SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES ? NUMBER 27 The Allende Meteorite Reference Sample Eugene Jarosewich, Roy 5. Clarke, Jr., and Julie N. Barrows EDITORS 2 4 SMITHSONIAN INSTITUTION PRESS Washington, D.C. 1987 ABSTRACT Jarosewich, Eugene, Roy S. Clarke, Jr., and Julie N. Barrows, editors. The Allende Meteorite Reference Sample. Smithsonian Contributions to the Earth Sciences, number27, 49 pages, 32 tables, 1986.?A reference material for comparative analytical studies and standardization was prepared from fresh, clean specimen material fromthe Allende, Mexico, Type CV3 carbonaceous chondrite fall of 8 February 1969. Fragments weighing 4 kg were powdered, homogenized, and split into 1 g and 5 gsubsamples. Analytical results for a total of 74 elements were provided by 24 analysts or groups of analysts. A variety of techniques were used, and many elements weredetermined by more than one technique. Reports from contributors of data outline their procedures and give their results in detail. Sample homogeneity has beenevaluated in terms of this body of data, and "recommended values" are suggested for 43 elements. OFFICIAL PUBLICATION DATE is handstamped in a limited number of initial copies and is recorded in the Institution's annual report, Smithsonian Year. SERIES COVER DESIGN: Aerial view of Ulawun Volcano, New Britain. Library of Congress Cataloging in Publication Data The Allende meteorite reference sample. (Smithsonian contributions to the earth sciences ; no. 27) Bibliography: p. Supt of Docs, no.: SI 1.26:27 1. Allende meteorite. 2. Chondrites (Meteorites)?Standards. 3. Radioactivation analysis. I. Jarose- wich, Eugene. II. Clarke, Roy S. III. Barrows, Julie N. IV. Series. QE1.S227 no.27 [QB756.A44] 550 s 86-600209 [523.5'1] Contents Page EDITORS' INTRODUCTION, by Eugene Jarosewich, Roy S. Clarke, Jr., and Julie N. Barrows 1 1. TRACE ELEMENT ANALYSES OF THE ALLENDE METEORITE REFERENCE SAMPLE BY NEUTRON ACTIVATION, by Ralph O. Allen, Jr 13 2. EMISSION SPECTROGRAPHIC ANALYSES OF TRACE ELEMENTS IN THE AL- LENDE METEORITE REFERENCE SAMPLE, by C.S. Annell 14 3. ABUNDANCES OF EIGHT ELEMENTS IN THE ALLENDE METEORITE REFER- ENCE SAMPLE DETERMINED BY NEUTRON ACTIVATION ANALYSIS, by P.A. Baedecker, C.-L. Chou, and J.T. Wasson 15 4. DETERMINATION OF TRACE ELEMENTS BY NEUTRON ACTIVATION ANALY- SIS IN THE ALLENDE METEORITE REFERENCE SAMPLE, by R. Becker, P. Koller, P. Morschl, W. Kiesl, and F. Hermann 16 5. SOME ELEMENTAL ABUNDANCES IN THE ALLENDE METEORITE REFERENCE SAMPLE DETERMINED BY NEUTRON ACTIVATION ANALYSIS, by W.D. Ehmann, D.E. Gillum, C.L. Sya, and A.N. Garg 18 6. BULK CHEMICAL ANALYSES OF THE ALLENDE METEORITE REFERENCE SAMPLE, by CJ. Elliott 20 7. INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS OF THE ALLENDE ME- TEORITE REFERENCE SAMPLE, by Lawrence Grossman and D.P. Kharkar 22 8. NEUTRON ACTIVATION ANALYSES OF SEVEN ELEMENTS IN THE ALLENDE METEORITE REFERENCE SAMPLE, by K.S. Heier, A.O. Brunfelt, E. Steinnes, and B. Sundvoll 24 9. DETERMINATION OF 6i3C AND TOTAL NONCARBONATE CARBON IN TWO SPLITS OF THE ALLENDE METEORITE REFERENCE SAMPLE BY MASS SPECTROMETRY, by J.M. Herndon and W.M. Sackett 25 10. MASS SPECTROMETRIC ISOTOPE DILUTION ANALYSIS OF LEAD AND THAL- LIUM IN THE ALLENDE METEORITE REFERENCE SAMPLE, by J.M. Huey and T.P. Kohman 26 11. BULK CHEMICAL ANALYSIS OF THE ALLENDE METEORITE REFERENCE SAMPLE, by Eugene Jarosewich 27 12. X-RAY FLUORESCENCE SPECTROMETRIC ANALYSIS OF THE ALLENDE ME- TEORITE REFERENCE SAMPLE, by M.J. Kaye and B.W. Chappell 28 13. NEUTRON ACTIVATION ANALYSIS OF SOME TRACE ELEMENTS IN THE ALLENDE METEORITE REFERENCE SAMPLE, by J.F. Lovering and R.R. Keays 30 14. CARBON ANALYSIS OF THE ALLENDE METEORITE REFERENCE SAMPLE BY STANDARD RAPID COMBUSTION METHOD, by Carleton B. Moore 31 15. MULTIELEMENT ANALYSES OF THE ALLENDE METEORITE REFERENCE SAM- PLE BY NEUTRON ACTIVATION AND SPARK SOURCE MASS SPECTROME- TRY, by G.H. Morrison, N.M. Potter, A.M. Rothenberg, E.V. Gangad- haram, and S.F. Wong 32 16. SPARK SOURCE MASS SPECTROMETER ANALYSIS OF THE ALLENDE METEO- RITE REFERENCE SAMPLE, by P.E. Muir, S.R. Taylor, and Brian Mason 34 17. DETERMINATIONS OF NA, K, RB, CS, BR, TE, AND U BY NEUTRON ACTI- VATION ANALYSIS IN THE ALLENDE METEORITE REFERENCE SAMPLE, by O. Miiller 35 in IV SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES 18. ANALYSIS OF RARE EARTH ELEMENTS IN THE ALLENDE METEORITE REF- ERENCE SAMPLE BY STABLE ISOTOPE DILUTION, by Noboru Nakamura and Akimasa Masuda . 38 19. BULK CHEMICAL ANALYSIS OF THE ALLENDE METEORITE REFERENCE SAMPLE, by J.H. Scoon 39 20. ABUNDANCES OF THE 14 RARE EARTH ELEMENTS AND 12 OTHER MAJOR, MINOR, AND TRACE ELEMENTS IN THE ALLENDE METEORITE REFERENCE SAMPLE BY NEUTRON ACTIVATION ANALYSIS, by D.L. Showalter, H. Wakita, R.H. Smith, and R.A. Schmitt 40 21. ANALYSES OF TRACE ELEMENTS IN THE ALLENDE METEORITE REFERENCE SAMPLE BY EMISSION SPECTROMETRY, by G. Thompson 43 22. ANALYSES OF OXYGEN AND SILICON IN THE ALLENDE METEORITE REFER- ENCE SAMPLE BY NEUTRON ACTIVATION, by A. Volborth 44 23. BULK CHEMICAL ANALYSIS OF THE ALLENDE METEORITE REFERENCE SAMPLE, by H.B. Wiik 45 24. X-RAY FLUORESCENCE SPECTROMETRIC ANALYSIS OF THE ALLENDE ME- TEORITE REFERENCE SAMPLE, by J.P. Willis 46 LITERATURE CITED 47 The Allende Meteorite Reference Sample Editors' Introduction Eugene Jarosewich, Roy S. Clarke, Jr., and Julie N. Barrows The fundamental significance of meteorites for such di- verse scientific fields as cosmochemistry, geochemistry, and planetary dynamics has become increasingly apparent dur- ing the past three decades. It is now generally accepted that meteorites are our most primitive rocks, providing a record of extraterrestrial events as ancient as the collapse of the solar nebula and as contemporary as recent solar flares. These characteristics have made meteorites sought-after subjects for interdisciplinary study, a practice that is now commonplace. Geochemists have been historically attracted to meteor- ites as a source of information on the distribution of chem- ical elements within the earth and the planetary system as a whole. Our concept of the distribution of the nonvolatile chemical elements in the planetary system is based on chem- ical analyses of the most abundant group of meteorites, the chondrites. The analysis of chondrites, however, presents problems beyond those normally encountered in the study of terrestrial rocks. Difficulties result from the mineral assemblages present in most chondritic meteorites. In ad- dition to major amounts of the common rock-forming min- erals olivine, pyroxene, and feldspar, they contain signifi- cant quantities of troilite (FeS) and the metallic phases kamacite (low-Ni Ni,Fe) and taenite (high-Ni Ni,Fe). The association of sulfide and metallic phases with silicates pre- sents both sampling and analytical problems. Early research- ers recognized these problems; they analyzed meteorites with care using chemical methods that at the time were still in their infancy. During the 19th and early 20th centuries large numbers of chondritic meteorite analyses were reported in the liter- ature in widely scattered sources. As mineralogical and chemical knowledge accumulated, it became obvious that Eugene Jarosewich and Roy S. Clarke, Jr., Department of Mineral Sciences, National Museum of Natural History, Smithsonian Institution, Washington, D.C. 20560. Julie N. Barrows, Department of Chemistry, Georgetown University, Washington, D.C. 20057. many of these analyses were seriously flawed. Urey and Craig (1953), in their comprehensive paper on the compo- sition of stone meteorites, reviewed the older literature and established the modern approach to the evaluation of me- teorite analyses. Mason (1965) modified the Urey and Craig criteria for acceptable analyses by introducing more rigor- ous mineralogical considerations. The discussion continues with no end in sight. It is now conducted, however, in an established climate of awareness of the need for constant critical evaluation of analytical techniques, procedures, and results. Interpreters of meteorite analyses have required progres- sively more accurate data as the problems they address have become more sophisticated. The use of standardized tech- niques that are monitored periodically by reference samples is a common strategy for increased accuracy and for inter- laboratory comparisons. Such reference materials are nec- essary for modern instrumental techniques because of their comparative approach. Two of the most widely used geologic reference samples have been the rock samples G-l and W-l, which have been used primarily for the study of precision and accuracy of chemical and spectrochemical methods as summarized by Fairbairn et al. (1951). Stevens et al. (1960) reviewed the eariler analyses of these two rocks, compiled new data, and suggested "recommended values." Fleischer (1965) updated this work with new analyses and new recommended values. At the time our work was undertaken in late 1969 there were several types of geological reference samples available that covered the compositional range of most common terrestrial materials (Webber, 1965; Abbey, 1972; Flana- gan, 1973, 1976; to list a few). For meteorites, however, such a reference sample