I 

Reference Samples in Geology 

And Geochemistry 

U.S. GEOLOGICAL SURVEY BULLETIN 1582 

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Reference Samples in Geology 

And Geochemistry 

By F. J. FLANAGAN 

The report discusses some 

history of analytical problems 

that resulted in early 

standards. Geologic samples 

of economic interest and 

general information are 

discussed by country of origin, 

whereas geochemical samples 

are mentioned by samples 

types and by their intended 

use. Numerous topics and 

problems for reference 

samples and their data are 

discussed. 

U.S. GEOlOGICAl SURVEY BUllETIN 1582 
DEPARTMENT OF THE INTERIOR 

DONALD PAUL HODEL, Secretary 

U.S. GEOLOGICAL SURVEY 

Dallas L. Peck, Director 

UNITED STATES GOVERNMENT PRINTING OFFICE: 1986 

For sale by the Distribution Branch, U.S. Geological Survey, 

604 South Pickett Street, Alexandria, VA 22304 

Library of Congress Cataloging-in-Publication Data 

Flanagan, F.j. (Francis James), 1915-

Reference samples in geology and geochemistry. 

(U.S. Geological Survey bulletin ; 1582) 

Bibliography: p. 56 

Supt. of Docs. no.: 119.3:1582 

1. Rocks-Composition. 2. Mineralogy, Determinative. 3. Sediments (Geology)-Composition. 

I. Title. II. Series. 

QE75.B9 no. 1582 [QE438] 557.3 s 85-600274 

[552'.06] 
CONTENTS 

Abstract 1 

Introduction and historical review 1 

Analysis of natural materials and mixtures 2 

Zinc ores 4 

Products made from ores 4 

1901 and precursors of geochemical standards 5 

Uniformity in rock analysis 6 

Plant pest control regulations 6 

Sources of information on reference samples 7 

Samples for geology and geochemistry 8 

Artificial samples 8 

Solutions 8 

Solid chemicals 8 

Mixtures of natural materials 8 

Glass samples for major and minor elements 8 

Glass samples for trace elements 9 

Dust and particulate samples 9 

Gelatin samples 10 

Implantation, dip, and urea samples 10 

Resin and polymer samples 10 

Silica gel samples 10 

Sludge ash sample 10 

Waste incineration ash 11 

General synthetic samples 11 

Natural samples of economic interest 11 

United States 11 

Great Britain 11 

France 12 

Germany 12 

Canada 12 

South Africa 12 

CMEA Countries 12 

Czechoslovakia 12 

German Democratic Republic 13 

Poland 13 

U.S.S.R. 13 

Austria 14 

BCR (Community Bureau of Reference, Brussels) 14 

Brazil 15 

Japan 15 

People's Republic of China 15 

Scandinavia 16 

Natural samples of geologic interest 16 

Geological and geochemical samples 16 

Geochemical exploration samples 17 

Archaeology 17 

Bauxite 17 

Clays and clay minerals 17 

Coals, coal ash, and cokes 18 

Counting standards 18 

Laterites 18 

Meteorites 18 

Minerals 19 

General 19 

Contents Ill 
Samples for geology and geochemistry-Continued 

Natural samples of geologic interest-Continued 

Minerals-Continued 

For microprobe 19 

For age determinations 19 

Phosphates 19 

Sediments 19 

Bay (Estuarine) 19 

Canal (River) 20 

Lake 20 

Marine 20 

Pond 20 

River (Radioactivity) 20 

Soils 20 

General 20 

Low-level radioactivity 20 

"Natural matrix" vs. spiked samples for radioactivity 20 

Stable isotope 21 

Geobotanical samples 22 

Topics and problems for reference samples and their data 23 

Reasons for reference samples 23 

Amount of a rock reference sample 24 

Reference samples vs. in-house standards 25 

Comminution and grindability 25 

Homogeneity, sampling errors, and the sample for analysis 25 

Small samples-Precautions and preparation 28 

Excess grinding and the FeO contents of rocks 30 

Large samples-Precautions and preparation 30 

Sieving 32 

Contamination by steel 33 

Homogeneity of reference samples 33 

Outliers 35 

Estimation of best values 36 

Certification factor 37 

Nomenclature for reference samples 37 

Are "best values" best? 38 

Confidence limits for a single datum 39 

Comparisons of data 40 

The analyst and the producer 41 

Reference samples identified through 1984 41 

References cited 56 

FIGURES 

1. Plot of the free iron (Fe0) contents of some reference samples determined by two 

chemical methods 33 

2. Confidence limits for a calibration line 39 

3. Confidence rectangles for assigning points x ,y to rock fields 40 

TABLES 

1. K20 in commercial fertilizers, determined by the chloroplatinate method 2 

2. K20 in commercial fertilizers, determined by variations of the chloroplatinate 

method 3 

3. K20 determined by the Association-recommended method 3 

4. Summary of methods relating sampling, errors, and particle size 28 

5. Reference samples 42 

6. Suppliers of reference samples 55 

IV Contents 
Reference Samples in Geology and Geochemistry 

By F. j. Flanagan 

Abstract 

The use of geologic reference samples may have started 

in the last quarter of the 19th century after analysts in England, 

Germany, and the United States deplored the large variation in 

data obtained by different analysts for the same constitutent in 

the same sample. Early samples involved in cooperative analysis, also known as "round robins," were mainly industrial or 

agricultural materials of economic value, or products derived 

from them. Data from some round robins were so diverse that 

"uniformity in analysis" was a part of early committee names. 

The first two geologic samples of the National Bureau of Standards were analyzed cooperatively. 

Samples for geology and geochemistry are classified as 

artificial samples or as natural materials of either economic or 

geochemical interest...:_the latter distinction not always possible. Artificial samples have been prepared in several substrates, 

and samples in other substrates may be limited only by the 

ingenuity of the analyst. 

The principal suppliers of samples of economic interest 

are discussed, by country, to show the range of samples prepared by organizations. Natural samples of geochemical interest are mentioned by sample type. Because of their intended 

use, some geochemical samples are restricted to analysts using 

specific techniques. 

Methods used for and precautions to be observed while 

preparing large or small rock samples are discussed. Excess 

grinding of small rock samples reduces the amount of FeO 

found in a rock analysis. Unavoidable contamin.ation occurs 

when processing rocks in steel. Tungsten carbide, and some 

mechanical equipment, should be avoided. A review of the 

allied subjects of homogeneity of a sample, sampling errors, 

and size of the sample grains shows that we have reinvented 

the wheel since 1885. 

Methods used to (1) test the homogeneity of samples, 

(2) eliminate outliers which some scientists reject repeatedly 

despite warnings of statisticians, and (3) estimate best values 

when the method for estimating should be part of the program 

for a sample are discussed. Calibration lines may be used to 

determine if "best values" in a series of several samples are 

really "best" and to furnish confidence limits for a single datum. 

The agreement of data by an analyst for a reference sample with data preferred by an issuing organization is usually 

described by one of several adjectives, a subjective procedure. 

A variation of a x2 method may be used if a producer specifies 

the exact number of data for the cooperative analytical program to be furnished by each analyst and then calculates the 

population estimates of the mean and standard deviation for an 

element in a sample. 

Because of the large increase in the number of reference 

samples of all types, a revised table listing samples that may be 

useful in geochemistry is included. It is not known if the samples, other than those of the U.S. Geological Survey, were 

collected in conformance with provisions of the Plant Pest 

Control Regulations of the U.S; Department of Agriculture, or 

of similar organizations in other nations. 

INTRODUCTION AND HISTORICAL REVIEW 

Reference samples in geology and geochemistry are 

now used so widely that many of us take for granted their 

availability. Yet little more than three decades ago, before 

the results of a cooperative study on G-1 and W -1 were 

published (Fairbairn and others, 1951), no reference samples of silicate rocks were available. The rocks in the cooperative study were generally known as granite G-1 and 

diabase W -1 by those concerned both with the study and 

with the distribution of the samples, but the two samples 

were soon promoted by users to the status of "standards." 

Reasons for this promotion may become evident if we consider why and when samples of geologic materials were first 

prepared and used. 

A search of the chemical and geological literature to 

determine when geologic reference samples were frrst used 

highlights the pertinence of the following remark by Pirsson 

(1918, p. 250) about the rise of petrology: "The beginnings 

of a particular branch of science are generally obscure and 

rooted so imperceptibly in the foundations on which it rests 

that it is difficult to point to any particular place in its 

development and say that this is the start." Standard samples 

went through an extended period of incubation, and the 

greatest hindrance to determining when geologic reference 

samples were frrst used has been the several changes in 

nomenclature since the last century. 

The trend in the last decade has been to refer to such 

materials as either reference samples, standard reference 

materials, or certified reference materials, with CRM as the 

accepted abbreviation for the latter. The term "standard 

sample" was used perhaps universally during the preceding 

half century. Prior to that, Hillebrand (1909), shortly after 

he transferred from the U.S. Geological Survey to the National Bureau of Standards, published the short note "The 

Bureau of Standards' Analyzed Samples," but in the following year [National] Bureau of Standards (1910) Circular 25 

Introduction and Historical Review 
had the title "Standard Analyzed Samples-General Information." 

Until this time ( 1909-1 0), samples of geologic materials that had been well analyzed during cooperative analyses were known by such simple terms as raw cement mixture 

(one sample was a mixture of two limestones), argillaceous 

limestone, or zinc ore, without such modifiers as "standard" 

or "analyzed." In England over half a centruy ago, steel 

samples were known, as they are today, as chemical standards-defined as "samples in suitable condition for analysis 

which have been already analytically standardized and are 

taken as having a definite recognized composition" (Ridsdale and Ridsdale, 1919, p. 15T). 

Analysis of Natural Materials and Mixtures 

Analysts of almost a century ago faced one problem 

that is still with us-the variation in data obtained by analysts determining the same constituent in presumably the 

same sample was unacceptably large. Many problems then 

concerned industrial or agricultural materials. The Potash 

Committee of the Association of Official Agricultural 

Chemists (AOAC) may have been among the first to distribute samples for analysis that were test samples but might 

be considered standard samples of either rocks, minerals, or 

ores, if one is allowed to define "standard sample" very 

loosely. 

Agricultural chemical work in the United States at 

that time (1880) was described by H.W. Wiley as "chaotic" 

(Bogert, 1908, p. 174). Agricultural commissioners and 

chemists met in 1880 to secure uniformity in analytical 

methods and formed a division of the chemistry subsection 

of the American Association for the Advancement of 

Science. The division existed for 4 years before the independent AOAC was formed on September 9, 1884. 

The chairman of the Potash Committee, the aforementioned H. W. Wiley, sent to members of the AOAC 

(Dabney, 1885) samples of six fertilizers containing potash. 

The set contained a commercial kainite (a mineral with the 

formula MgS04·KC1·3H20), a commercial high-grade 

phosphate with nitrate of potash, a commercial superphosphate, and three other samples of mixtures that were used as 

fertilizers. Of these, only the kainite may be considered a 

geologic sample. No details of the samples were given in the 

letter of transmittal, but Wiley noted that "the greatest care 

has been taken to secure uniformity in the samples sent out." 

The data, obtained in four laboratories by eight 

chemists, are given in tables 1 and 2. Table 1 contains data 

obtained by the chloroplatinate method recommended by the 

Potash Committee at a meeting of the AOAC in Philadelphia 

in 1884, and table 2 contains data obtained by slight variations of the method. The high and low values for each 

sample are indicated; in both tables, kainite is sample 1. 

Analyst E in table 1 obtained the highest data for five 

of the six samples, and analysts F and H each obtained 

lowest values for two samples. In table 2, analyst C determined three highest values and analyst G' two, whereas 

analysts B and B' each furnished two lowest values. Of 

greater importance are the higher means for five samples 

determined by the method recommended by the AOAC and 

the wider ranges of data by the same method with variations 

introduced by the analysts. 

In the following year another set of six samples, identified by number only, was sent by W.J. Gascoyne, then 

chairman of the Potash Committee. The report was published by Richardson (1886), who described the samples as 

(1) potassium sulfate, C.P., (2) commercial kainite, and 

(3-6) acid phosphates to which apparently had been added 

potassium sulfate and other salts so that the four samples had 

different K20 contents. The data are given in table 3. 

There is less variation in these data than in those in 

tables I and 2, except for the large range for the kainite data 

(sample 2). The low value of 12.06 percent by analyst L for 

the kainite accounts for 0.80 of the range of 3.40 percent, 

the high value of 15.46 by analyst K accounts for another 

1.81 percent, and the range, when these high and low values 

are removed, is a modest 0. 79 percent. Analyst I had the 

dubious distinction of reporting the highest data for four 

samples, and analyst L, the lowest data for four samples. 

The analysis of phosphate rocks continued to be a 

problem for the fertilizer industry, and the committee on the 

Table 1. K20 in commercial fertilizers, determined by the chloroplatinate method 

[In weight percent. H, high value; L, low value] 

Sample 

Analyst 2 3 4 5 6 

D -------------12.81 4.01 2.24L 2.46 3.20 3.54 

E -------------13.58H 4.64H 2.58H 2.66 3.23H 3.58H 

F -------------12.04L 3.98L 2.32 2.64 2.90 3.38 

G -------------12.44 4.24 2.37 2.74H 2.80L 3.38 

H-------------13.39 4.33 2.26 2.41L 2.99 3.34L 

Mean--------- -12.85 4.24 2.35 2.58 3.02 3.44 

Range - - - - - - - - - 1.54 .66 .34 .33 .43 .24 

2 Reference Samples in Geology and Geochemistry 
Table 2. K20 in commercial fertilizers, determined by variations of the chloroplatinate method 

[In weight percent. H, high value; L, low value] 

Analyst 2 3 

A -------------13.77 4.21 2.03 

B -------------12.41 3.61 1.68L 

B I------------ -12.03L 3.45L 1.76 

C -------------14.24H 4.23 2.48 

F'-------------12.04 4.21 2.34 

G' ------------12.80 4.47H 2.54H 

Mean---------- 12.55 4.03 2.14 

Range - - - - - - - - - 2.21 1.02 0.86 

analysis of phosphate rocks of the National Fertilizer Association published a report by Hagedorn and others (1909). 

The committee prepared four samples of phosphate rock 

(Tennessee Brown, Tennessee Blue, South Carolina, and 

Florida) and submitted portions to chemists of the Association and to analysts who specialized in fertilizer analysis. 

The object of the study was to determine which methods 

yielded uniform data so that the methods might be adopted 

by the Association. 

The National Bureau of Standards sample of Tennessee phosphate rock, NBS-56, was issued on February 2, 

1934, with a provisional certificate of analysis. The certificate notes that concordant data were obtained for "soluble 

iron" by the methods recommended by the Fertilizer Division of the American Chemical Society (Cameron and 

others, 1915), but that the amount of "soluble alumina" 

obtained by the methods was more than the total alumina 

Sample 

4 5 6 

2.38 3.07 3.27L 

2.25L 3.28 3.38 

2.27 3.23 3.47 

2.29 3.55H 3.59H 

2.74H 3.14 3.47 

2.61 2.90L 3.38 

2.41 3.39 3.42 

.49 .65 .32 

content of the sample. The certificate for a second phosphate 

rock (Florida Land Pebble), NBS-120, was issued on April 

11, 1939. 

Among industrial materials submitted to chemists for 

cooperative analysis was a mixture prepared by Eustis 

(1883), with the sample made to contain about 50 percent 

copper and all the impurities ordinarily present in a copper 

ore. Although the sample was an artificial mixture and not 

a natural material, the data obtained by 14 analysts ranged 

from 43.90 to 53.34 percent Cu, presenting a dismal picture 

of the state of the art in 1883 for determinations of copper 

in copper ore. Eustis also reported determinations for copper 

borings (samples obtained by drilling through pig copper), 

for which the agreement was much better, contrary to his 

expectations. 

At about the same time, there were similar problems 

in England caused by the diversity of data obtained by 

Table 3. K20 determined by the Association-recommended method 

[In weight percent. H, high value; L, low value] 

Sample 

Analyst 2 3 4 5 6 

A------------ -53.99 12.86 2.75 3.95 3.26 2.19 

B -------------54.09H 13.11 2.56 3.80 2.61 1.20L 

c -------------54.02 13.05 2.68 3.92 3.20 2.21 

D -------------53.76 13.33 2.71 3.79 3.18 2.17 

E -------------53.88 13.42 2.71 3.75 3.07 2.19 

F -------------53.98 13.04 2.57 3.91 3.20 2.20 

G -------------54.00 13.32 2.76 3.87 3.50 2.34 

H -------------54.08 13.65 2.58 3.89 3.22 2.13 

I--------------53.12L 13.43 3.10H 4.05H 3.59H 2.62H 

J--------------53.88 

K -------------53.33 15.46H 2.57 3.76 2.71 2.05 

L -------------53.96 12.06L 2.42L 3.40L 1.95L 1.86 

Average- - --- - - -53. 88 13.33 2.67 3.83 3.03 2.10 

Range - - - - - - - - - .97 3.40 .68 .65 1.64 1.42 

Introduction and Historical Review 3 
chemists analyzing the same sample. Carter-Bell (1883, 

p. 109) wrote: 

To the purely scientific man, whose aim is searching after 

truth, it must be sad to see his practical brethren disagree, 

and also to think that work, although done by so many, is 

often worse than useless, 

and (p. 110), 

It is no use disguising the fact that there has existed, and, 

unfortunately, does still exist, great discrepancies between 

the analyses of chemists. 

Carter-Bell also recalled (p. 111) a suggestion in 1871 by 

the president of the Newcastle [England] Chemical Society 

that researches be instituted to explain the varying results 

obtained in the examination and valuation of material. The 

problem may have been universal, as Grossman, a discussant of Carter-Bell's paper, stated (p. 113) that "the German 

Society of Chemical Industry has recommended certain 

methods for chemists connected with alkali works." 

Zinc Ores 

A committee of the Colorado Scientific Society was 

appointed to establish uniformity in the technical methods of 

analysis used in the Western United States, and the committee (Hawkins and others, 1893) reported determinations of 

zinc in five samples of ore by eight analysts. The data 

obtained by one analyst, L.G. Eakins of the U.S. Geological 

Survey, were accepted as the standard to which other data 

were compared. The minerals of the ore were listed, but 

other than the notation that the "greatest care [was] taken in 

the mixing of each large sample, so that uniformity * * * 

might be assured," no information was given. The cooperative determinations apparently did not deplete the supply of 

the five samples, as the report noted that "the committee will 

be glad to aid * * * in furnishing requisite material" 

(p. 191). 

In 1903, a subcommittee on zinc ore analysis of the 

central committee of the New York section of the Society of 

Chemical Industry (SCI) prepared three samples of zinc ore 

that were analyzed by 42 chemists. The Committee on Uniformity in Technical Analysis of the American Chemical 

Society (ACS) summarized (Hillebrand and others, 1904) 

the past work of the SCI's central committee, including the 

data for the three zinc ores obtained by the 42 chemists. The 

committee noted (p. 1651) that 

The showing of Tables I to IV is ample demonstration that 

analytical chemistry, as ordinarily practiced, is anything 

but an exact branch of the chemical profession. 

The subcommittee on zinc ore analysis, then a subcommittee of the ACS Committee on Uniformity in Technical Analysis, published a complete report (Stone and Waring, 1907), 

including a discussion of the data on the zinc ores. After a 

brief introduction, they remarked that "the results were very 

bad" -a rather mild comment compared with that made by 

the committee. 

4 Reference Samples in Geology and Geochemistry 

Products Made from Ores 

The last quarter of the 19th century was a period of 

rapid industrial development in the United States, but it was 

also a time of questioning of analytical data on products of 

industry because of the variations in data obtained by the 

same or different chemists. In 1881, Dudley, in an expansion of a study in two related papers presented orally 3 years 

earlier, tried to relate the contents of carbon, manganese, 

phosphorus, and silica to physical tests on steel rails for 

railroads to obtain an index for resistance to wear. The 

discussants of his papers, among whom were engineers, 

metallurgists, and steel producers, were reluctant to accept 

the word of a chemist (even though Dudley was employed 

by a railroad) on the proposed amounts of these elements 

necessary for a rail to wear well, and many questioned the 

state of the art of the determinations of these elements in 

steel. 

In the following year, Kent (1882) published a paper 

on the determination of manganese in steel, noting in his 

introduction the doubts of several discussants of Dudley's 

(1881) paper about the general accuracy of chemical analysis of steel made by "iron-works chemists." He also noted 

that, since the meeting at which Dudley presented his paper, 

"the practical value of chemical analyses" had been discussed at some length in the columns of "Iron Age." Kent 

reported data for a sample of drillings from a steel plate, 

6 X 2 X 1/4 in, that had been analyzed by 33 chemists. The 

data obtained by several methods ranged from 1.14 to 

0.303 percent Mn. Many papers on determinations of C, P, 

Mn, and Si were soon published. 

Langley (1891) recalled his 1888 suggestion that a set 

of steel samples, analyzed with extreme care, could serve as 

standards, thereby resulting in greater uniformity of analyses. The seven members of the American Committee on 

International Standards for the Analysis of Iron and Steel 

met on February 19, 1890, and decided that, rather than 

begin work on international standards, they should make a 

preliminary study of methods for determining carbon because of the many discrepancies and differences of opinion. 

Thereafter, reports of the Committee on International Standards appeared (Langley, 1892, 1893; Langley and Dudley, 

1894a, 1894b), as did papers on the need for standard methods by Dudley and Pease (1893) and by Jiiptner (1896). 

Dudley and Pease (1893, p. 502) pointed out that lack of 

agreement among different chemists working on the same 

sample "is no new state of affairs." 

The accuracy of commercial assays for silver in ores 

was questioned (Dewey, 1894). Dewey (1896) also discussed the accuracy of chemical analysis, including determinations for (1) manganese and phosphorus in steels, 

(2) P20 5 and KCl in studies by the Association of Official 

Agricultural Chemists (U.S. Department of Agriculture, 

Bureau of Chemistry Bulletin 43), and (3) copper, gold, and 

silver in copper borings and copper matte. The latter study 
had been suggested as a plan of cooperative action by 

Ledoux (1894), and Raymond (1895), to whom the data 

were sent at the request of Ledoux, reported the data after 

describing the preparation and sampling of the matte and the 

borings. 

A proposal for cooperative analyses of a copper slag 

published in 1901 was followed by a report by Smith (1903) 

on the chemical analyses by 22 chemists and by W.F. Hillebrand of the U.S. Geological Survey, whose data were used 

as the standard by which all other data were judged. Hillebrand was also requested to review the data critically. Smith 

noted that another set of samples would be prepared and that 

applications would be welcomed, not only from those employed in the copper industry, but from all who were interested in the advance of accurate chemical analysis. 

Cement, a product essential to industrial development, was the subject of a continued paper, "The Chemical 

and Physical Examination of Portland Cement," published 

by Stillman (1893, 1894) in five parts. In spite of the title, 

the papers were principally devoted to physical testing while 

reporting the chemical analyses of 11 cements. Later papers 

in the series (Stillman, 1894) contained references on cement from 1870 to 1892, but the references were principally 

concerned with production and testing. 

1901 and Precursors of Geochemical Standards 

Activity in the analysis of materials for the cement 

industry increased after the start of the 20th century. As a 

result of a circular in April 1901, Richardson (1902) published a report of the Society of Chemical Industry's Subcommittee on Uniformity in Analysis of Materials for the 

Portland Cement Industry. The report described the analyses 

of two samples by 14 analysts. As he had for other studies, 

W.F. Hillebrand analyzed the two samples, described as 

"Sample No. 1. Limestone from Vulcanite, N.J. and 

Ahnville, Penn., mixed in proper proportions for making 

Portland cement; Sample No. 2. Finished Portland cement 

made from material No. 1." The data contained in the tabulations, analyses I and II (Richardson, 1902, p. 14), are 

analyses by Hillebrand entered in the laboratory recordbook 

on June 22, 1901. Hillebrand critically reviewed the methods used by the 14 analysts. Richardson concluded the report by a suggested method for analyzing limestone, raw 

mixture, and Portland cement. 

A dissent from proposed standard methods of analysis 

was soon published by Stanger and Blount (1902). In addition to critically reviewing the second series of analyses of 

cements, Hillebrand (1903 p. 1207) recommended that 

the committee see to the preparation of a large sample of 

limestone mixture, sufficiently large to last for many years, 

which could be issued to all applying for it. 

Blount (1904) published a method for the analysis of cement. Hillebrand (1905) discussed the condition of analytical chemistry. 

The central committee of the New York Section of the 

Society of Chemical Industry had dissolved and the Council 

of the American Chemical Society directed the appointment 

of a new committee to pursue the aims of the former committee of the Society of Chemical Industry. The new committee published (Hillebrand and others, 1904) a summary 

of past work and listed as its policy the accomplishment of 

six objectives. In addition to an objective to test the accuracy and suitability of various methods in conjunction with 

the National Bureau of Standards, the objectives pertinent to 

standard or reference samples were (p. 1653) 

4. To prepare samples of materials of different character 

whose exact composition shall have been determined by the most careful analyses of experts. 

5. To place such samples in the care of the National 

Bureau of Standards for preservation and distribution 

to persons desiring to test their methods of analysis 

or of manipulation, or to check the work of students 

or technical chemists employed in works. 

Two authors of this committee report were employed by the 

U.S. Geological Survey (USGS) and later by the NBS. 

H.N. Stokes worked for the USGS from 1889 to 1892, and 

from 1984 until he transferred to the NBS in 1903. W.F. 

Hillebrand joined the USGS in 1880 and founded its first 

chemical laboratory in Denver, Colo. He worked there and 

in Washington, D.C., until he transferred in 1908 to the 

NBS to become its chief chemist, a position he held until his 

death. 

Andrews (1908) published a short note related to objective 5. He reasoned that, just as the NBS furnished industry with official standards of weight and volume, so also it 

might furnish chemical standards for industries dependent 

on chemical processes. He suggested two groups of materials to be standardized: (1) substances to be used for standardizing volumetric solutions, the solutions themselves, or 

both, and (2) standardized samples of commercial materials 

by which a manufacturer could control his entire analytical 

process. 

A material that corresponds to our present concept of 

a reference sample is the argillaceous limestone for which 

cooperative analyses were reported by Hillebrand, Dudley, 

Richardson, and Stokes ( 1906). The sample of about 200 lb 

was prepared and furnished by the Northhampton Portland 

Cement Company of Stockerton, Pa.; 94 percent of the 

powder passed a 200-mesh sieve. Determinations of silica in 

six small lots taken at intervals from the top to the bottom 

of the barrel were used to demonstrate the homogeneity of 

the material. Although preparers of other samples mentioned earlier had assured analysts and readers about the care 

taken to secure uniformity of their samples, this appears to 

have been the first sample for which the sampling and the 

constituent determined as a test for homogeneity were mentioned. 

The averaged analysis for the argillaceous limestone 

in National Bureau of Standards (1910) Circular 25 (and 

supplements issued later) appears to be the average of data 

Introduction and Historical Review 5 
obtained by W.F. Hillebrand of the USGS and by C.E. 

Waters of the NBS that had been previously reported by 

Hillebrand and others (1906). NBS-2, described as Zinc 

Ore D, is listed in the circular as having a zinc content of 

31.43 percent, and a reference to the report by Stone and 

Waring (1907) is given. Stone and Waring indicate (p. 264) 

that a new sample was prepared by grinding together three 

ores ~imilar to those used earlier (i.e., samples A, B, and C, 

Hillebrand and others, 1904, p. 1648, 1649), and that this 

sample, D, was sent out for analysis. 

Parenthetically, there are items in NBS Circular 25 

and in a more recent source that are of historical interest in 

determining the beginning of the NBS standard sample program. NBS Circular 25 (p. 5) notes: "In 1905, the committees of the American Chemical Society upon uniformity of 

technical analysis, and upon zinc ore analysis, assigned 

their samples to the Bureau of Standards for distribution." In 

his official history of the National Bureau of Standards, 

Cochrane (1966, p. 93), when discussing the NBS standard 

sample program writes: "This began in 1905 when the 

American Foundrymen's Association turned over to the Bureau its work of preparing and distributing samples of standardized irons to its member industries." 

Further history of the standardized irons of the American Foundrymen's Association is given in the 1981-83 

edition of the NBS Standard Reference Materials Catalogue, 

in which the four-page Bureau Circular 11, dated February 1 , 1906, is reproduced. The circular briefly describes 

the four cast irons and the one steel sample and gives the 

methods of analysis that were used. 

Uniformity in Rock Analysis 

Hillebrand (1894) tried to achieve some measure of 

uniformity when he published a plea for greater completeness in rock analysis. He used as an example an earlier 

analysis of a rock whose constitutents summed to 99.58 

percent without determinations of Ti02, Cr20 3, MnO, SrO, 

BaO, H20-, P20 5 , S03, F, and Cl, when a later analysis 

that included the constituents omitted summed to 100.21 

percent. Washington (1903, p. 41) classified rock analyses 

as excellent, good, fair, poor, and bad, depending on their 

accuracy and completeness. One committee (Richardson, 

1902) had the word "uniformity" as part of its title. Ridsdale 

and Ridsdale (1919) discussed chemical standards in relation to the unification of analysis. 

The papers on completeness and on uniformity, and 

Washington's classification of rock analyses, did not produce a permanent effect. Larsen (1938) found that the chemical analyses of amphiboles and other silicates by presumably competent analysts showed a surprising lack of 

agreement. He advocated that petrologists check analyses 

by comparing the norm and the mode, a procedure by which 

any experienced petrographer can find large errors in the 

analysis. 

6 Reference Samples in Geology and Geochemistry 

The rock analyses of G-1 and W-1 in U.S. Geological Survey Bulletin 980 (Fairbairn and others, 1951) 

shocked the geologic community sufficiently that improvements in rock analysis could be noted in later reports on 

these and other rock standards. Determinations of trace elements, principally the domain of optical emission spectroscopists three decades ago, are now being made by a variety 

of physical and chemical techniques. Many trace element 

data still leave much to be desired, if one can judge the data 

by forming ratios of several pairs of elements. 

Plant Pest Control Regulations 

Plant pest control regulations have existed in the 

United States since the Plant Quarantine Act of 1912 and the 

Federal Plant Pest Act of 1957. Canada is said to have 

regulations similar to those of the United States, and other 

nations may have their own restrictions. Some States in the 

United States may also have local regulations. 

The plant pest control regulations of the U.S. Department of Agriculture apply to all naturally occurring samples, but not to synthetic samples. One scarcely, if ever, 

finds these regulations, or their foreign equivalents, mentioned in the literature on reference samples. The U.S. regulations apply both to samples obtained in the United States 

and to those that are imported. 

The regulations cover the importation of plants, 

rocks, soils, and perhaps laterites into the United States and 

the interstate shipment of these materials among the several 

States. The quarantine is intended to prevent the introduction of the Imported Fire Ant, Japanese Beetle, Gypsy 

Moth, Browntail Moth, Whitefringed Beetle, Witchweed, 

Golden Nemathode, Burrowing Nematode, and Soybean 

Cyst Nematode into areas currently uninfested. 

One may safely assume that the 12 soil samples in 

Bamhisel (1978) were collected in conformance with the 

regulations, as many collaborators were from State agricultural experimental stations. Two authors of the report 

(Bowman and others, 1979) on four Canadian soils were 

members of Agriculture Canada. The three soil samples of 

the six geochemical exploration samples discussed by 

Allcott and Lakin (1975) were collected by USGS geologists under the provisions of a formal agreement between the 

USGS and the U.S. Department of Agriculture. This agreement, renewed yearly, has been in effect for more than two 

decades. 

Rock samples are generally examined before entry 

into the United States is permitted. Thus, the bulk sample of 

the Icelandic basalt, now USGS-BIR-1, was held in quarantine for more than a week at Norfolk, Va., the port of 

entry, while the pieces of rock were inspected. 

For many soil samples mentioned above, one must 

assume that the shipment of the large sample and the distribution of smaller portions as reference samples were made 

in conformance with the plant pest control regulations of the 
U.S. Department of Agriculture (Flanagan, 1975, p. 699). 

Soil samples and the Department of Agriculture quarantine 

regulations were mentioned earlier (Flanagan, 1974, 

p. 1731). 

Sources of Information on Reference Samples 

The short list of samples available from the [National] 

Bureau of Standards (Hillebrand, 1909) appears to have 

been the first for samples of interest to earth scientists. 

Silicate rock standards were mentioned by Curtiss and others (1940), who gave the rock names of the 12 samples that 

were later known as Rock Standards-Radium Rock Samples in National Bureau of Standards Circular 552, 3d ed., 

(1959). 

Taylor and Kolbe ( 1964) published a short list of 

sources of standards useful to earth scientists, and three 

other lists (Flanagan and Gwyn, 1967; Flanagan, 1970, 

1974) soon followed. Hague and others (1965) listed 

sources of standard reference samples, but not all of the 61 

sources listed furnished such samples. The guide to U.S. 

reference materials by Cali and Plebanski ( 1978) does not 

mention sources of internationally recognized rock samples 

under the heading of minerals, ores, and rocks (p. 10). 

The most valuable source of information for those in 

geochemistry is the journal "Geostandards Newsletter," for 

which volume 1, number 1, appeared in January 1977. The 

contents of the journal span a wide range of interest, from 

data on reference samples to announcements of new samples. A recent paper in the journal by Jecko and others 

( 1980) gives the compositions of about 96 iron ore standards 

and related materials from 12 countries and from the European Coal and Steel Community (ECSC). A column on 

standards for microprobe work has been a feature of the 

journal for some time, and recent issues have featured a 

"GeostandaRef Comer," bibliography of papers.containing 

data on geochemical reference samples starting In 1979. 

A recent bibliography in "Atomic Spectroscopy" by 

Lawrence ( 1980) has a cross index under the heading 

"Geochemistry," with sections on minerals, ores, rocks, 

silicates, and others. One occasionally finds lists of standard 

reference samples such as that of Lontsikh and Parshin 

(1980). Sobomov (1977) has determined uranium, thorium, 

and potassium in 14 USSR (domestic) rocks, ores, and 

concentrates, 9 of which were listed by Lontsikh and 

Parshin (1980). 

The journal "X-Ray Spectrometry" started a section, 

"Calibration Standards," in 1977 (v. 6, no. 3, p. 171), and 

such sections were published occasionally until what appears to be the final column in 1979 (v. 8, no. 3, p. 140). 

These sections briefly discuss standards that are available 

from commercial and government sources. The volume, 

number, page, and year of the issue of the journal in which 

these calibration standards sources appeared are listed 

below. 

v. 6, no. 3, p. 171 (1977), Columbia Scientific Industries 1 

v. 6, no. 4, p. 218 (1977), Brammer Standard Company, Inc. which, in 

addition to its own standards, distributes samples from (1) Iron and Steel 

Institute of Japan, (2) Bureau of Analysed Samples, Ltd, (3) CTIF 

(Centre Technique des Industries de Ia Fonderie), (4) IRSID (lnstitut de 

Recherches de Ia Siderurgie), (5) BAM (Bundesanstalt fiir Materialpriifung), (6) British Non-Ferrous Metals Research Association, (7) Henry 

Wiggin & Co., Ltd. (England), (8) International Alloys Ltd. (England), 

(9) G.L. Willan Ltd. (England), (10) Zinc et Alliages (France), and 

(11) Alpha Resources, Inc. (see later section on "Coals, Coal Ash, and 

Cokes"). 

v. 7, no. 1, p. 44 (1978), BNF Metals Technology Centre (formerly British 

Non-Ferrous Metals Research Association) 

v. 7, no. 3, p. 174 (1978), MBH Analytical Ltd. 

v. 7, no. 2, p. 99 (1978), a reprinting of Abbey (1977a) 

v. 7, no. 4, p. 249 (1978), U.S. Department of Energy, New Brunswick 

Laboratory (see later section on "Counting Standards"). 

v. 8, no. 3, p. 140 (1979), Bureau of Analysed Samples, Ltd. (see later 

section on "Great Britain"). 

Another journal, "American Laboratory," started a 

column on reference materials in the June 1980 (v. 12, 

no. 6) issue. A companion journal, "International Laboratory," published by the same organization, has not contained a similar column on reference materials. 

