T> 1 CU J J TTT Rock standards, 111: 

Manganese-Nodule Reference Samples

L~A-1 and USGS-Nod-P-1

GEOLOGICAL SURVEY PBOFESSIONAL PAPER 1155

USGS Rock Standards, III: 

Manganese-Nodule Reference Samples 

USGS-Nod-A-1 andUSGS-Nod-P-1

By F. J. FLANAGAN and DAVID GOTTFRIED

GEOLOGICAL SURVEY PROFESSIONAL PAPER 1155

Analytical data by various techniques and 

best estimates for some elements in 

two manganese-nodule reference samples

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1980
UNITED STATES DEPARTMENT OF THE INTERIOR 

CECIL D. ANDRUS, Secretary

GEOLOGICAL SURVEY 

H. William Menard, Director

Library of Congress Cataloging in Publication Data

Flanagan, Francis James, 1915- 

USGS rock standards, III.

(Geological Survey professional paper ; 1155) 

Bibliography: p. 

Supt. of Docs, no.: I 19.16:1155

1. Manganese nodules Composition. I. Gottfried, David, joint author. II. Title. III. Series: United States. Geological Survey. Professional paper ; 1155.

QE390.2.M35F43 552'.5 79-607084

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C. 20402
CONTENTS

Page

Abstract _________________________________--————————— 1

Introduction _________________________________—————————— 1

Preparation of samples _________________————————————————— 2

Experimental design for the determinations __________________——— 2

Semiquantitative spectrochemical analysis and homogeneity ___ ——————— — 2

Tests for homogeneity _________________—__————————————— 4

Estimation of best values ________________________-_____-—— 5

Selection process and lack of clear choices _____________-_____—- 7

Summary estimates and discussion _____________________—————— 8

Comparisons with data from Marsden Squares 049 and 116 ____________- 10

Availability of samples __________________________________—— 10

References cited ________________________________________ 12

TABLES

Page

TABLE 1. Estimates from the analysis of variance of computerized semiquantitative spectrochemical determinations of trace-elements data for USGS-Nod-A-1 and USGS-Nod-P-1 ________________ 3

2. Number of calculated F ratios smaller or larger than the fractile of the F distribution indicated _ 5 

3, 4. Summary of best estimates and confidence limits for averages of several elements in:

3. USGS-Nod-A-1 ______________________________________________ 8

4. USGS-Nod-P-1 ________________________________________________ 9

5. Comparison of best estimates for several elements in USGS-Nod-A-1 with estimates of the distribution of ths elements for data in samples from Marsden Square 116 __________________ 11

6. Comparison of best estimates for several elements in USGS-Nod-P-1 with estimates of the distribution of the elements for data in samples from Marsden Square 049 __________________ 11 

7, 8. Determinations of several elements, by instrumental neutron-activation analysis, by P. A. Baedecker, 

U.S. Geological Survey, in:

7. USGS-Nod-A-1 _______________________________________._______ 14

8. USGS-Nod-P-1 ________________________________________________ 15 

9,10. Determinations of several elements and oxides by John Marinenko, U.S. Geological Survey, in:

9. USGS-Nod-A-1 ________________________________________________ 16 

10. USGS-Nod-P-1 _______________________________________________________._____ 17

11. Determinations of U and Th in USGS-Nod-A-1 and USGS-Nod-P-1, by delayed neutron-activation

analysis, by H. T. Millard, Jr., and C. M. Ellis, U.S. Geological Survey _______________ 18 

12-21. Determinations of several elements in USGS-Nod-A-1 and USGS-Nod-P-1: 

12,13. By the National Physical Research Laboratory, South Africa:

12. USGS-Nod-A-1 _____"_________________________________ 18

13. USGS-Nod-P-1 ______________________________________ 19

14,15. By S. E. Calvert, Institute of Oceanographie Sciences, England:

14. USGS-Nod-A-1 _______________________________________ 20

15. USGS-Nod-P-1 ________________________________________ 21 

16,17. By R. T. T. Rantala, Bedford Institute of Oceanography, Canada:

16. USGS-Nod-A-1 ______________________________________ 22

17. USGS-Nod-P-1 __________________________________________ 23

18,19. By the National Institute for Metallurgy, South Africa:

18. USGS-Nod-A-1 ______________________________________ 24

19. USGS-Nod-P-1 _______________________________________ 25

in
IV CONTENTS

Page

TABLES 12-21. Determinations of several elements in USGS-Nod-A-1 and USGS-Nod-P-1—Continued 

20,21. By the Institute of Geological Sciences, England:

20. USGS-Nod-A-1 __________ —————— — — __-__________-_______ 26

21. USGS-Nod-P-1 ________________________________________ 27 

22, 23. Determinations of several elements in USGS-Nod-A-1 and USGS-Nod-P-1, by atomic-absorption 

spectrometry:

22. By David Piper, U.S. Geological Survey _________________________________ 27

23. By Lockheed Ocean Laboratory, California-- ——— ————— ——————— _____ ———— __———— 28 

24,25. Complete analyses by M. Saunders, Grant Institute of Geology, Scotland, of:

24. USGS-Nod-A-1 _________________- —— ___________________________ 28

25. USGS-Nod-P-1 _________________________________________________ 29 

26, 27. Determinations of several elements by David Felix, Ocean Mining Laboratory, California, in:

26. USGS-Nod-A-1 __________________________________________________ 30

27. USGS-Nod-P-1 __________________-__-_____________________________ 31

28, 29. Determinations of several elements, by atomic-absorption spectrometry, by Wayne Mountjoy, James 

G. Crock, and George Riddle, U.S. Geological Survey, in:

28. USGS-Nod-A-1 ________________________________________________________ 32

29. USGS-Nod-P-1 ______________________________________________ 33 

30,31. Chemical determinations of several constituents by Sarah T. Neil, U.S. Geological Survey, in:

30. USGS-Nod-A-1 _________________________________________________________________ 34

31. USGS-Nod-P-1 ___________________________________________________ 35

32,33. Averages of determinations of elements by all contributing analysts, in:

32. USGS-Nod-A-1 _________________________________________________ 36

33. USGS-Nod-P-1 ___________________________________________________ 38

CONVERSION FACTORS

Metric unit Inch-Pound equivalent

Length

millimeter (mm) 

meter (m) 

kilometer (km)

0.03937 inch (in) 

3.28 feet (ft) 

.62 mile (mi)

Area

square meter (m2 ) = 10.76

square kilometer (km2 ) = .386

hectare (ha) = 2.47

square feet (ft2 ) 

square mile (mi2 ) 

acres

Volume

cubic

liter

cubic

cubic

cubic

liter

liter

liter

cubic

centimeter (cm3 )

(L)

meter (m3 )

meter

hectometer (hm3 )

meter 

cubic meter

= 0.061 cubic inch (in«)

= 6(1.03 cubic inches

= 35.31 cubic feet (ft3 )

= .00081 acre-foot (acre-ft)

= 810.7 acre-feet

r= 2.113 pints (pt)

= 1.06 quarts (qt)

= .26 gallon (gal)

= .00026 million gallons (Mgal or

	10« gal) 

= 6.290 barrels (bbl) (1 bbl = 42 gal)

