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, number

27, 49 pages, 32 tables, 1986.—A reference material for comparative analytical

studies and standardization was prepared from fresh, clean specimen material from

the 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 g

subsamples. 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 were

determined by more than one technique. Reports from contributors of data outline

their procedures and give their results in detail. Sample homogeneity has been

evaluated 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. Jarosewich, 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 ALLENDE METEORITE REFERENCE SAMPLE, by C.S. Annell 14

3. ABUNDANCES OF EIGHT ELEMENTS IN THE ALLENDE METEORITE REFERENCE 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 ANALYSIS 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 METEORITE 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 THALLIUM 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 METEORITE 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 SAMPLE BY NEUTRON ACTIVATION AND SPARK SOURCE MASS SPECTROMETRY, by G.H. Morrison, N.M. Potter, A.M. Rothenberg, E.V. Gangadharam, and S.F. Wong 32

16. SPARK SOURCE MASS SPECTROMETER ANALYSIS OF THE ALLENDE METEORITE 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 ACTIVATION 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 REFERENCE 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 REFERENCE 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 METEORITE 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 diverse scientific fields as cosmochemistry, geochemistry, and

planetary dynamics has become increasingly apparent during 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 meteorites as a source of information on the distribution of chemical 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 chemical 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 addition to major amounts of the common rock-forming minerals olivine, pyroxene, and feldspar, they contain significant 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 presents both sampling and analytical problems. Early researchers 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 literature 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 composition of stone meteorites, reviewed the older literature and

established the modern approach to the evaluation of meteorite analyses. Mason (1965) modified the Urey and Craig

criteria for acceptable analyses by introducing more rigorous 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 progressively more accurate data as the problems they address have

become more sophisticated. The use of standardized techniques that are monitored periodically by reference samples

is a common strategy for increased accuracy and for interlaboratory comparisons. Such reference materials are necessary 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; Flanagan, 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 approximate the composition of meteorites.

There are two primary reasons why a meteoritic reference 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 sufficient powder for subsequent distribution. Some meteorite

finds that might have provided enough material were considered too contaminated by their terrestrial surroundings

to be useful. Secondly, the problem of preparation of homogeneous 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 carbonaceous 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 meteoritic 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 Smithsonian Research Foundation Grant 413616 and by partial

support from NASA Grant NGR-015-146 (B. Mason, Principal 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 further 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 polyethylene 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 particles (<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 polyethylene bottle, which was rolled on a jar-mill rolling machine. 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 material (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 representative 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 determined 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 absorption spectrophotometry (flame); x-ray fluorescence spectrophotometry (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 material.

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 elements are listed by atomic number (in parentheses). Table

1 also gives an overview of the methods that can be successfully used in the determination of a desired element, and it

can be seen that different analytical methods provide acceptable results. For example, neutron activation analysis

(NAA), a method used primarily in trace element work

gives satisfactory results for some major and minor elements.

"Recommended values" were derived for 43 of the elements 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 recommended 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 calculated 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 calculations 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 distributed between the two vials. These conclusions from the

analysis of variance are listed in Table 2 as NS (homogeneous) or S (heterogeneous). Of the 75 such tests made, the

element or oxide could be said to be distributed homogeneously 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 homogeneity 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. Nevertheless, 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 spectrometry; 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

3.40

3.36

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

6/25

7/4

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

X RF

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

X RF

X RF

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

12/29

20/1

22/10

10/3

12/32

20/20

1/3

4/22

16/10

16/32

1/13

6/23

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

16/32

1/32

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

X RF

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

X RF

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

X RF

X RF

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

X RF

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

6/25

7/4

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

1/13

6/23

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

X RF

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

6/11

1/27

13/23

4/26

4/26

9/14

6/25

7/4

5/1

8/27
12 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES

TABL E 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

Cr 2O3

M nO

MgO

CaO

Na 2O

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

X RF

XRF

NAA

ES

X RF

NAA

ES

X RF

NAA

X RF

XRF

NAA

NAA

flame

NAA

NAA

XRF

NAA

NAA

XRF

XRF

X RF

ES

X RF

NAA

XRF

NAA

ES

NAA

ES

XRF

NAA

ES

XRF

ES

Constituent

Ga

Br

Rb

Sr

Y

Zr

Pd

T e

Cs

Ba

La

Ce

Pr

Nd

Sm

Eu

Gd

T b

Dy

Ho

Er

T m

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 solutions 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 polyethylene 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, Charlottesville, 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 difference 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 samplegraphite 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 mixture, 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).

Constituent

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.:

<i

1425

1500

1650

1500

3700

3300

3350

4200

4500

615

535

525

5

14

12

65

90

11

12

11

15

<10

103

170

160

133

106

145

8

8

3

1500

1550

1950

3200

3250

3800

3900

675

590

475

4

12

90

90

11

12

12

Split/Position

8/31

110

150

121

135

106

127

8

7

<1

].:

<i

1425

1500

1400

1700

4400

3250

3300

3800

575

530

515

4

11

10

68

94

12

13

9

<10

117

123

143

175

135

7

7

3

1470

1720

1900

3250

4350

3550

700

510

510

4

10

87

91

9

10

10

20/5

110

185

165

120

123

162

7

8

<1

l.:

<i

1500

1450

1300

1550

3600

3950

3350

3800

4000

810

775

515

4

13

10

78

93

11

10

10

10

<10

117

125

173

175

172

106

7

8

3

1600

1820

2150

4200

3300

3750

3000

650

510

505

4

9

83

82

8

14

10

20/3

115

165

120

135

103

157

7

8

<1

l.:

<l

1550

1400

1600

3800

3950

3550

4200

3000

780

725

505

4

12

13

73

99

10

11

14

12

<10

110

125

143

185

105

155

8

8

3

1720

2300

3650

3500

3800

3150

675

510

4

12

88

87

9

12

11

14
3. Abundances of Eight Elements in

the Allende Meteorite Reference Sample

Determined by Neutron Activation Analysis

P.A. Baedecker, C.-L. Chou, and J.T. Wasson

Two splits of the Allende meteorite reference sample

were analyzed for Ni, Zn, Ga, Ge, Ir, Au, Cd and In by

radiochemical neutron activation analysis. Approximately

500 mg aliquots of each sample were packaged in fused

silica vials and irradiated along with appropriate flux monitors in the Ames Laboratory reactor at a flux of 1013

neutrons cm"2 sec"' for 66 hours. After cooling for 4 days

the samples were re-irradiated in the UCLA reactor for 3

hours at a flux of 2 X 10" neutrons cm"2 sec"1 to produce

the short-lived activities that are utilized in our procedure.

Details of our radiochemical separation procedure can be

found in Baedecker et al. (1971), Baedecker et al. (1972),

Baedecker et al. (1973), Muller et al. (1971), and Wasson

and Baedecker (1970).

The precision (one standard deviation on a single determination) of our method based on replicate analyses of

Allende and Orgueil meteorites is Ni, ±3%; Zn, ±9%; Ga,

±4%; Ge, ±6%; Cd, ±4%; In, ±4%; Ir, ±4%; Au, ±12%.

The accuracy of our results was evaluated by Chou et al.

(1976) based on a comparison of our Allende and Orgueil

data with those of other laboratories for the same meteorites. Our data for Ni, Zn, Ge, Cd, and In fell within ±5%

of the values obtained by other workers. Much larger interlaboratory biases were observed for Au and Ir, and although

our results were bracketed by those of other groups, the

accuracy of our data could not be adequately assessed. Our

data for the Allende meteorite reference sample (previously

published by Chou et al., 1976) are reported in Table 5. A

combined mean as well as means for the two separate bottles

are reported. The error limits reported are 95% confidence

limits on the mean. The agreement between the bottles is

well within our estimated error limits and shows no indication of inhomogeneity for the reference material for any of

P.A. Baedecker, United States Geological Survey, Reston, Virginia 22092. C.-L.

Chou, Department of Geology, University of Toronto, Toronto, Ontario M5S 1A1,

Canada. J.T. Wasson, Department of Chemistry, University of California, Los

Angeles, Los Angeles, California 90024.

the elements determined, in spite of substantial variations

between bulk Allende and that meteorite's spheroidal CaAl-rich inclusions (Chou et al., 1976).

ACKNOWLEDGMENTS.—We are indebted to R. Bild, R.

Glimp, J. Kimberlin, K. Robinson, and L. Sundberg for

assistance. Neutron irradiations at the UCLA and Ames

Laboratories reactors were handled by J. Brower and A.F.

Voight and their associates. This work was supported by

NSF Grant GA 32084.

TABLE 5.—Radiochemical neutron activation analyses of eight trace elements in two subsamples of the Allende meteorite reference sample (dash

indicates only one reading obtained).

