Applied Atomic Spectroscopy

Transcription

1 Applied Atomic Spectroscopy Volume2 Despite the development of alternative techniques, emission spectroscopy is still the means used to conduct the overwhelming number of metal analyses required by industry. Furthermore, as a result of the sensitivity of new plasma sources, the popularity of this method has dramatically increased in direct analyses of trace elements in polluted water and other applications. Acknowledging the continued and growing importance of atomic spectroscopy, both Volumes 1 and 2 will provide the reader with a working knowledge of its principles, instrumentation, and methodology. Basic information on every specialty is examined by experts from that area, with petroleum research, toxicology, clinical chemistry, photometry, biomedicine, and oceanography amply represented. Each chapter reflects major new developments in the field, such as the improved arc method for finding trace elements in refractories, and spectroscopy's role in biological matrix problems. The factors contributing to quality instrumentation are also discussed, along with innovative methods for analyzing various petroleum industry products.

2 MODERN ANALYTICAL CHEMISTRY Series Editor: David Hercules University of Pittsburgh ANALYTICAL ATOMIC SPECTROSCOPY By William G. Schrenk PHOTOELECTRON AND AUGER SPECTROSCOPY By Thomas A. Carlson MODERN FLUORESCENCE SPECTROSCOPY, VOLUME 1 Edited by E. L. Wehry MODERN FLUORESCENCE SPECTROSCOPY, VOLUME 2 Edited by E. L. Wehry APPLIED ATOMIC SPECTROSCOPY, VOLUME 1 Edited by E. L. Grove APPLIED ATOMIC SPECTROSCOPY, VOLUME 2 Edited by E. L. Grove TRANSFORM TECHNIQUES IN CHEMISTRY Edited by Peter R. Griffiths A Continuation Ordar Plan is available for this series. A continuation order win bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual -'!lpment. For turltter Information llleaae contact lhe publiaher.

3 Applied Atomic Spectroscopy Volume2 Edited by E.L.Grove /IT Research Institute Chicago, Illinois Springer Science+Business Media, LLC

4 Library of Congress Cataloging in Publication Data Main entry under title: Applied atomic spectroscopy. (Modern analytical chemistry) Includes bibliographical references and index. 1. Atomic spectra. I. Grove, E. L., QD96.A8A66 543' ISBN ISBN (ebook) DOI / Springer Science+Business Media New York Originally published by Plenum Press, New York in 1978 Softcover reprint of the hardcover I st edition 1978 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or o therwise, without written permission from the Publisher

5 Contributors Eleanor Berman Bruce E. Buell Division of Biochemistry, Cook County Hospital, Chicago, Illinois Union Oil Company of California, Brea, California H. Jager Institute for Atmospheric Environmental Research, Fraunhofer Society, Garmisch-Partenkirchen, Germany William Niedermeier Division of Clinical Immunology and Rheumatology, Department of Medicine, University of Alabama in Birmingham, Birmingham, Alabama v

6 Preface From the first appearance of the classic The Spectrum Analysis in 1885 to the present the field of emission spectroscopy has been evolving and changing. Over the last 20 to 30 years in particular there has been an explosion of new ideas and developments. Of late, the aura of glamour has supposedly been transferred to other techniques, but, nevertheless, it is estimated that 75% or more of the analyses done by the metal industry are accomplished by emission spectroscopy. Further, the excellent sensitivity of plasma sources has created a demand for this technique in such divergent areas as direct trace element analyses in polluted waters. Developments in the replication process and advances in the art of producing ruled and holographic gratings as well as improvements in the materials from which these gratings are made have made excellent gratings available at reasonable prices. This availability and the development of plane grating mounts have contributed to the increasing popularity of grating spectrometers as compared with the large prism spectrograph and concave grating mounts. Other areas of progress include new and improved methods for excitation, the use of controlled atmospheres and the extension of spectrometry into the vacuum region, the widespread application of the techniques for analysis of nonmetals in metals, the increasing use of polychrometers with concave or echelle gratings and improved readout systems for better reading of spectrographic plates and more efficient data handling. Many of the far-reaching and on-going changes in industry and environment control would not have been possible without developments in spectroscopy, and committees of ASTM are continuing their work on evaluation and consolidation of procedures. The available literature dealing with emission spectroscopy has until now been scattered among myriad sources and we in the field have long recognized an urgent need to gather the new ideas and developments together, in a convenient format. However, the enormous amount of work involved in preparing a comprehensive treatise on the subject has been a deterrent. Finally, this major collaborative effort was undertaken: Applied Atomic Spectroscopy, Volumes 1 vii