Weight

gram (g)

gram

metric tons (t)

metric tons

=r 0.035 ounce, avoirdupois (oz avdp)

= .0022 pound, avoirdupois (Ib avdp)

= 1.102 tons, short (2,000 Ib)

= 0.9842 ton, long (2,240 Ib)

Specific combinations

kilogram per square 

centimeter (kg/cm2 )

kilogram per square 

centimeter

cubic meter per second 

(mVs)

= 0.96 atmosphere (atm)

= .98 bar (0.&869 atm)

= So.3 cubic feet per second (ft3/s)

Metric unit Inch-Pound equivalent

Specific combinations—Continued

liter per second (L/s) = .0353 

cubic meter per second = 91.47

per square kilometer

[(ms/s)/km2 ] 

meter per day (m/d) — 3.28

meter per kilometer = 5.28

(m/km) 

kilometer per hour = .9113

(km/h)

meter per second (m/s) = 3.28 

meter squared per day = 10.764

(m2/d) 

cubic meter per second — 22.826

(m.8/s) 

cubic meter per minute =264.2

(m3/min)

liter per second (L/s) = 15.85 

liter per second per = 4.83

meter [(L/s)/mJ 

kilometer per hour = .62

(km/h)

meter per second (m/s) = 2.237 

gram per cubic = 62.43

centimeter (g/cm3 ) 

gram per square = 2.048

centimeter (g/cm2 ) 

gram per square = .0142

centimeter

cubic foot per second 

cubic feet per second per 

square mile [(ft3/s)/mi2 ]

feet per day (hydraulic 

conductivity) (ft/A) 

feet per mile (ft/mi)

foot per second (ft/s)

feet per second

feet squared per day (ft2/d)

(transmissivity) 

million gallons per day

(Mgal/d) 

gallons per minute (gal/min)

gallons per minute

gallons per minute per foot 

[(gal/min)/ft]

mile per hour (mi/h)

miles per hour

pounds per cubic foot (lb/ft3 )

pounds per square foot (lb/ft2 ) 

pound per square inch (lb/ins)

Temperature

degree Celsius (°C) 

degrees Celsius 

(temperature)

= 1.8 degrees Fahrenheit (°F) 

= [(1.8x°C)-f 32] degrees Fahrenheit
USGS ROCK STANDARDS, III: 

MANGANESE-NODULE REFERENCE SAMPLES 

USGS-NOD-A-1 AND USGS-NOD-P-1

By F. J. FLANAGAN and DAVID GOTTFRIED

ABSTRACT

Restricted amounts of manganese nodules from the Atlantic and Pacific Oceans have been processed as reference 

samples USGS-Nod-A-1 and USGS-Nod-P-1, respectively. 

Analysts used various analytical methods and the experimental design with the bottles of sample as the single variable of classification simultaneously to establish the compositions of the samples and to demonstrate the homogeneity of 

the powdered material. At the 5-percent probability level, 95.2 

percent of F tests for elements in Nod-A-1 and 96.6 percent 

of tests for those in Nod-P-1 are not significant, and these 

elements are inferred to be homogeneously distributed. Best 

estimates were obtained by the sequential procedure of (1) 

determining by Cochran's test which of k sets of data have a 

common variance, (2) calculating from this variance the 

standard deviation of the mean of six determinations, and 

(3) using this deviation to calculate the Studentized range to 

decide which means could have been derived from the same 

population mean. Present best estimates, in percentages, for 

elements of potential economic interest are:

Cu ....

Ni ......

Co . ...

Mn .....

Pt ---...

USGS-Nod-A-1

___ ... ___ 0.110

_ _______ .636

q-i i

_____ ___ 18.54

USGS-Nod-P-1

1.15

1.337

.224

29.14

.12

INTRODUCTION

Various aspects about manganese nodules on the 

sea floor have occupied the attention of mineral 

economists, economic geologists, and analysts for 

several decades. Mineral economists and economic 

geologists consider the related questions of whether 

the nodules are so distributed on the ocean floor that 

they may be readily mined and whether such elements as manganese, nickel, copper, and cobalt are 

present in sufficient amounts that the mining of the 

nodules and the recovery of these elements may be 

economically feasible. The chemical characteristics 

of manganese nodules, a source of scientific interest 

since their discovery during the voyage of the Challenger a century ago, have been the subject of reports in numerous journals, and data published 

through August 1973 have been compiled by Monget

and others (1976). Texts concerned with the several aspects about manganese nodules have been 

published by Mero (1965) and Glasby (1977).

The analysts using most chemical and physical 

techniques may be classified roughly into those who 

study the distribution of elements within individual 

nodules (studies that lead to theories about nodule 

formation) and those who are interested in the 

determination of several elements in a powdered 

nodule, the interest being either scientific or economic. The two classes of analysts, whose concerns 

are not mutually exclusive, also share the lack of 

a sufficient quantity of a nodule sample that may be 

processed as a natural reference material. The analysts therefore must resort to the use of pure chemicals, either as solids or in solution, or must use 

portions of the scarce analyzed nodules in their 

possession.

The availability of a large sample of manganese 

nodules that may be processed as a reference sample 

may be no panacea, because the variation in analytical data among analysts and among techniques 

may be as severe as those in data for rock reference 

samples by spectroscopic techniques (Flanagan, 

1979). Such possible wide variation in data may 

have prompted the Kennecott Copper Corp. to prepare a nodule sample to which the number GRLD126 was assigned (Raab, oral commun., 1974). This 

sample, intended to test interlaboratory determinations of several elements, was analyzed by six or 

seven laboratories, but a description of the sample 

and the data have not been published. Several laboratories that participated in the analyses use the 

sample as a provisional reference material.

Despite the suggestion that reference samples of 

manganese nodules be prepared (Flanagan, 1974, 

p. 1741), no such samples were being prepared by 

late summer 1975, to our knowledge. We therefore 

obtained about 100 pounds of nodules from each
USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

of two oceans (Atlantic and Pacific) from Deepsea 

Ventures, Inc., to whom we are indebted, and prepared them as reference samples. The sample from 

the Atlantic Ocean, processed as USGS-Nod-A-1, 

was taken from the Blake Plateau, and the other 

sample, now numbered USGS-Nod-P-1, was taken 

from the region of the Pacific Ocean of current 

interest in nodules. More precise locations for the 

samples are:

Location

Depth

USGS-Nod-A-1

31°02'N.

78°22' W.

788

USGS-Nod-P-1

14°50' N. 

124°28' W. 

4,340

PREPARATION OF SAMPLES

The samples were prepared by the procedure 

normally used for rock samples (Flanagan, 1967), 

with the following exception: The material of either 

nodule sample, after being processed through a roller 

crusher, was dried overnight in an oven at about 

150° F (65° C) before being placed in a ball mill. 

Soluble sea salts were not removed by washing the 

large crushed nodule samples with water. Hence, 

some portion of the sodium and chlorine data reported for either sample may be due to the sea 

salts.