"Pure and Applied Chemistry" occasionally publishes 

information on reference samples. Koch (1978) published a 

two-part paper on standard reference materials for trace 

analysis. He lists a number of ores and other reference 

materials in part 2, as well as the names and addresses of 

suppliers. Steinnes (1981) listed compositions he derived 

from the available data for the rocks described in USGS 

Professional Paper 840 (Flanagan, 1976b). Wainerdi (1979) 

published a similar report for Bowen's kale (Bowen, 1967). 

The International Organization for Standardization 

(ISO) published its first edition of the ISO Directory of 

Certified Reference Materials in 1982. The directory lists 

certified reference materials in 17 classes, of which the 

categories of (1) geology, (2) environmental, (3) glasses, 

ceramics, and refractories, and (4) biological, botanical, 

and foods may contain samples applicable to the general 

fields of geology and geochemistry. 

The ISO Directory mentions certified reference materials only in general terms and does not identify specific 

samples. The categories and general types of samples in 

table 1 are coded to the names and addresses of suppliers in 

table 2. Thus, the interested user must obtain a catalog or list 

of samples from a supplier before determining if the supplier 

has a specific sample. 

There are undoubtedly lists of reference samples that 

have not been published. One such list by John Winter 

(Freer Gallery of Art, Smithsonian Institution, Washington, 

DC, 20560) was titled "Sources of Reference Materials for 

Museum Laboratories" and was distributed at the 5th Triennial Meeting of the ICOM (International Council of Museums) Committee for Conservation, Zagreb, Yugoslavia, 

1978. Sources are identified for such materials as rocks, 

1

Company names and trade names are used for identification only and 

do not constitute endorsement by the U.S. Geological Survey. 

Introduction and Historical Review 7 
ores, minerals, metals and alloys, and glasses, and for 

standards for x-ray microanalysis, Munsell color, pigments, 

fibers, woods, and particles of known size. 

SAMPLES FOR GEOLOGY 

AND GEOCHEMISTRY 

Reference samples for determinations of elements in 

geologic samples represent a variety of materials. Many 

reference samples are recognized internationally, while others have been prepared as "in-house" standards for use with 

a limited distribution. Other samples were used in studies of 

the accuracy or precision of ore analysis. The samples differ 

widely in composition and in the purpose for which they 

were prepared. A convenient general classification for these 

materials is as follows: 

Artificial 

• Mixtures of chemicals as solutions or solids 

• Mixtures of natural materials 

• Glasses for major, minor, and trace elements 

• Samples made with other substrates 

Natural 

• Samples of economic interest 

• Samples of geologic and geochemical interest 

• Samples for geochemical exploration 

• Minerals for several purposes 

• Isotopic samples 

• Sediments, soils, laterites, and miscellaneous samples 

Artificial Samples 

Solutions 

Solutions of one or more chemicals, still needed for 

many methods, have been used to prepare standards for 

thin-film x-ray fluorescence analysis. Thus, Champion and 

others (1966) prepared a strontium standard of 250 f.Lg per 

gram by dissolving analytical reagent grade SrC03 in dilute 

HN03 and making to volume with water. They then used 

aliquots of the solution for the x-ray fluorescence determination of Sr in biological and geological samples, including 

G-1 and W-1. 

One commercial company, Columbia Scientific Industries (see "X-Ray Spectrometry," 1977, v. 6, no. 3, 

p. 171), micropipeites aliquots of solutions of one or more 

elements onto a cellulose fiber or a cellulose membrane 

filter and dries the solutions for use in thin-film x-ray work. 

The company also furnishes, either as dried solutions or as 

particulate deposits, standard reference strips for the analysis of air particulates. 

Solid Chemicals 

X-ray spectroscopists frequently use mixtures of pure 

chemicals as standards for determinations of major, minor, 

8 Reference Samples in Geology and Geochemistry 

and trace elements. Mixtures of solids have been used in 

optical emission spectroscopy. Bastron and others ( 1960) 

described the preparation of such standards for quantitative 

spectrochemical analysis, and Myers and others (1961) prepared similar samples for semiquantitative analysis. Both 

sets of standards for emission spectroscopy could be classified as mixtures of chemicals and natural materials. The 

major component of the two sets of standards is a feldspar 

selected for its high purity and for the absence of specific 

trace elements. Trace elements as pure oxides were then 

mixed with the feldspar. 

Knott, Mills, and Belcher (1978) prepared synthetic 

standards and listed the compositions of 3 base standards 

and of 10 iron ore calibration standards. They advocate the 

use of synthetic calibration standards for optical emission 

and x-ray fluorescence analysis. 

Mixtures of Natural Materials 

Mixtures have been used for various techniques, both 

as small portions for a specific purpose in a laboratory and 

as a large reference sample for wide distribution. A 50 

percent mixture of G-1 and W-1 was used by Rose, Adler, 

and Flanagan (1963) to furnish an additional calibration 

point for oxides for the x-ray fluorescence analysis of rocks. 

Because of the increase in the number of rock reference 

samples in the last two decades, a seemingly infinite number 

of mixtures in varying proportions can now be prepared by 

an analyst. 

One large Canadian sample, CCRMP-SY-3, is a 

mixture of natural materials. Faye and Sutamo (1976) note 

that a batch of syenite from the same source as SY -2 was 

ground autogenously with lumps of a concentrate containing 

uraninite, allanite, and betafite and that this material was 

coded as SY-3. 

The procedure of preparing a rock reference sample 

by adding concentrates of heavy minerals can be dangerous. 

Because of differences between the specific gravities of the 

rock (syenite, 2.6-2.7) and of the minerals (allanite, 3.0-

4.2; betafite, ~4; uraninite, massive, 6.4 and greater), the 

minerals may separate if the sample is stored in a laboratory 

subject to vibration. If an analyst does not thoroughly mix 

the contents of a bottle before sampling, heterogeneous data 

may be obtained. 

Data were reported by Lister and Gallagher (1970) for 

the first interlaboratory investigation of accuracy in ore 

analysis for which all but 2 of the 19 samples were mixtures 

of an ore and quartz. The samples analyzed for the second 

series reported by Lister ( 1977, 1978) were ores and concentrates. 

Glass Samples for Major and Minor Elements 

Because of the disturbingly large dispersion of data 

for G-1 and W-1 (Fairbairn and others, 1951), Fairbairn 

and Schairer (1952) prepared a glass whose composition 
was selected to approximate that of G-1. The amount (92 g) 

of the synthetic standard was limited, and analysts were 

selected because of the nearness of their determinations for 

G-1 and W-1 to the mean values. The precision of the 

determinations for this silicate mixture, called a haplogranite by Fairbairn and Schairer and., informally, "happy granite" by those associated with it, was scarcely different from 

the precision obtained by the same analysts for G-1. The 

supply of the glass was soon exhausted. 

Heidel ( 1971) used a glass standard in the electron 

probe analysis of lunar glass spheres. Smellie (1972) prepared nine glasses as electron probe standards for which he 

varied the percentage of Si02, Ti02, Al20 3, Fe20 3, MgO, 

MnO, and CaO. Na20 was not included as a constituent 

because of its erratic behavior under electron bombardment, 

and K20 was omitted because glasses containing 8 to 10 

percent K20 showed unacceptable heterogeneity. Smellie 

and others (1978) prepared six glasses for microprobe use. 

The basic flux consisted of Si02, Al20 3, and CaO, and the 

sums of these oxides amounted to 85, 95, and 99 percent for 

two sets of three samples each. They added approximately 

15, 5, and 1 percent of U 30 8 to one set of three samples and 

similar amounts of Th02 to the other three samples. 

The Society of Glass Technology ( 1980) listed the 

compositions of six standard glasses and of five glass sands. 

Glass Samples for Trace Elements 

Glasses were prepared for trace element analysis and 

for determinations of rare earths. Both the National Bureau 

of Standards (NBS) and the U.S. Geological Survey 

(USGS) had melts of a glass prepared by Corning Glass 

Works, and amounts of a large number of trace elements 

were added to result in samples with trace elements present 

at four concentration levels. 

The processing of the NBS samples from 100-

kilogram batches to 1- or 3-millimeter-thick slices of the 

glass canes has been described by Barnes and others ( 1973). 

They also present data obtained by isotope dilution mass 

spectrometry for lead, uranium, thorium, and thallium and 

note that some radial heterogeneity was observed in the 

wafers. A single whole wafer is therefore always used as the 

standard sample, and no subsampling of a wafer is permitted. 

The samples for the USGS were prepared similarly, 

but the glass canes furnished to the USGS were broken and 

powdered. Preliminary data on the USGS glass samples 

were reported by Myers and others (1970), and a compilation of data was published (Myers and others, 1976). 

A set of four glass standards for determinations of rare 

earths was prepared by Drake and Weil (1972). These samples, intended for microprobe work, were prepared in small 

quantities. The rare earths are present at about the 4 percent 

level, a factor of almost 100 times greater than the highest 

level in the NBS and USGS samples. 

Roche and Govindaraju (1973) reported data for two 

experimental glasses, VS-1 and VS-2, prepared in small 

amounts and for a larger sample, ANRT-VS-N. The first 

experimental glasses were prepared as lots of about 300 gm, 

whereas VS-N was prepared as a lot of about 10 kg. Both 

VS-2 and VS-N were made from a silicoaluminate glass to 

approximate the major composition of a phonolite. For the 

three samples, amounts of trace elements were added to the 

glasses to obtain a final concentration of 1,000 ppm of the 

elements expressed as the oxides, with 28 elements being 

added to the melt for VS-N. Data for nine other elements 

introduced into VS-N as impurities were also reported. Because of the phonolitic composition of the glass, VS-N 

might be considered a standard for major, minor, and trace 

elements, but its use for determinations of the major and 

minor oxides might soon deplete the amount of sample 

prepared. 

Dust and Particulate Samples 

Hashimoto and others (1976) prepared a homogeneous dust sample, AS-1, for comparisons of data on 

atmospheric dust samples. The airborne particulate matter 

was collected on a filter cloth attached to an air inlet of an 

air conditioning unit on an office building 50 m high. While 

those in geology may think of dust as finely powdered rock, 

the approximate average contents of several elements in the 

dust indicate that the sampling location may have been 

downwind from one or more commercial activities. 

Jecko and Ridsdale (1978) list certified values for two 

steel furnace dusts that were prepared to assist in pollution 

control of dusts discharged into the atmosphere by the iron 

and steel industries. Steger and others ( 1981) prepared a 

nonferrous reference dust, PD-1, from a zinc-copper 

smelter in Manitoba, Canada. The 200-gram units of the 

sample were heat-sealed in polyester-aluminum foilpolyethylene laminated pouches to prevent possible oxidation of the sulfide and metallic components of the sample 

while the portions were stored for future distribution. Recommended values for Pb (2. 75 percent), As (0. 77 percent), 

and Hg (389 tJ.g/g) were assigned. 

Dust samples are also known as particulate matter. 

NBS SRM-1648, Urban Particulate Matter, is a sample 

collected in St. Louis, Mo., in a bag-house especially designed for this purpose. Certified values are given for AI, 

Fe, K, Pb, Na, and Zn in percent, and for As, Cd, Cr, Cu, 

Ni, Se, U, and V in ppm. Values are also listed for 22 

major, minor, and trace constituents for which there were 

insufficient data for certification. 

Another urban dust, NBS SRM-1649, was collected 

in the Washington, D.C., area and is certified for five polycyclic aromatic hydrocarbons. Inorganic data include uncertified values for 5 elements present as minors and for 21 

elements present as traces. 

Samples for Geology and Geochemistry 9 
Gelatin Samples 

Anderson and others (1972, 1976) made reference 

materials with gelatin as the matrix. They first made a series 

of three samples with mercury at the 1.3, 0.12, and 0.02 

ppm levels. They note that the mercury contents remained 

constant for over a year and that gelatin of photographic 

quality, stored at room temperature and low relative humid-

-ity, remains stable for 10 years or more. They also made a 

gelatin base standard containing 25 trace elements ranging 

in concentration from 27 to 62 jJ.g/g, and this was analyzed 

by 11 laboratories. A summary of the test data for this 

sample, TEG-50A, is given in table 1 of Anderson and 

others (1976). The company, Eastman Kodak, has since 

issued two other gelatin multicomponent trace element reference materials, TEG-50--B, with data for 20 elements, 

and TEG-50--C, with data for 22 elements. 

Implantation, Dip, and Urea Samples 

Standards of these types were prepared by Gries and 

Norval (1975). Implantation standards are made by atomizing and ionizing an element and then accelerating the ions 

so that they penetrate a matrix. Such standards are limited 

to trace elements whose mass numbers are greater than those 

of the matrix element. 

Dip standards, used for confirmation of the implantation standards, are made by dipping aluminum foil in an 

aqueous solution of thallium sulfate. Urea standards are 

made by dissolving thallium sulfate in melted (140°C) urea. 

Diluted standards are made by melting and mixing known 

quantities of a master standard and pure urea. 

Bellon and others ( 1981) implanted 38 Ar ions in an 

aluminum foil target for use in the determination of radiogenic 40 Ar in rocks and minerals. Matus and others ( 1981) 

used ion implantation to make low concentration standards 

for use in spark source mass spectrometry. 

Wu and others (1982) used neutron activation analysis 

to measure the number of arsenic atoms per square centimeter that were implanted in silicon. Sun and others (1982) 

studied the implantation of phosphorus in silicon. They used 

neutron activation analysis to measure the phosphorus, and 

present two curves to show that the number of phosphorus 

atoms per square centimeter decreases with depth of penetration from 1,000 to 4,000A. 

Resin and Polymer Samples 

Kolomi'tsev and others (1974) prepared standards for 

neutron activation analysis with phenol-formaldehyde resin 

as the substrate. The samples were prepared as pellets about 

5 mm in diameter and 1 to 2 mm thick; the pellets weigh 

about 5 mg. The authors note that the technique is practically universal for all elements. Standards were prepared as 

single elements or as mixtures such as AI+ Ni + Zn +In or 

1 0 Reference Samples in Geology and Geochemistry 

Co+Sb+ Ag. These preparations are apparently unaffected 

by exposures to 1019 to 1022 n·cm- 2• 

Kayasth and others ( 1980) made standards for activation analysis by absorbing known amounts of ions on ionexchange resins. Feng and others (1983) reported data for 

rare-earth elements in reference samples obtained by x-ray 

fluorescence analysis after concentration of the elements on 

ion-exchange resin membranes. 

Rakovskii and others ( 1980) prepared irradiation 

standards using 3(5)-methylpyrazol that had been studied 

by Myasoedova and others (1976). The reagent, which 

forms complexes with many transition elements, undergoes 

a condensation reaction with formaldehyde and resorcinol in 

the presence of ammonia to form a solid polymer. Single 

elements or mixtures may be used. The standards are described as stable in the presence of the irradiation in a 

reactor with a wall temperature of up to 200°C. 

Lu and Cao ( 1982) describe their preparation of standards made from phenol formaldehyde resin (PFR). Three 

sets of such standards for (1) Fe, Co, Cr, Zn, and Ag, 

(2) Se, Sb, and Sc, and (3) Cu, W, Mo, Au, As, and Na 

were prepared for irradiation in a reactor with a flux of 

7X 1015 n·cm- 2·s- 1 for 10 to 20 hr. 

Silica Gel Samples 

The technique of coprecipitating silica gel has been 

used for a quarter of a century for preparing materials for 

hydrothermal experiments. Roy (1956) found that coprecipitating gels is an effective method for preparing homogeneous mixtures. Hamilton and Mackenzie (1960) used the 

technique to prepare homogeneous materials of the required 

compositions for their system, NaA1Si04-KA1Si04-Si02 . 

Luth and Ingamells ( 1965) used a volumetric combination 

of carefully standardized aqueous solutions of metal nitrates 

and hydroxides, and a soda- or ammonia-stabilized silica sol 

of high purity. Hamilton and Henderson ( 1968) prepared 

silicate compositions by a gelling technique and included an 

appendix listing recommended starting chemicals and their 

sources. 

Date (1978) prepared trace element reference materials by a coprecipitated gel technique. The multielement 

calibration standards were intended for use in the analysis of 

geologic materials by direct-reading emission spectrography. Date presented data for a number of elements and 

oxides in 10 rock reference samples. Breitwieser and Lieser 

( 1978) prepared standards of trace elements in silica gel for 

the determinations of elements in rocks and minerals by 

x-ray fluorescence spectroscopy. 

Sludge Ash Sample 

A sample of sludge ash was prepared by Knechtel and 

Fraser ( 1980) to serve as a reference sample for studies of 

the incineration of sewage sludge to reduce sludge volume. 
The chemical composition of the ash reflects the industrial 

nature of the city (Hamilton, Ontario) from whose municipal incinerator the sludge ash was obtained. Flegal (1980) 

has discussed the need for reference samples for environmental research and monitoring programs and gives data for 

nine trace elements in a homogenized digestor sludge sample obtained by two laboratories. 

Waste Incineration Ash 

Schmitt and others ( 1980) describe the preparation of 

and table data for a small reference sample ( 10 kg) of a 

waste incineration ash. The sample was prepared because 

(1) there was an unlimited amount of material available, 

(2) the material, after the burning process, was fairly homogeneous, and (3) the composition proved favorable for instrumental trace element analysis. 

Another batch of 500 kg of the ash was collected, and 

B .F. Schmitt (written commun., 1983) notes that the sample 

was sent to the lspra Research Center in July 1979 for 

processing. After the material was sieved, dried, powdered, 

homogenized, and bottled, an analytical program for the 

sample was started under the aegis of BCR (Community 

Bureau of Reference). As the deadline for analytical data 

has expired, it is anticipated that the reference sample will 

be available not earlier than the second half of 1984. 

General Synthetic Samples 

Many investigators using instrumental neutron activation analysis make irradiation standards to fit their specific 

problems. Among others, Mitchell and others (1977) added 

solutions of isotopically labeled trace elements to hydrated 

silica gel and dried these gels for 1 hr at 850°C. Leypunskaya and others (1975) prepared synthetic multielement 

standards to approximate the compositions of three Russian 

samples, trap rock ST -1 , gabbro-diorite SGD-1, and albitized granite SG-1, and of two USGS samples, BCR-1 

and GSP-1. Eddy and others ( 1980) prepared synthetic 

standards from solutions of pure chemicals by weighing 

mercury, scandium, and barium compounds as individual 

masses. They did not apply heat during the preparation of a 

solution containing arsenic, antimony, selenium, tellurium, 

and osmium. 

Natural Samples of Economic Interest 

The many reference samples of materials of economic 

interest generally reflect the interests of the preparer, of an 

industry, of a nation, or of some combination of these. 

Examples of institutes furnishing such samples are given for 

several countries. There are also commercial companies in 

several countries that prepare and sell reference samples. 

Organizations in several countries have samples of both 

economic and geochemical interest. 

Many powdered samples were prepared for other purposes, such as tests of the accuracy and precision of analysis, but were promoted to the status of standards, often by 

users of the samples. Such promotions are not entirely unjustified because of the data collected during the test. An 

early example of a promotion is the Zinc Ore D of Stone and 

Waring ( 1907), which was assigned the standard sample 

number NBS-2. 

United States 

The National Bureau of Standards has furnished 

standards for industry since the announcement by Hillebrand ( 1909) of the availability of the argillaceous limestone 

(NBS-I) and Zinc Ore D. In contrast to this humble beginning, a recent ( 1979-80) edition of the NBS Standard Reference Materials Catalog of 102 pages lists a seemingly infinite number of reference samples. 

The NBS also issued rocks for more than a decade, 

under the title "Rock Standards," with the subtitle "Radium 

Rock Standards." Twelve rock samples are listed in NBS 

Circular 552 (3d ed., April 8, 1959, p. 15) with the rock 

names and average radium contents. These rocks, first considered standards in 1951 , were not listed as available in 

NBS Miscellaneous Publication 241 issued March 12, 1962. 

The certificate for the former NBS 4984, Triassic Diabase, 

indicates that the sample was obtained from the Centreville 

Quarry, the source of USGS-W-I and W-2. 

An industry standard sample of metallurgical chrome 

ore was described by Hartford (1953). The report notes that 

portions would be made available to industrial laboratories 

needing such a standard. 

Great Britian 

The Bureau of Analysed Samples, Ltd. (BAS), was 

formed in 1935 to assume the task of preparing British 

Chemical Standards (BCS), a job that had been performed 

by Ridsdale & Co. since the first samples were prepared by 

C.H. Ridsdale and N.D. Ridsdale in 1916. The BAS 

devotes most of its efforts to spectrographic standards for 

cast irons and ferrous and nonferrous alloys. It also furnishes about 30 ores, fluxes, sinters, slags, and ceramic 

materials and several Euro-Standards of iron ores (Jecko, 

Pohl, and Ridsdale, 1977). Data have been published (Jecko 

and Ridsdale, 1978) for two Euro-Standards of steel furnace 

dusts. Croudace (1981) has determined the rare earth and 

other trace element contents of BCS soda and potash 

feldspar samples. Croudace and others (1982) report data 

obtained by neutron activation analysis for these two samples plus samples of bauxite (BCS 295), firebrick (EuroStandard 776-1), magnesite (BCS 389), dolomite (BCS 

368), and limestone (BCS 393). 

Samples for Geology and Geochemistry 11 
France 

Certified bulk compositions of 13 IRSID (lnstitut de 

Recherches de la Siderurgie) reference samples have been 

published (Jecko, 1977). The group consists of eight iron 

ores, a laterite, two iron ore sinters, a calcite, and a 

dolomite. Bourdieu and others (1970) and Jecko and Matraski (1973) discuss IRSID's nonmetallic samples. 

Jecko, Pohl, and Ridsdale (1977) list the compositions of six Euro iron ore standards and the addresses of the 

suppliers from whom samples can be obtained. Jecko, Ravaine, and Wittman (1980) discuss analytical methods used 

for IRSID's iron ores and table the compositions of 83 iron 

ore standards from the European Community, Germany, 

France, Japan, South Africa, Australia, Canada, Sweden, 

The United States, Romania, Poland, Czechoslovakia, and 

the U.S.S.R. 

The Federation Europeenne des Fabricants de 

Produits Refractaires (PRE) was mentioned by Neider 

(1975, p. 169) as one of the European organizations with 

which the Bundesanstalt fiir Materialpriifung (BAM) cooperates. The PRE furnishes several samples that are of 

economic and geochemical interest. The samples include 

clays, several chamottes (refractory clays), a calcined clay 

shale, and a bauxite. Palmer and others (1983) used x-ray 

fluorescence spectrometry to determine 20 trace elements in 

a PRE clay, two chamottes, the calcined clay shale, and the 

bauxite. Other samples of minor geochemical interest are 

available from the PRE. 

Germany 

Neider (1975) discussed the general scope of reference materials programs in the Federal Republic of Germany (FRG). Although the Bundesanstalt fiir Materialpriifung (BAM) and the Physikalisch-Technisches 

Bundesanstalt (PTB) have leading roles in the production, 

certification, and distribution of reference samples, there are 

commercial firms and private institutes in the FRG that 

produce reference samples. 

Pohl and Oberhauser ( 1978) of BAM list certified 

values for six iron ores, one iron ore sinter, and a manganese 

ore, and they include a reproduction of a certificate of analysis. Although two samples of slag were listed in its recent 

catalog, the major emphasis of BAM is on reference samples of cast irons, steels, and special alloys that are intended 

as analytical control samples. 

Canada 

Canadian activities are devoted largely to samples of 

economic interest. The first two samples, a syenite rock, 

SY-1, and a sulfide ore, SU-1, were distributed by the 

Canadian Association for Applied Spectroscopy (CAAS), 

and an initial report with data was published (Canadian 

12 Reference Samples in Geology and Geochemistry 

Association for Applied Spectroscopy, 1961). Reports containing accumulated data were published by Webber (1965) 

and by Sine and others (1969). Russell (1984) published a 

list of standards for use in the analysis of marine materials. 

The name of the CAAS was changed in June 1967 to 

the Spectroscopy Society of Canada (SSC), whose Standards Committee continued the work on reference samples. 

By mutual consent, the functions of the Standards Committee were transferred to the Mines Branch, Department of 

Energy, Mines, and Resources, in 1971 , and the Canadian 

Certified Reference Materials Project (CCRMP) assumed 

and expanded the previous program. Faye and Sutamo 

(1976, 1977) described CCRMP samples available for the 

earth sciences. A later list of CCRMP samples available was 

compiled by Steger (1980). Steger (1981) described the 

amended procedure for certification of CCRMP samples and 

summarized certified values for 30 elements in CCRMP 

samples of economic interest. 

South Africa 

The National Institute for Metallurgy (NIM) has published a number of in-house reports on its reference samples 

since the mid-1960's. In addition to reports on NIMROC 

samples (Steele and others, 1978; Steele and Hansen, 

1979), NIM's efforts have been devoted to samples associated with the growing mineral industry of South Africa. 

Thus, there are reports on two ferrochrome slags, a series of 

fluorspar samples, a precious metal ore (PT0-1 , from the 

Merensky Reef), a series of several minerals or ores containing rare earths, a magnetite and a hematite ore, two samples 

of chromium ore (Stoch and others, 1979), and three ferromanganese slags. Samples containing uranium were analyzed (Hansen and others, 1982) for use as standards by the 

South African uranium industry. NIM samples are available 

through the South African Bureau of Standards. The name 

of NIM was changed to the Council for Mineral Technology, and the organization and its reports are now known by 

the acronym MINTEK. 

CMEA Countries 

Reference samples of both economic and geologic 

interest that have been prepared as a cooperative effort by 

the member countries (Czechoslovakia, German Democratic Republic, Poland, the Soviet Union, Bulgaria, and 

Hungary) of the Council for Mutual Economic Assistance 

(CMEA) were listed by Valcha (1977), who also listed 

samples being prepared, or planned. Ostroumov ( 1979) 

gave the compositions of 18 reference samples prepared in 

five CMEA countries. 

Czechoslovakia 

Dempir (1978) listed several reference samples of 

rocks and ores being prepared by the Institute of Mineral 
Raw Materials, Kutna Hora, and gave estimates of the compositions of a granite, a gabbro, and a serpentinite. Dempir 

and Valcha (1982) discussed a standard reference material 

of fluorite, FM. 

Valcha (1979) briefly described the geology and mineralogy of a magnesite, MK, from Kosice, Czechoslovakia. 

After briefly describing the preparation of the material as a 

standard, he gives tables of attested or recommended values 

for several oxides and elements and a table of averages for 

28 elements. 

German Democratic Republic 

The 1980 catalog of the Amt fiir Standarisierung 

Messwesen und Warenpriifung (ASMW) lists the three minerals, galena GF-1, sphalerite SF-1, and pyrite PS-1, for 

which data were reported by Schron and others (1975). In 

addition to the original rocks (Grassmann, 1972; Schindler, 

1972) prepared by the Zentrales Geologisches Institut 

(ZGI), the catalog also lists ZGI samples anhydrite AN, 

feldspar sand FK, greisen GnA, and serpentinite SW, for 

which usable values were given by Abbey (1980). 

The ASMW c~n also furnish two chrome ores (CrErz 1 and 2), two manganese ores (Mn-Erz 1 and 2), a tin 

ore (Sn-ERZ 1), a fluorspar, a sinter, and three slags. 

Poland 

Plebanski (1975) discussed the national standard reference material program of Poland. He notes in his table 2 

that 36 standard reference materials of glass and ceramics 

were made up to 1972 and that 66 such samples, of which 

9 were to be under the control of PKNMiJ (Polish Committee for Standardization, Measures, and Quality Control), 

were planned for the period 197 5-80. He also lists 16 samples of ores and minerals that were made up to 1972, of 

which 2 were under the control of PKNMiJ, and a total of 

49 such samples, with 29 under the control of PKNMiJ, 

planned for the period, 1975-80. 

Plebanski also lists the types of samples and the 

sources from which information may be obtained, as follows: 

• Ferrous metallurgy materials and ores: 

Instytut Metalurgii Zelaza 

ul. Karola Miarki 12 

Gliwice, Poland 

• Nonferrous metallurgy materials and ores: 

Instytut Metali Niezelaznych 

ul. Sobieskiego 11 

Gliwice, Poland 

• Rocks: 

Instytut Geologiczny 

ul. Rakowiecka 4 

Warszawa, Poland 

Valcha ( 1977, table 1) listed three Polish rock salt 

samples (S-1, S-2, and S-3) and a zinc ore (ZnU) that were 

mentioned in Schindler and Scheutzow (1975, p. 130). 

Valcha (1977, table 3) also listed a sample of native sulfur 

planned by Poland. Jecko, Ravaine, and Wittman (1980) 

gave the composition of a Polish iron ore, sample 2.8/1. 

Plebanski (1979) edited a 57-page catalog (WZORMAT's Guide-Book) with the title "Physiochemical Certified Reference Materials." The text was consulted in the 

hope that geostandards for use by physiochemical measurement techniques might be mentioned, but the standards are 

for density, viscosity, relative humidity, pH, electrolytic 

conductance, ion activity, refractive index, optical rotation, 

spectrophotometry, atomic absorption, and pesticides. 

U.S.S.R. 

Gorozhanina and others (1971) of the All-Union Scientific Research Institute of Metrology, Sverdlovsk Branch, 

All-Union Scientific Research Center of the State Service 

for Standard Samples, prepared a list of standard samples 

issued in the U.S.S.R. The report in Russian, published in 

1969 by the Committee of Standards, Measures, and Measuring Instruments of the Soviet of Ministers of the 

U.S.S.R., was translated by M.C. Selby (National Bureau 

of Standards, Boulder, CO 80302), and the translation was 

published as NBS Special Publication 260-30 in 1971. 

Although most of the list is concerned with metals and 

alloys, there are many samples of interest to geochemists. 

For example, we find on page 19 of NBS Special Publication 260-30 a section "SS [Standard Sample] for the Determination of the Absolute Age of Geological Formations." In 

table 9 (p. 20), we find SS 2165, amazonite-microcline, with 

certified values for Rb of "about 0.11 percent" and for 

radiogenic Sr of "about 1. 75 JJ..g/g." Another amazonitemicrocline, SS 3/66, has a certified Rb content of"about 0.8 

percent" and a certified radiogenic Sr content of "about 4.0 

J.J..glg." A third sample for age determinations, SS 1165, a 

felsitic quartzitic liparitic porphyry, has a certified potash 

[K20?] content of 4.013 ± 0.38 percent and a certified radiogenic Ar content of 79.27 ± 1.35 ng/g. 

Among other samples of possible interest are 10 slags 

(table 20), 12 ore [?] concentrates (table 21), and 21 ores 

(table 22). Data for "general iron in conversion to iron 

oxide" [?], CaO, MgO, Si02 , MnO, At"20 3, and P20 5 are 

given in table 37 for a set of seven slags, SS 81 through SS 

87. 

Data for Si02, CaO, MgO, phosphorus [P or P20 5 ?], 

and sulfur are given for a dolomite, SS 60-B, and a limestone, SS 59-V. No data are given for another limestone, SS 

59-g. Data for three refractories, SS 56-b (Dinas brick), SS 

239 (chrome-magnesite), and SS 55a chamotte (refractory 

clay) are found in table 24. 

Four rock samples are mentioned in a short paragraph 

in Gorozhanina and others (1971, p. 53). Three rocks, diabase DIM-1, miaskite MIV-1, and peridotite (no sample 

designation), are also listed in Egranova and others ( 1981). 

Samples for Geology and Geochemistry 13 
Egranova and others ( 1981) have a sample designation, 

PIM-1, for the peridotite and, in addition, list IGEM (Institute of the Geology, Geochemistry, Petrology, and Mineralogy of Ore Deposits, Academy of Sciences of the U.S.S.R., 

Moscow) numbers for the four samples. One sample, 

"faceted diorite 'Rizhik' ," mentioned in Gorozhanina and 

others (1971) may be the same as "granodiorite 'Ryzhik"' in 

Egranova and others ( 1981) as the compositions of the two 

rocks are very similar. 

Lontsikh and Parshin ( 1980) listed reference samples 

prepared in their laboratory during the period 1968-78. Included in the list are 29 samples of various ores or concentrates and 3 rocks from the Institute of Geochemistry, 

Irkutsk (IGI). Tauson and others (1976) published estimates 

of the constituents normally determined in a rock analysis 

and of about 40 trace elements for the 3 rocks, ST-1A 

(trap), SGD-lA (essexite gabbro), and SG-1A (albitized 

granite), that were prepared as U.S.S.R. national standard 

samples. Lontsikh and others (1980) summarized the trace 

element data for the Irkutsk samples, including data reported by Abbey and Govindaraju (1978). 

There are also in the list two bauxites, three soils, and 

three samples prefixed by SDO which are described as clay 

or silt. The first of these three samples has an asterisk 

following "clay" in the listing "SD0-1, terrigenous clay," 

and the footnote for the table· begins, "The reference samples of bottoms (SDO)***." Because the term "bottoms" is 

not definitive, the original paper by Lontsikh and Parshin 

(1979, "Zhurnal Analiticheskoi Khimii," v. 34, no. 12, 

p. 2446-2452) was consulted. The final word in the description for SD0-1, "Glina," is translated "clay;" for SD0-2 

and SD0-3, the final transliterated word, "il," may have the 

meanings of silt, mud, ooze, or sediment. 

The footnote in the Russian paper may be translated 

"standard specimens of bottom sediments" and, in view of 

the four alternate translations of "il," the samples may be 

sediments from lakes, rivers, or oceans. Berkovits and 

Lukashin ( 1984) published data for three marine sediment 

samples, SD0-1, SD0-2, SD0-3, without U.S.S.R. state 

register (SR) numbers. Sample locations are as follows: 

SD0-1, eastern Pacific Ocean; SD0-2, central Pacific near 

Hawaii; and SD0-3, Red Sea. 

Egranova and others ( 1981), in their table 1, 

"Composition of Standard Samples," list four samples that 

are not listed in Lontsikh and Parshin (1980). These samples, RUS-1 through RUS-4, are apparently ore samples. 

Rather than the compositions indicated by the title of the 

table, 11 trace elements usually considered heavy metals are 

listed as certified components, without data. 

Egranova and others ( 1981) also list certified components, mainly trace elements without data, for four rocks, 

Miaskite MIV-1, Peridotite PIM-1, Diabase DIM-1, and 

"Ryzhik" granodiorite, that are identified by IGEM numbers 

rather than the usual U.S.S.R. State Register numbers for 

standards. Khitrov (1984) tabled certified values for major 

14 Reference Samples in Geology and Geochemistry 

and minor oxides and for 23 trace elements in samples of 

ultrabasic, basic, acidic, and alkalic rocks. 

Ginzburg and others (1983) discussed the idea of creating a state service for standard mineralogical samples. 

They suggest three classes of samples: diagnostic samples, 

samples for mineral properties, and samples for phase composition. 

Austria 

Suschny and Richman (1975) describe the analytical 

quality control program of the International Atomic Energy 

Agency (IAEA) in Vienna. They list in their table 3 (p. 94) 

the U30 8 contents and sample numbers of six uranium ores: 

torbernite (S-1 and S-2), carnotite (S-3), uraninite (S-4), 

and pitchblende (S-12 and S-13). One still finds determinations of the uranium contents of these ores, such as the data 

reported by Kuleff (1979), even though no stock of most 

samples remains. 

In addition to the ores, two marine sediments 

(SD-B-1 and SD-B-2) and a lake sediment (SL-1) are 

listed. A report on Soil-5, composed of the top 20 em of soil 

collected at the Agricultural Experimental Station, La 

Molina, Lima, Peru, was published by Dybczynski and 

others (1979). One might assume that the NBS soil, SRM4355, mentioned later may be the same as IAEA-soil-5, as 

they were collected at the same location. 

A comparison of the determinations of uranium, thorium, and potassium in three sedimentary rocks (two shales 

and a limestone) was published by Heinonen and others 

(1973) as an IAEA report. Suschny and Richman (1975) 

also list five plant materials that may interest geobotanists. 

