determine the performance of a nuclear device, paying Precipitate several times with particular attention to the overall nuclear NaOHandNH OH yield and the performance of specific parts 4 of the device. The rare earths (elements 57 through 71) and yttrium play an important role in achieving this goal. Recently escalating safety concerns require that we separate Precipitate with HF more of the rare earths from smaller samples. These smaller samples mean that we must be capable of detecting much lower levels of radioactivity. The purity of our samples affects the efficiency of the isotope separation process Pass through staturated (see the article by Chamberlin in this section) HC1 anion column and the accuracy of the counting process. Given these demands, it is crucial that our radiochemical procedures produce very pure, well-separated individual rare-earth elements. This article describes the success of some of our work in this area. Scavenge with H3PO4

Nevada Test Site debris is collected and brought to Los Alamos, where it is purified to produce samples that are rich in radioactivity Precipitate with NH4OH from the device. The samples are dissolved and then subjected to an analytical scheme that involves a series of steps to ensure radiochemical purification of the rare-earth elements (see flow chart on this page). This Scavenge using procedure separates the rare earths as a group; NaBrOg and HIO they are then separated from each other by S cation exchange chromatography.1 Our system, developed in the 1950s, uses elution of the absorbed rare-earth elements with varying concentrations of the organic acid oc-hydroxy- isobutyric acid (cc-HIB). Fractions are collected Precipitate with NH4OH twice in the tubes and each of the elements is detected visually by precipitation. Figure 1.1 (a) illustrates a good separation. After separation, the radioactivity for each rare earth is counted by either a Ge(Li) or a (3 detector. Some Dissolve in HC1 and add HC1•NH2OH I samples of individual rare-earth elements are also isotopically separated before they are counted.

Recently, we have had problems in Load onto columns separating the rare earths. These problems

16 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Weapons Chemistry

necessitated running yttrium as a separate 9. nn sample, which meant an increase in personnel exposure. Even after this change, we were still faced with a poor / separation 7.75 v [Fig. l.l(b)]. As a result of these problems and because we must analyze samples with much ~ 7.50 -\ lower levels of radioactivity, it was imperative that we re-evaluate and update our procedure. .E During this review, we investigated the use of 1 7.25 - \ 33- and 59-cm columns, a decreased flow rate 3 (from 3 to 2 ml/min), a new source of cc-HIB, ~ 7.00 and more careful control of the elution process. We are now able to separate the five elements ffl 6.75 shown in Fig. l.l(a). This separation allows us 3 To to isolate a small fraction from very z large activities of yttrium with no yttrium 6.50 \ contamination. For an isotopically pure sample, a plot of natural log (counts) vs time forms a 6.25 \ straight line with a slope equal to the decay 161 constant of the isotope—in this instance, Tb 6.00 (Fig. 1.2). 1 1 1 1 1 i 1 1 1 1 C) 2 4 6 8 10 12 14 16 18 20 22 At (days) We have also investigated the separation of , , , , and and now Fig. 1.2. The fi-counting plot for terbium data. have a protocol that works well.

Lu Tm There has been a significant increase in (a) our separations capability. By improving our chromatographic procedures, we are now able to reliably separate more of the rare earths and yttrium from a single sample, which obviates the need for two or more samples and decreases personnel exposure. Our new protocol allows us 0.065M 0.0775M 0.085M 0.10M 0.13M to separate five elements (lutetium, thulium, yttrium, terbium, ) from one sample I I I I I 1 I 50 100 150 200 250 300 350 into radiochemically pure fractions. We also have been able to obtain samples of sufficient purity that low-level P-counting can be Tb Eu successfully employed, as is shown by our (b) terbium work. We will continue to improve our procedures so that we are able to handle even larger suites of the rare earths by adding gadolinium or other rare earths.

0.0475M 0.075M 0.012« I I I I I 50 100 250 300 350 150 200 Tube Number

Fig. 1.1. Elution curves are shown for new methodology (a) and for previous methodology (b).

Isotope and Nuclear Chemistry Division Annual Report FY 1990 17 Weapons Chemistry

Isotope Separators: Three Steps can run 24 hr/day at a very consistent setting Forward and provide optimal purity. The sample can now be ready for counting in just over 1 day.

E. Phil Chamberlin, Hain Oora, Roland A. Another factor influencing isotopic purity is 7 Bibeau, Frank O. Valdez, and Michael G. Garcia the base vacuum level (10" mbar) maintained in the instrument. Since 1985, the separator has been As the Overview article explained, we are checked for leaks every time it is opened compelled by both technical and safety constraints and repumped. This process has resulted in a factor to use smaller amounts of radioactive debris in of 10 to 100 improvement in the vacuum level and our research. To accommodate these demands a concomitant r jduction in cross contamination while maintaining the high quality of our data, between waves. Introduction of insertable Faraday we examined issues associated with three aspects cups at the focal plane of each separator allows of isotope separator operation: shortening the direct measurement of the degree of tailing; turn-around time, increasing sample purity, Fig. 1.3 shows results obtained from running a and increasing our efficiency as measured by mixture of Prj^, Nd2O3, EU2O3, and Gd2O3. through-put of the sample material. Significant improvements have been made in all three areas. Of all the issues addressed, one of the most challenging was maintaining a consistent high Shortened turn-around time is especially efficiency for elements while using the surface- important in the case of rare-earth elements that ionization-type ion source (SIS), which is the case have relatively short-lived isotopes. Until recently, for -80% of the samples separated. The problem the separators were operated manually and could was very complex because sample preparation be run effectively only 8 hr/day. A sample requiring techniques, sample contaminants, and 24 hr of running time plus set-up and counting contaminants present within the tungsten preparation could take 4 days or more from the crucible material all reduce ionization efficiericy. completion of chemistry to the beginning of counting—a significant delay for isotopes with The SIS was pioneered by experimenters at half-lives of 2 to 4 days. Now, however, all our 2 separators operate using IBM PC/ATs; they Dubna and Lawrence Iivermore National

Gd GdO 1 M M 1 1 1 MM I I Pr Nd Eu PrOTb NdO EuO TbO 1 1 1 MM I n 1 ITT1 1 1 1 1 1 E ^

I—

til co cc ~ o i % CD

VJV 0.0 3.0 6.0 9.0 12.0 15.0 18.0 21.0 24.0 27.0 30.0 3 CHANNEL NUMBER (50 mS/Channe!) *10

Fig. 1.3. Results obtained when running a mixture ofPr^Og, NdgOs. Eu2O3 and Gd^Og illustrate the problems arising from use of oxide compounds. The Eu* beam is 10* more intense than the EuO* beam, but the PrO* beam is IS times as intense as the Pr+ beam; these ratios change with time.

18 Isotope and Nuclear Chemistry Division Annual Report FY 1990 WeaponsChemistry

3 Laboratory. Ionization efficiencies had been CAP IONIZING BODY PLUG SAMPLE SCHANNEL unpredictable at LANL; in early work, the source \ would sometimes ionize a sample with 50% efficiency, and at other times the sample would be rw // lost entirely. In 1986, our objective became to ionize — / f all rare-earth samples with at least 10% efficiency. We tackled the problem on three fronts: ion source TAPER V — hardware, sample chemistry, and separation procedures. Although we have achieved the 10% efficiency objective, we continue to investigate the Fig. 1.4. Schematic of the tungsten crucible shewing the hardware and procedure aspects of the problem. location of the sample and the retaining plug.

The crucial portion of the ion source is the during initial hearing. The crucible temperature is crucible (Fig. 1.4), which consists of a body and a raised slowly over several hours until sample ions cap, both fabricated from tungsten rod. The sample are detected at the nanoampere level. The crucible is loaded into the body and the cap is pressed into temperature is then held constant until the place. Within the ion source, electrons radially and ion currents have dropped bombard the cap and raise its temperature to below the 10-nA level. 3000 K, making its surface an efficient ionizer. As the cap temperature rises, heat flows along the These techniques have paid off in increased body, raises the sample temperature, and vaporizes sample ionization efficiency. Figure 1.5 shows the sample atoms. Atoms exiting the crucible through separation efficiency of europium, thulium, and the ionizing channel in the cap lose an electron to lutetium. Our experience thows that efficiency the hot tungsten surface. drops as vapor pressure increases. A much higher temperature is required to vaporize lutetium Another step toward higher efficiency was taken than europium. At higher temperatures, more when we realized pieces of sample were moving contaminants may come from the crucible, thus (like popcorn) within the crucible body during the reducing the ionization efficiency. initial bakeout process. Because the crucible's depth is adjusted to match the sample's vapor We have made great strides toward higher pressure characteristics, such movement puts efficiency. The work described by other the sample in the wrong temperature region. investigators indicates that there are additional The thermal distribution and ionization factors are steps we can take to improve our separators' highly nonlinear, so a small movement can result efficiency.4 in significant efficiency reduction. This problem was solved by using a deformable plug of tungsten wire to restrain the sample. The plug is similar to the wadding used in muzzle-loading rifles to hold the powder in place; here, the plug is firmly tamped into position over the sample.

Contaminants within the sample also cause problems; any low-work-function contaminant can coat the surface of the ionizing channel. Even a 40% monolayer coverage is enough to reduce the work function of the tungsten below the point at which it can efficiently ionize sample atoms. To solve this problem, we used the ion source itself to determine the contaminants. Test samples were prepared and contaminant ion currents were measured. We then modified our chemical 10 20 30 40 50 60 70 80 90 100 110 120 procedures to remove these contaminants. JUNE 1983 THROUGH NOVEMBER 1990

Some contaminants also evolve from within the Fig. 1.5. Separation efficiency for europium, thulium, and tungsten crucible material. The most abundant are lutetium samples between June 1980 and November 1990 The curve is the average of the preceding 10 data points potassium and calcium, which are easily removed (a trailing indicator) and confirms the upward trend.

Isotope and Nuclear Chemistty Division Annual Report FY 199019 Weapons Chemistry

Instrumentation for High Dynamic determines which portion of the ion beam will be Range Isotopic Analysis seen by the second stage or—in the simplest case—by an ion detector placed just behind it.

Jose A. Olivares Figure 1.7 is a mass spectrum of 2 jig of NBS-0002 uranium standard produced by the Mass spectrometry continues to be used first magnet and detector only. The certified heavily in pre- and postshot isotopic analysis value of 234U in this standard is 1.6 ppm of the of weapons debris. Uranium and 238u, The peak for the 238u isotope is not shown isotopic analysis are used to determine fission because it is so large (~5 x 107 ions/s) that it yield for the test devices. Postshot analysis of could damage the detector. Nevertheless, the other specific elements added to the weapon tail from the 238u is quite apparent throughout provides information on the geometric and the spectrum as an increasingly high and noisy chemical fractionation of the shot. Also, analysis background with increasing mass. The size of of long-lived isotopes formed by the interaction this tail determines the ability of the mass of neutrons with elemental tracers added to the spectrometer to discern a small peak. If a peak device are used to detect the neutron fluence of intensity similar to that of the 234U was and energy. These analyses test the mass present at mass 236 (or possibly 237), the spectrometer's ability to discern small amounts analysis would only be possible by careful of one isotope in the presence of large amounts background correction and long measuring of another one. For example, analyzing uranium times. Thus a determination of this type would for the 236u content can be very difficult because compromise the precision, accuracy, and time for 236TJ tends to be a few parts per million of the analysis when performed on a single-magnetic- total uranium present in the weapon and the sector mass spectrometer. This background level earth itself. with respect to the intensity of the major isotope is commonly referred to as the abundance Most of the mass spectrometers used for sensitivity of the instrument. The greater weapons diagnostics in INC Division are based the difference between the intensities of the on a single-magnetic-sector mass spectrometer. background tail and the tailing peak, the This device is not truly a mass analyzer but a greater the abundance sensitivity of the momentum separator; that is, species take instrument. If isobaric interferences and the different paths in the magnetic field according aberrations of the system design are minimized, to their respective mass and velocity. Figure 1.6 then the background is largely the result of shows a two-stage magnetic sector mass ion scattering from collisions with residual spectrometer. The first stage separates the gas molecules, walls, and slits in the mass ions created in the ion source by using the spectrometer. Although in a single-stage mass above process. The slit after the first magnet spectrometer the tails are present on both sides

MAGNETIC SECTOR

SOURCE SLIT So COLLECTOR SLIT Sii \ \

50 0.006" 51 0.020" Sii 0.034" 1\1" 12.956" E'.E" 70mrad Ro 12" MAGNETIC SECTOR 0 90 deg

Fig. 1.6. Two-stage magnetic-magnetic-sector-type mass spectrometer in the "S" configuration.

20 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Weapons Chemistry

of the peak, the high-mass tail is mostly the result of ions scattered at angles greater than the normal and can be minimized or eliminated by placing two or more beam-defining slits in the ion path. The low-mass side tail is caused by both ions scattered at wide angles and ions that have lost energy in or around the source region. The latter can be minimized by placing another magnetic sector following the first stage (see Fig. 1.6) or by placing an electrostatic analyzer (energy analyzer) following the first stage.

In INC Division, we have used both of the above solutions to achieve greater abundance sensitivity with our mass spectrometers, as can be seen in Fig. 1.8. The Group INC-11 mass spectrometry section has three multistage mass spectrometers; two are magnetic-magnetic instruments and one is a magnetic-electrostatic Fig. 1.8. The mass spectrum ofNBS-U0002 uranium type. Because the second analyzer (magnetic standard taken with a mass spectrometer designed as or electrostatic) can be placed in the "S" shown in Fig. 1.6. configuration shown in Fig. 1.6 or in the "C" configuration, we have studied the effect of four possible combinations on the extent of electrostatic sector instrument performs at peak tailing and have determined that the ~1 ppm on the low-mass side. configuration type has no effect. This issue, long the cause of disputes between instrument We have also studied the effect of source designers, is finally clarified. Our two-stage conditions on the overall abundance sensitivity magnetic-sector mass spectrometers perform of mass spectrometers. A study of filament size with tails that are equivalent to 0.5 ppm on has shown that decreasing the filament area the low-mass side and <0.02 ppm on the high- (where ions are created) by a factor of 2 mass side of the major peak. The magnetic- increases the abundance sensitivity by almost the same amount. Furthermore, when four different ionization methods were compared for their effect on instrument abundance sensitivity, we found that the sensitivity increased with ionization methods that operated at low temperatures. For example, thorium ionized on a triple filament at 2050°C showed 0.7-ppm abundance sensitivity, whereas technetium run at 1045°C performed with an outstanding abundance sensitivity of 0.026 ppm.

Fundamental studies such as these allow us to understand the physical phenomena that ultimately determine our capability to make measurements. As a result of our increased understanding of the limitations of present instrumentation, INC Division is well poised to design the new instruments required as weapons detector technology incorporates new isotopes that must be measui-ed at increasingly lower levels of detection. Fig. 1.7. Mass spectrum ofNBS-U0002 uranium standard taken with a single-stage magnetic sector mass spectrometer.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 21 Environmental Chemistry

Overview

Isotopic Analysis of Environmental Samples

9 Determining Co-Contaminant Speciation on Environmental Substrates

Biodegradation 6i TNT Environmental Chemistry

Overview available to the two approaches reflect this distinction. Waste management operates in fairly well controlled environments such as Eugene J. Peterson processing plants, where the amount of waste produced can be reduced, the waste can be The Isotopes and Nuclear Chemistry (INC) transformed into less hazardous substances, Division has a tradition of strong interest in all or the waste can be disposed of intelligently. areas related to the nuclear sciences, including On the other hand, environmental management the development of strategic weapons, nuclear must necessarily operate in diverse, moderately- energy, radioactive tracers, heavy-element to-poorly controlled, and often ill-defined chemistry, and nuclear physics. Because many domains—in regions both near and far from of these areas involve the production of the source of contamination. This lack of radioactive waste, our nuclear legacy requires definition and control demands a fundamental that we give attention to issues like waste understanding of the chemical and physical minimization and safe waste disposal. transformations and transport processes that We also have developed strong capabilities the waste can undergo. Issues such as uptake in other fields, including geochemistry, into living organisms, which pertain to the atmospheric chemistry, inorganic chemistry, ultimate fate of the waste, must also be and biochemistry, that play a role in assessing, considered. Once this characterization has understanding, predicting, and remedying been completed, it will be possible to undertake environmental problems. This section of the the ultimate step in the environmental annual report discusses several issues and management approach, which entails devising approaches to environmental problem-solving and implementing viable remediation strategies and highlights the efforts of INC Division to or in-situ stabilization schemes based on ensure a brighter future through environmental physical, chemical, biological, or coupled solutions. approaches.

There are two fundamentally different yet The waste management and environmental complementary approaches to environmental management approaches are complementary—a problem-solving. The first is based on a waste point that cannot be over-emphasized. Although management perception of the issues. The existing environmental contamination demands cornerstone of this approach is the use of the use of the environmental management new or proven engineering concepts to approach, thoughtful use of the waste minimize or control waste generation at its management approach will help reduce the need source. Its goal is to prevent waste from for further efforts in this arena. However, reaching the environment and spreading because waste generation is a necessary without restriction. The second approach consequence of evolving technologies, waste is based on an environmental management disposal will remain a necessary part of the perception, which recognizes that waste already waste generation cycle, and the potential for exists and, to some extent, will always exist in environmental contamination will continue to the environment. Its goal is to fully understand exist. Thus, effective environmental problem- how waste forms interact with environmental solving cannot take place without an integrated matrices so that effective remediation and waste management/environmental management storage strategies can be devised to remove approach. or stabilize the waste. Waste management research opportunities The most notable distinction between these comprise designing processes so that they approaches is the point at which intervention produce less waste, altering the waste that is takes place. The waste management approach produced, and disposing of the waste intervenes when the waste is produced, whereas intelligently. Environmental management the environmental management approach research opportunities include studies of intervenes after the release of the waste into transport and transformation, fate and uptake, the environment (whether it is deliberate or and remediation strategies. Technology accidental). The domains of intervention development opportunities encompass efforts

24 Isotope and Nuclear Chemistry Division An nual Report FY 1990 Environmental Chemistry

to characterize waste sites, development of compounds), speciation studies must consider analytical instrumentation, prediction models, the many complex interactions possible between and finally, technology demonstration, testing, these components. The second article in this and evaluation. The articles that follow section, by Morris et al., details some of our describe aspects of INC Division's recent laboratory studies directed at determining work in transport and transformation, our speciation in such mixed waste environments. biotechnology efforts directed at waste treatment and environmental remediation, The final challenge for environmental and our research in site characterization. management involves using our knowledge about transformation, transport, probable In many cases, past disposal practices may geological accumulation points (or sinks), have compromised the integrity of a waste residence times, and biological activity to disposal site. The soundness of each site must devise practical remediation strategies. be determined before cleanup strategies can be These will be based on physical, chemical, designed. Extensive monitoring is required to and biological approaches or combinations characterize both the disposal site and the of these three. The simplest approach will movement of contaminants away from it. With always be the "brute force" decontamination the analytical technologies currently available, of the polluted region. However, this type of the price tag for characterizing a single site is treatment produces its own wastes and will astronomical. The Environmental Protection frequently be too expensive and/or inefficient. Agency discovered this fact during the earliest The most effective methods will rely on stages of managing the Hazardous Waste direct physical, chemical, and/or biological Superfund, and the Department of Energy has intervention. The third article in this section, recently concurred as they began to deal with by Unkefer et al., describes a few of our environmental concerns at nuclear facilities. biotechnology development efforts that are directed at site remediation. Current analytical practices require that a contaminant be mobile before the characterization can begin. This process requires taking samples, documenting them, transporting them to an analytical facility, analyzing them for potential contaminants, measuring the quality of the analysis, and interpreting the data. Thus, characterizing a disposal site becomes a major and expensive element of waste cleanup. The first report in this section, by Perrin et al., describes INC Division's capabilities and activities in site characterization when actinides are present.

From the environmental management perspective, the key to effective waste management is the ability to predict the waste's behavior accurately. This means developing an understanding of how waste moves (transport) or how it changes (transformation) in the air, water, and underground systems or in living organisms at the microscopic or molecular level. The heart of understanding at this level is the characterization (called speciation) of waste components in pure phases and at the interfaces between these phases. Because many existing environmental sites contain mixed wastes (that is, radionuclides or toxic metals and organic

Isotope and Nuclear Chemistry Division Annual Report FY 1990 25 Environmental Chemistry

Isotopic Analysis of Environmental For the most part, the actinides, with the Samples exception of uranium and thorium, are man- made. Thus, they may have numerous sources that originate from a variety of processes and Richard E. Perrin, D. Wesley Efurd, and uses. Actinide sources are usually easily Moses Attrep, Jr. characterized by their isotopic abundance patterns, which are characteristic of their originating process or nuclear environment. Because of the emphasis on environmental issues that concern the evaluation and For example, uranium has three naturally remediation of actinide elements at contami- 238 235 234 nated sites, INC Division has developed a occurring isotopes: U, U, and U. In unique set of abilities for measuring these nature, uranium isotopic abundances are fixed; actinides. however, with the advent of the nuclear age and the use of uranium for reactors and nuclear devices, uranium has been isotopically altered to Analyses of the actinide elements have been enriched 235U. Spent uranium reactor fuel performed for several decades by conventional contains 236u that was produced by the neutron radiochemical separation techniques, which 3 23 capture of 2 5U: 235u(n,y)236u. Because 6U have become somewhat standardized and have does not exist in nature, its presence is a clear provided a great deal of useful information. indicator of that type of activity. Similarly, Levels of plutonium, for example, have been 233U is produced in environments where determined by the a radioactivity from neutrons react with 235U: 235U(n,2n)233U. the plutonium isotopes. Over 97% of the Figure 2.1 shows the uranium isotopes that radioactivity of the plutonium samples is 239 240 can be detected in an anthropologically altered represented by Pu and Pu. Detection sample. limits have been -0.02 pCi (equivalent to -8 x 108 atoms as 239Pu) per sample. However, growing environmental and safety Knowledge of these variations in isotopic concerns demand that we be able to detect far composition can be applied to environmental lower levels of plutonium. Another limitation samples when we need to determine the source of traditional radiochemical procedures is the (or origins) of uranium in natural samples. fact that these two isotopes (239pu and 240pu) We analyzed a suite of water samples for are indistinguishable through a spectrum both the isotopics and quantities of uranium. analysis. This article illustrates the potential The samples were collected under strict of mass spectrometric isotopic analysis as conditions and then analyzed for uranium a more complete method of analysis for the in our ultraclean facilities. The composite actinides. environmental water sample isotopics are shown in Fig. 2.1. Abundance of 235U and 234U have been enriched relative to 238U, At INC Division, we have developed mass 233 and there is a notable absence of U and spectrometric methods of analysis for a number 236 of actinides (uranium, plutonium, thorium, U, which are indicative of anthropogenic , and ) that not only uranium. At first glance, the amounts permit us to determine their presence at levels of 235TJ and 238u appear to be similar to those present in natural uranium. However, not discernable by conventional methods, but 23 also permit us to determine the isotopic mix of with mass spectrometric analysis, 6TJ is these elements with no ambiguity. A specially identified, indicating that the water sample designed building was constructed to provide contains both natural uranium and another the proper facilities to handle samples that component that is probably derived from contain extremely low levels of these elements. recycled uranium. This analytical detective The samples are processed and mass work has made it possible for us to assist in spectrometrically analyzed in a clean-room settling fundamental environmental issues environment to protect them from such as whether a particular water sample contamination from the external environment. is contaminated with industrial uranium. Our detection limits, determined by the specific The technology, developed by Los Alamos types of analyses, are typically 107 atoms. can now provide a clear answer of "yes" or "no."

26 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Environmental Chemistry

Applying the capabilities of isotopic assessment and quantification of the actinide 100 allows us to unambiguously determine the origins of certain actinides in environmental samples without compromising the quality of data by using large samples. Large samples present difficulties in the laboratory because 80 handling and processing procedures can introduce contamination.

Because we can measure levels of actinides more easily at levels of 107 than most conventional methods can and because we can provide the isotopic composition of these elements, we can develop a clearer • Natural Uranium picture of the environmental situation and 0 Recycled develop strategies in accordance with all of Reactor Grade the information from the analysis. 20 • Virgin Reactor Grade Most environmental samples contain • Environmental Water Sample man-made sources of uranium. This type of information is important in assessing liability and the remediation of such sources. INC Division personnel are expert in this type of ultra-sensitive analysis, which continues to be invaluable in environmental work. Careful chemical separations and very sensitive and precise mass spectrometry are keys in providing this capability. Simple quantitative analysis of uranium or other actinides is useful but without information about the isotopic composition, it would be impossible to reconstruct a complete picture of the sources of the environmental actinides.

J II „ I J 233 (j 234 u 235(J 236 (j 238|j

Fig. 2.1. Water samples were analyzed to determine the abundances of uranium isotopes from three sources.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 27 En viron men ta I Ch em istry

Determining Co-Contaminant cation exchanger that readily swells to Speciation on Environmental Substrates incorporate interlayer components, including organics.

David E. Morris, P. Gary Eller, C. Drew Tait, In our two-fold approach, we (1) conduct William H. Woodruff, and Stephen D. conventional wet chemistry experiments Conradson* (for example, measurements of adsorption isotherms) to ascertain the bulk (macroscopic) As our recognition of global environmental properties of the co-contaminant system, and contamination grows, it becomes increasingly (2) employ analytical methods to measure clear that the most difficult problems involve molecular-level, structure-specific properties mixtures of chemically and physically different (speciation) of the co-contaminants in pure contaminants. The mixed wastes or co- phases and at the phase interfaces. The contaminants found at US Department of analytical methods used depend on the specific Energy (DOE) facilities contain radionuclides— systems but are chosen from the many advanced especially the long-lived actinides—and organic spectroscopic tools available within the Division. reagents and solvents. The environmental matrix in which wastes exist is also very Our batch experiments on the interaction important when we are determining the between TBP and related neutral-donor transformation and transport properties of extractants with SAz-1 reveal that there is a co-contaminant systems. For example, many rapid and extensive uptake of the organics by clays and minerals strongly sorb contaminants the clay. This conclusion is based on (1) x-ray and serve as a primary barrier to migration. diffraction data that show an increase in the Conversely, it is well known that certain mineral clay interlayer spacing (dooi) from 9.5 A in the surfaces catalyze the decomposition of organics fully dehydrated clay to more than 25 A in the and metal complexes, thereby leading to still TBP-treated clay, and (2) thermal gravimetric dangerous and yet potentially more mobile analyses that indicate the weight losses for the contaminants. The complicated interactions treated clay that correspond to the volatilization between co-contaminants and environmental of TBP. Because the volatilization occurs at substrates must be understood before we can about the same temperature (~290°C) as that of fully assess the magnitude of the contamination the pure TBP (~270°C), these data also suggest problem and develop appropriate remediation that the binding of the extractant is weak. strategies. Vibrational data have also been obtained This article describes our recent efforts to for the TBP-treated clays. The characteristic determine the speciation of co-contaminants P=O stretching frequency shifts from 1282 cm"1 at the interface between solutions and in pure TBP to 1259 cnr1 in the clay samples. environmental substrates. By ascertaining the This is consistent with complexation of the TBP interfacial speciation, we can provide the most to interlayer Ca2+ ions and suggests that, at specific information possible for understanding least at high-TBP loading levels, ligation is an contaminant transformations and transport important uptake mechanism. processes. We have initially focused on waste components generated by the PUREX process, We have used several spectroscopic probes which uses neutral-donor extractants such as + to study the speciation of UO2 and its TBP tributylphosphate (TBP) in a solvent such as complex in solution and on SAz-1. The spectra kerosene to separate and purify actinides. of all samples (except the UO^/TBP/SAz-1 This process is used throughout the DOE sample) exhibit the same first-shell structure, complex, and contaminant plumes containing which demonstrates that no change in uranium PUREX components have been identified at valence has occurred and that the O=U=O several sites. The substrate chosen for our work structure remains intact under a variety of is a smectite clay (SAz-1) found in the semi-arid conditions. No strong U-U second shell features western US. This clay is a layered, high-capacity are seen. Thus, neither precipitation nor clustering processes is occurring—even in the clay samples. For all samples in solution, *GroupMEE-ll

28 Isotope and Nuclear Chemistry Division Annual Report FY1990 Environmental Chemistry

the coordination numbers and average bond macroscopic studies (such as determinations distances for the equatorial ligands are of adsorption isotherms) to characterize fully consistent with expectation. In particular, the interfacial chemistry of co-contaminants the TBP complex of uranyl nitrate in organic and bridge the gap from laboratory-scale solutions (for example, dodecane) is expected experiments to actual field-scale behavior. to be UO2iNO3)2*2TBP and should have an equatorial coordination number of six (2 from each nitrate and 1 oxygen from each TBP). For the clay samples treated with uranyl ion, with and without TBP, the data suggest that the speciation is more complicated. One possibility is that the clay has two or more distinctly different sites on which the uranyl species can sorb (such as interlayer and surface- bound). This hypothesis is supported by data from two other spectroscopic methods. Vibrational spectra show a splitting (~26 cm'1) of the characteristic symmetric U=O stretching + mode into two modes for the aqueous UO2 - treated clay, and luminescence spectra show substantial line broadening for the vibronic components of UO2 -clay samples compared + to those of dissolved UO2 samples. (a) 15 We have also used pulsed-laser photoacoustic Nd3' in Aqueous Solution 3+ Clay Phase spectroscopy to study the speciation of Nd in Supernatant the TBP/SAz-1 matrix. Because this method yields the functional equivalent of an electronic absorption spectrum, the speciation information 3+ is implicit. The chemistry of Nd is very similar in to that of other readily hydrolyzable metal ions such as Pu4+ and Am3+, and therefore it is < commonly used as a safer surrogate for these highly toxic contaminants. Figure 2.2 shows 3+ pulsed-laser photoacoustic spectra for Nd in 517 522 527 532 four different matrices. The distinct differences (changes in peak positions and bandshapes) in (b) 15 3 the spectra of all four samples clearly reflect a Nd - in 20% TBP/C,2HK 3+ Clay Phase difference in Nd speciation. Finally, we have _____ Supernatant evidence from these data that TBP in solution is very effective at leaching the metal ions 10 from the clay. Thus TBP plumes may mobilize mineral-bound metal contaminants and promote migration.

Our preliminary results suggest that our spectroscopic probes are very sensitive to speciation, both in solution and on the clay 517 522 527 532 substrates. Therefore, we are confident that Wavelength (nm) we can obtain the molecular-level information we need to adequately assess and predict transformation and transport processes in the Fig. 2.2. Pulsed laser photoacoustic spectra environment. We must continue to couple these demonstrate that the speciation and concentration spectroscopic studies with other traditional ofND3+ depends strongly on the matrix.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 29 Environmental Chemistry

Biodegradation of TNT The degradation was accomplished by using a mixture of bacteria we identified as Pseudomonas fluoresceins (P. fluoresceins) III, Pat J. Unkefer, Eloise Margiotta, P. fluoresceins II, P. alcaligines, and a Mary R. Stenger, and Marc Alvarez Xanthamonas species. One of these bacteria, P. fluoresceins III (shown in Fig. 2.3) is capable of completely degrading TNT; the P. fluoresceins TNT (2,4,6-trinitrotoluene) has been the III degrades the explosive when it is provided major conventional explosive used by the with a supplemental supply of . The US military over the past several decades. choice of this supplemental carbon source is As a consequence, TNT has contaminated crucial because we found that some carbon soils, ground , buildings, and equipment sources actually inhibit the degradation. We at numerous Department of Energy (DOE) then focused our efforts on choosing the correct and Department of Defense installations and most cost-effective supplemental carbon throughout the nation. This contamination source. We found that acetate, arginine, and resulted from explosives manufacture and yeast extract are especially good substrates, munitions fabrications as well as explosives and sugars are exceptionally poor substrates. and munitions decommissioning and disposal. The substrate chosen also influences—and may Our efforts are now focused upon developing even specify—the accumulation of specific cost-effective remediation technologies to solve intermediates. these problems. Our initial culture and degradation Incineration is usually regarded as an conditions were designed to screen for efficient and inexpensive disposal method for microorganisms that carry out oxidative wastes. However, few—if any—commercial incinerators will accept explosives or explosive- contaminated soils. An attractive and usually cost-effective alternative to incineration is bioremediation. Bioremediation employs the vast array of a microorganism's degradative reactions, which allow the microorganism to degrade most organic compounds. In our initial experiments, we targeted TNT, a universally employed explosive material. Success with this particular material has prompted us to begin studies on RDX and HMX, two other explosives commonly used by the military (Fig. 2.3).

To select a microoganism that will degrade a specific hazardous compound (in this case, TNT), we exploited the adaptive capabilities of a natural microbial population found growing with TNT. Those microorganisms that can use TNT as a nutrient source will have a competitive advantage over those that cannot, and therefore, the TNT-degrading microoganisms will establish themselves in the explosive-contaminated site. We removed TNT- degrading bacteria of various types from TNT- contaminated soil at Los Alamos and cultured them on media that contains a poor source of organic carbon and TNT. This process selected Fig. 2.3. Now that we have successfully isolated the for and enriched those bacteria that effectively bacteria that will degrade TNT, research is being directed toward bacti'ial activity to act similarity on degraded TNT. RDX and HMX.

30 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Environmental Chemistry

degradations. A review of past efforts to isolate TNT-degrading bacteria indicated that these experiments failed to obtain complete degradation and, in fact, resulted in reductive degradation products5"8 that were toxic and intractable to further degradation. These undesirable intermediates accumulated and persisted; they seriously limited the application and development of biodegradation of TNT as a practical process. However, the bacteria we obtained in our research efforts degrade TNT by oxidative chemistry; we found that they contain a TNT-dependent oxygenase. Oxygenase enzymes incorporate one or two atoms of oxygen into an aromatic compound, and this activity chemically labelizes the aromatic ring for cleavage and subequent degradation.9 This oxygenase enzyme apparently catalyzes the first step in the degradation of TNT. We have purified this enzyme and are now characterizing its activity and properties.

This work has received wide interest in both the scientific and national media, as is shown by the cartoon in Fig. 2.4. The TNT degradation process (as well as those now being developed for RDX and HMX) could be a valuable, cost- effective aid to environmental clean-up of contaminated sites in the DOE complex.