While one sample was being processed, the cover 

used to contain the nodule material in the mill was 

not secured in place until processing was resumed 

on the next day. The partly powdered material 

apparently absorbed sufficient atmospheric moisture 

overnight to form a cementlike mixture, which was 

deposited as layers on the vertical end pieces of the 

mill when it was operated. The layers, about 4 cm 

thick, were removed with a geologist's pick, broken, 

redried, and processed again in the mill. In cross 

section, broken pieces of the layers showed the 

variegated colors from black through purple to dark 

brown that are characteristic of manganese oxide 

materials.

One analyst, M. Saunders (table 24), later noted 

that both dried nodule samples rapidly absorbed 

moisture during weighing. When weighed portions 

of either sample were exposed to the atmosphere 

overnight, the portions absorbed about 10 percent 

moisture.

EXPERIMENTAL DESIGN FOR THE 

DETERMINATIONS

The analysts were expected to use the experimental design, with a single variable of classification,

that had been used almost exclusively in U.S. Geological Survey Professional Paper 840 (Flanagan, 

1976). The variable of classification would be three 

bottles of one nodule sample, and the analysts were 

to make determinations of an element on two portions from each bottle. The determinations among 

the bottles were to be made in random order.

Three bottles of each nodule sample were packaged as a set, and 22 such sets were sent to laboratories, both within and outside the Geological Survey, that had volunteered to contribute data. Data 

from those who reported are shown in the several 

tables, and their contributions are gratefully acknowledged.

Analysts were requested to remove the caps from 

the bottles of nodule samples and to place the bottles in an oven at 110° C for 24 hours before weighing portions for analysis. Those who were to use 

chemical procedures were requested to make their 

determinations on portions for which the entire 

sample was put into solution, and not just on the 

acid-soluble portion, so that chemical data would be 

directly comparable with data obtained by physical 

methods, such as optical-emission spectroscopy, 

X-ray-fluorescence spectroscopy, or instrumental 

neutron-activation analysis.

Not all analysts made the determinations as requested, because they lacked time or misunderstood 

the purpose of the experimental design; as a result, 

a few tables are not directly comparable with those 

of the majority. The tables are therefore presented 

in four categories, and tables within a category are 

randomized where possible. The categories are listed 

as follows:

1. Semiquantitative spectrographic analysis (see 

discussion below).

2. Data by analysts or organizations who made the 

determinations in the manner requested.

3. Data by those who may have misinterpreted the 

intent of the experimental design and who 

therefore introduced other variance components into the data.

4. Data by those who, principally because of a lack 

of time, were unable to complete the set of 

data requested.

SEMIQUANTITATIVE SPECTROCHEMICAL 

ANALYSIS AND HOMOGENEITY

The data in table 1—estimates derived from semiquantitative spectrochemical determinations of several elements in the samples—are discussed briefly. 

The USGS rocks first released in 1964 and for which
SEMIQUANTITATIVE SPECTROCHEMICAL ANALYSIS AND HOMOGENEITY 3

TABLE 1.—Estimates from the analysis of variance of computerized semiquantitative spectrochemical determinations of

trace-element data for USGS-Nod-A-1 and USGS-Nod-P-1

[Analyst: N. Rait, U.S. Geological Survey. Determinations, in parts per million, d.f., degrees of freedom; S, significant; NS, not significant; Neg., 

negative bottle variance obtained; F ratios tested at .Fo.95 or the fractile indicated in parentheses]

Nod-A-1

Element

B __ ___ .

Ba _____ -

Be __ _ .

Ce

Co _ _ .

Cr _ _ .

Cu _ _ _ .

Eu _ _ .

La _ __ .

Mn _ ___ .

Mo _ _ .

Nd _ _ _ .

Ni __ ___ .

Pb _ __ _.

Sc __ __ .

Sr _________

Tl __ __ _.

V _ _ _.

Y _ __ .

Yb _ _ _.

Zn _ __ .

Zr _ ___ .

Mean

94

978

8.5

930

1,093

14

807

4 1

152

._ 177,000

226

101

._ 3,150

788

13

- 1,062

148

261

138

16

460

4Q8

Standard

Bottle 

(d.f.-2)

Neg. 

Neg. 

.16 

Neg. 

34 

Neg.

21 

Neg. 

Neg. 

Neg. 

13 

1.4

264 

Neg. 

Neg. 

Neg. 

Neg. 

Neg.

Neg. 

Neg. 

33 

2.9

deviation

Error 

(d.f. = 3)

19

150 

1.37 

104 

70 

1.9

102 

.99 

14.7 

23,100 

19 

21

122 

115 

1.7 

110

27 

27

18 

2.6 

15 

64

Nod-P-l

Standard deviation

F ratio

0.24 NS 

.08 NS 

1.03 NS 

.26 NS 

1.47 NS 

.62 NS

1.08 NS 

.29 NS 

.54 NS 

.50 NS 

1.95 NS 

1.01 NS

10.3 NS (0.975) 

.36 NS 

.39 NS 

.07 NS

.82 NS 

.56 NS

.21 NS 

.22 NS 

10.53 NS (0.975) 

1.00 NS

Mean

120 

1,038 

1.5 

278 

1,100 

11.8

>3,200 

^3.3 

107 

252,000 

718 

^2.6

14,170 

470 

7.6 

332 

265 

265

55 

8.6 

1,530 

260

Bottle 

(d.f. = 2)

2.9 

136 

.67 

49

.81

8 

20,200

74

1,000 

Neg-. 

1.9 

76 

23 

17

16 

3.0 

119 

100

Error 

(d.f. = 3)

5.8

53 

.15 

43

.91

10 

21,200 

41

1,470 

35 

.78 

44 

12 

13

5.0 

.79

58 

24

F ratio

1.5 NS 

14.1 NS(0.975) 

41.9 S(0.99)

3.57 NS

2.60 NS

2.21 NS 

2.81 NS 

7.55 NS

1.92 NS 

28.38 NS (0.99) 

12.35 NS (0.975) 

6.93 NS 

8.33 NS 

4.36 US

20.86 NS (0.99) 

29.01 NS(0.99) 

9.50 NS 

36.798(0.99)

1 Average of 5 determinations.

there are two compilations of data (Flanagan, 1969, 

1976) are now used to supplement the original spectrographic standards made to approximate the composition of the "average" silicate (Myers and others, 

1961). Neither set of standards even remotely approximates the composition of manganese nodules, 

and because of the effects of the different matrices, 

spectrographic estimates for the nodules could be expected to deviate from any best values subsequently 

calculated.

Nevertheless, the data in table 1 serve a useful 

purpose. Because the size of the sample taken for 

the spectrographic technique is small, these data 

may serve as an initial indication of the homogeneity 

of the material. If the samples are homogeneous for 

this techniuqe, then as a first approximation they 

should be homogeneous for those methods for which 

a larger portion of sample is taken for analysis. 

The homogeneity of the material does not depend 

on the closeness of the data to any "true" value 

but on the variation between and within bottles of 

a sample. Thus, if for a given element the F ratio— 

the variation attributable to bottle means divided by 

the variation within these bottles—is not larger 

than the value listed in the table for the 95-percent 

fractile of the F distribution with the appropriate

degrees of freedom, one may infer that the element 

is homogeneously distributed among the bottles.