Constituent

Ni

Zn

Ga

Ge

Ir

Au

Cd

In

Split 1/

Position 13 Mean

Split 6/

Position 23

PARTS PER THOUSAND

14.0

14.6

107

98

132

6.2

6.2

5.6

16.9

18,1

17.8

0.78

0.81

0.80

0.14

433

27.0

29.5

30.4

14.3

PARTS PER

112

6.0

17.6

0.80

0.14

PARTS PER

433

28.9

14.0

15.0

MILLION

125

103

121

5.7

6.2

5.7

16.9

18.3

18.6

0.80

0.86

-

0.17

BILLION

429

27.5

30.4

28.7

Mean

14.5

116

5.9

17.9

0.83

0.17

432

28.9

Overall

mean

14.4±0.8

114+14

5.9±0.3

17.8±0.8

0.81±0.04

0.16

432±7

28.9+5.1

15
4. Determination of Trace Elements

by Neutron Activation Analysis in

the Allende Meteorite Reference Sample

R. Becker, P. Roller, P. Morschl, W. Kiesl, and F. Hermann

Trace elements in two splits of the Allende meteorite

reference sample were determined by neutron activation

analysis (NAA) followed by chemical separations of the

elements under consideration. Final counting of nuclides

was carried out by 7-ray spectrometry, using Nal(Tl) or

Ge(Li) detectors and an Intertechnique Company multichannel analyzer.

Rare earth elements (REE) were determined by irradiating 1 g of Split 3/Position 15 in the TRIGA Mark II reactor

for 7 hours at a thermal neutron flux of 10u neutrons cm"'

sec"'. The sample was then treated with HF, HNO3, and

HCIO4 for 2 hours in a teflon beaker at 250° C.

 I44Ce was

added for yield determination and 400 /ig of a REE-mixture

as a carrier. A multi-step group separation (Becker et al.,

1974) was used, and the separated REE-solution as well as

the standards were counted at several different decay times

using a 40 cm3 Ge(Li) detector.

For Zr and Hf, 500 mg samples of Split 3/Position 15

were irradiated together with standards for 2 hours in the

TRIGA Mark II reactor. The basic principle was the determination of Zr via its daughter product

 9/Nb, which originates from

 97Zr. ')7Nb was isolated by selective extraction

with methylisobutylketone (MIBK) in an aqueous solution

of HF-HCIO4. Hf was determined using its isotope

 18lHf

after two extractions with thenoyltrifluoracetone (TTA)

(Roller, 1971). Nuclides were counted by means of a 3 X 3

inch Nal(Tl) crystal.

The 300 mg of Split 3/Position 15 was sealed in a quartz

vial for the determination of Se and Te. The sample together with standards was irradiated for 3 days in the core

of the ASTRA reactor using a flux of 4 X 10u neutrons cm"2

sec"1. Te was determined indirectly via the 8.05-day

 K1II

daughter of 1.2-day

 ni '"Te and 25-min 13ITe. The iodine

was oxidized and extracted into CC14, stripped, and precipitated as Agl for yield determination. Se was precipitated

TABLE 6.—Neutron activation analyses of trace elements (ppm) in the

Allende meteorite reference sample. Means of values obtained from Split

9/Position 31 and Split 3/Position 15 are reported as there was almost no

deviation of concentrations between splits.

R. Becker, P. Koller, P. Morschl, W. Kiesl, and F. Hermann, Analytical Institute

of the University of Vienna, A-1090 Vienna, Austria.

Constituent

La

Ce

Pr

Sm

Eu

Gd

T b

Dy

Ho

Er

Yb

Lu

Zr

Hf

Se

Te

Mn

Cu

Ga

Au

Se

As

Sb

Sn

Re

Hg

Au

Mo

Os

Ru

Zn

Ir

Sc

Rb

Cs

In

Mean values

Single Analysis (3/15)

0.56

1.32

0.26

0.18

0.136

0.54

0.075

0.408

0.114

0.344

0.33

0.053

14.8

0.13

12.2

1.35

4 Analyses (3/15)

1250±90

115±12

5.60±0.45

0.14±0.02

6 Analyses (3/15 and 9/31)

10.5±1.0

1.9±0.2

0.04±0.01

0.30+0.1

0.020±0.002

0.035±0.004

0.15±0.01

2.5+0.2

0.40±0.08

0.85±0.08

125+6

0.51±0.1

9.8±0.9

1.3±0.3

0.10±0.02

<0.01

16
NUMBER 27 17

by Na^Or,, filtered, washed, and dried. The samples were

measured 6 days after the end of irradiation on a 3 X 3

inch Na(Tl) crystal (Morschl, 1972).

For Mn, Cu, Au, and Ga, 100 mg of Split 3/Position 15

was sealed in a quartz vial. The sample and standards were

simultaneously irradiated for 7 minutes in the core of the

ASTRA reactor using a flux of 3 X 1013 neutrons cm"2 sec"1.

After removal of silica with HNO3 and HF and dissolution

of insoluble fluorides by fuming with H2SO4, the elements

were separated (Morschl, 1972) on an anion-exchange column and measured by means of a 3 X 3 inch Nal(Tl) crystal.

Each 300-500 mg of Split 9/Position 31 and Split 3/

Position 15 was irradiated with standards for 5 days in the

ASTRA reactor for the determination of Se, As, Sb, Sn, Re,

Hg, Au, Mo, Os, Ru, Cr, Sc, Cs, Rb, Zn, In, and Ir. After

a cooling period of 1 day the elements were separated by

distillation and ion exchange steps according to an analytical

separation scheme that has been developed at the Analytical

Institute of the University of Vienna (Hermann et al.,

1971). The radiochemical determinations of the nuclides

were carried out by using a 40 cm3 Ge(Li) detector and a

400-channel 7-spectrometer (Intertechnique Company Selecteur Sa-40). Results of these determinations are given in

Table 6.
5. Some Elemental Abundances in

the Allende Meteorite Reference Sample

Determined by Neutron Activation Analysis

W.D. Ehmann, D.E. Gillum, C.L. Sya, and A.N. Garg

Eleven major, minor, and trace elements were determined using 14 MeV and thermal neutron activation analysis. O and Si were determined by 14 MeV instrumental

neutron activation analysis (INAA), according to the

method of Morgan and Ehmann (1970). The data presented

here are based on six replicate O and Si analyses of each

powder aliquant. The remaining elements were determined

by reactor INAA, or RNAA, employing high resolution

Ge(Li) spectrometry. The RNAA determinations of Zr and

Hf are based on a radiochemical separation procedure by

Kumar et al. (1977). All Zr data are corrected for the U

fission contribution to the indicator radionuclide

 9 'Zr. Primary standards were used for most of the elements deterW.D. Ehmann, D.E. Gillum, C.L. Sya, and A.N. Garg, Department of Chemistry,

University of Kentucky, Lexington, Kentucky 40506.

mined in this study, complemented by USGS Standard Rock

BCR-1 as a secondary standard.

Data for the 11 elements determined in this study are

presented in Table 7. The lettered columns present data

obtained on separate powder aliquants of each split/position

sample. Means for each split/position and the overall means

are also given. The data for Fe exhibit an appreciable

variation among the several aliquants analyzed. However,

there appears to be a positive correlation between the Fe

and Co data, which would suggest that the variation noted

here is due to inhomogeneity with respect to the metallic

phase content in the ~0.3 g aliquants used for these determinations. Only a single analysis is reported for both Zr and

Hf in Split 13/Position 32. However, we have independently (Kumar et al., 1977) determined Zr and Hf abundances in eight powder splits derived from a bulk specimen

TABLE 7.—Some elemental abundances in the Allende meteorite reference sample

(dash indicates not reported).

Constituent

O

Si

Fe

Cr

Na

Co

Sc

Zr**

Ce**

Ir

Hf**

Estimated

analytical

rel. error*

(%)

1-2

2

3-5

3-5

2-3

5

5

5

5-10

10-15

5-8

A

36.8

16.6

23.4

-

-

601

11.3

6.63

1.23

-

0.201

Split

B

36.4

16.5

23.1

-

-

619 i

11.1

-

-

-

-

13/Position 32

C

-

-

22.2

0.35

0.32

D Mean

PERCENT

36.6±0.2

16.6±0.1

21.2 22.5±0.5

0.34 0.34±0.01

0.30 0.31±0.01

PARTS PER MILLION

614

10.0

-

-

0.6

-

590 606±7

10.4 10.7±0.3

6.63

1.23

0.6 0.6

- 0.201

Split

A

-

-

24.0

0.38

0.35

1 /Position 24

B Mean

-

-

23.6 23.8±0.2

0.37 0.38±0.01

0.34 0.34±0.01

664 640 652±12

12.7

-

-

0.7

-

11.3 12.0±0.7

-

-

0.6 0.6±0.1

-

Overall

mean for

both splits

36.6

16.6

23.2

0.36

0.33

629

11.2

6.63

1.23

0.6

0.201

* Typical values based on experience in our laboratory.

