NBSIR 83-2786 Technical Activities 1983 Center for Analytical Chemistry U S. DEPARTMENT OF COMMERCE National Bureau of Standards National Measurement Laboratory Washington, D.C. 20234 October 1 983 Final Issued December 1983 Prepared for U.S. DEPARTMENT OF COMMERCE National Bureau of Standards Washington, D.C. 20234 NBSIR 83-2786 TECHNICAL ACTIVITIES 1983 CENTER FOR ANALYTICAL CHEMISTRY H. S. Hertz, R. A. Velapoldi, and J. K. Taylor, Editors U S. DEPARTMENT OF COMMERCE National Bureau of Standards National Measurement Laboratory Washington, D.C. 20234 October 1983 Final Issued December 1983 Prepared for U.S. DEPARTMENT OF COMMERCE National Bureau of Standards Washington, D.C. 20234 U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director Certain commercial equipment, instruments, or materials are identified in this report to specify adequately the experimental procedure. Such identification does not imply recommendation or endorsement by the National Bureau of Standards 3 nor does it imply that the materials or equipment identified are necessarily the best available for the purpose. TABLE OF CONTENTS Page I. CENTER FOR ANALYTICAL CHEMISTRY A. Center Overview 1 B. Voluntary Standardization and Quality Assurance 10 C. Laser Analytical Chemistry Group 13 1. Group Overview 13 2. Selected Technical Reports 14 a. Use of Laser-Enhanced Ionization in Flames for the Analysis of Standard Reference Materials. ... 14 b. Inclusion of Background Effects in the Computer Simulation of LEI in Flames 17 3. Outputs and Interactions 20 II. INORGANIC ANALYTICAL RESEARCH DIVISION A. Division Overview 23 B. Selected Technical Reports 35 1. A New Electrochemical Technique for the Estimation of Diffusion-Layer Thicknesses at Hydrodynamic Electrodes 35 2. Determination of Vanadium in Botanical, Biological, and Environmental SRM's Using High-Sensitivity, Pulse-Counting Isotope Dilution Thermal Ionization Mass Spectrometry . 37 3. Ultra trace Determinations of Critical Elements in Biological Materials Using Improved Radiochemical Separations 38 4. Material Transport 40 5. Analysis and Stability of Environmental Specimen Bank Samples 41 6. The Characterization of Metastable Excited State Atomic Species Produced in Thermal Vaporization Using Resonance Ionization Mass Spectrometry (RIMS) 44 7. Interferences in the Determination of Germanium Using Electrothermal Atomization Atomic Absorption Spectrometry 47 8. Gases-in-Metals Analysis 49 9. The Standard Potential of the Ag/AgCl Electrode for High Accuracy pH Measurements. 50 10. Resonance Ionization Mass Spectrometry of Iodine and Carbon 52 11. Thermal Release of Helium from Single Crystal Nickel . 54 12. Determination of Selenium in Subcellular Fractions to Study the Glutathione Peroxidase System 57 32 34 13. The Measurement of Natural Variation in the S/ S Ratio in Atmospheric Samples 59 14. Evaluation of the Isotope Dilution Method for Ultra trace Chromium Concentrations 62 i Page 15. Ion Optics of Single and Double Stage Mass Spectrometers 63 16. Development of Reference Materials for Acid Rain Studies 65 17. The Development of a Pulsed Thermal Atom Source For Use in RIMS 67 18. Characterization of Biological SRM's Using Atomic Spectrometry Techniques 69 19. Measurement of Iodine Concentrations and Isotope Ratios at Environmental Levels 72 20. Certification of Uranium Isotopic Standard Reference Materials 73 21. Neutron Depth Profiling and the Characterization of Dopant Distributions 74 22. An Automated Mass Spectrometer--Inlet System for Gas Analyses 76 23. Potential Limitation in the Use of Thin Metal Films as Transmittance Standards 78 24. The Effect of Manganese on the Determination of Sulfur by Optical Emission Spectrometry 80 25. Certification of NBS Buffer Materials 82 26. Standard Reference Materials 83 C. Outputs and Interactions 86 III. ORGANIC ANALYTICAL RESEARCH DIVISION 101 A. Division Overview 101 B. Selected Technical Reports 114 1. Synthesis and Characterization of Chemically Bonded C 18 Phases for Liquid Chromatography 114 2. Characterization and Comparison of Three Air Particulate Samples for Polycyclic Aromatic Hydrocarbon Distributions 119 3. Determination of Chlorinated Pesticide Residues in 10. Human Liver Specimens for the Pilot Environmental Specimen Bank Program 124 4. Certification of Selected Organic Compounds in SRM 1582, Petroleum Crude Oil 127 5. Determination of Relative Isomer Content in SRM 916, Bilirubin 131 6. Determination of Organic Nutrients in SRM 1549, Non-Fat Milk Powder 132 7. Use of Polynuclear Aromatic Hydrocarbon Generator Columns for Calibrating Air Sampling Systems 135 8. Detection of Arson—Analysis of Accelerant Residues on Soot 137 9. Analysis of EPA Performance-Evaluation Standard Samples 138 Preparation and Certification of SRM Calibration Solutions 139 ) Page 11. Reference Methods for Certification of Seven Enzymes in SRM 909 142 12. Metal -Ion Affinity Chromatography Supports for Protein Separation 144 13. Thin-Layer Isoelectric Focusing for Sensitive Protein Analysis 145 14. Nitrogen-15 NMR Spectrum Editing by the DEPT Technique 145 15. Two-Dimensional, DEPT Heteronuclear J-Resolved Carbon-13 NMR Spectroscopy 149 16. Preparation and Analysis of a Quality Assurance Sludge Material 153 17. Investigation of Desorption Mechanisms in Laser Desorption and Field Desorption Mass Spectrometry. 