The conclusions resulting from the analysis of 

variance of the semiquantitative spectrographic determinations that have the form of quantitative data 

are of some interest. Of the 22 elements for which 

complete sets of data are available for USGS-NodA-l, the calculated F ratios for 20 sets of data are 

not significantly larger than the allowable value of 

FO.DS (d.f. 2,3) =9.55, and the two remaining F ratios 

are not significant when tested against F0 ..nr> (d.f. 

2,3) = 16.0. We may conclude on the basis of these 

spectrographic data that the elements determined 

are homogeneously distributed among the bottles.

Complete sets of data for 19 elements are available for USGS-Nod-P-1. As the six determinations 

for cobalt are identical, no F test could be made, and 

cobalt is distributed homogeneously. The calculated 

F ratio is not significant at FOM for 11 elements 

and at FQ^r> for 2 others, and these elements may be 

inferred to be homogeneously distributed.

Of the remaining five elements for which sets of 

data are complete, the F ratios for three elements 

do not equal or exceed the allowable value for 7^.99 

(d.f. 2,3), and ratios for two elements exceed this 

value. Because the allowable ratio, 30.8, is rather
USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

large, the five elements appear to be heterogeneously 

distributed.

Perhaps because of the semiquantitative nature 

of the technique, we should not be unduly worried 

by the five conclusions of heterogeneity, but some 

brief discussion is justified. Samples to be analyzed 

routinely by the technique are never dried, and the 

powdered nodule samples were also not dried. Furthermore, the nodules from the Pacific were partly 

covered with a thin coating of gray pelagic clay. 

This clay was not removed from the nodules, and 

the small amount of clay was incorporated in the 

ground sample. The tendency of both the nodule 

material and the clay to absorb atmosphere moisture 

and the tendency of clays to absorb cations may be 

partly responsible for some of the demonstrated 

heterogeneity.

TESTS FOR HOMOGENEITY

The elements silicon through manganese were reported as percentage of either the oxide or the element, probably because no method of reporting had 

been specified. The elements reported as the oxides 

were reduced by the appropriate gravimetric factor 

to percentages of the elements before the analysis 

of variance. Such transformations from oxide to 

element also reduce the variation among the determinations of an element. Cobalt, copper, and nickel 

are considered as minor elements in the nodules, 

and data are listed therefore as percentages because 

their contents in the samples equal or exceed 0.1 

percent. Elements usually considered as trace elements in rocks but reported as percentages were 

converted to parts per million by multiplying by 10 4 

and adding nonsignificant zeros where necessary; 

these data were used in the calculations for the 

analysis of variance and for the best values.

The data in tables 7 through 21 presented no special problems, and the calculations of the analysis 

of variance were made on a laboratory calculator for 

which a program was available. The data in tables 

22 and 23 also presented no special problems, as one 

analyst reported averages of two determinations 

and the other made determinations on a single portion from each bottle of sample; these data cannot 

be used in the calculations. The data in tables 24 

and 25 are rather complete comprehensive analyses 

of each sample, and these single determinations 

also cannot be used. However, the data in tables 26 

to 29 were presented in a form that required a 

change in the analysis of variance.

The analyst who contributed the data shown in 

tables 26 and 27 apparently planned to make a 

single determination on a portion from each bottle 

of both samples on a single day and then repeat the 

procedure on two other days. However, the solution for the single determinations for bottle 2 of 

USGS-Nod-P-1 was contaminated on the first day, 

and data were therefore not reported. An extra set 

of determinations on a portion from bottle 2 was 

reported for the third day. The analyst, by his decision to make determinations on three days, added 

another variable of classification (days) to the 

original design with a single variable of classification (the bottles). As the extra determinations for 

bottle 2 were made on day 3, these determinations 

could not be legitimately substituted for the missing 

determinations for day 1. We therefore decided to 

omit the two determinations on day 1 and the extra 

determination on day 3 and to treat the remaining data as a two-way analysis of variance, with 

the bottles and the days as the two variables of 

classification. The results of the analysis of variance 

reflect the significance of these variables of classification. Although the determinations for USGSNod-A-1 were completed according to the plan of 

the analyst, we decided to treat both samples similarly, and the determinations for Nod-A-1 on days 

2 and 3 were also used in the two-way analysis of 

variance and in the calculations for best estimates.

The data in tables 28 and 29 presented a similar 

problem. The analysts for these determinations had 

intended to make the determinations in two "runs," 

but some determinations were delayed for about two 

months. To simplify matters, we ignored the delay 

and treated the data as a two-way design with bottles of sample and "runs" as the two variables of 

classification.

In other tables of data, one or both determinations 

for a bottle of sample were missing in a few places. 

Such missing data reduced the number of bottles to 

two, and the changes in degrees of freedom for both 

bottles and for error are given in footnotes. Where 

data are missing, the laboratory means and variances were not used in the calculations of best values. Data reported as less than some lower limit 

were treated the same as missing data. Data in the 

form < x belong to the ordinal scale of measurement 

(Stevens, 1946) and cannot be treated by the same 

mathematical or statistical procedures as the ordinary quantitative data that are classified as the ratio 

scale of measurement.

The conclusions resulting from the F tests in the 

analysis of variance for the quantitative data con-
ES1IMATION OF BEST VALUES

firm the conclusions from similar tests with the 

semiquantitative spectrochemical data. Table 2 

shows the frequencies, by element and by the fractile 

of the F distribution, for the significance or nonsignificance of the F ratios for those quantitative 

data for which the analysis of variance could be 

made. The proportion of F ratios not significant at 

F0 . 95 (118/124 = 0.952 for USGS-Nod-A-1, and 

115/119 = 0.966 for USGS-Nod-P-1) furnish convincing evidence for both samples that most elements are indeed homogeneously distributed among 

the bottles.

ESTIMATION OF BEST VALUES

"Best" values for elements or oxides in rock reference samples have been derived by many (Abbey,

1977; Christie and Alfsen, 1977; Ellis and others, 

1977; Flanagan, 1969, 1976; Govindaraju and de la 

Roche, 1977; and Sutarno and Faye, 1975), but objections can be made to some methods. Deriving 

best values from large compilations of data is tedious; calculating them where the data are reported 

in equivalent form is much easier. We decided to 

derive best values for the data for the nodules by 

a procedure involving three steps:

1. Determine which of the k sets of data have a 

common variance.

2. From this common variance, calculate the standard deviation of the means of the n determinations.

3. Use this standard deviation to obtain the Studentized range to determine which of the

TABLE 2.—Number of calculated F ratios smaller or larger than the fractile of the F distribution indicated

Si ___ _ ___

Al __ __ ____

Fe

Mg _________

Ca _

Na __ __ —

K __ __ ____

Ti ___ __

P __ _______

Mn __ ____

Co __ _ — -

Cu ____ __

Ni __ _ _

As __________

Ba _____ _

Be __________

Ce __________

Cr _ _ ____

Eu ___ _

Gd __________

Hf _ ___ __

La __________

Li ___ ____

Lu __________

Mo _________

Nd __________

Pb __________

Rb __________

Sb

Sc __________

Sm ________

Sr __________

Tb __________

Th _

Tm _________

U ___________

V __________

Y

Yb __________

Zn ___ ____

Zr ________

USGS-Nod-A-l

<.Fo.es <Fo.s75 <Fo.s*> >.Fo.»9

5

6

4 1

K

2

5 _ 1

4

4

6

-i

9

7

6

1 _

1

1

1

1

1

1

1

1 _ _

5

1

4

1

1

1 -

3

1

1 _ 1

1

2 _

3

1 _

1

6 _

1

USGS-Nod-P-l

<Fo.BB <Fo.S75 <Fo.m

K

6

71-

K

0

41_

6

4

6 1 _

6 _ _

K

1

K

1

1

1

1

1

1

1

1

1

5

1

5

1

1

1

1

3

1

2

1

2

2

1 . _

1 _ _

K

1

>/Yo»

-

Total __ 118 115
USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

several means can be considered to have been 

derived from the same population mean. We 

then consider the average of the several means 

so selected as the best estimate.

