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Methods for Geochemical Analysis \ o 70 n m O n U.S. GEOLOGICAL SURVEY BULLETIN 770 o r Methods for Geochemical Analysis Edited by PHILIP A. BAEDECKER Analytical methods used in the Geologic Division
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Methods for Geochemical Analysis \ o 70 n m O n U.S. GEOLOGICAL SURVEY BULLETIN 770 o r Methods for Geochemical Analysis Edited by PHILIP A. BAEDECKER Analytical methods used in the Geologic Division laboratories of the U.S. Geological Survey for the inorganic chemical analysis of rock and mineral samples U.S. GEOLOGICAL SURVEY BULLETIN 770 DEPARTMENT OF THE INTERIOR DONALD PAUL MODEL, Secretary U.S. GEOLOGICAL SURVEY Dallas L. Peck, Director UNITED STATES GOVERNMENT PRINTING OFFICE: 987 For sale by the Books and Open-File Reports Section, U.S. Geological Survey, Federal Center, Box 25425, Denver, CO Library of Congress Cataloging in Publication Data Methods for geochemical analysis. (U.S. Geological Survey bulletin ; 770) Bibliography: p. Supt. of Docs, no.: I 9.3:770. Geochemistry, Analytic. I. Baedecker, Philip A. II. Series. QE75.B9 no. 770 [QE56.3] 557.3s [55.9] CONTENTS INTRODUCTION P. A. Baedecker INI CHAPTER A Analysis of geologic materials by direct-current arc emission spectrography and spectrometry D. W. Golightly, A. F. Dorrzapf, Jr., R. E. Mays, T. L. Fries, and N. M. Cbnklin CHAPTER B Inductively coupled plasma-atomic emission spectrometry F. E. Lichte, D. W. Golightly, and P. J. Lamothe CHAPTER C Atomic absorption methods P. J. Aruscavage and J. G. Crock CHAPTER D Chemical methods of separation for optical emission, atomic absorption spectrometry, and colorimetry S. A. Wilson, J. S. Kane, J. G. Crock, and D. B. Hatfield CHAPTER E Analysis of geologic materials by wavelength-dispersive X-ray fluorescence spectrometry J. E. Taggart, Jr., J. R. Lindsay, B. A. Scott, D. V. Vivit, A. J. Bartel, and K. C. Stewart CHAPTER F Energy-dispersive X-ray fluorescence spectrometry R. G. Johnson and B.-S. L. King CHAPTER G Major and minor elements requiring individual determination, classical whole rock analysis, and rapid rock analysis L. L. Jackson, F. W. Brown, and S. T. Neil CHAPTER H Instrumental neutron activation analysis of geochemical samples P. A. Baedecker and D. M. McKown CHAPTER I Determination of uranium and thorium by delayed neutron counting D. M. McKown and H. T. Millard, Jr. CHAPTER J Radiochemical neutron activation analysis of geologic materials G. A. Wandless CHAPTER K Isotope-dilution mass spectrometry J. A. Philpotts Al Bl Cl Dl El Fl Gl HI II Jl Kl Any use of trade names is for descriptive purposes only and does not imply endorsement by the U.S. Geological Survey Volume Contents INTRODUCTION By P. A. Baedecker The laboratories for analytical chemistry within the Geologic Division of the U.S. Geological Survey are administered by the Office of Mineral Resources. The laboratory analysts provide analytical support to those programs of the Geologic Division that require chemical information and conduct basic research in analytical and geochemical areas vital to the furtherance of Division program goals. Laboratories for research and geochemical analysis are maintained at the three major centers in Reston, Virginia, Denver, Colorado, and Menlo Park, California. The Division has an expertise in a broad spectrum of analytical techniques, and the analytical research is designed to advance the state of the art of existing techniques and to develop new methods of analysis in response to special problems in geochemical analysis. The geochemical research and analytical results are applied to the solution of fundamental geochemical problems relating to the origin of mineral deposits and fossil fuels, as well as to studies relating to the distribution of elements in varied geologic systems, the mechanisms by which they are transported, and their impact on the environment. In 984, a review of the role of analytical chemistry within the Geologic Division was conducted by an ad hoc