** Data obtained on a fifth aliquant of Split 13/Position 32, but are here listed in the column for

liquant A.

18
NUMBER 27 19

of Allende from our research collection. The values of Zr

= 6.29±0.29 (la) ppm and Hf = 0.200±0.014 (la) ppm

obtained from these bulk sample splits are in good agreement with the standard reference powder data presented

here. These Zr data are lower than we previously reported

(Morgan et al., 1969) for several bulk Allende samples. As

noted in later work from our laboratory (Ehmann and Chyi,

1974), laboratory glassware contaminated with the highly

charged Zr4+ and Hf+ ions could introduce low levels of

contamination, which would appreciably alter the results

obtained for relatively small meteorite samples that contain

very low concentrations of Zr and Hf. Results obtained for

typically larger samples of standard rocks with much higher

Zr and Hf contents would not be significantly affected.

Segregation of expensive glassware which must be reused

into categories according to expected Zr and Hf abundance

levels and extensive cleaning procedures have eliminated

these problems, which apparently affected a number of the

earlier low level RNAA studies.
6. Bulk Chemical Analyses of

the Allende Meteorite Reference Sample

C.J. Elliott

Bulk chemical analyses of Split 19/Position 11 and Split

10/Position 31 of the Allende meteorite reference sample

were performed employing the chlorination technique for

separation of the phases and classical chemical methods. It

was intended to analyze the meteoritic splits by the method

of Moss et al. (1967) but a magnetic separation could not

be achieved, apparently owing to the fineness of the powders and the intimate mixing of the minerals. Accordingly,

C.J. Elliott, Department of Mineralogy, British Museum (Natural History),

London SW7 5BD, England.

TABLE 8.—Flow chart for chemical analyses of the Allende meteorite

reference sample.

the meteorite powders as received were chlorinated, and

the resulting modifications to the method are indicated in

the scheme given in Table 8.

A good separation of metal and sulfides from the silicate

seems to have been achieved since only 0.12% Ni (calculated

on the whole meteorite) was detected in the insoluble residue. This result indicates also that the amounts of awaruite

and taenite, which are not attacked by chlorine, are small.

Chlorination did, however, release 3% of the total MgO.

The reason for this is not clear unless it can be shown that

some of the magnesium-bearing silicate phases are attacked

TABLE 9.—Bulk chemical analyses and analyses of elements in silicate,

sulfide, and metal phases of the Allende meteorite reference sample.

San

Chlor:

Yon-volatiles

100 ml water

wash

1

Silicate

and

unreacted

metal

Silicate Analysis

Si

Al

Ti

Cr

Fe

Ca

Mg

Mn

K

Na

Co

Ni

i l e

nation

1

Bulk wash

to 100 mis

(W)

(W)

Ni

Co

Mn

Cr

Fe

Na

K

Al

Mg

Mn

Si

Zn

1 st

1

Dry

Flask

(X)

(X)

Fe

S

P

Ga

Ti

Volatiles

2nd

I

75 mis

H20

wash

(Y)

(Y)

Fe

S

P

Ga

Ti

Si

3rd

1

25 mis

7N HC1

reflux

(Z)

(Z)

Fe

S

Ge

-

-

Constituent

SiO,

TiO2

A12O3

Cr2O3

FeO

MnO

MgO

CaO

Na2O

K2O

P2O5

Fe

Ni

Co

S

Total

Split 19/

Position 11

PERCENT

34.15

0.16

3.18

0.43

22.45

0.12

24.50

2.71

0.47

0.048

0.23

6.17

1.47

0.071

2.20

98.36

Split 10/

Position 31

34.48

0.17

3.19

0.45

22.81

0.12

24.92

2.58

0.47

0.05

0.23

6.28

1.45

0.076

2.01

99.29

SULFIDE AND METAL PHASES (ppm)

Cu

Zn

Cr

Mn

Ti

P

Ge

Si

68.0

14

13

300

10

18

«0.9

< 8 5

76

9

19

230

8

13

« 4 7

20
NUMBER 27 21

TABLE 10.—Wahl norms for bulk chemical analyses of the Allende

meteorite reference sample.

Constituent

Olivine

Hypersthene

Diopside

Perovskite

Anorthite

Chromite

Nepheline

Chlorapatite

Iron

Split 19/

Position 11

70.02

4.38

3.86

0.27

6.43

0.63

2.32

0.55

Split 10/

Position 31

71.20

4.70

3.32

0.29

6.44

0.64

2.32

0.55

Jarosewich

(1970:45, col. 3)

78.20

.00

3.20

0.26

6.95

0.76

2.16

0.55

1.17

by chlorine; previous analytical work of Moss et al. (1967)

has established that chlorine does not release Mg from

olivine-hypersthene and olivine-bronzite chondrites.

The bulk compositions of the meteorite powders are

given in Table 9, together with the proportions of trace

elements in the metal and sulfide phases. Trace elements in

the silicate phase have not been determined because of the

analytical difficulties encountered. However, work is in

hand to establish the mechanism of the reaction between

chlorine and the silicate phases of this meteorite.

If our results are compared with those of Jarosewich (in

Clarke et al., 1970), it will be seen that, whereas the determinations of total iron content are in agreement, the distribution of this iron is different. The absence of hypersthene

and the excess FeO in the norm indicate that the FeO

content of Jarosewich's analysis is too high (Table 10).

No explanation can be advanced for the low summation

of the analysis of Split 19/Position 11; repeat analyses did

not reveal any major discrepancy in the composition of the

silicate.
7. Instrumental Neutron Activation Analysis of

the Allende Meteorite Reference Sample

Lawrence Grossman and D.P. Kharkar

We have used instrumental neutron activation analysis to

determine the concentrations of twelve elements in two

splits of the Allende meteorite reference sample—Split 4/

Position 25 and Split 7/Position 10. The abundances of

Mn, Na, Sm, La, Co, Fe, Sc, and Cr were determined in

both bottles. In addition, Yb, Eu, Ir, and Au were determined in only one bottle. Slight sample heterogeneities

within a single bottle were indicated by the Co, Fe, and Sc

analyses. No significant differences between the two bottles

were observed for any of the elements determined in both.

For the analyses, the powdered samples were further

ground in an agate mortar and four 25 or 50 mg portions

of Split 7/Position 10 and two 50 mg portions of Split 4/

Position 25 along with five duplicate silicate standards were

accurately weighed into quartz vials, which were previously

cleaned by boiling in hot concentrated HNO3. Duplicate

Au and Ir standards were prepared by pipetting standard

solutions of these elements onto crushed quartz substrates

inside quartz vials of the same size as those used for the

samples and evaporating to dryness. A "blank" quartz vial

was also included with the samples and standards. The vials

were heat-sealed and packed radially in an aluminum cylinder and irradiated in the Union Carbide "swimming pool"

reactor at Sterling Forest, New York.

The irradiation times and counting sequence used here

are similar to those described by Turekian and Kharkar

(1970) and Kharkar and Turekian (1971). The first irradiation lasted 30 minutes in a highly thermalized portion of

the reactor at a flux of about 4.5 X 1012 neutrons cm"2

sec"1. Three hours after removal from the pile the vials

were unpacked, washed with HNO3, and counted vertically

in a bored lucite holder resting on the top of a 25 cm3

coaxial Ge(Li) detector coupled to a 2048-channel analyzer.

All spectra were punched onto paper tape for data reduction by an IBM 7094-7040 computer. In all the counting,

the distance from the bottom of the vials to the detector

was adjusted with lucite blocks so as to give a maximum

dead time of 14%-16% for the "hottest" sample.

Lawrence Grossman, Department of Geophysical Sciences, University of Chicago,

Chicago, Illinois 60637. D.P. Kharkar, LFE Environmental Corporation, 2030

Wright Avenue, Richmond, California 94804.

Each sample and standard and the blank vial were

counted for 200 seconds or 500 seconds for the first analysis

to measure

 5bMn (t./2 = 2.58 hr). The samples were then

allowed to "cool" for a day to reduce the background

interference of

 56Mn and other short-lived activities and

then each was counted for 2000 seconds to measure

 24Na

(t* = 15 hr).

After the determination of Mn and Na, the samples,

standards, and blank were repacked and sent for a threeday irradiation at a flux of 2 X 1013

 neutrons cm"2 sec"1.