The question of which of the k sets of data, each 

with n determinations, have a common variance 

was resolved with Cochran's test for the homogeneity of variances (a brief discussion and tables are 

available in Dixon and Massey, 1951). Sample variances, with n — 1 = 5 degrees of freedom, were calculated for all sets of data that included six determinations of an element by each of the several 

laboratories. The variances of the k groups of data, 

omitting the factor of the technique used, were 

listed in a column from the least to the greatest 

variance. Starting with the third least variance (the 

two lowest variances may be tested, where necessary, by the F ratio), the sums to the 3rd, 4th . . . 

Mh variances (s2 ) are listed in an adjacent column; 

Cochran's test, (Largest s2 )/(Sum s 2 ), is then made 

with the largest variance. Because analysts did not 

use methods of equal precision for the same element, the kiln, (the greatest) variance can be a very 

significant part of the sum of the fe-1 smaller 

variances, as shown in the tabulation for the calculations for cobalt in USGS-Nod-A-1. Many texts 

contain tables at probabilities p = 0.05 and p = 0.01 

for Cochran's test, where the allowable values are 

for k variances, each with v degrees of freedom. 

We used the test iteratively until a homogeneous 

set of variances was reached. For several elements 

in the samples, we accepted a test that was not significant at the greater ratios for p = 0.01 so that a 

set of three or more homogeneous variances might 

be available.

No.

9

8

7

6

5

4

3

2

1

Variances 

( X10«)

1,160

97

17

15

8

7

3

1

1

Cumulative 

sum of 

variances (xio6 )

1,309

149

52

35

20

12

5

—— -

Largest s2

Sums2

0.8862

.6510

.3269

Significant (S) or 

- Not significant (NS) 

p = 0.05 p = 0.01

S

S

NS

S

S

In the tabulation of the variances for cobalt the 

ratio of the seventh variance over the sum of the 

first seven (17xlO- G /52xlO- 6 ) does not exceed the 

allowable ratio for Cochran's test at p = 0.05. The 

calculated ratio is not significant, and the lowest 

seven variances are accepted as a homogeneous set.

From this homogeneous set of variances, we then

calculate the standard deviation of the means of 

the n ( = 6) determinations. In calculations where 

the numbers of determinations are unequal, usually 

the individual variances multiplied by their respective degrees of freedom are summed, and the sum 

thus obtained is divided by the sum of the degrees 

of freedom. The procedure is less complicated where 

variances are calculated from equal numbers of 

determinations.

In the tabulation for the cobalt variances, the 

sum of the seven smaller variances, 52x10-°, is 

divided by the number of variances, 7, to obtain the 

average of the set of homogeneous variances. When 

this result, 7.4x10-°, is divided by 6, the number 

of determinations for each variance, and the square 

root is taken, we obtain 1.11 xlO~3 as the standard 

deviation of the mean of six determinations. As each 

variance has 5 degrees of freedom, we have 35 degrees of freedom associated with this standard 

deviation of the mean. Standard deviations for the 

other elements are calculated similarly.

The averages of the data are then tested by the 

Studentized range to determine if all or some of the 

means form a homogeneous group. The means of 

the several sets of data are ordered, the means being 

taken for the purpose of discrimination to more 

decimal places than are generally warranted. The 

order for the cobalt averages, each calculated to four 

digits, is 0.3900, 0.3363, 0.3265, 0.3215, 0.3128, 

0.3127, 0.3080, 0.2813, and 0.2527. We may see that 

this ordered set of means shows appreciable variation and that we may need to use the procedure iteratively. The range of these nine averages is then 

divided by the standard deviation of the mean to 

yield an estimate of the Studentized range. Tables 

for the allowable values for percentage points of 

the Studentized range are given in Bennett and 

Franklin (1954, p. 188-189), and elsewhere, for 

samples of size n, each with v degrees of freedom, 

where these degrees of freedom are the sums of the 

degrees of freedom for the several laboratory variancs included in the homogeneous variance.

The range for the 9 cobalt means is 0.14, which 

yields, when divided by the standard deviation of 

the mean, l.llxlO- 3 , an estimate of 126 for the 

Studentized range. This is far larger than the allowable values of 4.68 for the 5-percent point or 5.58 

for the 1-percent point of the Studentized range for 

the set of 9 means with 35 degrees of freedom. The 

average, 0.39, is the extreme mean of the group, 

and it is omitted from further consideration. The 

range, 0.08, of the remaining eight means is also 

highly significant for values for 8 means and 35
ESTIMATION OF BEST VALUES

degrees of freedom, and the extreme mean, 0.2527, 

is then dropped. After further iteration, we determined that the values in the order 0.3128, 0.3127, 

and 0.3080 form a homogeneous group, and their 

average, 0.311 percent cobalt, is taken as the best 

estimate. The average of the original 9 means is 

0.319, a value not too far from the best estimate. 

The agreement between the two estimates is probably due to the almost symmetrical differences between the best estimate and the two extreme means, 

an event that happens infrequently for the groups 

of means of the remaining elements for the two 

samples. Best estimates for the remaining elements 

were calculated similarly.

SELECTION PROCESS AND LACK OF 

CLEAR CHOICES

During the selection process, we frequently arrived at some step where we had to make a decision, 

but criteria for these decisions may be absent or 

perhaps conflicting because of their subjectivity. 

Tables 3 and 4 contain a number of best estimates 

listed as means without upper and lower confidence 

limits, and some discussion of difficulties encountered in the selections seems warranted. The laboratory averages for determinations for Nod-A-1 that 

are discussed for several elements below may be 

found in table 32 and those for Nod-P-1 in table 33.

Silicon.—The highest laboratory average for 

Nod-A was obtained by atomic-absorption spectroscopy, and the two lowest averages by X-ray fluorescence. After the two extreme means were eliminated, averages of 1.82, 1.73, and 1.63 remained. 

If the middle value is paired with either extreme 

of these three, the Studentized range is not significant at p = 0.01 for either pair. However, because 

the lowest average, 1.63, was obtained by X-ray 

fluorescence and the two higher means by gravimetry, the average of 1.82 and 1.73 was accepted as the 

best value.

The highest average for silicon in Nod-P, 6.97, 

was obtained by atomic-absorption spectroscopy, but 

this is the extreme mean that was eliminated first. 