committee of senior Division managers. The committee concluded that a lack of familiarity on the part of those submitting samples for geochemical analysis with the wide range of analytical techniques available could result in the misapplication of some techniques to various geochemical problems; for example, highly precise analyses could be applied to problems for which only approximate answers are needed or can be obtained in other ways. Conversely, investigators might request too few analyses or data by techniques that are not precise enough for the problem at hand; for example, potential waste occurs when data on a desired element, such as cesium, is obtained by requesting a broad-spectrum Instrumental Neutron Activation Analysis, which requires perhaps an order of magnitude more time and effort than if cesium alone were determined by the same method or possibly another. In addition to these concerns, analytical chemists often are concerned that those who use analytical data have little appreciation for the factors that affect the quality of that data and the challenges and complexity of analytical chemistry as a scientific discipline. The committee report stated, ...clearly, an increased understanding of modern analytical techniques by all potential users of chemical data in the Geologic Division is a highly desirable goal. Toward that end we are recommending that a publication entitled Methods for Geochemical Analysis be prepared, which will cover all aspects of the techniques currently available. This volume is in response to that recommendation. In many respects, the current volume supplants two previous publications that were designed to familiarize scientists within the Geologic Division with the analytical capabilities that were (or are) available in the laboratories of the Division. The first edition of the Manual of Laboratory Services of the Division's Geochemistry and Petrology Branch was published in 956. That document was subsequently revised in 974 by the Office of Geochemistry and Geophysics. This volume is more restricted than either of the above publications in that the previous reports contained sections on geochronology, electron optics, X-ray crystallography and diffraction, mineralogic and petrographic analysis, organic analysis, thermodynamics, geophysical methods, and so forth; the coverage offered by this volume, however, is limited to modern methods of inorganic analysis. In the preparation of Methods for Geochemical Analysis, the authors also have adopted a different approach to the subject matter. Rather than to provide a simple documentation of available services, they have attempted to treat each topic in much greater depth. Thus, each chapter contains sections on fundamental principles, an overview of the method as practiced in each center, the limitations of the technique (such as matrix, chemical, and spectral interferences), and the sensitivity, precision, and accuracy of each technique. The goal was to prepare a single volume that would provide the nonchemist reader with a broad coverage of geochemical analysis as a scientific discipline, a good understanding of the inherent difficulty of analyzing complex geologic matrices that are highly variable in composition, and sufficient technical detail to understand the factors that can affect the quality (precision and accuracy) of the analysis of the geologic sample. To again Introduction INI quote the 984 analytical chemistry review report, It is hoped that a widespread familiarization with this document by members of the Division will provide the basis for a more informed dialogue on chemical problems between geologists and analytical chemists. At this point, I think it worthwhile to repeat a few sections from the introduction to the 956 Manual of Laboratory Services because, although the technology of analytical chemistry has changed dramatically, the following general comments regarding routine and nonroutine analysis and analytical accuracy remain as valid today as they were 30 years ago: The service work of