Four water samples for isotopic work discussed elsewhere, 

V-SMOW (Vienna SMOW), SLAP, NBS-1, and NBSlA, are also included in Suschny and Richman (1975). 

Recent IAEA lists (IAEA, 1983, 1984) no longer 

contain the six uranium ores discussed above, and the two 

older marine sediments, SD-B-1 and SD-B-2, are now 

listed as out of stock. However, four phosphate samples for 

uranium, Soil-6 for 90Sr, 137Cs, 54Mn, and 239Pu, Soil-7 for 

multielement trace analysis, and three new marine sediments, SD-N-111, SD-N-1/2, and SD-N-2, are expected 

to be available in 1984. 

In place of the depleted uranium ore samples (S-1 

through S-6) there are now four pitchblendes (S-7, -8,-12, 

and -13), and three thorium ores (S-14, -15, and -16) that 

may be available in late 1983 either as reference materials 

or as certified reference materials. A feldspar, IAEA-F-1 , 

is a reference material for uranium and potassium. Belyaev 

and Sobornov ( 1981) reported determinations of uranium, 

thorium, and potassium in a number of reference samples, 

including IAEA-F-1. 

BCR (Community Bureau of Reference, Brussels) 

In addition to the four cokes, the six concentrates 

(three zinc, two lead, and one tin), the copper ore mentioned 
in Colombo and Rossi (1978), and the Moroccan phosphate 

(BCR-32) mentioned in the paper by Serrini (1981), BCR 

has reference samples for oxygen in nonferrous metals and 

alloys. 

BCR is preparing a coal for ash, sulfur, volatile constituents, and specific heat. Three samples of plants and one 

of milk powder are intended for determinations of Cd, Cu, 

F, Hg, Mn, Pb, and Zn. Schramel and Xu (1982) determined beryllium in three reference samples by ICPS (inductively coupled plasma spectrometry); one sample was a 

BCR plant sample, BCR-61, Riparioides. 

In addition to three zinc concentrates for 8 elements, 

two lead concentrates for 10 elements, six zinc concentrates 

(BCR-26 through BCR-31) for their zinc contents, and a 

manganese ore for its Mn content, samples of lead from 

three sources are being analyzed for 10 trace elements, and 

copper from three sources is being analyzed for Au and Ag. 

Other samples such as superphosphate and glasses are being 

analyzed for major and minor constituents. Bastin and 

others (1981 , 1982, 1983) described the BCR certification 

process for the zinc concentrates, BCR-26 through BCR31 , in a three-part paper. 

BCR also has a fly ash sample. Griepink and others 

( 1983) described the certification of a fly ash resulting from 

the combustion of a pulverized coal. Although the specific 

reference sample (BCR-38) is not mentioned in the text of 

Griepink and others (1983), one may safely assume that the 

sample is BCR-38 because the certified values in table 6 of 

the text agree exactly with those in an addendum to a catalog 

( 1982) of BCR-certified materials. 

Brazil 

Rasberry ( 1981) reports in a column on reference 

materials that, in addition to 18 steel and bronze alloys, the 

Instituto de Pesquisas Tecnol6gicas do Estado de Sao Paulo 

(IPT) has available 4 iron ores, 4 argillaceous clays, a phosphate, and a limestone, for each of which the particle size 

is less than 0.074 mm (200 mesh). Information on these 

samples of economic or geochemical interest may be obtained from the Chief of Analytical Standards, IPT, Caixa 

Postal 7141, 01000 Sao Paulo--SP-Brazil. IPT added a 

burnt refractory, IPT -51, a manganese ore, IPT -52, and a 

potash feldspar, IPT-53, in 1984. 

Japan 

The Iron and Steel Institute of Japan (ISIJ) is reported 

in "X-Ray Spectrometry" (1977, v. 6, no. 4, p. 218) as 

having two fluorspar standards, two ferroalloys, and eight 

ores. Jecko and others (1980) list the chemical compositions 

of 13 Japanese iron ore standards, but they do not give the 

source from which the samples may be obtained. Terashima 

( 1979) reported determinations of carbon and sulfur in four 

iron ore samples and one chromium ore from the ISIJ, and 

Feret (1982) reported data for six iron ore standards from the 

ISIJ. 

People's Republic of China 

The People's Republic of China (PRC) has started a 

program of geochemical reference samples. Yang and Liu 

(1983) reported methods and data for seven ore samples for 

uranium, thorium, and radium. The samples were prepared 

by the Bureau of Uranium Geology, Beijing. 

A set of eight stream sediments for use in geochemical 

prospecting was prepared under the general direction of the 

Research Group of Geochemical Reference Standards of the 

Ministry of Geology and Mineral Resources, Beijing. Data 

for the major and minor oxides and for trace elements for the 

samples, numbered GSD-1 through GSD-8, appear as 

"usable" values in table 40A of Abbey ( 1983). There are 

uncertain values or magnitudes for 22 trace elements that 

were not published. Included among the 22 elements are 

several rare earths. Zhang and others (1982) and Yuan and 

Chen ( 1982) reported determinations of rare earths and other 

elements using neutron activitation analysis. 

C.H. Tong (Chengdu College of Geology, Chengdu, 

Sichuan, written commun., 1983) sent the author the compositions of two ultrabasic rocks, DZI-1 and DZI.-2, and 

of two chromite reference samples, DZCr-1 and DZCr-2. 

The data for each set of samples include the constituents 

usually determined in a rock analysis and the contents of the 

6 platinum group metals and of 19 trace elements. Abbey 

( 1983, table 120) included most data for the two ultrabasic 

rocks but did not include data for the chromites. Chen and 

others (1982) reported determinations by neutron activation 

methods for the two rocks. Both C.H. Tong and Xuejing 

Xie (Institute of Geophysical and Geochemical Prospecting, 

Langfang, Hebei, 102801, PRC, written commun., 1983) 

note that there are eight soil reference samples. 

Reports containing data on new reference samples 

appeared in the June 1984 issue (no. 3) of "Ho Chi Shu" 

[Nuclear Techniques]. The number of reference samples of 

stream sediments has increased from 8 to 12, and Chen and 

others ( 1984) reported determinations of La and of nine rare 

earth elements in samples, GSD-1, to GSD-12. A set of 17 

secondary reference samples of stream sediments from Gilin 

Province, PRC, was prepared, and Zhao (1984) reported 

instrumental neutron activation (INAA) determinations of 3 

major and minor elements (Fe, K, and Na) and of 18 trace 

elements in samples GRD-30 through GRD-46. 

Data for two types of reference samples for archaeometry were reported by Li ( 1984). Determinations of 

Na, K, and Fe, and of 16 trace elements, are reported for a 

porcelain reference sample, KPS-1. Seven samples of 

bronze containing copper in the range 68-86 percent, tin in 

the range 10-26 percent, and lead in the range 5-11 percent 

were perepared as flat cylinders 20 mm in diameter by 3 mm 

high. Tong and others (1984) report determinations of Cu 

Samples for Geology and Geochemistry 15 
and Fe in percent and of 2I trace elements for a secondary 

basalt reference sample, S-CRB. S-CRB is a small sample 

of the Columbia River Basalt, and the determinations agree 

well with values for BCR-I from a source not cited. INAA 

data for reference samples of peach leaves, a coal fly ash, 

and a river sediment were reported by Su and Zhang ( I984) 

and by Sun and others (1984). 

Scandinavia 

Christie (1975) gives the rock names and geologic 

references for three samples, larvikite (ASK-I), schist 

(ASK-2) and sulfide ore (ASK-3), prepared by the Analytisk Sporelement Komite (ASK). He describes sample 

preparation and tests for homogeneity and tables recommended trace element contents resulting from roundtable 

discussions involving most of the 22 Nordic analysts. 

Compositions of two iron ores, Nr. 9 and Nr. IO, are 

listed by Jecko and others ( I980) in their table 6. Footnote 

2 of the table notes that the samples are from Sweden and 

that the producer is "IMF" (the acronym is not explained). 

Feret ( I982) described an x-ray fluorescence method 

for routine analysis of iron ores. Standards analyzed were 

four samples of the Krivoi Roj ore (U.S.S.R.), two BCS 

ores, six samples from the Iron and Steel Institute of Japan, 

five concentrates, described as standards, from LKAB, 

Malmberget, Sweden, and a sample of Malmberget pellets. 

The acronym LKAB is not explained, and the availability of 

the LKAB samples is not known. 

Leif Ericson (scientific attache, Swedish Embassy, 

Washington, D.C., written commun., I983) notes that IMF 

is probably Institutet fOr Metallforskning (Institute for Metal 

Research, Drottning Kristinas vag 48, S-II4 28 Stockholm) 

but that the acronym has not been adopted by the Institute. 

LKAB is an abbreviation for Luossavaara-Kirunavaara Aktiebolag (Sturegatan 38, Box 26044, S-I004I, Stockholm). 

The I983/84 catalog of Analytical Standards AB (Pl. 

2366, S-434 00 Kungsbacka, Sweden) lists numerous 

standards of different types from many producers. The list 

includes three fluorspars and four iron ores produced by the 

Swedish Institute for Metal Research, whose sample numbers are prefixed by JK (Jemkontorets Analysnormaler). 

Natural Samples of Geologic Interest 

Geological and Geochemical Samples 

The preparation of a reference sample of "a" rock, 

ore, or mineral may lead to future misinterpretation. A laboratory may wish to have, for example, a powdered granite 

to use as a "control" for analyses and may select any granite 

for the purpose. This sample may eventually be promoted to 

a sample of "the ___ granite," though the promotion 

may not be warranted because of deficiencies in the selection or sampling of the rock or in the preparation of the 

powdered sample. 

16 Reference Samples in Geology and Geochemistry 

The preparation of "a" granite should be avoided, as 

the precautions necessary for processing a sample from a 

specified locality require only a little additional effort and 

may result in a reference sample of geologic and geochemical significance. A geologist who knows the area should 

select and sample the rock, and contamination during the 

mechanical processing to a powder should be minimized. 

There are now many samples that meet these criteria. 

Data for rock or mineral samples that meet these criteria, as well as artificial materials such as glass, slag, and fly 

ash that may be useful in silicate analysis, were discussed by 

Abbey ( I980). The principal preparers of reference samples 

for geology, in alphabetical order of their acronyms, are 

(1) ANRT-CRPG (Association Nationale de Ia Recherche 

Technique-Centre de Recherches Petrographiques et 

Geochimiques), (2) ASK (Analytisk Sporelement Komite); 

(3) CCRMP (Canadian Certified Reference Materials Project); (4) GSJ (Geological Survey of Japan); (5) NIM (National Institute for Metallurgy); (6) USGS (U.S. Geological 

Survey); and (7) ZGI (Zentrales Geologisches Institut, East 

Berlin). 

Abbey (1977a) also discusses data for samples from 

three other institutions, Queen Mary College (U.K.), 

Leningrad University, and Institute of Geochemistry 

(Irkutsk, U.S.S.R.). Either the samples from these sources 

were prepared for limited distribution or insufficient data for 

them exist in the literature. The three samples from Irkutsk 

have been identified by two different sample numbers. 

Abbey and Govindaraju ( I978) published determinations by 

their organizations for constituents of the Irkutsk samples, 

along with the established, certified, or unreliable results 

given by Tauson and others (1976). 

Determinations of several constituents of a new 

Japanese andesite (JA-1) and a new basalt (JB-2) were 

reported by Kato and others ( 1978), and the mercury contents of the two samples were reported by Flanagan and 

others (1982). Atsushi Ando, Geological Survey of Japan, 

recently announced (written commun., I982) the availability of a rhyolite, JR-1. New samples JB-3 (a basalt from 

Mount Fuji), JGb-I (a gabbro from Abukuma), JR-2 (another rhyolite, from Wada-Toge), and JP-I, peridotite, as 

well as replacement samples JB-Ia and JG-la, are available 

for analysis. Geochemists will eventually be able to make 

some interesting comparisons of data for these new samples 

with data for similar samples of continental origin. Ando 

( I984) summarized the status of all GSJ rock reference 

samples. Terashima and others (1984) published rock analyses and the contents of I6 trace elements for JA-1, JB-2, 

JB-3, JGb-I, JR-I, and JR-2. 

A gabbro, GOG-I (Gruppo Ofioliti, Gabbro, I), 

from a northern Appenine ophiolite sequence, the Bracco 

Massif(A. Mazzucotelli, written commun., I980), is being 

used by the Gruppo di Lavoro sulle Ofioliti Mediterrannee 

of CNR, Italy, as an interlaboratory standard, and data have 

been published by Boy and Mazzucotelli (1976), Benedetti 
and others (1977), Mazzucotelli and others (1976), and 

Harris and others (1981). A preliminary report was published by Ivanov (1981) on a Bulgarian granite, G-B, that 

was prepared and introduced (Aleksiev and Boyadjieva, 

1966). 

An International Working Group of the Association 

Nationale de Ia Recherche Technique has been established, 

and samples for this group are prepared and distributed by 

the Centre de Recherches Petrographiques et Geochimiques, 

Nancy, France. A report on recent samples of ANRT, an 

anorthosite (AN-G), a basalt (BE-N), and a granite (MAN), was published by Govindaraju (1980). 

A tonalite, T-1, from the Msusule pluton, Tanganyika, was prepared and distributed (Burks and Pallister, 

1961) and data for the sample were published (Thomas and 

Kempe, 1963). Bowden and Luena (1966) published a short 

note cautioning against the use of the limited trace element 

data for T-1 to establish working curves. G. Luena (written 

commun., 1975) confirmed that the supply of T -1 was 

exhausted and that no replacement was contemplated. 

Potts and others ( 1981) prepared a fine-grained granite as an in-house irradiation standard. They calibrated several rare earths in the sample by the method of standard 

additions. Potts ( 1983) proposed adoption of the microgranite, AC(OURS), as a trace element reference sample. 

S.Y. Taha reported (written commun., 1975) that the 

Jordan oil shale JOS-1 was destroyed in a laboratory fire. 

Another shale, SD0-1, was prepared by the USGS as an 

analytical reference sample at the request of the U.S. Department of Energy, Morgantown (W. V.) Energy Research 

Center. Leventhal and others (1978) published preliminary 

data for the sample. Moore (1978) described the preparation 

of the Purington shale sample, KnC-ShP-1, and tabled the 

available data. 

Geochemical Exploration Samples 

Reference samples for geochemical exploration were 

described by Allcott and Lakin (1975), and the analytical 

data were published (Allcott and Lakin, 1974, 1978). Rose, 

Hawkes, and Webb (1979) prefer these as reference samples 

for exploration geochemistry because of their relatively high 

contents of most elements of interest. 

Archaeology 

Both artificial and natural samples have been used as 

standards for archaeological investigations. The artificial 

samples were the pottery standard PS-I of Perlman and 

Asaro (1969), whose supplies are exhausted, and the medieval ceramic samples of Pigeat and Lahanier (1974), who 

restricted distribution to those in archaeology. The USGS 

series of rocks G-2 through BCR-1 is frequently requested 

by those in archaeology, but the supplies of GSP-1, PCC-1, 

DTS-1, and BCR-1 are exhausted. 

John Winter, Freer Gallery of Art, Smithsonian Institution, distributed a list, "Sources of Reference Materials 

for Museum Laboratories," at the 5th Triennial Meeting of 

the ICOM (International Council of Museums) Committee 

for Conservation held in Zagreb, Yugoslavia, in 1978. 

Bauxite 

The National Bureau of Standards issued four replacement bauxites, NBS-69b (Arkansas), NBS-696 (Suriname), NBS-697 (Dominica), and NBS-698 (Jamaica). 

Another bauxite, ANRT -BX-N (Roche and Govindaraju, 

1971), was obtained from Mine de Maou, Brignoles (Var), 

France. Both the BAS (BCS) and the PRE have a bauxite 

reference sample. A lateritic bauxite, SLB-1, was prepared 

by the IVIC (Instituto Venezolano de Investigaciones Cientificas, Caracas). 

Clays and Clay Minerals 

The National Bureau of Standards issued certificates 

for NBS-97, flint clay, and NBS-98, plastic clay, on August 31 , 1931. These were replaced on October 8, 1969, by 

NBS-97a and NBS-98a. Flanagan and others (1977) listed 

determinations of trace elements in the older clays by other 

analysts, sample localities (where known) of the available 

samples of clays and feldspars, and determinations of trace 

elements in the clay and feldspar samples by instrumental 

neutron activation analysis. 

The American Petroleum Institute sponsored a project 

on clay minerals (API Project 49, Clay Mineral Standards). 

Starting in 1949, the project issued eight reports, separately 

paginated, that included x-ray diffraction data, chemical 

analysis, pH, differential thermal analysis, base exchange, 

magnetic susceptibility, particle size, staining tests, and infrared spectra. The preliminary reports, starting with a glossary of clay mineral names by Kerr and Hamilton (1949), 

were later reprinted, bound in a single volume, and issued 

by the American Petroleum Institute ( 1951). The 1968-69 

catalog of Ward's Natural Science Establishment, Inc., 

listed 32 reference clay minerals collected from the same 

localities as those of API Project 49, but the samples were 

not listed in the 1976-77 catalog. 

Two other organizations have prepared clay materials 

and other nonmetallic minerals. Van Olphen and Fripiat 

(1979) give a brief history of the two projects, sponsored by 

the Clay Minerals Society (CMS) and the Organization for 

European Cooperation and Development (OECD), and the 

samples that are available. Chemical analyses of the samples are included in tables, but few trace element data are 

available. Flanagan and others (1982) reported the mercury 

contents of the CMS clay minerals. 

Other organizations have clay samples available. The 

IPT (Instituto de Pesquisas Technol6gicas do Estado de Sao 

Paulo, Brazil) has three clays, including a plastic clay. The 

Samples for Geology and Geochemistry 17 
PRE (Federation Europeenne des Fabricants de Produits 

Refractaires) has one clay and two samples of chamotte 

(refractory clay). 

Coals, Coal Ash, and Cokes 

Coal ashes and cokes, even though they are artificial 

samples, are included in this category because they are 

prepared from coals. 

- The present NBS catalog lists two samples, SRM 

1632a, Trace Elements in Bituminous Coal, and SRM 

1633a, Fly Ash. Khalil and others ( 1980) report the oxygen 

contents of the coal and its predecessor, of the present fly 

ash and its predecessor, and of four commercial coal standards, AR 216, 217, 218, and 220. 

The last four samples are no longer listed in a descriptive price list by Alpha Resources (P.O. Box 199, 3090 

Johnson Road, Stevensonville, MI 49127), but the firm has 

11 coals and 2 coke standards for S in the range 0.4 to 

5 percent, and 9 coal ashes listing the ash contents and the 

analysis for 10 of the 14 constituents usually determined in 

a rock analysis. Alpha Resources also furnishes 11 coals and 

2 cokes for S, ash, volatile matter, fixed carbon, and BTU, 

and another series of 2 cokes and 10 coals for proximate 

analysis, ultimate analysis, forms of sulfur, and the analysis 

for ash. 

The establishment at Argonne National Laboratory of 

a Premium Coal Sample Program to prepare and furnish 

homogenized coal samples of several types was announced 

in "Chemical and Engineering News" (September 26, 1983, 

v. 61, no. 39, p. 18). One objective of the program is to 

furnish coal samples for research in the physical and chemical properties of the coals. The coals, mined from freshly 

exposed seams, will be sealed immediately in stainless steel 

drums under argon to prevent oxidation and to control humidity. Some part of the mined coal will remain stored in 

the stainless steel drums to provide a reserve supply of large 

pieces, but most of any sample will be pulverized into two 

different sizes and smaller sample portions will be sealed in 

glass vials. The first sample is expected to be processed in 

1984, and a total of eight coal types is expected by 1986. An 

advisory committee with members from industry, academia, 

and government will select the types of coal for the program. 

Colombo and Rossi (1978) list the C, H, S, P, and ash 

contents and the calorific values for four coke samples, 

BCR-1 through BCR-4. The 1982 International Organization for Standardization (ISO) Directory of Certified Reference Materials notes that two lignites for the determination 

of U30 8 are available from Junta de Energia Nuclear, Ciudad Universitaria, Madrid, 3, Spain. 

Counting Standards 

The U.S. Department of Energy, New Brunswick 

Laboratory, lists a number of counting standards and other 

18 Reference Samples in Geology and Geochemistry 

materials in "X-Ray Spectrometry" (1978, v. 7, no. 4, 

p. 249). The counting standards are made b~ d~luting pitc.hblende with either dunite or silica, and by d1lutmg monazite 

sand with either dunite or silica. Historically, such standards, made by diluting either pitchblende or monazite sand 

with dunite, were prepared by the NBS between 1945 and 

1950, and the standards were available to organizations 

involved in search for uranium and thorium deposits on 

behalf of the U.S. Atomic Energy Commission (USAEC). 

When the USAEC established a laboratory in New 

Brunswick, N.J., in about 1953, the remaining supplies of 

these samples were transferred to the New Brunswick 

Laboratory. 

The Environmental Monitoring Systems Laboratory of 

the U.S. Environmental Protection Agency also furnishes 

counting standards. The laboratory's major emphasis appears to be on radionuclide samples in solution that were 

prepared and calibrated by the NBS, but it also h~s a numb~r 

of special reference samples of naturally occumng matenals. For example, the laboratory has (1) a pitchblende and a 

dilution of this sample for measurements of 238U and 235U; 

(2) a monazite and a diluted monazite for measurements of 

232Th and 228Th; and (3) a sample of uranium mill tailings 

and a dilution of this sample, plus another mill tailings 

sample (a composite from 16 mills), all three samples designed for measurements of the daughter products, 23<Yfh, 

226Ra, and 210Pb. A sample of the Mancos Shale, prepared 

by the NBS and calibrated for 228Ra and 226Ra, is also 

included. 

Laterites 

The terms "laterite" and "soil" may be used indiscriminately by some of us, but they have specific meanings for 

soil scientists and geologists. The composition of a lateritesample, M10-1, available from IRSID (lnstitut de 

Recherches de la Siderurgie) was given by Jecko (1977). 

Two Venezuelan laterites, VL-1 and VL-2, were prepared 

by the IVIC. A certificate of analysis for Si02, Al203, Ti02, 

Fe20 3, and loss on ignition has been issued for VL-1. 

Schorin and LaBreque ( 1983) published details of and data 

for VL-1 and reproduce the certificate of analysis. 

Meteorites 

Hohenberg and Kennedy (1981) present previously 

unpublished data for the Bjurbole standard meteorite for 

I-Xe dating and discuss the homogeneity of the sample. The 

Smithsonian Institution has prepared a portion of the Allende meteorite for analysis, and data for the sample appear 

frequently. Clarke and others ( 1970) describe the recov~ry 

of specimens from the strewnfield for the Allende meteonte, 

a type III carbonaceous chondrite, and discuss the morphology, mineralogy, petrography, and chemical composition of 

specimens. 
Minerals 

General 

Hiigi and others (1975) summarized data obtained at 

18 laboratories and gave recommended values for the major 

and minor oxides for Basel-I b, biotite, and Basel-lh, hornblende. They give tentative values for Basel-la, 

anorthoclase, a sample from Mount Kibo, Kilimanjaro, 

Tanzania. Stem (1969) discussed the chemical composition 

of the anorthoclase. Only mercury data have been published 

(Flanagan and others, 1982) for biotite, USGS-Btt-1, and 

hornblende, USGS-Hbl-1. 

A calcite, DOl-l, and a dolomite, D02-1, are among 

13 samples for which Jecko (1977) listed average bulk compositions as the elements. After Ca and Mg were converted 

to carbonates and the Si, AI, Fe (as Fe20 3), Ti, P, Mn, and 

S were converted to the oxides, the average analysis of the 

calcite summed to 99.17 percent, including 94.15 percent 

CaC03 and 1.25 percent MgC03 (sum, 95.40 percent). 

Similarly, the analysis of the dolomite summed to 100.13 

percent, including 53.70 percent CaC03 and 42.92 percent 

MgC03 (sum, 96.62 percent). 

Schron and others (1975) published the accumulated 

data for three sulfide mineral standards, Galena GF-1, 

Sphalerite SF-I , and Pyrite PS-1. 

For Microprobe 

Minerals for microprobe use have been in laboratories 

for some time but have been available among scientists only 

on a personal basis. The arsenopyrite microprobe standards 

Asp-200 and Asp-57 mentioned in Lowell and Gasparrini 

(1982, p. 237) appear to be such in-house standards. Ingamells (1978) lists 16 minerals that are available in small 

quantities. He discusses the compositions of these and other 

minerals in a "Microprobe Column," a feature of 

"Geostandards Newsletter" since volume 2, number 2 

(1979). 

Jarosewich (1972) published the compositions of minerals (hornblende, pyrope, omphacite, and two garnets) 

used as microprobe standards and later reported 

(Jarosewich, 1975) the compositions of another hornblende 

and a basaltic glass for similar use. Jarosewich, Nelen, and 

Norberg (1979, 1980) listed the compositions of 25 minerals, 4 natural glasses, and 1 synthetic glass prepared as 

microprobe reference samples at the Smithsonian Institution. 

A variety of reference samples for electron probe 

analysis are available from Tousimis Research Corporation 

(P.O. Box 2189, Rockville, MD 20852). In addition to 

about 60 elements purified (99. 7 percent or better) and prepared as reference samples, the company furnishes about 50 

binary compounds and about 75 minerals for electron probe 

analysis. Mori (1983) uses chemicals and minerals as 

electron-probe standards, but sample numbers for minerals 

are not given. 

For Age Determinations 

A sample of muscovite, USGS-P-207, a reference 

sample for both K-Ar and Rb-Sr measurements, has been 

exhausted since 1972 and a final compilation of data was 

published (Lanphere and Dalrymple, 1976). The availability 

of a hornblende, MMhb-1, for 40 Ar-39 Ar dating was announced in "Geochimica et Cosmochimica Acta" ( 1979, 

v. 43, p. 278), and details of the preparation and calibration 

were given by Alexander and others (1978). 

GL-0, a pure glauconite weighing about 28 kg, was 

prepared by Roche and others (1976). Odin (1976) discussed the analytical data for argon, potassium, strontium, 

and rubidium. Cassignol and others ( 1977) discuss measurements on GL-0 to determine its 40 Ar content. 

Following the suggestion of Compston and others 

(1969), the NBS issued NBS 607, made from the -200 

+325 mesh fraction of NBS 70a, potash feldspar. They 

certify Rb (523.90 ppm), Sr (65.485 ppm), and 87Srt86Sr 

(1.20039, normalized to 86Sr/88Sr=O.ll94). 

Phosphates 

In addition to the latest phosphate rock of the NBS, 

other phosphate samples have been announced. Serrini 

( 1981) published a short note on a Moroccan phosphate rock 

(BCR-32), and the certificate of analysis is reproduced in 

the paper. Gliksman and others (1980) report the CaO contents of 10 IMC samples and of 4 AFPC samples. The IMC 

samples were developed by the International Minerals and 

Chemical Corporation for use as standards in the phosphate 

industry, and the AFPC samples are available from the 

Association of Florida Phosphate Chemists. Jenke and 

Diebold ( 1982) present major and minor oxide data by ICPS 

(inductively coupled plasma spectrometry) and AAS 

(atomic absorption spectrometry) for two phosphates, NBS120b and WPO 42 (Western Phosphate Organization). The 

source from which WPO 42 may be obtained is unknown, 

but NBS-694, a sample of western U.S. phosphate from 

Conda, Idaho, is being prepared. 

Sediments 

Bay (Estuarine) 

The NBS issued SRM 1646, Estuarine Sediment, a 

bottom sediment furnished by the Virginia Institute of 

Marine Sciences, Gloucester Point, Va. The material was 

dredged from the Chesapeake Bay (37°11.1' N, 76°17.1' 

W). Certified values are given for 16 major, minor, and 

trace elements, and noncertified values are given for 19 

elements. The certified value for As (11.6 ppm) and the 

noncertified values forCe (80 ppm) and thorium (10 ppm) 

may reflect the industrial nature of the Newport NewsPortsmouth area on the James River, about 15 km southwest 

of the collection point. 

Samples for Geology and Geochemistry 19 
Canal (River) 

The NBS issued SRM 1645, River Sediment, which 

was collected from the Indiana Harbor Canal, near Gary, 

Ind. The rather high values for Pb (714 ppm), Hg (1.1 ppm), 

Sb (51 ppm), and As (66 ppm) may be due to the industries, 

including iron and steel, in Gary. 

Lake 

A lake sediment, IAEA-SL-1 , for determinations of 

trace elements has been available for almost a decade from 

the International Atomic Energy Agency. Merritt (1980) 

describes the collection and preparation of gyttja, a highorganic bottom sediment from Perch Lake at the Chalk 

River Nuclear Laboratories. Gyttja is a gelatinous sediment 

containing about 8 percent solids; approximately 50 percent 

of these solids is organic matter. Perch Lake in the Chalk 

River Nuclear Laboratories Waste Management Area has 

received low levels of 90Sr, 6

°Co, and other radionuclides 

for more than 25 years, but the radioactivity is confined to 

the top 30 em of material. The National Bureau of Standards 

is handling analytical program, and certification of the material is expected shortly. 

Marine 

Two marine sediments, IAEA-SD--B-1 and IAEASD--B-2, for measurement of fission products were available from the IAEA for about a decade. There is no more 

stock of these sediments, but three new standards have been 

prepared and are being analyzed. A marine sediment, 

USGS-MAG-1, was described by Manheim and others 

(1976), and Gladney and Goode (1981) summarized the 

data in the literature for this and other USGS samples. Two 

other marine sediments, MESS-1 and BCSS-1, were announced by Berman ( 1981) of the National Research Council of Canada; he lists reliable values for 24 constituents of 

the samples. 

Pond 

Iwata and others (1981) collected a pond sediment at 

the University of Tokyo and tabled the contents of 4 major 

elements and 10 trace elements. The preparation of this 

pond sediment may have been prompted by the study of 

Goldberg and others ( 1976) of the metal pollution in sediments of the Palace moat, Tokyo. 

River (Radioactivity) 

A river sediment for the measurement of environmental radioactivity was issued by the NBS as SRM-4350-B. 

The certificate lists eight certified radionuclides and another 

nine radionuclides for which no corroborative measurements were available for comparison. The sediment was 

collected from the Columbia River, about 20 mi ( ~32 km) 

downstream from Hanford, Wash. 

20 Reference Samples in Geology and Geochemistry 

Soils 

General 

Twelve soil samples were prepared by the Soil Mineralogy Work Group of the Southeastern United States. The 

samples were described and the data given by Barnhisel 

(1978). These soil samples were intended for soil scientists 

rather than geochemists. Trace element data for Soil-5 of 

the International Atomic Energy Agency were published by 

Dybczynski and others ( 1979). IAEA-Soil-6 and -7 may be 

available in 1984. 

Among the reference samples of the U.S.S.R. listed 

by Lontsikh and Parshin (1980) are soils SP-1, -2, and -3. 

Egranova and others (1981) list the 14 trace elements, but 

not the data, that were certified for the three soils. 

Four soil samples issued by the CCRMP were described and data given in CANMET Report 79-3 (Bowman 

and others, 1979). Steger ( 1980) summarized the data on 

these and other CCRMP samples. Three soil samples were 

among the six geochemical exploration samples described 

by Allcott and Lakin (1975). The very high mercury content 

(Flanagan and others, 1982) of one soil from Utah reflects 

the mineralized area from which the sample was collected. 

Low-Level Radioactivity 

A soil for the measurement of environmental radioactivity, prepared as NBS SRM-4353, was collected at the 

Rocky Flats Plant ( ~ 105°00' W, 39°50' N), near Golden, 

Colo., and is certified for 13 radionuclides. An outline map 

of the location is given by Volchok and others (1980), who 

also describe the mechanical processing of the sample. A 

table of the probabilities that k analytical samples out of n 

contain hot particles of 239+240Pu is given in the certificate 

for n=l, k=l, to n=4, k=4, for sample sizes of 1, 2, 5, 

10, and 20 g. As one might expect, the probabilities of 

sampling hot particles increase with increasing sample 

weights. 

Another sample, NBS SRM-4355, is a soil collected 

at the IAEA Agricultural Experiment Station, La Molina, 

Lima, Peru (where IAEA-Soil-5 was also collected; Inn 

and others, 1984, p. 95). As many fallout nuclides cannot 

be measured, the sample is intended as a blank, or a very 

low-level standard for the measurement of environmental 

radioactivity. The sample is certified for six nuclides and for 

upper limits for five other nuclides. The certificate lists 

concentrations of 15 elements that can be recommended 

with a relatively high degree of confidence, of 19 elements 

with a reasonable degree of confidence, and of 23 elements 

given for information only. 

"Natural Matrix" vs. Spiked Samples for Radioactivity 

There are differing opinions about the efficiency of 

spiked samples or "natural matrix" samples. Bowen (1978) 

contends that the most generally useful standard materials 
are those that have been in contact, in their natural environments, with the radionuclides sought for the longest time 

possible and under the least special conditions. He notes that 

such materials would be analogous to samples in the biological literature described as "metabolically contaminated." 

Olson ( 1980) prefers synthesized standards in natural 

matrices. He notes that standardized samples of individual 

nuclides may be combined quantitatively to produce a standard with selected ratios and levels of nuclides, and that such 

standards can be added to a chosen matrix to provide an 

optimum test. Olson notes that, for a natural matrix standard, nuclides are determined in the presence of the other 

nuclides in the material and at the levels at which they 

occur. Analyzed samples contain the biases of the analytical 

methods used in their standardization, and these biases are 

passed on to the procedures the sample is intended to check. 

Volchok and Matuszek (1980), in a comment following Olson's (1980) paper, note that "spiking" can introduce 

biases from the presumption that the spike has been introduced in the same chemical form, valence state, or particle 

size as the radionuclide in the "real" sample. They note that 

Olson failed to discuss public acceptance of radiological 

data, and that public acceptance is enhanced when reference 

is provided to interlaboratory comparison using natural 

standards. 

Bowen and Volchok ( 1980) discuss the merits of 

spiked sample standards. In addition to listing five criteria 

that calibrated test samples must meet if they are to be 

useful, they discuss special problems that require spiked 

samples and give suggestions for preparers and users of 

spiked samples. As examples of successful cases of spiked 

standards, they cite the soils prepared by Sill and Hindman 

(1974) and by Schulz, Tompkins, and Babcock (1976), and 

the spiked standard pottery clay prepared by the NBS. 

Sill and Hindman (1974) described the preparation of 

standard soils containing known quantities of a desired radionuclide. They used water to make a paste of 100 g of the 

-200 + 3 25 mesh fraction of a soil in a platinum dish. They 

slowly added 1 mL of a solution of a purified carrier-free 

nuclide, stirring the mud during and after the addition to 

ensure homogeneous distribution of the nuclide. After drying the mud and weighing it, they weighted the soil remaining in the dish. After determining the activity of the soil in 

the dish, they corrected the activity of the large sample. 

They then added - 200 mesh material of the same unspiked 

soil to obtain a sample of about 1,800 g, which was blended 

overnight to ensure homogeneity. They prepared a second 

standard from a different soil and heated it for 1 hr at 700°C 

to approximate conditions in laboratory ignitions. They diluted an aliquot of this standard 54-fold with no detectable 

loss of homogeneity or accuracy of the diluted standard. 

Another standard, diluted 934 times from the original 100 g 

of spiked soil, showed evidence of heterogeneity. 

Schulz, Tompkins, and Babcock (1976) chose three 

California soils, ( 1) a forest soil rich in organic matter and 

slightly acid, (2) a neutral fertile valley alluvial soil, and (3) 

an alkaline calcareous soil. The soils were passed through a 

16-mesh ( -1-millimeter) sieve before blending. They prepared stock solutions of 239• 240Pu and 241 Am and diluted 

portions of these solutions to 100 mL with distilled water. 

They added each of these 100-milliliter solutions to 16 kg of 

a soil in a Patterson-Kelley liquid-solid blender, rinsing the 

containers for the solutions with two 50-milliliter portions of 

distilled water to ensure complete transfer of the nuclides to 

the soil. They then blended the soil plus the added solutions. 

