OAK RIDGE NATIONAL LABORATORY Gptrat.EB by ONION Carbidt CORPORATION • -F0r the U S ATOMIC ENERGY COMMISSION
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QRNL-TM-4370 ) CHEMICAL DEVELOPMENT SECTION B SEMIANNUAL PROGRESS REPORT MARCH 1, 1973 TO AUGUST 31, 1973 : S V1 'i! ' I «« Jb fS ' A .-V W-t-' . t " • •/ OAK RIDGE NATIONAL LABORATORY GPtRAT.EB BY ONION CARBIDt CORPORATION • -f0R THE U S ATOMIC ENERGY COMMISSION \ H - ORNL-TM-U370 Contract No. W-7^05-eng-26 CHEMICAL DEVELOPMENT SECTION B SEMIANNUAL PROGRESS REPORT March 1, 1973 to August 31, 1973 PART I Compiled "by c. D. Scott c. A. Burtis D. J. Crouse L. M. Ferris ——— NOTICE J. C. Mailen This report was prepared as an account of work Pitt sponsored by the United States Government. Neither W. W. the United States nor the United States Atomic Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, com- pleteness or usefulness of any information, apparatus, product or process disclosed, or represents that its use would not infringe privately owned rights. FEBRUARY 1974 NOTICE This document contains information of a preliminary nature and was prepared primarily for internal use at the Oak Ridge National Laboratory, It is subject to revision or correction and therefore does not represent a final report. OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee 37^30 operated "by UNION CARBIDE CORPORATION for the U.S. ATOMIC ENERGY COMMISSION 'M & ^WTI t's iii TABLE 0? CONTENTS Page PUBLICATIONS ix ORAL PRESENTATIONS xiii SUMMARY xix 1. INTRODUCTION 1 2. FAST ANALYZER DEVELOPMENT Z 2.1 Miniature East Analyzer ?. 2.1.1 Instrumentation Development k 2.1.2 System Performance and Evaluation lo 2.1.3 On-Line Computer 3U 2.1.U Development of Chemical Assays 37 2.1.5 Dynamic Loading of Liquids 37 2.1.6 Fluorescence Monitor 5k 2.1.7 Light Scattering Monitor 61 2.1.8 Portable Data Printer 70 2.2 Portable Fast Analyzer 71 2.3 Fluorescence Fast Analyzer 72 2.3.1 Instrumentation 75 2.3.2 Fluorescence Sensitivity and Fluorescence Tracers 77 2.3.3 Fluorescence Polarization Measurements 75 2.3.U Fluorescence Referencing 62 2.3.5 Calculation of Enzyme Activity and Substrate Concentration 35 2.3.6 Effectiveness of Dynamic Referencing 5?" 2.3.7 Development of Enzyme Analyses yl 2.3.8 Immunological Assays . 10U 2.3.9 Fluorometric Determination of Uranium 112 2.3.10 Future Development 112 2.k Chemical Assay Methods llU 2.H.1 Triglycerides for Large 15-Place GeMSAEC llU 2.k.2 Serum Uric Acid with the Miniature Fast Analyzer 121 2.1+.3 Additional Serum Chemistry Assays for Miniature Fast Analyzer 127 2.5 Evaluation and Operation of Fast Analyzers in a Clinical Laboratory . 