Fig. 2.4. Cartoon shows concept of bacteria that consume TNT explosive materials.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 31

Actinide and Transition Metal Chemistry

Overview particular actinide metal is an important predictive tool. Other research efforts in INC Division seek to apply this knowledge in creative Carol J. Burns solutions to specific problems of separation or immobilization of actinides at DOE sites. Work has continued on a program to conceptually Fundamental knowledge of the inorganic design and synthesize ligands capable of metal- chemistry of the d- and f-transition block specific binding that can be used for detection elements is the basis from which the chemical and separation. During the past year, a series and physical behavior of metal-containing of acylpyrazolone complexes linked with four systems may be predicted. The actinide and to eight methylene units has been synthesized transition metal chemistry carried out in INC to explore the liquid-liquid extraction properties Division is a vital resource for Los Alamos of linked chelating ligand systems. The research related to our nation's defense compound displays a substantial selectivity capability, energy independence, and the for plutonium(IV) and thorium(IV) over preservation of the environment. The Division uranium(VI), americium(III), europiumdll), is home to many efforts that attempt to bridge (IH), and aluminum(III). The extraction the gap between these needs and the knowledge system is also highly selective for plutonium(IV) and skills of our scientists. over thorium(IV) and has potential for application in sensors and separations. The chemistry of actinide elements continues to be a major focus of research within the The article by Clark and Watkin in this Division. Unique expertise and facilities are chapter discusses some interesting advances in available at Los Alamos for the study of these preparative thorium chemistry and points out elements, and the Laboratory's commitment another important facet of the actinide chemistry to the safe and conscientious handling of program in the study of these elements under radioactive materials provides an ideal environmentally relevant conditions. It is exciting atmosphere for investigation of their physical to note that our basic research in actinide and chemical properties. We have established coordination chemistry has already been used productive collaborations with scientists in to help solve waste problems in the Laboratory. Nuclear Materials Technology (NMT), During the past year, actinide metal Chemistry and Life Sciences (CLS), and oxidations studied in conjunction with the Theoretical (T) Divisions with the goal of organoactinide program have been combined with understanding the electronic and structural expertise in sol-gel chemistry to develop schemes features of actinide complexes as a function of for economical transformation of potentially oxidation state and ligand environment. One reactive uranium scrap metal into insoluble aspect of these investigations is INC Division's oxides, which may be stored more safely. program in the relatively underdeveloped field of organoactinide chemistry. We have been able to advance the understanding of bonding in such While seeking to understand the properties species through studies of uranium and thorium of the actinide elements themselves, we are also complexes in unusual coordination environments. applying these unique properties to the solution During the past year, we have been able to of other problems at the Laboratory. A rather synthesize a new class of uranium organoimido novel application of plutonium involves its use as a probe for structural elucidation of proteins. complexes, {[(Me3Si)2N]2U(|i.-NAr)}2, and examine the mechanism of their formation. In collaboration with the CLS Division and The recent discovery that the analogous thorium Physics-LANSCE , we have incorporated systems cannot be synthesized by the same 240pu(Hi) into the calcium binding sites of preparative route suggests unappreciated the protein calmodulin (CaM). CaM is an differences in the electronic structure of the important protein that mediates calcium- early actinides. regulated processes in biological systems such as muscle contraction, hormone secretion, neurotransmitter release, etc. The solid-state Establishing a basis of knowledge relating to crystal structure of CaM is known, but solution the steric and electronic factors that contribute to studies indicate that this is not the in vivo the stability of the coordination environment for a structure. Plutonium-240 has exceptional

34 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Actinide and Transition Metal Chemistry

resonance neutron scattering properties that the Laboratory. Specific materials produced provide us with a "ruler" to measure the include coatings of rhodium, iridium, and binding distances in CaM. We have successfully zirconium carbide. During the past year, incorporated 240Pu into the calcium binding we have also developed a method to produce sites and measured the width of the dumbbell- amorphous uranium nitride (UN) by a shaped protein by means of neutron scattering, combination of solution methods and low- and we are now attempting to measure the temperature heating; this methodology has longer distance—the length of the dumbbell. great potential for extension to other ceramic This line of research may have far-reaching powders. Research in film deposition is applications in many bioscience fields. supported by investigation of novel synthetics methodologies in transition metal chemistry, Recent events have served to highlight our such as the use of the large-scale metal vapor synthesis reactor supported jointly by INC timely research on catalytic transformations of and NMT Divisions. A closely related effort small molecules by transition metal complexes. entails an investigation of the electronic The passage of a more stringent clean air structure of homoleptic transition metal legislation this year has followed hard on the complexes, especially in relation to metal- heels of numerous news reports suggesting ligand interactions. The article by Wheeler that industrial emissions of pollutants, such et al. describes recent results that involve the as sulfur and nitrogen oxides, are responsible synthesis of a homologous series of high-valent for widespread damage in the nation's national transition metal alkoxide complexes and parks. Improvements in the efficiency of comparison of their electronic structures as pollution abatement devices will only follow elucidated by physical characterization and from the development of more sophisticated theoretical calculations. schemes for degradation of these simple molecules. During the past year, ongoing research efforts in catalytic reduction of sulfur Our inorganic synthetic capabilities are dioxide by the organometallic molybdenum also being used in support of the development sulfide complex (Me5C5)2Mo2S4 have expanded of new radiopharmaceuticals. Bryan et al. to include the examination of the chemistry of describe a new effort in the inorganic chemistry sulfur dioxide with the analogous of technetium. Our experience in handling dimer, as well as with the related complex radionuclides combines well with our expertise (Me5C5)2Cr2S5. In the latter system, we have in transition metal chemistry to create successfully isolated the initial product of sulfur circumstances uniquely suited to an u dioxide coordination, (Me5C5)2Cr2(|i-S)(u-S2)2( - investigation of the properties of this lone S2SC>2). The solid-state structure of this system d-transition element with no stable isotopes. reveals an interesting dative interaction with a The chemistry of technetium is rapidly finding second molecule of sulfur dioxide in the lattice, application in a number of other research which suggests important new insights into the efforts, including our internationally recognized mechanism of key oxygen transfer processes in program in transition metal dihydrogen this system. chemistry. Technetium may be an element for which molecular hydrogen adducts exist, as The Division's efforts in preparative indicated by the results of theoretical transition metal chemistry have been expanded, calculations conducted in collaboration with in part because of a new collaborative effort with researchers in T Division. We are attempting to the Polymers and Coatings Group (MST-7) synthesize examples of this class of compounds. involving preparation of thin-film metal and It is likely that the separations chemistry of ceramic coatings by organometallic chemical technetium will be of future interest as a result vapor deposition. The use of organometallic of the Laboratory's proposed concept in compounds as volatile reagents for the accelerator transmutation of waste. Growing deposition of these films has many advantages, concern about many aspects of technetium including the control of microscopic chemistry illustrates the broad applicability stoichiometry and the ability to use lower of inorganic chemistry in INC Division projects. temperatures in the deposition process. We are We are committed to maintaining this necessary encouraged by the interest this work has drawn technology base to meet future challenges in the from a variety of programmatic efforts within Laboratory.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 35 Actinide and Transition Metal Chemistry

Convenient Entry into the Inorganic ThX4L'4 where U = pyridine, acetonitrile, etc. and Organometallic Chemistry of [Eq. (2)]'. Thorium THF Th + 2X THF -> ThX4(THF)4 (1) 2 0°C David L. Clark and John G. Watkin

The inorganic and organometallic chemistry tol of thorium is of considerable research interest; ThX4(THF)4+4L' ThX4L4+4THF (2) it encompasses thermochemical studies of metal-ligand bond strengths,10'11 catalytic processes,12"13 C-H bond activation,14 and The stoichiometry of these complexes has been established by elemental and most recently, the first authentic examples of 1 molecular thorium (III) complexes.15 Almost thermogravimetric analysis, H nuclear exclusively, the starting point in synthetic magnetic resonance (NMR) integration us thorium chemistry has been from the thorium internal standards, and infrared spectroscopy. tetrahalides, ThX4 (in which X = chlorine, For ThBr4(THF)4, a single-crystal x-ray , and ). The anhydrous thorium structure determination revealed a distorted tetrahalides have all been prepared by high- dodecahedral coordination geometry about the temperature reaction between thorium metal central thorium atom with Th-Br and Th-0 and elemental halogen. When prepared in this distances of 2.86 and 2.55 A, respectively. traditional manner, thorium tetrahalides are The view of this molecule shown in Fig. 3.1 polymeric solids16 that are insoluble in common emphasizes the dodecahedral coordination organic solvents and quite unreactive. To obtain geometry. a hydrocarbon-soluble, synthetically useful starting material, it is necessary to sublime These Lewis-base adducts of thorium thorium tetrachloride in vacuum at high tetrahalide have proven to be excellent synthetic temperature (700°C) before it is used; this may precursors to a range of inorganic thorium produce only a few grams of purified product complexes, in part because of their favorable each day. To avoid this problem, we have solubility in hydrocarbon solvents. For example, developed a convenient low-temperature reaction of ThBr4(THF)4 with four equivalents solution route to organic-solvent-soluble Lewis of bis(trimethylsilyl)amide in refluxing base adducts of thorium tetrahalides that are toluene produces the known metallacycle14 in easy to prepare and serve as excellent high yield; this reaction is routinely performed precursors to a variety of new and known in our laboratory on a 3- to 50-g scale [Eq. (3)]. complexes of thorium. tol Clark and Sattelberger demonstrated that ThX4(THF)4 + 4NaN(SiMe3)2 uranium metal turnings react readily with reflux elemental iodine in organic donor solvents to [(Me Si) N] Th[N(SiMe )(SiMe CH2)] (3) produce Lewis-base adducts of uranium triiodide 3 2 2 3 2 17 of general formula Ul3L4 (L = Lewis-base). Employing a similar strategy, we have found As a part of our investigations into the that a slight excess of thorium metal turnings inorganic chemistry of thorium, we are reacts smoothly with elemental halogen in THF preparing thorium alkoxide complexes as (tetrahydrofuran) solution at 0°C to yield highly models for speciation and transformation of soluble complexes of the general formula actinides in the environment. The thorium ThX4(THFj4 (in which X = Br or I) in -90% yield tetrahalide complexes described here have [Eq. (1)]. These reactions are routinely allowed us to follow two distinct preparative performed in our laboratory on a 100- to 150-g approaches to a range of new thorium alkoxide scale in a single day. The THF adducts readily species: (1) direct metathesis of the thorium exchange with other Lewis base solvents (II) in tetrahalide with an alkali-metal salt of the toluene solution to form a series of hydrocarbon- appropriate alkoxide, and (2) amine elimination soluble donor complexes of the general formula by treatment of the metallacycle with alcohols.

36 Isotope and Nuclear Chemistry' Division Annual Report FY 1990 Aetinide and Transition Metal Chemistry

Using these two strategies, we have been able to prepare a host of new thorium alkoxide complexes. To show the usefulness of these approaches, we will outline some of our recent results that employ the aliphatic tert-butoxide ligand.

Eeaction of ThI4(THF)4 with four equivalents of potassium tert-butoxide in the presence of pyridine, followed by crystallization from hexane, leads to the isolation of a bis-pyridine t adduct of thorium tert-butoxide, Th(OBu )4(py)2. Crystals suitable for x-ray diffraction were grown from hexane at -40°C and exhibited a pseudo-octahedral geometry about the thorium atom with the two pyridine ligands occupying cis positions (Fig 3.1). Two significantly different Th-0 bond lengths are seen in the molecule: 2.16 A for the tert-butoxide ligands trans to pyridine and 2.20 A for the tert-butoxide ligands trans to one another. The pyridine ligands exhibit a Th-N distance of 2.76 A.

Treatment of the metallacycle with four equivalents of tert-butanol in toluene at room temperature, followed by workup from hexane, produces the dimeric alcoholate ThaCOBu^gCHOBut). Deprotonation of the thorium alcoholate with sodium hydride allows the isolation of the hexane-soluble sodium salt NatTh^COBu^t)]. We carried out a single-crystal x-ray structure determination on a crystal grown from hexane at -40°C. This procedure revealed the expected dimeric structure with a confacial bioctahedral geometry around the thorium centers, as seen in Fig. 3.1. The Th-0 bond lengths are 2.16 for terminal tert-butoxide ligands and 2.31 and 2.48 A for alkoxides bridging thorium and sodium, respectively. ThfOBu'Upy), The sodium ion is coordinated to four oxygen atoms of the tert-butoxide ligands; two of these occupy bridging positions and two are being terminal ligands.

Our new organic-solvent-soluble Lewis base adducts of thorium tetrahalides have proven to be excellent synthetic precursors to a wide variety of new inorganic complexes of thorium, as is illustrated for the thorium tert-butoxide system. This new starting material offers exciting opportunities for further explorations NaTh (OBu')g of the chemistry of thorium, and we are hopeful 2 that they will offer a convenient entry into thorium's relatively unexplored trivalent Fig. 3.1. Views of the molecular structures of oxidation state. ThBr4(THF)4, Th(OBut)4, Py2, and NaTh2(OBu%.

Isotope and Nuclear Chemistiy Division Annual Report FY 1990 37 Actinide and Transition Metal Chemistry

Stereochemical Consequences of The x-ray crystal structures of 1 and 2 (shown Electronic Structure in Fig. 3.2) reveal edge-shared bi-octahedral geometries for both compounds. Their short metal-metal distances of 2.7897 (8) A (W-W) Jeffrey C. Bryan, David L. Clark, and 2.5319 (7) A (Re-Re) suggest the presence David Wheeler, and Alfred P. Sattelberger of a single and double bond, respectively. The M-O(axiaJ) (W-O(3) = 1.879 (6) A, W-O(4) = 1.887 (6) A, Re-O(3) = 1.888 (4) A, Re-O(4) = 1.907 (4) A) The realization that many aspects of the distances are significantly shorter than the other structure of inorganic complexes are dictated M-0 distances, which implies strong n bonding by electronic factors marked a turning point in interactions. We believe that these interactions studies of organometallic and inorganic and the alkoxide orientation between the two chemistry. To understand why a particular structures can be rationalized by studying their complex assumes one structure and not another electronic structures. is one of chemistry's fundamental goals. The necessity of this understanding is apparent when one considers that structure often plays a critical We used Fenske-Hall quantum mechanical role in determining reactivity. Reactivity, in turn, calculations to examine the electronic structure describes how a complex behaves. Therefore, of Re2(OH}[o as a model complex; the results are understanding structure/reactivity relationships shown in Fig. 3.3. The interaction of the OH affects almost all areas of chemistry—from the ligand set with the Re2 core can be visualized in development of new catalysts and new materials terms of the overlap of the metal orbitals with to the synthesis of organometallic anticancer the a and K lone-pair orbitals of the sp hybridized drugs. In efforts to discern the relationship oxygen of the OH- ligand set. For each OH', there between molecular structure and electronic is a low-lying a lone-pair and a higher lying set structure, metal-metal bonded complexes have of two degenerate JI lone-pairs. If only the sigma been examined by both experiment and interactions are considered, one orbital of each calculation. While we were investigating the chemistry of high-valent transition metal fluorides, we discovered routes to both ditungsten decamethoxide [W^OMe^ 0] and dirhenium decamethoxide [Re2(OMe)10]. Isolation of these two unique high-valent complexes afforded us an excellent opportunity to investigate the relationships between molecular structure, electronic structure, and reactivity.

The reduction of colorless WF2(OMe)4 with powder in THF generates a mixture of red tungsten(V) products [W2Fx(OMe)10.x, where x = 1-3]. Individual components of this mixture can be isolated and characterized, or the mixture can be reacted directly with an excess of sodium methoxide in THF to form an indigo-colored complex [W^OMe^ o d)] as the only soluble tungsten product (-50% overall yield).

When ReFg is condensed into a solution of Si(OMe)4 and CH3CN at -40°C and allowed to warm slowly, a mixture of products is formed, including Re2(OMe)10 (2) and Re2F2(OMe)g. This mixture reacts with excess Mg(OMe)2(HOMe)2 in THF and yields 2 as the only nonvolatile,

toluene-soluble product (-60% from Fig. 3.2. X-ray crystal structures ofW2 (OMe)I0 and Re2 ReF6). (OMe)10.

38 Isotope and Nuclear Chemistry Division Annual Report FY1990 Actinide and Transition Metal Chemistry

1C Re2(OH)10 Re2(OH)10 (OH)10 ' "o only" "o + n " "o only"

lone pair

Fig. 3.3. Orbital interactions in Re2(OH)10.

10+ interaction requires that the bridging oxygens degenerate set of Re2 K, 8, 8*, and it* orbitals is used to create metal-ligand a bonds. This assume a planar geometry in 1. "a only" picture yields a ground state electronic configuration of 5*2a2. The small energy gap We have synthesized and structurally between the highest occupied molecular orbital characterized a fundamental series of (HOMO) and the lowest unoccupied molecular homologous metal-metal dimers. This series, if one includes the known Ta2(OMe)10, span the orbital (LUMO) is similar to that observed for 1 2 2 "isoelectronic" Re2Cl10. When the 7t-bonding range of d°-d° to di-d to d -d . The results of interactions are "switched on," we see that structural analysis are rationalized as a direct alkoxide-metal 7t interactions can only take result of the calculated electronic structure of place between Re2 5 and 8* orbitals and the each complex. As well as studying the reactivity n orbitals of the axial alkoxides. This rc-bonding of the series, we are further examining the interaction destabilizes the 5 and 5* orbitals and electronic structures with techniques such as generates a sizeable HOMO-LUMO gap, yielding photoelectron spectroscopy, electronic absorption a diamagnetic o27i2 complex with a metal-metal spectroscopy, electrochemistry, and additional double bond. (more advanced) calculations.

The structures of the complexes indicate that both the axial and bridging alkoxides adopt different orientations. The axial alkoxides are parallel to the metal-metal bond in 2, but are perpendicular to it in 1 (Fig. 3.2). Additionally, the oxygen atoms of the bridging alkoxides are planar in 1, indicating sp2 hybridization, but are pyramid-like in 2, indicating that O(5) is sp3 hybridized. These structural differences can be explained by calling on our knowledge of the electronic structure. Both complexes possess an empty S-symmetry orbital. In complex 2, the axial oxygens donate electron density into this orbital, thereby determining their orientation relative to the double bond (Fig. 3.4). In complex 1 however, the empty metal rc-type orbitals interact with the axial ligands, and the 5 orbital is available to interact with the bridging oxygens (Fig. 3.4). This Fig. 3.4. Structural differences in complexes 1 and 2.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 39 Actinide and Trap.sition Metal Chemistry

Synthesis of the First Technetium(VII) complex, (2) the electron donor ability of the Imido Complexes ligand, or <3) the steric encumbrance about the metal—and therefore, the stability of the complex; thus, these ligands offer greater Jeffrey C. Bryan, Carol J. Burns, and Alfred flexibility in complex design. P. Sattelberger When three equivalents of 2,6-diisopropyl- Technetium chemistry is a relatively young isocyanate cArNCOj are heated to 100'C for and underdeveloped field. The half-lives of 18 hr with trimethylsilylpertechnetate [TcO3fOSiMe3j] in hexamethyldisiloxane technetium isotopes are short on the geologic 20 time-scale, which all but eliminates natural (Me^SiOSiMes^ solvent, a deep green abundance of the element. Only in the last trisfarylimidojtrimethylsiloxytechnetium 30 years has one isotope ("Tc, with a half-life complex, Tci'NArj:/OSiMe3A and three of 2.1 x 105 yr and a of 292 keV; equivalents of CO2 are formed ^Fig. 3.5;. become available in appreciable quantities from Similar reactivity is observed with the reprocessing of nuclear reactor materials. 2,6-dimethylphenylisocyanate (Ar'NCO), Technetium isotopes also are unstable to decay which forms Tc(NAr'j3

Most of the known chemistry of technetium is the result of the preeminence of 99mTc (with a half-life of 6 hr and a gamma decay of 140 keV), as a noninvasive imaging agent in nuclear medicine. Over 80% of the millions of diagnostic imaging procedures each year use complexes of 99i"Tc, which is obtained from 99Mo/s9mTc generators. Over the past 15 years, technetium chemistry research has focused primarily on the synthesis and radiopharmaceutical applications of a relatively narrow range of complexes; that is, TcO2Ln and TcOL^, which contain technetium in the +5 oxidation state and are designed to be stable and mobile in aqueous biological systems. The development of a new generation of technetium radiopharmaceuticals will depend upon additional basic research into the inorganic chemistry of technetium.19

We are developing synthetic methodologies to isolate and characterize technetium complexes that contain ligands currently unknown for technetium but well established for metals exhibiting similar chemistry. We initially decided to investigate imido ligands (NR2";, which are quite common for complexes of other elements near technetium in the periodic table. Imido ligands are also isoelectronic to the oxo ligand 'O2';, which is very common among technetium radiopharmaceuticals. Imido ligands have a distinct advantage over oxo ligands in that the R ^organic? group of the imido ligand Fig. 3.5. Synthesis and reactivity of Te(XAr)3(OSiMe3 .•; can be varied to affect il) the lipophilicity of the R = methyl, ethyl, and allyl.

40 Isotope and Suclear Chemistry Division Annual Report FY 1990 Actinide and Transition Metal Chemistry

These complexes are the first examples electronic donation by imido ligands is the of technetium imido complexes21 where M-N-C angle; as it increases, so does the level technetium is in its highest possible oxidation of electron donation by the ligand. As can be state—the +7 state. There are only a handful seen in Fig. 3.6, the Tc-N-C angle—and thus of known technetium(VII) complexes; they all the level of electron donation by the imido contain oxo (O2~) and/or halide (F~, Cl", Br") group—increases from left to right. This trend ligands, are often very reactive with air, and can be directly related to the donor ability of are frequently unstable towards reduction. the fourth group attached to technetium, which 2+ The complexes described here contain neither decreases in the order "OSiMe3 > Me" > Hg . oxo nor halide ligands, are only slightly air- It is also interesting to note that the geometry sensitive, and are remarkably stable towards of the complex transforms from tetrahedral to reduction; for example, Tc(NAr)3(OSiMe3) trigonal pyramidal, reflecting the increasing exhibits a reversible reduction at -1.77 V. electronic dominance of the imido ligands as the donor ability of the fourth ligand decreases.

The trimethylsiloxy COSiMe3) ligand in Tc(NAr)3(OSiMe3) is readily removed or We have prepared the first technetium(VII) replaced (Fig. 3.5). The Tc(NAr)3(OSiMe3) reacts imido complexes. These complexes are readily quickly at room temperature with alkyl prepared and are excellent starting materials Grignard reagents (RMgCl) in THF to form for a variety of complexes. We have also deep green-blue Tc(NAr)3R. This material is demonstrated that the three imido ligands of also reduced to technetium(V) by two Tc(NAr)3X increase electron donation as the equivalents of sodium/ amalgam donor ability of X decreases. We plan to continue and forms the mercury-bridged technetium to explore Tc(NAr)3(OSiMe3) chemistry by dimer Hg[Tc(NAr)3]2. Finally, it reacts with preparing alkylidene and alkylidyne complexes, trimethylsilyliodide (ISiMe3) to form Tc(NAr)3I which are still unknown for technetium. and hexamethyldisiloxane (Me3Si0SiMe3).

We have grown single crystals of the Tc(NAr)3(OSiMe3), Tc(NAr)3Me, and the Hg[Tc(NAr)3]2 complexes by slow evaporation of THF solutions and have determined their structures by x-ray diffraction. (These structures are illustrated in Fig. 3.6 with selected bond distances and angles.) A simple measure of

Tc = N 1.754 (7) A 1.757 (13) A 1.718 (10) A ^Tc-N-C 155.8(6)° 166.4(11) ° 174.4(10) ° ^X-Tc-N 108.8(3)° 101.9(6)° 97.6 (4) ° xN-Tc-N 110.1(3)° 115.9(6)° 118.3(2)°

Fig. 3.6. ORTEP representations ofTc(NAr)3(OSiMe3), Tc(NAr)3Me, and HglTc(NAr)3]2. The isopropyl groups on the arylimido ligands have been omitted for clarity.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 41 Geochemistry

Overview Multicomponent Tracer Experiments at Mammoth Hot Springs in Yellowstone

Using Surface Ages to Understand Geological Processes

Geochemical Studies Using Long-Lived Members of the Uranium Decay Series Geochemistry

Overview Division, Laboratory, and the DOE itself has created widespread opportunities for contributions to basic science. For example, the David R. Janecky atmospheric expertise and analytical/sampling capabilities developed for nuclear tests through Interaction between man and earth is the 1950s have subsequently been used to the core of human existence. We use a wide provide the basic information on global variety of resources, including air, water, oil, atmospheric dynamics and chemistry that has and metals. Therefore, we are increasingly been the foundation for our present-day concerned as we note the marked changes in research in global climate change. the earth that have resulted from man's activities. Some of these environmental Three-dimensional models of general changes are long lasting and difficult or atmospheric circulation are now being coupled impossible to quickly reverse after they have with atmospheric chemistry to help us explore occurred. By characterizing and deciphering the chemistry/climate linkages. Our recently fundamental chemical processes that occur in completed simulations of the global atmospheric the earth's system—with or without human distribution of Freon-11 give us confidence that influence—we can gain important insight for model dynamics are properly transporting this both resource and environmental analyses. inert gas throughout the troposphere and The Isotope and Nuclear Chemistry Division stratosphere. Simulations of methylchloroform contributes to basic and applied research efforts are providing new information about the through analytical, experimental, theoretical, atmospheric distribution of hydroxyl radicals and field studies. that initiate oxidation reactions to remove pollutants from the atmosphere. We also have As a part of the US Department of begun to explore the chemical consequences Energy (DOE) complex, Los Alamos originally of methane oxidation, including the formation developed its viewpoint and environmental of carbon monoxide and carbon dioxide, their research programs from a national security interaction with NOX, and consequences for perspective. The early focus was defense- the earth's ozone. These efforts are necessary related but has expanded over past decades to steps toward simulation of the distribution and encompass energy resources and subsequently reaction controls of ozone in the troposphere. environmental processes as the interrelated requirements of national security and a healthy The evolution of geochemistry research society have become obvious. Most of our in INC Division has followed a path similar to previous efforts in INC Division were directed that of atmospheric chemistry—from applied toward characterizing nuclear tests—first in the research to a balance of both applied and basic air and later underground. The nature and large science. Our expertise in analyses of rocks and scale of these tests required the development the chemical reactions between rocks and fluids of unique expertise and analytical capabilities developed as part of the underground testing coupled with a broad understanding of earth program and led us into work on geothermal, processes. Among these capabilities are petroleum, and environmental projects. ultrapure chemical separation, ultrasensitive Investigations of rock/water interactions and radioactive counting and mass spectrometry, element migration encompass experimental, element- and compound-specific vibrational analytical, field, and computational modeling spectroscopy, and field sampling. Computational studies of rock/fluid reactions in hydrothermal modeling expertise has also been developed to systems, and the results are applicable to the enhance the analytical efforts and to integrate discovery and recovery of energy—whether the results. geothermal or fossil. The article by Janecky et al. in the report discusses innovative concepts that were developed for directly tracing chemical This focus on applied science, however, hydrologic migration and reactions in geologic has not limited our contributions to basic systems and were tested in the field this research to understanding earth system past year. These studies required accurate processes. In fact, the complexity of the applied thermodynamic and speciation data on aqueous problems and the multidisciplinary nature of the solutions. To meet this need, heat capacities of

44 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Geochemistry

simple and mixed electrolytes are being data we can compare to modeling calculations measured by flow calorimetry, and spectroscopic for the wide variety of radionuclides of interest. techniques are being used to determine the To characterize the present state of a hydrologic molecular structure of components in natural system and its future evolution, we evaluate and model systems. We must also improve our processes that influence mineral transform- understanding of the behavior of electrolyte ations and stability. By determining isotopic solutions in the region very near the critical signatures of selected rocks, we are able to point of water if we are to model natural characterize long-term or discontinuous systems and develop environmental cleanup geologic processes such as volcanic eruptions. technologies that involve a supercritical Aspects of this work are discussed in the papers processing step. discussing the uranium series and rare-gas surface dating in this section. Our analytical capabilities also provide detailed information on a range of geological Our research efforts in geochemistry and processes. Direct spectroscopic measurements atmospheric chemistry address issues that have revealed the existence of aqueous are vital to the DOE's mission, but we have metalloid-organic complexes and mixed-ligand expanded the information base beyond the metal-organic-halide complexes. Detailed scope of the problems directly at hand. studies on interactions between organic The continuing transition to an integrated environmental contaminants and clay minerals awareness of environmental issues and also employ such measurements. Ultrasensitive emphasis on solutions in local, national, mass spectrometry analyses are being used to and international efforts will require a shift characterize transport and chemical processes in our foci, but our efforts must continue to that involve natural trace radionuclides. emphasize an understanding of basic earth Analyses of disequilibrium in uranium processes. The three articles that follow this series products provide overview represent current examples of INC chronologic tools for studying young geologic Division's contributions to basic scientific systems; these tools are applicable to a range knowledge through efforts that were funded of processes discussed in the article by Murrell by both applied and basic research sources. et al. in this section. Poths et al. report on the ways we can use measurements of rare gases generated by cosmic rays on exposed rock surfaces to provide unique quantitative information about processes at the very surface of the earth. Another trace-element study not discussed in this report uses chemical signatures to examine the processes involved in mass extinctions in the geologic record.

Under the auspices of the Yucca Mountain Project, we are employing a range of applied and basic research efforts to examine the fluid flow, elemental transport, and geologic history of the site. Distributions of cosmogenic and fallout radionuclides are being analyzed to characterize the infiltration of precipitation and the velocity of water movement through the unsaturated zone. Our ongoing solubility and speciation studies of waste radionuclides provide necessary information for modeling calculations and for flow and transport experiments. Simultaneously, diffusion and dynamic transport studies produce baseline

Isotope and Nuclear Chemistry Division Annual Report FY 1990 45 Geochemistry

Multicomponent Tracer Experiments at environmental pollution), our research efforts Mammoth Hot Springs in Yellowstone have focused on developing a large suite of organic tracer molecules. Quantification of tracers is accomplished primarily by gas chromatography/mass spectroscopy to provide David R. Janecky, W. Dale Spall,* 2 3 Paul R. Dixon, and Gregory K. Bayhurst efficient detection and differentiation. - In some systems, the dissolved organic concentrations Chemical tracer experiments are used in a are low enough that it is possible to use variety of systems, including environmental, oil, commercially available compounds, whereas in gas, and water systems as well as geothermal contaminated environmental sites or petroleum reservoirs to determine permeability, flow reservoirs, stable-isotope-labeled equivalents connectivity, and heterogeneity within a provide selectivity and far lower detection geologic/geophysical or engineered framework. limits. This research is based on atmospheric Engineered systems such as pipelines and tank and biochemical tracer experience in INC systems have also been examined by these Division24"26 as well as previous experience techniques. In addition, recent applications of with natural inorganic and organic tracers tracers have examined chemical reaction in geologic systems. processes. More novel and complex problems in both environmental and petroleum systems are We conducted a field test of multicomponent increasing our reliance on the detailed tracer approaches in the Mammoth Hot Springs characterization of reservoirs that can be system during June 1990, in collaboration with provided by tracer experiments. Yellowstone National Park and US Geological Survey (USGS) personnel. Surface expressions of Despite the demonstrated value of chemical geothermal systems have complex relationships tracers, they are underutilized—probably with the underlying source as a result of lateral because previous tracer approaches had several transport, recharge, and recirculation of heated limitations. Perhaps the most significant of these limitations are the small number of available tracer chemicals and the reliance on radioactive elements withir this group. For example, in an oil field experiment examined by Allison et al.,22 four of the seven tracers used were radioactive (one tritium and three isotopes). The current stringent restrictions on release of any radioactive compounds, particularly in North America, mean that even fewer tracers are •viable. With only a limited suite of tracers, we can obtain unambiguous results only for simple questions of connectivity, small fields, or the best constrained subsection of a field. However, the situations in which tracer data would be most useful in guiding production, remediation, or barrier enhancement are those that involve Injection Sites larger, complex systems with three-dimensional Climatus heterogeneities. In general, the more tracer compounds used and the broader the range of chemical behavior, the more diagnostic the experiments become. This technique is the geochemical equivalent of the medical Terraces application of a CAT scan.

Because the most economically significant applications of tracers involve organics (for example, to define petroleum reservoirs or Fig. 4.1. Map of the tracer experiment conducted at *Group CLS-1 Mammoth Hot Springs, Yellowstone National Park.