was not available, and terrestrial reference samples were not always suitable for comparison with the analyses of meteorites. Typically, both the level of trace elements in meteorites and the concentration relations of a specific element to concentrations of other elements with which it is associated differ greatly from those present SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES in terrestrial materials. The differences are such that even mixtures of different reference samples will not approxi- mate the composition of meteorites. There are two primary reasons why a meteoritic refer- ence material had not been prepared previously. The first and most important is that a suitable meteorite had not been available in adequate amount for preparation of suf- ficient powder for subsequent distribution. Some meteorite finds that might have provided enough material were con- sidered too contaminated by their terrestrial surroundings to be useful. Secondly, the problem of preparation of ho- mogeneous samples had not been solved. Meteorites that had been considered were primarily ordinary chondrites containing 5-15% metal. It is very difficult, and in fact almost impossible, to pulverize a large sample containing metal of various grain sizes to less than 100 mesh particles so that a reasonable homogeneity may be assured. The Allende, Mexico, meteorite fall of 8 February 1969 (Clarke et al., 1970) provided a solution to these problems. The meteorite was a fresh fall available in large quantity. Early work established that it was a rare Type III carbona- ceous chondrite that contained very little metal and was easy to homogenize. The availability of this meteorite led us to undertake the preparation and distribution of a me- teoritic reference sample. An important additional stimulus was the need of the scientific community for a reference material for the analyses of returned lunar samples. ACKNOWLEDGMENTS.?Several participants at the Apollo 11 Lunar Science Conference in Houston in 1971, W.D. Ehmann, P.A. Baedecker, J.W. Morgan, G.H. Morrison, and A.A. Smales, discussed with one of the authors (EJ.) the need for a meteoritic reference material for chemical analyses. Their suggestions and enthusiastic support for this project are acknowledged. We wish to thank Mrs. P. Brenner for her diligent and meticulous preparation of the sample and cataloging of the individual splits. Also, we thank F.J. Flanagan of the U.S. Geological Survey for sharing his experience and advising on the details of sample preparation, for his suggestions on statistical evaluation of the results, and for a general critique of the paper. This work was made possible by the Smithson- ian Research Foundation Grant 413616 and by partial support from NASA Grant NGR-015-146 (B. Mason, Prin- cipal Investigator). Sample Preparation Two pieces from a 35 kg AHende meteorite specimen (NMNH 3529), one of 2.4 kg and the other of 1.6 kg, were selected for preparation of the sample powder. Fusion crust covered approximately 35 percent of the surfaces of both pieces and was removed by sandblasting. The pieces were then cleaned of entrapped dust using a jet of compressed air followed by brushing with a nylon brush. These pieces were powdered separately and combined into one 4 kg sample powder. Fragmentation and powder preparation were carried out in a clean room in which no other laboratory activities were conducted. The two large pieces were broken to fragments of about 1 cm using a hardened steel pestle and a steel plate placed in a plastic tray. The few small chips that were projected beyond the tray were excluded from the sample to avoid contamination. The cm-size fragments were fur- ther broken down in a diamond mortar, and they were then ground by hand in an agate mortar to fine powder. The powder was passed through a 100-mesh nylon sieve with the aid of a nylon brush and collected in a 2-gallon poly- ethylene bottle previously cleaned with dilute nitric acid and distilled water. No metal particles large enough to be retained by the 100-mesh sieve were found in the 4 kg of powdered sample, but the powder does contain small par- ticles (<100 mesh), which are attracted by a magnet. Special care was taken in the preparation of the sample to minimize contamination, thus keeping the sample compositionally as close as possible to the fresh meteorite. The sample powder was homogenized in the large poly- ethylene bottle, which was rolled on a jar-mill rolling ma- chine. Twenty-nine portions weighing either 32 g or 160 g were taken from this powder and split into 1 g or 5 g subsamples using the 32-position U.S. Geological Survey stainless steel conical splitter (Flanagan, 1967). Small plastic vials, also previously cleaned with dilute nitric acid and distilled water, were used to collect the subsamples. Each vial was given split and position numbers. Two subsamples, selected on the basis of a table of random numbers, were made available to participating laboratories for analyses. Evaluation of Homogeneity Homogeneity at the subsample level is a prerequisite for a useful reference powder. When a large quantity of mate- rial (for instance, 1 g) is used to calibrate an instrument or to check an analytical method, a representative sample may be comparatively easily obtained. However, if very small subsamples are used (10-100 mg), as is common in trace element analyses, it may be difficult to obtain a represent- ative sample. If the powder is not ground sufficiently fine, for instance, the presence or absence of an element residing in a specific over-sized grain may significantly affect the results on that aliquot. To avoid problems of this nature our material was finely ground, sieved to assure particle size of less than 100 mesh, thoroughly mixed, and carefully split. The particle size distribution of the powder was deter- mined on a 15 g subsample with the following results: Mesh Size Percent <100 >160 1.5 <160 >200 11.1 <200 >300 18.0 <300 69.4 NUMBER 27 More than 85% of this subsample passed the 200-mesh sieve and less than 2% of it was retained on the 160-mesh sieve. Summary of Results The contributed papers in this report were prepared during the early to mid 1970s by the authors who present their analytical data on the Allende reference material and describe their methods. Major, minor, and trace elements were determined by a variety of techniques. Included among them were gravimetric (grav), colorimetric (color), and titrimetric (titr) analyses; flame and/or atomic absorp- tion spectrophotometry (flame); x-ray fluorescence spectro- photometry (XRF); neutron activation analysis (NAA); mass spectrometry (MS); emission spectrometry with various sources (ES); and isotopic dilution analysis (ID). Although these techniques have been described extensively in the literature, we asked contributors to present brief summaries of their methods so that readers may evaluate specific results. Vincent (1952), among others, commented on the importance of giving this type of detailed background ma- terial. Table 1 presents a summary of the data. Major and minor elements were tabulated as oxides in the conventional order for reporting meteorite analyses; results for the other ele- ments are listed by atomic number (in parentheses). Table 1 also gives an overview of the methods that can be success- fully used in the determination of a desired element, and it can be seen that different analytical methods provide ac- ceptable results. For example, neutron activation analysis (NAA), a method used primarily in trace element work gives satisfactory results for some major and minor ele- ments. "Recommended values" were derived for 43 of the ele- ments for which there were sufficient data in the following way: the mean and standard deviation of all analyses was calculated; those analytical values occurring beyond one standard deviation from this mean were excluded (marked by asterisk), and the second mean was calculated. This second mean is the recommended value. This admittedly arbitrary device excluded widely varying results from the calculation of recommended values and resulted in small standard deviations. An exception to this procedure was made for Fe and Ni, for which all neutron activation results were excluded. The wide variation in these results (21.1 %- 26.7% for Fe) would have seriously biased the recom- mended value in favor of a technique that is known to be much less precise than titrimetric and x-ray fluorescence techniques. Means and recommended values were not cal- culated for those elements for which only a few varying results were available, although the data are listed. The homogeneity of the reference powder was estimated from data provided by contributors. For those sets of data that consist of an independent determination of an element in two portions of sample from each of two vials, the set of four data was considered as an experimental design with a single variable of classification (the two vials). The calcula- tions for the analysis of variance for this design are given in statistical texts, including Dixon and Massey (1951). The calculations result in two mean squares: one for the variation in the data attributable to the means of the data in the vials and the