AlllOb 171SS8

NBSIR 82-2620

Annual Report 1982

Center for Analytical Chemistry

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Washington, DC 20234

October 1982

Final

Issued December 1982

QC

100

U56

#82-2620

1982

C . 2

Prepared for U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington, DC 20234

NBSIR 82-2620

ANNUAL REPORT 1982

CENTER FOR ANALYTICAL CHEMISTRY

C. W. Reimann, R. A. Velapoldi, and J. K. Taylor, Editors

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Washington, DC 20234

October 1982

Final

Issued December 1982

Prepared for U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington, DC 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, 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 7 C. Pilot National Environmental Specimen Bank Program 10

D. Service Analysis 21

E. Laser Analytical Chemistry Group 23

1. Group Overview 23

2. Selected Technical Reports 24

a. Computer Simulation of Charge Transport and

Current Detection Following Ionization in Flames. . 24

b. Characterization of Pulsed LEI Current Detection

and Implications for Analytical Measurements. ... 26

c. Stark Modulated Infrared Diode Laser

Spectroscopy 30

d. Measurement of the Isotopic Ratios: 12 C/ 13 C and

14 N/ 15 N 33

3. Outputs and Interactions 34

II. INORGANIC ANALYTICAL RESEARCH DIVISION

A. Division Overview 37

B. Selected Technical Accomplishments 47

1. High-Accuracy pH Measurements 47

2. Resonance Ionization Mass Spectrometry of Vanadium,

Molybdenum, and Rhenium 48

3. Depth Profiling of Bismuth in Silicon and Tin with

Low-Energy Neutrons 51

4. Determination of Provenience of Artifacts with Lead

Isotope Ratio Measurements 54

5. Treatment of Sources of Variability in the

Inductively Coupled Plasma (ICP) Technique 56

6. Effect of Natural Isotopic Variability on Accurate

Determination of Sulfur by Neutron Activation

Analysis 58

7. Application of ID/MS to the Determination of sulfur

in Biological and Environmental Standards 60

8. Development of a Laser Mass Spectrometry Laboratory. . . 62

9. Design and Construction of a Modern Facility for the

Production of Ultrapure Reagents 64

10. Improved Procedure for the Determination of Cyanide

by Ion Chromatography with Electrochemical Detection . . 65

11. Direct Determination of Calcium in Urine Using a Thermally-Regulated D.C. PI asma-Echel le

Spectrometer 66

12. Determination of Ultratrace Concentrations of

Chromium by Isotope Dilution Mass Spectrometry 67

i
Page

13. Improved Radiochemical Procedures for High

Sensitivity Measurements of Ultratrace

Concentrations of Tin and Mercury 68

14. Isotopic Fractionation of Gallium on an Ion

Exchange Column 69

15. Improved Sensitivity in Instrumental Activation

Analysis Using the Compton Suppression Technique .... 70

16. Development of an Isotope Dilution Mass Spectrometric Procedure for Iodine in Botanical Materials ... 72

17. Ion Optics of Magnetic Sector Mass Spectrometers .... 73

18. The Use of a Chromium Internal Standard for the

Analysis of Diverse Iron-Chromium-Nickel Alloys 75

19. Development of a Precise Static Leach Test and the

Evaluation of Simulated Nuclear Waste Glasses for

a Reference Material 77

20. New Concepts in the Design and Fabrication of

Fluorescent Glass Standards for Use in

Nondestructive Crack Testing 78

21. Characterization of Selected Trace Elements in the

Chesapeake Bay 79

22. Research to Develop Isotope Dilution Mass

Spectrometry for Ultratrace Concentrations

of Cadmium 84

23. The Use of Round Robins to Evaluate State-of-the-Art

Uranium and Plutonium Measurements by Thermal

Ionization Mass Spectrometry 85

24. Standard Reference Materials 87

C. Outputs and Interactions 90

III. ORGANIC ANALYTICAL RESEARCH DIVISION

A. Division Overview 105

B. Selected Technical Accomplishments 119

1. The Effect of C 18 Surface Coverage on Selectivity

in Reversed-Phase HPLC 119

2. Determination of Ambient Temperature Vapor Pressures

of Polycyclic Aromatic Hydrocarbons 123

3. Determination of Polycyclic Aromatic Hydrocarbons in

Complex Mixtures Using HPLC with Mobile Phase and

Fluorescence Wavelength Programming 125

4. Vidicon Based Fluorescence Detection for Qualitative

and Quantitative Analyses in HPLC 128

5. Certification of SRM 1649, Urban Dust/Organics, for

Selected Polycyclic Aromatic Hydrocarbons 129

6. Determination of Nitro-Polycycl ic Aromatic Hydrocarbons Using Post-Column Reduction to Fluorescent

Amino Derivatives ^1

7. Methods for the Determination of Vitamins in Milk. . . . 135

8. Certification of an SRM for the Anticonvulsant Drugs

Carbamazepine and Valproic Acid in Serum 137
Page

9. Research Results on the Analysis of Polychlorinated

Biphenyls in Oils 139

10. Analysis of a California State Reference Material

for Pesticides in Sediments 142

11. Design and Construction of a Sampling System for

Woodburning Stove Gases and Particulate Samples 143

12. Development of Methods for the Determination of Toxic

Organic Compounds in Aqueous Leachates of Hazardous

Wastes and Development of a Quality Assurance Sludge

Material 144

13. GC/MS Determination of Acidic and Basic Compounds

in a Shale Oil Process Water 148

14. Development of an Isotope Dilution/Mass Spectrometric

Definitive Method for the Determination of Serum Urea. . 150

15. Improved Instrumentation for Organic Isotope

Dilution/Mass Spectrometry Measurements 153

16. Preparation of Solutions of Stable Isotope Labeled

Marker Compounds for Use in the Analysis of

Priority Pollutants 156

17. Surface-Enhanced Raman Spectroscopy of N-Methylpyridinium Cation and Pyridine: Identification

of Surface Species 158

18. Electrochemical and Spectroelectrochemical Studies

of Copper and Iron Bleomycin Complexes 159

19. Polymer Modified Electrodes: Electrocatalytic

Sensors for Detection of Organic Analytes 160

20. Theoretical Analysis of Charge Transport in

Polymer-Modified Electrodes 161

21. Characterization of an Angiotensin I SRM by Proton

NMR Spectroscopy at 400 MHz 163

22. The Synthesis, Purification, and Characterization of

2-Methyl thio-oxazol ine Derivatives of Pentoses and

Hexoses 166

23. An Efficient Two-Step Synthesis of a Novel

15 N-Labeled Cyclonucleotide: 2,3'-Anhydro-l-$-Dfructofuranosyluracil- 15 N 2 -l ' ,6 ' -diphosphate 168

24. Confirmation of the Standard Wavelength for the

100 °S Point of the International Sugar Scale by

Polarimetric Measurements with a Dye Laser 172

25. Implementation of and Initial Research in

Two-Dimensional Electrophoresis for Protein

Separations 174

26. Total Protein Content Certification of SRM 909,

Human Serum 175

27. Construction of a Toxic Chemicals Handling

Laboratory 175

C. Outputs and Interactions 177
Page

IV. GAS AND PARTICULATE SCIENCE DIVISION

A. Division Overview 191

B. Selected Technical Accomplishments 199

1. Isotopic Abundance Measurements with the Laser

Microprobe Mass Analyzer 199

2. Microbeam Analysis of Diffusion — Induced Grain

Boundary Migration 201

3. Electron Beam Broadening in Thin Films of Uranium

Alloys Analyzed in the Analytical Electron Microscope. . 204

4. Status of the Quantitative Electron Probe

Microanalysis Programs FRAME and FRAME C 205

5. Crystallographic Contrast in Ion Microprobe Analysis

of Inconel 206

6. Development of a Comprehensive Algorithm to Calculate

the Spectral Output Distribution of X-Ray Tubes for

X-Ray Spectrometry 208

7. Certification of Thin-glass Films as Standard

Reference Materials for X-ray Spectrometry and

Microanalysis 209

8. X-Ray Spectrometri c Analysis of NBS-SRM Bovine Liver

and Pine Needles After Separation and

Preconcentration 211

9. Evaluation of Personal Monitors 213

10. Measurement of the Temperature Dependence of the

Ozone Absorption Cross-Section in the Ultraviolet. . . . 216

11. Completion of Reference Ultraviolet Photometer for

Ozone Calibrations 216

12. Photoacoustic Detection of HC1 217

13. A Study of Measurement Interference In The

Photoacoustic Detection of N02 by Argon-Ion

Laser Excitation 219

14. Accelerator Mass Spectrometry (AMS) 222

15. Receptor Modeling and Radiocarbon in Aerosols:

Source Apportionment 224

16. Methodology for Vapor Pressure Measurements of

Organics in the 10 to 10~ 5 Pascal Range 226

17. Development of Multicomponent Toxic

Organics-in-Ai r Standards 228

18. Standards for Measurement of Atmospheric Carbon

Dioxide 229

19. Development of Protocols for Providing Traceability

of Commercial Gas Standards to NBS SRM Gas Mixtures. . . 231

20. Design and Evaluation of a High-Rate Passive

Sampler for Ambient Levels of Nitrogen Dioxide 234

21. Development of Mixtures of 36 Ar and 40 Ar for

Characterization of the Atmosphere of Venus 236

22. Development of Parts-per-Bi 1 1 ion Nitrous

Oxide-in-Air Standard Reference Materials 237

C. Outputs and Interactions 240

IV
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 development of measurement

methodology and standards and provision of measurement services in the field

of analytical chemistry. Analytical measurements provide a foundation for

scientific and technological research and development concerning materials and

their practical application. Moreover, analytical measurements are increasingly used as the basis for industrial, regulatory, and medical decisions.

The Center serves as the National reference laboratory for assuring the

reliability of analytical measurements.

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 of and demand for analytical measurements in

modern society is reflected in the diversity of SRM's produced in the Center.

These standards are widely used in such diverse areas as the metal and chemical industries and in clinical and environmental laboratories. Each standard

is supported by research on homogeneity and stability and is certified as to

chemical composition using the most reliable analytical methods available.

Analytical chemistry is increasingly being called upon to provide key

data for highly complex sample types - hazardous chemical and nuclear wastes,

body fluids, plant and animal tissues, foods, and high-technology materials.

Often, analytical values as a function of location within a sample are needed. As the demands upon analytical chemistry become more sophisticated,

the problem of standardization becomes more challenging both in terms of the

number and the complexity of the proposed standard materials. As it is not

reasonable to contemplate the development of standards to deal with every

measurement problem, the Center's program must be multifaceted, seeking a variety of avenues to influence the quality of analytical measurements made in

the U.S. In addition to the issuance of standards, the Center exerts influence

through close contacts with various communities by means of workshops, symposia,

and participation in standards committees. Through such contacts, priorities

are established for the production of standards and mechanisms are set in

place for their effective use.

NOTE: 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, nor does it

imply that the materials or equipment identified are necessarily

the best available for the purpose.

1
The program of the Center strives to achieve a balance among the

provision of currently needed standards and research efforts on new types of

standards and methods of measurement. The work of the Center is performed in

three divisions, each focusing upon specific sample types — inorganics,

organics, and gases and particles. Within each division there are several

groups representing separate analytical chemical disciplines, e.g., mass spectrometry and electrochemistry. One group, the Laser Analytical Chemistry

Group, is attached to the Center office. Each division is responsible for a program in basic and applied research and maintains contacts with appropriate

communities

In the following, the major recent activities and technical directions of

the divisions and groups mentioned above are given.

1. Outputs and Interactions

a. Publications

Reimann, C. W. , Velapoldi, R. A., and Taylor, J. K. , "Technical Activities

1981, Center for Analytical Chemistry", NBSIR 81-2425.

Demas, J. N., Bowman, W. D., Zalewski, E. F., and Velapoldi, R. A., "Determination of the Quantum Yield of the Ferri oxalate Acti nometer with

Electrically Calibrated Radiometers", J. Phys. Chem. 85_, 2766-71 (1981 ).

Zalewski, E. F., Geist, J., and Velapoldi, R. A., "Correcting Excitation and

Emission Spectra: Past Procedures and New Possibiliites". Proceedings

of ASTM Conference on "New Directions in Molecular Luminescence",

March 1982.

Velapoldi, R. A., White, P. A., May, W. E., and Eberhardt, K. R. , "The

Spectrofl uorimetric Measurement of Polynuclear Aromatic Hydrocarbons in

the Aqueous Effluent of Generator Columns". Submitted: Analytical

Chemistry.

Taylor, J. K. , "Quality Assurance of Chemical Measurements", Anal. Chem.

53, 1 588A-1 596A (1981).

Taylor, J. K. , "The Analytical Chemist", CHEMTECH, p. 285, May (1982).

Crummett, W. B., and Taylor, J. K. , "Guidelines for Data Acquisition and

Data Qaulity Evaluation in Environmental Chemistry", in "IUPAC

Collaborative Interlaboratory Studies in Chemical Analysis", Edited by

Egan, H. E., and West, T. S., Pergammon Press, Oxford and New York (1982).

Kratochvil , B. G. , and Taylor, J. K. , "A Survey of the Recent Literature on Sampling for Chemical Analysis", NBS Tech. Note 1153, January 1982.

Taylor, J. K. , "Guidelines for Evaluating the Blank Correction", submitted

to ASTM Journal of Environmental Measurements and Applications.

2
Taylor, J. K. , "Validation of Analytical Methods", submitted to ASTM

Journal of Environmental Measurement and Applications.

Taylor, J. K. , "Reference Materials - How They Are or Should be Used",

submitted to ASTM Journal of Environmental Measurement and Applications.

Taylor, J. K. , "The Use of Range Control Charts in Analytical Chemistry,"

submitted to ASTM Journal of Environmental Measurement and Applications.

b. Tal ks

J. K. Taylor, "Data Acquisition and Data Quality Evaluation in Environmental

Chemistry" - American Society for Quality Control, Newark, DEL.,

December 14, 1981

Velapoldi, R. A., "Luminescence and Spectrophotometry" NBS/ADABSE Workshop,

October 16-17, 1981

J. K. Taylor, "Quality Assurance Programs", EPA Las Vegas, NV, January 12,

1982.

J. K. Taylor, "The Role of Analytical Chemistry in a Materials Research

Laboratory", University of Petroleum and Minerals, Dhahran Saudi Arabia,

February 9, 1982.

J. K. Taylor, "Profile of a Modern Analytical Chemistry Laboratory", University

of Petroleum and Minerals, Dhahran, Saudi Arabia, February 10, 1982.

Reimann, C. W. , "Trace Constitutents in Human Tissue: Reliability of Measurements", National Institute of Child Health and Human Development,

March 9, 1982.

Reimann, C. W. , "The NBS Specimen Bank Program", College of American

Pathologists, Committee on Environmental and Iatrogenic Toxicology,

Chicago, Illinois, April 1, 1982.

J. K. Taylor, "Quality Assurance of Chemical Measurements", E. I. DuPont Co.,

Wilmington, Delaware, April 27, 1982.

J. K. Taylor, "Principles of Quality Assurance", F & DA, Philadelphia, PA,

May 17, 1982.

J. K. Taylor, "Controlling the Quality of Chemical Measurements",

Ruder Boskovic Institute, Zagreb, Yugoslavia, June 22, 1982.

J. K. Taylor, "Evaluating the Quality of Chemical Data", Ruder Boskovic

Institute, Zagreb, Yugoslavia, June 23, 1982.

Velapoldi, R. A., "The Center for Analytical Chemistry" and "Luminescence

and Spectrophotometry", Center for Industrial Research - Oslo University,

Oslo, Norway, June 3, 1982.

3
Velapoldi, R. A., "Overview of the Center for Analytical Chemistry - Technical

Programs", University of Trondheim, Trondheim, Norway, June 8, 1982.

Reimann, C. W., "Standardization of Health Measurements", Advisory Group on Chemoprevention, National Institutes of Health, July 14, 1982.

J. K. Taylor, "Reference Materials - How They Are or Should Be Used",

ASTM C-26 Symposium, Knoxville, TN, August 9, 1982.

Reimann, C. W. , "Proposal to Create a Subcommittee on Analytical Chemistry",

National Academy of Sciences, Committee on Chemical Sciences,

August 17, 1982.

J. K. Taylor, "Validation of Analytical Methods", ACS, Kansas City, MO,

September 15, 1982.

J. K. Taylor, "Quality Assurance of Chemical Measurements", ACS Short

Course, Philadelphia, PA, September 24-25, 1982.

Reimann, C. W., "Trends Affecting Analytical Laboratories: Problems and

Opportunities", LABCON 82, Chicago, Illinois, September 28, 1982.

c. Committee Assignments

Curt W. Reimann

Member, Regulatory Affairs Committee, American Chemical Society

Member, Instrumentation Advisory Panel, ANALYTICAL CHEMISTRY

Co-Chairman, Symposium on Improving the Analytical Chemistry/Regulatory

Interface

Invited Observer, Ad Hoc Subcommittee of the American Chemical Society

Joint Board/Council on Science: "Principles to Improve the Utility

of Analytical Chemical Data for Public Purposes".

Member, American Chemical Society Task Force on Scientific Information

to Government

Member, AdHoc Task Force to Design American Chemical Society Study of the

Health of the Chemical Sciences

Member, Analytical Laboratory Managers Association

John K. Taylor

Member, IS0/TC48, Laboratory Glassware and Related Apparatus

IS0/TC48/SC1 , Volumetric Glassware

I SO/TCI 46 , Air Quality

I SO/TCI 46/SC3 , Ambient Measurements

Chairman, IS0/TC147, Water Quality

Member, I SO/TCI 47/SCI /Terminology

I SO/TCI 47/SC2 , Chemical, Physical, Biochemical Methods of Analysis

IS0.TC147.SC6, Sampling

ANSI TAG, IS0/TC147, Water Quality

ANSI TAG, IS0/TC172, Optical Instruments

ASTM D19, Water

4
Chairman, ASTM D19.01,07, International Standards

ASTM D19.05, Inorganic Constituents

ASTM D19.07, Sediments

ASTM D22, Atmospheric Analysis

ASTM D22.04, Workplace Atmospheres

Vice Chairman, ASTM D22.05, Calibration-Precision-Accuracy

Member ASTM 22.01, Quality Control, Cochairman

ASTM D22.09, USTAG to TC 146

ASTM E34, Occupational Safety and Health

ASTM E36, Criteria for the Evaluation of Testing & Inspection

Laboratories

ASTM E41 , Laboratory Apparatus

ASTM E41.01, Glass and Plastic Apparatus

ASTM E41.06, Weighing Devices

ASTM E41.07, Microchemical Apparatus

Collaborative Testing Subcommittee - Standard Methods

Advisory Committee - CHEMTECH (ACS)

ACS Committee on Environmental Chemistry - Subcommittee on Environmental Analytical Chemistry

NBS Museum Committee

NBS 80th Anniversary Celebration Committee

NBS Advisory Committee, State Measurement Needs Survey

NBS Representative - Interagency Advisory Committee on Water Data

Ranee A. Velapoldi

Working Advisor, ASTM, Committee E7 on Nondestructive Testing,

Subcommittee E7.03 on Liquid Penetrant and MPI Methods, Task

Group E7.03.03 on E-270 Glossary Revision

Member, ASTM, Committee El 3 on Molecular Spectroscopy, Subcommittee

E13.06 on Molecular Luminescence

Task Group E13.06.01 on Presentation of Corrected

Fluorescence Spectra

Task Group E13.06.02 on Recommended Practices on Molecular

Fluorescence Spectroscopy

d. Center Colloquium Series

October 13, 1981 - Dr. Jacques Versieck, Department of Internal

Medicine, "Problems in Trace Element Analysis

of Human Samples", Ghent, Belgium.

November 12, 1981 - Prof. Alan D. Adler, Western Connecticut,

State College, "Scientific Investigation of the

Shroud of Turin".

December 9, 1981 - Dr. Kent K. Stewart, U. S. Department of

Agriculture, Beltsville, MD., "Flow Injection

Analysis; A Useful Tool for Laboratory

Automation"

.

5
February 10, 1982

April 14, 1982

May 19, 1982

June 9, 1982

Dr. John Kilty, FBI, "Chemistry in the FBI

Laboratory"

Dr. John Wohlgemuth, Solarex Corp., "Photovol taics

The Status of Today's Technology and Its Long Term

Potential "

Frederick Brech, Fisher Scientific Company, "The

Application of Science in the Examination of

Works of Art".

Barbara A. Miller, National Gallery of Art, "Using

X-Ray Fluorescence Analysis to Investigate

Chemical Factors in the Discoloration of Paper".

Lucia C. Tang, Library of Congress, "Direct

Determination of Elements in Conservation Materials

By Flameless Atomic Absorption Spectroscopy."

J. A. Conkling, Washington College, "Investigation

of Pyrotechnic Mixtures by Thermal Analysis".

6
B. Voluntary Standardization and Quality Assurance

1. Voluntary Standardization

The availability of carefully evaluated methods, standardized by the

consensus of knowledgeable analysts is recognized as an essential component

of the quality assurance of chemical measurements. Where such methods are closely related to standard reference materials and to appropriate quality

assurance programs, a high quality of data is possible. Closely related to

this is the requirement for evaluated and standardized analytical data.

Accordingly, the Center has played and continues to play an active role

in the voluntary standardization process, both nationally and internationally.

More than one-third of the staff engages in some aspect of this activity and

leadership is provided in the following important standardization committees

and organizations:

Altogether the Center is represented on more than one hundred separate

committees, and task groups of various standardization organizations. Such

activity provides the opportunity for direct transfer of Center technology to

a wide range of constituency. The contacts made at meetings of such organizations provide valuable input into the long-range planning of the Center.

A minor but important role also has been played in liaison with several

other organizations. These include the International Organization for Legal

Metrology, and the NVLAP program for accreditation of testing laboratories.

Representation on the Coordinating Council for Recommended Methods, Office of

Water Data Coordination, Department of the Interior has been a mutually

beneficial activity.

2. Quality Assurance

Quality Assurance of measurements is aimed at obtaining data that is

technically sound and legally defensible. The former requires methodology and

measurement practices fully adequate for the end use of the data. The latter

demands that all aspects of the measurement process must meet the critical

test of peer review and of adversarial examination as necessary. The Center's

thrust in quality assurance is in two directions - its internal program,

and providing assistance to others in their efforts to obtain quality data.

Quality of output has always been the prime objective of the CAC. Its

research outputs have always been subject to both internal and external peer

review. Its policy for applied measurements has been to follow the craftsmanartisan approach, based on redundancy to minimize errors and bias. Numerical

ASTM C-26

ASTM D-19

ASTM D-22

ASTM E-02

ASTM E-07

I SO/TCI 46

ISO/TCI 47

IUPAC

Nuclear Fuel Cycle

Water

Sampling and Analysis of Atmospheres

Emission Spectroscopy

Nondestructive Testing

Air Quality

Water Quality

Commission on Atomic Weights

7
data are not released until fully validated by one or more of the following

techniques - confirmation by independent measurements; use of carefully

evaluated methodology; peer review of the data.

The formalized quality assurance plan adopted by the Center incorporates

the same measurement philosophy. Its chief difference from previous practices

is the improvement of documentation. At the same time a new level of review,

for quality assurance aspects, is also instituted. The QA plan further

emphasizes the role of planning in both research and applied investigations.

In particular, quality assurance plans, specific for each investigation - the

certification of an SRM is an example - will be developed prior to initiation

of work. Other agency sponsored work will be subjected to the same procedure.

Considerable effort has been devoted during the past year to introducing

the QA plan to the staff of the Center. This has included holding a series of

group discussions on various aspects of quality assurance and the scheduling

of several seminars with invited speakers.

The QA plan of the NBS Office of Standard Reference Materials closely

parallels that of the CAC. Since the certification of SRM's is a major Center

activity, this is an essential requirement. To test the adequacy of both

plans, three pilot programs for the certification of SRM's, using the plans,

are in progress - one in each of the CAC Divisions. While no difficulties are anticipated, any modifications of either QA plan will be made which appear to

be necessary.

The second aspect of the Center's QA activities relates to assistance

provided to the technical community. The Quality Assurance Seminars developed

on a pilot basis in FY 1981 have been fully implemented during the past year.

The Seminars consist of 2-day sessions in which participants look in depth at

the measurement process, consider sources of error and quality control procedures, examine the role of reference materials for data quality assessment,

and review statistical techniques for evaluating data. The Seminars also

schedule workshops with Center personnel for discussion of good measurement

practices in selected areas of analytical measurements.

The Seminar Series was announced by a mailing directed to known purchasers

of SRM's. The original plan was to hold two seminars of 30 persons each.

Because of a large response, this was expanded to 5 seminars with 50 persons

in attendance at each. A special textbook was prepared containing the visual

materials presented, and also several reprints of NBS papers concerned with

quality assurance. Because of its outline nature, the visual materials are not readily understandable to nonattendees and hence are not available for

general distribution. However, the reprints are available on request.

In addition to the seminars described above, special seminars of a similar nature were prepared and presented to meetings of the Environmental

Protection Agency and the Food and Drug Administration, at the request of

these agencies.

In addition to the above, all of the divisions of the Center have provided

assistance to the quality assurance efforts of other government agencies during

past years. These were concerned with the development of special quality assurance materials and collaborative test materials, including the supervision

8
of collaborative tests. Details are described in the overviews and technical

accomplishments of the divisions that provided the services.

A major activity of the undersigned during the past year has been the

development of a set of criteria for evaluating the capability of state

metrology testing laboratories, and a procedure for certifying them in specified areas of testing competence. A laboratory must demonstrate both general

competence as well as competence in specific test area(s) in order to be

certified.

The criteria for general competence consist of basic minimum standards

for organization, human resources, and facilities and general equipment. The

laboratory personnel must demonstrate the attainment of general competence in

basic metrological testing practices, as well. In addition, a certified

laboratory must have established and implemented a comprehensive measurement

quality assurance program.

Laboratories that substantially meet the above general criteria will be

certified by the NBS Office of Weights and Measures in one or more of 15

competence areas, as merited. Such certification will be based on demonstration of measurement expertise in the use of recognized test procedures, the

a v a i 1 a b 1 i 1 i ty of appropriate special equipment, and measurement standards

traceable to NBS.

The evaluation of laboratories will be based partly on their own critical

self-appraisal according to detailed criteria contained in the plan, and on the judgment of the NBS Office of Weights and Measures on this and other

information, including site visits. This certification program will be

initiated in calendar year 1983.

John K. Taylor

9
C. Pilot National Environmental Specimen Bank Program

1. Introduction

Since 1975, the Center for Analytical Chemistry at the National Bureau of

Standards (NBS), in conjunction with the U.S. Environmental Protection Agency,

has been involved in research directed toward the establishment of a National

Environmental Specimen Bank (NESB). In 1979 a pilot NESB program was initiated

at NBS to evaluate the feasibility of a national program by providing research

and experience in the various aspects of specimen banking (i.e., collection,

storage, and analysis of selected environmental specimens). The major goals

of this pilot effort are: (1) to develop protocols for sample collection and

storage of four types of environmental accumulators; (2) to evaluate and

improve analytical methods for the determination of both trace element and

organic pollutants in these biological matrices; (3) to evaluate long-term

storage at various conditions; and (4) to provide a "bank" of valid samples

for retrospective analyses in future years.

Since 1980, human liver specimens (the first sample type of the pilot

program) have been collected, stored, and analyzed. The development of the

sample collection and storage protocol and the implementation of the analytical

methodologies for the trace element determinations have been summarized in

previous reports [1,2]. During the past year the following tasks were accomplished: (1) evaluation of the trace element data for 36 livers collected

during the first year; (2) completion of liver sample collection and processing for the second year samples; (3) improvements in the development and

application of the cryogenic homogenization technique for biological samples;

(4) preliminary evaluation of storage conditions after one year storage;

(5) improvements in analytical methods for Cr, Sn, and Pt; (6) initiation of

second year liver analyses for trace elements; (7) implementation of methods

for determination of organochlorine pesticide residues in livers; and

(8) initiation of collection of a second sample type, mussels.

2. Research in Cryogenic Homogenization Techniques

NBS has developed and evaluated the use of Teflon disk mills for the

cryogenic homogenization of soft tissues. The initial performance evaluation

for a Teflon mill with a 100 g capacity demonstrated the value of this technique. During the past year disk mills with larger capacities (200 g and

1000 g) have been designed and fabricated. For the homogenization of liver

specimens, a mill with a capacity of ^200 g was constructed. This mill (with

a total volume of 2500 cm3

) can be modified by inserting one large disk and

ring or a smaller disk and two rings; the capacity is 200 g or 300 g, respectively. This design flexibility is necessary because the mills require a minimum filling of 50 percent of the capacity to achieve optimum performance.

For homogenization of the mussel samples, a mill with a capacity of 1000 g has

been constructed and the performance evaluated. This larger mill has a total

volume of 6500 cm3 and contains one disk and three rings. The performance of

the mills can be rapidly evaluated by sieving the frozen tissue powder after

homogenization. Two different tissue types have been used to evaluate the

performance of the mills: beef liver to simulate the behavior of the NESB

human liver specimens and pork belly fat to simulate human adipose tissue.

10
After four minutes of cryogenic grinding, the homogenates were sieved at

cryogenic temperatures in a set of 40 to 200 mesh sieves. The results of

these experiments are shown in figure 1. The beef liver homogenate completely

passes a 40 mesh sieve and shows a distinct distribution among the sieves.

Most of the fat passes even a 100 mesh sieve, however, a small amount of

coarse material is left on the 40 mesh sieve probably because of caking due to

temperature increase during the milling procedure. For this type of tissue

(i.e., fat) temperatures during grinding must be maintained as close as possible to the liquid nitrogen (LN2 ) temperature.

3. Analytical Results

The results of the determination of 31 trace elements in 36 liver specimens were reported previously [1]. An interesting result of this study is the

very narrow range of concentration data for many essential trace elements

(figure 2) as compared to the wide scatter of pollutant element concentrations

(figure 3). For example, the concentrations of Se vary by only a factor of

1.8 and other essential elements (Mg, Co, Cu, and Zn) vary by only a factor of

2-3.5, whereas several pollutant elements (A1 , As, Cd, Hg, Pb, and T1 ) vary

by as much as a factor of 100. When compared to the literature data of the

trace element content of human tissues compiled by Iyengar (3) (solid lines in

figures 2 and 3), the elemental concentrations found in these liver samples,

in particular for the pollutant elements, are generally at the lower side of

the previously reported data.

Some interesting findings can be pointed out to illustrate the potential

utility of a specimen banking program in relation to monitoring environmental

trends. For example, the range of Se data is much lower if individuals from

the same geographical location are compared. Evaluation of the data by the

NBS Statistical Engineering Division revealed a statistically significant

difference in average Se values for samples from Baltimore (0.44 yg/g) compared

to Minneapolis (0.51 yg/g) and Seattle (0.56 yg/g). Similar evaluations

indicated that possible geographic differences may exist for several other

elements. The trace element data were also evaluated with respect to possible

correlations of variables such as age and sex with elemental concentration and

correlations of different elements with each other. Because of the relatively

small data set, the results were only partially successful in suggesting some possible correlations. However, as real-time analyses provide additional data

in each year of the pilot program, the potential for substantiating these

possible correlations will increase significantly.

During the past year, recently developed activation analysis procedures were utilized for the determination of Cr, Pt, and Sn. The newly installed

Compton Suppressor system lowers the limit of detection for Cr and Pt. Cr can now be detected at 5 ng/g and Pt at 2 pg/g. With this improved sensitivity

the instrumental determination of Cr at the lowest previously reported levels

will be possible. In ten liver specimens, which have been banked for one year, Cr was measured at between 9 ng/g and 40 ng/g. This procedure will be

applied to provide baseline levels for Cr from the second year sample collection. Pt was determined in 13 specimens of the first year collection and

found to range from 5 to 57 pg/g. The application of the radiochemical procedure for Sn on ten specimens gave results of between 0.16 and 0.71 yg/g.

The analytical protocol for the second year analysis will reflect these

11
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homogenization.

12
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Figure 4. Gas chromatograms from the analysis of human liver samples.

(A) Liver sample from NBS/EPA Pilot Program, (B) Liver

homogenate from German Pilot Environmental Specimen Bank

Program.

15

i

lorobi

phenyl

(i.S.)
improvements in sensitivity for the activation analysis procedures and will

also include the radiochemical procedure for the determination of Sn.

A new list of elements to be measured by atomic absorption spectroscopy

(AAS) includes A1 , Cr, Ni , Cu, As, Se, Cd, Hg, and Pb. The results from AAS

will complement the neutron activation analysis data and provide quality

assurance on selected elements determined by both methods (i.e., A1 , Cr, Cu,

Se, Cd, and Hg). Selected samples will also be analyzed by isotope dilution

mass spectrometry for determination of Pb, T1 , and Cu. In addition, a fourth

independent technique, differential pulse anodic stripping voltammetry, will

be applied by the Institute for Applied Physical Chemistry, KFA JUlich, in

the Federal Republic of Germany to determine Pb and Cd.

As part of the storage evaluation study, the liver samples were investigated for moisture loss after one year storage. The samples were removed from

storage and weighed; the results are summarized in Table 1. The weights of

the whole specimens have an estimated uncertainty of about 1 percent or more

owing to the inaccuracy of autopsy room equipment and differing weights of

packaging and labeling materials. For the subsamples, where we have much

better control over weighing errors, some interesting trends were observed.

The freeze-dried samples all showed a slight gain in weight which is not

surprising since the room temperature storage cabinet is not desiccated. On

the other hand, all samples stored at -25 °C showed a slight dehydration.

Visual inspection of the subsamples stored at -25 °C revealed water crystals

on the inside of the Teflon container and lid indicating a separation of water

from the liver homogenate. This separation would make subsampling of test

portions from the sample impossible. The first results from the reanalysis

of samples for determination of trace elements after one year storage revealed

no significant change in concentrations.

Table 1. Weight of Specimen Bank Samples After One Year Storage

and Freeze-Drying.

A. Weight Change with Different Storage Conditions

Storage No. of % Wt. Standard

Sample Type Sample Wt. Condi ti on Samples Change Deviation

Liver specimen 110 - 200 g <_ -120 °C <1

Liver subsample 5 - 9 g Freeze-dried 19 +0.7 0.23

- 25 °C 23 -0.23 0.13

- 80 °C 24 -0.1 0.13

£

-120 °C 33 -0.03 0.13

B. Variations in Water Loss After Freeze-Drying

1. Dry wt/fresh wt for different livers Range = 0.206 - 0.306

2. Relative difference in factors between

subsamples of the same liver <_ ± 1 . 5%

16
Analytical methodology for the determination of organochlorine pesticide

residues in human liver has been developed and the analyses of 30 samples from

the second year collection are now in progress. A typical gas chromatogram

from the analysis of one of the liver samples is shown in figure 4A. The

following organochlorine compounds, which are present in most human liver

samples, are currently measured: hexachlorobenzene , 3-isomer of hexachlorocyclohexane ( 3 -BHC), heptachlor epoxide, trans-nonachlor , p,p'-DDE, dieldrin,

p,p'-DDD, and p,p'-DDT.

A sample of a human liver homogenate from the German Pilot Environmental

Specimen Bank was analyzed as part of an interlaboratory comparison of methods.

The gas chromatogram from the analysis of the German liver homogenate is shown

in figure 4B and the quantitative results are summarized in Table 2. The

quantitative results from the analysis of a liver sample from the NBS pilot

program are also given in Table 1 for comparison. Of particular interest in

comparing the two samples is the large quantity of hexachlorobenzene present

in the German sample as compared to the U.S. sample. In addition, when

quantitation is on an extractable fat basis, the U.S. sample is higher in

concentrations of several compounds.

The gas chromatograms shown in figure 4 contain aldrin, pentachlorobenzene, and/or decachlorobi phenyl as internal standards for quantitation.

Recent results indicate that quantitation based on aldrin provides more

reproducible results than pentachlorobenzene or decachlorobiphenyl . In

addition, aldrin is rarely found in biological samples since it is readily

converted to dieldrin.

Table 2. Concentrations of Selected Organochlorine Pesticide Residues in

Human Livers Samples 9

.

b c German Homogenate U.S. Sample

ng/g ng/g ng/g ng/g

Compound (wet wei ght) extractable fat (wet wei ght) extractable f

Hexachlorobenzene 413 ± 20 3110 ± 260 8

+ 3 190 ± 66

a-BHC — -- 0.9 + 0.1 23 ± 2 3-BHC 88 ± 9 670 ± 120 44 + 12 1100 ± 330

Trans-nonachlor 8 ± 1 60 ± 15 27 + 6 670 ± 170

p , p ' -DDE 305 ± 9 2310 ± 315 195 + 59 4840 ± 1590

Dieldrin 22 ± 4 170 ± 40 83 + 38 2030 ± 960

p ,p

1 -DDD 34 ± 5 260 ± 60 — --

p,p'-DDT 25 ± 5 190 ± 40 25 + 6 606 ± 163

Measurements based on three samples, uncertainty is ±la calculated standard

deviation based on 2 degrees of freedom.

^13% average extractable fat.

c 4% average extractable fat.

17
4. Second Specimen Type - Mussels

The second sample type for incorporation into the NBS pilot program is

marine mussels ( Mytilus edulis ). A sampling/storage protocol has been developed in cooperation with investigators familiar with mussel collection, i.e.,

the U.S. EPA Mussel Watch Program. Mussel samples for the NBS pilot bank will

be collected from four sites, i.e., two on the Northeastern coast and two on the Western coast of the U.S. Sites with relatively low and high levels of

pollutants such as heavy metals and hydrocarbons will be selected on each

coast. These sampling sites will be selected in cooperation with the EPA and

will correspond to present sites for the EPA Mussel Watch Program. As in the case of the human liver sample collection, the sampling protocol was designed

to avoid contamination by metals and organic compounds. Mussels are closed at

collection and, therefore, provide some natural protection against contamination during sampling. However, special precautions are followed to minimize

the possibility of contamination during sampling, i.e., avoid contact of

mussels with metal, uncovered hands, plastics, creosoted pilings, etc. The

mussels are thoroughly rinsed and scrubbed to remove debris, sediment, and

other foreign material and shipped frozen (dry ice) to NBS. At NBS the

samples will be sealed in Teflon bags and stored under various conditions. If

mussels are to be stored without shells (or as a homogenate), the shells are removed as soon as possible at NBS under clean room conditions using a special

titanium tool (to limit trace metal contamination to only one metal).

The development of sampling, processing, and storage protocols for the

second specimen type, mussels, offered somewhat different problems and

required the addressing of different questions than those for human livers.

For example, the following questions were considered:

• How many mussels constitute a sample?

• What is the expected variability among "pools" of 70-100 mussels

from the same site?

• Should the mussels be stored in the shell, shucked (whole), or

as homogenates?

The mussel sampling and storage evaluation strategies for the NBS pilot program were designed, in cooperation with NBS statisticians, to address these

questions. Initially, samples will be collected at one site to determine the

"variability" of these "pools" of mussels. These data will then be used to

evaluate the probablity of detecting changes during the storage of the mussel

samples under various conditions.

The storage evaluation scheme will be based on the comparison of samples

(batches or pools of 70-100 mussels) stored as homogenates, whole (in shells),

and whole (without shells). A number of batches (^15) will be homogenized and

analyzed immediately after collection to determine batch-to-batch variability.

Subsamples from the mussel sample homogenate will be stored in Teflon jars.

Other batches of mussels will be stored whole (in shells) and whole (without

shells) in Teflon bags. The whole mussel and the mussel homogenate samples

will be stored under various conditions and reanalyzed after one to three

years storage for comparison with the analyses performed prior to storage.

Mussels from the first site will be collected in October, 1982.

18
5. Storage of Biological /Environmental SRM's

A major task of the NBS pilot program is the evaluation of long-term

storage of biological specimens to assess chemical and/or biodegradation

effects on the organic and inorganic constituents. An important aspect of a specimen banking activity should also be the inclusion of biological Standard

Reference Materials (SRM's) for comparison. The biological /environmental

SRM's listed in Table 3 have been selected for storage in the NBS pilot speci- men bank facility. Four of these certified materials, i.e., bovine liver,

oyster tissue, wheat flour, and air particulate matter, are matrices representative of the four specimen types to be studied in the pilot program. Several

units of each SRM will be stored in the LN 2 vapor freezers and at room temperature. Selected SRM's will be analyzed at various time intervals during

the storage evaluation.

Table 3. Biological/Environmental SRM

Specimen Banking.

's for Environmental

SRM No. Description Constituents Certified

1566 Oyster Tissue Trace elements

1567 Wheat Flour Trace elements

1575 Citrus Leaves Trace elements

1577B Bovine Liver Trace elements

1580 Shale Oil Organics (PAH, phenols,

and N-heterocycl ics)

1633 Coal Fly Ash Trace elements

1645 River Sediment Trace elements

1646 Estuarine Sediment Trace elements

1647 Priority Pollutant PAH

(in acetonitrile)

Organics (PAH)

1648 Urban Particulate Matter Trace elements

1649 Urban Dust/Organics Organics (PAH)

Interactions with National and International Programs

In May 1982, NBS representatives participated in the "International

Workshop on Environmental Specimen Banking and Monitoring as Related to

Banking" in Saarbrucken, Germany and the "7th Annual U.S. /German Seminar of

State and Planning on Environmental Specimen Banking" in Munich, Germany.

These meetings provided for exchange of information related to research and

operational experience in environmental specimen banking. At present, the

pilot specimen banking programs in the U.S. and Germany are by far the most

developed. In Japan, a small pilot bank is underway and in Canada a bank of

frozen wildlife specimens exists which were collected during monitoring programs. At these meetings plans for future interactions between the existing

pilot programs in U.S. and Germany were discussed. As a result of these

19
meetings, we have initiated an interlaboratory comparison for the determination of chlorinated pesticide residues in human liver between NBS and three

laboratories involved in the German specimen bank program. Samples from the

two pilot banks have been exchanged for this purpose. In addition, aliquots

of liver specimens from the NBS specimen bank are being analyzed in Germany

for selected trace elements as part of an intercomparison. These sample

exchanges will provide valuable information on the comparability of analytical

data generated in the two banking programs.

As a result of NBS specimen banking activities, NBS researchers have been

invited to participate in several additional workshops in related areas. As

a follow-up meeting to the 1980 "Workshop on Research Needed to Improve Data

on Mineral Content of Human Tissues" sponsored by the American Institute of

Nutrition and the National Science Foundation, a workshop was held on "Protocols--Mineral/Element Analysis of Human Tissues" in 1981. The goal of

this workshop was to prepare specific guidelines and protocols for sample

selection, collection, preservation, and analysis of human tissues. The liver

sampling protocol and homogenization procedures developed in the NBS pilot

program were adopted at this workshop as models for the collection/processing

of human tissue. NBS representatives also were invited to participate in an American Medical Association resource conference on "Trace Minerals: Current

and Developing Concerns" and in an Advisory Group Meeting of the International

Atomic Energy Commission on "Nuclear Techniques in Environmental Health

Studies of Mineral Pollutants."

References

[1] C. W. Reimann, R. A. Velapoldi, and J. K. Taylor, eds., Center for

Analytical Chemistry Annual Report, NBSIR 81-2425, U.S. Dept, of

Commerce, National Bureau of Standards (1981).

[2] R. Zeisler, S. H. Harrison, and S. A. Wise, eds., The Pilot National

Environmental Specimen Bank - Analysis of Human Liver Specimens, EPA

Annual Report, in press.

[3] G. V. Iyengar, W. E. Kollmer, and H. J. M. Bowen, The Elemental

Composition of Human Tissue and Body Fluids, Verlag Chemie, WeinheimNew York (1978)

S. A. Wise, Project Manager; K. A. Fitzpatrick, S. H. Harrison, W. F. Kline,

S. F. Stone, R. Zeisler

The following members of CAC have participated in providing analytical

research and data for the program during the past year:

C. F. Allen, S. N. Chesler, R. R. Greenberg, L. R. Hilpert, J. K. Langland,

W. A. MacCrehan, E. A. I. Michaels, T. C. Rains, T. A. Rush

20
D. Service Analysis (11310 and 14304)

R. W. Burke

An important and unique activity within the Center for Analytical

Chemistry is its service analysis function. Within the scope of this activity,

the technical staff of CAC frequently gives advice, performs expert compositional analyses, and provides state-of-the-art calibrations on a very broad

range of research and industrial materials. This service is openly available

to NBS staff and to all federal, state, and local government agencies. In

special instances where CAC has clearly demonstrated a unique analytical

capability, this service is also available to private industry.

All requests for analytical services are handled initially by the service

analysis coordinator who is responsible for discussing the measurement needs

of the customer, recommending the most suitable approach, and indicating what

the approximate costs will be. In instances where the analytical problem is

quite complex or the analysis requires specialized considerations, the

customer is placed in direct contact with the appropriate staff member for

an in-depth discussion of the matter.

This is the twenty-first year that the service analysis program has

existed as a formal program within the analytical chemistry group. Throughout

this period, the technical staff has been, and continues to be, highly cooperative and dedicated to providing timely, informative, and cost effective

analyses. A special effort continues to be made throughout the Center to

provide this service with a minimum of disruption to on-going programs.

Currently, the turnaround time for the more routine analyses ranges from a few days to about two weeks.

All analytical work is performed on a cost reimbursable basis. Within

NBS, funds are transferred by an interdivision work order; outside work is

handled by a purchase order. All billings are performed by the service

analysis coordinator.

In FY 82, 114 service analyses were carried out by CAC staff at a cost of

$226 K. In FY 81, the corresponding numbers were 134 analyses and a cost of

$181 K. The most notable change in the number of requests was from within NBS

where only 29 jobs were performed this year as compared to 51 in FY 81. This

number of in-house requests reflects approximately a 50 percent decrease from

the average number received in each of the three years immediately preceeding.

The service analysis function is broadly regarded by the CAC staff as an exceedingly important and integral part of its yearly activities. Not only

does it fulfill a specific need for the customer, but also it provides an excellent means for NBS analysts to identify new and sometimes unfamiliar

areas of emerging research and development that will require better analytical

measurements and standardization for the future. The verification and recalibration of the gaseous and the glass transmittance SRM's that are performed

under the service analysis function provides NBS with a long-term evaluation

of their field stability and guarantees industry a continuing supply of these

standards whose usefulness is extended considerably beyond the time period

specified in the original certification. Additionally, several good research

21
papers are published each year as spin-offs from the service analysis activities. At least two such papers are currently in preparation. One entails the

preparation of accurate isotopic argon mixtures for interplanetary atmospheric

measurements; the other involves the use of microanalytical techniques for

examining the microcrystalline structure of cements and thereby elucidating

their hardening mechanisms.

The argon work required the careful gravimetric-sequential flush preparation of two concentrations of gas standards having equal molar concentrations

of argon-36 and argon-40. One mixture was prepared to contain 25 ppm of each

isotope; the other contained 50 ppm of each. Both mixtures were stored in

carbon dioxide at a pressure of 500 psi. Initially these standards will be

used for the interl aboratory calibration of the mass spectrometers and the gas

chromatographs involved in the analysis of the atmospheric samples that were brought back from the United States and the Russian missions to Venus in 1978.

In the cement studies, members of CAC, using microanalysis and compositional

mapping techniques, have studied the processes of mineralization in the

hardening of cement pastes in conjunction with scientists from the Center for

Building Technology. The formation of various minerals as a function of aging

has been studied in order to ascertain the relationships between initial

particulate size distributions and final solid state reaction products. A

combination of quantitative microanalyses at arrays of points, combined with

x-ray area scans, has been used for diagnostic analyses. Preliminary evaluation of the data indicates that the spatial distributions of the calcium

hydroxide and the calcium silicate hydrate resemble that of the initial size

distribution of the particulate tricalcium silicate used to make the pastes.

This observation suggests that this initial distribution controls the solid

state reactions over very long periods of time.

22
E. Laser Analytical Chemistry Group

1. Group Overview

The main objective of this group is to develop new approaches to

performing accurate chemical analyses. Our primary emphasis remains on the use of lasers as highly selective and sensitive spectroscopic probes. In

addition to our ongoing studies of the laser enhanced ionization in flames

technique, we are collaborating with other Center staff on laser ionization

mass spectrometric techniques.

The laser enhanced ionization (LEI) in flames technique has now been

developed to incorporate computer wavelength control of two dye lasers, one of

which was purchased this year. The two-photon excitation process shows detection limits at the 10 pg/mL level for most of the elements. Analyses of

especially difficult to analyze samples have been performed with accurate

results being obtained. We believe that the fundamental mechanism for signal

collection is understood, and we are in the process of computer modeling the

phenomenon with the objective of being able to predict the behavior of the

mechanism which can then allow us to select parametric values of the LEI

system to optimize its analytical capability.

A study of the tunable infrared diode laser has been completed. This

project, which was started four years ago, was performed during a significant

evolution of the diode technology. This technology has now been developed

to a point where it can provide a useful system for chemical analysis. In

previous years we had improved the stability of the laser and designed the

optical system to minimize errors in the absorption spectroscopic technique.

Recently, we have demonstrated the measurement of isotopic ratios and its

utility in the highly selective Stark spectroscopy.

The group is collaborating with Center staff on a new project called

material transport. The project was initiated as the result of studies made

several years ago at NBS on the effluent of a spark discharge used for optical

emission spectroscopy. When such effluent is passed into an inductively coupled

plasma (ICP), a highly accurate analytical spectroscopic technique results.

Apparently, the spark produces atomic vapor (e.g., from a metal sample) which

condenses rapidly into very small particles which can be efficiently atomized

in the ICP. This system, which has been developed commercially, has apparent

high accuracy and reduces matrix effects as evidenced by the use of a single

reference material for all iron bearing materials for example. We propose to

characterize the matter produced by the spark with respect to type, amount

and composition. If compositional bias between the components in the spark

effluent and the sampled bulk material is minimal, experiments will be devised

to determine the pertinent variables in the transport process. If the process

can be understood, it may be possible to devise an atom reservoir that is

amenable to accurate and sensitive quantitative spectroscopic analysis by

several analytical methods including those utilizing a laser.

Emphasis will be placed upon the analysis of practical samples by the LEI

technique while at the same time optimizing various parameters in the analysis

system for quantitative analysis as contrasted to optimization for research

purposes. Collaboration between our staff and that of the Divisions will

23
continue in the areas of laser mass spectrometry, IR laser diode spectroscopy,

and material transport phenomena.

J. R. DeVoe, Group Leader; G. J. Havrilla, R. McDiffett, F. C. Ruegg,

R. L. Sams, J. C. Travis, G. C. Turk, J. Wen.

2. Selected Technical Reports

a. Computer Simulation of Charge Transport and Current Detection Following

Ionization in Flames (11310)

J. C. Travis

This project was undertaken in collaboration with Dr. Peter K. Schenck

of the Center for Materials Science. A computer program was developed to

simulate the transport of electrons and ions through a flame following pulsed

ion formation by laser enhanced ionization (LEI). Sequential plots of the

electron and ion distributions as a function of time provide a "movie" showing

the response of both species to electric field, diffusion, and coulombic selfrepulsion. In addition, the program computes the charge induced on each

electrode by each of the charge distributions in the flame. The time derivative of this induced charge over the duration of the electron/ion dissipation

process yields the predicted LEI signal pulse shape. Agreement of these pulse

shapes with experiment over a variety of applied voltages, laser beam positions, etc., provides the primary evidence of the validity of the model, since

no effective experimental probe of the actual LEI ion/electron distributions

has been devised.

Figure 5 shows a typical frame of the ion/electron distribution "movie",

160 ns after the beginning of a 5 ns laser pulse occurring 0.3 cm from the

cathode, with the anode located at 1.2 cm. The assumed initial electric field

distribution corresponds roughly to 850 volts applied across a low background

ionization flame (e.g. H2 /air). At 160 ns, the electrons may be seen to have

moved about half of the distance from the point of origin to the anode,

expanding considerably under the influence of diffusion. The ions have hardly

moved nor diffused, reflecting the mass dependence of both mobility and diffusion. The effect of the ion and electron charge clouds on the internal

electric field (through Poisson's equation) may be seen in the plot of the

perturbed field. This effect was exaggerated by assuming the initial generation of a large number of ions and electrons by the laser, corresponding to

the upper end of the dynamic range of LEI.

The electron and ion current signal pulses for the same simulation are shown in Figure 6. The electron pulse may be seen to drop to half current in

about 350 ns, while the ion pulse (multiplied x 100 for display) peaks around

5 ys, and continues well beyond the 5.5 ys shown. The relative shapes and

peak positions of the two pulses are complex functions of geometry and applied

voltage, and agree qualitatively with experimental data.

The model has been particularly helpful in understanding the detailed

nature of the interference to signal collection that is encountered when

easily ionized matrices are aspirated. Specifically, such matrices modify the

24
Figure 5. Plot of field (left axis) and relative number density (right

axis) vs. distance from cathode for ions and electrons produced initially by laser beam at 0.3 cm. This plot represents

a calculation of the state of the system at 160 ns after the

T i me (.fJ sec)

Figure 6. Plot of induced current signal as a function of time.

The ion current has been multiplied 100X.

25

Ni_jmb>er~

Gens

i

t
electric field gradient in the flame and change the current pulse profile.

The model permits a theoretical study of the effect of beam position, applied

field, and detection bandwidth on LEI signal. Such a study should permit

optimization of experimental parameters to minimize such interferences, and

should lead to the formalization of correction protocols for this type of

matrix effect.

The model is presently being extended to include calculation of the

background field from first principles. Further possible extensions of the

program include increasing the laser pulse length to study the transient-tosteady state transition and inclusion of a second spatial dimension to more realistically model cylindrical diffusion.

b. Characterization of Pulsed LEI Current Detection and Implications for

Analytical Measurements (11310)

George Havrilla, John Travis, Gregory Turk

Considerable effort has been devoted during the past year to understanding

the details of how a signal is electronically registered when pulsed-laser

enhanced ionization (LEI) occurs in an electrically probed flame. This has

involved the development of a model which allows computer simulation of pulsed

LEI signals along with experimental verification of this model under conditions

likely to be encountered during analytical application of LEI spectrometry.

Prior research on pulsed LEI has been done using signal processing optimized

for sensitivity. The filtering and amplification procedures that were

utilized, substantially distorted the shape of the LEI pulse, and much information regarding the signal detection process was lost. High time-resolution

measurements of the LEI signal pulse have now been made with a minimum of

electronic distortion, and comparison with theoretical predictions can now be

made.

Following a laser pulse, two LEI current pulses are detected, the first

is caused by the motion of the electrons and the second by the ions. Figure 7 shows an LEI electron pulse for 100 yg/mL of iron. The pulse duration, 300 ns,

is considerably longer than the 10 ns laser pulse. It shows a sharp leading

edge, limited by the response function of the amplifiers, with a trailing

decay as predicted by the model. The observed double peak, which is not

predicted by the model, appears to be caused by the electric field distribution between the electrodes in the flame. In the model, the field is assumed

to follow a linearly decreasing function from the cathode to some point

between the electrodes. In practice, the field has been measured and found to

follow a non-linear and discontinuous function resulting from non-uniform

flame composition. The corresponding ion pulse, shown in figure 8, peaks ^6 ys

after the electron pulse, with a peak amplitude ^100 times less than that of

the electron pulse. Again, the shape of the pulse is consistent with the

modeled predictions. In terms of sensitivity, the ion peak is of no interest

for analytical measurements, because it is a long pulse of low amplitude, and

normally gated integration is used to observe only the electron signal.

26
LEI

SIGNAL

Figure 7. Laser-enhanced ionization electron pulse from

100 yg/mL iron.

27
Figure 8. Laser-enhanced ioization ion pulse from 100 yg/mL iron.

The truncated pulse at 0.2 ys is the electron pulse.

The shape of both the ion and the electron pulse is controlled by the

magnitude and profile of the electric field in the flame, which causes the

movement of the LEI charges. There are a number of experimental variables

which affect the electric field magnitude and profile. Among them are the

applied voltage, the electrode separation, the laser beam position, and the

concentration of charged species present in the flame background. The latter

of these variables is perhaps the most important because it can vary from

sample to sample depending on the concentration of species in the sample which

can be ionized by the flame without laser excitation, i.e. alkali metals.

When alkali metals are aspirated into a LEI flame, the electric field tends to

increase in the vicinity of the cathode, and decrease near the anode. Figure

9 shows LEI pulses observed for 100 yg/mL Fe with varying amounts of Na in the

solution matrix when the laser beam is located near the cathode. With the

beam in this position, the effect of increased Na concentration is to increase

the electric field strength sensed by the LEI produced charged species.

28
TIME (/zsec)

Figure 9. Laser-enhanced ionization electron pulses for 100 yg/mL of iron

with varying levels of sodium present in the solution matrix.

This in turn moves the electrons toward the anode at higher velocities, inducing

a larger signal current, but for a shorter period of time. The result is

shorter pulse widths, with higher peak currents. The integrated pulse areas remain constant, except for the highest Na levels, where the electric field is so intense that the movement of the ions can be detected. Obviously for

analytical application, a measurement of peak area will be less susceptible to

matrix ionization interference than a peak height measurement.

29
c. Stark Modulated Infrared Diode Laser Spectroscopy (11310)

R. Sams

Diode laser spectroscopy (DLS) is nearly unsurpassed for the analytical

detection and analysis of all trace gases, except homonuclear di atomics and

noble_gases. We have been able to measure analytes with relative abundances

of 10' 11 to 1

0

_1

2

using a modest length multipass cell (28 transits with a basic path length) and second derivative detection technique. The selectivity

of the technique, which is limited by the linewidth of the molecular transition, is a complex function of the number of molecules in the mixture to be

analyzed and the relative positions and intensities of the transitions. The

linewidth of the laser, which is very narrow relative to the width of the

molecular energy level, helps only by improving deconvolution efficacy. If no analyte line can be found which is free of line interference from another

molecule, it may be possible to isolate the molecular transition via Stark

modulation spectroscopy. In this technique, an electric field is applied to

the analyte molecule to cause a shift in the energy state of the molecule.

For example, the first order, rotational energy level shift AW for symmetric

top rotors is:

All MK

AW -yE

J(J + 1)

where y is

rotational

order and is AW

the dipole moment, E is the applied electric field and J, K, M are quantum numbers. For linear molecules the Stark effect is second

y

2 E2 2Bh

Since values of B rotational constant and/or y can vary by several decades, selectivity of analysis can be enhanced even if the

Stark unshifted lines of analyte and interfering molecules overlap completely.

We are reporting on preliminary measurements using this technique, to

show its ability to improve selectivity in analysis. The basic system is

shown in figure 10 where the cell is replaced by a Stark cell consisting of

two optically polished stainless steel plates 2.5 cm x 5 cm x 40 cm long in

a vacuum housing. The plates are separated by six, 2-mm spacers. A high

voltage gradient (1,000 - 50,000 volts per cm) is applied using one kHz sine wave modulation. A voltage modulation is applied to the plates and the diode

is tuned through the transition of interest, thereby producing a conventional

first derivative signal.

As a demonstration of this technique, Cl CN , a molecule which has a large

dipole (2.8 Debye), was used with an interfering molecule N 2 0 which has a small dipole (0.17 Debye). In figure 11, the spectra of these molecules are shown, each separately, both together, and with Stark modulation. It is seen that the Stark modulation spectrum is greatly simplified (only one major

transition of C1CN remains). The selectivity has been greatly enhanced, but,

the sensitivity is reduced. All linear molecules have small second order

Stark effects. In other molecules, such as those with "symmetric top or rotors", the Stark effect is much larger. The sensitivity of this method with

these molecules should be comparable to DLS with a significant improvement in

selectivity and thereby inherent accuracy.

30
Cold

Head J2o

JO

CO

(0 0.0)MBX<o

II Q.<O

31

Figure

10.

Diode

laser

optical

system.
Source

Modulation,

C1CN BSource

Modulation,

N,,0 CSource

Modulation,

C1CN +N?00-

Stark

Modulation,

C1CN oCM

32

Infrared

strip

chart

absorption

plots

of

intensity

(arbitrary

units)

vs.

wavelength.

A,B?

and C

show

spectra

without

Stark

modulation.

Almost

perfect

line

overlap

is

observed

at

the

position

of

the

Stark

modulated

line

D.

The

Stark

modulated

line

which

is

free

from

interference

is

located

at

2216.4

cm” 1

and

is

the

R(l)

35C1

line.
d. Measurement of the Isotopic Ratios: 1

C/ 1

3

C and 14 N/ 15 N (11310)

R. Sams

Using the laser diode system described in last year's annual report, we

have demonstrated the reproducibility of the isotopic ratio measurements of

1

C/ 1

3

C in C02 and 14 N/ 13 N in N 2 0 to about 0.1 percent. Several methodologies

which utilize our recently completed microcomputer system were evaluated and we report here on two which produced the best results.

The first method (signal averaging) was to scan the diode wavelength at

a rate of one point per 160 microseconds and average the data normally over

1000 scans of 256 points each. In using this technique we were forced to D.C.

couple the InSb detector to the data collection system because A.C. coupling

severely distorted the signal, prohibiting accurate measurements. The detector

has a D.C. offset, caused by normal background radiation, which has to be back

biased to maintain a significant dynamic range. There was also a small drift

in the D.C. level which produced a small error in the data. The relative

ratios of 1

C/1

3

C and 14 N/ 15 N using this technique are given in Table 4 along

with the standard deviation of the measurements. Since different diodes were

used for the two gases, and each diode has its own wavelength instability,

slightly different errors result. The reported errors are the standard deviations of the average of a group of 10 measurements consisting of 1000 sweeps

each. The reported ratios are those of the maximum intensities of each line.

Absolute ratios of 12 C to 13 C or 14 N to 15 N can be derived from line intensity

measurements, but the signal averaging method is best suited to measure the

ratio relative to a known standard.

Table 4. Isotopic Ratio Measurements.

Lock and Jump

Molecule Transition Band Ratio

12

c 160

2

P (34) 10°1-10°0

|i » 13

c 16

0

2

R (36) 01

1 1-01

] o |1

14

n

2

16

0 P (10) 02°-02*0

j1 b

14

n 15n 16o R (ID 00°l-00°0 j 1.1528 (0.00009)°

Signal Averaging

Ratio

2.70370 ( 0 . 0830

)

C

1.1522 (0. 00024)°

a Lock and jump method not developed at time of these measurements.

^Error in parentheses is one standard deviation of the average based on

49 degrees of freedom.

Error in parentheses is one standard deviation based on 9 degrees of freedom.

The second method (lock and jump) was to lock the diode frequency to the

transition of interest by using a cell containing the analyte and by using

conventional locking to the first derivative of the absorption signal. The

33
same transition was then measured in a sample cell using the second derivative

of the absorption signal. The diode was modulated at 9.1 kHz and twice this

frequency was used in the lock-in amplifier to achieve the proper signal.

Forty measurements of an absorption peak were computer averaged. The diode was then unlocked and jump tuned to the other appropriate transition and

relocked. Again, forty measurements were taken and averaged. The ratio was then computed and the process was repeated fifty times. The average value and

its reproducibi 1 i ty are shown in Table 4. The lock-jump technique was not

developed at the time of the carbon isotopic ratios. However, it worked very

well for nitrogen.

The amount of sample required is quite small; approximately 200 nmoles

for N2 0 and 400 nmoles for C02

. The samples can be recovered if necessary.

Ratios of other atoms, 16 0: 17 0: 18 0, are easily measured in both C02 and N 2 0.

It has been demonstrated that relative isotopic ratios of 1

C/ 1C and

14 N/ 15 N can be measured to a precision of approximately 0.1 percent relative

standard deviation of the average using a laser diode system. A major factor

which limits the accuracy is the temperature control of the diode system.

Long term (more than one hour) temperature stability (better than 0.2 K) is

required if an accuracy of better than 0.05 percent is to be attained.

3. Outputs and Interactions

a . Publications

Turk, G. C., DeVoe, J. R. , and Travis, J. C., "Stepwise Excitation Laser

Enhanced Ionization Spectrometry" , Anal . Chem. , 54 , 643-645 (1982).