46 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Geochemistry

water. In the Mammoth area, a better understanding of near-surface hydrothermal solution distribution and connections is needed - to protect the springs from disturbance by local and external development and to avoid environmental contamination through (qdd ) inadvertently connected geothermal and _ cultural water systems. o n to - i: We injected a suite of organic tracers (acetic c o8 acid, benzoic acid, phenolic acid, alanine, and O glycine) into the Devil's Thumb Sink Hole at the -I base of the active terrace system. Fluorescein and rhodamine-WT dye tracers were introduced 0.1 by USGS researchers (Fig. 4.1). Subsequently, - t-butyl alcohol was introduced into Clematis i Creek at a sink hole below the terraces. We 0.05 n [L sampled the hydrothermal solution outflow at Boiling River and the MHS-2 seep on the Fig. 4.3. Fluorescein tracer at Chinese Gardens Slough Gardner River. At Chinese Gardens, we took (wide bars) compared to Boiling River (narrow bars at samples of water flowing through the west 20,10, and 0 min before slough samples) for 450,570, 690, bank slough of the Gardner River (-1.25 km 810, and 4713 min after injection. downstream from Boiling River). further away at Devil's Thumb. In addition, We detected tracer outflow in all sampling the t-butyl alcohol pulse is much less dispersed, locations. Because samples were taken at which is consistent with more constrained 10-min intervals at Boiling River, we have a channel flow in the karstic aquifer. The good definition of tracer breakthrough and combination of behavior we observed would peak structure (Fig. 4.2). The transport of be expected for weak acids interacting with t-butyl alcohol from Clematis Creek Sink Hole the basic travertine substrate. was faster than that of the other tracers injected Fluorescein tracer breakthrough at the MHS-2 seep is identical to that at Boiling River, but peak concentrations are higher (Fig. 4.2). This result is consistent with the higher temperature outflow at the MHS-2 seep. At Chinese Gardens, I the samples reveal tracer breakthrough that lags g 0.015 Ml significantly behind that of Boiling River—which inj i '\ \ 2 is consistent with longer underground transport. ra CD 5=. 0.010 if L This research successfully demonstrated the Ic value of a multicomponent tracer experiment. 1/ /\V\ Separating tracers and increased dispersion sa fll /\ VV i 0.005 III / I \\ as a function of simple chemical parameters o K/ V\ provides us with insight into underground s chemical interactions and the complexity of 0 000 the flow paths. Simultaneous comparison 0 1000 2000 3000 4000 5000 of different flow paths was also roughly Minutes after injection demonstrated. In addition, our tracer recovery experiments at the Chinese Gardens Slough Fig. 4.2. Breakthrough points are shown for various added significant information about the areal tracers at Boiling River. Solid lines indicate t-butyl extent of directly connected outflow from the alcohol (fushia), phenolic acid (blue), fluorescein (black), Mammoth terraces (Fig. 4.3). We continue to benzoic acid(orange), acetic acid(green), alanine (fine evaluate and model the chemical and physical black dash), and glycine (red dashed line), as well as the MHS-2 seep (large dashed line represents fluorescein). processes integrated by this data set.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 47 Geochemistry'

Using Surface Ages to Understand For this age-dating process, we require a Geological Processes sample from a surface that is minimally eroded—as determined by preservation of the flow's original surface texture. Olivine, which is Jane Poths and Ernest A. Bryant known to retain helium over geological timescales, is separated from the basalt. The Until recently, it has been difficult to olivine is crushed in a vacuum to release a determine the age of a surface formed by a "trapped" component, which reflects the isotopic geological process, such as erosion or volcanic compositions of gases trapped in fluid inclusions eruption, on the 103- to 105-yr timescale. This that formed in the magma chamber. The age range is too young to be readily accessible crushed olivine is then melted and releases by potassium- dating methods, and the cosmic-ray-induced 3He as well as any residual necessary conditions frequently are not trapped helium. By using Cerling's production satisfied for 14C dating. However, if one can rate28 for 3He in olivine, we can then determine date surfaces on this timescale, it could become the surface exposure age for the sample. a powerful tool for determining the timeframe for erosion, glaciation, landslides, and recent volcanic eruptions. We are applying to these geological problems a promising new technique for surface exposure dating—a process that uses the noble gases formed by the natural cosmic ray bombardment of rock surfaces.

Although cosmic radiation impinging on the Earth is highly attenuated in the atmosphere, -0.1% reaches the surface and causes nuclear reactions in exposed rock surfaces (Fig. 4.4). The detectable products of such reactions are either radionuclides with half-lives of-106 yr (10Be and 26A1) or extremely rare stable nuclides (3He and 21 Ne). We are using the accumulation of 3He and 21Ne to address the specific problems of the Lathrop Wells, Nevada, eruption history, and erosion rates in the Los Alamos area.

The Lathrop Wells volcanic center is a small cinder cone with a number of associated basalt flows. Potassium-argon ages for various flows are -150 ka (with large uncertainties). However, the very well preserved morphology of the cinder cone and the minimal soil development suggest that the last eruptive episode built up the cone less than 20 ka ago. We wish to date the various flows at this center to determine the timing and number of eruptive episodes. This, in turn, will tell us something about the volcanic plumbing system; for example, details of the replenishment and duration of its magma chamber. From a practical point of view, this knowledge would help us assess volcanic hazard from the center for the nearby site of a proposed high-level 27 Fig. 4.4. Creation of rare gases inside minerals through nuclear waste repository. interaction with cosmic radiation.

48 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Geochemistry

Our initial results yield exposure ages ranging from 23 000 ± 4000 years to 42 000 ± 6000 years for volcanic bombs from the summit of the cone. Two separate lava flows give ages of 45 000 ± 6000 years and 60 000 ± 6000 years. Because the exposure age is a minimum estimate for the eruption age, this work indicates that the most recent volcanism at the Lathrop Wells site occurred at least 23 000 years ago. The question of duration of thee volcanism requires further investigation.

In a second application of the noble-gas age dating method, we are estimating erosion rates in the Los Alamos area. The mesa surfaces are composed of Bandelier Tuff, which was deposited in an eruption 1.13 Ma ago. Yet an "apparent" surface exposure age calculated from the buildup of cosmogenic noble gases will be much younger, reflecting the erosion rate of the surface. We have estimates for both the surface production rate of cosmogenic noble gases and the exponential depth dependence of the attenuation of cosmic rays, and we assume that the erosion rate is constant over time; therefore, we can calculate an erosion rate based on the apparent exposure age.

We have determined the concentrations of cosmogenic 21Ne and 3He in quartz and feldspar separated from surface samples from four locations on one mesa. However, only 21Ne was useful because these minerals showed substantial loss (>90%) of cosmogenic 3He relative to 21Ne. A sample from a road cut, which was shielded from the production of cosmogenic nuclides, served as a blank. Lack of excess 21Ne in this shielded sample confirms our attribution of the 21Ne found in the surface samples to a cosmogenic source.

From our data, we calculate erosion rates ranging from 1.0 to 3.0 cm/ka; the analytical precision is -0.5 cm/ka. The true uncertainty is larger because of unknowns related to the production rate and depth attenuation for . The erosion rates derived for Los Alamos are similar to the values of 0.9 to 1.1 cm/ka obtained for Hawaii.29 This research is a first step in determining parameters for models of long-term landform modification. This technique also shows promise for calculating the rate at which blocks are spalled off cliffs—another common mass loss process for the desert mesas.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 49 Geochemistry

Geochemical Studies Using Long-Lived of the mantle generates magma has been used Members of the Uranium Decay Series to date ocean basalts erupted within the past 350 ka. Figure 4.6 illustrates this approach for the Endeavour segment of the Juan de Fuca Michael T. Murrell, Steven J. Goldstein,* Alan Ridge, which lies off the northwest coast of the M. Volpe, David R. Janecky, Jose A. Olivares, US. Our dating techniques were used on the Bryan L. Fearey, and Richard E. Perrin** oldest samples to define asymmetric spreading rates that agree with estimates from paleomagnetie and topographic data. Samples The current quiet revolution in isotope near the ridge axis appear to be younger than geochemistry involves the application of mass expected, which suggests either accelerated spectrometry to measure the uranium decay spreading or a broad zone of recent volcanic series. The use of uranium series disequilibrium activity near the axis. Our ability to obtain for studies of geocfr onology, geochemistry, and such information for spreading centers is environmental science dates back 30 or 40 years. vital to our effort to understand the processes However, isotope geochemists—accustomed that create oceanic crust. to high-precision uranium-, - , or samarium-neodymium mass Uranium-series techniques are being spectrometric data for very small samples— used to date recent volcanic eruptions in the have not always taken advantage of uranium- southwestern US. The 238U-230Th isochron for series techniques because of the poorer precision a flow at Lathrop Wells, Nevada, indicates an and larger sample size requirements typical of these decay counting techniques. The situation eruption age of-150 ka (Fig. 4.7). This date began to change in 1986 when Edwards et a/.30 agrees with potassium-argon age dates for this showed that it was possible to use high-precision location but is older than ages obtained uranium-thorium dating for small coral by less direct methods. The article by Poths samples. Since this work appeared, there has et al. in this section describes additional age information for Lathrop Wells that has been been a flurry of activity as many laboratories 3 applied mass spectrometry to uranium-series obtained by He cosmogenic exposure age studies. techniques being deyeloped in Group INC-7. This information will be used to evaluate the risk from volcanic activity to the storage of Decay schemes for the longer-lived members 238 235 232 high-level radioactive waste at Yucca Mountain, of the U, U, and Th series are shown Nevada, over the next 20 ka. in Fig. 4.5. The geochemistry group of INC Division has collaborated with others to develop techniques for the chemical separation and mass spectrometric measurements of these elements. Radioactive disequilibrium, produced 238u by chemical or physical processes that enrich 447«109 or deplete one of these daughters relative to a 235U parent, can be used to calculate geologic time. 5 The timescale available for study by these 7S4X1D methods is determined by the half-life of the daughter and ranges from 10 to 106 years. A |i These clocks are ideal for studies that deal (" Pal with the past and future of mankind, such y3.2e x 10 J as determining paleoclimate changes and assessing geologic hazards.

226 r Th 206- Disequilibrium between 238u-230iph and -0 x ' D 23OTh-226Ra produced when partial melting

*Group HSE-9 Fig. 4.5. Decay scheme for the longer-lived members of **and collaborators from Argonne National Laboratory the 238U, 23SU, and 232Th series. Half-lives are shown in and the University of California, Santa Cruz years below each nuclide.

50 Isntone and Nuclear Chemistm Division Annual Reaort FY 1990 Geochemistry

Recent volcanic activity at Mt. Shasta, n QR California, has also been examined by uranium- i 1 s^ series disequilibrium techniques. The results 1 - WR "^^ .-- provide the first demonstration that the degree 23O 226 SZ of Th- Ra fractionation among minerals 0.90 - with relatively high /thorium ratios, OJ r3 ^:- such as plagioclase and hornblende, can be used OLIVINE ^*>[AGIOCLASE to determine the ages of very young (5- to 10-ka) s? o ...-••

In a joint collaboration with Argonne Fig. 4.7. Uranium-thorium isochron for whole rock and mineral separates forLathrop Wells, Nevada, Whole rock National Laboratory, high-precision uranium- (WR) samples from two different flows show no uranium- series age measurements for travertine deposits thorium disequilibrium and plot on the equiline. near thermal-springs have been used to study However, mineral separates from one of these rocks glaciation and hydrothermal systems at define an isochron of 150 ka. Yellowstone. These data show that the elevation of travertine deposition at Yellowstone has Bear Creek since 9.8 ka. Such information is responded to climate-controlled changes in important for paleoclimate studies being meteoric recharge rates and water-table conducted for the Yellowstone region. elevation. We have been able to bracket the age of Pinedale glaciation by travertine ages of 53.6, 46.3 ka and 22.1,18.6 ka, and we have The capability to measure geologic time also determined that travertine deposition has in a new or more precise manner has often been continuous at Mammoth Hot Springs and led to new insights on natural processes, and this is proving to be the case as we apply mass spectrometry to uranium-series disequilibrium studies. If our work in this field can be • 1.9 ± 0.6 cm/yr integrated with other techniques for measuring . 4.0 ± 0.7 cm/yr geologic time (for example, cosmogenic nuclides 3 10 14 26 3.0 cm/yr like He, Be, C, and A1), it should be possible to gain a better understanding of the Earth's history over the last 1 Myr.

100 150 200 250 U-ThAge(yrx103;

Fig. 4.6. A plot of distance from the center of the spreading axis vs uranium-thorium age for samples from the Endeavour segment of the Juan de Fuca Ridge. Spreading is asymmetric, with faster rates to the west. Samples closest to the ridge are younger than expected.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 51 Nuclear Structure and Reactions

Overview

Direct Mass Measurements of the Neutron-Rich Through Chlorine

SNOing in Los Alamos—.Neutrinos in the Nineties

The Exotic-Beam Facility—A New Initiative

• +•

TSSife'Sft^sK M8M Nuclear Structure and Reactions

Overview insight into the nuclear structure of low-Z nuclei that have a large excess of neutrons.

Gilbert W. Butler INC Division has joined Los Alamos Group P-3 and many other institutions in Canada, Nuclear science studies have always been the United Kingdom, and the US to form the an important aspect of both applied and basic SNO (Sudbury Neutrino Observatory; research programs in INC Division. The role collaboration, which has obtained funding of nuclear chemistry is changing rapidly as to build a large underground heavy-water national priorities change, and INC Cerenkov detector that will be able to measure Division—with its traditionally strong all types of neutrino interactions. Previous multidisciplinary approach and its unsurpassed neutrino experiments were sensitive only to capabilities in ultrapure chemical processing electron neutrinos, and the observed fluence of radioactive and nonradioactive species, was lower than theory predicts. The SNO ultrasensitive mass spectrometry, and extensive vessel will be able to detect electron, muon, automated counting facilities for all types of and tau neutrinos, and thus will be able to radioactivity—is well suited to solving a wide determine the total number of neutrinos range of nuclear science problems. Nuclear emerging from the sun. This large-scale science research in INC Division is summarized experiment, which should be completed and on these several pages. ready to take data in 1994, is explained in the article by Wilhelmy et al. in this section. The three articles that follow this overview highlight three diverse areas: systematic studies Another aspect of solar neutrino research of the nuclear mass surface through direct mass is the molybdenuin-technetium solar neutrino measurements of very neutron-rich low- and experiment. We have now processed technetium medium-Z nuclides by the Time-of-Flight from 40 tons of molybdenite collected during Isochronous (TOFI) spectrometer at the the AMAX Corporation's roasting of ores from Los Alamos Meson Physics Facility (LAMPF); the Henderson mine. We measured the 98Tc/"Tc an update on the Sudbury Neutrino Observatory, and the 97Tc/"Tc ratios (5.03 x 10"6 and 3.88 x the large international collaboration that plans 10'6, respectively) as well as a ratio of 8.79 x to search for information on both the flavor and 10"16 for the "Tc/molybdenum. Our analyses the spectra of the neutrino distribution on earth; give a value of 27.7 atoms of 9sTc in 1 g of and a new initiative to study the feasibility of molybdenum; we have not yet completed the Cand propose plans for) an exotic beam facility run of a full-scale blank for 98Tc. On the that would provide high-intensity beams of basis of decreasing "Tc/molybdenum ratios radioactive nuclei for use in advanced nuclear in samples from the second to the third day science, materials science, and astrophysics of roasting, we believe there was some residual studies. non-solar-neutrino-produced technetium from earlier roasted molybdenites from shallower mines and from molybdenites with higher In our studies of nuclei far from stability, uranium and thorium concentrations. we have used the TOFI recoil spectrometer at We have proposed completion of our large LAMPF to perform a large number of direct blank measurement, small-scale studies mass measurements of neutron-rich nuclei. of the roaster memory problem, and The most recent example of this work, which development of a laboratory roaster to process is detailed in the article by Wouters et al., is 1 to 10 kg of molybdenite for "Tc measurements the direct determination of the masses of 34 24 (to minimize blanks from reagents); however, nuclei from F to ^Cl. These measurements we have not yet obtained funding for this effort. were used to

54 Isotope and Xuctear Chemistry Division Annual Report FY 1'jitO Nuclear Structure and Reactions

a target-ion source-mass separator system, In addition to the research described above, a heavy ion post-accelerator, and an we maintain a strong interest in several new experimental area—all of which combine to initiatives. One of these involves extending the produce up to 1011 radioactive nuclei per second direct mass measurement techniques that were with energies ranging from 1 to 10 MeV/amu. pioneered on TOFI to higher mass resolutions Such a facility is of great scientific interest by using the heavy ion storage ring at the because a vastly increased number of projectiles UNILAC accelerator in Darmstadt, Germany. would become available for conducting nuclear Another area of interest is the excitation of science studies, with particular emphasis on 235mu (E* = 75 eV) by thermal heating at the extremely neutron- or proton-rich nuclei. INC NOVA laser facility at Lawrence Livermore and MP Divisions hosted the "Workshop on the National Laboratory. In support of this Science of Intense Radioactive Ion Beams" at experiment, we have built and tested a low- Los Alamos in April 1990. David Vieira of pressure proportional counter to measure Group INC-11 is a member of the national Auger electrons. steering committee that will prepare both a scientific justification and a design concept for The research described above is a clear this type of facility. There is strong local interest indication of the considerable interest and in siting this facility at LAMPF because of the expertise INC Division brings to a wide existing facility and considerable accelerator variety of initiatives in the nuclear science expertise available there. field. This field is changing rapidly as national priorities change, and the technical staff of Over the past several years, INC Division INC Division will undoubtedly continue to has continued to investigate a variety of cold rise to the challenge in the future. fusion phenomena. We have monitored neutron background levels with a well-type neutron counter. Our interest in these measurements has been to determine the long-term performance of the detection system and to learn to recognize the difference between real high-multiplicity events and system noise. We are now able to recognize and disregard high-multiplicity neutron events that occur outside the central well of the detector. After these are eliminated, there are still events that have multiplicities higher than can be accounted for by random coincidences; these represent real cosmic-ray-induced events. In these cases, however, we seldom see an event in which more than four neutrons are detected (<0.1/day). We have also tried to reproduce a series of experiments reported by workers in the Soviet Union, during which LiD dissolved in heavy water resulted in the liberation of neutrons. Our detection efficiency is ~100 times that reported by the Soviet workers, but we have been unable to find any evidence for neutron production. In another set of experiments, we used a small ball mill, placed close to our neutron counter, to pulverize samples of TiD. By pulverizing the deuterium-bearing material, we hoped to test the idea of fracture-induced fusion, but again, we were unable to detect any production of neutrons.

Isotope and Nuclear Chemistry Division Annual Report FY ]9i)0 Nuclear Structure and Reactions

Direct Mass Measurements of the apparatus, located at the Los Alamos Meson Neutron-Rich Isotopes of Fluorine Physics Facility, consists of a transport line, the TOFI spectrometer, and associated detector through Chlorine systems. A small fraction of the recoiling neutron-rich nuclei, which are produced through fragmentation reactions, are captured, prefiltered, Jan M. Wouters, David Vieira, and conveyed by the transport line to the and Gilbert W. Butler* spectrometer. This line also contains detectors for measuring the velocity of each ion. The TOFI The masses of the neutron-rich sodium spectrometer is isochronous; thus each ion's flight- isotopes with N > 20 manifest an enhanced time through TOFI is directly proportional to its binding energy anomaly that has challenged mass-to-charge ratio (Fig. 5.1) and independent experimentalists and theorists ever since they 31 of its velocity. Because the separation in mass were first reported. It was thought that this between isobars is small and not resolvable by anomalous feature resulted from a reordering of using TOFI, we use a Bragg detector

to-charge, velocity, energy and energy loss 1 - characteristics for each ion of interest as it passes through our experimental apparatus. This 4.2 A 3.8 3.6 3.4 3.2 3 2.8 2.6 M/Q *In collaboration with scientists from Utah State University, Logan, Utah; Universitat Miinchen, Miinchen, Fig. 5.1. A taw time-of-flight spectrum is shown in (a); Germany; Physikalisches Institut, Universitat Giessen, the same data for one Z, now gated byQ,is shown in (b) Giessen, Germany; and Nanjing University, Nanjing, with one line magnified to show the high mass-to-charge People's Republic of China resolution.

56 Isotope and Nuclear Chemistry Division Annual Report FY1990 Nuclear Structure and Reactions

mass-to-charge (M/Q) calibration. The A identification is accomplished by using the kinetic energy relation and the measured velocity and Al energy. Q is determined using this A and the high- precision measurement of M/Q. Z comes from a lookup table that identifies the Z ridge lines in a plot of ion range vs maximum dE/dx. The M/Q calibration is then obtained by fitting the centroid of each identified M/Q line (Fig. 5.1) to the *-*- literature M/Q values and correcting for local nonlinearities. A final crosscheck of the new CD masses is possible because we measure for each 2 Na Q. ion two or more charge states that have different X CD M/Q ratios. CO

Our measurements of 34 nuclei cover the O Wildenthal Z region from fluorine to chlorine and include masses for 36A1, 38Si, 41P, and 43S, which are the most neutron-rich isotopes measured for these A Warburton elements. We have compared our masses to etal. several shell model theories and mass models in this region. Except for slight discrepancies, the masses for the most neutron-rich nuclei of 0 through chlorine agree quite well with -2 theory. The most interesting results are obtained 12 14 16 18 20 22 24 26 28 through comparisons of our experimental work and shell model theories for the sodium region. Neutron Number

Figure 5.2 compares our data to the shell Fig. 5.2. The weighted average of our data (error bars) model calculations of Wildenthal (USD) and compared to the Wildenthal (USD) and the Warburton Warburton et al. (WBMB).34"35 The comparison (WBMB) shell model calculations. with the USD shell model illustrates the reason experimentalists and theorists are interested in Our results demonstrate that the region of the sodium masses: there is good agreement enhanced binding previously found near 32Na is between USD theory and experiment throughout real, although the enhancement is roughly one- the entire sd-shell except for the N = 20 isotones 31 half as large as originally reported. Comparison that are centered about Na. of our masses to shell model calculations show that this region of enhanced binding can be understood To date, the WBMB calculation is the most in terms of particle-hole neutron excitations across complete attempt to expand the shell model the sd and fp shells. The systematics of low-lying formalism beyond the sd shell and to account energy levels from these models indicate that the for the above discrepancies. The interaction nuclei with Z = 10-12 and N = 20-22 can be used in this model enables the calculation of described as an island of inversion in which the ground-state masses using separate model nuclei are prolate-deformed. For the neutron-rich spaces encompassing 0,1-, 2-, and 3-particle- through chlorine, our data agree hole neutron excitations. In Fig. 5.2, we have well with a variety of models, demonstrating the plotted the calculation that best agrees with the well-behaved nature of these nuclei. The experiment; non-0 particle hole excitations are remaining discrepancies between theory and only required for the and experiment, especially for the island of inversion . The agreement is substantially nuclei, suggest the need for (1) full sdfp model improved over the USD calculation for the region space calculations, (2) additional masses, and of the sodium anomaly and underlies the local (3) measurements of the spins, parities, and nature (Z = 10-12, N = 20-22) of the enhanced excitation energies of low-lying states in this binding energy effect. region.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 57 Nuclear Structure and Reactions

SNOing in Los Alamos—Neutrinos in the major energy-producing nuclear reaction the Nineties in the sun—the proton burning. Because there is little doubt about the rate of this reaction, it is highly unlikely that these Thomas J. Bowles,* Bruce T. Cleveland,* deviations are the result of inadequacies Peter J. Doe,* Steven R. Elliott,* Malcolm M. in our understanding of solar processes.

Fowler, R. G. Hamish Robertson,* Thomas C. 40 Spencer,* David J. Vieira, Jerry B. Wilhelmy, • Theoretical investigations of what has John F. Wilkerson,* and Jan M. Wouters become known as the MSW effect have predicted that if the neutrino has a specific We are entering a very stimulating era of finite mass and interaction probability neutrino research. There are emerging hints (mixing angle), there can be an oscillation that neutrinos may have a finite mass (and as the neutrino traverses the solar volume, possibly a relatively large magnetic moment), in which an electron-type neutrino can be and these may herald the much-sought-after transformed into a different lepton-family "physics beyond the Standard Model." Several neutrino- Because the Davis, Kamiokande, converging theoretical and experimental and SAGE experiments measure only investigations are driving these elusive particles electron-type neutrinos, other species to the center of interest in modern physics. formed by oscillation will remain undetected.

• At CERN's LEP (Large Electron ), • One of cosmology's central questions has collider experiments studying the decay of become: Is there is enough matter in the the Z° have established36 that there are universe to—through gravitational only the three already known lepton families attraction—eventually stop the Big-Bang- (e, u, and x). initiated expansion and thus close the universe? We know the visible matter of the • R. Davis and coworkers have consistently universe is only -5% of that required for measured a solar electron neutrino fluence at closure, and if the universe is to be closed, approximately one-third the level predicted there must be substantial "dark matter." by solar models. They are now presenting Though all type of exotica are proposed for tantalizing information that the neutrino this dark matter, one of the most attractive fluence is anticorrelated with the well-known is the neutrino. If the heaviest neutrino has 11-yr sun spot cycle37—thus hinting at a very a mass of 25 to 100 eV, there should be large neutrino magnetic moment. sufficient neutrino mass to close the universe. • The Kamiokande experiment in Japan has obtained spectral information on the high- By combining the results from the current energy neutrino fluence and has confirmed experiments, it is possible to obtain values for the two theoretical parameters—Am2 = 10 6eV2 the Davis results on solar neutrino 2 1 5 2 suppression.38 (They were, however, and sin 26 = 10" - (Ref. 41). Where Am is the unable to confirm the sun spot squared mass difference between the mixing anticorrelation reported by Davis.) neutrino types and 6 is related to the strength of the interaction and is expressed as a "mixing • The SAGE experiment, which studies solar angle." If we invoke one other theoretical argument —known as the "see saw" neutrino capture on , has reported 42 preliminary results39 showing a neutrino mechanism, which states that the mass of a production level that is well below that neutrino should be approximately proportional predicted by the solar model. This to the square of the mass of its lepton family experiment (unlike the Davis and member (mVx ~ a mx)—then: mVc « mVu« mv.. Kamiokande experiments that can only If we further assume that the neutrino detect high-energy neutrinos) is sensitive to experiment measures an oscillation between the two lightest family members (the ve and low-energy electron neutrinos generated by 2 1 3 the Vjjj, then (Am ) - = mv ~ 10" eV and, by 8 : Group P-3 the see-saw mechanism, mVe of order 10~ eV,

•58 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Nuclear Structure and Reactions

and mVt of order 10° eV. Although these values liberated in the reaction. Because neutrino are very small, this certainly does not mean that reactions are very rare (we expect neutrinos the masses of the neutrinos are inconsequential. to produce 4500 charged current interactions, In addition to driving us toward new physics, 1138 scattering events, and 6380 neutral current it appears that the mass of vT is of the correct interactions per year in the detector volume), order to have significant cosmological extreme care must be taken to limit background implications. events. Ultra radiopurity of all materials is required. Although this is all very exciting, more experimental data is required. The gallium Researchers from INC Division are taking an detection experiments are just beginning and active role in ensuring the required radiopurity will not have definitive results for a few years. of the materials, designing and testing neutral The Davis and Kamiokande efforts will continue current detector prototypes, performing to provide improved data on solar fluences of simulation studies of the neutron transport electron neutrinos. But perhaps the most critical and capture probabilities, assisting in the experiment to prove these conjectures is now in engineering design of the acrylic vessel that the design and construction phase. If the MSW contains the heavy water, and writing and effect is the cause of the observed low fluence evaluating the data-acquisition software. The of electron-type neutrinos, this type of neutrino capital costs of the project have received full must have undergone a flavor oscillation and funding from US and Canadian agencies, and reached earth as another lepton family neutrino. mining excavations for the experimental facility Neutrinos of any flavor undergo the neutral have begun. The current schedule calls for the current interaction, and therefore, this is the project to become operational by the end of 1994. mechanism that must be detected if we are to All members of the collaboration are optimistic measure the total fluence of neutrinos. The that this experiment will provide definitive crucial test of this theory is to determine the insights into some of the most fundamental total number of neutrinos emerging from the physics questions facing modern science. sun. If, as current experiments imply, there is a decrease in the number of electron neutrinos, a compensating increase in other neutrino types should make the sum of all neutrinos equal the Deck support structure solar model prediction. Vessel VW\A supp0/ At Los Alamos, Groups INC-11 and P-3 have joined the SNO (Sudbuiy Neutrino Observatory) collaboration, which is the first proposed experiment capable of measuring all types of Acrylic 43 vessel neutrino interactions. This large experiment (12-m will be located some 6800 ft underground in an diam) operating mine near Sudbury, Ontario. The active volume of the detector will consist of 1000 tons of D2O—an ideal detector material because it permits measurement of all three types of neutrino-matter interactions: the charged-current, neutrino scattering, and neutral current. The first two reactions will be detected by measuring the Cerenkov radiation Shielding emitted by the recoiling relativistic electrons; rocks some 10,000 photomultipliers will surround the Photomuitipliers Monte with reflectors heavy-water volume. Figure 5.3 presents a rock schematic of the new spherical design of the SNO vessel. The neutral current will be NOTE: Structure is 6800 ft below surface determined by detecting radiation emitted following nuclear capture of the neutrons Fig. 5.3. Schematic configuration ofihe SXO detector.

Isotope and Nuclear Chemistry Division Annual Repurt FY 59 Nuclear Structure and Reactions

The Exotic-Beam Facility—A New The Los Alamos workshop on the science of Initiative intense radioactive ion beams was held in April 1990. The broad scope of scientific interest prompted by the workshop was reflected by the Jan M. Wouters and David J. Vieira attendance of over 100 scientists representing 30 institutions in 10 countries and by the INC Division is supporting a new North participation of scientists from the Accelerator American initiative to establish an exotic- Technology, Isotopic and Nuclear Chemistry, beam facility that would be used for nuclear, Meson Physics, Physics, Space Science and astrophysical, and materials science research. Technology, and Theoretical Divisions at Los INC Division's expertise in nuclear chemistry, Alamos.44 Five primary topics were examined mass separators, and mass spectrometry allows at this workshop: (1) nuclear reactions, (2) the us to address both the scientific and technical nuclear structure of nuclei far from stability, challenges facing the development of such a (3) nuclear astrophysics, (4) atomic physics, facility. Moreover, the existing Los Alamos materials science and applied research, and Meson Physics Facility (LAMPF) is an ideal (5) facilities. candidate for such a facility because the present concept couples a target-ion source mass One interesting (and somewhat controversial) separator system and a heavy-ion post- highlight r-1 the meeting involved discussions of accelerator (using the so-called ISOL isotope *h<> rharacterization and possible exploitation separator/post-accelerator approach) to a of nuclei lying near the neutron dripline. These medium-energy, high-intensity light-ion nuclei are believed to possess "neutron-halos," accelerator. With such a system, secondary- 11 in which the neutron distribution extends far beam intensities of up to 10 jS-unstable nuclei beyond that of the protons because of a low per second with energies from 1 to 10 MeV/amu neutron separation energy. Neutron-halos, if are possible. they exist, would represent a form of nuclear matter lying between normal nuclear matter The substantial impact this facility could and pure neutron matter. Thus, studies of have on nuclear science and related studies will neutron-halo nuclei could function as miniature be a direct result of employing a wide range of laboratories in which the nature of neutron short-lived, low-energy beams available to matter is examined; the results could be used to scientists (see Fig. 5.4). These beams will be understand such important astrophysical objects used to produce record intensities of exotic as neutron stars. Neutron-halo nuclei could also nuclei lying far from the valley of beta stability. be used to induce very cold subbarrier fusion reactions or used to produce other exotic nucleis such as 262Fm—a process that could elucidate The immediate goal of the scientists interested new fission pathways. in exotic beam research is to clearly define a set of scientific objectives and to pioneer research and development that will address technological Exotic beams would be employed to produce issues facing an exotic-beam facility. Since 1989, a much wider range of nuclei that could be members of INC Division have participated in characterized by their decay modes (for example, the exotic beam effort by (1) helping formulate nuclei with very high caused by more the 1989 National Scientific Advisory Council favorable competition with fission). The search long-range plan in which the concept of an exotic- for unusual nuclear shapes, such as triaxial and beam facility emerged as the highest priority of hyperdeformed (3:1 major-to-minor axis), would the low-energy nuclear science community, be enhanced through high-spin studies using (2) cohosting, with the Meson Physics Division, exotic beams. a Los Alamos workshop on the science of exotic beams, and (3) working to establish an exotic Nuclear structure information is important beam initiative and a supporting scientific in the pursuit of both astrophysics and community. We are now helping to develop materials science. Knowledge of basic nuclear an exotic-beam proposal and forming an properties (for example, mass, half-life, and international collaboration to begin pilot research neutron-capture cross section) is essential when and development experiments at LAMPF. modeling astrophysical phenomena such as

60 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Nuclear Structure and Reactions

supernova explosions. The nuclear science paper being written by the steering committee studies described above would also provide an will outline the scientific case for peer review extensive set of new data with which to improve and lay the framework for a site-specific present nuclear models and to promote more proposal. Moreover, this committee is serving reliable predictions of exotic species beyond the as the focal point for a nascent user community range of current experiments. In materials that now numbers in excess of 200 scientists science, implantation of radioactive nuclei who have expressed a strong interest in and knowledge of nuclear level structures and pursuing exotic beam research. lifetimes can be used to probe the local electronic environment for a variety of new At Los Alamos, scientists from INC Division materials; high specific activity beams will are coordinating efforts to examine some of the reduce damage and perturbation to the material technical research and development issues being studied. The above examples are not related to building an ISL. Using INC's diverse separable, but rely on synergistic interaction background in nuclear science and related between the various studies to fully exploit the technologies, the scientific expertise of our potential of exotic-beam research. collaborators, and LAMPF's unique high- intensity proton beam, we plan to build a The workshop attendees accomplished two prototype thin-target, helium-jet-fed mass primary goals: they outlined a provocative and separator system that would address production far-reaching scientific program that would issues related to the advancement of the ISL employ exotic beams and they encouraged the initiative. Our immediate goals are to measure immediate preparation of an exotic-beam the yields of specific radioactive nuclides from proposal. A steering committee of nine scientists such a system and to establish a research from Canada and the US was selected by the program that uses these nuclides. We hope to workshop chairmen. This committee has already build a strong scientific and technical research gathered information from several subpanels to effort that will promote LAMPF as a leading (1) enumerate the scientific goals for an exotic- contender for the national IsoSpin Laboratory. beam facility, now called the IsoSpin Facility (ISL) initiative, and (2) prepare a design concept for the ISL that will meet these goals. A white

80 — • |) stability • Life time > 1 hr 126 • 1 hr > Lite time > 1 sec 1 sec> Life time > 100 ms _m -Q • 100ms > Lite time 1 j^^fk BIP*-— 50 2 40 n o 8i2

jn 20 C 50 100 Neutron Number Fig. 5.4. Beams routinely available at heavy-ion accelerators are those for the stable isotopes (black). An exotic- beam facility could produce beams of any nucleus with a half-life greater than 100 ms (blue, green, and yellow). Such beams would be especially critical for nuclei with half-lives between 1 hr and 100 ms (green andyeUow), where radioactive targets are not available.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 61 Biochemistry and Nuclear Medicine