other for the variation within the vials (also called the error mean square). These mean squares, frequently abbreviated MS(V) and MS(E) respectively, are used to form the F ratio, MS(V)/ MS(E). We have used the 95 percentile of the F distribution (95% confidence level) for the value not to be exceeded by the ratio calculated from the data and the appropriate value is Fo.'ir, (d.f. 1,2) = 18.5 where there is one degree of freedom (d.f.) for the vials and two (d.f.) for the error term. If the calculated F ratio does not exceed the value of 18.5 then the variation due to the vial means is not significantly larger (NS) than the variation within the two vials; and the element or oxide may be said to be homogeneously distrib- uted between the two vials. These conclusions from the analysis of variance are listed in Table 2 as NS (homogene- ous) or S (heterogeneous). Of the 75 such tests made, the element or oxide could be said to be distributed homoge- neously among the vials for 71 tests. Based on the estimates that are listed in Table 2, we conclude that the Allende reference powder is homogeneous at the 95% confidence level for 44 of the 48 elements. The apparent significant inhomogenity of O, Cs, Ce, and Tb may instead represent analytical problems. A more elaborate statistical evaluation of sample homo- geneity would be desirable but the required data are not available. Most elemental values determined by different techniques and in different laboratories establish a high level of homogeneity for the reference powder. Neverthe- less, individual users are encouraged to evaluate critically the available data in the context of the use they contemplate. SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES TABLE 1.?Summary of analytical results on the Allende meteorite reference sample drawn from 24 laboratories (means and recommended values have been calculated and are given; contributors are identified by the number of their paper (see "Contents"); several results reported in contributions as elements (in ppm) are given as oxides (in percent) in this table; asterisk indicates result not included in calculation of "recommended value." Abbreviations for methods: color = colorimetric analysis; ES = emission spectrom- etry; flame = flame or atomic absorption spectrometry; grav = gravimetric analysis; ID = isotopic dilution analysis; LECO = carbon by LECO; MS = mass spectrometry; NAA = neutron activation analysis; Pnfld = Penfield water determination; SSMS = spark source mass spectrometry; titr = titrimetric analysis; XRF = x-ray fluorescence spectrometry). Constituent Results Method PERCENT SiO2 *35.5(avof2) 34.15 34.48 34.11 34.26 34.07 (av of 2) 34.12 (av of 2) 34.28 34.27 34.70 34.53 34.10 *33.65 *33.62 NAA grav grav grav grav XRF XRF grav grav NAA NAA grav XRF XRF 34.27?0.46 (mean) 34.28?0.21 (recommended TiO.2 0.16 0.17 0.17 0.13 0.16 0.16 0.15 (av of 2) 0.15(avof 2) 0.15 0.13 *0.19 *0.18 0.13 0.140 0.141 color color NAA NAA color color XRF XRF NAA NAA color color color XRF XRF Contributor 5 6 6 11 11 12 12 19 19 22 22 23 24 24 value) 6 6 8 8 11 11 12 12 15 15 19 19 23 24 24 0.15?0.02(mean) 0.15?0.01 (recommended value) AljjO, 3.21 3.36 3.18 3.19 3.403.36 3.27 3.29 3.22 (av of 2) 3.23 (av of 2) *3.6 *3.6 *3.71 *3.67 3.27 (av of 2) NAA NAA grav grav NAA NAA grav grav XRF XRF NAA NAA grav grav NAA 1 1 6 6 8 8 11 11 12 12 15 15 19 19 20 Split/ Position 13/2 19/11 10/31 20/2 20/7 5/10 9/18 20/1 22/10 19/14 8/26 20/20 1/3 4/22 19/11 10/31 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 20/1 22/10 20/20 1/3. 4/22 16/10 16/32 19/11 10/31 6/257/4 20/2 20/7 5/10 9/18 6/24 12/29 20/1 22/10 10/3 Constituent Results Split/ Method Contributor Position PERCENT 3.23 (av of 2) 3.43 3.20 3.30 3.35?0.17(mean) NAA NAA XRF XRF 20 23 24 24 3.28?O.O8 (recommended value) Cr2Os 0.5363 0.5203 0.5391 (avof9) 0.5407 (av of 7) 0.5350 (av of 9) 0.5294 (av of 9) 0.50 (av of 2) 0.56 (av of 2) *0.43 *0.45 0.4709 (av of 4) *0.4648 (av of 2) 0.528 0.539 0.54 0.52 0.54 (av of 2) 0.54 (av of 2) 0.53 0.51 0.53 0.54 *0.6263 (av of 2) *0.6087(avof 2) *0.44 *0.44 *0.59 0.55 0.55 0.54 0.52?0.05 (mean) NAA NAA ES ES ES ES NAA NAA color color NAA NAA NAA NAA color color XRF XRF NAA NAA color color NAA NAA ES ES color NAA XRF XRF 1 1 2 2 2 2 5 5 6 6 7 7 8 8 11 11 12 12 15 15 19 19 20 20 21 21 23 23 24 24 0.53?0.02 (recommended value) MnO 0.1800 0.1756 0.2043 (av of 7) 0.2050 (av of 7) 0.2097 (av of 7) *0.2213 (avof 5) *0.1614(avof6) *0.12 *0.12 0.2053 (av of 4) NAA NAA ES ES ES ES NAA color color NAA 1 1 2 2 2 2 4 6 6 7 12/32 20/20 1/3 4/22 16/10 16/32 1/32 8/31 20/5 20/3 13/32 1/24 19/11 10/31 7/10 4/25 6/25 7/4 20/2 20/7 5/10 9/18 6/24 21/29 20/1 22/10 10/3 12/32 10/13 11/11 20/20 20/20 1/3 4/22 16/10 16/32 1/32 8/31 20/5 20/3 3/15,9/31 19/11 10/31 7/10 NUMBER 27 TABLE 1.?Continued. Results Method PERCENT 0.1999 (av of 2) 0.192 0.192 0.20 0.19 0.21 (avof 2) 0.21 (avof 2) 0.187 0.187 0.18 0.18 0.1821 (avof 2) 0.1801 (avof 2) 0.193 0.198 0.199 NAA NAA NAA color color XRF XRF NAA NAA color color NAA NAA color XRF XRF Contributor 7 8 8 11 11 12 12 15 15 19 19 20 20 23 24 24 Split/ Position 4/25 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 20/1 22/10 10/3 12/32 20/20 1/3 4/22 Constituent Na2O K2O Results Method PERCENT 0.456 0.453 *0.42 (av of 2) 0.46 (av of 2) 0.47 0.47 *0.4966 (av of 4) 0.4798 (av of 2) 0.458 0.457 *0.43 *0.43 0.48 (av of 2) 0.48 (av of 2) 0.47 0.47 0.4489 (av of 3) 0.4516 (avof 3) 0.45 0.45 0.436 (avof 2) 0.451 (avof 2) 0.47 0.46 0.45 NAA NAA NAA NAA flame flame NAA NAA NAA NAA flame flame flame flame NAA NAA NAA NAA flame flame NAA NAA NAA XRF XRF 0.46+0.02 (mean) 0.46?0.01 (recommended 0.036 0.033 0.048 0.05 0.034 0.043 0.03 0.03 0.04 (av of 2) 0.04 (av of 2) 0.04 0.04 0.0355 (av of 3) 0.0348 (av of 3) 0.03 0.03 *0.0265 (av of 2) *0.0265 (av of 2) 0.046 0.033 0.034 NAA NAA flame flame NAA NAA flame flame XRF XRF NAA NAA NAA NAA flame flame NAA NAA NAA XRF XRF Contributor 1 1 5 5 6 6 7 7 8 8 11 11 12 12 15 15 17 17 19 19 20 20 23 24 24 value) 1 1 6 6 8 8 11 11 12 12 15 15 17 17 19 19 20 20 23 24 24 Split/ Position 16/10 16/32 13/32 1/24 19/11 10/31 7/10 4/25 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 5/1 8/27 20/1 22/10 10/3 12/32 20/20 1/3 4/22 16/10 16/32 19/11 10/31 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 5/1 8/27 20/1 22/10 10/3 12/32 20/20 1/3 4/22 MgO CaO 0.19?0.02(mean) 0.19?0.01 (recommended value) 24.50 24.92 *25.5 24.2 24.54 24.69 24.52 (av of 2) 24.47 (av of 2) *23 *23 24.50 24.51 *25.65 24.79 24.81 24.51 ?0.72 (mean) grav grav NAA NAA grav grav XRF XRF NAA NAA grav grav grav XRF XRF 6 6 8 8 11 11 12 12 15 , 15 19 19 23 24 24 24.59?0.20 (recommended value) 2.7 2.5 *2.71 2.58 *2.8 2.5 2.65 2.63 2.60 (av of 2) 2.60 (av of 2) 2.7 2.5 2.60 2.53 2.5 (av of 2) *2.4 (av of 2) 2.58 2.56 2.57 NAA NAA grav grav NAA NAA grav grav XRF XRF NAA NAA grav grav NAA NAA grav XRF XRF 1 1 6 6 8 8 11 11 12 12 15 15 19 19 20 20 23 24 24 19/11 10/31 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 20/1 22/10 20/20 1/3 4/22 16/10 16/32 19/11 10/31 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 20/1 22/10 10/3 12/32 20/20 1/3 4/22 P*O5 0.04?0.01 (mean) 0.04?0.01 (recommended value) 2.59?0.09 (mean) 2.58?0.07 (recommended value) 0.23 0.23 0.24 0.25 0.25 (av of 2) 0.25 (av of 2) 0.26 color color color color XRF XRF color 6 6 11 11 12 12 19 19/11 10/31 20/2 20/7 5/10 9/18 20/1 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES TABLE 1.?Continued. Constituent Results Split/ Method Contributor Position PERCENT 0.26 *0.21 0.230 0.244 color color XRF XRF 19 23 24 24 0.24?0.02 (mean) 0.24?0.01 (recommended value) Fe** 21.7 22.1 22.5 (av of 4) 23.8 (av of 2) 23.55 (av of 2) *23.76(avof 2) 22.99 (av of 4) 22.52 (av of 2) 22.1 22.3 23.53 23.62 23.45 (av of 2) 23.57 (av of 2) 23.5 23.5 23.56 23.50 26.7 (av of 2) 25.9 (av of 2) 23.16 23.67 23.68 NAA NAA NAA NAA titr titr NAA NAA NAA NAA titr titr XRF XRF NAA NAA titr titr NAA NAA titr XRF XRF 1 1 5 5 6 6 7 7 8 8 11 11 12 12 15 15 19 19 20 20 23 24 24 23.55?0.16(mean) 23.57?0.08 (recommended value) Ni** 1.3 1.4 1.43 (av of 2) 1.45 (av of 2) *1.47 1.45 1.44 1.52 1.39 1.42 *1.27(avof 2) *1.27(avof 2) 1.42 1.42 1.40 1.39?0.07(mean) NAA NAA NAA NAA grav grav NAA NAA grav grav XRF XRF grav grav grav 1 1 3 3 6 6 8 8 11 11 12 12 19 19 23 1.42?0.02 (recommended value) 22/10 20/20 1/3 4/22 16/10 16/32 13/32 1/24 19/11 10/31 7/10 4/25 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/2920/1 22/10 10/3 12/32 20/20 1/3 4/22 16/10 16/32 1/136/23 19/11 10/31 6/25 7/4 20/2 20/7 5/10 9/18 20/1 22/10 20/20 ** All NAA results for Fe and Ni excluded. See "Summary of Results." Co 0.0670 0.0677 0.0569 (av of 6) 0.0557 (av of 6) 0.0628 (av of 6) NAA NAA ES ES ES 1 1 2 2 2 16/10 16/321/32 8/31 20/5 Constituent Results Method PERCENT 0.0639 (av of 5) 0.0606 (av of 4) 0.0652 (av of 2) 0.071 *0.076 0.0600 (av of 4) 0.0579 (av of 2) 0.0695 0.0692 0.06 0.06 0.0565 (av of 2) 0.0567 (av of 2) 0.0600 0.0610 0.0749 (av of 2) 0.0728 (av of 2) 0.074 0.070 0.069 0.06?0.01 (mean) ES NAA NAA color color NAA NAA NAA NAA color color XRF XRF SSMS SSMS NAA NAA ES ES NAA Contributor 2 5 5 6 6 7 7 8 8 11 11 12 12 15 15 20 20 21 21 23 0.06+0.01 (recommended value) S *2.20 *2.01 2.14 2.13 2.08 (av