Travis, J. C., Turk, G. C., and Green, R. B. , "Laser Enhanced Ionization

Spectrometry", Anal . Chem . , 54 , 1006A - 1018A (1982).

Schenck, P. K. , Travis, J. C., Turk, G. C., and 0'Haver, T. C., "Laserenhanced Ionization Flame Velocimeter" , Appl . Spectrosc. 36, 168-171

(1982).

DeVoe, J. R. , Velapoldi, R. A., Langland, J. K., and Hancock, D. K., NBSIR

81 -2407 ( R ) "Intruder Tagging and Identification Using Luminescent

Particles, August 1982.

Maki, A. G. and Sams, R. L., "High Temperature, High Resolution Infrared

Spectral Measurements on the HNC-HCN Equilibrium System", J. Chem.

Phys . 75(9), 4178 - 4182 (1981).

Maki, A. G. and Sams, R. L., "High Resolution Infrared Spectrum and Structure

Determination for Carbon Diselenide (CSe2 )", J. Mol. Spec. 90, 215-221

(1981).

Frommer, C., Lovejoy, R. W. , Sams, R. L., and Olson, W. B. , "The Infrared

Spectrum of the vi Band of SiD 3 H", Mol . Spec . 89 , 261-267 (1981 ).

34
b. Talks

Travis, J. C., "Laser-Based Methods for Ultra-Sensitive Detection of Atomic

and Molecular Absorption", 11th ACS Northeast Regional Meeting, Rochester,

N. Y. , October 21 , 1981

.

Travis, J. C. , Turk, G. C., and DeVoe, J. R., "Toward Real Sample Analysis by

Laser Enhanced Ionization in Flames", Eastern Analytical Symposium,

New York, N.Y., November 18, 1981.

Travis, J.C., "The Characterization and Application of Laser Enhanced

Ionization in Flames", Department of Chemistry, Wayne State University,

Detroit, Michigan, November 30, 1981.

Travis, J. C. , "Limits to Sensitivity in Laser Enhanced Ionization",

183rd National ACS Meeting, Las Vegas, Nevada, March 30, 1982.

Travis, J. C., Havrilla, G. J., Turk, G. C., and Schenck, P. K. , "Analytical

Implications of the Signal Collection Process in Laser Enhanced

Ionization", 183rd National ACS Meeting, Las Vegas, Nevada,

March 31, 1982.

Travis, J. C., "The Characterization and Application of Laser Enhanced

Ionization in Flames", Analytical Chemistry Division, Oak Ridge

National Laboratory, Oak Ridge, TN, May 3, 1982, and Department of

Chemistry, University of Tennessee, Knoxville, Tennessee, May 4, 1 982

.

Kagann, R. H., Sams, R. L., and Elkins, J. W. , "Intensities of Halocarbon F-ll

and F-12 by Infrared Fourier Transform Spectroscopy in the 8-16 ym

Region", Thirty-Seventh Symposium on Molecular Spectroscopy, The

Ohio State University, Columbus, Ohio, June 17, 1982.

DeVoe, J. R., "Application of Laser Spectroscopy to the Remote Analysis of

Molten Metal." American Iron and Steel Institute Subcommittee

Workshop on Process Control Sensors for the Steel Industry held at

NBS, July 28, 1982.

Travis, J. C., "Trace Metal Analysis by Laser Enhanced Ionization in Flames",

Los Alamos Scientific Laboratory, August 17, 1982.

Elkins, J. W. and Sams, R. L., "Measurement of Nitrous Oxide and Halocarbons

F-ll and F-12 by Fourier Transform Infrared and Tunable Diode Laser

Spectrometers", IX Federation of Analytical Chemistry and Spectroscopy

Societies, Philadelphia, PA, September 23, 1982.

Travis, J. C., "Optogalvanic Spectroscopy", NATO Advanced Study Institute

on Analytical Laser Spectroscopy, Erice, Sicily, Italy,

September 23, 1982.

35
c. Committee Assignments

James R. DeVoe

NBS Committee on Selection of Microprocessors for the Storeroom

Fillmer C. Ruegg, Jr.

NBS Committee on Selection of Microprocessors for the Storeroom

Gregory C. Turk

CAC Colloquium Committee

36
II. Inorganic Analytical Research Division

Ernest L. Garner, Chief

Barry I. Diamondstone, Deputy Chief

A. Division Overview

The diverse analytical methodology in the Inorganic Analytical Research

Division is organized functionally into four broad areas; activation analysis,

atomic and molecular spectrometry, analytical mass spectrometry, and electroanalytical chemistry. This structure provides both the flexibility and the

analytical capability to address a wide variety of research problems, as well

as to carry out the full range of analyses required by NBS, and for other

Federal agencies and other institutions, either private or public, when

requested and appropriate. Working within this framework to provide maximum

public benefit, the research and measurement priorities of the Division are established on the basis of: (1) advancing and maintaining analytical

chemical metrology, (2) providing the basis for chemical standardization, and

(3) addressing the need for accurate chemical characterization of inorganic

species to make a substantial contribution to solving problems of national

importance confronting government and industry.

Substantial progress has been made within the Division in the area of

competence research. Considerable effort has been put forth to establish

neutron depth profiling as a tool for compositional mapping and to investigate

ion structures/mechanisms as a means of developing a better understanding of

the basic processes in thermal ionization mass spectrometry. In addition to

these competence activities, now in their second year, a first year effort has

been initiated to investigate sample transport processes in spark discharges.

Potential benefits to be derived from this research include a decrease or elimination of matrix effects and identification of spark source variables

that produce systematic errors. The total competence effort has already paid

significant dividends in terms of new findings in the laboratory, establishing

collaborative research with other institutions, attracting visiting scientists

and postdoctoral candidates, and developing related programs sponsored by other

government agencies. As one of several examples, visiting scientists and

postdoctoral candidates have made significant contributions to the establ ishment

of the depth profiling facility and to the measurement of selective elements

using resonance ionization mass spectrometry.

With competence research as the cutting edge for exploring new directions

in analytical chemistry, other research efforts are directed toward targets of

opportunity to maintain and improve chemical metrology. This diversified

program covers atomic weight research, inorganic constituents in steel processing wastes, recycled oil, trace metals in waste materials, NDE dye penetrants,

specimen bank research, and methods research for certifying a variety of SRM's.

For example, major achievements in the area of methods research include

development and successful application of isotope dilution mass spectrometry

(ID/MS) for trace quantities of iodine in biological materials, analysis of

ultratrace concentrations of cadmium in blood., and the improvement of

analytical procedures for ultratrace levels of chromium. New facilities

include a laboratory for high accuracy pH measurements and a modern facility

for the determination of gases in metals. The addition of these two facilities

37
will help to reestablish widely needed capabilities that have not been available at NBS for the last decade. Continued evaluation and application of the

Compton suppression technique has improved detection limits and provided

increased sensitivity for selected elements such as chromium, aluminum, zinc,

and vanadium. Each of these achievements have substantially enhanced the

quality of trace element determinations performed on a regular basis in the

Division.

As in past years, the Division has provided major analytical services for

the certification of SRM's. The magnitude of this involvement is reflected by

analyses carried out on more than 75 different SRM's covering many of the

material types and most of the major categories of the inventory. In addition

to measurement services for SRM's, significant contributions were made to the

preparation and characterization of materials for use as quality assurance

standards for other government agencies. Of particular significance has been

the development, preparation, and distribution of the first synthetic sludge

material for use as a quality assurance standard in the characterization of

priority elements in waste residues. This particular standard is but the

first in a series leading to the ultimate certification of a much needed

material that exhibits the characteri sties and matrix effects found in a "real

world" waste material. Other measurement services have been provided to

complete or support commitments to broad-based programs in environmental

measurements, resource recovery, and recycled oil. During the coming year

measurement services for these latter areas will be reduced and/or replaced

by other commitments.

New opportunities for other agency research and services are being

developed or explored in promising areas such as glass standards for nuclear

waste storage, resonance ionization mass spectrometry , iodine at ultra-trace

levels, and methods development to determine toxic/essential nutrient elements

in food/health materials. One of the more promising and far reaching new areas is tracer studies for acid precipitation. This effort will seek to

develop a means of identifying the sources and tracking the fall-out of sulfur

using unique isotopic and elemental ratioing schemes. In addition, increased

emphasis will be placed on the development of stable reference materials and

analytical protocols to characterize pH, conductance, acidity, and trace

metals in acid precipitation.

For the immediate future, a nearly equal split between research, the

certification of Standard Reference Materials, and analytical support for

problems of national importance will constitute the major portion of the

Division's programs. As in previous years, new proposals will be directed at

other government agencies in a manner which will complement on-going and

long-term research. In addition, the Division will pursue, in collaboration

with the Center, those areas of analytical chemistry which have been

identified in the long-range planning process as appropriate for increased

growth or new directions.

38
1 . Activation Analysis Group: Overview

The principle objectives of the Activation Analysis Group continue to be

the development of nuclear analytical techniques for better sensitivity,

higher selectivity, and increased accuracy. A high level of competence has

been developed for various reactor-based activation analysis techniques which

include instrumental and radiochemical neutron activation analysis (INAA

and RNAA), prompt gamma activation analysis (PGAA), and the nuclear track

technique (NTT). Non-reactor-based techniques include photon activation

analysis (PAA), fast neutron activation analysis, and charged particle activation analysis, which have been used on a more limited scale. With this wide

variety of techniques, support is provided for the diversified NBS and other

agency programs requiring analytical measurement services. For example,

simultaneous multielement determinations over a broad dynamic range in complex

matrices as well as highly selective determinations of constituents in the

sub-nanogram range have been provided for programs such as Standard Reference

Materials, Environmental Measurements, Recycled Oil, Resource Recovery,

Nuclear Safeguards, and other disciplinary research programs at NBS.

During the past year, major research efforts have been directed toward

the demonstration of multielement capabilities of INAA procedures. With an appropriate combination of PGAA and several INAA determinations, at suitable

irradiation and decay intervals, it has been possible to determine more than

thirty trace elements in such diverse matrices as liver homogenate, coal, fuel

oil, and air particulates. Recent research on instrumental means for background reduction complemented these activities. The evaluation of the newly

acquired Compton suppressor system for application to multielement determinations resulted in increased sensitivity for several crucial elements. The

continuing evaluation of compton suppression techniques using specific

detector combinations will provide unique activation analysis sensitivities

for such elements as A1 , V, Cr, Ni , Zn, and Pt.

Considerable effort has been spent in support of the Pilot National

Environmental Specimen Bank (NESB) program. The cryogenic homogenization

technique has been improved to accommodate samples up to 1000 g. Sieving

experiments at cryogenic temperatures have supported the previous data which

had indicated that homogenates processed in the newly developed Teflon disk

mills will pass a 40 mesh sieve. The on-going evaluation of the trace element

baseline data collected during the first year showed some interesting trends

due to the variations in the sample population. For future analyses, a selection of samples which better match epidemiological population data will

be considered. Activation analysis data are currently being evaluated to

determine the effects of the first year of storage. The second year collection baseline analyses have been initiated using improved instrumental

multielement techniques.

The development and installation of the neutron beam depth profiling

facility and the first determinations of depth profiles in collaboration with

other researchers in the competence program is another important step towards

the continuous expansion of research activities. There is a significant

potential in exploring this and other "unconventional" activation analysis

techniques for future applications especially in the important areas of

materials research. To match future needs in high purity materials, gases in

39
metals and distribution of elements, more research must be conducted in the areas of "unconventional" use of reactor neutrons as well as in the use of

non-reactor activation sources.

Research efforts during the coming year will focus on the extension of

the multielement procedures. For example, the measurements needed to characterize the irradiation facilities after the planned increase of the NBS

reactor power to 20 MW will be used to initiate and evaluate "absolute" or monitor activation analysis. This technique will provide results on more elements, since the occurrence of unexpected elements will not preclude their

quantitation. For the NESB specimens, an optimized analytical protocol will

be developed which can overcome the restrictions of this specific matrix. In

the area of non-conventional activation analysis, the use of a fast transfer

system for analysis via very short-lived isotopes will be evaluated. It is

also anticipated that procedures for the determination of gases in metals will

be investigated. However, in this area, access to a source of fast neutrons

and/or charged particles is necessary.

Rolf L. Zeisler, Group Leader; M. James Blackman, Kathleen A. Fitzpatrick,

Ronald F. Fleming, Robert R. Greenberg, Gary Harrington, Sally H. Harrison,

John K. Langland, Richard M. Lindstrom, George J. Lutz, Trudi E. Mitlehner,

James R. Vogt

2 . Analytical Mass Spectrometry Group: Overview

The primary objectives of the Analytical Mass Spectrometry Group are the

development and maintenance of capabilities for high accuracy isotopic ratio

measurements and the application of these measurements to analytical chemistry.

The increasing need for high quality analytical measurements on sub-microgram

amounts of material requires continual improvement in chemical separation and

purification techniques and mass spectrometric instrumentation. To accomplish

these objectives, the Mass Spectrometry Group is composed of essentially two

sub-groups. The chemistry sub-group is responsible for all of the chemical

aspects of the Groups work. Separation science, isotopic equilibration,

sample dissolution, purification, and "contamination-free" sample handling

are primary concerns in this area. The instrumental sub-group specializes in

inorganic mass spectrometry. This sub-group has considerable expertise in

high accuracy mass spectrometric isotope ratio measurements and is responsible

for developing improved methodology and instrumentation for thermal ionization,

spark source, electron impact and surface ionization mass spectrometry

.

During the past year, the Group continued to have a favorable balance

between research and analytical samples due primarily to the research funds

for the investigation of ionization mechanisms and ion structures received

through the Competence Building Program. During FY 82, work on the laser mass spectrometer neared completion. Pulsed and CW laser sources have been

installed and two mass spectrometer systems, a time-of-fl ight (TOF-MS) and a magnetic sector, have been assembled. Research output from the laboratory,

has included the multi photon ionization of acetone and residual g^ses losing

tje TOF-MS and the first reported formation and measurement of Mo , Re , and

V ions using resonance ionization mass spectrometry (RIMS).

40
Research in ion optics progressed considerably during this year. A more

accurate formulation of the magnitude and extent of magnetic stray fields has

been developed. This has been incorporated into a large computer program that

solves the basic equations of motion of charged particles in a magnetic field.

As a result, refined calculations of the geometrical parameters of existing

instruments have been performed with resultant improvements in the design of new instruments. A program to display graphically the ion beam movement is

currently under development.

Progress has been made on the modification of instrumentation and on the

development of fully automated, high accuracy mass spectrometers . Improved

filament controls have been installed on most of the thermal source mass spectrometers. Performance has been excellent with "down-time" reduced nearly

to zero. An improved emission regulator has been designed and constructed and

is currently under evaluation. Tests of a computer system for controlling the

filament temperature have been successfully completed. The first digital,

automatic gaussmeter/control ler has been constructed and is currently being

cal i bra ted.

An automated gas source mass spectrometer with a triple collector is

nearly ready for operation in the normal mode with full automation expected in

the near future. A new, fully automated, manifold system and inlet system for

this instrument has been completed and is under test. Computer interfaces for

both systems are under construction.

In the area of isotope ratio measurements, work is progressing toward a redetermination of the atomic weight of gallium. High-precision methods have

been developed for both the assay and mass spectrometry of gallium. Improved

methodology for isotope dilution mass spectrometry (ID/MS) continues to be a major output of the Group. The first ID/MS method for trace iodine in botanical materials has been developed and applied to the determination of iodine in

SRM 1572, Citrus Leaves. The newly developed thermal method for sulfur has

been applied to biological and environmental SRM's. Ultra-trace concentrations

of cadmium in blood have been determined by high-sensitivity (pulse-counting)

mass spectrometry . ID/MS determinations of chromium have been extended to the

ultra-trace level

.

In several key areas, research and measurement activities were augmented

by long term guest workers. For example. Dr. Pedro Morales of the Institute

of Physics, University of Mexico has been working on magnetic stray fields and

gas source mass spectrometry. Mr. Eddy Michiels of the Central Bureau for

Nuclear Measurements, Geel , Belgium, worked on lead in foods and cadmium in

blood. Ms. Emile Deal, a guest worker from the Smithsonian Institution,

Washington, DC, is working on the determination of provenience of artifacts

by lead isotopic ratios. In addition, several scientists have visited NBS for

extended periods, primarily for enrichment in state-of-the-art isotope

dilution mass spectrometry.

Again this year, expertise was utilized for several programs that support

mass spectrometry . A new pure-reagents laboratory was completed and is

supplying ultra-pure acids and solvents to fulfill the needs of analysts

within the Division as well as those in outside laboratories. A study of the

precision and accuracy of Kjeldahl nitrogen determination in steel SRM's is

41
currently in progress. The efficiency of oil extraction from mill scale is

under investigation. The project on trace element characterization of the

Chesapeake Bay was completed with the evaluation of the particulate data which

produced specific relationships between elements and groups of elements. A

precise leach test for a proposed glass nuclear waste reference material was developed.

Research plans in the immediate future will focus on ion mechanisms, ion

optics, atomic weights, and the development of chemical and mass spectrometric

procedures for isotope dilution analysis. Competence plans include research

on the processes controlling resonant ion formation using thermal atomization

sources, interpreting anomalous resonant ion formation, and applying the RIMS

capabilities to studies of atomic and molecular vaporization and ionization in

thermal sources. Research is also planned to investigate negative ion mass spectrometry using complex emitting surfaces and to develop methodology for

the utilization of negative ions in the presence of high electron current

densities. Another significant project is the development of a fully automated, digitally controlled, off-axis mass spectrometer. The improvement of

spark source measurements by simultaneous dual collection of ion currents and

by high speed peak switching will be investigated. Completion of the redetermination of the atomic weight of gallium is planned and measurements leading

to a redetermination of the atomic weight of lithium will be initiated. New

chemical separation techniques and mass spectrometric methodology to lower

detection limits and to increase the library of elements determinable by ID/MS

will be given major attention.

Thomas J. Murphy, Group Leader; I. Lynus Barnes, Ellyn S. Beary,

William A. Bowman, III, Karen A. Brletic, Emile C. Deal, John D. Fassett,

John W. Gramlich, Emerson F. Heald, William R. Kelly, Howard M. Kingston,

George M. Lambert, Lawrence A. Machlan, John R. Moody, Larry J. Moore,

Pedro A. Morales, Paul J. Paulsen, Lura J. Powell, Ronald W. Shideler,

Mary E. Stone

3 . Atomic and Molecular Spectrometry Group: Overview

The Atomic and Molecular Spectrometry Group faced with an ever increasing

demand for improved accuracy and sensitivity, continually strives to develop

new techniques for spectrochemical analyses. Efforts towards achieving this

goal have primarily been in the areas of sample preparation, matrix modification, and expanded mul ti-el ement capabilities.

A significant effort has been expended in the area of the inductively

coupled plasma (ICP) and the direct current plasma (DCP)/echel 1 e spectrometers

to improve analytical measurements and basic methodology. A major accomplishment has been the development of a system which thermally regulates the

DCP/echelle spectrometer. This system largely eliminates intensity drift due

to shift in wavelength. In addition, the development of a matrix buffering

technique has improved the accuracy of the analytical measurement. To isolate

variability in the ICP, on-line analysis of variance (ANOVA) software has been

developed.

42
Atomic absorption (AAS) with electrothermal ionization has a high

sensitivity for approximately 45 elements. However, the technique is subject

to many chemical and inter-elemental interferences. Matrix modification

techniques have been developed to alleviate many of the interferences and to

improve the accuracy of the analytical measurements. Research to develop a universal matrix modifier to eliminate interferences in graphite furnace AAS

was initiated two years ago and is still in progress. Methods have been

developed, in conjunction with an adaptation of the L'vov platform, to minimize

most of the interferences encountered with electrothermal atomization for all

priority pollutants encountered in environmental and biological materials.

The combination of the L'vov platform and matrix modification has led to

improved accuracy and sensitivity for trace elemental analysis.

In molecular spectrometry , significant progress has been made in the

production of SRM quality metal -on-quartz transmittance standards. This year,

a number of sets of this SRM (2031) will be available for issue. In a closely

related effort, the calibration of SRM 930, glass filter transmittance standards, is continuing. More than 1000 sets of this SRM have been issued since

its introduction in 1970; approximately 50 sets are returned yearly to this

Group for verification or recalibration. Research is in progress to produce

several types of fluorescent glass standards for use in nondestructive crack

testing. The major development in this area has been the decision to switch

from the previously studied uranyl-doped silicate glass to a terbium-doped

phosphate glass as the basis for these standards. The fluorescence-temperature

coefficient of the terbium glass is at least an order of magnitude less than

the uranyl glass and should be usable with no auxiliary thermostating, even under conditions where temperature changes are as large as 20 °C.

Major areas of involvement of the Atomic and Molecular Spectrometry Group

have been in the characterization of Standard Reference Materials, participation in programs of national concern, and the performance of service analysis.

A few of the Group's accomplishments this past year have included the application of spark emission spectrometry to the acceptance testing, homogeneity

testing and elemental analysis for the SRM metal program, and the utilization

of AAS, ICP, and DCP for homogeneity testing, and characterization of minor

and trace elements in metals, envionmental , and biological SRM's. AAS with

electrothermal atomization and matrix modification was used to survey the

concentrations of 11 elements in 56 different FDA injectable materials and to

provide analytical data on specimen bank samples, acid rain standards, and

hazardous waste leachate solutions. DCP was used to determine 12 elements in

30 leachate solutions from glasses proposed as formulations for nuclear waste

encapsulation. Spark emission spectrometry and combustion techniques for

carbon and sulfur analysis were used to determine the composition of the

structural steel involved in the accident at the Hyatt Regency Hotel in

Kansas City.

Future research will place greater emphasis on understanding and controlling the fundamental excitation process occurring in atom-production sources. Other activities will include the development of a solid sampling technique to

be used in conjunction with ICP for the elemental analyses of biological

tissues and fluids, the improvement of the precision and accuracy of DCP by

the use of internal standards and improved nebulization systems, the evaluation of an ICP/AFS system for mul ti -el ement analysis, the evaluation of a gas

43
generation procedure for DCP, the evaluation and method development of stateof-the-art instrumentation for carbon, sulfur, hydrogen, oxygen, and nitrogen

in metals, the intercomparison of physical methods for verifying photometric

linearity, the extension of the capability of the high-accuracy spectrophotometer to the near-infrared region, the investigation of group separation using

non-selective chelating agents as a basis of shortening the chemical preparation

for multielement isotope dilution mass spectrometry, and the development of a universal matrix modifier to AAS with electrothermal atomization. In addition,

a major effort will be made to use the Zeeman/atomic absorption spectrometer

for analyses of metals in high-solid matrices and to study metal ion speciation

for As, Cr, and Zn in a variety of materials using a hybrid AAS unit.

Theodore C. Rains, Group Leader; Carol G. Blundell, David E. Brown,

Robert W. Burke, Therese A. Butler, Barry I. Diamondstone, Michael S. Epstein,

Radu Mavrodineanu, Jerry D. Messman, Kimberly I. Moran, John A Norris,

Douglas J. Patin, Theresa A. Rush, Roger M. Stone, Robert L. Watters, Jr.

4. El ectroanalytical Chemistry Group: Overview

The objectives of the El ectroanalytical Chemistry Group are the development and application of electrochemical principles for chemical analysis. The

techniques employed include amperometry, conductimetry , coulometry, ion

chromatography , potentiometry, and voltammetry. Research activities are directed toward attaining a more thorough understanding of the complex chemical

systems encountered during the development and implementation of high-accuracy

analytical procedures ranging from ultra-trace determinations in a myriad of

matrices to assays of ultra-pure chemicals. The popularity and utility of

electrochemical techniques for chemical analysis is expanding due to advances

in technology. The Electroanalytical Chemistry Group intends to take an active role in this expansion through innovative research that incorporates

all of the techniques described above. Emphasis will be in the areas of

speciation, multi -component analyses, and measurement assurance.

This year a major effort has been expended in re-establishing the

capability for making high-accuracy pH measurements. The necessary instrumentation has been assembled, tested, and calibrated. Highly stable silver/silver

chloride reference electrodes have been prepared for use in the emf measurement

cells without liquid junctions. Preliminary measurements have been made on solutions of dilute mineral acids and of standard pH buffer materials in

anticipation of an extensive recertification program that is scheduled for

next year and which will involve several of the Standard Reference Materials

(SRM's), pH and pD buffers, which are now in short supply. One of the

materials, the sodium carbonate/sodium bicarbonate pair, has already undergone

acceptance testing. This new pH facility will also enhance our ability to

conduct pH research in conjunction with the Acid Rain Program.

High purity arsenic tri oxide was assayed for certification as a reductimetric SRM using control led-current, high-precision coulometry. Coulometry

was used for the measurement of acidity in simulated rainwater samples and

also in the analysis of high purity acids for use as ion chromatography standards. The one-year tenure of a guest worker from Japan, Dr. Tatsuhiko Tanaka,

has resulted in a comprehensive study of current efficiencies at various types

44
of electrodes in relation to the coulometric titration of uranium with

electro-generated titanous ion.

Ion chromatography (IC) was wel 1 -uti 1 ized in the Standard Reference

Material program for the determination of sulfur in six types of oil (ranging

from 0.14 to 4.5 weight percent sulfur) and in four different coals (ranging

from 0.5 to 4.7 weight percent sulfur). These energy-rel ated materials were combusted in a high-pressure oxygen bomb which efficiently converts all sulfur

to sulfate. The sulfate is subsequently quantitated by comparison with

sulfate standards using the ion chromatograph . Botanical Standard Reference

Materials (Pine Needles, Wheat Flour, and Tomato Leaves) were analyzed for

sulfur and chlorine by a similar procedure.

In response to a request from another government agency, an improved

method for the determination of cyanide ion was developed using ion chromatography with electrochemical detection. The procedure is highly sensitive and

selective for cyanide, capable of detecting 1 part per billion in solution.

Interference from sulfide or iodide is insignificant unless the concentration

of these species greatly exceeds that of cyanide. This method has been applied

to assess potential cyanide transport in an industrial setting and could be

adapted to the monitoring of air and particulates for trace levels of cyanide.

Chlorine was determined in cadmium sulfide samples by IC to fulfill a request for analytical services. This procedure has been recently published.

In a cooperative effort with Catholic University, several leachate samples of

glasses and rocks (basalt and granite) were analyzed for anionic content. As

part of the NBS-effort in nuclear waste storage research, this Group was responsible for the pH, nitrate, and fluoride measurements in the leach-test

protocol study. Fluoride was determined in SRM urine samples using ionselective electrodes. After a critical evaluation of the analytical work on the reductimetric assay of sodium oxalate (SRM 40h), the certificate was upgraded from provisional to final.

The Acid Rain Program is continuing with an increased emphasis on research

leading to the development of reference materials and analytical protocols

which will provide traceability to the National Measurement System and assure accurate measurements. A fourth series of Simulated Precipitation Reference

Materials (SPRM IV) has been characterized with respect to chemical composition. A program to monitor the stability of SPRM IV, stored in glass and in

polyethylene, has been initiated, while the study of SPRM I through SPRM III,

stored only in glass, has just recently been completed. Experiments are in

progress to assess the long-term stability of dilute acid solutions in polyethylene. Results of these stability projects indicate that the solutions

prepared to date that have been stored in glass are not stable with respect to

pH, conductance, acidity, alkali metals, or the concentration of several

transition elements. Among the recommended changes to be included in the

fifth set of samples are the use of polyethylene bottles, and the separation

of the major components from the trace elements which must be stored under

different conditions for maximum stability. Future research in this program

will focus on gaining a better understanding of this complex analytical

problem, on establishing practical and theoretically sound protocols for the

measurement of pH and acidity, on developing stable reference standards, and

45
on initiating a study of potential source identification based on lead and

sulfur isotopic analyses and elemental ratioing.

A high priority project for the coming year will be the certification of

pH and pD buffer materials. In addition, proposals have been advanced to

study liquid-junction potentials and reference electrodes and to develop the

concept of relating the MBS operational pH scale directly to the Faraday

through the coupling of coulometry and the hydrogen gas electrode. This

research will be conducted in conjunction with the Acid Rain Program and could

also be linked to clinical and oceanographic studies. With the aid of an NRC/NBS Postdoctoral Research Associate, voltammetric research will be

initiated into the nature and causes of background currents encountered in

trace-level amperometric and voltammetric determinations at solid electrodes.

Investigations in ion chromatography will concentrate on using the electrochemical detector to enhance selectivity and sensitivity and to augment the

types of anions determinable by IC. Foremost on the list are ultra-trace

determinations of sulfur as sulfide and analyses of foods for iodide. A

workshop, jointly sponsored with the National Committee for Clinical Laboratory Standards will be held next spring to discuss direct potentiometry in

blood, with particular regard to sodium measurements.

William F. Koch, Group Leader; E. June Maienthal, George Marinenko,

Kenneth W. Pratt, Jr., Jeffrey W. Stolz, Tatsuhiko Tanaka, David M. Taylor

46
B. Selected Technical Reports

(Inorganic Analytical Research Division)

1. High-Accuracy pH Measurements (14301)

W. F. Koch, G. Marinenko

The measurement of pH is one of the most common analytical measurements

performed both in the field and in laboratories around the world. Its application cross-cuts many disciplines including analytical chemistry, biology,

medicine, material science, and nuclear chemistry, as well as a variety of

environmental and energy projects. The concept of pH can be described in

the strictest theoretical sense; however, the realization of pH (the actual

measurement) is possible only in the practical sense and, at present, must be

based on quasi -thermodynamic foundations. This in no way detracts from the

usefulness of the measurement, but it does make it highly dependent on the

standards used to define the pH scale. The operational pH scale used in the

United States and in much of the world is defined in terms of a series of

standard buffer solutions issued and certified through the Office of Standard

Reference Materials.

In order to maintain the standards in this important area of chemical

metrology and to expand the utility and applications of pH measurements, a new

high accuracy pH/potentiometry facility has been established. Construction of

the facility is complete with the acquisition and assembly of the critical

elements and instruments. A large control 1 ed-temperature water bath which

is used to thermostat the pH measurement cells is operational over the range

0 to 50 °C. The accurate measurement of the bath temperature (±0.01 °C) is

obtained through the use of a calibrated quartz thermometer. The quartz

thermometer provides the accuracy required for pH research along with the

flexibility and convenience that is unobtainable with platinum resistance

thermometers.

The emf measurements are made with a calibrated digital voltmeter

interfaced to the pH cells and to standard Weston cells through a panel of

hermetically-sealed, reed switches. These switches were chosen for their low

noise characteristics, low contact resistance, and null leakage current. A

digital barometer, calibrated versus the working standard of pressure at NBS,

is used to ascertain the pressure of hydrogen gas in the pH measurement cell.

Several configurations of silver/silver chloride reference electrodes have

been prepared for use in the hydrogen cells without liquid junctions. These

have been tested for physical and chemical stability, reproducibi 1 i ty , temperature coefficient and hysteresis, all parameters critical to accurate pH measurements. Considerable differences have been observed among the potentials of the

various types of electrodes, although within-set agreement of the electrodes

prepared on a silver wire support is excellent (±0.05 mV). The classical

configuration using a platinum wire as the support performed less satisfactorily. Additional research is needed to elucidate these variations. Preliminary

pH measurements have been made on solutions of dilute acids and of standard

buffer materials. Measurements leading to the certification of renewal SRM pH

and pD buffer materials, which are now in short supply, will commence in FY 83.

Automation of the facility for routine measurements is anticipated.

47
In addition, research is proposed to link the existing pH scale directly

to a fundamental physical constant, specifically the Faraday. This will be

accomplished through the use of high accuracy coulometry to determine, on an absolute basis, the hydrogen ion content of dilute solutions of highly purified

mineral acids. The activity coefficients of these simple solutions can be

calculated from thermodynamic considerations. These solutions will then be

systematically compared with the primary standard buffer materials which now serve to maintain the NBS practical pH scale. A thorough examination of

reference electrodes and liquid junction potentials will be a necessary part

of this endeavor.

Future applications of this new pH facility will include the preparation

of accurate pH standards to assure quality in analytical measurements and the

expansion of the utility of the NBS pH scale as both a practical and a theoretical analytical tool. An important goal of this program is to produce and

distribute pH standards which simulate the varying matrices and ionic strengths

encountered in solutions such as acidic precipitation, body fluids, and

seawater.

2. Resonance Ionization Mass Spectrometry of Vanadium, Molybdenum, and

Rhenium (51108)

J. D. Fassett, F. E. Lytle, L. J. Moore, J. C. Travis

Resonance ionization mass spectrometry (RIMS) is an innovative technique

combining mass spectrometry with laser photoionization to selectively and

sensitively produce ions from a gas phase reservoir of atoms. The technique

exploits both the limited bandwidth and intense photon flux inherent in laser

radiation. By tuning the laser to a discrete electronic transition of an element where the photon absorption cross section is increased many fold (a

resonant process), the ionization probability becomes similary increased due

to the stepwise absorption of subsequent photons. This particular technique

differs from other spectroscopic techniques in that the absorption or emission

of photons is not directly measured, only the ions that are produced are measured. Thus, there exists a combined elemental selectivity (due to the

ionization) and isotopic selectivity in the measurement process. To date, resonance ionization has been studied predominantly in ionization chambers

without mass selected measurement and only for a limited number of elements

(potassium and a few rare earth elements), although possible schemes for resonance ionization of a majority of the elements in the periodic table have

been published by other researchers. As part of a multiyear competence

research program in ionization mechanisms and ion structures, a RIMS system

has been built (described in another technical report), and resonance ionization of the elements V, Mo, and Re has been demonstrated.

The formation of atomic ions using resonance ionization requires a source

of neutral atoms which can be supplied by either single or multiple filament

thermal ion sources used in conventional stable isotope mass spectrometry.

Langmuir vaporization of salts or metals deposited on a filament surface will

produce a gas phase reservoir of neutral atoms under the appropriate conditions. One of the prime motives for the development of RIMS was the

48
investigation of the thermal ionization process to understand the mechanisms

in Langmuir vaporization and ion formation. The results to date indicate that

Langmuir vaporization is ideally matched with RIMS and valuable information

in both processes will be gained.

Three elements, V, Mo, and Re, whose ionization potentials are 6.7, 7.1,

and 7.9 eV, respectively, have been initially investigated by RIMS. The

coherent radiation provided by a Nd-YAG laser pumping a tunable dye laser with

a frequency-doubled output was used to access resonance levels of the elements

that were vaporized from the modified thermal ion source of a magnetic sector

mass spectrometer. Molybdenum atoms were produced from molybdic acid reduced

under hydrogen on the rhenium substrate; vanadium atoms were produced from

V0C1 3 dried on the rhenium substrate; and rhenium atoms were produced directly

from one rhenium filament substrate. The microgram quantities of V or Mo

produced steady state reservoirs of gas phase atoms which were not depleted in

the experiment at operational temperatures of 1275 °C and 1590 °C, respectively. Detection and measurement of the mass selected ions were accomplished

with a 17-stage electron multiplier whose amplifed output was coupled to a boxcar averager synchronized to the laser pulse and. delayed for the appropriate

time-of-flight of the ion.

The spectroscopy of ionization has proved to be extremely interesting.

Three resonance lines of Mo (3002.211, 3112.12, 3132.59 A) and two resonance

lines each of Re (2976.29, 299.31 A) and V (2942.35, 2943.20 A) were investigated. The spectral structure varied considerably among the elements and

includes the appearance of non-resonant peaks, non-resonant background, and

differing resonant peak shapes, intensities, and laser power dependencies.

Figure 12 illustrates part of the Mo spectrum. The two non-resonance lines

and shoulder to the 3132.59 A resonance line have yet to be satisfactorily

explainer). The sharpest resonance 0

l ine observed to date has been the

2976.29 A line of Re equal to 0.3 A at half maximum.

Saturation of the ionization signal has been observed at readily attainable laser powers, from which it can be inferred that ionization efficiencies

are 100 percent in the laser focal volume exposed to ion source extraction

optics. These preliminary results also indicate that there exists a trade

off that must be made between optical selectivity and sensitivity in this

experimental arrangement of RIMS because of the quadratic nature of 2-photon

non-resonance ionization background caused by the saturation broadening of

optical transitions at laser powers required for 100 percent ionization.

49
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50
3. Depth Profiling of Bismuth in Silicon and Tin with Low-Energy

Neutrons (51109)

R. G. Downing, R. F. Fleming

A depth profiling facility similar to the one at the Institute LaueLangevin Research reactor in Grenoble, France [1] is currently being developed

at the National Bureau of Standards Research Reactor. Profiling is accomplished

by evaluating the residual energy of those particles escaping the parent matrix

due to in situ nuclear reactions induced by low-energy neutrons. Concentrations

and depth distributions are then made having a yviovi knowledge of the

matrices' stopping function and counting statistics. Since the primary 'neutron

beam imparts a negligible amount of energy in this process, this technique

offers the attractive possibility of causing minimal direct damage to samples

which have the appropriate isotopic species.

Of the species traceable in the above manner, bismuth is of particular

interest in that it yields delayed alpha particle emission upon activation.

All other known species are prompt particle emitters upon activation and

therefore are confined to analyses only during the irradiation process on the

reactor beam line. Bismuth's unique property thereby allows the activated

sample to be conveniently removed to a remote counting site for profiling.

Parallel measurements have been conducted on bismuth distributions by means of neutron depth profiling (NDP) and secondary ion mass spectroscopy

(SIMS) to demonstrate the synergistic possibilities of combining depth profiling techniques. As an example, Figure 13 shows the bismuth distribution in a 30 keV bismuth implant in silicon [2] (dose = 4.4 ± O.lxlO15 atoms/cm2

) determined by SIMS and the corresponding energy spectrum as measured by NDP.

In this particular case, the implant is shallow enough that essentially no energy loss occurs for the alpha particle traveling in the silicon. As a result, the width of the energy distribution measured by NDP is determined by

the spectrometer response function. Knowing the total dose of bismuth in the

sample, the integrated counts in the NDP spectrum can be used to determine a calibration factor for the system.

A second bismuth-containing sample was then analyzed. This sample con- sisted of an approximately 2.5 ym- thick bismuth layer evaporated on a tin

substrate, heated in air at 150 °C and rapidly cooled. A SIMS depth profile

of the resulting layer revealed mixing of the bismuth and tin, with an apparent surface peak in both bismuth and tin overlying a layer of bismuth-tin

alloy of homogeneous composition. Obviously, both tin and bismuth cannot

increase at the surface. The apparent enhancement is at least partially due

to matrix effects on the secondary-ion intensities. A NDP profile of the same layer confirmed the existence of a real surface bismuth peak as well as the

homogeneous subsurface layer. The bismuth calibration factor obtained from

the bismuth-silicon implant can be used to derive the number of bismuth atoms

per unit volume in the homogeneous layer. Assuming the density of this layer

to be approximately that of tin, the major component, and determining the

number of tin atoms per unit volume by difference, yielded a Bi/Sn atom ratio

of 0.14 in the homogeneous layer. This ratio corresponds very well with the

solubility of bismuth in tin at the temperature of heat treatment. A SIMS

51
Bi in Si 4.4e 15 @ 30keV

3/24/B2

S . I . M . S . C

at/cc

10E 22

Depth (pm)

Figure 13. Depth distribution of bismuth implanted at 30 keV

into silicon, as determined by SIMS.

Inset: corresponding profile as measured by NDP.

52
sensitivity factor SBi/Sn = ( IBi/CBi )/( ISn/CSn) can thus be calculated from

this NDP atom ratio (CBi/CSn) and the SIMS intensities (IBi/ISn) measured in

the homogeneous layer. A value for SBi/Sn of 2.9xl0”2 can be determined from

these calculations. Finally, by using this SIMS sensitivity factor, the

initial portion of the SIMS depth profile can be corrected to yield an apparent concentration ratio axis, as shown in Figure 14.

This example demonstrates the potential for synergistic interaction of

neutron profiling with the more commonly available methods for depth profiling.

Although at present the NDP technique is limited in application to elements of

adequate sensitivity, refinement of the charged particle spectrometer to

include coincidence counting may extend the method to additional systems.

References

[1] Biersack, J. P., Fink, D., Henkelmann, R. A., and Muller, K.,

"The Use of Neutron Induced Reactions for Light Element Profiling

and Lattice Localization," Nucl . Inst. Meth., 149 , 93 (1978).

[2] The Bi-Si sample was kindly supplied by Dr. John Baglin of IBM

(Yorktown Heights); the dose was derived from a round-robin study

by Rutherford backscattering (Baglin, unpublished results).

1 . 0 -,

Concentration (atom fraction)

of Bi in a Bi-Sn layer as

• measured by SIMS

Figure 14.

-•

0 i

1 i—i 1 1 1 1 1

1 ' 1

1

1—

i

0 0.5 1.0 1.5 Depth (^m)

SIMS depth profile of bismuth in the bismuth-tin alloy

layer with sensitivity factor corrections applied to

derive a concentration axis.

53
4. Determination of Provenience of Artifacts with Lead Isotope Ratio

Measurements (11310)

I. L. Barnes, E. C. Deal

For more than ten years, the Mass Spectrometry Group has collaborated

with a number of museums in providing information concerning the possible

provenience of artifacts through the measurement of lead isotopic ratios.

Useful information comes from the fact that each lead deposit in the world

has a unique set of lead isotopic ratios which are preserved in the statue,

coin, glass vessel, etc. made with the smallest amounts of lead. Because the

isotopic differences are usually very small, a high accuracy measurement

procedure like the one developed at NBS is required.

The demand for this measurement information has increased to the point

where the services of a full time analytical chemist are required in order to

meet minimum needs. Fortunately, a grant from the Smithsonian was made available to the Freer Gallery to support a Freer employee as a guest worker at

NBS for two years. Although the first year has been largely devoted to training

in the chemical and mass spectrometric procedures necessary for high accuracy

measurements, useful results have been obtained. The results from analyses of

samples provided by R. Brill of the Corning Museum of Glass, P. Meyer of the

Metropolitan Museum of Art, and T. Chase of the Freer Gallery, are shown,

along with a summary of previous data, in the following figures.

The ellipses shown in Figure 15 have been defined by the analyses of

nearly 1,000 ores or objects of known Egyptian, Greek (L), English (E),

Spanish (S), or Italian area (X) origin. The two data points just to the left

of the "L" region were obtained from metallic objects taken from a ship wreck

discovered off the coast of Greece and the results are consistent with a Turkish origin. The data point within the "E" region is from a piece of

yellow, opaque glass of "European or Chinese" origin. The data point within

the "L" region is from a glass bead found in Japan and believed to be of

Chinese origin and is discussed generally below.

Figures 16 and 17 are extensions (same scale) of the upper right and

lower left of Figure 15. It should be noted that the data from these samples

tend to group into three clusters, two to the upper right and one to the

extreme lower left, of the expanded graph. This is consistent with the small

amount of previous data from samples of presumed Chinese origin. It may be

possible in the future to determine the location of these three geologically

different regions of manufacture if samples of native ores could be obtained.

To date, only a very few galenas have been obtained. The few samples

analyzed of known forgeries of Chinese objects have yielded data which falls

in or near the "L" or "S" regions. At present, the significance of this

information is not clear.

54
Figure 15.

Plot of lead 207/206 versus

lead 208/206 ratios. Ellipses

have been defined by a large

number of previous samples.

Figure 16.

Extension of the lower left

of Figure 15 (same scale).

Data points (M) are from

Chinese bronzes from the

Metropolitan Museum of Art.

Figure 17.

Extension of the upper right

of Figure 15 (same scale).

Data points are from samples

of Chinese glass and bronze

objects from (B) the Corning

Museum of Glass, (C) the

Freer Gallery of Art, and

(M) the Metropolitan

Museum of Art.

LEAD 208/206 RATIO

55
5. Treatment of Sources of Variability in the Inductively Coupled Plasma

(ICP) Technique (14625)

R. L. Watters, Jr.

The Inductively Coupled Plasma (ICP) technique has been applied to

certification as well as homogeneity assessment of various elements in Standard Reference Materials (SRM's). For an element being determined at a concentration well above its detection limit, the ICP technique can achieve

short-term precision of less than one percent relative standard deviation

(RSD). Under such conditions, the principal source of variability is random

nebulizer noise. However, for homogeneity assessment, duplicate analyses on several batches of material are required to provide the analyst with the

number of degrees of freedom necessary to make a meaningful statement concerning the between batch variance. Unfortunately , when the number of samples is

increased, the corresponding increase in the time of analysis usually allows

other sources of variability, such as nebulizer drift, to affect the quality

of the results. Two approaches have been used to address this problem.

The first approach involves sample preparation procedures which reduce

the amount of non-random nebulizer variability. It has been found that when

samples of an organic matrix are wet-ashed using perchloric acid, the resulting

solutions cause appreciable nebulizer pressure drift (approximately one psi).

During simultaneous multielement analysis, a corresponding drift in element

net intensities has been observed. The degree of intensity drift for a given

element depends on its optimum observation point in the plasma flame relative

to the compromise observation point chosen for all elements. An alternate

sample digestion procedure has been used for the ICP certification analysis of

SRM 1084 and 1085, Wear Metals in Oil. Ten elements were determined in aqueous

solutions of the two materials following a sealed-tube dissolution using hydrochloric and nitric acids. In this particular case, up to 0.5 g of oil can be

digested with the resulting solution containing two percent HN03 by volume.

For the samples prepared to date, no detectable pressure drift has been

observed during long-term nebul ization.

The second approach to isolating variability associated with sample

batches was to develop software for on-line data analysis of variance (ANOVA).

This development was possible only after the completion of the communication

network and protocols mentioned in last year's annual report. A modification

to the commercial ICP software package was also required because the analysis

data are stored in a format suitable only for report writing. The output

subroutine of a report writing program was modified to write sample identification numbers and associated analytical data into a separate ASCII file which

can be accessed by other computers. This file can be transferred to the NBS

main computer for analysis by the OMNITAB software or to a Z-80 microcomputer

for analysis by BASIC 80 software. For SRM homogeneity studies, the file can

be transferred to the microcomputer for an analysis of variance of hierarchic

data with three sources of variation. The first application of this approach

was in the determination of magnesium in duplicate samples from 11 bottles of

SRM 1549, Powdered Milk. The samples were run in random order using four

instrumental integrations for each. Estimates for variance in (1) SRM bottles,

(2) sample preparation and instrumental drift, and (3) instrument integrations were calculated in a total of five minutes after reading the data from the

56
minicomputer disc. An average value for each SRM bottle and the standard

ANOVA, Table 5» is printed on one page for each element determined.

Using these two approaches, one source of variance in the sample introduction step of the ICP technique can be significantly reduced and estimates

of three sources of variance in the entire analytical scheme can be calculated.

Table 5. ICP Results for Mg in Powdered Milk.

(yg/g)

SRM Bottle Sample 1 Sample 2

12-2 1210.00 1201.12

06-2 1185.63 1213.25

10-2 1177.67 1247.55

01-1 1265.73 1177.13

11-1 1186.38 1248.90

03-2 1256.65 1224.13

07-1 1202.28 1240.50

02-1 1213.70 1168.35

09-2 1186.30 1204.35

08-1 1204.92 1210.07

04-1 1196.67 1206.52

Analysis of Variance for Element Mg

Source of Variation Sum of Squares D.F

Between Groups 16246.843 10

(SRM Bottles)

Between Samples 45017.498 11

Within Groups

Within Samples 12731.806 66

Total 73996.200 87

Mean Square

1624.680

4092.500

192.906

The mean squares estimate the following:

1624.680 = V( 0) + 4 V(l) + 8 V( 2)

4092.500 = V(0) + 4 V(l)

192.906 = V( 0)

Where V ( 2 ) = SRM-Bottle-to-SRM-Bottle Variance

V(l) = Sample-to-Sample Variance and Instrument Drift

V(0) = Variance Due to Instrumental Integrations

The estimates are:

V( 2) = -308 (essentially zero)

V(l) = 975

V(0) = 193

57
6 . Effect of Natural Isotopic Variability on Accurate Determination of

Sulfur by Neutron Activation Analysis (11310)

R. F. Fleming, R. M. Lindstrom

The instrumental neutron activation analysis of sulfur depends on the

activity of 37 S produced from the 36 S isotope which has a natural abundance

of approximately 0.02 percent. Wide variations in the isotopic ratios of

naturally occurring sulfur were first demonstrated by the McMaster group

using mass spectrometric techniques and has since been documented for thousands of samples. The effects on accurate activation analysis of any isotopic

fractionation are usually negligible for reactions on isotopes of major

abundance. However, for isotopes of minor abundance, such as 36 S, accurate

activation analysis requires that either the isotopic compositions of both

the samples and standards be the same or that the compositions of both be

explicitly known.

Although careful mass spectrometry can determine the 3

6

S/ 3

2

S ratio directly, the isotopic fractionation of 34 S is typically measured and expressed as

6 34 S

( 34 $/ 32 s) sample

( 34 S/ 32 S) standard

x 1000

Meteoritic troilite (FeS) is the usual standard (6 34 S = 0) since it is believed

to reflect the mean solar system abundance and has not been fractionated. Seawater sulfur is uniformly enriched in 34 S by 20 parts per thousand (6 34 S = +20

o/oo). Volcanic sulfur has a range of 6 34 S from -10 to +10 o/oo while the S 34

in coal and petroleum ranges from -30 to +30 o/oo. The range of published

values for 6 34 S is from -53.1 o/oo for a Texas marcasite (FeS 2 ) to +86.7 o/oo

for a barite (BaS04 ) from the Japan Sea. Using the theoretical relation for

the fractionation of sulfur isotopes, one can estimate the spread in the

abundance of naturally occurring 36 S:

1 n ( 1 +6 3

6

S ) = (1.90 ± 0.01 ) 1 n ( 1 +6 3

4

S

)

1 n ( 1 +6 3

3

S ) = (1.94 ± 0.01

)

_1 ln(l+6 34 S)

This model predicts a maximum difference of 29 percent in the 37 S specific

activity of sulfur samples irradiated under the same conditions. The 6 34 S

spread for coal and petroleum is large enough to limit the accuracy of sulfur

determination to ±15 percent, regardless of the precision of the measurement.

Other nuclear techniques which depend on the properties of the major isotope

32 S , such as prompt-gamma neutron capture activation analysis (PGAA) or fastneutron activation followed by counting of 32 P, are only slightly affected by

isotopic fractionation.

In this work, the systematic error from the isotopic variability is

demonstrated by determining the 3 S counting rate per unit mass of sulfur

produced after irradiation of five 6 34 S standards from McMaster University

(the SL-277 series) as well as a galena, a barite, and an elemental sulfur

standard. Several other sulfurs of unknown isotopic composition including

the NBS SRM 371 g were also run. The McMaster samples were converted from

58
Ag2 S to H 2 S with HC1 , and from H 2 S to S with I 2 , followed by purification of

the product. The volcanic samples and some of the laboratory sulfurs were

purified by recrystallization. The samples, weighing from 12 to 90 mg, were irradiated in the NBS reactor, and after a fixed decay time, the 3103 keV

gamma ray was counted with a germanium detector. Zinc flux monitors were run with each irradiation to assure the constancy of the neutron flux, and small

corrections were made for dead-time and pulse pileup.

There is a six percent difference in response among sulfurs from commercial suppliers, perhaps a three percent difference among the volcanic sulfurs,

and an apparent 6 34 S = 0 for the SRM sulfur. The results for the standards

are plotted against 6 34 S in Figure 18, with each data point representing the

average of at least two measurements and the error bars representing counting

statistics (la) only. The solid line is the predicted curve based on equation

two, normalized to the measured activity for sample SL-277-1

.

In summary, it has been demonstrated that the known isotopic variability

of 36 S results in a corresponding inaccuracy in the measurement of sulfur by

neutron activation and that this effect is well predicted by the theory. The

worst-case limit on the measurement accuracy is ±29 percent; however, this

uncertainty can be halved if one uses a standard of known isotopic composition.

Figure 18. Sulfur-37 specific counting rate versus 34 S variation in

parts per thousand for the eight isotopic standards.

59
7. Application of ID/MS to the Determination of Sulfur in Biological

and Environmental Standards (14307)

W. R. Kelly, P. J. Paulsen

The new procedure developed last year for the determination of sulfur

using thermal ionization mass spectrometry has been further investigated and

applied to a variety of materials with sulfur concentrations ranging from

3 ppm to 4.5 percent. In addition, this technique has been applied to the

precise measurement of the sulfur isotopic composition of the above materials.

Because the sulfur isotopic composition is variable in nature as a result of mass dependent fractionation, it is necessary to measure the composition in

each sample in order to calculate accurately the sulfur concentration. The

isotopic composition of sulfur is approximately 95 percent 32 S, 0.75 percent

33 S, 4.2 percent 34 S, and 0.02 percent 36 S.

To determine sulfur concentration, appropriate quantities of sample, 34 S

enriched spike, along with nitric and hydrochloric acids are equilibrated in a sealed pyrex tube (modified Carius tube) to prevent loss of volatile sulfur

compounds. The oxidized sulfur (S04 _

) that is formed is subsequently reduced

to H 2 S and precipitated as As 2 S 3

. The As 2 S 3 is dissolved in an NH 3 -As(+3)

solution to yield an As/S atom ratio of two and a sulfur concentration of

100 pg S/mL. About 1.5 yg S is loaded on a rhenium filament with silica gel.

Sulfur isotopic ratios are measured as the AsS

+ ion. Since As is mononuclidic,

the ion intensities at masses 107, 108, 109, and 111 from 75 AsS are directly

proportional to the abundances of sulfur 32, 33, 34, and 36.

The results obtained for sulfur in freeze dried Bovine Liver (SRM 1577a

and 1577b) illustrate the high accuracy and precision that can be obtained by

this technique. Two batches (a and b) were prepared from a single lot of

bovine liver. Six bottles from each batch were analyzed and the data are given in Table 6. The "a" samples were packaged material whereas the "b"

samples were taken from different barrels of the unpackaged material.

Replicate analyses of both materials differ by only one to three units in the

third place indicating both good measurement precision and sample homogeneity.

The mean sulfur values for the "a" and "b" materials are indistinguishable

even though there was considerable difference in weight loss during vacuum

drying. This demonstrates that the drying procedure reduces all samples to

the same weight basis and indicates that improper drying could cause an inaccuracy of several percent. The total spread in the sulfur contents within

the "a" and "b" materials is 0.25 percent and 0.52 percent relative and

indicate the degree of homogeneity in sulfur content.

In Table 7 are listed the high level biological samples that have been

certified. Both the sulfur concentration and the 3

2

S/ 3

4

S ratios are given.

The larger uncertainties of the coal concentrations reflect the larger spread

in the replicate values. All of these organic materials have 3

2

S/ 3

4

S ratios

that are different. The coal SRM's show a range of 1.6 percent in their

32 S/ 34 S ratios which is a factor of 10 greater than the typical measurement

imprecision. The variation of the 32 S/- 4 S ratio in nature has been used to

trace the origin and mode of formation of rocks, minerals, ore deposits, and

fossil fuel deposits. Another important use, which has only recently been

explored, is the use of the differences in 3

2

S/ 3

4

S to identify sources of

60
sulfur compounds in both wet and dry deposition. It may prove possible to

distinguish between natural and anthropogenic sources of sulfur in specific

locations.

Table 6. Sulfur Concentration in SRM's 1577a and 1577b, Bovine Liver

as Determined by Thermal Ionization Mass Spectrometry.*

Bottle # S% Wt. Loss

1 0.7836 1.50

2 0.7852 1.54

3 0.7848 1.49

4 0.7856 1.50

5 0.7842 1.40

6 0.7837 1.63

Mean 0.7845

Uncertainty ±0.0046

3d 0.7863 3.88

4c 0.7846 4.39

4d 0.7841 6.26

5d 0.7851 4.40

7d 0.7851 5.39

9d 0.7822 5.21

Mean 0.7846

Uncertainty ±0.0061

Table 7. Sulfur Concentrations and 3

S/ 3S Ratios in Biological Materials.*

%S 32 S/ 34 S

SRM 1572, Citrus Leaves 0.4066 + 0.0022 22.63

SRM 1 577a , Bovine Liver 0.7845 + 0.0046 22.56

SRM 1577b , Bovine Liver 0.7846 + 0.0061 22.56

SRM 2682, Coal 0.4934 + 0.0092 22.70

SRM 2683, Coal 1.896 + 0.033 22.36

SRM 2684, Coal 3.076 + 0.090 22.73

SRM 2685, Coal 4.761 + 0.188 22.55

*In both Tables 6 and 7, the uncertainty for an individual

determination was calculated as the linear sum of the 95 percent

confidence interval (ts) for the six analyses, the 95 percent

confidence interval (ts) for ten spike calibration mixes, and the

uncertainty in the blank. This last quantity was assumed to be

equal to the largest blank observed. In Table 7, the measured

isotopic ratios have not been corrected for instrumental mass fractionation and thus are not absolute ratios.

61
8. Development of a Laser Mass Spectrometry Laboratory (51108)

J. D. Fassett, L. J. Moore, J. C. Travis

The objectives of the research in laser mass spectrometry are to develop

highly sensitive and selective atom counting technology and to investigate

the vaporization, isotopic discrimination, and ionization behavior of

inorganic compounds in thermal ion sources. The measurement impetus for this

research derives from projected sensitivities and selectivities for the

formation and measurement of ions. Atomic ionization sensitivity and selectivity are available using tunable laser radiation for resonance ionization.

A capability for selective isotopic measurements is being developed using

laser induced ion fluorescence for mass-selected high velocity ions.

The first phase of the development of this laboratory has been completed

(Figure 19). Laser and mass spectrometry systems were selected to provide

maximum flexibility to access all but the most difficult atomic ionization

potentials in the periodic table. A 700 mJ pulsed Nd-YAG laser, which pumps

a tunable dye laser coupled to a frequency doubler, generates highly coherent

wavelengths down to the near UV (^260 nm). The output of the pulsed laser

system can be directed to the ionization region of a time-of-fl ight or a magnetic sector mass spectrometer to permit efficient and selective removal

of electrons using the principles of resonance ionization. A second laser

system consists of a continuous wave (CW) argon ion laser used to pump a scanning single mode tunable dye laser. The output of the CW system can also

be routed to the ionization region of either mass spectrometer or to the

detector region of the magnetic sector instrument. Continuous wave radiation

can be used to produce ions directly or to selectively excite electrons to

Rydberg states prior to electrostatic stripping of the electron. The single

mode CW output can also be used to produce laser induced ion fluorescence

( LI I F ) in mass-selected ions and to study atomic fluorescence of neutral

species in thermal vapor plumes.

A real time diagnostic capability has been developed to probe thermal

vapors using the laser time-of-fl ight mass spectrometer combination. A

complete mass spectrum can be produced for each laser or electron impact

pulse using a 200 MHz transient digitizer with 4096 5-nsec channels. Successive spectra can be computed, averaged, recorded, and sequentially displayed.

This capability will be used to characterize complex thermal vapors and to

evalute the feasibility of inorganic valence state speciation. The resonance ionization mass spectrometry (RIMS) of Mo, Re, and V has been observed and

is described in another technical report.
Figure 19. NBS laser mass spectrometry laboratory.

63
9. Design and Construction of a Modern Facility for the Production of

Ultrapure Reagents (11310)

E. S. Beary, J. R. Moody

Two previous acid facilities, set up in existing modular laboratories

,

were unsuccessful due to corrosion, poor ventilation, and potential safety

problems. The new laboratory was specifically designed to overcome all

previous difficulties and provide a permanent safe laboratory for purified

acid preparation. The laboratory has been operational for nearly a year, and

it is now possible to compare theoretical operating parameters with actual

experience. Two basic requirements governed the design of the laboratory:

(1) the provision of high volume, single pass, class 100 supply air with an

all plastic exhaust sytem and (2) careful control of the balance of air flows;

removing acid fumes at their source without either introducing fumes into

the laboratory or permitting fumes to escape the area outside the laboratory.

Within the laboratory, the primary concern was to eliminate those

materials which contained metals (a source of contamination) or which could

be attacked by fumes or by contact with acids. This latter factor largely

determines the useful life of the laboratory and, as learned from previous

experience, compromise usually results in failure of the component. In

general, the first year's experience has indicated that the design principles

and choice of materials were valid. Most of the relatively minor problems

have been related to plumbing (leaks) or plastic ductwork (leaking joints).

The flooring should have been PVC but reasonably priced flooring made from

PVC is not available in the U.S. The substitute material, a proprietary

formulation, is functional but difficult to keep clean.

The potential for spills or accidents is in itself greatly reduced

because of laboratory design. All acid spills would be automatically

contained and conducted to a drain. Spills in the distillation module itself

are automatically diluted with water. Because of the improved and precise

control of air supply and fume exhaust, no free acid odor can be detected in

the laboratory.

The new laboratory, shown in Figure 20, is presently operating at full

capacity with 13 stills installed for the continuous production of five

mineral acids and the occasional purification of a sixth material such as HBr, HOAc or any one of a number of solvents. In addition, the facility has

storage capacity for about 250 L of purified acid and about 100 clean Teflon

bottles. An exhaust hood with non-reci rcul ati ng air is in use for the

cleaning of Teflon bottles and labware for trace metal analyses in an effort

to save the clean laboratory from further corrosion due to uncontrolled acid

fumes. By any measure of product quality, product quantity, or efficiency

of production, all expectations have been achieved. The lifetime of this

laboratory will surely be many times longer than previous efforts have

produced. In addition, there is a significantly improved level of safety

for those within the environment without any sacrifice in terms of quality

of product or utility of the laboratory.

64
Figure 20. Ultrapure Reagent Laboratory.

10. Improved Procedure for the Determination of Cyanide by Ion Chromatography

with Electrochemical Detection (14215)

W. F. Koch

The use of cyanide is widespread and vital to industries involved in such

commercially important operations as electroplating, extracting precious

metals, chelating metals, case hardening of steels, and fumigating orchards.

The extreme toxicity of cyanide requires that its use be strictly controlled

and that proper monitoring be in effect to guard against environmental con- tamination. To address the question of trace level contamination and prompted

by a request for assistance by another government agency, a highly sensitive

and selective method for the determination of cyanide has been developed. The

method employs ion chromatography with electrochemical detection (IC/EC) and

determines free, uncomplexed cyanide ion in aqueous solution.

Sample preparation for this procedure is minimal. Aqueous samples may be

analyzed directly while dust and particulate samples need only to be extracted

into an aqueous solution to dissolve the soluble cyanide. This is most conve- niently effected through agitation in an ultra-sonic bath. The solution must

be filtered before analysis in order to avoid fouling of the chromatographic

65
columns. Commercial ly-avai 1 able anion exchange columns with high ion-exclusion

properties are used to separate the cyanide ion from other anions. A suppressor column is not required in this application of ion chromatography. The

eluent contains 15 mmol/L ethyl enedi amine, 5 mmol/L sodium hydroxide, 2.5

mmol/L borax, and 1.0 mmol/L sodium carbonate. It is pumped through the

IC/EC system at the rate of 4 mL/min.

The detection system uses a commercially available three electrode

potentiostat and a flow-through cell. The working electrode is a silver rod;

the reference is a silver/silver chloride electrode; and the counter electrode

is platinum. Samples and standards are injected into the IC/EC system by means of a 50 y L sample loop. Under these conditions, the peak retention time

for cyanide is approximately five minutes. The amperometric signal at the

peak is proportional to cyanide concentration with a minimum detection limit

of one part per billion (ppb) and with linearity from this level to one part

per million (ppm). The range can be extended to higher levels with smaller

sample loops or by dilution of the sample.

Due to the excellent chromatographic resolution of sulfide, iodide, and

cyanide, no serious interference exists unless the concentration of iodide or sulfide greatly exceeds that of cyanide. This represents a considerable

advantage over the ion-selective electrode and the colorimetric procedures

commonly used in cyanide analyses, which are severely biased by the presence

of trace quantities of sulfide and to a lesser extent of iodide. Furthermore,

the IC/EC procedure extends the minimum detection limit at least one order of

magnitude below that attainable by the commonly used procedures.