The NBS prepared a standard pottery clay spiked with 65Zn, 113Sn, 113mln, 137Cs, 137mBa, and 139Ce by the method 

of Sill and Hindman (1974). Radionuclides in solution were 

added to about 100 g of slurried clay which was then dried 

and blended into about 20 kg of the same clay. 

Stable Isotope 

There are a number of reference samples for comparisons of stable isotope ratios. Gonfiantini ( 1978) notes that 

V-SMOW (Vienna Standard Mean Ocean Water) was prepared by mixing distilled water with small amounts of other 

waters to bring its isotopic composition as close as possible 

to that of SMOW defined by Craig (1961). Another sample, 

known by the acronym SLAP (Standard Light Antarctic 

Precipitation), was made by melting Antarctic ice and fim 

collected by E. Picciotto, Universite Libre de Bruxelles, 

Belgium. SLAP is depleted in the heavy hydrogen and oxygen isotopes. GISP (Greenland Ice Sheet Precipitation) is a 

water sample prepared by W. Dansgaard, University of 

Copenhagen, Denmark, by melting Greenland fim, and its 

isotopic composition is intermediate between those of VSMOW and SLAP. Two other water samples are NBS-I, 

prepared by distilling Potomac River water, and NBS-lA, 

prepared from snow from Yellowstone National Park, Wyo. 

Some isotopic compositions versus SMOW are given for 

these five water samples in table 6 in Gat and Gonfiantini 

(1981, p. 39). Wit and others (1980) published data on the 

absolute hydrogen isotopic ratio of V -SMOW and SLAP. 

Friedman and Gleason (1973) prepared a silicate reference sample for 180 analysis. A glass sand from Africa, 

NBS-28, was examined both microscopically and isotopically. It was found to be relatively free of mineral grains 

other than quartz and to have a minor amount of inclusions 

relative to other sands examined. Matsuhisa (1974) determined the 180 value of the sample to be +9.5 per mil 

relative to SMOW, a value 0.5 per mil lower than that 

reported by Friedman and Gleason. 

Friedman and others ( 1982) published isotopic data 

for two new carbonate stable-isotope standards, TS Limestone (NBS-19), a marble of unknown origin, and Carbonatite (NBS-18) collected from Fen, Norway. The preparation of stable-isotope carbon dioxide reference samples, 

NBS-16 and NBS-17, from tanks of commercial liquified 

carbon dioxide and of commercial C02 gas is described by 

Samples for Geology and Geochemistry 21 
Coplen and Kendall (1982). A paper on a new carbonate 

standard (Iceland Spar) for 180-BC by Gary P. Landis 

(1983) was published in a new journal, "Isotope Geoscience." The sample was obtained outside the main portal 

of the Harding mine, and an Iceland Spar pit is shown on the 

geologic map of the Harding pegmatite in Montgomery 

(1950). 

An undated informal information sheet of the International -Atomic Energy Agency (P.O. Box 100, A-1400, 

Vienna, Austria) lists several other stable isotope standards, 

as follows: 

• NBS-30: a sample of biotite separated by I. Friedman, 

J.R. O'Neil, and G. Cebula, U.S. Geological Survey, 

from a portion of the Lakeview Mountain Tonalite, 

Southern California Batholith (Larsen, 1948) collected 

by L. T. Silver, California Institute of Technology. 

• OGS: a sample of barium sulfate precipitated from ocean 

water sulfate by Y. Horibe, University of Tokyo. The 

sample is intended for intercalibrating 34S and 180 measurements in sulfates. 

• Soufre de Lacq: a sample of natural elemental sulfur from 

the Lacq (France) deposit provided by E. Roth, Centre 

d'Etudes Nucleaires, Saclay, France. Its 34S/32S ratio, 

measured in Saclay versus CDT (Canon Diablo 

Troilite), is + 17 .3±0.4 per mil. 

• IAEA N-1 and N-2: two artificial samples of ammonium 

sulfate prepared by E. Salati, Centro de Energia Nuclear na Agricultura, Piracicaba, Brazil. The 15N/ 14N 

ratios of the samples, measured in Piracicaba versus 

NBS-14 (atmospheric nitrogen), are + 1.36±0.20 per 

mil for N-1 and +20.85±0.20 per mil for N-2. 

Another sample, NBS-20, is mentioned in Coplen 

and Kendall ( 1982). The sample is briefly described by Neir 

(1950, table 6) as a Jurassic limestone from Solenhofen, 

Bavaria, and it is one of a number of reference samples 

listed by Mohler (1955) as available from the NBS for 

isotopic work. 

Craig ( 1957, table 5) lists averages of determinations 

of &Be and &180 in eight samples. Included among the 

samples are a portion of the Solenhofen limestone obtained 

from Nier (1950) and a portion ofNBS-20. Craig (1957, p. 

146) notes that the material from Nier and NBS-20 represent different samples of the Solenhofen limestone, the NBS 

sample having been recently acquired from the USGS. Historically, thick slabs of the fine-grained Solenhofen limestone were used in the USGS printing plant for maps, a 

practice essentially discontinued in the mid-1930's when 

copper plates became the principal method used for maps. 

NBS-20, prepared from a slab weighing approximately 100 

lb, was given to the NBS by Irving Friedman (U.S. Geological Survey, Denver, CO 80225, written commun., 1984). 

Craig ( 1957) also listed the averages for a sample of 

the Te Kuiti limestone. Blattner and Hulston (1975) announced the availability of a sample of the Te Kuiti limestone and a sample of an unnamed low- 180 coarse-grained 

22 Reference Samples in Geology and Geochemistry 

calcite. Blattner and Hulston (1978) reported data resulting 

from an interlaboratory comparison of proportional variations of geochemical &180 scales, designating the Te Kuiti 

limestone TKL-1 , and the unspecified but pure calcite 

(Kaikoura) K-2. Their table 2 contains a summary of determinations of carbon isotope compositions of TKL-1 and 

K-2 by different analysts. 

Coplen and others ( 1983) published averages, obtained by one laboratory, of &180 values of 13 reference 

samples relative to V-SMOW and PDB. Craig (1957, p. 

135) had defined PDB as a Cretaceous belemnite, Belemnitella americana , from the Peedee Formation of South 

Carolina. Coplen and others (1983) also listed in their table 

2 average determinations of &Be relative to PDB for eight 

reference samples. 

Geobotanical Samples 

There are a number of biological reference samples 

that can be used for geobotanical investigations. Among the 

earlier such samples is the powdered kale sample for which 

Bowen (1967) discussed the elemental analyses. Wainerdi 

( 1979) critically examined the published data on Bowen's 

kale. He recommended values for 12 major, minor, and 

trace constituents, gave "indicated values" for 16 major, 

minor, and trace elements, and made no recommendations 

for 15 other elements. 

The wheat flour (SRM 1567), the rice flour (SRM 

1568), the citrus leaves (SRM 1572, in preparation), the 

tomato leaves (SRM 1573), and the pine needles (SRM 

1575) of the NBS might be useful for geobotanical investigations. Pinta (1977a, 1977b) lists data for leaves from nine 

trees-cotton, palm, and rubber trees from Africa, eucalyptus, olive, and orange trees from Spain, peach and apple 

trees from France, and a golden apple tree from Belgium. 

He also gives data for codia (a globular shrub) from New 

Caledonia, maize from Spain, and an unspecified vine from 

France. Troll and Farzaneh (1980) determined fluorine in 

the samples listed by Pinta (1977a). 

Japanese tea leaves were prepared by Fuwa and others 

(1978) as a possible standard reference material. Okamoto 

and others (1978) prepared leaves of the pepperbush tree, 

known to accumulate Zn, Mn, Co, Ni, and Cd, as a standard 

reference material. The homogeneity of a Chinese sample, 

peach leaves, was tested by Tu and Leiser (1984a, 1984b). 

Schramel and Xu (1982) reported the beryllium content of a reference sample of riparioides, an aquatic plant. 

The sample of riparioides, undergoing certification at the 

time of publication, appears to be a sample from the Community Bureau of Reference with the number BCR-61, and 

the sample is so listed in the 1982 BCR catalog. The catalog 

lists two other botanical samples, BCR-60, aquatic plant 

(lagarosiphon), and BCR-62, olive leaves. 

The latest IAEA catalog, titled "Analytical Quality 

Control Services Program, 1983-1984," lists several botan-
ical samples, as follows: hay (powder), V-10; seaweed, 

AG-B-1; rye flour, V-8; and cotton cellulose, V-9. 

The U.S.S.R. also has botanical reference samples. 

Shafrinskii (1977) gives a very brief and general discussion, 

almost the equivalent of an announcement, of the development of standard samples of plant materials. Nalobin and 

others ( 1980) table estimates of the parameters of regression 

equations but give no analytical data. The plant sample 

names (subject to later change) and numbers are as follows: 

grain-grass mixture, SBMT-01; wheat grain, SBMP-01; 

and potato tubers, SBMK-01. Nalobin and others do not list 

the U.S.S.R. state registry numbers (USSR SRN) for standard samples; this seems to be a practice for reference samples of rocks, ores, and soils. 

Savinova and others ( 1981) discuss the direct simultaneous spectrographic determination of copper and molybdenum in soils and plants. Their emphasis, however, is on 

soils; they give in table 2 the certified contents and amounts 

ofCu, Co, Mo, Mn, Ni, and V found in three soil standards, 

SP-1, -2, and -3. A figure shows calibration curves for 

determining Cu, Co, and Mo in plants. 

Karpukova and others (1982) report x-ray fluorescence determinations of Na, Mg, AI, Si, S, and Cl in the 

potato, wheat, and grass standards using the same sample 

numbers as in Nalobin and others (1980). They also report, 

in table 2, determinations of P, K, and Ca in these samples 

and in 14 other botanical samples. Samples in a column 

titled "Standard Sample (SS)" have numbers such as "SS of 

wheat straw No. 1-78," where 1-78 may be a State Registry Number. 

Zvyagintsev (1983) tables "standard accuracies" for 

plant analysis of standard samples of potato, wheat, and 

mixed grass, the materials being further identified as 

SS 1483-78, SS 1418-78, and SS 1485-78, respectively. 

Lacking other evidence, one might assume that samples 

identified in Nalobin and others (1980) by prefixes such as 

SBMT may, in fact, be the same samples identified in 

Zvyagintsev (1983) by what appear to be U.S.S.R. State 

Registry Numbers. 

TOPICS AND PROBLEMS FOR 

REFERENCE SAMPLES AND THEIR DATA 

Reasons for Reference Samples 

The most obvious reason a reference sample is available is that some person or institute prepared a sample to 

help solve an existing problem. Whereas there were no 

standards about a century ago, but only samples that had 

been analyzed cooperatively by a number of chemists, we 

now seem to have an ever-increasing number of reference 

samples designed for specific purposes. In addition to reference samples analyzed by many chemists throughout the 

world, we often find internal, or in-house, standards such as 

the limestone and the clay-slate of the Geochemical Institute 

of the University of Gottingen for which data were reported 

by Abo-Rady (1979). As one might expect, the scientific 

value of the numerous formal and informal reference samples ranges from very good to questionable. 

The age of standards in the United States began with 

the establishment of the National Bureau of Standards (31 

Statutes at Large, Fifty-Sixth Congress, Sess. II, Chapter 

872, An act to establish the National Bureau of Standards) 

on March 3, 1901. A few years later, Andrews (1908) 

addressed the question, "What can be done to enhance the 

value of the work of the Bureau of Standards to the chemical 

industries?" He suggested two groups of materials to be 

standardized: (1) substances used for standardizing volumetric solutions (or the solutions themselves), and (2) standardized commercial materials by which manufacturers can control their analytical processes. 

In the following year, Ebaugh (1909) mentioned in an 

editorial the preparation of iron standards by a foundrymen's association [American Foundrymen's Association 

(Cochrane, 1966, p. 93)], the standardized irons and steels 

of the NBS (Hillebrand, 1909), the four phosphate rocks of 

the American Fertilizer Association (Hagedorn and others, 

1909), and the samples of products that were prepared and 

distributed by the Committee on Analysis of Fats, Soaps, 

and Glycerine of the American Chemical Society (ACS). 

Ebaugh believed that the ACS Division of Industrial and 

Engineering Chemistry might do yeoman's service by 

preparing, standardizing, and distributing samples for which 

there might be a demand. Ebaugh's editorial was followed 

shortly by a letter to the editor by Jones (1909), who suggested that standardized samples of bituminous coals and 

cokes be the first to be considered. 

Although many reference samples have been prepared 

for specific reasons, it has been evident for more than two 

decades that one should no longer prepare a rock, mineral, 

or ore standard for a single purpose. The USGS rocks G-1 

and W -1, and the older NBS samples, were prepared 

mainly for determinations of their major and minor constituents. However, the literature of two decades ago contains many papers on determinations of trace elements in 

G-1 and W -1 and in NBS samples of economic rather than 

geologic interest by, among others, Shimp and others 

(1957), Grabowski and Unice (1958), Turekian and Carr 

(1961), Clark and Swaine (1963), Filby (1964), Taylor and 

Kolbe (1964), and Ball and Filby (1965). Another example 

of a use for which a sample was not intended is discussed in 

the paper by Compston and others ( 1969) on the feasibility 

of using NBS 70a K-feldspar as a Rb-Sr age reference 

sample. 

As scientific inquiry is obviously not inhibited by the 

purpose for which reference samples were prepared, the 

preparer should try to anticipate future needs by conforming 

to the requirements for the most sensitive, accurate, and 

precise methods available now and in the foreseeable future. 

Topics and Problems for Reference Samples and their Data 23 
If reference materials are prepared carefully for these refined methods, they should be satisfactory for methods with 

less stringent requirements. Because newer methods with 

better sensitivity might be developed in the future, preparers 

of geochemical reference samples should ensure that their 

method of preparation does not add significant amounts of 

contaminating elements that may change the geochemistry 

of the rock samples. 

There is no easy answer to the question of which rock 

standards should be prepared. The potential preparer might 

consult the paper by Nockolds (1954) to determine which 

igneous rocks are not represented in a list of available standards. Although most work in geology concerns igneous 

rocks, similar consideration might be given to metamorphic 

rocks-and Parker ( 1977) has inquired about the need for 

sedimentary rock samples. Appel (1980) discussed a possible reference sample of a banded-iron formation, including 

the economic implications for the mineralization of gold and 

other elements. Abbey and others (1983) published data on 

four Canadian iron-formation samples, and a report was 

published (Govindaraju, 1984b) on two GIT-IWG samples, 

iron formation, IF-G, and albite, AL-l. 

One can obtain a number of samples in which some 

constituent, say Si02, will cover the entire range for the 

igneous rocks in Nockolds (1954), but it would be time 

consuming to prepare these rocks as reference samples. It 

would then be a more difficult problem to find geoanalysts 

willing to contribute good data to establish the compositions 

of these samples. Many geochemists are involved in topical 

studies representing only part of the spectrum of igneous 

rocks, and they may be reluctant to contribute data that may 

not be immediately applicable to their study. 

A better criterion for selecting rocks as candidate reference samples may be based on trace element geochemistry, specifically a large void that may exist in the information about the trace element contents of existing samples. As 

an example, the best value for Ce in W -1 divided by the 

average of the best Ce values for DTS-1 and PCC-1 yields 

a concentration ratio of 3 x 102• The similar ratio for the La 

contents is also 102. 

Because the supply of W-1 was depleted in 1972, 

several of us collected another large sample of the Centreville Diabase, a sample now known as W-2. P.C. Ragland 

and J .R. Butler of the University of North Carolina collected 

a large portion of a North Carolina dolerite, now DNC-1, 

and Karl Gronwold of the Nordic Volcanological Institute, 

Reykjavik, collected a large portion of an Icelandic basalt, 

BIR-1. The best estimates for Ce and La in these new 

samples show two levels of Ce and La between W -1 and the 

two ultramafic samples. 

Approximate Ce and La contents of some USGS rocks (in ppm) 

DTS-1 PCC-1 BIR-1 DNC-1 W-1 W-2 BHV0-1 BCR-1 

Ce 0.06 0.09 

La .04 .15 

1.6 

.63 

9.1 

3.6 

23 23.4 

9.8 10.4 

24 Reference Samples in Geology and Geochemistry 

41 

17 

54 

26 

Another criterion for selecting a sample is the replacement of an important but now depleted sample, provided the 

original sampling location is precisely known. Thus, when 

the supply of the Twin Sisters Dunite, DTS-1, was nearly 

depleted, R.W. Tabor of the USGS, one of the original 

collectors of DTS-1, collected about 600 lb ( -270 kg) of 

the same rock at the original location. This sample has been 

processed at DTS-2 and, except for trace elements in the 

thin veins of chromite in the rock, the compositions of 

DTS-1 and DTS-2 may be similar. 

Amount of a Rock Reference Sample 

G-1 and W -1 were prepared as 90 and 210 lb of 

powder, respectively (Fairbairn and others, 1951), and the 

portions of the samples were contained in 2-ounce (60-

milliliter) bottles. After 15 years of distributing the samples, 

the contents of the 2-ounce bottles were subsampled into 

4-dram ( ~ 14 milliliter) vials, thereby extending the supply 

of G-1 until 1965, and of W -1 until 1972. 

When considering the program of rock samples that 

resulted in the series G-2 through BCR-1, I decided to 

process enough rock to yield at least 2,000 one-ounce (30-

milliliter) bottles of each sample. I estimated that these 

amounts would last about 25 yr, but requests from scientists 

in the NASA Lunar Program resulted in an accelerated distribution of portions, thereby reducing their anticipated lifetimes. 

The production of rock reference samples is costly to 

both producers and analysts. On the basis of experience with 

two sets of rock samples, I believe that a reference sample 

should be not less than 250 kg, an amount that should last 

about 30 years. Tauson and others (1976) recommended 

amounts of at least 500-600 kg, and Govindaraju and others 

(1977) prepared a 1-ton granite reference sample. Govindaraju and Mevelle (1983) list the amounts of CRPGANRT samples prepared. 

A greater amount should be processed if the geochemistry of the rock indicates that it may be more important than 

samples currently available. The problems of processing a 

500-kilogram sample are less than twice those of processing 

a 250-kilogram sample. A large amount may be processed 

through the steps of powdering and mixing, the powder 

sampled into a number of bottles estimated to last some 

years, and the remaining mixed powder stored in airtight 

plastic containers for future sampling into bottles. 

A word of caution is in order for those who would 

prepare a large portion of a rock as a reference sample: 

Whether we crush the large sample to a grain size of 114 in 

( ~6 mm) or to a powder passing a 200-mesh screen, the 

distribution of the minerals and of the particle sizes may be 

described by one of several statistical distributions, the Poisson being the simplest. 

If we crush a granite to pass a 1/4-inch screen, excluding the dubious procedure of selecting material in some size 
range, say - 1/4-inch + 100 mesh, there are problems to 

consider. Information on which of several minerals in a rock 

is crushed more readily to a powder is scarce. Biotite, often 

occurring in rocks as "books," is difficult to crush to fine 

grain sizes: some methods of size requction may affect the 

H20 contents or the crystal structure of the mineral. 

Zircon crystals smaller than 200 mesh have been 

found between leaves of the books of mica in this laboratory. A producer might decide to subsample the If4-inch 

material into five lots, powdering one lot now and the other 

four lots later as more reference sample is needed. 

In the extreme case in which only one book of mica 

is present in the bulk sample, only one of the five lots can 

contain the book of mica. By subsampling the coarse material, the producer introduces an error in the determinations 

of zirconium and hafnium and of trace elements concentrated in the mica, and the error cannot be corrected by 

powdering the five lots individually, assuming that the five 

lots are not then mixed as a unit. The producer should 

therefore subsample only after the entire amount of bulk 

material is powdered as a unit to some specification, say 

passing 200 mesh. 

Reference Samples vs. In-House Standards 

The relation between reference samples and in-house 

standards is emphasized by the depletion of four USGS 

rocks of the 1964 series. In spite of an urging that, 

"university laboratories and other organizations * * * consider the preparation of in-house standards that will both 

conserve the supply of valuable international reference materials and ensure the individual organization of a plentiful 

supply of secondary standards for their own use" (Flanagan, 

1974, p. 1739), less than 1 percent of those requesting 

USGS rocks indicate that they intend to prepare in-house 

standards and calibrate them. I have the impression (as may 

other producers) that many scientists feel they can request 

and receive samples as often as they wish. 

Members of organizations are again urged to prepare 

a portion, say 10 kg, of two or more local rocks as in-house 

standards. They could then determine the contents of several 

elements in the rocks by the method of standard additions. 

This would both conserve the supply of reference samples 

and ensure a lasting supply of two or more in-house standards. Potts and others ( 1981) calibrated a granite as an 

in-house irradiation standard by the method of standard additions. Despite the failure of requesters of samples to mention that they intend to prepare their own standards, the 

number of reference samples that may be called, collectively, "in-house" standards has increased greatly in the last 

decade. 

Perez and others ( 1979) prepared four samples of 

igneous rocks weighing 10 to 15 kg each; "in-house" was 

included in the formal title of the report. Two olivine basalts 

were collected at an outcrop at Ciudad Universitaria, 

Mexico City, and a dacite and a rhyolite were obtained from 

road cuts at nearby locations. The samples were the first to 

be collected for a project on Mexican Reference Samples for 

Geochemistry. The report gives chemical analyses and 

C.I.P.W. norms (Cross and others, 1902) for the four samples, plus determinations by instrumental neutron activation 

analysis and some preliminary data obtained by spark source 

mass spectrometry. 

Comminution and Grindability 

The preparer of a rock standard should have some idea 

of the potential difficulties before starting to process a sample. One might expect, for example, that a crystalline igneous rock would be much easier to crush than a glassy or 

microcrystalline rock. 

One measure of the difficulty of crushing is the work 

index -the work required to reduce a unit weight of a rock 

from a theoretically infinite size to the size at which 80 

percent will pass a 100-micrometer screen. Table 8-3, Average Work Indexes for Various Materials, in the "Chemical 

Engineers' Handbook" (Snow and others, 1973) lists several 

crystalline rocks whose work indices approach those of 

glassy rocks. The work indices for the several rocks range 

from 14 to 22. Mica has a high index of 134 because of its 

crystalline form and the work necessary to crush the flat 

plates of mica to pass a 100-micrometer screen. 

Other sources of information on crushing rocks include the "Handbook of Mineral Dressing; Ores and Industrial Minerals" by Taggart (1945) and the summary of investigations on crushing by Gross ( 1935), which includes a 

bibliography of 128 references. Gross (1938), in U.S. 

Bureau of Mines Bulletin 402, discusses the many variables 

in crushing and grinding and gives an annotated bibliography of 142 references. Texts on mineral dressing similar to 

that of Gaudin (1939) should contain similar information. 

Homogeneity, Sampling Errors, and the 

Sample for Analysis 

Many powdered rock reference samples are homogeneous. When considering the preparation of a rock as a 

reference sample, the frrst question for both the collecting 

geologist and the preparer is whether the candidate rock is 

suitably homogeneous. Chayes (1967), as a result of point 

counting of thin sections of the rock now known as G-2, 

concluded that there should be no concern about the rock 

being heterogeneous prior to crushing. By inference, the 

powdered sample should also be homogeneous for determinations of major and minor oxides. If a reference sample of 

a coarse-grained rock is desired, a similar study of the rock 

might be made prior to other work. 

For reassurance about the grain size to which rock 

samples should be crushed so that the powders will be homogeneous, one might consult the section on Sampling and 

Topics and Problems for Reference Samples and their Data 25 
Testing by Behre and Hassialis (1945) in Taggart's 

"Handbook of Mineral Dressing." They derived, starting 

with the binomial distribution, a rigorous expression that 

may be used to calculate the amount of sample necessary, 

given a specified grain size, or the error that may be incurred 

for a given amount of sample. The several examples in 

tables may be used as models to calculate the grain size of 

a crushed rock not to be exceeded if one wishes to set an 

upper limit for the error that may be incurred when sampling 

the rock powders. 

In a pair of related papers, Reiss and others (1945) 

and John and others (1945) used the binomial distribution 

for an expression to reduce misrepresentation of data (errors) to some desired value. The authors include a graph 

relating the percent relative sampling error, the number of 

particles in the sample, and the percentage of the desired 

constituent. 

Bennett and Franklin ( 1954) discuss the size-weight 

ratio, 

weight of largest particle of impurity x 100 

weight of reduced sample b ' 

for sampling coal. The variance component due to subsampling is unlikely to exceed bx where x is the percentage 

proportion of impurity in the large sample. Bennett and 

Franklin note that this value provides an overestimate of the 

variance component due to subsampling since the impurity 

is unlikely to consist of particles all of which are of the 

maximum size. 

Benedetti-Pichler ( 1956) has an excellent section on 

the theory and principles of sampling for chemical analysis 

in which he discusses sampling error and its relation to 

particle size distribution. Laffitte ( 1957) use the Poisson 

distribution to calculate errors, giving examples for CaO in 

a granodiorite, Si02 in a granite, and P20 5 in a gneiss 

containing grains of apatite. Visman (1962, 1969) discussed 

sampling constants, defining his sampling constant on page 

12 of the earlier paper. Gy ( 1967) also discussed a sampling 

constant and published a text (Gy, 1979) on the sampling of 

particulate matter. 

Other papers on sampling errors and related topics 

published in the 1960's are by Wickman ( 1963), who used 

the Poisson distribution, Wilson (1964), the multinomial, 

and Kleeman (1967), the binomial. Kleeman (1967, p. 46) 

recommended that "all standard rock powders *** be 

ground initially to pass a 230-mesh sieve and that where the 

analyst wishes to take samples smaller than 0.5 g, a portion 

of the main bulk be ground to an impalpable powder." 

Clifton and others (1969) used the Poisson distribution in 

their discussion of sample size and meaningful gold analysis. 

Ingamells and others (1972) tabled sampling constants for several components of reference samples and minerals in their discussion of laboratory sampling error in 

geochemistry and geochronology. Scilla and Morrison 

26 Reference Samples in Geology and Geochemistry 

(1977) and Drummer, Fassett, and Morrison (1978) used the 

sampling constant concept in their papers on sampling error 

in ion microprobe analysis. Harris and Kratochvil (1974) 

used the binomial distribution for sampling error and gave 

the formula by Benedetti-Pichler (1956) for the number of 

grains required to obtain a representative sample. Flanagan 

( 1976a) used the Poisson distribution without the covariance 

term as an approximate method for computing errors due to 

sampling rock powders. Birger and Bruk (1977) used the 

Poisson distribution to ensure that a sample of gold-bearing 

ore was representative. Moore (1979) used the Poisson distribution to derive an expression for sampling errors. 

The allied subjects of particle size, sample size, and 

sampling error have been discussed in texts and journals 

devoted to mining and metallurgy since the start of this 

century. Errors in assays may have concerned postMedieval assayers (Agricola, 1950), as one may infer from 

the English translation of the first Latin edition ( 1556) of De 

Re Metallica a suggestion that replicate samples be assayed. 

Brunton ( 1896) published a study whose aim was to 

determine the fineness to which crushing must be carried to 

obtain data within an allowable limit of error when sampling 

gold and silver ores. In addition to diagrams for determining 

this fineness, he concluded that the size to which ore should 

be crushed before sampling so that assays would be within 

an allowable limit of error depends on: 

1. The weight of the sample. The smaller the sample, the 

finer the material must be crushed. 

2. The relative proportion between the value of the richest 

mineral and the average value of the ore. High-grade 

ores may be crushed more coarsely and the data will 

still be within the same percentage error. 

3. The specific gravity of the richest mineral. A high 

specific gravity for the richest mineral will affect the 

assay of the sample, and fine grinding is indicated. 

4. The number of particles of the richest mineral in the 

sample. Fine grinding is necessary when there are few 

such particles. 

The principles underlying the four conclusions of 

Brunton (1896) were mentioned earlier by Reed (1885). 

After summarizing three rules (adequate mixing, impartial 

selection (sampling), and proper relative comminution) that 

should govern a properly conducted ore sampling operation 

(Reed, 1882), Reed (1885, p. 353) wrote: 

***what rule is to guide us as to the degree of fineness to 

which we should crush or grind before each successive 

reduction? I conceive the principle involved to be the 

following: 

The divergence of any portion of a lot of ore from the 

average percentage composition of the whole is due to the 

excess or deficit of one or more particles. The effect on the 

result will be the greatest when pieces causing this divergence are of the largest size and richest quality. 

Reed then gives a formula for the diameter of the 

largest particle size to which a lot of ore must be crushed or 
ground so that the largest allowable error will not be exceeded. The variables in the formula, 

D=0.05 [mpe]l[s k (f-l)a] 113 

are the diameter, D, of the largest particle, the grade, m, 

and quantity, p , of the lot of ore, the largest allowable error, 

e, the specific gravity, s, and the gold or silver content, k, 

of the richest specimens, the number of parts, f, into which 

the lot is divided, and the number of pieces, a, of size, D, 

and value, k, that can be in excess or deficit in the portion 

chosen for the sample. 

Reed (1885) gave a table for crushing amounts of ore 

of three grades. The maximum permissible diameters of 

pieces for combinations of amounts and grades of ore are 

listed in inches, but he added the practical equivalents of the 

diameters as coconut, fist, orange, egg, walnut, chestnut, 

pea, and wheat. 

Hofman ( 1901), in his discussion of crushing and 

sampling, gave a table prepared by Vezin (uncited work, 

1866). The table contains data for the minimum weight of 

sample in pounds for the diameter of the largest piece of ore 

in inches or millimeters, and the table reflects the constant 

ratio between the weight of the sample and the size of the 

largest particle that should be maintained through every 

stage of commercial crushing and sampling. Hofman included a table of safe sample weights to be taken, based on 

the diagrams of Brunton (1896), and a slightly condensed 

version of the table of Reed (1885, p. 357) in which the 

maximum permissible sizes of ore for a given grade are 

listed only as the practical units of coconut, fist, or orange. 

Richards ( 1903), after discussing Brunton's ( 1896) 

paper, plotted sample weights versus diameters of the 

largest particles, where the weights are proportional to the 

squares of the diameters of the particles. Samter (1908) in 

his short review paper on the theory and practice of sampling granular materials, listed the four conclusions of 

Brunton (1896) and derived a formula for the largest piece 

of ore that is similar to the formula of Reed (1885). He also 

reproduced the tabulation in Richards (1903, p. 850) for 

amounts of ore to be taken for different grain sizes, and the 

larger table of Richards (1903, p. 852) for sample weights 

to be taken when sampling ores of six different grades. 

Griffin (1909), after discussing the paper of Brunton (1896), 

showed that variations in analytical data are normally distributed. 

Bailey (1909a, 1909b) used the "size-weight percentage" in his paper on sampling coal. This criterion is the 

same as the size-weight ratio in Bennett and Franklin (1954, 

p. 485), who refer to Bailey (1909a), but the size-weight 

ratio is a percentage because of the multiplication by 100. 

Bailey's size-weight percentage is a formal name given to 

the ideas in Hofman ( 1901) and Richards ( 1903), and it 

appears to be a simplification of the formula of Reed ( 1885). 

Demond and Halferdahl (1922a) in their paper on the 

mechanical sampling of ore used the expression 

W=kDa, 

where W is the weight of ore, D is the diameter of the largest 

particle, and k and a are constants. They tabled sampling 

data for several crushing plants where a , the exponent to 

which the diameter is raised, ranged from 1.0 to 3. 76. They 

noted that an a as low as 1.4 should never be used and that 

a should never be as great as 3. 0. In a later paper on sampling spotty gold ores (Demond and Halferdahl, 1922b), 

their example of the amount of gold ore necessary for particles of various sizes reminds one of the similar example in 

Wickman (1963). 

Behre, in his section 21 on sampling in the earlier 

edition of Taggart's (1927) "Handbook of Ore Dressing," 

mentioned the four factors (allowable error, worth of the 

valuable mineral, size of largest pieces in the lot, and the 

size and number of pieces of valuable mineral) that govern 

the minimum weight of sample allowable. Among other 

items, he discussed the diagrams of Brunton (1896) and the 

formula of Demond and Halferdahl ( 1922a), but he did not 

give the formula in Behre and Hassialis (1945) derived from 

the binomial. 

Analysts have recognized errors in their work for 

many years. Benedetti-Pichler (1922) discussed the sources 

and magnitude of percentage errors in quantitative analysis. 

For the electrolytic determination of copper in various materials containing copper, including alloys, he recommended 

(Benedetti-Pichler, 1923, p. 321) that a 5- to 10-gram sample in a 250- or 500-milliliter flask be dissolved in nitric 

acid, the solution filled to the mark, and a 50-milliliter 

aliquot taken for analysis. He later made a similar suggestion about a large powdered sample and a small aliquot of 

a solution of this sample in his text on the microtechniques 

of inorganic analysis (Benedetti-Pichler, 1942, p. 238). 

Mika (1928), in his contribution to sampling, derived 

the relation between the minimum weight of sample and the 

amount of pulverization required. Baule and BenedettiPichler (1928) started with the binomial distribution to 

derive a formula that allowed one to calculate the error 

resulting from the sampling procedure. The formula could 

also serve for determining the necessary particle size as well 

as the minimum weight of sample. Baule and BenedettiPichler also noted that one equation in Mika (1928) applies 

only for a special case. 

The preceding discussion of the several methods is 

not intended to be exhaustive. The summary of methods by 

author, year, and abbreviated method in table 4 shows that 

many of us have reinvented the wheel. Five authors, not 

including Bennett and Franklin, used the size-weight relation, three used sampling constants, five used the binomial 

distribution, and six started with the Poisson distribution, 

which may be derived from the binomial. 

One may infer from the differences between years of 

publications in table 4 that the list of references is not exhaustive. A search of literature published during the first 

half of the century may depend as much on luck as on 

Topics and Problems for Reference Samples and their Data 27 
Table 4. Summary of methods relating sampling, errors, and 

particle size 

Author Year Method 

Reed ..................... 1885 Sample weight/size of largest particle 

Brunton .................. 1896 Four written conditions (see text) 

Hofman .................. 1901 Sample weight/size of largest particle 

Richards .................. 1903 Sample weight/size of largest particle 

Griffin ................... 1909 Variation in data and normal distribution 

Bailey .................... 1909a Size-weight percentage 

Demond and Halferdahl ..... 1922a W=kDa 

Baule and Benedetti-Pichler .. 1928 Binomial 

Behre and Hassialis ......... 1945 Binomial 

Reiss and others ........... 1945 Binomial 

Bennett and Franklin ........ 1954 Size-weight ratio 

Laffitte ................... 1957 Poisson 

Visman ................... 1962 Sampling constant 

Wickman ................. 1963 Poisson 

Wilson ................... 1964 Multinomial 

Gy ...................... 1967 Sampling constant 

Kleeman .................. 1967 Binomial 

Clifton and others .......... 1969 Poisson 

Visman ................... 1969 Sampling constant 

lngamells and others ........ 1972 Sampling constant 

Harris and Kratochvil ....... 1974 Binomial 

Flanagan .................. 1976b Poisson 

Birger and Bruk ............ 1977 Poisson 

Moore ................ -.... 1979 Poisson 

perserverance, as the titles of earlier papers on the subject 

are not always as explicit as those of Samter (1908, "Theorie 

und Praxis der Probenahme komiger Materialien (Erze) "), 

of Mika ( 1928, "Theoretische Beitrage zur Probenahme"), 

and of Baule and Benedetti-Pichler (1928, "Zur Probenahme aus komigen Materialien"). 

Most of the methods relating particle size, sampling 

errors, and the amount of analytical sample to be taken may 

be used to (1) calculate the error that might be incurred, 

given a specified weight of sample, (2) specify the amount 

of sample to be taken to keep sampling errors at or below 

some level, or (3) specify the grain size to which a sample 

must be crushed so that -significant sampling errors may be 

avoided. Calculations by most methods should show that 

errors due to sampling heterogeneous materials may be ignored if the material is powdered to pass a 200-mesh sieve 

or, for Kleeman (1967), a 230-mesh sieve. 