The samples, standards, and blank, after another acid wash,

were counted for 5000 seconds each from 5 to 8 days after

removal from the pile for short-lived nuclides (1+0La,

 153Sm,

175Yb, 198Au). Then the samples were re-counted 13 days

later to obtain data for long-lived nuclides (152Eu,

 60Co, 59Fe,

4<iSc, 51Cr, I92Ir). The counting times were 5000 or 10,000

seconds for each sample, 5000 or 20,000 seconds for each

standard, and 5000 seconds for the blank.

The nuclides, 7-ray peaks, and half-lives of elements

analyzed and their concentrations in the standards chosen

for each element are shown in Table 12. The concentrations

of Eu, Co, Fe, Sc, and Cr are based on the "best" values in

TABLE 11.—Elemental abundances in the Allende meteorite reference

sample. (Values in ppm unless otherwise indicated; errors due to counting

statistics are Mn (0.5-1.0%), Na (0.6-1.0%), Sm (13-14%), Yb (95%), La

(14-18%), Eu (60-93%), Co (0.2%), Fe (0.4%), Sc (0.8%), Cr (2%), Ir

(3.7%), Au (6.9%); ND = not determined).

Constituent

Mn

Na

Sm

Yb

La

Eu

Co

Fe(%)

Sc

Cr

Ir

Au

Split 7/

Position 10

1564, 1590,1574, 1633

3668,3608, 3686, 3774

0.22,0.36,0.41

0.35,0.30

0.47

0.15,0.17,0.12,0.13

622,611,578, 590

23.28,22.89,22.69,23.10

11.6, 11.5, 10.2, 10.4

3308, 3205,3137, 3238

0.87, 0.91

0.16

Split 4/

Position 25

1533, 1564

3556, 3563

0.27, 0.46

ND

0.38

ND

570,587

22.24, 22.80

10.0, 10.2

3140,3220

ND

ND

22
NUMBER 27 23

TABLE 12.—Nuclides counted and standards used for each element in neutron activation analyses of the

Allende meteorite sample (SP = standard pottery (Perlman and Asaro, 1969); dash indicates either no data

or not repeated).

Constituent

Product

nuclide

7-ray peak

(keV)

Half-life

(hrs)

Best values for standard chosen (ppm)

BCR-1 SP W-l G-l GSP-1

Mn

Na

Sm

Yb

La

Eu

Co

Fe

Sc

Cr

Ir

Au

•

wMn

2 4Na

l53Sm

175

 Yb

M 0La

I52Eu

6 0Co

59 F e

46Sc

5 1Cr

I92 Ir

i98 A u

874

1369

103

396

1596

1408

1332

1100

889

320

468

412

2.58

15.00

47.00

101.04

40.22

108624

45991

1080

2016

667

1776

64.8

1320

24,000

-

-

25.20

2.26

35.15

92955

33.10

_

-'

_

-

2610

5.78

2.80

44.90

1.43

13.10

9286

19.85

114

-

_

1320

24,200

104

73300

317.5

20616

2.79

30200

the silicate standards as determined by Katz and Grossman

(1976). For the remaining elements, the data for the Standard Pottery were taken from Perlman and Asaro (1969)

and the data for the rest of the standards from the compilations of Fleischer (1969) and Flanagan (1969).

The values obtained for Allende samples are shown in

Table 11, along with 1 a uncertainties due to counting

statistics.

The 317 keV peak of

 192Ir interferes with the 320 keV

peak of

 slCr. Using the spectrum of our Ir monitor, we

found that 10-12% of the counts under the Cr peak were

due to the presence of Ir in Allende and the Cr counts were

corrected accordingly.

For each of the elements Co, Fe, and Sc, the concentration range determined within a single bottle exceeds that

expected on the basis of 2<T counting statistics. We attribute

these wide ranges to sample heterogeneity resulting probably from the small sample sizes employed here.

The test for a difference between the means of the

determinations in material from Split 7/Position 10 and

that from Split 4/Position 25 failed at the 95% confidence

level for Mn, Sm, Co, Fe, Cr, Sc, and Na, the elements for

which at least duplicate determinations are available for

each split. For the remaining elements, La, Eu, Yb, Ir, and

Au, insufficient data were available to evaluate the similarity

of the two bottles.

ACKNOWLEDGMENTS.—The authors wish to thank Dr.

Karl K. Turekian, in whose laboratory this work was performed, for his advice and encouragement. Our thanks go

also to Dr. Amitai Katz for his advice in the selection of

data on the elemental abundances in the silicate standards.

This research was supported in part by AEC grant AT(11-

1)3573, formerly used for studies of standard reference

materials.
8. Neutron Activation Analyses of Seven Elements

in the Allende Meteorite Reference Sample

K.S. Heier, A.O. Brunfelt, E. Steinnes, and B. Sundvoll

Elemental abundances were obtained by neutron activation analysis (Brunfelt et al., 1977). The samples were

determined relative to USGS standard sample BCR-1. The

assigned values are listed in Table 13.

TABLE 13.—Bulk concentrations of 38 elements in the Allende meteorite reference sample (Al corrected

for contribution from the

 28Si(n,p)28

 Al reaction).

Constituent

Na

Mg

Al

K

Ca

Ti

Cr

Mn

Fe

Ni

Cl

Sc

V

Co

Cu

Zn

Ga

As

Split 6/

Position 25

PERCENT

0.340

15.4

1.80

0.028

2.0

0.10

0.361

0.149

22.1

1.44

PARTS PER MILLION

316

12.0

93

695

97

107

6.0

0.87

Split 7/

Position 4

0.339

14.6

1.78

0.036

1.8

0.08

0.369

0.149

22.3

1.52

265

11.8

96

692

101

77

4.6

0.94

Constituent

Rb

Sr

In

Cs

Ba

La

Ce

Sm

Eu

Tb

Dy

Ho

Yb

Lu

Hf

Ta

W

Ir

Th

U

Split 6/

Position 25

PARTS PER MILLION

0.86

<20

0.031

<0.1

<10

0.46

1.21

0.324

0.15

0.090

0.34

0.088

0.22

0.065

0.21

<0.1

0.20

0.79

<0.3

<0.07

Split 7/

Position 4

0.77

<20

0.041

<0.1

<10

0.48

1.30

0.336

0.16

0.075

0.38

0.092

0.25

0.039

0.24

<0.1

0.29

0.76

<0.3

<0.07

K.S. Heier, A.O. Brunfelt, E. Steinnes, and B. Sundvoll, Mineralogisk-Geologisk

Museum, Oslo, Norway.

24
9. Determination of

 613C and Total Noncarbonate

Carbon in Two Splits of

the Allende Meteorite Reference Sample

by Mass Spectrometry

J.M. Herndon and W.M. Sackett

Two splits from the Allende meteorite reference sample

were analyzed for *13C and total noncarbonate carbon by

mass spectrometry. The values reported are expressed in

terms of

3C =

(

13C/12C sample

(

I3C/12C) standard

- I X 1000

relative to the Chicago PDB material used by Craig (1953).

The measurements were actually made relative to NBS

carbon isotope reference sample #21. A value of —28.25

%o relative to Chicago PDB standard was used to obtain the

results reported here. The total percent noncarbonate carbon was determined from the volume of CO2 produced

after sample preparation.

About 0.8 g of each sample was treated with 3M HC1 and

evaporated to dryness; the residue was heated in a closed

system to 850° C with pure O2 in the presence of CuO

catalyst. SO2 was removed by passing the gases over silver

wool at elevated temperatures. The CO2 was collected in a

trap at liquid nitrogen temperature. Isotopic measurements

were made with a nuclide model RMS-6-60 isotope ratio

mass spectrometer (Nuclide Associates, State College, Pennsylvania) equipped with a tungsten ribbon (0.001 X 0.003

inch) electron impact source. This instrument is equipped

with dual, room temperature, balanced capillary inlets for

J.M. Herndon, Department of Chemistry, University of California, San Diego, La

folia, California 92037. W.M. Sackett, Department of Oceanography, Texas A

& M University, College Station, Texas 77843.

sample and reference, with switching between the samples

accomplished by a solenoid. Before each run, small adjustments in the inlet pressure are made with a mercury piston

to give identical nuclide electrometer amplifier voltages for

the sample reference. The ratio of the ion current of the

beam focused on the Faraday cup to that falling on the

collector plates is read from the 4-dial General Radio 1454

A Kelvin-Varley voltage divider with the last digit in the

ratio interpolated from a recorder tracing of the remaining

imbalance from the null. The vibrating reed electrometer

is operated to measure the approach to null on the 100 m V

full scale range. A separate voltage divider is used for the

reference sample and is switched into the circuit when the

sample and reference compounds are alternated. The

switching time interval is approximately 2 minutes. Identical

ratios are obtained on the reference when the divider is

used and also when the reference is introduced from both

sides.