With this improved method for the rapid determination of cyanide, the means are available to assess potential cyanide transport in those cases where

health and environment are major concerns. Research is continuing to assess

the precision and accuracy of this procedure and to expand its applications.

1 1 . Direct Determination of Calcium in Urine Using a Thermally-Regulated

D.C. Plasma-Echel le Spectrometer (14306)

C. G. Blundell, M. S. Epstein

Wavelength drift and order drift, both thermally-induced, were two major

problems that had been encountered in this laboratory in the use of the dc

plasma/echelle spectrometer. The dc plasma source is directly mounted on the

aluminum baseplate of the echelle spectrometer and the heat generated by the

plasma raised the temperature of the baseplate several degrees Celsius during

eight hours. The resulting drift severely limited the precision and accuracy

obtainable with the plasma spectrometer and made it necessary to develop a temperature stabilization system.

Thermal regulation is performed by a temperature sensor/controller which

monitors the temperature at the critical grating/prism mount and keeps that

temperature to within ±0.05 °C by switching on and off a heating tape which

surrounds the spectrometer baseplate. The system largely eliminates intensity

drifts due to wavelength and order changes as long as the other contributing

66
factors which influence the heat gain/loss characteristics of the spectrometer

(i.e., room temperature, exhaust system flow rate, solvent being aspirated,

and alignment of the plasma plume) are reasonably well controlled.

Table 8 presents the results of a homogeneity study of SRM 2673 (Urine)

in which calcium was determined directly using the 445.478 nm Ca line. Nine

discreet samples at each of the two levels were analyzed after a dilution of

3:25. The determination was a test not only of the ability of the temperature

regulation system to maintain stable spectrometer conditions, and thus allow

a highly precise determination, but also of the reaction of the sample introduction system to a very complex matrix (high alkali and organic content).

The use of a standard addition technique was required; an 85 percent recovery

of spiked calcium was found. The analytical precision obtained (0.6 to 0.9

percent RSD) is limited by the sample transport system. Further refinements

are being investigated to improve the precision of the method.

Table 8.

Urine Sample

Normal Trace Constituent Level

Elevated Trace Constituent Level

a ± one standard deviation of the

Ca, yg/mL

105.3 ± 0.9

a

105.7 ± 0.6

a

mean.

12. Determination of Ultratrace Concentrations of Chromium by Isotope

Dilution Mass Spectrometry (14215)

K. A. Brletic, L. J. Powell

Because of its role as an essential trace metal, the accurate analysis of

chromium has been of great concern to nutritionists over the past 10-15 years.

The analysis of chromium has proven to be difficult due to the chemical

complexity of the element and the fact that chromium is present at low or sub-nanogram per gram concentration levels in most biological samples. As a result, recent studies have indicated that many of the earlier literature

values for chromium in biological materials are in error [1].

A previously developed isotope dilution mass spectrometric technique

provided accurate analyses of chromium in a variety of environmental, botanical, and biological matrices [2]. However, this technique lacked sensitivity,

making it difficult to analyze many of the critical biological samples such

as serum and urine.

The chemical preparation involves spiking the sample with one microgram

of 50 Cr, dissolution with nitric and sulfuric acids, and separation of chromium

by solvent extraction into methyl isobutyl ketone. The chromium is back

extracted into water and reduced with a HN0 3 -H2 02 solution prior to analysis.

67
A new mass spectrometric procedure, which improves the instrumental

sensitivity for chromium by more than a factor of fifty, has been developed.

This method involves the sequential drying of silica gel, chromium( 1 1 1

)

nitrate and boric acid onto a rhenium filament. The filament is then transferred to a nitrogen atmosphere and heated to 830 °C using an optical pyrometer

to precisely control the filament temperature. This sample mounting procedure

is the critical step in achieving ion currents of 3-5x10 n A for 250 nanograms

of chromium.

This method has been applied to SRM 1253, Phosphorized Copper and SRM

1577a, Bovine Liver, with excellent results. During the next year, plans are being developed to look at other matrices such as SRM 1549, Powdered Milk (in

which the chromium concentration is estimated to be less than 50 nanograms per

gram) and human body fluids which are thought to contain less than one nanogram

per gram of chromium. The determination of chromium in body fluids will pose

a particular challenge because the accuracy of the analysis is highly dependent

on the magnitude and variability of the analytical blank. To analyze these

materials, the blank must be controlled at the pi cogram level, a project which

will require significant research to identify and eliminate sources of contamination, while maintaining sufficient chemical recovery of the chromium.

References

[1] Veillon, C., Patterson, K. Y., Guthrie, B. E., Wolf, W. R.

,

and Mertz, W., "The Chromium Story - or - How to Start an Entire Field Over," FACSS VIII, 1982.

[2] Dunstan, L. P. and Garner, E. L., "Chemical Preparation of

Biological Materials for Accurate Chromium Determination by

Isotope Dilution Mass Spectrometry," Trace Substances in

Environmental Health XI, D. D. Hemphill, ed., 1977.

13. Improved Radiochemical Procedures for High Sensitivity Measurements of

Ultratrace Concentrations of Tin and Mercury (11310)

R. R. Greenberg

Although instrumental neutron activation analysis can be used to determine

a large number of elements in most matrices, some critical elements are frequently obscured by high background levels of radiation or by interfering

elements. With appropriate radiochemical separations, a large number of

additional elements can be determined at the ppb and even sub-ppb levels.

Tin and mercury are two elements which are of both environmental and biomedical

importance. Although radiochemical separation procedures have been previously

developed for these elements, recent applications have required better

sensitivity and therefore improved separation from interfering elements.

Tin has previously been separated from Orchard Leaves (SRM 1571) with an iodide extraction into toluene. However, approximately one percent of the

selenium was found to accompany tin through this procedure which elevated the

background level of radiation. Although this did not seriously affect the

determination of tin in Orchard Leaves or Citrus Leaves (SRM 1572), it did

68
produce serious problems in other materials such as Bovine Liver (SRM 1577)

and human livers from the National Environmental Specimen Bank (NESB) program.

Several modifications in the procedure, including a selenium volatilization

step after sample dissolution (using H 2 02 and HF), a pre-extracti on wash with

chloroform, and a back-extraction of tin into an aqueous Na 2 EDTA solution,

reduced the fraction of selenium accompanying tin to <0.05 percent. With

these modifications, the tin content of Bovine Liver (SRM 1577) was found to

be 20 ± 3 ng/g (Is for six samples). The tin concentrations in eleven human

livers were also determined. Four subsamples of human liver homogenate were

analyzed and the precision was better than one percent (Is).

Mercury has previously been separated from a number of matrices by solvent

extraction using nickel diethyldithiocarbamate [N i

( DDC

)

2 ] in chloroform.

Large fractions (10-50 percent) of copper and bromine accompany mercury and

can interfere with the L97 Hg isotope by elevating the background level of

radiation. A small fraction of the selenium (<0.01 percent) also accompanies

mercury and directly interferes with the 279 keV y-ray of 203 Hg. Two additional steps were found to greatly improve the separation of mercury from

these other elements. The use of a chloroform wash prior to extraction with

Ni(DDC) 2 , and a post extraction wash with aqueous Na 2 EDTA reduced the accom- panying copper and bromine by a factor of 3-10, and the selenium by a factor

of 10-100. With these modifications no selenium could be detected in any of

the samples via other, more intense y-rays. These improvements allowed

mercury to be determined in Bovine Livers (SRM's 1577a and 1577b) at the 3-5

ng/g level with uncertainties of only 2-3 percent (la) due to counting

statistics. SRM 1577 (Bovine Liver) was analyzed as a control and the present

value of 16.0 ± 0.3 ng/g (la counting statistics) clearly demonstrates the

improvement in the method when compared to the previously determined value of

16.8 ± 0.9 ng/g (la); the uncertainty due to counting statistics has been

reduced by a factor of three.

In summary, the modifications described greatly improved the separation

of tin and mercury from other, interfering radionuclides. As a result, the

detection limits for both elements were greatly reduced, and the analytical

uncertainties due to counting statistics were significantly reduced.

14. Isotopic Fractionation of Gallium on an Ion Exchange Column (11310)

J. W. Gramlich, L. A. Machlan

The possibility of isotopic fractionation during ion exchange purification has serious consequences for isotope dilution mass spectrometry and

geochronol ogical isotope ratio measurements. Unless quantitative isotopic

recovery is achieved from the ion exchange separation, biased results may be

generated. Isotopic fractionation during ion exchange separations has been

reported in the literature for some elements such as calcium, potassium, and

chlorine; however, these studies have received little attention and have been

generally overlooked or disregarded by scientists engaged in ion exchange

separations for isotopic analysis. The work reported here confirms that

isotopic fractionation can occur during chemical purification and emphasizes

the importance of careful examination of all possible sources of systematic

bias during the development of a chemical separation and purification procedure.

69
Previous studies by the Mass Spectrometry Group have indicated isotopic

variations in high purity gallium metal. For example, high precision measurements of the 69 Ga/ 71 Ga ratio on 15 samples from different lots and a number of

worldwide, commercial manufacturers show a 0.25 percent variation in the

isotopic ratio. The general trend of decreased 69 Ga/ 71 Ga ratio with increasing

purity implies that isotopic fractionation takes place during the purification

process. In order to ascertain whether the isotopic variations are natural or are due to the purification process, it is necessary to survey the gallium

isotopic composition in natural ores.

Gallium is difficult to purify from natural materials because iron, which

is difficult to separate from gallium, strongly interferes with the mass spectrometric measurement. In an attempt to quantitatively separate iron from

gallium, an anion exchange column in the thiocyanate form was utilized.

Yields from the column were extremely low (25-30 percent recovery) and the

recovered gallium was depleted in 69 Ga relative to the expected value.

Measurement of the gallium fraction that had remained on the column showed

an enrichment in 69 Ga.

An experiment was conducted to quantitatively evaluate the rate of elution

from the column and the isotopic composition in each eluted fraction. Two

columns were set up and approximately 200 mg of gallium with a measured

isotopic composition of 69 Ga/ 71 Ga = 1.5283 ± 0.0001 (Is) were loaded onto each

column. Twelve elution fractions were collected from each column after which

the columns were stripped to remove any remaining gallium. A weighed portion

of each of the fractions was spiked with 71 Ga for isotope dilution analysis to

determine the gallium content while the remainder of the fraction was used to

determine the isotopic composition. Both column experiments confirmed the

initial observation of column fractionation. Ratios ranged from 69 Ga/ 71 Ga = 1.5148 for early fractions off the column to 1.5308 for the final stripping

fraction.

15. Improved Sensitivity in Instrumental Activation Analysis Using

the Compton Suppression Technique (14301)

J. R. Vogt, R. L. Zeisler

A persistent problem in instrumental activation analysis is the reduction

of sensitivity caused by background events in the gamma-ray spectra resulting

from Compton scattering within the detector. While this problem is less severe with large germanium detectors than with sodium iodide detectors--

primarily because the higher resolution and higher atomic number of germanium

increases the peak-to-Compton ratio--the Compton background still precludes

reaching the ultimate sensitivity of the detector. The usual technique that

has been used to reduce the background from Compton events is to surround the

primary detector with a second detector--usual ly sodium iodide--in an anticoincidence mode. Detection of Compton scattered photons in the secondary

detector blocks pulse conversion in the analog-to-digital converter.

Although many Compton suppression systems have been described in the

literature during the past twenty years, only those associated with low level

70
counting of environmental radioactivity or with prompt-gamma activation

facilities appear to be used routinely to produce quantitative data.

During the past year, a Compton suppression system has been set-up and

evaluated. The system consists of a Nal(Tl) annulus and an integral line

Nal(Tl) well detector used to surround all but the rear of the 19 percent,

1.79 KeV Ge(Li) primary detector. The electronics consist of an anti-Compton

analyzer (containing the coincidence circuitry) and an amplifier. A random

pulse generator is used to correct the gamma-ray photopeak areas for losses

due to the coincidence system and pulse pile-up. For this system, the sample

is inside the Nal(Tl) anti -Compton shield, rather than outside as in some other designs. Since there is no detection of scattered photons in the

forward direction [to the rear of the Ge(Li) detector], the suppression at

lower spectral energies is not as good as in systems where the Ge(Li) detector

is surrounded more completely. However, the suppression factor on the Compton

edge for Cs-137 is still about eight, for the middle of the spectrum about

4-5, and at the back-scatter peak about 3.5. Since the improvement in sensitivity follows roughly the square root of the background, the increases in

sensitivity for these portions of the spectrum are approximately 2.8, 2.1,

and 1.9, respectively.

With the sample inside the Nal(Tl) shield, both coincident photopeaks and

Compton events for radionuclides with cascading transitions are suppressed.

This effect reduces the spectral background more than simple Compton suppression. There are both positive and negative effects of the suppression of

coincident gamma-rays. The positive aspect is that the sensitivities of

non-coincident gamma-rays are improved. This can be of benefit in matrices

where coincident gamma-rays account for a substantial part of the activity,

such as Sc-46 in environmental materials and Na-24 and Br-82 in biological

materials. For example, in SRM 1633a, Fly Ash, the values obtained using

Zn-65 are 238.0 ± 6.6 ppm (2s) without the Compton suppression system, and

227.1 ± 2.2 ppm (2s) with the Compton suppression system. The certified value

is 220 ± 10 ppm. The negative aspect is that the sensitivity and accuracy of

radionuclides having coincident gamma-rays are reduced. This is particularly

significant for longer lived radionuclides for which coincident gamma-rays

are common.

The loss of photopeak counts due to coincidence losses and pile-up can be

corrected to less than ±1 percent using a random pulser, up to a non-suppressed

ADC deadtime of 10 percent. At higher deadtimes--such as may be necessary to

obtain significant counting rates for low levels of short half-life radionucl ides--the system tends to become erratic and is not readily correctable.

This tends to explain why--as noted earl ier--quanti tati ve data in the literature using Compton suppression are associated with applications involving low

level counting and prompt-gamma activation, where the deadtime is usually

<10 percent.

Overall, the system does improve the sensitivity of activation analysis

for radionuclides which do not have coincident gamma-rays or relatively short

half-lives. This sytem should be particularly appropriate for chromium, and

investigations involving this element are in progress.

71
16. Development of an Isotope Dilution Mass Spectrometric Procedure for

Iodine in Botanical Materials (11310)

J. W. Gramlich, T. J. Murphy

Iodine is an essential trace element, yet it's concentration is not

certified in any of the food or botanical type Standard Reference Materials

(SRM's). While some of these SRM's have "information" values for iodine

(provided by neutron activation analysis), they could not be certified since

they were determined by only one technique. Therefore, a research program was initiated to develop an isotope dilution mass spectrometric method for trace

iodine in botanical materials.

Since iodine is a mononuclidic element, a radioactive isotope was selected

for spiking. SRM 4949, Iodine-129 Radioactivity Standard, was selected since

129 I has a half-life of 1 . 6x 1

7 years and the SRM has a favorable 127 I/i 2 ^i

ratio of 0.16. It was necessary to stoichiometri cal ly equilibrate the spike

isotope and the natural iodine of the sample. Various wet-ashing methods were

studied using 125 I as a tracer. The method developed was shown to quantitatively retain iodine by oxidation to iodate while destroying the botanical

matrix.

In brief, the procedure involves transferring a sample of the botanical

material to a FEP-Teflon bottle and spiking with a known quantity of 129 I. The spiked sample is wet-ashed with fuming nitric and perchloric acids. The

solution is then diluted, transferred to a centrifuge tube, and the insoluble

potassium perchlorate separated. Iodate is reduced with a hydrazine solution

and the resulting iodide is coprecipitated with chloride by the addition of

silver nitrate solution. The mixed AgCl-AgI precipitate is separated by

centrifugation, washed with dilute ammonium hydroxide solution to remove most

of the AgCl and dissolved in ammoniacal cyanide solution for mass spectrometric

analysis.

Ionization and mass spectrometric analysis of iodine as a negative ion

requires an ionization filament with a very low work function to produce a favorable ratio of charged to neutral species. Filament materials normally

used for positive ion mass spectrometry do not meet this requirement; however,

LaB 6 has a very low work function (approximately 2.6 eV). The procedure

developed for the iodine mass spectrometry involves the coating of a rhenium

filament with lanthanum hexaboride by electrophoretic deposition from an anhydrous methanol suspension of the compound. The filament is then heated in

a vacuum to sinter the LaB6 and to remove surface adsorbed impurities which

poison the filaments; adsorbed gases form a dipole layer at the surface of the

filament which modifies the surface potential and work function. The iodine

as Agl is then loaded onto two side sample filaments of a triple filament ion source. The use of LaB6 as the ionizing filament has improved the sensitivity

for iodine measurement by approximately 104 over techniques previously used in

this laboratory. Intense and sustained ion beams can be produced on samples

containing as little as 10 nanograms of iodine.

This new method has been applied to the determination of iodine in SRM

1577, Citrus Leaves. The value found, 1.88 ± 0.12 (2a) yg/g, is in excellent

72
agreement with the neutron activation value of 1.84 ± 0.14 (la) yg/g. On the

basis of these determinations, the concentration of iodine in this SRM will be

certified. This will be the first botanical SRM to be certified for trace

iodine concentration. The method will be applied to other SRM's in the near

future.

17. Ion Optics of Magnetic Sector Mass Spectrometers (11310)

I. L. Barnes, W. A. Bowman, P. A. Morales

A program has been initiated to establish the theoretical background for

the design and construction of new mass spectrometers using other than normal

field entry, referred to as "off axis entry" mass spectrometers. The critical

parts of this program have been limited to magnetic sector instruments, with

the addition of multi -component systems such as electrostatic sectors, auadrupoles, hexapoles, and solenoids to come later. It was also decided at the

beginning of the program that only "real" systems would be considered even though it was realized that this would greatly complicate the program. This

meant that magnetic stray fields would be considered, and that only ion beams

of finite height and width would be used. Thus, the first two areas studied were stray fields and the mathematical formulation of the passage of ion beams

through magnetic sectors.

Historically, stray fields have been considered in the design of mass spectrometers using an approximation based on a simple function of the magnetic

gap, though it has long been recognized that this was, at best, a crude approximation. To better understand the magnitude and shape of the stray field, two

gaussmeters were carefully calibrated. One was used to control the field

while the other, mounted on a precision slide was used to measure the field at

5 mm increments from within the magnet to 40 cm away. Measurements were made

on a line normal to the pole face, at various angles inclined to the face, on

a line 0.5 cm up from the center and on each side of the center line; thus, a map of the field was obtained.

With the help of K. Eberhardt of the Statistical Engineering Division, it was determined that the data were best fitted by a hyperbolic expression of

the following form:

1 + exp (Bx+E) + x l (Bx+E) z - 4C(Ax z +Dx+l)

v

2C

where y

= field; x = distance; and K, B, E, C, A, and D = constants. A plot

of this function is shown in Figure 21 (solid line). The measured points are shown as open circles. The above expression is valid for all fields from

1000-9000 gauss and examination of the residual errors indicates that each

point is fitted to within 1 percent. The above measurements indicate that

within the experimental error, the NBS 90° magnet produces a uniform field

every place within 2 cm of an edge. Data obtained in a repeat of the experiment, at the University of Mexico with a magnet of different design and gap

width, fit the same expression with only slight differences in the constants.

Although a universal formula has not been found, its development does appear

73
Figure 21. Plot of measured field versus distance from magnet pole

face. Measured values (o); calculated values ( ).

to be possible. While the above expression cannot be directly integrated,

numerical methods such as cubic splines and Simpson's method have been used

with sufficient accuracy. A repeat of the experiment inside of a flight tube

gives identical results indicating that the normal construction materials have

no effect on the stray field.

In conjunction with studies of stray fields, a general investigation of

ion optics has been conducted and has provided significant improvements in the

design of the NBS mass spectrometers. A charged particle leaving a source at

a small angle to the normal and with a small change in energy yields a set of

five equations of motion with 27 terms each and 8 unknowns. To solve these,

at least three parameters of the instrument must be fixed. The resulting

equations are then best solved using a matrix transformation method. This has

been done utilizing the NBS Univac 1100/82 and a matrix program called

"TRANSPORT" originally written at the Stanford Linear Accelerator Laboratory.

This has been very useful but unfortunately gives the position of the ions

only at the beginning and end of the flight path. To further explore the

effects of the field, "TRANSPORT" was used to rapidly choose a promising

geometry and this information was used in a program called "MASMEX" that was written at NBS to trace up to 27 different ions through that geometry, with

the position of the ions given in 1 mm increments. Currently, a graphics

program to plot the enormous amount of data obtained from this program is

under development.

74
As a result of the work done during the past year, it has been determined

that the best focussing properties for a particular geometry are strongly

related to the ratio r = gap height/radius . However, this ratio is limited to

a range of 0.05 to 0.144. In addition, the off-axis angle of entry of ions

for best focussing of ions is a function of this ratio and varies from 24° to

32°. Thus, the gain in dispersion that may be obtained varies from 1.8 to 2.6.

There are several new configurations that need to be carefully examined since

in these cases, the stray field seems to have an important influence on the

dispersion gains. Further work in this area is necessary but new mass spectrometer designs with greatly increased capabilities seem assured.

18. The Use of a Chromium Internal Standard for the Analysis of Diverse

Iron-Chromium-Nickel Alloys (14301)

D. E. Brown, J. A. Norris

Emission spectrochemical analyses normally require standards which closely

match the matrices of the unknown samples and which cover the concentration

ranges of the elements present in the unknowns. In the homogeneity testing

and analysis of candidate Standard Reference Materials (SRM's) covering a wide

range of matrices and elemental concentrations, it is not always possible to

have standards that totally match the unknown.

One approach to the analysis of a wide variety of iron-chromium-nickel

alloys is the use of a chromium internal standard. In Table 9, a representative selection of Fe-Cr-Ni alloys and their matrix compositions are shown.

In addition to the elements given in the table, many of these alloys contain

significant amounts of W, Ti, A1 , V, Nb, and Ta. At the present time, over

40 separate alloys are available as SRM's. Chromium is not presently being

used as an internal standard in tertiary alloys; however, it is the best

candidate for use as an internal standard. The nickel concentration in these

alloys is more variable while the iron concentration is typically determined

by difference. In addition, the use of iron as an internal standard would

require a complete sample analysis since the concentration ratio method of curve plotting is necessary as a result of the considerable matrix variations.

Table 9. Fe-Cr-Ni Alloys.

Values in %

Alloy Fe Cr Ni_ Co Mo

Stainless Steel 60-80 13-24 7-24

Incoloy 36 13 40 6

Inconel 10 16 74

Hastell oy 23 21 46 9

Waspaloy 2 19 56 13

Rene-41 0.5 20 53 12 10

75
Since chromium is independently determined, the sample analysis need not

be complete and the ratio of the desired element to chromium concentration is

all that is required for instrument calibration. High concentrations of

elements such as Co, Mo, and W can cause direct element line interference

problems on the available vacuum spectrometer. When this occurs, the

particular standard involved is not used for the element or elements in

question.

Using this technique, it has been possible to calibrate the vacuum spectrometer for the elements C, P, S. Mn, Si, Ni, Fe, V, Ti, Mo, Cu , Co, Sn

AT , Nb, Ta, Zr, B, Pb, and W. With these instrumental curves, routine homogeneity tests have been run on new SRM's 1244, 1245, 1246, 1247, C2400,

C2400a, C2401 , C2401a, and C2402, while simultaneously providing approximate

analyses for future quantitative chemical determinations. Typical results for

the C2400-C2402 series SRM's are given in Table 10.

Table 10. Homogeneity Test Values.

Carbon Phosphorus Sulfur

SRM Level %RSD Level %RSD Level %RSD

2400 .043 4.38 .016 2.64 .001 18.5

2400a .039 4.17 .012 4.06 .002 14.7

2401 .066 3.79 .025 2.56 .030 2.28

2401a .037 9.55 .013 5.08 .015 4.75

2402 <.02 .017 4.25 .027 3.50

Manganese Si 1 i con Nickel

2400 .74 1.55 .61 2.49 3.43 2.38

2400a .60 1 .44 .62 2.52 3.12 1.67

2401 1.10 1.51 .80 2.34 3.87 2.80

2401a .83 1.21 .76 1.89 3.55 2.35

2402 .70 3.29 .91 4.04 50.5 1 .00

Iron Vanadi urn Molybdenum

2400 73.8 .17 .09 2.79 .25 2.35

2400a 74.5 .16 .04 2.56 .10 2.32

2401 63.3 .19 .22 2.53 2.22 1.87

2401a 63.5 .17 .15 1.68 2.13 1.66

2402 8.7 2.87 .29 4.36 13.7 2.82

76
19. Development of a Precise Static Leach Test and the Evaluation of

Simulated Nuclear Waste Glasses for a Reference Material (11310)

M. S. Epstein, H. M. Kingston, W. F. Koch, G. Marinenko,

D. J. Cronin (Div. 565)

One long range goal of nuclear waste storage is the development and

promulgation of a precise and accurate nuclear waste leaching test. Studies

at NBS have produced a significant breakthrough in the ability to obtain

reproducible leach results. Previously, the results of similar tests were

found to differ by as much as an order of magnitude for replicate samples.

Recently, a round robin study was conducted by 25 national and world laboratories; the results of the study showed poor agreement among these laboratories

in a specific static leach test coordinated by the Materials Characterization

Center (MCC) of the Department of Energy.

The existing static leach test MCC-1 was used as the starting procedure

for the work carried out at NBS. The variables in the test were identified

both theoretical ly and through data provided by the MCC. As a result, the

test was redesigned in specific areas to eliminate many variables by providing

more stringent control of temperature, surface roughness. Eh, C02 (pH interferent), and leachant loss during the test. In order to carefully control

these parameters, a distilled water leaching system was designed which

maintained, monitored, and recorded the above conditions for 28 days.

In addition to controlling the test parameters, the potential of a reference simulated nuclear waste glass was evaluated. One complex base

glass reference material and 12 additional glasses having modified compositions

were made at NBS. Each of the 12 modified glasses were a statistically

engineered compositional variation of the base glass. The analytical results

from these 12 altered glass matrices provided valuable information about the

separate components of the glass system. A 13-component empirical equation

was designed to statistically evaluate the influence of each component on the

leach characteristics

.

Statistical evaluation of the leachate data for 12 pairs of glasses and

of the seven replicates of the base glass showed a high degree of precision in

the 28 day modified leach test. The precision does not resemble the poor

reproducibility normally obtained from current leach data but is more similar

to the reproducibility expected of compositional analysis. For seven of the

nine elements tested, no significant error component larger than the error

associated with the dc plasma elemental measurements of the leach solutions

could be identified. The uncertainty at the Is level of the seven base glass

replicates is within the measurement uncertainty of the instrumental techniques

used to analyze the final leachate solutions.

On the basis of these results, the Materials Characterization Center has

designated the base composition of simulated nuclear waste glass to be the

future reference material. It will be made in a large quantity and distributed

as a reference for all future leaching work related to nuclear waste materials

and mechanisms.

77
In addition, information on the significance of glass homogeneity was obtained, the simultaneous elemental determination of a selected group of

elements was accomplished, and certain mechanistic information was obtained

that explained why the uncertainty for Zn was approximately 10-20 percent.

The major source of this uncertainty was non-reproducible adsorption onto the

container walls during the 28 day test.

It is anticipated that after the production of the reference glass, this

specialized equipment will be used to elucidate subtle mechanistic information

which will further refine this relatively new field of analytical measurement.

20. New Concepts in the Design and Fabrication of Fluorescent Glass

Standards for Use in Nondestructive Crack Testing (11310)

R. W. Burke, D. K. Hancock

Fluorescent dye penetrant testing continues to be one of the most widely

used nondestructive methods for detecting minute cracks and flaws in metallic

surfaces. The basic test, as currently performed, is essentially the same as originally developed. It entails coating the part to be tested with the

fluorescent dye penetrant, wiping off the excess dye from the exposed surface,

applying a developer, and measuring the fluorescence of the resulting indication. While many improvements have been made in the formulation of highly

sensitive penetrants, efforts to quantify reproducibly these improvements in

terms of their relative fluorescent brightness and crack-measuring capabilities

continue to be thwarted by the nonavailability of suitable fluorescent standards for calibrating the test equipment.

Initial efforts to develop fluorescent glass standards for use with

various NDE tests led to a serious consideration of two types of standards.

One consisted of a rectangular piece of uranium-doped glass mounted in a metallic heat sink for enhancing temperature stability; the other type was an assemblage of glass fibers having a series of graded diameters and uranium

concentrations. The first type of standard was intended for the reproducible

calibration of spectrofluorimetric instrumentation while the second type was envisioned as a working standard for improving the reliability with which the

intensities and widths of fluorescent indications could be measured.

As a result of understanding more clearly the needs of industry and the

problems associated with their "mass production," several changes in the

makeup and design of these standards were considered desirable. During the

past year, efforts have focussed on perfecting these changes. The most significant change was the decision to use an alternative fluorescent glass that

could be substituted for the uranium-doped glass. Two factors were instrumental in this decision. The predominant factor was that the fluorescent

temperature coefficient of uranium-doped glass is much larger than originally

anticipated. Our measurements have shown that the fluorescence of this glass

decreases approximately 0.9 percent per degree Celsius in the temperature

range of 20-40 °C. A second factor was a safety issue involved in the in-house

production and fabrication of uranium-containing materials. Subsequent

studies showed that the fluorescence of terbium-doped glass is very similar

78
to that of uranium-doped glass. Like uranium, terbium-doped glass fluoresces

in the green region of the spectrum and as a consequence exhibits excellent

coincidence with both the fluorescence of most dye penetrants and the mesopic

eye response function. In addition, the range of fluorescent intensities

obtainable with terbium-doped glass is relatively large since doping levels

up to 45 to 50 weight percent are possible. Its main advantage for use as a standard, however, is the fact that its fluorescent temperature coefficient is

at least an order of magnitude smaller than uranium-doped glass.

The other major change in the research effort has concerned the approach

to producing a fluorescent standard that can be used in conjunction with the

measurement of crack indications. Because of significant handling and

mounting problems, the glass fiber approach has been replaced by a system in

which fluorescent indications of varying widths and relative intensities are obtained by ruling a series of narrow slits in opaque films that have been

evaporated directly on polished glass flats having different terbium concentrations. Six to eight slits per side are planned with widths ranging from

5 to 100 micrometers.

Current efforts are concerned with the systematic evaluation of the

various formulations of terbium-doped silicate and phosphate glasses now on hand and the subsequent selection of one of these as the base formulation that

will be used for the preparation of the two types of fluorescent standards

being proposed. At the present time, the phosphate glasses have the apparent

advantage because they are intrinsically more fluorescent. This property may

be due to the fact that the phosphate matrix is more transparent to ultraviolet

radiation and hence the energy reaching the terbium fluorophor is more intense.

Once the optimum base glass composition has been chosen, it will be fabricated

into forms that are easily incorporated into NDE tests. As an instrumental

calibrant, particular emphasis will be placed on providing a configuration and

size that is compatible with "typical" or most widely used commercial instrumentation. At the same time, the final decision will be made on which

evaporated film will be used in the production of the simulated crack indication standard. The goal here is to identify a film that is durable, exhibits

a matte finish which closely approximates that of a typical metal specimen,

and can be properly ruled. Based on the projected progress, it is believed

that samples of both types of standards will be ready for field evaluation in

the near future.

21 . Characterization of Selected Trace Elements in the Chesapeake Bay

(11310)

E. S. Beary, J. D. Fassett, R. R. Greenberg, B. R. Hardas, W. R. Kelly,

H. M. Kingston, J. R. Moody, T. C. Rains, W. S. Liggett (Div. 714)

Trace element measurements for a large mul ti -di sci pi inary study of the

Chesapeake Bay have been completed. As part of this study, water samples were collected at 51 sites and both the particulate and dissolved fractions were

analyzed for Cd, Ce (particulate only), Co, Cr, Cu, Fe, Mn, Mo, N i , Pb, Sc,

Sn, Th, U, and Zn. Two types of samples, surface and bottom, were collected

and analyzed using specific chemical preconcentration and separation techniques

79
developed for neutron activation analysis (NAA) and graphite furnace atomic

absorption spectrometry (GFAAS). The data are the first environmental

analyses of this kind to yield a data set at the 95 percent confidence limit

that allows rigorous statistical evaluation of elemental relationships.

The concentrations of 14 elements in the dissolved fractions were evaluated by direct comparison with naturally occuring seawater levels. At several

locations in the Bay, two toxic elements (lead and tin) were elevated by two

orders of magnitude over normal seawater levels. Similar levels of organo-tin

were found by other researchers. Most of the dissolved iron concentrations

were approximately the same as that found in seawater. However, a number of

bottom samples collected at some of the deepest locations had significantly

greater iron concentrations. The elevated levels appear to be due to anoxic

conditions in the bottom sediments. Similarly, the manganese concentrations

had maxima at these same locations. Uranium and molybdenum were found in

higher concentrations in seawater than fresh water. As a result, the concen- trations of these two elements can be used to trace the seawater content of

the water column throughout the Bay. The uranium isotopic ratios of seven selected samples were investigated and found to be normal to within 0.7 percent

error. The dissolved thorium concentrations in samples taken near the mouth

of the Bay were approximately two orders of magnitude greater than previously

reported seawater values. The dissolved concentrations of the remaining

elements (Cd, Cr, Co, Cu, Ni , Se, and Zn) appeared to be relatively similar

to the levels normally found in seawater.

The information obtained from the raw particulate elemental concentration

data has been difficult to interpret in the past. Since the concentrations

were reported in elemental mass (ng) per unit volume (mL) of water, the total

amount of particulate mass suspended at the time of sample collection strongly

affected the results. Variations in current, tide, temperature, biota, wind

conditions, etc. can greatly influence the total amount of particulate material

suspended in the water column. To circumvent the problem of variable mass loading, a double normalization procedure was used to compute crustal enrichment factors. The concentration of each element in the sample was divided by

the concentration of a reference element, in this case scandium, and the

resulting value was divided by the ratio of these elements in average crustal

materi al

Scandium was chosen as a reference element because it has essentially no anthropogenic uses and its chemistry is relatively simple (single oxidation

state, limited dissolved particulate interactions). The usefulness of this

technique can be illustrated by comparing the variability in the cerium

concentrations and the cerium enrichment factors (EF). The concentrations

varied by a factor of 300 from site to site, while the EF varied by a factor

of 1.5 and the observed standard deviation over the entire Bay was just 10

percent. The EF's for thorium were similar to those of cerium. Figure 22 was constructed to show all of these cerium EF's simultaneously. The environmentally active and anthropogenical ly abundant elements had significanly more

complex ranges and patterns of enrichment factors than the elements used as multiple controls.

80
CRUSTAL ENRICHMENT FACTOR FOR CERIUM

RELATIVE TO SCANDIUM (WEDEPOHL) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

77D30M 39D40M - 77D10M 76D50M 76D30M 76D1 OM 75D50M 75D30M 39D40M

39D25M 39D2SM

+ 0.00

0.80

39D5M • 39D5M

38D45M- 38D45M

38D25MH 38D25M

38D5M - 38D5M

37D45M- 37D45M

37D25M- 37D25M

37D5M 37D5M

Figure 22. The crustal enrichment factors for cerium relative to

scandium in the particulate fraction.

36D45M

77D30M

TOP

7701 OM 76D50M 76D30M 7601 OM 75D50M

36D45M 75D30M

BOTTOM

81
Almost all of the iron EF's were relatively similar to those of Ce and Th.

However, a few samples had slightly elevated EF's. These samples were collected

at some of the deepest locations within the Bay and appear to be linked to

anoxic reactions in the sediment at these locations. The enrichment factors

for cobalt, manganese, and nickel appeared to trace the flow of Potomac River

water for quite some distance down the Bay. This was observed through the

elevated EF's for the surface samples as compared to generally uniform EF's

for the bottom samples. Figure 23 shows this relationship for cobalt. It was also found that a number of samples had greatly elevated cadmium enrichment

factors. This appeared to be a result of crustal weathering of naturally

occurring cadmium deposits and not anthropogenic sources. These deposits and

their erosion have also been documented by other researchers. The enrichment

factors for lead exhibited a great deal of variability; most of the samples

had lead EF's approximately five ( i . e . , five times greater than Pb/Sc ratio

for average crustal material). For the elements chromium, copper, and

uranium, the enrichment factors appeared relatively similar to naturally

occurring material. Molybdenum was below the detectable limits in most

samples and tin could not be detected in any of the particulate samples. Zinc

suffered from severe blank problems arising from the filter material used;

however, samples near the top of the Bay had very high mass loadings and zinc

appeared to be slightly enriched.

Although most elements were found at levels that could be explained by

natural mechanisms, both dissolved and particulate lead and dissolved tin

appeared elevated over normal at some locations. Using enrichment factors,

the cobalt, manganese, and nickel clearly traced the flow of the Potomac River;

however, it is not clear if the elevated EF's are due to natural or anthropogenic causes. The nature of the samples challenged several existing areas of analytical work. The analysis of ppb and ppt elemental concentrations in a salt matrix led to a new separation preconcentration method for neutron

activation analysis. This procedure provides solid resin pellets containing

16 trace elements with no alkali, alkaline earth, or halogen element interferences. These pellets are placed directly into the reactor for irradiation.

In addition, the statistical evolution of extensive blank data helped to characterize blank behavior at these ultra-trace levels and showed the inadequacies

of using a normal distribution. Lastly, the 2-3 orders of magnitude fluctuation of the particulate concentration data led to the application of enrichment

factors which have been used in air particulate analyses but had not been

applied to a aqueous systems. The choice of a reference element and secondary

check elements also proved ideal. This technique provided a means by which

the data and its environmental significance could be evaluated based on statistical concepts. Additional work is currently in progress with the

Statistical Engineering Division to investigate additional correlations within

these data sets.

82
77D30M

39D40M - 7701 OM 7606OM 76D30M 76D10M 75D50M

39D25M39D5M

38D45M -

38D25M

38D5M -

37D45M37D25M

37D5M •

36045M-i

75D30M

39040*4 TOP

CRUSTAL EIR1MOT FACTO* FOR COBALT RELATIVE TO SCANDIUM (VEOEFOML) AREA OF CIRCLE IS D1RECTLT PROFORT I ORAL TO ENRICHMENT FACTOR BOTTOM SATFLE (PARTICULATE) 39D25M

39D5M

3804 5M

38D25M

38D5M

37D45M

37D25M

3705M

36D45M

77D30M

Figure 23

7701 OM 76D50M 7603OM 7601 OM 75D50M 75D30M

The crustal enrichment factors for cobalt relative to

scandium in the particulate fraction.

83
22. Research to Develop Isotope Dilution Mass Spectrometry for Ultratrace

Concentrations of Cadmium (14301)

J. D. Fassett, W. R. Kelly, E. A. I. Michiels

The certification of materials for low-level or ultratrace (sub ng/g)

constituents has become increasingly important to satisfy both present and

future needs for quality assurance in critical segments of industry, public

health, and environmental monitoring. The use of microchemistry combined with

pulse counting mass spectrometry results in the requisite sensitivity for the

determination of ultratrace components from complex materials. Under clean room conditions, it is possible to separate an element from grams or less of

starting material and determine isotopic composition and elemental concentration with a high degree of accuracy. Because of the biotoxicity of Cd, the

ability to measure its concentration at low levels in subgram samples with

high precision and accuracy is essential for establishing natural levels and

detecting anthropogenic contamination. A procedure has been developed to

determine cadmium at ultratrace levels in biological materials.

The fundamental limitation on accuracy and precision in ultratrace meas- urement is the magnitude and uncertainty in the chemical blank, where the

chemical blank arises from dissolution and separation of the samples and mass spectrometric loading. As a result, the research required to create a successful analytical procedure for ultratrace measurement necessitates extensive

effort to develop clean and efficient chemical dissolution and separation

procedures, as well as extensive effort to identify and to quantify all sources

of blank. The primary sources of blank were studied and are summarized in

Table 11.

Table 11

Reagent blanks

hno 3 HC1

HC104 HBr(ACS)

HBr(cleaned)

Column Blank (1.5 mL resin)

Loading Blank

Total System Blanks

Sources of Cadmium Blank,

Determinations

3

3

2

1

1

1

5

5

Range

0.6-5. 3 pg/g

1 .5-5.7 pg/g

27,30 pg/g

650 pg/g

10 pg/g

62 pg

2. 2-2. 9 pg

65-190 pg

The yields of several alternative chemical separation procedures were verified through radioactive tracer experiments both on synthetic samples and

real blood samples. A comparison of procedures using strongly basic anion

resin in the bromide and chloride forms was made. The higher blank of the

bromide system discounted the increased efficiency of separation achieved.

Thus, the selected procedure used two anion exchange columns in the chloride

84
form: a 1 mL column for the separation of Cd from all other elements and a second very small (0.06 mL) "clean-up" column.

Samples of blood weighing about two grams were spiked with ni Cd and

dissolved using wet ashing oxidation. The Cd was separated and mass spectrometrically analyzed using a single filament silica gel technique which

entailed drying sequentially layers of silica gel, sample, and phosphoric

acid on the surface of a rhenium filament. The sample loading procedure was critical in achieving good signal intensity. The analysis was done at 1100 °C.

Both 114 Cd/ 1 1

Cd and 112 Cd/ 1 1Cd ratios were measured which allowed internal

normalization corrections for isotopic fractionation to be made.

Four CDC bovine blood samples were analyzed. The cadmium concentration

of these samples ranged from 7.01-7.09 ng/g. The internal normalization

procedure improved measurement precision by a factor of three (1.6 to 0.50

percent, la) as well as resulted in a +5.0 percent correction due to isotopic

fractionation. Blank corrections were typically 0.5 percent. Although these

bovine blood Cd concentrations were much higher than expected, the procedure

developed here would allow analysis of the blood from "normal" humans containing cadmium levels of 0.3-0. 6 ng/g with predicted uncertainties better than

10 percent.

23. The Use of Round Robins to Evaluate State-of-the-Art Uranium and

Plutonium Measurements by Thermal Ionization Mass Spectrometry (11310)

J. D. Fassett, J. W. Gramlich, W. R. Kelly, L. A. Machlan

One of the best ways of standardizing and improving both measurement

practices and techniques is by interlaboratory analysis programs or round

robins. When properly designed and managed, round robins can be used to

define and advance the state-of-the-art of a technique. Work was completed

during the last year for two round robin programs designed to investigate

different aspects of the measurement of uranium and plutonium. These programs

are traceable to a national measurement base since all measurements can be

directly related to wel 1 -characterized assay and isotopic Standard Reference

Materials. To the international nuclear scientific community which participated in these round robins, the quality and uniformity of measurement of the

safeguarded, fissionable isotopes of uranium and plutonium have profound

implications for standardization and new methods research.

Initially, NBS participated in the i nterl aboratory experiment IDA-80

(Isotope Dilution Analysis, 1980) which was managed by the Safeguards Project

of the Federal Republic of Germany in cooperation with more than 50 other

laboratories worldwide. The program was designed to assess the precision and

accuracy of U and Pu elemental concentration measurements and isotopic compositions in solutions from nuclear installations and reprocessing plants. IDA-80

was based upon a similar round robin program, IDA-72, which had 22 participants

and was completed in 1975.

NBS and the Central Bureau for Nuclear Measurements (CBNM), Geel Establishment, Belgium, jointly provided assay and isotopic reference values for

85
the uranium and plutonium samples used in IDA-80. IDA-80 differed from IDA-72

in that for IDA-80 an evaluation of accuracy was possible, since all reference

measurements were traceable to NBS Standard Reference Materials. Thirty-nine

samples were analyzed at NBS including: input from a reprocessing plant, both

spiked and unspiked samples; synthetic uranium and plutonium mixture(s), both

spiked and unspiked samples; and a mixed uranium and plutonium spike. At NBS,

the unspiked samples were spiked with aliquots of SRM 933 ( 235 U) and SRM 996

( 244 Pu) and separate aliquots of the samples were spiked with the spike solutions provided. All samples were equilibrated using an oxidation-reduction

procedure. The uranium and plutonium were then separated and purified by

anion exchange chromatography

Plutonium samples were analyzed by high sensitivity thermal ionization

mass spectrometry using ion counting detection. A one nanogram sample was required for each measurement. Uranium was analyzed by thermal ionization

mass spectrometry using Faraday cup detection and triple filament loading of

a 4 yg sample for each measurement. Isotopic fractionation corrections were made relative to SRM 947 where the 240 Pu/ 239 Pu ratio was measured to 0.06

percent (la, N=28) and SRM U-500 where the 235u/238y ra tio was measured to

better than .02 percent. Measurement precisions were better than 0.1 percent

for all samples with excellent agreement between NBS and CBNM measurements.

This level of agreement between the laboratories providing baseline values now make it possible to complete the most extensive and meaningful evaluation,

national as well as international, of laboratories conducting safeguards

measurements

A second round robin investigating the high sensitivity measurement of

uranium and plutonium loaded onto anion exchange resin beads was conducted by

NBS and completed in the past year. The resin bead technique has been proposed

for use in routine analysis of nuclear materials especially suited for reactor

dissolver solutions formed in fuel reprocessing. This technique is innovative

in both the sampling step and the use of high sensitivity pulse counting

detection for isotopic ratio measurements. The resin bead provides the matrix

for separation, physical transportation , and thermal ionization. High sensitivity detection is necessitated by the nanogram size samples which are used

to minimize radioactivity . Eight laboratories participated in the round

robin, five of which reported results for all samples. The size of the round

robin reflected the small number of laboratories capable of making high

sensitivity measurements of both uranium and plutonium.

In addition to the blind samples, the SRM's U-100, U-500, and U-900 were

sent to all participants in order to assess the linearity of individual

measurement systems. Standards were also provided to allow for external

normalization of isotopic fractionation by the participating laboratories

The blind samples were gravimetrical ly prepared from SRM's: the spike SRM's

993 ( 235 U) and 995 ( 233 U) and assay SRM 960 (natural U) were used to prepare

the uranium samples; the spike SRM 996 ( 244 Pu) and assay SRM 949e ( 239 Pu) were

used to prepare the plutonium samples. By using SRM's to prepare the blind

samples, reference values could be assigned with uncertainties calculable from

the uncertainties of the individual SRM's. The dominant contribution to the

uncertainty of the isotope reference values of the blind samples was the

uncertainties in the assays of the spikes, since weighing uncertainties and

isotopic composition uncertainties were negligible. Beads containing uranium.

86
beads containing plutonium, and beads containing both uranium and plutonium

were prepared, distributed, and analyzed as part of the round robin.

A number of generalized conclusions can be made concerning the resin bead

sample loading technique as a result of this round robin: (1) the technique

is convenient for shipping, handling, and inventorying very small amounts of

uranium and plutonium; (2) a few nanograms of U and Pu can produce a signal

intensity adequate for making precise measurements of major isotopes; and

(3) laboratories familiar with handling small samples can routinely use this

technique. The median accuracy for major isotopic measurement was +0.10

percent; the accuracy of 90 percent of the measurements was between -0.35

percent and +0.85 percent of the reference value; 50 percent of the measurements

ranged between ±0.15 percent of the reference values. Isotopic fractionation

control was concluded to be a major source of imprecision, and calibration

of isotopic fractionation was the major source of inaccuracy for both uranium

and plutonium. The results of the round robin were comparable to other blind

studies using conventional instrumentation and methodology, such as IDA-72.

24. Standard Reference Materials (14306 and 14307)

B. I. Diamondstone

The analysis and certification of Standard Reference Materials (SRM's)

has again been a major part of the total scientific effort of this Division.

The fiscal resources for work leading to the issuance of SRM's falls into two

categories; STRS--Scientific and Technical Research Services and WCF--Working

Capital Funds. The efforts in these two areas account for about 25 percent of

the total working budget of the Division with input being provided by the

entire scientific staff.

This year, five different research projects were funded by the Office of

Standard Reference Materials under the STRS program. The STRS portion of the

funding is intended for the preliminary research necessary to develop the

methodologies required for the actual production of SRM's. On the other hand,

the WCF projects are those which result in the actual certification for

chemical composition of a marketable standard. This year, analyses were carried out on more than 75 different SRM's covering a variety of matrices

including metals, fossil fuels, nuclear materials, and biologicals. In some cases, each certification can involve 20-30 individual analyses on each

potential SRM.

One important accomplishment this year has been the application of

recently acquired methodologies for the accurate determination of sulfur in a number of SRM's. Using isotope dilution mass spectrometry and ion chromatography, sulfur has been determined in coal and fuel oil SRM's at four and

six concentration levels, respectively. In the area of health and environmental standards, work has continued on the certification of important

elements in a variety of SRM's such as Mercury in Water, Citrus Leaves,

Bovine Liver, Urban Dust/Organics, and Trace Metals on Filters. Additionally,

work has begun leading to the certification of two important future SRM's,

Urine and Powdered Milk which will be analyzed for a large number of trace

and major constituents.

87
About 40 percent of the budget allocated for Standard Reference Materials

goes towards acceptance testing, homogeneity determination, and eventual

certification of both trace and major constituents of a large number and

variety of metals. The importance of this area of effort is best illustrated

by the fact that nearly 10,000 units of metal SRM's have been sold through

the first eight months of FY 82.

The SRM's on which work was carried out this year and the STRS research

projects, along with the relative effort in staff-years (SY), are shown in

Tables 12 and 13.

Table 12. WCF Work Carried Out on Standard Reference Materials.

Division 551 , FY 82

SRM Number Title Effort, SY

950b

U020a , U005a , U030a

2682, 2683, 2684, 2685

1622b, 1621b, 1620a, 1619,

1623a, 1624a

1244, 1245, 1246, 1247,

864, 865, 866, 867

1225, 1226, 1173, 1223,

1134, 1254, 125b, 36b,

Cl 285 , Cl 285a , 1270, 1270a

1641b, 1642b

1566, 1567, 1568, 1572,

1573, 1575, 1577a, 1646

930d

2670, 2671a, 2672a

83d, 40b

1581

1549

2676b

Cl 231, Cl 232, C2400-C2402

Cl 290-C1 292 , 334, 122h

Cl 251 -Cl 253

1643a

1649

371 g , 1620a, 143c

Uranium Oxide 0.1

Uranium Isotopics

Sulfur in Coals

Sulfur in Fuel Oils

Inconels and Incalloys

Low Alloy Steels 1

Mercury in Water 0.

Trace Elements in Botanicals 1.

Glass Filters for Spectrophotometry 0.

Trace Elements in Urine

Primary Chemical Standards

Chlorine in PCB's

Trace Elements in Powdered Milk

Trace Metals on Filters

High Alloy Cast Steels

High Alloy Cast Irons

Copper Benchmarks

Trace Elements in Water .1 Trace Elements in Urban Dust/Organics .1 Sulfur 32/34 Isotope Ratio Standards ^2

8.0

88

co

c\j

c\j o

cvj^oooi

— n

ro

ro

oo
Table 13. STRS Projects Underway.

Task

Measurement of pH

Radiochemical and

Instrumental Background Reduction

Gases in Metals

Gas Isotope Dilution

Mass Spectrometry

Ultratrace Analyses by

High Sensitivity Pulse

Counting Mass

Spectrometry

Division 551, FY 82

Descri ption Effort, SY

Complete development of methods 0.8

for measurement of pH in preparation for renewal of existing

SRM's.

Develop facilities and methodology .4

for increasing the sensitivity of

elements such as As, Sb, Se, Cr, and

Mo in biological and environmental SRM's

using activation analysis.

Re-establish procedures for the bomb .4

distillation Kjeldahl technique for

nitrogen determinations and procure

equipment to perform analysis of oxygen,

nitrogen, and hydrogen in complex metal

matrices.

Establish ID/MS methodology aimed at .6

determining carbon, hydrogen, oxygen,

nitrogen, and sulfur in various SRM

matrices.

Develop procedures aimed at providing .6

ultratrace level elemental determinations

for V, Ag, Cd, U, Sn, and Si in a variety

of SRM matrices.

2.8

89
C. Outputs and Interactions

(Inorganic Analytical Research Division)

1 . Publ i cations

Greenberg, R. R. , Zoller, W. H., and Gordon, G. E., "Atmospheric Emissions

of Elements on Particles from the Parkway Sewage-Sludge Incinerator,"

Environ. Sci. Technol . , 1_5, 64 (1981 ).

Messman, J. D. and Rains, T. C., "Determination of Tetraal kylead Compounds

in Gasoline by Liquid Chromatography-Atomic Absorption Spectrometry ," Anal. Chem., 53, 1632 (1981).

Rains, T. C., "Determination of Aluminum, Barium, Calcium, Lead, Magnesium,

and Silver in Ferrous Alloys by Atomic Emission and Absorption

Spectrometry," Symposium on New Analytical Techniques for Trace

Constituents of Metallic and Metal -Bearing Ores, ASTM STP 747,

pp. 43-54, (1981).

Traub, R. D., Rains, T. C., Garruto, R. M. , Gajdusek, D. C., and

Gibbs, C. J., "Brain Destruction Alone Does Not Elevate Brain

Aluminum," Neurology, 31_, 986 (1981 ).

Gramlich, J. W. and Shideler, R. W. , "Programmable Sample Drier for

Thermal Ionization Mass Spectrometry ," NBS Tech. Note 1154, 1982.

Di amondstone , B. I., Burke, R. W. , and Garner, E. L., "Improved Leach

Measurements on Solid Waste," ASTM Standardization News, pp. 28-33,

1982.

Barnes, I. L., "The Use of Stable Isotopes in Research in Chemistry," in

"Stable Isotopes in Chemistry and Physics Research," I. Freedlander,

ed., National Academy of Science Report, 1982.

Barnes, I. L, Murphy, T. J., and Michiels, E. A. I., "Certification of

Lead Concentrations in Standard Reference Materials by Isotope

Dilution Mass Spectrometry ," J. Assoc. Off. Anal. Chem., 65, 953

1982.

Bower, V. E. Davis, R. S., Murphy, T. J., Paulsen, P. J., Gramlich, J. W.

,

and Powell, L. J., "Recalculation of the Faraday Constant Due to a New Value for the Atomic Weight of Silver," J. Res. Nat. Bur.

Stand. (U.S.), 87, 21-22 (1982).

Fassett, J. D. and Kelly, W. R., "The Mass Spectrometri c Analysis of

Uranium and Plutonium Loaded Anion Exchange Resin Beads: An

Interlaboratory Round Robin," in Analytical Chemistry in Nuclear

Technology, W. S. Lyon, ed., Ann Arbor Science, Ann Arbor, MI,

1982, pp. 131-138.

Fleming, R. F. and Lindstrom, R. M. , "Limitations on the Accuracy of

Sulfur Determination by NAA," Trans. Am. Nucl . Soc., 41_, 223 (1982).

90
Gramlich, J. W. , Machlan, L. A., Brletic, K. A., and Kelly, W. R.

,

"Thermal-Ionization Isotope-Dilution Mass Spectrometry as a Definitive

Method for Determination of Potassium in Serum," Clinical Chemistry,

28, 1309-1313 (1982).

Harrison, S. H. and Zeisler, R., "Distribution of Pollutant and

Essential Elements in Human Livers," Trans. Am. Nucl. Soc., 41, 209

(1982).

Koch, W. F. and Stolz, J. W. , "Analysis of Chloride-Doped Cadmium Sulfide

by Ion Chromatography ," Anal. Chem. , 54, 340 (1982).

Moody, J. R., "Some Considerations of Analytical Chemical Methodology

Relevant to Testing of Leachates from Radioactive Solids," Nuclear

and Chemical Waste Management, 3_, 29 (1982).

Moore, L. J., Murphy, T. J., Barnes, I. L., and Paulsen, P. J., "Absolute

Isotopic Abundance Ratios and Atomic Weight of a Reference Sample

of Strontium," J. Res. Nat. Bur. Stand. (U.S.), 81_, 1-8 (1982).

Powell, L. J., Murphy, T. J., and Gramlich, J. W. , "The Absolute Isotopic

Abundance and Atomic Weight of a Reference Sample of Silver," J.

Res. Nat. Bur. Stand. (U.S.), 87, 9-19 (1982).

Rains, T. C., Rush, T. A., and Butler, T. A., "New Innovations in Atomic

Absorption Spectrometry with Electrothermal Atomization for Lead in

Foods," J. Assoc. Off. Anal. Chem., 65, 994-998 (1982).

Zeisler, R. and Greenberg, R. R. , "Procedure for the Determination of

the Platinum Baseline in Biological Materials," Trans. Am. Nucl.

Soc. , 41_, 219 (1982).

Burke, R. W. , Paulsen, P. J., Maienthal, E. J., and Lambert, G. M. , "Validation of the Sulfur Concentration of Selected Iron-Base NBS

Standard Reference Materials by Isotope Dilution Spark Source Mass

Spectrometry ," in press.

Fassett, J. D. and Kelly, W. R., "Round Robin Analysis of Anion Exchange

Resin Beads Loaded with Nanogram Amounts of Uranium and Plutonium

by Thermal Ionization Mass Spectrometry ," in press.

Greenberg, R. R. and Kingston, H. M. , "Simultaneous Determination of

Twelve Trace Elements in Estuarine and Sea Water Using Pre-Irradi ation

Chromatography ," in press.

Kingston, H. M. and Lutz, G. J., "Adsorption and Stability Prior to

Analysis of Simulated Nuclear Waste Leachate," in press.

Koch, W. F. and Marinenko, G., "Simulated Precipitation Reference Materials

Measurement of pH and Acidity," Proc. of the Symposium on Sampling

and Analysis of Rain, in press.
Koch, W. F., Marinenko, G., and Stolz, J. W., "Simulated Precipitation

Reference Materials, IV," in press.

Mielenz, K. D., Weidner, V. R. , and Burke, R. W. , "Heterochromatic

Stray Light in UV Absorption Spectrometry : A New Test Method," in

press.

Moody, J. R., "The Sampling, Handling, and Storage of Materials for

Trace Analysis," Philosophical Transactions of the Royal Society

(London) , in press.

Moody, J. R. and Beary, E. S., "Purified Reagents for Trace Metal Analysis,"

in press.

Zeisler, R. , Harrison, S. H., and Wise, S. A., "Analysis of Human Liver

Specimens in the U.S. Pilot National Environmental Specimen Bank

Program," Proc. Intern. Workshop on Environmental Specimen Banking

and Monitoring as Related to Banking, Saarbrucken, FRG, May 10-

15, 1982, in press.

Zeisler, R. and Greenberg, R. R. , "Ultratrace Determination of Platinum

in Biological Materials Via Neutron Activation and Radiochemical

Separation," in press.

Wise, S. A., Fitzpatrick, K. A., Harrison, S. H., and Zeisler, R.

,

"Operation of the U.S. Pilot National Environmental Specimen Bank

Program," Proc. Intern. Workshop on Environmental Specimen Banking

and Monitoring as Related to Banking, Saarbrucken, FRG, May 10-

15, 1982, in press.

Burke, R. W. and Mavrodi neanu , R. , "Accuracy in Analytical Spectrophotometry," submitted for publication.

Epstein, M. S. and Blundell, C. G., "Determination of Calcium and Copper

in Urine Using a Thermally Regulated D.C. Plasma Echelle Spectrometer,"

submitted for publication.

Epstein, M. S. and Winefordner, J. D., "Summary of the Usefulness of

Signal -to-Noise Treatment in Analytical Spectrometry ," submitted

for publication.

Fleming, R. F., "Neutron Self-Shielding Factors for Simple Geometries,"

submitted for publication.

Greenberg, R. R. and Kingston, H. M., "Trace Element Analysis of Natural

Water Samples Using Neutron Activation Analysis and Chelation

Chromatography," submitted for publication.

Heald, E. F. and Moore, L. J., "Thermodynamic and Kinetic Studies of

Isotopic Fractionation in the MFTIS," submitted for publication.

Kingston, H. M. , Cronin, D. J., and Epstein, M. S., "An Examination

of the MCC-1 Leach Method: Experimental Technique," submitted for

publ i cation.

92
Kingston, H. M., Greenberg, f^. R., Beary, E. S. , Hardas, B. R., Moody,

J. R. , and Rains, T. C., "The Characterization of the Chesapeake

Bay: A Systematic Analysis of Toxic Trace Elements," submitted for

publication.

Marinenko, G., Koch, W. F., and Etz, E. S. , "High Precision Coulometric

Titration of Uranium," submitted for publication.

Messman, J. D., Epstein, M. S., Rains, T. C., and O'Haver, T. C.,

"Performance Characteristics of a Continuum-Source Echelle Wavelength

Modulated Atomic Absorption Spectrometer," submitted for publication.

Moore, L. J. , "The Highly Precise and Accurate Measurement of Neodymium

and Samarium Isotope Ratios," submitted for publication.

Moore, L. J. and Murphy, T. J., "High Accuracy Barium Isotope Ratio

Measurements and Isotope Dilution Applications to Standard Reference

Materials," submitted for publication.

Pella, P. A. Kingston, H. M. , Sieber, J. R,, and Feng, L., "X-Ray

Spectrometric Analysis of NBS SRM Bovine Liver and Pine Needles

After Separation and Preconcentration on Cation Exchange Resin

Filters," submitted for publication.

Yaffe, Y. , Flessel, C. P. , Wesolowski, J. J., del Rosario, A., Guirguis,

G. N., Martias, V., Gramlich, J. W., Kelly, W. R. , DeGarmo, T. E.,

and Coleman, G. C., "Identification of Lead Sources in California

Children Using the Stable Isotope Ratio Techniques," submitted for

publication.

2. Talks

Fassett, J. D. and Kelly, W. R. , "The Mass Spectrometric Analysis of

Uranium and Plutonium Loaded Anion Exchange Resin Beads: An Interlaboratory Round Robin," 25th Conference on Analytical Chemistry in

Energy Technology, Gatlinburg, TN, October 7, 1981.

Koch, W. F. , "Simulated Precipitation Reference Materials: Measurement

of pH and Acidity," ASTM Symposium on Sampling and Analysis of

Rain, Philadelphia, PA, October 7, 1981. Invited

Lindstrom, R. M. , "Compositional Analysis of Solar-Grade Silicon,"

160th Meeting of the Electrochemical Society, Denver, CO, October

12, 1981. Invited

Rains, T. C., "State of the Art of Atomic Absorption Spectrometry,"

NBS-ADABSE Analytical Chemistry Workshop, National Bureau of

Standards, Gaithersburg, MD, October 18, 1981. Invi ted

Rains, T. C., Rush, T. A., and Butler, T. A., "New Innovations in Atomic

Absorption Spectrometry with Electrothermal Atomization for Lead in

Foods," 95th AOAC Annual Meeting, Washington, DC, October 19, 1981.

93
Epstein, M. S. , "D.C. Plasma/Echelle Spectrometry," NBS-ADABSE Analytical

Chemistry Workshop, National Bureau of Standards, Gaithersburg, MD

October 19, 1981

Watters, R. L., "ICP Spectrometry," NBS-ADABSE Analytical Chemistry

Workshop, National Bureau of Standards, Gai thersburg , MD, October

19, 1981.

Norris, J. A., "Preparation of Ferrous Standard Reference Materials:

SRM 1226: A Case History," Iron and Steel Chemists Meeting,

Pittsburgh, PA, October 28, 1981.

Epstein, M. S., "Some Unique and Not-So-Unique Applications of Plasmas

to Analytical Atomic Spectroscopy," Perkin-Elmer Corporation,

Norwalk, CT, November 2, 1981. Invited

Zeisler, R. , Harrison, S. H., and Wise, S. A., "Specimen Banking and

Trace Analysis," Clinical Pathology Conference Series, Univ. of

Maryland Hospital, Baltimore, MD, November 4, 1981. Invited

Barnes, I. L., "Trace Element Analysis State-of-the-Art ," Central Ohio

Valley Secti on--ACS , Huntington, WV, November 9, 1981.

Barnes, I. L., "Trace Element Analysis State-of-the-Art," Kawawha Valley

Section--ACS, Charleston, WV, November 10, 1981.

Barnes, I. L., "Trace Element Analysis State-of-the-Art," Upper Ohio

Valley Section--ACS, Marietta, OH, November 11, 1981.