128 2.5.1 15-Place GeMSAEC Fast Analyzer 128 2.5.2 Miniature Fast Analyzers 129 2.5.3 Population Studies 130 2.6 References for Section 2 138 BLANK PAGE iv Page 3. GENETIC MONITORING 1^2 3.1 Sample Preparation lU2 3.1.1 First Prototype Rotor IU3 3.1.2 Advanced Rotor Design lU5 3.2 Automated Elution Electrophoresis lU8 3.3 Isoenzyme Stripping by Use of the Fast Analyzer 150 3.U References for Section 3 157 U. HIGH-RESOLUTION ANALYTICAL SYSTEMS 158 U.l Prototype Systems 158 U. 2 Computer Systems l6l U.2.1 System Description l6l U.2.2 Computer Programs 162 U. 3 Systems Development - 170 U.3,1 Cation Exchange Separation of Ninhydrin-Positive Constituents 171 4.3.2 Liquid Chromatographic Analysis of Blood Serum . 177 U.3.3 Application of Fluorescamine to Monitoring of Urinary Polyamines l8o U. 3 • Analysis of Nucleosides and N-Bases 19U .3.5 Separations Systems ;.... * 196 U.U Identification of Body Fluid Constituents 203 U.U.I New Identifications 20U U.U. 2 Identification of a-Methoxyhomovanillic Acid 2 QU U.U. 3 Urinary Nucleoside Excretion by Patients vith Cancer 206 U.5 Bxoerimental ?,ecults and Applications 217 U.5.1 Effects of L-BOPA and a DOPA Decarboxylase Inhibitor 217 U.5.2 LC Profiles of Aromatic Acids for Children with Neurological Disorders 228 U.5.3 Body Fluid Constituents of Patients with Rare Pathologic Conditions 232 U.5.U Urinary Metabolites of U-Hydroxyacetanilide .... 235 U.6 References for Section U 239 5. HACKOI>'OLECuLAH SEPARATIONS Zkk 5.1 Purification of Erythropoietin 2UU 5.1.1 Preparation of Affinity Columns 2U5 5.1.2 Purification by Indirect Affinity Chromatography 2U7 cccxii Page 5.2 Purification of Colony Stimulating Factor 250 5.3 Isolation of Purified Transfer Ribonucleic Acids 252 5.3.1 Selection of Factor Tu 255 5.3.2 Isolation of Factor Tu 256 5.3.3 Complex I and II Formation 259 5.U Distribution of Products 265 5.5 Separation and Comparison of Sequence of Three Formylmethionine tRNAs from E. coli 268 5.5.1 Separation of tRNA|Met and tRNA™e^ 269 5.5.2 Comparison of Ribonuclease Tx and Pancreatic Ribonuclease Digests 269 5.5.3 Relationships Among Three tRNAsfMet 270 5.6 Sequence Studies on Phenylalanine tRNA from Calf Liver 270 5.6.1 Base Composition of Calf Liver tRKAPhe 27k 5.6.2 pancreatic Ribonuclease Digestion of tRNAph© ... 276 5.7 References for Section 5 278 6. HYDROGEN PRODUCTION 28l 6.1 Enzymatic Hydrogen Production 28l 6.2 Thermal Hydrogen Production 285 6.3 References for Section 0 286 7. WATER POLLUTION STUDIES 288 7.1 Automated Analysis of Dissolved Organic Compounds in Polluted Waters 288 7.1.1 Effluents from Sewage Treatment Plants 290 7.1.2 Natural Waters 303 7.2 Environmental Effects of Antifoulants 311 7.3 References for Section 7 * 3i2 8. RADIOACTIVE WASTE DISPOSAL 315 8.1 Radiation Effects in Salt Mine Waste Repositories 31p 8.1.1 Radiation and Stored Energy of Salt Specimens .. 323 8.1.2 Results of Thermal Annealing Studies 325 8.1.3 Correlation of Energy Storage Data 328 8.1.U Evolution cf Hg upon Salt Dissolution 336 8.1.5 Loss of Water from Lyons Salt During Radiation Exposure 339 8.1.6 Gases in Unirradiated and Irradiated Lyons Salt 3^1 8.1.7 Future Work 3^ vi Page 8t2 Waste Disposal "by Hydraulic Fracturing 8.2.1 Waste Injections 3^5 8.2.2 Environmental Impact Statement 3^-8 8.2.3 Sludge Characteristics 3^8 8.2.1* Leaching