the Branch falls into two categories, routine and research (including custom), which are neither completely nor even too sharply separated at any time. Depending on the circumstances, a routine determination may become a research problem, or what was originally a research problem may in time become a routine process. The Branch is constantly testing new methods with the aim of developing rapid routine determinations as the geologists indicate their need for them...research determinations are those made by methods we do not ordinarily use; they may include determinations made on samples of unusual composition, or the analysis for some element or elements at lower concentration ranges than previously handled, or the development of new chemical, spectrographic, mineralogical, X-ray, or other methods. They may involve adaptation of existing methods and apparatus. Study and judgment are required to select the best method for the specific problem, standards must be set up to insure the validity of the results, and much time spent in checking possible interferences. Research work of this type may result in the development of new lines of attack on unsolved problems. The following general comments on the analytical accuracy are also still applicable: To conserve laboratory effort, it is equally important not to request excessive accuracy and sensitivity; the accuracy of the analysis need be no better than the sampling techniques and the use which will be made of the analyses [my emphasis]...it is difficult to be specific or even to generalize about the accuracy of analytical results when there is a great variation in the type of samples analyzed and in the methods employed. A method which gives a certain accuracy on one type of material frequently does not give the same accuracy when applied to another type. Information on the mineralogical composition of the sample helps the chemists in the selection of methods of analysis and makes possible more and better analyses. The requester should give full details of any information he may have on the mineralogical and chemical makeup of his samples. As an introduction to the topics covered in this publication and as a guide to alternative methods of analysis, the following table may prove useful. Listed for each element are estimates of sensitivity for the most common techniques used for their determination in geochemical samples. The term sensitivity is a general term for the lower limits of measurement for a given analytical test and is most often expressed as either a detection limit or determination limit. The detection limit is the minimum concentration of analyte required for a positive decision that an analysis indicates a qualitative detection, and the determination limit is a higher level of concentration that will give a satisfactory quantitative result with a given relative standard deviation (such as ±0 percent). Both estimates are dependent on the analytical noise associated with measurement above the background or blank level for a given analytical procedure, and, for multielement analytical methods, the sensitivity limits are often matrix dependent and, therefore, may vary from sample to sample. The sensitivity levels provided by the table should be looked upon as working determination limits for a silicate rock matrix. As stated above, the method with the greatest sensitivity should not be identified as the best method for any given problem. The most sensitive methods are most often the most labor intensive. The method of choice is based on the answers to the following questions: What minimum levels of precision, accuracy, and sensitivity are required to solve the problem at hand? is a broad spectrum, multielement characterization required? and what interferences may preclude the analysis of a particular matrix by a given technique? Each of these questions should be answered by close collaboration between geologist and analyst at the onset of each geochemical study. ACKNOWLEDGMENTS Each chapter in this volume has benefited from review by