Small Samples-Precautions and Preparation 

Inspection of either compilation of data on the USGS 

samples (Flanagan, 1969, 1976c) shows numerous data obtained by the isotope dilution-mass spectrometric (IDMS) 

method for elements in the series of samples G-2 through 

BCR-1. The possible use of IDMS for lead isotopes was 

considered prior to preparation of these reference samples, 

but the numerous determinations resulting from the NASA 

28 Reference Samples in Geology and Geochemistry 

Lunar Program were not anticipated in 1963. The samples 

were, therefore, not sieved, for two reasons: (1) the task of 

sieving at least 100 kg of powder for each rock sample 

would have been enormous; and (2) lead might have been 

introduced into the samples if the screen was soldered to a 

sieve frame. 

The decision to avoid sieving is not new: in 1908, 

Hillebrand advocated not sieving rock samples prepared for 

analysis. He did not specify the material of the wire cloth for 

the sieves, and the frames may have been made of brass. 

Since brass scratches readily, brass would be removed from 

any surfaces of the sieves by ground silicate rocks, whose 

hardness may vary from 5.5 to 6.5 on Moh's scale of hardness. 

Thompson and Bankston (1970) describe tests for 

contamination using Specpure Si02 and CaC03 and a natural quartz sand. Half-gram portions, about the size used in 

their analytical program, were powdered in several small 

grinding devices and sieved through several screen materials. The authors present emission spectrographic data to 

indicate the level of contamination. 

Hillebrand ( 1908), in a paper on the effect of grinding 

on the water and ferrous iron contents of rock and minerals, 

confirmed the conclusion of Mauzelius ( 1907, p. 7) that "the 

percentage of ferrous iron is diminished by pulverizing, and 

no other explanation can be given for this than that one of 

the minerals contained in the rock has been oxidized during 

the grinding." Both authors used some form of a "diamond" 

steel mortar, although Hillebrand's was called an "Ellis' 

mortar" (Hillebrand, 1907, p. 46). Both men used agate 

mortars to grind to a grain size of 0.18 mm ( 100 mesh) or 

finer. Mauzelius did not state if his was a hand operation, 

but Hillebrand noted that grindings for 20 or 30 min were by 

hand and that those for a longer time were by a McKenna 

mechanical grinder. The latter was a primitive version of 

automatic mortar grinders, for example, the Fisher grinder, 

which has been used for at least the last three decades. 

Grinding can cause changes both in some chemicals 

and in the crystallography of some minerals. Lea (1893) 

reported some decomposition of silver chloride, sodium 

chloraurate, and other chemicals when compounds were 

ground with a mortar and pestle. Jamieson and Goldsmith 

(1960) reported some changes in natural and synthetic carbonates when portions were ground in a mechanical mortar 

for periods of up to 3 days. The changes were noted in x-ray 

diffraction patterns after grinding for several intervals of 

time. 

Bums and Bredig (1956) showed that calcite, the 

stable form of calcium carbonate, can be converted to the 

metastable form, aragonite, by grinding. X-ray diffractometer traces of CaC03 after grinding for periods of 0.5 to 38.3 

hr showed an increase in peak heights for aragonite and a 

simultaneous decrease in peak heights for calcite. The 

metastable form reverts rapidly to calcite when heated to 

about 400°C. 
The effects of grinding on the water and ferrous iron 

contents of rock samples have been amplified since the 

introduction of mechanical grinders not of the mortar-andpestle design. The most common type of grinder formerly 

used to powder samples is the disc or plate grinder. The 

older models were driven by belts connecting the motor and 

the drive shaft for the disc, but direct-drive models have 

been available for at least two decades. For both types, the 

stationary plate through which the sample is fed is hinged to 

the frame of the grinder and the movable plate is attached to 

the shaft. The distance between the stationary and movable 

plates may be adjusted for the desired grain size of the 

finished product. 

Another grinder for small amounts of rock sample is 

the vertical Braun sample grinder which has curved movable 

and stationary plates. This grinder is useful for small 

amounts (s200 g) of sample. The curvature of both plates 

may be roughly described as the bottom half of a hyperboloid of a single sheet, the hyperboloid being generated by 

revolving a hyperbola around its axis of symmetry erected 

vertically. The movable lower plate is threaded to the vertical shaft, and the stationary plate, with a hole in the center 

through which sample is fed, is attached to the unit. Grinding occurs between the upper surface of the movable plate 

and the undersurface of the stationary plate, which may be 

adjusted for the desired grain size of the product. Steel 

plates of several compositions and ceramic plates are available. 

One should avoid using steel plates for either the disc 

grinder or the vertical Braun grinder. Particles of rock being 

powdered between the surfaces of plates may be smeared 

with iron and, probably, with some of the elements used for 

making the steel alloys. The free iron (Fe0) introduced into 

the sample will be determined as part of the FeO, thus 

destroying some of the usefulness of the Fe+3/Fe+2 ratio as 

a measure of the oxidation state of the rock unit. The amount 

of heat generated by the grinding action of plates of any 

material on the powdered material may oxidize some of the 

original ferrous iron and may cause loss of either H2o- or 

H20+, which are normally determined in a rock analysis. 

Ceramic plates have the advantage that the principal 

contaminant will be the main constituent of the ceramic, 

alumina. It is not known if one can correct for the alumina 

introduced as excess corundum in the calculated C.I.P.W. 

norms. The ceramic plates will also become warm or hot to 

the touch, thereby, perhaps, causing some oxidation of the 

ferrous iron and some loss of either water. The ceramic 

plates cannot be operated continuously and must be allowed 

to cool. While cooling, the plates frequently crack and small 

pieces of either plate may break and fall. 

The most promising equipment for powdering small 

amounts ( ~ 50-100 g) of rock reduced to a small grain size 

( ~ 10 mesh or 2 mm) are ring and puck mills, of which the 

Spex Shatterbox and the Siebtechnik Mill are examples. The 

puck, ring, and inside of the container may be made of 

porcelain or agate. Neither material causes significant contamination (but see Reay, 1981, for oxidation of FeO), and 

the porcelain or agate parts do not become too warm during 

intermittent laboratory operations. 

The more costly agate containers are liable to break 

along natural fracture planes in the agate when rather coarse 

material ( ~ 114 in, 6 mm, or larger) is powdered, and it is 

recommended that rock fragments not larger than 10 mesh 

(2 mm) be used. In normal use in this laboratory, a sample 

load of 50 to 75 g can be reduced in 3 to 5 min to a powder, 

most of which will pass through a 200-mesh screen. 

A tungsten carbide container is available for these 

small mills, but it should be avoided at all costs in a laboratory that prepares geologic samples for analysis. Agus and 

Hesp ( 197 4) report a study in which 20-gram portions of a 

sand, with no determinable tungsten and cobalt, were processed for periods of 15, 25, 35, and 45 s in a tungsten 

carbide container. The powdered samples, in order of increasing grinding times, contained 600 to 2,000 ppm Wand 

80 to 300 ppm Co. The operation of a tungsten carbide 

container is efficient but dangerous in a laboratory dealing 

with geologic materials. The grinding medium may be noted 

in several places, but records may be lost and a future 

geoscientist may search for nonexistent tungsten deposits. 

Schroll ( 1975, p. 27) discusses the introduction of 

contaminants, including tungsten and cobalt from tungsten 

carbide, into a sample during rock powdering. Joron and 

others (1980), in a study of basalts from the East Pacific 

Rise, found that some samples were contaminated because 

they were processed aboard the ship by a tungsten carbide 

container for the Shatterbox. In addition to the usual tungsten and cobalt, they mention possible contamination by 

tantalum and niobium. 

A pulverizer useful for soft materials, but not for 

silicate rocks, is the MIKRO-SAMPLMILL, or MikroPulverizer. This laboratory used one of these pulverizers, 

known locally as a hammer mill, for processing lignites 

because the lignites would become warm, partially oxidize, 

and stick to both plates of a disc grinder. Similar pulverizers 

with hammers of different shapes are used industrially for 

materials softer than silicate rocks, including mica for beneficiation. 

The hammer mill with brass or steel hammers works 

efficiently for soft materials, but the hammers and the materials of which the mill body and screens are made will cause 

significant contamination if used for silicate rocks. The pulverizing action of the mill may result in a short lifetime for 

hammers made of porcelain. 

Moore (1978) powdered the Purington Shale sample, 

KnC-ShP-1, by processing the sample through a hammer 

mill having stainless steel hammers. He first tested his 

crushing and powdering procedure by passing a 10-kilogram 

aliquot of the shale through a jaw crusher, then passing it 

twice through a roller mill set at different openings, and 

finally powdering it in the hammer mill. The stainless steel 

Topics and Problems for Reference Samples and their Data 29 
screens of the hammer mill lost 6.08 g during processing. 

Moore assumed a proportional loss of the same order of 

magnitude for the hammers and calculated that 25 to 50 ppm 

of iron were added to the sample. 

Beaulieu ( 1971) described a dust-free grinding installation in which he used a miniature jaw crusher and a miniature disc pulverizer. The ceramic jaw plates were about 5 em 

wide by 13 em long and the pulverizer had ceramic plates 

about 4 em in diameter. 

A laboratory cylinder mill for small samples, principally coal, is described by Schlesinger and others (1963). A 

small ball mill using an alumina ball inside a Pyrex tube ( 45 

mm outside diameter) is described by Kita (1981). The mill 

can be evacuated to 10-3 torr or can be operated under 3 atm 

pressure, but the lower piece of glass tubing must be replaced after it has been used several times. A pulverizer for 

mica (Neuman, 1956) has sharp knife edges to split mica 

particles floating in air without causing lattice distortions for 

x-ray work. Abbey and Maxwell (1960) used a common 

kitchen device, a Waring blender, to pulverize up to 15 g of 

a bulk sample of mica in water. 

Small laboratory ball mills of either the centrifugal or 

the planetary type are available commercially. The grinding 

bowls and balls are made of agate, sintered corundum (either 99.7 or 85 percent A 120 3), tungsten carbide (93 percent 

WC, 6 percent Co), chrome steel (12 percent Cr, 2 percent 

C), stainless steel (18 percent Cr, 8 percent Ni), and zirconium oxide (97 percent Zr02). Only the agate and the sintered corundum bowls and balls are appropriate for powdering small rock samples. 

Several suppliers of laboratory apparatus and reagents 

in the United States advertise a small, high-speed grinding 

apparatus called the MICRO-MILL. The grinder, with dimensions 5lf2X7X 11 in (140x 178X278 mm), can accept 

. sample volumes of between 20 and 50 mL and has interchangeable grinding chambers and milling blades. As the 

blades may rotate up to 20,000.rpm, the temperature of the 

grinding chamber may be maintained by heat exchangers, 

for which hose connections for 6.4 mm (inner diameter) 

tubing are provided. The chamber and the blades may be 

stainless steel "hard faced" with stellite. There are two compositions, in percent, for stellite given in Gardner and Cooke 

(1968): (1), Co 59.5, Mo 22.5, Cr 10.77, Fe 3.11, Mn 2.04, 

C 0.87, Si 0. 77, S 0.08, and P 0.04; and (2) Co 75, Cr 20, 

and W 5. These three materials for the chambers and blades 

should be avoided, as they will introduce some important 

trace elements into rock samples at the speed at which the 

blades rotate. 

Excess Grinding and the FeO Contents of Rocks 

The effects of excess grinding on the FeO contents of 

rocks should not be underestimated. French and Adams 

(1972) found that when they ground a portion of the doler30 Reference Samples in Geology and Geochemistry 

ite, I-3, from Queen Mary College for 20 min, the original 

FeO content of just over 10 percent was reduced by 0. 5 

percent and that this rate of oxidation was maintained as the 

grinding time continued to about 60 min, when the measured FeO content was about 8 percent. 

Reay (1981) studied the effect of disc mill (ring and 

puck) grinding on some rock-forming minerals. There were 

observable losses in the FeO contents of a chlorite, a biotite, 

and a greenschist, but not of an actinolite, when sample 

portions were analyzed after several different grinding times 

of up to 360 s. The most dramatic change is shown in 

figure 2 of Reay (1981, p. 180), in which the FeO contents 

of a chlorite are plotted against the number of times the 

grinding mill was opened for sampling. The FeO content, 

about 18 percent for material sampled after the first opening, 

was slightly less than 13 percent after the mill was opened 

the ninth time. 

Keller (1955) noted that, during laboratory grinding 

of montmorillonite, the iron in the clay may be oxidixed 

sufficiently so that the effect is observable by simple tests. 

Mackenzie and Milne (1953) dry-ground a muscovite in a 

mechanical agate mortar for up to 24 hr and plotted the 

increase of cation-exchange capacity with increasing grinding times. Fitton and Gill (1970) attribute oxidation of ferrous iron in a rock powdered in a puck and disc mill to 

atmospheric oxidation. A sample ground in a sealed mill for 

6 min contained 6.1 percent FeO, but another portion contained 5. 5 percent when the mill was opened and resealed at 

each minute for 6 min. 

Large Samples-Precautions and Preparation 

Implicit in the preparation of small samples for analysis in a laboratory is the question, "With what should I 

contaminate the sample?" The question is more important 

for rock reference samples, as contamination introduced at 

any step between the rock formation and the powdered 

product will be included in the composition of the reference 

sample. 

It is therefore incumbent upon the preparer of a reference sample to avoid all possibilities of contamination. If 

the preparer of a sample has, for example, only one jaw 

crusher, one roller crusher, and one ball mill for processing 

rock samples, each piece of machinery should be thoroughly 

cleaned before starting to prepare a sample. It is obviously 

more efficient to finish processing a large sample, even over 

a period of several days, before using the equipment for 

other rocks, as it would not be necessary to reclean the 

machinery. 

There is another source of contamination, commonly 

referred to as cross-contamination. This can occur not only 

from machinery that was not cleaned, but also from dust in 

the air arising from the processing and from chips of another 

rock being processed adjacent to the reference rock. The 
apparatus used to process reference rocks should be isolated 

from all other crushing and grinding activities; in a large 

organization that also prepares other rocks, ores (or mineralized samples), and coals, the equipment for preparing the 

four types of samples should be isolated from one another. 

One institution prepared samples with a minimum of 

contamination. Ando (1967), in a notice about the availability of the granodiorite GSJ-JG-1, noted that the larger 

pieces of the rock were broken with a mortar and pestle 

made of the rock and the sample was powdered between two 

large pieces of the same rock. The basalt GSJ-JB-1 was 

prepared similarly (Kurasawa, 1968). 

A common contaminant of many powdered rock 

standards is iron, together with some unknown fraction of 

other elements used in making steel. Some iron is first 

introduced in the field when the geologist hits an outcrop 

with a steel pick or sledge hammer to obtain the sample to 

be prepared. The contamination may be in the form of 

metallic streaks; the pieces of rock may be examined in 

either the field or the laboratory and the suspect pieces 

discarded. 

If one obtains the sample from a quarry, drill bits may 

cause some contamination and one should be careful that 

blasting caps containing mercury fulminate are not used. 

Mercury is an element of environmental concern (U.S. Geological Survey, 1970; Friberg and V ostal, 1972), and the 

mercury contents of rock standards may be used as background levels for environmental studies. Flanagan and others ( 1982) infer that the high and extremely variable mercury content of USGS-W -1 may be due to the use of 

blasting caps containing mercury fulminate before the collection of the sample in December 1946. 

When large pieces of rock are brought to the laboratory, they are generally hit with a geologist's pick or a 

sledge hammer to reduce the pieces to a size about half that 

of a man's fist, a size that will fit readily between the jaws 

of the laboratory crusher. The nature and amount of contamination introduced is about the same as in the field, and 

inspection of the pieces is recommended. 

A jaw crusher is usually the first mechanical step in 

size reduction by most organizations that prepare rock 

standards. Crushers may range in size from a heavy-duty 

laboratory model having steel jaw plates about 4 x 8 in to 

pilot plant models whose plates may measure 1 x 1112 ft. Jaw 

crushers and other machinery used for primary particle size 

reduction are illustrated and discussed in many texts on ore 

and mineral dressing. 

The jaw crusher used for processing USGS standards 

has flat plates, about 4.5 X9.5 in, made of high-manganese 

steel that resists machining. The plates are attached by flatheaded bolts whose heads are beveled to fit a beveled .hole 

at the intersection of the diagonals of the plates. The maximum opening between the bottoms of the two plates is about 

3/s in, but this gap may be reduced by inserting "shims" (thin 

metal plates of the same size as that of the jaw plate but of 

varying thicknesses) between the stationary plate and the 

frame of the crusher to which the plate is attached. 

It is frequently advantageous when processing a large 

amount of sample (> 100 kg) to operate a crusher first with 

the maximum gap between plates and then to reprocess this 

crushed material through a narrower gap. One should not 

feed too much rock between the jaw plates at one time, as 

some partially crushed material may not pass between the 

bottom edges of the plates. This may cause pieces to be 

crushed or rubbed numerous times by the plates, thereby 

increasing the possibility of contamination by iron and manganese. The smaller particle sizes passing the narrower gap 

are more amenable to the text step in size reduction. 

Another jaw crusher commonly used has plates that 

are ostensibly designed to grasp the pieces of rock during 

crushing, thus preventing the pieces from slipping on the 

steel plates and perhaps resulting in more efficient crushing. 

When viewed from the end, the working side of either plate 

is a series of rounded ridges and valleys. 

The ridges wear or chip away fairly readily, with 

maximum wear occurring down to or below the intersection 

of the diagonals of the plates. One make of jaw crusher has 

ridged plates attached by recessed bolts at the four comers. 

Maximum wear for any jaw plates occurs at the intersections 

of the diagonals of the plates, but contamination by iron 

from flat plates is less severe. If there were a choice, the 

ideal crusher for a rock standard would have flat plates 

attached at the four comers of the plates. Maximum wear 

occurs on the jaw plate that moves. 

Graff (1973) showed different compositions for 

crushed rocks and for the dust collected during jaw crushing. Dust -collection systems should remove only dust that 

would escape the container for catching the product. Dust 

should be collected at an elevation lower than that of the 

container for receiving the crushed sample. 

The next step in size reduction is usually a roller 

crusher. The two rolls, which rotate in opposite directions, 

introduce little or no contamination by iron into the sample 

when the crusher is operating properly. The bearings for the 

shaft on either side of a roll are held in place by a large 

spring. These springs allow the space between the rolls to 

widen sufficiently to pass an oversize piece of hard rock that 

is too large to be crushed between the rolls. Experience has 

shown that is is preferable to pass the granular material 

through the rolls twice, first with the rolls about 118 in apart 

and then with the rolls touching. This two-stage treatment, 

plus a system to mechanically feed coarser materials into the 

rolls at a constant rate, will produce a crushed product 

having a fairly uniform size distribution and a minimum of 

oversized particles. 

The first two USGS rocks, G-1 and W-1, were powdered in ball mills. Both samples were screened through 

sieves, G-1 to pass an 80-mesh screen and W-1 to pass a 

100-mesh screen. The Canadian sulfide ore (SU-1) was not 

ground, but the syenite rock (Sy-1) was pulverized (CanaTopics and Problems for Reference Samples and their Data 31 
dian Association for Applied Spectroscopy, 1961, p. 160) in 

a Braun pulverizer whose plates were set to yield -100-

mesh material. The material of which the plates were made 

was not specified, but it is known that the sample was not 

screened. Ignoring possible contamination by iron and the 

heating effect of the plates on the powder, the plate or disc 

grinders are efficient for samples of small size but an inordinate amount of processing time is required as the sample 

size increases from an ounce or two to 100 kg or more. 

Ball mills for powdering rock samples are now used 

by at least three organizations, the Canadian Certified Reference Materials Project, the National Institute for Metallurgy, and the U.S. Geological Survey. Ball mills are made 

for different capacities, and both conical and cylindrical 

mills are used. The mills may be unlined, the steel body of 

the mill serving as the liner, or they may be lined. The 

linings include Belgian burr stone (a silicate of unknown 

composition, judging from the commercial literature on ball 

mills), rubber, porcelain, and other materials. The balls may 

be made of steel, Belgian burr stone (sized, rounded cobbles), porcelain, or other materials. 

It is reasonable to avoid steel liners and balls to prevent the introduction of iron into the powdered rocks. A 

rubber or plastic liner for the mill should not be used because of determinations of carbon in igneous rocks (Flanagan and others, 1976b). The use of Belgian burr stone is not 

unreasonable, but if contamination occurs the mode of occurrence of the contaminating element or the average chemical composition of the stone must be determined for possible corrections. I decided to use a liner and balls made of 

porcelain, the principal component of which is alumina 

( ~88 percent A1 20 3). I estimated the amount of alumina 

added ( ~0.1 percent) during the preparation of rock powders (Flanagan, 1967), but I doubt if one can correct for this 

alumina as excess corundum in the C.I.P.W. norms (Cross 

and others, 1902). Semiquantitative spectrochemical estimates of the trace elements in a powdered ball indicate that, 

with the estimated wear on the balls, trace elements are not 

added in amounts that will affect the trace element compositions of the rocks. 

It is not always necessary to avoid steel, rubber, or 

plastic liners when powdering a sample. The magnetite reference sample (Stoch, 1978b) is an obvious exception. The 

ore was received as damp-ground material that was air-dried 

in the sun on drying racks. After screening through 150 

mesh and initial blending, final blending and grinding were 

done in a rubber-lined mill using 110-kilogram batches of 

material with 125 kg of steel balls. The steel balls would not 

add detectable contamination by iron and alloying elements, 

and the use of the rubber-lined mill seems permissible because it is unlikely that carbon will ever be determined in 

this reference sample as it has been in volcanic rocks. 

There is an additional advantage of using a ball mill 

for powdering samples. During the preparation of the USGS 

samples issued in 1964, I noticed that the steel shell of the 

32 Reference Samples in Geology and Geochemistry 

mill was slightly warmer than room temperature. I therefore 

stopped the operation of the mill several times, removed its 

cover (a procedure requiring an elapsed time of less than 1 

min), and measured the temperaure of the powder in the 

mill. An average of several measurements showed that the 

powder was about 5°C warmer than room temperature. 

Therefore, powdering in a mill should not affect the FeO or 

H20 contents of the reference sample. 

Sieving 

Some organizations sieve the entire batch of a sample, 

while others avoid screening entirely. Although Hillebrand 

( 1907) emphasized that metal sieves should not be used, 

determinations of isotopic compositions by IDMS make it 

almost imperative that sieving be avoided. If lead solder is 

used to attach the screen to a frame, determinations of 

major, minor, and most trace elements should not be affected, but there may be a disastrous effect on geologic ages 

that depend on IDMS determinations of lead isotopes. If 

silver solder is used, some contamination might be expected, even though silver solder is much harder and hence 

more resistant to wear. If a rock standard is sieved, details 

of the sieving operation should be given in a prominent 

place in an introductory paper on the reference sample. 

USGS samples were not sieved. Small portions used to test 

particle-size distributions are always discarded. 

This laboratory uses nylon cloth screens with a frame 

made of two pieces of either nylon or acrylic tubing, rather 

than the usual brass or stainless steel. The diameter of the 

tubing is 5 112 in, and the wall thickness is lf4 in. One half 

(1/s in) of the outside wall thickness is removed to a depth 

of about 0. 2 in by machining the bottom end of the top piece 

for a frame, and a similar amount is removed from the inside 

wall thickness of the upper end of the lower piece for the 

frame. A piece of nylon screen material is placed between 

the two matched ends, and the top and bottom pieces of the 

frame are firmly pressed together to hold the nylon cloth 

tightly. Excess nylon cloth outside the frame is removed. 

Sieves varying in diameter from 2 to 12 in have been 

available for years from chemical supply houses. Larger 

round screens with diameters of 18, 24, 30, 48, 60, and 72 

in are used commercially. These screens are also called 

separators, as each screen may have an exit spout through 

which oversized material not passing a screen is removed. 

Such screens or separators are generally used in industry, 

where some particle-size separation of a commercial 

product is desired. 

One company furnishes a sieve-testing apparatus that 

has screen trays 18 in wide by 26 in long, a clear screen area 

of 2 l/3 ft2, and a screen capacity of 1 ft3• This sieve-tester 

might be used by a producer who wishes to sieve a rock 

reference sample of about 100 kg, but the screen wire cloth, 

mad~ of steel, brass, or phosphor bronze, may introduce 

contamination into the sample. 
Contamination by Steel 

In addition to the contamination of small samples by 

tungsten and cobalt discussed by Agus and Hesp ( 197 4) and 

by Joron and others ( 1980), large reference samples may 

contain free iron (Fe0) owing to the processing of rocks in 

a jaw crusher. Ritchie (1968) determined free iron in a 

number of standards; the data he obtained by two chemical 

methods are plotted in figure 1. The solid diagonal line 

extending from the origin at an angle of 45° may be called 

the line of equivalence, as all plotted points would fall on 

this line if the methods were equivalent. The dashed line is 

the least squares line of regression showing the relation 

between the two methods. The plotted points for the USGS 

rocks released in 1964 show that these rocks are generally 

less contaminated by free iron than are other samples. 

Because of the importance of FeO in a rock analysis, 

the free iron contents of all geochemical reference samples 

should be determined. The FeO contents of the rocks determined by analysis may then be corrected, if necessary, by 

subtracting the FeO equivalent of Fe0. 

One might expect negligible contamination from a 

jaw crusher used to crush relatively soft materials such as 

coals, but Senftle and others (1982), in a study of the magnetic properties of pulverized coal, found a total steel contamination of about 0.02 percent. This estimate is about the 

same as the free iron contents of some silicate rock reference 

samples reported by Ritchie ( 1968). Senftle and others 

(1982) present a scanning electron microscope photograph 

showing curled shavings of magnetic particles whose compositions are major Fe and minor Mn. 

50 

1; 

>< 40 * "'C 

0 

£i 

Q) 

E 30 

N 

u 

:J 

u 

~ 20 

OQ) 

u.. 

10 

GR 

Q-+134 

• USGS 

0 CRPG 

$ ZGI 

1::. MAT 

GM 

$-+ 129 

10 20 30 40 50 60 

Fe0 by HgCI2 method (%x1o3) 

Figure 1. Free iron (Fe0) contents of some reference samples 

determined by two chemical methods. (Data from Ritchie, 

1968.) 

Homogeneity of Reference Samples 

Methods for determining the homogeneity of reference samples are numerous and depend on the physical state 

of the sample and the analytical technique used. For powdered samples, the methods depend on whether the test is 

made before or after bottling, or both. The methods range in 

complexity from simple statements about the precision of 

the method to several statistical techniques and designs. 

Barnes and others (1973), using the IDMS method, 

determined uranium, thorium, lead, and thallium in wafers 

cut from 2-meter rods of the NBS trace-elements-in-glass 

standards. The wafers were randomly selected from 100 or 

more rods, thereby representing concentrations of the elements over the length of the glass cane pulled for a specific 

sample. The authors write that "within the experimental 

limits show in Table 1 , the results indicate that this material, 

on the basis of 1-gram samples, is remarkably homogeneous 

for the four elements analyzed over a length of 400 or more 

feet." They later indicate that "the homogeneity * * * may be 

further demonstrated by plotting these data * * * . " They 

note that some radial heterogeneity exists across the face of 

a single wafer and specify that a whole wafer should be used 

as the analytical sample. 

During the discussion following a talk by Flanagan 

(1975), W.R. Shields of the National Bureau of Standards 

noted that USGS-BCR-1 had been found to be heterogeneous for thorium. He used the criterion that data on sample 

portions differed between bottles by more than one order of 

magnitude beyond the capabilities of the IDMS method. 

Such statements are common in the literature of analytical chemistry. They suffer, however, the disadvantage 

that the statements about homogeneity, or the lack thereof, 

cannot be made with an assigned probability. 

Boyd, Finger, and Chayes (1969), in a paper on computer reduction of electron-probe data, used the homogeneity index, defined as the ratio of the observed standard 

deviation to the standard deviation predicted from counting 

statistics. A sample is considered heterogeneous if the index 

is greater than 3. Under the assumption that the counts are 

normally distributed, the index is a standardized normal 

deviate and the index of 3 will cover about 99 percent of the 

area under the normal curve. 

Jarosewich and others (1979, 1980) used the same 

homogeneity index. Drake and Weill (1972, p. 180) approach this index when they write," a sample is considered 

homogeneous when the standard deviation of the mean of a 

large number of spot analyses is equal to the uncertainty due 

to counting statistics." 

A routine procedure for testing the homogeneity of 

electron microprobe data was described by Marinenko and 

others (1979). The total counts acquired in a preset time, 

usually 10 s, are fed to both a teletype and a fast strip 

recorder. The specimen stage of the probe, controlled by a 

periodic ratemeter, can be advanced in steps of from 1 to 10 

Topics and Problems for Reference Samples and their Data 33 
f.-liD, and data can be collected at each new spot. The homogeneity required depends on the intended use of the sample, 

and measurement conditions can be chosen so that the Poisson limits are within the desired level of homogeneity. The 

technique was used to test the homogeneity of a research 

material, Glasses for Microanalysis (RM-30), and several 

alloys. 

Another method used to reflect sample heterogeneity 

is that of Myers and others (1976). They made quantitative 

spectrochemical determinations for 23 elements in two portions from four bottles of each powdered glass sample. 

Because line intensities in emission spectrography are exponentially related to concentration, they transformed the data 

logarithmically and calculated sl, an estimate of the log 

variance among bottles of sample. They then obtain a factor 

for predicting the limits of variation introduced by heterogeneity by F =antilog sA , and the factor, F , is a geometric 

deviation. The authors table such geometric deviations for 

the 23 elements in the samples but do not specify an acceptable upper limit for the deviations. 

Valcha ( 1977) suggested the F ratio for testing homogeneity, and Dempir ( 1978) gave an example for a reference 

sample of glass sand. Using x-ray fluorescence and an iron 

line, Dempir counted the responses from single portions 

taken from each of 50 randomly selected bottles of the sand 

and calculated the variance, si, of these counts. He then 

took 50 subsamples from a single randomly chosen bottle, 

counted the responses from these portions, and calculated 

the variance, Sf, of these 50 counts. As a result of the 

nonsignificance of the variance ratio, F =si/ Sf, he accepted 

the alternate hypothesis that iron is distributed homogeneously among the bottles of glass sand. Similar conclusions were reached for Ti02 and MnO. This F ratio differs 

from that in the usual analysis of variance for an experimental design as there is only a single datum per bottle, except 

for the bottle from which 50 subsamples were taken, and the 

variation within bottles cannot be estimated. 

The Mines Branch, Ottawa (now CANMET), published a series of reports (McAdam and others, 1971, 1973a, 

1973b; Faye and others, 1974; Steger and others, 1975; 

Ingles and others, 1977) on their reference samples of economic interest. In many reports, the t test or the "standard" 

t test at 5 percent probability is used to determine the homogeneity of one or more elements in two bottles of sample. It 

may be assumed that the t test is the usual test of the difference between two means, but the F ratio, necessary to 

determine if the two variances are homogeneous prior to 

pooling the variances for the t test, is not mentioned. 

Steele and others (1975) used both F ratios and t tests 

to determine if a reference sample of a precious metal ore, 

PT0-1, was homogeneous, and they discuss the mode of 

occurrence of related pairs of precious metals for which a 

few significant differences were found. Stoch and Steele 

( 1978) used the t test on the analytical data submitted, after 

rejecting averages that were outliers. The t test on analytical 

34 Reference Samples in Geology and Geochemistry 

data was also used by Stoch ( 1978b) and by Stoch and others 

(1979). 

Scheaffer ( 1971) discussed a test for the homogeneity 

of a mixture composed of particles of different types and 

sizes. The test is based on variances and covariances, with 

x2 as the test statistic. 

The analysis of variance for demonstrating homogeneity now appears to be the technique used most frequently. The method has been used both before and after a 

sample has been bottled. After bottling, the technique may 

be used in testing preliminary data for one or more elements 

before the samples are issued for analysis, and the analysis 

of variance is frequently used to test data submitted by 

contributing laboratories. 

The experimental designs include one-way (a single 

variable of classification-the bottles) and two-way (two 

variables-laboratories and bottles) analysis of variance, 

and a one-way nested classification (Faye and others, 1975) 

in which the variance components are between laboratories, 

between bottles within laboratories, and within bottles. The 

one-way analysis of variance was used for USGS rocks 

(Flanagan, 1976b), for USGS manganese nodules (Flanagan 

and Gottfried, 1980), and for clay and feldspar reference 

samples (Flanagan and others, 1977). 

Lister ( 1978) used the one-way analysis of variance to 

show that Co in samples IGS 22 and IGS 23 was homogeneously distributed. He determined Co by neutron activation 

analysis in two portions from each of 10 containers of the 

samples, and the between-container variance was not significantly larger than the within-container variance at the 5 

percent level. 

There are problems concerning the use of the analysis 

of variance in the literature. One problem is the possible 

introduction of a variance component related to the day on 

which determinations were made. This may occur when a 

large number (75 to 100, or more) of portions of several 

samples are randomized in a single large random order and 

then analyzed over a period of several days or weeks. This 

procedure may introduce the variance component of between days or between weeks into the error term, which 

normally consists of the error of the method, errors due to 

sampling the heterogeneous powdered material, and random 

error. 

When such components are introduced, the information generally cannot be retrieved unless the experiment was 

designed for this purpose. There are designs by which variations due to time may also be estimated, including the 

Y ouden Squares discussed in Cochran and Cox ( 1950) and 

in other texts on statistics and experimental design. 

The problem of negative unit (bottle) variances occurs 

even when the design appears appropriate. Negative bottle 

variances are embarrassing, as variances are, by definition, 

positive. Statisticians have not solved the problem of negative variances, and bottle standard deviations resulting from 

them have been tabled both as "Neg." (Flanagan, 1976b) 
and as a numerical standard deviation followed by an italicized "i" (Flanagan and others, 1977) to indicate a negative 

variance as the source of the estimate. Until statisticians 

solve the problem, the use of "Neg." in tables of data seems 

less objectionable. 

Outliers 

The rejection of suspected outliers has been of intense 

interest to both analysts and statisticians for several decades. 

Many analysts reject outliers on the basis of their knowledge 

of the analytical methods, while statisticians have approached the problem from both practical and theoretical 

viewpoints. Grubbs ( 1950, p. 30) notes that the rejection of 

outliers may be just as much a practical or commonsense 

problem as a statistical one and that sometimes the practical 

or experimental viewpoint may outweigh any statistical contributions. Kruskal (1960) notes that it is very important to 

say something about outlier observations, that it is a dangerous oversimplification to discuss apparently wild observations in terms of inclusion in, or exclusion from, a more or 

less conventional analysis, and that the anomalous observation may be saying that here is something from which we 

may learn a lesson. 

Anscombe ( 1960) discussed some history of the rejection of outliers. "Statistics of Extremes" by Gumbel (1958) 

is an early text devoted to the theory of extreme values; a 

more recent text on outliers is that of Barnett and Lewis 

(1978). Grubbs (1969, p. 2) gave both general rules and 

statistical criteria for outliers. Harvey (197 4) discussed the 

detection and correction of outliers in geochemical analysis. 

Prescott (1979) gave a sequential test for many outliers, to 

be used in place of repeated applications of procedures for 

single outliers. Tietjen and Moore (1972) discussed several 

outliers and the masking effect. Rosner (1975) compared 

several "many outlier" procedures, finding that the extreme 

Studentized deviate (ESD) is slightly more efficient. 

Mikeshina (1966) published a short review on the occurrence and elimination of anomalous values. 

Several methods have been used for rejecting outliers 

in data for reference samples. The methods are used for 

rejection from a set of data by a laboratory, from means of 

sets of data by several laboratories, and from averages in 

compilations of data. Frequently, those who eliminate outliers are not sufficiently specific about the kind of data 

considered. 

Steele and others ( 197 5) used three procedures for the 

precision metal sample PT0-1. They first discarded any 

data differing by more than three standard deviations from 

means of sets of data. After calculating new estimates of the 

means and standard deviations from the remaining data, 

they again rejected data beyond 3 standard deviations, and 

repeated the process until there were no further rejections. 

Stoch and Steele ( 1978) and Stoch ( 1978a, 1978b) also used 

this procedure, whereas Stoch, Steele, and Copelowitz 

(1976) used x ±2s as their criterion for retaining data from 

which best values are calculated. Roche and Govindaraju 

(1971) eliminated data outside of x ± s before arriving at 

preferred means (x1) and medians (M1). 