of 2) 2.11 (avof2) *2.04 2.10 2.07 2.07 2.10?0.05(mean) grav grav grav grav XRF XRF grav grav XRF XRF 6 6 11 11 12 12 19 19 24 24 2.10?0.03 (recommended value) H2O <0.1 <0.1 0.17 0.16 0.00 0.096 0.131 C 0.23 0.25 0.27 0.26 0.27 *0.29 0.22 0.22 0.28 0.25?0.03 (mean) Pnfld Pnfld Pnfld Pnfld Pnfld Pnfld Pnfld MS MS LECO LECO LECO LECO grav grav grav 0.25+0.02 (recommended O 36.6 (av of 2) 36.37 {av of 4) 36.64 (av of 4) NAA NAA NAA 11 11 19 19 23 24 24 9 9 11 11 14 14 19 19 23 value) 5 22 22 Split/ Position 20/3 13/32 1/24 19/11 10/31 7/10 4/25 6/25 7/4 20/2 20/7 5/10 9/18 6/24 12/29 10/3 12/32 10/13 11/11 20/20 19/11 10/31 20/2 20/7 5/10 9/18 20/1 22/10 1/3 4/22 20/2 20/7 20/1 22/10 20/20 1/3 4/22 4/11 8/23 20/2 20/7 19/21 19/22 20/1 22/10 20/20 13/32 19/14 8/26 NUMBER 27 TABLE 1.?Continued. Constituent Results Method Contributor Split/ Position Constituent Results Method Contributor Split/ Position Li (3) Be (4) B(5) F(9) Cl(17) Sc(21) V(23) 1.3 1.4 4 3 (av of 2) 0.03 0.03 1.0 1.0 <5 <5 56 53 316 265 11.8 12.3 12(avof 7) 11 (av of 6) 10(avof 7) 11 (av of 7) 9.8 (av of 4) 10.7 (av of 4) 12.0(avof2) 10.9 (av of 4) 10.1 (avof 2) 12.0 11.8 10 10 12.1 (avof 2) 11.9 (avof 2) 10 PARTS PER MILLION ES ES ES ES SSMS SSMS ES ES PARTS PER MILLION SSMS SSMS SSMS SSMS ES ES SSMS SSMS NAA NAA NAA NAA ES ES ES ES NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA 11?1 (mean) 11?1 (recommended value) 100 *120 84 (av of 4) 85 (av of 4) 84 (av of 4) 87 (av of 4) 93 96 91.4 (avof 2) 91.6 (avof 2) *77 89 89 89 *113 (avof 2) *111 (avof 2) 100 NAA NAA ES ES ES ES NAA NAA XRF XRF SSMS SSMS NAA NAA NAA NAA ES 2 2 2 2 15 15 21 21 15 15 15 15 21 21 15 15 15 15 20 20 23 12 12 15 15 15 15 20 20 21 1/32 8/31 20/5 20/3 6/24 12/29 10/13 11/11 6/24 12/29 6/24 12/29 10/13 11/11 6/24 12/29 6/25 7/4 16/10 16/32 1/32 8/31 20/5 20/3 3/15,9/31 13/32 1/24 7/10 4/25 6/25 7/4 6/24 12/29 10/3 12/32 20/20 16/10 16/32 1/32 8/31 20/5 20/3 6/25 7/4 5/10 9/18 6/24 12/29 6/24 12/29 10/3 12/32 10/13 Cu (29) Zn (30) Ga(31) *73 (av of 2) 104 (avof 2) ES ES 21 23 94?12 (mean) 92?6 (recommended value) 11/11 20/20 137 (avof 10) 135 (avof 9) 151 (avof 10) 139 (avof 10) 115 (avof 6) 97 101 95.3 (av of 2) 96.1 (avof 2) *230 *230 120 120 125 (avof 2) 135?44(mean) ES ES ES ES NAA NAA NAA XRF XRF NAA NAA ES ES ES 119? 19 (recommended value) 112 (av of 2) 114 (avof 2) 114 (avof 2) 113 (avof 2) 112 (avof 3) 116 (avof 3) *125(avof 4) 107 *77 *130.5(avof 2) *130.5(avof 2) 100 100 110 110 111 + 13 (mean) ES ES ES ES NAA NAA NAA NAA NAA XRF XRF NAA NAA ES ES 110?5 (recommended value) 9.0 7.0 7 (av of 4) 7 (av of 4) 8 (av of 4) 8 (av of 4) 6.0 (av of 3) 5.9 (av of 3) 5.60 (avof 6) 6.0 4.6 5.4 (avof 2) 5.5 (avof 2) 5 5 *25 *23 (av of 2) NAA NAA ES ES ES ES NAA NAA NAA NAA NAA XRF XRF NAA NAA ES ES 2 2 2 2 4 8 8 12 12 15 15 21 21 23 2 2 2 2 3 3 4 8 8 12 12 15 15 21 21 1 1 2 2 2 2 3 3 4 8 8 12 12 15 15 21 21 1/32 8/31 20/5 20/3 3/15,9/31 6/25 7/4 5/10 9/18 6/24 12/29 10/13 11/11 20/20 1/32 8/31 20/5 20/3 1/13 6/23 3/15,9/31 6/25 7/4 5/10 9/18 6/24 12/29 10/13 11/11 16/10 16/32 1/32 8/31 20/5 20/3 1/13 6/23 3/15,9/31 6/25 7/4 5/10 9/18 6/24 12/29 10/31 11/11 8?6 (mean) 6?1 (recommended value) SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES TABLE 1.?Continued. Constituent Results Method Contributor Split/ Position Results PARTS 3.2 (avof 2) 3.2 3.0 *2.3 3.0 2.9 (avof 2) 3.0 (av of 2) ~3 Split/ Method Contributor Position PER MILLION XRF SSMS SSMS SSMS SSMS NAA NAA XRF 12 15 15 16 16 20 20 24 9/18 6/24 12/29 1/27 13/23 10/3 12/32 1/3 PARTS PER MILLION Ge (32) As (33) Se(34) Br (35) Rb(37) Sr(38) Y(39) 17.6 (avof 3) 17.9 (avof 3) 11 11 1.9 (avof 4) 0.87 0.94 3 3 10.5 (avof 4) 12.2 7.4 (avof 2) 1.54 (avof 2) 1.52 (avof 2) 1.3 1.3 1.3 1.3 1.3 (avof 4) *0.86 *0.77 1.32 (avof 2) 1.26 (avof 2) 1.2 ?1.5 1.2 1.2 <5 <8 (av of 2) 1.0 1.3 NAA NAA SSMS SSMS NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA ES ES ES ES NAA NAA NAA XRF XRF SSMS SSMS NAA NAA ES ES XRF XRF 3 3 15 15 4 8 8 15 15 4 4 13 17 17 2 2 2 2 4 8 8 12 12 15 15 17 17 21 21 24 24 1.2?0.2(mean) 1.2?0.1 (recommended value) 1/13 6/23 6/24 12/29 3/15,9/31 6/25 7/4 6/24 12/29 3/15,9/31 3/15 6/11 5/1 8/27 1/32 8/31 20/5 20/3 3/15,9/31 6/25 7/4 5/10 9/18 6/24 12/29 5/1 8/27 10/13 11/11 1/3 4/22 13 (avof 3) 10 (avof 3) 11 (av of 3) 12 (avof 3) <20 <20 14.69 (avof 2) 14.71 (avof 2) *27 *27 8 8 (av of 2) 14.2 14.1 14?6 (mean) ES ES ES ES NAA NAA XRF XRF SSMS SSMS ES ES XRF XRF 12?3 (recommended value) <10 <10 3.2 (avof 2) ES ES ES ES XRF 2 2 2 2 8 8 12 12 15 15 21 21 24 24 2 2 2 2 12 1/32 8/31 20/5 20/3 6/25 7/4 5/10 9/18 6/24 12/29 10/13 11/11 1/3 4/22 1/32 8/31 20/5 20/3 5/10 3.0?0.3 (mean) 3.1?0.1 (recommended value) Zr (40) Nb(41) Mo (42) Ru (44) Pd (46) Ag (47) Cd (48) In (49) 14.8 6.63 7.5 (avof 2) 7.7 (avof 2) 11 10 11 11 6.4 6.4 *48 *51 (avof 2) 8.3 8.0 15?15(mean) NAA NAA XRF XRF SSMS SSMS NAA NAA SSMS SSMS ES ES XRF XRF 9?3 (recommended value) <1 (avof 2) <1 (avof 2) 0.72 0.76 0.48 0.53 <2.5 <2.5 2.5 (avof 4) <2 <2 (av of 2) 0.85 (avof 4) 0.66 (av of 2) 0.62 (av of 2) <1 <1 (avof 2) 0.433 0.432 (avof 2) 0.58 (av of 2) 0.57 <2 <2 (av of 2) 0.0289 (av of 3) 0.0289 (av of 3) <0.01 (avof 4) 0.031 *0.041 XRF XRF SSMS SSMS SSMS SSMS XRF XRF NAA ES ES NAA NAA NAA ES ES NAA NAA NAA NAA ES ES NAA NAA NAA NAA NAA 4 5 12 12 15 15 15 15 16 16 21 21 24 24 12 12 15 15 16 16 24 24 4 21 21 4 13 13 21 21 3 3 20 20 21 21 3 3 4 8 8 3/15 13/32 5/10 9/18 6/24 12/29 6/24 12/29 1/27 13/23 10/13 11/11 1/3 4/22 5/10 9/18 6/24 12/29 1/27 13/23 1/3 4/22 3/15,9/31 10/13 11/11 3/15,9/31 6/11 13/20 10/13 11/11 1/13 6/23 10/3 12/32 10/13 11/11 1/13 6/23 3/15,9/31 6/25 7/4 NUMBER 27 TABLE 1.?Continued. Constituent Sn(50) Sb(51) Te (52) Cs (55) Ba (56) La (57) Results Method Contributor PARTS PER MILLION 0.028 0.027 (avof 2) NAA NAA 0.031 ?0.005 (mean) 20 20 0.029?0.001 (recommended value) 0.30 (avof 4) <20 <20 0.04 (av of 4) 0.085 0.088 1.35 1.1 (avof 2) 1.1 (avof 2) 1.1 (avof 2) <1 <1 <1 <1 0.10 (avof 4) <0.1 <0.1 0.1 0.09 0.10 0.092 (av of 3) 0.096 (av of 3) 5 (av of 2) 4 (av of 2) 4 (av of 2) 4 (av of 2) <10 <10 *12 *12 5.1 5.7 <2 <2 (av of 2) 3 4 6?3 (mean) NAA ES ES NAA NAA NAA NAA NAA NAA NAA ES ES ES ES NAA NAA NAA SSMS SSMS SSMS NAA NAA ES ES ES ES NAA NAA SSMS SSMS SSMS SSMS ES ES XRF XRF 4?1 (recommended value) 0.48 0.47 0.56 0.47 *0.38 0.46 0.48 0.56 0.56 0.6 *0.7 0.53 NAA NAA NAA NAA NAA NAA NAA SSMS SSMS NAA NAA SSMS 4 21 21 4 15 15 4 13 17 17 2 2 2 2 4 8 8 15 15 16 17 17 2 2 2 2 8 8 15 15 16 16 21 21 24 24 1 1 4 7 7 8 8 15 15 15 15 16 Split/ Position 10/3 12/32 3/15,9/31 10/13 11/11 3/15,9/31 6/24 12/29 3/15 6/11 5/1 8/27 1/32 8/31 20/5 20/3 3/15,9/31 6/25 7/4 6/24 12/29 1/27 5/1 8/27 1/32 8/31 20/5 20/3 6/25 7/4 6/24 12/29 1/27 13/23 10/13 11/11 1/3 4/22 16/10 16/32 3/15 7/10 4/25 6/25 7/4 6/24 12/29 6/24 12/29 1/27 Constituent Ce (58) Pr (59) Nd (60) Sm (62) Results Split/ Method Contributor Position PARTS PER MILLION 0.52 0.5121 (avof 2) 0.5149 (avof 2) 0.50 (av of 2) 0.51 (avof 2) SSMS ID ID NAA NAA 16 18 18 20 20 0.52?0.07 (mean) 0.52?0.04 (recommended value) *1.45 1.40 1.32 1.23 1.21 1.30 1.2 1.3 *1 *1 1.43 *1.45 1.328 (avof 2) 1.335 (avof 2) 1.35 (avof 2) 1.43 (avof 2) 1.30?0.14(mean) NAA NAA NAA NAA NAA NAA SSMS SSMS NAA NAA SSMS SSMS ID ID NAA NAA 1 1 4 5 8 8 15 15 15 15 16 16 18 18 20 20 1.33?0.08 (recommended value) *0.26 0.22 0.21 0.19 0.20 0.21 (avof 2) 0.21 (avof 2) 0.21 ?0.02 (mean) NAA SSMS SSMS SSMS SSMS NAA NAA 4 15 15 16 16 20 20 0.21 ?0.01 (recommended value) *0.92 0.94 1.00 0.99 1.009 (avof 2) 1.009 (avof 2) 1.01 (avof 2) *1.08(avof 2) 0.99?0.05 (mean) SSMS SSMS SSMS SSMS ID ID NAA NAA 15 15 16 16 18 18 20 20 0.99?0.03 (recommended value) 0.31 0.35 *0.18 0.33 (av of 3) 0.37 (av of 2) 0.324 0.336 0.36 0.35 0.34 NAA NAA NAA NAA NAA NAA NAA SSMS SSMS NAA 1 1 4 7 7 8 8 15 15 15 13/23 2/20 5/4 10/3 12/32 16/10 16/32 3/15 13/32 6/25 7/4 6/24 12/29 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 3/15 6/24 12/29 1/27 13/23 10/3 12/32 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 16/10 16/32 3/15 7/10 4/25 6/25 7/4 6/24 12/29 6/24 10 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES TABLE 1.?Continued. Constituent Results Split/ Method Contributor Position PARTS PER MILLION 0.36 0.30 0.32 0.3284 (av of 2) 0.3269 (av of 2) 0.334 (av of 2) 0.361 (avof2) NAA SSMS SSMS ID ID NAA NAA 15 16 16 18 18 20 20 0.33?0.04 (mean) 0.34?0.02 (recommended value) Eu(63) 0.106 0.109 0.136 0.14 (av of 4) *0.15 *0.16 0.1 *0.09 0.1 0.1 0.10 0.11 0.1133 (av of 2) 0.1125(avof 2) 0.116 (av of 2) 0.116 (av of 2) NAA NAA NAA NAA NAA NAA SSMS SSMS NAA NAA SSMS SSMS ID ID NAA NAA 1 1 4 7 8 8 15 15 15 15 16 16 18 18 20 20 0.12?0.02(mean) 0.11?0.01 (recommended value) Gd (64) *0.54 0.42 0.42 *0.36 0.39 0.4134 (av of 2) 0.4050 (av of 2) 0.45 (av of 2) 0.44 (av of 2) NAA SSMS SSMS SSMS SSMS ID ID NAA NAA 4 15 15 16 16 18 18 20 20 0.43?0.05 (mean) 0.42?0.02 (recommended value) Tb (65) 0.08 0.08 0.075 0.090 0.075 0.077 0.075 0.1 0.1 0.07 0.07 0.078 (av of 2) 0.084 (av of 2) NAA NAA NAA NAA NAA SSMS SSMS NAA NAA SSMS SSMS NAA NAA 0.081?0.010(mean) 1 1 4 8 8 15 15 15 15 16 16 20 20 0.081+0.010 (recommended value) Dy (66) 0.408 *0.34 NAA NAA 4 8 12/29 1/27 13/23 2/20 5/4 10/3 12/32 16/10 16/32 3/15 7/10 6/25 7/4 6/24 12/29 