7 viii PREFACE and 2 have been written by a group of authors, each of whom has an intimate and expert working knowledge of a special area within the discipline. Individual chapters are treatments in depth of new developments, placed within an historical perspective, in many instances incorporating much of the author's own experience. I wish to extend my special thanks to all the collaborators for their cooperation and patience. The courtesy of the book and journal publishers who gave permission to reproduce figures and tables is gratefully acknowledged, with special thanks to the U.S. Geological Survey. We also wish to thank the many practicing spectroscopists for their suggestions and help during the editing process, and last, though not least, Mrs. E. L. Grove and Nancy Robinson for editing, typing, and helping to keep detail in order. E. L. Grove

8 Contents Contents of Volume 1 Chapter 1 Precious Metals H. Jager 1.1 Introduction 1.2 Emission Spectroscopy Analysis of Noble Metals Sample-Graphite Techniques Metallic Samples Comparison of Methods Determination of Noble Metals in Other Metals and Materials Graphite Electrode Globule Arc Other Methods Determination of Noble Metals in Geologic Samples, Minerals, and Ores Normal Geochemical Analysis Methods with Increased Sensitivity Enrichment Techniques New Developments in Spectral Analysis Flame Techniques FES, AAS, and AFS o Interferences Single Elements in Solution Analysis of Noble Metals Determination of Noble Metals in Geologic Samples, Minerals, and Ores Flameless Techniques Solid Fuel Graphite Cuvette Graphite Rod ix xvii

9 X CONTENTS 1.4 X-Ray Fluorescence Original Form of the Material and Sample Type Interferences Enrichment Techniques Precision, Accuracy, and Detection Limits Other Techniques Activation Analysis Technique Interferences Applications References Chapter 2 Petroleum Industry Analytical Applications of Atomic Spectroscopy Bruce E. Buell 2.1 Introduction Definition and Scope of Petroleum Industry Crude Oil Importance, Composition, and Origin Importance Composition Crude Oil Fractions and Refining Origin of Crude Oils and Metal Content Theories of Origin Literature on Biogenic Origins of Crude Oil Characteristics of Crude Oil That May Relate to Metal Content Origin History of Atomic Spectroscopy Applications Emission Spectrographic and Spectrometric Methods Flame Spectrometric Methods Atomic Absorption Methods Atomic Fluorescence Methods Current Use of All Techniques Review of Literature Reviews Growth of Literature Instrumental Techniques Emission Spectrographs Advantages Excitation and Analysis Techniques Emission Spe"trometers (ESD) i fnstrujdeata&ion

10 CONTENTS xi Advantages and Disadvantages Excitation and Analysis Techniques Flame Emission Spectrometers (FE) Instrumentation Repetitive Wavelength Scanning in the Derivative Mode Atomic Absorption (AA) Instrumentation Nonflame and Boat in Flame Methods Atomic Fluorescence (AF) Burner-Nebulizer Systems History Atomic Absorption and Partial Consumption-Laminar Flow Burners Flame Emission and Total Consumption Burners Organic Solvent Nebulization Detection Limits for Various Techniques Flame AA Nonflame AA Atomic Fluorescence Flame Emission Plasma Torch Arc and Spark Detection Limits for Nonmetallic Elements Special Techniques to Increase Sensitivity Comparison of Flame AA and FE Detection Limits Additional Readings on Instrumentation Techniques Interferences for AA and FE Spectral Interferences Spectral Line Interferences Spectral Molecular Interferences Physical Interferences Chemical Interferences Hydrocarbon Systems Reduce Chemical Interferences Compensating for Interferences-La as Releasing Agent Interferences for the Hg Cold Vapor Method Interferences in Hydrogen Flames (As, Se, etc.) Interferences for Nonflame Methods Antipollution New Regulations Wastewater Disposal and Cleanup Analytical Problems Chromium

