NBSIR 80-21 64 /f Technical Activities 1980 Center for Analytical Chemistry C. W. Reimann, R. A. Velapoldi, L. B. Hagan, and J. K. Taylor, Editors National Measurement Laboratory National Bureau of Standards U.S. Department of Commerce Washington, DC 20234 October 1980 I Final Issued December 1980 Prepared for National Bureau of Standards Department of Commerce Washington, D.C. 20234 NBSIR 80-2164 TECHNICAL ACTIVITIES 1980 CENTER FOR ANALYTICAL CHEMISTRY C. W. Reimann, R. A. Velapoldi, L B. Hagan, and J. K. Taylor, Editors National Measurement Laboratory National Bureau of Standards U.S. Department of Commerce Washington, DC 20234 October 1980 Final Issued December 1980 Prepared for National Bureau of Standards Department of Commerce Washington, D.C. 202340 U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary Jordan J. Baruch, Assistant Secretary for Productivity. Technology, and Innovation NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director i : ’ Mk * ^ •\ JtSs^vnvIfTwi^^^ vm 8 t g^aHp'iADiww L I tH ‘V ^ . -tV?Vv '^S® ‘r.- ...j » K • , ' i'-t.'i'ns( ^- ,'r.f «., ^•^,,. ... •*ri»!\ •2-''.-«v, . '. V%' J'’-“1f. , .;•.•, ‘:TS*«^,j,,.„ '— 'i-"‘'-'!5,, si- ' ' •' ' , ,', .'"'gP r' *ifi . M'"'- -.-JiW' i>^+' -’,''.y?,s ,l ' ' i' .• • j"< ‘' '^ '-Hjr ’*'r . » -ffl; '^'IP' >>3iaAi> /» inii ..« ^’ •’ •'• 'i ' ' '• ' *\' • •/' ' '* •/' ^•"''' it’em '. ! \' ^ui-tr \ ,* «si ^.» i '^arV''^TfrL.' 'lua* . — ' ’ "'4 • > • V;^ ^ ;. ''. ^v^7< , -yt: T^ 'Oi.liMW , .>V. ' , f! • -Air C' '*T^ ; :«'V' w; ^’' ,; ,’ fe. •<ij(!l1l*'TW4lt>C' Xl M^7«a4.'f, .1 ® kiftr • •' >a & '‘•iW’ I'MiL.,' 'T f «. vS V '^C’Hik. Asvk ^sry«*W*;W ^ - <^ •' ,a ' vffeSM' 'liSL 'MMB TABLE OF CONTENTS Page I. CENTER FOR ANALYTICAL CHEMISTRY A. Center Overview 1 B. Voluntary Standardization and Quality Assurance Coordination 4 C. National Environmental Specimen Bank 8 D. Service Analysis 21 E. New Competence Building Program — FY '81 23 F. Instrument Development Group 26 1 . Group Overview 26 2. Selected Technical Accomplishments 28 a. Studies of the Charge-Collection Mechanism in Laser Enhanced Ionization Spectrometry 28 b. Atomic Resonance-Line Lasers for Atomic Spectrometry 33 c. Reduction of Ionization Interferences in Laser Enhanced Ionization Spectrometry 36 d. Detection Limits of Some Trace Molecules of the Atmosphere by IR Diode Laser Absorption .... 38 e. Trace Organic Analysis by Multi photon Ioniza- tion 41 f. Instrumentation Project 45 3. Outputs and Interactions 46 II. INORGANIC ANALYTICAL RESEARCH DIVISION A. Division Overview 49 B. Selected Technical Accomplishments 59 1. D.C. Plasma Emission Spectrometry 59 2. The Halogen Content of Lubricating Oils 61 3. Measurement of the Co-60 to Co- 59 Ratio in Micro- particles 62 4. Cryogenic Homogenization of Tissue 64 5. Rapid Analysis of Toxic Metals in Biological Tissue and Fluids by Atomic Absorption Spectrometry .... 66 6. Comparative Measurements of Zinc-70 Enrichment in Human Plasma Using Neutron Activation Analysis and Thermal Ionization Mass Spectrometry 68 7. Trace and Toxic Elemental Study of the Chesapeake Bay 69 8. Characterization of Potentially Hazardous Wastes — Development of Rotary Extractor and Quality Assurance Standards 72 9. Development of an Improved Gravimetric Method for the Determination of Aluminum in Bauxite 75 10. Fission Track Monitor 77 11. Interferences in the Inductively Coupled Plasma (ICP) Technique 77 12. Atomic Weight of Silver 79 1 13. High Accuracy Mass Spectrometric Isotopic Analysis of Uranium 81 14. Half-Life of 2*+ipu 82 15. High Precision Pulse-Counting 83 16. High Accuracy Method for Determining Sulfur in Iron Base Alloys 84 17. Standard Reference Materials 86 C. Outputs and Interactions 89 III. ORGANIC ANALYTICAL RESEARCH DIVISION A. Division Overview 99 B. Selected Technical Accomplishments 110 1. Isotope Dilution/Mass Spectrometry Definitive Method Developed for Creatinine in Serum 110 2. Human Serum Reference Material (SRM 909) Ill 3. FI uoroimmunoassay Procedure Developed for Dinitrophenol s in Water 112 4. Development of Methods for Determination of the Aromatic Carbon Content of Recycled Oils by High- Field ^^C NMR Spectroscopy 113 5. Research on Two-Dimensional Proton NMR Spectroscopy and Its Application to SRM Q-Glucose 118 6. Analysis of Sodium Pyruvate and Its Impurities by Proton NMR Spectroscopy at 400 MHz 121 7. Analysis of Boat Conformations of a-D-Al tropyranoside Derivatives by Interpretation of Highly Coupled Proton NMR Spectra 124 8. Laser Polarimetry and Its Application to Recertifi- cation of Sucrose SRM (SRM 17c) 131 9. Certification of Generator Columns for Polynuclear Aromatic Hydrocarbons in Water (SRM 1644) 131 10. First Natural Matrix Trace Organic SRM Issued for Shale Oil (SRM 1580) 134 11. Synthesis, Isotopic and Purity