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 3/15 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 16/10 16/32 3/15 6/25 7/4 6/24 12/29 6/24 12/29 1/27 13/23 10/3 12/32 3/15 6/25 Constituent Results Split/ Method Contributor Position PARTS PER MILLION 0.38 0.41 0.41 0.44 0.47 *0.5056 *0.5020 0.43 (av of 2) 0.45 (av of 2) 0.43+0.05 (mean) NAA SSMS SSMS SSMS SSMS ID ID NAA NAA 8 15 15 16 16 18 18 20 20 0.42+0.03 (recommended value) Ho (67) 0.114 0.088 0.092 *0.12 *0.12 0.1 0.1 0.09 0.10 0.114 (av of 2) 0.113 (av of 2) 0.10?0.01 (mean) NAA NAA NAA SSMS SSMS NAA NAA SSMS SSMS NAA NAA 4 8 8 15 15 15 15 16 16 20 20 0.10?0.01 (recommended value) Er (68) *0.344 *0.27 0.28 0.28 0.28 0.3031 0.3031 0.30 (av of 2) 0.30 (av of 2) 0.30+0.02 (mean) NAA SSMS SSMS SSMS SSMS ID ID NAA NAA 4 15 15 16 16 18 18 20 20 0.29?0.01 (recommended value) Tm (69) 0.053 0.064 0.056 (av of 2) 0.055 (av of 2) Yb (70) 0.26 0.30 *0.33 *0.33 *0.22 *0.25 *0.33 0.28 0.29 0.31 0.3161 0.3133 0.30 (av of 2) 0.30 (av of 2) 0.29?0.03 (mean) SSMS SSMS NAA NAA NAA NAA NAA NAA NAA NAA SSMS SSMS SSMS SSMS ID ID NAA NAA 16 16 20 20 1 1 4 7 8 8 15 15 16 16 18 18 20 20 0.30?0.02 (recommended value) 7/4 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 3/15 6/25 7/4 6/24 12/29 6/24 12/29 1/27 13/23 10/3 12/32 3/15 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 1/27 13/23 10/3 12/32 16/10 16/32 3/15 7/10 6/25 7/4 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 NUMBER 27 11 TABLE 1.?Continued. Constituent Lu(71) Hf(72) W(74) Re (75) Os (76) Ir (77) Results Split/ Method Contributor Position PARTS PER MILLION *0.041 0.048 0.053 *0.065 *0.039 0.06 0.06 0.05 0.06 0.0468 0.0462 0.048 (av of 2) 0.050 (av of 2) NAA NAA NAA NAA NAA NAA NAA SSMS SSMS ID ID NAA NAA 0.051 ?0.008 (mean) 1 1 4 8 8 15 15 16 16 18 18 20 20 0.052?0.006 (recommended value) *0.35 *0.30 *0.13 0.201 0.21 0.24 0.20 0.19 0.2 0.2 0.20 0.22 NAA NAA NAA NAA NAA NAA SSMS SSMS NAA NAA SSMS SSMS 0.22?0.06 (mean) 1 1 4 5 8 8 15 15 15 15 16 16 0.21 ?0.01 (recommended value) 0.20 0.29 0.2 0.2 0.020 (av of 4) 0.063 (av of 2) 0.064 (av of 2) 0.40 (av of 4) 0.73 (av of 2) 0.77 (av of 2) 0.80 (av of 3) 0.83 (av of 2) *0.51 (avof4) 0.6 (av of 2) 0.6 (av of 2) *0.89 (av of 2) 0.79 0.76 0.79 (av of 2) NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA 8 8 15 15 4 13 13 4 13 13 3 3 4 5 5 7 8 8 13 16/10 16/32 3/15 6/257/4 6/24 12/29 1/27 13/23 2/20 5/4 10/3 12/32 16/10 16/32 3/15 13/32 6/25 7/4 6/24 12/29 6/24 12/29 1/27 13/23 6/25 7/4 6/24 12/29 3/15,9/31 6/11 13/20 3/15,9/31 6/11 13/20 1/136/23 3/15,9/31 13/32 1/24 7/10 6/25 7/4 6/11 Constituent Au (79) Hg (80) Pb (82) Bi (83) Th (90) Tl(81) 204pb U(92) Results Method Contributor PARTS PER MILLION 0.74 0.73?0.12(mean) NAA 13 0.74?0.09 (recommended value) *0.22 *0.25 0.14 0.17 0.15 (av of 4) 0.14 (av of 6) 0.16 *0.11 (avof 2) 0.13 (av of 2) 0.16?0.04(mean) NAA NAA NAA NAA NAA NAA NAA NAA NAA 1 1 3 3 4 4 7 13 13 0.15?0.01 (recommended value) 0.035 (avof 4) 1.138 1.538 1.6 1.0 1.57 1.49 *12 *12(avof 2) 4.04?4.92 (mean) NAA ID ID SSMS SSMS SSMS SSMS ES ES 4 10 10 15 15 16 16 21 21 1.39?0.25 (recommended value) 0.028 (avof 2) <2 <2 (av of 2) 0.5 0.5 <0.3 <0.3 2.2 (av of 2) 1.6 (avof 2) 0.070 (avof 2) 0.063 0.063 PARTS PER 53.1 20.30 26.24 <0.07 <0.07 16 (avof 2) 16 NAA ES ES NAA NAA NAA NAA XRF XRF NAA SSMS SSMS BILLION ID ID ID NAA NAA NAA NAA 13 21 21 1 1 8 8 12 12 13 16 16 10 10 10 8 8 17 17 Split/ Position 13/20 16/10 16/32 1/13 6/23 3/15,9/31 3/15,9/31 7/10 6/11 13/20 3/15,9/31 4/26 9/14 6/24 12/29 1/27 13/23 10/31 11/11 6/11 10/13 11/11 16/10 16/32 6/25 7/4 5/10 9/18 6/111/27 13/23 4/26 4/26 9/14 6/25 7/4 5/1 8/27 12 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES TABLE 2.?Summary of the analysis of variance for 48 elements based on 75 replicate analyses (mean = average of replicate analyses as given in contributed paper in percent or ppm; conclusion (at 95% confidence level): NS = not significant (homogeneous); S = significant (heterogeneous); contributor = contributed paper as listed in Contents; method = analytical method using abbreviations as listed in Table 1). Constituent SiO2 TiO2 AI2OS Cr2O3 MnO MgO CaO Na2O K.2O P*O5 Fe Ni Co S o Sc V Cu Zn Mean 34.09 0.15 3.22 3.25 0.534 0.54 0.62 0.206 0.21 0.181 24.49 2.60 2.5 0.44 0.48 0.450 0.443 0.04 0.035 0.027 0.25 23.51 1.27 0.0584 0.0566 0.0738 2.09 36.50 Conclusion PERCENT NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS S Contributor Method 12 12 12 20 2 12 20 2 12 20 12 12 20 5 12 17 20 12 17 20 12 12 12 2 12 20 12 22 PARTS PER MILLION 11 12.0 85 91.5 112 142 95.7 113 NS NS NS NS NS NS NS NS 2 20 2 12 20 2 12 2 XRF XRF XRF NAA ES XRF NAA ES XRF NAA XRF XRF NAA NAA flame NAA NAA XRF NAA NAA XRF XRF XRF ES XRF NAA XRF NAA ES NAA ES XRF NAA ES XRF ES Constituent Ga Br Rb Sr Y Zr Pd Te Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Re Os Ir Au Th Mean Conclusion Contributor Method PARTS PER MILLION 130.5 7 5.4 1.53 1.29 12 14.70 3.2 3.0 7.6 0.64 1.1 0.094 4 0.5135 0.50 1.331 1.39 0.21 1.009 1.05 0.3276 0.347 0.1129 0.116 0.4092 0.44 0.081 0.44 0.113 0.30 0.055 0.30 0.049. 0.063 0.75 0.6 0.12 1.9 NS NS NS NS NS NS NS NS NS NS NS NS S NS NS NS NS S NS NS NS NS NS NS NS NS NS S NS NS NS NS NS NS NS NS NS NS NS 12 2 12 17 12 2 12 12 20 12 13 17 17 2 18 20 18 20 20 18 20 18 20 18 20 18 20 20 20 20 20 20 20 20 13 13 5 13 12 XRF ES XRF NAA XRF ES XRF XRF NAA XRF NAA NAA NAA ES ID NAA ID NAA NAA ID NAA ID NAA ID NAA ID NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA NAA XRF 1. Trace Element Analyses of the Allende Meteorite Reference Sample by Neutron Activation Ralph 0. Allen, Jr. Two splits of the Allende meteorite reference sample were analyzed for 22 major, minor, and trace elements by instrumental neutron activation analysis. A 500 mg sample of each specimen in a polyethylene vial was irradiated for 1 minute in the University of Virginia nuclear reactor at a flux of ~10K neutrons cm"2 sec"1. The 7-ray spectra were taken within minutes of the irradiation with a 20 cm3 Ge(Li) detector and a 512-channel analyzer for the analysis of A1, Ca, and V. The samples were counted about 8 hours after the irradiation for the determination of Mn and Na. This procedure is similar to that described by Wakita et al. (1970). The same samples were then irradiated for 2 hours at a flux of ~10]< neutrons cm"2 sec"1 along with aqueous solu- tions of the standards. Each polyethylene vial was wrapped with a weighed iron wire. The specific activities of these iron wires were used to correct for any variations in flux between the vials. After allowing the radioactive samples to cool for ~12 hours, they were transferred to new polyeth- ylene vials for counting. Gamma-ray spectra were taken with either a 40 cm3 or a 70 cm3 Ge(Li) detector coupled to a 4096-channel analyzer. The counting procedure was similar to that described by Gordon et al. (1968). The following elements were measured: Fe, Na, K, Ni, Mn, Cr, Co, Sc, V, Hf, Au, Ga, Th, La, Ce, Sm, Eu, Tb, Yb, and Lu. For most elements two or more photopeaks were used for the calculations and in some cases two different isotopes were used. The results are summarized in Table 3. Sample B-10 is Split 16/Position 10 and sample B-11 is Split 16/Position 32 of the Allende meteorite reference sample. Sample B-9 Ralph O. Allen, Jr., Department of Chemistry, University of Virginia, Charlottes- ville, Virginia 22901. is Split 7/Position 4 of the USGS Standard BCR-1, which was analyzed at the same time as the Allende samples. Within the analytical uncertainties there is no great differ- ence between the two Allende samples. TABLE 3.?Neutron activation analyses of two subsamples of the Allende meteorite reference sample (B-10 = Split 16/Position 10; B-l 1 = Split 16/ Position 32) and USGS Reference Sample BCR-1 (dash indicates not determined). Constituent Fe2Os* Na2O K2O AI2OS CaO Ni Mn Cr Co Sc V Hf Au Ga Th La Ce Sm Eu Tb Yb Lu B-10 Allende 16/10 B-11 Allende 16/32 PERCENT 31.0?0.5 0.456?0.001 0.036?0.006 3.21+0.05 2.7?0.3 1.3?0.1 31.6?0.5 0.453?0.009 0.033?0.006 3.36?0.15 2.5?0.4 1.4?0.1 PARTS PER MILLION 1394?27 3670?63 670?10 11.8?0.2 100?40 0.35?0.15 0.22?0.05 9.0?0.7 0.5?0.2 0.48?0.04 1.45?0.14 0.31?0.04 0.106?0.007 0.08?0.02 0.26?0.03 0.041?0.008 1360?30 3560+52 677?10 12.3?0.4 120?30 0.30?0.15 0.25?0.5 7.0?0.7 0.5?0.2 0.47?0.04 1.40?0.10 0.35?0.04 0.109?0.007 O.O8?O.O2 0.30?0.03 0.048?0.006 B-9 BCR-1 7/4 3.13?0.06 3.30?0.03 1.68?0.03 13.6?0.3 7.0?0.6 - 1352?30 16?4 38.7?0.8 38.6?0.6 440?50 4.1?0.3 - 21.8?1.4 7.8?1.4 24.2?0.2 52.5?2.8 6.95?0.05 2.10+0.05 1.15?0.10 3.44?0.10 0.523?0.010 Total Fe reported as 13 2. Emission Spectrographic Analyses of Trace Elements in the Allende Meteorite Reference Sample C.S. Annell Emission spectrographic analyses were performed for 14 elements in four splits of the Allende meteorite reference sample. Each sample split was quartered twice and one quarter of the original sample was ground in an agate mortar. A 200 mg portion of each finely ground sample was mixed with 50 mg of graphite powder by grinding together in an agate mortar, and the mixtures were stored in polyethylene capsules. Three methods of d.c. arc emission spectroscopy were used. Method 1: A 15 A arc in air vaporized a 25 mg sample- graphite mixture to