The range for the four remaining means, 6.65, 6.64, 

6.38, and 6.36, is unacceptably large as is the range 

when the two extreme averages are discarded. The 

two higher and the two lower means, when paired, 

do not differ within themselves. We cannot resort 

to the analytical method as a criterion for our choice 

because both gravimetry and X-ray fluorescence 

were the methods for each pair. The average of the 

four means is therefore accepted as a provisional 

estimate without confidence limits.

Aluminum.—Of the six available averages for the 

aluminum content of Nod-A, only two means, 2.06 

and 2.04, survived the selection process, and the 

average of 2.05 percent aluminum is accepted as the 

best value. The Studentized range for three means 

for Nod-P, 2.59, 2.56, and 2.41, did not exceed the 

tabled value for p = 0.01, and their average is accepted as the best value. The acceptance of a wider 

range for means for Nod-P is due to the larger 

standard error of the mean (0.05 as against 0.03) 

and to the higher acceptable values for the range 

for three rather than two means.

Magnesium.—All differences between adjacent 

pairs of means for magnesium in Nod-A proved 

significant at p = 0.01 because of the small standard 

error of 0.01, and the average of the four means, 

2.93, 2.89, 2.85, and 2.80, was accepted as a provisional estimate without limits. We had no problem 

in the selection for Nod-P.

Sodium.—The two lower of the three means for 

Nod-A were accepted, but there was no choice for 

the three means for Nod-P, and their average is 

taken without limits.

Titanium.—The small standard error, 0.004, for 

titanium in Nod-A results in the choice of two 

identical means, 0.32, and in the rejection of 0.28 

and 0.29. The still smaller standard error, 0.002, 

for Nod-P leaves no choice, and the average of the 

four means is taken as a provisional estimate.

Cobalt.—The small standard error, 0.0011, for 

the means for cobalt in Nod-A resulted in the rejection of all but three of the nine means available. 

The rounded average of the three means, 0.311 percent cobalt, is accepted as the best value. The selection process, again with a small standard error of 

0.0011, resulted in two pairs of means for Nod-P, 

0.2287 and 0.2280, and 0.2203 and 0.2200, that differed between but not within themselves. As there 

is no criterion for a choice, the average of the four 

means is listed as a provisional estimate.

Nickel.—The selection of a best estimate for 

nickel in Nod-A presented no difficulties, and the 

average of 0.636 percent nickel, calculated from 

laboratory means, 0.6400, 0.6372, and 0.6300, whose 

Studentized range was acceptable, is taken as the 

best value. However, the selection for Nod-P produced surprises. The two lowest means, 1.243 and 

1.276, were rejected first because they were far 

removed from the center of gravity of the distribution of the eight means. Further tests showed that 

the Studentized range for the three largest means, 

1.40, 1.395 and 1.382 (average, 1.392) is not significant at p = 0.01 but that the range for the next
8 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

three lower means, 1.350, 1.328, and 1.32 (average, 

1.333), is significant.

Without the benefit of the several tests with the 

Studentized range, one might normally accept the 

grand average, 1.337, of the eight means as the best 

estimate of central tendency. As the average, 1.392, 

of the three means deemed acceptable by the test 

is far removed from the grand average of the eight 

means, this grand average is accepted as the conditional best estimate without confidence limits. 

Future data from other analysts will undoubtedly 

resolve this dilemma.

SUMMARY ESTIMATES AND DISCUSSION

The best estimates obtained by the Studentized 

range and the provisional estimates obtained when 

the dispersion among the means was too large are 

given in tables 3 and 4. Because the elements to be 

determined were not specified, the number of means 

for either type of estimate is variable. The number 

of variances used for the standard error of the mean 

may be obtained by dividing the degrees of freedom 

shown in tables 3 and 4 by the number of degrees of 

freedom (five) for each laboratory variance. The 

number of laboratory means that were used for best 

estimates will differ because of the selection process; 

the numbers of means that survived this process are 

given in tables 3 and 4. The numbers of averages

from which the provisional estimates without confidence limits were calculated are given in parentheses.

Laboratory averages for all elements in both 

samples are listed in tables 32 and 33 to facilitate 

comparisons of the estimates by different analysts. 

The column headings indicate the table number from 

which the averages were taken. The number of determinations included in these averages is noted 

in each column heading as "n = x," where x is the 

number. This provision is necessary because not all 

data reported by two analysts were used in the 

analysis of variance for reasons of symmetry, and 

two other analysts had insufficient time to complete 

the requested work. Nonsignificant zeros added 

where percentage of an element or oxide reported 

by analysts was converted to parts per million are 

indicated by the lowercase letter "o."

In either table the spread of the data for the 

major or minor elements produced no surprises, except perhaps for one or two elements. The hypothesis associated with the analysis of variance—that 

the content of an element differed among bottles 

of the sample—was not accepted for the determinations of cobalt, copper, and nickel by any analyst 

whose data were amenable to the analysis of variance; eight analysts or laboratories have therefore 

effectively inferred that these elements are homogeneously distributed among the bottles of samples.

TABLE 3.—Summary of best estimates and confidence limits for averages of several elements in USGS-Nod-A-1

[Estimates in percent or in parts per million, as indicated. Estimates in brackets are averages, without limits, of the number of laboratory means

shown in parentheses. Student's to.us was used for confidence limits]

Si _ _

Al _ __ _

Fe _ _ _ _ _

Mg _________

Ca _

Na

K _ _ __

Ti _ __ _ _

P _ _

Mn __ __

Co __ _ _

Cu _ _ __ __

Ni _ __

Ba _ __ __

Mo __ _ _

Pb __ _____

Sr ________

V __ _ _ _

Zn _ __

Standard error

of mean

0 099

.032

049

.0099

flOQ

.0056

.0086

.004

.007

.050

.0011

.0010

.0024

30.8

8.7

8.2

13.7

6.2

4.6

Degrees of

freedom

20

25

30

25

30

1 ^

30

20

1 ^

25

35

35

35

15

30

25

20

10

30

Best

Lower limit <

Percent

1 7^7

1.995

10.861

10.964

7CK

.485

.315

.588

18.459

Of|Q

.1082

.632

Parts per million

1.616

/loo

831

1 794

579

values and confidence limits

Mean <

1.775

2.05

10.932

ro oan L^.o/j

11.03

.775

^o

.32

.60

18.545

.311

10QQ

.636

1,670

448

846

1,748

[770]

587

Upper limit

1.813

2.105

11.003

11.096

.785

.515

.325

.612

18.631

.313

.1116

.640

1,724

463

861

1,772

595

Number of 

laboratory

for best 

values

2

2

6

(4)

4

2

4

2

2

4

3

7

3

3

3

2

3

(3)

4
SUMMARY ESTIMATES AND DISCUSSION

TABLE 4.—Summary of best estimates and confidence limits for averages of several elements in USGS-Nod-P-1

[Estimates in percent or in parts per million, as indicated. Estimates in brackets are averages, without limits, of the number of laboratory means

shown in parentheses. Student's to.ss was used for confidence limits]