Analyses, and Prepara- tion of Solutions of Stable Isotope Labeled Marker Compounds for Priority Pollutant Analysis 136 12. Evaluation of a Spectroel ectrochemical System Using ^-Tol idine 138 13. Development of a System for Computer-Controlled Rapid Electrochemical Measurements 140 14. Development of a High-Sensitivity Dual -El ectrode Detector for Liquid Chromatography 141 15. Estimation of Thermodynamic and Kinetic Data from Spectroel ectrochemical Studies Using Digital Simulations 141 16. Method Development for Determination of Ambient Temperature Vapor Pressures of Polynuclear Aromatic Hydrocarbons 146 17. Combined LC/MS Techniques for Direct Quantitative Analysis of Individual Organic Compounds in Complex Mixtures 148 18. Correlation of Liquid Chromatographic Retention Data with Molecular Shapes for Polycyclic Aromatic Hydrocarbons 148 i i 19 . Application of Mul ti-Dimensional Chromatography to Trace Organic Compound Quantitation 150 20. Development of a Procedure for the Analysis of Polychlorinated Biphenyls in Recycled Oils 152 21. Development of a Fourier Transform Infrared Spectrometer-Gas Chromatograph Interface and Its Application to Pollutant Identification 153 C. Outputs and Interactions 154 IV. GAS AND PARTICULATE SCIENCE DIVISION A. Division Overview 165 B. Selected Technical Accomplishments 174 1 . Intercomparison of O3 and NO2 Measurement Standards by Gas Phase Titration 174 2. Development of Atmospheric Nitrous Oxide and Halo- carbon Standards 176 3. The Determination of Infrared Line Intensities for Selected Molecules Using Diode Laser and Fourier Transform Infrared Spectroscopy 179 4. The Measurement of Temperature Dependence of Ozone Absorption Cross-Sections in the Ultraviolet 180 5. Standards for Measurement of Atmospheric Carbon Dioxide 182 6. Industrial Preparation of Traceable Gas Certified Reference Materials 183 7. Standard for Measurement of Benzene and Perchlor- ethylene in Workplace Atmospheres 184 8. Motor Vehicle Manufacturers Association Program for Heavy Duty Vehicle Emissions Standards 185 9. Evaluation of the Coherent Anti-Stokes Raman Spectroscopy (CARS) Capillary Waveguide Detection System for High Performance Liquid Chromatography . 187 10. Measurement of Ambient Sulfur Aerosols by a New Fast Response Flame Photometric Instrument 189 11. Monte Carlo Electron Trajectory Calculation of Beam Spreading Effects in Thin Foils in the Analytical Electron Microscope 190 12. General Expression Developed for the X-ray Bremsstrahlung Intensity Data 192 13. Development of a Sequential Simplex Procedure for Resolving Spectral Interference in Energy Dispersive X-ray Spectrometry 194 14. Development of a New Procedure for Calibration of a Crystal Spectrometer for Relative Line Intensity Measurements 195 15. Successful Raman Microprobe Analysis of Opaque Particles 197 16. Development and Characterization of a New Raman Microprobe with Multichannel Optical Detector .... 200 17. Ion Microprobe and Laser Microprobe Mass Analysis of Inorganic Particulates 203 18. Evaluation of Counter Error in the Development of Asbestos Standards for the Electron Microscope .... 206 19. The Development of Thin Glass Films as Potential Standards for X-ray Spectrometric Calibration 207 20. Low Velocity Wind Tunnel Facility for the Evaluation of Personnel Dosimeters 211 21. Enhanced Detection of Molecules Near a Surface by Raman Spectroscopy Excited by Evanescent Waves .... 212 22. Statistical Evaluations of the International Radio- carbon Cross Calibration Exercise, and of the Natural Radiocarbon Fluctuations 214 23. Advances in Small Sample Radiocarbon Measurement Techniques; Application to the Assay of Individual Atmospheric Chemical Species 220 C. Outputs and Interactions 223 I. Center for Analytical Chemistry Curt W. Reimann, Director Ranee A. Velapoldi, Deputy Director A. Center Overview The Center for Analytical Chemistry develops and maintains the scientific competences and the experimental facilities necessary to provide the Nation with the basis for uniform measurements through develop- ment of measurement methodology and provision of measurement services in the field of analytical chemistry. Analytical measurements provide a foundation for all aspects of scientific and technological research and development concerning materials and their practical application. Further- more, results of analytical measurements are increasingly used as the basis for regulatory, medical, and industrial decisions. It is essential that these measurements be reliable and the Center serves as the national reference laboratory for assuring this reliability. The principal means by which the Center serves as a national reference laboratory is through the development and issuance of standard reference materials (SRM's). The ubiquity