Overview

Metabolism of Methylotrophic Bacteria

Structure of Cytochrome c Oxidases: Sequence and Analysis of the Subunit He Gene

Labeled Biologically Active Peptides for Myasthenia Gravis Research

, *gffltv ; Biochemistry and Nuclear Medicine

Overview labeled compounds to important biochemical problems. First, the program "Mechanisms in Respiration" examines the fundamental Clifford J. Unkefer and Dennis Phillips mechanism by which all organisms generate energy. Nitrogen-15-labeled compounds are used The National Stable Isotopes Resource is to probe the structure of metallo-redox centers in the foundation for biochemical research in INC the proteins involved in respiration. Results of the Division. The National Institute of HeaHh funds sequence analysis of eytochrome bao are reported the Resource to develop biomedical applications in this section. Also described in this section are some results from the program "Metabolism of of the low-abundance stable , 13 nitrogen, and oxygen. When enriched above their Methylotrophs," which uses C-labeled , the stable isotopes 13C, 15N, compounds and NMR spectroscopy to probe the and 17.18O are used to follow complex chemical metabolism of methylotrophic bacteria and the and biochemical processes. The power of these mechanism of methanol dehydrogenase. Finally, isotopes derives in part from the elegant in a new INC Division effort, we will examine spectroscopic techniques used to detect them. protein-DNA interactions by using stable isotopes These methods allow determination of not only and NMR spectroscopy. the extent of labeling, but also the chemical identity of a labeled product. This powerful Our ability to conceive and research combination of stable isotope labeling and the applications of accelerator-produced spectroscopic characterization has contributed to radioisotopes from LAMPF defines our our understanding of living systems. For example, unique position in the nuclear medicine stable isotopes are used in combination with NMR research community. Past research successes spectroscopy to probe complex structure-function and our future radioisotope research needs relationships in proteins and nucleic acids. In drive our isotope production requirements. addition, stable isotopes are used to trace complex We continue a team approach in our activities, metabolic pathways in bacteria, plants, and including (1) radioisotope production and animals. These techniques have also been used distribution, (2) separation chemistry research clinically to characterize human metabolism. for isotope recovery and new isotope development, (3) development of radioisotope The low-abundance isotopes of carbon, generator systems, (4) development of nitrogen, and oxygen are enriched by cryogenic radiolabeling technology, and (5) the distillation of carbon monoxide and nitrous oxide. application and biological testing of For biomedical research, isotopes separated radiolabeled compounds. Highlights of as CO or NO must be incorporated into useful activities in these areas are given here. compounds. The enrichment process, developed in INC Division, has been successfully commercialized. However, the major obstacle to Radioisotopes produced in INC Division the more general use of stable isotopes is the facilities are used extensively in nuclear medicine relatively poor availability of useful compounds research, but our user community has a wide labeled with stable isotopes. To this end, the variety of interests encompassing biochemistry, Resource carries out vigorous research and environmental chemistry, geochemistry, development of new methods for the synthesis oceanography, basic nuclear physics, and of labeled compounds. Current research focuses astrophysics. Our isotopes are also used in the in three areas: (1) stereoselective synthesis of nuclear power and chemical industries. In FY 1990, labeled L-amino acids, (2) site specific labeling of a total of 12 Ci of 10 different radioisotopes in 121 nucleosides and nucleotides, and (3) biosynthesis shipments were provided to 58 external of symmetrically labeled porphyrins. This year, organizations and to 2 groups at the Laboratory. the Resource welcomed to its staff Louis A. Silks The number of different radioisotopes produced for from the Department of Chemistry at the external distribution was reduced to permit University of South Carolina, who is developing optimum use of resources and to maximize return synthetic routes to 15N-labeled nucleotides. on isotope sales in accordance with the require- ments of the DOE Office of Isotope Production and Distribution revolving fund; FY 1990 revenues Associated with the Resource are three basic were 37# higher than in FY 1989. research efforts that apply stable, isotopically

64 Isotope and Sudear Chemistry Division Annual Report FY 1990 Biochemistry o.nd Nuclear Medicine

An important development that affected our minimizing loss of antibody immunoreactivity. distribution activities was the US Food and Drug The synthesis involves the novel use of polymeric Administration (FDA) approval of the ^Sr/^Rb solid-phase supports, which should increase biomedical generator, developed by Squibb yields, purity, and functionality of the molecules Diagnostics, for clinical use in evaluation of relative to traditional solution phase approaches. coronary artery disease by positron emission tomography. Because we are a primary supplier 82 Metallation yields of N-benzylporphyrin- of the bulk Sr for the generator, we were required antibody conjugates have often been less than to register with the FDA as a Drug Manufacturing expected. To gain a better understanding of these Establishment and to implement an FDA approved reactions, we studied the kinetics of free program in manufacturing procedures. porphyrin metallation and metallation of porphyrin-antibody conjugates. The overall rate Most of our isotope separation research is for the conjugate reaction is about one half that of aimed at improving existing recovery the free ligand reaction. We are investigating methodologies to increase efficiency, minimize amino acid polymers as linker molecules to bind the amounts of hazardous and radioactive wastes porphyrins to monoclonal antibodies. The linkers generated, and facilitate waste handling should permit conjugation of higher numbers of procedures. This work has produced new methods porphyrins to the antibody without compromising for processing three of our most important targets: antibody immunoreactivity; this work may the molybdenum target for 82Sr, the ZnO target increase labeling yields and efficiency. for 67Cu, and the EbBr target for 68Ge. In addition to improved efficiency and reduced wastes, the Our application of 67Cu-labeled peptide new procedures add valuable radioisotopes to our 88 88 fragments in research on Myasthenia gravis, a inventory. We recover Zr/ Y and carrier-free severe autoimmune disease that affects 75Se from the molybdenum, 7Be, 48V, 59Fe, and 72 7 neuromuscular transmission, is discussed in an 5iCr from the ZnO, and 75Se, 72Se/ As, 3As, article by Mercer-Smith et al. in this section. and 74As from the RbBr. There have been several accomplishments in The improved RbBr process was a direct 72 72 our lung cancer and lymph-node imaging projects. result of the work being done on the Se/ As Using computerized image analysis, we have biomedical generator system—exemplifying the gained a deeper understanding of the mechanism continued synergism between the isotope of 5,10,15,20-tetrakis(4-carboxyphenyl)porphine production and research portions of the program. (H2TCPP) localization in lung cancer cells. Chemical procedures developed for separation of Biostatistical analysis of data on the localization and in an automated generator of H2TCPP in sputum samples from lung cancer were integrated into the RbBr target process to patients demonstrated that the intensity of provide 72Se, which was cyclically processed to 72 induced fluorescence in cells containing H2TCPP recover pure fractions of carrier-free As. This could accurately distinguish between patients material is used in positron emission tomographic with lung cancer and those without. Results also (PET) phantom imaging studies to demonstrate 72 suggested that H2TCPP could be used to identify the value of As as a PET agent. In these studies, patients with in situ carcinoma, a very early stage 72As produced images comparable in quality to 1S lung cancer. In a joint project between Los Alamos those of F, a well-established PET isotope. The and Johns Hopkins Medical Center, H2TCPP and generator project now focuses on automation of a monoclonal antibody that is specific for lung the selenium-arsenic separation chemistry. cancer cells were tested for their combined ability to identify malignant cells in sputum samples. Our radiolabeling work has emphasized Results demonstrate that a two-stage diagnostic synthesis of unsymmetrical tetraarylporphyrins, approach using these two materials might greatly which are excellent biftmctional chelating agents enhance the ability to detect carcinoma in situ. having one unique site for attachment to In a preliminary study, we demonstrated that monoclonal antibodies. Promising results have H2TCPP has a high affinity for lymphoma cells. This finding suggests that H2TCPP and been obtained in the synthesis of tetrameric 67 "spider porphyrins" composed of linked CuTCPP might be used to follow the spread of tetraarylporphyrins. Such compounds will make lymphoma in lymph nodes and possibly to treat possible higher levels of radiolabeling while this deadly disease.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 65 Biochemistry and Nuclear Medicine

Metabolism of Methylotrophic Bacteria dehydrogenase (MDH) catalyzes the oxidation of methanol. Instead of the nicotinamide or flavin cofactors required by other dehydrogenases, Clifford J. Unkefer MDH contains the novel organic cofactor, pyrroloquinoline quinone (PQQ) (shown in We are examining the physiology and Fig. 6.1), which is thought to serve as a 2e72H+ biochemistry of methylotrophic bacteria. redox carrier that accepts electrons from the These soil-borne organisms are unique because oxidation of methanol and donates them to they use, as their source of carbon and energy, the cytochrome chain. Genetic studies prove simple one-carbon compounds such as that MDH activity requires PQQ; however, methane, methanol, or methylamine. These there is no proof for the direct involvement organisms are important for three reasons. of PQQ in the catalytic mechanism of MDH. (1) Their ability to grow on one-carbon The objective of this project is to understand compounds gives methylotrophs the catalytic mechanism of the PQQ-dependent considerable industrial potential because MDH from the methylotroph Metkylobacterium they can produce useful substances from extorquens AMI. Presently, PQQ is known only inexpensive and renewable precursors in bacterial alcohol dehydrogenases and glucose such as methanol. dehydrogenase. However, amine oxidases from mammals contain a similar quinone cofactor, (2) Methylotrophs play an important role in trihydroxy phenylalanine. The mechanistic the global cycling of carbon; they oxidize details of the PQQ-dependent MDH will serve and assimilate most of the methane as a paradigm for these important quinone- produced by microbial methanogenesis. mediated amine oxidations. (3) Because methylotrophs can catabolize a variety of organic compounds, they will likely play an important role in the The MDH catalytic cycle can be expressed as bioremediation of polluted environments. two coupled reactions. First, the oxidized form of For example, these organisms can degrade the enzyme (MDH0X) that contains the quinone chlorinated hydrocarbons such as form of PQQ accepts two electrons from chloroform and trichloroethylene that methanol, yielding formaldehyde and a reduced are major soil and ground water form of the enzyme (MDHre(i); to complete the pollutants. Results from the studies catalytic cycle, MDHre(j donates electrons to a carried out in this program will provide soluble c-type cytochrome (cytochrome Ci) to a foundation for the industrial application regenerate MDHOX. PQQ remains enzyme bound of these important bacteria. throughout the catalytic cycle and is thought to The oxidation of methanol to formaldehyde cycle between the quinone (MDH0X) and quinol is essential to the growth of methylotrophic (MDHre

HN COO- COO" N" 1 e", H+

•ooc "OOC

PQQ PQQH* (quinone) (semiquinone)

Fig. 6.1. PQQ in its oxidized (quinone), one (semiquinone)- and two (quinol)-electron reduced forms.

66 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Biochemistry and Nuclear Medicine

MDHrea. We are studying the first half of the we proved that PQQ is biosynthesized from reaction that involves the oxidation of methanol tyrosine and that 13C-labeled tyrosine serves and other primary alcohols. as a convenient precursor for the biosynthesis of specifically labeled PQQ. For example, adding 13 Although first described as a methanol L-[3',5'- C2]tyrosin8 to the culture medium of methylotrophs enriches PQQ specifically with oxidizing enzyme, MDH has a broad substrate 13 specificity and can oxidize a variety of primary C at C-5 and C-9a. The organism produces PQQ labeled at C-4 and C-la from L-[2',6'- alcohols. Because incubation with alcohols 13 13 C2]tyrosine. The C NMR spectra of [5,9a- causes changes in the UV spectrum of MDH, 13 13 its binding of substrate is thought to involve C2]- and [4,la- C2]-PQQ each contain only formation of an adduct between the alcohol and two signals from the labeled . Reaction PQQ. One reasonable adduct, a hemiketal, could with benzyl alcohol shifts the C-5 carbonyl form by nucleophilic attack by the alcohol at the upfield by more than 80 ppm to 5 94.1, whereas quinone carbons of PQQ. Figure 6.2 shows one the resonance of C-4 shifts downfield by 13 ppm. of several isomeric hemiketals formed through Identical observations were made when samples attack by alcohol at the C-5 carbonyl of PQQ. of labeled PQQ were incubated with methanol. Although no direct evidence existed for its Because the NMR signal at 5 94.1 has a typical formation, the hemiketal between alcohol chemical shift for a hemiketal carbon, we substrate and MDH-bound PQQ is thought to conclude that the quinone of PQQ readily forms be an intermediate in the oxidation of substrate. hemiketals with primary alcohols. The C-5 To provide direct evidence for the formation of carbonyl of PQQ reacts more readily than the the hemiketal with the C-5 carbonyl of PQQ, C-4 carbonyl when treated with alcohols. we examined its reaction with primary alcohols by 13C NMR spectroscopy. Natural abundance Work is under way to prepare MDH samples PQQ in the presence of methanol yielded a that contain 13C-labeled PQQ. Our NMR complicated 13C NMR spectrum that contained observation of these samples in the presence 28 resonances from PQQ; 14 of these resonance of substrate alcohols, inhibitors, and activators signals were attributable to the quinone form will allow identification of the structure of of PQQ. In addition, the spectrum contained intermediates involved in the MDH catalytic signals from an adduct of PQQ formed by cycle. These experiments will contribute to our reaction with methanol. A resonance signal at understanding of the mechanism of quinone- 93.7 ppm is consistent with this adduct being a dependent enzymes and the biochemistry and hemiketal. However, the significant shifts in all physiology of methylotrophic bacteria. the signals from the adduct made it impossible to decide if the hemiketal was formed by reaction at the C-4 or C-5 carbonyls.

To distinguish between hemiketal formation at C-5 or C-4, we used a sample of PQQ specifically labeled with 13C. Previously,

H , COO" H 1 COO^ n\ 1 DOO" ,N"~ft2 coo- N~X \ 8 A [ If T 7, J / •*". -^ N )H QOC ^*^k J 5 -ooc' O H H ^ ° 0 R R

Fig. 6.2. Formation of a hemiketal by reaction of a primary alcohol with the C-5 quinone carbon of PQQ.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 €7 Biochemistry and Nuclear Medicine

Structure of Cytochrome c. Oxidases: of the proteins that compose the terminal Sequence and Analysis of the Subunit oxidases. As isolated, the enzyme from Thermus contains two protein subunits to lie Gene which three iron and two are bound in an unknown manner; a third subunit appears James A. Fee, Penelope Springer, and to be lost during purification. The cytochrome c Michael W. Mather oxidase genes in Thermus are contiguous on the chromosome and appear to be transcribed in Understanding energy conservation in the order He -> I-» III. We have now completely microorganisms is crucial to understanding determined the DNA sequence of the Subunit lie their roles in a host of natural processes as gene and carried out extensive analysis of its 49 well as their impact on anthropogenically deduced amino acid sequence. The results compromised ecosystems. Toward that end, support the topological model shown in Fig. 6.4, scientists in the Biochemistry Section of Group and several important observations can be made INC-4 are addressing the problem of how from our data. Subunit lie is formed from the electron transfer reactions in cell membranes fusion of two very different proteins, the amino- are coupled to proton translocation across that terminal portion is similar to other known membrane. The cartoon in Fig. 6.3 illustrates Subunit II sequences, and the carboxyl-terminal the Mitchell "hypothesis," which is now widely portion is typical of known cytochrome c accepted as an essential paradigm in sequences. The latter domain probably has bioenergetics.45>46 a three-dimensional structure similar to other cytochromes c (Ref. 49). The Subunit II portion of the protein is composed of two distinct Bacterial electron transport chains are quite domains. The transmembrane domain is diverse—able to accept electrons from a wide probably anchored within the plasma membrane variety of reductants and to direct them to a by means of two hydrophobic segments of amino similarly diverse array of oxidants. Although acid sequence that form membrane-spanning a number of metals are involved in the electron transfer processes, including iron, copper, , nickel, molybdenum, and possibly tungsten, iron and copper are the most common. We have been working for some time on the terminal oxidase of Thermus thermophilus, cytochrome caa3- Methods for purification and results of physical characterizations were reviewed47 in 1986, after which an effort toward determining the structure of this enzyme was initiated. Structure determination of membrane proteins is complicated by the difficulty of obtaining single crystals suitable for diffraction work, and such crystals have not been reported for any cytochrome c oxidase. However, crystals of bacterial photoreaction centers were obtained, Fig. 6.3. Schematic representation of the principal and the resulting three-dimensional structure features of the chemiosmotic theory. A respiratory chain of these proteins has greatly advanced the field of electron transfer enzymes spans the inner membrane 4 of a cell or organelle. This membrane is completely of photosynthesis. ** There are fundamental + analogies between the physiological function closed and essentially impermeable to protons (H ). The respiratory enzymes couple the oxidation of a reduced of photoreaction centers and that of terminal substrate (represented by NH) to the translocation of oxidases, and the two systems are both of H+ across the membrane. Most commonly, the oxidant great importance. Therefore, a primary goal is O2, which is reduced to water. This process stores of bioenergetics research is to provide a energy in a trans-membrane proton gradient. Other structure for terminal oxidases. transmembrane enzyme complexes are able to use the energy stored in the proton gradient for various energy- requiring processes. For example, the adenosine Our current strategy involves, in part, triphosphate (ATP) synthase couples the inward determining the one-dimensional structures translocation ofH+ to the phosphorylation ofADP, yielding the "high-energy" compound ATP.

68 Isotope and Nuclear Chemistry Division Atinual Report FY 1990 Biochemistry and Nuclear Medicine

a-helices. We suspect that the intermembrane 321 domain lies outside the cytoplasm in the space • ® © © © © between the inner plasma membrane and the outer membrane or cell wall.

C^ocrrorr* c The amino acid sequence gives some clue to ©V ©@i © 250 \ where the metals are bound. The heme C is ©I ® • almost certainly covalently bound to cysteine [C] residues 231 and 234; the histidine LH] V © residue at 235 and the methionine [M] residue '••••••I at 287 serve as axial ligands to the Fe. The M, C, and H residues in the 146 to 192 region of •© the sequence, marked by a carat, are possible „,©©©ff ©© © © © V© ligands to one of the copper ions; which amino 0 f acid residues are bound and their spatial • © © ©® © arrangements remain to be established. 192 189 185 18 r~, ©__ ©®© rf aaiii!ii»Mi»«M

Fig. 6.4. Topological presentation ofT . thermophilus cytochrome caa3 subunit lie. The amino acid residues of subunit lie are displayed in sequence and oriented with respect to the bacterial inner membrane. Horizontal solid lines represent the lipid bilayer membrane; the cytoplasmic side is labeled "In," and the intermembrane side is labeled "Out." The amino acid residues are represented by filled circles. Residues that are conserved among all reported subunit II or cytochrome c sequences, as appropriate, are enclosed by a small square and indicated by the single-letter code. Residues predicted to be axial ligands to the C heme are marked with an asterisk. Residues that have been proposed as possible ligands to the CuA copper ion are marked with a caret. The putative membrane-spanning portions of the sequence are arranged across the membrane in helical net fashioruCharged residues are indicated by a circled plus (lys orarg) or minus (asp orglu) next to the residue. (For a more detailed version of this illustration, see Ref. 49.)

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Biochemistry and Nuclear Medicine

Labeled Biologically Active Peptides for autoantibodies in rats.57 The peptide used for Myasthenia Gravis Research labeling has a tripeptide cap of (Lys-Gly-Gly) on the N-terminus to provide an extra lysine residue for covalent attachment of the N-benzyl porphyrin; the peptide sequence is designated Janet A. Mercer-Smith, Jeanette C. Roberts, a Dean A. Cole, Daniel J. McCormick,* Vanda A. H i25-i47- We have prepared and characterized copper porphyrin-Ha125-147 conjugates

The acetylcholine receptor is a 290 kD glycoprotein consisting of glycosylated subunits of 0.2P76. Peptide 125-147 of the acetylcholine receptor a su.bunit is exposed at the neuromuscular junction and can induce 0.0 experimental myasthenia gravis, T cell Ha.,25..i7. C.TACtiR immunity, and receptor modulating Agent Used in Test injection *Neuroimmunology Laboratory. Mayo Clinic '"Hunter College, City University of Mew York Fig, €.5. Delayed hypersensitivity skin responses in "Provided by the Medical Radioisotopes Production immunized rats. Peptides shown in shaded boxes are Section of Group INC-11. those used in the initial immunization.

70 Isotope and Xuclear Chemistry Division Annual Report FY 1990 Biochemistry and Nuclear Medicine

67 H(*i25-147 (which is the only difference between Experiments with CuCS3P-Ha! 25-147 it and the native sequence of Ho^ 25447) does not conjugates were designed to determine the effect significantly affect the peptide's antigenicity. that the radiolabeled peptide conjugate has on Control experiments using rats immunized with lymph node cell proliferation in animals that adjuvant alone indicate that the antigenicity had been immunized with Ha.125.147. There is a caused by the peptides is specific because the standard survival curve in which higher doses of control rats did not exhibit hypersensitivity the radiolabeled peptide conjugate (at constant when they were exposed to the myasthenigenic peptide dose) cause decreased lymph node cell 67 peptides or d.TAChR. Therefore, delayed proliferation (Fig. 6.6). Thus, the CuCS3P- hypersensitivity T cell function, specific for the Ha.j 25.147 conjugates inhibit lymph node cell autoantigen Ha.j25.147, was maintained after proliferation in cells from the Haj 25-147 modification of H0425.147 to form the CuCS3P- immunized rats. Whether or not this is a result Hc.125.147 conjugates. of the presence of 67Cu or specific binding of the 67 CuCS3P-Hai25-i47 conjugates to lymph node cells is not clear. However, this experiment does By measuring the specific incorporation of 67 3H-thymidine into lymph node cells, we examined demonstrate the cytotoxicity of Cu, which is to be expected from its nuclear decay properties. the ability of the CuCS3P-Ha125_i47 conjugates to stimulate T cell proliferation in populations of Additional studies are needed to determine the peptide-specific immune lymph node cells. Control mechanism and specificity of the inhibition of studies indicated that T cells proliferate appro- lymph node cell proliferation. priately under these experimental conditions. Both CuCS3P-Ha;L25..i47 conjugates and Ha125-i47 These studies indicate N-benzyl porphyrins have comparable selectivity in stimulating can be covalently attached to small autoantigenic cellular proliferation in animals previously peptides and metallated with copper under immunized with Ha.125.147. These studies indicate conditions that maintain the immunoreactivity 67 that the CuCS3P-Ha125.i47 conjugates have of these molecules. The CuCS3P-Hai25.i47 retained the antigenicity of the H0425.147. conjugates are immunologically comparable to the unmodified peptide. Preliminary studies 67 67 We examined the recognition of CuCS P- with Cu-labeled peptides indicate that Cu 3 has a potent cytotoxic effect. Further studies will H0425-147 by antibodies from peptide-immunized 67 rats. Polyclonal and monoclonal antibodies demonstrate whether Cu-labeled conjugates derived from rats immunized with Ha^ 25-147, can be used to kill T cells involved in production Hai25-i47 [peptide lacking N-terminal tripeptide of autoantibodies responsible for the pathological cap (Lys-Gly-Gly)], or H

Isotope and Nuclear Chemistry Division Annual Report FY 1990 71 Materials Chemistry

Overview

Synthesis and Characterization of Novel Low-Dimensional Materials

Radioisotope Research and Development: Materials Issues in Targetry

Conductivity of Polystyrene Film When Exposed to Nitrogen Dioxide: A Novel Sensor Materials Chemistrv

Overview The second article, by Heaton et al., describes important materials science issues associated with the Division's production of medical Alfred P. Sattelberger radioisotopes at the Los Alamos Meson Physics Facility (LAMPF). Selections of target materials These are difficult times for the US materials for the production of specific radioisotopes are science community. Funding for basic and based on a number of criteria, including atomic applied research has declined in real dollars mass, isotopic distribution, purity, physical over the past decade and foreign competition properties, and the isolation of the desired on both fronts has increased dramatically. The medical radioisotopes. The atomic mass of the challenge for the 1990s is to develop integrated elements in the target materials determines programs that take concepts and ideas to which isotopes are produced during proton marketable end-products in a timely fashion. bombardment. The ease and speed of chemical To meet this challenge, we must bring together workup and the consideration of waste the often fragmented elements of materials minimization issues help members of the science. Integrated programs that combine Division's Medical Radioisotopes Research materials modeling, theory, characterization, Program determine the appropriate target synthesis, and processing offer the best material. The third article in this section opportunity for delivering new products to the describes a novel nitrogen dioxide sensor marketplace for present and future applications. developed by Steve Agnew of Group INC-4 At Los Alamos, we are in a unique position to and Bill Christensen and Dipen Sinha of build such an integrated effort; our expertise Group MEE-11. This device was cited by R&D in all these areas spans several disciplines Magazine as one of the 100 most significant and line organizations. technical products of 1990. The plaque commemorating the team's "R&D 100 Award" hangs proudly in the TNC Division office. The Materials research in INC Division has new NO2 sensor, exhibiting high selectivity, grown significantly over the past few years. relies on the self-ionization of N2O4—the dimer + Much of the success of our current programs of NO2—to NO NO3" within a polystyrene film. results from combining the Division's traditional strengths in synthetic and structural inorganic chemistry and optical and vibrational INC Division scientists are involved in spectroscopies with the strengths of other various other materials chemistry studies, Laboratory divisions in materials theory, including organometallic chemical vapor characterization, and processing. The articles deposition, metal vapor synthesis, and chemical in this section detail recent accomplishments sensors, which are described briefly here. by INC-Division personnel in three different areas of materials research. The first article, Organometallic Chemical Vapor Deposition by Huckett et al., describes the synthesis and characterization of new low-dimensional Chemical vapor deposition (CVD) is a process materials derived from oxidizable diruthenium in which gaseous reactants are decomposed (for example, by heat, with photons, or by chemical tetracarboxylates, Ru2(O2CR)4 (R = alkyl or aryl group), and the reducible-organic-bridging reaction) to provide solid-state materials such ligand dimethyldicyanoquinonediimine. as metals, metal carbides, metal nitrides, etc. This effort began as a collaboration between One example of CVD, the III-V semiconductor scientists from Groups INC-4 and T-ll who gallium arsenide, forms by the chemical reaction wanted to understand the properties of quasi- of trimethylgallium with arsine at elevated one-dimensional materials incorporating temperatures. With the increasing demand mononuclear transition metal complexes and for advanced and high-performance materials, bridging . The evolution of the research CVD has become an essential technology. to new materials based on metal dimers and CVD coatings are used to retard wear, corrosion, organic bridges resulted from not only the and erosion; to inhibit oxidation in extreme team's expertise in organic chemistry, but environments; and to join carbon-carbon also their extensive experience with metal- composites. CVD is also used to manufacture metal multiply-bonded binuclear complexes. or enhance the densities of composites and other materials that are difficult to svnthesize

74 Isotope and Xucleur Chemistry Division Annual Report FY 1990 Materials Chemistry

by other methods. CVD is not a line-of-sight >100:l. Such high ratios minimize the process—a feature of some technical importance. thermodynamically favorable condensation In fact, CVD is ideal for coating complex shapes of metal atoms back to bulk metal. Laboratory such as tools, tubes, and parts with holes or scientists are using the reactor to prepare recesses. organometallic complexes that are difficult or impossible to prepare by conventional Collaborations between Groups INC-4 and synthetic techniques. Target compounds MST-7 are developing new low-temperature include catalyst and materials science (<250°C) routes to metal, mixed-metal, metal precursors. We are also interested in the carbide, metal nitride, and metal oxide films preparation of zerovalent organoactinide complexes such as bis(hexa- from volatile organometallic precursors. 6 A recent success in this research was the methylbenzene)uranium, (n -C6Me6)2U, preparation of high-purity, nanocrystalline a type of molecule that is currently unknown films of rhodium and iridium from volatile in actinide organometallic chemistry. 3 organo-allyl complexes of the type M(n -C3H5)3. Applications for these low-temperature films Chemical Sensors include weapons diagnostics, liners for In addition to the work described in the containers used to encapsulate highly article by Agnew et al., there is considerable radioactive isotopes, and oxidation protection research activity in the chemical sensor area coatings for polymers. The CVD team is also throughout the Laboratory. Los Alamos investigating the preparation of zirconium scientists have recognized that although many carbide films from zirconium organometallics programs around the country develop chemical and aluminum films from aluminohydride sensors based on existing materials and precursors. ZrC is a desirable refractory coating fabrication methods, few programs are devoted for uranium fuel rods; aluminum coatings have to the development of entirely new advanced potential applications in a variety of areas, materials and materials chemistry for the including optical coatings for mirrors. sensors needed in new and increasingly challenging applications. Scientists from Metal Vapor Synthesis Group INC-4 are exploring covalently-bound The interaction between "naked" metal atoms multilayers of transition metals and specialized and organic substrates is conceptually one of the ligands on glass substrates for sensor most straightforward synthetic procedures for applications, where the transducer effect is the preparation of organometallic complexes. an optical, electrochemical, or surface acoustic For example, the co-condensation of tungsten wave change. In addition, new chemical atoms with toluene at cryogenic temperatures receptors are being developed for anions and provides a high-yield route to the zerovalent cations. An interdivisional team is designing tungsten compound bis(n6-toluene)tungsten. and synthesizing new reagents and polymer The latter compound can also be prepared by coatings for remote sensors that exhibit high standard solution chemical routes but only in sensitivity and selectivity for specific anions (for example, F" and NO3") and cations (such as yields of -1%. New compounds, some with + +2 +4 unique synthetic potential, are available by H , Cd , and Pu ). These remote sensors are means of metal vapor synthesis techniques. important in both on-line process chemistry and Through a collaboration of INC and NMT environmental site characterization. Divisions, a state-of-the-art metal vapor synthesis reactor has been constructed at Site TA-21. This reactor, only the third of its kind in the world, uses an electron beam to vaporize metal atoms from the surface of bulk-metal targets under cryogenic, high- vacuum conditions. An adjustable inlet system provides a continuous feed of organic ligand to the reaction zone (the walls of the reactor) concomitant with metal deposition. In a typical synthetic run, the ratio of ligand to metal is

Isotope and Nuclear Chemistry Division Annual Report FY 1990 75 Materials Chemistry

Synthesis and Characterization of with the bimetallic center. Also, this bridging Novel Low-Dimensional Materials ligand forms charge-transfer organic metals and therefore provides the possibility for creating stacks of partially reduced conductors in a Sara C. Huckett, Carol J. Burns, second dimension. Evaluating the properties David L. Clark, Tracey Frankcom, of such materials allows us to rationally synthesize related systems and to chemically J. D. Thompson, and Basil I. Swanson tune materials for particular applications. The evaluation of known charge-density- wave (CDWj inorganic solids and charge The [Ru2(O2CR)4»DMDCNQI]x systems transfer organic conductors for application are prepared in THF through the process as electronic and nonlinear optical materials represented in either Eq. (1) or (2). On the basis represents a major thrust of materials research. of elemental analysis and infrared (IR) spectral However, little effort is being devoted to the data, reaction (1) appears to produce purer rational design of entirely new systems. Most products and is used preferentially. of the suitable, well-characterized materials that Reaction (1) occurs with a striking color change are available for these applications are organic. from the red-brown Ru2(O2CR)4 and yellow However, because inorganic elements not only DMDCNQI reactants to an intense shade of affect the elasticity, flexibility, and conductivity blue. (This same blue color is observed for 58 of macromolecular chains, but also have the Na[DMDCNQI]2 radical anion salt.) The potential for being fixed on supports, we seek products of this reaction precipitate from the to incorporate transition metals into the chain THF solution and cannot be redissolved in structure. A variety of approaches have been organic solvents such as Et2O, hexane, CH2C12, taken to link mono-metal centers59 in one- or THF. This observation supports the proposed dimensional materials, but the potential range polymeric nature of these materials. Elemental of compounds is limited by these routes. Our analysis of the R=Me, Et, Tol, and Mes adducts research focuses on linking metal dimers with (Tol = p-tolyl, Mes = 2,4,6-mesityl) indicates that organic bridging ligands. This approach ensures the compounds are 1:1 adducts the strong metal-metal interactions necessary and DMDCNQI. for the formation of conducting inorganic polymers. Additionally, it is proposed that two stable oxidation states of a metallic subunit are Ru2(O2CR)4 + 1-2 DMDCNQI -+ [Ru2(O2CR)4* DMDCNQI]* necessary for the formation of conducting inorganic systems;2 thus, the flexibility of the electronic configuration of dimeric units provides a distinct advantage over mononuclear Ru2(O2CRj4 Cl + Na[DMDCNQI]2-> [Ru2(O2CR)4» DMDCNQI],, complexes. + NaCl + DMDCNQI

We chose the -carboxylate- The new chain materials were characterized bridged dimers, Ru2(O2CR)4, for the initial by several spectroscopic techniques. The IR investigations. These compounds are well- spectra of [Ru2(O2CR)4«DMDCNQI]x provide characterized, synthetically accessible, and have important evidence for the symmetrical the o2K282n*28*2 electronic configuration. The coordination of the DMDCNQI ligand because partially filled n and 5 orbitals are important only one vCsN band is observed. The IR spectra with respect to creation of a conduction band also show there is no Peierls distortion leading by overlap with the JC symmetry orbitals of the to a mixed valence ground state (-L-M2+-M2+-L- bridging ligand. This type of interaction should M3+-M3+-L-) as observed for the MMX system produce IVCT (bandgap) energies less than K4[Pt2(P2O5H2)4Cl]«3H2O (Ref. 60). The shift those for known c-systems. The 2,5-dimethyl- in frequency of the vCa%- vibration indicates dicyanoquinonediimine (DMDCNQI) bridging rc-backbonding from the Ru2 center to the ligand shown in Fig. 7.1 was chosen to link the DMDCNQI ligand. We observed additional ruthenium dimers; this ligand is easily reduced modes in the aromatic region, which supports and can form self-doped, mixed-valence chains the formulation of the bridging ligand as an by undergoing spontaneous redox chemistry aromatic radical anion.