Element Standard error 

of mean

Degrees of 

freedom

Best values and confidence limits

Lower limit < Mean < Upper limit

Number of 

laboratory 

means used 

for best 

values

Percent

Si __

Al _ __ _

Fe

Mg- _________

Ca __ _ __

Na _ _ __

K __ __ _

Ti __ ___ __

P _ _ _

Mn _ _ __

Co __ __ __ _

Cu __ ______

Ni

0.016 

.049 

.031 

.0085 

.012 

.0043

.012 

.002 

.002 

.080 

.0011 

.0049 

.0064

15 

25 

30 

20 

30 

10

35 

10 

15 

20 

35 

30 

30

_ __ [6.508] _________

2.466 2.55 2.634 

5.727 5.78 5.833 

1.975 1.990 2.005 

2.167 2.187 2.207 

1.R4

1 .030 1.05 1.070 r.3oi

.199 .203 .207 

29.002 29.14 29.278 

f.2241

1 .143 1.151 1.159 

[1 .3371

(4) 

3 

4 

4 

6 

(3)

3 

(4) 

3 

3 

(4) 

4 

(8)

Parts per million

Ba __ __ __

Mo __ _ __

Pb

Sr ____ __ ___

V _ __ __

Zn __ __ __

27.7 

4.1 

5.8 

3.3 

10.3 

5.9

10 

20 

25 

10 

15 

25 1.585

[3,3£

[76 r^E

[68

. _ _ [56

1.59

0] _ _

2] _ _ _

5]

2] _ _ _

7]

5 1,605

(3) 

(5) 

(6) 

(3) 

(3) 

2

In view of these inferences, one might have expected 

the laboratory averages for these elements of potential economic interest to be more closely grouped 

than the data in tables 32 and 33 indicate.

Data for several trace elements are sparsely distributed in tables 32 and 33. An average by a single 

laboratory is reported for 19 of the 32 trace elements listed, and 13 of these 19 were included in 

the suite of elements determined by instrumental 

neutron-activation analysis.

The trace elements molybdenum, vanadium, and 

zinc may be of economic interest, depending on the 

commercial process used for treatment. Although 

most laboratories that determined these elements 

by completing the requested work found the elements to be homogeneously distributed in the samples, the dispersion among laboratory means is too 

large. Further analytical work will be necessary 

to obtain better estimates for these elements, especially if the samples are to be used as reference 

materials for future determinations that may form 

the basis for an economic decision.

Conspicuous by their absence in tables 32 and 33 

are estimates for gold and the platinum metals. 

Harriss and others (1968, table 2) have determined 

palladium, iridium, and gold in nodules taken from 

near the sites for Nod-A-1 and Nod-P-1.

After this paper had been completed, P. J. Aruscavage (written commun., 1979) determined platinum, palladium, and ruthenium in the two nodule 

samples. The three precious metals were determined 

by a method involving fire assay and flameless 

atomic-absorption spectroscopy with the same experimental design used while obtaining other data 

for these samples. His averages of six determinations, by samples and by elements, are given as 

follows:

Platinum-metal contents

[In parts per billion]

Sample

USGS-Nod-A-1 _____ 

USGS-Nod-P-1

Pt

453 

123

Pd

2.5 

5.6

Ru

18

4.7

The possible recovery of the platinum metals and 

gold as byproducts of a commercial extraction process designed for an anticipated production of 1-3 

million tons of nodules per year (Pearson, 1975) 

might lower the unit cost of the mining and extraction operations and thereby make more attractive 

the economic decision to proceed.

Chemical determinations of several constituents 

in both nodule samples were furnished by Sarah T. 

Neil of the U.S. Geological Survey, Menlo Park, 

Calif., after the manuscript had been completed. 

We corrected these determinations, which were on 

sample portions not dried, to a dry basis (105° C)
10 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

using the determinations of H2 0~ for each portion 

of sample. Gravimetric factors were used to convert 

data reported as oxides to elements.

The data by Neil are shown in tables 30 and 31, 

and her averages are listed with all other averages 

in tables 32 and 33. The analysis of variance, under 

the usual assumptions for the design with a single 

variable of classification, results in F ratios that are 

not significant at F0 . 9 .-, for 34 of the possible 35 tests; 

the remaining ratio is not significant at Fo.<j 7 r,- Although data for two elements (titanium and sodium) 

in Nod-A and for three (titanium, sodium, and 

calcium) in Nod-P are outside the range of data 

provided by other analysts, we feel that these additional data would not significantly affect calculated 

best values. These data, plus others published later, 

will be used in calculations to revise or establish 

best values.

Anne E. Childress of the U.S. Geological Survey 

determined niobium in the two samples with the 

same experimental design used by the other analysts. Analyses of variance of the data showed that 

niobium was distributed homogeneously in the bottles of both samples. Childress obtained averages of 

43.2 parts per million niobium for six determinatins for Nod-A-1 and 21.2 parts per million for 

Nod-P-1. These estimates were confirmed by Esma 

Y. Campbell, who found averages for two determinations of 43.8 parts per million niobium for 

Nod-A-1 and of 21.4 parts per million for Nod-P-1.

The contents of some lithophilic elements such as 

the rare earths, zirconium, hafnium, niobium, 

thorium, and uranium, shown in tables 32 and 33, 

are similar to the contents of these elements in fractionated crustal rocks. The relatively high abundances of these elements in the nodules, which contain high amounts of chalcophilic elements, pose an 

interesting problem for future geochemical research 

because of the low abundance of lithophilic elements 

in sea water and in basaltic rocks typical of the 

ocean floor.

COMPARISONS WITH DATA FROM 

MARSDEN SQUARES 049 AND 116

Because of the differences among data published 

for elements determined in manganese nodules, we 

have shown estimates for our nodule samples and 

those of the distribution of data on samples from 

the Marsden Squares that include the collection 

areas for our samples. Monget and others (1976), in 

their compilation, have listed the pubished data by

the number of the Marsden Square, the rectangles 

enclosed by each 10° of longitude and latitude.

Our estimates for Nod-A-1 are listed in table 5 

with estimates of the distribution of data from 

Marsden Square 116, and our estimates for NodP-1, together with estimates for Marsden Square 

049, are given in table 6. We feel that our data and 

those from the squares should not be formally compared, because of the extremely low sampling density in the two squares—one sample per 100,000 

km2 in square 049 and one sample per 20,000 kmin square 116. The USGS samples were probably 

taken from test sites with areas of less than 35 km2 , 

whereas Marsden Square 049 covers about 1,550,000 

km2 and square 116 in the Atlantic Ocean, about 

500,000 km2 after the land area included in the 

square is subtracted.

The ranges shown in the data for the samples 

from each Marsden square are very wide. Although 

some dispersion may be partly due to analytical 

methods and error, the major part may be due to 

compositional differences among single nodules that 

were analyzed. In addition to the average for manganese, the averages for copper and nickel, the two 

elements of considerable economic interest in the 

two USGS samples, agree well with, or exceed, the 

averages of data for the respective squares, but our 

cobalt averages are one-quarter to one-third lower. 

The manganese contents of the USGS samples are 

both about 6 percent (absolute) higher than the 

averages of similar data for samples from the corresponding squares.

AVAILABILITY OF SAMPLES

Because of the limited amounts of the two samples, we must have restrictions on their distribution 

until commercial exploitation begins and more material is available for future reference samples. Requests are anticipated from those who wish to use 

the samples as standards and from those who, in 

addition, wish to confirm or improve the estimates 

given here. Information on the availability of the 

samples may be obtained from either author.