completion. First order spectra from 2300 to 4800 A were photographed using a 3.4 m Ebert spectrograph. The spectra were examined for 38 elements. Method 2: A 25 A arc in an atmosphere of argon was used selectively to volatilize and determine nine elements: Ag, Au, Bi, Cd, Ge, In, Pb, Tl, and Zn. To do this, a 25 mg sample-graphite was spectrochemically buffered with 30 mg of Na2CO3. Second order spectra in the 2400-3650 A region were recorded with a 3 m Eagle spectrograph. Method 3: A 12.5 mg portion of the sample-graphite mix- ture, buffered with 20 mg of K2CO3, was vaporized in a 15 A arc in air for the determination of Cs, Rb, and Li. The 3 m Eagle spectrograph was used to record first order spectra in the 6500-9000 A region. Based on data for the general composition of the Allende meteorite, a matrix of high Si, Fe, and Mg containing proportionate amounts of Al, Ca, Na, and Ti as oxides or carbonates was prepared and sintered. This matrix was used for dilution of other standards and mixtures to provide spectra and inter-element reactions comparable to those for meteorites. For those elements determined by emission spectroscopy (Method 1), a coefficient of variation of 15% of the amount present is assigned. Methods 2 and 3, specifically designed for a selective group of elements, both have a coefficient of variation of 10% of the amount present. The results of the analyses are listed in Table 4. The following elements were looked for but not detected; if C.S. Annell, United States Geological Survey, Reston, Virginia 22092. present, their concentrations are below those indicated in parenthesis (in ppm): Ag (0.2), As (4), Au (0.2), B (10), Bi (1), Cd (8), Ce (100), Cs (1), Ge (1), Hf (20), Hg (8), In (1), Mo (2), Nd (100), P (2000), Pb (1), Pt (3), Re (30), Sb (100), Sn (10), Ta (100), Te (300), Th (100), Tl (1), U (500), and W (200). TABLE 4.?Emission spectrographic analyses of trace elements (ppm) in four subsamples from the Allende meteorite reference sample (elements listed in order of decreasing volatility in the d.c. arc). Constit- uent Zn Cu Ga Cs Rb Li Mn Cr Co Ba Sr V Sc Y 1/32 120 113 120 150 125 150 6 7 <1 l.: by dropwise addition of NaNO2 solution in the presence of CC14. Br~ remained in the aqueous phase. 12 was extracted into CC14, the violet solution transferred to another funnel, and I2 back-extracted into H2O by adding Na2SO3 solution. The I -I2 extraction cycle was repeated twice. The final aqueous I" solution was heated to expel excess SO2 and I~ precipitated as Agl, which was weighed for chemical yield. 131I was counted on a 3 X 3 inch solid Nal(Tl) crystal and the 0.365 meV 7-peak was used for evaluation. The Br~ solution was acidified to at least 3N by adding 8N H2SO4. Br~ was oxidized to Br2 by dropwise addition of KMnO4 solution in the presence of CC14. Br2 was extracted into CC14 by intense shaking, the yellow- brown solution transferred to another funnel, and Br2 back- extracted into 3N H2SO4 by adding Na2SO3 solution. The Br~-Br2 extraction cycle was repeated twice. The final Br~ solution was heated to expel excess SO2 and Br~ was precip- itated as AgBr, which was weighed for chemical yield. *2Br was counted on a 3 X 3 inch solid Nal(Tl) crystal and the 0.55 meV 7-peak was used for evaluation. A sample of the Allende powder weighing 100 mg, and a U monitor were irradiated for 2 hours in the core of TRIGA for the determination of uranium. The chemical processing of samples and monitor was started 20 minutes after irradiation. Because of the short-lived 2:WU, a rapid chemical procedure for the separation of U must be used. Each Allende powder was fused in Na2O2 with 15 mg U carrier in a nickel crucible. The fusion cake was dissolved in 6N HC1 and the solution filtered through a plug of glass wool to remove undissolved silica and part of the NaCl. A new ml of concentrated HC1 was added to the filtrate to make it at least 6N. The filtrate was passed through an 8 X 1.2 cm Dowex 1, X-8, 100-200 mesh anion exchange column to absorb the (UO2)L+-chloro complex. The column was washed several times with a few ml of 6N HC1. Then (UO2)~'+ was eluted with 40 ml 0.4N HNO3 and the eluate collected in a beaker containing 40 g Ca(NO3)2-4H2O and 4 ml concentrated HNO3. U was extracted into diethyl ether and the ether phase washed three times with 15 ml of a solution containing 40 ml 0.4N HNO:i, 4 ml concentrated HNCS, and 40 g Ca(NO3)2-4H2O. U was back-extracted into H2O and the ether still present evaporated. To the acidic U solution 1 ml 0.1N EDTA solution was added to complex Ca2+. Then NH4OH was added until a pale yellow color appeared. U was precipitated by adding 4 ml 2% 8- hydroxyquinoline in 3% acetic acid solution and by buffer- ing the solution to pH 7 with a 10% ammonium acetate solution. The U precipitate was filtered, washed with H2O, and dissolved with 2N HC1, and the U solution was trans- ferred to a plastic counting tube. The 7-ray spectrum of 2:<9U was counted using a 3 X 3 inch Nal(Tl) scintillation well counter and a 400-channel pulse height analyzer. The 74 keV line of ?'U was used for evaluation of the intensity. This line has a high peak height to background ratio and is therefore especially valuable for the detection of uranium amounts in the nanogram range. In addition, the half-life of -WU (b/, = 23.5 min) was controlled by counting the U solutions of samples and monitors at least twice. The chem- NUMBER 27 37 ical yield of U was determined by transferring the U solu- tion to a beaker quantitatively and by re-precipitating U with 8-hydroxyquinoline. To achieve complete precipita- tion 2 ml of the reagent was added to the 2N HC1-U solution and the acid neutralized as above. The U precipitate was collected in a weighed glass filter crucible, washed with HyO, dried at 105? C, and weighed. The yield was -50%. The U monitor, weighed as solution on aluminum foil, was dissolved with 15 mg U carrier in 10 ml 6N HC1 and 1 ml concentrated HNO3. The solution was passed through a Dowex-1 ion exchange column and the chemical separation, counting, and yield determination performed as described above. The chemical yield was ~60%. The results of the replicate analyses are compiled in Table 24. All elements except Rb and U (only one U run for Split 8/Position 27), were determined at least twice in both splits. The agreement between analyses of each split is satisfactory as shown in Table 24. The errors are about ?3% for most elements, but are somewhat higher for Te and U. In com- paring the mean values of Split 5/Position 1 and Split 8/ Position 27, it appears that these splits are derived from a well-homogenized powder, because no obvious differences with respect to the analyzed elements exist. ACKNOWLEDGMENTS.?We are indebted to the TRIGA reactor group of the Deutsches Krebsforschungszentrum, Institut fur Nuklearmedizin, Heidelberg, and to the FR2 reactor team of the Gesellschaft fur Kernforschung, Karls- ruhe, for performing the irradiations. The collaboration of Mrs. S. Hasse and D. Kaether is gratefully acknowledged. 18. Analysis of Rare Earth Elements in the Allende Meteorite Reference Sample by Stable Isotope Dilution Noboru Nakamura and Akimasa Masuda Rare earth elements were determined by the stable iso- tope dilution technique in two splits of the Allende meteo- rite reference sample. Results are given in Table 25. TABLE 25.?Stable isotope dilution analysis (in ppm) of rare earth elements in the Allende meteorite reference sample (a and b are duplicate analyses of each split; dash indicates data not available). Noboru Nakamura, Department of Earth Sciences, Kobe University, Nada, Kobe 657, Japan. Akimasa Masuda, Department of Chemistry, Science University of Tokyo, Tokyo 162, Japan. Constituent La Ce Nd Sm Eu Gd Dy Er Yb Lu Split 2/Position 20 (a) 0.5052 1.330 1.004 0.3288 0.1125 0.4130 0.5056 0.3031 0.3161 0.0468 (b) 0.5190 1.325 1.014 0.3280 0.1141 0.4138 - - - - Split 5/Position 40 (a) 0.5077 1.320 1.010 0.3303 0.1130 0.4138 0.5020 0.3031 0.3133 0.0462 (b) 0.5220 1.350 1.008 0.3234 0.1119 0.3961 - - _ - 38 19. Bulk Chemical Analysis of the Allende Meteorite Reference Sample J.H. Scoon Two samples of the Allende meteorite reference sample, identified as Split 20/Position 1 and Split 22/Position 10, were analyzed for major and minor elements using wet chemical methods (Table 26). Silica was determined by dehydration with hydrochloric acid and volatilization with hydrofluoric acid. The silica remaining in solution after this operation was recovered by dehydration of the solution obtained from the pyrosulfate fusion of the R2O3 precipitate. Alumina was obtained by difference from the R->O3 precipitate. Total iron was deter- mined by titration with eerie sulfate solution after treatment of an aliquot of the RjO3 solution in a silver reductor. Ferrous iron was determined by the modified Pratt method. Manganese was determined colorimetrically as permanga- nate after oxidation with potassium periodate. Titanium was estimated similarly using hydrogen peroxide. Calcium was precipitated as oxalate and ignited and weighed as oxide. Magnesium was precipitated as magnesium ammo- nium phosphate and ignited and weighed as Mg2P2C>7. Sodium and potassium were determined using an E.E.L. flame photometer. Total