Barnes, I. L. , "Trace Element Analysis State-of-the-Art," Northern

West Virginia Secti on--ACS , Morgantown, WV, November 12, 1981.

Barnes, I. L., "The Atomic Weights of the Elements," Chemistry Dept.,

West Virginia University, Morgantown, WV, November 12, 1982.

Barnes, I. L., "Trace Element Analysis State-of-the-Art," Western

Maryland Secti on--ACS , Cumberland, MD, November 13, 1981.

Moody, J. R., "Applications of High Precision Davies-Gray Titrations to

Standards for Safeguards," American Nuclear Society, San Francisco,

CA, December 1, 1981. Invited

Moody, J. R., "The Sampling, Handling, and Storage of Materials for

Trace Analysis," Royal Society Symposium on Recent Advances in

Analytical Chemistry, London, UK, December 8, 1981. Invi ted

Rains, T. C., "Inter-Laboratory Quality Control Program and Reference

Samples," University of Minnesota's 3rd Annual Midwest Conference

on Environmental Laboratory Technology, Minneapolis, MN, December

8, 1981. Invi ted

94
Rains, T. C., "Atomic Absorption Analysis of Hazardous Waste Materials,"

University of Minnesota's 3rd Annual Midwest Conference on Environmental Labortory Technology, Minneapolis, MN, December 9, 1981.

Invi ted

Moody, J. R., "Trace Analysis with Limited Resources," Analytical

Symposium, Harwell Laboratories , UK, December 11, 1981. Invi ted

Barnes, I. L., "The Evaluation of Magnetic Stray Fields," National

Bureau of Standards, December 12, 1981.

Moody, J. R. , "The Use of Isotope Dilution Mass Spectrometry for Accurate

Analysis of Reference Materials and Standards," Central Bureau for

Nuclear Measurements Analytical Seminar, Geel , Belgium, December

15, 1981. Invi ted

Moody, J. R. , "High Accuracy Trace Analysis by Isotope Dilution Mass

Spectrometry ," Univ. of Ghent/Institute for Nuclear Science Joint

Analytical Seminar, Ghent, Belgium, December 16, 1981. Invited

Epstein, M. S. , "Aspects of Quality Control in the Use of a D.C. Plasma

for the SRM Certification Process," Conference on Plasma Spectrochemistry, Orlando, FL, January 4, 1982. Invited

Moody, J. R. , "Modification of Laboratories for Safety and Trace Analysis,"

Laboratory of the Government Chemist Engineering Staff Meeting,

London, UK, January 6, 1982. Invi ted

Marinenko, G., "Absolute Electroanalytical Measurements at NBS," Seminar

at IBM Instruments, Inc., Danbury, CT, February 26, 1982. Invi ted

Epstein, M. S., "Atomic Absorption Spectroscopy," ACS Short Course,

Pittsburgh Conference, Atlantic City, NJ, March 6, 1982.

Rains, T. C. , "Atomic Absorption Spectrometry," ACS Short Course,

Pittsburgh Conference, Atlantic City, NJ, March 6, 1982.

Marinenko, G. , "Absolute Electroanalytical Measurements at NBS," Seminar

at Pennsylvania State University, March 19, 1982. Invited

Powell, L. J., "The Atomic Weight of Silver and a New Value for the

Faraday Constant," U.S. Naval Academy, Department of Chemistry,

Annapolis, MD, March 23, 1982. Invi ted

Epstein, M. S., "Some Applications of Dye Lasers to Analtyical Atomic

Spectroscopy," Villanova University, Dept, of Chemistry Seminar,

Villanova, PA, March 30, 1982. Invited

Rains, T. C., "State of the Art of Sample Preparation for Environmental

Analyses," Dept, of Chemistry, Murray State University, Murray, KY,

April 6, 1982. Invited

95
Rains, T. C. , "Characterization of Standard Reference Materials," Penwalt

Corporation, Calvert, KY, April 7, 1982. Invi ted

Rains, T. C., "Analytical Chemistry at the National Bureau of Standards,"

Western Kentucky University, Dept, of Chemistry Seminar, April 8, 1982.

Invi ted

Shideler, R. W. , "Operational Amplifiers as Used in Modern Measuring

Instrumentation," National Bureau of Standards Group Seminar,

Gaithersburg, MD, April 12, 1982.

Rains, T. C. , "The State of the Art of Sample Preparation for Atomic

Absorption and Emission Spectrometry," Penn-York Section of SAS,

Corning, NY, April 27, 1982. Invi ted

Kingston, H. M. and Cronin, D. J., "An Examination of the MCC-1 Leach

Test Method, Part II: Experimental Technique," 2nd Semiannual

Workshop on the Leaching Mechanisms of Nuclear Waste Forms, Gaithersburg,

MD, May 1982. Invi ted

Cronin, D. J. and Kingston, H. M., "An Examination of the MCC-1 Leach

Test Method, Part III: Comparison of Glass Compositions," 2nd

Semiannual Workshop on the Leaching Mechanisms of Nuclear Waste

Forms, Gaithersburg, MD, May 1982. Invi ted

Rains, T. C., "State of the Art of Sample Preparation for Atomic Spectroscopy," 2nd Annual Multi-Discipline Symposium, Chicago Section of

SAS, Chicago, IL, May 3, 1982. Invited

Zeisler, R., Harrison, S. H. , and Wise, S. A., "Analysis of Human

Liver Specimens in the U.S. Pilot National Environmental Specimen

Bank Program," Intern. Workshop on Environmental Specimen Banking

and Monitoring as Related to Banking, Saarbrucken, FRG, May 12, 1982.

Invited

Norris, J. A., "Line Interferences in Optical Emission Spectroscopy,"

Lehigh Valley SAS, Reading, PA, May 14, 1982.

Zeisler, R. , "Recent Experience in the Analysis of Specimens in the

U.S. Pilot NESB Program," 6th U.S. /German Bilateral Meeting on Specimen Banking, Neuherberg FRG, May 17, 1982. Invi ted

Zeisler, R. , "Neutron Activation Analysis Procedures Applied to

Human Liver Analysis," 6th U.S. /German Bilateral Meeting on Specimen

Banking, Neuherberg, FRG, May 17, 1982. Invi ted

Norris, J. A., "Line Interferences in Optical Emission Spectroscopy,"

Technical Committee on Chemical Analyses AISI, Boston, MA, May 19,

1982.

Kelly, W. R. and Paulsen, P. J., "The Isotopic Analysis of Sulfur,"

Division of Geological and Planetary Sciences, California Institute

of Technology, Pasadena, CA, June 4, 1982. Invi ted

96
Moody, J. R., "Applications of Clean Room Technology to Inorganic and

Organic Trace Analysis," Philip Morris Research Center, Richmond,

VA, June 4, 1982.

Garner, E. L., Gills, T. E. , and Moore, L. J., "The Current Status and

Future Role of NBS SRM's in the Nuclear Energy Community," ASMS,

Honolulu, HI, June 8, 1982. Invi ted

Greenberg, R. R., Kingston, H. M., and Rains, T. C., "Trace Elemental

Characterization of the Chesapeake Bay Water Column," American

Nuclear Society Meeting, Los Angeles, CA, June 8, 1982. Invited

Kelly, W. R. and Paulsen, P. J., "The Determination of Microgram Quantities

of Sulfur by Thermal Ionization Mass Spectrometry," 30th Annual

Conference on Mass Spectrometry and Allied Topics sponsored by

American Society for Mass Spectrometry, Hilton Hawaiian Village,

Honolulu, HI, June 9, 1982. Invited

Moore, L. J., "Laser Mass Spectrometry for the Production and Measurement

of Inorganic Ions," ASMS, Honolulu, HI, June 9, 1982.

Zeisler, R. and Greenberg, R. R. , "Procedure for the Determination of

the Platinum Baseline in Biological Materials," American Nuclear

Society Annual Meeting, Los Angeles, CA, June 9, 1982. Invi ted

Zeisler, R. and Harrison, S. H., "Distribution of Pollutant and

Essential Elements in Human Livers," American Nuclear Society

Annual Meeting, Los Angeles, CA, June 9, 1982.

Fleming, R. F. and Lindstrom, R. M., "Limitations on the Accuracy of

Sulfur Determination by NAA," American Nuclear Society Annual

Meeting, Los Angeles, CA, June 10, 1982.

Norris, J. A., "NBS Standard Reference Materials," Northwest ICP Users

Conference, Seattle, WA, June 16, 1982.

Kelly, W. R. and Paulsen, P. J., "The Isotopic Analysis of Sulfur,"

Dept, of Chemistry, Arizona State University, Tempe, AZ, June 18, 1982.

Invited

Moore, L. J., "Current Trends in Inorganic Mass Spectrometry," Hitachi

Ltd., Naka Works, Ibaraki-ken, Japan, June 22, 1982. Invi ted

Moody, J. R. , "New Developments in Laboratory Design in the USA," Lab

Design 82, International Conference on Laboratory Design and

Servicing, London, UK, June 23, 1982. Invi ted

Moore, L. J., "Current Trends in Inorganic Mass Spectrometry and Isotope

Metrology," Japan Atomic Energy Research Institute, Tokai-mura,

Ibaraki-ken, Japan, June 23, 1982. Invited

97
Moore, L. J., "Some New Measurement Concepts in High Sensitivity Mass

Spectrometry," Hamamatsu T.V. Co., Hamamatsu City, Japan, June

24, 1982. Invi ted

Moore, L. J., "Recent Advances in Inorganic Mass Spectrometry and

Analytical Chemistry," Toyota Motor Corporation, Toyota City,

Japan, June 25, 1982. Invi ted

Moore, L. J., "Highly Sensitive and Selective Stable Isotope Measurements

Using Laser Mass Spectrometry," 5th Intern. Conf. on Geochronology

,

Cosmochronology and Isotope Geology, Nikko National Park, Nikko,

Japan, June 29, 1982.

Kingston, H. M. , "The Leach Testing Evaluation of Simulated Nuclear

Waste Glasses: Can It Be Done Precisely?" Division Seminar,

National Bureau of Standards, Gai thersburg , MD, July 1982.

Rains, T. C. , "Application of AAS for Trace Elemental Analysis in

Biological Fluids," Center for Clinical Research, London, England,

July 12, 1982. Invi ted

Rains, T. C., "Atomic Absorption Spectrometry : A Challenge in the

Analysis of Environmental and Biological Materials," First Biennial

National Atomic Spectroscopy Symposium, Sheffield, England, July 13,

1982. Invited

Rains, T. C. and Butler, T. A., "Determination of Chromium Species in

Environmental Samples by Atomic Absorption Spectrometry ," First

Biennial National Atomic Spectroscopy Symposium, Sheffield, England,

July 13, 1982.

Norris, J. A., "Quantitative and Semiquanti tative Analyses, Statistics,

and Direct Reading Spectrochemical Analysis," Modern Industrial

Spectroscopy, Arizona State University, Tempe, AZ, August 2, 1982.

Fassett, J. D., Travis, J. C., Moore, L. J., and Lytle, F. E., "Resonance

Ionization of Mo, V, and Re Vapor Phase Atoms," Microbeam Analytical

Society Annual Meeting, Washington, DC, August 11, 1982. Invited

Fassett, J. D., Travis, J. C., Moore, L. J., and Lytle, F. E., "Some

New Approaches to the Formation and Measurement of Metal Ions," 9th

Annual Meeting of the Federation for Analytical Chemistry and

Spectroscopy Societies, Philadelphia, PA, September 1982.

Rains, T. C., "Atomic Absorption Spectrometry , " ACS Short Course,

National ACS Meeting, Kansas City, MO, September 11, 1982.

Paulsen, P. J. and Kelly, W. R., "Analysis of Sulfur in NBS Standard

Reference Materials by Thermal Ionization Mass Spectrometric Isotope

Dilution," National ACS Meeting, Kansas City, MO, September 14, 1982.

98
Powell, L. J., Brletic, K. A., and Garner, E. L., "A High Sensitivity

Method for the Determination of Chromium by Isotope Dilution Mass

Spectrometry," 9th Annual Meeting of the Federation for Analytical

Chemistry and Spectroscopy Societies, Philadelphia, PA, September 20, 1982.

Invited

Zeisler, R. , "Bio-monitoring for Environmental Health: Use of INAA,

RNAA, PGAA, and Role of Specimen Banks," IAEA Advisory Group Meeting

on Nuclear Techniques in Environmental Health Studies of Mineral

Pollutants, Athens, Greece, September 20, 1982. Invited

Epstein, M. S., "Multi -Element Characterization of Simulated Nuclear

Waste Leachates Using a D.C. Plasma," 9th Annual Meeting of the

Federation of Analytical Chemistry and Spectroscopy Societies,

Philadelphia, PA, September 21, 1982. Invited

Rains, T. C., Rush, T. A., and Butler, T. A., "Improved Precision and

Accuracy by Electrothermal Atomization/Atomic Absorption Spectrometry

in Environmental Samples," 9th Annual Meeting of the Federation for

Analytical Chemistry and Spectroscopy Societies, Philadelphia, PA,

September 22, 1982.

Moody, J. R. , "The Preparation and Certification of Environmental

Standard Reference Materials," 9th Annual Meeting of the Federation

for Analytical Chemistry and Spectroscopy Societies, Philadelphia,

PA, September 23, 1982. Invited

Rains, T. C. and Powell, L. J., "Sample Preparation Workshop," 9th

Annual Meeting of the Federation for Analytical Chemistry and

Spectroscopy Societies, Philadelphia, PA, September 24, 1982.

Invited

3. Committee Assignments

I. Lynus Barnes

Member, Department of Health, Education, and Welfare, The Chemistry

Task Force of the National Shellfish Sanitation Program

Washington Editorial Review Board

International Union of Pure and Applied Chemistry, Commission

of Atomic Weights

Secretary, IUPAC, Commission on Atomic Weights, Subcommittee for

Assessment of Isotopic Abundances

Robert W. Burke

Member, ASTM D-34, Waste Disposal

ASTM E-03, Chemical Analysis of Metals

Barry I. Diamondstone

Member, ASTM D-34, Waste Disposal

ASTM D-34. 02. 01, Section on Batch Extractions

ASTM E-03, Chemical Analysis of Metals

99
Michael S. Epstein

Member, ASTM D-19, Water

Board of National Correspondents, ICP Information Newsletter

Editorial Advisory Board, Progress in Analytical Atomic Spectroscopy

Assistant Program Chairman, Federation for Analytical Chemistry and

Spectroscopy Societies

Chairman-Elect, Bal timore-Washington Section of the Society for

Applied Spectroscopy

Delegate, FACSS Governing Board for the Division of Analytical

Chemistry of the American Chemical Society

Ronald F. Fleming

Member, Organization and Planning Committee, the Fourth International

Conference on Neutron Transmutation Doping of Semiconductors

Committee on Accelerator-Based Neutron Research at NBS Center

Colloquium Committee

John W. Gramlich

Member, Institute of Nuclear Materials Management Committee N15.9.3,

Non-Destructive Assay (Physical Methods)

Robert R. Greenberg

Member, NBS Chemistry Storeroom Committee

Trace Element Analysis Committee, Biomedical Division, American

Nuclear Society

Howard M. Kingston

Member, ASTM C-26.05, Methods of Test

ASTM C-26.07, Waste Materials

Task Group Leader, C-26.05, Leachate Analysis Methods

William F. Koch

Member, ASTM D-19, Water

ASTM D-19. 02, General Specifications and Technical Resources

ASTM D-19. 05, Inorganic Constituents in Water

ASTM D- 22 , Air

Chairman, Teller's Committee, Chemical Society of Washington

John K. Langland

Member, NBS Electronics Storeroom Committee

Lawrence A. Machlan

Member, ASTM C-26, Nuclear Fuel Cycles

ASTM C-26.05, Test Methods

Secretary, ASTM C-26. 01, Editorial and Terminology

100
George Marinenko

Member, ASTM D-19, Water

ASTM D-19. 01, Saline in Brackish Waters

ASTM D-19. 05, Inorganic Constituents in Water

ASTM D-19. 05. 03. 06, Ozone

Chairman, ASTM D-19. 05. 04. 03, Voltammetry

ASTM D-19. 09. 01 .04, Chlorine in Saline Water

ASTM D-19. 09. 06, Redox Potentials

ASTM D-19. 09. 07, pH in Saline Water

National Capital Section of t

r e Electrochemical Society

Blum Award Arrangements, Co"mittee of toe Electroc r e~i cal

Society

John R. Moody

Member, ASTM D-19, Water

ASTM D-19. 05, Inorganic Constituents in Water

Audit Committee, Chemical Society of Was r ingtor,

Thomas J. Murphy

Member, American Chemical Society Committee o

r Analytical 'eage r cs American Cne^ical Society Committee or '-'embers hi p Affairs

International Union of a

r c Applied Cremistry ' IIPAC)

,

Commission or. Atomic Weights a

r d Isotopic Abundances

International Union o~ D jre a

r d Applied Chemistry 'IU^-C),

Subconri ttee ~or the Assess~e r t o~ Isctosic At J

r Cc r ces,

Commission on Atomic Weights a

r d Isotopic Abundances

Chairman, American Cne~ical Society Adnissions Cormittee

Audit Committee, C

r e-ica1 Society o

r Was r ington

Councilor, Chemical Society of Washington

John A. Norris

'•‘e-ber, AS

- E-02.01 , r

J

r da~e r ta' Practices

ASTM E-02.02, Statistics

ASTM E-02.04, Sa~pl~:r

g and Standards

ASTM E-02.06, Lead, Tin, Zinc

ASTM E-02.07, Aluminu"

ASTM E-02.08, Refractory Metals

ASTM E-02.09, Ferrous

ASTM E-02.10, Miscellaneous Non-Metal lie vaterials

Secretary, AST?-' E-02, Emission Soectrosccpy

Lecturer, Annual Short Course, Modern Industrial Spectrosco :y.

Arizona State University, Tempe, AZ

Lura J. Powell

Member, Audit Committee, C m em

- lea' Society cf ftss r ' r gtc^

Progra~ Committee, American Society ~cr vass S:edt r c~etry

Chairman, Con-ittee o

r Isotope ^atio '-'eas J r e~e r ts , -mericar Society

for wass Spectrometry

101
Theodore C. Rains

Member, Proposal Evaluation Committee for National Science Foundation

AOAC Committee on Automated Methods

Editorial Board of Annual Reports on Analytical Atomic Spectroscopy

(The Chemical Society of London) and the Canadian Journal of

Spectroscopy

Subcommittee No. 6 on Methods of Air Sampling and Analysis

ASTM E-02.10, Non-Metal lie Materials

ASTM E-02.13, Nomenclature

ASTM D-01 , Paint and Related Coatings

ASTM D-19, Water

President, Society for Applied Spectroscopy

Director, Professional Development Program for the Bal timore-Washington

Section of the Society for Applied Spectroscopy

Professor-in-charge, ACS Short Course on "Atomic Absorption Spectroscopy"

Task Force Leader in Scientific Instrumentation Information Network

and Curricula (SUNG) for project on "Atomic Absorption Spectroscopy"

Column Editor, Journal of Applied Spectroscopy

Ronald W. Shideler

Member, NBS Electronics Storeroom Committee

Robert L. Watters, Jr.

Assistant Program Chairman, Federation for Analytical Chemistry

and Spectroscopy Societies

Rolf L. Zeisler

Member, IAEA Advisory Group on Nuclear Techniques in Environmental

Health Studies of Mineral Pollutants

Chairman, Trace Element Analysis Committee, Biomedical Division,

American Nuclear Society

102
4. Other

a. Seminars

October 16, 1981 Robert E. Michael is. Office of Standard Reference

Materials, National Bureau of Standards, Washington,

DC, "Testing and Characterization of SRM's"

December 3, 1981 Michael S. Epstein, Atomic & Molecular Spectrometry

Group, Inorganic Analytical Research Division,

National Bureau of Standards, Washington, DC,

"Problems (and a Few Solutions) Using a D.C.

Plasma/Echelle Spectrometer for Analytical

Atomic Spectroscopy"

January 28, 1982 William R. Kelly, Mass Spectrometry Group,

Inorganic Analytical Research Division, National

Bureau of Standards, Washington, DC, "The

Determination of Sulfur by Thermal Ionization

Mass Spectrometry"

February 18, 1982 James R. Vogt, University of Missouri on IPA

with Inorganic Analytical Research Division,

National Bureau of Standards, Washington, DC,

"Activation Analysis of Obsidian"

March 16, 1982 G. L. Fisher, Occupational Health and Safety

Division, National Bureau of Standards, Washington,

DC, "Ease in the Workplace"

April 15, 1982 William P. Reed, Office of Standard Reference

Materials, National Bureau of Standards, Washington,

DC, "Preparation and Certification of Standard

Reference Materials"

May 13, 1982 Louis Brown, Department of Terrestrial Magnetism,

Carnegie Institution of Washington, Washington,

DC, "Accelerator Mass Spectrometry Applied to

Be-10"

June 8, 1982 P. Goel , Indian Institute of Technology, "NonMagmatic Origin of Iron Meteorites"

July 8, 1982 Howard M. Kingston, Mass Spectrometry Group,

Inorganic Analytical Research Divison, National

Bureau of Standards, Washington, DC, "The Leach

Testing Evaluation of Simulated Nuclear Waste

Glasses: Can It Be Done Precisely?"

103

III. Organic Analytical Research Division

Harry S. Hertz, Chief

Dennis J. Reeder, Deputy Chief

A. Division Overview

The Organic Analytical Research Division conducts research to develop and

improve techniques for the preparation, purification, characterization , and

analysis of organic compounds and uses these techniques in the solution of

analytical problems related to national needs. The Division's research is

carried out by six groups organized along functional lines: Bioanalytical

Techniques, El ectrochemi stry , Gas Chromatography, Liquid Chromatography, Mass

Spectrometry , and Spectroscopy. During the past year, the Division has been

actively engaged in the application of organic analytical chemistry to mea- surement problems related to energy, the environment, health and clinical

chemistry, and food and nutrition. Results of Division research are utilized

by industry, other Federal agencies, public and private institutions, and

research programs at the National Bureau of Standards.

The year just completed has been very productive for the Organic Analytical Research Division. During this period 45 publications have been published

or are in press in archival journals. A third competence project, Bioanalytical

Techniques - The Use of Proteins in Analytical Chemistry, has been added to

the research already being carried out in Organic El ectrochemi stry and the

Analysis of Ionization Mechanisms and Ion Structures.

As in past years, our research efforts have been in support of basic

organic analytical chemistry, in support of other agency requests and in short

term projects performed on a service analysis basis. A major service effort

during the past year has been a review of the Environmental Protection Agency

Monitoring Study for Organic Chemicals in the Love Canal Area. Although we believe this was an extremely important undertaking, it did impact our abilities

to advance our research in the ion structures competence project.

A matter of pride for the Division during the past year was the recognition of Drs. Robert Schaffer and Alexander Fatiadi for their contributions to

research in clinical chemistry and synthetic organic chemistry, respectively.

Dr. Schaffer was honored with the Roe Award of the Capitol Section of the

American Association for Clinical Chemistry and Dr. Fatiadi with the

Hillebrand Award of the Chemical Society of Washington.

The results of our research are described in some detail in the group

overviews and individual technical reports which follow. Some aspects of this

research deserve particular highlighting. We have been most pleased with our

initial efforts in the new competence program on Proteins in Analytical

Chemistry. Research in two-dimensional electrophoresis has begun and efforts

are underway to correlate protein migration with impurities in the sodium

dodecyl sulfate used in the electrophoretic system. Also, as part of this

research, a collaborative effort has already begun with marine biologists of

the National Oceanic and Atmospheric Administration; we are using immunoelectrophoresis to investigate patterns of proteins for species identification

in commercial flounder. In our Organic Electrochemistry program, theoretical

105
and experimental studies have been carried out on the diffusion of substances

through polymer films bound to electrode surfaces. In a joint effort between

the Electrochemistry and Liquid Chromatography Groups, methods for the analysis

of ni tro-polynucl ear aromatic hydrocarbons have been investigated. These

compounds are of particular concern due to their potential health hazard and

their presence on particulate matter arising from diesel emissions. A novel

method has been developed involving reduction of the nitro moiety to an amino

function with subsequent, highly sensitive fluorescence detection. This

project has been undertaken as a cooperative effort with the Coordinating

Research Council, a group representing the automotive, petroleum, and farm

equipment industries. In a collaborative effort with the State of California,

we have evaluated a round robin material for the analysis of pesticides on soil. We have developed high resolution gas chromatographic methods allowing

us to separate greater than 100 chlorinated pesticides and PCB compounds.

Research efforts on our combined liquid chromatography/mass spectrometry

system have continued with the implementation of our ultrasonic probe for

reversed-phase liquid chromatography and applications to the direct analysis

of drugs in serum and carboxylic acids in a shale oil process water. With the

availability of an advanced pulse programmer for the 400 MHz nuclear magnetic

resonance spectrometer initial research has been carried out in heteronuclear

two-dimensional NMR. In examinations of tripalmitin, a candidate Standard

Reference Material (SRM), proton coupled 13 C multiplets have been displayed

separately from 13 C chemical shift information.

A number of new and challenging SRM's have been certified during the past

year. Of particular interest are SRM's for PCB's in oil and for urban air

particulate matter. Due to federal regulations governing the declaration of

oils as hazardous wastes, based upon their PCB content, it is extremely

important that analyses for these widely-used transformer fluids be performed

as accurately as possible. This SRM permits an accuracy check on such analyses

for the first time. The urban air particulate matter certified for a number

of polynuclear aromatic hydrocarbons represents the first solid matrix material

certified for its native content of trace organic species. In addition, the

human serum SRM has been upgraded through the certification of urea content

and through an information value for total protein content. Finally, the

certification of a drinking water SRM with certified concentrations for common halocarbons is currently underway. This SRM has been challenging both from

the preparation and analysis standpoints.

During the past year, the toxic chemicals handling laboratory, a major

safety feature for the Center for Analytical Chemistry, has been completed.

We believe we now have a unique facility for the storage and handling of

toxic chemicals. We invite visits to this laboratory and would be happy to

discuss interesting aspects of the design of this laboratory. We are currently

completing the design of a new gas chromatography laboratory and plan on beginning construction early in the coming year.

In keeping with the research planning which we have been actively doing

for the past several years, we anticipate pursuing some very exciting research

areas during the coming year. In the bi oana.lytical competence area, investigations will begin on the modification of proteins to tailor them as markers

for our two-dimensional electrophoretic system and on the examination of the

106
silver staining process for visualizing proteins separated by gel electrophoresis. We will be examining the "di ffusional " current-time response of

polymer film modified electrodes as part of our continuing research on chemically modified electrodes. We will be furthering our research on the

analysis of ion structures through the photodissociation of ions of low

internal energy. Research in high resolution chromatography will continue in

the areas of isotope dilution gas chromatography, examination of liquid

chromatographic retention mechanisms, and multidimensional gas and liquid

chromatography. During the coming year, we plan to expand our research

efforts in heteronucl ear two-dimensional NMR and to explore the potential of

this technique.

Finally, as pointed out in last year's annual report, we have made major

new thrusts in the application of our research to the areas of organic

nutrient analysis and hazardous waste analyses. We have implemented research

programs in both these areas and are anticipating worthwhile research results

in the coming year.

1 . Bioanalytical Group: Overview

A major thrust of the Bioanalytical Group during the past year has been

initiation of a competence program in bioanalytical research. The use of

proteins in analytical chemistry is a rapidly growing area of interest and

offers capabilities not possible with many instrumental methods. We are starting work on developing competence in the use of proteins as analytical

reagents and on developing sensitive methods for determining the purity of

proteins. Our efforts began by implementing access to a library of specialized reprints whose titles and references were entered into a mi crocomputer

data base. In addition, contacts were made with many research users of

two-dimensional el ectrophoresis (2-DE) in November 1981, at a meeting on 2-DE

held at the Mayo Clinic. Laboratory equipment to perform 2-DE was set up and

methods were examined for generating gradient polyacrylamide gels, for

handling thin (0.7 mm) gels, and for staining and photographing gels.

Isoelectric focusing in long (170 mm) tube gels was implemented, with

ampholytes from several manufacturers being used.

A study of the effect of the composition of sodium dodecyl sulfate (SDS)

preparations on 2-DE separations was begun with ten different lots of the

detergent. The relative purity of the materials was examined by gas chromatography after hydrolyzing the sulfate esters to free the long-chain (C 10 , C 12 > C 14 ) alcohols. The banding patterns of several proteins versus the relative

composition of the SDS preparations are being correlated.

A modest joint research effort using electrophoresis was started with the

Sandy Hook Marine Laboratory, NOAA, Department of Commerce, to investigate

patterns of proteins in commercial flounder. Immunoelectrophoresis was used,

the antiserum being provided by the National Fish Health Research Laboratories,

Department of Interior.

Coordinating work leading to the certification of SRM 1599, Anticonvulsant Drug Level Assay Standard, was completed during this year. Release of

that SRM is due in the last quarter of FY 82. Measurements leading to the

107
certification of the total protein content of SRM 909, Human Serum, were made

by an accepted biuret method for which SRM 927, Bovine Serum Albumin, served

as the primary protein standard.

A major continuing activity is the investigation and implementation of

minimal-error-prone, wet-chemical steps into our ID/MS methods, i.e., for

samplings, spikings, and analyte isolations that are performed before the

GC/MS measurements. For our serum-urea method, we synthesized 18 0-urea to

replace the commercially available 15 N 2 -urea which we used initially as the

internal standard. Its substitution by 18 0-urea obviates possible isotopeeffects in the N-C bonds that form in converting the urea into volatile - 5-0-methyl uraci 1 . Also we found improved conditions for obtaining the

derivative from urea. For our serum-creatinine ID/MS method (for which we synthesized methyl -labeled 2 H 3 -creati ni ne to avoid an analogous isotope effect

that could arise on using commercially available 15 N-labeled creatinine), we

are exploring an alternative wet-chemistry process for effecting separation of

the creatinine. Previously, spiked samples were ultrafil tered to remove most

of the protein, and the creatinine was then separated by HPLC from creatine

and other substances in the sample. Now we are separating the creatinine by

LC using ion-exchange, the effluent containing the creatinine is freeze-dried,

and the creatinine is extracted from the residue. This approach is very

simple to carry out and appears to be subject to fewer sources of error.

In collaboration with the Mass Spectrometry Group, the urea ID/MS method

was used to determine definitive values for urea in SRM 909 and also in a series of serum pools. The urea levels in the latter were also determined by

a study group of the AACC Standards Committee using a candidate reference

method. The absence of bias of the latter method was established by comparison. Manuscripts on the ID/MS method and the comparison of the reference

method with the ID/MS method are being prepared for publication.

Our paper on a multi laboratory-evaluated serum-sodium reference method

has been published in Clinical Chemistry . We also co-authored a publication

under the AACC Standards Committee on the interlaboratory testing of a candidate reference method for uric acid.

A joint study with the Electrochemistry Group has been published in

Angewandte Chemie on the behavior of oxocarbon salts of croconic acid and its

dicyanomethylene derivatives. These compounds in N_, N-di methyl formamide

undergo two consecutive, reversible, one-electron transfers to produce stable

radical ions and neutral croconates.

In the coming year, we will continue investigations on the effect of

materials purity on 2-DE separations of selected proteins. We will also study

silver staining of gels to improve the sensitivity of detection. Several

proteins will be studied in depth, with the objective of selectively modifying

their charge and molecular weight to provide markers for the 2-DE system.

We expect to be able to complete our ID/MS work on creatinine and to

complete the development of an ID/MS method for total triglycerides.

Robert Schaffer, Group Leader; Alex Cohen, Alexander J. Fatiadi,

Dennis J. Reeder

108
2 . Electrochemistry Group: Overview

The competence building program in organic electrochemistry has made good

progress this year and we have begun applying the results of our research to

NBS programmatic areas. During the fourth year of this effort, full staffing

has been maintained and most of the major pieces of equipment are now operational, although some needs still exist for instrumentation to achieve our planned research goals.

Our activities are now focused on the study of organic redox reactions

using state-of-the-art electrochemical techniques: cyclic voltammetry and

rotating ring-disk electrochemistry; hybrid techniques such as spectroelectrochemistry and liquid chromatography with electrochemical detection; the

preparation, study, and application of chemically modified electrodes; and

the theoretical modeling of electrochemical processes in support of the Group

research areas.

In the area of spectroelectrochemistry , copper and iron bleomycin

complexes are being studied in an effort to define more clearly the role of

the metal ion in the mechanism of bleomycin action. Spectroel ectrochemistry

provides qualitative information concerning the identity of solution species

and quantitative data such as the formal redox potential and number of

electrons involved in the redox process. From data obtained by cyclic

voltammetry, coulometry and atomic absorption spectroscopy, a reduction

mechanism for Cu (II) bleomycin is proposed which involves the subsequent

dissociation of the Cu(I) complex, and reduction of the free Cu ( I ) to copper

metal

Iron bleomycin exhibits quasi-reversible behavior at glassy carbon electrodes and its spectroel ectrochemi cal behavior was consequently studied in a specially constructed optically transparent electrode cell with a reticulated

vitreous carbon working electrode which exhibits thin-layer behavior. The

spectroel ectrochemical data were analyzed by means of Nernst plots to give the

n value and formal potential for the redox process.

Cyclic voltammetry, chronocoulometry , and spectroelectrochemistry are being used to examine electrode reactions of the laser dye 4-[2-( 5-phenyl - oxazolyl )]-l -methyl pyridinium tosylate. We are attempting to elucidate the

nature of the process(es) responsible for the complex electrochemical behavior

of this compound in aqueous solutions. In non-aqueous solution, the complex

anodic behavior observed in aqueous solutions disappears, and both reduction

and oxidation appear to be diffusion controlled.

Another project underway is an investigation of the spectroelectrochemistry of cyanine laser dyes. Using the cationic dye 1 ,1' -diethyl -4,4' -carbocyanine iodide, we have examined the reduction of the cation to a radical

molecule in dimethyl formamide at a gold electrode. Cyclic voltammetry

indicates a one-electron reduction that is both chemically and el ectrochemi

cally reversible. Spectroelectrochemistry shows a virtually quantitative

conversion from the cation which is accompanied by a sharp visual color change

from azure blue to violet. Furthermore, the radical product appears to be

exceptionally stable, undergoing no obvious decomposition over several hours

in a thin-layer cell

109
A series of experiments were undertaken to clarify the role of the anion

in surface-enhanced Raman scattering (SERS) measurements involving the

N-methylpyridinium cation (NMP+

) and to identify the actual surface species

observed in such experiments. We studied the effects of varying the anion,

pH, and electrochemical potential, performed competition experiments in which

both pyridine and NMP

+ were present in the electrolyte, and compared the

ordinary Raman spectrum of the solid si lver-pyridine complex, Ag(py) 2 N03, with

the various SER spectra obtained. By these experiments, we demonstrated that

different pyridine/NMP+ species are responsible for the observed spectra.

In addition, it appears that surface-induced and/or photochemical reactions

may produce species not originally present in the sample solution.

Ni tro-polycycl ic aromatic hydrocarbons are a class of highly mutagenic

compounds found in the environment and for which analytical methods are currently needed. In collaboration with the Liquid Chromatography Group,

the detection of nitro-aromatic compounds by electrochemical methods has been

approached in several ways. The direct reductive detection approach is complicated by the requirement of atmospheric oxygen exclusion and thus the detection

limits found were somewhat poorer than some alternative detection methods.

Considerable work was devoted to a scheme for coulometric conversion of the

nitro to an amino group for subsequent detection. Since only the amine

products were suitable for fluorescence detection and these were generated

inefficiently, this conversion route was abandoned. A simpler approach to the

nitro-to-amino conversion was achieved using a Jones reductor. The Jones

reductor column is inserted in the outlet stream after the reversed-phase

column but in front of the fluorescent or amperometric detectors. This

approach resulted in an efficient and quantitative conversion.

Chemically modified electrodes may provide sensors which will allow the

selective and sensitive detection of organic analytes (e.g., organohal ides)

.

Chemical modification by polymer films offers the advantages of inherent

chemical and physical stability, i ncorporation of large numbers of catalytic

sites, and relatively facile electron transport across the film. We have

followed two approaches in polymer film electrode fabrication: electrochemical initiated polymerization and spin-dip coating. These two approaches

allow a much greater degree of flexibility in polymer film type, thickness,

and morphology. However, the most important aspect is that we are given a greater latitude in the subsequent mode of catalyst immobilization.

Another area of investigation is the behavior of charged or uncharged

film penetrants. The ultimate catalytic efficiency of these polymer film

electrodes will depend to a great extent on the influx of these substrate

molecules across the film interface. We have started both theoretical and

experimental investigations, which we hope will shed light on the factors

that influence diffusion of substrate molecules in the polymer films.

Polymer films of [ Ru

^

^

( b i py

)

2 (4-VP) 2 ]*2PF6 (where bipy is bipyridine and

VP is vinyl pyridine) have been obtained via electrochemical initiation of an anionic polymerization of the vinyl monomer. These films have shown very

facile electron transfer through the film and catalytic oxidation of organic

carboxyl ates . We have also utilized these Ru^(bipy) 2 (4-VP) 2 polymer films

in the evaluation of the role and relative influence that migration plays in

the "di ffusional " current-time response of these polymer film electrodes.

110
This area of research is still being pursued and the soon-to-be-completed

computerized equipment will greatly facilitate this study.

The immobilization of cationic catalysts within a cationic exchange

polymer has been demonstrated. The immobilization scheme consists of two

parts: spin-dip coating of the polymer onto the electrode and then subsequent

ion exchange of the cation of interest. These films have shown electrochemical response with cations such as methyl viologen, methylene blue, and

Ru

II

(bipy) 3

.

In electrochemical studies using polymer-coated electrodes, there are indications that the transport of the charged electroactive species through

the polymer layer may take place not only by diffusion, but also by electromigration. We have made a theoretical analysis of chronoamperometry using

polymer-coated electrodes. Equations were developed for the concentration

distributions of the charged electroactive species and for the current as a function of time. Using the curves generated by these equations, it is now possible to estimate the fraction of the total current due to electromigration

and to determine whether the migration current adds to or opposes the diffusion current. Such information is vital to our understanding of charge

transport processes in polymer-modified electrodes.

Our plans for the coming year call for continued research on several of

the above projects with expanded efforts in the area of chemical modification

of electrodes as selective organic sensors. Because of the loss of our two

full-time spectroelectrochemists (one completing her graduate studies at NBS

and the other her tenure as a post-doctoral fellow), research in this area o* our program will be reduced. We have added a new graduate student in the

spectroel ectrochemi stry area. Our basic studies are expected to be rapidly

adapted to address the analytical needs of the Center.

Richard A. Durst, Group Leader; Elmo A. Blubaugh, Jr., Kathryn A. Bunding,

Richard T. Burke, Mary Lou Fultz, William A. MacCrehan, Gwendolyn S. Marbury,

William T. Yap

3. Gas Chromatography Group: Overview

Three areas of basic analytical research have been explored by the Gas

Chromatography Group during the past year. First, our effort in combined gas

chromatography/Fourier transform infrared spectroscopy ( GC/ I R) has been

continued and two additional Group members have been trained on the instrumentation. The GC/FTIR was used to identify polychlorinated biphenyls (PCB)

congeners present in individual liquid chromatographic fractions of Arociors

1242, 1254, and 1260. In addition, several more PCB spectra were obtained and

added to our spectral search library. Second, a collaborative study was initiated with the Center for Fire Research (CFR) in which trace organic

analysis was applied to residues of electrical insulation after exposure to

fire conditions. Chemical markers were sought as indicators of electrically

initiated fires. While such markers were not specifically identified, other

valuable data on organic residues were collected. Third, a multi-year program

was started, again with the CFR, to monitor organic emissions resulting from

wood combustion. A prototype sampling system was built by members of the Gas

111
Chromatography Group to collect both gaseous and condensed organics. Gas

chromatographic profiles of phenolic compounds emitted from wood burning

stoves were constructed as a function of position and temperature within the

exhaust stack.

As in past years, the Group has been actively involved in the Standard

Reference Material program. We have participated in the certification

analyses for the following materials:

1. Polychlorinated Biphenyls in Oil, SRM 1581 - Completed analyses of

Aroclors 1242 and 1260, each in motor and transformer oil matrices

2. Washington Urban Dust, SRM 1649 - Completed gas chromatographic

analyses for a selected number of polycyclic aromatic hydrocarbons

3. Petroleum Crude Oil, SRM 1582 - Dibenzothiophene analyses completed

and analyses for phenols are underway

4. Organics in Drinking Water, SRM 1639 - Ampouling has been completed

and analyses for carbon tetrachloride, trichloroethane, bromodichloromethane , dibromochloromethane, tetrachloroethylene , bromoform,

chloroform, and bromotrichloromethane are underway

5. Ethanol in Wine, SRM 1590 - Recertification of ethanol content

completed

The ampouling of the Drinking Water SRM required the development of a packaging technique to maintain the physical integrity of the SRM and also

prevent losses of highly volatile components. The SRM is prepared and

delivered to the ampouling machine from a collapsible Teflon bag, thermostated

to 0 °C.

A gas chromatographic method has been developed for analysis of pesticides

in human tissues. Using this method, we can quantitate over 100 pesticides

and PCB congeners in a single chromatographic run. Using this procedure, a homogeneity study of a human liver tissue homogenate was also completed. This

pesticide procedure was modified for soil samples and was employed to successfully confirm the pesticide content of a State of California proficiency

testing soil sample.

We have prepared and quantitated a number of polychlorinated biphenyl

( PCB)-containing oil samples for a joint NBS/ASTM round robin. These samples

have PCB contents between 10-300 ppm. Results from the collaborative laboratories are now being collated and reviewed for publication in FY 83.

In collaboration with the Mass Spectrometry Group, another set of marker

compounds, to be used by EPA in its Level I Method, has been prepared and

stability studies are underway. For a new program with EPA, high-resolution

gas chromatography is also being applied to the analysis of ten specified

organic compounds added to a natural sludge matrix.

During the past year, a new automated gas chromatograph was obtained and

is operating successfully. This unit has been used for overnight unattended

analyses. In addition, a state-of-the-art sulfur specific flame photometric

detector (FPD) has been procured for the automated gas chromatograph and

112
optimized for petroleum samples. The FPD has been successfully used in the

certification of the content of dibenzothiophene in SRM 1582 (34 ± 1 ppm).

Plans for an enlarged gas chromatography laboratory have been prepared.

This new facility will provide working space for approximately five chemists

and will accomodate ten gas chromatographs and ancillary equipment.

During FY 83 we will continue to pursue our programs in GC/FTIR and

combustion modeling. Also, we plan to further our competence in the areas of multidimensional and isotope dilution gas chromatography

.

Stephen N. Chesler, Group Leader; Delmo Enagonio, Franklin R. Guenther,

Reenie M. Parris, Richard E. Rebbert

4. Liquid Chromatography Group: Overview

The major emphasis of research in the Liquid Chromatography Group con- tinues to be focused in two areas: the development of a clearer understanding

of the retention mechanisms involved in normal- and reversed-phase liquid

chromatography and the development of selective detection procedures and

systems for specific compounds and classes of compounds. The results from

these efforts are applied to the determination of individual compounds in

complex biomedical, environmental, and food matrices. These research efforts

have resulted in 34 publications being co-authored (frequently with members of

other groups) by members of the group during the past year.

Specific research accomplishments for the past year include: (1) Investigation of the effect of octadecylsilane (C-18) surface coverage on the relative

retention (selectivity) of polynuclear aromatic hydrocarbons (PAH) and sulfur

containing polycyclic aromatic compounds. Changes in elution order were often

observed as the C-18 surface coverage increased and were greatest for non- planar solutes such as polyphenyl arenes. (2) Development, in collaboration

with the Mass Spectrometry Group, of an ultrasonic probe for introducing

reversed-phase LC effluents into a mass spectrometric ion source. Although

mentioned in concept last year, the operation of the ultrasonic probe was realized during the past year. The LC/MS system was used to measure the

concentrations of valproic acid in human serum and aliphatic acids in a shale

oil process water. (3) Completion of the development of our gas saturationHPLC method for measuring vapor pressures in the ambient temperature range.

Vapor pressures and heats of sublimation/vaporization were measured for 15

compounds with vapor pressures ranging from 50 to 10~ 6 Pa. (4) Completion of

the development of methods for the determination of Vitamin D2 and lactose in

powdered milk formulations in preparation for certifying these analytes in an SRM. (5) Development of a vidicon-based fluorescence detection system for

qualitative and quantitative analysis of HPLC effluents. The performance of

the system was evaluated by quantifying a number of PAH in an extract of

SRM 1649, Urban Dust. (6) In collaboration with the Organic Electrochemistry

Group, investigation of several approaches to the selective determination of

nitro-PAH derivatives in complex mixtures. The most promising approach

involves the isolation of a nitro-PAH fraction on a cyano-amino column,

separation of individual nitro-PAH species by reversed-phase HPLC, on-line

zinc catalytic reduction of nitro- to amino-PAH, and spectrofl uorometri

c

113
detection. (7) Development of sample preparation and HPLC procedures for the

determination of PAH in mussels in conjunction with the Pilot National

Environmental Specimen Bank program. (8) Extension of on-line multidimensional

HPLC investigations to the analysis of amino- and ni tro-substi tuted PAH

compounds. Class separations were found possible and analytical separations

among class members were achieved. We experienced problems with desorption

of these compounds from our interface column and are currently investigating

^several possible solutions to this problem.

The group has actively participated in the NBS Standard Reference Material

( SRM) program. During the past year, the LC Group was involved in the certification of the following SRM's: (1) SRM 1649, Urban Dust/Organics. An HPLC

method involving gradient elution and fluorescence wavelength programming was

one of the two analytical techniques used to measure 13 PAH in extracts of

this material. This SRM is intended primarily for use in the evaluation and

calibration of analytical methods for the determination of PAH on atmospheric

particulate matter or on similar materials. (2) SRM 1599, Antiepilepsy Drugs

in Human Serum. HPLC methods were used to determine the concentrations of

valproic acid and carbamazepine in a 1 yoph i 1 i zed human serum material. This

SRM will be used for calibration and standardization of procedures employed in

clinical laboratories. (3) SRM 998, Angiotensin I. HPLC was used in the

determination of the purity and total peptide content of this material. This

material will be used as a reference material for radioimmunoassay of renin

and can also be used as a peptide standard. (4) SRM 1639, Organics in

Drinking Water. HPLC, using a photoconductivity detector, was one of the

techniques used to verify the concentrations of seven halocarbons in this

methanol solution. This SRM is intended for the preparation of aqueous solutions for quality assurance in the analysis of halocarbons in drinking water.

(5) SRM 1595, Tripalmitin. HPLC was used to aid in the determination of the

purity of this material. This SRM is intended to be used as a reference

material for the determination of triglycerides in human serum.

SRM activities currently in progress include the certification of

p-aminobenzoic acid in phenacetin (SRM for differential thermal gravimetric

analysis), organics in petroleum crude, and indeno(1 ,2 ,3-cd)pyrene generator

columns. Next year we anticipate certifying a diesel particulate extract

for PAH and nitro-PAH content as well as certifying a phenol s-in-hexane

calibration solution SRM.

During the past year, Drs. Freeman Allen, Pomona College, Claremont, Ca.,

and Corazon Vogt, University of Missouri, Columbia, Mo., conducted sabbatical

research in our Group. Dr. Allen was primarily involved with the development

of sample preparation procedures for the determination of pesticides and PAH

in human and animal tissues. Dr. Vogt investigated the feasibility of using

reductive amperometry for 1) direct HPLC detection of ni tro-substi tuted PAH,

and 2) on-line reduction of non-fl uorescent nitro-PAH to their highly

fluorescent amino derivatives with subsequent fluorescence detection.

During the coming year we plan to continue our efforts in LC/MS and our studies in retention mechanisms. The latter should be bolstered by the

arrival of Dr. Lane Sander, an NRC Postdoctoral Fellow from the University

of Washington.

114
We plan to continue our efforts in multidimensional HPLC and expand our competence in pre- and post-column deri vi tization techniques. We will reduce

slightly our efforts in the environmental area while expanding our efforts in

the clinical and food analysis areas.

Willie E. May, Group Leader; Charles F. Allen, Jeanice M. Brown-Thomas

,

Richard G. Christensen, Walter F. Kline, Sam A. Margolis, William J. Sonnefeld,

Corazon R. Vogt, Robert B. Weker, Stephen A. Wise

5. Mass Spectrometry Group: Overview

The Mass Spectrometry Group has devoted the major part of its efforts to

the quantitation of individual compounds in complex mixtures, the development

of high-resolution mass spectrometric techniques for the analysis of high

molecular weight compounds, the continued development of a liquid chromatography/mass spectrometry (LC/MS) interface compatible with reversed-phase

LC, and research, begun last year, which is part of a competence building

program, "Analysis of Ionization Mechanisms and Ion Structures." Other agency

and programmatic research continue to be concentrated in the environmental

and clinical areas.

Development of isotope dilution definitive methods for the quantitation of

human serum constituents has continued in collaboration with the Bioanalytical

Techniques Group. A human serum Standard Reference Material, SRM 909, released

in 1980 was previously certified for the concentrations of cholesterol,

glucose, and uric acid. A method has been developed for urea and the collection of data for certification is complete. The results of a cooperative

study with the Karol inska Institute comparing isotope dilution/mass spectrometry (ID/MS) methods for cholesterol has been published in Clinical Chemistry

and a manuscript describing the two ID/MS methods developed for glucose will

appear in Biomedical Mass Spectrometry in September. Methods are being

developed for creatinine and triglycerides

Further work, joint with the Liquid Chromatography Group, has been

done on the LC/MS interface developed at NBS over the last several years.

Development of a system which employs continuous sample preconcentration and

ultrasonic nebulization for the introduction of aqueous mobile phases has

been completed.

A method to obtain complete high-resolution field desorption spectra and

accurate mass measurements using silver sulfonate salts for mass calibration

with photoplate detection has been developed. Tests on a variety of peptides

have given satisfactory results over the range of 300-1150 mass units. This

work will comprise the Ph.D. thesis to be presented to The American University

by a guest worker in our Division, Rafael Espi nosa-Leni z

Research has continued on development of isotopically labeled marker

compound standards for use in the proposed Environmental Protection Agency

(EPA) "Master Analytical Scheme" for priority pollutant analysis. Additional

sets of internal standards have been prepared and delivered to EPA. These new standards consist of two or three concentration levels each of five different

mixtures and contain a total of twenty deuterated compounds and one unlabeled

115
compound. Work is in progress on confirming the chemical and isotopic stability of these solutions. Similar sets of labeled marker compound standards are being prepared for use by EPA and its contractors in a "Comprehensive Scheme

for Soils, Sediments, and Sludge."

Research in the environmental area has focused mainly on the development

of accurate quantitative methods for the determination of trace level organic

compounds in aqueous wastes associated with energy production. High-resolution

capillary column gas chromatography/mass spectrometry with selected ion

monitoring has provided the selectivity and sensitivity necessary for quantitation of individual organic species in complex samples such as a shale oil

process water and in aqueous leachates of hazardous wastes (Solvent Refined

Coal II Vacuum Still Bottoms, H-Coal Filter Cake) at the part-per-bi 1 1 ion

( p g/L ) level. Initial experiments have been carried out to develop both

electron impact and methane chemical ionization GC/MS methods for the determination of individual organic compounds in a Wilmington crude oil. The

methods will be used for a Wilmington Crude Oil SRM certification. Work has

begun, in conjunction with the Gas and Particulate Science Division, on the

development for EPA of standards for trace (ppb) toxic organic chemicals in

air. The group continues to provide support for other environmental projects

within the Division such as the qualitative identification of polynuclear

aromatic hydrocarbon species in the Washington Urban Dust which has recently

been issued as SRM 1649.

A competence building program in mass spectrometry , "Analysis of Ionization Mechanisms and Ion Structures," was begun in October 1980. One part of

this program involves laser induced metastable ion generation as a selective

probe for molecular structure. The photodissociation of ions created by

electron impact was observed for a variety of molecules last year using borrowed equipment. This year permanent equipment--an argon ion laser, a chopper,

optics, and a lock-in ampl ifier--has been installed, and the dependence of

the photodissociation on wavelength observed in other laboratories has been

confirmed. A second part of the program, the study of the collision of ions

with reactive neutral species, was scheduled to begin this year. An existing

quadrupole mass spectrometer has been modified by the manufacturer to the

triple quadrupole required. During this year both of the principal investigators in the competence building program served on the NBS panel which

reviewed the analysis for organic chemicals performed by EPA in its Love Canal

Monitoring Study.

Research planned for the coming year includes: continuation of the

ongoing environmental projects with particular attention to the use of alternative ionization techniques, such as chemical ionization and negative chemical

ionization to obtain increased sensitivity and/or selectivity of detection for

quantitation; development of isotope dilution definitive methods for creatinine

and triglycerides , and implementation of improvements to the instrumentation

used; and, for the competence building program, the study of the photodissociation of ions of low internal energy, such as field desorbed ions, as a potential source of structure information and the start of studies on the

collision of ions with reactive neutral molecules.

Edward White V, Group Leader; Rafael Espinosa-Leniz , Laurence R. Hilpert,

Stanley Meiselman, Kristy L. Richie, Lorna T. Sniegoski, Michael J. Welch,

Corazon R. Vogt

116
6. Spectroscopy Group: Overview

During the past year, the Spectroscopy Group has energetically continued

its programs in organic analysis by NMR spectroscopy , polarimetry, SRM certification, and the synthesis of isotopically labeled and unlabeled bioorganic

materials. The Group has declined in number as the two NBS-NRC postdoctoral

research associates have completed their appointments.

During the past year, substantial progress has been made with the analytical application of NMR spectroscopy. Proton NMR at high field has been used

in two different ways to complete certification of the Angiotension I SRM;

firstly, by measurement of acetate content, and secondly, for verification of

amino acid composition.

Proton nuclear Overhauser effect difference techniques have been used at

400 MHz for proof of the identity of a commercial sample of 13-methyl pi cene needed for theoretical studies of liquid chromatographi c retention times.

This project involved comparative studies of the high field spectra of a group

of related PAH.

Studies of the proton and 15 N NMR of neomycin B and its related aminoglycosides have now been completed. Our initial, intuitive analysis of the

complex 400 MHz proton NMR spectrum of neomycin B has been confirmed by twodimensional, J-resolved NMR techniques, thus verifying our previous 15 N results that the conformation of the L-idose moiety is different from that

reported in the literature. A paper on the 15 N component of this work has

been accepted for publication by the Journal of the American Chemical Society .

Our postdoctoral research project on the synthesis and analysis of

intermediates leading to anti -tumor nucleosides and nucleotides has been

pursued in several new directions. A new class of 2-methyl thio-oxazol ine

derivatives of carbohydrates has been synthesized by methyl ation of 2-thiono

oxazolidine derivatives. The 13 C and 15 N isotopically labeled modifications

of the methyl thio intermediates have been studied extensively by multi nuclear

NMR techniques with the objective of developing correlations of heteronucl ear NMR parameters with structure.

In work designed to test the synthetic utility of carbohydrate oxa- zolines, a novel fructose diphosphate (FDP) analogue of cyclouridine has been

synthesized by condensation of the 2-amino oxazoline derivative of FDP with

methyl propynoate.

The previous syntheses of 2-amino oxazoline derivatives of monosaccharides

have been extended to a variety of di saccharides and a tri saccharide, including

examples in the cellobiose, lactose, maltose, palatinose, 3-0-a-Q-glucosyl

arabinose, 3-0-B-Q-galactosylarabinose, and maltotriose series. Studies of

the 15 N NMR spectra of the

* 5 N labeled modifications have indicated a dependence of 15 N chemical shifts on the ring size of the sugar moiety.

A substantial upgrading of the capability of the WM-400 spectrometer has

been accomplished this year by installation of an advanced pulse programmer.

This installation required quite major revisions of the console hardware and

of the computer software so that for 2-3 months, only partial operation of the

117
spectrometer was possible. The new pulse programmer permits simultaneous

pulses and phase control on the observe, decoupling, and receiver channels,

thereby opening a new realm of multiple pulse, heteronuclear two-dimensional,

and polarization transfer experiments. Work on certification of the Tripalmitin SRM has continued during the year, and the pulse programmer has allowed

the first two-dimensional, J-resolved 13 C NMR spectra of tripalmitin to be

obtained, in which the proton coupled, 13 C multiplets are displayed separately

from the 13 C chemical shift information. Sensitivity enhancement by cross polarization (polarization transfer) methods is being implemented for 13 C and

i5 N NMR. Instrumentation plans for the coming year include installation of a magnetic tape drive to facilitate archival mass data storage for both CP-200

and WM-400 NMR spectrometers, and also a computer switchable, 13 C/proton dual

frequency preamplifier and probe (for the WM-400) that will allow the

automated, sequential acquisition of proton and 13 C NMR spectra from 5-mm

samples during overnight runs.

In polarimetric work designed to secure international agreement on a proposed change to the 100 °S calibration point of the sugar scale, the laser

wavelength used for measurements of highly pure sugar solutions at NBS in 1978

has been verified by measurements of internationally standardized quartz

rotators. Future plans in this area include the ongoing calibration service

for quartz plates submitted by industry, and the use of the high accuracy

polarimeter for recertification of the dextrose SRM, work in which high field

proton and 13 C NMR are also expected to play an important role.

Bruce Coxon, Group Leader; Robert M. Davidson, Diane K. Hancock

118
B. Selected Technical Reports

(Organic Analytical Research Division)

1 . The Effect of Ci fi Surface Coverage o

r Selectivity Ps . e^sec-'^se

HPLC (11320)

W. E. May, S. A. Wise

Several recent studies in the literature have repo r *ed selection.. cifTer- ences for polycyclic aromatic hydrocarbons on different ocrsoec.. 1 si ' are

(C18 ) liquid chromatographic column packing materials. "he .nderstard'l r g of

the origin of such selectivity differences would al'o-i the cr '•onatograpner tc

"custom design a column to optimize a particular separation. ~o ^ . estimate

the origin of these selectivity differences, the C- e S-^-ace co. adages

(umoles/m2

) of seven different CL E packing materials ..ere determined -re- surface area measurements [Brunauer, E-rstt, a

r c Tel'er ll~ gas aascoton

method" and percent carbon measurements or the chemical/ ~oc*-'ed s'iica

packing. Based on the C 18 surface coverage data a

r d ~c r

- r fc r^iV

r

. three of the C1S materials were determined to be polymeric 1 leases r: feu-*

were determined to be monomeric' phases.

Some interesting trends .-.ere obser.ed between retert'or on ~cz~e r 'z . 5 . polymeric C ig phases. For example, chrysene and benz[al

r e rs.e'-se

elution order as the surface coverage increases and :m r / e.g..

terphenyls, quaterpheny Is, ard oneny

" -suostit uteo are r eoa' ,‘eo arge'*,

relative to fused ring PAH, on monomeric t!'‘a

r cr polymeric C : -aoe^'a's.

Selectivity differences have bee'- cbse r ,ed for 3Ar 0

- different eos of C :

: material from the same source. The effect of Clfi surface coverage on : -- selectivity was investigated by examining six lots of 5 x>lyraer*c C : E packing material from one manufacturer. ~r 5 :bysica‘ character* st* cs ".a.,

surface area and percent carbon of these six lots a

r e sumrear-lzed in 'a: 'a

As expected k

1 , the capacity “actor, for a test solace. benzo[<T pyrene Ea :

. increases with increasing surface coverage. The select". ity c" -fe-'ences

(relative to BaP on five different polymeric C-L

z columns a

r c a ~c " ome r * 0 I column are illustrated in figures 23 a

r d 24. ~ne unus^a' behav'O'* of o*'a r _.

PAH (figure 24^ and other nor-planar 3A- SjC r as pnenantr r :"3_ ! £-c_':“a'*a"0" 'a^a

(no. 5 in figure 23} and 1 ,2,3,4,5,6,7,8-tetrabenzonap^thalene : figure 23) indicate that solute planarity has a significant affect o" :: - retention. Other structural features of the solute S-.C" as lengt^-to-b^adt^

ratio also affect the reversed-g^ase retention. In ge'‘£ r a' . the se'ect*',ity

factor (a) for PAH solutes with length-to-breadth '-atios g'*£at£ r t-a r '.63

increase significantly wit r increasing ca r bor surface co.a r aga e.g. , cqitdcj'': nos. 17-19 and 21-23 in figure 23), whereas a for solutes with s _ a'a r ratios

tend to decrease with increasing surface coverage. S" - "'ar '-esuts r a.e zee- observed for sulfur-containing PAH. T

r e selectivity -> format *cn

*' r -* g_ es 23 and 24 can be used to select the appropri ate cc'^ - '* for opti - * zat" or of a particular separation. r uture studies will focus cr deterr j -* * ng t-e z- -Ter- ences in the nature of the bonded sur-aces for mononne-'ic a

r o Dc ye * c o^ases

which account for these selectivity changes.

119
Table 14. Physical Characters sti cs for Different Lots of

Polymeric C 18 Material 3

.

Col umn % C

Surface Area

(m2 /g) b

Surface Coverage

(ymol/m2

) k ' ( BaP)

c 1423S 4.5 ± 0.3 d

48.5 4.3 ± 0.3

d

2.7

1467 7.7 ± 0.6 61 .0 5.8 ± 0.5 3.3

1460-12 7.7 ± 0.4 60.0 5.9 ± 0.3 3.5

1465 7.5 ± 0.5 61.6 5.6 ± 0.4 4.0

1703 8.0 ± 0.3 50.1 7.4 ± 0.3 5.0

1460-3 8.1 ± 0.3 48.3 7.8 ± 0.3 6.3

a Vydac 201TP 5 ym materials. c 85% CH3 CN in H 2 0.

Determined by BET. Uncertainty is ±la for three determinations.

Figure 23. Selectivity factor (a), relative to benzo[a]pyrene , of selected

polycyclic aromatic hydrocarbons on a monomeric C 18 column and

five polymeric Cj 8 columns. (Polymeric columns arranged in order

of increasing k' of benzo[a]pyrene.

)

120
e

121

Figure

24.

Selectivity

factor

(a),

relative

to

benzo[aJpyrene

,

of

selected

biaryl

PAH

on

a

monomeric

C

18

column

and

five

polymeric

C

18

columns.

(Polymeric

columns

are

arranged

in

order

of

increasing

k'

of

benzo[a]pyrene.

)
122

Figure

25.

Coupled

column

HPLC/vapor

generator

column

assembly.
2. Determination of Ambient Temperature Vapor Pressures of Polycyclic

Aromatic Hydrocarbons (11320, 14230)

W. E. May, W. J. Sonnefeld

During the past decade, increased concern has developed about the environmental impact of anthropogenic trace organic compounds. One factor which

governs the transport of organic compounds, both in the workplace and in the

general environment, is the volatility of these compounds. The vapor pressure

of a compound determines, in part, the rate of evaporation from industrial or waste sites, as well as the compound's tendency to be adsorbed by particulate

matter present in the environment. Vapor pressure data can be combined with

aqueous solubility data to calculate Henry's law constants, which can be used

to predict the equilibria of dissolved organics in water with their atmospheric concentrations. The determination of the vapor pressures of organic

compounds in the ambient temperature range (0-50 °C) is therefore important to

permit the development of environmental transport models, as well as for the

assessment of possible health hazards present in the atmosphere.

During the past few years, we have developed a gas-saturation method

utilizing high performance liquid chromatography (HPLC) for analyte measurement. The HPLC is directly coupled to the vapor saturator (generator) column,

thus avoiding the associated problems of subsampling and sorption/desorption

efficiencies found in some of the earlier methods. Furthermore, the time for

the determination is decreased, since small volumes are collected and the

entire amount of analyte, not an aliquot, is ultimately measured.

The experimental system (figure 25) is composed of three sections: a generator column for the production of an analyte saturated vapor; an extraction section for the collection and concentration of the analyte vapor; and a reversed-phase HPLC system for the measurement of the collected material.