11 xii CONTENTS Mercury Cadmium Lead Accuracy of Analytical Methods for Water Analysis Metal Analysis as a Means of Identifying Crude Oil Spills Heavy Metal Analysis Applied to Air Pollution Methods of Analysis Grouped by Product Type Water and Oil-Field Brines Water Produced and Used Reviews and Books Variations in Elemental Composition of Waters Water Analysis-Emission Methods Water Analysis-Atomic Absorption Methods Atomic Fluorescence Methods Flame Emission Methods Concentration and Separation Methods Evaporation Solvent Extraction Solid Extractions or Cocrystallization Ion Exchange Precipitation Methods Crude Oils Importance of Crude Oil Metal Content Metallic Elements Found in Crude Oils Nature of Metal Compounds in Crude Oil Nature of Metalloorganic Compounds Metal Porphyrin Compounds Separation and Measurement of Porphyrin Compounds Emission Methods for Detennining Metals in Crude Atomic Absorption Methods Flame Emission Methods Metal Surveys Using Other Techniques of Analysis References from Foreign Countries Wear Metals and Additives in Used and New Lubricating Oils History and Applications of Emission Methods Emission Spectroscopic Techniques Atomic Absorption Methods Atomic Fluorescence Methods Flame Emission Methods Relative Merits of Most Popular Methods Particle-Size Influence Matrix Errors Caused by Oil Composition Oils

12 CONTENTS xiii Gasoline and Light Petroleum Distillates (LPD) Lead in Gasoline Miscellaneous Elements Diesel Fuels, Turbine Fuels, Gas Oils, and Feedstocks for Refinery Processing Units Emission Spectrographic and Spectrometric Methods Atomic Absorption Methods Flame Emission Methods Atomic Fluorescence Methods Comments on Methods Catalysts Used in Petroleum Refining Operations Emission Methods Flame Emission Methods Atomic Absorption Methods Miscellaneous Heavy Petroleum Products Analytical Problems Imposed by Viscosity Analytical Methods-Emission Spectroscopy Atomic Absorption and Flame Emission Methods Analysis of Cokes Petrochemical and Agricultural Products Agricultural Petrochemicals History, Reviews, and Analytical Methods Atomic Absorption and ESD Methods Soil Analysis by AA Fertilizers Unusual Applications Geochemical Applications Geochemistry in Mineral Exploration Analytical Methods-Emission Spectroscopy Flame Emission Methods Atomic Absorption Methods References Chapter 3 Analytical Emission Spectroscopy in Biomedical Research William Niedermeier 3.1 Introduction Spectrometric Methods Equipment and Materials Methods Sample Preparation Preparation of Standards Spectrometric Procedure Discussion

13 xiv CONTENTS 3.3 Computerized Evaluation of Results Mathematical Relationships Fit of the Equation to the Data Confidence Limits Background Threshold Values Discussion Studies on Trace Metals in Patients with Rheumatoid Arthritis Collection of Specimens Results Discussion Effect of Chrysotherapy on Trace Metals Methods Results Trace Metals in Dental Caries Collection of Samples Results Discussion Cardiovascular Disease Myocardial Infarction Methods Results Discussion Atherosclerosis Metals in the Environment Pattern Recognition Multivariate Analysis of Variance Duncan Analysis Cluster Analysis Discriminant Analysis References Chapter 4 Application of Spectroscopy to Toxicology and Clinical Chemistry Eleanor Berman 4.1 Introduction Spectroscopic Applications to Analyses of Organic Substances Ultraviolet Spectrophotometry Infrared Spectroscopy Mass Spectrometry Fluorimetry and Phosphorimetry

14 CONTENTS XV 4.3 Application of Spectroscopy to Trace Metal Analyses of Biological Materials X-Ray Spectroscopy Emission and Atomic Absorption Spectroscopy Specific Applications of Emission and Atomic Absorption Spectrophotometry Sodium and Potassium Calcium Magnesium Lithium Copper Iron Zinc Gold Manganese Nickel Cobalt Chromium The Toxic Metals Lead Cadmium Thallium Antimony Arsenic Beryllium Mercury Selenium Miscellaneous Metals Plasma Emission Spectrometry References Author Index 319 Subject Index 341

15 Contents of Volume 1 Chapter 1 Photographic Photometry James W. Anderson Chapter 2 Laser Emission Excitation and Spectroscopy R. H. Scott and A. Strasheim Chapter 3 Electrode Material and Design for Emission Spectroscopy J. W. Mellichamp Chapter 4 Behavior of Refractory Materials in a Direct-Current Arc Plasma: New Approaches for Spectrochemical Analysis of Trace Elements in Refractory Matrices Reuven Avni Chapter 5 Preparation and Evaluation of Spectrochemical Standards A. H. Gillieson Chapter 6 Applications of Emission and X-Ray Spectroscopy to Oceanography Geoffrey Thompson xvii

16 Applied Atomic Spectroscopy Volume 2