TABLE 14.—Mass spectrometric determination of *13C and total noncarbonate carbon in the Allende meteorite reference sample.

 m C reported

relative to Chicago PDB standard (Craig, 1953).

Constituent

Split 4/

Position 11

Split 8/

Position 23

61

 *C vs. PDP (ppt)

Total noncarbonate

carbon (%)

-18.4±0.1

0.23±0.04

-l7.9±0.1

0.25±0.04

25
10. Mass Spectrometric Isotope Dilution Analysis

of Lead and Thallium

in the Allende Meteorite Reference Sample

J.M. Huey and T.P. Kohman

The determination of lead and thallium in the Allende

meteorite reference sample was performed by the mass

spectrometric isotope dilution technique. In the first sample, Split 4/Position 26 (our No. M-85), both elements were

determined by volatilization in our standard heating schedule. In the second sample, Split 9/Position 14 (our No. M86), several volatile fractions were collected at different

temperatures and analyzed separately and the total contents

determined by addition. The data on elementary contents

are summarized in Table 15. We have listed total Pb and

J.M. Huey and T.P. Kohman, Department of Chemistry, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213.

i04Pb separately because the latter is the nonradiogenic

isotope and indicates primordial lead. We feel that the

differences between the two samples are much greater than

the uncertainties of measurement and are real sample differences.

TABLE 15.—Lead and thallium in the Allende meteorite reference sample

(ND = not determined).

Constituent

Split 4/

Position 26

Split 9/

Position 14

Total Pb (ppm)

204Pb(PPb)

Tl (ppb)

1.138±0.014

20.30±0.25

53.1±0.8

1.538±0.014

26.24±0.23

ND

26
11. Bulk Chemical Analysis of

the Allende Meteorite Reference Sample

Eugene Jarosewich

Bulk chemical analysis of two splits of the Allende meteorite reference sample was performed in essentially the same

manner as described earlier (Jarosewich, 1966) with one

modification. The sample for major and minor elements

was not separated for analysis into acid soluble and acid

insoluble portions.

About 1 g of powdered sample was used for the determination of major and some minor elements. Since the

sample contains small quantities of metal, it was first treated

with dilute HC1 to remove the metal and prevent its reaction

with the platinum crucible. The undissolved portion was

fused with Na2CO3 and the melt dissolved in HC1 and

combined with the earlier HC1 filtrate. This solution was

then analyzed for silicon, aluminum, iron, calcium, magnesium, and titanium employing modified classical methods

ofHillebrandetal. (1953), Peck (1964), and Sandell (1959).

Silica was separated from the HC1 solution by double

dehydration and filtration and determined by evaporation

with HF. From the filtrate the R2O3 group was precipitated

twice with NH4OH. The precipitate was dissolved in dilute

H2SO4 and evaporated to fumes and the residual silica

separated. An aliquot of the R2O3 solution was used in the

determination of iron by reduction in a silver reductor and

titration with K2Cr2O7. A second aliquot, from which interfering elements were removed by a mercury cathode, was

used for the determination of aluminum and titanium.

From one portion of this solution aluminum was precipitated with 8-hydroxyquinoline; a second portion was used

for the colorimetric determination of titanium employing

Tiron. Manganese was removed with zirconyl chloride from

the filtrate obtained after separation of the R2O3 group

(Peck, 1964), and from the resulting filtrate calcium was

doubly precipitated with oxalic acid and magnesium with

dibasic ammonium phosphate.

For the determination of nickel, sulfur, phosphorus, cobalt, and manganese, 1 g of sample was dissolved in bromine

water and HNO3 and treated with HF to remove silica. The

residue was filtered off, fused with Na2CO3, and combined

with the main solution. Nickel was precipitated with dimethylglyoxime and sulfur with BaCl2 after reduction of

E. Jarosewich, Department of Mineral Sciences, National Museum of Natural

History, Smithsonian Institution, Washington, D.C. 20560.

Fe3+ with zinc in HC1 solution. Phosphorus was determined

colorimetrically with molybdovanadate, chromium with diphenylcarbazide, cobalt with nitroso-R-salt, and manganese

as permanganate.

Sodium and potassium were determined flame photometrically after dissolving a 100 mg sample in HF and

H2SO4. Combined water was determined by the Penfield

method, using PbO and PbCrO4 as a flux. Carbon was

determined employing a LECO carbon analyzer. Metallic

iron was dissolved with HgCl2-NH4Cl and titrated with

K2Cr2O7.

The results of the two splits and their averages are given

in Table 16, as well as the bulk composition derived by

assignment of appropriate oxidation states.

TABLE 16.—Bulk chemical analysis (percent) of the Allende meteorite,

reference sample (* = calculated on the basis of microprobe data for metallic

phase: 68% Ni, 31% Fe, and 1.6% Co; metallic Fe was determined chemically and metallic Ni and Co assigned on the basis of this analysis; remaining

Ni and Co were calculated as sulfides; remaining S was calculated as FeS;

remaining Fe was calculated as FeO).

Constituent

SiO2

TiO2

A12O3

Cr2O3

FeO

MnO

MgO

CaO

Na2O

K2O

P2O5

H2O(+)

H2O(-)

C

s

FeS

NiS

CoS

Fe

Ni

Co

Total

Total Fe

Split 20/

Position 2

34.11

0.16

3.27

0.54

0.20

24.54

2.65

0.43

0.03

0.24

<0.1

0.01

0.27

2.14

0.15

1.39

0.06

23.53

Split 22/

Position 7

34.26

0.16

3.29

0.52

0.19

24.69

2.63

0.43

0.03

0.25

<0.1

0.02

0.26

2.13

0.11

1.42

0.06

23.62

Average

34.19

0.16

3.28

0.53

0.20

24.62

2.64

0.43

0.03

0.25

<0.1

0.02

0.27

2.14

0.13

1.41

0.06

23.58

Bulk

composition

34.19

0.16

3.28

0.53

26.84

0.20

24.62

2.64

0.43

0.03

0.25

<0.1

0.02

0.27

4.11*

1.73*

0.08*

0.13

0.29*

0.01*

99.80

23.58

27
12. X-Ray Fluorescence Spectrometric Analysis

of the Allende Meteorite Reference Sample

MJ. Kaye and B.W. Chappell

Two splits of the Allende Meteorite Reference Sample

have been analyzed in duplicate for major, minor, and trace

elements by x-ray fluorescence spectrometry. Methods of

analysis are essentially similar to those used by us for lunar

samples (Compston et al., 1970). Details of techniques are

set out more fully here.

Trace elements were determined by measuring emission

of characteristic radiation from 1.5 g of sample and correcting for matrix effects by either measuring or calculating

mass absorption coefficients (Norrish and Chappell, 1977).

Absorption coefficients were measured directly for Rb Ka

and Sr Ka radiations (Table 17), after which the powdered

material was recovered and used in emission measurements.

The Sr Ka coefficient was used for Sr and extrapolated for

Y, Zr, and Nb measurements; the Rb Ka coefficient was

used for Rb, Th, Ni, Cu, Zn, and Ga measurements. For

elements emitting at longer wavelengths than the Fe Ka

absorption edge (V, Cr, Co), a calculated Fe Ka absorption

coefficient was used. This was based on the major element

analysis and the mass absorption coefficient data of Heinrich

(1966), a correction factor (X 0.929) being applied, based

on the difference between measured and calculated absorption coefficients in terrestrial basalts.

Pellets for emission measurements were prepared using

the method of Norrish and Chappell (1977). Boric acid

pellets, produced in this way, do not affow complete samp/e

recovery. For other less abundant meteorite samples and

for lunar samples we prepare emission samples in a plastic

covered Mylar sleeve as described by Compston et al.

(1970). The present method is capable of producing slightly

more reproducible results.

Intensities were corrected for nonlinearity of background

using pellets of Spex AI2O3 and SiO2 and Herasil glass

(Chappell et al., 1969) and for spectral overlap (Norrish

and Chappell, 1977). Calibrations were made against synthetic standards prepared by grinding pure salts or oxides

with quartz (Compston et al., 1970). All measurements were

M.J. Kaye and B. W. Chappell, Research School of Chemistry, Australian National

University, Canberra 2600, Australia.

made on a Philips PW 1220 spectrometer; instrumental

conditions are given in Table 20.

Trace element results are given in Table 19. Stated

precision limits represent 95% confidence based on variation in observed emission measurements. Data for the USGS

standard reference basalt BCR-1, obtained concurrently,

are also listed.

TABLE 17.—Mass absorption coefficients of the Allende meteorite reference sample for Rb Ka and Sr Ka radiations (error limits represent 95

percent confidence of mean of four mass absorption measurements; split

numbers are those of authors).