U.S. Geological Survey scientists. The following individuals have contributed thoughtful reviews to one (or in some cases two) of the chapters: Joseph G. Arth, Robert A. Ayuso, Charles R. Bacon, Michael H. Bothner, David A. Brew, David A. Clague, Gerald K. Czamanski, Walter E. Dean, Franklin C.W Dodge, Bruce R. Doe, Michael P. Foose, Carter B. Hearn, Rosalind T. Helz, Edward W. Hildreth, Joel S. Leventhal, Stephen D. Ludington, Frank T. Manheim, Andrei Sarna-Wojcicki, John Stuckless, and Howard E. Taylor. I wish to thank Janet Sachs for her editorial assistance. I also wish to thank Mary Catherine Kiel and Carol A. Popish for their clerical assistance. IN2 Methods for Geoch«mlc*l Analysis N P DCES ICPS XRF SP DCSW As DCES ICPS CSAA HYAA DCSW INAA Sb DCES ICPS CSAA HYAA DCSW INAA Bi DCES ICPS CSAA 0.0 HYAA DCSW RNAA e-5 0 S ICPS XRF SA C Se DCES ICPS CSAA HYAA DCSW INAA Te DCES ICPS b LOGO 30 CSAA 0.02 DCSW RNAA Po Tm DCES 5 ICPS 20 CICP 0.05 INAA 0.5 RNAA.00 Md 00 F C ISE Cl XRF C ISE Br INAA I At Yb DCES ICPS CICP 0.05 INAA 0. 2 RNAA.005 No He Ne Ar Kr Xe Rn Lu DCES 20 ICPS 20 CICP 0.0 INAA 0.0 RNAA le-4 Lw Table of determination limits for silicate rock analysis [In mterograms per gram] H Li DCES ICPS 70 2 FAAS 2 Na DCES 20 ICPS 000 FAAS XRF 500 INAA 0 K DCES 700 ICPS 000 FAAS 2 XRF 200 INAA 00 Rb DCES 3 ICPS 00 FAAS 4 XRF 2 INAA 5 RNAA 0.05 Cs DCES 3 FLAA 4 INAA 0. RNAA.00 Fr Be DCES ICPS CSAA 0. Kg DCES 20 ICPS 500 FAAS XRF 000 Ca DCES 0 ICPS 500 XRF 200 Sr DCES ICPS 2 FAAS 5 XRF 2 INAA 50 RNAA 0'. 2 Ba DCES ICPS FAAS 20 XRF 5 INAA 00 RNAA 0.05 Ra Sc DCES ICPS 2 INAA 0.0 Y DCES ICPS 2 XRF 2 CICP 0.0 La DCES 0 ICPS 2 XRF 5 INAA 0.02 CICP 0. RNAA.00 Ac Ti DCES 30 ICPS 00 XRF. 200 SP 0 Zr DCES 3 ICPS 5 XRF 5 INAA 00 Hf DCES 20 ICPS 0 INAA 0. FAAS GFAA HYAA CICP CSAA CVAA DCES DCQS DCSW DNAA FA C ICPS INAA ISE RNAA SP SA XRF V DCES ICPS GFAA SP Nb DCES ICPS XRF SP Ta -- Atomic Absorption, Flame -- Atomic Absorption, Graphite Furnace -- Atomic Absorption, Hydride Generation -- Chemical separation - - Chemical Separation -- Cold Vapour Atomic (Absorption --DC Arc Emission Spectrography -- DC Arc, Quantitativ B Spectrogr uphy --DC Arc emission spectroscopy, Short Wavelength Fi ^ - - Ion Chroma Cography -- Inductivelv Coupled DCES 300 INAA 0.03 Inductively Coupled Plasma Spectroscopy Atomic Absorption (FAAS or GFAA) itration (GFAA or DCES) Plasma emi is ion Spect rography -- Instrumental Neutron Activation Analysis -- Ion Selective Elect rode - - Radiochemical Neutron Activation Analysis -- Spectophotometry -- automated Sulfur Analyser -- X-Ray Fluorescence Cr DCES ICPS FAAS XRF INAA Mo 4 20 DCES ICPS 2 INAA 0 SP 0.05 W DCES INAA SP Mn DCES ICPS FAAS XRF INAA Tc Re 20 DCES 0.+ ICPS Fe DCES ICPS FAAS XRF INAA Ru DCES ICPS FA Os DCES 20 ICPS 30 RNAA 5e-6 Co DCES ICPS FAAS INAA Rh DCES ICPS FA Ir DCES ICPS FA 0.02 INAA 0.0 RNAA le-6 Ni DCES ICPS FAAS GFAA XRF INAA Pd DCES ICPS 20 FA.00 RNAA le-4 Pt DCES 20 ICPS 30 FA 0.0 Cu DCES ICPS FAAS CSAA XRF Ag DCES ICPS FAAS CSAA 0.0 RNAA le-5 Au ICPS 4 FA 0.05 CSAA 0. DCSW 0.2 INAA.005 RNAA le-6 Zn DCES ICPS FAAS XRF DCSW 0.0 INAA Cd DCES ICPS FAAS 30 2 CSAA 0.02 DCSW 0. RNAA le-5 Hg DCES 000 ICPS 70 CVAA 0.02 DCSW B DCES ICPS SP DCQS Al DCES ICPS FAAS XRF SP Ga DCES ICPS INAA In DCES 0 ICPS 0 RNAA le-4 Tl DCES ICPS 2 DCES 4 ICPS 5+ GFAA RNAA 0 50 GFAA 0.05 DCSW RNAA le-4 C Si DCES FAAS XRF Ge Sn DCES ICPS CSAA Pb DCES ICPS FAAS CSAA Ce DCES 40 ICPS 4 CICP 0. XRF 5 INAA 0. 5 RNAA.005 Th DCES 50 ICPS 4 INAA 0. DNAA RNAA,.00 Pr DCES 00 ICPS 0 CICP 0. Pa Nd DCES 30 ICPS 20 CICP 0. INAA 2 RNAA.005 U DCES 500 ICPS 00 INAA 0. 5 DNAA 0. RNAA.00 Pm Np DCES 0 ICPS 50 CICP 0. INAA 0. 5 RNAA 5e-4 Pu Eu DCES 2 ICPS 2 CICP 0.0 INAA 0.02 RNAA le-4 Am Gd DCES 30 ICPS 0 CICP 0. INAA 2 RNAA.005 Cm Tb DCES 30 ICPS 20 CICP 0.4 INAA 0. RNAA IE-4 Bk Dy DCES 20 ICPS 4 CICP 0. INAA 0 Cf Ho DCES 7 ICPS 4 CICP 0.02 INAA 0. 