Studies 3^9 8.3 Wet Oxidation of Plutonium 355 8.U References for Section 8 356 9. ENVIRONMENTAL SURVEYS 359 9.1 The Nuclear Fuel Cycle - Milling of Uranium Ores 359 9.2 Nuclear Industry Wastes 3^1 9.2.1 Use of Evaporation for the Treatment of Liquids in the Nuclear Industry 361 9.2.2 Solid Waste Practices at Nuclear Power Plants 3^3 9.3 Mercury Studies 3^ 9.3.1 Survey of Mercury Reprocessors 3^5 9.3.2 Usage of Mercury by Agencies of the U.S. Government 3^5 9.U Biological Response to Proprietary Chemicals Used in Cooling Water <... * 3^6 9.5 References for Section 9 3^7 10. SEPARATIONS PROCESSES 368 10.1 Recovery of Uranium from Wet-Process Phosphoric Acid . 368 10.1.1 Process Flowsheet 3^9 10.1.2 Solvent Composition 370 10.1.3 Effects of Process Variables on Extraction ... 370 lO.l.U stripping of Uranium 371 10.1.5 Process Demonstration 372 10.2 Separation of Radium from Uranium Ore Tailings 378 10.3 Separation of Alpha Emitters from Reprocessing Wastes 381 10.k High-Pressure Ion Exchange Studies 386 10.5 References for Section 10 391 11. CHEMICAL APPLICATIONS OF NUCLEAR EXPLOSIVES 39^ 11.1 Contamination by Tritium ...... 392 11.2 Contamination by Fission Products 396 11.3 References for Section 11 397 vii Page 12. CHEMISTRY OF RADIOIODINE .. 398 12.1 Mercuric Nitrate Scrubbing Process 398 12.1.1 Methyl Iodide Removal in Packed and Bubble-Cap Columns 399 12c1.2 Decomposition Rates of Various Organic Iodides ij-02 12.1.3 Process Demonstrations 12.2 Formation of Organic Iodides in Process Systems 1+10 12.3 References for Section 12 . Hll 13. CTR SUPPORTIVE RESEARCH ^12 13.1 Equilibria in the Hydrogen Isotope—Lithium Systems .. ^12 13.1.1 Total Pressure Method * U13 13.1.2 Partial Pressure Method h22 13.2 Phase Equilibria in the Li-K System I+23 13.3 Permeation of Deuterium Through Structural Metals at Low Pressures ^27 13.^ Permeation of Deuterium Through Metals Coated with Oxide Films k35 13.5 Chemisorption of Tritium on C-raphite ^3$ 13.6 EffectAnalogs osf Stronof Molteg Magnetin Saltcs Fields on Aqueous bk2 13.7 Thermodynamics and Mass Spectrometry of Vanadium Fluorides W? 13.8 The Solubilities of Hydrogen, Deuterium, and Helium in Molten Li2BeF4 kb-9 13.9 References for Section 13 ^+50 lU. THERMODYNAMICS OF MOLTEN-SALT SYSTEMS lU.l Chemistry of Tellurium in Molten Li2BeF4 lk.2 Electrostatic Energies and Heats of Formation of 3d Metallic Difluorides b57 lU.3 Lattice Energies of Cubic Alkaline-Earth Oxides. Affinity of Oxygen for Two Electrons ^60 1I4.4 Relationship Bet-ween Sonic Velocity and Entropy in Molten UCfe k66 lU.5 References for Section lU U69 15. COAL CONVERSION STUDIES U72 15.1 References for Section 15 ^ viii Page APPENDIX I k75 APPENDIX II 1+93 PUBLICATIONS Author(s) Title Publication Arnold, W. D., R. Preliminary Evaluation of Methods 0RNL-TM-U02U. Salmon, K. H. for the Disposal of Tritiated Lin, and W. Water from Nucleaily Stimulated deLaguna Natural Gas Wells Burtis, C. A., W. F. Development of an Analytical System Clin. Chem.