Constituent

No. 138

Split 5/Position 10

No. 274

Split 9/Position 18

Rb

Sr

25.65±0.35

22.04±0.29

25.64±0.22

22.01±0.21

TABLE 18.—X-ray spectrometric analysis (percent) of Allende meteorite

reference sample (total excludes H2O and C; split numbers are those of

authors; a and b are duplicate analyses of each split).

Constituent

SiO2

TiO2

A12O3

FeO

MnO

MgO

CaO

Na2O

K2O

P2O5

S

Cr2O3

NiO

Sum of trace

elements as

oxides

Less O = S

Total

No. 138

Split 5/

Position 10

(a)

34.10

0.15

3.24

30.33

0.21

24.46

2.60

0.48

0.04

0.25

2.06

0.54

1.62

0.12

1.03

99.17

(b)

34.04

0.15

3.20

30.00

0.21

24.57

2.59

0.48

0.03

0.25

2.09

0.54

1.62

0.12

1.04

98.85

No. 274

Split 9/

Position 18

(a)

34.13

0.15

3.20

30.34

0.21

24.51

2.60

0.48

0.03

0.25

2.11

0.54

1.62

0.12

1.05

99.24

(b)

34.10

0.15

3.25

30.31

0.21

24.42

2.60

0.48

0.04

0.25

2.11

0.54

1.62

0.12

1.05

99.15

Average

of

4 analyses

34.09

0.15

3.22

30.25

0.21

24.49

2.60

0.48

0.04

0.25

2.09

0.54

1.62

0.12

1.04

99.11

28
NUMBER 27 29

Sodium was determined on 0.1 g of sample by flame

photometry using a lithium internal standard. Other major

and minor elements were measured on fused samples by xray fluorescence spectrometry using the specific technique

of Norrish and Hutton (1969). Additional sodium nitrate

was added to give the equivalent of 10% Na2O and 90%

Allende powder in a 0.28 g sample. This was necessary to

achieve oxidation and retention of sulfur during fusion.

Instrumental conditions corresponded to those of Norrish

and Hutton (1969) (Table 20), except that a LiF(200) crystal

was used for potassium measurements, and Mg, Al, Si, P,

and S were measured with x-ray tube operating at 2 kW.

Calibration was made against the USGS rock standards

GSP-1, AGV-1, BRC-1, PCC-1, and W-l. These had been

calibrated previously using synthetic primary standards.

Trace element results are given in Table 19 and major

element results in Table 18.

TABLE 19.—Trace element results (in ppm) for the Allende meteorite reference sample and USGS BCR-1

reference basalt (error limits represent 95 percent confidence of mean; split numbers are those of authors;

a and b are duplicate analyses of each split).

Constituent

Rb

Sr

Th

Zr

Nb

Y

V

Co

Cu

Zn

Ga

No. 138

Split 5/Position 10

(a)

1.30+0.08

14.65±0.13

3.0±1.0

7.3±0.4

< 1

3.1+0.1

91.7±0.7

565±2

95.3±1.1

130.9±0.7

5.5±0.4

(b)

1.34±0.10

14.72±0.14

1.4+0.7

7.6±0.4

<1

3.2±0.1

91.1±0.9

564+2

95.2±1.1

130.0±0.9

5.3±0.2

No. 247

Split 9/Position 18

(a)

1.26±0.10

14.56±0.14

1.4±0.5

7.6±0.5

< 1

3.1±0.1

91.1±0.6

567±3

96.6±0.9

130.8±0.5

5.4±0.3

(b)

l.26±0.10

14.85±0.10

1.7±0.8

7.8±0.3

< 1

3.2±0.1

92.0±0.6

567±2

95.5±0.6

130.2±0.8

5.5±0.4

Mean

1.29

14.70

1.9

7.6

<1

3.2

91.5

566

95.7

130.5

5.4

BCR-1

46.7

329

5.7

186

11

33

376

38

14

123

21

TABLE 20.—Instrumental conditions for x-ray emission measurements of trace elements in the Allende

meteorite reference sample. Conditions refer to Philips PW 1220 spectrometer; pulse height selector set to

1-2 V window for flow proportional counter (FPC) and 0.8-2.2 V for scintillation counter (SC); cycles

refer to multiples of 200 second counts on peak and 100 second counts on each background position.

Element

V

Cr

Co

Ni

Cu

Zn

Ga

Rb

Sr

Y

Zr

Nb

Th

Line

Ka

Ka

Ka

Ka

Ka

Ka

Ka

Ka

Ka

Ka

Ka

Ka

L a i

X-ray tube

target

W

W

W

Au

Au

Au

Mo

Mo

Mo

Mo

W

W

Mo

kV,

niA

55,36

55,36

55,36

62,32

62,32

62,32

100,20

100,20

100,20

100,20

100,20

100,20

100,20

Collimator

(jum)

160

160

480

480

480

480

480

480

480

480

480

160

160

Crystal

LiF(220)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

LiF(200)

Detector

FPC

FPC

SC

SC

SC

SC

SC

SC

SC

SC

SC

SC

SC

Backgrounds

(°20)

±1.75

±0.90

±0.40

±0.40

±0.40

±0.40

±0.40

±0.30

±0.35

+0.40

±0.40

±0.35

±0.23

Cycles

10

10

10

10

10

10

35

50

35

35

40

40

15
13. Neutron Activation Analysis of Some Trace Elements

in the Allende Meteorite Reference Sample

J.F. hovering and R.R. Keays

Two splits from the Allende meteorite reference sample

were analyzed for nine trace elements by neutron activation

analysis. Results are summarized in Table 21.

TABLE 21.—Neutron activation analysis of the Allende meteorite reference

sample (dash indicates results not reported).

Constituent

Split 6/Position 11

Aliquot 1 Aliquot 2

Split 13/Position 20

Aliquot 1 Aliquot 2

PARTS PER MILLION

J.F. Lovering and R.R. Keays, School of Geology, University of Melbourne,

Parkville, Victoria 3052, Australia.

Re

Os

Ir

Au

Pd

Se

T e

T h

Bi

0.063±0.001

0.76±0.01

0.80±0.01

0.10±0.01

0.59±0.01

0.062±0.001

0.70±0.01

0.78±0.01

0.12±0.01

O.72±O.O1

0.064±0.001

0.79±0.01

0.74±0.01

0.10+0.01

0.56±0.01

PARTS PER BILLION

7600

1100

77

27

7200

1100

63

29

-

-

-

-

0.063±0.001

0.75±0.01

-

0.15±0.01

0.67±0.01

-

-

-

-

30
14. Carbon Analysis of

the Allende Meteorite Reference Sample

by Standard Rapid Combustion Method

Carleton B. Moore

Carbon analysis was performed on two splits of the Allende meteorite

reference sample employing the standard rapid combustion method

with a LECO carbon apparatus: for Split 19/Position 21, C = 0.268%;

for Split 19/Position 22, C = 0.28r,%.

Carleton B. Moore, Department of Geology, Center for Meteorite Studies, Arizona State University,

Tempe, Arizona 85281.

31
15. Multielement Analyses of

the Allende Meteorite Reference Sample

by Neutron Activation and

Spark Source Mass Spectrometry

G.H. Morrison, N.M. Potter, A.M. Rothenberg,

E.V. Gangadharam, and S.F. Wong

Multielement analyses were performed for 45 elements

on two splits of the Allende meteorite reference sample

employing neutron activation analysis (NAA) (Morrison et

al., 1969) and spark source mass spectrometry (SSMS) (Morrison and Kashuba, 1969). These techniques were applied

earlier in the analyses of USGS rock standards (Morrison et

al., 1969; Morrison and Kashuba, 1969) and lunar samples,

meteorites, and tholeiites (Morrison et al., 1970a, 1970b;

Morrison et al., 1971).

Two 5 g aliquots of powdered meteorite were received

bearing the identification numbers: Split 6/Position 24 and

Split 12/Position 29. For NAA, duplicate 200 mg samples

of each split were weighed directly into suitable containers

for irradiation. For SSMS, 2 g aliquots of each split were

ground in an agate ball and mortar mill for 4 hours, and

two 1 g aliquots of each were mixed in 1:1 ratio with

National Carbon Company ultrapure graphite. The mixes

were briquetted into disks, which were quartered, and the

quarters used as electrodes in the mass spectrometer.

For nondestructive NAA, the 200 mg aliquots of samples

were placed in clean polyethylene vials and irradiated in the

Cornell TRIGA Mark II reactor successively at the following

flux levels: 6 X 10I() neutrons cm"' sec"1 for 45 seconds for

Al and V; 2 X 10" neutrons cm"2 sec"1 for 40 seconds for

Mg; and 2 X 1012 neutrons cm"2 sec"1 for 90 seconds for

Mn. Following these irradiations and gamma-spectrometric

measurement, the same samples were sealed in high purity

quartz ampules and irradiated at a flux of 3.5 X 10]i

neutrons cm"2 sec""1 for 8.5 hours for radiochemical NAA

involving chemical group separations after a decay of 15

G.H. Morrison, N.M. Potter, A.M. Rothenberg, E.V. Gangadharam, and S.F.