The generator column consists of a tube filled with either the pure

analyte or with an inert support material on which the analyte has been coated.

Two methods of collecting and concentrating the effluent from the generator

column have been employed: a packed superficially porous octadecylsilane

column and a cryogenic trap. Comparable results have been obtained with these

two collection devices.

The vapor pressures of organic compounds for which adequate HPLC detectors

are available can be measured over a vapor pressure range from 50 to 10~ 6 Pascals. The accuracy has been estimated to be better than 95 percent by a propagation of errors treatment, with an average precision less than 6 percent

relative standard deviation. The method has been used to determine the vapor

pressures of selected polynuclear aromatic hydrocarbons (PAH) in the temperature range of 283.15 to 323.15 K (Table 15). The determination time ranges

from 15 minutes to 3 hours depending on the total volume sampled and the flow

rate of the generator column. The results of the measurements of the vapor

pressures are generally in good agreement with extrapolated results reported

in the literature which were determined using different methods at higher

temperatures (Table 16). The enthalpies of sublimation for the PAH were determined from the temperature dependence of the vapor pressures and compared

to literature values, with agreements of better than 15 percent (Table 17).

123
4 Table 15. Values of Constants for Calculating Vapor Pressures (Pascals) of

Polynuclear Aromatic Hydrocarbons Between 283.15 and 323.15 K.

Log P° = -A/T + B Compound A^

Naphthalene 3960.03 + 58.9 14.299 + 0.200

Acenaphthylene 3821.55 + 23.7 12.768 + 0.079

Acenaphthene 4535.39 + 47.3 14.669 + 0.159

FI uorene 4616.07 + 30.2 14.385 + 0.101

Phenanthrene 4962.77 + 32.8 14.852 + 0.109

Anthracene 4791.87 + 50.3 12.977 + 0.170

Fluoranthene 4415.56 + 46.2 11.901 + 0.155

Benz[ajanthracene 4246.51 + 132.2 9.684 + 0.431

Pyrene 4760.73 + 26.2 12.748 + 0.087

Naphthalene (D 8 ) 3689.52 + 27.6 13.392 + 0.09

Phenanthrene (D 10 ) 4704.13 + 31 .5 14.060 + 0.11

a The uncertainty of the constants A and B are the standard deviations

based on >15 measurements at a minimum of 4 different temperatures

Table 16. Vapor Pressures of Polynuclear Aromatic Hydrocarbons at 25.0 °C.

PAH Vapo r Pressure, Pa

Compound This Work

Literature Values Extrapolated

to 25 °C

Naphthalene 10.4 + 0.2 10.8, 10.8, 12.3

Acenaphthylene (8.9 +

• 0.2) x 10" 1

Acenaphthene (2.87 + 0.9) x 10'1 3.7 x 10" 1

, 3.8 x 10" 1

FI uorene (8.0 + 0.2) x 10"2 8.8 x 10"2

, 12.7 x 10"2

Phenanthrene (1.61 + 0.04) x: 10"2 2.27 x 10“2

, 1.87 x 10“ 2

Anthracene (8.0 + 0.2) x 10"4 8.3 x 10"4

, 4.9 x 10“4

, 10.4 x 10"4

, 8.6 x 10“ 4

, 11.1 x 10"4

FI uoranthene (1.23 + 0.07) x; 10' 3

Pyrene (6.0 + 0.2) x 10" 4 8.8 x 10"4

, 2.7 x 10“4

Benz[a]anthracene (2.8 + 0.1) x 10" 5 2.2 x 10" 5

Note: All values are interpolated or extrapolated from log vapor pressure

vs. 1/T(K) relationships. The mean values are shown with the standard

deviation calculated from the average of the relative standard deviations for triplicate measurements at each of 4 or more temperatures

124
Table 17. Average Enthalpy of Sublimation of Polynuclear Aromatic Hydrocarbons in kJ/mol Over the Temperature Range 10-50 °C.

Compound

Naphthalene

Acenaphthylene

Acenaphthene

Fluorene

Phenanthrene

Anthracene

Fluoranthene

Pyrene

Benz[a_]anthracene

This Work a

75.8 ± 1.1

73.2 ± 0.5

86.8 ± 0.9

88.4 ± 0.6

95.0 ± 0.6

91.8 ± 0.9

84.6 ± 0.9

91.2 ± 0.5

81 .3 ± 2.5

aH °

,

kJ/mol

Literature Values^

72,.4, 72,.7, 83..5

84,.7, 82,.1

82,.1, 82,.8

86,.6

103.• 8, 97..5, 98,.5 102.,8, 92.,0

84..7

94..1, 95..2, 80,.1 105

a The uncertainty is ±1 standard deviation of the slope determined by a least-squares treatment of the raw data.

^Values are the average enthalpy of sublimation over the

experimental temperature range in each study.

3. Determination of Polycyclic Aromatic Hydrocarbons in Complex Mixtures

Using HPLC with Mobile Phase and Fluorescence Wavelength Programming

(11320, 14306)

W. E. May, S. A. Wise

One of the most common problems associated with the analysis of polycyclic

aromatic hydrocarbons (PAH) in complex mixtures is the identification and

quantification of individual isomers. Quantitative information on individual

isomers is important because biological (toxicological) properties of many PAH

have been shown to be isomer specific.

Reversed-phase high performance liquid chromatography (HPLC) has become

a powerful tool for the separation of individual parent PAH. Retention in

reversed-phase HPLC increases with the degree of alkylation. Thus, a serious

problem associated with the identification of PAH based only on chromatographic

retention in reversed-phase HPLC is the co-elution of alkyl substituted

homologs of smaller PAH. For example, some alkyl phenanthrenes and anthracenes

elute in the region where pyrene and fluoranthene elute; alkyl pyrenes and

fluoranthenes co-elute with benz[a_]anthracene and chrysenes, etc. In the past we have circumvented this problem by initially fractionating complex mixtures

into isomeric PAH families via chromatography on an ami nosilane column with a non-polar mobile phase, i.e., hexane. Each family can then be individually

125
analyzed in a reversed-phase system, free of interferences from alkylated

species of lower aromatic carbon number.

An approach that we have employed during the past year involves the use

of reversed-phase HPLC with mobile phase (gradient elution) and fluorescence

wavelength programming. In this approach, resolution of PAH with respect to

time is achieved chromatographical ly . The fluorescence excitation and emission

wavelengths being monitored are also changed with respect to time, so that

each PAH being measured is monitored at wavelengths that are optimized for its

detection. Since individual PAH have characteristic fluorescence spectra, it

is possible to accurately measure one PAH in the presence of another known

co-eluting PAH by the proper choice of detection parameters which need not be

excitation or emission wavelength maxima. In addition, the characteristic

nature of these spectra can aid in identification. The selectivity achieved

using this approach is shown by comparison in figure 26. The upper chromatogram is a UV trace of the analysis of an extract of SRM 1649, Urban Dust/

Organics. Individual PAH are practically indistinguishable. The remaining

four chromatograms represent the analysis of the same extract using fluorometric wavelength programming. The specific excitation and emission

wavelength pairs used and the compound measured are identified in Table 18.

Table 18. Fluorescence Conditions for the LC Determination of

Selected PAH in Atmospheric Particulate Matter.

Wavelengths (nm)

(see figure 26)

Excitation Emi ssion

285 450

a 2 400 440

X 3 295 405

X 4 330 385

X 5 285 385

X 6 290 360

270 360

*8 300 500

PAH Quantified

fluoranthene and 7-methylfluoranthene (I.S.)

a

perylene-d 12 (I.S.) and perylene

benzo[k_]fluoranthene, benzo[ajpyrene, and benzo[ ghi

j

perylene

pyrene

benz[a_]anthracene, dibenz[<a,hjanthracene, and benzo[ ghi

j

perylene

phenanthrene

chrysene

i ndenop ,2,3-cdjpyrene

a I.S. - internal standard.

126
FLUORESCENCE

INTENSITY

FLUORESCENCE

INTENSITY

I

(excitation

285

nm,

emission

450

nm)

W J m

10 20

BENZO(k)

< FLUORANTHENE

2 *3

10 20 30 40 SO 10 20 30 40 50

Excitation

(x)

Emiss - (X)

X X = 285 450

X 2 = 400 440

X 3 = 295 405

X 4

= 330 385

X 5 = 285 385

X 6 = 290 360

X 7 = 270 360

>*

OO II CO OO 500

TIME (min)

Figure 26. Reversed-phase fluorescence wavelength programming

method for analysis of raw particulate extract.

127
The hardware requirements for implementation of this technique are an HPLC pumping system capable of gradient elution and retention time reproducibility of ±6 seconds In a 45 minute gradient, and a spectrofluorometric

detector capable of rapid scanning and excitation and emission wavelength

programming. Wavelength accuracy and reproducibility needs to be ±2 and

±1 nm, respectively, with 10 nm slits.

This approach has been used in the certification of SRM 1649 and will be

used to further measure PAH in extracts of mussels and diesel exhaust particulates.

4. Vidicon Based Fluorescence Detection for Qualitative and Quantitative

Analyses in HPLC (11320)

T. H. Begley, W. E. May, R. A. Velapoldi

The increased Interest in mul tiwavel ength detection In HPLC has led to

the development of vidicon based detection systems. These systems are capable

of measuring the absorbance or emission spectra of the eluting compounds

on-the-fly. In particular, vidicon systems used to measure the fluorescence

of compounds offer high sensitivity and selectivity for HPLC. The use of HPLCvidicon systems has not yet been applied for the routine analyses of complex

samples where quantitative information about many components is desired.

We have successfully used an HPLC-vidicon system to determine quantitatively numerous polycyclic aromatic hydrocarbons in the NBS Urban Dust/Organics

SRM 1649 (see Table 19). Summarized in the table are PAH concentration values

determined by selective wavelength integration intervals ( W 1 1 , column 1),

signal -to-noise optimized WII (column 2), weighted HPLC averages from the SRM

certificate (quadrature addition of ± values, one standard deviation of the

mean, column 3), and the SRM certified values (column 4). Detection limits

for these compounds have been determined and are in the 0.08-0.1 ng range.

A method to extract the qualitative spectrum of a weakly fluorescing

component from a formidable background also has been developed. The method Is based on a linear approximation of the background behavior. Studies included

optimization of the wavelength integration interval (WII) with respect to

si gnal-to-noise ratio, the use of the ratio technique to determine the purity

of a chromatographic peak, and the use of second derivative spectroscopy to

deconvolute co-eluting components.

128
Table 19. Analysis of NBS SRM 1649, Urban Dust/Organics

Compound Concentration, yg/g

Selective WII

a SNR Optimum WII

a HPLC Avq.

b

SRM

C

Fluoranthene 7.1 1+ o OO

CL (35)

e 7.5 ±1 .

2

d

(251

)

e 7.0 ±0.5 d

7 . 1±0 . 5

Benz[a] anthracene 2.1 ±0.5 (ID 2.1 ±0.2 (301) 2.7 ±0.3 2 .6±0 .3

Chrysene 4.0 ±0.6 (ID 9.0 ±3.0 (251) 3.6 ±0.2

Benzo[y fluoranthene 6.5 ±0.1 (35) 7.0 ±0.6 (301) 6.2 ±0.3

Perylene 0.7 ±0.3 (11) 1.1 ±0.9 (179) 0.8 ±0.04

Benzo[kJ f 1 uoranthene 2.2 ±0.3 (11) 2.7 ±0.6 (301) 2.0 ±0.1

Benzo[^] pyrene 1.2 ±0.7 (11) 2.6 ±0.3 2 . 9± 0 . 5 Benzo[ghi]perylene 3.5 ±0.2 (11) 4.1 ±0.3 (243) 4.5 ±0.7 4 . 5± 1.1

Dibenz[cuh] anthracene o 1+ o

OJ o (11) 0.86±0.4 (221) 0 . 41 ±0 . 07

a WII = Wavelength Integration Interval.

SNR = Signal -to-Noise Ratios.

^Fluorescence with wavelength programming. See Technical Accomplishment #3 for

further details on method. 7-Methyl fluoranthene used as internal standard.

Certified SRM values. The estimated uncertainties are intended to correspond

to approximately 95% confidence limits. They represent an evaluation of the

combined effects of method imprecision, possible systematic errors among

methods, and material inhomogeneity.

d

All ± values are one standard deviation of the mean.

e Numbers in parentheses are the width of WII in channels.

5. Certification of SRM 1649, Urban Dust/Organics, for Selected Polycyclic

Aromatic Hydrocarbons (14306)

S. N. Chesler, W. F. Cuthrell , W. E. May, R. E. Rebbert, S. A. Wise

In recent years, many analysts have expressed interest in examining the

organic content of SRM 1648, Urban Particulate Matter, which is certified only

for its trace element content. As a result, NBS has issued a similar urban

particulate material (collected in the Washington, D.C. area) which has been

certified for several polycyclic aromatic hydrocarbons (PAH). SRM 1649, Urban

Dust/Organics, is issued in 10 g quantities to provide ample material for a number of organic compound measurements.

As with the certification of other SRM's, two independent analytical

procedures were used for the determination of selected PAH. Different sample

extraction solvents, internal standards, and clean-up procedures were used

prior to the separation and quantification by capillary column gas chromatography (GC) and high performance liquid chromatography (HPLC) as described

129
previously (CAC Annual Report, 1981). The analytical results of these

analyses are summarized in Table 20 for 14 PAH. The liquid chromatographic

results are reported separately for the analyses using 7-methylfluoranthene

and perylene-d12 as the internal standards (LC-I and LC-II in Table 20).

Results using perylene-d 12 as the internal standard were generally more precise than those determined using 7-methylfluoranthene. The certified

values for 5 PAH are given in Table 21. The values for the remaining PAH

(see Table 20) are provided to the user only as informational values since

they were determined using only one method or sufficient agreement between

the two methods was not achieved.

Table 20. Summary of Results by the Various Analytical Methods.

Concentration, yg/g

Compound GC [4]

ai LC-I [18] LC-II [9]

Phenanthrene — — 4.5 ±0.3 b

(9)

*F1 uoranthene 7.3 ±0.2 b

(4) 7.0 ±0.5b

(24) 6.8 ±0.4 (9)

Pyrene 7.2 ±0.2 (4) 6.3 ±0.4 (17) 6.2 ±0.2 (9)

Chrysene — 3.5 ±0.1 (5) 3.7 ±0.2 (9)

*Benz[a] anthracene 2.4 ±0.1 (4) 2.8 ±0.3 (18) 2.4 ±0.1 (3)

Tri phenyl ene — 1.7 ±0.1 (3)

Perylene 0.84±0.09 (4) o

oo o+1 o • O (17) 0.65±0.02 (9)

Benzo[e]pyrene 3.3 ±0.2 (4) — —

*Benzo[aJ pyrene 3.0 ±0.3 (4) 2.6 ±0.4 (18) 2.6 ±0.1 (9)

Benzoyl fluoranthene — 6.2 ±0.3 (18) —

Benzo[k]fl uoranthene — 2.0 ±0.1 (18) 2.1 ±0.1 (9)

*Benzo[ghi]perylene 4.7 ±0.2 (4) 3.9 ±0.8 (12) 5.2 ±0.6 (9)

Di benz[a_,h]anthracene — — p". o 'd- +1 o o (9)

*Indeno[l ,2,3-cd]pyrene 3.3 ±0.3 (4) 3.4 ±0.4 (16) 3.6 ±0.2 (9)

a Number in [ ] indicates number of samples extracted.

^Uncertainty is one standard deviation of the mean.

p Number in ( ) indicates number of measurements.

indicates compounds with certified values in Table 21.

Note: LC-I used 7-methylfluoranthene as the internal standard and LC-II

used perylene-d12 as the internal standard.

130
Table 21. Certified Values for Selected Polycyclic Aromatic Hydrocarbons

.

Compound Concentration, yg/g

a

Fluoranthene 7.1 ± 0.5

Benz[a_]anthracene 2.6 ± 0.3

Benzo[a] pyrene 2.9 ± 0.5

Benzo[ghi]perylene 4.5 ± 1.1

Indeno[l ,2,3-cd]pyrene 3.3 ± 0.5

a The certified value and the estimated uncertainty listed for a constituent

are contained in the union of 95% confidence intervals computed separately

for each analytical method and represents an evaluation of the combined

effects of method imprecision, possible systematic errors among methods,

and material inhomogeneity. The estimated uncertainty is intended to

correspond to approximately 95% confidence limits.

In addition to the quantitation of these major PAH constituents in SRM

1649, we have qualitatively characterized the complex PAH mixture extracted

from the urban dust using multidimensional chromatographic techniques (i.e.,

LC-LC and LC-GC/MS). Over 40 unsubstituted PAH and sulfur-containing polycyclic aromatic compounds and numerous al kyl -substituted PAH have been

identified from the Washington urban dust. Based on the current interest in

the determination of PAH in air particulate samples, SRM 1649 should find

widespread use in environmental analyses and serve as a useful benchmark

sample for interlaboratory comparison of PAH determinations and for methods

development.

6. Determination of Nitro-Polycyclic Aromatic Hydrocarbons Using Post-Column

Reduction to Fluorescent Amino Derivatives (11320, 51101 )

W. A. MacCrehan, W. E. May, W. J. Sonnefeld, C. R. Vogt

Nitro-polycyclic aromatic hydrocarbons (NPAH) are a class of compounds

of recent and increasing environmental concern. 1 -Nitropyrene and several

dinitro-PAH have been shown to be among the most potent mutagens studied by

the Ames assay. These compounds have been detected in gasoline and diesel

engine emissions and in urban air particulate samples. Thus it is important

to develop accurate measurement methods for NPAH.

Several avenues have been explored as possible means of selective and

sensitive detection of NPAH in complex matrices. One simple approach is to use UV absorbance detection at a wavelength of 405 nm. Some of the other

matrix constituents also absorb at this wavelength. We are presently using

this approach in conjunction with other detection methods. However, this

technique is not as sensitive or selective as we would like. We have also

evaluated the use of reductive amperometric detection of the nitro group at a glassy carbon electrode. The hydrodynamic current-potential curves and the

131
LC detection limits have been measured for six NPAH. However, the use of this

approach for gradient elution is quite cumbersome since oxygen must be rigorously excluded. The most promising approach for detection of NPAH appears

to be chemical conversion to the amines, which may be detected by either

fluorescence or oxidative amperometric detection.

The classical synthetic method for converting nitro compounds to their

corresponding amines is reduction by metals in the presence of acid. We have

adapted this approach with several constraints in mind. In order to achieve

optimal performance for the liquid chromatographic separation, the compounds

should be separated as the nitro derivatives, as the amines are often poorly

behaved in the chromatographic system. The conversion must be done in an on-line fashion with little band broadening. It is important to achieve a high yield in the reduction to achieve reproducible results. In particular,

the presence of unreduced NPAH must be minimized as these compounds have been

shown to be fluorescence quenchers and could interfere with the detection of

the amines formed. The pH of the solvent also has to be controlled as a compromise between sufficient acidity to favor the reduction:

R - N02 + 6H

+

+ 3M° + RNH2 + 2H 2 0 + 3M

+2

and yet not so acid as to protonate the aryl amine product:

R - NH2 + H +

-> R - NH 3 + pK

a

= 4.7

since the R - NH 3 + moiety is not fluoresent. Three pH values were tested:

5.0 and 5.8 (ammonium acetate/acetic acid) and 6.2 (ammonium succinate/succinic

acid) using zinc as the reducing metal. The fluorescence signal was diminished

about 15 percent at pH 5.0, with pH 5.8 and 6.2 giving equivalent signals.

Several metals were compared for their efficiency of reduction of NPAH to

amines. A small column (5 x 0.32 cm) was dry packed with fine particles (200

to 320 mesh) of each metal to be evaluated. This column was inserted after

the column and UV detector of the LC but in front of the fluorescence detector.

Using a 0.025 mol/L ammonium acetate buffer and a 1.0 mL/min flow rate, the

conversion efficiency was determined for 1-nitropyrene and 1 -ni tronapthalene.

Fairly large amounts of the test compounds were injected and the total volume

for the peak eluting from the column through the fluorescence detector was collected. A sample of this fraction was reinjected and monitored with the UV

detector. Two peaks were found for the "reduced" eluates: the expected amine

and a trace of the unreacted nitro compound. By comparison to an appropriate

standard, the conversion efficiency was evaluated. Zinc was found to give

efficiences of 97-100 percent whereas cadmium gave only 55 percent. Aluminum,

aluminum amalgamated with mercury, and magnesium were also evaluated but

produced tiny bubbles in the eluent stream (probably from the reduction of

hydrogen ion to hydrogen gas) and were thus unsuitable from a mechanical

standpoint for use in the reductor column.

The effect of the concentration of electrolyte was also studied using

zinc as the reductor packing. No conversion of the NPAH occurred when no electrolyte was used. As little as 0.001 mol/L of electrolyte caused substantial conversion, but the highest efficiency was found for a concentration

of 0. 1 mol/L buffer.

132
A gradient elution chromatographic separation was developed for NPAH

using the following compounds: 1-nitronapthalene, 2-nitrofluorene, 9-nitroanthracene, 2-nitronapthalene, 1-nitropyrene, and 3-nitroperylene. The

gradient program changed at 5 percent/minute from 60 percent CH 3 CN (0.025

mol/L NH4 0Ac pH 5.8) to 90 percent CH 3 CN (0.025 mol/L NH4 0Ac pH 5.8) at a 40

percent nonlinear rate. A chromatogram of an extract of the Washington Urban

Particulate Matter SRM is shown in figure 27. The upper trace is the 405 nm absorbance of the unchanged compounds and the lower trace is fluorescence

monitoring at 400 nm excitation (450 nm emission cut-off filter) after reduction in the zinc column. Only two peaks matched the retention time of our standards: 1-nitropyrene (1-NPyr) and 3-nitroperylene (3-NPer). Since this

is a direct extract with no prior fractionation, many of the peaks may be

compounds other than NPAH. In particular, quinones and simple polycyclic

aromatic hydrocarbons have been found in similar samples and would be detected

under these conditions. Current work involves fractionating diesel and air

particulate extracts to separate extraneous compounds from the nitro compounds.

We are also acquiring some quinones and dinitro-PAH to try to identify some of

the unknown peaks in these samples.

We are actively trying to acquire additional NPAH compounds and are measuring the fluorescence spectra and electrochemical current-potential

curves of the reduced compounds. This will allow us to choose the optimum

conditions for fluorescence or oxidative amperometric detection. Of particular

interest are the dinitro-PAH since they also have been found to be highly

mutagenic. They are present in much smaller amounts than the mononitro

compounds and will thus present more of a challenge for detector selectivity

and sensitivity.

133
Relative

Fluorescence

Absorbance

at

AOS

nm

Figure 27. Gradient elution liquid chromatographic

134
7. Methods for the Determination of Vitamins in Milk (14301)

J. M. Brown-Thomas , S. A. Margolis, L. Watts, R. B. Weker

The primary objective of this program is to develop new methods and to

apply established methods for the accurate measurement of organic nutrients,

including vitamins, in food materials. Specifically, we expect to initially

provide reference or certified values for organic nutrients in a proposed

nonfat, dry milk SRM. During FY 81 we examined methods for the measurement of

Vitamin D, lactose, and nicotinic acid. During the past year, we have improved

the extraction methods for nicotinic acid and completed our work on Vitamin D and lactose. During FY 83 we anticipate completing our SRM measurements on nicotinic acid and beginning work on thiamin, lactic acid, and pyridoxine.

The accepted methods for the extraction of nicotinic acid from food

matrices, such as autoclaving in strong acid or base, are harsh and lead to

the formation of many undesirable products. Therefore, we have developed a milder extraction procedure using sul fosalacyl ic acid (SSA) as a protein

precipitant in the presence of hydrochloric acid. This procedure allows the

quantitative extraction of added nicotinic acid from milk samples. However,

the use of this extraction method requires the modification of the analytical

procedure to remove the highly UV-absorbing SSA before nicotinic acid analysis.

This was achieved by using multidimensional chromatographic analysis. The

sample was applied to an octadecylsilane (ODS) reversed-phase column which

preferentially retained the SSA. The nicotinic acid was subsequently adsorbed

onto an ami nosilane column (connected in series to the ODS column) and eluted

with a phosphate buffer gradient. This method allows the quantitation, of

nicotinic acid in milk samples which have been supplemented with 62 yg of

nicotinic acid per gram of milk powder (containing 10 yg of native nicotinic

acid by microbiological assay). The research to complete development of this

assay procedure will include the refinement of the chromatographic process and

development of a process for weak basic hydrolysis of the covalently bonded

nicotinamide and its conversion to nicotinic acid.

The method developed for the analysis of Vitamin D involved the use of

enzymatic (lipase) hydrolysis, HPLC separation of Vitamins D2 and D 3 from the

milk matrix with Vitamin D 3 as the internal standard, and a sequential HPLC

procedure for final separation and quantitation. The lipase hydroyzate was fractionated on a cyanopropyl si 1 ane (CN) column using a 2 percent isopropyl

alcohol/hexane mobile phase. Fractionation of a milk extract on a CN column

is illustrated in figure 28. The lipase hydrolyzate fraction is between the

dashed lines. Vitamin D2 was separated from Vitamin D 3 and other co-extracted

components by chromatography of the Vitamin D containing fraction on an acetonitrile mobile phase (figure 29). The D vitamins were measured by UV

detection at 267 nm. The results of the analysis of Vitamin D2 in a coirmercial

milk formulation and in the SRM candidate dry milk material are summarized in

Table 22.

The lactose content of the SRM candidate dry milk material was measured by

HPLC utilizing a carbohydrate column. The lactose was eluted with 80 percent

acetonitrile/water and measured with a refraction index detector (figure 30).

By use of an external standard, the lactose content was found to be 44±1 percent

(g/g) in the candidate SRM and 34±1 percent (g/g) in a commercial milk sample.

135
Figure 28. Fractionation of a milk extract

on a CN column.

Figure 30.

no

Analysis of a milk fraction for Vitamin D2 on a reversed-phase column.

t>M

o

u

O

Analysis of lactose in

a milk sample on a reversed-phase column.

136
Table 22. Concentration of Vitamin D 2 in Dry Milk.

Samp! e

Commercial Fortified Material -Box 1 Commercial Fortified Material -Box 2 Commercial Fortified Material -Box 3

Unfortified SRM candidate

D ? (ng/g mil k ± SD)

83 ± 3

a

70 ± 3

95

<10

a ± values represent standard deviation of a single measurement.

8. Certification of an SRM for the Anticonvulsant Drugs Carbamazeplne and

Valproic Acid in Serum (14306)

D. P. Enagonio, W. F. Kline, W. E. May, D. J. Reeder

In 1978, the NBS Office of Standard Reference Materials (OSRM) issued

Standard Reference Material 900, Antiepilepsy Drug Level Assay Standard.

SRM 900 contained four anticonvulsant drugs, phenytoin, ethosuxlmide , phenobarbital, and primidone. Since 1978, two additional drugs, valproic acid

and carbamazepine, have become significant in the treatment of epilepsy.

Consequently, a need exists for a Standard Reference Material containing

these drugs. This year, the NBS OSRM will issue SRM 1599, which will contain

valproic acid and carbamazepine at three concentration levels in freeze-dried

human serum. Two independent analytical procedures were developed and used

to certify the concentration levels of each drug in SRM 1599.

Determination of the drug levels by high performance liquid chromatography (HPLC) required a separate analytical procedure for each drug. Valproic

acid was determined by a pre-column derivatization procedure in which valproic

acid and an internal standard (cyclohexane carboxylic acid) were converted to

their respective phenacyl esters after extraction from the serum matrix. The

derivatized species were then measured by HPLC with UV absorbance detection at

254 nm. The concentration of valproic acid in the samples was determined from

the area ratio of the derivatized valproic acid and internal standard versus

the concentration of valproic acid in working standards.

The concentration levels of carbamazepine were determined by direct

injection of reconstituted serum onto an HPLC reversed-phase column with 285 nm

UV detection. Quantitation was accomplished by using bracketing external

standards prepared in blank serum with concentrations around the target values

of each SRM concentration level. We found it necessary to prepare external

standard solutions in the blank serum rather than in an organic solvent, to

correct for binding of carbamazepine to serum protein.

For the gas chromatographic (GC) analyses, known amounts of suitable

internal standard compounds (cyclohexane carboxylic acid for valproic acid and

cyheptamide for carbamazepine) were added to samples of the SRM, prior to

extraction and analysis. The drugs and internal standards were extracted from

137
the reconstituted SRM with chloroform. The chloroform layer was removed and

concentrated to 50-200 yL. Multiple injections of these concentrates were made into the gas chromatograph.

The peak area ratio of drug to internal standard was compared with that

similarly obtained from calibration samples. The calibration samples were

s prepared from blank serum to which known amounts of drug and internal standard were added. For each measurement, two calibration samples were used; one in

which the concentration of drug and internal standard was 5 percent greater

than the nominal concentration of drug in the SRM sample, and the other in

which it was 5 percent less.

Tables 23 and 24 summarize the results obtained from each of the two

independent procedures used in the certification of this SRM. Data reflecting

the matrix effect associated with the HPLC determination of carbamazepine are given in Table 24. The certified concentration levels given in Table 25 are weighted averages of the results obtained from the GC and HPLC methods. The

range gives an indication of the uncertainty of the certified value.

Table 23. Summary of Results Obtained

for Valproic Acid.

from Analysis of SRM 1599

Concentration

Level

Target Cone.

(yg/mL)

Measured Cone. , yg/mL

HPLC GC

High 145 144.5 ± . 89

a 140.4 ± .78'

Medium 65 67.0 ± .93 71 .2 ± .42

Low 15 14.6 ± .25 14.3 ± .08

Uncertainties are expressed as the standard deviation of the mean concentrations.

Table 24. Summary of Results

Carbamazepi ne. Obtained from Analysis of SRM 1599 for

Concentration

Level

Target Cone.

(yg/mL)

Measured Cone., yg/mL

HPLC

a HPLC

b

GC

High 19.9 17.5 ± 0.30

c 19.9 ± 0. 27

c 18.9 ± 0.05

Medium 9.4 8.20 ± 0.31 8.94 ± 0.04 8.60 ± 0.06

Low 3.0 2.60 ± 0.2 2.60 ± 0.03 3.0 ± 0.13

a Ignores matrix effect, external standard made up in acetonitrile/water.

^Corrects for matrix effect, external standard prepared in serum base.

r Uncertainties are expressed as the standard deviation of the mean concentrations.

138
Table 25. Certified Concentrations for SRM 1599 (yg/mL)

Valproic Acid Carbamazepi ne Low

Level

Medium

Level

High

Level

Low

Level

Medium

Level

High

Level

Concentration

level

14.5 69.1 142.5 2.8 8.8 19.4

Range of

between

results

methods

0.3 4.2 4.1 0.4 0.3 0.9

9. Research Results on the Analysis of Polychlorinated Biphenyls in Oils

(14660, 14306)

S. N. Chesler, F. R. Guenther, R. M. Parris, R. E. Rebbert

The hybrid technique developed in our laboratory that utilizes both high

performance preparative scale liquid chromatography and capillary column gas

chromatography for the determination of polychlorinated biphenyls (PCB's) in

hydrocarbon matrices has been used in the certification of a Standard Reference

Material (SRM 1581) and for the analysis of 11 PCB-in-Oil NBS/ASTM round robin

samples

SRM 1581, Polychlorinated Biphenyls in Oil, consists of separate solutions

of Aroclor 1242 and Aroclor 1260, each in a transformer oil and a motor oil

base. Certified concentrations are listed in Table 26. This SRM is designed

to be used as an external standard for analytical calibrations as well as a benchmark for interlaboratory comparisons. This SRM will be especially useful

to the electrical industry where PCB contamination of transformer cooling

fluid is of present concern, and in the motor oil recycling (re-refining)

industry where inadvertent contamination of the recycling stock by PCBcontaining fluids is a problem.

Table 26. SRM 1581, Polychl orinated Biphenyls in Oils, Certified

Concentrations of Aroclor 1242 and Aroclor 1260 in

Motor and Transformer Oils.

Matrix Aroclor Type Concentration, yg/g

d

Motor Oil 1242 100 ± 1 Motor Oil 1260 100 ± 2 Transformer Oil 1242 100 ± 1 Transformer Oil 1260 100 ± 3

Uncertainty is expressed at the 95% confidence level.

139
In order to evaluate currently-used methods for the determination of

Aroclors in oil matrices, a collaborative study was conducted by us, the NBS

Recycled Oil Program, and the American Society for Testing and Materials (ASTM

Committee D-2). Sets containing 11 oil samples representati ve of a range of

PCB contamination in terms of Aroclor type and concentration were prepared and

distributed to 19 laboratories. The oil matrices ranged from a virgin motor

oil base to a used lubricating oil that had been collected for recycling

purposes. All samples were gravimetrically prepared by us, except samples D and H which were used as supplied by the Office of Recycled Materials. Table

27 lists descriptions of the round robin samples and the results of our analyses as one of the participating laboratories. A chromatogram of sample

J (see Table 27) is shown in figure 31. Quantitative data obtained and

descriptions of the analytical technique used by each laboratory have been

compiled and are being evaluated to identify accurate and efficient methods

for the analysis of oils for PCB contamination.

Table 27. NBS/ASTM Round Robin Samples.

Code Sample NBS Results, ug/g

a

A 5.9

D ppm Aroclor 1 260/BC7345 oil 6.2 + 0.3 Aroclor 1260

B,F

C 41.0 ppm

b Aroclor 1 242/BC7345 oil 41 + 1 Aroclor 1242

C 148.3 b

ppm Aroclor 1 260/BC7345 oil 147 + 4 Arocl or 1260

D BC7345i motor oil Not Detected 0

E ,G

C 41 .0 PPm? Aroclor 1242 and 41 + 1 Aroclor 1242

19.9

D ppm Aroclor 1 260/BC7345 oil 19.8 + 0.6 Aroclor 1260

H BC7227 oil 165 + 10 Aroclor 1260

I 96.6

b

ppm Aroclor 1254/used oil 5482 80 + 7 Aroclor 1254

J 1 :9

b #81-:355-H oil/used oil 5379 25.4 + 0.7 Aroclor 1242

48 + 5 Arocl or 1254

40 + 3 Aroclor 1260

MOt

°BC7425

A

oii

tiVe (CR' 82R 5°° 5)/ No rec°8" izi» ble PCB Pattern

a 0ne LC fractionation, three GC runs; uncertainty expressed as 1 std. dev.

bwt/wt

.

duplicate samples.

^Detection limit of <1 ppm Aroclor.

140
141

Time

(min)

Figure

31.

Gas

chromatogram

of

HPLC

fraction

of

NBS/ASTM

round

robin

sample
1 0 . Analysis of a California State Reference Material for Pesticides in

Sediment (14625)

S. N. Chesler, W. F. Kline

We have completed an analysis of a California State Department of Health

Services (CSDHS) "Pesticides on Soil" test material. This material was prepared by CSDHS and consists of a soil spiked with six chlorinated pesticides

at the yg/g level. This material will be used by CSDHS for proficiency

testing of laboratories participating in a CSDHS study of hazardous waste

analytical methodology. NBS was asked to analyze this material because CSDHS

wanted confirmation of its own analysis prior to releasing this material for

proficiency testing. NBS participated to satisfy CSDHS concerns as well as to gain experience in this analytical area.

The CSDHS test soil consisted of a finely divided dry sediment. Three

5.00 g soil samples were Soxhlet extracted with 300 mL of a 1:1 mixture of

hexane and acetone. Prior to extraction, 3 mL of aqueous 0.2 mol/L NH4 Cl were

added to the sediment to assure sample wetting during extraction. In addition,

9.74 yg of pentachlorobenzene and 10.38 yg of 2,2' ,4,4' ,5 ,5 ' -hexachl orobi phenyl

in 1 mL of hexane were added to each unextracted sample to serve as internal

standards (IS). Two solutions containing known amounts of each analyte and

each internal standard were also Soxhlet extracted for determination of

analysis response factors.

All samples were Soxhlet extracted for 18 hours and the extracts were analyzed by gas chromatography (GC) with electron capture detection. The GC was equipped with an immobilized phase wall -coated fused silica open tubular

column. Duplicate analyses of the calibration solutions were used to determine

gram response factors which were subsequently employed in the internal standard

calculations for the sediment extracts. Independent calculations of the six

analyte concentrations were made using each of the two IS compounds. The

three sample extracts were analyzed at least in triplicate, and the results

are exhibited in Table 28 along with the results obtained by CSDHS.

The results listed in the table are sufficiently encouraging that we are planning to propose that a pesticides on soil Standard Reference Material

(SRM) be funded for issuance in FY 84. This SRM could be used as a primary

standard for calibration of such complex analyses, and as a primary standard

against which proficiency testing samples such as the one being released by

the CSDHS could be evaluated.

142
Table 28. Results

Spiked

yg/g

of Analyses of Pesticide Test

NBS

a

Material

CSDHS

L.CV C 1 Mean S . D.

b

% S.D. Mean S.D. % S.D

Lindane 8 7.63 .16 2 7.68 .48 6

Heptachlor 6 4.08 .10 2 4.65 .51 11 Aldrin 3 3.08 .10 3 2.91 .22 8

Heptachlor Epoxide 8 7.37 .17 2 7.32 .59 8

Dieldrin —C

1.64 .04 2 1.44 .19 13

p

,p ' -DDT 4 4.01 .18 4 3.76 .31 8

a Based on analyses of replicate samples.

^Standard deviation of the mean (la).

c Natural contaminant in the soil.

1 1 . Design and Construction of a Sampling System for Woodburning Stove Gases

and Particulate Samples (25005)

F. R. Guenther

To assess the relative contribution of woodburning stove emissions to

respirable atmospheric particulate matter, profiles of gas and particulate

discharge must be examined. Although both organics and inorganics can be

utilized in this profile, the carcinogenic and mutagenic properties of some organics increase the importance of the organic contribution. During the past

year, a preliminary study of the organic emissions from a wood stove has been

completed.

In this preliminary study, collection and analysis of the phenolic fraction from the wood stove stack emissions has been emphasized. The sampling

system consisted of a Pyrex gas sampling tube inserted through the walls of

the stack into the center of the flow stream. The emission gases were drawn

through this tube and through a porous polymer XAD-2 trap. The organics

contained on the trap were removed by extraction with methylene chloride. The

extraction was done immediately after sample collection. An internal standard

was added to the extract after extraction, the sample was evaporatively con- centrated and injected onto a semi preparative ami nosilane liquid chromatographic column, and the fraction of the eluent containing the phenols was collected. This fraction was then evaporatively reconcentrated and analyzed

by gas chromatography with a low-bleed, medium-polarity capillary column

(DX-2)

Condensable organics were collected on a fine mesh screen inserted into

the stack below each gas sampling port. These screens were extracted with

methylene chloride in a sonic bath and analyzed by the same procedure outlined

above.

143
Collection positions were located at the bottom and top of the stove

stack. The wood stove utilized in these experiments was equipped with a baffle electronically controlled to limit stack temperatures to within 10 °C

of a preset value. Collections were made at stack temperatures of 80-90 °C,

110-120 °C, and 140-150 °C.

The preliminary findings showed that 1) the relative amounts of individual

phenolic species from this wood stove were essentially constant at the temperatures examined, 2) approximately 5-13 percent of the phenols present in the

gas stream at the bottom of the stack was removed to the stack walls before

reaching the top collection port, 3) phenolic production in the wood stove is

inversely proportional to stack temperatures.

Plans for next year include: 1) redesigning the collection system, such

that inorganics can also be determined (inorganic analyses will be done under

the direction of Dr. William Zoller at the University of Maryland);

2) analyzing other compound classes such as polycyclic aromatic hydrocarbons,

nitrogen-containing polycyclic aromatic compounds, ketones, and aldehydes;

3) collection from residential fireplaces and stoves; and 4) collection from

newly designed wood stoves, such as those equipped with catalytic converters.

12. Development of Methods for the Determination of Toxic Organic Compounds

in Aqueous Leachates of Hazardous Wastes and Development of a Quality

Assurance Sludge Material (14215, 14626)

D. P. Enagonio, L. R. Hilpert, C. R. Vogt

Over the past few years, increasing concern has been expressed over the

potential adverse environmental and health effects associated with hazardous

wastes. The Resource Conservation and Recovery Act of 1976 requires the

identification of hazardous wastes based, in part, on chemical characterization of the waste and, in part, on the mobility or Teachability of toxic

chemical components of the waste. During the past year, we have developed

measurement methods for the analysis of toxic organic compounds in aqueous

leachates of hazardous wastes and methods for the preparation and analysis

of a quality assurance sludge material.

One of the several promising processes for the conversion of coal to

liquid fuels is the solvent refined coal (SRC II) process. One aspect of the

process still under investigation is the handling of the vacuum still bottom

solid waste material. An SRC II vacuum still bottom material was characterized

by gas chromatography/mass spectrometry (GC/MS). A sample of ground material

was extracted with methylene chloride, and an aliquot of this extract analyzed

by GC/MS on a 30 m SE-52 fused silica capillary column. The total ion chromatogram is shown in figure 32. Most of the peaks identified were polynuclear

aromatic hydrocarbons (PAH).

144
(a) phenanthrene (q) m/e 266

(b) anthracene « m/e 252 benzofluoranthene

(c) Carbazole & Ci-subst (S) benzo[e]pyrene

phenanthrene/anthracene (t) benzo[ajpyrene

(d) Ci-subst phenanthrene/ (U) perylene

anthracene (V) m/e 266

(e) fluoranthene (w) m/e 278 12 isomers

(f) pyrene (X) m/e 276

(g) Ci-subst fluoranthene/pyrene (y) m/e 276

9 isomers

(h) Ci-subst fluoranthene/pyrene (Z) m/e 276

0) Ci-subst fluoranthene/pyrene (aa) m/e 276

0) m/e 252 (bb) m/e 290

00 benz[a]anthracene (cc) m/e 276

0) chrysene/triphenylene (dd) m/e 290

(m)

(n) m/e 252 lefrtmare m/e 252 i 16lsomers (ee)

(ff) m/e 290

m/e 290

15 isomers

(o)

(P)

m/e 266 ( iK

m/e 266 , 15lsomers

Figure 32. Total ion chromatogram of CH2 C1 2 extract of SRC II vacuum still bottoms material.

Aqueous leachates of a homogenized SRC II vacuum still bottom material

(particle size 250 um) were prepared using the EPA (dilute acetic acid) leach

procedure [1], and the ASTM-A (distilled water) leaching method [2]. The

leachates were carried through a solvent extraction scheme to isolate the

acids and base-neutral compounds. The extraction scheme was developed and

tested using a series of synthetic aqueous leachates. The method efficiently

extracted 20 target analytes from water at the 10 yg/L level. The organic

extracts of the SRC II vacuum still bottom leachates were analyzed by GC/MS in

the selected ion monitoring (SIM) mode for quantitation, and the full scanning

mode for confirmation of identifications. The results of the quantitative

determinations are shown in Table 29.

145
Table 29. Concentrations of Compounds in Bulk Aqueous Leachates of

SRC II Vacuum Still Bottom Material.

Concentration (M9/L)

a

Analyte ASTM-A Leachate EPA Leachate1

2-picol ine 0.24 ND

C

phenol 6.68 1.09

o-cresol 1.63 0.18

naphthalene 0.38 0.20

qui nol i ne 0.39 ND

1 ,4-naphthoqui none 0.15 0.08

dibenzothiophene 0.02 ND

phenanthrene 0.06 0.05

carbazole 0.76 0.46

fl uoranthene 0.02 0.02

a Values are the average of two determinations.

^This is commonly referred to as the EP leach procedure.

c Not detected.

The direct hydrogenation process for the conversion of coal to liquid

products is known as the H-coal process. Aqueous leachates of a solid waste

from the H-coal process were also extracted and analyzed by GC/MS. Concentrations of organics in the H-coal leachate we examined (see Table 30) were significantly higher than in the leachate of the SRC II vacuum still bottom

material. It should be noted that the wastes we examined may not be representative of the SRC II and H-coal processes in general. The H-coal sludge

is being analyzed by five laboratories to determine the interlaboratory

variability in the leaching and analysis of a waste material. The results

from this study will help to refine methods for the leaching and analysis of

hazardous wastes.

Work was initiated this year on the preparation and analysis of a quality assurance sludge for the EPA. The initial step involved selection of a suitable sludge material. Selection criteria included: 1) a material which

contained "toxic" organic compounds at trace levels (1-50 ppm); 2) a material

in which the target analytes were stable; and 3) a material which could be

analyzed with current EPA methodology.

146
Table 30. Concentrations of Compounds in EPA Leachates of H-Coal Material.

Analyte Cone. (yq/L)

a Analyte Cone. (pg/L)

a

pi coline ND

b

1 -naphthyl amine 2.6 ± 0.3

phenol 241 ± 20 4-ami nobiphenyl ND

o-cresol 97 ± 6 dibenzothiophene 4 ± 1 naphthalene 257 ± 9 phenanthrene 71 ± 13

quinol ine 34 ± 8 carbazole 322 ± 44

1 ,4-naphthoqui none ND fl uoranthene 10 ± 4

acenaphthylene ND benz[a]anthracene 2.4 ± 0.6

2-naphthol

A

12 ± 0.1

a Values are the average of three determinations ± the standard deviation

based on 2 degrees of freedom.

b

Not detected.

A liquid waste has been selected for analysis. The following target

analytes are to be determined in the sludge: phenol, m-dichlorobenzene,

pentachlorophenol , hexachlorobenzene, phenanthrene, fluoranthene, benzidine,

pyrene, n-propyl phthalate, benz[a]anthracene, and dioctyl phthalate. The

target analytes are not natively present in the sludge, therefore, the material

will be fortified by addition of the compounds to bring the concentrations

within the 10-50 ppm range.

A gas chromatographic method utilizing high-resolution capillary columns

with flame ionization detection has been developed for quantitative measurement of all of the analytes, except the phenol and m-dichlorobenzene. These

compounds will be determined by GC/MS with selected ion monitoring. Plans for

next year include an interlaboratory comparison to evaluate variability and

laboratory accuracy in the analysis of this liquid sludge.

References

[1] "Test Methods for Evaluating Solid Wastes: Chemical /Physical

Properties," Federal Register 45: 98; May 19, 1980.

[2] "Proposed Methods for Leaching of Waste Materials," 1979 Annual

Book of ASTM Standards, Part 31.

147
13. GC/MS Determination of Acidic and Basic Compounds in a Shale Oil Process

Water (11320)

L. R. Hi 1 pert, K. L. Richie

Over the past few years, there has been an increasing concern over the

potentially toxic compounds associated with the processing of alternate

fuels. Some of these organic compounds may eventually be transported into the

environment as gaseous or liquid effluents. In order to evaluate potential

environmental impact, feedstocks, process streams, fuels, and effluents must

be analyzed for their trace organic compound content. The results of these

analyses cannot be evaluated without knowing the accuracy of the analytical

data obtained. To begin assessing the accuracy of the methodology and analytical data, we have developed interlaboratory comparison materials which can

be used to assure comparability among U.S. Department of Energy laboratories

and NBS. The participating laboratories, known as the DOE/NBS Analytical

Characterization Group, regularly conduct studies in the quantitative analysis

of trace organic constituents in materials such as shale oil, solvent refined

coal, and aqueous effluents obtained during production of these alternate

energy sources. The participants also meet to discuss the strengths and

weaknesses of the analytical methods as well as results of interlaboratory

comparison studies.

As a result of discussions held at recent Analytical Characterization

Group meetings, the DOE/NBS program is currently focusing on intercomparison

studies of a shale oil process water. High resolution capillary column gas

chromtography/mass spectrometry (GC/MS) with selected ion monitoring has been

used to quantitate organic acids and bases at the yg/mL level in a shale oil

process water.

Process water, which was obtained from a simulated in situ retort, was subjected to simple acid/base extractions to isolate basic and acidic components. The extracts were concentrated and analyzed by GC/MS. Figure 33 shows

a total ion chromatogram of the organic acids extracted from the process

water. The normal aliphatic acids and phenol are identified.

Quantitative determinations were made by GC/MS with selected ion monitoring using a standard addition technique. NBS results are listed in Table

31 together with the results reported by the other participating laboratories.

Results by our laboratory for the basic compounds are listed in Table 32.

Results from the participating laboratories have not been reported at this

time.

As seen in Table 31 there is a wide range among the values reported by

the various laboratories, which strongly emphasizes the need for the continuing

development of accurate analytical methodology and for interlaboratory

compari sons

.

The Analytical Characterization Group will meet in November to discuss

and compare the results and methods used in current analyses as well as to

decide upon the next material for an interlaboratory comparison study.

148
149

Figure

33.

Total

ion

chromatogram

of

GC/MS

analysis

of

organic

acids

and

phenol

in

a

shale

oil

process

water.
Table 31. Interlaboratory Comparison of Shale Oil Process Water Analysis.

Concentrations (yg/mL)

NBS Lab 1 Lab 2 Lab 3 Lab 4 Lab 5

n-Butanoic acid 50±8a 17.0 70± 1

95 52 82.3±7.4

n-Pentanoic acid 72±9 — -- 130 90 -- n-Hexanoic acid 88±4 54.6 107± 5 160 91 86.4±8.6

n-Heptanoic acid 1 49± 9 -- — — 94 -- n-Octanoic acid 140±8 — — — 96 -- n-Nonanoic acid 82±5 -- — -- 62 -- n-Decanoic acid 38±2 — — -- 23 -- Phenol 16±4 31.6 32± 4 25 19 17.211.2

Precision expressed as one standard deviation of the mean for three standard

addition experiments.

Table 32. NBS Analytical Results for Basic Compounds in a Shale Oil Process Water.

Concentration

Compound (yg/mL)

Aniline 1 .3 ± .2

a

2,4,6-Trimethylpyridine 21.7 ± 1.8

Isoquinoline .8 ± .06

Precision expressed as one standard deviation of the mean for three standard addition experiments.

14. Development of an Isotope Dilution/Mass Spectrometric Definitive Method

for the Determination of Serum Urea (11320, 14306)

A. Cohen, H. S. Hertz, R. Schaffer, L. T. Sniegoski, M. J. Welch,

E. White V, W. T. Yap

Definitive methods provide the clinical chemistry community with an accu- racy base to which reference, and ultimately, field methods can be compared.

We have been involved for several years in the development of definitive

methods for organic serum analytes and have successfully developed such

methods for cholesterol, glucose, and uric acid. Another clinically important

analyte is serum urea, which is used as a measure of kidney function and in

protein metabolism studies. Work has now been completed on a method for serum

urea which is of sufficient accuracy and precision to be considered a definitive method.

150
This method utilizes isotope/ dilution mass spectrometry, as have all of

the other definitive methods for organic serum analytes. A brief description

of the method is as follows: A weighed quantity of urea- 18 0 is added to a known weight of serum such that the labeled/unlabeled urea ratio is near 1:1.

After an equilibration period, the sample is freeze-dried and the urea is

extracted from the residue and sublimed. The sublimate is added to a mixture

of diketene and glacial acetic acid in a vial, which is then sealed and heated

at 82-84 °C for two days. Under these conditions urea is converted in high

yield to 6-methyluraci 1 . After the solvent and unreacted diketene are evaporated, bis(trimethylsilyl )acetamide is added to convert the product to

6-methyluraci 1-diTMS. Calibration standards, consisting of known amounts of

the labeled urea- 18 0 and pure Standard Reference Material (SRM) 912, Urea,

are also converted to the derivative. For each sample, the two standards,

whose unlabeled/labeled weight ratios most closely bracket that of the sample,

are selected. The sample and its two standards are injected onto a 30-meter

SE-30 SCOT gas chromatographic column operated at 125 °C in the following

sequence: One standard is injected, followed 5-1/2 minutes later by the

sample and 11 minutes later by the other standard.

+ After a 25 minute retention time, the ion abundance ratios for the (M- 15) ions at m/z 255 (unlabeled)

and 257 (labeled) are measured for each of the three peaks. Measurements are made in the electron impact (El) mode at 70 eV, utilizing magnetic field

switching. The ratio from the sample is compared, using linear interpolation,

with the ion abundance ratios from the standards to find the quantity of

unlabeled urea in the sample. For each sample, measurements are repeated, on

a second day with the order of standards reversed, and the mean of the two

days' measurements is taken as the reported result.

Because of contributions of the labeled urea derivative at the mass monitored for the unlabeled derivative, and vice versa, the relationship

between weight ratios and ion abundance ratios is not truly linear. A mathematical study was performed to find the maximum error possible when linear

interpolation was used with our bracketing standards. The worst case, which

occurs when the ratios of the two standards are the farthest apart and the

bracketed sample falls midway between the two, was found to be less than 0.04

percent for our standards. Thus linear interpolation can be used without

correction. A description of this mathematical study has been submitted for

publication in Biomedical Mass Spectrometry .

The method was used to measure urea levels in both freeze-dried and

frozen serum pools. Three sets of samples were prepared from SRM 909, a freeze-dried human serum pool. Each set consisted of two samples from each of

three vials of SRM 909. The results are summarized in Table 33, including the

overall mean value which is the certified concentration for the SRM.

As a test for hidden interferences in the above measurement conditions,

two samples from each set were remea^red using different pairs of ions;

first, El measurements of the (M-30) ions at m/z

+ 120 and 121, and second,

chemical ionization (Cl) measurements of the (M+l) ions at m/z 271 and 273.

These results, along with the previous results for those six samples, are shown in Table 34.

151
Table 33. Urea Levels Found in the Human Serum SRM by the

ID/MS Definitive Method (6 samples per set).

Mean C

V

Set mg urea/g serum pellets %

1 7.236 0.07

2 7.249 0.17

3 7.247 0.06

Statistical Summary: Mean = 7.244; CV's - replicates

0.14%, sets 0.10%, reproducibility 0.17%.

Standard error of average = .00439, CV = 0.06%.

Table 34. Urea Levels Found in Six Human Serum SRM Samples Using

Three Different Pairs of Ions.

Mean

Ions Measured mg urea/g serum pellets

CV % Difference from

% (255/257) Results

255/257

120/121

271/273

7.242

7.239

7.240

0.12

0.12 -0.05

0.12 -0.03

The urea level was also measured in five frozen serum pools from a Centers for Disease Control round robin study. Three sets, each consisting

of one sample per pool, were independently prepared. The results are shown

in Table 35.

Table 35. Urea Levels Found in Five Round Robin Frozen Serum Pools

by the ID/MS Definitive Method.

Pool

Mean

mg urea/g serum

CV

%

Control 1 Control 2 Unknown 7 Unknown 8

Unknown 9

.2393

.8828

1.525

.3564

.8259

0.13

0.14

0.23

0.13

0.15

One sample from each pool was remeasured using the alternate ions. The mean differences from the results for the 255/257 ions were +0.03 percent for

the 120/121 ions and +0.01 percent for the 271/273 ions. These pools were

also analyzed at CDC by the coupled-enzyme candidate reference method. Their

results for the five pools differed from our results by -0.58 percent to +1.15

percent, differences which are small compared with the imprecision of their

measurements, thus providing strong evidence that no serious systematic bias

exists between the two methods.

152
For a method to be considered definitive, the results must be free of

significant bias and be of high precision. This ID/MS method for urea has

provided high precision results for both freeze-dried and frozen serum. Confirmatory measurements at alternate ions demonstrate that no significant

biases exist among the three measurement conditions. Thus the probability of

a hidden interference is very small, since such an interference, to remain

undetected, would have to co-el ute with the 6-methyl uraci 1 -diTMS and contribute proportionally the same at the three ions measured. No other source of

significant bias has been found, therefore, the requirements for a definitive method have been satisfied. A manuscript describing the method is in

preparation.

Development of definitive methods for creatinine and triglycerides is

in progress and a method for digoxin is in the planning stage. Each method

developed will be used to certify the concentration of the corresponding

analyte in the Human Serum SRM.

15. Improved Instrumentation for Organic Isotope Dilution/Mass Spectrometry

Measurements (11320, 14301)

S. Meiselman, F. Ruegg (550), R. Shideler (550), M. J. Welch, E. White V

Our ongoing project to develop definitive methods for organic serum

analytes requires instrumentation of high stability to provide the necessary

precision. All of our work to date has been with serum analytes present in

relatively high concentrations. As future work turns to analytes in lower

concentration, our instrumentation must be even more stable than before, if we are to continue successful development of definitive methods. Our approach to

improved instrument stability has been to seek to upgrade existing instrumentation, rather than to purchase costly, new systems. In recent years, upgrades

have included replacement of the mass spectrometer source diffusion pump with

a turbomolecular pump for reduction of pressure fluctuations, installation of

a pressure regulated flow system in the gas chromatograph, installation of a variable splitter at the head of the GC column, and the use of fused silica

tubing for the transfer line in the GC/MS interface.

Recently we have replaced both the multiple ion monitoring system and our

old data handling system with a new system assembled principally from components

available in the NBS storeroom. The new system, diagrammed in figure 34, is

designed to provide computer control for certain instrument parameters which

have to be rapidly and reproducibly changed, as well as to handle data acquisition and reduction. A 64 K microcomputer controls switching of the magnetic

field for each measurement cycle, through a 16 bit digi tal -anal og converter

(DAC). After each switch of the magnetic field, the computer waits for a signal indicating that the field has stabilized before generating a triangular

waveform through a ±150 volt power supply. This waveform, whose frequency and

amplitude are computer controlled, is sent to the mass spectrometer detector

beam deflection plates a preset, integral number of times for each measurement

cycle. This provides for more reproducible data acquisition than achieved

with the old system in which the waveform was generated continuously and the

measurement began at random points across the waveform. The ion intensity

signal generated by the electron multiplier is fed through a solid state

153
o

c

g> in

>*

</> C

cl> _cc

o

154

Figure

34.

Diagram

of

the

upgraded

organic

isotope

dilution

mass

spectrometer

system.

*New

components.
preamplifier, built at NBS, which provides better stability and linearity of

response than the vacuum tube device which came with the mass spectrometer.

The signal, after passing through the original amplifier for the mass spectrometer, is digitized by an analog-digital converter (ADC). The computer

generates two real-time displays of the data; numerical data is shown on a CRT, and an analog signal is sent to a strip chart recorder for display of the

ion chromatograms for the unlabeled and labeled species. After data acquisition is complete for each sample, the computer corrects the accumulated data

for baselines measured before the elution of the analyte and calculates the

ratio of the corrected ion abundances of the labeled and unlabeled species.

The ratios are displayed on the CRT and the accumulated counts and ratios are

fed to a printer for permanent record. The computer is interfaced to a dual

disc drive for access to operating programs, and parameter files for each

analyte.

The new system exhibits improved precision and greater reliability,

enabling us to measure serum urea levels with an overall relative precision

of 0.17 percent, compared with 0.2-0. 4 percent overall precisions for

cholesterol and glucose with the old system. The computer provides the

capability of controlling other instrumental parameters and modifying our data acquisition and reduction as necessary.

Our most recent system upgrade has been installation of an NBS-built

circuit to control the ion source temperature in the mass spectrometer.

Previously, the ion source temperature changed while measurements were being

made and corrections were through manual adjustments in the heater current.

The new circuit senses the temperature in the source and adjusts the heater

current appropriately. This improvement simplifies the operator's task and we also expect it to make ion source conditions more stable, leading to better

preci sion.

Plans for further improvements include acquisition of an electron-impactonly ion source for the instrument to use in conjunction with our combined

electron-impact chemical -ionization source. Such a source, optimized for one mode of ionization, is expected to provide more stable operation in that mode

than is possible with the combination source. We also plan to test a new ion

selection method in which the magnetic field is held constant and the ion beam

is switched at the deflection plates. Such a system should allow for less

delay time between measurement cycles since magnetic hysteresis effects, which

now limit the switching rate, will be avoided. The major effort required for

this new technique is the generation of the necessary software for the existing

system.

155
16. Preparation of Solutions of Stable Isotope Labeled Marker Compounds for

Use in the Analysis of Priority Pollutants (14220)

J. M. Brown-Thomas , S. N. Chesler, D. P. Enagonio, F. R. Guenther,

W. F. Kline, W. E. May, R. M. Parris, R. E. Rebbert, L. T. Sniegoski,

E. White V

A "Master Analytical Scheme" being developed by contractors of the

Environmental Protection Agency is intended to allow qualitative and quantitative analysis of priority pollutants in water by gas chromatography/mass

spectrometry. This scheme provides for the analysis of "purgeable," "extractable," and "intractable" organic compounds in surface and drinking water and

in industrial, energy-related, and municipal effluents. Nominal lower

quantifiable limits are 0.1 yg/L for drinking water, 1 yg/L for surface water,

and 10 yg/L for effluents. A similar "Comprehensive Scheme for Soils,

Sediments, and Sludge" is also being developed. For use in these analytical

schemes, NBS has developed internal standards consisting of solutions of

deuterated organic compounds in water or methanol. The standards are to be

added to a specified sample volume. For analysis of "purgeables ,"

1 yL of the

standard solution in methanol in a 1 yL disposable glass capillary pipet

sealed in a melting point tube is added to 250 mL of sample, and the melting

point tube and pipet are crushed to add the deuterated standards to the sample.

For analysis of "extractables" and "intractables," 5 to 10 mL of marker

compound solution from a sealed ampoule is added to a 1 or 2 L sample. From

March 1980 to July 1982, 33 sets of marker compound solutions, "purgeables,"

"extractables," and "intractables," were prepared and from 40 to 100 ampoules

of each set were shipped to EPA.

From each set of standards prepared, approximately 20 ampoules were

retained by NBS for studies of stability and homogeneity. Analysis by gas

chromatography and liquid chromatography of sets prepared in March - June 1980

and in February - April 1981 showed no significant instability or inhomogeneity

(vial-to-vial variation) during storage at 4 °C for up to eleven months.

The most recently prepared marker compound solutions, prepared in July

1982, were the first made for the "Comprehensive Scheme for Soils, Sediments,

and Sludge." These sets contained 19 deuterium-labeled compounds and one non-deuterated fluorine-containing compound. One of the deuterium-labeled

compounds, 2-naphthalene-d7 -sul fonic acid, was not commercially available and was synthesized at NBS. The concentrations of the sets are given in Table 36.

Sixty ampoules of each set will be shipped to EPA.

All compounds used in the marker compound solutions were checked for

chemical purity by mass spectrometry and by either gas chromatography or liquid chromatography, as well as for isotopic purity by mass spectrometry.

156
Table 36. Marker Compound Solutions for Use in the "Comprehensive

Scheme for Soils, Sediments, and Sludges".

Concentration in Sample after

Addition of Standard (yg/L)

Compound Set 1 Set 2

PURGEABLES

3

Naphthalene-ds 5.0 49.1

Anisole-d 3 2.2 27.1

Chlorobenzene-d 5 4.6 4.3

Bromoethane-d 5 0.45 5.1

STRONG ACID EXTRACTABLES

b

Benzoic-d 5 acid 0.99 104.0

Heptanoic-di 3 acid 10.0 99.5

EXTRACTABLES

0

o-Xyl ene-di 0 2.0 108.0

Ni trobenzene-d 5 105.5 517.7

Naphthal ene-d 8 21 .5 498.8

Acri di ne-d 9 19.4 99.5

Phenol -d 6 96.1 387.8

Propiophenone-d 5 — 104.5

1 -Phenyl -d 5 -ethanol -- 518.2

Peryl ene-di 2 1 .2 98.2

Acetophenone-d 5 -- 104.1

NEUTRAL INTRACTABLES

d

t-Butanol -d 9 117.1 581 .2

Ni trobenzene-d 5 21 .6 103.7

IONIC INTRACTABLES

d

n-Butyl -d 9 -amine 120.2 553.0

n-Butyric-dy acid 7.9 547.2

2-Naphthal ene-d 7 -sul fonic acid*H 2 0 105.5 508.5

N-Ethyl -2-fl uorobenzyl ami ne 107.2 525.8

2- Phenyl ethyl -d 4 -amine 103.7 513.3

a

l yL solution in methanol added to 250 mL sample.

b

5 mL solution in methanol added to 2 L sample.

c

5 mL solution in methanol added to 1 L sample.

d

7.5 mL (Set 1) or 10.0 mL (Set 2) aqueous solution added to 1 L sample.