Steele and others (1975) also used the coefficient of 

kurtosis, b2, and the coefficient of skewness, ~. These 

tests were also repeated until no further data were rejected. 

They also used one of the applicable Dixon (1953) criteria, 

repeating the process until no further rejections occurred. 

The Dixon criteria were among several procedures discussed by Grubbs (1969), who notes (p. 13) that "these 

techniques are not generally recommended for repeated rejection, since if several outliers are present in the sample the 

detection of one or two spurious values may be 'masked' by 

the presence of other anomalous observations . " 

Geary's "a" statistic (Pearson and Hartley, 1956) was 

used iteratively in several NIM (National Institute for Metallurgy, South Africa) reports to identify and reject outliers. 

The test, the ratio of the mean deviation to the standard 

deviation, was proposed by Geary (1935) as a test of normality. 

The robust standard deviation was used by Stoch 

(1978a, 1978b) to eliminate gross outliers. He obtained this 

standard deviation by arranging observations in ascending 

order of magnitude, removing one-sixth of the results from 

each extreme, and dividing the range of the remaining data 

by two. This estimate of the standard deviation is about 

one-third of the range, a procedure used by statisticians 

when a quick but not necessarily accurate estimate of the 

standard deviation is desired. 

Christie and Alfsen ( 1977) constructed histograms of 

data in compilations and fitted third-degree polynomials to 

the histograms. They calculated the partial correlation coefficient and the maximum of the polynomial, where the maximum serves to estimate the mode of the distribution. When 

the partial correlation coefficient was less than 0. 7, extreme 

values were gradually removed, but in no case was more 

than 10 percent of the data eliminated. 

Christie and Alfsen also used a gamma transformation 

to obtain a symmetrical distribution. The mean and standard 

deviation of the distribution are calculated and transformed 

back to the original data. The mean is a reliable estimate of 

the true concentration, but the standard deviation (an 

"interlaboratory" estimate) yields a confidence interval that 

is more or less asymmetric around the mean. The authors 

note that it is possible to establish strict criteria for rejecting 

outliers. 

Ellis, Copelowitz, and Steel ( 1977) used the dominant 

cluster method iteratively to reject outliers until one of four 

alternate conditions was met so that the iterations could be 

halted. After the rejections had stopped, the mean of the 

remaining data was reported as the mode. The mode may be 

estimated without curve-fitting, and the technique is independent of the distribution. 

Topics and Problems for Reference Samples and their Data 35 
In his critical study of published data on the USGS 

rocks Abbey (1970), after noting that 18 percent of the data 

for USGS-G-2 were beyond one standard deviation from 

the mean, decided to reject the 15 percent of the data farthest 

removed from the means. He then calculated preferred 

means for the data not rejected. Noting that not all laboratories reported the same number of data per USGS sample, he 

used an arbitrary rating system for data obtained by laboratories that could be classified as major contributors. He then 

calculated averages of data obtained by the eight "best" 

laboratories, i.e., those that scored highest in his rating 

procedure. 

I previously rejected, formally or informally, data 

beyond three standard deviations as not belonging to the 

same population as the remainder of the data. In the formal 

sense, the average and standard deviation of the data·, not 

including the suspected outlier(s), were calculated and data 

beyond there standard deviations were rejected as not belonging to the population. Informally, one-third of the range 

of the data was used to estimate the standard deviation. An 

occasional wild datum would be summarily rejected for, as 

Anscombe (1960, p. 124) notes, in sufficiently extreme 

cases where a reading may be grossly spurious, no one 

hesitates about such rejections. 

Colombo ( 1980) proposed a plot method to determine 

the mode of a set of skewed data. He arranged n data in 

ascending order of magnitude, ranking the lowest datum 1 

and the highest, n. He then plotted each rank against its 

paired determination and estimated the mode. The method 

is the same, except for the transposed x- andy-axes, as the 

S-curves used by Stevens and Niles ( 1960) for the distributions of constituents in G-1 and W-1. Das (1979) discussed 

geometric means as probable values for data. 

Lister (1978) notes that in a paper on the accuracy of 

ore analysis (Lister and Gallagher, 1970), the t test, three 

standard deviations, skewness, and kurtosis were used to 

eliminate outliers. Lister ( 1978) shows S-curves for Zn in a 

nickel concentrate, IGS 20. The plot contains 8 data near 

0.5 percent Zn and 26 data near 0.1 percent. The interval for 

the mean and standard deviation contained none of the 34 

data. He, therefore, rejected the eight high data solely on the 

basis of analytical common sense. 

Dybczynski (1980) compared the effectiveness of various procedures for the rejection of outliers. He showed that 

the concurrent use for four criteria (Dixon's test, Grubbs 

test, the skewness test, and the kurtosis test) at small 

(p =0.01) or moderate (p =0.05) significance levels gives 

better results than the use of any single test. He also compared results by his method with those by Student's t, the 

dominant cluster mode, and the gamma transformation. 

Estimation of Best Values 

The estimation of best values is concerned both with 

compilations of data and with analytical programs by issu36 Reference Samples in Geology and Geochemistry 

ing organizations to establish values for the samples furnished. The techniques range from roundtable meetings of 

the analysts involved to the analysis of variance of data 

submitted by cooperating laboratories. 

Christie (1975) noted that recommended values for 

three geologic samples were selected in a series of 

roundtable meetings of participating analysts. The means 

were based on two or more values in good agreement that 

were reported by at least two analysts who were from different laboratories and who used different methods. 

Abbey (1970) calculated averages of data by the eight 

"best" laboratories that scored highest in his rating procedure. Abbey and others (1975) used the same scoring system 

to obtain "select means" of the 9 laboratories that were 

major contributors of data and of 11 laboratories that were 

minor contributors of data, the laboratories in both sets 

having scored 51 or greater in his rating system. These 

select means yielded high summations for the rock analysis; 

after the data were reexamined and conspicuous outliers 

rejected, new select means were calculated as recommended 

values. 

Roubault and others ( 1966) and Roche and Govindaraju (1971, 1973, 1976) calculated preferred means, ib 

and medians, M 1, from those data within x ±s for all data in 

compilations. Ando and others (1971, 1974) calculated consensus means, Xc, from data included in x ±2s. 

McAdam and others ( 1971) list three methods to obtain the mean and 95 percent confidence limits: (1) analysis 

of variance, generally after rejecting data beyond 2s from 

the mean, and treating all sets of data from laboratories as 

independent, (2) weighted means to give a minimum variance, and (3) weighted means by the inverse of the square 

root of the variance. Method 1 was used to obtain the mean 

and confidence limits for the alluvial sand, PTA, and 

method 2 was used for estimates for the Cu-Ni matte, PTM. 

Most Mines Branch (CANMET) reports (McAdam and others, 1973a, 1973b; Faye and others, 1974, 1975; Steger and 

others, 1975; Ingles and others, 1977; Sutamo and others, 

1978) used analysis of variance to arrive at best values and 

confidence limits. 

Stoch (1974a, 1974b), after rejecting outliers, used 

the means of the data not rejected as recommended values. 

Stoch and others (1976), after rejecting outliers from some 

limited data for a series of five samples containing 0.2 to 44 

percent rare earth oxides, used two criteria for preferred 

values. If there were more than six values that were not 

rejected, preferred means were calculated if the coefficient 

of variation was less than (1) 15 percent for values exceeding 0.1 percent, or (2) 30 percent for values less than 0.1 

percent. 

Stoch and Steele (1978) derived means and medians 

for three ferromanganese slags, after rejecting outliers. 

Means were accepted when the distribution of the data was 

approximately normal, and the median was accepted for a 

non-normal distribution. 
Steel and others (1975) considered four methods to 

obtain best values: (1) the mean of averages of sets of data, 

(2) minimum variance, (3) inverse variance, and (4) analysis of variance. Although there was close agreement among 

the means, except for those obtained by minimum variance, 

they accepted as preferred values the means calculated by 

the inverse variance method because the weighting is more 

equitable. Stoch (1978a, 1978b) accepted as certified values 

the means calculated by the inverse variance method. 

Ellis and Steele ( 1982) discuss five robust indicators 

of central value, noting that the mean is unreliable. Lister 

( 1982, p. 181), in his discussion of weighting results, notes 

that bias may occur if one laboratory submits 10 data and 

another only 2. 

Another method for obtaining best values is one 

Flanagan and Gottfried ( 1980) used for manganese nodule 

samples. Although the method involves iteration, it avoids 

the numerous repetitions of one or more different tests for 

outliers that others use to arrive at final values. In many 

reports on reference samples in which the analysis of variance, following the rejection of outliers, is used, the reader 

will find no reference to the assumptions underlying the 

analysis of variance (Eisenhart, 1947), or to the consequences when these assumptions are not satisfied (Cochran, 

1947). 

The method is the sequential procedure of (1) determining which of k sets of n data have a common variance, 

thus satisfying one of the assumptions, (2) from this common variance, calculating the standard deviation of the 

means of n (=6) determinations, and (3) with this standard 

deviation and the Studentized range, determining which laboratory means could have been derived from the same population mean. The average of the means so selected is taken 

as the best estimate. 

Certification Factor 

A certification factor is used by Sutamo and Faye 

(1975). They define this factor as the ratio of the confidence 

interval of the consensus value, c , for a selected element, 

expressed as a percentage, to the mean within-laboratory 

coefficient of variation. They note that the recommended 

certification factor of :54 can be explained on the basis that 

the confidence interval is twice the product of the value 

taken from the t-distribution and the magnitude of the coefficient of variation of the censensus value. They note that for 

a large number of laboratories (2:20), t0 _9r2. For the confidence interval, therefore, 2t0_9r4. 

Colombo and Rossi ( 1978) discussed as a criterion of 

quality the ratio S L/ M , called a certification parameter. S L is 

the between-laboratories standard deviation obtained in the 

analysis of variance and M is the consensus (certified) value 

of the element being estimated. 

Nomenclature for Reference Samples 

The nomeclature for the samples with which we deal 

has varied greatly over the last eight decades. From the 

original terms "analyzed samples" and "standard analyzed 

samples," used for the early products of the National Bureau 

of Standards, and "chemical standards," used by the Bureau 

of Analysed Samples, we progressed through "NBS standard samples" and "standard rocks G-1 and W-1" in the 

literature up to the 1960's. 

The term "standard rocks" seems especially inappropriate as Krech and others (1974) described a standard rock 

suite, but they remove any doubt about the purpose of the 

rocks by giving their report the full title "A Standard Rock 

Suite for Rapid Excavation Research." One of their rocks is 

the Westerly Granite, the source of G-1 and G-2. 

Many of us knew NBS samples by the formal designation NBS Standard Sample XX, generally reduced to NBSXX. Circular 552 (3d ed.) of the National Bureau of Standards, published in 1959, was titled "Standard Materials 

Issued by the National Bureau of Standards." The 1965 

edition of NBS Miscellaneous Publication 260 introduced 

the subject as "Standard Reference Materials," with 

"Standards of Certified Chemical Composition" as the title 

of the frrst table. The NBS now calls its samples "certified 

reference materials" if the data for samples are of sufficient 

merit to warrant a certificate of analysis, and "reference 

materials" if the data are insufficient. 

Outer producers who certify samples are the National 

Institute for Metallurgy (Stoch and others, 1979), whose 

samples and certificates are distributed by the South African 

Bureau of Standards, the International Atomic Energy 

Agency (Dybczynski and others, 1979), the Council for 

Mutual Economic Assistance (CMEA) countries (Valcha, 

1977), the IRSID (lnstitut de Recherches de Ia Siderurgie), 

which distributes iron ores and other nonmetallic samples 

(Jecko, 1977), the Bundesanstalt fiir Materialopriifung for 

the German iron ores and other samples (Pohl and Oberhauser, 1978), the BCR (Community Bureau of Reference; 

see Colombo and Rossi, 1978), and the Bureau of Analysed 

Samples in England. 

The frrst two Canadian samples were called "syenite 

and sulfide standards" by Webber (1965) and "sulfide ore 

and syentite rock standards" by Sine and others (1969). 

Canadian samples a decade ago were called "standard reference materials" (McAdam and others, 1971), but shortly 

thereafter "certified reference materials" (Faye and others, 

1974), a practice that has continued (Steger, 1980). 

Recent practice has been to call such samples 

"geological reference mateials" (Steele, 1978), "rock reference samples" (Govindaraju, 1980), or "geochemical reference samples" (Govindaraju, 1980), the latter being abbreviated GRS. V alcha ( 1977) uses both "standard reference 

materials" and "geochemical standard reference materials." 

Lontsikh and Parshin (1980) use "standard reference samTopics and Problems for Reference Samples and their Data 37 
pies" and Lontsikh and others (1980), "reference rock samples." Because our profession has dealt with reference samples of geologic interest for most of this century, perhaps we 

should standardize our nomenclature for such samples. 

One can argue that the terms "geological reference 

sample" and "rock reference sample" are not sufficiently 

definitive, as the standard rock suite prepared by Krech and 

others ( 197 4) might be included in the definition in the 

absence of information on the purpose of the rocks. The 

~erm "geochemical reference sample" used in Govindaraju 

(1980, p. 49) would, therefore, seem the most appropriate 

generic name for the samples with which we deal. The term 

could include rocks, minerals, ores, soils, and sediments. 

By inference, the name could be extended to plant or leaf 

samples used in geobotanical investigations, and to fresh or 

marine waters used in studies of the interaction of water and 

sediments. 

Nomenclature also concerns the name applied to estimates given by producers of samples or by others who feel 

qualified to judge the validity of the data. Thus, the adjectives that modify, "values" are "certified," "attested," 

"recommended," "usable," "preferred," "probable," 

"possible," and "best." The terms "average" or "magnitude" 

may be used when an author feels that the quality of the data 

does not warrant a more precise description. 

"Certify" or "attest," which have a legal connotation, 

have the same approximate meaning in English-confirm 

formally, or affirm to be correct, true, or genuine. The legal 

connotation in "certified" or "attested values" may have 

some undesirable effects if one can demonstrate unequivocally that the certified or attested value is incorrect. One 

certified value shown to be incorrect is mentioned in Rose, 

Adler, and Flanagan (1963, p. 84). 

"Recommend" has the less forceful meaning of 

"commend to the attention of another as reputable, worthy, 

or desirable." Definitions for "usable" and "preferred" are 

obvious, and "best," as used in Flanagan and Gottfried 

( 1980), indicates that the population of data for a constituent 

in a sample has been determined by Studentizing the range 

of averages of sets of data by the standard deviation of the 

means of n determinations. This procedure is a method of 

rejecting means of sets of data as outliers, that is, the rejected means are not part of the population. 

For some certified or attested values, one sees only 

these values; for others, all data are available. For example, 

for the Moroccan phosphate BCR-32, Serrini (1981) published an introductory paper with a copy of the certificate of 

analysis but noted that a technical report on the several 

aspects of the certification is available. Other organizations 

publish averages of the data, or the entire set of data including the averages, that are used in the calculations for final 

values. 

Steele ( 1978) notes that a producer of a sample should 

consider the requirements of a potential user. The user may 

be dissatisfied if the certificate or accompanying report does 

38 Reference Samples in Geology and Geochemistry 

not contain sufficient information to enable him to judge the 

quality of the compositional values, or to use the sample in 

the correct manner. 

Thus, the producer of a geochemical reference sample 

might furnish in a published paper, or in a separate report, 

a brief description of the location and geology of the site 

from which the sample was taken, a reference to a more 

detailed geologic report, the entire set of analytical data, and 

the method, including references, for deriving the final estimates. 

Are "Best Values" Best? 

The question of which "best values" are really "best" 

must bother analysts who wish to use any set of reference 

samples, including a mixture of samples from several organizations, as points on a calibration line for their work. 

Abbey ( 1977b) notes that many workers use numerical data 

without reading and understanding the pertinent backgound 

information. For most analytical work in the literature, the 

most important background information, the data for the 

calibration line, is not available. 

Producers of new reference samples receive data from 

analysts of these samples with a note that reference samples 

x, y, and z, plus appropriate values, were used for the 

calibration. Although this information is important, it will 

not allow a producer or user to judge the value of the new 

data. The analyst should furnish the equation for the calibration line, and the mean, variance, and range of both the 

elemental contents of the standards and the responses of the 

analytical system to these standards (Flanagan, 1981). 

Even if the analyst furnishes the data described above, 

there may be a problem with the calibration line. Many 

analysts routinely subtract the blank value from the responses of their standards and then plot or calculate the 

calibration line. If the blank is zero, there is no problem; 

however, blanks are generally some value greater than zero. 

Higgins ( 1964) discussed some consequences of subtracting the blank prior to calculating the calibration line. 

After giving the equations for the variance of the slope with 

and without subtracting blanks, he tables the ratio of the two 

variances for n selected values of the calibration points. 

While the variances are equal for one calibration point, the 

ratio of the variances with and without subtracting blanks 

increases with the number of calibration points, or with the 

number of times the blank is subtracted. Thus, the variance 

of the slope after subtracting blanks for eight points is 1. 98 

times the variance when no subtraction is made. 

Both Abbey ( 1977b) and Flanagan ( 1981) suggested 

determining some element( s) in a number of reference samples by a reliable method. Abbey suggested plotting the 

signal obtained against the assigned concentrations to see if 

the plotted points are sufficiently close to a straight line. It 

would be better to calculate the equation for the line, as the 
intercept (or blank), a, is part of the equation y =a +bx. 

Further, two or more portions of each sample for a calibration point should be analyzed for· an element, especially if 

one is to make a judgement about the inadequacy of one or 

more best values. 

If an analyst finds that a best value for one or more 

reference samples is incorrect, this information should be 

published, together with supporting data, for the benefit of 

all users. I doubt that any scientist who has calculated best 

values is so sensitive that he believes his estimates are infallible. 

Confidence Limits for a Single Datum 

The calibration (regression) line suggested in the previous section to check the linearity of best values can also 

be used to obtain confidence limits for a single determination. Equations for calculating the two branches of the hyperbola that form the confidence limits around a line of 

regression are given in statistical texts, including Bennett 

and Franklin (1954), Mandel (1964), and Brown and Hollander ( 1977). An example of the confidence limits for a 

calibration line is shown in figure 2, in which the equation 

in Bennett and Franklin ( 1954, p. 229) was used with data 

from one of the several calibration lines in Flanagan and 

others (1982). 

50 

Ui 

z 

0 40 

(i) 

> 0 

..... 

a: 

<( 30 I Calibration line, 

~ Y=4.1 +2.05X w 

en 

z 

0 

.:l. 20 95% confidence limits en 

w for calibration line a: 

10 

5 10 15 20 25 

Hg (nanogram) 

Figure 2. Confidence limits for a calibration line. (Data from 

Flanagan and others, 1982 .) 

Calibration lines are familiar to all analysts. As normally used, one takes the response, y, of an element, x, in 

an unknown sample and extends a horizontal line from the 

y-axis to intersect the calibration line, then extends a vertical 

line from this intersection to the x-axis, from which one 

estimates the amount, x, of the element in the unknown 

sample. 

One might think, (as I assumed, erroneously) that 

confidence limits for x could be obtained by intersecting 

both branches of the hyperbola that form the confidence 

band by the horizontal line from the y-axis and by extending 

vertical lines from both intersections to the x-axis. The 

intersection of both vertical lines with the x -axis would yield 

confidence limits for a single datum. Mandel and Linnig 

( 1957) mentioned this procedure for estimating limits for x, 

given y, and the asymmetric confidence limits for x that are 

obtained. 

The equation, however, yields only limits for an estimated y, given x, and Natrella (1969, p. 242) notes that one 

must reverse the usual roles of x and y in the calculations to 

obtain the confidence bands around the line x =a' +b 'y. 

These confidence limits for x, given y, are symmetrical and 

will furnish confidence limits for a single determination of 

an element, x, in an unknown sample. Eisenhart (1939) 

discussed the theoretical aspects of both regression lines, 

y=a+bx and x=a' + b'y. 

There is a practical application of confidence limits 

for a single determination. Geologists and geochemists 

study rocks of the same type from different geographic areas 

and may wish to decide if the same magma could be responsible for the formation of the several rocks. To accomplish 

this, they usually plot a number of points x ,y of data for two 

elements in samples. The correlation diagram thus obtained 

eventually shows fields for the plots x ,y of the same rock 

type where the fields inay differ among geographic areas. 

The definition of these fields might be hastened if 

analysts would furnish geologists with confidence limits for 

single determinations of elements x and y. The geologist 

could then plot both elements with their limits. Since, for 

every x within an interval C<x<D, there may be a corresponding yin the interval, E<y<F, the points x ,y and their 

limits may be plotted, as an approximation, in the form of 

a confidence rectangle. Such rectangles may help define the 

rock fields in preliminary stages of the investigation. 

Figure 3 shows plotted confidence rectangles for 

points x ,y (small circles), where neither or both rectangles 

intersect both rock fields (large circles). In the upper figure, 

the rectangle intersects both rock fields, but the point x ,y 

may be said to belong to field B because of the greater area 

(and therefore greater confidence) that is common to the 

rectangle and the field. 

In the lower figure, where the rectangle intersects 

neither field, one has three choices: ( 1) measure the distance 

from point x ,y to both fields and assign the point to the 

nearer field, (2) measure the distance between the nearest 

Topics and Problems for Reference Samples and their Data 39 
y 

X 

Figure 3. Confidence rectangles for assigning points x ,y to 

rock fields. 

point on the rectangle and both fields, and assign the point 

to the field for which the distance is a minimum, or 

(3) change the value of a in tn-Z,a in the equation to calculate confidence limits for- the calibration line and recalculate 

so that there will be an area common to one field and the 

rectangle. 

Small computers now available in many laboratories 

may be programmed to calculate the confidence limits for a 

single observation. Blaedel and Iverson (1976) discuss a 

calculator program that yields confidence limits for either 

regression (calibration) line, y =a +bx or x =a' +b 'y. 

There are subroutines in the program that allow one to 

calculate the confidence limits for a single datum, x, given 

a response, y . They note that an outline of the program is 

available on request. 

Comparisons of Data 

The confidence limits for a single datum, as described 

in the preceding section, could serve as an answer to the 

40 Reference Samples in Geology and Geochemistry 

question, How good are your data? The same question may 

have been asked implicitly by those who have analyzed 

reference samples since the limestone, NBS-1, was issued. 

Authors, after analyzing a reference sample, frequently table their determinations adjacent to data preferred 

by the organization issuing the sample. The authors then 

describe the agreement of their data with those preferred by 

the issuing organization by such words as "excellent," 

"good," "fair," or "poor." A similar procedure has been 

used, either implicitly or explicitly, by authors of papers on 

the lunar samples, where their analyses of BCR-1 or other 

samples are listed. 

I suggested a solution to the problem for rock analysis 

(Flanagan, 1964), but the method is only an approximation, 

as no effort was or could be made in Stevens and Niles 

( 1960) to define the population estimates for the means and 

standard deviations of the data for G-1. Sample BCR-1 may 

be one of the most analyzed samples still in existence in 

many laboratories, but estimates I gave in two compilations 

(Flanagan, 1969, 1976c) are only best scientific guesses. 

There was, and still is, no reasonable method to estimate 

population values for the mean and standard deviation of the 

data for BCR-1, or other samples in the series, as analysts 

published data for portions of a sample ranging from n = 1 

to n > 10 for the same constituent. Lister (1982, p. 181) 

notes that bias may occur when one laboratory submits 10 

data and another only 2. I do not remember any compilations of data on samples for which such bias cannot occur. 

I calculated, whenever possible, the grand mean x, 

and the standard error of the mean, sx, of sets of six determinations for a number of constituents for recent USGS 

samples (Flanagan and Gottfried, 1980; Flanagan, 1984). I 

used the technique of x2 (Flanagan, 1984) to show that the 

probability that 39 constituents of W-1 and W-2 differed is 

less than 0.05 percent. 

An analyst may make valid comparisons of his or her 

data with some norm by calculating (observed-expected)/ 

s , where "observed" is the datum of the analyst, "expected" 

is the grand mean, x, of the constituent, and sis the population standard deviation for W-2 obtained by multiplying sx 

by v6. The result of the calculation is a standardized normal deviate, and the square of such a deviate is a chi square 

with one degree of freedom. 

These values of x2 and the degrees of freedom are 

additive and thus, by referring to tables of x2, the analyst 

can determine if his or her reported constituent is part of the 

population of data represented by x, or if his single determinations of several constituents may be part of the population 

data for these elements. In addition to yielding an overall 

estimate of the agreement between a set of determinations 

for elements and the population estimates for these elements, the magnitudes of individual values of x2 may indicate those elements for which there may be analytical problems. The technique may be used with USGS samples W-2, 

DNC-1, and BIR-1 and with the two manganese nodule 
samples for constituents for which .X and s-x were calculated, 

but I am unaware of other reference samples that may be 

used to make such calculations. 

The Analyst and the Producer 

Steele ( 1978) published a guide for reporting analytical data on geochemical reference samples. The 13 instructions in the guide, a consensus of 15 members of a committee to consider the subject, were designed so that the 

producer of a sample could extract maximum information 

from the data. In addition to the 13 instructions, the analyst 

might add the equation for the calibration line and other data 

(Flanagan, 1981). He might also note whether he subtracted 

the blank from the responses of his standards (Higgins, 

1964). 

The producer should furnish as much preliminary information on the sample as possible so that those who might 

wish to cooperate in the analytical program can have the 

maximum information on which to base a decision. Thus, 

the information might include 

1. The rock type and location (including coordinates), and 

an abstracted description of the geologic setting, mineralogy, and petrography if a reference to a geologic 

report is not available; 

2. A somewhat detailed description of the method of preparation, if the method was not described elsewhere; 

minor changes in published methods may be noted; 

3. Possible contaminants introduced into the sample. Free 

iron resulting from jaw crushing should be determined 

so that the FeO content of the rock may be corrected, 

if necessary; 

4. The experimental design to be used by the analyst or the 

producer; 

5. A list of elements for which determinations are desired 

and their approximate ranges for ores. Some rocks or 

minerals may be prepared for determinations of a few 

elements, which should be listed. For some rocks, a 

producer might list elements believed to be more important than others; 

6. A closing date for submission of data. 

REFERENCE SAMPLES IDENTIFIED 

THROUGH 1984 

The number of both reference samples and their suppliers has increased dramatically since a previous list 

(Flanagan, 1974), and a revision of the latter should have 

been made several years ago. The older list contained 217 

entries, but the revised list given here (table 5) has more 

than 830 entries, some of which list more than one sample 

of the same type by the same supplier. 

During the past decade, many needs in the general 

field of geostandards mentioned in the previous list (Flanagan, 1974) have been satisfied. There are now many minerals for microprobe work, though ores for microprobe studies 

seem to be confined to "in-house" standards. Ore reference 

samples for analysis are now quite numerous and are available from suppliers throughout the world. 

There has been a welcome increase in the number of 

rock samples of all types, including dolomites and limestones. However, more trace element data should be reported for the dolomites and limestones and for the several 

bauxites now listed in the table. The number of limestones 

and dolomites, after trace element data are acquired, should 

be gratifying to the numerous scientists who have asked 

about carbonate rocks with known amounts of trace elements. The number of large samples of rock-forming minerals has increased. 

Reference samples of manganese nodules, along with 

two "in-house" samples, have been prepared. The need for 

a better method of communication among producers and 

users of reference samples was mentioned in the previous 

list (Flanagan, 1974, p. 1741), and this void has been filled 

by publication, in January 1977, of the first semiannual 

issue of "Geostandards Newsletter," a journal devoted to all 

aspects of geochemical reference samples. 

Archaeology seems, on the basis of my limited acquaintance with archaeologists and analysts of archaeological specimens, to be the one field for which reference samples are still restricted or nonexistent. The use of one or 

more clays as reference samples for pottery analysis (Flanagan and others, 1977) is not an adequate solution to the 

problem, because clays, when fired, lose volatile constitutents and the clay material undergoes changes in composition, the changes depending on the temperature of firing. 

A reference sample might be made from a commercially fired brick used for houses. The use of such brick has 

both advantages and disadvantages. One immediate question is which clay to use, as pottery specimens are collected 

from numerous sites throughout the world. Even if one 

could obtain a consensus from archaeologists about a 

specific clay, the costs of collecting and shipping the clay to 

a brick yard and of the subsequent firing of the brick would 

be prohibitive. 

Thus, on the theory that some reference sample is 

better than no sample, a local clay deposit might be inspected and, if the clay is suitable, 200 lb (90 kg) or more 

of brick could be processed as a reference sample that might 

last 50 years. The grog used to stiffen the wet clay should 

be broken pieces of fired brick, not rocks such as phyllite or 

schist that are often added by brick manufacturers when a 

house brick of a different color is desired. Most brick makers can specify their firing temperature within a narrow 

range, and thin sections of the brick may help to determine 

firing temperatures achieved by ancient potters. 

Table 5 is arranged in the same format as the 1974 

list. Rocks, minerals, and classes of samples such as botanical, glasses, isotopic, ores, refractories, sediments, and 

Reference Samples Identified Through 1984 41 
soils are entered alphabetically. Samples within these several classes are also ordered alphabetically. 

The four headings within table 5 give the following 

information: (1) the name of the material, (2) the abbreviation of the organization that prepared the material and the 

sample number, if available, (3) the number assigned to the 

supplier from which the sample must be obtained, and 

(4) remarks, notes, or references that may assist the reader 

in the selection of samples. Compositions of many rocks, 

minerals, sediments, and soils are given in Govindaraju 

(1984a). 

The names and addresses of the suppliers and the 

number assigned each supplier are given in table 6. A samples must be obtained from, and generally only from, the 

organization that corresponds to the supplier number in 

table 5. Some published reports list the suppliers from 

whom samples may be obtained. Thus, Jecko, Pohl, and 

Ridsdale ( 1977, p. 131) list the addresses from which EuroStandards prepared by their organizations may be purchased. Valcha (1977, p. 113) gives a table listing the exporting companies responsible for the sale of reference 

samples for the six CMEA (Council for Mutual Economic 

Assistance) countries. 

Some explanation of the material in table 5 is desirable. Dashes in the Number column indicate that no sample 

number is given. Dashes in the Supplier column may indicate one of several things: (1) the sample is an "in-house" 

sample that may be available only to scientists working on 

a specific problem, (2) the sample is out of stock, (3) the 

supplier is not identified in a reference, or (4) two sediment 

samples, prepared and numbered by two organizations, that 

were renumbered by a third organization when the samples 

were used for an analytical "round robin" test. 

Questions marks (?) in the Supplier column indicate 

the source is unknown. The largest number of such entries 

is for U.S.S.R. samples; it was difficult to find in the original or translated journal articles the source from which the 

samples may be obtained. A question mark in the Remarks 

or References column following the term "in-house" indicates that the sample was mentioned in a journal article but 

that the status of the sample was not specified. 

"Price list" in the Remarks or References column 

generally indicates that a catalog and price list are available 

from the supplier. 

Table 5. Reference samples 

[Cone, concentrate; In prep., in preparation; mixt., mixture; qtz, quartz; 

SS, standard sample for some U.S.S.R. samples; SRN, State Registry 

Number for U.S.S.R. samples. Acronyms for organizations used in sample 

identification numbers are given in the text. Some acronyms are included 

with or may be derived from the names of organizations in table 6] 

Name 

Actinolite, see 

Amphibole 

Adularia, see 

Feldspar 

Number Supplier Remarks or References 

42 Reference Samples in Geology and Geochemistry 

Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References 

Alabaster, see 

Gypsum 

Albite, see 

Feldspar 

Alevrolite= 

Aleurite 

SA-l 54 

Almandine, see ------------------

Garnet 

Amphibole R-2535 30 

Actinolite 

Crocidolite 

Engels 

------------------ 20 

OECD-07 31 

------------------ 30 

Grunerite R-2469 30 

Hornblende USNM 111356 26 

Riebeckite 

sodium 

Tremolite 

Andesite 

USNM 143965 

Basel 1-h 

MMhb-1 

4-190, 4-234 

26 

2 

14 

30 

USGS-Hb1-l 7 

PSU 4-222 30 

PSU 6-040 30 

PSU 4-206 30 

USGS-AGV -1 7 

USGS-AGV-2 7 

USGS-AMH-1 7 

GSJ-JA-1 11 

GSJ-JA-2 11 

GSR-2 

DFG-KA-3 

54 

IGI. U.S.S.R. SRN 811-

76, Lontsikh and 

Parshin (1980). 

Microprobe. lngamells 

(1980b). 

Microprobe. Price list. 

Van Olphen and Fripiat 

(1979). 

Microprobe. Ingamells 

(1978). 

Microprobe. lngamells 

(1980b). 

Microprobe. Jarosewich 

and others (1980). 

Microprobe. Jarosewich 

and others (1980). 

Hiigi and others (1975). 

Alexander and others 

(1978). For 40Arf39Ar. 

Geochimica et Cosmochimica Acta, v. 43, 

p. 278 (1978). 

Microprobe. Ingamells 

(l980b). 

Not analyzed. 

Microprobe. Ingamells 

(1980b). 

Microprobe. Ingamells 

(1979). 

Microprobe. Ingamells 

(1978). 

Microprobe. Muller and 

Strauss (1984). 

Flanagan (l976b). 

Replacement for AGV -I 

from the same location. 

Not processed. 

From Mount Hood, Ore. 

Not analyzed. 

Kato and others (1978). 

In prep. A. Ando (written 

commun., 1984). 

Chinese sample. 

DFG in-house sample. 

LantiMeyer and others 

(1981). 

------------------ -----·-- DFG in-house sample. 

Anhydrite 

Anorthite, see 

Feldspar 

Anorthoclase, 

see Feldspar 

Anorthosite 

Apatite 

ZGI-AN 37 

Basel 1-a 2 

USNM 133868 26 

ANRT-AN-G 

M0-6 

USNM 104021 

24 

55 

26 

Meyer and others 

(1981). 

AMSW price list. Ostroumov (1979). 

Hiigi and others (1975). 

Microprobe. Jarosewich 

and others (1980). 

Govindaraju (1980). 

IGEM 1040. Khitrov 

(1984). 

Microprobe. Fluorapatite. 

Jarosewich and others 

(1980). 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Apatite-Continued Bauxite-Continued 

Beeson ------------------ 30 Microprobe. lngamells SB-I 54 U.S.S.R. SRN 729-75. 

(1978). Sobornov (1977). 

------------------ 20 Microprobe. Price list. SB-2 54 U.S.S.R. SRN 730-75. 

Aragonite ------------------ 20 Microprobe. Price list. Sobornov (1977). 

Archaeological PRE 72/6 36 Price list. For trace eleBronze KBS I-I 7 samples. Li (1984). ments, Palmer and othPorcelain KPS-I Li (1984). ers (1983). 

Ardennite PSU 5-I44 30 Microprobe. lngamells B-I Also B-2, B-3. Rojas Pi-

(1978). mente! (1984). 

Arsenopyrite ------------------ 20 Microprobe. Price list. calcined BCS-394 22 Price list. 

ASP-57 Microprobe. Two in-house lateritic . IVIC-SLB-1 39 ---------------------- samples. Lowell and Benitoite USNM 86539 26 Microprobe. Jarosewich 

Gasparrini (1982). and others (1980). 

Augite, see ---------... -------- ------------- .. -------- ------------------ 20 Microprobe. Price list. 

Pyroxene Beryl -........ -------------- 20 Microprobe. Price list. 

Azurite ------------.. ----.. 20 Microprobe. Price list. Biotite USGS-Btt-I 7 Not analyzed. 

Basel I-b 2 Hiigi and others ( I975) 

Barite (see ------------------ 20 Microprobe. 2 samples. Bern 4-B 2 For Rb-Sr dating. 

Ores) Price list. PSU 5-llO Out of stock. 

Basalt USGS-BCR-I Out of stock. PSU 5-ll2 30 Microprobe. Ingamells 

UCB-BCR-2 25 For Xe-1. (1980a). 

GSJ-JB-1 Out of stock, A. Ando R 2208 30 Microprobe. Ingamells 

(written commun., (1980b). 