Wong, Department of Chemistry, Cornell University, Ithaca, New York 14853.

hours. Gamma-spectrometry was employed for measurement of the radionuclides.

The counting system consisted of a 30 cm3 coaxial Ge(Li)

detector (Nuclear Diodes) coupled to a 4096-channel analyzer (Northern Scientific). The spectra were read directly

onto computer-compatible magnetic tape, which was then

processed by an IBM 360/65 computer. Details of the

activation procedures have been given by Morrison et al.

(1969).

For mass spectrometry, the electrodes were sparked in a

GRAF-2 double focusing mass spectrograph (Nuclide Associates). Different settings of magnet currents and charge

collections were used to reduce interferences. USGS standard diabase W-l was used as a comparative standard, and

sensitivity factors were calculated for use in computing the

quantitative results. A Jarrell-Ash microdensitometer was

used to read the photoplates and the data were processed

on a PDP-11 computer.

Table 22 lists the results obtained from duplicate analyses

of each of the two splits received. The means and average

deviations (AD) for each split are presented, as well as an

overall mean and relative standard deviation (RSD) based

on all values for each element.

With regard to the precision of the measurements, the

average RSD for the 26 elements determined by NAA is

6%; for the 28 elements determined by SSMS it is 7%. Only

Be, Cs, Ce, Eu, Lu, W, and Pb have RSDs above 10% and

these can be attributed to analytical problems associated

with their determinations. Since the reproducibility of most

of the elements determined is within the 10% precision

capability of the techniques employed, results for the duplicate analyses of each split as well as the results for both

splits are essentially the same, so that the material can be

considered homogeneous.

32
NUMBER 27 33

TABLE 22.—Results of duplicate analyses on two samples of the Allende meteorite reference sample

(Split 6/Position 24, Split 12/Position 29) (AD = average deviation; RSD = relative standard deviation).

Constituent

MAJORS

Na

Mg

Al

K

Ca

Ti

Cr

Mn

Fe

TRACE

Method

NAA

NAA

NAA

NAA

NAA

NAA

NAA

NAA

NAA

ELEMENTS

Li

Be

B

F

Sc

V

Co

Cu

Zn

Ga

Ge

As

Rb

Sr

Y

SSMS

SSMS

SSMS

SSMS

NAA

SSMS

NAA

SSMS

NAA

NAA

NAA

SSMS

NAA

SSMS

SSMS

SSMS

Mean

Split 6

AD

(%)

Mean

Split 12

PERCENT

0.35

14

1.9

0.03

1.9

0.09

0.36

0.145

23.5

PARTS

1.3

0.03

1.0

56

10

77

89

600

230

100

5

11

3

1.2

27

3.2

3.7

1.8

1.6

3.2

5.2

0.33

0.01

0.24

1.1

0.35

14

1.9

0.03

1.8

0.08

0.35

0.145

23.5

PER MILLION

0.80

14

5.5

0.09

2.4

7.0

4.6

0.08

1.3

5.0

1.3

2.3

3.4

3.3

1.1

2.7

1.4

0.03

1.0

53

10

89

89

610

230

100

5

11

3

1.5

27

3.0

AD

(%)

4.3

1.6

3.4

0

2.7

2.4

0.56

1.1

3.0

1.1

9.1

8.0

1.3

3.4

4.8

3.5

1.3

0.22

1.6

2.0

3.1

10

1.7

3.7

6.0

Overall

mean

0.35

14

1.9

0.03

1.9

0.09

0.35

0.145

23.5

1.3

0.03

1.0

55

10

83

89

610

230

100

5

11

3

1.4

27

3.1

RSD

(%)

4.7

2.3

3.1

3.6

5.9

4.3

0.51

0.96

2.5

6.8

14

7.8

3.3

3.4

11

4.7

1.7

1.2

4.3

2.7

3.8

8.6

11

3.3

6.1

Constituent

Zr

Nb

Sb

Cs

Ba

La

Ce

Pr

Nd

Sm

Eu

Gd

T b

Dy

Ho

Er

Yb

Lu

Hf

W

Pb

Method

SSMS

NAA

SSMS

NAA

SSMS

SSMS

SSMS

NAA

SSMS

NAA

SSMS

SSMS

SSMS

NAA

SSMS

NAA

SSMS

SSMS

NAA

SSMS

SSMS

NAA

SSMS

SSMS

NAA

SSMS

NAA

NAA

SSMS

Mean

Split 6

AD

(%)

PARTS PER

11

11

0.72

0.085

0.1

12

0.56

0.6

1.2

1

0.22

0.92

0.36

0.34

0.1

0.1

0.42

0.077

0.1

0.41

0.12

0.1

0.27

0.33

0.06

0.20

0.2

0.2

1.6

2.8

0.05

0.69

4.3

0

2.1

1.4

3.3

5.2

14

8.8

1.1

1.6

1.6

4.5

15

1.3

0.65

0.49

6.5

8.3

6.2

I.I

0.15

18

2.3

-

4.6

2.1

Mean

Split 12

MILLION

10

11

0.76

0.088

0.09

12

0.56

0.7

1.3

1

0.21

0.94

0.35

0.36

0.09

0.1

0.42

0.075

0.1

0.41

0.12

0.1

0.28

0.28

0.06

0.19

0.2

0.2

1.0

AD

(%)

5.2

-

0.86

0.11

18

2.5

1.4

10

1.2

7.5

0

1.2

2.1

7.9

11

3.0

1.7

2.7

0.91

3.1

4.2

1.8

11

1.4

13

2.9

-

17

6.7

Overall

mean

11

11

0.74

0.086

0.1

12

0.56

0.6

1.2

1

0.22

0.93

0.36

0.35

0.1

0.1

0.42

0.076

0.1

0.41

0.12

0.1

0.28

0.30

0.06

0.19

0.2

0.2

1.3

RSD

(%)

5.0

0.095

2.8

4.1

19

2.6

1.7

5.6

6.6

14

8.0

1.7

3.0

6.9

11

16

1.7

2.3

7.3

5.9

8.0

5.6

9.1

10

18

3.5

12

14

27
16. Spark Source Mass Spectrometer Analysis of the

Allende Meteorite Reference Sample

P.E. Muir, S.R. Taylor, and Brian Mason

Two splits from the Allende meteorite reference sample

were analyzed for 22 trace elements by spark source mass

spectrometry. The analytical technique for the spark source

mass spectrometer has been described by Taylor (1971) and

Taylor and Gorton (1977). The method utilizes the rare

earth element Lu as an internal standard. The samples were

mixed in equal amounts with a graphite mix containing 50

ppm Lu as the oxide. Two electrodes were then prepared

inside polyethylene slugs, using a steel die and a hydraulic

press. The electrodes were mounted in the source of an

AE1 MS7 spark source mass spectrometer and subjected to

a high-voltage spark. The ion beam was recorded on an

llford Q-2 photographic plate. A series of graded exposures

was obtained, which ensured that a wide range of element

concentration was covered. The intensity of nuclide lines

for the various elements was determined with a photodensitometer. The ratio of this intensity to the intensity of the

internal standard line on the same exposure is directly

related to element concentration. Calibration of element to

internal standard intensity ratio to elemental abundance

was obtained by the use of well-analyzed rock standards,

such as W-l, G-l, BCR-1, and AGV-1. Accuracy and precision of the technique are dependent upon the total number of exposures used to calculate the abundance of each

element. For this project three photoplates were exposed

for each sample, each with about 14 exposures. This resulted in the abundance of each element being based on 10

to 15 determinations. Lutetium is an ideal internal standard

for the lanthanide elements, so excellent precision and

P.E. Muir and S.R. Taylor, Research School of Earth Sciences, Department of

Geophysics and Geochemistry, Australian National University, Canberra 2600,

Australia. Brian Mason, Department of Mineral Sciences, National Museum of

Natural History, Smithsonian Institution, Washington, D.C. 20560.

accuracy is obtained for these elements. Accuracy decreases

for elements with mass number below 100 because of increasing background. There is also a greater possibility of

interference from metal carbides and oxides in this mass

region. The precision obtained for most elements is about

±5% and accuracy is about ±b%, but this varies somewhat

according to the element in question. Results are listed in

Table 23.

TABLE 23.—Spark source mass spectrometer analysis (in ppm) of two

samples of the Allende meteorite reference sample (dash indicates no data).