157
17. Surface-Enhanced Raman Spectroscopy of N-Methylpyridinium Cation and

Pyridine: Identification of Surface Species (51101, 51301)

K. A. Bunding, R. A. Durst

There has been considerable controversy over the mechanism of the surfaceenhanced Raman scattering (SERS) effect and the identification of the species

producing the enhancement. Since not all molecules show enhancement, the role

of particular enhancing sites as well as molecular orientation and moleculesurface interactions seemed to be very important to the explanation of the

phenomenon.

We have reported SERS from N-methylpyridinium iodide (NMPI) solutions in

contact with a silver electrode [1], Since most molecules which show surface

enhancement in an electrochemical cell (e.g., pyridine, piperidine, carboxylates, and cyanide) have unshared pairs of electrons, the observation of SERS

in the N-methylpyridinium cation (NMP+

) was significant. However, attempts

to obtain SER spectra from N-methylpyridinium chloride (NMPC1) solutions at a potential of -0.6 V were unsuccessful until trace amounts of iodide were added

[1]. This result implies a major role for the iodide ion either in the

enhancement mechanism itself or in promoting adsorption of the cation, perhaps

via co-adsorption or the formation of a surface complex.

A series of experiments was undertaken to clarify the role of the anion

in SERS measurements involving the NMP cation and to identify the actual

surface species observed in such experiments. We have examined the effect of

varying the anion, the pH, and the electrochemical potential; we have performed

competition experiments in which both pyridine (py) and NMP

+ were present in

the electrolyte; and we have compared the ordinary Raman spectrum of the solid

silver-pyridine complex Ag(py) 2 N0 3 with the various SER spectra obtained.

The SER spectra of NMPBr and NMPC1 , unlike NMPI, show bands that are due

to pyridine as well as NMP

+

. Since there is no pyridine initially present in

the solution and there is no electrochemical reaction

+ in the potential range

studied, this must be due to decomposition of the NMP to pyridine by surfaceinduced and/or photochemical reactions. The decomposition theory is further

supported by the increase in relative intensity of the pyridine bands with

time.

Competition experiments performed with both pyridine and NMP in the

solution confirmed the presence of pyridine bands in the SER spectra of NMPBr

and NMPC1 and their absence in NMPI spectra. Apparently the I is more selective for the organic cation. Thus, even if NMPI were to decompose to

pyridine, this would not be observable. In order to assign the new bands in

the NMPBr and NMPC1 spectra to pyridine, the spectra of the silver-pyridine

complex, Ag(py) 2 N03 , pyridine in solution and the SER spectra of pyridine at

-0.2 and -0.6 V were taken. This allows a clear assignment of H-bonded

pyridine bands and Lewis-coordinated pyridine bands. We see in the spectra

at the more positive potential, -0.2 V, both Lewis- and H-bonded pyridine and

at -0.6 V, only H-bonded pyridine.

The spectrum of pyridine in KI at -0.35 V is very different from that in

KC1 . This suggests that in KI the silver Lewis-acid sites are not available

158
to pyridine or are somehow modified; also the H-bonded species is not enhanced.

The lack of enhancement for the solution species suggests that the enhancement

mechanism is not effective beyond the double layer.

By studying the effects of anion, pH, and potential variations and by

competition experiments, we have demonstrated that different pyridine/

pyridinium species are responsible for the observed spectra. In addition, it

appears that surface-induced and/or photochemical reactions may produce

species not originally present in the sample solution. It is also clear from

this work that care must be exercised in assigning SER bands to sample components without consideration of possible decomposition to other species.

Reference

[1] Bunding, K. A.; Bell, M. I.; Durst, R. A. Chem. Phys. Lett. 89,

54 (1982).

18. Electrochemical and Spectroel ectrochemical Studies of Copper and Iron

Bleomycin Complexes (51101)

M. L. Fultz

The bleomycins are a family of structurally similar glycopeptide antibiotics that are isolated as copper complexes from the bacterial strain

Streptomyces verticill us . Bleomycin exhibits antitumor activity and has been

used to treat squamous cell carcinomas, lymphomas, and testicular carcinomas.

In vitro , bleomycin exhibits DNA-strand scission when bound with iron and

oxidized by molecular oxygen. However, its in-vivo action is not clearly

understood. Current studies have not resolved the fundamental question of

whether there are several distinct pharmacological agents among bleomycin and

its complexes or whether there is a single proximate agent in-vivo .

To more clearly define the role of the metal ion in the mechanism of

bleomycin action, a study of the redox properties of the copper and iron

complexes has been undertaken. A previous study of copper bleomycin found the

copper reduction to be irreversible at a carbon paste electrode. Attempts to use coulometry to determine the number of electrons involved in the reduction

were not successful. Our studies have shown copper bleomycin to exhibit electrochemical ly irreversible reduction at mercury and glassy carbon electrodes

at approximately -0.53 V vs. SCE and pH 7. Copper bleomycin exhibited no electroactivity at platinum and gold electrodes. The cyclic vol tammograms

also showed a redox couple at more positive potentials close to the

Cu( II )+Cu(0) couple. Thin-layer coulometry at a mercury-gold minigrid electrode gave an n value of 1.3. Atomic absorption analysis of the electrode

used for the coulometry showed that it contained 100 times the background

level of copper metal. The following mechanism has been proposed to account

for these observations:

Cu(II)-Blm Cu( I )-Blm --^ Cu( I)+Blm

Cu(metal

)

159
A pH study of copper-bleomycin showed more negative reduction potentials with

increasing pH. This agrees with the hypothesis that reduction of one of the

amine ligands is necessary for reduction of the copper.

Iron-bleomycin exhibits quasi-reversible redox behavior at glassy carbon

electrodes. In order to study the spectroelectrochemistry of iron-bleomycin,

we constructed an optically transparent electrode consisting of reticulated

vitreous carbon with a pore size of 100 pores/square inch. This electrode

exhibits thin-layer behavior because of the small size of the pores. By

monitoring the 384 nm absorption band of iron(III)-bleomycin, the oxidation

and reduction of iron-bleomycin was monitored. The concentrations of oxidized

to reduced species at various potentials applied to the electrode were calculated. Nernst plots of the data show a one electron reduction with a formal

potential at pH 7 of -0.090 V vs. SCE. This agrees well with values obtained

by spectrophotometric titrations.

19. Polymer Modified Electrodes: Electrocatalytic Sensors for Detection of

Organic Analytes (14625, 51101)

E. A. Blubaugh, Jr.

Polymer modified electrodes may provide sensors which will allow the

selective and sensitive detection of organic analytes (organohal ides , etc.).

Polymer films offer the advantages of inherent chemical and physical

stability, i ncorporation of large numbers of catalytic sites, and relatively

facile electron transport across the film.

We have followed two approaches in polymer film electrode fabrication.

These are electrochemical initiated polymerization and spin-dip coating.

These two approaches allow a much greater degree of flexibility in polymer

film type, thickness and morphology. However, the most important aspect is

that we are given a greater latitude in the subsequent mode of catalyst

immobilization.

The most challenging area of investigation is the behavior of charged or uncharged film penetrants. The ultimate catalytic efficiency of these polymer

film electrodes will depend to a large degree on the influx of these substrate

molecules across the film interface.

We have started both theoretical and experimental investigations, which

we hope will shed light on the factors which influence diffusion of substrate

molecules in the polymer films. Some of these factors are solvent, degree of

solvation, electrode potential, and charge, if any, on the penetrant.

Polymer films of [Ru

1

(bi py) 2 (4-VP) 2 ]• 2PF6 (where bipy is bipyridine and

VP is vinyl pyridine) have been obtained via electrochemical initiation of an anionic polymerization of the vinyl monomer. Ruthenium bipyridyl complexes

show very interesting and potentially exploitable (catalytic films) excited

state chemistry.

Ru

n (bipy) 3 +hv -* Ru

III

(bipy) 2 (bipy)“

160
The transient excited state molecule is both a powerful oxidant and reductant

and allows the photocatalytic oxidation or reduction of organic solution

species. Polymer films of Ru

II (bipy) 2 (4-VP) 2 have been obtained, characterized, and electrochemical ly evaluated. These films have shown very facile

electron transfer through the film and have demonstrated catalytic oxidation

of organic carboxylates. This reaction does not take advantage of the abovementioned photocatalytic reaction. The ECC reaction mechanism ( i . e . , electron

transfer followed by two subsequent chemical reactions) for the oxidation of

organic carboxylates occurs in the following steps. The electron transfer

reaction oxidizes the ruthenium in the complex from II to III. The

ruthenium( III) complex then catalytical ly oxidizes the carboxylate to the

radical anion (C02 ) which undergoes further reaction with the Ru(II) complex

to produce a Ru(II) bipyridyl radical anion. This radical anion in turn

produces a visible luminescence during the annihilation reaction with the

Ru(III) complex. The luminescence resulting from the annihilation of the

oxidized and reduced components should allow the very sensitive detection of

R-C02 components.

We have utilized these Ru

i:i (bipy) 2 (4-VP) 2 polymer films in the evaluation

of the role and relative influence that migration plays in the "diffusional

current-time response of these polymer film electrodes. This area of research

is being pursued and computer-controlled equipment will be completed soon to

allow this study to be further explored.

The immobilization of cationic (organic and inorganic) catalysts also has

been demonstrated. We have immobilized these cationic species within a cation

exchange polymer. The immobilization scheme is performed in two steps: spindip coating of the polymer onto the electrode and subsequent cation exchange

of the catalyst of interest. These films have shown electrochemical response

with cations such as methyl viologen, methylene blue, and Ru

1

( bi py

)

3

. Preliminary results indicate that the methyl viologen modified electrode shows

evidence for the catalytic oxidation of organohal ides

.

20. Theoretical Analysis of Charge Transport in Polymer-Modified Electrodes

(51101)

W. T. Yap

In studies of electrochemistry using polymer-coated electrodes, there are indications that the transport of the charged electroactive species through

the polymer layer may take place not only by diffusion due to concentration

gradients, but also by migration due to the potential gradient. We have made

a theoretical analysis for chronoamperometry using polymer-coated electrodes,

taking into account the effects of diffusion and migration in a constant

potential gradient, i.e., constant electric field. Equations were developed

for the concentration distributions of the charged electroactive species and

for the current, y, as a function of time, t. Figure 35 shows the product y/t

as functions of /t. Curve 4 is for the case where the transport is only by

diffusion, i.e., no migration effect. The horizontal portion at short time

for curve 4 corresponds to the classical behavior described by the Cottrell

161
Figure 35. Plot of the product of current and square root of time

ms . square root of time for several values of constant

electric fields.

162
equation. Curves 1 to 3 show cases where the diffusion current is augmented

by the migration current, the electric field decreases from curve 1 to curve

3. Curves 5 to 7 depict the cases where the migration current opposes the

diffusion current, the electric field increases from curve 5 to curve 7.

Preliminary results from experiments using poly-Ru-vinyl bi pyridine show

curves similar to that of curves 1 to 3.

A paper will be published wherein we will present the theory and also

give a procedure for estimating the apparent diffusion coefficient and the

ionic mobility of the charged electroactive group from the current-time

curve [1].

Reference

[1] Yap, W. T , ; Durst, R. A.; Blubaugh, E. A.; Blubaugh, D. L. J. Electroanal. Chem. (in press).

21 . Characterization of an Angiotensin I SRM by Proton NMR Spectroscopy at

400 MHz (14306)

B. Coxon, S. A. Margolis

The high sensitivity and dispersion of the WM-400 NMR spectrometer have

allowed it to be used in certification of the Angiotensin I SRM in two ways.

Solutions for analysis by proton NMR were conveniently prepared by dissolution

of a single unit (0.5 mg) of the SRM in 100 percent deuterium oxide (0.5 mL).

Under these conditions, suppression of the HOD signal was not necessary, and

spectra with good signal :noise ratio were obtained by signal averaging of

2,000 scans.

The major non-peptide impurity (or counterion) in the Angiotensin I SRM

is acetate and, therefore, a method was developed for analysis of acetate

content by proton NMR. Because the acetate methyl proton signal at 6 1.922 was found to overlap some of the proton signals of the angiotensin I (see

figure 36), an acetate-free sample of angiotensin I was prepared first, in

order to determine an accurate proton count for the signals underlying the

acetate peak. Removal of the acetate from the sample was achieved by two

lyophilizations of the material with 0.01 mol/L hydrochloric acid. Analysis

of this sample by proton NMR indicated that it was indeed free of acetate and

that the proton count in the spectral region of interest was three. Thereafter, the samples of the SRM were analyzed without lyophi 1 ization , and the

appropriate value of the spectrum integral for the three protons was subtracted

from the total integral of the acetate methyl peak and its underlying signals,

in order to obtain the integral of the acetate peak. The appropriate value of

the integral for three protons was determined by averaging of the integrals of

a total of 29 proton signals in the high field region, including many of those

that originated from the methyl, methylene, and methine protons of angiotensin

I. Proton NMR determinations on six samples of the SRM yielded a mean acetate

content of 1.36 ± 0.08 (± one standard error) molecular equivalents of acetate

per mole of angiotensin I.

163
Figure 36. Proton NMR spectrum of angiotensin I at 400 MHz in 100% D2 0. The

peptide concentration is 0.5 mg/0.5 mL D2 0. The notations above

the peaks indicate the specific proton assignments of each signal

or group of signals (indicated by a horizontal line).

164
Integration of a number of other well-resolved proton multiplets in the

NMR spectra of the six samples of Angiotensin I SRM gave information on its

amino acid composition (see Table 37). Specific, well-defined proton signals

for each amino acid (see figure 36) were identified by use of published spectra

and pH induced spectral shifts [1,2], and by comparison of the 400 MHz proton

NMR spectra of angiotensin I, II, and valine 5-angiotensin II at acid and

neutral pH. The particular signals that were used for quantitation of the

amino acids are indicated in Table 37.

Table 37. Analysis of the Amino Acid Content of the

Angiotensin I SRM by Proton NMR.

Amino Acid

Proton Signals Used Relative Amino Acid

for Quantitation Content ± S.D. (n=6)

Aspartic acid (Asp) 6-CH2

1 .04 + o o Histidine 6 ( H i

6 ) H-2 & H-4 0.99 + 0.05

Histidine 9 (His 9 ) H-2 & H-4 0.99 + 0.03

Isoleucine (lie) y-CH2 0.98 + 0.04

Leucine (Leu) a-CH 0.98 + 0.04

Leucine + Arginine

(Leu + Arg)

y-CH2 (of both) and

3-CH (leucine) 0.99 + 0.02

Phenylalanine (Phe) Phenyl 1.00 + 0.03

Proline (Pro) B-CH 2 & 6-CH2

1 .00 + 0.04

Tyrosine (Tyr) o^ and m aromatic 1.03 + 0.03

Valine + Isoleucine

(Val + lie) a-CH (both) 1 .05 + 0.02

Precision expressed as the standard deviation of a single measurement.

The results obtained by this non-destructive technique are in good agreement with those obtained earlier by acid hydrolysis of the SRM followed by

high pressure, ion exchange chromatography of the resulting amino acids. The

proton NMR results independently confirm the amino acid composition of the SRM

and also establish the proline content.

References

[1] Glickson, J. D.; Cunningham, W. D.; Marshall, G. R. Biochemistry

12: 3684; 1973.

[2] Piriou, F.; Lintner, S.; Fernandjian, S.; Fromageot, P.; Khosla,

M. C.; Semeby, R. R.; Bumpus, F. M. Proc. Natl. Acad. Sci . USA 77:

82; 1980.

165
22. The Synthesis, Purification, and Characterization of 2-Methyl thio-oxazol ine

Derivatives of Pentoses and Hexoses (11 320, 51 301 )

B. Coxon, R. M. Davidson, S. A. Margolis, E. White V

During the past ten years, oxazoline derivatives of carbohydrates have

been used as intermediates in the stereospecific synthesis of such anti -tumor

nucleosides as 1 -3-Q-arabinofuranosyl cytosine (ara C) and 1 -B-D-arabinofuranosyl adenine (ara A). In continuation of our investigation of tRe synthesis and

analysis of 2-amino oxazoline derivatives of carbohydrates (see CAC Annual

Report, 1981), we have studied the preparation and analytical characterization

of a relatively new class of carbohydrate derivatives, the glycosyl

2 -methyl thio-oxazol ines. These derivatives are potentially useful intermediates

for the development of efficient nucleoside syntheses that would be completely

stereospecific and that would not require the use of anhydrous conditions,

exotic catalysts, or protecting groups. Toward these goals, 2-methyl thiooxazol ine derivatives have been prepared from Q-arabinose, Q-lyxose, Q-ribose,

and Q-xylose in the aldopentose series, and from Q-allose, Q-altrose,

Q-galactose, and Q-glucose in the aldohexose series. The synthetic approach

adopted was to convert the free aldoses to 2-thiono-(l ,2-dideoxy-D-aldo)[l ,2-

d]-2-oxazol idine derivatives (some of which were known previously) by treatment

with an alkali metal thiocyanate and concentrated hydrochloric acid. The

2-thiono derivatives were then methylated with methyl iodide in the presence

of a base catalyst. In principle, such methylations might proceed to give one or more of several products, including those resulting from N-, 0-, or S-methylation. However, 13 C NMR studies of the products from our optimized

methods have indicated that in general, only one methyl group is introduced

and its 13 C chemical shift is consistent with S-methylation and not with N- or 0-methyl ati on.

The types of structures involved are illustrated in figure 37, and the

conditions of the methylation reaction were studied initially using 2-thiono

derivatives of Q-arabinose and Q-lyxose, with tri ethyl amine as catalyst.

Improved results in terms of the predominance of a single product were obtained

when sodium methoxide was used as a catalyst in methanol, at room temperature.

A rapid, general procedure has been developed in which the free aldose is

converted to the 2-thiono-oxazol idine derivative without isolation of the

product, which is then methylated directly in a one-pot reaction. With the

ultimate objective of preparing biologically active nucleosides labeled with

stable isotopes such as 13 C or 15 N, 2-methylthio derivatives labeled with

these isotopes have also been synthesized from 2-thiono derivatives that were

prepared by use of thiocyanate-* 3 C and - 15 N. The 2-methyl thio-oxazol ine

derivatives have been purified by preparative, reversed-phase HPLC, and

characterized by elemental analysis, infrared spectroscopy , and proton and

13 C NMR spectroscopy at high field. Mass spectrometry of the products has

been initiated.

For the pentosyl 2-methyl thio-oxazol ines, the type of ring (furanoid or pyranoid) adopted by the pentosyl moiety has been proved by observation of the

multiplicities of the H-5, H-5 ' , and hydroxyl signals in proton NMR spectra

measured at 400 MHz under hydroxyl proton coupled conditions (DMS0-db solutions). If the structure is pentopyranoid, then H-5 and H-5 1 do not exhibit

coupling to a hydroxyl proton under these conditions, and the hydroxyl proton

166
167

Figure

37.

Proton

NMR

spectra

of

2-methyl

th

i

o- (

1

,2-dideoxy-3-Q-lyxopyrano)[l

,2-d]-2-oxazol

ine

and

2-thiono-[l

,2-dideoxy-3-D-lyxopyrano)[l

,2-d]-2-oxazol

idine

in

D

2

0

at

400

MHz.
signals each appear as doublets due to coupling with H-3 and H-4. On the

other hand, if the structure in question is pentofuranoid , H-5 and H5

' display

couplings to HO- 5 which itself appears as a triplet, whereas HO-3 resonates as

a doublet. Examples of both furanoid and pyranoid 2-methyl thio-oxazol ines

have been found in the pentose series. Similar considerations are being used

to define the ring type for the 2-methyl thio-oxazol ine derivatives in the

hexose series, except that it is necessary to determine if H-4 or H-5 is

coupled to a vicinal hydroxyl proton.

The assignments for the 13 C NMR spectra of the pentose and hexose

2-methyl thio-oxazol ine derivatives have been confirmed by selective proton

decoupling experiments using proton frequencies developed from the specific

assignments of the high field proton spectra (see figure 37). Detailed 15 N NMR studies of the 15 N-labeled derivatives are planned for the near future.

23. An Efficient Two-Step Synthesis of a Novel 15 N-Labeled Cyclonucleotide:

2,3 l -Anhydro-l-g-D-fructofuranosyluracil- 15 N 9 -1 1 ,6* -diphosphate

(11320, 51301 )

B. Coxon, R. M. Davidson, S. A. Margolis

The utility of carbohydrate oxazoline derivatives as intermediates in the

synthesis of potential anti-tumor nucleosides and nucleotides has been tested

by condensation of an oxazoline derivative of fructose diphosphate with

methyl propynoate. In 1970, Sanchez and Orgel [1] reported a one-step synthesis

of a-cytidylic acid from Q-ri bose- 5- phosphate under potentially prebiotic

conditions. Therefore, because Q- fructose-1 ,6-diphosphate is an inexpensive

commercially available starting material and is stereochemical ly related to

arabinose and psicose (and hence to ara A and ara C), we envisioned a conve- nient two-step synthesis of a nucleotide that could also be used to generate

products labeled with stable isotopes such as carbon-13 and nitrogen-15.

Labeling with nitrogen-15 increases the ease with which 15 N NMR spectra

can be obtained from small quantities of material, and labeling with carbon13, or nitrogen-15, or both provides extremely useful materials for the study

of tautomeric equilibria, reaction mechanisms, and biochemical degradation.

The reaction of fructose-1 ,6-di phosphate (FDP) with cyanamide in

methanol ic solution with guanidine carbonate as catalyst for 24 hours at room temperature yielded a new oxazoline derivative, namely 2-amino-(2,3-dideoxy-gQ-fructofurano) [2 ,3d]-2-oxazol 1ne-l ' ,6' -di phosphate (FDP-Oxazol ine). Unlabel ed

and 13 C and 15 N labeled versions of this derivative have been purified by

HPLC and characterized by proton and 15 N NMR at high field. The 15 N NMR

spectra of solutions of FDP-oxazol ine- 15 N 2 in deuterium oxide have been found

to develop additional 15 N resonances over the course of 24 hours. The nature

of this process is to be investigated further.

Condensation of the FDP-oxazol ine with methyl propynoate in saturated

aqueous ammonium hydrogen carbonate at 90 °C for 0.5 hour yielded 2,3'-

anhydro-l-B-Q-fructofuranosyluracil-1 ' ,6' -di phosphate (FDP cyclo U, see

168
reaction scheme). This cyclonucleotide is a fructose diphosphate analogue of

cyclouridine (cyclo U). After purification by HPLC, the FDP cyclo U was characterized by ultraviolet absorption and proton and 15 N NMR spectroscopy.

Its UV absorption spectrum is extremely similar to that of cyclo U (x max 223

and 246 nm vs. 222 and 249 nm) . The vinyl region in the 400 MHz proton NMR

spectrum of FDP cyclo U- 15 N2 is very similar to that of cyclo U- 1 ^(see

..figure 38). The aliphatic region of the proton spectra (see figure 39) of FDP

cyclo U and its 15 N£ labeled analog show a multiplicity of heteronuclear

coupling information. 13 C and 31 P NMR studies remain to be done.

Reference

[1] Sanchez, R. A., Orgel , L. E., J. Mol. Biol. 47: 531-543; 1970.

“FDP CYCLO U”

Scheme 1. Scheme for the synthesis of l-$-D-fructofuranosyluracil- 15 N 2 -l ' ,6 '

diphosphate (FDP cyclo U- 15 N 2 ) from fructose-1 ' ,6

1 -diphosphate (FDP).

169
Hh!J

'=N.H-e =2' 9 Hz 3J.s n , h.5 =4.9 Hz

H-6 15

I

N2

“labeled CYCLO U

H-1' Jl

b (p.p.m.)

Figure 38. Vinyl regions of the proton NMR spectra (at 400 MHz) of solutions

of cyclouridine- 15 N 2 (cyclo U- 1

N 2 ) ,2 ,3' -anhydro-l-B- D-fructofuranosyluracil- 15 N 2 -1 1 ,

1 -di phosphate (FDP cyclo U- T5 N 2 ) and FDP

(cyclo U) in D 2 0.

170
Figure 39. Aliphatic regions of the proton NMR spectra (at 400 MHz) of

2,3' -anhydro-1 -6-Q-fructofuranosyl uraci 1 -1

1 ,61 -di phosphate ( FDP

cyclo U) and FDP cyclo U- 15 N 2 , with and without homonuclear spin

decoupl ing of H-5.

4 171
24. Confirmation of the Standard Wavelength for the 100 °$ Point of the

International Sugar Scale by Polarimetric Measurements with a Dye Laser

(11320)

B. Coxon, D. K. Hancock, H. Layer (523)

The 100 °S point of the International Sugar Scale is defined as the

optical rotation of the normal sugar solution [1] at the wavelength of the

green line of the mercury isotope 198 Hg(x w =546.2271 nm). As part of our contribution to international efforts in establishing a revised 100 °S point

value, it was decided that the effective wavelength of the Philips low pressure

mercury lamp which was used as a light source in the 100 °S point measurements

should be compared with that of the 198 Hg isotope. Since optical rotation is

directly related to the frequency of the source, this comparison was made by

measuring the optical rotation of an internationally measured long quartz

rotator, PTB #2, both with a single frequency dye laser locked to the green

198 Hg line and with the commonly used Philips mercury lamp as light sources.

Optical rotation determinations made at NBS in 1978 indicated a rotation

discrepancy for a quartz control plate between measurements made with the

Philips mercury lamp and those made with a dye laser locked to the center of a Doppler-broadened mercury emission from a hollow cathode lamp. This finding

necessitated further measurements.

Our present measurements utilized a recently developed system [2] for

locking the single frequency dye laser to the 7s 3 S, to 6p 3 P 2 transition of a mercury isotope by means of saturated absorption in a high vacuum quartz cell

excited by a radiofrequency discharge. This technique represents a significant

increase in accuracy over previous measurements (which used a hollow cathode

tube) for two important reasons. Firstly, in previous measurements, the dye

laser was locked to the Doppler-broadened profile of a lamp containing natural

mercury, the output of which includes emissions from four mercury isotopes.

Secondly, in the commercial lamp that was used, the electrical discharge was sustained by a neon buffer gas, so that the average wavelength of the emission

from this lamp can vary significantly as the operating conditions, the neon pressure, and the discharge current are varied.

In the present measurements, saturated absorption was used to lock the

dye laser to the Lamb dip of either the 202 Hg or the 198 Hg isotopes which were excited by radiofrequency energy instead of by a direct current discharge. To

accomplish this, a special tube was constructed and was filled with highly

purified mercury; no buffer gas was used. An optical interference filter was used to prevent spurious emissions from the dye laser from entering the

polarimeter. This system has increased the resolution of the wavelength

determination by a factor of 300 relative to the system which utilized a hollow cathode tube.

Table 38 compares ratios (R = [a. ]/Ca|_| e|s| e

] ) of optical rotations measured

on quartz plate PTB #2 with various light sources of wavelength X and with the

helium-neon laser.

172
Table 38. Optical Rotation Ratios (R)

a for Quartz Plate PTB #2

and Wavelengths (x) Calculated Therefrom.

Wavelength (x, nm)

Optical Rotation

Ratios (R)

a Calculated from

Light Source Dispersion Equation

202 Hg

c 1.36629145 546.2278

1.36629170 546.2278

1.36628886 546.2283

i98 Kg

d 1.36627892 546.2302

1.36627678 546.2306

1.36627678 546.2306

Hg lamp 1.3662712 546.2317

1.3662764 546.2306

1 .3662760 546.2307

1.3662752 546.2309

1.3662676 546.2323

1.3662802 546.2299

a R = [a

x ]/[a HeNe ].

b

X = 0.07360154 + 0.571645053 (R + 0.03957273)"°

558379782 . c Dye laser locked to 202 Hg isotope.

b

Dye laser locked to 198 Hg isotope.

Also in Table 38 are wavelengths X that have been calculated from an explicit form of the quartz dispersion equation, which was derived by fitting

NBS data for PTB #2, PTB #3, and data of the Physi kal isch-Techni sche

Bundesanstal t (PTB). Comparison of the calculated effective wavelength of the

Philips lamp and the dye laser locked to the 198 Hg isotope shows excellent

agreement, indicating that no wavelength correction need be made to the 100 °S

point data. This work cleared the way for consideration of a revised 100 °S

point value at the 18th Session of the International Commission for Uniform

Methods of Sugar Analysis (ICUMSA) in June of this year. However, as a result

of this meeting, all recommendations pertaining to the new scale have been

deferred until the economic and legislative aspects of it can be considered.

Because of effects on trade, the implementation of restandardizing quartz

plates will not now be decided until the 1986 meeting of ICUMSA at the earliest.

This work also suggests the feasibility of using the NBS high precision

polarimeter with a long quartz rotator as a wavelength measuring device.

Deviations of our calculated wavelengths from the theoretically determined

wavelengths for the 7s 3 S, to 6p 3 P2 transition of the mercury isotopes appear

to result from the fit of the compos i te dispersion equation used. Given

sufficient data for a single long quartz rotator, it should be possible to

derive an individual dispersion equation that would allow one to determine an accurate emission wavelength by means of a simple optical rotation measurement.

173
References

[1] "The 'normal sugar solution' is defined as 26.0160 g of pure sucrose weighed in vacuo and dissolved in pure water at 20.00 °C to 100.000

cm 3

. This corresponds to a concentration of 26.0000 g of sucrose weighed with brass weights in air under normal conditions (1013 mbar

pressure, 20 °C, 50% relative humidity in 100.000 cm 3 of solution at

20.00 °C)." (Officially adopted at the 13th Session of ICUMSA, 1962.)

[2] Kroll, M. Optics Letters 7; 151; 1982.

25. Implementation of and Initial Research in Two-Dimensional Electrophoresis

for Protein Separations (11 320, 511 11 )

D. K. Hancock, D. J. Reeder

Separation and characterization of proteins for eventual use as analytical

reagents was implemented with competence building funding. Since this is a new area of research at NBS, an extensive literature search was conducted and

reprints were obtained. References and titles were entered into a microcomputer

data base for rapid access. At a meeting on two-dimensional electrophoresis

(2-DE) held at the Mayo Clinic, contacts were made with many research users of

this technique. Laboratory equipment to perform 2-DE was set up and methods

were examined for generating gradient polyacrylamide gels, for handling thin

(0.7 mm) gels, for staining, and for photographing gels. Isoelectric focusing

in long (170 mm) tube gels was implemented using ampholytes from several

manufacturers.

To perform studies on the role of materials purity on separations In the

2-DE system, we began initial investigations with sodium docecyl sulfate (SDS),

a detergent used extensively in the 2-DE separations. The relative composition

of SDS obtained from ten different manufacturers' lots was examined by gas

chromatography after hydrolyzing the sulfate esters to free the long-chain

(C 10 , Ci 2 » C 14 ) alcohols. The gas chromatograms revealed a wide range of

differences in purity of the SDS, with varying ratios of C 12 to C 10 or C 14 . The SDS from each of the ten lots was subsequently incorporated into the

sample buffer and running buffer for one-dimensional separations and comparison

of banding patterns of six different serum proteins. Correlation of the serum protein banding patterns versus SDS composition is in process.

A modest joint research effort using electrophoresis was started with the

Sandy Hook Marine Laboratory, N0AA, Department of Commerce, to investigate

electrophoretic protein patterns of different species of flounder. Initially,

we ran serum protein patterns for summer, winter, yellowtail, and windowpane

flounder to ascertain species interrel ationhi ps and identify similar proteins.

Serum was separated by gel filtration chromatography as well as by affinity

chromatography and fractions were analyzed by electrophoresis and Immunoelectrophoresis. Antiserum for performing immunoel ectrophoresi s (IEP) was provided by the National Fish Health Research Laboratories, Department of the

Interior. Stained IEP slides are now being prepared for photography and for

comparison of interrelationships.

174
Future studies will continue to be centered on the role of materials in

the electrophoretic separation process. Studies to determine the mechanism of

silver staining are being extended to develop more efficient and sensitive

staining procedures. Finally, work will be initiated on modification of

proteins for use as stable markers in the 2-DE system.

26. Total Protein Content Certification of SRM 909, Human Serum (14306)

D. J. Reeder

The widespread acceptance of SRM 909, Human Serum, by the clinical community as a standard for inorganic and organic analytes has been enhanced by

supplying an information value for the protein content of the reconstituted

serum. Because SRM 909 is being used as a standard for many other clinical

measurements, requests from many clinical laboratories have been received by

the Office of Standard Reference Materials for a protein value on the human serum reference material. Serum protein measurements are a routine clinical

measurement, with laboratories often using bovine serum albumin (SRM 927) as a protein standard. Total protein measurements of serum, cerebrospinal fluid,

and urine give physicians information concerning a patient's state of hydration, nutrition, and renal condition, as well as revealing potential tumors of

bone marrow.

Measurements leading to certification of the protein value were made by

using the biuret method for protein developed by Doumas, et al

.

[1]. Bovine

Serum Albumin, SRM 927, was used as the protein standard. We performed the

biuret measurements by analyzing ten vials of SRM 909 and ten vials of SRM 927

on two successive days with freshly made reagents each day and reading the

absorbance on two separate spectrophotometers. Preliminary calculations

result in a value of 63.3 ± 0.3 mg/mL (1 a). More complete statistical analysis of all of the parameters, using several modeling approaches, is underway.

Reference

[1] Doumas, B. T.; Bayse, D. D.; Carter, R. J.; Peters, T.; and

Schaffer, R. Clin. Chem. 27: 1629-1796; 1981.

27. Construction of a Toxic Chemicals Handling Laboratory (11397)

S. N. Chesler, H. S. Hertz

During 1981 an NBS design concept for a toxic organic chemicals handling

laboratory was realized, in terms of a detailed plan prepared by an architectural and engineering consultant. Based upon this plan, construction of a toxic chemicals handling laboratory began in March 1982. The facility is now essentially complete, and we anticipate bringing it into operation during the

last few months of 1982.

The laboratory is designed for air to flow over the investigator, then

over the work area, and finally through a filter before being exhausted or recirculated. Air is circulated through the laboratory at 8000 cubic feet

175
per minute (CFM) and exhausted through the hoods and toxic chemicals storage

cabinets at 1400 CFM. These air flows result in laboratory air being changed

every 24 seconds and totally exhausted every 2.3 minutes. The volume and

direction of air flows dilute any airborne contamination and direct it away

from the laboratory personnel and into charcoal filters for removal. Filtered

air and fresh air enter the laboratory through HEPA filters designed to remove

any particulate material which might be present.

Toxic chemicals are stored in cabinets which are continuously exhausted

and purged with 400 CFM of room air. The direction of air flow again assures

that air passes over laboratory workers, then chemicals, and finally through a charcoal exhaust filter when the cabinet is opened.

Two Class II, Type II safety hoods are located in the center of the laboratory. These hoods will be the sole location for transferring and weighing

operations requiring the handling of pure liquid and crystalline toxic

materials

We are currently writing a detailed protocol for use of the laboratory.

This protocol will include proper procedures for entering and exiting the

laboratory, for the use of the laboratory, for comprehensive recordkeeping

for handling emergency situations, for proper disposal of wastes, and for

maintaining and cleaning the facility.

176
C. Outputs and Interactions

(Organic Analytical Research Division)

1 . Publ ications

Botto, R. E. and Coxon, B., High-Field Proton and Nitrogen-15 NMR Spectroscopy

of Neomycin B, Abstracts of Am. Chem. Soc . Natl . Mtg

.

, New York, NY

Botto, R. E. and Coxon, B., Neomycin B Studied, NBS Dimensions 65 (7), 17-18

Christensen, R. G., Hertz, H. S., Reeder, D. J., and White V, E., Development

in the Analysis of Priority Pollutants by Liquid Chromatography/Mass

Spectrometry and Immunoassay Procedures, Adv

.

in the Identification and

Anal, of Org. Poll, in Water 1, Lawrence H. KeTTh, ed., Ann Arbor Science

Publishers, Ann Arbor, MI, 447-453 (1 981 ).

Christensen, R. G. , White V, E., and Hertz, H. S., LC/MS Interface Capability

Extended, NBS Dimensions 65 (6), 17 (1 981 ).

Coxon, B., Two-Dimensional Proton NMR Spectroscopy of Hydroxyl Proton Coupled

a- and g-Q-Glycopyranoses at 400 MHz, Abstracts of Am. Chem. Soc. Natl.

Mtg. , New York, NY (1981).

Coxon, B. and McAlpine, J. , Structural Analysis of Fortimicin Antibiotics by

Means of Proton Coupled Nitrogen-15 NMR Spectra, Abstracts of Am. Chem.

Soc. Natl. Mtg. , New York, NY (1981).

Davidson, R. M., White V, E., Margolis, S. A., Coxon, B. , and Oppenheimer,

N. J., Nitrogen-15 NMR and Mass Spectral Characterization of Some Doubly

15 N-Labeled ( 15 N 2 -) 2-Amino Oxazoline Derivatives of the Pentoses and

Hexoses, Abstracts of Am. Chem, Soc. Natl. Mtg. , New York, NY (1981).

DeVoe, J. R. , Velapoldi, R. A., Langland, J. K., and Hancock, D. K., Intruder

Tagging and Identification Using Luminescent Particles, NBSIR 81-2407

(1 981 )

.

Doumas, B. T., Bayse, D. D. , Carter, R. J. , Peters, T. , Jr., and Schaffer, R.,

A Reference Method for the Determination of Total Serum Protein.

I. Development and Validation, Clin. Chem. 27 , 1642-1650 (1 981 ).

Doumas, B. T. , Bayse, D. D., Bauer, K. , Carter, R. J., Elevitch, F., Garber,

C. C., Graby, R. A., Hause, L. L., Mathes, A., Peters, T. , Jr., Rand,

R. N., Reeder, D. J., Russell, S. M., Schaffer, R., and Westgard, J. 0.,

A Reference Method for the Determination of Total Protein. II. Test for

Transferability, Clin. Chem. 27 (10), 1651-1654 (1981 ).

Durst, R. A., Views on the Current Status of the pH Scale, Blood pH, Carbon

Dioxide, Ox

“ ~ J Calcium- Ion , 0. Siggaard-Andersen , ed. , Copenhagen,

(1981 ).

(1981).

1 1 -22 (1 981

177
Durst, R. A., Slggaard-Andersen, 0., and Maas, A. H. J., Reference and Quality

Control Materials for pH and Blood Gases, Blood pH, Carbon Dioxide,

Oxygen, and Calcium-Ion, 0. SI qqaard- Andersen , ed . , Copenhagen, 89-100

(1981 ).

Espinosa-Leniz, R., Garard, J. E., and White V, E., A Method for the Mass

Calibration of Photoplates in Field Desorption and Its Application to

Some Peptides, Abstracts of the 29th Annual Conference on Mass Spectrometry and Allied Topics, Minneapolis, MN, May 24-29 (1981 ).

Fatladi, A. J., (Book Review) Periodic Acid and Periodates, Synthetic Reaqents

4, 147-335 (1 981 ).

Howell, B. F., Chesler, S. N., Hilpert, L. R., and Reeder, D. J. , Low Molecular

Weight Leachables from Medical Grade Polymers, Annual Report to the

Bureau of Medical Devices (FDA), for the period of February 1980 to

December 1 980 (NBSIR 81-2436) (1981 ).

Konash, P. L., Wise, S. A., and May, W. E., Selective Quenchofluorometric

Detection of FI uoranthenic Polycyclic Aromatic Hydrocarbons in HighPerformance Liquid Chromatography, J. Liq. Chromatoq. 4, 1339-1349

(1981 ).

MacCrehan, W. A. and Durst, R. A., Dual -El ectrode Liquid Chromatography

Detector for the Determination of Analytes with High Redox Potentials,

Anal. Chem. 53, 1700-1704 (1981 ).

Roberts, G. D. and White V, E., The Mass Spectra of Some Silver Salts, Orq

.

Mass Spectrom. 16 (12), 546-550 (1981).

Schaffer, R. , Velapoldi, R. A., Paule, R. C. , Mandel , J., Bowers, G. N., Jr.,

Copeland, B. E., Rodgerson, D. 0., and White, J. C. , A MultilaboratoryEvaluated Reference Method for Determination of Serum Sodium, Clin. Chem.

27, 1824-1828 (1981 ).

White V, E., Hertz, H. S., and Christensen, R. G., Continuous-Flow Solution

Concentrator and Liquid Chromatograph/Mass Spectrometer Interface and

Methods for Using Both, U.S. Patent No. 4,281,246 (July 28, 1981).

Wise, S. A., Bonnett, W. J., Guenther, F. R. , and May, W. E., A Relationship

Between Reversed-Phase C 18 Liquid Chromatographic Retention and the Shape

of Polycyclic Aromatic Hydrocarbons, J. Chromatog. Sci . 19, 457-465

(1981 ).

Yap, W. T. and Durst, R. A., Electron Transfer in Molecules with Interacting

Multiple Redox Centers, J. Electroanal, Chem. 130 , 3-8 (1981 ).

Blubaugh, E. A. and Doane, L. M., A Vacuum Thin Layer Electrochemical Cell for

Nonaqueous Spectroel ectrochemistry, Anal . Chem. 54 (2), 329-331 (1982).

Chesler, S. N., Guenther, F. R., May, W. E., and Parris, R. M. , SRM's for

Accurate Analyses of PCBs in Oil, ASTM Standardization News 10 (6), 15-20

(1982).

178
• Davidson, R. M., Margolis, S. A., and Coxon, B., An Efficient Two-Step Synthesis of a Novel 15 N-Laheled Cyclonucleotide: 2 ,3' -Anhydro-1 -3-QFructofuranosyl uracil

15 N 2 -1 1 ,6' -Diphosphate, Abstracts of Am. Chem . Soc.

Natl. Mtg. , Las Vegas, NV (1982).

Doane, L. M. and Fatiadl, A. J., Electrochemical Oxidation of Several Oxocarbon Salts in N,N-Dimethylformamide, J. Electroanal . Chem. 135 , 1 93-209

Cl 982)

.

Doane, L. M. and Fatiadi, A. J., Mechanism of the Electrical Conductivity in

Potassium Croconate Violet, J. Res. NBS 87 , 257-260 (1982).

Doherty, R. M., Stewart, J. M., Mighell, A. D. , Hubbard, C. R. , and Fatiadi,

A. J., The Structure of the 1:1 Molecular Complex of Pyrene and Dicyanomethylenecroconate, Acta Cryst, B38 , 859-863 (1982).

Duncan, P., Goshman, N., Bayse, D. D., Schaffer, R., et al

.

, A Candidate

Reference Method for Uric Acid in Serum. II. Interlaboratory Testing,

Clin. Chem. 28, 291-293 (1982).

Fuller, J., Muth, E., Doane, L. M., and Blubaugh, E. A., Optically Transparent

Thin-Layer Electrode for Organic Solvents, Anal. Chem. 54 , 604-604 (1982).

Hancock, D. K. , Subject 5: 100 °S Point of Sugar Scale, B. Coxon, Referee,

U.S. National Committee on Sugar Analysis Report for 1982 Meeting, New

Orleans, LA (1 982).

Hancock, D. K. , Subject 6: Optical Rotatory Dispersion of Quartz Rotators,

A. L. Cummings, Referee, U.S. National Committee on Sugar Analysis Report

for 1982 Meeting, New Orleans, LA (1982).

Hancock, D. K. , Velapoldi, R. A., DeVoe, J. R. , and Blackburn, D. H., Inorganic

Ion-Doped Glass Beads as Microspectrofl uorimetric Standards, Abstracts of

the 1982 Pittsburgh Conference, held March 8-12 , 1982, Atlantic City, NJ

(1982).

Hertz, H. S., Hilpert, L. R., and Richie, K. L., Measurement of Trace Organic

Pollutants in Water, Abstracts from the 1982 Pittsburgh Conference,

Atlantic City, NJ [1 982).

Kirchhoff, W. H., Hertz, H. S., Ku, H. H., Liggett, W. S., McClendon, L. T.,

Taylor, J. K. , and White V, E., Review of Material Provided by EPA on the

Analysis for Organic Chemicals in the EPA Love Canal Monitoring Study,

NBSIR 82-2511 (1 982).

Kline, W. F. , Enagonio, D. , Reeder, D. J., and May, W. E., Chromatographic

Methods for the Determination of Valproic Acid and Carbamazepine in

Freeze- Dried Human Serum, Abstracts of the 1982 Pittsburgh Conference,

held March 8-12, 1982, Atlantic City, NJ (1982).

MacCrehan, W. A., A Centrifugal Filtration System Modified to Minimize Losses

of Organomercury Cations, Anal. Chem. 54 , 838-839 (1982).

179
Margolls, S. A., Reference Materials for Organic Nutrient Measurement, NBS

SP 635, U.S. Gov't Printing Office, Washington, DC 0982).

Schaffer, R. , Sniegoski, L. T. , Welch, M. J., White V, E., Cohen, A., Hertz,

H. S., Mandel , J., Paule, R. C., Svensson, L. , Bjdrkhem, I., and

Blomstrand, R., Comparison of Two Isotope Dilution/Mass Spectrometric

Methods for the Comparison of Total Cholesterol, Clin. Chem. 28 (1),

5-8 (1982).

Sonnefeld, W. J., Zoller, W. H., May, W. E., and Wise, S. A., On-Line Multidimensional Liquid Chromatographic Determination of Polycyclic Aromatic

Hydrocarbons, Anal. Chem. 54 (4), 723-727 (1982).

Sonnefeld, W. J. , Zoller, W. H., Wise, S. A., and May, W. E., On-Line Multidimensional High-Performance Liquid Chromatography Coupling Normal- and

Reversed-Phase Systems, Abstracts of the 1982 Pittsburgh Conference,

held March 8-12, 1982, Atlantic City, NJ (1982).

White V, E., (Book Review) Interpretation of Mass Spectra, Third Edition,

Biomed. Mass Spectrom. 9 (6), iii-iv (1982).

Ausloos, P., Rebbert, R. E., and Lias, S. G. , Pulse- and Gamma-Ray Radiolysis

of Cyclohexane: Ion Recombination Mechanisms, Rad. Phys. and Chem. , in

press.

Botto, R. E. and Coxon, B., Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy of Neomycin B and Related Aminoglycosides, J. Am. Chem. Soc

, in press.

Bunding, K. A., Durst, R. A., and Bell, M. I., Surface-Enhanced Raman Spectroscopy of N-Methylpyridinium Cation and Pyridine: Identification of

Surface Species, J. Electroanal. Chem. , in press.

Coxon, B. and Reynolds, R. C., Synthesis of Nitrogen-15 Labeled Amino Sugar

Derivatives by Addition of Phthal imide- 15 N to a Carbohydrate Epoxide,

Carbohyd. Res. , in press.

Doane, L. M. and Fatladi, A. J., Electrochemical Oxidation of Croconate Salts

and Evidence of Chemical Equivalency of Carbonyl Oxygen Atom and Dlcyanomethylene Group, Angew, Chem. Intern. Ed. Engl. , in press.

Durst, R. A., The International pH Scale, pH and Blood Gases , W. G. Zljlstra,

ed., Groningen, The Netherlands, in press.

Durst, R. A., Blubaugh, E. A., Bunding, K. A., Fultz, M. L., MacCrehan, W. A.,

and Yap, W. T., Organic Electrochemical Techniques Having Potential

Clinical Application, Cl in. Chem. , in press.

Fatiadi, A. J. , (Book Review) Synth£tic Applications of Cyano Compounds, The

Chemistry of the Cyano Group (Hebrew University of Israel), in press.

Fatiadi, A. J., Preparation and Synthetic Applications of Cyano Compounds, The

Chem. of the Cyano Group , Suppl

C, S. Patal, ed. , Wiley, London, in

press.

180
Fatiadi, A. J., The Oxidation of Organic Compounds by Active Manganese Dioxide,

Oxidative Procedures in Org. Chem. Involving Metal Compounds , W. J. Mljs,

ed. , Plenum Press, London , in press.

Fitzpatrick, K. A., Harrison, S. H., Zeisler, R. , and Wise, S. A., Evaluation

of the Sampling and Storage Protocol for Human Liver Samples, in The

Pilot Natl . Environ. Specimen Bank -- Anal . of Human Liver Samples , R. Zeisler, S. H. Harrison, and S. A. Wise, eds., EPA Report, in press.

Fultz, M. L. and Durst, R. A., Mediator Compounds for the Electrochemical

Study of Biological Redox Systems, Anal . Chlm . Acta , in press.

Kline, W. F. , Allen, C. F., Chesler, S. N. , Hllpert, L. R., and Wise, S. A.,

Development of Analytical Methodology for the Determination of Organochlorine Compounds in Human Liver Samples, in The Pilot Natl. Environ.

Specimen Bank -- Anal, of Human Liver Samples , R. Zeisler, S. H. Harrison,

and S. A. Wise, eds., EPA Report, in press.

Kline, W. F. , Enagonio, D., Reeder, D. J., and May, W. E., Liquid Chromatographic Determination of Valproic Acid in Human Serum, J. Liq. Chromatog

.

, in press.

Kong, R. C. , Lee, M. L., Tominaga, Y., Pratap, R., Iwao, M., Castle, R. M. , and Wise, S. A., Capillary Column Gas Chromatographic Resolution of

Isomeric Polycyclic Aromatic Sulfur Heterocycles In a Coal Liquid, J. Chromatog. Sci, , in press.

MacCrehan, W. A., Determination of Organomercury Cations in Tissue Samples

Using Liquid Chromatography with Amperometric Detection, in The Pilot

Natl. Environ. Specimen Bank -- Anal, of Human Liver Samples , R. Zeisler,

S. H. Harrison, and S. A. Wise, eds., EPA Report, in press.

Margo! is, S. A., Reference Materials for Organic Nutrient Measurement:

Proceedings of a Workshop Held at NBS, Gaithersburg, Maryland, October 23,

1 980, in press.

May, W. E., Chesler, S. N. , Hertz, H. S., and Wise, S. A., Analytical Standards

and Methods for the Determination of Polycyclic Aromatic Hydrocarbons in

Environmental Samples, J. Environ. Anal. Chem. , in press.

Schaffer, R. , Mandel , J., Sun, T., Cohen, A., and Hertz, H. S., Evaluation of

the AACC Candidate Reference Method for Serum Glucose Using an ID/MS

Method, in press as an NBS Special Publication.

Sniegoski, L. T. , White V, E., and Konash, P. L. , Synthesis of 2-Naphthal ened 7 Sulfonic Acid, J, Labeled Compounds and Radiopharm. , in press.

Sonnefeld, W. J., Zoller, W. H., May, W. E., and Wise, S. A., On-Line Multidimensional Liquid Chromatographic Determination of Polycyclic Organic

Material in Energy Related Fuel Oils, in Polynuclear Aromatic Hydrocarbons : Phys. and Biol. Chem. , M. Cooke and A. J. Dennis, eds.,

Battelle Press, Columbus, OH, in press.

181
Wasik, S. P. , Miller, M. M., Tewari , Y. B., May, W. E., Sonnefeld, W. J.

DeVoe, H., and Zoller, W. H., Determination of the Vapor Pressure,

Aqueous Solubility, and Octanol -Water Partition Coefficient of Hydrophobic Substances by Coupled Generator Column/Liquid Chromatographic

Methods, Res. Rev. , in press.

White V, E. , Welch, M. J., Sun, T. , Sniegoski, L. T. , Schaffer, R. , Hertz,

H. S., and Cohen, A., The Accurate Determination of Serum Glucose by

Isotope Dilution/Mass Spectrometry — Two Methods, Blomed. Mass Spectrom. , In press.

Wise, S. A., Analytical Techniques for the Determination of Petroleum Hydrocarbons and Combustion Products, in Pollution and the Protection of Water

Qua! i ty . Hemisphere Publishing, New York, in press'.

Wise, S. A., High-Performance Liquid Chromatography for the Determination of

Polycyclic Aromatic Hydrocarbons, Chapter 5 in Handbook for Polycyclic

Aromatic Hydrocarbons , A. Bjtfrseth, ed. , Marcel Dekker, New York, NY, in

press

Wise, S. A., Interlaboratory Comparisons and the Use of Reference Materials

for Quality Control of Analytical Methodologies, in Pollution and the

Protection of Water Quality , Hemisphere Publishing, New York, in press.

Wise, S. A., The National Environmental Specimen Bank -- Background and

History, in The Pilot Natl . Environ. Specimen Bank -- Anal . of Human

Liver Samples , R. Zeisler, S. H. Harrison, and S. A. Wise, eds., EPA

Report, in press.

Wise, S. A., Allen, C. F., Chesler, S. N., Hertz, H. S., Hilpert, L. R., May,

W. E. , Rebbert, R. E. , and Vogt, C. R., Characterization of Air Particulate Material for Polycyclic Aromatic Compounds, EPA Report, in press.

Wise, S. A., Bowie, S. L., Chesler, S. N., Cuthrell, W. F. , May, W. E. , and

Rebbert, R. E., Analytical Methods for the Determination of Polycyclic

Aromatic Hydrocarbons on Air Particulate Matter, in Polynuclear Aromatic

Hydrocarbons : Phys , and Biol . Chem. , M. Cooke and A. J. Dennis, eds..

Battel! e Press, Columbus, OH, in press.

Wise, S. A., Fitzpatrick, K. A., Harrison, S. H., and Zeisler, R., Operation

of the U.S. Pilot National Environmental Specimen Bank Program, Proc.

Intern. Workshop on Environ. Specimen Banki ng and Monitoring as Rel ated

to Banking , held in Saarbrucken, Germany, May 10-14, 1982, in press.

Yap, W. T. , Durst, R. A., and Blubaugh, E. A., Chronoamperometry of PolymerModified Electrodes: Charge Transport by Diffusion and Migration, J. Electroanal. Chem. , in press.

Zeisler, R., Harrison, S. H. , and Wise, S. A., Analysis of Human Liver Speci- mens in the U.S. Pilot National Environmental Specimen Bank Program,

Proc. Intern. Workshop on Environ. Specimen Banki ng and Monitoring as Related to Banking , held in Saarbrucken, Germany, May 10-14, 1982,

in press.

182
Zeisler, R., Harrison, S. H. , and Wise, S. A., eds.. The Pilot National

Environmental Specimen Bank -- Analysis of Human Liver Specimens, EPA

Report, in press.

Bunding, K. A., Bell, M. I., and Durst, R. A., Surface-Enhanced Raman Spectrum

of N-Methyl pyridinium Ion on a Silver Electrode, Chem. Phys. Lett. , submitted for publication.

Davidson, R. M., Margolis, S. A., White V, E., Coxon, B., and Oppenheimer,

N. J., A New, Facile Synthesis of Pento- and Hexo-Furanosyl 2"-Amino

Oxazoline Derivatives, Carbohyd. Res. , submitted for publication.

Fatiadi, A. J., Permanganate Ion: An Old, But Still Novel Oxidant in Organic

Chemi stry , Oxidate Procedures Invol ving Metal Compounds in Org . Chem. , submitted for publication.

Margolis, S. A. and Konash, P. L., The HPLC Analysis of Diastereomers and

Structural Analogs of Angiotensins I and II, Anal. Biochem. , submitted

for publ i cation.

May, W. E., Brown-Thomas , J. M., Chesler, S. N., Guenther, F. R. , Hilpert,

L. R. , Parris, R. M., Richie, K. L., Sonnefeld, W. J., Wise, S. A., and

Hertz, H. S., Interlaboratory Comparisons of Quantitative Analyses of

Individual Compounds in Simple and Complex Mixtures, submitted for

publ ication.

May, W. E., Miller, M. M., Tewari , Y. B., Brown-Thomas, J. M., and

Goldberg, R., The Solution Thermodynamics of Some Slightly Soluble

Hydrocarbons in Water, J. Chem. Eng. Data , submitted for publication.

Roberts, G. D. and White V, E. , Silver Sulfonates as Mass Standards in Field

Desorption Mass Spectrometry, Anal . Chem. , submitted for publication.

Sniegoski, L. T. and White V, E. , Synthesis of 1 -Dodecyl -d 2 s Phosphate, J. Labeled Compounds and Radiopharm. , submitted for publication.

Sonnefeld, W. J. , Zoller, W. H., and May, W. E., A Dynamic Coupled-Column

Liquid Chromatographic Method for Determination of Vapor Pressures of

Organic Compounds, Anal . Chem. , submitted for publication.

Yap, W. T. and Doane, L. M., Determination of Diffusion Coefficients by

Chronoamperometry with Unshielded Planar Stationary Electrodes, Anal

.

Chem. , submitted for publication.

Yap, W. T., Schaffer, R., Hertz, H. S., White V, E., and Welch, M. J., On the

Difference Between Linear and NonLinear Models in Bracketing Procedures

in Isotope Dilution/Mass Spectrometry, Biomed. Mass Spectrom. , submitted

for publication.

183
2. Talks

S. A. Wise, "Research in the NBS Environmental Specimen Bank Relating to Human

Nutrition," Holiday Inn City Line, Philadelphia, PA, October 20, 1981 . Invited

S. A. Wise, "Analytical Methods for the Determination of Polycyclic Aromatic

Compounds on Air Particulate Matter," Sixth International Symposium on Polynuclear Aromatic Hydrocarbons, Columbus, OH, October 29, 1981.

W. E. May, "Verification of Analytical Results Through Use of Several Independent Techniques for Quantitation," Chemical Characterization of Hazardous

Substances in Synfuels Workshop, Battelle Pacific Northwest Laboratory,

Richland, WA, November 6, 1981. Invi ted

R. A. Durst, "Organic Electrochemical Research at the National Bureau of

Standards," Chemistry Department, University of Pittsburgh, Pittsburgh,

PA, November 19, 1981. Invited

S. A. Wise, "Characterization of Polycyclic Aromatic Hydrocarbons in Urban

Particulate Matter," Aerosol /Small Particle Seminar, National Bureau of

Standards, Gaithersburg, MD, November 20, 1981. Invited

W. E. May, "Analytical Methods and Standards for the Determination of PAH in

Environmental Samples," Second International Congress on Analytical

Techniques in Environmental Chemistry, Barcelona, Spain, November 27,

1981.

B. Coxon, "NMR Spectroscopy at 400 MHz," National Institutes of Health,

Bethesda, MD, December 9, 1981. Invited

W. E. May, "Use of HPLC in the Determination of Potentially Toxic Compounds

in Alternate Fuels," Chemistry Department, Alabama A&M University,

Huntsville, AL, December 10, 1981.

H. S. Hertz, "Analytical Chemical Capabilities of the National Bureau of

Standards," Pittsburgh Energy Technology Center, Pittsburgh, PA,

December 16, 1981. Invited

R. A. Durst, "Reference Electrodes and Standards for Biomedical Measurements,"

Symposium on Electrochemical Sensors in Medicine and Medical Research,

Park City, UT, January 11, 1982. Invited

H. S. Hertz, "Clinical Chemistry and Related Programs at the National Bureau

of Standards," Veterans Administration, Washington, DC, February 8, 1982.

Invited

H. S. Hertz, "Quantitative Trace Organic Analysis," Aberdeen Proving Grounds,

Edgewood, MD, March 10, 1982. Invited

D. K. Hancock, "Inorganic Ion-Doped Glass Beads as Microspectrofluorlmetrlc

Standards," 1982 Pittsburgh Conference on Analytical Chemistry and

Applied Spectroscopy, Atlantic City, NJ, March 10, 1982.

184
K. A. Bunding, "The Surface- Enhanced Raman Spectroscopy of N-Methyl pyridlnlum

Ion on a Silver Electrode," American Physical Society Meeting, Dallas,

TX, March 11, 1982.

H. S. Hertz, "Measurement of Trace Organic Pollutants in Water," 1982

Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy,

Atlantic City, NJ, March 11, 19.82. Invited

W. J. Sonnefeld, "On-Line Multidimensional High-Performance Liquid Chromatography Coupling Normal- and Reversed- Phase Systems," 1982 Pittsburgh

Conference on Analytical Chemistry and Applied Spectroscopy, Atlantic

City, NJ, March 11 , 1982.

A. J. Fatiadi, "The Hillebrand Award Address: Chemistry of Oxocarbons and

Pseudo-Oxocarbons. New Organic Semiconductors," The Chemical Society of

Washington, Knights of Columbus, Arlington, VA, March 11, 1982.

W. F. Kline, "Chromatographic Methods for the Determination of Valproic Acid

and Carbamazeplne in Freeze-Dried Human Serum," 1982 Pittsburgh

Conference on Alalytical Chemistry and Applied Spectroscopy,

Atlantic City, NJ, March 12, 1982.

H. S. Hertz, "Research in Isotope Dilution Mass Spectrometry and Combined

Liquid Chromatography/Mass Spectrometry for Clinical Analysis," Johns

Hopkins University, Baltimore, MD, March 12, 1982. Invited

B. Coxon, "NMR Spectroscopy of Carbohydrates at 400 MHz," School of Medicine,

Johns Hopkins University, Baltimore, MD, March 19, 1982. Invited

R. M. Davidson, "An Efficient Two-Step Synthesis of a Novel 15 N-Labeled Cyclonucleotide: 2,3' -Anhydro-1 -3-D- Fructofuranosyl uracil - 15 N 2 -1

' ,6 1 - Di phosphate," American Chemical Society Meeting, Las Vegas, NV, April 2, 1982.

R. M. Parris, "Analysis of Polychlorinated Biphenyls in Waste and Lubricating

Oils," Student Seminar, University of Maryland, College Park, MD,

April 12, 1 982.

B. Coxon, "NMR Spectroscopy at High Field," Chemistry Department, University

of Maryland, College Park, MD, April 13, 1982. Invited

L. R. Hllpert, "Analyses of Aqueous Leachates of SRC II Vacuum Still Bottoms,"

Review Meeting on Hazardous Wastes, Pittsburgh Energy Technology Center,

Pittsburgh, PA, April 14, 1982.

E. A. Blubaugh, "Organic Electrochemical Techniques of Potential Clinical

Application," Symposium on Advanced Analytical Concepts for the Clinical

Laboratory, Riverside Motor Lodge, Gatl inburg, TN, April 30, 1982.

R. G. Christensen, "Quantitative Trace Analysis by Reversed- Phase LC/MS,"

Society for Applied Spectroscopy Meeting, Ramada Inn, Chicago, IL,

May 4, 1982. Invited

185
S. A. Wise, "Operation of the U.S. Pilot National Environmental Specimen Bank

Program," International Workshop on Environmental Specimen Banking and

Monitoring as Related to Banking, University of Saarland, Saarbriicken

,

Germany, May 9, 1982.

R. Schaffer, "Definitive Methods for Organic Analytes for Clinical Chemistry,"

Fourth International Symposium on Quantitative Mass Spectrometry in Life

Sciences, Ghent, Belgium, May 13, 1982. Invited

S. A. Wise, "Analytical Techniques for Organic Analysis of Environmental

Samples," Seventh Annual U.S. /German Seminar of State and Planning for

Specimen Banking, Munich, Germany, May 17, 1982. Invited

S. A. Wise, "Experimental Design for Collection and Storage of Mussels,"

Seventh Annual U.S. /German Seminar of State and Planning for Specimen

Banking, Munich, Germany, May 18, 1982, with K. Kafadar. Invited

L. R. Hilpert, "Quantitative Analysis of Individual Organic Compounds In an SRC II Coal Liquid," U.S. Department of Energy, Sixth Annual Meeting on the Characterization of Coal-Derived Material, Ramada Inn, Pittsburgh,

PA, May 20, 1982. Invited

W. J. Sonnefeld, "Multidimensional HPLC Techniques Applied to the Determination

of Polycyclic Aromatic Compounds in Complex Mixtures," Sixth International

Symposium on Column Liquid Chromatography, Cherry Hill Inn, Cherry Hill,

NJ, June 7, 1982.

S. A. Wise, "The Effect of Cjg Surface Coverage on Selectivity in ReversedPhase Liquid Chromatography of Polycyclic Aromatic Hydrocarbons," Sixth

International Symposium on Column Liquid Chromatography, Cherry Hill Inn,

Cherry Hill, NJ, June 7, 1 982.