76 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Materials Chemistry

We obtained information concerning the electronic configuration of the metal dimer electronic structure of the materials from plays an important role in the formation of diffuse reflectance spectroscopy. We observed this new class of one-dimensional systems. low-energy bands at 993,1158, and 1423 nm The rhodium dimer does not undergo redox in the diffuse reflectance spectrum of reactions with DMDCNQI to form chains as [Ru2(O2CPh)4»DMDCNQI]x, which could shown for Ru2(O2CR)4 in Eq. (1); this most correspond to intervalence charge transfer, probably results from the filled c27r4S2Jt*48*2 metal-to-ligand charge transfer, or 5 -> 5* bands. configuration of Rh2(O2CR)4 as compared to 62 2 4 2 2 2 By analogy to the Ru2(O2CR)4Cl systems, the o 7t 5 Ji* 8* for Ru2(O2CR)4. These types of 1158-nm band would be assigned to the 5 -> 5* observations provide a basis for making rational transition for [Ru2(O2CPh)4»DMDCNQI]x. choices concerning either the synthesis of new However, it is also reasonable that this materials or the tuning of existing systems transition may shift either to higher or lower linked by organic bridging groups. energies by interaction of the metal center with the DMDCNQI ligand (that is, 993 or 1423 nm). We will continue to explore the magnetic Although specific assignments have not been and electronic properties of the made, these spectra demonstrate strong [Ru (O CR) »DMDCNQI] materials. coupling between the DMDCNQI anion and 2 2 4 x 3+ The dependence of these properties on the Ru2 complex ion. modifications of the dimeric subunit are particularly important because it provides a Preliminary magnetic measurements for the means for fine tuning the new one-dimensional [Ru2(O2CR)4«DMDCNQI]x systems (R = H, Me, materials. We will also continue our efforts Tol) suggest that the R substituent plays a role to obtain new synthetic materials. New in controlling the types of magnetic interactions complexes—prepared by both incorporation (for example, intrachain vs interchain)63-64 that of other dimeric units and other Ji-symmetry occur. Additional measurements at a variety of bridging ligands—will extend the range of field strengths for the series of compounds will properties and the potential applicability of be required to obtain a clear understanding this class of materials. of the underlying interactions in these materials. Efforts to obtain analogous materials from Rh2(O2CEt)4 demonstrate that the

R R R R R R R R

\ —Ru •Ru L——Ru — Ru L-

k |\ ^ K R R R R R R R R

Me N \= 1 _ N =/ °

\= Me

Fig. 7.1. Proposed chain structure of[Ru2(O2CR)4»DMDCNQIlx

Isotope and Nuclear Chemistry Division Annual Report FY 1990 77 Materials Chemistry

Radioisotope Research and 82Sr for this purpose; the 82Sr is produced by Development: Materials Issues irradiating natural molybdenum metal. The in Targetry average atomic mass of molybdenum is 95.94 amu, which arises from the natural isotopic distribution of 92Mo(14.84%), 94Mo(9.25%), 95Mo(15.92%), 96Mo(16.68%), 97Mo(9.55%), Richard C. Heaton, Eugene J. Peterson, 98 Dennis R. Phillips, and Wayne A. Taylor Mo(24.13%), and l°°Mo(9.63%). To produce valuable radioisotopes at the In addition to 82Sr, we produce several other Isotope Production Facility (IPF), INC Division's strontium radioisotopes that possess conveniently Medical Radioisotopes Research Program uses short half-lives—with the exception of 85Sr (half- the excess 800-MeV proton beam produced by life = 64.8 days). Shipping 85Sr presents problems the Los Alamos Meson Physics Facility (LAMPF) because the specification that the material be to irradiate various target materials. The IPF and used in a Squibb clinical generator requires that nature of the program are described in Sec. 8 of the activity ratio of 85Sr to 82Sr be less than 5 to 1; this report and in a Los Alamos Technical this ratio is typically about 2.5 to 1 after chemical Bulletin.1 In this article, we discuss some of the processing. Decay increases this ratio to 5 to 1 in materials technology issues associated with just 4 to 6 weeks because the 85Sr has the longer targetry for isotope production. half-life—thus the shelf-life of the isotope is limited for generator applications. This problem Several important issues arise during the would be alleviated if the molybdenum target material did not contain the higher mass isotopes processes of choosing the target and encapsulation 85 materials for the irradiation. For each target, that lead to production of Sr. we must consider the atomic mass and isotopic distribution of elements in the substance, We investigated the enhanced production the chemical form and its purity, the physical of 82Sr on molybdenum foil targets that were phase and form, material density, melting and enriched to 97.37% in 92Mo. Significantly more boiling temperatures, and chemical reactivity. 82Sr relative to 85Sr was observed in 92Mo targets For encapsulation material, we must consider than in natural abundance molybdenum targets. thermal and chemical properties, machinability, Results show that we can produce more 82Sr (with weldability, strength, and elemental composition. a shelf-life of 8 to 12 weeks) by using the enriched target material. Because the process involving The atomic mass of the elements used for enriched 92Mo is more expensive, it will be target material directly determines which isotopes necessary to develop procedures for recovering are produced during the irradiation. In the and reusing the enriched target material. spallation process, many isotopes with atomic numbers and masses lower than those of the Target processing methodology helps target elements are produced. As an empirical determine the choice of a target material. For rule of thumb, we observe production of isotopes example, we have evaluated production of 26A1 with masses 10 to 15 atomic mass units (amu) (half-life = 7.2 x 105 yr) on two different materials lower than the target elements. Generally, we (silicon and potassium chloride). Although we choose the target that will have atomic masses found the silicon target an effective medium no heavier than necessary to produce the desired for producing 26A1, the difficulties and expense isotope. This minimizes the number of higher associated with dissolution of the silicon when mass spallation products and simplifies the we used hydrofluoric acid/nitric acid mixtures separation chemistry. in a hot-cell prompted us to consider alternative targets. Potassium chloride, with its significant For example, 82Sr (half-life = 25.6 days) is the water solubility and the appropriate atomic parent of 82Rb, a positron emitter used to evaluate masses of both chlorine and potassium for cardiac function by positron emission tomography. spallation production of 26A1, appeared to be a The 82Rb is separated from the strontium in a better choice. We developed an effective recovery biomedical generator developed by Squibb procedure and determined that potassium Diagnostics. INC Division's Medical Radioisotopes chloride was indeed an excellent alternative Research Program is a primary supplier of the to silicon for 26A1 production.

78 Isotope and Nuclear Chemistry Diuision Annual Report FY 1990 Our targets are loaded onto the LAMPF stringers in carriers fabricated of 6061 aluminum. Usually sealed by welding, these carriers are designed to hold a variety of target encapsulation configurations. The most commonly used is a canteen fabricated of 304 stainless steel and about the size and shape of a hockey puck (Fig. 7.2). For smaller target volumes, we sometimes use containers reminiscent of shotgun shells, which are composed of 304 stainless steel or copper (Fig. 7.3). A single carrier can contain up to three shotgun shells—and thus permits us to irradiate multiple target materials on one stringer.

We must consider carefully the composition of the encapsulation material and how it interacts with the target material, especially under irradiation conditions. Some of our targets are Fig. 7.3. Aluminum target carrier for radioisotope salts with melting temperatures near or below production, showing targets in shotgun shell the elevated temperature during irradiation. configuration at right. These targets are prepared by melting the salts and pouring the molten substance into the allow short-lived radioisotopes to decay away. encapsulation. After irradiation, all of the salts The only long-lived gamma emitting radioisotopes show evidence of at least partial melting because that should have been observed are 22Na and of poor heat dissipation while in beam. Under 26A1. However, the dissolved target solution also such conditions, metals from the encapsulation contained radioisotopes of cobalt, manganese, vessel are etched into the target matrix. These rhodium, /, and yttrium. elements and their spallation products must be The stable elements present in the steel— considered as we develop recovery chemistries for predominantly iron, chromium, and nickel—were the isotopes of interest. The potassium chloride found in the dissolved target solution at mass target is an excellent example: the target was levels many orders of magnitude higher than the "cooled" for several months after irradiation to desired 26A. The recovery procedure must be able to remove these; these stable impurities can be of significant concern if the radioisotope to be recovered is of the same element as the impurity. The stable isotope will follow the same chemistry as the radioisotope and a product solution of very low specific activity might result. To alleviate these problems with 304 stainless steel, we are evaluating 5086 aluminum alloy and commercially pure titanium metal as encapsulation material.

We have found that choice of materials for targets, target encapsulations, carriers, gaskets, bolts, and other hardware often involves compromises based upon many considerations, and we are continually searching for better materials and methods. As a result, we have found that targetry for spallation production Fig. 7.2. Aluminum target carrier for radioisotope of radioisotopes is an ever-evolving technology. production, showing target in hockey puck configuration at left.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 79 Materials Chemistry

Conductivity of Polystyrene Film To further explore the interaction of nitrogen When Exposed to Nitrogen Dioxide: dioxide gas with the polystyrene film, we A Novel NO2 Sensor constructed the special aperture cell shown in Fig. 7.5. Two free-standing films of polystyrene William E. Christensen, Dipen N. Sinha,* and were cast in this cell's opposing apertures; Stephen F. Agnew the inner sides of each film were exposed to the N02/nitrogen mixture; any film changes were Nitrogen dioxide, a common pollutant in recorded with infrared absorption spectroscopy. urban smog, is a rigidly controlled substance in the industrial workplace. Although many Figure 7.6 shows a typical plot of the time- sensors for determination of NO2 vapor have dependence of conductivity following NO2 been developed, they tend to be very expensive exposure of this sensor; three exposures and and/or nonselective. evacuations occurred over a period of an hour. Our investigation showed the film's conductance 1 We have discovered a novel NO2 sensor changed from a base level of <1 x lO" ^ S/cm that operates on a principle quite distinct from (determined separately) to ~2.75 x 10'11 S/cm— any other NO2 sensor; that is, self-ionization a change of -3 orders of magnitude. of the analyte. To our knowledge, no other NO2 sensors have used self-ionization as a method To understand the exact nature of the of detection, despite the high selectivity for interaction of NO2 with the polystyrene film, corresponding analytes that this method entails. we used the aperture cell shown in Fig. 7.5. This The high selectivity comes about because few cell allowed us not only to expose the films to the substances undergo self-ionization reactions. NO2/N2 mix, but also to observe the films directly The device also has the advantage of being by infrared before, during, and following the inexpensive. exposure. The primary form of NO2 within the film is actually N2O4; no free NO2 was observed. The sensor described here uses the self- No chemical degradation of the film occurred ionization of N2O4 within a polystyrene film (that is, nitration of the polymer) with short to transport charge between electrodes (that is, exposures up to several hours; this is consistent an effective insulating plastic starts conducting with previous work,65 in which only the electricity), where corresponding oxidation and exposure of such films to elevated temperatures reduction of the N2O4 occurs. The unexpected resulted in any measurable nitration product. appearance of ionic conductivity in a nonpolar matrix occurs because of the unusual nature of N2O4 chemistry in the condensed phase—it is nonpolar in its molecular form but undergoes — 0.75 cm ready self-ionization to NO+NOg near the Quartz electrodes. The sensor is thus extremely ^Substrate specific to NO2 because few molecules have this interesting dual property of (1) being absolutely nonpolar in their nonionic form and (2) readily undergoing ionization. Electrode Area Polystyrene films were cast onto 1.25 cm interdigitated electrodes shown in Fig. 7.4. This electrode consists of 50 interdigitated "fingers" of film on a quartz substrate, 15 um wide and 15 jam apart, which provides a total active area of of 0.5 x 0.3 cm. This type of electrode facilitates low-conductance measurements by virtue of having a large ratio of electrode perimeter P to electrode spacing d (P/d = 32,768). Contact Pads

*GroupMEE-U Fig. 7.4. Interdigitated electrode system.

80 Isotope and Nuclear Chemistry Division Annual Report FY1990 Materials Chemistry

A variety of NO2 sensors devices have been 3.0-T developed and many are available commercially. N020ff

Our new device, however, appears to operate by 10/ S /"I an entirely different principle than any other 2.5- NO2 sensor: when it is exposed to NO2,the "•o 2.0- conductivity of this otherwise insulating film off substantially increases. >> •> 1.5- off ict i There have been many reports on the _> 1f C 1.0- f self-ionization of N2O4 under a variety of o 1 66 68 O 1 conditions. " This molecule represents an 02on ^"^on U.O | i i j unusual example of self-ionization because all 0 10 20 30 40 50 other species that undergo self-ionization are Time (min) originally polar, such as water, AsF5, PF5, and H2SO4. The N2O4 self-ionization reaction involves transformation of this nonpolar Fig. 7.6. Conductivity vs time for a series of exposures of molecule into nitrosonium nitrate, NO+NOj a polystyrene-film-coated interdigitated electrode We suggest that the transport of charge within exposed to 1:10 NO2 in N2 vlv. the film occurs because of this self-ionization and propose the following cathodic and anodic NO2 mixtures. This decrease directly relates to processes: removal of N2O4 from the fikn; the conductivity of the film during exposure actually increases Cathodic slowly, showing no indication of degradation. 3/2 N O + e" —> NO + NO + Also, we have observed a diminution of film 2 4 2 response and even no response with vigorous drying and elimination of residual benzene Anodic solvent from the film. We attribute this N2O4 + Au° —> Au+ + NO3 + NO + e' diminished response to a delamination of the film from the electrodes, which is induced The bulk of the N2O4 provides a "salt bridge" by strains accompanying film swelling and through the polystyrene, enabling it to conduct deswelling. Polystyrene's affinity for N2O4 is nitrosonium and nitrate ions that are created so large that absorption of NO2 actually leads at each of the electrodes. to swelling of the film; subsequent evacuation of N2O4 induces a sufficient strain in the film The peak conductivity decreases with to separate it from the electrode surface. subsequent exposures of the device to identical

This device for sensing NO2 offers a new and unique method that could be widely applied in a variety of situations. Although we have not demonstrated any tremendous sensitivity of this device for NO2 vapor, we have discovered the underlying principle of its operation, and consequently can make many improvements such as appropriate surface preparation of the

NO2 and N2 gas mixture Polystyrene films cast electrodes, functionalized polystyrene to from benzene solution enhance surface adhesion, integrated sensing electronics, and the use of AC conductance instead of DC. These changes would conceivably 500 urn allow us to detect sub-parts-per-million NO2 without interferences from other ambient gases.

250 u.m

Fig. 7.5. Aperture cell for infrared transmission measurements of films exposed to NO2 gas.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 81

Division Facilities and Laboratories

INC-Division Facilities and codes can be 15 to 30 times faster. This system Laboratories has a disk storage capacity of 10 gigabytes, a 120-megabyte solid state disk with high-speed input/output, and two laser printers. There Jose A. Olivares are 48 terminal ports connected to the system through a protected distribution network that In addition to the Omega West Reactor, the extends throughout the Site TA-48 secure area. Radioisotope Research Facility, and the Mass An encrypted ?ecure network is supported for Spectrometry Facility, which are described in connection to the ICN and to 17 other classified the articles immediately following, INC Division systems at Los Alamos. is proud of its many state-of-the art laboratories and facilities described below. Classified Radiochemistry Document Repository Division-Wide Computer Systems Group INC-7 operates and maintains a Group INC-11 supports a Division-wide classified document repository for the Division. computing system in the open environment This vault facility is Los Alamos' historic and a small, secure system for classified resource for all weapons radiochemical computations, database management, computer diagnostic data and associated test performance modeling, documentation preparation, and evaluations. Located at Site TA-48, the 1200-ft2 process control. The major components are facility houses a high-density mobile storage located at Site TA-48 in Building RC-1. system with nearly 450 linear feet of storage shelves, a computer room for the Group INC-7 The extensive open system has nine VAX classified DEC-Vector 6000-410 computer computers functioning as distributed processors system, two work rooms, and an office area on the Laboratory's Integrated Computer for the document custodian. To track documents Network (ICN); this system permits authorized (currently estimated in excess of 50,000), users to access more than 2000 other nodes on -100 monthly send/receive transactions, and the ICN as well as all major open computing thousands of other document control actions, facilities at the Los Alamos Central Computing we maintain a bar-code database on the Facility. classified computer. In a high-priority effort, INC personnel have already used the INGRES The most recent addition to our system, a database management system to bar-code and VAX 8700, forms the boot node for our "MAGIC" enter more than 50% of our classified cluster of nine VAX computers. This cluster documents into the document control database. currently has a disk capacity of 18 gigabytes This system will allow us to easily access for program and data storage and includes documents for inventory and use by staff. 14 laser printers. The network has 250 terminal Historical logbook documentation of previous connections and supports connections to three classified document use will gradually be other on-site VAX computers and to a high-speed entered into the database. Current and future data link to the ICN. During the past year, we radiochemistry test data are also being have upgraded the network's data transmission electronically transferred and stored within the speed from 56 to 256 kilobytes. A DEC-Router weapons radiochemistry INGRES database in 2000 has also been installed for increased the secured computer system. reliability in the network's DECNET connections. Detector Development Laboratory This facility was implemented jointly by The secure system is a distributed processor INC and P (Physics) Divisions to develop special connected to the classified partition of the detector systems. The laboratory consists of a integrated computer network (ICN). This system vacuum chamber simulator for accelerator consists of a newly installed DEC-Vector 6000- environ-ments, multiwire proportional counters 410, which is approximately seven times faster that use thin polypropylene windows and fine than the previous VAX-780. The processor wire grids, and a multisegmented system to vectorizes Fortran compiled codes and executes detect and identify nuclear particles over a wide them simultaneously. Execution time for some range of masses and energies. The laboratory

84 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories

has recently added capabilities for solid state development of ultrasensitive abundance detection of low-energy protons from a low- (l:1013) measurement techniques. energy proton gun as well as data acquisition through a computer acquisition-measurement Collaboration with experimenters, both and control system. within and external to the Laboratory is encouraged. In one of our collaborations, Time-of-Flight Isochronous (TOFI) we separate a particular isotope at 50-keV ion Spectrometer energy, decelerate to 500 eV, and re-attach an The TOFI spectrometer and its associated electron to the ion in a cesium gas cell. The transport line are the major compontnts of a presence of individual atoms of the isotope is facility designed to measure the masses of then determined by photon excitation, followed by detection of prompt decay photons. energetic, recoiling nuclear reaction products. The TOFI facility is located at LAMPF to take advantage of the high yields of exotic light Photoacoustic/Photothermal Spectroscopy nuclei produced in interactions between the Facility intense 800-MeV proton beam and heavy- and Staff members from Groups INC-4, INC- 7, medium-mass targets. Using measurements and INC-11 collaborate to develop and maintain of the recoil's transit time through the spectro- a state-of-the-art facility for laser-excited meter, we can direct mass measurements with photoacoustic and photothermal spectroscopy precisions of 100 to 1000 keV, depending on (PAS/PTS). This facility consists of two separate production rates. To date, we have measured the instruments, both based upon nanosecond- masses of more than 60 neutron-rich nuclei that timescale pulsed neodymium:YAG/dye laser n 66 range from Li to Fe. With the development of systems with a wavelength extension to provide a new atomic number identification technique tunability from 200 to 900 nm. and by employing a high-geometry, beta-neutron detection system, we can use TOFI as a fast- recoil tagging device to determine several decay One instrument is housed in Group INC-4 properties of these exotic species. laboratories in an open area at Site TA-21 and the second is in a secure area in the Chemistry and Metallurgy Kesearch Building. The latter Electromagnetic Isotope Separator Facility instrument is dedicated to programmatic Group INC-11 operates and maintains three objectives of the Yucca Mountain project that electromagnetic isotope separators in the secure involve ultratrace detection and speciation of area at Site TA-48. Each separator is capable actinides in environmental samples. The of ~1 mg/day (all isotopes) collection rate. Each instrument at Site TA-21 is intended for general isotope is enhanced in purity by ~104 relative to research and analytical purposes, including the isotopic ratio in the feed material. Higher (1) development of PAS/PTS as an collection rates are possible for selected ultrasensitive analytical tool for a wide range elements. Almost all elements in the periodic of environmental contaminants such as metals, table can be separated. The total amount organics, and metal/co-contaminant systems; collected vs amount fed ranges from 0.1 to 50%, (2) establishment of a remote-sensing capability depending on the element. Alpha-particle for PAS/PTS that would employ fiber-optic emitters and highly radioactive samples with techniques for in situ analysis in downhole long half-lives cannot be separated at this time; or hostile environments; (3) investigation however, the oldest of the three separators can of optical and data reduction techniques to be converted to separate such samples if there advance the applicability and sensitivity of is sufficient interest. PAS/PTS to the limits of feasibility; and (4) application of PAS/PTS to problems in The primary function of the facility is to chemical reactivity and photodynamics of provide support to the Division's weapons spectroscopically silent and radiationless analyses program, which has the highest phenomena. The fact that this instrument priority for scheduled machine time. The is located in an open area of the Laboratory remaining time is available for ion source encourages collaborations with academic and industrial scientists and allows direct development, production of ultrapure "spikes" participation of uncleared Laboratory personnel. for mass spectrometer calibration, and

Isotope and Nuclear Chemistry Division Annual Report FY1990 85 Division Facilities and Laboratories

Counting Room Facility areas of high explosives, small-molecule The Group INC-11 Data Acquisition activation, actinide and fluorine chemistry, (Counting Room) Section operates and and several other molecular design projects. maintains a sufficient variety and number of calibrated detector systems to quantitatively Condensed Matter Spectroscopy determine a wide array of radioactive nuclides Group INC-4 operates and maintains an that are important in the weapons extensive optical spectroscopy facility in radiochemical diagnostics program. Counting the uncleared area of Site TA-21. The room equipment includes alpha-, beta-, instrumentation includes several spectrometers gamma-, x-ray, and fission detectors, most for spontaneous and resonance Raman of which are coupled to a computer-based scattering, Fourier Transform-Raman studies, data acquisition and analysis system. infrared absorption, electronic absorption and emission measurements, photoacoustic The extensive list of detectors and counters spectroscopy, and transient Raman and that are currently operational in the counting electronic absorption spectroscopy on the room includes 16 high-resolution nanosecond timescale. Specialized equipment gamma-ray detectors, 9 high-efficiency Nal(Tl) is also available for variable temperature gamma-ray detectors, 6 high-resolution solid- (4 to 600 K) and pressure (0 to 30.0 GPa), state alpha detectors, 4 Frish-grid alpha/fission ultraviolet and near-infrared resonance Raman, counters, 3 internal 2- n gross-alpha counters, and ultrahigh resolution Fourier transform 8 beta proportional counters, 2 trochoidal infrared studies. This facility supports basic positron counters, and 2 x-ray proportional and applied research programs in energetic counters. materials, photophysics and photodynamics, materials research, bioinorganic chemistry, We are extensively upgrading the sample geochemistry, and environmental chemistry; changer control and data readout systems it is used by scientists throughout the for the beta counters, and the first two Laboratory and from several universities. refurbished counters are now operational. Local microprocessor control of each counter Animal Facility for Biomedical Studies and sample changer, extensive error checking The Nuclear and Biological Chemistry and self-testing, and a fully air-driven system Section of Group INC-11 maintains National for the sample changer mechanism are major Institute of Health-approved animal facilities in components of this new system. the Biomedical Building at Site TA-53 (LAMPF). This facility is used to evaluate the biological Single-Crystal X-Ray Diffraction Facility properties of radiolabeled compounds. The 2 Group INC-4 maintains and operates a animal housing room has an area of 230-ft single-crystal x-ray diffraction capability that and an independent ventilation system. The is unique within the Laboratory. The facility room is approved by the Los Alamos Animal consists of three automated single-crystal Use Committee for housing small animals and diffractometers that have the capability of data by the Health and Safety Division for housing animals that are radioactive. The adjacent collection at temperatures between -160 and 2 1000°C. Data collection capabilities at high 230 ft animal surgery/imaging room contains pressures (to 300 kbar) are also available. a Picker DYNA-4 gamma camera connected to A variety of structure solution packages are a Picker PCS-512 computer for processing maintained, including the Los Alamos system nuclear images, a Capintech radioisotope TEXRAY and another package developed at the calibrator, and leaded glass shielding for University of California at Los Angeles. Both personnel injecting animals with radiolabeled precession and Weissenberg cameras are used. compounds. The current output is 50 to 60 crystal structures per year; our maximum capability is -150. We The facility also includes a 230-ft2 tissue- have made an effort to develop a facility that is culture/histology room that is kept at a positive user friendly to knowledgeable but nonexpert pressure. This room houses a 6-ft laminar flow structural chemists. We provide support for hood, a double incubator, a Zeiss IM invtjrtor basic and applied research programs in the fluorescent microscope equipped with a

86 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories computerized camp>-a unit, an ultralow temperature freezer (-85°F), an automated tissue processor with a tissue embedding system, a glass-knife maker, a refrigerated slow-speed centrifuge, an ultracentrifuge with zone-rate controller and density-gradient rotor, and a Perkin-Elmer LS-4 spectrofluorometer.

A computerized image microscopy laboratory is also part of the Biomedical Facility. This laboratory is used to measure the light emitted from fluorescent probes that are localized in tissue cells. The laboratory houses a Zeiss upright fluorescent microscope with an attached cooled intensified CCD video camera and a computerized image analysis system.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories

Omega West Reactor

Donald L. Hull, Gerald F. Ramsey, Michael M. Minor, Sammy R. Garcia, and David L. Finnegan

The Omega West Reactor (OWR), operated by Group INC-5, has operated for over 34 years (Fig. 8.1). Its primary purpose is to provide an intense steady-state flux of thermal and epithermal neutrons for use by Los Alamos experimenters and scientists from other laboratories. During FY 1990,19 Los Alamos groups and 10 outside laboratories used the OWR to irradiate 10 415 samples (see Table 1). In addition, 4700 experimental hours were logged, in large part by the Explosives Technology Group (M-l), as is shown in Table 2. A substantial fraction of the experimental work done at the OWR by Groups M-l, WX-5, and WX-3 supports the weapons program.

To provide these experimenters with a source of neutrons, the OWR is normally operated at a thermal power of 8 MW, 7.5 hr per day, 5 days per week. At 8 MW, the thermal neutron flux in the core is 9 x 1013 neutrons/cm2 s, and the fast neutron flux (>0.1 MeV) is 5.6 x 10*3 neutrons/cm2 s. In FY 1990, we replaced the OWR's aging equipment listed in the sidebar on page 91. This process was made possible by Bush Amendment allocations and other resources. Because the safety of older reactors is always a concern, a reassessment of the OWR's lifetime was performed this year. This reassessment gives the OWR a minimum of 10 years of safe operation.

6" Through 12" Square Ports Ports 6" Beam Ports In support of the environmental restoration with Shutter. (ER) work at Los Alamos, Group INC-5 proposes to use its instrumental neutron activation analysis (INAA) technique to determine trace metals in soils. At this time, all certified EPA 6" Beam Ports Radiography (Environmental Protection Agency) techniques Cave for identifying trace metals in soils require that every sample be dissolved before analysis. Thousands of samples are expected from characterization studies for hundreds of solid Heavy Concrete. Shield waste management units at Los Alamos; therefore, a less expensive method is desirable. Fig. 8.1. Horizontal cross section of the OWR. A technique must be certified by the EPA before

88 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories

the data obtained by the technique can be used possible in each sample analyzed. The scheme officially. If EPA certification can be obtained for can be changed if a particular element or group the OWR'S INAA technique, we can of elements is desired. substantially reduce the cost and time needed for analysis—which would be a great benefit to Cost-Effective Analysis the ER program. The capabilities available On a routine basis, INAA can be done fairly through the OWR INAA could help solve some inexpensively. Because the runs are fully of the ER's analytical problems discussed below. automated, more samples can be run in less time, which means lower cost for each sample. Multielement Analysis In addition, the technique can simultaneously The 45 elements shown in Fig. 8.2 can be analyze multiple elements, so the cost is less routinely determined in most samples. Although per element. The current cost for analysis it is rarely a problem with environmental ranges from $50 to $150 per sample, depending samples, intense radioactivity in one or more upon the elements of interest; the ER estimate of the major elements in a sample may mask for a complete analysis is $5000 per sample. the presence of some trace elements. Our current INAA scheme includes delayed neutron Flexibility in Sample lype and Size counting, which is a specific measurement for 235U concentration. The INAA technique allows great flexibility in sample type and size; samples from several milligrams up to 5 g can be accommodated. Most Automated Analysis types of solid samples are easily analyzed, but The OWR is the only Department of Energy the elements determined depend greatly on the facility in this country that has the capability sample matrix. Liquid samples can be analyzed of running fully automated INAA. We have the for short-lived isotopes; however, liquids must ability to analyze between 40 and 200 samples be sealed in quartz vials during analysis for per day, depending upon the elements of long-lived isotopes, which increases the time interest. In our usual scheme, samples are and expense for each sample. Thicker liquids counted three times—for short-, intermediate-, such as oils can be sealed in irradiation vials and long-lived isotopes. Our current setup has and analyzed, and other liquids can be freeze- been devised to determine as many elements as dried and then analyzed easily.

t »

i .'4 Hffy " vm

US

Isotope and Nuclear Chemistry Division Annual Report FY 1990 89 Division Facilities and Laboratories

Ability to Customize and Optimize Analysis 4 weeks. If only uranium is needed from the for Elements of Interest sample, 200 samples a day could be run and We can also optimize irradiation and analyzed by delayed neutron counting. If a cornting times for elements of interest. By short-lived isotope of an element such examining the half-lives of these elements as as fluorine were needed (half-life = 11s), well as those in the sample matrix, we can the analyses of 200 samples could be done in create conditions that will give the greatest 2 days. However, if a long-lived isotope or a sensitivity for the element of interest while full multielement analysis is needed, the minimizing the interference from the elements turnaround time for the samples would be in the sample matrix. 3 to 4 weeks for 50 samples; 50 samples could be counted each day, but the samples would need to Other types of activation analysis are also decay 3 weeks before the long-lived isotopes available at the OWR. For many elements, could be counted. epithermal neutron activation analysis (ENAA) is more sensitive. For example, Technique for Sample Survey or Screening thorium, iodine, and barium can be more The OWR INAA techniques can easily be sensitively detected (by a factor of 20) through used to survey or screen samples. Using the INAA. Prompt gamma activation analysis multielement capability as well as the is efficient for a number of elements not automated sample analysis, we can quickly detectable by INAA, including , nitrogen, monitor large numbers of samples to see if oxygen, and silicon. This technique has better further analysis is necessary. The cost of the detection limits than INAA for a number of automated analyses should not be prohibitive elements, including , gadolinium, and could be effective for avoiding unnecessary and samarium. expensive analyses. For example, when oil samples were screened for chlorine PCBs, Fast Turnaround Time for Many Elements only these samples with high levels of chlorine The turnaround time for each sample is underwent the expensive analysis specifically determined by the half-lives of the elements to detect PCBs. We were able to screen over 200 of interest, but it can vary between 2 days and samples a day by this procedure.

H H He

Li Be B C N O F Ne

Na Mg Al Si p S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te 1 Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn

Fr Ra Ac

Ce Pr Nd Pm Sm Eu Go- Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw

Fig. 8.2. Forty-five elements can be routinely determined in most samples.

90 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories

Equipment Modifications and Replacements at OWR in FY1990

Upgraded crane CTO-2 to 6 tons Drain project with waste collection tank Installed a waste collection tank for Rm. 101 floor drains and Rm. 102 decontamination sink Rerouted Rm. 102 sink drains to sanitary system drains Rerouted Bldg. 44 floor drains to waste tanks Combined Baltimore and fluor tower drains Rerouted Rms. 106-115 drains to sanitary system New remote area monitors New annunciator system Line voltage conditioners for NAA, OWR control console, and prompt gamma system New primary system valves MCI and MC3 Overhauled air-operated valves 1 through 11 New water softener New electrical switch gear in Bldg. 44 Replaced Baltimore cooler damper motor Replaced all chart recorders New bypass valve controller New resin in Illco demineralizer New boilers for Bldg. No. 1 heat New Bldg. No. 1 water heater Capped sanitary system overflow New portal monitor Decommissioned Water Boiler reactor

Isotope and Nuclear Chemistry Division Annual Report FY 1990 91 Division Facilities and Laboratories

Radioisotope Research Facility and The Isotope Production Facility (IPF) at Applications LAMPF consists of an automated insertion and retrieval system at the LAMPF beam stop that allows us to insert target materials, including Richard C. Heaton, Eugene J. Peterson, and metals, alloys, and salts (see the complementary Dennis R. Phillips article in Sec. 7). There are currently nine target stringers that can be inserted and irradiated simultaneously (Fig. 8.3). After irradiation, the The Medical Radioisotopes Research and targets are highly radioactive (>100,000 Rem); Production Program's two major components therefore, they are remotely removed from the (1) make use of the excess beam of 800-MeV LAMPF beam to be processed in the hot-cell protons from the Los Alamos Meson Physics facility located at Site TA-48. This facility Facility (LAMPF) to produce radioisotopes of comprises 13 hot cells that are fitted with demonstrated or potential value in medicine or master/slave manipulators and shielded by biomedical research, and (2) provide these 18-in. lead glass windows and high-density materials to the nuclear medicine and concrete walls (Fig. 8.4). biomedical research communities. Because we can use the intense beam current at LAMPF to produce many radioisotopes in quantities that Radioisotope Applications cannot be produced anywhere else in the world, Research and development is a vital our research effort focuses on developing new component in our integrated nuclear medicine radioisotopes. We distribute radioisotopes in program. During the past decade, we have various stages of development—from those used used the LAMPF beam facilities and our IPF strictly for research to those with commercial targeting facility to develop technologies and clinical applications. The availability of necessary for producing valuable radioisotopes. large quantities of radioisotopes affords many We have concentrated on nuclides that are not excellent opportunities both for our internal easily produced at comparable purities and biomedical research activities and for many quantities at other facilities. external organizations and customers. The Medical Radioisotopes Research and Production We have now developed a substantial Programs serve a vital function as a national number of isotopes. The following three resource for radioisotopes that are used in examples illustrate our commitment to nuclear medicine.6^ provide the nuclear medicine community with radionuclides that can be employed as tools Facilities in clinical and research work. One of our major responsibilities is the distribution of radioisotopes that have demonstrated or potential value in medicine and biomedical research. This aspect of our program takes advantage of LAMPF's intense beam current (1.1 mA) to produce large quantities of rare radioisotopes. We have assembled an integrated team of scientists and technical support personnel to develop targetry, perform irradiations, chemically isolate and purify the nuclides of interest, characterize product solutions using state-of-the-art analytical instrumentation and techniques, and distribute radioisotopes to the nuclear medicine research community and our own in-house investigators. This effort includes a strong R&D base that is essential for devising new separation schemes to improve product purity and availability and exploring methods to produce new radioisotopes with potential Fig. 8.3. Diagram of the Isotope Production Facility at applications in nuclear medical research. LAMPF.