water was obtained by the Penfield method. H2O~ was obtained from loss in weight at 105? C. Phosphorus was determined colorimetrically by the vana- domolybdate method. Chromium was estimated colorimet- rically using diphenyl carbazide. Nickel was precipitated as the red dimethylglyoxime complex, dried, and weighed. Sulfur was precipitated as BaSO4 after sodium carbonate J.H. Scoon, Department of Mineralogy and Petrology, University of Cambridge, Cambridge CB2 3EW, England. fusion and extraction; allowance was made for reagent blank. Carbon was determined by wet oxidation with chromic acid and phosphoric acid. The carbon dioxide formed was weighed in absorption tubes. Any carbonate present was first decomposed by heating with phosphoric acid alone. TABLE 26.?Bulk chemical analysis of two samples of the Allende meteorite reference sample (in %). Constituent SiO2 A12O3 Cr2Os Fe2O3 FeO MnO MgO CaO Na2O K2O H2O+ H2CT TiO2 P2O5 NiO S c Total Less S = O Total Total Iron as Fe Split 20/ Position 1 34.28 3.71 0.53 nil 30.31 0.18 24.50 2.60 0.45 0.03 0.11 0.06 0.19 0.26 1.81 2.04 0.22 101.28 0.88 100.40 23.36 Spit 22/ Position 10 34.27 3.67 0.54 nil 30.23 0.18 24.51 2.53 0.45 0.03 0.10 0.06 0.18 0.26 1.81 2.10 0.22 101.14 0.90 100.24 23.32 39 20. Abundances of the 14 Rare Earth Elements and 12 Other Major, Minor, and Trace Elements in the Allende Meteorite Reference Sample by Neutron Activation Analysis D.L. Showalter, H. Wakita, R.H. Smith, and R.A. Schmitt Two splits of the Allende meteorite reference sample, Split 10/Position 3 and Split 12/Position 32, were analyzed for the 14 rare earth elements (REE) and 13 major, minor, and trace elements. Two 1 g aliquants of each sample split were subjected to sequential instrumental neutron activa- tion analysis (IN A A), followed by radiochemical neutron activation analysis (RNAA), as outlined by Schmitt et al. (1970) and Rey et al. (1970). The sequence began with a determination of the Al abundance via INAA by a 1 minute activation in a low thermal neutron flux of ~5 X 106 neutrons cm"2 sec"1, followed by counting with Nal(Tl) 7-ray spectrometry. Ca, V, Na, and Mn were also determined by INAA with a 5 minute activation (~8 X 10" neutrons cm"' sec~]); spectra were taken with a Ge(Li) detector coupled to a 2048- channel analyzer. Samples and standards were then sub- jected to a 3 hour activation in a high thermal neutron flux (~1.6 X 1012 neutrons cm"" sec"1) and the abundances of Cr, Sc, Fe, and Co were obtained by counting with Ge(Li) 7-ray spectrometry. After about one month's radioactive decay, the samples and standards were activated for 3 hours at a thermal neutron flux of ~ 1.6 X 1012 neutrons cm"2 sec"1, allowed to decay for 2 to 3 days, and again reactivated for 1 hour at the same thermal neutron flux. This procedure was employed in order to maximize the long-lived REE activities and to minimize the level of 15-hour 24Na during radiochemical processing of the activated samples. The samples were allowed to decay for ~30 minutes after acti- vation before chemical separations were started. The abun- dances of K, In, Cd, Y, and the 14 REE were determined by RNAA. D.L. Showalter, Department of Chemistry, Wisconsin State University, Stevens Point, Wisconsin 54481, USA. H. Wakita, Department of Chemistry, University of Tokyo, Hongo, Tokyo, Japan. R.H. Smith (deceased). R.A. Schmitt, Department of Chemistry and The Radiation Center, Oregon State University, Corvallis, Oregon 97331, USA. Analytical results are listed in Table 27. The associated errors represent the statistical counting uncertainties plus the overall estimated error, which includes the estimated errors in counting geometries and the conventional chemi- cal standardization of the activation elemental standards. Column six lists the average abundance values for the four samples analyzed in this work and column seven gives the corresponding Allende data of other workers. For the major, minor, and trace elements, Al to Cd in Table 27, the average precision was ?4.0%, with a range from 0.7 to 16%. The precision was above 7% for only one element (Ca, 16%) and is the upper limit for the other ten elements of this group. This large Ca uncertainty is entirely due to the low counting statistics obtained for 8.8-minute 49Ca, which was counted together with 5.8-minute 5ITi and 3.77-minute 52V. The precision for Ca could be improved to below ?10% if V were excluded from the joint INAA for Ca and V. Despite the large Ca error, the average value agrees with other workers (King et al., 1969, and Clarke et al., 1970) who used other techniques. As noted in the last two columns of Table 27, the agree- ment between the averages of this work and others for Al, Ca, Mn, K, Sc, and In indicates that these elements are homogeneously distributed, at least for the three or more fragments that were sampled and analyzed by various groups. Apparently the elements Fe, V, Cr, Co, and Cd are heterogeneously distributed among the various fragments. Variations for V, Cr, and Co that were obtained from various Allende fragments are probably real. The same INAA technique in our laboratory yielded 26.3+0.5% Fe (this work with 4 g) and 21.9?0.4% (Wakita and Schmitt, 1970, with a 2 g interior piece) for two different Allende fragments. Emery et al. (1969), also using INAA, obtained 27.8% Fe, which agrees within 2p of this work and which abundance value is above the 23.8%, 23.6%, and 24.4% 40 NUMBER 27 41 obtained by Clarke et al. (1970), King et al. (1969), and Morgan et al. (1969), respectively. At present we are not able to explain why the Fe values obtained via INAA are about 10% higher than those obtained by conventional techniques. Furthermore, we believe that the Fe value ob- tained by the standard methods are more accurate than the INAA results. The very uniform In abundances observed in this work and that by Wakita and Schmitt (1970) and the similar chalcophilic character of In and Cd tend to cast some doubt on the validity of either the lower value of Cd, 0.19?0.01 ppm (Wakita and Schmitt, 1970), or the average higher value of 0.58?0.04 ppm of this work. Perhaps the large variations in Cd abundances are real and represent sampling problems. Assuming trace elemental uniformity within each carbonaceous meteoritic type, the close agreement of the Cd of 0.58 ppm of this work with 0.52 ppm Cd found in Mokoia, another Type III carbonaceous chondrite (Schmitt etal., 1963), the reliability of the lower Cd value, 0.19 ppm, may be questioned. To settle this point, Cd should be determined in many additional Allende fragments. REE and Y abundances of this work agree in general with those determined in another fragment by Wakita and Schmitt (1970), who have discussed the relationships of the REE abundances in Allende with other carbonaceous classes. The average precision, expressed as a sample stand- ard deviation, is ?3.5% for the REE + Y, with a precision range of ?1 to 10%. The element Nd yielded the poorest precision of ?10%, this resulted mainly from counting statistics. The light REE, La to Bd, are enriched by an TABLE 27.?Composition of the Allende meteorite reference sample (two 1 g aliquants of each split were taken for analysis). Element Al Ca Fe Mn Na K V Gr Co Sc In Cd Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Split 10/Position 3 10-1 1.74?0.05 1.4?0.3 27.0?1.3 1410?35 3260?160 210?20 115?20 4330?130 753?38 12.2?0.6 0.028?0.001 0.62?0.06 3.0?0.1 0.49?0.02 01.36?0.06 0.21?0.01 0.98?0.05 0.341?0.013 O.117?O.OO5 0.45?0.02 0.077?0.005 0.45?0.02 0.113?0.004 0.30?0.01 0.053?0.002 0.30?0.01 0.048?0.002 10-2 1.72?0.05 2.2?0.4 26.4?1.3 1410?35 3210?160 230?20 110?20 4240?130 744?37 12.0?0.6 a 0.54?0.05 2.8?0.1 0.50?0.02 1.34?0.06 0.21?0.01 1.04?0.05 0.327?0.012 0.115?0.005 0.44?0.02 0.079?0.005 0.41?0.02 0.115?0.004 0.29?0.01 0.058?0.002 0.30?0.01 0.048?0.002 Split 12/Position 32 12-1 1.70?0.05 1.6?0.3 26.1?1.3 12-2 PERCENT 1.72?0.05 1.8?0.3 25.7?1.3 Average 1.72?0.02 1.8?0.3 26.3?0.5 PARTS PER MILLION 1390?35 3280?160 220?20 112?20 4190?130 734?36 11.8?0.6 0.027?0.001 0.57?0.06 2.9?0.1 0.49?0.02 1.42?0.06 0.21?0.01 1.18?0.06 0.362?0.014 0.116?0.005 0.43?0.02 0.084?0.005 0.45?0.02 0.112?0.004 0.30?0.01 0.056?0.002 0.30?0.01 0.050?0.002 1400?35 341O?17O 220?20 110?20 4140?130 721?36 11.9?0.6 0.027?0.001 b 3.1?0.1 0.53?0.02 1.44?0.06 0.21?0.01 0.98?0.05 0.359?0.014 0.116?0.05 0.44?0.02 0.083?0.005 0.45?0.02 0.113?0.004 0.29?0.01 0.053?0.002 0.30?0.01 0.049?0.002 1400?10 3290?90 220?10 112?3 4230?80 738?14 12.0?0.2 0.027?0.001 0.58?0.04 3.0?0.1 0.50?0.02 1.39?0.05 0.21?0.00 1.05?0.10 0.347?0.016 0.116?0.001 0.44?0.01 0.081?0.003 0.44?0.02 0.113?0.001 0.30?0.01 0.055?0.003 0.30?0.00 0.049?0.001 Other work 1.7l?0.05c, 1.73e, 1.75f 2.0?0.2c, 1.87e, 1.8f 21.9?0.4c, 24.4?0.4d, 23.8', 23.6f, 27.8g 1450?40c, 1400e, 1300f, l700g 3370?100c, 3300?100d, 3300', 3000f 200e, 250f, 1800?1200g 130?22c, 70e, l70f 3680?100c, 3900?100d, 3600e, 4200f, 4200g 640?20c, 650?40d, 600e, 700f, 600g 11.0?0.5c, 12.2?0.2d, lle, 10g 0.027?0.001c 0.19?0.01c 3.0?0.1c, 2e 0.44?0.02c, 0.7e 1.25?0.06c, le 0.20?0.01c, 0.2e 0.91?0.05c, 0.9e 0.29?0.01c, 0.5e 0.107?0.005c,0.1e 0.43?0.02c, 0.6e 0.074?0.005c, 0.09e 0.42?0.02c, 0.6e 0.12?0.1c,0.1e 0.31?0.02c, 0.3e 0.049?0.001c 0.32?0.02c, 0.4e 0.058?0.002c * The In value determined for 10-2 is 0.02?0.01; the large error limit is imposed due to an analyzer malfunction during counting. b The Cd value for 12-2 could not be determined because of a laboratory accident during the chemical processing. c Wakita and Schmitt, 1970; specimen NMNH 3496. d Morgan et al., 1969; specimens NMNH 3610 and ASU S-5211. e Clarke et al., 1970; specimens NMNH 3509 and 3511. f King etal., 1969. g Emery etal., 1969. 