L. T. Sniegoski, "Synthesis and Use of Isotopically Labeled Materials in the

Development of Reference Materials at the National Bureau of Standards,"

International Symposium on the Synthesis and Applications of Isotopically

Labeled Compounds, Kansas City, MO, June 8, 1982.

E. White V, "Quantitative Trace Analysis by Reversed-Phase LC/MS Employing

Continuous Sample Preconcentration," American Society for Mass Spectrometry Meeting, Hi 1 ton-Hawai ian Village, Honolulu, HI, June 10, 1982.

L. R. Hilpert and K. L. Richie, "Mass Spectrometric Determination of Trace

Organic Compounds in Aqueous Wastes Associated with Energy Production,"

American Society for Mass Spectrometry Meeting, Hil ton-Hawaiian Village,

Honolulu, HI, June 11 , 1982.

W. E. May, "Multidimensional HPLC Analysis Applied to the Determination of PAH

and Related Compounds in Complex Mixtures," Ohio Valley Chromatography

Forum, Hyeston Woods State Park Lodge, Oxford, OH, June 18, 1982.

186
K. A. Bunding, "Surface- Enhanced Raman Investigations of Surface Species:

N-Meth.yl pyridinium and Pyridine Competition," International Conference

on Electronic and Molecular Structure of Electrode- Electrolyte

Interfaces, Eccles Conference Center, Utah State University, Logan, UT,

July 29, 1982.

R. A. Durst, "Surface-Enhanced Raman Spectroscopy of N-Methylpyridinium Cation

and Pyridine: Identification of Surface Species," International Confer- ence on Electronic and Molecular Structure of Electrode-Electrolyte

Interfaces, Eccles Conference Center, Utah State University, Logan, UT,

July 29, 1982.

H. S. Hertz, "Results of Interlaboratory Quantification of Organics in Fossil

Energy Leachates," Laramie Energy Technology Center, Laramie, WY,

August 3, 1982. Invited

D. J. Reeder, "Certification Methods for SRM 1599: A New Anticonvulsant Drug

Standard," Anaheim, CA, August 9, 1982.

B. Coxon, "Nitrogen-15 NMR Spectroscopy of Aminoglycosides," Eleventh International Carbohydrate Symposium, University of British Columbia,

Vancouver, British Columbia, Canada, August 23, 1982.

M. L. Fultz, "An Electrochemical and Spectroel ectrochemlcal Study of Copper

Bleomycin and Iron Bleomycin," 1982 Federation of Analytical Chemistry

and Spectroscopy Societies, Philadelphia, PA, September 20, 1982.

W. E. May, "Liquid Chromatographic Methods for the Determination of Polycyclic

Aromatic Hydrocarbons in Air Particulate Extracts," 1982 Fall American

Chemical Society Meeting, Kansas City, MO.

W. E. May, "First-Line Supervision of an Analytical Research Group," 1982 Fall

American Chemical Society Meeting, Kansas City, MO.

3. Committee Assignments

Harry S. Hertz

Chairman, ASMS, Committee on Education

Member, ASTM, Committee D19 on Water

Member, CEQ, Interagency Task Force on Environmental Data and Monitoring

Air Pollution Data and Monitoring Working Group, Task Group in

Anticipatory Monitoring

Board of Directors, NCCLS

Technical Advisor, OIML, SP26, Subcommittee Sr5 on Reference Materials

for Calibration of Instruments Meant for Checking Substances During

Medico-Biological and Research Analyses

187
Bruce Coxon

Secretary, ASTM, Committee E13.07 on Nuclear Magnetic Resonance,

Committee El 3 on Molecular Spectroscopy

Associate Referee, International Commission for Uniform Methods of Sugar

Analysis, Subcommittee 5 on 100 °S Point of Sugar Scale

Referee, U.S. National Committee on Sugar Analysis, Subcommittee 5 on 100 °S Point of Sugar Scale

Richard A. Durst

Member, Advisory Board, Analytical Chemistry

Member, ASTM, Committee D19 on Water

Member, Board of Advisory Editors, Ion-Selective Electrode Reviews

Member, Department of the Interior, Office of Water Data Coordination,

Task Group 5 on Chemical and Physical Quality of Water and Sediments

Secretary, IFCC, Scientific Committee, Analytical Section, Expert Panel on pH and Blood Gases

Member, Instrument Society of America, Subcommittee SP76.02 on Electrochemical Analyzers

Member, IUPAC, Committee V on Analytical Chemistry, Subcommittee 5 on Electroanalytical Chemistry

Member, NCCLS, Subcommittee on Electroanalytical Methods

Member, NCCLS, Subcommittee on pH and Blood Gases

Consultant on Electrochemistry , U.S. Army, Task Group on Medical Bioengineering R&D Laboratory

Laurence R. Hi 1 pert

Member, ASTM, Committee D34 on Waste Disposal

Dennis J. Reeder

Member, AACC

Study Group on Cortisol

Study Group on Total Serum Protein

Associate Member, IFCC, Expert Panel on Drug Effects in Clinical Chemistry

Chairman, NCCLS, Subcommittee on Specific Plasma Proteins

Member, NCCLS, Subcommittee on Total Protein

Robert Schaffer

Member, AACC, Committee on Standards

Subcommittee on Cholesterol

Subcommittee on Creatinine

Subcommittee on Electrolytes

Subcommittee on Glucose

Subcommittee on Iron

Subcommittee on Theophylline

Subcommittee on Urea

Subcommittee on Uric Acid

Member, NCCLS, Area Committee for Clinical Chemistry

Subcommittee on Calibration Reference and Control Materials

Subcommittee on Quantities and Units

Subcommittee on Reference Methods and Materials

Member, Council for National Reference System in Clinical Chemistry

188
4. Other

a. Seminars

October 2, 1981 Olmes Bisi, University of Modena, "Transitional Metal

Silicides: Their Chemical Bonds and Electronic

Structure".

October 16, 1981 Dennis J. Reeder, National Bureau of Standards,

"Proteins in Analytical Chemistry".

October 19, 1981 Kathryn A. Bunding, National Bureau of Standards,

"Surface-Enhanced Raman Spectroscopy Experiments With

Substituted Pyri dines and Their Theoretical

Imp! i cations"

.

October 22, 1981 Charles H. Lochmuller, Duke University, "The Role of

Chemically Modified Surfaces in Chromatographic

Resolution".

February 19, 1982 James I. Garrels, Cold Spring Harbor Laboratory,

"Two-Dimensional Electrophoresis: From Specialized

Laboratory to Data Management".

March 3, 1982 Alexander J. Fatiadi, National Bureau of Standards,

"Chemistry of Oxocarbons and Psuedo-Oxocarbons : New

Organic Semiconductors".

March 22, 1982 Robert M. Davidson, National Bureau of Standards, "An

Efficient Two-Step Synthesis of a Novel 15 N-Labeled

Cycl onucl eotide : 2,3 1 -Anhydro-1 -3-D-Fructofuranosyl

uraci 1

15 N 2 -1

' ,6

1 -Diphosphate"

.

May 4, 1982 Elena Katz, Perkin-Elmer Corporation, "The Use of

Small Particles in High-Speed Liquid Chromatography"

.

May 6, 1982 Dennis Schuetzle, Ford Motor Company, "Identification

of Nitrated Polynuclear Aromatic Hydrocarbons in the

Envi ronment"

.

July 15, 1982 Richard Laub, Ohio State University, "How to Separate

Almost Anything from Practically Everything Else".

August 5, 1982 Georges Guiochon, Laboratoire de Chimie Analytique

Physique, France, "Bidimensional Chromatographic

Analysis".

August 13, 1982 Bruno Petti nger, Fritz Haber Institute der Max Planck

Gesel lschaft, Berlin, West Germany, "Influence of

Foreign Metal Atoms Deposited at Electrodes on Local

and Non-Local Processes in SERS".

189
b. Conferences Sponsored

October 18-24, 1981 - W. E. May, Workshop on "A Survey of State-of-the-Art

Instrumental Methods for Chemical Analysis," jointly

sponsored by the National Bureau of Standards and the

Association for the Development and Advancement of

Black Scientists and Engineers (ADABSE), National

Bureau of Standards, Washington, DC.

August 25-26, 1982 - W. E. May, The Analysis of PAH in Complex Mixtures,

Coordinating Research Council Workshop, National

Bureau of Standards, Washington, DC.

c. Seminars Organized

H. S. Hertz, Workshop on the Teaching of Mass Spectrometry, American Society

for Mass

d. SRM

1) SRM

2) SRM

3) SRM

4) SRM

5) SRM

6) SRM

7) SRM

8) SRM

9) SRM

10) SRM

11) SRM

12) SRM

909, Human Serum

998, Angiotensin

1514, DTA Purity Set (In Process)

1549, Powdered Skim Milk (In Process)

1581, Polychlorinated Biphenyls in Oil

1582, Petroleum Crude Oil (In Process)

1590, Wine

1 595, Tripalmitin

1599, Valproic Acid and Carbamazepine in Human Serum

1639, Drinking Water (In Process)

1647, Priority Pollutant Polynuclear Aromatic Hydrocarbons

1649, Urban Dust/Organics

190
IV. Gas and Particulate Science Division

Harry L. Rook, Chief

Raymond L. McKenzie, Deputy Chief

A. Division Overview

The Gas and Particulate Science Division performs research on new and

improved techniques for the measurement of chemical composition on a microscopic scale and conducts research on measurement methods for gaseous

molecules in controlled mixtures and at trace atmospheric levels. The results

of this research are applied to NBS and other international standards programs

and, in selected areas, applied to high priority national problems as addressed

by other federal agencies and private industry. The Division's programs are carried out by four groups with scientific effort divided approximately equally

between gas analytical research and microanalytical research.

During the past year, substantial progress has been made on the Compositional Mapping competence building program. Research on the new ion microscope

has been directed toward quantitative two dimensional mapping of chemical

features on an x,y planar sample. To aid this type of analysis, a DeAnza

image array processor is being interfaced between a special television output

of the ion microscope signal and the Division DEC VAX computer. This system,

when complete, will directly acquire ion images in digital form from the

channel plate detector of the ion microscope and allow automated image processing of chemical and isotopic data. The speed and memory capacity of the VAX

will allow direct transformation of the large data arrays obtained in two and

three dimensional compositional mapping and will allow construction of three

dimensional compositional images. A second accomplishment in this program has

been the intercomparision of depth profile information derived independently

by neutron and ion depth profiling techniques. The results of that joint

study were recently reported at the annual Microbeam Analysis Society Meeting

in Washington, DC. Other accomplishments in microanalysis research include

the final measurement and certification of the first Asbestos SRM; the development of accurate isotopic measurements using laser microprobe mass analysis

(LAMMA) on sample sizes as small as a few femtograms of total material;

research leading to chemical and isotopic characterization of individual

submicrometer particles; and finally, the development of a method for sequential instrument analyses of single particles by AEM and LAMMA.

In the area of atmospheric and gas measurement research, major achievements include the development of a multicomponent atmospheric standard

co-certified for C02 and N 2 0 concentrations with information on the F-ll and

F-12 concentrations; the development of an optoacoustic technique for the

measurement of the gaseous HC1 molecule with a potential sensitivity below

0.1 ppm by volume; successful measurements of the carbon-14 content of samples

as small as 100 yg total mass by Accelerator Mass Spectrometry; the accurate

preparation and analysis of ppb level multicomponent organic constituents in

air-gas mixtures; and finally, the completion of CRM traceability protocols

for SRM containing NO, S02 and propane.

191
As in the past, the Division has been a major contributor to the NBS SRM

program both in research leading to new and better standards as well as in the

certification of current SRM's. Over 2600 individual samples of more than 65

different SRM's have been analyzed for certification during the year.

Future directions in microanalysis research will continue to focus on quantitative compositional mapping and the development of quantitative analytical methods for the ion microscope and the LAMMA. This research will include

multidimensional chemical and isotopic mapping; automated imaging of chemical

maps; mul ti parameter analysis using two or more microanalytical techniques;

and the development of computer techniques for data reduction and for the

transformation of chemical maps containing large multielement data sets.

Future directions in gas analytical research will build on the recent successes in diode laser photometry and in optoacoustic spectroscopy and the

need to develop independent primary measurement methods for many of the

simple gaseous molecules presently certified by gravimetry and comparator

analysis. Research in the coming year will include: isotope dilution gas mass spectrometry for the accurate analysis of C02 ; the measurement of

improved photometric cross sections for use in diode laser IR photometry;

research into response mechanisms of electron capture detectors for use in

trace gas analysis; and finally a collaborative study of material transport

from spark discharges on bulk samples to regions of analytical interest.

1 . Microanalysis Research Group: Overview

The Microanalysis Research Group carries out research to advance the

development and application of microbeam analysis techniques for the chemical,

crystallographic, and morphological characterization of matter on the micrometer and sub-micrometer spatial scales. The analytical techniques utilized

are based on primary (excitation) particle beams of electrons, ions, or photons, and secondary (analytical) signals of x-rays, inel astical ly scattered

electrons, inelastically scattered photons, and ions. The techniques include

electron microprobe analysis, analytical electron microscopy, electron energy

loss spectrometry, secondary ion mass spectrometry, laser micro-Raman spectrometry, and laser microprobe mass analysis. Research is conducted on several

aspects of each technique, including (1) advancing understanding of the basic

physics of sample excitation and attenuation of the secondary radiation;

(2) developing methods of quantitation; (3) producing standards and techniques

as a means of disseminating developments; (4) applying results of the research

to develop improved compositional mapping techniques; and (5) the study of

specific analytical problems in support of NBS and other government agency

activities.

A major highlight of FY-82 has been analytical research on the CAMECA

IMS-3F ion microscope, an advanced form of secondary ion mass spectrometer.

The ion microscope is an imaging mass spectrometer which provides true

microscope images of the surface of a sample formed with secondary ions of

a particular mass-to-charge ratio. The edge resolution of these images is

less than 1 micrometer, and the system is capable of operating with a mass

192
resolution greater than 10,000. The system has been used initially for the

study of depth distributions of ion-implanted arsenic in silicon in support of

the development of an SRM (in conjunction with the Center for Electronics and

Electrical Engineering) and for the study of the participation of oxygen in

the phenomenon of diffusion-induced grain boundary migration (in conjunction

with the Center for Materials Research). The ion microscope will be a major

component in the development of the Compositional Mapping Facility. To

implement this facility, a DeAnza image array processor was also acquired

during FY-82 and is now being interfaced to the DEC VAX computer and to a special television camera. This system will directly acquire ion images in

digital form from the channel plate detector of the ion microscope and allow

automated image processing.

During FY-82, the final stages of the production and certification of an Asbestos Counting Material SRM were completed. This project has involved

extensive staff effort and has required the development of new techniques of

standardization for this unusual standard. This SRM is expected to have a significant impact in standardizing the electron microscope techniques used

to determine environmental asbestos exposure.

Further investigations into the analytical capabilities of the laser

microprobe mass analyzer (LAMMA) have been carried out to assess the potential

of this instrument for trace and isotopic analysis. Limitations to the

accuracy and precision of isotopic ratio measurements have been identified.

In particular, the performance of the ion detector and the digital transient

recorder have been examined. Despite the limitations imposed by these components, useful isotopic measurements were carried out on nanogram quantities of

osmium in a joint study with Lawrence Livermore Laboratory to establish the

decay rate of rhenium-187.

A major advance in the analysis of sub-micrometer particles was achieved

by the development of techniques for sequential analysis of individual submicrometer particles by means of an analytical electron microscope (AEM) and

laser microprobe mass analysis (LAMMA). Following non-destructive AEM analysis

for morphology, major chemical elements, and crystallography, useful mass spectra were obtained with the LAMMA from individual particles as small as 0.1

micrometer in diameter, which is equivalent to a particle mass of approximately

10 femtograms. The combination of morphology, elemental and isotopic analysis,

and crystallography provides an extensive characterization of a particle.

AEM-LAMMA combined analysis will be a major area of activity in the near

future for our Group in cooperation with other Groups in CAC and elsewhere at

NBS as we explore the unique capabilities of these complementary techniques.

We have continued our studies of electron interactions in solids in support of electron microprobe and analytical electron microscope measurements.

The Monte Carlo simulation technique has been adapted to special sample

geometries appropriate to the AEM. In order to simulate more closely electron

interactions in the target, the phenomenon of fast secondary electron production has been included in the simulation. This phenomenon appears to be

especially important in setting an ultimate limit to the spatial resolution of

spectrometries based on inner shell ionization at high beam energies.

193
During FY-82 we have extended our interactions with other groups at NBS.

Microbeam analysis techniques have been utilized in support of (1) the development of neutron beam depth profiling (in conjunction with the Inorganic

Analytical Research Division); (2) studies of the phenomenon of diffusioninduced grain boundary migration (in conjunction with the Metallurgy Division);

(3) depth distribution of arsenic in silicon (in conjunction with the Center

for Electronic and Electrical Engineering); and (4) studies of the microstructure of cement (in conjunction with the Center for Building Technology).

Plans for activities of the Microanalysis Research Group for FY 83/84 are principally centered around research in all of our existing microanalytical

methods, and especially into compositional mapping with the ion microscope and

extending our understanding of sub-micrometer analysis by means of laser microprobe mass analysis and analytical electron microscopy. To achieve more useful

quantitative elemental and isotopic analysis with the LAMMA, considerable

improvement must be realized in the detection and signal digitization systems

as well as in an understanding of the physical factors which control the

ionization process. To implement these LAMMA studies, and to advance the

state of quantitative analysis by means of analytical electron microscopy, we plan to work actively in the development of "high technology" standards for

sub-micrometer analysis; sputtered glass thin films represent the first venture

in this area. Finally, since our past experience has shown that active involvement with applications of mi croanalysi s to high priority problems provides a useful stimulus to research, we anticipate continued collaboration with researchers

within NBS, with several universities and with other government agencies.

Dale E. Newbury, Group Leader; Adville A. Bell, David S. Bright,

Gregory R. Downing, Edgar S. Etz, Inga I. Holl, Ryna B. Marinenko,

Robert L. Myklebust, Patrick J. Sheridan, David S. Simons, John A. Small,

Eric B. Steel, Barbara B. Thorne

2. X-ray Fluorescence Group: Overview

The X-Ray Fluorescence Group performs research on improved techniques for

sample preparation and matrix effect calculations to increase the sensitivity

and accuracy of x-ray fluorescence spectrometry with respect to the chemical

composition of bulk samples.

In FY 82, the X-Ray Spectrometry Group has completed a study on the

application of a preconcentration method using cation-exchange resin filters

for the analysis of selected elements in NBS-SRM's 1577 Bovine Liver and 1575

Pine Needles. During this work we investigated several sample dissolution

methods to improve recoveries of elements such as iron. A research paper on this work has been submitted for publication. Important progress has also

been made in the development of an algorithm for the calculation of the

spectral output distribution of x-ray tubes. This is an important step in our program towards the development of a comprehensive fundamental parameters

method for quantitative x-ray analysis. We plan to continue the development

of our fundamental parameter algorithm and to assess the accuracy of interelement corrections calculated from theory when applied to acutal samples. We are also in the process of certifying thin glass films to serve as NBS-SRM

x-ray spectrometer standards. A major portion of our work consists of the

194
quantitative analysis and homogeneity testing of renewal SRM's. During this

year we have characterized a number of alloy SRM's with our automated

wavelength-dispersi ve spectrometer.

Future directions in x-ray fluorescence research will focus on the

continued development of a comprehensive fundamental parameters method for

matrix effect calculations. We also plan to evaluate the expected increase

in x-ray signal -to-background with a toroidal monochromator especially

designed for energy-dispersive x-ray fluorescence analysis.

Peter A. Pella, Group Leader; Anthony A. Marlow, John S. Sieber

3 . Atmospheric Chemistry Research Group: Overview

The Atmospheric Chemistry Research Group conducts research on measurement

techniques for ambient concentrations of atmospheric species in both the gas

and particle (liquid and solid) phases. This research includes the development

of both collection and in situ analytical methods. A primary objective of

this research is the extension of existing techniques and the development of new analytical techniques for the detection and characterization of trace and

ultratrace level atmospheric materials.

Several important accomplishments have been achieved in spectroscopic

analytical methods. 1) The work on determination of the ozone ultraviolet

absorption cross-section values and the temperature dependence of the absorption cross section has continued this year. Detailed measurements of the

temperature dependence from 210 to 295 K of the eight principal Dobson bands

have improved the accuracy of these coefficients such that the inconsistencies

previously encountered in comparing data obtained by various ground-based

measurement techniques have been resolved. 2) The design and construction of

a new standard reference ozone photometer has been completed and is in the

final stage of evaluation and calibration. The photometer, to be used as the

calibration standard by the EPA, has an accuracy of 2 percent (limited by the

uncertainty of the cross-section value) and a precision of better than 0.3

percent. 3) In a continuation of studies of the measurement of N02 by photoacoustic spectroscopy, a detailed characterization of a measurement interference mechanism involving energy transfer from excited N02 molecules to 02 , resulting in decreased sensitivity as a function of the oxygen concentration,

has been concluded. 4) A second major accomplishment in photoacoustic

spectroscopy has been the development of an optoacoustic technique for the

measurement of HC1 . This technique has an extrapolated sensitivity of 50 ppb by

volume and provides the only available in situ measurement method for this

very important reactive atmospheric gas.

Several major accomplishments have been achieved relating to the measurement and interpretation of radiocarbon concentration and isotope ratios in

atmospheric and environmental samples. The application of Accelerator Mass

Spectrometry to radiocarbon measurements has resulted in the ability to measure

samples as small as 100 yg-carbon with an accuracy of 10 percent. This was achieved through the development of very precise quantitative chemical conversion and transport processes of minute quantities of carbonaceous samples.

The continued development of receptor modeling and source apportionment

195
techniques has occured in parallel to the improvements in radiocarbon analysis.

This year, advances have occurred in the application of source modeling techniques including insights on experimental design to maximize the accuracy and

resolution of source parameters by various analytical techniques.

Gas and particle personnel monitor development and evaluation have continued this year for the EPA. Several NO2 passive samplers have been investigated

under static conditions and in the wind tunnel to evaluate sampling errors that occur due to wind velocity and directional effects. A new sampler for

N02 was developed that has a sampling rate that makes it compatible with the

sampling parameters of the Portable Ambient Aerosol Sampler developed last

year. This demonstrates the feasibility of developing a portable sampler

capable of providing exposure measurements of both gaseous and inhalable

particulate atmospheric materials. The Personal Ambient Aerosol Sampler has

been intercompared with stationary samplers this year to validate its perfor- mance characteristics against commonly used field methods (the dichotomous

sampler). The sampler performed very well and there is an interest by the

EPA to incorporate it in field studies they are conducting.

A number of studies have been initiated this year in various aspects of

particle characterization. A major component of a Center-wide collaborative

study on the transport of material from bulk samples by spark discharge is the

characterization of the size and elemental composition of the material sampled

and transportable from the sample. Experiments have been designed and

initiated to study this process. A collaborative study with members of the

Fire Research Division is underway to measure the refractive index of aerosols

and smoke particles. The study will be extended to measure the refractive

indices of droplets of supersaturated solution formed by evaporation. The

supersaturated solutions are stable in sub-micrometer droplets and will provide

a way to measure and compare the refractive indices with those of the bulk

solution.

Research activities anticipated for the next year include: a) continued

development of spectroscopic and optoacoustic measurement techniques of major

and trace constituent atmospheric gases; b) application of radiocarbon con- centration and isotope ratio measurements to atmospheric hydrocarbon samples;

c) continued characterization of the wavelength and temperature dependence of ozone ultraviolet absorption cross-section values; d) application of source

and receptor modeling techniques to environmental studies (including possible

involvement in an acid-rain study); e) characterization of sampling and

transport from bulk materials by spark discharge; f) study of the optical

properties of particles and droplets by in situ measurements; and g) development of application of the Laser Analytical Microprobe Mass Analyzer for

analysis of particulate samples.

Raymond McKenzie, Group Leader; Arnold Bass, Robert Continetti, Lloyd Currie,

Robert Fletcher, Alan Fried, Robert Gerlach, Rudy Kelly, George Klouda,

David Krask, James Norris, Gerald Tompkins

196
4. Gas Metrology Group: Overview

The Gas Metrology Group conducts fundamental and applied research leading

to the advancement of measurement science and the development of accurate and

reliable standards for a variety of gaseous species. These species comprise

both inorganic and organic materials that are volatile at room temperature.

Basic measurements and research are carried out to assure that the standards

that are developed are accurate and stable, as well as to further the

scientific understanding of the chemical instability and physicochemical

behavior of gaseous species. The Group interacts directly with technical

staffs at NBS, universities, other agencies, and industry, as well as with

appropriate interagency committees (e.g., Interagency Committees on Carbon

Dioxide and Climate, Stratospheric Ozone Protection, Indoor Air Quality) and

international bodies (e.g., International Standard Organization and the World

Meterological Organization). In addition, a limited gas analysis service,

utilizing the unique capabilities of the Group, is provided to other groups at

NBS and to other national and international government agencies.

A major accomplishment of the Group this year has been the establishment

of primary gas standards for C02 in air at atmospheric concentrations which were intercompared with manometric measurements made by Scripps Institute of

Oceanography (SIO). This ensures that an effective and logical transfer can

be made to NBS from SIO, which has provided C02 standards to the World

Meterological Organization and NOAA for the past two decades. NBS, hence,

will become the focal point for C0 2 standards to quantify measurements of

atmospheric C02 and has been designated as lead agency for C02 atmospheric

standards by the Interagency Committee on C0 2 and Climate.

Related to the development of C02 standards has been research which is

leading towards the co-certification of N 2 0 and C02 at atmospheric concentrations and concentration information on freons F- 11 and F-12 in the same standards. Laser-diode and Fourier transform infrared spectroscopy (FTIR)

studies have continued on N 2 0, F-ll, and F-12. Measurements recently completed

on the strongest band systems of F-ll and F-12 in an "atmospheric window" by

FTIR indicate absorbances 17 percent and 5 percent greater, respectively, than

those values used in recent greenhouse warming calculations.

A third component of the Group's gas standards work has been the furtherment of the Certified Reference Materials (CRM's) traceability program which

defines protocols by which commercial gas standards manufacturers can develop

pollutant gas standards (CRM's) at concentrations that are directly traceable

to NBS SRM's. In addition to CO, protocols have now been prepared for NO,

S02 , and propane CRM's. This program is carried out in concert with the

Compressed Gas Association and EPA to ease past excessive demands on NBS gas

SRM stocks, and to concomitantly ensure that needed reliable gas standards

are readily available to industry and national air quality monitoring programs.

In the organic gas standards area, major accomplishments have been the

certification of concentrations and stabilities for SRM gas cylinder mixtures

containing benzene and tetrachloroethylene, the accurate preparation of

ppb-level gravimetric organic gas mixtures, and the accurate preparation of a set of trace level multicomponent organic gas mixtures in nitrogen.

197
Research on a high-rate passive personal sampler has been completed. The new sampler is capable of providing time-integrated data to quantify personal

ambient exposures to N02

. This sampler design, which is simple and inexpensive,

has been characterized and calibrated, and found to provide measureable

exposure information in as little as an hour. The sampler is sensitive to

below 10 ppb N02 /hour exposures, and insensitive to humidity or the presence

of NO.

Ancillary accomplishments include the preparation and analysis of mixtures

of 36 Ar and 40 Ar and the provision of the mixtures in eight cylinders to NASA.

Half of these were sent to the USSR. The mixtures were prepared at the request

of NASA for calibrating mass spectrometers and gas chromatographs used in the

U.S. Pioneer and USSR Venera missions for analyzing the atmosphere of Venus.

Future research plans of the Gas Metrology Group include: (1) continuing

research in laser/FT infrared spectroscopy as an accurate and sensitive

analytical technique. (2) research for identification and measurement of gas

instability and reaction products using FTIR and mass spectrometry

(3) investigation of electron capture (EC) response mechanisms and characteristics for quantifying low-level EC-sensitive gas species; (4) research on the use of gas chromatography for thermodynamic data; and (5) assessment of

candidate "absolute methods" for quantification of gas mixtures.

Walter L. Zielinski, Jr., Group Leader; Barry C. Cadoff, William F. Cuthrell,

William D. Dorko, James W. Elkins, Ernest E. Hughes, Patricia A. Johnson,

Gerald D. Mitchell, Richard C. Myers, George C. Rhoderick, William P. Schmidt,

Gerald A. Sleater, James E. Suddueth.

198
B. Selected Technical Accomplishments

(Gas and Particulate Science Division)

1 . Isotopic Abundance Measurements with the Laser Microprobe Mass Analyzer

(11330)

D. S. Simons

The Laser Microprobe Mass Analyzer (LAMMA), which combines a laser

ablation ionization source with a time-of-flight mass spectrometer, has proven

to be a versatile tool for materials analysis of particles and thin sections.

Because a mass spectrometer is used as the detector of the emitted ions, the

LAMMA is capable of determining isotopic as well as elemental abundance information. However, only one published study to date has exploited this isotopic

capability.

The determination of isotopic abundances in the LAMMA is inherently more

precise than the determination of elemental abundances. In the latter case relative ionization efficiencies among elements can be strongly affected by

the details of the laser-solid interaction, in analogy with the well-known

matrix effects that arise from the ion-solid interaction in secondary ion mass spectrometry (SIMS). Matrix effects are usually not significant for the

isotopes of a given element since they all have the same electronic properties.

The best relative precision for a single isotopic ratio determination on the LAMMA obtained to date is about 5% (one standard deviation). The isotopic

ratios among the major isotopes of lead, which was present as a constituent of

a thin glass film, were measured with the LAMMA. The relative standard deviations of the ratios for 10 separate spectra of closely spaced regions in the

film ranged from 4% to 6% and were independent of whether the calculations of

the ratios were based upon peak amplitudes or integrated peak areas.

The dynamic response of the transient waveform recorder that is used to

digitize and store the mass spectrum is an important factor that affects the

precision of isotope ratio measurements. Although the precision of the

analog-to-digital converter may be 8 bits for input signals that vary slowly

with time, the effective bit resolution is severely degraded when the measured

waveform has major frequency components that approach the bandwidth of the

recorder. Specific sources of error in analog-to-digital conversion that are frequency dependent include integral and differential nonlinearities, missing

codes, and aperture uncertainty. Since the channel contents can change by a factor of 2 in adjacent channels when a mass peak is sampled at 10 ns per

channel, it is clear that very high frequency components are present in the

input signal train from the LAMMA. It has been found that the precision of

the transient recorder for these pulses corresponds to 4 or 5 bits rather than

8. This completely accounts for the measured ratio precisions that are observed.

An example of the potential application of the LAMMA to isotopic analysis

problems is the determination of the half-life of Re-187 by measuring the

ingrowth with time of Os-187 in a sample of rhenium that has been spiked with

a known amount of a reference isotope such as 0s-190. For this experiment,

199
the total quantity of Os-187 created in one year from 1 kg of rhenium is about

6 ng. With the current state-of-the-art, no other mass spectrometric technique

can do a routine isotopic analysis of osmium with this amount of material.

As a test of the capability of the LAMMA to perform this type of measurement, an unknown set of samples of osmium chloride containing approximately

10 ng of osmium with non-natural isotopic composition was supplied by

Dr. Manfred Lindner of Lawrence Livermore Laboratory. A similar sample of

natural osmium was used to calibrate the nonlinear response of the electron

multiplier detector. The correction factor for this effect was as large as 30% of the measured ratio for the conditions of this experiment.

A spectrum of the non-natural osmium sample is shown in figure 40. It is

estimated that less than 1 pg of osmium was consumed in acquiring a single

spectrum. Isotopic ratios were calculated from peak areas of 10 such spectra,

corrected for detector nonlinearity, and averaged. The resulting values are shown in Table 39 along with the revealed isotopic composition of the sample.

It is clear that the LAMMA is capable of determining isotopic ratios from less

than 1 ng of osmium with an accuracy better than 3% when the ratio value is

greater than 0.2. These preliminary results give confidence that the LAMMA

can be used to improve the accuracy with which the half-life of Re-187 is

presently known.

Mass

Figure 40. LAMMA spectrum of osmium with non-natural

isotopic content.

200
Table 39. Isotopic Ratios of Osmium: Non-Natural Mixture.

Average of 10 Spectra

189/188 190/188 192/188

Ratio determined

by LAMMA

0.037

±0. 002

a 0.233

±0.008

0.263

±0.007

Calculated ratio 0.031 0.232 0.256

a 0ne standard deviation of the mean.

2. Microbeam Analysis of Diffusion - Induced Grain Boundary Migration (51109)

D. E. Newbury

Diffusion-induced grain boundary migration is a recently recognized lowtemperature phenomenon that can lead to unexpected grain boundary migration

and vastly enhanced mass transport in polycrystall ine materials. Diffusion of

solute along grain boundaries can cause the boundaries to migrate and sweep

across grains, mixing in solute at rates and concentrations which cannot be

matched by ordinary lattice diffusion at the same temperature. In conjunction

with members of the NBS Metullurgy Division (T. J. Piccone, D. B. Butrymowicz,

J. R. Manning and J. W. Cahn), microbeam analysis techniques were used to

study solute distributions at grain boundaries in polycrystalline copper

annealed in the presence of zinc and arsenic vapors [1]. An x-ray area scan

of a typical grain boundary area in the Cu-Zn system is shown in figure 41a,

along with a line profile compositional trace, Figure 41b. The composition is

found to vary with a wave-like periodicity with increasing amplitude toward

the migrating boundary front. Note that the troughs of the waves coincide

with the troughs actually visible in the x-ray area scan. In the studies with

arsenic as a solute, it was further noticed that the sum of all elements

detected dropped anomalously in the region of the migrating boundary, which

suggested the presence of an undetected light element. This sample was examined by secondary ion mass spectrometry in the_ion microscope with a cesium primary beam. Ion images for 16 0~ and 75 As" indicated the coexistence

of these elements in the region swept out by the migrating boundary, Figures

42a and 42b. By subtracting the sum of all elements found in quantitative

x-ray microanalysis from 100%, the amount of oxygen incorporated in the copper

was estimated to be of the order of 2-5 weight percent. This is a remarkable

observation in view of the fact that the bulk solubility of oxygen in copper

is only of the order of 0.01 weight percent. The oxygen may be present in the

grain boundary region in the form of a finely divided copper oxide with a size

below the spatial resolution of the analytical techniques. Further experiments on this and other systems are planned.

Reference

[1] T. J. Piccone, D. B. Butrymowicz, D. E. Newbury, J. R. Manning,

and J. W. Cahn, "Diffusion-induced Grain Boundary Migration

in the Cu-Zn System" Scripta Metal! urgica, 16_ (1982) 839-843.

201
Figure 41a. X-ray area scan of zinc at migrated

grain boundaries.

Figure 41b. Quantitative zinc line profile along Cu-Zn

grain boundary.

202
203
3. Electron Beam Broadening in Thin Films of Uranium Alloys Analyzed in the

Analytical Electron Microscope (11330)

R. L. Myklebust, D. E. Newbury

The spatial resolution of microanalysis by the technique of analytical

electron microscopy is defined by a combination of the size of the primary

electron beam and the degree of elastic scattering of the beam electrons.

Various models have been developed for the calculation of beam broadening

based on analytic descriptions of scattering (single, plural, and multiple

regimes) and on discrete simulation of electron trajectories (Monte Carlo

electron trajectory simulation). Previously, the available experimental

data on beam broadening that are useful for testing these theories have been

derived from specimens of low to intermediate atomic number (e.g. , A1 to Fe).

Since the cross section for elastic scattering increases as the square of the

atomic number, there is considerable interest in examining beam broadening

in targets of high atomic number.

A series of experiments were carried out in conjunction with A. Romig of

Sandia National Laboratory to measure beam broadening in alloys of uranium and

to compare the results of those measurements with various model calculations.

The U-Mo and U-Nb systems were chosen because in both of these systems, a lamellar eutectic is formed, providing sharp, planar interfaces between a pure

uranium phase containing less than 0.1 wt% solute and a phase containing the

alloying element (either U2 Mo i ntermetal 1 ic or U-12 vit% Nb solid solution).

This sharp partitioning of the solute element provides an ideal marker for

beam broadening. In the experiment, a beam of known diameter was stepped

across a carefully oriented boundary. Energy dispersive x-ray spectrometry was used to measure the x-ray emissions at each location along a line parallel to

the interface. A resulting profile is shown in figure 43. Monte Carlo calculations were performed with a simulation specifically adapted to the case of a planar interface. This simulation carefully considered the partitioning of

scattering steps across the interface, and also considered the change in

scattering power across the interface. The results of the calculation are also shown in figure 43. In general, the agreement realized between experiment

and calculation is good. In the near boundary region, the profile is controlled mainly by the characteristics of the beam size, shape, and intensity

distribution. The effects of scattering can be detected principally in the

tail of the distribution. Additional experiments are planned to examine this

portion of the distribution in greater detail. With this information, the

analytic and Monte Carlo models for beam broadening can be refined.

204
Figure 43. Molybdenum signal normalized to U2 Mo phase as a function of position across a U2 Mo/U interface.

4. Status of the Quantitative Electron Probe Microanalysis Programs

FRAME and FRAME C (11330)

R. L. Myklebust, B. Thorne

The electron probe quantitative analysis programs, FRAME and FRAME C,

have been under development in our laboratory for the past several years.

FRAME computes the quantitative chemical compositional data for electron probe

microanalyses obtained with crystal or wavelength dispersive spectrometers

whereas, FRAME C computes the quantitative results for electron probe data

obtained with an energy dispersive lithium-drifted silicon detector. These

programs have been developed for specific instruments and in the computer

language associated with that instrument. For example, FRAME C was written

in FLEXTRAN to run on a Tracor Northern multichannel analyzer. Because of

this, it has been difficult to transfer these programs from one computer to

another without a great deal of effort.

205
During the past year we have reconstructed both programs to run on the

VAX computer in Fortran 77. Since this is the new standard for Fortran, it was selected as the language for both programs. There may still be some minor

differences among various computers, principally in the way files are read and

written; however, these differences should not affect the use or results of

the programs in any substantive way.

In the past, each version of FRAME C was written to operate on a specific,

computer-based multichannel analyzer. This made each version unique. The new versions of both programs should operate on any computer that has Fortran.

The user does have to give up the ability to process his data using functions

on his multichannel analyzer and move the spectral data into a file on a computer. This is partially offset by greatly increasing the speed with which

the data can be processed.

The programs have been tested and confirmed to operate properly. There

is some documentation remaining to be added to the programs and some simple

operating instructions left to write for the user, otherwise, both programs

are complete. We have a rather large number of requests for the programs §nd we will begin filling these orders as soon as possible. Since both programs

have been extensively described in the past, a publication consisting of only

the source code together with some examples is planned.

5. Crystallographic Contrast in Ion Microprobe Analysis of Inconel (51109)

D. E. Newbury, D. S. Simons

Certain metallic alloy samples are known to exhibit crystallographic

artifacts during Secondary Ion Mass Spectrometric (SIMS) analysis. That is,

different crystal grains of a polycrystal 1 i ne specimen show different absolute

and relative ion yields of the major constituents, even though the elemental

composition of each grain is identical. The effect has been seen most commonly

in nickel -based alloys.

Several previous studies have illuminated various aspects of this problem.

McHugh [1] demonstrated strong grai n-to-grain variations in absolute ion yields

of Fe, Cr, and Ni from an inconel sample under oxygen bombardment but claimed

that relative sensitivities of these elements were essentially invariant.

Bernheim and Slodzian [2] studied the angular dependence of secondary ion

emission from a Ni-2%Cr single crystal under argon or oxygen bombardment, and

with oxygen flooding of the surface. They found that Cr/Ni yields varied with

angular position of the target and hypothesized that these variations were a consequence of differences in implanted oxygen concentration. Christie et al .

[3] found that relative sensitivities of Fe, Cr, and Ni from nickel-based

alloys vary with surface oxygen coverage and that these variations could be

indexed by a matrix ion species ratio. Shiraiwa et al .

[4] showed that

crystallographic contrast exists in ion images of Fe, Cr, and Ni from high

ni ckel -chromium steel and inconel under oxygen bombardment, but the contrast

is eliminated when nitrogen is used as the sputtering ion.

We have incorporated the results of these previous reports into a comprehensive study of crystallographic contrast in the nickel -based alloy inconel

206
X-750. Individual crystal grains in a polycrystal 1 ine sample were characterized

by electron channeling in a scanning electron microscope to determine their

crystal orientations. Selected grains were then individually analyzed in an Applied Research Laboratory Ion Microprobe Mass Analyzer with oxygen bombardment to determine differences from grain to grain in sputtering rate, near- surface depth profiles, relative sensitivities of major species, and spectral

indicators of oxygen concentration.

In figure 44, the closed circles represent the relative sensitivities,

expressed as sensitivity factors, of iron and chromium with respect to nickel

for 13 individual crystallites, measured at ambient instrument pressure. Each

data point is plotted versus the measured ion ratio Cr0/Cr2 which was found to

be a sensitive spectral indicator of oxygen concentration at the site of ion

emission. The open circles represent data from the same crystallites taken at

elevated oxygen pressure in the sample chamber. One notes that smooth curves

(solid lines) can be drawn through the data with typical deviations of less

than 10 percent (dashed lines).

CrO/Cr2 Figure 44. Relative sensitivities for Fe/Ni and Cr/Ni in various

crystal letes of different orientations plotted as a function of the measured CrO /Cr2 + secondary ion ratio.

Several observations can be drawn from this study. First, elevated

oxygen pressure in the sample chamber nearly eliminates the grain-to-grain

variations in the relative sensitivities of the major elemental constituents

of inconel under ion bombardment. Second, the curves of figure 44 can be used

to correct for crystal lographic contrast under ambient instrument pressure by

specifying relative sensitivity factors to be applied according to the measured

ion ratio Cr0/Cr2 of an individual crystallite. Finally, figure 44, along

with other data from this study, shows that crystallographic contrast in

inconel arises from grain-to-grain differences in near-surface oxygen

concentration.

207
The oxygen is incorporated by implantation from the primary oxygen ion

beam and by surface deposition from gaseous oxygen in the sample chamber.

Possible mechanisms for the influence of oxygen flooding on secondary ion

yield include: (1) Compensation for sputtering rate differences due to

orientation which leads to differences in the quantity of implanted oxygen

at the sputtering front; and (2) Modification of ion channeling due to the

formation of an amorphous oxide layer at the surface.

References

[1] J. A. McHugh, Secondary Ion Mass Spectrometry , in Methods and

Phenomena . Methods of Surface Anal vsis . S. P. Wolsky and

A. W. Czanderna, eds. (North Holland, Amsterdam, 1976).

[2] M. Bernheim and G. Slodzian, Int. J. Mass Spectrom; Ion Phys.,

20, 295 (1976).

[3] W. H. Christie et al . , Appl . Surf. Science, 3, 329 (1979).

[4] T. Shiraiwa et al . , Ion Microprobe Analysis of Steel Using

Oxygen and Nitrogen Primary Ions, Second U.S. -Japan Joint

Seminar on SIMS (Takarazuka, Japan, 1978).

6. Development of a Comprehensive Algorithm to Calculate the Spectral Output

Distribution of X-Ray Tubes for X-Ray Spectrometry (11330)

L. Feng, P. A. Pella, J. Small

Several researchers have worked on fundamental parameter models for use

in quantitative x-ray spectrometry . Perhaps the best known work in the field

is that of Criss and co-workers of the Naval Research Laboratory, who developed

a comprehensive computer program called NRLXRF to correct for x-ray absorption/

enhancement effects in thick specimens. In such approaches, it is necessary

to calculate the spectral output of the x-ray tube for excitation of the

sample. Because parameters such as backscattering factors, fluorescence

yields, and ionization cross sections are not known with sufficient accuracy,

it is important to use measured x-ray output spectral distributions to develop

a reliable algorithm. Most of the published x-ray tube spectra are somewhat

restricted to a narrow range of tube voltages and target atomic numbers-FJRLXRF,

for example, uses approximations extrapolated from just a few x-ray tubes

operated from 45-50 kV. We are currently working on an algorithm which generates the ratio of characteristic line x-ray intensity to continuum with the use of extensive experimental data measured by electron microprobe spectrometry.

The data were obtained at various electron accelerating voltages from 10-40 kV

and cover a wide range of atomic numbers. The detector used was a Si (Li)

solid-state detector. From these data we have obtained preliminary fitting

parameters for various targets as a function of atomic number and voltage to

calculate the ratios of characteristic to continuum x-ray intensities. As an example, a comparison of the ratio of the K characteristic line intensity to

continuum as a function of tube voltage for

a

a chromium target tube are sum- marized in Table 40. The table includes values obtained from the NBS algorithm

208
as well as experimentally determined values for spectral data at NBS, and

values calculated from NRLXRF. The better agreement of the NBS calculated

values with the experimental values as compared to NRLXRF at tube voltages

less than 25 kV suggests that an improvement in the accuracy of the quantitative fundamental parameter approach may be possible.

Table 40. Comparison of Ratio of Ka Characteristic Line Intensities to

Continuum as a Function of Tube Voltage for Cr Target Tube.

Ratio

kv NRLXRF NBS (Calc'd) NBS (Expt'l)

10 1.595 2.373 2.300

15 3.436 4.071 4.350

20 4.792 5.279 5.250

25 5.903 6.201 6.050

30 6.845 6.938 6.700

35 7.661 7.549 -- 40 8.390 8.871 7.550

45 9.041 8.53 - - 8.538a

7.68

a

8.05

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7. Certification of Thin-glass Films as Standard Reference Materials for

X-ray Spectrometry and Microanalysis (14210)

P. A. Pella, E. Steel

We have completed the mounting of over 200 glass films prepared by focused

ion-beam sputtering in flat aluminum ring holders. Several films were selected

for characterization from various runs in which the total mass loadings were

about 172 ug/cm2

. These films (i.e., K-1612 glass) were each measured by

energy-dispersive x-ray spectrometry to characterize the elemental homogeneity

and composition for A1 , Si, Ca, V, Mn, Co, and Cu. A film of about the same mass loading was selected for determination of microhomogeneity and for

quantitation by electron probe microanalysis.

In Table 41 are summarized the x-ray intensities normalized to the total mass loading for the average of 13 films. The relative standard deviation of

the set ranged from 1 to 1.5%. Electron probe data indicated that a trend in

composition was noted from low to high for calcium and high to low for Si from

the edge to the film center. The difference in composition from the high

209
point to low point for calcium was 6% relative and 3% relative for silicon.

The minor constituent elements, e.g., Co and Cu appeared to be evenly distributed. These results indicate that the overall uniformity as shown by electron

probe microanalysis was satisfactory for certification of these films as NBS

SRM's for x-ray spectrometer calibration. The final certification of these

films will be accomplished after the compositions of a few selected films are analyzed by atomic absorption and neutron activation techniques.

Table 41. X-ray Intensity Normal ized to Mass Loading for K-•1612 Glass.

counts/yg/cm2

Film #

Mass Loading

yg/cm2 A1 Si Ca V Mn Co Cu

1-13

Average 172.0 41.42 173.4 799 284 633 200 641

Std. Dev. 0.7 0.51 1.7 10 5.7 9.1 2.7 7 % RSD 0.4 1.2 1.0 1.3 1.5 1.4 1.3 1.1

We have finished the fabrication of another glass target (i.e., K-2084)

containing Si, K, Ti , Fe, Zn, and Pb, and have prepared a few sets of sputtered films for evaluation. Several films were subjected to various conditions

of humidity to test the film integrity. These films showed no evidence of

deterioration even when subjected to hot water vapor. Therefore, this particular film composition was determined to be satisfactory for producing standard

films. Electron probe microanalysis of the elemental microhomogeneity,

however, showed serious problems in the uniformity from edge-to-edge for the

elements Ti and Pb. Figure 45 shows a scan of the lead content of the film

from edge-to-edge in 30-one mm step increments. There is about a 25 percent

change in lead content over the film diameter. We are presently modifying the

ion-beam instrument to allow some translation of the substrate stage in

addition to rotation and in this way expect to achieve better uniformity of

film composition.

Glass films are also being prepared for use as standards in microanalysis. These films are less than one micrometer thick and are mounted on

3 mm transmission electron microscope mounts. Previous work has shown that

glass K-411 has sufficient homogeneity for a standard and this year the films'

stability under high voltage electron beam bombardment in an analytical

electron microscope was investigated. Under a fine point beam, the concentrations of Mg and Ca were low with respect to Si. However, under most other

beam conditions, i.e., defocussed spot or rastered area, the film compositions

are stable. Work is continuing by studying glasses of other compositions in

order to determine the optimum sputtering conditions for preparing uniform

thin films.

210
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8. X-Ray Spectrometric Analysis of NBS-SRM Bovine Liver and Pine Needles

After Separation and Preconcentration (11330)

L. Feng, P. A. Pella, J. Sieber

A preconcentration method for the x-ray spectrometric analysis of trace

elements in coal, urban particulate, and urine including detection limits has

been described [1]. Chelex-100 was used to separate trace elements from

alkali and alkaline earth; the separated metals were quantitatively loaded on cation exchange resin filters and subsequently determined by x-ray spectrometry. During the past year we have extended this method to the analysis of

other types of biological samples such as NBS-SRM's 1577, 1577a, 1577b Bovine

Liver and 1575 Pine Needles. We found that with little modification of our published procedure we could measure iron, manganese, copper, and zinc with an accuracy of ±10% as compared to the certified values. A summary of the results

are included in Table 42. As shown in the table the recoveries for all

elements except iron was better than 95%. Several sample dissolution techniques were investigated in an effort to improve the iron recovery. We found

that temperatures of 300 °C or more were necessary in the perchloric acid

digestion procedure to get better iron recovery. Analysis of NBS-SRM 1577

Bovine Liver using quartz and PFA Teflon for dissolution and digestion gave a

211
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212
result of 246 yg/g with an uncertainty of ±10 yg/g based on three replicate

measurements. This represents a recovery of 92 percent. A technical paper

describing this work is being prepared for publication in Analytical Chemistry.

Reference

[1] Kingston, H. M. and Pella, P. A., Anal. Chem. 53, 223-227 (1981).

9. Evaluation of Personal Monitors (14210)

R. A. Fletcher

During the past two years, we have conducted research on the design and

evaluation of a number of Personal Environmental Monitors (PEM's). As part of

this project, laboratory evaluation of the NBS personal particulate monitor

was completed last year. This year, field testing of the monitor has been

undertaken, and the feasibility of incorporating simultaneous gas monitoring

into the device is being studied. In response to a redefinition of inhalable

particulate the monitor has been retrofitted with a new inlet and the unit

has been recharacterized. The gas monitoring effort to date has involved

evaluating a number of small N02 samplers. This report will discuss changes

to the particulate monitor, describe field testing and detail the new gas

sampling efforts.

The inhalable particle size range has been redefined from ^15 ym to <10 ym

aerodynamic diameter (A.D.), based on the Chan-Li ppmann empirical inhalation

curve. As a result, a 10 ym A.D. particle size cut (50% penetration) inlet

modification was made to the NBS particle monitor. The cut characterise cs were determined using laboratory generated monodisperse oleic acid particles

containing a fluorescein dye tracer. Results indicate that the cut size is

very close to 10 ym and well within the new inhalable criteria.

The NBS particulate monitor, with the 10 ym diameter inlet, was field

tested at the University of Arizona (Tucson, AR). An EPA dichotomous particle

sampler was employed as an EPA accepted reference monitor for ambient

particulates.

Both monitors separate and collect fine (<3.5 ym) and coarse (<05 ym)

size particles on filter substrates that allow gravimetric and chemical

analysis. Gravimetric analysis was performed on both size fractions from the

NBS and dichotomous samplers. These filters were subsequently analyzed for

sulfate since ambient sulfate aerosol is predominately found in the fine

particle size fraction and is therefore a good tracer for that size range.

The agreement between the two monitors was good, with the total ambient

particulate sulfate concentration agreeing exactly.

One of the most widely known passive N02 gas samplers is the Palmes tube.

This diffusionally-limited sampler collects N02 on triethanolamine treated

metal screens located at the closed end of a small tube. The N02 collection

rate at quasi-static (<0.2 m/s) wind velocity was measured to be 96 percent of

the predicted value.

213
The Palmes tube was tested at wind velocities of 1 and 2.4 m/s in the NBS

wind tunnel test facility to determine its dynamic N02 collection efficiency.

N02 was generated by oxidation of NO with air and was injected into the

flowing stream of the wind tunnel through 9 jets equally spaced over a turbulent mixing grid.

A chemiluminescence detector was employed down-stream to measure the N02 concentration within the tunnel. The detector was calibrated daily with

NBS permeation tubes.

The velocity and directional dependence is shown in figure 46. This

figure shows the ratio of N02 collected by the Palmes tube to the amount that

should have been collected based on the molecular diffusion rate of the gas

in the tube and the N02 concentration in the air stream as determined by the

chemiluminescence detector. Parallel wind orientation (X) did not affect the

sampling rate, while perpendicular (0) orientation created a 10-15 percent

increase in N02 collection efficiency. It is thought that turbulent mixing

across the tube opening shortens the effective diffusion path and thus increases

the N02 collection rate for the perpendicular case.

Figure 46. Palmes tube N02 collection efficiency as a function of wind speed.

(0) denotes tube orientation perpendicular to the wind stream and

(X) denotes orientation parallel with the stream. The bars

indicate the relative standard deviation for each speed and tube

orientation.

214
A number of passive gas samplers have been evaluated to identify a device

with a high enough collection rate to be useful for low level environmental

N02 monitoring. The sampler found to be most promising is a device in which

the metal screen has been replaced with a glass fiber filter treated with

triethanolamine. Evaluation test results are shown in figure 47 for a quasistatic wind velocity (< 0.2 m/s), N02 concentrations ranging from 0 . 08 - 3.1 ppm,

and relative humidity values ranging from 15-70 percent. The collection rate was determined from the slope of a linear least squares fit to the data to

be 5.3 yg N02 /ppmh.

Figure 47. The rate of N02 collected as a function of gas concentrationexposure duration product. An unweighted linear least squares

fit gives 5.3 yg/ppmh as the collection rate.

Small, passive gas samplers of this type can be used in conjunction with

the NBS particle monitor to determine human exposure to noxious gases as well

as inhalable particulates. This is an important advance in light of the

numerous gas pollutants such as N02 , CO, radon, formaldehyde, and organic

vapors being found in homes and indoor environments where people spend the

vast majority of their lives.

215
10. Measurement of the Temperature Dependence of the Ozone Absorption

Cross-Sections in the Ultraviolet (11330)

A. M. Bass

The project for determination of the temperature dependence of the ozone ultraviolet absorption cross-sections is approximately two-thirds completed.

As discussed in previous annual reports, a critical need exists in the upperatmosphere research-community for accurate, detailed values of these cross- sections for analysis of observational data and for modelling calculations.

We plan to determine these values over the wavelength range 200 nm to 700 nm and over the temperature range 200 K to 300 K. At the present time we have

completed measurements over the wavelength region 250 to 340 nm (Hartley and

Huggins Bands) at three temperatures: 295 K, 243 K, and 228 K. Measurements

have been started at 273 K and will be completed during the coming year.

We have also completed detailed measurements of the temperature variation

from 210 K to 295 K of the cross-sections at the wavelengths of the eight

principal Dobson bands, used for ground-based observations of the ozone total

column density. Dr. W. Komhyr (N0AA) and Dr. C. Mateer (Environment Canada)

have applied these new data to the analysis of ozone data obtained from

various sources and have concluded that the problem of inconsistent data

obtained from different types of observations (Dobson, Satell i te-BUV , SBUV)

when using the older (1957 Vigroux) coefficients, appears now to be substantially solved by use of the new coefficients.

Extension of these measurements to shorter wavelengths, 200 to 250 nm,

is important for application to observations at high altitudes in the

mesosphere. Those measurements will be done in the coming year, as well as extension of the temperature range to the lowest value we can achieve in the

present apparatus (about 210 K)

.

1 1 . Completion of Reference Ultraviolet Photometer for Ozone Calibrations

(11330)

A. M. Bass

For several years NBS has maintained a 3-meter long ultraviolet photometer

to be used as a national standard for calibration of ozone monitors. The

photometer, which operates on the principle of the absorption of ultraviolet

mercury radiation (253.7 nm) by ozone, has been operating satisfactorily and

has been providing calibration services for federal and state agencies and for

private industry. The accuracy of the 3-meter photometer is estimated to be

about ±2%, the uncertainty coming mainly from the uncertainty in the value of

the ozone absorption cross-section at 253.7 nm. The imprecision of the concen- tration determination is estimated to be about 10% relative at 50 ppb, and

decreasing to about 0.5% relative at the highest concentration used.

In 1979 the U.S. Environmental Protection Agency promulgated a new calibration procedure for ozone based on ultraviolet absorption photometry.

The EPA recently requested our assistance in the design and construction of a

216
new photometer to serve as a primary standard for the EPA laboratories. This

work, which was done in collaboration with Dr. R. Paur of EPA, is nearly

finished. A photometer of novel design has been constructed, and testing and

calibration are underway now in our laboratory.

The new standard is a double-beam photometer with an effective path length

of about 172 cm. Absorption of the 253.7 nm line of the mercury spectrum by ozone is determined by means of a very sensitive detection system. From the

measured absorbance and known path lengths, application of the Beer-Lambert

law yields the value of the ozone concentration in the sample. The temperature

and pressure of the sample of ozone in air are continuously recorded and

corrections for these parameters are automatically made. The entire measurement

process is controlled by a desk top computer, and the data are automatically

reduced and stored on magnetic tape.

Preliminary testing of the new instrument in the EPA laboratories in

North Carolina and at NBS has confirmed that the performance of the photometer

is in accordance with or better than design specifications. Over the range of

concentrations from 100 to 1000 ppb of ozone in air the precision of the

concentration determination is better than ±0.3%. The accuracy of the measurement is limited to approximately ±2% principally because of the cross-section

uncertainty mentioned above. A detailed intercomparison of the 3-meter long

photometer and the new standard instrument is now underway in our laboratories.

12. Photoacoustic Detection of HC1 (11330)

Alan Fried

Hydrochloric acid (HC1) is believed to be a key atmospheric species

present both as a hygroscopic gas and as a liquid acid aerosol. This molecule

plays a pivotal role in the movement of chlorine across the air-sea interface

and into the gas phase in the troposphere. In the stratosphere, HC1 acts as a critical, photochemical ly inert reservoir for chlorine atoms cycling through a complex series of 0 3 destruction reactions. Unfortunately, our basic understanding of the role that HC1 plays in the atmosphere is founded on very few

measurements. Because of the rather low ambient background concentrations and

the reactive hygroscopic nature of the HC1 molecule, meaningful atmospheric

measurements require a detection system meeting several stringent criteria:

(1) detection of HC1 in the ppb range, (2) high selectivity from many potential

interfering species, and (3) detection in a manner that preserves the integrity

of the HC1 concentration in the probed volume (i.e., no sample perturbation

due to losses and/or chemical interactions on instrument surfaces).

The goal of our research was to develop a sensitive photothermal detection

system for continuous real-time measurements of HC1 in the lower troposphere.

The results reported here represent the initial phase of this research with a prototype laboratory system. In this study, a discretely tunable deuteriumfluoride (DF) laser was used to selectively excite HC1 transitions in the

3.6 - 4.1 y atmospheric spectral window. The strongest absorption, occurs at

3.63 ym between the P(6) absorption line of H

3

Cl and the P 2 ( 3 ) laser transition.

217
The output of the DF laser, operating at a 1 pul se-per-second repetition

rate, was focused into the center of a glass photoacoustic cell, schematically

shown in figure 48. Sound waves, associated with the rapid conversion of the

laser absorbed energy into translational modes, were detected with an electret

microphone sealed in the cell wall. Amplified signals from the microphone were subsequently fed into an oscilloscope for visual display or processed by a boxcar integrator, and read out using a strip chart recorder.

To Pump

Figure 48. Schematic of photoacoustic HC1 analyzer.

Trace concentrations of HC1 in air were conti nously drawn through the

photoacoustic cell. The flow was directed perpendicular to the axis of the

laser beam, as shown in figure 48. Trace mixtures were generated by diluting

cylinder HC1 , at a nominal cylinder concentration of 50 ppm in N 2 , with air in

a glass mixing chamber close to the photoacoustic cell inlet. The concentration of HC1 at the cell inlet was determined by bubbling the gas through

solution and performing acid-base titrations. An independant acid-chloride

determination was made by diverting the flow through ultra-pure nylon filters.

The quantitatively trapped acid-chloride was subsequently measured by neutron

activation using the 1642.0 and 2167.0 keV 38 C1 gamma-ray peaks.

Although these two techniques were very useful in the present study in

providing us with independent HC1 calibrations, they are not specific enough

for HC1 to be used directly in the ambient atmosphere.

In accordance with theory, the measured photoacoustic response shows a linear relationship with HC1 concentration. From a linear-least-squares fit

of these data and independent noise measurements, we deduce that the minimum

detectable HC1 concentration falls within the range 66-108 ppb. The sensitivity, however, was enhanced by approximately a factor of 2, yielding a predicted detection limit in the range of 50 ppb when ambient air at 44

percent relative humidity was used as the diluent gas in place of dry cylinder

218
air (H2 0=157 ppm). In this more realistic mode of operation, the signal

amplitude increased because of the unique nature of water vapor in collisionally quenching vi brational ly excited HC1 . In contrast, using dry cylinder

air, the relaxation of HC1 and hence the generation of sound, occurs on a much

longer time scale; this results in a dramatically lower signal amplitude. At

the HC1 concentrations used in these comparisions direct absorption of the

laser by H 2 0 and HDO were found to produce negligible interference, and thus

can be ruled out as the cause of this signal enhancement.

Although our present detection limit is substantially above our goal, we are investigating several enhancement techniques that should lower this detection limit well below 1 ppb. At this sensitivity, we will not only have the

capability to assess anticipated spectral interferences , heretofore not

observed, but also will be able to demonstrate novel techniques to minimize

their effect.

13. A Study of Measurement Interference In The Photoacoustic Detection of N0? By Argon-Ion Laser Excitation (11330)

Alan Fried

Nitrogen dioxide (N02 ) is a molecule of major importance in the chemistry

of the atmosphere. As with all molecules of atmospheric interest, there has

been an on going quest for development of increasingly more sensitive and

selective detection methods for studies in both the ambient environment and

the laboratory. Over the past few years, we have been actively involved in

developing and employing sensitive photoacoustic detection techniques for

measuring N02 in various laboratory studies (figure 49). In one such study [1], we employed photoacoustic detection for measuring N02 concentrations produced

in the gas phase titration (GPT) of nitric oxide (NO) with ozone (0 3 ) in

accordance with the bimolecular reaction:

NO (excess) + 0 3 = N02 + 02 (1)

PRESSURE GUAGE

Figure 49. Photoacoustic detection system for N02

.

219
The 488.0-nm line from an argon-ion laser was used as the excitation

source. Since NO is transparent at this wavelength, N02 can be measured

directly without an interfering response from NO. Despite this discrimination, photoacoustic detection of N02 at 488.0 nm, and for that matter

throughout the entire visible region suffers from a lack of information

regarding potential interferences . The present investigation was designed to

study interferences by the major species present in the GPT experiments: NO,

03 , 02 , N 2 and H2 0 vapor. In this study, two types of interferences were

considered: (1) interference by direct absorption of the 488.0 nm laser line

and (2) interference by energy transfer to metastable states of the matrix

gas with a concomitant loss in photoacoustic response.