92 Isotope and Nuclear Chemistry Division Annual Report FY1990 Division Facilities and Laboratories

We have developed and refined the production the DOE Office of Isotope Production and and recovery of 67Cu; currently, more than 20 Distribution is completing a long-range plan researchers world-wide depend upon our reliable that will ensure future isotope availability. This production of this nuclide. These scientists and plan incorporates the concept of a National those within our own program have made Biomedical Tracer Facility, which is envisioned tremendous progress in developing applications as a multiuser center for radioisotope production for this isotope in the diagnosis (and possible research, applications, and education. The therapy) of a variety of tumor types. accelerator and ancillary equipment for the facility must be flexible and capable of meeting Aluminum-26 is another radionuclide that the demands of various user communities. is gaining attention. It has potential as a tracer In addition, Congressional mandate requires in environmental studies and Alzheimer's that such a facility will sell radioisotope goods research. Because it has a very long half-life, and services to recover costs of operation, this isotope is difficult to produce in useful maintenance, depreciation, health, safety, quantities; however, our program developed a and environment protection, and production and recovery method for 26A1 that decomissioning. It appears that a facility employed a silicon target. We have improved our housing a 100-MeV, 750-pA accelerator with production capabilities by using KC1 targets— ancillary equipment can be built to satisfy the a refinement that greatly simplifies the recovery facility's three complementary missions and process. meet the Congressional requirement for cost recovery. INC-Division scientists are working closely with the DOE to provide documentation The Medical Radioisotopes Research and outlining the complete scope and justification Production Programs have also been prominent in for this facility. Los Alamos' effort to transfer technology from the Laboratory to industry. This symbiosis encourages more rapid application and evaluation of new radiopharmaceuticals in clinical settings and significantly shortens the time between discovery and patient trials. One major example of this technology transfer is the biomedical generators, which involve an easily produced, long-lived parent that can be shipped to researchers who remove the useful short-lived isotope as needed. Our program -t Los Alamos pioneered the development of the 82Sr/^2Rb generator, as well as actual production of the parent 82Sr. Rubidium-82 is a positron-emitting isotope with a 75-s half-life. As a monopositive cation, 82Rb is taken up by the heart muscle and thus is valuable as a heart imaging/diagnostic agent for positron emission tomography. Rubidium-82 has recently been approved by the FDA for radiopharmaceutical use.

National Biomedical Tracer Facility The near-future availability of isotopes produced by Department of Energy (DOE)- funded accelerators will continue to depend on adequate operating budgets for the Los Alamos and Brookhaven physics facilities, which permit parasitic isotope production activities. However, both producers and radioisotope users generally agree about the need for a dedicated accelerator facility to meet the researchers' demands for Fig. 8.4. An operator uses remote manipulators in a Mot short-lived isotopes. In response to this need, cell to perform a radioisotope-recovery process.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 93 Division Facilities and Laboratories

Mass Spectrometry Facilities Special Ionization Techniques At the AWRDF, isotopic analysis of actinides (for example, uranium, plutonium, Jose A. Olivares americium, and neptunium) are performed on a regular basis for the weapons diagnostics The Division's main mass spectrometry program, environmental assessment programs, facilities are operated by Group INC-7 and are and safeguards projects. We regularly analyze located at Site TA-48. The Weapons Diagnostic actinides by TIMS after chemistry is Instrumentation and Development Building performed for sample clean-up and (WDID) houses two mass spectrometers (one preparation. The sample analysis procedure single and one double sector) that are used for developed by INC group members70 can detect resonance ionization (RIMS), thermal as few as 105 atoms of certain nuclides and ionization (TIMS), and deuteromethane gas determine isotopes of particular elements by analysis mass spectrometry. There are also two using no more than 108 atoms. During these high-power argon continuous-wave lasers as procedures, the actinides are electroplated well as three wavelength-selective dye lasers. onto a rhenium thermal ionization filament and are coated with . The platinum The Advanced Weapons Radiochemical serves as a diffusion layer for the sample Diagnostics Facility (AWRDF) contains 11 clean- atoms and provides an increased ionization room chemistry laboratories and 7 clean-room efficiency (atoms detected to atoms loaded) instrument laboratories. This building has been approaching 1%. occupied for 2 years and instruments are still being moved into the facility from an older We perform technetium isotopic analysis laboratory area in another building. The new for geochemical, environmental, and clean-room laboratories currently contain four radionuclide migration projects. In addition, single-magnetic-sector mass spectrometers for TIMS and one 3.5-in. Nier-design Mattauch- we use a unique detector for solar neutrino Herzog geometry mass spectrometer. production. In this experiment, INC's Instrumentation now being built in the scientists have been able to detect as few as 108 atoms of 98Tc and 97Tc in 107 kg of AWRDF includes a renovated 6-in. Nuclide 71 dual-detector gas analysis mass spectrometer molybdenite ore. The technetium isotopes converted for silicon isotopic analysis and are thought to have been formed by high- another double-magnetic sector for TIMS. energy solar neutrinos over the past several We also have scheduled construction of a million years. These measurements are made 10-in. Nier design Mattauch-Herzog geometry possible by using a very efficient negative mass spectrometer and an RF-quadrupole mass ionization technique that takes advantage of a spectrometer for ion source development in oxide ionization enhancer and FY1991. INC's double-sector magnetic mass spectrometers. The AWRDF was designed to minimize environmental contamination of ultralow- At the AWRDF, we also are age-dating level samples. The clean-room laboratories young (<350,000-yr) volcanic rocks by a are constructed of particulate-free, corrosion- technique that employs the naturally occurring resistant materials. Critical work areas are 238u radioactive disequilibriam in rocks and bathed by vertically flowing laminar class-100 minerals. Measured disequilibrium between filtered air (<100 particles/m3). secondary isotopes in the uranium series (234U, 230Th, and 226Ra) indicates the length The WDID and AWRDF buildings are part of time since fractionation during the magma of a special limited-access open area within generation processes. For example, although is a rare element in geologic samples, Site TA-48. The area will remain open until 72 such time as special projects determine procedures developed by INC scientists allow otherwise. This provision will allow access to us to measure radium isotopic ratios and visiting scientists, postdoctoral fellows, and abundances with high precision (1 to 2% 2am) other workers with minimal security checks. on as little as 1 to 10 fg of total radium.

94 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Division Facilities and Laboratories

Resonance Ionization Mass Spectrometry elemental analysis by employing mass The ionization of atoms by laser photons spectrometers that use glow discharge and provides a major selectivity advantage. inductively coupled plasma ion sources. These Selectivity is achieved by a two-photon technologies help retain INC's position as one of technique in which the first photon is tuned the premier mass spectrometry laboratories in to a specific resonant excited state of the atom the country and will provide a major resource while the second photon ionizes the atom. This for environmental restoration initiatives. process, used in INC's RIMS facility, allows for complete elemental selectivity for isotopic ratios in excess of 106. Enhanced ionization has also been achieved with INC's lasers. For example, using the two photon process, we have enhanced by a factor of 30 the usual signal achieved for thorium ionization. Our studies show that this improvement is currently limited by laser power. A new external laser cavity being built around the atomization filament should increase this factor by at least 1 order of magnitude before saturation out of the excited state limits the number of ions that can be formed.73

High Dynamic Range Instrumentation INC's double-sector mass spectrometers are used to measure high dynamic range isotope ratios (up to 10"8) because the inherent background caused by ion scattering is reduced in sector instruments. We plan to add a third stage of filtering to these mass spectrometers to increase their abundance sensitivity sufficiently that ratio measurements beyond the 10"9 range will be possible. This third filtering stage, now being developed, includes a deceleration lens system with or without an RF quadrupole mass spectrometer. Work at Extrel Corporation, under contract with INC Division, has already shown that an RF quadrupole by itself is capable of abundance sensitivities of 5 x 10'8. The combination of these types of mass spectrometers with sector mass spectrometers and isotope separators may well allow us to measure ratios in the 10"12 range—approaching measurements that are possible now only by using very complex and scarce accelerator-based mass spectrometers.

New Directions in Mass Spectrometry New efforts in mass spectrometry will include the development of high-current ion sources. These sources, which include microwave and surface ion sources, should make it possible to increase the precision and accuracy of high-abundance measurements. We also plan to add analytical techniques in

Isotope and Nuclear Chemistry Division Annual Report FY 1990 95 APPENDIX

Division Personnel

Advisory Committee

Program Appendix: Division Personnel

Division Personnel * Gregory J. Kubas Laboratory Fellow Jiri Kubicek INC-DO (667-4457) Eloise A. Margiotta Buildings RC-29 and 34, TA-48 * Michael W. Mather Raymond C. Medina * Alexander J. Gancarz, Jr. Valerie D. Ortiz Division Leader Katherine L. Salgado * Alfred P. Sattelberger * Nancy N. S. Sauer Deputy Division Leader * Louis A. Silks, III Elizabeth A. Strietelmeier * Bruce R. Erdal * Paul H. Smith Technical Coordinator Penelope A. Springer Barbara J. Anderson * Basil I. Swanson Joann W. Brown Section Leader Marjorie M. Daniels *CarletonD. Tait Audrey L. Giger * Clifford J. Unkefer Janey Headstream William E. Wageman Jody H. Heiken * William H. Woodruff * Sara B. Helmick Laboratory Fellow S. Kathleen Kelly Jerilyn S. Mosso * Edward S. Patera Project Leader INC-5 (667-4151) Cathy Schuch Omega Site, TA-2 * Donald L. Hull Group Leader INC-4 (667-6045) Buildings 3 and 150, TA-21 * David L Finnegan * Sammy R. Garcia * Robert R. Ryan Michael D. Kaufman Group Leader * Michael M. Minor * Pat J. Unkefer Janet S. Newlin Deputy Group Leader * Gerald F. Ramsey t Thomas C. Robinson Lorraine Abney t Michael P. Wheeler * Stephen F. Agnew * James R. Brainard * Carol J. Burns Section Leader INC-7 (667-4498) * C. Thomas Buscher Radiochemistry Building, TA-48 Douglas G. Eckhart Deborah S. Ehler * David B. Curtis Scott A. Ekberg Group Leader * Phillip G. Eller * Robert W. Charles Camille D. Faucette Deputy Group Leader * James A. Fee Section Leader Ruben D. Aguilar * John R. Fitzpatrick Hong T. f Eduardo Garcia Joseph C. Banar Kathleen Gorman-Bates Gregory K. Bayhurst John L. Hanners * Timothy M. Benjamin * Scott Kinkead * Ernest A. Bryant Section Leader t John H. Cappis * Clarence J. Duffy * June T. Fabryka-Martin * Staff Member * Bry

98 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Division Personnel

* Allen S. Mason t Maureen A. Flynn * Arend Meijer * Malcolm M. Fowler * Charles M. Miller Jose B. Garcia Project Leader Michael G. Garcia * Terrence Morgan * Russell E. Gritzo * Eugene J. Mroz Virginia T. Hamilton Michael T. Murrell * Richard C. Heaton ; Allen E.Ogard Section Leader * Jose A. Olivares Allen N. Herring II * Richard E. Perrin * David E. Hobart Section Leader David C. Jamriska *JanePoths Marcella L. Kramer Eddie L. Rios Robert M. Lopez Alice M. Rodriguez Carla E. Lowe * Pamela Z. Rogers * Michael R. Maclnnes * Donald J. Rokop Sixto Maestas Technical Coordinator M. Lorraine Martinez C. Elaine Roybal Lisa M. McCurdy * Norman C. Schroeder Gail J. McFarlane firma Sharpnack * Janet Mercer-Smith Henrietta Tixier Section Leader * Kurt Wolfsberg * Geoffrey G. Miller Section Leader Alan J. Mitchell Jane C. Zongker * David C. III * David E. Morris Thomas A. Myers * Hain Oona INC-11 (667-4546) * Charles J. Orth Radiochemistry Building, TA-48; Laboratory Fellow LAMPF Building, TA-53 Martin A. Ott Loretta F. Olivas * William R. Daniels Phillip D. Palmer Group Leader * Dennis R. Phillips * Eugene J. Peterson Frederick R. Roensch Deputy Group Leader Matthew J. Roybal * Kimberly W. Thomas * Robert S. Rundberg Deputy Group Leader Raymond G. Schofield Richard C. Staroski * Kent Abney * Zita V. Svitra * Moses Attrep * Wayne A. Taylor Phyllis L. Baca * Joseph L. Thompson Raquel A. Beatty * Inez R. Triay M. Romayne Betts Frank O. Valdez Roland A. Bibeau * David J. Vieira Melanie Blain Team Leader * Scott M. Bowen * Jerry B. Wilhelmy * Timothy P. Burns Laboratory Fellow Gilbert W. Butler * Jan M. Wouters Section Leader Kathleen Wright * Edwin P. Chamberlin * Mary Anne Yates Section Leader Michael R. Cisneros * David L. Clark * David D. Clinton Laboratory Associates * Dean A. Cole Joy Drake * Donald W. Barr, INC-DO * Deward W. Efurd * Merle E. Bunker, INC-5 Section Leader Ruth Capron, INC-4 Joel E. Farnham * Bruce J. Dropesky, INC-DO

Isotope and Nuclear Chemistry Division Annual Report FY 1990 99 Appendix: Division Personnel

* George P. Ford, INC-11 • Lori VanderSluys, INC-4 Carmen Geoffrion, INC-11 Karen Velarde, INC-4 * Sylvia D. Knight, INC-11 Shannon Wells, INC-11 Marjorie E. Lark, INC-11 * Francine O. Lawrence, INC-11 Joe Montoya, INC-4 Frank Newcom, INC-5 Undergraduate Assistants * John W. Starner, INC-5 * Paul Wagner, INC-11 Elizabeth Behrena, INC-4 * Herbert Williams, INC-5 Heather Bogenholm, INC-11 t David Yandell, INC-11 Alison R. Cartwright, INC-11 John A. Davis, INC-11 t Lynda S. Halloran, INC-DO William D. Hill, INC-11 Postdoctoral Appointees Lillian Hinsley, INC-DO Jeannie S. Holterman, INC-4 Kimberly A. Bagley, INC-4 Jason M. Kritter, INC-4 John M. Berg, INC-11 Samuel P. Larson, INC-11 Jeffrey C. Bryan, INC-4 Daniel S. Lyons, INC-4 Paul R. Dixon, INC-7 Darren Meadows, INC-4 Robert J. Donohoe, INC-4 Craig A. Milroy, INC-11 Stephen K. Doom, INC-4 David A. Nix, INC-11 f Benjamin Hay, INC-4 Bridgett Peacock, INC-DO t Sara C. Huckett, INC-4 Sophie Pynn, INC-11 Stephen G. Johnson, INC-7 Michael Taylor, INC-11 DeQuan Li, INC-4 Emerson Tongco, INC-11 Warren A. Oertling, INC-4 Jill L. Wilson, INC-4 Louis D. Schulte, INC-11 David C. Smith, INC-4 Page 0. Stoutland, INC-4 Kristene Surerus, INC-4 Undergraduate Interns Andreas Toupadakis, INC-4 Alan M. Volpe, INC-7 t Lori Green, INC-DO John Watkin, INC-11 Patricia L. Mixon, INC-DO David R. Wheeler, INC-4 t Natalie Stroud, INC-DO Laura A. Worl, INC-4 t Scott Thompson, INC-DO tJeanY. Yang, INC-11 Summer Teacher Leonard R. Quintana, INC-11 Undergraduate Co-op Students Graduate Research Assistants William H. Straight, INC-7 John R. VanMarter, INC-11 Amy Brumbaugh, INC-11 t Stephanie T. Chacon, INC-4 t Lynda Descheemaeker, INC-DO f Thomas Duran, INC-4 High School Co-op Students Tracey M. Frankcom, INC-4 Rowena R. Gibson, INC-4 Ray G. Danen, INC-11 Alexander Judy, INC-4 Anne M. Gary, INC-DO f Theresa A. Miller, INC-7 t Bradley Giles, INC-4 John A. Musgrave, INC-7 Jeannie S. Holterman, INC-4 Janet Nelson, INC-4 Jonathan M. Jones, INC-DO Sherry Newmyer, INC-11 Jason M. Kritter, INC-4 Sean D. Reilly, INC-4 Bridgett Peacock, IXC-DO Mary Stenger, INC-4 Alicia Reagan, INC-5 Hardy Siefert, INC-11 T Leslie D. Sandoval, INC-4

100 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Advisory Committee

Advisory Cort'mittee

Committee Chairman

(1988-1990) Prof. Gordon E. Brown, Jr. Department of Geology Stanford University Stanford, CA 94305-2115

Committee Members

(1985-1990) Prof. Harry B. Gray Chemistry 127-72 California Institute of Technology Pasadena, CA 91125

(1989-1991) Prof. Gary M. Hieftje Department of Chemistry A169 Chemistry Bldg. Indiana University Bloomington, IN 47405

(1986-1990) Prof. Heinrich D. Holland Dept. of Earth and Planetary Sciences Harvard University Cambridge, MA 02138

(1987-1990) Prof. Anthony Turkevich Enrico Fermi Institute The University of Chicago 5630 Ellis Avenue Chicago, IL 60637

(1990-1995) Prof. Joan S. Valentine Dept. of Chemistry and Biochemistry University of California, Los Angeles 405 Hilgard Avenue Los Angeles, CA 90024-1569

(1984-1990). Prof. George E. Walker Dean of Research Work and Development Department of Physics Swain West 233 Indiana University Bloomington, IN 47405

Isotope and Nuclear Chemistry Division Annual Report FY 1990 101 Appendix: Program Funding

Program Funding

FY 1990 Funding Profile Operating $ 29.8 M Capital $ 1.7 M Total $31.5M

Defense Programs

Civilian Radioactive Waste Management

Energy Research OBES 6% OHER 5% OHENP 3%

Laboratory R&D

Work for Others DOE 6% NIH 5% DoD 3% Other 2%

102 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Program Funding

Project Principal Investigator $K WEAPONS CHEMISTRY

Test Operations (DOE/DP) CM. Miller 7785.8 Sunburn (DIA) M.R. Maclnnes 351.7 NDEV Test (DOE/DP) CM. Miller 243.0 LANL Staff Support/Off-Site (DOE/DP) A.E. Ogard 182.5 Photon Burst Technology (ISR) B.L. Fearey 127.5 Photon Burst Mass Spectrometry (DOE/DP) B.L. Fearey 126.4 Test Analysis I (DoD) M.R. Maclnnes 96.3 High Explosive Technology (DOE/DP) B.I. Swanson 94.0 Advanced Weapons Engineering (DOE/DP) R.R. Ryan 92.3 WFO (DOE/NVOO) CM. Miller 82.1 Weapons Physics (DOE/DP) CM. Miller 80.0 Replacement Parts for Mass Spectrometers (WSRC) R.E. Perrin 71.0 Special Projects (DOE/DP) B.I. Swanson 65.7 Test Analysis II (DoD) M.R. Maclnnes 48.2 International Safeguards (DOE/DP) R.E. Perrin 41.1 Current Weapons (DOE/DP) A.P. Sattelberger 25.0 Multiple-Station Plating Apparatus (NBL) R.E. Perrin 12.0 Directed Energy VI (DOE/DP) CM. Miller 7.0 Scientific Review Committee (LLL) D.W. Barr 5.0 Magnet Support for Mass Spectrometers (WSRC) R.E. Perrin 4.5 9541.1 ENVIRONMENTAL CHEMISTRY

Yucca Mountain Project (DOE/OCRWM) E.S. Patera 4075.9 Technical Support (RFP) B.R. Erdal 689.0 Hydrology Radionuclide Migration (DOE/NVOO) J.L. Thompson 652.9 Bacterial Degradation of Contamination (DoD) P.J. Unkefer 203.6 Rocky Flats Support (RFTO) R.R .Ryan 129.0 Methylthropic Bacteria Metabolism (DOE/OBES) C.J. Unkefer 105.0 Bacterial Sequestering Agents/Actinides (ISR) P.J. Unkefer 99.7 Bacterial Degradation of Explosives (ISR) P.J. Unkefer 90.0 Technical Support/Off-Site (RFP) D.C. Moody 90.0 Halogens in the Stratosphere (ISR) E.J. Mroz 81.0 Intelligent Process Technologies (ISR) E.J. Peterson 65.0 ER RCRA/CERCLA Assessment (DOE/DP) P.G. Eller 56.0 WM Treatment (DOE/DP) N.C. Sauer 54.8 ER RCRA/CERCLA Assessment (DOE/DP) D.L. Finnegan 50.0 Energy Technology Program Office (Indirect) B.R. Erdal 50.0 Safety Assessment for Rocky Flats (RFP) L.F. Brown 44.7 Plutonium Recovery Project (EGG/RF) J.R. Fitzpatrick 40.0 Global Climate Change (ISR) E.J. Mroz 30.0 Radiochemistry Analysis Evaluation (EGG/RF) D.W. Efurd 30.0 Advanced Models for Global Change (DOE/OHER) E.J. Mroz 23.0 WM Disposal (DOE/DP) N.C. Sauer 22.0 RFP RN Air Sampling Assessment (EGG/RF) E.J. Mroz 20.0 HSE Environmental Support (Indirect) N.C. Sauer 11.0 Health Physics (DOE/DP) J.C. Zongker 7.5 Director Management and Administration (Indirect) B.R. Erdal 6.0 Atmospheric/Climate (IGPP) J. Fabryka-Martin 6.0 Director Postdoc Subsidy (Indirect) 54.5 6786.6

Isotope and Nuclear Chemistry Division Annual Report FY 1990 103 Appendix: Program Funding

Project Principal Investigator $K ACTINIDE AND TRANSITION METAL CHEMISTRY

Process Technology Development (DOE/DP) P.G. Eller 476.7 Transition Metal Mediated Reactions (DOE/OBES) G.K. Kubas 372.0 Main Group Element Chemistry (ISR) A.P. Sattelberger 225.0 Actinide Organometallic Chemistry (DOE/OBES) A. P. Sattelberger 206.0 DSO Soft Kill Program (DoD) A. P. Sattelberger 178.4 Molecular Receptors for Actinides (ISR) P.H. Smith 175.0 Metal Complex Models for Hydrogen Uptake (ISR) G.K. Kubas 162.0 ERD/Valence Chemistry Transuranics (ISR) P.G. Eller 145.0 Actinides in Near Neutral Solutions (DOE/OBES) D.E. Hobart 145.0 Metal Production (DOE/DP) P.G. Eller 96.0 Energy Conversion by Inorganic Photodynamics (ISR) W.H. Woodruff 94.0 Superacid Neutralization of Sea Mines (DoD) S.A. Kinkead 65.5 New High Energy Oxidizer Systems (DoD) S.A. Kinkead 14.2 Director Postdoc Subsidy (Indirect) 21.5

2376.3

GEOCHEMISTRY

Geochemistry - INC (DOE/OBES) D.R. Janecky 802.9 Data Base Review (DoD) A.S. Mason 272.5 Contaminant Reaction Chemistry (DOE/OHER) P.G. Eller 168.1 Plutonium Geochemistry (ANSTO) D.B. Curtis 102.8 Nuclear Chemistry Support (DoD) K. Wolfsberg 80.0 Elemental Abundances (NASA) C.J. Orth 77.1 Anomalies in Geologic Record (ISR) C.J. Orth 76.0 U-Th Disequilibrium Geochronology (ISR) B.L. Fearey 61.5 Advanced Concepts - INC (DOE/OBES) D.R. Janecky 49.1 Cation Exchange (ISR) R.S. Rundberg 40.0 Advanced Oil Recovery Technology (ISR) R.W. Charles 25.0 Mini Grant Research (IGPP) C.J. Orth 15.0 Mini Grant Research (IGPP) J. Poths 12.0 DIR-Navajo Assistance (Indirect) R.W. Charles 10.0 Mini Grant Research (IGPP) D.R. Janecky 9.0 Analysis of Long Duration Exposure (NASA) G.W. Butler 4.3 Professional Services (AND R.S. Rundberg 4.0 Space Plasma Physics (ISR) G.W. Butler 4.0 Director Postdoc Subsidy (Indirect) 22.9 1836.2 NUCLEAR STRUCTURE AND REACTIONS

Nuclear Chemistry Research at LAMPF (DOE/OHENP) D.J. Vieira 406.3 Solar Neutrino Flux (DOE/OHENP) K. Wolfsberg 199.0 Galium Solar Neutrino (DOE/OHENP) J.B. Wilhelmy 179.0 Sudbury Neutrino Observatory Research (ISR) J.B. Wilhelmy 175.0 Nuclear Phenomena in Metals (DOE/OBES) C.J. Orth 65.0 Director Postdoc Subsidy (Indirect) 9.4

1033.7

104 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Program Funding

Project Principal Investigator $K BIOCHEMISTRY AND NUCLEAR MEDICINE

Medical Radioisotopes (DOE/NE) E.J. Peterson 2100.0 Medical Isotopes Sales (DOE/OHER) E.J. Peterson 305.4 National Stable Isotopes Resource (NIH) J.A. Fee 827.8 Medical Eadioisotopes Research (DOE/OHER) J.A. Mercer-Smith 611.2 Imaging Agents for Lymph Nodes (DOE/OHER) D.A. Cole 318.8 Mechanisms in Respiration (NIH'i J.A. Fee 305.2 Chemistry of Radiopharmaceuticals (ISR) J.A. Mercer-Smith 249.0 Vibrational Spectroscopy (NIH) W.H. Woodruff 216.0 Superoxide Dismutasis (NIH) J.A. Fee 148.6 New Biomedical Generators (DOE/OHER) D.R. Phillips 148.5 Structure-Function Correlation in Signal Peptides (ISR) J.R. Brainard 93.0 Neutron Scattering Studies (ISR) J.A. Fee 50.0 Preservation of Transfused Red Blood Cells (DoD) T. Yoshida 48.8 Novel Fluorine Probe Flow Cytometry (ISR) J.A. Fee 40.0 Biomedical Research Support (NIH) J.A. Fee 15.9 Small Equipment Grant (NIH) J.A. Fee 7.5 Director Postdoc Subsidy (Indirect) 51.0

5536.7 MATERIALS

Conducting Polymers as Synmetals (DOE/OBES) B.I. Swanson 201.0 Chemistry of Shocked Energetic Materials (ISR) B.I. Swanson 170.0 Mixed Valence Solids (ISR) B.I. Swanson 128.0 Electronic and Nonlinear Optical Material (ISR) C.J. Burns 100.0 CMS Interdisciplinary Research (ISR) B.I. Swanson 80.0 ERD/HTSC Structure-Function (ISR) R.R. Ryan 75.0 ERD/RTES to Films and Protect Coating (ISR) N.C. Sauer 75.0 Chemistry of Reacting He (DoD) B.I. Swanson 70.1 In-Situ Chemical Sensor Applications (ISR) P.H. Smith 50.0 Fiber Optics Sensors (IGPP) M.M. Murrell 5.0 Director Postdoc Subsidy (Indirect) 8.7

962.8 MAJOR FACILITIES

Special Projects - OWR (DOE/DP) D.L. Hull 662.5 Special Projects - TSA (DOE/DP) D.L. Hull 607.0 Omega West Reactor (Indirect) D.L. Hull 350.0 Irradiation Services (Various) D.L. Hull 34.7 Nitrogen-14 Product (Mound) J.R. Fitzpatrick 4.0 1658.2

Division Total 29 731.6

Isotope and Nuclear Chemistry Division Annual Report FY 1990 105 Appendix: Publications

PUBLICATIONS R.J. Donohoe, CD. Tait, and Basil I. Swanson, "Resonance Raman Evidence for Electron and INC-4 Hole Defect Asymmetry in the Quasi-one- dimensional Mixed-valence Solid [PtIJ(en)2] S.F. Agnew and B.I. Swanson, "A New Model [PtIV(en)2Cl2][ClO4]4 (en = ethylenediamine)," for Pressure-Induced Shifts of Electronic Chem. Mater. 2(3), 315-319 (1990). Absorption Bands as Applied to Neat CS2 and CS2 in h-hexane and Dichloromethane Solutions," Juergen Eckert, Gregory J. Kubas, John H. Hall, J. Phys. Chem. 94(2), 995-1002 (1990). P. Jeffrey Hay, Caroline M. Boyle, "Molecular Hydrogen Complexes. 6. The Barrier to Rotation 2 S.P. Armes, M. Aldissi, S. Agnew, and of TI -H2 in M(CO)3(PR3)2(n2-H2) (M = W, Mo; S. Gottesfeld, "Synthesis and Characterization R = Cy, i-Pr): Inelastic Neutron Scattering, of Aqueous Colloidal Dispersions of Poly( Vinyl Theoretical, and Molecular Mechanics Studies," AlcohoD/Polyaniline Particles," Mol. Cryst. Liq. J. Am. Chem. Soc. 112(6), 2324-2332 (1990). Cryst 190, 63-74 (1990). R.D. Fulton, R.R. Ryan, and J.H. Hall, Mahfoud Belhadj, John M. Jean, Richard A. "Structure of Acid Phthalate," Ada Friesner, John Schoonover, and William H. Crystallogr., Sect. C: Cryst, Struct. Commun. Woodruff, "Theoretical Analysis of Resonance C46(9), 1621-1622 (1990). Raman Spectra from the Blue Copper Protein Azurin," J. Phys. Chem. 94(5), 2160-2166 (1990). J. Gammel Tinka, R.J. Donohoe, A.R. Bishop, and B.I. Swanson, "Electron and Hole Polaron J.R. Brainard, "Applicability of Biodegradation Asymmetry in a Two-band Peierls-Hubbard for Treatment of LDR Wastes at Rocky Flats Material," Phys. Rev. B: Condens. Matter, Plant, Golden, Colorado," Los Alamos Technology 42(16-B), 10566-10569 (1990). Office, EGG-RFP report (September 30,1990). A.A. Gonzalez, K. Zhang, S.L. Mukerjee, J.R. Brainard and G.A. Rosenberg, CD. Hoff, G. Rattan, K. Khalsa, and "7-Aminobutyric Acid Formation from Glucose: G.J. Kubas, "Thermodynamic and Kinetic Metabolic Pathway," J. Neurochem. 55(1), Studies of Binding Nitrogen and Hydrogen to 353-354 (1990). Complexes of Chromium, Molybdenum, and Tungsten," ACS Symp. Ser, Bonding Energ. J.R. Brainard, B.A. Strietelmeier, P.H. Smith, Organomet. Compd. 428,133-147 (1990). P. J. Langston-Unkefer, and R.R. Ryan, "Chelator-Enhanced Dissolution of Plutonium B.P. Hay and A.P. Sattelberger, "Synthesis, Oxyhydroxides," Los Alamos Technology Office, Characterization, and Electron-transfer EGG-RFP report (September 30,1990). Reactivity of Norbornyl Complexes of Cobalt in unusually High Oxidation States," Inorg. Chem. C.J. Burns, W.H. Smith, John C. Huffman, and 2(2), 130-133 (1990). A. P. Sattelberger, "Uranium(VI) Organoimido Complexes," J. Am. Chem. Soc. 112(8), 3237- G. Khalsa, K. Rattan, G.J. Kubas, C. J. Unkefer, 3239 (1990). L.S. Van der Sluys, K.A. Kubat-Martin, "Molecular Hydrogen Complexes of the D.T. Cromer, R.R. Ryan, S. Kathikeyan, and Transition Metals. 7. Kinetics and Thermo- R.T. Paine, "Structure Studies of Uranyl dynamics of the Intercon version between Complexes of Diphenyl-Dimethyl Aminosul- Dihydride and Dihydrogen Forms of finylmethyl Phosphine Oxide and Diisopropyl- W(CO)3(PR3)2H2 where R = Isopropyl and Tolylsulfmylmethyl Phosphonate Ligands," Cyclopentyl," J. Am. Chem. Soc. 112(10), Inorganica Chimica Ada 172(2), 165-172 (1990). 3855-3860 (1990).

J.T. Dickenson, L.C. Jensen, S.C. Langford, E.M. Larson, F.W. Lytle, P.G. Eller, R.B.Greegor, R.R. Ryan, and E. Garcia, "Fracto-emission from M.P. , and J. Wong, "XAS Study of Deuterated Titanium: Supporting Evidence for Lanthanide Ion Speciation in Borosilicate a Fracto-Fusion Mechanism," J. Mater. Res. Glass," J. Non-Cryst. Solids, 06(1), 57-62 5(1), 109-122 (1990). (1990).

106 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Publications

M.W. Mather and J.A. Fee, "Plasmid-associated Phosphide Complexes. Implications for Aggregation in Thermus thermophilus HB8," Organolanthanide Bonding and Reactivity," Plasmid 24(1), 45-56 (1990). Inorg. Chem. 2(1), 38-41 (1990).

M.W. McElfresh, J.H. Hall, R.R. Ryan, A.P. Sattelberger, "Organorhenium Imido J.L. Smith, and Z. Fisk, "Structure of the Heavy- Complexes: Syntheses, Structure and Fermion Superconductor Uranium- Reactivity," Inorg. Chem. 2(3), 273-276 (1990) (UBe13)," Ada Crystallogr., Sect. C: Cryst, Struct. Commun. C46(9), 1579-1580 (1990). N.N. Sauer, E. Garcia, and R.R. Ryan, "Soluble and Volatile Precursors for the Preparation of D.E. Morris, CD. Tait, R.B. Dyer, Superconducting Films," in Better Ceramics J.R. Schoonover, M.D. Hopkins, Through Chemistry IV, B.J.J. Zelinski, A. P. Sattelberger, and W. H. Woodruff, C.J. Brinker, D.E. Clark, and D.R. Ulrich, Eds., "Spectroscopy and Structure of Quadruply (Materials Research Society, Pittsburgh, Bonded Complexes under Extreme Pressure Pennsylvania, 1990), Vol. 180, pp. 921-924. (Re2X82-, Mo2C14(PMe3)4)," Inorg. Chem. 29(18), 3447-3452 (1990). N.N. Sauer E. Garcia, K.V. Salazar, R.R. Ryan, and J. A. Martin, "Isolation and Structural E.C. Niederhoffer, CM. Naranjo, K.L. Bradley, Characterization of the Copper-Barium-Alkoxide and J. A. Fee, "Control of Escherichia coli Cluster Ba2Cu2(OR)4(acac)4«2HOR (R = Superoxide Dismutase (sodA and sodB) Genes CH2CH2OCH3) from Precursor Solutions to by the Ferric Uptake Regulation (fur) Locus," YBa2Cu307 Thin Films," J. Am. Chem. Soc. J. Bacterial. 172(4), 1930-1938 (1990). 112(4), 1524-1528 (1990).