I982). 4-I66 30 Microprobe. Ingamells 

GSJ-JB-Ia II Available, 1984. (l980b). 

GSJ-JB-2 Out of stock, A. Ando LP-6 Bio 30 Microprobe. Ingamells 

(written commun., (1978). 

1982). ------------------ 20 Microprobe. Price list. 

GSJ-JB-3 II From Mount Fuji, Japan. Boracite ----------- ..................... 20 Microprobe. Price list. 

Available 1983. Botanical 

USGS-BHVO-I 7 Flanagan (1976b). Aquatic plant 

USGS-BIR-1 7 From Iceland. Flanagan Lagarosiphon 

(1984). m major BCR-60 16 Price list. 

ANRT-BE-N 24 Govindaraju (1980). Platihypnidium 

CRPG-BR 24 Govindaraju and de Ia riparioides BCR-6I I6 Price list. 

Roche (1977). Barley, grains ss 6-77 Karpukova and others 

ZGI-BM 37 AMSW list. Ostroumov (1982). 

(1979). Bean? ss 5-78 Karpukova and others 

GSR-3 33 Chinese sample. (1982). 

NBS-688 6 Price list. Cereal? ss 3-77 Also SS 4-78. Karpukova 

S-CRB In-house. Tong and others and others (1982). 

(1984). Feed, cattle ? ss 3-78 Karpukova and others 

DSDP-BOB-I In-house. Croudace (1981); (1982). 

Marsh and others chicken? ss 5-77 Karpukova and others 

(1983). (1982). 

DSDP-A II 92 In-house, DFG. Eninger Flour, corn IAEA V-1 27 IAEA (1984). For Hg. 

and Puchelt (1980); rice NBS 1568 6 Price list. 

Meyer and others wheat NBS 1567 6 Price list. 

(1981). IAEA V-2 27 IAEA (1984). For Hg. 

Pu-la Also Pu-lb, Pu-11. In- IAEA V-2/1 27 IAEA (1984). For trace elhouse, DFG. Meyer and ements. 

others (l98I). IAEA V-5 27 IAEA (1984). For I. 

M0-2 55 IGEM 1023/1029. Grass, mix- SBMT-I U.S.S.R. SRN 1485-78. 

Sobornov (1983); ture Zvyagintsev (1983). 

Khitrov (1984). Hay, flour IAEA-V-10 27 For trace elements. IAEA 

NS-43 In-house. Van der Sloot (1984). 

and Zonderhuis (1979). grass ss 4-77 Also SS 7-77. Karpukova 

BARC-B-78 In-house. Reddy and and others (1982). 

others (1982). Kale, ------------------ Wainerdi (1979). 

Bauxite ANRT-BX-N 24 Mine de Marou, Brignoles Bowen's 

(Var), France. Govin- Leaves 

daraju (1982). Apple, 

NBS-69b 6 Arkansas. Price list. golden ---- .. ------------- Pinta (l977a). 

NBS-696 6 Suriname. Price list. orange ..................................................... Pinta (l977a). 

NBS-697 6 Dominica. Price list. Artichoke ----------... ------- Pinta (l977a). 

NBS-698 6 Jamaica. Price list. Citrus ------------------ Pinta (l977a). 

BCS-395 22 Price list. Codia -- ... -------.. -.. ----- Pinta (l977a). 

BaH Hungary. Ostroumov ,discolor 

(1979). Cotton -... -... -----,---- ... -.. -... Pinta (l977a). 

~eference Samples Identified Through 1984 43 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Botanical-Continued Carnotite-Continued 

Leaves-Continued IAEA-S-3 27 Out of stock. 

Cotton-Continued Cassiterite (see ---... -------------- 20 Microprobe. Price list. 

IAEA-V-9 27 For trace elements. IAEA also, Ores) 

(1984). Cement, Port- BCS-372 22 Price list. 

Eucalyptus ----.. -----------... - Pinta (1977a). land 

Maize --... --... ----... -- .. -- .. - Pinta (1977a). NBS-633 6 Price list. NBS-633 to 

Olive ... ... -... ----... --... --... --- Pinta (1977a) . -639. 

BCR62 16 Price list. IPT-38 38 Price list. Also IPT -46. 

Orange .......................................... Pinta (1977a). 6 samples Control samples, 

Orchard NBS 1571 6 Price list. Forschungs-institut fiir 

Palm --------.. -- ... --.. --.. Pinta (1977a). Zementindustrie. Troll 

Peach ----·------------- Pinta (1977a). and Farzaneh (1978). 

82301 54 Su and Zhang (1984); Sun AR-5170 23 Price list. 4 samples. For 

and others ( 1984). major and minor oxides. 

Pepperbush NIES-1 34 Okamoto and others Chalcocite ------------------ 20 Microprobe. Price list. 

(1978); Nakahara and Chondrite, see 

others (1982). Meteorite 

Rubber ------------------ Pinta (1977a). Chromite USNM 117075 26 Microprobe. Jarosewich 

Tea ... ----------... -- ... --... Fuwa and others (1978). and others (1980). 

Tomato ------------------ Pinta (1977a). PSU 1436 30 Microprobe. Ingamells 

Vine? ------------------ Pinta (1977a). (1978) 

Peas ss 7-78 Karpukova and others ---.. -------------- 20 Microprobe. Price list. 

(1982). DZCr-1 33 Also DZCr-2. Chinese 

Pine needles NBS 1575 6 Price list. samples. 

Plant tissue Chrysotile, see ------------------ .. ---------............... ------- Cotton AR-4401 23 Price list. For S. Serpentine 

Peach AR-4402 23 Price list. For S. Cinnabar -------------... ---- 20 Microprobe. Price list. 

Soybean AR-4403 23 Price list. For S. Clays, clay minPotato SBMK Karpukova and others erals 

(1982). U.S.S.R. SRN Bentonite ------------------ Dempir (1978). 

1483-78, Zvyagintsev Clay 2 samples Dempir (1978). 

(1983). 3 samples 49 No sample numbers in ISO 

IAEA V-4 27 IAEA (1984). For trace el- (1982). 

ements. PRE 7212 36 Price list. Palmer and othRye (flour) IAEA V-8 27 IAEA (1984). For trace el- ers (1983) for trace eleements. ments. 

Seaweed IAEA AG-1-1 27 Out of stock. Brick NBS-679 6 In prep. 

IAEA AG-B-1 27 IAEA (1984). For radionu- Calcined PRE 72/5 36 Price list. Palmer and othelides. shale ers (1983) for trace eleSpinach NBS 1570 6 Price list. ments. 

Straw, wheat ss 8-77 Also SS 1-78. Karpukova Flint NBS-97a 6 Price list. 

and others (1982). NBS-97b 6 In prep. Same area as 

Sunflower, NBS-97. 

cake ss 8-78 Karpukova and others Para IPT-28 38 Price list. 

(1982). plastic NBS-98a 6 Price list. 

ground ss 1-77 Karpukova and others NBS-98b 6 In prep. Same area as 

(1982). NBS-98. 

Wheat, grains SBMP-1 Karpukova and others refractory ---------------.. -- Bulgaria. Planned. Table 

(1982). U.S.S.R. SRN 3, Valcha (1977). 

1484-78, Zvyagintsev chamotte SS-55a Gorozhanina and others 

(1983). (1971). 

Brick Fe-poor PRE 72/3 36 Price list. Palmer and othFire BCS 315 22 Price list. ers (1983) for trace eleES 776-1 22 BCS price list. ments. 

Silica BCS 267 22 Price list. Fe-rich PRE 72/4 36 Price list. Palmer and othhigh purity BCS 313 22 Price list. ers (1983) for trace eleBrookite ---·-------------- 20 Microprobe. Price list. ments. 

Sio Simao IPT-42 38 Price list. 

Calcite -----...... ----------- 20 Microprobe. Price list. terrigene, SD0-1 54 U.S.S.R. SRN 1757-80, 

ISRID-001-1 28 Jecko (1977). see Lontsikh (1981). 

OECD-12 31 Van Olphen and Fripiat Sediment, 

(1979). Marine 

Calcsilicate QMC-M-3 44 Status unknown. In-house? Cookeite CMS-CAr-1 15 Van Olphen and Fripiat 

Carbonatite USGS-COQ-1 7 Not analyzed. (1979). 

CCRMP-OKA-1 5 For Nb. Price list. Steger Corrensite CMS-CorWa-1 15 From Packwood, Wash. 

(1983). Gibbsite OECD-10 31 Van Olphen and Fripiat 

SAROCK S-8 21 National reference sample, (1979). 

Frick (undated). illite CMS-IMt-1 15 Van Olphen and Fripiat 

Carnotite NBL-4 18 Also NBL-5. Price list. (1979). 

44 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Clays-Continued Coal fly ash-Continued 

Illite-Continued AR-4201 23 Price list. Also AR-4202. 

OECD-05 31 Van Olphen and Fripiat For major and minor ox-

(1979). ides. 

Illite-smectite CMS-ISMt-1 15 Van Olphen and Fripiat Cobalite ---------------·-- 20 Microprobe. Price list. 

(1979). Coke BCR-001 16 Price list. 4 cokes for C, 

Kaolin .. ------......... ---..... -... - Dempir (1978) . H, S, P, ash, and 

UNS-KK 17 Valcha (1977). Same sam- calorific V"'iue. 

pie as in Dempir AR-719 23 Price list. 2 cokes for S 

(1978)? only. 

Kaolinite OECD-03 31 Van Olphen and Fripiat AR-733 23 Price list. 2 cokes for S, 

(1979). ash, volatile matter, 

Montmorill- fixed C, and BTU. 

onite AR-771 23 Price list. 2 cokes for 

Ca CMS-SAz-1 15 Van Olphen and Fripiat proximate, ultimate, and 

(1979). inorganic analysis, and 

CMS-STx-1 15 Van Olphen and Fripiat forms of S. 

(1979). Coloradoite ---- .................................... 20 Microprobe. Price list. 

Mica CMS-Syn-1 15 Synthetic. Van Olphen and Cordierite -------·---------- 20 Microprobe. Price list. 

Fripiat (1979). Corundum USNM 6575 26 Microprobe. Synthetic. 

Na CMS-SWy-1 15 Van Olphen and Fripiat Jarosewich and others 

(1979). (1980). 

Nontronite CMS-NG-1 15 Van Olphen and Fripiat Counting CCRMP-BL-1 5 Price list. 5 samples. 

(1979). Steger (1983). 

Ripidolite CMS-CCa-1 15 Van Olphen and Fripiat Th NBL-79A 18 Price list. 8 samples. 

(1979). u NBL-42-1 18 Price list. II samples. 

Saponite CMS-SapCa-1 15 From Ballarat, Calif. Covellite -------------·---- 20 Microprobe. Price list. 

Sepiolite CMS-SepSp-1 15 From Spain. Sep-Nev-1, Crocidolite, see ------------------ Nevada. Amphibole 

Smectite CMS-SWa-1 15 Van Olphen and Fripiat Crocoite ................................................... 20 Microprobe. Price list. 

(1979). Cryolite ... .............................................. 20 Microprobe. Price list. 

Vermiculite CMS-VTx-1 15 Van Olphen and Fripiat SK-I U.S.S.R. SRN 1824-80. 

(1979). Lontsikh (1981). 

Coal NBS 1630 6 Price list. Hg in coal. Dacite DFG-KA-2 DFG in-house sample. USGS-CLB-1 52 In prep. Restricted distri- Meyer and others 

bution. (1981). 

BCR-065 16 Price list. For ash, S, and 

calorific value. 

Delafossite ................................................. 20 Microprobe. Price list. 

AR-1721 23 Price list. II samples for Denningite PSU 61-1431 30 Microprobe. lngamells 

(1978). S, ash, volatile matter, Deposit, hot USGS-GXR-3 Allcott and Lakin (1975, fixed C, and BTU. spring 1978). AR-751 23 Price list. 9 samples for Diabase (doler- QMC-1-3 44 Status uncertain. In-house? 

ash and inorganic analy- ite) sis. DIM-I 55 Now MO-l. IGEM 1004/ 

AR-1701 23 Price list. II samples for S I 006/l 047, Khitrov 

in the range 0.40 to (1984). Egranova and 

5.00% S. others (1981). AR-773 23 Price list. 10 samples for USGS-W-2 7 Replacement for W -1, proximate, ultimate, and Flanagan ( 1984). inorganic analysis and USGS-DNC-1 7 Flanagan (1984). forms of S. SAROCK S-18 21 National reference sample, AR-1800 23 Price list. 4 samples. For Frick (undated); Victor 

24 trace elements. (1983). 

NEMI-85 Hart and others (1982). Diatomite Czechoslovakia. Planned. 

bituminous NBS-l632a 6 Price list. For trace ele- ------------------ Table 3, Valcha (1977). ments. 

Kennel 20 Microprobe. Price list. Diopside, see ------------------ ----------------- ... ---- ----------- .. ------ Pyroxene Lignite -------------.. ---.. 49 Two samples for U30 8. PSU 63-1827 30 Microprobe. Ingamells Subbitumi- NBS-1635 6 Price list. For trace ele- (1978). nous ments. Diorite ANRT-DR-N 24 Govindaraju (1982). 

Coal ash BE-l Also BS-1. In house?, DI-S 55 U.S.S.R. Sobornov 

Bergakademie Freiberg. (1983). 

Loos and others (1980). Disthene, see ANRT-DT-N 24 Govindaraju (1982). 

Coal fly ash NBS-1633a 6 Price list. Kyanite 

BCR-038 16 Price list, For As, Cd, Co, Dolomite BCS-368 22 Price list. 

Fe, Hg, Mn, Na, Pb, GI-ADT 13 Schroll (1977). Troll and 

and Zn. Farzaneh (1978). 

82201 54 Su and Zhang (1984); Sun GFS-400 10 Price list. Plus blends. 

and others (1984). ISRID-002-l 28 Price list. Jecko (1977). 

Reference Samples Identified Through 1984 45 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Dolomite-Continued Feldspar-Continued 

SS-60-8 Gorozhanina and others potassium-Continued 

(1971). ANRT-FK-N 24 Govindaraju (1984b), in 

---------------- ...... Bulgaria. Planned, Table press. 

3, Valcha (1977). NBS 70a 6 Price list. See also NBS 

------------------ 20 Microprobe. Price list. 607 

, Mn R-2027 30 Microprobe. Ingamells NBS 607 6 Price list. For Rb and Sr. 

(1980b). IAEA-F-1 27 IAEA (1984). U, Th, and 

Dunite USGS-DTS-2 7 Replacement for DTS-1. K in Belyaev and 

Not analyzed. Sobomov (1981). 

MU-2 55 IGEM 1021. Khitrov IPT-53 38 Price list. 

(1984). sodium BCS-375 22 Price list. 

, chrysolite NIM-D 21 Price list. Now SARM-6. NBS 99a 6 Price list. 

Steele and others (1978); Feldspar sand ZGI-FK 37 Price list. Ostroumov 

Steele and Hansen (1979). 

(1979). Fluorapatite USNM 104021 26 Microprobe. Jarosewich 

Dust (particulate) and others (1980). 

Atmospheric AS-I Hashimoto and others Fluorite UNS-FM 17 Price list. Dempir and 

(1976). Valcha (1982). 

NBS-1648 6 Price list. For 6 major and ------------------ 20 Microprobe. Price list. 

minor, and 8 trace ele- Fluorspar BCS 392 22 Price list. 

ments. SARM 14 21 Also SARM 15. Price list. 

NBS-1649 6 Price list. For 5 polycyclic NBS 79a 6 Price list. 

aromatic hydrocarbons. JK-C 53 Also JK-D and -E. SweFerrous den, Institutet fOr 

Electric ES-876-1 28 Price list. Jecko and Rids- Metallforskning. 

dale (1978). high grade NBS 180 6 Price list. 

LD con- ES-877-1 28 Price list. Fly ash (see EPA-9 19 For 226Ra and 228Ra. 

verter also Coal Fly 

Nonferrous CCRMP-PD-1 5 Price list. Steger (1983). Ash) 

Elbaite, see -------...... --------- -------.. ------------ ... - Gabbro CCRMP-MRG-1 5 Price list. Steger (1983). 

Tourmaline USGS-GSM-1 7 Not analyzed. 

Epidote ------------------ 20 Microprobe. Price list. GSJ-JGb-1 II Available. 

Eskolaite ------... ----... ------ 20 Microprobe. Price list. GLOM-GOG-I 45 Mazzucotelli and Vannucci 

Essonite, see ------------------ -------- ... ------------- (1980). 

Garnet M0-3 55 IGEM 1013. Khitrov 

(1984). 

Fayalite USNM 85276 26 Microprobe. Jarosewich M0-5 55 IGEM 1039. Khitrov 

and others (1980). (1984). 

Fe formation IWG-IF-G 24 Govindaraju (1984b). M0-4 55 IGEM 1014. Sobomov 

CCRMP-FeR-1 5 4 samples. Abbey and oth- (1983). Khitrov (1984). 

ers (1983). ---------... -------- Composition of unknown 

Feldspar R701 12 Uchida and others (1979). gabbro, table 6, Dempir 

1 sample 49 No sample number in ISO (1978). 

(1982). Gabbro-diorite SGD-1 Malyshev and others 

-------... -----.... ---- 3 samples. No numbers or (1980). 

suppliers in Dempir Gabbro-essexite SGD-lA 54 U.S.S.R. SRN 521-74. 

(1978). Tauson and others 

GSJ-JF-1 11 In prep. A. Ando (written (1976), Sobomov 

commun., 1984). (1977). 

Adularia ------------------ 20 Microprobe. Price list. Gahnite USNM 145883 26 Microprobe. Jarosewich 

Albite ----------------...... 20 Microprobe. Price list. and others (1980). 

GIT -IWG-AL-1 24 Govindaraju (l984b). Galena GF-1 37 Price list. Schron and othMAS-3 33 Chinese sample. ers (1975). 

Anorthite USNM 137041 26 Microprobe. Jarosewich --------- .......................... 20 Microprobe. Price list. 

and others (1980). Garnet USNM 87373 26 Microprobe. Jarosewich 

Anorthoclase -------------...... --- 20 Microprobe. Price list. and others (1980). 

Basel 1-a 2 Hiigi and others (1975) USNM 110752 26 Microprobe. Jarosewich 

USNM 133868 26 Microprobe. Jarosewich and others (1980). 

and others (1980). Almandine -... --... --...... ---... ----- 20 Microprobe. Price list. 

Microcline USNM 143966 26 Microprobe. Jarosewich Essonite -------------- ........ - 20 Microprobe. Price list. 

and others (1980). Pyrope USNM-143968 26 Microprobe. Jarosewich 

Orthoclase PSU Or-lA 30 Microprobe. Ingamells and others (1980). 

(1978). Gases Several 6 Price list. 

------------ .................. 20 Microprobe. Price list. Glass No. 2 32 Price list. 6 samples. Soc. 

Plagioclase ------------------ 20 Microprobe. Price list. of Glass Technology 

Labradorite USNM 115900 26 Microprobe. Jarosewich (1980). 

and others (1980). Several 49 No sample numbers in ISO 

potassium BCS-376 22 Price list. (1982). 

46 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Glass-Continued Granite-Continued 

2 samples 51 No sample numbers in ISO Gran-I In-house, Netherlands. 

(1982). Van der Sloot and ZonOCB-66-15 In-house? Anderson and derhuis (1979). 

Aeer (1982). Table l, NS-8 In-house, Netherlands. 

Rosholt and others Van der Sloot and Zon-

(1971). derhuis (1979). 

basaltic USNM 113716 26 Microprobe. 3 glasses. .. -----... ---------- ... Analysis of a granite, table 

Jarosewich and others 5, Dempir (1978). 

(1980). Abtal- -----·------------ In-house, DFG, Meyer and 

fission track NBS 961 6 Price list. 4 glasses. others (1981). 

high B NBS 93 6 Price list. Alaskite SG-2 USSR SRN 812-76. 

low B NBS 92 6 Price list. Sobomov (1977). 

opal NBS 91 6 Price list. albitized SG-lA 54 USSR SRN 520-74. TauPb-Ba NBS 89 6 Price list. son and others (1976), 

phonolitic ANRT-VS-N 24 Synthetic. Roche and Sobomov (1977). 

Govindaraju (1973). aplitic QMC-1-l 44 In-house? Status uncertain. 

rare earths ------------------ 4 Microprobe. Drake and F-bearing SAROCK S-16 21 National reference sample, 

Weill (1972). Frick (undated). 

rhyolitic USNM 72854 VG568 26 Microprobe. Jarosewich high GVCH-1 USSR SRN 344-73. 

and others (1980). Lontsikh (1981). 

soda lime Hypersthene G2-S Sobomov (1983). 

container NBS 621 6 Price list. micro- AC(OURS) 8 Potts and others ( 1981). 

flat NBS 620 6 Price list. Potts (1983). 

tektite USNM 2213 26 Microprobe. Jarosewich Granitoid S0-2BI74 USSR SRN 707-75. 

and others (1980). Sobomov (1977). 

trace elements NBS 608 6 Price list. Also NBS 609- Granodiorite USGS-GSP-1 Out of stock. A replace619. ment sample is being 

USGS-GSB Also GSC, GSD, and considered. 

GSE. Myers and others GSJ-JG-1 11 Ando and others (1974). 

(1976). GSJ-JG-la II Available, 1984. 

Glass sand No.1 32 Price list. Also samples "Ryzhik" 55 IGEM 1003. Egranova and 

2-5. Soc. of Glass Tech- others (1981). Now 

nology (1980). MK-1, Khitrov (1984). 

NBS 81a 6 Price list. MK-2 55 IGEM 1012/1028. 

UNS-SS 17 Ledger and others (1980). Sobomov (1983). 

low Fe NBS 165a 6 Price list. Khitrov (1984). 

Glauconite GL-0 24 For 40Ar and for chem. Greigite ------------------ 20 Microprobe. Price list. 

analysis. Roche and oth- Greisen ZGI-GnA 37 Price list. Belyaev and 

ers (1976). Sobomov (1981). OsGold-quartz USGS-GQS-1 Out of stock. troumov (1979). 

Granite GIB-G-B 43 Aleksiev and Boyadjieva Grunerite, see -------- ... --------- ---------------------- (1966). Ivanov (1981). Amphibole 

QMC-1-1 44 In-house? Status uncertain. Gypsum ----------...... ------ 20 Microprobe. Price list. 

ANRT-GS-N 24 Govindaraju (1984b), in OECD-13 31 Van Olphen and Fripiat 

press. (1979). 

CRPG-GA 24 Govindaraju and de Ia (alabaster) 2 samples 49 No sample numbers in ISO 

Roche (1977). (1982). 

GRPG-GH 24 Govindaraju and de Ia 

Roche (1977). Halite --------·--------- 20 Microprobe. Price list. 

NIM-G 21 Price list. Now SARM-1. Hausmannite ---------.... -------- 20 Microprobe. Price list. 

Steele and others Hematite GFS-453 10 Plus blends. Price list. 

(1978). Steele and -........ ----------... --- 20 Microprobe. Price list. 

Hansen (1979). Hemimorphite ------- ... ---------- 20 Microprobe. Price list. 

GSJ-JG-2 11 In prep. A. Ando (written Hessonite ------------------ ---------------------- commun., 1984). =Essonite: 

GSR-1 33 C.H. Tong (written com- see Gamet 

mun., 1984). Hornblende, see -----·-- ---------- ---.. ------------------ USGS-G-2 7 Hanagan (l976b). Amphibole 

ZGI-GM 37 Price list. Ostroumov USNM 143965 26 Microprobe. Jarosewich 

(1979). and others (1980). 

ANRT-MA-N 24 Govindaraju (1980). Basel 1-h 2 Hiigi and others (1975). 

MK-3 55 IGEM 1018. Sobomov MMhb-1 14 Alexander and others 

(1983). Khitrov (1984). (1978). For 40Arf39Ar. 

MK-4 55 IGEM 1025/1027. Geochimica et CosSobomov (1983). mochimica Acta, v. 43, 

Khitrov (1984). p. 278 (1978). 

GI-S Sobomov (1983). 4-190, 4-234 30 Microprobe. Ingamells 

KA-1 In-house, DFG. Meyer and (1980b). 

others (1981). USGS-Hbl-1 7 Not analyzed. 

Reference Samples Identified Through 1984 47 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Hornblendite MU-3 55 IGEM 101511030. Khitrov Isotopic-Continued 

(1984). 15Nf14N IAEA-N-1 9 Also N-2. Synthetic, from 

Hypersthene, ------------------ ---------------------- ammonium sulfate. 

see Pyroxene 180 See 13C, D, and S. 

NBS-28 9 African glass sand. FriedIlmenite USNM 96189 26 Microprobe. Jarosewich man and Gleason 

and others (1980). (1973). 

------------------ 20 Microprobe. Price list. Pb NBS 981 6 Also 982, 983. Price list. 

Ilvaite ------------------ 20 Microprobe. Price list. Natural, equal atom 

Isotopic, stable (206/208), and radioAg, as NBS 978 6 Price list. genic (92% 206) leads. 

AgN03 206Pb spike NBS 991 6 Price list. 

40Arf39Ar Pu NBS 946 6 Price list. Also 947, 948. 

Biotite BS-1 Alexander and Davis Varying Pu isotopic 

(1974, p. 927). compositions. 

ZBH-25 Wang (1983). Rb, as RbCI NBS 984 6 Price list. 

GA 1550 Australian Nat. Univ. Re, as metal NBS 989 6 Price list. 

Wang (1983). s OGS 9 IAEA. 34Sf32S, but not 

Hornblende NL-25 Alexander and Davis 180f160, measured. 

(1974, p. 927). Synthetic BaS04 precipFY12a Univ. of Leeds. Roddick itated from sea water. 

(1983). ------------------ 9 Soufre de Lacq. IAEA. 

Hb3gr Alexander and Davis Naural elemental S. 

(1974, p. 927). Roddick Si, as metal NBS 990 6 Price list. 

(1983). Sr, as SrC03 NBS 987 6 Price list. 

MMhb-1 14 Alexander and others U, as U30 8 NBS U-0002 6 Price list. Also U-005 to 

(1978). U-970. Varying U isoZBJ Wang (1983). topic compositions. 

Meteroite St. Severin Alexander and Davis 

(1974, p. 927). Jasperoid USGS-GXR-1 Allcott and Lakin (1978). Nepheline Toronto? Alexander and Davis 

(1974, p. 927). Kalinite ------------------ 20 Microprobe. Price list. 

B, as H3B03 NBS 951 6 Price list. Kaolin UNS-KK 17 Ostroumov (1979). Valcha 

B, 95% BIO (1977). enriched NBS 952 6 Price list. Kimberlite SAROCK S-7 21 National reference sample, Biotite NBS-30 9 ---------------------- Frick (undated). 13C MU-4 55 IGEM 1020. Khitrov 

limestone NBS-19 9 For 180 and nc. Friedman (1984). and others (1982). Kyanite ------... ----------- 20 Microprobe. Price list. 

carbonatite NBS 18 9 For 180 and nc. Friedman ANRT-DT-N 24 Govindaraju (1982). and others (1982). 

Iceland ------------------ 50 For 180 and 13C. Landis 

spar (1983). Laterite M09-l 28 Jecko (1977). 

Cl, as NaCl NBS-975 6 Price list. IVIC-VL-1 39 Also VL-2. Schorin and 

C02 NBS-16 9 Prepared from commercial LaBreque (1983). 

liquified C02. Coplen Larvikite ASK-I 40 Christie (1975). 

and Kendall (1982). Lepidolite NBS 183 6 Price list. 

NBS-17 9 Prepared from commercial PSU 60-1252 30 Microprobe. Ingamells 

C02 gas. Coplen and (1978). 

Kendall (1982). ------------------ 20 Microprobe. Price list. 

Cr, as Cr NBS-979 6 Price list. Lignite ------------------ 7 Two samples for U30 8. 

nitrate Limestone GI-LLL-1 13 Schroll (1977). 

Cu, as metal NBS-976 6 Price list. IAEA-Sed-3 27 Out of stock. For U, Th, 

D NBS 30 9 Also for 180. and K, Heinonen and 

V-SMOW 9 Also for 180. For D/H, see others (1973). 

de Wit and others ZGI-KH 37 Price list. Ostroumov 

(1980). For 180f16Q, (1979). 

Baertschi (1976). GFS-401 10 Plus blends. Price list. 

SLAP 9 Also for 180. de Wit and IPT-44 38 Price list. 

others (1980). Price list. SS-59-V Also SS-59-g. 

GISP 9 Isotopic comp. between Gorozhanina and others 

SLAP and V -SMOW. (1971). 

de Wit and others AR-4111 23 Price list. Also AR-4112. 

(1980). Available(?) For major and minor 

1985. dioxides. 

Limestone, NBS-20 9 argillaceous NBS-lc 6 Price list. 

Solenhofen calcitic IPT-35 38 Price list. 

TS NBS-19 9 For 13C and 180. Friedman dolomitic NBS-88a 6 Price list. 

and others (1982). BCS-393 22 Price list. 

Mg. as metal NBS 980 6 Price list. IPT-47 38 Price list. 

48 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Limestone-Continued Nodule, Mn USGS-Nod-A-l 7 Also Nod-P-l. Hanagan 

dolomitic-Continued and Gottfried ( 1980). 

GSR-6 33 C.H. Tong (written com- Schafer-I Also -2. In-house? Kormun., 1984). kisch and others (1979). 

SI-1 54 IGI. U.S.S.R. SRN 813- Norite NIM-N 21 Price list. Now SARM-4. 

76. Sobomov (1977). Steele and others (1978); 

Solenhofen NBS-20 9 See Isotopic. Nier (1950); Steele and Hansen 

Coplen and Kendall (1979). 

(1982). Olivine USNM 111312/444 26 Microprobe. Jarosewich 

Lujavrite NIM-L 21 Price list. Now SARM-3. and others (1980). 

Steele and others (1978); USNM 2566 26 Microprobe. Jarosewich 

Steele and Hansen and others (1980). 

(1979). Forsterite MAS-I 33 Chinese sample. 

MSHCH-4 55 IGEM 1024/1033. Khitrov 

(1984). Omphacite, see ------------------ ---------------------- Pyroxene 

Magnesite BCS 319 22 Price list. Orthoclase, see ------------------ ---------------------- UNS-MK 17 Valcha (1979). Ostroumov Feldspar 

(1979). Osumillite USNM 143967 26 Microprobe. Jarosewich 

OECD-11 31 Van Olphen and Fripiat and others (1980). 

(1979). Ores 

------------------ 20 Microprobe. Price list. Ag-Au ------------------ Number and supplier not 

------------------ 3 samples, Dempir (1978). given. Dempir (1978). 

SAROCK S-11 National reference sample, AI 

Frick (undatred). alumina? SS-198-a Gorozhanina and others 

chrome BCS 369 22 Also BCS 370. Price list. (1971). 

high purity BCS 389 22 Price list. bauxite SS-190-a Gorozhanina and others 

low Si02 BCS 396 22 Price list. (1971). 

Magnetite GFS-450 10 Price list. Au CCRMP-MA-1 5 Also MA-2. Price list. 

USNM 114887 26 Microprobe. Jarosewich Steger ( 1983). 

and others (1980). SZp-1 U.S.S.R. SRN 1789-80. 

------------------ 20 Microprobe. Price list. Lontsikh (1981). 

Malachite ------------------ 20 Microprobe. Price list. float cone. SZK-1 U.S.S.R. SRN 1787-80. 

Manganosite ------------------ 20 Microprobe. Price list. Lontsikh (1981). 

Mariupolite MSHCH-2 55 IGEM lOll. Khitrov SZK-2 U.S.S.R. SRN 1788-80. 

(1984). Lontsikh (1981). 

Marl, ferriferous ISRID M08-l 28 Jecko (1977). float tails SZH-1 U.S.S.R. SRN 1790-80. 

Mellite ------------------ 20 Microprobe. Price list. Lontsikh (1981). 

Messelite ------------------ 20 Microprobe. Price list. gravity tails SZH-2 U.S.S.R. SRN 1791-80. 

Meteorite Lontsikh (1981). 

Allende ------------------ 26 Clarke and others (1970). sulfide SZR-1 Lontsikh and Parshin 

Bjurbole ------------------ Hohenberg and Kennedy (1980). 

(1981). Ba, barite IGS-38 41 Lister (1978). 

St. Severin ------------------ For 40Arf39Ar. See Iso- ----------... ------- Number and supplier not 

topic. given. Dempir (1978). 

Miaskite MIV-1 55 IGEM 1001/1005, Egra- Be SS-288 Gorozhanina and others 

nova and others (1981). (1971). 

Now MSHCH-1, Co IGS-24 41 Lister (1978). 

Khitrov (1984). SS-294 Gorozhanina and others 

Microcline, see ------------------ ---------------------- (1971). 

Feldspar Co-Ni SNK-1 U.S.S.R. SRN 1346-78. 

Micro lite PSU 5-006 30 Microprobe. Ingamells Lontsikh and Parshin 

(1978). (1980). 

PSU 5-010 30 Microprobe. Ingamells SNK-2 U.S.S.R. SRN 1347-78. 

(1980b). Lontsikh and Parshin 

Molybdenite ------------------ 20 Microprobe. Price list. (1980). 

Monazite ------------------ 20 Microprobe. Price list. Cr IGS-30 41 Lister (1978). 

Monazite sand NBL-7-A 18 Price list. JSS-870-l 12 Terashima (1979). 

Monzonite ------------------ Planned. Table 3, Valcha SARM-8 21 Price list. Also SARM-9. 

(1977). Stoch and others (1979). 

Mud, see Silt or ------------------ ---------------------- Cr-Erz-1 37 Price list. Also Cr-Erz-2. 

Sediment 166-v Valcha (1977). Ostroumov 

Muscovite Bern 4-m 2 Odin and others (1982). (1979). 

chromite SS-132-a Also SS-166-B. 

Nealite ------------------ 20 Microprobe. Price list. Gorozhanina and others 

Nepheline (1971). 

syenite USGS-STM-1 7 Flanagan (l976b). cone. SS-275 Also SS-90. Gorozhanina 

SNS-2 54 U.S.S.R. SRN 1345-78. and others (1971). 

Lontsikh and Parshin Grecian 

(1980). chrome BCS-308 22 Price list. 

Reference Samples Identified Through 1984 49 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Ores-Continued Ores-Continued 

Cu SS-183 Also SS-184. Gorozhanina Fe-Continued 

and others (1971). Hematite-Continued 

Chalcocite- IGS-1 41 Also IGS-2, -3, and -4, Romp in JSS-800-3 12 Terashima (1979). Jecko 

qtz. mix. Lister (1978). and others (1980). 

chalcopyrite IGS-5 41 Lister (1978). Krivoi Rog 3-d ? V alcha (1977). Feret 

cone. (1982). Sample 3d-l in 

cone. NBS-332 6 Price list. Ostroumov (1979)? 

CCRMP-CCU-1 5 Price list. Steger (1983). Labrador NBS 692 6 Price list. 

SS-250 Gorozhanina and others Lincoln- BCS 30111 22 Price list. 

(1971). shire 

-----------------... 3 samples. No numbers or Magnetite SARM-12 21 Price list. 

supplier. Dempir (1978). Musan JSS-812-2 12 Terashima (1979). 

CuPl Poland. Valcha (1977). Nimba NBS 693 6 Price list. 

copperkeis RUS-2 U.S.S.R. SRN 792-76. Philippine JSS-830-3 12 Terashima (1979). 

(chalco- Egranova and others Sibley NBS 27f 6 Price list. 

pyrite) (1981). Siderite SS-216-a Gorozhanina and others 

dissem- --·--·------------ Bulgaria. Planned. Table (1971). 

inated 3, Valcha (1977). Sinter ES-676-1 22 BCS Price list. 

mill heads NBS-330 6 Price list. BCS-378 22 Price list. 

NBS-331 6 Price list. IRSID-A01-1 28 Also A02-l. Jecko (1977). 

USGS-GXR-4 Allcott and Lakin (1978). ------------...... --.. - 37 Price list. 