42 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES average of ~ 12% in the Allende meteorite reference sample over the corresponding REE abundances in fragment NMNH 3496 (Wakita and Schmitt, 1970), while the average ratio of the heavy REE (Tb to Lu plus Y) abundances in the Allende meteorite reference sample to fragment NMNH 3496 is 1.00; i.e., essentially identical heavy REE abun- dances were obtained in two different Allende fragments. The relative enrichment of light REE may be ascribed to a larger content of accessory minerals such as plagioclase in the Allende meteorite reference sample relative to fragment NMNH 3496. ACKNOWLEDGMENTS.?This study was supported by NASA grant NGL 38-002-020 and NASA contract NAS9- 8097. We thank the TRIGA nuclear reactor group at Oregon State University for sample activations. This contribution is dedicated to the memory of our deceased friend, Richard H. Smith. In the field of meteo- ritics he was one of the collaborators who first measured accurately the fundamental rare earth elemental abun- dances in chondritic, achondritic, and other types of meteo- rites. 21. Analyses of Trace Elements in the Allende Meteorite Reference Sample by Emission Spectrometry G. Thompson Two splits from the Allende meteorite reference sample were analyzed for trace element composition. Results were obtained by direct-reading optical emission spectrometry with d.c. arc excitation. Details of the technique and preci- sion and accuracy (?5-10%) are given by Thompson and Bankston (1969). Results are listed in Table 28. TABLE 28.?Trace element analysis of the Allende meteorite reference sample (in ppm) (standard matrix used for analyses of Split 10/Position 13 and Split 1 I/Position 11 (a) had the composition: SiO2 39.4%, A12O3 11.3%, Fe2O, 30.4%, MgO 6.7%, CaCO3 10.0%, NaCl 1.1%, KC1 1.1%; standard matrix used for analysis of Split 11/Position ll(b) had the composition: SiO2 48.2%, A12OS 13.9%, Fe2O3 9.3%, MgO 7.4%, CaCO3 16.5%, Na2CO3 2.8%, KC1 1.0%, TiO2 0.9%; dash indicates not determined). G. Thompson, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543. Constituent Ag B Ba Bi Cd Co Cr Cu Ga Li Mo Ni Pb Rb Sn Sr V Zn Zr Split 10/ Position 13 <1 <5 <2 <2 <2 740 3000 120 25 4 <2 >1000 12 <5 <20 8 100 110 48 Split (a) <1 <5 <2 <2 <2 700 3000 120 25 4 <2 >1000 10 <5 <20 8 85 110 54 11/Position 11 (b) <1 - <2 <2 <2 >500 >2000 - 20 2 <2 >2000 13 <10 - 8 60 - 47 43 22. Analyses of Oxygen and Silicon in the Allende Meteorite Reference Sample by Neutron Activation A. Volborth Two splits from the Allende meteorite reference sample have been analyzed for oxygen and silicon by neutron activation analysis. Each split was analyzed for oxygen by comparison to four carefully prepared standards. The ac- tual number of counts selected per determination varied from 1,000,000 to 1,400,000 depending on the total neu- tron flux during each experiment. For silicon, results of each split represent the mean and actual deviation of two independent determinations of 300,000 counts each or 600,000 counts total; thus a theoretical standard deviation of 775 counts or 0.13% applies for each of these determi- nations. Details of the technique are given in Vincent and Volborth (1967), Volborth and Vincent (1967), and Vol- A. Volborth, North Dakota State University, Fargo, North Dakota 58102. borth et al. (1975, 1977a,b), and the results are given in Table 29. TABLE 29.?Neutron activation analysis (%) of oxygen and silicon in two subsamples of the Allende meteorite reference sample. Constituent and standard no.* OXYGEN 157 183 184 187 mean SILICON Split 19/ Position 14 (Rabbitt 190) 36.30 36.43 36.32 36.41 36.37?0.06 16.22?0.00 Split 8/ Position 26 (Rabbitt 191) 36.74 36.69 36.65 36.47 36.64?0.12 16.14?0.03 * Composition of standard numbers: 157 = 100% SiO2, quartz; 183 = 50% AI2O3, 50% SiO2; 184 = 30% A12O3, 70% SiO2; 187 = 20% A12O3, 60% SiO2, 20% Fe2O3. 44 23. Bulk Chemical Analysis of the Allende Meteorite Reference Sample H.B. Wiik Split 20/Position 20 from the Allende meteorite refer- ence sample was analyzed for major, minor, and trace elements. Results and methods used for the analysis are given in Table 30. TABLE 30.?Bulk chemical analysis of the Allende meteorite reference sample. H.B. Wiik, The Geological Survey of Finland, Otaniemi, Finland. Constituent Fe Ni Co FeS (S) SiO2 TiO<, AI2OS FeO MnO MgO CaO Na2O K2O PaOs ?H2O Cr2Os C Total Total Fe Sc V Cu Split 20/ Position 20 Method PERCENT 0.1 1.40 0.069 6.17 (2.25) 34.10 0.13 3.43 24.62 0.193 25.65 2.58 0.47 0.046 0.21 0.00 0.59 0.55 0.28 100.04 23.16 PARTS 10 100-108 120-130 extraction with HgCI2 gravimetric from main analysis neutron activation calculated from S (as BaSO4) gravimetric + colorimetric colorimetric neutron activation calculated from total Fe, metallic Fe, and FeS colorimetric gravimetric gravimetric, oxalate to carbon- ate at 520? neutron activation neutron activation colorimetric gravimetric colorimetric neutron activation gravimetric PER MILLION neutron activation emission spectroscopy emission spectroscopy 45 24. X-Ray Fluorescence Spectrometric Analysis of the Allende Meteorite Reference Sample J.P. Willis Two splits of the Allende meteorite reference sample were analyzed for major, minor, and trace elements by x- ray fluorescence spectrometry. The two 5 g samples re- ceived for analysis were ground separately for 1 hour in a specially cleaned automatic agate mortar. Of the finely ground powder 4 g was briquetted with a Bakelite/H3BO3 backing and used for the determination of Na, S, Nb, Zr, Y, Sr, Rb, and Ba. The remaining 1 g portions were dried at 120? C in preheated Vitreosil silica crucibles then heated to constant weight at 1050? C in a furnace. Three 0.28 g portions of each sample were fused, cast as disks following the method of Norrish and Hutton (1969), and used for determining Fe, Mn, Cr, Ti, Ca, K, P, Si, Al, and Mg. Each disk was counted twice and each briquette three times, and the results averaged. All determinations were carried out by x-ray fluorescence spectrometry using a Philips 2 kW PW 1220 semi-automatic x-ray spectrometer. The major elements (except Na and S) TABLE 31.?Instrumental variables in analyses of the Allende meteorite reference sample by x-ray fluorescence (FPC = flow proportional counter; SC = scintillation counter). Constituent Fe, Mn, Cr Ti, Ca, K Si, Al Mg P, S Ba Na Sr, Rb Nb, Zr, Y X-ray tube target W Cr Cr Cr Cr Cr Cr Mo W Crystal LiF(220) LiF(200) EDDT and PET ADP Ge LiF(220) Gypsum LiF(220) LiF(220) Detector FPC FPC FPC FPC FPC FPC FPC SC SC Collimator Fine Fine and coarse Coarse Coarse1 Coarse Fine Coarse Coarse2 Coarse2 1 An asymmetric PHA window was used to limit the contribution of P fluorescence from the ADP crystal. 2 An additional 4-inch secondary collimator was used in front of the scintillation counter. J.P. Willis, Department of Geochemistry, University of Capetown, Rondebosch, Cape Province 7700, South Africa. were determined using the technique and correction factors of Norrish and Hutton (1969). Mass absorption corrections were made in determining S and Ba using the data of Birks (1963) and using Cr K? as the effective primary radiation. No absorption corrections were made for Na. Mass absorp- tion coefficients for the determination of the remaining trace elements were measured by the method of Reynolds (1963). The analytical techniques have been described else- where (Willis etal., 1969; Cherry etal., 1970). Instrumental variables are listed in Table 31. Results are listed in Table 32. TABLE 32.?Analyses of two subsamples of the Allende meteorite reference simple and USGS reference sample BCR-1 by x-ray fluorescence spectrom- etry (total Fe reported as FeO; N/A = not applicable; ND = not determined; dash indicates not reported). Constituent SiO2 TiO2 A12O3 FeO MnO MgO CaO Na2O K2O P2O5 H2CT S Cr2O3 Nb Zr Y Sr Rb Ba Split 1/ Position 3 Split 4/ Position 22 PERCENT 33.65 0.140 3.20 30.45 0.198 24.79 2.56 . 0.46 0.033 0.230 0.096 2.07 0.55 33.62 0.141 3.30 30.47 0.199 24.81 2.57 0.45 0.034 0.244 0.131 2.07 0.54 PARTS PER MILLION <2.5 8.3 ~3 14.2 1.0 3 <2.5 8.0 <3 14.1 1.3 4 SD (2a) 0.34 0.006 0.07 0.16 0.006 0.46 0.03 0.02 0.002 0.016 N/A 0.02 0.02 N/A 1.1 N/A 0.3 0.4 1 BCR-1 ND ND ND ND ND ND ND ND ND ND ND ND ND 12.6 193 37.7 334 47.3 - 46 Literature Cited Abbey, S. 1972. "Standard Samples" of Silicate Rocks and Minerals?A Review and Compilation. Geological Survey of Canada Paper, 72(30): 11 pages. Baedecker, P.A., C.-L. Chou, E.B. Grudewicz, andJ.T. Wasson 1973. Volatile and Siderophilic Trace Elements in Apollo 15 Samples: Geochemical Implications and Characterization of the Long-lived and Short-lived Extralunar Materials. In Proceedings of the Fourth Lunar Science Conference. 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