J.B. Nielsen, S.A. Kinkead, and P.G. Eller, N.N. Sauer, and R.A. Penneman, "Rocky Flats "A New Synthesis of Xenon Oxytetrafluoride NOX Abatement Project Final Report," Los (XeOF4)," Inorg. Chem. 29(18), 3621-3622 (1990). Alamos Technology Office, EGG-RFP report, (September 30,1990). J.B. Nielsen, S.A. Kinkead, J.D. Purson, and P.G. Eller, "New Syntheses of Xenon D.C. Smith, S.G. Pattillo, N.E. Elliott, Hexafluoride (XeF6) and Xenon Tetrafluoride," T.G. Zocco, C.J. Burns, J.R. Laia, and Inorg. Chem. 29(9), 1779-1780 (1990). A.P. Sattelberger, "Low-temperature Chemical Vapor Deposition of Rhodium and Iridium Thin Robert A. Penneman and Roger A. Mead, Films, Mater. Bes. Soc. Symp. Proc., 168 (Chem. Vap. "Contributions of Chemistry in Early Day Deposition Refract. Met. Ceram.), 369-374 (1990). Los Alamos," American Chemical Society, Washington, DC (1990). P.H. Smith, L.D. Schulte, K.D. Abney, J. Mercer-Smith, D.S. Ehler, and R.R. Ryan, S.D. Reilly, C.F.V. Mason, and P.H. Smith, "Stabilization of Cadmium in Pond Sludge and "Cobalt(III) Dicarbollide: A Potential Cesium- Pondcrete," Los Alamos Technology Office, 137 and Strontium-90 Waste-Extraction Agent," EGG-RFP report (September 30,1990). Los Alamos National report, LA-11695 (1990). L.S. Van der Sluys, J. Eckert, O. Eisenstein, J.H Hall, J.P. Ritchie, K.-Y. Lee, D.T. Cromer, E.M.Kober, J.C. Huffinan, S A Jackson, T.F. Kbetzle, G. J. Kubas, and D.D. Lee, "Shape Selection in the R J. Vergamini, and KG. Caulton, "An Attractive cis- Association of Diaminoguanidinium Cation with effect of Hydride on Neighbor Iigands: Experimental Counterions," J. Org. Chem. 55,1994-2000 and Theoretical Studies on the Structure and (1990). Intramolecular Rearrangements of F^H^Cn2- H2XPEtPh2)3," J. Am. Chem. Soc. 112(12), A. P. Sattelberger, "Organo-f-element Thermo- 4831-4841 (1990). chemistry. Absolute Metal-Ligand Bond Disruption Enthalpies in Bis(pentamethylcyclo- W.G. Van der Sluys and A.P Sattelberger, pentadienyl)-samarium Hydrocarbyl, Hydride, "Actinide Alkoxide Chemistry," Chem. Rev. Dialkylamide, Alkoxide, Halide, Thiolate, and 90(6), 1027-1040 (1990).

Isotope and Nuclear Chemistry Division Annual Rvpoi-t FY 1990 107 Appendix: Publications

W.G. Van der Sluys, A.P. Sattelberger, and Electronic and Atomic Collisions (Sixteenth M.W. McElfresh, "Uranium Alkoxide Chemistry. International Conference on the Physics of V. Synthesis. Characterization and Inter con- Electronic and Atomic Collisions Abstracts of version of Ur.'Jiium(IV) Tert-butoxide Complexes," Contributed Papers, New York, New York, USA, Polyhedron 9(15-16), 1843-1848 (1990). 26 July-1 August, 1989) A. Dalgarno, R. S. Freund, M. S. Lubell, and T. Lucatorto, C. Varotsis, W.H. Woodruff, and G.T. Babcock, Eds. (North-Holland Physics, Amsterdam, The "Time-resolved Raman Detection of |i(Fe-O) in Netherlands, 1989), p. 18. an Early Intermediate in the Reduction of Pxygen by c Cytochrome Oxidase," J. Am. J.S. Gaffney, N.A. Marley, and D.R. Janecky, Chem. Soc. 112(3), 1297 (1990). "Comment on the Dissolution of Quartz as a Function of pH and Time at 70°C," Geochim. C. Varotsis, W.H. Woodruff, and G.T. Babcock, Cosmochim. Ada 53,1469-1470 (1989). "Direct Detection of a Dioxygen Adduct of Cytochrome a3 in the Mixed Valence R.D. Loss, K.J.R. Rosman, J.R. DeLaeter, Cytochrome Oxidase/Dioxygen Reaction," D.B. Curtis, T.M. Benjamin, A.J. Gancarz, J. Biol. Chem. 265(19), 11131-11136 (1990). W. J. Maeck, and J.E. Delmore, "Fission-Product Retentivity in Peripheral Rocks at the Oklo T. Yoshida and M. Dembo, "A Thermodynamic Natural Fission Reactors, Gabon," Chem. Geol. Model of Hemoglobin Suitable for Physiological 76, 7184 (1989). Applications," Am. J. Physiol. 258, C563-C577 (1990). N.A. Marley, P. Bennett, D.R. Janecky, and J.S. Gaffney, "Spectroscopic Evidence for Organic Diacid Complexation with Dissolved Silica in Aqueous Systems. I. Oxalic Acid," Org. INC-5 Geochem. 14, 525-528 (1989).

R.W. Morris, G.J. Taylor, H.E. Newsom, K. Keil, A.S. Mason, "Atmospheric Tritium and S.R. Garcia, "Highly Evolved and Measurements at Background Levels" Ultramafic Lithologies from Apollo 14 Soils," in Los Alamos National Laboratory report Proceedings of the 20th Lunar and Planetary LA-CP-89-36 (February 1989). Science Conference, Houston, Texas, 1989 (Lunar and Planetary Institute, Houston, Texas, P.S.Z. Rogers and C.J. Duffy, "Comparison of 1990). Calibration Methods for Flow Heat-Capacity Calorimeters and Heat Capacities of Concentrated NaCKaq) to 598 K," J. Chem. Thermodynamics 21, 595-614(1989). INC-7 J.M. Simonson, R.E. Mesmer, and P.S.Z. Rogers, M.E. Berndt, WE. Seyfried, Jr., and "The Enthalpy of Dilution and Apparent Molar D.R. Janecky, "Plagioclase and Epidote Heat Capacity of NaOH(aq) to 523 K and 40 Buffering of Cation Ratios in Mid-Ocean Ridge MPa," J. Chem. Thermodynatnics 21, 561-584 Hydrothermal Fluids: Experimental Results in (1989). and Near the Supercritical Region," Geochim. Cosmochim. Ada 53, 2283-2300 (1989). J.I. Kim, G. Buckau, E. Bryant, and R. Klenze, "Complexation of Americium(III) with Humic D.S. Burnett, D.S. Woolum, T.M. Benjamin, Acid," Radiochim. Ada 48,135-143 (1989). P.S.Z. Rogers, C.J. Duffy, and C. Maggiore, "A Test of the Smoothness of the Elemental J.N. Andrew, S.N. Davis, J. Fabryka-Martin, Abundances of Carbonaceous Chondrites," J-Ch. Fontes, B.E. Lehmann, H.H. Loosli, Geochim. Cosmochim. Ada 53, 471-481 (1989). J-L. Michelot, H. Moser, B. Smith, and M. Wolf, "The In-Situ Production of Radioisotopes in Rock B.L. Fearey, R.A. Keller, and CM. Miller, Matrices with Particular Reference to the Stripa "Multiphoton Atomic Ionization Spectroscopy Granite," Geochim. Cosmochim. Ada 53,1803- and Phenomena of Lutetium Via RIMS," in 1815(1989).

108 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Publications

J.T. Fabryka-Martin, S.N. Davis, D. Elmore, and 1989, M.S. Feld, J.E. Thomas, and P.W. Kubik, "In-Situ Production and Migration A. Mooradian, Eds. (Academic Press, Inc., of I29j jn the stripa Granite, Sweden," Geochim. Boston, Massachusetts, 1989), pp. 95-97. Cosmochim. Ada 53,1817-1823 (1989). S.J. Goldstein, M.T. Murrell, and R.W. Williams, D.R. Janecky, "Review of Simulating the Earth: "Half-Life of 229Th," Phys. Rev. C 40 (6), 2793- Experimental Geochemistry" Am. J. Sci. 289, 2795 (1989). 1206-1207 (1989). D.R. Janecky, R.M. Haymon, T.M. Benjamin, E.J. Mroz, M. Alei, J.H. Cappis, P.R. Guthals, P.S.Z. Rogers, and G.K. Bayhurst, "Microscopic A. S. Mason, and D.J. Rokop, "Detection of Distribution of Trace Elements in Minerals Multiply Deuterated Methane in the (Chlorites, Sulfides, Sulfates) in Submarine Atmosphere," Geophys. Res. Lett. 16, 677-678 Hydrothermal Systems," in Proceedings of the (1989). 6th International Symposium on Water I Rock Interaction, D L. Miles, Ed. (Balkema, D.J. Rokop, N.C. Schroeder, and K. Wolfsberg, Rotterdam, Netherlands, 1989), pp. 327-330. "High Sensitivity Technetium Analysis Utilizing Negative Thermal Ionization Mass Spectro- S.J. Goldstein, M.T. Murrell, and D.R. Janecky, metry," in Advances in Mass Spectrometry, "Dating Young Morb from Juan de Fuca & Proceedings of the 11th International Mass Gorda Ridges by 238u_230rh Disequilibrium," Spectrometry Conference held at Bordeaux, 29 Trans. Am. Geophys. Union (EOS) 70 (43), 1160 August-2 September 1988, P. Longevialle, Ed. (1989). (Heyden & Son Ltd, London, 1989), Vol. 11B, pp. 1788-1789. D.R. Janecky, J.T. Wells, and B.J. Travis, "Cellular Automata Calculations for Coupled S.J. Goldstein, M.T. Murrell, and D.R. Janecky, Flow and Chemical Reactions at Surfaces and in "Th and U Isotopic Systematics of Basalts from Pore Networks: Initial Results," Trans. Am. the Juan de Fuca and Gorda Ridges by Mass Geophys. Union (EOS) 70 (43), 1088 (1989). Spectrometry," Earth . Sci. Lett. 96,134- 146 (1989). A. Meijer, "U-Th-Pb Partitioning Behavior in the Upper Mantle: Implications for the Origin of A. Meijer, I. Triay, S. Knight, and M. Cisneros, High-Mu Components and the fPb Paradox',11 "Sorption of Radionuclides on Yucca Mountain Trans. Am. Geophys. Union (EOS) 70 (43), 1412 Tuffs," in Proceedings of the Topical Meeting on (1989). Nuclear Waste Isolation in the Unsaturated Zone Focus '89, September 17-21, 1989, Las T.L. Miller, W.H. Zoller, and D.R. Janecky, Vegas, Nevada (American Nuclear Society, "Elemental and Molecular Composition of La Grange, Illinois, 1989), pp. 113-117. Volatile Species in Magmatic Vapors," Trans. Am. Geophys. Union (EOS) 70 (43), 1410 (1989). G.K. Bayhurst and D.R. Janecky, "Anhydrite Solubility in Salton Sea Brine," in Proceedings E.J. Mroz and A.S. Mason, "Deuterated of the 198th National American Chemical Methane in the Atmosphere," Trans. Am. Society Meeting, Miami, Florida, September Geophys. Union (EOS) 70 (43), 1017 (1989). 10-15, 1989. A.S. Mason, "Data Base Review (Dust Cloud R.W. Charles, "Basic Research into Characterization)," Los Alamos National Environmental Issues: An Approach from Laboratory report LA-CP-89-527 (December Los Alamos National Laboratory," report 1989), p. A-5. prepared for US DOE/BES (December 1989). B.L. Fearey, D.C. Parent, R.A. Keller, and B.L. Fearey and CM. Miller, "Novel Lutetium CM. Miller, "Doppler-Free Saturation Spectroscopic Interactions Via CW Rims," in Spectroscopy of Lutetium Isotopes Via Laser Spectroscopy IX, Proceedings of the Ninth Resonance Ionization Mass Spectrometry," International Conference on Laser Spectroscopy, J. Opt. Soc. Am. B7(l), 38 (1990). Bretton Woods, New Hampshire, June 18-23,

Isotope and Nuclear Chemistry Division Annual Report FY1990 109 Appen dix: Pit blications

A. Meijer, S-T. Kwon, and G.R. Tilton, "U-Th-Pb P.S.Z. Rogers, J.M. Simonson, and R.E. Mesmer, Partitioning Behavior During Partial Melting in "Standard State and Excess Thermodynamic the Upper Mantle: Implications for the 'Pb Properties of NaOH(aq) to 573 K and 40 MPa," in Paradox' and the Origin of High Mu Com- Proceedings of the V. M. Goldschmidt Conference, ponents," J. Geophys. Res. 95 (Bl), 433-448 (1990). Baltimore, Maryland, May 24,1990 (1990).

N.S. Nogar, R.C. Estler, B.L. Fearey, A.M. Volpe and M.T. Murrell, "Measurement of CM. Miller, and S.W. Downey, "Materials 226Ra/228Ra Isotopic Ratios and Radium Analysis by Laser and ion Beam Sputtering with Abundances in Young Volcanic Rocks by Mass Resonance Ionization Mass Spectrometry," Spectrometry," in Proceedings of the Nucl. Instr. & Methods in Physics Research B V. M. Goldschmidt Conference, Baltimore, B44, 459-464 (1990). Maryland, May 24, 1990 (1990), p. 89.

C.J. Capobianco, M.J. Drake, and P.S.Z. Rogers, John Musgrave, "Precious and Base Metal Depo- "Experimental Solubilities and Partitioning sition in an Active Hydrothermal System, Sulphur Behavior of Noble Metals among Lithophile Springs Area, Valles Caldera, New Mexico," in Magmatic Phases," in Lunar and Planetary Science Program with Abstracts: Great Basin Symposium: (Lunar and Planetary Institute - Universities Space Geology and Ore Deposits of the Great Basin, Research Institute, Houston, 1990). Sparks, Nevada, April 15,1990, p. 105.

M.R. Carroll, S.R. Sutton, D. Woolum, J.A. Musgrave and D.I. Norman, "State of the K. Lewotsky, and P.S.Z. Rogers, "Kr and Xe Sulphur Springs Hydrothermal System, Valles Diffusion and Solubility in Silicate Melts and Caldera, New Mexico" PACROFI III, Abs. with Glasses," in Lunar and Planetary Science Programs (1989), p. 62. (Lunar and Planetary Institute, Universities Space Research Institute, Houston, 1990). R.A. Levich, E.S. Patera, P.M. Ferrigan, and P.L. Wilkey, "The International Stripa Project- W.M. Fairbank, Jr., R.D. Labelle, R.D. Pan, Technology from Cooperation in Scientific and E.P. Chamberlin, R.A. Keller, CM. Miller, and Technological Research on Nuclear Waste B.L. Fearey, "Ultrasensitive Isotope Analysis by Disposal," in Proceedings of the American Photon Burst Mass Spectrometry," Abstr. Pap. Nuclear Society International Conference on Amer. Chem. Soc. 199, 70-Nucl (1990). High-Level Nuclear Waste, Las Vegas, Nevada, April 8-12,1990 (1990). A.S. Mason, "Characterization of Airborne Dust," Los Alamos National Laboratory P.R. Dixon, D.M. Rye, and D.R. Janecky, "Fluid Technical Bulletin LALP-89-22 ( 1990). Flow Connections to Basement Rocks Below Sedimentary Basins: Evidence from the Base P.R. Dixon, D.R. Janecky, and D.M. Rye, "Origin Metal Deposits in Ireland," in Proceedings of of Isotopically Heavy Sulfides from the Kildare the Chapman Conference on Crustal Scale Inlier Deposits, Co., Kildare, Ireland," in Fluid Transport: Magnitude and Mechanisms, Proceedings of the V. M. Goldschmidt Conference, Snowbird, Utah, June 4-8, 1990 (1990). Baltimore, Maryland, May 24,1990 (1990). P.H. Hemberger, D.R. Janecky, and W.D. Spall, C.J. Duffy, "Low Temperature Zeolite "Field Measurement of Environmental Contam- Transformations in Tuff," in Proceedings of the inants by Ion Trap Mass Spectrometry," in V. M. Goldschmidt Conference, Baltimore, Proceedings of the Eleventh Annual Meeting of Maryland, May 24,1990 (1990). the Society of Environmental Toxicology and Chemistry (1990). M.T. Murrell, S.J. Goldstein, A.M. Volpe, B.L. Fearey, R.E. Perrin, and R.W. Williams, D.R. Janecky, B.J. Travis, G. Zyvloski, "Measurement of Long-Lived Members of the N. Rosenberg, and J.T. Wells, "3-D Numerical Uranium Decay Series by Mass Spectrometry," Models for Examining Processes in Geothermal- in Proceedings of the V.M. Goldschmidt Hydrochemical Systems," in Proceedings of the Conference, Baltimore, Maryland, May 24, 1990 (1990), p. 68.

110 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Publications

Chapman Conference on Crustal Scale Fluid E.S. Patera, D.E. Hobart, A Meijer, and R.S. Transport: Magnitude and Mechanisms, Rundberg, "Chemical and Physical Processes of Snowbird, Utah, June 4-8, 1990 (1990). Radionuclide Migration at Yucca Mountain, Nevada," J. Radioanal. Nucl. Chem. 142 (1), 331- D.J. Rokop, N.C. Schroeder, and K. Wolfsberg, 347 (1990). "Mass Spectrometry of Technetium at the Sub- Picogram Level," Anal. Chem. 62 (13), 1271- W.D. Spall, D.R. Janecky, P.R. Dixon, 1274 (1990). G.K. Bayhurst, and W.H. Straight, "A Multicomponent Tracer Experiment in E.J. Mroz, "Fingerprinting the Sources of Mammoth Hot Springs System," in Proceedings Atmospheric Methane," Los Alamos National of the Eighth Annual Yellowstone Physical Laboratory Technical Bulletin LALP-90-20 Science Symposium (1990). (June 1990). T.L. Miller, W.H. Zoller, B.M. Crowe, and R.D. Aguilar, M. Attrep, Jr., D.B. Curtis, D.L. Finnegan, "Variations in Trace Metal and J.T. Fabryka-Martin, R.E. Perrin, and halogen Ratios in Magmatic Gases through an F.R. Roensch, "Plutonium Geochemistry: Eruptive Cycle of the Pu'u O'o Vent, Kilauea, Natural Plutonium in Uranium-Enriched Rock," Hawaii: July-August 1985," J. Geophys. Res. 95 Los Alamos National Laboratory report (B8), 12607-12615 (August 1990). LA-11865-PR (June 1990). CD. Tait, D.R. Janecky, and P.S.Z. Rogers, S.M. Bowen and T.M. Benjamin, "Using "Speciation of Aqueous (II) Chloride Scandium as a Radiochemical Detector," Solutions Using Optical Spectroscopies," in Los Alamos National Laboratory report Proceedings of the Fall National Meeting of the LA-11865-PR (June 1990). American Chemical Society, Geochemistry Division, Washington, D.C., August 26-31, 1990 . D.B. Curtis, "Isotope Measurement and Production Laboratory," Los Alamos National D.R. Cole, D.B. Curtis, D.J. DePaolo, Laboratory report LA-11865-PR (June 1990). T.M. Gerlach, J.C. Laul, H. Shaw, B.M. Smith, and N.C. Sturchio, "Isotope Geochemistry: A C.J. Duffy, "Monte Carlo Simulation of the Smectite- Critical Component of Energy Research," Los Illite Transformation," Los Alamos National Alamos National Laboratory report Laboratory report LA-11865-PR (June 1990). LA-11849-MS (September 1990).

D.R. Janecky, "Geochemistry Overview," A. Meijer, "Yucca Mountain Project Far-Field Los Alamos National Laboratory report Sorption Studies and Data Needs," Los Alamos LA-11865-PR (June 1990). National Laboratory report LA-11671-MS (September 1990). A.S. Mason, D. L. Finnegan, and G.K. Bayhurst, "Characterization of the MISERS GOLD Dust S.J. Goldstein, M.T. Murrell, D.R. Janecky, Cloud," Los Alamos National Laboratory report J.R. Delaney, and D.A Clague, "Geochronology LA-11865-PR (June 1990). and Petrogenesis of MORB Using 238u230rh Disequilibrium," in Proceedings of the Seventh E.J. Mroz, "Fingerprinting the Sources of International Conference on Geochronology, Atmospheric Methane," Los Alamos National Cosmochronology, and Isotope Geology, Canberra, Laboratory report LA-11865-PR (June 1990). Australia, September 24-29,1990(1990).

D.R. Janecky, "Modeling Dynamic A. Meijer and P.S.Z. Rogers, "Pb Distribution Hydrothermal Processes by Coupling Sulfur in Ultramafic Nodules from the Upper Mantle Isotopic Distributions with Chemical Mass Beneath the Western United States," in Transfer: Approach," in Chemical Modeling in Proceedings of the Seventh International Aqueous Systems II, ACS Symposium Series, Conference on Geochronology, Cosmochronology, D.C. Melchior and R. L. Basset, Eds. (American and Isotope Geology, Canberra, Australia, Chemical Society, 1990), pp. 226-233. September 24-29, 1990(1990).

Isotope and Nuclear Chemistry Division Annual Report FY 1990 111 Appendix: Publications

A.M. Volpe and J.D. MacDougall, "Geochemistry Zone: FOCUS '89, Las Vegas, Nevada, and Isotopic Characteristics of Mafic (Phulad September 18-21, 1989 (American Nuclear Ophiolite) and Related Rocks in the Delhi Society Publication, Illinois, 1989) pp. 118-124. Supergroup, Rajasthan, India: Implications for Rifting in the Proterozoic," Precambrian D.E. Hobart, J.L. Lyman, R. Holland, G.W. Loge, Research 48 (1/2), 167-191 (1990). J. Trewhella, D.L. Clark, and A.P. Sattelberger, "Los Alamos Contribution to the Actinide Newsletter," Los Alamos National Laboratory document LA-UR-90-924 (1990). INC-11 N. Imanishi, D.J. Vieira, G.W. Butler, J.P. Bocquet, J.R. Brissot, H.R. Faust, R.S. Rundberg, and B.J. Dropesky, "Cross M.M. Fowler, J.B. Wilhelmy, M. Asghar, and Section Measurements of the Pion Single- M. Djebara, "Characteristics of Mass and Charge-Exchange Reaction i2C(n+,Ji°)12N(g.s.)," 229 Nuclear Charge Distributions of Th(nth,f), Phys. Rev. C 42,1061-1067 (1990). Implications for Fission Dynamics," Zeitschrift furPhysik A335, 41 (1990). J. Kleinberg, "Collected Radiochemical and Geochemical Procedures—FlAh Edition," Los D.A. Cole, J.A. Mercer-Smith, J.K. Norman, Alamos National Laboratory report, LA-1721 S.A. Schreyer, K.P. Bullington, J.C. Roberts, and (1989). D.K. Lavallee, "Copper-67 Labeled Porphyrin Localization," Advances in Experimental D.E. Morris, D.E. Hobart, P.D. Palmer, Medicine and Biology 258, 259-272 (1990). R.G. Haire, and J.R. Peterson, "Voltammetric Investigation of the (IV/III) Couple in D.A. Cole, J.A. Mercer-Smith, S.A. Schreyer, Concentrated Aqueous Carbonate Solutions," J.K. Norman, and D.K. Lavallee, "The Biological Radiochim. Acta 49,125-134 (1990). Characteristics of a Water Soluble Porphyrin in Rat Lymph Nodes," Nucl. Med. Biol, Int. J. J.B. McClelland and D.J. Vieira (compilers), Radiat. Appl. lustrum. B 17, 457-464 (1990). "Proc. of the Workshop on the Science of Intense Radioactive Ion Beams," Los Alamos National X. Feng, R.J. Estep, and B.J. Dropesky, "Cross Laboratory Conference report LA-11964-C Section for the 27Al(p,27t+)28Mg Reaction at 800 (April 10-12,1990). MeV," Phys. Rev. C 42, 451-452 (1990). J.A. Mercer-Smith, D.A. Cole, J.C. Roberts, M.M. Fowler, S.B. Larson, and J.B. Wilhelmy, D. Lewis, M.J. Behr, and D.K. Lavallee, "The "Neutral Current Detector Development Biodistribution of Radiocopper-Labeled Progress," Los Alamos National Laboratory Compounds," Advances in Experimental document LA-UR-90-3107 (1990). Medicine and Biology 258103-121 (1990).

M.M. Fowler and J.B. Wilhelmy, "Th and U M.N. Namboodiri, H.C. Britt, D.J. Fields, Measurements in Acrylic," Los Alamos National L.F. Hansen, R.G. Lanier, D. Massoletti, Laboratory document LA-UR-90-3108 (1990). B.A. Remington, T.C. Sangster, G.L. Struble, M.L. Webb, M. Begemann-Blaich, T. Blaich, D.E. Hobart, D.E. Morris, P.D. Palmer, M.M. Fowler, J.B. Wilhelmy, Y.D. Chan, R.G. Haire, and J.R. Peterson, "Spectroscopic A. Dacal, A. Harmon, J. Pouliot, R. Stokstad, and Redox Properties of Berkelium in S. Kaufman, F. Videbaek, Z. Fraenkel, Nuclear Complexing Aqueous Carbonate and Citrate Dynamics and Nuclear Disassembly, Solutions," Radiochim. Ada 49,119-124 (1990). J. B. Natowitz, Ed., (World Scientific, Singapore, 1989) p. 449. D.E. Hobart, D.E. Morris, P.D. Palmer, and T.W. Newton, "Formation Characterization, and D.A. Nix and J.B. Wilhelmy, "A Deuteron-Triton Stability of Plutonium(IV) Colloid: A Progress Colliding-Beam Fusion Reactoi\" Los Alamos Report," Proceedings of the Topical Meeting on National Laboratory dokcument LA-UR-90-3505 Nuclear Waste Isolation in the Unsaturated (1990).

112 Isutupe and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Publications

E.S. Patera, D.E. Hobart, A. Meijer, and R.S. Rundberg, "Chemical and Physical Processes of Radionuclide Migration at Yucca Mountain, Nevada," J. Radioanal. Nucl. Chem. 142, 331-347 (1990) (invited).

M.S. Quinby-Hunt, P. Wilde, C.J. Orth, and W.B.N. , "Elemental Geochemistry of Black Shales—Statistical Comparison of Low-Calcic Shales and Other Shales," U.S. Geological Survey Circular 1037, 8-15 (1989).

J.C. Roberts, Y.E. Adams, D. Tomalia, J.A. Mercer-Smith, and D. K. Lavallee, "Using Starburst Dendrimers as Linker Molecules to Radiolabel Antibodies," Bioconjugate Chemistry 2, 305-308 (1990).

J. Rogowski, J. Alstad, M.M. Fowler, D. De Frenne, K. Heyde, E. Jacobs, N. Kaffrell, G. Skarnemark, and N. Trautmann, "Evidence for Intruder States in mRh," Z. Phys. Z— Atomic Nuclei 337, 233-234 (1990).

H.L. Seifert, D.J. Vieira, H. Wollnik, and J.M. Wouters, "Increased Secondary Electron Yield from Thin Csl Coatings," Nucl. Inst. and Meth. in Phys. Res. A 292, 533-534 (1990).

A.C. Wahl, J.E. Bigelow, W.T. Carnall, G.R. Choppin, R.E. Connick, Z. Fisk, G. Friedlander, D.C. Hoffman, E.K. Hulet, A.E. Martell, Y. Maruyama, T.G. Spiro, N. Sutin, and J.B. Wilhelmy, "Transplutonium Elements Research Assessment," (National Academy Press, Washington, DC, 1990).

J.B. Wilhelmy and M.M. Fowler, "Neutral Current Detection in Diluted Heavy Water," Los Alamos National Laboratory document LA-UR-90-2918(1990).

Isotope and Nuclear Chemistry Division Annual Report FY 1990 113 Appendix: Presenta tions

PRESENTATIONS D.T. Cromer, "History of the Commonly Used X-Ray Scattering Factors," American Crystal- lographic Association, 40th Anniversary Meeting, New Orleans, Louisiana, April 8-13,1990. INC-4 R.J. Donohoe, L.A. Worl, and B.I. Swanson, S.F. Agnew and D. Sinha, "Thin-layer Detectors: "Polarons and Bipolarons in Weak 1-D CDW NO2 Detection with Polystyrene Thin Layers," Solids: Spectral Studies of Local States in Department of Energy Real-Time Subsurface II [Pt (en)2][PtiV(en)2Br23[C104]4 and [Pt«(en)2]- Monitoring of Groundwater Workshop, Dallas, IY [Pt (en)2I2][C104]4," International Conference Texas, April 17-18,1990. on Science and Technology of Synthetic Metals '90, Tubingen, West Germany, September 2-7, John M. Berg, C. Drew Tait, David E. Morris, 1990. and William H. Woodruff, "Actinide Speciation by Photothermal Spectroscopies: Instrumen- R.J. Donohoe, L.A. Worl, and B.I. Swanson, tation Development," 1990 Materials Research "Spectroscopic Studies of Polarons and Society Fall Meeting, Symposium P, "Scientific Bipolarons Defect in the Strongly Localized Basis for Nuclear Waste Management XIV," II IV CDW Solid [Pt (en)2][Pt (en)2Cl2][ClO4]4," Boston, Massachusetts, November 26-29,1990. International Conference on Science and Technology of Synthetic Metals '90, Tubingen, J.C. Bryan, J.C. Huffman, M.M. Miller, and West Germany, September 2-7,1990. A.P. Sattelberger, "Synthesis, Characterization, and Reactivity of Rhenium(V) Alkoxide Dimers R.B. Dyer, 'O. Einarsdottir, J.J. Lopez-Garriga, Containing Metal-Metal Double Bonds," K.A. Bagley, S.J. Atherton, R.A. Goldbeck, American Chemical Society Meeting, T.D. Dawes, and W.H. Woodruff, "Evidence for a Washington, DC, August 27-31,1990. Low-Spin Cytochrome a3 Transient Following Photodissociation of CO-Cytochrome Oxidase," J.C. Bryan, M.M. Miller, and A.P. Sattelberger, Biophysical Society Annual Meeting, Baltimore, "Synthesis, Characterization, and Reactivity of Maryland, February 18-22,1990. Technetium(VII) Imido Complexes," American Chemical Society Meeting, Washington, DC, P. Gary Eller, Scott A. Kinkead, and Jon B. August 27-31,1990. Nielsen, "F-Element Compound Synthesis Employing Powerful Halogenating Agents at A.R. Bulou, Donohoe, and B.I. Swanson, "Lattice Low Temperature," 200th American Chemical Dynamics in MX Chains: Phonons Modes Society National Meeting, Washington, DC, Associated with Polaronic and Bipolaronic August 26-31,1990. Defects in PtX CDW Systems," International Conference on Science and Technology of P.G. Eller, David E. Morris, David L. Bish, Synthetic Metals '90, Tubingen, West Germany, Steven D. Conradson, and Robert R. Ryan, September 2-7,1990. "Intercalation Reactions of F-Element/Organo- phosphorus Co-Contaminants with Smectitic C. J. Burns, M.M. Miller, and G.K Kubas, Clays," 200th American Chemical Society National "Activation of Sulfur Dioxide By Mononuclear Meeting, Washington, DC, August 26-31,1990. Complexes," American Chemical Society Meeting, Washington, DC, August 27-31,1990. S.W. Hall, L.R. Avens, J.C. Huffman, M.M. Miller, and A.P. Sattelberger, "Synthesis, S.D. Conradson and E. Newnam, "Research Characterization and Reactions of Thorium* IV) Opportunities at the Proposed Los Alamos XUV- and Uranium(IV) Bis(Trimethylsilyl)Phosphide FEL User Facility," Society of Photo-Optical Complexes," American Chemical Society Instrumentation Engineers Technical Program Meeting, Washington, DC, August 27-31,1990. Committee Conference, Los Angeles, California, January 14-19,1990.

114 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Presentations

Sara Huckett, Carol J. Burns, and Basil I. John B. Nielsen, Scott A. Kinkead, and P. Gary Swanson, "New Chains Materials from Eller, "Chlorination Studies of Plutonium and Binuclear Metal Complexes with Bridging Uranium Oxides Using NH4C1 and HC1," Aromatic Ligands," International Conference on American Chemical Society Meeting, Science and Technology of Synthetic Metals '90, Washington, DC, August 27-31,1990. Tubingen, West Germany, September 2-7, 1990. R.A. Penneman, "Contributions of Chemistry in Sara Huckett, Laura A. Woi-1, Robert Donohoe, Early Day Los Alamos," 200th American and Basil I. Swanson, "Origin of the Vj Chemical Society Meeting, Washington, DC, Dispersion and Fine Structure in the Mixed- August 26-31,1990. Valence Linear Chain [Pt(en)2][Pt(en)2Br2] [C1O4]4," American Chemical Society Meeting, N.N. Sauer, E. Garcia, R.R. Ryan, and Washington, DC, August 27-31,1990. J.A. Martin, "Soluble and Volatile Precursors for the Preparation of Superconducting Films," S.A. Kinkead, J.B. Nielsen, and P.G. Eller, "New Materials Research Society National Meeting, High Energy Oxidizer Systems for Propellant San Francisco, California, April 16-21,1990. and Energy Storage Applications," Third Annual Contractors' Meeting in High Energy Density Daniel J. Simpson, Cliff J. Unkefer, Thomas W. Materials, February 25-28,1990. Whaley, and Babetta L. Marrone, "A New Fluorogenic Probe for the Cytochrome P-450 Gregory J. Kubas, "Dihydrogen Coordination: Cholesterol Sided Chain Cleavage Enzyme," The Studies of Cleavage Rotational Barriers, Proton- Endocrine Society Meeting, Atlanta, Georgia, ation, and Deprotonation of V2-H2," Conference June 20-24,1990. on Coordination Chemistry, Dinard, France, May 13-17,1990. D.C. Smith, C.J. Burns, andA.P. Sattelberger, "Photophysical Characterization of Neutral Gregory J. Kubas, "Chemical Bonding of Monomeric Bis(Alkoxide) and Bis(Amide) Uranyl Hydrogen Molecules to Transition Metal Complexes,' American Chemical Society Meeting, Complexes," International Symposium on Boston, Massachusetts, April 22-27,1990. Metal-Hydrogen Systems Fundamentals and Applications, Banff, Alberta, Canada, D.C. Smith, S.G. Pattillo, N.E. Elliot, J.R. Laia, September 2-7,1990. and A.P. Sattelberger, "Low Tempei'ature Organometallic Chemical Vapor Deposition Gregory J. Kubas and Robert R. Ryan, (OMCVD) of Rhodium and Iridium Thin Films," "Catalytic Hydrogenation and Oxygen Transfer American Chemical Society Meeting, Boston, Reactions of SO2 and NO on Sulfide Ligands of Massachusetts, April 22-27,1990. Cp*2Mo2S4" American Chemical Society Symposium on Soluble Metal Chalcogenides, D.C. Smith, Stevan G. Pattillo, Norman E. Washington, DC, August 26-31,1990. Elliot, Thomas G. Zocco, Joseph R. Laia, and A.P. Sattelberger, "Low Temperature David E. Morris, C. Drew Tait, John M. Berg, Organometallic Chemical Vapor Deposition Stephen K. Doom, and William H. Woodruff, (OMCVD) of Rhodium and Iridium Thin Films," "Photothermal Spectroscopic Studies of Actinide 11th International Conference on Chemical Speciation in the Environment," American Vapor Deposition, Seattle, Washington, Chemical Society Meeting, Washington, DC, October 14-19,1990. August 27-31,1990. D.C. Smith, A.P. Sattelberger, J.C. Desantis, E.C. Niederhoffer, CM. Naranjo, K.L. Bradley, S.G. Pattillo, N.E. Elliot, and Joseph R. Laia, and James A. Fee, "Novel Iron Dependent "Organometallic Chemical Vapor Deposition," Regulatory Mechanisms for Bacteria] Super-oxide Southeast-Southwest Regional American Dismutases," invited seminar for 1990 Gordon Chemical Society Meeting, New Orleans, Research Conference on Metals in Biology, Louisiana, December 5-7,1990. Ventura, California, January 21-26,1990.