5 Es Er DCES 5 ICPS 4 CICP 0.05 Fm CHAPTER A Analysis of Geologic Materials by Direct-Current Arc Emission Spectrography and Spectrometry By D. W. GOLIGHTLY, A. F. DORRZAPF, JR., R. E. MAYS, T. L. FRIES, and N. M. CONKLIN U.S. GEOLOGICAL SURVEY BULLETIN 770 Methods for Geochemical Analysis CONTENTS Abstract Al Introduction Al General capabilities Al Basis of technique Al Experimental A2 General A2 Sample preparation and handling A3 Standards A4 Control of direct-current arc plasmas A4 Atmospheres A4 Buffers A4 Instrumentation and facilities A5 Data collection A0 Accuracy and precision of analysis All Conclusions All References cited A2 FIGURES. Vertical direct-current arc (idealized) A2 2. Generalized arrangement of components for direct-current arc spectrography A3 TABLES. Semiquantitative analysis by direct-current arc spectrography: Elements and lower determination limits A6 2. Quantitative analysis by direct-current arc spectrography and direct-reading spectrometry: Elements and lower determination limits A8 3. Quantitative analysis by direct-current arc spectrography of some chalcophiles plus gold and phosphorus: Elements and lower determination limits A0 4. Generalized groupings of elements according to lower determination limits by quantitative direct-current arc spectrography and spectrometry A2 Contents III Analysis of Geologic Materials by Direct-Current Arc Emission Spectrography and Spectrometry By D. W. Golightly, A. F. Dorrzapf, Jr., R. E. Mays, T. L. Fries, and N. M. Conklin Abstract Direct analysis of diverse geologic materials for more than 68 elements occurring at trace and subtrace concentrations is achieved by direct-current arc spectrometric methods. The basis and capabilities of the methods currently used in the analysis of geological samples at the U.S. Geological Survey are described. The lower limits of determination for quantitative and semiquantrtative methods are listed for all elements now determined by direct-current arc spectrography and Spectrometry. INTRODUCTION The direct-current (d-c) arc is one of several electrical discharges used as light-emitting sources in analytical atomic spectroscopy. The high-temperature, radiating, gaseous volume between the two electrodes that determine the position of an arc in space is termed a laboratory plasma. This plasma is a very high temperature gas (5,000-7,000 K, in the core) that is capable of atomizing, ionizing, and exciting quantized emissions (photons) from most elements of the periodic system. Spectral measurements on light emitted from a d-c arc into which a natural or fabricated material is vaporized provide the basis for determining the concentrations of up to 68 elements at trace levels. This chapter provides a brief overview of some of the characteristics and capabilities of d-c arc Spectrography (photographic plate detection) and Spectrometry (electrical detection). Comprehensive treatments of this subject can be found in Boumans (966) and Ahrens and Taylor (96). General Capabilities In general, low part-per-million (micrograms of element per gram of sample) concentrations of most of the naturally occurring elements can be measured for arced samples ranging in mass from 0 to 20 mg. Only solid-phase samples can be analyzed conveniently by this technique, and these samples typically are finely pulverized (-00 to -200 mesh) rocks, minerals, soils, residues, ferromanganese crusts and nodules, ashes from plants, peats, and coals, whole coals, ceramics, or metals. All elemental analyses by this method are based on comparisons of measured spectral signals between samples and standards. Thus, good, naturally occurring, and synthesized reference materials are essential to highquality analyses. Quantitative analyses that are accurate to within ±0 percent can be achieved routinely by available methods for up to 55 elements. Semiquantitative analyses for up to 64 dements can be done with a typical uncertainty of-33 and +50 percent. Basis of Technique Emission of electromagnetic radiation from free atoms and ions is quantized, in accordance with the Bohr frequency condition: AE hp, where AE is the photon energy, h is Planck's co
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