Cu-Mo CCMP-HV-1 5 Price list. Steger (1983). Fe, general 

Cu-Pb Cu-Pb? Poland. Ostroumov (1979). Australia 1 sample ? Table 5, Jecko and others 

Same as CuPI in Valcha (1980). 

(1977)? Czecho- 13 samples Table 8, Jecko and others 

Cu-Zn RUS-1 U.S.S.R. SRN 791-76. slovakia (1980). 

sulfide Egranova and others European 7 samples Table 1, Jecko and others 

(1981). Com- (1980). 

F munity 

Fluorite IGS-39 41 Lister (1978). France 16 samples 28 Table 3, Jecko and others 

UNS-FM 17 Dempir and Valcha (1980). 

(1982). Germany 8 samples 29 Pohl and Oberhauser 

--------... --------- ? Mongolia. Planned. Table (1978): Table 2, Jecko 

3, V alcha (1977). and others (1980). 

Fluorspar SARM-14 21 Also SARM-15. Price list. Japan 13 samples 12 Table 4, Jecko and others 

BCS-392 22 Price list. (1980). 

NBS 79a 6 Price list. Poland 1 sample Table 8, Jecko and others 

JK-C 53 Also JK-D and -E. Swe- (1980). 

den, Institutet for Romania 4 samples ? Table 7, Jecko and others 

Metallforskning. (1980). 

Flusspat 37 Price list. Soviet 16 samples Table 9, Jecko and others 

3 samples Numbers and supplier not Union (1980). 

given. Table 3. Valcha Sweden 2 samples Table 6, Jecko and others 

(1977). (1980). 

high NBS 180 6 Price list. Hg 3 samples Numbers and suppliers not 

grade given. Dempir (1978). 

Fe ES-871-1 22 BCS Price list. Also ES- Li 

681-1 and ES-682-1. Lepidolite NBS 183 6 Price list. 

IPT-21 38 Price list. Also IPT-23, Petalite NBS 182 6 Price list. 

-27, and -30. Spodumene NBS 181 6 Price list. 

LKAB N3/1974 Sweden. Plant production Mn 

cone. 's? Feret (1982). NBS 25 c 6 Price list. 

JK-11 53 4 samples. Sweden, Insti- SARM-16 21 Price list. Also SARM-17. 

tutet fOr Metallforsk- BCS 176/2 22 Price list. 

ning. ES 633-1 22 Price list. Pohl and Oberagglomerate SS-211 Gorozhanina and others hauser (1978). 

(1971). SS-44-b Gorozhanina and others 

Algarrobo JSS-813-2 12 Terashima (i979). (1971). 

banded CCRMP-FeR-1 5 4 samples. Price list. 44g U.S.S.R., Valcha (1977). 

Abbey and others Ostroumov (1979). 

(1983). IPT-52 38 Price list. 

IWG-IF-G 24 Govindaraju (1984b), in Mn-Erz-1 37 Price list. Also Mn-Erz-2. 

press. cone. SS-112-a Also 130a. Gorozhanina 

Canada NBS-690 6 Price list. and others (1971). 

(cone.) pyrolusite IGS 29 41 Lister (1978). 

CCRMP-SCH-1 5 Price list. Also MW-1. Mo 

Steger (1983). cone. CCRMP-PR-1 5 Price list. Steger (1983). 

Hematite SARM-11 21 Price list. NBS 333 6 Price list. 

50 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Ores-Continued Ores-Continued 

Mo-Continued So-Continued 

molybdenite IGS 8 41 Lister (1978). cassiterite ·················· U.S.S.R. SRN 168-71. 

Egranova and others cone. (1981). molybdenite IGS 6 41 Lister (1978). .................. U.S.S.R . SRN 169-71. 

qtz. Egranova and others 

mixt. (1981). 

Mo-W IGS 27 41 Lister (1978). .................. U.S.S.R. SRN 322-73. 

Nb SS-277 Gorozhanina and others Egranova and others 

(1971). Also SS-281. (1981). 

.................. U.S.S.R . SRN 575-74. 

carbonatite CCRMP-OKA-1 5 Price list. Steger (1983). Egranova and others 

columbite IGS 33 41 Lister (1978). (1981). 

columbite SVT-15 U.S.S.R. SRN 349-73. cassiterite IGS-6 41 Lister (1978). 

cone. Lontsikh and Parshin cone. 

(1980). cassiterite- IGS-13 41 Lister (1978). 

loparite SVT-l6a U.S.S.R. SRN 350-75. qtz. cone. Lontsikh and Parshin mixt. 

(1980). cone. 's SK0-1 Also SK0-2 to -8. 

Nb cone. SVT-9 U.S.S.R. SRN 107-71. U.S.S.R. SRN 1284-79 

Lontsikh and Parshin to 1291-79. Lontsikh 

(1980). and Parshin (1980). 

Nepheline SNS-1 IGl. U.S.S.R. SRN 728- SS-138 Also SS-148. Gorozhanina 

75. Sobomov (1977). and others (1971). 

Ni cone. IGS 20 41 Lister (1978). Sn-W IGS-26 41 Lister (1978). 

SS-297 Gorozhanina and others ----.. ------------- 4 samples. Numbers or 

(1971). suppliers not given. 

laterite IGS 23 41 Lister (1978). Dempir (1978). 

norite IGS 21 41 Lister (1978). Sn-W-Be -------............. -.. ---.. U.S.S.R. SRN 323-72. 

serpentinite IGS 22 41 Lister (1978). Egranova and others 

Ni-Cu-Co CCRMP-SUla 5 Price list. Steger (1983). (1981). 

Pb cone. CCRMP-CPB-1 5 Price list. Steger (1983). ----- ... --- ... -----... -- U.S.S.R. SRN 342-73. 

galena IGS 12 41 Lister (1978). Egranova and others 

cone. (1981). 

galena-qtz. IGS 9 41 Lister (1978). Sulfide ------------------ Hungary. Valcha (1977). 

mixt. (polyPb-Zn ------------------ 4 samples. Numbers and metallic) 

suppliers not given. 

Dempir (1978). 

SS-140 Gorozhanina and others Ta CCRMP-TAN-I 5 0.236% Ta. Price list. In-

(1971). formation sheet as an RUS-3 Kuznetsova and Morgulis addendum to Steger (1983). (1983). 

RUS-4 Kuznetsova and Morgulis tantalite SVT-14 U.S.S.R. SRN 348-73. 

(1983). Lontsikh and Parshin cone. IGS 28 41 Lister (1978). (1980). 

Pt SARM-7 21 Price list. Formerly NIM- IGS-34 41 Lister (1978). 

PT0-1 Ta-Nb 

Black sand CCRMP-PT A-I 5 Price list. Steger (1983). albitized SVT-5 U.S.S.R. SRN 103-71. 

Cu-Ni CCRMP-PTM-1 5 Price list. Steger (1983). granite Lontsikh and Parshin matte (1980). 

sulfide CCRMP-PTC-1 5 Price list. Steger (1983). amazonite SVT-1 U.S.S.R. SRN 101-701. cone. granite Lontsikh and Parshin 

REE (1980). 

Bastnaesite IGS 40 41 Also IGS 41. Ore and carbonatite SVT-3 U.S.S.R. SRN 102-71. 

cone. Lontsikh and Parshin 

monazite IGS 36 41 Lister (1978). (1980). 

S, native ------------------ Poland. Planned. Table 3, SVT-12 U.S.S.R. SRN 346-73. 

Valcha (1977). Lontsikh and Parshin 

Sb CCRMP-CD-1 5 Price list. Steger (1983). (1980). 

-----·------------ 4 samples. Numbers or cone. SVT-6 U.S.S.R. SRN 104-71. 

suppliers not given. Lontsikh and Parshin 

Dempir (1978). (1980). 

Se-Te SS-287 Gorozhanina and others SVT-8 U.S.S.R. SRN 106-71. 

(1971). Lontsikh and Parshin 

Sn NBS 137 6 Price list. (1980). 

SS-136 Gorozhanina and others SVT-17 U.S.S.R. SRN 651-75. 

(1971). Lontsikh and Parshin 

Sn-Erz I 37 Price list. (1980). 

Reference Samples Identified Through 1984 51 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Ores-Continued Ores-Continued 

Ta-Nh-Continued U-Continued 

pegmatite SVT-7 U.S.S.R. SRN 105-71. Witwaters- SARM-29 21 Price list. 

Lontsikh and Parshin rand 

(1980). U-Th CCRMP-BL-1 5 Price list. Also DL-1 a and 

SVT-13 U.S.S.R. SRN 347-73. DH-la. Steger (1983). 

Lontsikh and Parshin v 

(1980). cone. SS-290" Gorozhanina and others 

Th IAEA-S-14 27 IAEA (1984). For U and (1971). 

Th. Th 0.1%. w CCRMP-TLG-1 5 Price list. Steger (1983). 

IAEA-S-15 27 IAEA (1984). For U and Also samples Ct-1 and 

Th. Th 0.05%. BH-1. 

IAEA-S-16 27 IAEA (1984). For U and wolfnlmite IGS-25 41 Lister (1978). 

Th. Th 1%. Zn ZnU Valcha (1977). Ostroumov 

monazite EPA-3 19 For 232Th and 228Th. (1979). 

EPA-4 19 EPA-3 diluted 10:1 with cone. CCRMP-CZN-1 5 Price list. Steger (1983). 

low activity soil. sphalerite BCR-26 16 Price list. Also BCR 27-

Ti BCR 31. For Zn. 

ilmenite IGS-31 41 Lister (1978). sphalerite BCR--108 16 Price list. Also BCR 109 

ilmenite SS-154-a Gorozhanina and others BCR 110. For trace elecone.? (1971). ments. 

rutile IGS-32 41 Lister (1978). cone. IGS-19 41 Lister (1978). 

u CCRMP-BL-2 5 Also BL-2a, -3, -4, -4a, sphalerite- IGS-17 41 Also IGS-18. Lister 

and -5. Price list. qtz. (1978). 

Steger (1983). mixt. 

EJB-l-81 52 7 samples. Yang and Liu Zn-Cu sui- CCRMP-RU-1 5 Price list. Steger (1983). 

(1983). fide 

USFRS-73.5 U.S.S.R. Sobomov Zn-Pb-Sn- CCRMP-KC-1 5 Steger (1983). Out of 

(1983). Cu stock. Now KC-Ia 

UR-1145 U.S.S.R. Sobornov (Steger and Bowman, 

(1983). 1984). 

UR-47S U.S.S.R. Sobornov Zn-Sn-Cu- CCRMP-MP-1 5 Also MP-la. Price list. 

(1983). Pb Steger (1983). 

S-316 Also 317-319. Australian Zr zircon IGS-35 41 Lister (1978). 

AEC ores, table 6, BCS-388 22 Price list. 

Hitchen and Zechanow- cone. SARM-13 21 Price list. 

itsch (1980). SS-296 Gorozhanina and others 

CUP-liS Canadian Uranium Produc- (1971). 

ers standard, table 6, 

Hitchen and Zechanowitsch (1980). Paratellurite ... ....................................... ..~ ...... 20 Microprobe. Price list. 

acid leach SARM-21 21 Also SARM-27 and -28. Pegmatite SO-IBn4 U.S.S.R. SRN 706-75. 

residue Price list. Sobornov (1977). 

calcrete SARM-22 21 Price list. Peridotite USGS-PCC-1 7 Out of stock. 

carnotite NBL-4 18 Price list. Also NBL-5. GSJ-JP-1 II Available 1984. A. Ando 

IAEA-S-3 27 Out of stock. (written commun. 

head SARM-31 21 Price list. 1984). 

sample PIM-1 55 IGEM 1002/1007. EgraKaroo SARM-30 21 Price list. nova and others (1981). 

pitchblende NBL-6A 18 Price list. Now MU-1, Khitrov 

IAEA-S-7 27 IAEA (1984). 0.527% (1984). 

U30 8. Petalite NBS 182 6 Price list. 

IAEA-S-8 27 IAEA (1984). 0.140% Phlogopite CRPG-Mica-Mg 24 Govindaraju (1979). 

U30 8. Phonolite DFG-KA Meyer and others (1981). 

IAEA-S-12 27 IAEA (1984). 0.014% In-house sample. 

U30 8. Phosphate NBS 120 b 6 Price list. 

IAEA-S-13 27 IAEA (1984). 0.039% BCR32 16 Price list. Serrini (1981). 

U308. WP042 Jenke and Diebold (1982). 

EPA-I 19 For 238U and 235U. IPT-18 38 Price list. 

EPA-2 19 EPA-I diluted 10:1 with NBS 694 6 Western phosphate from 

low activity soil. Conda, Idaho. 

pyrite SARM-23 21 Also SARM-25 and -26. PH-I Also PH-2. Iraq standards, 

cone. Price list. Barbooti and Jasim 

slimes SARM-24 21 Price list. (1982). 

tailings CCRMP-UTS-1 5 Also UTS-2, -3, and -4. IAEA-S-17 27 Also S-18 and -19. IAEA 

Steger and Smith (1983). Interlaboratory 

(1984). comparisons for U. 

torbernite IAEA-S-2 27 Out of stock. IAEA-S-20 27 IAEA (1983). Interlaborauraninite IGS-37 41 Lister (1978). tory comparisons for 

IAEA-S-4 27 Out of stock. Ra/U and mu. 

52 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Phosphate-Continued Sand 

......................................... Hungary. Table 3, Valcba Feldspar ZGI-FK 37 Price list. Ostroumov 

(1977). (1979). 

NBL-lA 18 Price list. U3 0 8, O.QlSO% Glass NBS 8la 6 Price list. 

NBS l65a 6 Price list. (superphos- BCR-33 16 Price list. UNSSpS 17 V alcha (1977). Ostroumov phate) (1979). 

Plagioclase, see ------------------ 20 Microprobe. Price list. 1 -s 32 Price list. Soc. of Glass 

Feldspar Technology (1980). 

Psilomelane ------------------ 20 Microprobe. Price list. Monazite NBL-7a 18 Price list. 

Pyrite PS-1 37 Price list. SchrOn and others (1975). Sandstone GSR-4 33 C.H. Tong (written com-

....................................... 20 Microprobe. Price list. mun., 1984). 

Pyrolusite --.. -----... --------- 20 Microprobe. Price list. Scapolite PSU 63-1805 30 Microprobe. Ingamells Pyromorphite --------.. ------....... 20 Microprobe. Price list. (1978). 

Pyrope, see USNM-143968 26 Microprobe. Jarosewich PSU 62-1703 30 Microprobe. Ingamells 

Garnet and others (1980). (l980b). 

Pyroxene PSU Px-1 30 Microprobe. lngamells ·················· Microprobe. Price list. 

(1978). (rneionite) USNM R 6600-1 26 Microprobe. Jarosewich 

5-180 30 Microprobe. lngamells and others (1980). 

(l980b). 

Augite USNM 122142 26 Microprobe. Jarosewich Scheelite ·················· 20 Microprobe. Price list. 

and others (1980). 

MAS-2 33 Chinese reference sample. Schist USGS-SOC-I 7 Flanagan (l976b). ------------------ 20 Microprobe. Price list. ASK-2 40 Christie (1975). 

Diopside USNM 117733 26 Microprobe. Jarosewich QMC-M-2 44 In-house? Status uncertain. 

and others (1980). garnet SAROCK S-13 21 National reference sample, 

Hypersthene USNM 746 26 Microprobe. Jarosewich Frick (undated). 

and others (1980). sillimanite SAROCK S-12 21 National reference sample, 

Omphacite USNM 100607 26 Microprobe. Jarosewich Frick (undated). 

and others (1980). 

Pyroxenite NIM-P 21 Price list. Now SARMS-5. Sediment 

Steele and others (1978); Bay NBS 1646 6 Price list. 

Steele and Hansen (estuarine) 

(1979). BFG In-house? Ackermann and 

others (1979); Meyer 

and others (1981). 

Quartz USNM R 17701 26 Microprobe. Jarosewich Canal (river) NBS 1645 6 Price list. 

Lake IAEA-SL-1 27 IAEA (1984). and others (1980). gyttja NBS- 6 In prep. For low level ra- ----------.. ------- Rojas (1984), for 6 oxides, dioactivity.Merritt 

Ag, As, Au, Pb, S, and (1980). 

w. Marine USGS-MAG-I 7 Manheim and others 

SAROCK S-17 21 National reference sample, (1976). 

Frick (undated). IAEA-SD-B-1 27 IAEA (1984). Also B-2. 

Quartz latite USGS-QL0-1 7 Flanagan (l976b). For fission products. 

BCSS-1 42 Berman (1981). 

MESS-I 42 Berman (1981). 

Refractories EMRM-MS Beasley and others (1982). 

Brick, Dinas SS-56-b Gorozhanina and others Same as IAEA-SD-B-3 

(1971). (p. 5, Volchok and 

Feiner (1979)). 1\,umed- IAEA-SD-B-3 27 IAEA (1983). Also SD40% Al203 NBS-76a 6 Price list. N-1. Ballestra and 

60% Al203 NBS-77a 6 Price list. Fukai (1983). 

70% Al203 NBS-78a 6 Price list. IAEA-SD-N-1/l 27 IAEA (1983). For lower 

IPT-51 38 Price list. level fallout for transChrome NBS-103a 6 Price list. uranium elements. 

Chrome- SS-239 ? Gorozhanina and others Available 1984 (?). 

magnesite (1971). IAEA-N-2 27 IAEA (1983). For lower 

level fallout than IAEA- Clay SS-55a Gorozhanina and others SD-N-111. Available 

(chamotte) (1971). 1984 (?). 

Silica NBS-198 6 Price list. Also NBS-199. IAEA-SD-N-112 27 IAEA (1983). For trace elRhodocrosite --.. --------.. ------ 20 Microprobe. Price list. ements. Available 1984 

Rhyolite USGS-RGM-1 7 Flanagan (1976b). (?). 

GSJ-JR-1 11 Also JR-2. Available SD0-1 to -3 ? Supplier not listed in 

1983. Ber:kovits and Lukashin 

NBS-278 6 Price list. (1984). 

Riebeckite, see ----------·------- ........ ------------"' --.. -- Pond NIES-2 34 Iwata and others (1981). 

Amphibole Nakahara and others 

Rock salt S-1 ? Also S-2 and -3. Table 1, (1982). 

Valcha (1977). River NBS 4350-B 6 Price list. Environmental 

Rutile ------------------ 20 Microprobe. Price list. radioactivity. 

Reference Samples Identified Through 1984 53 
Table 5. Reference samples-Continued Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References Name Number Supplier Remarks or References 

Sediment-Continued Silt, see Sedi- ----- ..... ----------... -... -------... -- ... --------.. 

River-Continued ment, marine 

GSD-1 47 Also GSD 2-8. Zhang and volcanic SD0-2 54 IGI. U.S.S.R. SRN 1756-

others (1982); Yuan and terri gene 80. Lontsikh (1981). 

Chen (1982). calcareous SD0-3 54 IGI. U.S.S.R. SRN 1753-

81-01 Su and Zhang (1984); Sun 80. Lontsikh (1981). 

and others (1984). Skarn ---------... -- ... -.. --- GDR. Planned. Table 3, 

S-14 21 Also S-19 and -20. Victor Valcha (1977). 

(1983). Slag SS-81 Also SS-82 to -87. 

GRD-30 33 17 samples from Gilin Gorozhanina and others 

Province, China. Zhao (1971). (1984). 3 samples 37 Price list. 

EMRM-RS Beasley and others (1982). BAM 826-1 29 Price list. Also BAM 827-

Portion of NBS RM 45B 1. 

(Volchok and Feiner JK-51 53 6 samples. Sweden, Insti-

(1979)). tutet for MetallforsknBFG In-house? Ackerman and in g. others (1979). basic BCS 395 22 Price list. Also BCS 381 

NBS RM 45B 6 Price list. Also see van der and 382/1; ES-879-1. 

Sloot and Zonderhuis basic open SS-80-V Gorozhanina and others (1979). hearth (1971). 

Senarmonite ---------------... -- 20 Microprobe. Price list. blast furnace BCS 367 22 Price list. 

Serpentine ANRT-UB-N 24 Govindaraju (1982). SS-79-V Also 267 and 267-a. 

ZGI-SW 37 Price list. Ostroumov Gorozhanina and others 

(1979). (1971). 

SAROCK S-15 21 National reference sample, CCRMP-SL-1 5 Price list. Steger (1983). 

Frick (undated). conventor, SS-311 Gorozhanina and others 

Chrysotile OECD-05 31 Van Olphen and Fripiat vanadium (1971). 

(1979). 02 SS-262 Gorozhanina and others 

Shale 46 w 4100 In-house, van der Sloot (1971). 

and Zonderhuis ( 1979). open hearth SS-203-b Also 204-a and 205-a. 

From Wards Scientific Gorozhanina and others 

Establishment. (1971). 

USGS-SD0-1 7 Not analyzed. Lechler and phosphate BAM-826-1 29 Price list. 

Leininger (1979). Frost Thomas IRSID-SO 1-1 28 Jecko and Ravaine (1978). 

and others (1982) for Thomas BAM-827-1 29 Price list. 

INAA data. phosphate 

IAEA-Sed-1 27 For U, Th, and K. Slate ZGI-TB 37 Price list. Clay shale in 

Heinonen and others Ostroumov (1979). 

(1973). From Schoen- ZGI-TB-2 37 Price list. 

berg, Germany. Sludge ash CCIW-IS-1 3 Knechtel and Fraser 

IAEA-Sed-2 27 For U, Th, and K. (1980). 

Heinonen and others Smithsonite --------- ................... 20 Microprobe. Price list. 

(1973). From Yxhult, Sodalite PSU 4-296-8 30 Microprobe. lngamells 

Sweden. (1978). 

NASC "North American Shale Soil ......................... ------ 12 soils for soil scientists. 

Composite," Gromet and Barnhisel (1978). 

others (1984). Supply IAEA-Soil-5 27 Dybczynski and others 

nearly exhausted. (1979). 

GSR-5 33 C.H. Tong (written com- IAEA-Soil-6 27 IAEA (1984). For 90Sr. 

mun., 1984). 137Cs, 54Mn, and 239Pu. 

black ZGI-TS 37 Price list. Ostroumov Available 1984 (?). 

(1979). IAEA-Soil-7 27 IAEA (1984). For trace elcarbonaceous SAROCK S-9 21 National reference sample, ements. Available 1984 

Frick (undated). (?). 

Cody USGS-SCo-1 7 Flanagan (1976b). CCRMP-S0-1 5 Also S0-2 to -4. Price 

Green River USGS-SGR-1 7 Flanagan (1976b). list. Steger (1983). 

Mancos EPA-8 19 For 226Ra and 228Ra. USGS-GXR-2 Also GXR-5 and -6. AllOil SIND-I Lechler and Leininger cott and Lakin (1978). 

(1979). Frost and others USGS-D-C 35 Also D-D. Crock and 

(1982). Sevemson (1980). 

AR-1900 23 Price list. Also AR-1901. GSS-1 33 Also GSS-2 to GSS-8. 

For oil or water yield. C.H. Tong (written 

Purington KnC-ShP-1 46 Moore (1978). commun., 1984). 

NBS 4353 6 Price list. From Rocky Siderite ------------------ 20 Microprobe. Price list. Flats Plant, Golden, 

Silica BCS 313 22 Price list. Colo. 

Sillimanite ---------------- ... - 20 Microprobe. Price list. DFG In-house? Meyer and othBCS 309 22 Price list. ers (1981), table 3. 

54 Reference Samples in Geology and Geochemistry 
Table 5. Reference samples-Continued 

Name 

Soil-Continued 

Co-Cu-Ni 

rich 

Sphalerite 

Sphene, see Titanite 

Staurolite 

Stibnite 

Sulfide 

Sulfur 

Syenite 

nepheline 

Talc 

Tellurite 

Titanite 

Tonalite 

Tourmaline 

Elbaite 

Trachyte 

Trap 

Tremolite, see 

Amphibole 

Turquoise 

Ulexite 

Ultrabasic rock 

Vanadinite 

Water 

Number 

ELR-007 

ISPRA 

SP-1 

SP-2 

SP-3 

SAROCK S-10 

SF-I 

ASK-3 

CCRMP-SY-2 

NIM-S 

NS-1 

SRS-S-1 

USGS-STM-1 

SNS-2 

OECD-08 

MRT-T-1 

USGS-TLM-1 

PSU 4-206 

RARC-TKT 

ST-IA 

DZI-1 

IAEA-W-4 

Supplier Remarks or References 

54 

54 

54 

21 

37 

20 

20 

20 

40 

20 

5 

21 

48 

7 

54 

31 

20 

20 

20 

30 

7 

30 

20 

20 

20 

33 

20 

27 

Also ELR-008. McQuaker 

and others (1979). 

Meyer and others (1981), 

table 3. 

U.S.S.R. SRN 901-76, 

Lontsikh and Parshin 

(1980). 

U.S.S.R. SRN 902-76, 

Lontsikh and Parshin 

(1980). 

U.S.S.R. SRN 903-76, 

Lontsikh and Parshin 

(1980). 

National reference sample, 

Frick (undated). 

Price list. Schron and others (1975). 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Price list. 

Christie (1975). 

Microprobe. Price list. 

Also SY-3. Price list. 

Steger (1983). 

Price list. Now SARM-2. 

Steele and others (1978); 

Steele and Hansen 

(1979). 

Kukharenko and others 

(1968). 

In-house. McDonough and 

Nelson (1984). 

Hanagan (l976b). 

U.S.S.R. SRN 1345-78. 

Lontsikh and Parshin 

(1980). 

Van Olphen and Fripiat 

(1979). 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Ingamells 

(1978). 

Supply exhausted. (1975). 

Not analyzed. 

Microprobe. Ingamells 

(1980b). 

Microprobe. Price list. 

In-house. Reddy and 

others (1982). 

IGI. U.S.S.R. SRN 519-

74. Tauson and others 

(1976). Egranova and 

others (1981). 

Microprobe. Price list. 

Microprobe. Price list. 

Also DZI-2. 

Microprobe. Price list. 

IAEA (1984). For 19 trace 

elements. 

Table 5. Reference samples-Continued 

Name Number Supplier Remarks or References 

Water-Continued 

sea IAEA-SW-N-2 

Willemite 

Wollastonite 

Wulfenite 

Zincite 

Zircon 

sand 

BCS-388 

27 

20 

20 

20 

20 

20 

22 

51 

IAEA (1984). For 90Sr, 

!37CS, transuranics. 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Price list. 

Microprobe. Price list. 

Price list. 

No sample number in ISO 

(1982). 

NOTE.-The following information became available too late to be included in 

the table: 

I. A paper with data for and descriptions of four tropical soil reference samples 

(K-3, CS-1, SAu-l, and SUR-I) and a lateritic bauxite, BAK-1, was published by 

K.E. Burke (1985, First co-operative study on four tropical soil samples and one 

lateritic bauxite (Suriname) proposed as geochemical reference samples: Geostandards Newsletter, v. 9, no. l, p. 69-78). 

2. The South African Committee for Certified Reference Materials (SACCRM) 

announced the availability of four new reference samples, as follows: 

l. SARM-18, coal from the Witbank coal field in eastern Transvaal. This sample 

may be the same as or similar to coal sample NEMI-B5 in table 5; 

2. SARM-19, coal from the coal fields of the Orange Free State; 

3. SARM-20, coal from the coal fields in the Sasolburg area of the Orange Free 

State; and 

4. SARM-32, phosphate rock from Phalobora, northeastern Transvaal. 

3. A paper with a description of and data for an in-house basalt, B-78 (in table 

5), was published by P.B. Pawaskar, B.S. Manerkar, and M. Sankar Das (1985, An 

in-house reference rock standard: Gilbert Basalt, B-78: Analysis and estimates: Geological Society of India Journal, v. 26, no. 3, p. 219-224). 

Table 6. Suppliers of reference samples 

1. Chief, Branch of Exploration Research, U.S. Geological Survey, Box 

25046, DFC, MS 973, Lakewood, CO 80225, U.S.A. 

2. Th. Hiigi, Mineralogisches-Petrographisches Institut, Universitat 

Bern, CH-3012 Bern, Switzerland. 

3. J.L. Fraser, Environment Canada, Environment Protection Service, 

Waste Water Technology Centre, P.O. Box 5050, 867 Lakeshore 

Road, Burlington, Ont., Canada L7R 4A6. 

4. D.P. Weill, Center for Volcanology, University of Oregon, Eugene, 

OR 97403, U.S.A. 

5. H.F. Steger, Canadian Certified Reference Materials Project, Canada 

Centre for Mineral and Energy Technology, 555 Booth Street, 

Ottawa, Canada KIA OGl. 

6. Office of Standard Reference Materials, Room B-311 Chemistry 

Building, National Bureau of Standards, Washington, DC 20234, 

U.S.A. 

7. Branch of Analytical Chemistry, Stop 972, U.S. Geological Survey, 

Reston, VA 22092, U.S.A. 

8. P.J. Potts, Dept. of Earth Sciences, Open University, Walton Hall, 

Milton Keynes MK7 6AA, United Kingdom. 

9. For North and South America: 

I.L. Barnes, Room A-23 Physics Building, National Bureau of 

Standards, Washington, DC 20234, U.S.A. 

For Europe and other continents: 

R. Gonfiantini, International Atomic Energy Agency, P.O. Box 

100, A-1400, Vienna, Austria. 

10. G. Frederick Smith Chemical, Co., P.O. Box 23344, Columbus, OH 

43223, U.S.A. 

Reference Samples Identified Through 1984 55 
Table 6. Suppliers of reference samples-Continued 

11. Atsushi Ando, Geochemistry and Technical Service Department, Geological Survey of Japan, 1-1-3 Higashi, Yatabe, lbaraki, 305, 

Japan. 

12. Iron and Steel Institute of Japan, 9-4, 1-Chome, Otemachi, Chiyodaku, Tokyo, Japan. 

13. E. Schroll, Geotechnisches Institut (BVFA), Arsenal, A-1030 Vienna, 

Austria. 

14. E.C. Alexander, Jr., Department of Geology and Geophysics, University of Minnesota, Minneapolis, MN 55455, U.S.A. 

15. W.D. Johns, Source Clay Minerals Repository, Department of Geology, University of Missouri, Columbia, MO 65201, U.S.A. 

16. Community Bureau of Reference-BCR, Directorate General XII, 

Commission of the European Communities, 200, rue de Ia Roi, 

B-1049, Brussels, Belgium. 

17. Vaclav Zyka, Director, Institute of Mineral Raw Materials, 28403 

Kutna Hora-Sedlec, Czechoslovakia. 

18. Nancy M. Trahey, Department of Energy, New Brunswick Laboratory 

D-350, 9800 South Cass Avenue, Argonne, IL 60439, U.S.A. 

19. Environmental Monitoring System Laboratory, U.S. Enivronmental 

Protection Agency, P.O. Box 15027, Las Vegas, NV 98114. 

20. Tousimis Research Corporation, P.O. Box 2189, Rockville, MD 

20852, U.S.A. 

21. South African Bureau of Standards, Private Bag Xl91, Pretoria, 0001, 

South Africa. 

22. Bureau of Analysed Samples, Ltd., Newham Hall, Newby, Middlesbrough, Cleveland, England TS8 9EA. 

23. Alpha Resources Inc., 3090 Johnson Road, Stevensville, MI 49127, 

U.S.A. 

24. K. Govindaraju, Centre de Recherches Petrographiques et Geochimiques, C.O. No. 1, 54500 Vandoeuvre-Nancy Cedex, France. 

25. John H. Reynolds, Department of Physics, University of California, 

Berkeley, CA 94720, U.S.A. 

26. Eugene Jarosewich, Department of Mineral Sciences, Smithsonian 

Institution, Washington, DC 20560, U.S.A. 

27. International Atomic Energy Agency, Analytical Quality Control Services, Laboratory Seibersdorf, P.O. Box 100, A-1400 Vienna, 

Austria. 

28. Prolabo, 12, rue Pelee, B.P. 200, 75526 Paris Cedex 11, France. 

29. Bundesanstalt fiir Materialpriifung (BAM), Unter den Eichen 87, 

Berlin 45, Federal Republic of Germany. 

30. C.O. Ingamells, 2970 Xenon Street, Denver, Wheat Ridge, CO 

80215, U.S.A. 

31. Mlle. S. Caillere, Laboratoire de Mineralogie du Museum National 

d'Histoire Naturelle, 61, rue de Buffon, Paris 5e, France. 

32. Society of Glass Technology, 20 Hattam Gate Road, Sheffield, SlO 

5BT, England. 

33. Xuejing Xie, Deputy Director, Institute of Geophysical and Geochemical Prospecting, Langfang, Hebei, 102801, People's Republic of 

China. 

34. National Institute for Environmental Studies (NIES), 16-2, Onogawa, 

Yatabemachi, Tsukuba-Gun, Ibaraki, Japan. 

35. J.G. Crock, Branch of Analytical Chemistry, U.S. Geological Survey, 

Box 25046, DFC, MS 928, Lakewood, CO 80225, U.S.A. 

36. Federation Europeenne des Fabricants de Produits Refractaires, 44, 

rue Copernic, 75016 Paris, France. 

37. Amt fiir Standarisierung, Messwesen und Warenpriifung (ASMW), 

Wallstrasse 16, 1026 Berlin, German Democratic Republic. 

38. Agrupamento de Materials de Referenda, Divisao de Quimica e Engenharia Quimica, Instituto de Pesquisas Tecnol6gicas do Estado de 

Sao Paulo (IPT), Cidade Universitana Armando de Salles Oliveira, 

05508 Sao Paulo-SP-Brazil. 

39. J.J. LaBrecque, Instituto Venezolano de Investigaciones Cientificas 

(IVIC), Apartado 1827, Caracas, 1010A, Venezuela. 

56 Reference Samples in Geology and Geochemistry 

Table 6. Suppliers of reference samples-Continued 

40. O.H.J. Christie, Rogaland District High School, Studiesenteret Ullhandhaug, N-4001 Stavanger, Norway. 

41. Brian Lister, Institute of Geological Sciences, 64 Gray's Inn Road, 

London, WCIX 8NG, England. 

42. Marine Analytical Chemistry, Standards Program, Chemistry Division, National Research Council, Montreal Road, Ottawa, Canada 

KIA OR9. 

43. El. AI. Ivanov, Institute of Geology, Bulgarian Academy of Sciences, 

Sofia, Bulgaria. 

44. A.B. Poole, Department of Geology, Queen Mary College, Mile End 

Road, London, El, 4NS, England. 

45. A. Mazzucotelli, Instituto di Petrografia, Universita di Genova, Pallazo delle Scienze, 16132 Genova, Italy. 

46. D.M. Moore, Department of Geology, Knox College, Gallesburg, IL 

61401. 

47. Junta de Energia Nuclear, Ciudad Universitaria, Madrid 3, Spain. 

48. A.A. Kukharenko, Department of Mineralogy, Leningrad State University, Leningrad V-164, U.S.S.R. 

49. Japan Standard Sample Committee, c/o National Chemical Laboratory 

for Industry, 1 Higashi 1-Chome, Yatabemachi, Tsukuba-Gun, 

lbaraki, Japan. 

50. Gary P. Landis, U.S. Geological Survey, MS 405, Federal Center, 

Denver, CO 80225, U.S.A. 

51. Ceramic Society of Japan, 22-17, 2-Chome, Hyakunicho, ShinjyukuKu, Tokyo, Japan. 

52. Research Institute, Bureau of Uranium Geology, Beijing, People's 

Republic of China. 

53. Analytical Standards AB, Pl. 2366, S-434 00, Kungsbacka, Sweden. 

54. A.P. Vinogradov Institute of Geochemistry (IGI), Siberian Branch, 

U.S.S.R. Academy of Sciences, Irkutsk, U.S.S.R. 

55. Institute of the Geology, Geochemistry, Petrology, and Mineralogy of 

Ore Deposits (IGEM), U.S.S.R. Academy of Sciences, 

Staromonetny 35, Moscow, U.S.S.R., 109017. 

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-:,U.S. GOVERNMENT PRINTING OFFICE: 1986 - 491-405 - 226/20109