Isotope and Nuclear Chemistry Division Annunl Report FY 1990 115 Appen dix: Presen ta tion s

P.H. Smith, J.R. Brainard, B.P. Hay, and W.G. Van Der Sluys, D.C Smith, M.T. Paffett, R.E. Ryan, "Proton and Anion Binding Prop- and A. P. Sattelberger, "Low Temperature Route erties of An Octa Aza Cryptand," American to Uranium Nitrides," American Chemical Chemical Society Meeting, Boston, Massachusetts, Society Meeting, Boston, Massachusetts, April April 22-27,1990. 22-27,1990.

B.I. Swanson, "Local States in One-Dimensional W.G. Van Der Sluys, D.E. Morris, W.H. Smith, SDW and CDW Materials: Spectral Signatures A.P. Sattelberger, WE. Streib, and J.C. for Polarons and Bipolarons in MX Chains," Huffman, "Uranium(IV)—Alkoxide Complexes," University of Wisconsin, Department of American Chemical Society Meeting, Boston, Chemistry, Madison, Wisconsin, March 29,1990, Massachusetts, April 22-27,1990. and Northwestern University, Department of Chemistry, Evanston, Illinois, April 2,1990. J. Weinrach, M. Hawley, S. Huckett, and B.I. Swanson, "STM Studies of MMX and MX Basil I. Swanson, Robert Donohoe, J. Tinka Chains: Experimental Evidence for Superlattice Gammel, and Alan R. Bishop, "Local States in Structure in Quasi-One-Dimensional CDW One-Dimensional SDW and CDW Materials: Solids," International Conference on Science and Spectral Signatures for Polarons and Bipolarons Technology of Synthetic Metals '90, Tubingen, in MX Chains," International Conference on West Germany, September 2-7,1990. Science and Technology of Synthetic Metals '90, Tubingen, West Germany, September 2-7,1990. William H. Woodruff, David E. Morris, Kim R. Dunbar, Laura Pence, Robert J. Donohoe, and B.I. Swanson, R.J. Donohoe, L.A. Worl, C. Anthony Arrington, "Spectroscopic Studies of A.D.F. Bulou, C.A. Arrington, J.T. Gammel, the Photochemistry of [Rh (NCCH ) ]4+," 200th A. Saxena, and A.R. Bishop, "Local States in 2 3 10 One-Dimensional CDW Materials: Spectral National American Chemical Society Meeting, Signatures for Polarons and Bipolarons in MX Washington, DC, August 26-31,1990. Chains," Symposium on Photoinduced Charge Transfer in Molecular Crystals and Liquid Laura A. Worl, Earl Danielson, Geoffrey F. Crystals, Rochester, New York, June 6-9, 1990. Strouse, Janet Younathan, Thomas J. Meyer, "Light Induced Processes of MLCT Excited States B.I. Swanson, L.A. Worl, R.J. Donohoe, Attached to a Soluble Polymer," Invited seminar S. Huckett, I. Batistic, A.R. Bishop, and to the American Chemical Society Meeting, J.T. Gammel, "Local States in NiBr, A Weak Boston, Massachusetts, April 22-27,1990. SDW MX Chains," International Conference on Science and Technology of Synthetic Metals '90, Laura A. Worl, Robert J. Donohoe, Sara C. Tubingen, West Germany, September 2-7,1990. Huckett, Alain Bulou, and Basil I. Swanson, "Near Infrared Resonance Raman Studies of C. Drew Tait, David E. Morris, John M. Berg, Local States in NiBr, A Weak Spin-Density Wave Stephen K. Doom, and William H. Woodruff, Material," American Chemical Society Meeting, "Photothermal Spectroscopic Studies of Actinide Boston, Massachusetts, April 22-27,1990. Speciation in the Environment," Symposium P, "Scientific Basis for Nuclear Waste Management Laura A. Worl, Robert J. Donohoe, Sara C. XIV," Boston, Massachusetts, November 26-29, Huckett, Alain Bulou, and Basil I. Swanson, 1990. "Spectral Signatures for Defect States in the Halogen-Bridged Transition Metal Linear Chain Lori Stepan Van Der Sluys, Kenneth Caulton, Complexes, PtBr," American Chemical Society and Gregory J. Kubas, "Reactivity of Metal Meeting, Boston, Massachusetts, April 22-27,1990. Dihydrogen Complexes: Studies of Mo and W," American Chemical Society Meeting, Boston, Massachusetts, April 22-27,1990.

116 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Presentations

INC-5 I.R. Triay, A. Meijer, M.R. Cisneros, G.G. Miller, D.E. Hobart, P.D. Palmer, R.D. Aguilar, and M.E. Bunker and J.W. Starner, "Level Structure R.E. Perrin, "Sorption Behavior of Americium in of 256pm: Experiment vs. Theory," International Tuff Samples and Pure Minerals Using Syn- Conference on Structure of Nom-otational States thetic and Natural Groundwaters," "Migration of Deformed Nuclei, Dubna, USSR, April 2-6, '89," Second International Conference on 1990. Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, M.E. Bunker and J.W. Starner, "Level Structure Monterey, California, November 6-8,1989. of 256pm: Experiment vs. Theory," International Conference on Nuclear Spectroscopy and Shape S.J. Goldstein, M.T. Murrell, and D.R. Janecky, of Atomic Nucleus, Leningrad, USSR, April 10- "Dating Young MORB from Juan de Fuca and 13.1990. Gorda Ridges by 238u_230Th Disequilibrium," Fall 1989 American Geophysical Union Meeting, San Francisco, California, December 4-8,1989. M.M. Denton, S.R. Garcia, and M.M. Minor, "A Distributed Data Acquisition System for D.R. Janecky, J.T. Wells, and B.J. Travis, Gamma Spectral Analysis," poster session "Cellular Automata Calculations for Coupled presented at the 7th Symposium on Radiation Flow and Chemical Reactions at Surfaces and in Measurements and Applications, Ann Arbor, Pore Networks: Initial Results," Fall 1989 Michigan, May 21-24,1990. American Geophysical Union Meeting, San Francisco, California, December 4-8,1989.

INC-7 G. Luedemann and G.K. Bayhurst, "Dust Charac- terization Program," RS-1 Users Conference, M. Attrep, Jr., J.T. Fabryka-Martin, D.B. Curtis, New Orleans, Louisiana, December 6-8,1989. M.P. Baker, and G.E. Eccleston, "Test of Model A. Meijer, "U-Th-Pb Partitioning Behavior in the for Radionuclide Generation in Natural Upper Mantle: Implications for the Origin of Uranium Deposits," "Migration '89," Second High-Mu Components and the 'Pb Paradox'," International Conference on Chemistry and Fall 1989 American Geophysical Union Meeting, Migration Behavior of Actinides and Fission San Francisco, California, December 4-8,1989. Products in the Geosphere, Monterey, California, November 6-8,1989. E.J. Mroz and A.S. Mason, "Deuterated Methane in the Atmosphere," Fall 1989 A.E. Norris, "36C1 Studies of Water Movements American Geophysical Union Meeting, San for the Yucca Mountain Project," Yucca Francisco, California, December 4-8,1989. Mountain Project Director's and Technical Project Officers' Meeting, Las Vegas, Nevada, J.A. Musgrave and J.B. Hulen, "Vien, Vug, and November 3,1989. Fracture Mineralization and Paragenesis of Continental Scientific Drilling Program D.R. Janecky, J.T. Wells, and B. J. Travis, Coreholes VC-2A and VC-2B, Valles Caldera, "Cellular Automata Calculations for Coupled New Mexico," Fall 1989 American Geophysical Flow and Chemical Reactions at Surfaces and in Union Meeting, San Francisco, California, Pore Networks: Initial Results," Geological December 4-8,1989. Society Annual Meeting, St. Louis, Missouri, November 6-9,1989. A.E. Norris, "Chlorine Isotopic Measurements," United States Nuclear Waste Technical Review R.E. Perrin, "Improved Target Values, What Board Meeting, Denver, Colorado, December Criteria," 1989 American Nuclear Society 11-12. 1989. Winter Meeting, San Francisco, California, November 26-30,1989.

Isotope and Nuch'.ar Chemistry Division Annual Rvport FY 1990 117 Appendix: Presentations

S. Goldstein, "Study of the Exogenic Geochemical A.E. Norris, H.W. Bentley, S. Cheng, P.W. Kubik, Cycle Using Radiogenic Isotopes," University of P. Sharma, and H.E. Gove, ^Chlorine Studies Florida, Gainesville, Florida, January 24-28,1990. of Water Movements Deep Within Unsaturated Tuffs," Fifth International Conference on S. Goldstein, "Application of Radiogenic Isotopes Accelerator Mass Spectrometry, Paris, France, to Hydrologic Problems," United States April 22-27,1990. Geological Survey, Menlo Park, California, March 1,1990. P.R. Dixon, D.R. Janecky, and D.M. Rye, "Origin of Isotopically Heavy Sulfides from the Kildare W.M. Fairbank, Jr., R.D. Labelle, J. Pan, Inlier Deposits, Co. Kildare, Ireland," E.P. Chamberlin, B.L. Fearey, R.A. Keller, and V.M. Goldschmidt Conference, Baltimore, CM. Miller, "Measurement cfTrace Isotopes by Maryland, May 24,1990. Photon Burst Mass Spectromeury," Laboratory Assessment Group on Effluent Research Program C. J. Duffy, "Low Temperature Zeolite Review Presentation, Colorado State University, Transformations in Tuff," V.M. Goldschmidt Fort Collins, Colorado, March 9,1990. Conference, Baltimore, Maryland, May 24,1990.

S. Goldstein, "Geochronology and Petrogenesis M.T. Murrell, S.J. Goldstein, A.M. Volpe, of MORB Using U-Th Disequilibrium," B.L. Fearey, R.E. Perrin, and R.W. Williams, University of Maryland, College Park, "Measurement of Long-Lived Members of the Maryland, March 2,1990. Uranium Decay Series by Mass Spectrometry," V.M. Goldschmidt Conference, Baltimore, A.W. Laughlin, R.W. Charles, W.L. Mansker, Maryland, May 24,1990. A.J. Peaches, and R. Koch, "An Assessment of the Diamond Potential of the Navajo J.A. Musgrave and D.I. Norman, "State of the Lamprophyric Diatremes," Geological Society of Sulphur Springs Hydrothermal System, Valles America Cordilleran Section Meeting, Tucson, Caldera, New Mexico: From Fluid Inclusion Arizona, March 14-16,1990. Evidence," Third Biennial Pan-American Conference on Research on Fluid Inclusions, R.A. Levich, E.S. Patera, P.M. Ferrigan, and Toronto, Ontario, Canada, P.L. Wilkey, "The International Stripa Project: May 20-22,1990. Technology Transfer from Cooperation in Scientific and Technological Research on Nuclear CD. Tait, D.R. Janecky, and P.S.Z. Rogers, Waste Disposal," American Nuclear Society "Speciation of Aqueous Palladium(II) Chloride International Conference on High-Level Nuclear Solutions Using Optical Spectroscopies," Fall Waste, Las Vegas, Nevada, April 8-12,1990. National Meeting of the American Chemical Society, Geochemistry Division, J.A. Musgrave and D.I. Norman, "Precious and Washington, DC, August 26-31,1990. Base Metal Deposition in an Active Hydrothermal System, Sulphur Springs Area, P.S.Z. Rogers, J.M. Simonson, and R.E. Mesmer, Valles Caldera, New Mexico," Great Basin "Standard State and Excess Thermodynamic Symposium: Geology and Ore Deposits of the Properties of NaOH(aq) to 573 K and 40 MPa," Great Basin, Reno, Nevada, April 15,1990. V. M. Goldschmidt Conference, Baltimore, Maryland, May 24,1990. B.L. Fearey, "Thorium RIMS Status and Future," INC-7 Group Meeting, Los Alamos A.M. Volpe and M.T. Murrell, "Measurement of National Laboratory, Los Alamos, New Mexico, 226Ra/228Ra Isotopic Ratios and Radium April 16,1990. Abundances in Young Volcanic Rocks by Mass Spectrometry," V.M. Goldschmidt Conference, Baltimore, Maryland, May 24,1990.

118 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Presentations

J.A. Musgrave, P.Z. Rogers, J.B. Hulen, and R.W. D.R. Janecky, B.J. Travis, G. Zyvloski, Charles, "Nuclear Microprobe Determination of N. Rosenberg, and J.T. Wells, "3-D Numerical Trace Element Distribution in the Continental Models for Examining Processes in Geothermal- Scientific Drilling Program Corehole VA-2A, Hydrochemical Systems," Chapman Conference Valles Caldera, New Mexico," American on Crustal Scale Fluid Transport: Magnitude and Geophysical Union, Spring 1990 Meeting. Mechanisms, Snowbird, Utah, June 4-8,1990. Baltimore, Maryland, May 29-June 1,1990. D.R. Janecky and W.D. Spall, "New Tracer Technology for Geochemical Tomography," A.M. Volpe and M.T. Murrell, "Radium-Barium Economic Summit: Development of New Tracer Partitioning and Uranium Series Disequilibria Technology for Geochemical Tomography, in Rocks and Minerals Determined by Mass Houston, Texas, July 6,1990. Spectrometry," American Geophysical Union, Spring 1990 Meeting, Baltimore, Maryland, B.L. Fearey, S.G. Johnson, and CM. Miller, "High Ionization Efficiency Techniques for May 29-June 1,1990. Continuous Wave Resonance Ionization Mass Spectrometry," Fifth International Symposium J. Fabryka-Martin, M. Attrep, Jr., R.D. Aguilar, on Resonance Ionization Spectrometry and its D.B. Curtis, and F. Roensch, "Natural Analogues Applications, Varese, Italy, September 16-21, of Plutonium Retention and Migration" (poster 1990. session), Fourth Natural Analogue Working Group Meeting, Pitlochry, Scotland, June 12-15, B.L. Fearey, S.G. Johnson, M.T. Murrell, and 1990. CM. Miller, "Thorium Resonance Ionization Mass Spectrometry for Geochronological and J.C. Banar, E.P. Chamberlin, M.T. Murrell, Geochemical Applications," Fifth International J.A. Olivares, R.E. Perrin, E.L. Rios, and Symposium on Resonance Ionization Mass D.J. Rokop, "Comparison of Four Mass Spectro- Spectromety and its Applications, Varese, Italy, meter Configurations for High Abundance September 16-21,1990. Sensitivity Measurements," Thirty-Eighth American Society Mass Spectroscopy Conference S. J. Goldstein, M.T. Murrell, D.R. Janecky, on Mass Spectrometry and the Allied Topics, J.R. Delaney, and D.A. Clague, "Geochronology Tucson, Arizona, June 3-8,1990. and Petrogenesis of MORB Using 238U-230Th Disequilibrium," International Conference on Geo- J.A. Olivares, J.C. Banar, E.P. Chamberlin, chronology, Cosmochronology, and Isotope Geology, M.T. Murrell, R.E. Perrin, D.J. Rokop, and Canberra, Australia, September 24-29,1990. E.L. Rios, "Comparison of Four Mass Spectrometer Configurations for High A. Meijer and P.Z. Rogers, "Pb Distribution in Abundance Sensitivity," Thirty-Eighth American Ultramafic Nodules from the Upper Mantle Society Mass Spectroscopy Conference on Mass Beneath the Western United States," Spectrometry and the Allied Topics, Tucson, International Conference on Geochronology, Arizona, June 3-8,1990. Cosmochronology, and Isotope Geology, Canberra, Australia, September 24-29,1990. P.R. Dixon, D.M. Rye, and D.R. Janecky, "Fluid J. Poths, B.M. Kennedy, E.A. Bryant, and Flow Connections to Basement Rocks Below J.H. Reynolds, "Noble Gases in Sediments Sedimentary Basins: Evidence from the Base Associated with Natural Gases," International Metal Deposits in Ireland," Chapman Conference on Geochronology, Cosmochronology, Conference on Crustal Scale Fluid Transport: and Isotope Geology, Canberra, Australia, Magnitude and Mechanisms, Snowbird, Utah, September 24-29,1990. June 4-8,1990.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 119 Appendix: Presentations

INC-11 M.M. Fowler, S.B. Larson, and J.B. Wilhelmy, "Neutral Current Detector Development T.P. Burns and J.A. Mercer-Smith, "Design of a Progress," Sudbury Neutrino Observatory Paramagnetic Contrast Imaging Agent Through Collaboration Meeting, Chalk Rive:. Ontario, the Use of Molecular Modeling," Fall 1990 Canada, September 13-16,1990. National American Chemical Society Meeting, Washington, DC, August 25-31,1990. M.M. Fowler, "The Status of Cold Fusion at Los Alamos," Western Electronics Show and D.A. Cole, D.C. Moody, L.E. Ellinwood, Convention 1989, San Francisco, California, M.G. Klein, J.A. Mercer-Smith, J.K. Norman, November 14-16,1989. R.O. Eikleberry, D. Lewis, G. Saccomonno, J.J. Becktel, and D.K. Lavallee, "A Synthetic M.M. Fowler, "The Status of Cold Fusion at Los Porphyrin with High Affinity for Lung Cancer Alamos," Stanford Linear Accelerator Center, Cells and Inflamed Lymphatic Tissue," invited Stanford, California, December 14,1989. presentation for International Symposium on New Trends in Radiopharmaceutical Synthesis, R. Grieve, P. Robertson, M. Bouchard, C. Orth, Quality Assurance, and Regulatory Control at M. Attrep, and R. Bottomley, "Impact Melt the American Chemical Society National Rocks from New Quebec Crater," Meteoritical Meeting, Washington, DC, August 26-31,1990. Society Meeting, Vienna, Austria, July 31- August4,1989. D.A. Cole, D.C. Moody, L.E. Ellinwood, M.G. Klein, R. Michels, G. Saccomonno, and S.J. Henderson, S.E. Rokop, P.A. Seeger, J.J. Becktel, "Localization of Porphyrin in D.K. Blumenthal, D.E. Hobart, P.D. Palmer, Sputum Cells from Uranium Miners with Lung H. Crespi, J. Trewhella, "Calmodulin Structure Cancer," American Chemical Society for Studies Using Neutron Scattering: Peptide Photobiology, 18th Annual Meeting, Vancouver, Interactions and Measurements of Distances British Columbia, Canada, June 16-20,1990. Between Calcium-Binding Sites," 34th Annual Meeting of the Biophysical Society, Baltimore, D. Erb, R. Atcher, J. Beaver, L. Mausner, and Maryland, February 18,1990. E. Peterson, "The Future of Accelerator Production of Radioisotopes in the United D.E. Hobart, P.D. Palmer, J. Trewhella, States," invited presentation for International S.E. Rokop, S. Henderson, and EA. Seeger, Symposium on New Trends in Radiopharma- "Plutonium-240 Resonance Neutron Scattering for ceutical Synthesis, Quality Assurance, and Structural Elucidation of the Protein Calmodulin," Regulatory Control at the American Chemical 200th American Chemical Society National Society, National Meeting, Washington, DC, Meeting, Washington, DC, August 26-31,1990. August 26-31,1990. D.E. Hobart, D.E. Morris, D.L. Clark, M.M. Fowler, J.C. Gursky, and J.B. Wilhelmy, P.D. Palmer, K.R. Ashley, and T W. Newton, "Preparation of Actinide Targets and Sources "Raman, Fluorescence, and Diffuse Reflectance Using Nonaqueous Electrodeposition," invited talk Spectra of Actinide Oxides and Silicates," Heavy at the 15th World Conference of the International Elements Chemistry Research Reports Session, Nuclear Target Development Society, Santa Fe, Washington, DC, August 26-31,1990. New Mexico, September 9-12,1990. D.E. Hobart and D.E. Morris, "Raman M.M. Fowler and J.B. Wilhelmy, "Thorium and Spectral Characterization of Actinide Solution Uranium Measurements in Acrylic," Sudbury and Solid State Complexes," International Neutrino Observatory Collaboration Meeting, Chalk Chemical Congress of Pacific Basin Societies, River, Ontario, Canada, September 13-16,1990. Honolulu, Hawaii, December 17-22,1989.

120 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Presentations

J.A. Mercer-Smith, D.A. Cole, J.K. Norman, C.J. Orth, M. Attrep, Jr., and L.R. Quintana, S.A. Schreyer, J.C. Roberts, R.A. Fawwaz, and "Elemental Abundance Patterns Across Bio- D.K. Lavallee, "Porphyrins and Metallo- Event Horizons: The K/T, C/T, P/T, F/F, and O/S porphyrins as Site-Selective Agents," Joint 45th Events," Fourth International Meeting on Northwest/1 Oth Rocky Mountain Regional Global Bioevents, Oxford University, United American Chemical Society Meeting, Targeted Kingdom, September 24-28,1990. Drug Delivery Symposium, Salt Lake City, Utah, June 13-15,1990. E.J. Peterson, L.E. Wangen, K.C. Ott, R E. Muenchausen, K.M. Hargis, T.W. Whaley, J.A. Mercer-Smith, J.C. Roberts, D. Lewis, and W. J. Parkinson, "Development of Inherently S.L. Newmyer, L.D. Schulte, T.P. Burns, Safe and Environmentally Acceptable P.L. Mixon, A.L. Jeffery, S.A. Schreyer, Intelligent Processing Technologies for HTS D.A. Cole, S.D. Figard, V.A. , Materials," Superconductivity: The Manu- M. Hayashi, and D.K. Lavallee, "Radio- facturing Challenges Conference and Tabletop metallating Antibodies and Biologically Active Exhibits, Chicago, Illinois, October 16-18,1989. Peptides," invited presentation for International Symposium on New Trends in Radiopharma- D.R. Phillips, "Los Alamos Workshop on the ceutical Synthesis, Quality Assurance, and Science of Intense Radioactive Ion Beams Regulatory Control at the American Chemical Materials Science/Atomic Physics/Isotope Society National Meeting, Washington, DC, Production," Los Alamos Workshop on the August 26-31,1990. Science of Intense Radioactive Ion Beams Materials Science/Atomic Physics/Isotope D.E. Morris, CD. Tait, J.M. Berg, S.K. Doom, Production, Los Alamos National Laboratory, W.H. Woodruff, "Photothermal Spectroscopic Los Alamos, New Mexico, April 10-12,1990. Studies of Actinide Speciation in the Environment," 200th National American D.R. Phillips, D.A. Nix, W.A. Taylor, T.P. Burns, Chemical Society Meeting, Washington, DC, and A.M. Emran, "Chemistry and Concept for August 26-31,1990. an Automated Se-72/As-72 Generator," 200th National Meeting, American Chemical Society, D.E. Morris, CD. Tait, P.G. EUer, Washington, DC, August 26-31,1990. S.D. Conradson, and W.H. Woodruff, "Spectroscopic Studies of Radionuclide-Organic J.C. Roberts, Y.A. Adams, J.A. Mercer-Smith, Co-Contaminants on Environmental Subsurface and D.K. Lavallee, "Antibody-Mediated Drug Matrices: Lanthanide(III) and UO22+ Species Delivery: Comparison of Random Versus Site- on Smectites," 200th National American Specific Antibody Modification Techniques," Chemical Society Meeting, Washington, DC, Joint 45th Northwest/1 Oth Rocky Mountain August 26-31,1990. Regional American Chemical Society Meeting, Targeted Drug Delivery Symposium, Salt Lake S. Newmyer, J. Mercer-Smith, L. Schulte, City, Utah, June 13-15,1990. T. Burns, D. Lewis, and D. Lavallee, "Carbohydrate Region Radiolabeling of Tumor Specific Antibody R.S. Rundberg, I.R. Triay, M.A. Ott, and Via N-(p-Nitrobenzyl) Tetraaminomethylphenyl A.J. Mitchell, "Observation of Time Dependent Porphine," Santa Fe Graduate Medicinal Dispersion in Laboratory Scale Experiments Chemistry Conference, sponsored by the with Intact Tuff," Migration '89, Monterey, Department of Pharmaceutical Sciences at the California, November 6-10,1989. University of Arizona, July 6-8,1990.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 121 Appendix: Presentations

H.L. Seifert, H. Wollnik, D.J. Vieira, and X.L. Tu, X.G. Zhou, V.G. Lind, D.J. Vieira, J.M. Wouters, "Increased Secondary Electron J.M. Wouters, Z.Y. Zhou, and H.L. Seifert, "Mass Yield for MicroChannel Plate Fast Timing Determinations of Exotic Neutron-Rich Recoils Detectors," American Physical Society Division in the Z=14-26 Region," American Physical of Nuclear Physics Meeting, Asilomar, Society Division of Nuclear Physics meeting, California, October 12-14,1989. Asilomar, California, October 12-14,1989.

J.L. Thompson and J.S. Gilmore, "Migration of X.L. Tu, "Mass Determinations of Exotic Fission Products at the Nevada Test Site: Neutron-Rich Recoils in the Z=16-26 Region," Detection with an Isotopic Tracer," Migration Utah State University Physics Seminar, October '89, Monterey, California, November 6-10,1989. 17,1989.

J.L. Thompson, "Radionuclide Migration Studies J.G. Watkin, M.M. Miller, and D.L. Clark, "A at the Nevada Test Site," International Convenient Entry into the Inorganic and Chemical Congress of Pacific Basin Societies, Organometallic Chemistry of Thorium," Meeting American Chemical Society, Honolulu, Hawaii, Abstracts, Division of Inorganic Chemistry, The December 18-22,1989. American Chemical Society, National Meeting, Washington, DC, August 26-31,1990. J. Trewhella, D.K. Blumenthal, D.E. Hobart, P.D. Palmer, S.E. Rokop, P.A. Seeger, J.B. Wilhelmy, "Sudbury Neutrino Observatory," S.J. Henderson, "Neutron Scattering Studies of American Chemical Society National Meeting, Calmodulin and its Interactions with Target Boston, Massachusetts, April 22-27,1990. Enzyme Binding Domains," 15th International Congress and General Assembly. International J.B. Wilhelmy and M.M. Fowler, "Neutral Union of Crystallography, Bordeaux, France, Current Detection in Diluted Heavy Water," July 19-28,1990. Sudbury Neutrino Observatory Collaboration Meeting, Chalk River, Ontario, Canada, I.R. Triay, A. Meijer, M.R. Cisneros, G.G. Miller, September 13-16,1990. A.J. Mitchell, M.A. Ott, D.E. Hobart, P.D. Palmer, R.E. Perrin, and R.D. Aguilar, J.B. Wilhelmy, "Fission Studies with Radioactive "Sorption of Americium in Tuff and Pure Beams," Los Alamos Workshop on the Science of Minerals Using Synthetic and Natural Intense Radioactive Ion Beams, Los Alamos Groundwaters," Migration '89, National Laboratory, Los Alamos, New Mexico, Monterey, California, November 6-10,1989. April 10-12,1990.

I.R. Triay, R.S. Rundberg, A.J. Mitchell, J.B. Wilhelmy, "Fission in the Light M.A. Ott, D.E. Hobart, P.D. Palmer, Transactinium Region," Workshop on T.W. Newton, and J.L. Thompson, "Size Transactinium Science, Oakland, California, Determinations of Plutonium Colloids Using June 6-8,1990. Autocorrelation Photon Spectroscopy," Migration '89, Monterey, California, November 6-10,1989. J.B. Wilhelmy, "Nuclear Properties of the Transplutonium Elements," Transplutonium I.R. Triay, A.J. Mitchell, and M.A. Ott, Elements Research Assessment Panel for the "Radionuclide Migration Studies for Validating National Research Council, Albuquerque, Sorption Data—Past, Present, and Future," New Mexico, July 30-31,1990. Radionuclide Adsorption Workshop, Los Alamos, New Mexico, September 11-12,1990.

122 Isotope and Nuclear Chemistry Division Annual Report FY 1990 J.B. Wilhelmy, "SNOing in Los Alamos— Neutrinos in the Nineties," INC-11 '90 Seminar Series, Los Alamos National Laboratory, Los Alamos, New Mexico, November 16,1990.

J.M. Wouters, "ISOLAB-A New Initiative," Los Alamos Meson Physics Facility Users meeting, Los Alamos, New Mexico, August 13,1990.

J.M. Wouters, D.J. Vieira, X.L. Tu, X.G. Zhou, V.G. Lind, H.L. Seifert, and Z.Y. Zhou, "Extension of the Mass Surface for the Elements of Chlorine Through Iron," 8th International Conference on Atomic Masses and Fundamental Constants, Jerusalem, Israel, September 9-14, 1990. (Invited talk—an abstract was published, but the meeting was cancelled due to the Iraq- Kuwait war.)

X.G. Zhou, X.L. Tu, V.G. Lind, D.J. Vieira, J.M. Wouters, K.E. G. Lobner, Z.Y. Zhou and H.L. Seifert, "Mass Measurement of Z=7-19 Neutron-Rich Nuclei Using the TOFI Spectrometer," American Physical Society Division of Nuclear Physics Meeting, Asilomar, California, October 12-14,1989.

X.G. Zhou, "Mass Measurement of Z=9-18 Neutron-Rich Nuclei Using the TOFI Spectrometer," Utah State University Physics Seminar, October 17,1989.

Z.Y. Zhou, "Mass Measurements and Search for Isomeric States in Exotic Nuclei," Utah State University Physics Seminar, October 20,1989.

Isotope and Nuclear Chemistry Division Annual Report FY 1990 123 Appendix: Division Meetings and Seminars

Division Meetings and Seminars Louis Schulte, "Development of Tetraaryl- porphyrins as Bifunctional Chelating Agents for Advisory Committee for Isotope Medical and Environmental Uses" and Nuclear Chemistry Division, July 17-21,1990 Jan Wouters, "Exotic (Radioactive) Ion Beam Project"

Alex Gancarz, "Response to 1989 Committee Alex Gancarz, "Structuring Ourselves for a Report and Summary of Division Activities" Competitive Research Environment"

Bob Ryan,"Isotope and Structural Chemistry Bruce Erdal, "Environmental Initiatives Overview" Discussion"

Terry Smith, "Research Reactor Overview" Jim Brainard, "Rocky Flats—Biotechnology"

Dave Curtis, "Isotope Geochemistry Overview" Nan Sauer, "Rocky Flats—NOX Abatement"

Bill Daniels, "Nuclear and Radiochemistry Eric Niederhoffer and Paul Smith, "Rocky Overview" Flats—Cadmium Treatment"

Dave Curtis, "Los Alamos Global Climate Ines Triay, "Rocky Flats—Contaminant Removal Change Initiative: Role of INC Division" by Sedimentation"

Al Sattelberger, "New Opportunities for Alex Gancarz, "Facility Issues Facing INC Inorganic Chemistry Research in INC Division: Division" Organometallic Chemical Vapor Deposition and "Tc Chemistry"

Woody Woodruff, "Energy Conversion by Inorganic Systems: Cytochrome Oxidase and Rh2(CH3CN)10]4+" Pat Unkefer, "Overview of Environmental Chemistry"

Jim Brainard, "Siderophore-Mediated Actinide Mobilization"

Pat Unkefer, "TNT Biodegradation"

Jim Fee, "Overview of Biochemistry Activities"

Jim Fee, "Recent Advances in Cytochrome Oxidase Research"

Janet Mercer-Smith, "Overview of Biomedical Research"

Dennis Phillips, "Arsenic Radioisotopes in Medicine, Biology, and the Environment"

Dean Cole, "Uptake of Porphyrins in Tumors and Sites of Inflammation"

124 Isotope and Nuclear Chemistry Division Annual Report FY 1990 Appendix: Division Meetings and Seminars

Division Seminars

"The Swiss Program for Radioactive Waste Disposal—a Brief Overview of Selected Topics," Dr. Jan Boehringer, NAGRA, Switzerland, November 15,1989

"Chemical Behavior of Actinides During the Chernobyl Accident," Prof. Igor Khodakovsky, Vernadsky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Sciences, Moscow, USSR, August 3,1990

"Main Trends in Scientific Research at the Vernadsky Institute, Moscow," Prof. Boris Myasoedov, Deputy Director, Vernadsky Institute of Geochemistry and Analytical Chemistry of the USSR Academy of Sciences, Moscow, USSR, September 4,1990

"Concepts for Dealing with Radioactive Waste in the USSR," Prof. Alexander Nikiforov, Director, All-Union Scientific and Research Institute of Inorganic Materials Named after Academician A. Bochvar, Moscow, USSR, September 4,1990

"Fun and Games in the Department of Energy Office—Arms Control in Washington," Allen Ogard, Group INC-7, Los Alamos National Laboratory, Los Alamos, New Mexico, November 28,1990

Isotope and Nuclear Chemistry Division Annual Report FY 1990 125 Appendix: References

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19X lantnru* nnri NurJvnr C.hpinistrv Dinisinn Attiu/nJ Rvnnrt FY 1QQO The four previous reports in this series, unclassified, are LA-10709-PR, LA-11034-PR, LA-11291-PR, and LA-11865-PK.

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