Interference by direct absorption of the laser was studied by flowing

each of the gases of interest directly into the photoacoustic cell, bypassing

the permeation calibration system. Base line signals measured in this manner

for pure N 2 , pure 02 , a 50 ppm N0/N2 mixture and for H2 0 vapor concentrations

ranging from 20 ppm up to an estimated concentration of 0.3% were all found to

be identical. Interference by energy transfer was studied by directing the

matrix gas of interest over the permeation tube into the photoacoustic cell

and recording the resulting N02 response. The N02 photoacoustic responses in

pure N 2 and in the 50 ppm N0/N2 mixture were found to be identical. The

response in pure 02 , however, was markedly lower. The decreased response

caused by 02 was found to be independent of N02 concentration but clearly

dependent on the 02 concentration, as shown in figure 50.

VOLUME PERCENT 02 Figure 50. The ratio of sensitivity measured in 02 /N2 mixtures to

that in pure N 2 is plotted as a function of 02 concen- tration at a fixed N02 concentration around 1150 ppb.

220
As can be seen, the decrease in response is dependent on the 02 composition, having a pronounced slope at low 02 concentrations and reaching a limiting value at high concentrations. This 02 effect can be reduced by

adding H 2 0 vapor in the 100-200 ppm concentration range. Higher concentrations

of water vapor around 0.3%, resulted in complete signal recovery. These

results are only preliminary and more studies are neededto quantify the

effect.

Such behavior, however, is related to the fact that H 2 0 vapor, is an effective quenching partner. In the case of quenching electronically excited

N02 (N02 *), H 2 0 vapor has been found to be ^6 times more effective than either

02 or N 2 [2],

One interpretation of these observations is that H 2 0 vapor effectively

competes with processes which in the presence of 02 short-circuit the mechanism

responsible for generation of heat, namely N02 *+M->N02 +M. One such process

consistent with the observations above, is that of energy transfer. In such

a mechanism, energy is transferred from N02 * to the metastable 0 2 ( x a ) electronic state of 02 in accordance with: ^

N0 2 * + 02 ( 3 E g

) - N02 + O^Ag). (2)

The x a state of 0 2 is extremely long-lived, having a radiative lifetime of

y about 45 minutes, and based on a quenching rate constant of 2.2 x 10~ 18 cm3 • molT 1 • sec" 1 at the 02 pressures used in this study (600 torr), the

colli si onal relaxation lifetime is on the order of 23 ms. Since the chopping

period used in the present study was much shorter than this (1/250 Hz) the

energy thus transferred to 0 2 ( 1 Ag) would be effectively trapped, thereby

reducing the total amount of energy degrading to heat during the "on" period

of each chopper cycle and hence reducing the photoacoustic response.

The results presented in this preliminary investigation significantly

impact on photoacoustic measurements of N02 carried out at 488.0 nm and

perhaps at other visible wavelengths. The determination of N02 concentration

from such measurements, both in the laboratory and in the atmosphere, would

be in error unless precautions are taken to insure that the matrix gases are of similar composition in the measurement and calibration phases, as was the case in the gas phase titration measurements carried out concurrent with this

study. Small differences in 02 content, however, as might be expected from

different air cylinders, would cause a negligibly small effect.

References

[1] Fried, A., Hodgeson, J. A., Analytical Chemistry 54, 278

(1982).

[2] Myers, G. H., Silver, D. M. , and Kaufman, F. , J. Chem.

Phys. 44, 718 (1966).

221
14. Accelerator Mass Spectrometry (AMS) (11330)

L. A. Currie, G. A. Klouda

Since the First Conference on Radiocarbon Dating with Accelerators

(Rochester, 1978), research and applications of AMS have burgeoned. Dedicated

tandem accelerators have been ordered or installed in at least five different

countries; and applications to atmospheric science, archeology, hydrology,

tectonics, glaciology, geology, oceanography, and cosmochemistry are underway

with a host of long-lived nuclides ranging from 10 Be to 129 I. The technique

has revolutionized the measurement of natural and artificial long-lived radionuclides through the direct measurement of isotope ratios (to ^10~ 15

) rather

than specific radioactivity.

For 14 C, AMS provides an increased sensitivity of about 10 5 compared to

conventional radiocarbon dating techniques. Thus far, the NBS program in

Environmental Radiocarbon represents the only application of AMS to atmospheric

carbonaceous aerosols, and our experiments at Rochester and Tucson are unique

also in terms of sample size (<100 yg-carbon) and carbon isotope separationimplantation as a linked ("hyphenated") technique. Our first experiment at

Rochester was designed as an exploratory evaluation of sample preparation

techniques and the application of a conventional tandem van de Graff to the

measurement of small samples (<500 yg-carbon) containing natural levels of

radiocarbon. Our just-completed experiment at the University of Arizona

represented the first use of that "dedicated" tandem to unknown samples, and

it demonstrated the capability of that machine to measure submilligram samples

to an accuracy of ^10%. (The subsequent installation of an improved sample

holder at Tucson has improved this figure to 3-5%).

A summary of our Tucson data is given in Table 43, in which accelerator

parameters and radiocarbon results are tabulated for a series of standards,

blanks and carbonaceous aerosol samples. The importance of these results is

two-fold: (1) samples as small as 100 yg (contemporary radiocarbon) can be

measured with an accuracy of ^10%; (2) individual chemical fractions of

carbonaceous aerosols with as little as 100 yg can be assayed by AMS-thus

complementing our miniature gas counter measurements (>5 mg-carbon) at NBS.

This hundredfold increase in sensitivity means that isotopic carbon measurements may be used for high resolution (time, space, composition, particle

size) studies of multiple sources of carbonaceous gases and aerosols as opposed to our prior work which focussed on the gross discrimination of

fossil from biogenic carbon sources.

222
Table

43.

Results

of

Accelerator

Mass

Spectrometry-Environmental

Radiocarbon

Measurements.

(Tucson,

May

1982)

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to 21 o CL i— X QC •r— E o u_ o OO +-> rO CO oo

cu 's. ^ '—» a oo

O z 1

CO E

Cl (/) 2: E 1 <u cu El - DC Ll- O —

>

to OO CO

O •r— 00 Cxi CO i

o -a co +-> oo o 4-> ro E ro CU rO cn CO +-> a> e r— E 1 cn CD CD Z5 E c o CU O

<0- •5+ a a) i

CD J2

CD E cu o E rO e 2: e CU +j o <c i

•f— ai cc o; re 1—

O i—

+-> oo JO LU E co

O

re e cu o o o cc _J ro

223
1 5. Receptor Modeling and Radiocarbon in Aerosols: Source Apportionment

(11330)

L. A. Currie, R. W. Gerlach, G. A. Klouda

Important progress in both experimental and theoretical studies of carbo- naceous aerosol sources has taken place during the past year. Cooperative

work with a number of laboratories, in this country and abroad, has made

possible the collection of samples representing a variety of sites and circumstances, and a pattern of fossi 1 /biogenic carbon contributions is consequently

emerging. The theoretical exercise took place specifically at the request of

the EPA and it was designed to evaluate the strengths and limitations of

current methods of source apportionment based on multi species analysis of

receptor (aerosol) samples.

Experimental investigations of 14 C in air particulate samples, carried

out with the NBS mini gas proportional counting system, are summarized in

Table 44 for three classes of sampling regions. The percentages of contemporary carbon listed correspond to the median values for a range of individual

samples. Examination of these data show that, with certain important

exceptions, the urban aerosols were largely fossil in origin, whereas the

rural samples were mostly biogenic. Special exceptions are Portland, Utah-oil

shale lands, and Barrow. In these three studies, radiocarbon measurements

have given definitive confirmation to other data (emissions, meteorology,

chemical composition) that the aerosol carbon has unusual contributions from:

wood-burning (Portland), oil shale dust (Utah), and transpolar European

aerosols (Barrow).

Table 44. Radiocarbon Dating of Atmospheric Particles.

Sampling Location Contemporary-C (%) Comment

(Sub)urban Salt Lake City 28

Denver 29 "Brown Cloud"

Houston 34

Los Angeles 39

Portland, OR 77 Vegetative Burning

Rural Utah - Oil Shale Lands 64 Baseline Data — Desert 88

Abastumani (USSR) 80

Shenandoah Valley 92

Remote Barrow, AK 27 "Arctic Haze"

Considerably more information concerning source types and strengths has

been gained from temporal and compositional patterns for the various regional

samples. In figure 51, for example, the time sequence is shown for the EPA

(1980) study in Houston. Some common trends are clear from this exhibit, as well as an apparent coordinated discontinuity in slope. That is the increase

(on Sept. 13) of total carbon and Pb together with the decrease in 14 C and

224
100

14c

(%)

0

•

O

•

• • • • •

10

c

(Mg/m3

)

o

o

o

o

o

o

0

2 • •

•

K/Fe • •

• •

0

1

Pb

(^9/m3

)

X

X X

X

X

X

X

0 1 1 1 1 1 1 I 10 11 12 13 14 16 18

Observation Dates (Sept. 1980)

Figure 51. Houston — receptor data.

K/Fe suggests an injection of automotive (as opposed to vegetative) carbon on that day. The generally high 14 C values as well as K/Fe ratios has caused

some re-thinking about possible vegetative carbon sources in the Houston area, one likely candidate being the burning of rice hulls.

Quantitative source apportionment of samples such as those collected in

Houston is accomplished by receptor modeling (RM) techniques. A detailed

laboratory intercomparison of the accuracy and precision of RM took place this

spring through the use of a simulation data set generated in our laboratory.

This exercise was based on realistic source profiles, and dispersion behavior,

real meteorological data, and known source strengths and error structure.

Using this simulated data set we were able to evaluate different models (ridge

regression, factor analysis, weighted least squares, . . .) employed by some

nine laboratories, and draw conclusions regarding the strengths and weaknesses

of the alternative models. Highlights from our analysis of both the simulation process, itself, and from the laboratory performances are given in

225
Table 45. It appears that this sort of data intercomparison exercise bears an importance for complex analytical chemical data evaluation procedures ("Chemometrics") which is a direct analogue to SRM intercomparison exercises for the

evaluation of analytical chemical methods.

Already it has demonstrated the need for far more careful treatment of

uncertainties in receptor modeling, and it has shown how improved design of

the measurement process--including individual particle analysis and isotopic

analysis, for example--can minimize source mis-assignments and break the

col linearity which greatly limits sensitivity and precision.

Table 45. Conclusions: Simulation Process.

• Data proved suitable for realistic, reliable tests of: — Deconvolution method resolving power, accuracy, limitations — RM design requirements (sampling, measurements)

• Dispersion model inadequate for emission data use; plume size,

variability too great; no line sources

• Future exercises should include: - Direct replication, sensitivity studies — Multiple receptors, geographic (source, receptor) information - Morphological, isotopic data — Extended "world list", number of unknowns — Discrete feedstock changes, modified sampling schedule

(0700/1900)

16. Methodology for Vapor Pressure Measurements of Organics in the 10 to 10~ 5

Pascal Range (14210)

E. Hughes, G. Sleater, W. Zielinski

Research was carried out to evaluate methodology proposed by the U.S.

Environmental Protection Agency (Federal Register 45-227, pp. 77345-77350,

21 November, 1980) for use by the chemical industry for_the determination of

the vapor pressure of organic compounds in the 10 to 10~ 5 Pascal range. The

proposed methodology was developed by Stanford Research Institute under EPA

contract in an attempt to standardize methodology for vapor pressure data on new chemicals which, under law (Toxic Substances Control Act), industry must

provide to EPA prior to industrial production of new chemicals.

The proposed methodology, based on gas saturation by the test chemical,

the time-integrated adsorption of the gas on a suitable solid sorbent, its

quantitative desorption and analysis by a suitable analytical technique, was thoroughly examined experimentally by NBS. The study revealed that the

greatest uncertainty of the proposed method involves the desorption step

prior to analysis. Desorption efficiency was found to vary as a function of

sorbent characteristics, the accuracy and methodology of loading test compounds

226
on the sorbent for desorption efficiency determinations, the nature of the

extraction solvent used for desorption of that compound, the loading level of

the test compound on the sorbent, and the desorption time. To illustrate,

using maleic anhydride as the test compound and charcoal as the sorbent, gas

chromatographic (GC) peak area (arbitrary units) varied for six different

desorption solvents from about 2,900 (CS2 ) to 35,400 (acetone) after a 1-hour

desorption time, with no GC peak obtained after a 17-hour desorption time.

Desorption efficiency for naphthalene from charcoal varied with naphthalene

loadings (NL) from about 35% (0.8 mg NL) to about 45% (2.5 mg NL).

Further research investigated variables associated with the experimental

gas-saturation system and the measurements. These included proper alignment

of the heating lamps in the constant temperature chamber for improved temperature control, flow-rate calibration and measurement correction as a function

of ambient temperature and pressure, and other factors contributing to

measurement system stability and method standardization.

The detailed research findings were provided to participants (8 laboratories) involved in an NBS-coordinated round-robin to assess inter- and intralaboratory variance for the proposed EPA vapor pressure method. Research was also carried out to evaluate an alternate method for vapor pressure measurements. The alternate method, which does not use a sorbent, is based upon

direct capture of the vapor of the test compound in a cold solvent trap which

was then directly subjected to analysis. An intercomparison of the two methods

is given in Table 46. A final assessment of the proposed method will be made

at the conclusion of the round-robin study.

Table 46 Intercomparison of Proposed EPA Method and Cold Trap Method for

Vapor Pressure Determinations.

Test Vapor Pressure (Pascals) 9

Number of Temperature

Test Compound Replicates °C

Naphthalene 15 30.0

8 30.0

Naphthalene 2 35.2

4 35.2

Maleic Anhydride 9 30.0

6 30.0

Benzophenone 9 30.0

aAverage value (standard deviation).

Cold Trap Proposed Method

17.8 (2.1)

18.0 (2.7)

26.8 (1.2)

36.8

(0.9)

56.1 (10.2)

57.4 (14.4)

0.120 (0.08)

227
17. Development of Multicomponent Toxic Organics-in-Air Standards (14210)

W. Cuthrell, W. P. Schmidt

Stable standards are required to maintain and verify the quality assurance

of low concentration toxic organic vapor measurements needed to assess personal

exposures in the industrial workplace atmosphere. Research efforts on the

development of single component standards have now led to the completion of

the certification of concentration and stability for benzene gas cylinder

Standard Reference Materials (SRM's) at 9.76 and 0.25 parts-per-mil 1 ion (ppm)

by mole, respectively.

Preliminary work on the preparation of ppm multicomponent toxic organic

mixtures using a recently developed microgravimetric approach revealed that a variable number of components of the mixture gave significant deviation (±2%

relative) between their calculated and analyzed concentrations. This procedure

was based upon initial preparation of small glass tubes containing weighed

amounts (0.1-10 mg) of specific organics (one organic/tube), heat-sealing the

tubes, introducing 4-6 tubes in a teflon sleeve connected to an evacuated gas

cylinder, and breaking the tubes inside the sleeve to load the cylinder with

the weighed organics. The cylinder was then pressurized with the matrix gas

(nitrogen) and subsequently analyzed by gas chromatography against reference

standards. Because of the observed deviations, this procedure was modified to

include the cooling of weighed sample tubes with dry ice prior to sealing and

loading the evacuated cylinder one tube at a time using a 1 /8-inch Teflon

sleeve. The modified procedure gave no significant deviations between calculated

and analyzed concentrations for any organic studied so far. Originally, only

five or six organic compounds could be added to a cylinder. Based on the success of the improved procedure, as many as 20 compounds can now be added to

a single cylinder if the need should arise.

The preparation of ppb level gravimetric mixtures has been accomplished

through the use of smaller organic compound sample weights (0.1 mg) or, in some cases, the use of larger cylinders (150 rather than 30 cubic feet) to

allow using larger sample weights (greater precision) and still obtain the same dilution. Binary and tertiary organic cylinder mixtures have been

compared with more concentrated organic cylinder mixtures, and the concentrations have been found by analysis to agree well with those predicted from the

gravimetric data (e.g., Table 47).

Furthermore, individual gas mixtures prepared to contain vinyl chloride,

chloroform, benzene, toluene, tetrachloroethylene, and chlorobenzene have

shown no evidence of changes in concentration over the past two years. These

individual mixtures will serve as the basis for future toxic organic vapor

SRM's.

More recently, a set of gravimetric organic gas mixtures containing four

aromatics (benzene, toluene, chlorobenzene, and bromobenzene) at the 10 ppb

to 2 ppm (by mole) concentration levels has been prepared to assess the

feasibility of issuing such a mixture as an SRM. No problems were encountered

in preparing and analyzing this set of mixtures. Determination of their

stability is now in progress.

228
Table 47. Comparison of Gravimetrical ly-Calculated and Analyzed Standards for

Low (<200 ppb) Concentration and High-Capacity Cylinder Mixtures.

Cyl inder

Capacity

(ft 3

)

Vinyl Chloride

Calculated Analyzed

- Organic Levels, ppb

Benzene

Calculated Analyzed

Tetrachl oroethyl ene Calculated Analyzed

30 73 72 — — — —

30 — — 45 47 — —

30 — — — — 141 142

150 227 222 258 251 — —

150 — — 24 22 9712 9700

150 638 633 840 834 1038 1040

As an adjunct to the development of trace organic constituent standards

in cylinders, research was carried out on the feasibility of developing such

standards in permeation tubes. Investigation of long-term storage parameters

indicated that the only problem was the external absorption of the permeated

organic by the polymer (Teflon) of the permeation device when stored in a static (non-flow) system. When permeation tubes were stored in this manner,

it was noted that, during subsequent use in a constant air flow system, the

device required up to seven weeks to return to its certified permeation rate.

It is hence being recommended that users of such organic gas standards store

permeation tubes in a slowly, continuously-flowing system.

Future work in this program will focus on the generation of multicomponent

toxic organic standard mixtures in cylinders at the sub-ppm level, and the

preparation of sub-ppm level standards for more volatile organics (e.g.,

chloroform, carbon tetrachloride).

18. Standards for Measurement of Atmospheric Carbon Dioxide - (11330)

E. Hughes, R. Myers, G. Sleater

Work on Standard Reference Materials (SRM's) for analysis of atmospheric

carbon dioxide has progressed in two areas: the evaluation of the accuracy of

the standards and the analysis of the SRM's. The question of accuracy has

been addressed through preparation of a new series of gravimetric standards

and by comparison of NBS-analyzed samples to the analysis of the same samples

analyzed at Scripps Institute of Oceanography (SIO) last year. The samples

which will ultimately become SRM's have been obtained and analyses are in

progress.

A number of gravimetric standards have been prepared which duplicate

those previously prepared, and which extend the range above and below the

existing standards. These new standards have been intercompared with the

229
older standards, and the agreement between the calculated concentration and

the measured concentration, is as good as would be predicted from the agreement among the earlier gravimetric standards.

These gravimetric mixtures constitute a precise and presumably accurate

set of standards. The precision can be evaluated from the analytical data,

but the accuracy can only be estimated from the known sources of error. Since

the possibility always exists that some source of error might go unnoticed, it

is essential that some independent confirmation of the concentration be available. We had reported in last years report on such an independent confirmation,

involving three samples which were analyzed using the manometric technique.

These early results suggested a possible bias between values determined by the

two measurement systems (NBS and SIO) of about 0.1 ppm. Consequently, six

more samples were analyzed by SIO during March of 1982 and the results

confirmed an apparent relative bias of about +0.16 ppm. The results of the

second analysis are shown in Table 48.

Table 48. Comparison of Analysis by NBS and

of Carbon Dioxide in ppm.

SIO Concentration

Sample No. NBS

a SI0

b A NBS-SI0

1 335.80 335.62 + 0.18

2 335.56 335.47 + 0.09

3 342.54 342.36 + 0.18

4 342.88 342.64 + 0.24

5 351.30 351.14 + 0.16

6 351.32 351.03 + 0.29

Average + 0.19

Analyzed by comparison to gravimetric standards.

^Analyzed by absolute manometric measurement of each component.

The differences shown are consistent with those previously observed. It

should be noted at this point that the NBS values were calculated assuming

that the reagents used to prepare the gravimetric samples were 100% pure.

This was known not to be an exact assumption; thus considerable effort has

been expended in analyzing the purity of the reagent air and carbon dioxide.

The carbon dioxide was determined to be 99.91% pure, with the principal

impurities being nitrogen, oxygen, and water vapor. The analyses were performed using mass spectrometry and gas chromatography. The problem of

determining the purity of the air was not so straight-forward. Gross impurities, other than carbon dioxide, affect the calculated concentration of carbon

dioxide only in so far as they affect the assumed molecular weight of air.

230
Such gross impurities can be easily recognized, and in this case none were

found present. The presence, however, of minute quantities of carbon dioxide

affects the calculated value directly.

The reagent air had been stripped of the carbon dioxide by passage

through "Ascarite" with the assumption of complete carbon dioxide removal.

Attempts to prove the validity of the assumption were difficult. Replicate

measurement by several techniques, including gas chromatography , non-dispersive

infrared measurements, and catalytic reduction of the carbon dioxide followed

by gas chromatographic measurement of the methane generated yielded a variety

of results varying from zero to 2 ppm C02 in the air. After much effort,

consistent values of 0.16 ppm were obtained by two of the methods. Taking

into account the purity of the carbon dioxide (99.91%) and the concentration

of the C02 in the reagent air, the total correction to the NBS values (C NBS)

would be (C NBS-0.16). If all assumptions are correct, the NBS and SIO

results are now indistinguishable from each other.

19. Development of Protocols for Providing Traceability of Commercial

Gas Standards to NBS SRM Gas Mixtures (14210)

E. Hughes, G. Rhoderick

The purpose of the Certified Reference Material (CRM) program is to

increase the availability of accurate gas standards. The CRM's, being secondary standards, are related to appropriate SRM's and the CRM concentration must

be within ±1% of the SRM concentration. The CRM's are to supplement the

existing SRM stock and are intended for traceability for gas mixtures at con- centrations of a complementary SRM.

The manufacturer produces a batch of CRM's related to SRM's of a given

concentration. The batch is analyzed by measuring one member as an internal

standard against the SRM and then analyzing the other CRM's in the batch

against the batch standard. An auditor, in this case Research Triangle

Institute (RTI), selects two samples which are analyzed against the appropriate

SRM. All data is sent to NBS for review and statistical analysis. NBS

determines whether all requirements are met according to previously established

criteria [1].

During the past year, nine batches of carbon monoxide in nitrogen con- sisting of 205 CRM's, two batches of carbon monoxide in air consisting of 53

CRM's, and one batch of nitric oxide in nitrogen consisting of 17 CRM's have

met the requirements for Certified Reference Materials. Table 49 gives the

contents, nominal concentrations, manufacturer, number of CRM's and date for

each batch.

In addition to those listed in Table 49, there are three batches of

nitric oxide in nitrogen and three batches of carbon monoxide in nitrogen

which are still undergoing analysis and investigation.

231
Table 49. Certified Reference Materials

CRM Content Manufacturer

Nominal

Concentration

Number of

Samples

Date

Completed

co/n2 Matheson 50 ppm 11 2/5/82

CO in Air AIRC0 42 ppm 17 2/9/82

C0/N2 AIRC0 1000 ppm 11 3/2/82

co/n2 Scott 1000 ppm 36 3/3/82

co/n2 Scott 250 ppm 30 3/15/82

CO in Air Scott 42 ppm 36 3/15/82

co/n2 AIRC0 2400 ppm 17 3/16/82

co/n2 AIRC0 8% 11 4/26/82

co/n2 Scott 10 ppm 36 4/28/82

no/n2 AIRC0 500 ppm 17 5/21/82

co/n2 Scott 25 ppm 36 5/21/82

co/n2 AIRC0 5000 ppm 17 7/22/82

The main problem of the program is indicated by the data of the nitric

oxide-in-nitrogen CRM's. The 100 and 1000 ppm nitric oxide-in-nitrogen CRM's

appear to be unstable. Additional measurements are being made to try to

determine whether the disagreements are due to imprecision or instability.

Table 50 shows data for the 1000-ppm batch as analyzed by the manufacturer.

The data shows that several samples have decreased in concentration from one analysis to the next. This behavior suggests that some samples are unstable,

but it would be difficult to prove that the lot is either stable or unstable.

Samples whose concentrations had decreased at each succeeding analysis

appear to be unstable. If this decrease of about 0.5% in six months is real,

then after one year's time, the concentration would decrease by 1%, which

would not be tolerable for a CRM. Accordingly, the batch should be analyzed

again three months from the last analysis. The 100 ppm nitric oxide-innitrogen batch reflects the same type of behavior and it too is to be

reanalyzed.

Another problem which has been observed is due to the imprecision of

measurement by the producer. A batch may be measured several times but the

imprecision of measurement makes it difficult to recognize stability or variability problems.

232
Table 50. Data for 1000 ppm N0/N2 of CRM vs. Internal Standard.

Sample

No.

Concentration 3

12/17/81

Concentration3

1/25/82

Concentration 3

6/7/82

Di fferences 3

6/7 - 12/17

1 954.1 953.3 951 .6 -2.5

2 954.1 955.4 953.6 -0.5

3 953.8 954.0 953.5 -0.3

4 953.3 953.8 956.7 +3.4

5 955.0 954.7 950.8 -4.2

6 953.8 953.6 950.0 -3.8

7 953.7 953.1 952.4 -1 .3

8 953.0 954.0 955.7 +2.7

9 954.4 953.5 952.2 -2.2

10 955.4 954.9 954.2 -1.2

11 953.9 955.4 954.7 +0.8

12 955.0 955.4 055.5 +0.5

13 955.6 954.6 954.7 -0.9

14 954.2 955.7 955.6 +1.4

15 954.5 955.4 954.7 +0.2

16 954.6 955.6 956.7 +2.1

17 954.3 953.5 951.5 -2.8

18 953.3 954.5 953.8 +0.5

Concentration is in parts per million by mole.

Most of

manufacturer

see Table 51

between 1 .0

uncertainty.

the certifications have gone very smoothly with no problems. The

and RTI have agreed very well on almost all of the CRM batches,

. The uncertainty for the concentration of a batch has been

to 1.2% on the average, with only a few having a somewhat higher

Appendices for the Procedure on CRM's have been written for carbon

monoxide, nitric oxide, and sulfur dioxide, the last two having been completed

this past year. The Appendix for propane has been written and submitted for

approval

.

Reference

[1] Hughes, E. E. and J. Mandel . A Procedure for Establishing Traceability

of Gas Mixtures to Certain National Bureau of Standards' SRM's.

NBSIR 81-2227, NBS EPA-6001 7-81 -010 , May 1981.

233
Table 51. Comparison of Manufacturers' and Auditors' Concentrations

Concentration, ppm by mole

Percent

CRM Manufacturer Manufacturer RTI Di fference

50 ppm C0/N2 Matheson 47.2 + 0.6 ppm 47.3 + 0.5 ppm 0.2

50 ppm CO/Air AIRC0 42.4 + 0.5 ppm 42.4 + 0.5 ppm 0.0

1000 ppm C0/N2 AIRC0 946 + 9 ppm 944 + 9 ppm 0.2

1000 ppm C0/N2 Scott 970 + 7 ppm 972 + 7 ppm 0.2

250 ppm C0/N2 Scott 240.0 + 2.4 ppm 244.4 + 2.4 ppm 0.1

42 ppm CO/Air Scott 42.7 + 0.4 ppm 42.7 + 0.4 ppm 0.0

2400 ppm C0/N2 AIRC0 2400 + 24 ppm 2414 + 24 ppm 0.4

8% C0/N2 AIRC0 7.70 + 0.08% 7.72 + 0.08% 0.3

10 ppm C0/N2 Scott 9.90 + 0.11 ppm 9.94 + 0.11 ppm 0.4

25 ppm C0/N2 Scott 24.3 + 0.3 ppm 24.3 + 0.3 ppm 0.0

500 ppm N0/N2 AIRC0 470 + 5 ppm 470 + 5 ppm 0.0

5000 ppm C0/N2 AIRC0 4682 + 47 ppm 4691 + 47 ppm 0.2

20. Design and Evaluation of a High--Rate Passive Sampler for Ambient Level

of Nitrogen Dioxide (11330)

B. Cadoff

Passive gas samplers are used to measure time-average concentrations of

pollutant gases and vapors. These devices sample the atmosphere through mass transport of the gas by diffusion or permeation with subsequent trapping on

an appropriate absorbing chemical or surface. Generally, these samplers have

been devised for the industrial environment where concentrations of particular

gases may be one to two orders of magnitude higher than in non-industrial

ambient atmospheres. We have developed a high-rate sampler, employing

triethanolamine as the absorbing agent, that can obtain adequate samples of

N02 in a few hours or less at ambient concentrations.

The sampler is constructed from a Nuclepore 47 mm aerosol holder which

is fitted with a Nuclepore 0.8 ym polycarbonate membrane. A fiberglass disc

containing triethanolamine is placed beneath the membrane. The base of the

aerosol holder is capped with a polyethylene stopper. Before sampling, the

sampler is kept in an air-tight enclosure (such as a jar). To sample ambient

air, the sampler is removed from the jar. The total exposure time is recorded,

and the sampler is placed back in its container for subsequent laboratory

analysis.

234
The analytical work-up is done directly inside the sampler; the method

utilizes Saltzman reagent to produce a violet-colored solution. This procedure

has been adapted from one reported by Palmes et al . , [1].

Table 52 shows representative data obtained over a range of concentrations of N02 , at two levels of relative humidity, and varying ratios of N0/N02

. It is seen that the concentration of NO has no effect on the sampling of N02 and that there is no effect on changing the relative humidity level from 20

percent to 60 percent. The sampler gives consistent results for concentrations

of N02 ranging from 61 to 329 ppb, and sampling times as short as 1 hour. It can be seen (Table 52) that the ratio of N02 measured to the integrated

exposure (A/B) varies only slightly, indicating a good consistency of sampler

performance for all conditions.

Table 52. Laboratory Evaluation of High-Rate Personal Sampler for

Nitrogen Dioxide.

no2 (ppm)

Exposure

(hr) no/no2

Percent

R. H.

Integrated

Exposure

(ppm-hr) [B]

N02 Found

(yg) [A]

Ratio

A/B

0.061 1.00 5.5 20 0.061 0.815 13.4

0.078 1.00 7.6 60 0.078 1.06 13.6

0.329 1.00 6.3 20 0.329 4.29 13.0

0.260 2.47 12.1 60 0.641 8.26 12.9

0.124 4.60 5.0 60 0.578 7.28 12.6

0.129 4.60 4.8 20 0.595 7.32 12.3

0.074 12.00 7.6 20 0.888 10.3 11.6

The lowest integrated exposure investigated was 0.061 ppm-hr. However,

it is estimated that integrated exposures of approximately one-fifth this

amount can be measured; or stated another way, an exposure to 12 ppb for one hour should be measurable with this sampler. A paper describing these results

is currently in review for submission to Analytical Chemistry [2].

References

[1] Palmes, E. D., Gunnison, A. F. , DiMattio, J., and Tomczyk, C.

Am. Ind. Hyg. Assoc. J . , 1976 , (37), 570.

[2] Cadoff, B. C. and Hodgeson, J. "Design and Evaluation of a High-Rate Passive Sampler for Ambient Levels of Nitrogen

Dioxide", to be submitted.

235
21 . Development of Mixtures of 36 Ar and 40 A r for Characterization of the

Atmosphere of Venus (11330)

W. Dorko, G. Rhoderick

Several mass spectrometers and gas chromatographs were involved in the

U.S. Pioneer and Russian Venera missions to Venus in 1978. The interpretation

and correlation of the data produced by these instruments was difficult to

perform to the required degree of accuracy. To resolve this difficulty,

several standards for intercalibration of the instruments were needed. Due to

the importance of these experiments, NASA asked NBS to prepare two mixtures

(Table 53) consisting of Argon-36 and Argon-40 in a matrix of carbon dioxide.

The critical factors were that the 36 Ar to 40 Ar ratio be known with an uncertainty of less than 0.5 percent relative, and that the ratio be close to

uni ty.

The best method of producing the mixtures would be by gravimetrical ly

blending pure gases into cylinders. However, due to the weighing limitations

of the analytical balances and the low concentration level of the argon in the

final mixtures, they could not be blended directly. Hence, an intermediate

mixture was made, from which the final mixtures were produced. The basic

procedure used to prepare mixtures 1 and 2 was as follows:

(a) each of the three reagent gases was procured by NBS and

analyzed to determine the type and the amount of the

impuri ti es

.

(b) weighed amounts of 36 Ar, 40 Ar, and CO2 were added to two

evacuated cylinders to produce mixtures "A" and "B" which were numerically 5000 ppm 36 Ar and 5000 ppm 40 Ar in CO2

.

(c) weighed amounts of mixture "B" were added to two other

evacuated cylinders, after which weighed portions of CO2 were added to produce mixtures 1 and 2.

Because it was not practical to monitor the weight loss/gain of cylinders

during the blending process, the mixtures were compounded by observing partial

pressures to get to nominal concentrations, while the final results were calculated from the weight data. A special blending manifold was developed

for preparing the "A" and "B" mixtures. There was a possibility that some of

the argon isotopes were not quantitatively flushed into the sample cylinder.

Table 53. 36 Ar/40 Ar Mixtures Requested.

Concentration, ppm by mole

Component

36 Ar

40 Ar

C02

Mixture 1 25 ± 2 25 ± 2

bal ance

Mixture 2 50 ± 4

50 ± 4

bal ance

236
Therefore, after the final addition of the C02 , gas potentially trapped at two

locations in the manifold was analyzed for argon to adjust the calculations.

To calculate the concentrations in cylinders "A" and "B", it was necessary

to know the weights of the 36 Ar, 40 Ar, and C02 added, and the impurities in

these individual gases (note: an impurity of 36 Ar was found in the 40 Ar).

After correcting for impurities, the concentrations of 36 Ar and 40 Ar in "A" were determined to be 0.5051 (±0.0006) and 0.5078 (±0.0004) respectively;

those for "B" were determined to be 0.4922 (±0.0006) and 0.4946 (±0.0004),

respectively. The 36 Ar/40 Ar ratio determined by gas mass spectrometry agreed

well with that determined from the mixing data, thereby confirming the

blending results.

The final two mixtures were prepared and the concentrations were determined (Table 54) after correcting the 40 Ar concentration for the amount

of that impurity found in the matrix carbon dioxide. Gas mass spectrometry

was also used to confirm the argon isotope ratios of the final mixtures. The

values obtained for these mixtures were well within the requisite specifications. Mixture 1 was then transferred into four cylinders and mixture 2 transferred to four other cylinders resulting in four sets of two cylinders

each. The four sets were forwarded to NASA; NASA then forwarded two sets to

Russia.

Table 54. 36 Ar/40 Ar Standard Mixtures Prepared.

Mixture

Concentration (ppm by mole)

36 Ar 40 Ar

Ratio

36 Ar/40 Ar

1 24.70 ± 0.04 24.93 ± 0.03 0.9908 (±0.0015)

2 49.12 ± 0.07 49.46 ± 0.05 0.9931 (±0.0015)

22. Development of Parts-per-Bi 1 1 ion Nitrous Oxide-in-Air Standard Reference

Materials (14306)

J. W. Elkins, E. E. Hughes, P. A. Johnson, R. L. Sams (550)

Three major areas of concern motivated our interest in undertaking the

development of gas mixtures containing nitrous oxide (N 2 0) in air at ambient

concentration levels (270-330 ppb) as Standard Reference Materials (SRM's):

(1) the effect of N 2 0 on reducing stratospheric ozone; (2) the "greenhouse"

effect of N 2 0 on climatic changes; and (3) the role of N 2 0 in the Earth's

nitrogen cycle. Recent figures released by the National Research Council [1]

indicate that a doubling in the atmospheric concentration of N 2 0 may result

in about a 10% reduction in stratospheric ozone (twice the reduction predicted

for a doubling of freons F-ll and F-12), which would decrease the screening

effect of stratospheric ozone for harmful solar ultraviolet radiation reaching

the Earth's surface. Further, N 2 0 has strong infrared absorption bands in the

"atmospheric window" which results in a stronger "greenhouse" warming effect

per mole for N 2 0 increases than for atmospheric carbon dioxide increases

(current models predict a global temperature rise of 0.7 K for N 2 0 doubling

237
(^300 up to 600 ppb) and a 2.9 K for C02 doubling (^300 to 600 ppm [2]). In

addition, biologists are interested in ascertaining the transformation rate of

ammonium to nitrate in studies of the Earth's nitrogen cycle by measuring

changes in N2 0 concentration [3].

The research strategy in the development of these SRM's has been initially

to prepare gravimetric standards at ppm-levels, then dilute to ppb-levels by

gravimetry. Verification of assigned concentration values is being based on intercomparing standards using electron capture-gas chromatography (EC-GC) and

tunable diode laser-infrared spectroscopy (TDL-IR). Table 55 shows a comparison of results for concentration in various standards by both EC-GC and TDL-IR.

The calculated concentrations (Meas. Cone.) shown refer to the predicted values

from a plot of detector signal versus gravimetric concentration. A set of 15

gravimetric standards at ppb-levels were prepared from four different ppm-level

gravimetric standards. Intercomparison of the standards against each other

by EC-GC showed that the reproducibility of the preparation of gravimetric

standards was better than ±0.15% (maximum range). An initial set of SRM's has

been analyzed, with reproducibility of replicate samples of better than ±0.2%

(maximum range). Therefore, it appears that individual SRM's of N 2 0-in-air

should be certifiable to ±0.5% (two standard deviations). Homogeneity studies

of our initial set of SRM's of the same nominal concentration, indicate that

each cylinder must be certified separately.

Infrared techniques offer the possibility of not only comparative measurements (e.g.. Table 55), but also for absolute determinations of concentration.

We are currently in the process of determining individual intensities for

lines in the v 3 band system of N 2 0. This infrared parameter (along with total

pressure, temperature, and pathlength measurements) will give independent

verification of concentration values.

Table 55. Comparison of Electron Capture-Gas Chromatography (EC-GC) and

Tunable Diode Laser-Infrared Spectroscopy (TDL-IR) Measurements

N 2 0 Gravimetric Standards (GRAV).

GC-EC TDL-IR

Sample #

Grav. Cone,

(ppb)

Meas. Cone,

(ppb) A %

Meas. Cone,

(ppb) A %

1 259.7 259.7 0 259.7 0

2 275.1 275.1 0 274.8 -0.1%

3 284.2 284.0 +0.07% 284.4 -0.07%

4 323.7 323.2 -0.15% 323.7 0

238
References

[1 ] Causes and Effects of Stratospheric Ozone Reduction:

An Update , National Research Council, National Academy

Press, Washington, D.C. pp. 339 (1982).

[2] Lacis, A., J. Hansen, P. Lee, T. Mitchell, and S. Lebedeff,

Geophys . Res. Lett. , 8, 1035-1038 (1981).

[3] Elkins, J. W. , Wofsey, S. C., McElroy, M. B., and Kaplan, W. A.

in Estuaries and Nutrients , ed. by B. J. Neil son and L. E. Cronin, Humana Press, N. J. 447-464; Wofsy, S. C. McElroy,

M. B., and Elkins, J. W. , Science 213 , 754-757 (1981 ).

239
C. Outputs and Interactions

(Gas and Particulate Science Division)

1. Publications

McPeters, R. D., Bass, A. M. , "Anomalous Atmospheric Spectral Features

Between 300 and 310 nm Interpreted in Light of New Ozone Absorption

Coefficient Measurements," Geophysical Research Letters, Vol . 9,

No. 3, 227-230 (1982).

Rehm, R. G., Bright, D. S., "First Order Kinetic Titrimetry" Anal. Chem.,

54, 398-401 (1982).

Fletcher, R. A., Bright, D. S., "NBS Portable Ambient Particulate Sampler,"

Final Report for NBS to EPA, Agreement No. AD-1 3- F-0-034-0, Exposure

Monitors 9/80-8/81

.

Currie, L. A., "Nuclear and Chemical Dating Techniques: Interpreting the

Environmental Record," Proceedings of American Chemical Society

Symposium Series No. 176, (1982).

Currie, L. A., "Particulate Carbon: Atmospheric Life Cycle," (1982).

Currie, L. A., "Quality of Analytical Results, with Special Reference

to Trace Analysis and Sociochemical Problems," Pure and Applied

Chemi stry . , Vol. 54. No. 4, 715-754, (1982).

Currie, L. A., Klouda, G. A., "Counters, Accelerators, and Chemistry,"

American Chemical Society Symposium Series, No. 176, Nuclear and

Chemical Dating Techniques Inter preting the Environmental Record

(1982).

Currie, L. A., Klouda, G. A., Gerlach, R. W., "Radiocarbon: Nature's

Tracer for Carbonaceous Pollutants," Proceedings of the Conference

on Residential Solid Fuels, Environmental Impacts and Solutions,

published by Oregon Graduate Center (1981).

Cooper, J. A., Currie, L. A., and Klouda, G. A., "Assessment of Contemporary

Carbon Combustion Source Contributions to Urban Air Particulate

Levels Using C-14 Measurement," Env . Sci . & Tech. , v 1

5

, 1045 (1981 ).

Rogers, L. B. , Crummett, W. B., Currie, L. A., Palconer, W. E., Libby,, R. A.,

Reilley, C. N., Shylts, W. D., Westgard, J. 0., and Wilson, M. K.

,

"Recommendations for Improving the Reliability and Acceptability of

Analytical Chemical Data Used for Public Purposes," Chem. Eng. News

44 (1 982).

Gerlach, R. W., Kowalski, B. R., "The Generalized Standard Addition Method:

Intermetal 1 ic Interferences in Anodic Stripping Voltammetry,"

Analytica Chimica Acta , Vol. 134, 119-127 (1982).

240
Kowalski, B. R., Gerlach, R. W., Wold, H., "Chemical Systems Under Indirect

Observation," in Systems Under Indirect Observation Casual ity* Structure*

Predl ction . North- Hoi 1 and , 191-207 (1 982).

Steinbach, W. R. , Lohrstorfer, C. F., and Etz, E. S., "Analytical Application

of a Multiplex Detector Raman Microprobe," Microbeam Analysi s--l 982 , Heinrich, K. F. J., Ed., San Francisco Press (1982).

Purcell, F. , Etz, E. S., "A New Spectrograph with Multichannel Optical

Detector for the Raman Characterization of Microparticles," Microbeam

Analysi s--l 982 , Heinrich, K. F. J., San Francisco Press (1 982 )

.

Grynpas, M. D. , Etz, E. S., Landis, W. J., "Studies of Calcified Tissue by

Raman Microprobe Analysis," Microbeam Analysi s--l 982 , Heinrich, K. F. J.,

Ed., San Francisco Press (1 982)

.

Fletcher, R. A., Bright, D. S., "NBS Portable Ambient Particulate Sampler

NBS-EPA Report," Project No. 553-3455, Agreement No. AD-BF-0-034-0.

Fletcher, R. A., Bright, D. S., McKenzie, R. L., "The NBS Portable Ambient

Aerosol Sampler Proceedings of the EPA National Symposium on Recent

Advances in Pollutant Monitoring of Ambient Air and Stationary Sources."

(1982).

McKenzie, R. L. , Bright, D. S., Fletcher, R. A., Hodgeson, J. A., "Development

and Characterization of Personal Exposure Monitors for Particulates,"

Proceedings Issue Journal of Environmental International .

Fried, A., Hodgeson, J. A., "Laser Photoacoustic Detection of Nitrogen Dioxide

in the Gas-Phase Titration of Nitric Oxide with Ozone," Anal. Chem. 54_,

278 (1982).

Fried, A., "A Study of Measurement Interference in the Optoacoustic Detection

of N0 2 by Argon-Ion Laser Excitation," Applied Spectroscopy , 35(5) (1982)

Hughes, E. E., "Certified Reference Materials for Continuous Emission

Monitoring," JAPCA 32, No. 7, 708-11 (1982).

Kagann, R. H., "Infrared Absorption Intensities for OCS," J. Mol. Spectrosc.,

94, 1 92-1 98 (1 982).

Marinenko, R. B., "Preparation and Characterization of K-411 and K-412 Mineral

Glasses for Microanalysis: SRM 470," NBS Spec. Pub. 260-74, (1982).

Newbury, D. E. , "What is Causing Failures of Aluminum Wire Connections in

Residential Circuits," Analytical Approach in Analytical Chemistry (1982)

Joy, D. C., Newbury, D. E. , Davidson, D. L., "Electron Channeling Contrast

in the Scanning Electron Microscope," J. Applied Physics (1982).

Romig, A. D. , Newbury, D. E., Myklebust, R. L., "Beam Broadening in a Strongly

Scattering Target in the Analytical Electron Microscope," Microbeam

Analysi

s

(1982).

241
Newbury, D. E., "Beam Broadening In the Analytical Electron Microscope,"

Microbeam Analysis (1982).

Piccone, T. J., Butrymowicz, D. B. Newbury, D. E., Manning, J. R., Chan,

J. W., "Diffusion- Induced Grain Boundary Migration in the Cu-Zn

Systems," Scripta Metal 1 urgica , 16 , 839-843 (1982).

Goldstein, J. I., Newbury, D. E., Echlin, P., Joy, D. C., Flori, C.,

Lifshin, E. , Scanning Electron Microscopy and X-ray Microanalysis , Plenum Press (1 981 )

.

Small, J. A., "Quantitative Particle Analysis in Electron Beam Instruments,"

Scanning Electron Microscopy , Vol . 1 , 447-461 (1981 ).

Steel, E. B., Small, J. A., Sheridan, P. J., "Analytical Errors in Asbestos

Analysis by Analytical Electron Microscopy," NBS Special Publication 619

Asbestos Standards: Materials and Analytical Methods, U.S. Government

Printing Office (1 982).

Leigh, S. Steel, E. B., Small, J. A., Sheridan, P. J., Filliben, J.,

"Statistical Considerations in the Preparation of Chrysotile Filter

Reference Materials: Filter Homogeneity," NBS Special Publication 619

Asbestos Standards: Materials and Analytical Methods, 1). S. Government

Printing Office (1982).

Myklebust, R. L. , Small, J. A., Newbury, D. E., "Quantitative Electron Probe

Microanalysis of Fly Ash Particles," Atomic & Nuclear Methods in Fossil

Energy Research, Plenum pp. 285-294 (1982).

Mylkebust, R. L., Small, J. A., Newbury, D. E., "Errors Observed in the

Analysis of Particles Mixtures by Overscanning," Scanning Electron

Microscopy , Vol. 1, 477-482. (1981).

Small, J. A., Steel, E. B., "Asbestos Standards: Materials and Analytical

Methods," NBS Special Publication (1982).

Steel, E. B. Small, J. A., Sheridan, P., "Analysis by Analytical Electron

Microscopy," Analytical Errors in Asbestos, NBS Special Publication

619 (1 982).

Leigh, S., Steel, E. B., Small, J. A., Sheridan, P. J., Filliben, J.,

"Statistical Considerations in the Preparation of Chrysotile Filter

Reference Materials," NBS Special Publication (1982).

Currie, L. A., Gerlach, R. W. Klouda, G. A., Ruegg, F. C. Tompkins, G. B.,

"Miniature Signals and Miniature Counters: Accuracy Assurance Via

Microprocessors and Mul ti parameter Control Techniques," submitted for

publication to the 11th International Radiocarbon Conference.

242
Currie, L. A. Klouda, G. A., Continetti, R. E., Kaplan, I. R., Wong, W. W.,

Dzubay, T. G. , Stevens, R. K., "On the Origin of Carbonaceous Particles

in American Cities: Results of Radiocarbon "dating" and Chemical

Characterization," submitted for publication to the 11th International

Radiocarbon Conference (1982).

Schell, W. R., Swanson, J. R., Currie, L. A., "Anthropogenic Changes In

Organic Carbon and Trace Metal Input to Lake Washington," submitted for

publication to the 11th International Radiocarbon Conference (1982).

Cadoff, B. C., Hodgeson, J. A., "Design and Fabrication of a High-Rate Passive

Sampler for Ambient Levels of Nitrogen Dioxide," submitted for publication in Analytical Chemistry (1 982).

Kagann, R. H., Elkins, J. W. , Sams, R. L., "Absolute Band Strengths of

Halocarbons F-ll and F-12 in the 8-16 ym Region, Journal of

Geophysical Research (in press).

Fried, Alan, Berg, Walter, "Photoacoustic Detection of HC1," submitted for

publication (1982).

Kagann, R. H., "Infrared Absorption Intensities for N 2 0, J. Mol. Spectrosc ., (in press).

Schmidt, W. P. , Rook, H. L., "The Development of Accurate, Stable Gas

Standards for Trace Levels of Benzene and Tetrachl oroethyl ene

,

submitted for publication to Analytical Chemistry (1982).

Schmidt, W. P., Rook, H. L., "The Development of Standard Reference Materials

Containing Selected Toxic Organic Vapors in Compressed Gas Mixtures,"

Proceedings of the U. S. Environmental Protection Agency National

Monitoring Symposium, (in press).

Simons, D. S., "Isotopic Analysis with the Laser Microprobe Mass Analyzer,"

in Microbeam Analysis , (in press).

Downing, R. G., Fleming, R. F. , Simons, D. S., Newbury, D. E., "NeutronInduced Reactions and Secondary Ion Mass Spectrometry: Complementary

Tools for Depth Profiling," Microbeam Analysis , (in press).

2. Talks

Bright, D. S., Myklebust, R. L., Newbury, D. E., "Stereo Representations of

Monte Carlo Electron Trajectories," MAS, Washington, D.C. (1982).

Currie, L. A., "Role of Isotopic and Trace Analysis in Understanding Man's

Impact on Atmospheric Pollution," Montgomery College, Rockville, MD.

(2/11/82).

243
Currie, L. A., "Development of Ultrasensitive Radiocarbon Measurement

Techniques and their Application to Determining Man's Contribution

to Atmospheric Carbonaceous Matter," The Pittsburgh Conference,

Symposium on Advanced Techniques & Standards in Environmental

Measurements, (3/11/82).

Currie, L. A., "Synthetic Aerosol Data Set - Analysis and Interpretation,"

Rougemont, North Carolina (3/16/82).

Currie, L. A., "Receptor Models, Isotopic Tracers, and Multidimensional

Chemical Analysis," University of Alberta, Canada, (4/22/82).

Currie, L. A., "Miniature Signals and Miniature Counters: Accuracy Assurance

via Microprocessors and Mul ti parameter Control Techniques," University

of Washington , Seattle, Washington, (6/23/82).

Currie, L. A., "Anthropogenic Changes in Organic Carbon and Trace Metal

Input to Lake Washington," University of Washington, Seattle,

Washington, (6/22/82).

Currie, L. A., "On the Origin of Carbonaceous Particles in American Cities;

Results of Radiocarbon "Dating" and Chemical Characterization," University

of Washington, Seattle, WA (6/24/82).

Chabay, I. S., "The Bigger They Are, The Harder They Fall: Accurate Aerosol

Size Measurements by Doppl er-Shift Spectroscopy," American Association

for Aerosol Research, Miramar Sheraton Hotel, Santa Monica, CA (2/19/82).

Etz, E. S., "Materials Characterization by Raman Microprobe Spectroscopy,"

Dept, of Analytical Chemistry and Failure Analysis, COMSAT Laboratories

(12/17/82).

Etz, E. S., "A New Spectrograph with Multichannel Optical Detector for the

Raman Characterization of Microparticles," Joint Meeting of Electron

Microscopy, Society of America (EMSA) and the Microbeam Analysis

Society (8/12/82).

Etz, E. S., "Studies of Calcified Tissue by Raman Microprobe Analysis,"

Joint Meeting of the Electron Microscopy, Society of American (EMSA),

and the Microbeam Analysis (8/13/82).

Etz, E. S., "Analytical Applications of a Multiplex Detector Laser-Raman

Microprobe," Joint Meeting of the Electron Microscopy Society of

America (EMSA) and the Mi.crobeam Analysis Society (8/9-13/82).

Etz, E. S., "Raman Microprohe Spectroscopy in Materials Characterization,"

Department of Physics, University of Miami, Coral Gables, FL (4/16/82).

Etz, E. S., "Raman Scattering in the Microscopic Domain: Analytical Application of the Raman Microprobe," School of Chemistry, Georgia Institute of

Technology, Atlanta, GA (4/15/82).

244
Etz, E. S., "Raman Microprofcie Analysis and Developing Applications to

Biomedical Studies," Papanicolau Cancer Research. Institute, Miami,

FL (’4/20/82}

.

Elkins, J. W., and Sams, R. L., "Measurements of Nitrous Oxide and

Halocarbons F-ll and F-12 hy Fourier Transfer Infrared and

Tunable Diode Laser Spectrometers," IX Federation of Analytical

Chemistry and Spectroscopy Societies, Philadelphia, PA (9/23/82).

Elkins, J. W., "Development of Ultra-Trace Gas Standards," Scott Environmental

Technology, Plumsteadvill e, PA (12/7/82).

Fletcher, R. A., Bright, D. S., McKenzie, R. L., "NBS Portable Ambient

Aerosol Sampler," EPA Monitoring Symposium (5/82).

Fletcher, R. A., "The NBS Portable Ambient Aerosol Sampler," EPA National

Symposium on Recent Advances in Pollutant Monitoring of Ambient Air

and Stationary Sources, Raleigh, NC (5/7/82 )

.

Fried, Alan., "Application of Photothermal Detection Techniques for

Tropospheric Measurements of HC1 and Other Species of Atmospheric

Interest," (4/7/82).

Fried, Alan., "Photothermal Spectroscopic Techniques," A Course Lecturer

Presented in 2 Lectures at a Workshop Held at NBS "A Survey of Stateof-the-Art Instrumental Methods for Chemical Analysis," (10/18/82).

Fried, Alan., "Application of Photothermal Detection Techniques for

Tropospheric Measurements of HC1 and Other Species of Atmospheric

Interest," Presented at NCAR, Coulder, Colorado (3/18/82). Invited

Fried, Alan., "Trace Detection of Atmospheric Molecules by Photothermal

Techniques," Presented at IBM Research Labs, San Jose, Calf., (8/12/82).

Invited

Fried, Alan., "Application of Photothermal Techniques for Trace Detection of

N0

? in the Troposphere," Presented at NASA's Instrumentation Workshop

for H 0 and N 0 Tropospheric Species, (8/16-20/82) Palo Alto, Calf,

x y x y

Invited

Gerlach, R. W., "Description of Procedures for Generating Aerosol Data Set

and Properties of the Data Set," Environmental Protection Agency,

Quail Roost Conference Center, Rougemont, North Carolina (3/15/82).

HUghes, E., E. , "Certified Reference. Material s for Continuous. Monitoring,"

Air Pollution Control Association, Specialty Conference on Continuous

Emission Monitoring, Denver, Colorado (11/11/81).

Kagann, R. H. , Sams, R. L., and Elkins, J. W., "Intensities of Halocarbon

F-ll and F-12 by Infrared Fourier Transform Spectroscopy in the 8-16

245
McKenzie, R. L., "Development and Characterization of Personal Samplers for

Respirable Particulates and Gases," International Symposium on Indoor

Air Pollution, Health and Energy Conservation, University of

Massachusetts Amh.ersj:, Massachusetts (10/15/81).

Newbury, D. E., "Monte Carlo Calculations of Electron Interactions In

Samples with Special Geometries," Workshop on Electron Beam - Specimen Interactions in Solids, Asilomar, CA (4/20/82).

Newbury, D. E., "Beam Spreading in the Analytical Electron Microscopy,"

Microbeam Analysis Society - Electron Microscopy Society of America

Joint Conference (8/10/82).

Newbury, D. E. , "Beam Broadening in a Strongly Scattering Target in the

Analytical Electron Microscope," Microbeam Analysis Society - Electron Microscopy Society of America Joint Conference (8/10/82).

Newbury, D. E., "Stereographic Presentation of Monte Carlo Electron

Trajectory Simulation Results - Electron Microscopy, Society of

America Joint Conference (8/13/82).

Newbury, D. E. , "Recent Developments in Microbeam Analysis Techniques,"

Microbeam Analysis Society, Scientific Research Lab, Ford Motor Co.

Engr, Res. Center (11/5/81).

Schmidt, W. P., "Development of SRM's Containing Selected Organic Vapors

in Compressed Gas Mixtures," Environmental Monitoring Systems Lab.

Environmental Protection Agency, Mission Valley Inn, Raleigh, NC

(5/6/82).

Simons, D. S., "Isotopic Analysis with the Laser Microprobe Mass Analyzer

(LAMMA)," American Society for Mass Spectrometry, Honolulu, Hawaii

(6/9/82).

Simons, D. S., "Laser Microprobe Mass Spectrometry," Workshop on Laser

Mass Spectrometry for the Production and Measurement of Inorganic

Ions, American Society for Mass Spectrometry, Honolulu, Hawaii

(6/8/82).

Small, J. A., "Microprobe Analysis of Particles 0.05-10 ym in Diameter,

University of Maryland Nuclear and Atmospheric Chemistry Division

Seminar (1/29/82).

Small, J. A., "The Analysis of Asbestos Fibers by Analytical Electron

Microscopy Development of Reference Filter Standards, Pittsburgh

Conference (3/82).

246
3. Committee Assignments

Harry Rook

Member, ASTM D-22 Sampling and Analysis of Atmospheres

Member, ASTM D-22. 05 Calibration

Member, ASTM D-22. 07 Precision and Accuracy of Methods

Member, Office of Water Data Coordination, Committee 5F

Raymond McKenzie

Member, ASTM D-22 Sampling and Analysis of Atmospheres

Member, ASTM D-22. 03 Monitoring Instrumentation

Member, ASTM D-22. 05 Calibration

Member, ASTM D-22. 07 Precision and Accuracy of Methods

David Bright

Member, NBS Postdoctoral Selection Committee

Member, ASTM E-29 Particle Size Measurement

Member, ASTM SC. 10 Liquid Particle Measurement

Lloyd Currie

Member, Intersociety Committee - Methods of Air Sampling and Analysis

Member, International Committee for the Calibration of the Radiocarbon

Time Scale

Member, Model Validation Subcommittee - Receptor Modeling Workshop

Member, CAC Computer Utilization Committee

William Dorko

Member, American Chemical Society, Washington Section, Board of Managers

Edgar Etz

Member, ASTM D-22 Methods of Sampling and Analysis of Atmospheres

Ernest Hughes

Member, IS0/TC 158 Gas Analysis

Member, IS0/TC 158/SC-l Methods for Preparation and Definition of Gas

Mixtures for Calibration

Member, IS0/TC 158/WG-2 Transfer Lines and Sampling

Member, IS0/TC 158/WG-3 Evaluation of the Characteristics of Analysis

Member, IS0/TC 158/WG-4 Analysis of Natural Gas

Member, IS0/TC 158/WG-l Terminology

Robert Myklebust

President Microbeam Analysis Society (National Council)

Member, ASTM E-2 Emission Spectroscopy

Member, ASTM E-2. 04 Standard Reference Materials

Chairman, Arrangements for 1982 MAS/EMSA National Meeting

Dale Newbury

Chairman, Microbeam Analysis Society

Chairman, Technical Program Committee

Chairman, National Council for the MAS

Member, ASTM E-42 Surface Analysis

Member, Journal of Microscopy, Editorial Review Board

Member, Scanning, Editorial Review Board

247
Peter Pella

Memher, ASTM E-2 Emission Spectroacopy

Member, ASTM E-2.Q2 Statistics, Calibration and Standardization

Gerald Sleater

Member, ASTM D-22 Sampling and Analysis of Atmospheres

Member, ASTM D-22. 06 Source Sampling

Member, ASTM D-22. 07 Precision and Accuracy of Methods

Walter Zielinski

Member, Interagency Committee on C0 2 and Climate

Member, Stratospheric Ozone Protection

Member, Indoor Air Quality

Member, ASTM D-22 Sampling and Analysis of Atmospheres

4. Other

Prof. Georges Slodzian, Center de la

Recherche Scienti fique, Orsay, France,

"Recent Advances in Instrumentation for

Secondary Ion Microscopy,".

(.NBS Sponsor: D. Simons)

Prof. Jack Dodd, Hamilton, New York,

"Schlieren Microscopy of Small Particles,"

(NBS Sponsor: H. Rook)

Permatina S. Goel , Department of Chemistry,

Indian Institute of Technology, Kanpur, India,

"Non-magnetlc Origin of Iron Meterorites ,"

(NBS Sponsor: L. Currie)

Prof. Richard Laub, Chemistry Department,

Ohio State University, "How to Separate

Almost Anything from Practically Everything Else,"

(NBS Sponsor: W. Zielinski)

b. Standard Reference Materials

X-Ray Fluorescence

1248C Alloy

1244 Alloy

1245 Alloy

1246 Alloy

1247 Alloy

Cl 285 Alloy

Cl 85A Alloy

Cl 1 37 , C1137A Alloy

a. Senlnars

August 2 , 1 982

March 22, 1982

June 1 , 1982

July 15, 1982

248
Gas Metrology Group

1625 S02 Permeation Tube, 10 cm 1626 S02 Permeation Tube, 5 cm

1627 S02 Permeation Tube, 2 cm

1629 N02 Permeation Tube

2653 N02 /Air 250 ppm

2654 N02 /Air 500 ppm

2655 N02 /Ai r 1000 ppm

2656 N02 /Ai r 2500 ppm

1683 N0/N 2 1684 N0/N 2 1685 N0/N2 1686 N0/N 2 1687 N0/N2 2630 N0/N 2 2631 N0/N2

1677 C0/N2 1678 C0/N 2 1679 C0/N 2 1680 C0/N 2 1681 C0/N 2

2612 CO/Air

2613 CO/Air

2614 CO/Air

1658 CH4 /Air

1659 CH4 /Air

1660 CH4 /C Hg/

Ai r

1661 S02 /N2 1662 S02 /N2 1663 S02 /N 2 1664 S02 /N 2

2627 N0/N 2 2628 N0/N 2 2629 N0/N2

1670 C02 / Ai

r

1671 C02 /Ai

1672 C02 /Ai

50 ppm

100 ppm

250 ppm

500 ppm

1000 ppm

1500 ppm

3000 ppm

10 ppm

50 ppm

100 ppm

500 ppm

1000 ppm

10 ppm

18 ppm

42 ppm

1 ppm

10 ppm

4 ppm CH4

500 ppm

1000 ppm

1500 ppm

2500 ppm

- 1 ppm C 3 Hg

5 ppm

10 ppm

20 ppm

330 ppm

340 ppm

350 ppm

1911 Benzene Permeation Tube

1805 Benzene/N2 0.25 ppm

1806 Benzene/N2 10 ppm

249
,
NBS-114A (REV. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See in structions)

1. PUBLICATION OR

REPORT NO.

NBSIR 82-2620

2. Performing Organ. Report No. 3. Publication Date

December 1982

4. TITLE AND SUBTITLE

Annual Report 1982, Center for Analytical Chemistry

5. AUTHOR(S)

C. W. Reimann, R. A. Velapoldi, J. K. Taylor

6. PERFORMING ORGANIZATION (If joint or other than N B S. see instructions) 7. Contract/Grant No. national bureau of standards

DEPARTMENT OF COMMERCE 8. Type of Report & Period Covered

WASHINGTON, D.C. 20234

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City. State. ZIP)

10.

SUPPLEMENTARY NOTES

J Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11.

ABSTRACT ( A 200-word or less factual summary of most significant information . If document includes a significant

bi bliography or literature survey, mention it here)

This report summarizes the technical activities of the Center for Analytical

Chemistry at the National Bureau of Standards. It emphasizes activities

over the Fiscal Year, 1982 in the Laser Analytical Chemistry Group, the

Inorganic Analytical Research Division, the Organic Analytical Research

Division, and the Gas and Particulate Science Division. In addition, it

describes certain special activities in the Center including quality

assurance and voluntary standardization coordination, the National

Environmental Specimen Bank, and service analysis coordination.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolon s) Analytical chemistry; analytical services; gas ana particulate science; inorganic

analytical chemistry; National Environmental Specimen Bank; organic analytical

chemistry; quality assurance; voluntary standardization.

13. AVAILABILITY

Uni i mi ted

(XT] For Official Distribution. Do Not Release to NTIS

~l Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402.

Q3! Order From National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

15. Price

USCOMM-DC 6043-P80

1J.U.S- GOVERNMENT PRINTING OFFICE: I 98 3-38 0' 9 ; 7 . - 37J
H