155 18. Development of an Isotope Dilution/Mass Spectrometry Definitive Method for the Determination of Serum Creatinine 157 19. Two-Dimensional Electrophoresis System Implemented for Protein Separation and Identification 160 20. Laser Photodissociation of Ions and Reactive Ion/Molecule Collisions: Instrumentation and First Results 161 21. Determination of Polynuclear Aromatic Hydrocarbons in Environmental Samples Using Negative Chemical Ionization Mass Spectrometry 163 22. Polyethylene Methacrylate Coated Electrodes--Nonaqueous Solvent-Stable Polymer Film Electrode Modified with Methyl viologen 166 23. Use of a Zinc Scrubber Column for In-Line Removal of Oxygen from HPLC Mobile Phases 168 24. High-Performance Liquid Chromatographic Methods for the Determination of Nitro-Polynuclear Aromatic Hydrocarbons (N-PAH) in Complex Mixtures 173 25. Spectroelectrochemical Investigations of Cyanine Dyes , Rutheni urn- ( bi pyri di ne 2 di thiocarbamate Complexes, and Copper Dithiocroconates 179 26. Theoretical Modeling of the Double Step Chronocoulometry and Spectroelectrochemistry of Systems with Strong Product Deposition 181 C. Outputs and Interactions 184 IV. GAS AND PARTICULATE SCIENCE DIVISION A. Division Overview 197 B. Selected Technical Reports 205 1. Cross-Coupled Interaction of Thermal , Electrical, Mechanical, and Chemical Parameters of Polymeric Permeation Devices 205 2. Band Strength Measurements of Propane by Fourier Transform Infrared Spectroscopy 206 iii Page 3. Sampling and Measurement of Nitrous Oxide, Carbon Dioxide, and Methane in the Amazon 209 4. Stability Studies of NO in N 2 SRM's 213 5. Evaluation of Degree of Sorption in Collection of Trace-Organic Vapors on Sorbents 216 6. Round-Robin Assessment of Gas Saturation Test Method Proposed by EPA for Generating Vapor Pressure Data on Organic Chemicals 218 7. Development of Techniques for Preparation and Analysis of ppb Level Toxic Organic Standards 221 8. Pollutant Levels in Non-protected and Protected National Archival Storage Areas 222 9. Toxic Gases from Lithium Battery Discharges 225 10. Mathematical Chemistry: Design and Evaluation of the Analytical Measurement Process, Detection Limits, and Multidimensional Data 227 11. Origins of Carbonaceous Gases and Aerosols: Survey of Recent Measurement Advances and Results 231 12. Detection of HC1 at the Sub-Parts-Per-Bill ion Level Using Tunable Diode Laser Absorption 234 13. Completion of Measurements of the Temperature Dependence of the Ozone Absorption Cross-section in the Vacuum Ultraviolet 236 14. Reference Ultraviolet Photometer for Ozone Calibration and Assay 237 15. Completion of the Respirable Quartz SRM 239 16. Use of Monte Carlo Electron Trajectory Simulation for Basic Studies in Analytical Electron Microscopy 240 17. Visualization of the Three-Dimensional Nature of the Electron Interaction Volume in Solids 243 18. An Evaluation of X-ray Loss Due to Electron Backscatter 246 19. Studies of the Depth Distribution of Boron in Glass by Neutron Depth Profiling and Secondary Ion Mass Spectrometry 248 20. Detection and Analysis of Organic Monolayers by Laser Microprobe Mass Analysis 250 21. Standard Reference Material for Analysis of Asbestos by Electron Microscopy 251 22. Visibility of Asbestos Fibers in the Scanning Electron Microscope 253 23. An Analytical Algorithm for Calculation of Spectral Distributions of X-ray Tubes for Quantitative X-ray Fluorescence Analysis 254 24. Comparison of Theoretical a-Coefficient Fundamental Parameter Method with NRLXRF for Quantitative X-ray Analysis 258 25. Final Measurements and NBS Certification of Thin-Glass Standard Reference Samples for X-ray Spectrometry and Microanalysis 260 C. Outputs and Interactions 261 iv I. Center for Analytical Chemistry Harry S. Hertz, 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 development of measurement methodology and standards and provision of measurement services in the field of analytical chemistry. Analytical