Constituent

Y

Zr

Nb

Cs

Ba

La

Ce

Pr

Nd

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

Hf

Pb

Th

Split 1/

Position 27

2.3

6.4

0.48

0.10

5.1

0.53

1.43

0.19

1.00

0.30

0.10

0.36

0.07

0.44

0.09

0.28

0.053

0.29

0.05

0.20

1.57

0.063

Split 13/

Position 23

3.0

6.4

0.53

-

5.7

0.52

1.45

0.20

0.99

0.32

0.11

0.39

0.07

0.47

0.10

0.28

0.064

0.31

0.06

0.22

1.49

0.063

34
17. Determinations of Na, K, Rb, Cs, Br, Te, and U

by Neutron Activation Analysis in

the Allende Meteorite Reference Sample

0. Muller

Seven minor and trace elements have been determined

in the Allende meteorite reference sample. Replicate analyses were performed on Split 5/Position 1 and Split 8/

Position 27 of the reference powder using neutron activation analysis and radiochemical separations.

The irradiations of the Allende samples were mainly

performed in the core of the TRIGA Mark I reactor of the

Deutsches Krebsforschungszentrum, Institut fur Nuklearmedizin, Heidelberg, at a neutron flux of ~10 M

 neutrons

cm~" see"'. Samples were also irradiated in the high flux

reactor FR2 of the Gesellschaft fur Kernforschung, Karlsruhe, at a flux of ~8 X 1013

 neutrons cm"2 sec"1. Contributions to (n,7)-produced nuclides by interfering (n,p),

(n,a), and U(n,f) reactions have been determined or estimated. For most nuclides analyzed in this work the correction was small or negligible. We observed, however, a

distinct interference of

 24Mg(n,p)24Na, the amount of which

was considered in the calculation of the sodium concentration. Mg is a major element in Allende, about 15%.

Four different schemes for chemical analysis were used

for the following groups of elements: (1) Na, K, and Cs; (2)

Na, K, Rb, and Cs; (3) Br and Te; and (4) U.

For the determination of Na, K, and Cs, 100 mg of

Allende powder and Na, K, and Cs monitors were irradiated

for 4 hours in the core of the TRIGA reactor. The samples

were dissolved with carriers in HF and HC1O4. The dry

residue was dissolved in IN HC1. Na, K, and Cs were

separated by passing the solution through a 25 X 0.8 cm

Dowex 50, X-8, 50-100 mesh cation exchange column and

eluting with IN HC1. For the Na fraction no additional

chemical processing was necessary. Potassium was precipitated with sodium tetraphenylboron, the precipitate filtered

and dissolved in 6N HC1, the solution scavenged twice with

Fe and Mn carriers, and K was again precipitated as above

and converted to KC1O4. The purification of the Cs fraction

was similar to that for K; the final step was precipitation as

O. Muller (deceased), Max-Planck-Institut fur Kernphysik, Heidelberg 1248,

West Germany.

CssBi-Jc,, by which complete separation from K was

achieved. Monitor solutions of Na were weighed on Mylar

foil and those of K and Cs on highly pure aluminum foil

before irradiation. The monitors were chemically processed

as described above. The 7-activities of

 24Na, 42K, and U4mCs

were counted using 3X 3 inch Nal(Tl) scintillation counters

and a 400-channel pulse height analyzer. Na and K were

counted in solution (well counter), and Cs was mounted as

CsaBijJy and counted within the solid crystal. The chemical

yields of Na and K were measured by atomic absorption

and the Cs yield was determined gravimetrically as CsaBiyloFor the determination of Na, K, Rb, and Cs, 90 mg of

Allende powder was irradiated in the high flux reactor FR2

of the Gesellschaft fur Kernforschung, Karlsruhe, for 24

hours at a flux of ~8 X 1013 neutrons cm"2 sec"'.

Na, K, Rb, and Cs monitors and USGS standard diabase

W-l as a reference sample, were irradiated simultaneously.

The high neutron flux is necessary to produce sufficient

activity of

 H(iRb (t./s

 = 18.7 day) and

 I34Cs (t* = 2.05 yr).

Cesium, measured as ' H'"Cs in the first procedure, was

determined now as

 1S4Cs. The meteorite and diabase samples were dissolved with carriers in HF and HC1O4. The

dry residue of perchlorates was ground with pure ethanol.

The perchlorates of K, Rb, and Cs remained undissolved

and were collected on filter paper. The alcoholic filtrate

containing the Na was evaporated, the residue dissolved in

IN HC1, and Na separated by passing the solution through

a Dowex 50 column as before. The perchlorates of K, Rb,

and Cs were dissolved in H2O and the solution scavenged

twice with Fe and Mn carriers (hydroxide precipitations).

K, Rb, and Cs were precipitated with sodium tetraphenylboron and converted to perchlorates, which were rinsed

with 5 ml of H2O into a plastic counting tube. Because of

the different 7-energies of

 42K, 86Rb, and 134Cs, these nuclides can be measured together; the resolution of the

Nal(Tl) detector is sufficient.

 42K was counted first and,

after its decay,

 HbRb and 134Cs. A Na monitor solution was

weighed on Mylar foil and equilibrated with the Na carrier

after irradiation. This solution was used for counting after

35
36 SMITHSONIAN CONTRIBUTIONS TO THE EARTH SCIENCES

TABLE 24.—Results of neutron activation analysis of the Allende meteorite

reference sample (* activation in the high flux reactor FR2, Karlsruhe; all

other values from activation in the TRIGA reactor, Heidelberg).

Constituent

Na

K

Rb

Br

Te

Cs

U

Split 5/

Position 1

3420

3260

3310*

301

288

297*

1.2*

1.52

1.56

1.0

1.2

91

94

92*

16

15

Mean

with error

PARTS PER

3330±90

295±7

1.2

1.54±0.02

l.l±0.1

PARTS PER

92±2

15.5

Split 8/

Position 27

MILLION

3410

3230

3420*

291

287

288*

1.2*

1.54

1.50

1.0

1.2

BILLION

96

96

9 5 *

16

Mean

with error

3350±100

289±2

1.2

1.52±0.02

l.l±0.1

96+1

16

Average

of splits

3340

292

1.2

1.53

1.1

94

16

appropriate dilution with water. A mixed K, Rb, and Cs

monitor solution was weighed on highly pure aluminum foil

and dissolved with carriers in HC1 after irradiation. The

heavier alkali elements were chemically processed and

counted as described above without separation. The chemical yields of Rb and Cs were determined in an aliquot of

the alkali solution, by reactivation and the yields of Na and

K by atomic absorption spectrometry.

For the Br and Te analysis, 100 mg of Allende powder

and Br and Te monitors were irradiated for 14 hours in

the core of TRIGA. Chemical processing was started 15 hours

after the end of irradiation. A waiting period of at least 4

hours is necessary to allow for the decay of

 lslTe to 13II (tv,

= 25 min). The monitors, which were pipetted on highly

pure aluminum foil, were dissolved in the presence of NaBr

and Nal carriers with 2N NaOH in a nickel crucible, dried,

and fused with Na2O2. The fusion cake was treated as

described below for the meteorite samples. Each meteorite

powder was fused with Na2O2 in the presence of NaBr and

Nal carriers in a nickel crucible. The fusion cake was

dissolved in H2O and the solution boiled to destroy excess

H2O2. Na2SOs was added and the solution weakly acidified

with 4N H2SO4 to reduce BrO:r and IO:r to Br~ and I".

The whitish residue was filtered off and discarded. The

filtrate was transferred to a separatory funnel and I~ was

oxidized to IL> 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 yellowbrown solution transferred to another funnel, and Br2 backextracted 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 precipitated 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 buffering 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 transferred 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 TM'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 solution to a beaker quantitatively and by re-precipitating U

with 8-hydroxyquinoline. To achieve complete precipitation 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 comparing 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, Karlsruhe, 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 isotope dilution technique in two splits of the Allende meteorite 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 determined 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 permanganate 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 ammonium 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 vanadomolybdate method. Chromium was estimated colorimetrically 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

Cr 2Os

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 activation 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 subjected 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 activation before chemical separations were started. The abundances 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 chemical 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 agreement 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 obtained 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 standard 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, ll e, 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 abundances 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 meteoritics he was one of the collaborators who first measured

accurately the fundamental rare earth elemental abundances in chondritic, achondritic, and other types of meteorites.
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 precision 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 actual number of counts selected per determination varied

from 1,000,000 to 1,400,000 depending on the total neutron 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 determinations. Details of the technique are given in Vincent and

Volborth (1967), Volborth and Vincent (1967), and VolA. 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 reference 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 carbonate 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 xray fluorescence spectrometry. The two 5 g samples received 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 absorption coefficients for the determination of the remaining

trace elements were measured by the method of Reynolds

(1963). The analytical techniques have been described elsewhere (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 spectrometry (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
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