The powder density of the processed material is 

less than that of powdered igneous rocks, and a full 

bottle is estimated to contain not more than 30 

grams. The units of issue will be packaged routinely 

from the randomized stock of the samples, and some 

bottles may be only half filled as a result of our 

normal sampling procedure. Neither the authors 

nor this laboratory has hand specimens of the nodules from which the two samples were made.
ESTIMATES FOR MARSDEN-SQUARE AND USGS SAMPLES 11

TABLE 5.—Comparison of best estimates for several elements in USGS-Nod-A-1 with estimates of the distribution of the

elements for data in samples from Marsden Square 116

[Data for Marsden Square from Monget and others (1976). Estimates in percent or in parts per million, as indicated, n, number of determinations;

"x, average; s.d., standard deviation]

Element U b(jrb

Nod-A-l n

Estimates

X

of data from Marsden Square 116

s.d. Lower

Range

< Upper

Percent

Si _ ._—_-_

Al __ ______

Fe ___ _

Mg _ __ _

Ca _ _ __ _

Na __ __

K ___________

Ti __ _ _

P __ __

Mn __ _____

Co ___ _

Cu _ _ _ __

Ni ______

1.78 

2.05 

10.93 

2.87 

11.03 

.77

.50 

.32 

.60 

18.54 

.311 

.110 

.636

20 

20 

24 

16 

23

17 

21 

17 

23 

9 

23 

24

1.76 

1.6 

11.38 

1.97 

• 14.30

.30

.27 

2.08 

12.64 

.44 

.116 

.412

1.48 

.88

4.4 

.67 

7.12

.10 

.15 

2.35 

3.75 

.05 

.062 

.156

0.3 

.1 

1.6 

1.09 

1.9

.14 

.06 

.05 

6.9 

.38 

.03 

.13

5.9 

2.8 

20.0 

3.70 

28.7

.54 

.68 

7.0 

21.5 

.55 

.26 

.77

Parts per million

Ba _

Mo

Pb __ __

Sr __ _ __

V _

Zn __ ___ _

1,670

448 

846 

1,748 

770 

587

6 

8 

20

~8

1,107 

1,658 

1,660

508

1,570 

295 

684

94

350 

1,200 

676

390

4,300 

2,100 

3,380

670

TABLE 6.—Comparison of best estimates for several elements in USGS-Nod-P-1 with estimates of the distribution of the

elements for data in samples from Marsden Square 049

[Data for Marsden Square from Monget and others (1976). Estimates in percent or in parts per million, as indicated. r>, number of determinations;

~, average; s.d., standard deviation]

Element U oLro 

xr«j p i

n

Estimates

X

of data from Marsden Square 049

Range

Lower < Upper

Percent

Si _ —

Al _ ____

Fe _ _

Mg __ _ __

Ca ____ _-

Na _ __ __

K __ _ _____

Ti __ __

P

Mn __ __

Co _ _ _

Cu _ ___ _

Ni __ _

6.51

2.55

5.78

1.99

2.19

1.64

1.05

.30

.20

29.14

.224

1.15

1.33

12 

10 

18

4 

14

9

11 

2 

18 

17 

17 

18

7.62 

3.43 

7.69 

1.90

1.4

.93

.46 

.12 

23.8 

.307 

1.00 

1.18

1.59

.57 

2.24 

.11 

.24

.22 

.15 

(average) 

4.10 

.091 

.22 

.32

5.4 

2.8 

2.4 

1.7 

.9

.69 

.29

18.5 

.10

.47 

.47

11.2 

4.6 

10.4 

2.0 

1.8

1.40

.74

32.9

.44 

1.4 

1.9

Parts per million

Ba ________

Mo_ _ __

Pb __ _ ____

Sr _______

V _ __ _ _

Zn _ _ __

2,350

762

555

682

567

1,505

~9 

9

8 

3 

8

520 

911 

795 

587 

856

152 

482 

182 

121 

337

380 

280 

510 

460 

400

900 

1,700 

990 

700 

1,400
12 USGS ROCK STANDARDS: MANGANESE NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

REFERENCES CITED

Abbey, Sydney, 1977, Studies in "standard samples" for use 

in the general analysis of silicate rocks and minerals, 

pt. 5, 1977 edition of "usable" values: Canada Geological 

Survey Paper 77-34, 31 p.

Andermann, George, and Kemp, J .W., 1958, Scattered X-rays 

as internal standards in X-ray emission spectroscopy: 

Analytical Chemistry, v. 30, no. 8, p. 1306-1309.

Baedecker, P. A., Rowe, J. J., and Steinnes, E., 1977, Application of epithermal neutron activation in multielement 

analysis of silicate rocks employing both coaxial Ge(Li) 

and low energy photon detector systems: Journal of 

Radioanalytical Chemistry, v. 40, nos. 1 and 2., p. 115-146.

Bennett, C. A., and Franklin, N. L., 1954, Statistical analysis 

in chemistry and the chemical industry: New York, John 

Wiley and Sons, 724 p.

Christie, 0. H. J., and Alfsen, K. H., 1977, Data transformation as a means to obtain reliable consensus values for 

reference materials: Geostandards Newsletter, v. 1, no. 

1, p. 47-49.

Dixon, W. J., and Massey, F. J., Jr., 1951, Introduction to 

statistical analysis: New York, McGraw-Hill, 370 p.

Ellis, P. J., Copelwitz, I., and Steele, T. W., 1977, Estimation 

of the mode by the dominant cluster method: Geostandards Newsletter, v. 1, no. 2, p. 123-130.

Flanagan, F. J., 1967, U.S. Geological Survey silicate rock 

standards: Geochemica et Cosmochimica Acta, v. 31, no. 

3, p. 289-308.

———— 1969, U.S. Geological Survey standards—II. First 

compilation of data for the new USGS rocks: Geochimica 

et Cosmochimica Acta, v. 33, no. 1, p. 81-120.

———— 1974, Reference samples for the earth sciences: Geochimica et Cosmochimica Acta, v. 38, no. 12, p. 1731- 

1744.

———— 1976, Descriptions and analyses of eight new USGS 

rock standards: U. S. Geological Survey Professional 

Paper 840, 192 p.

———— 1979, Have trace element data on rocks by spetroscopic methods improved? Part , Geoanalysis '78, A 

symposium on the analysis of geological materials: 

Canada Geological Survey Paper 79- , [In press].

Glasby, G. P., ed., 1977. Marine manganese deposits: New 

York, Elsevier, 523 p.

Govindaraju, K., and de la Roche, H., 1977, Rapport (1966- 

1976) sur les elements en traces dans trois roches standards geochimiques du CRPG; Basalte BR et Granites, GA 

et GH: Geostandards Newsletter, v. 1, no. 1, p. 67-100.

Harriss, Robert C., Crocket, J. H., and Stainton, M., 1968, 

Palladium, iridium, and gold in deep-sea manganese 

nodules: Geochimica et Cosmochimica Acta, v. 32, no. 10, 

p. 1049-1056.

Mero, J. L., 1965, The mineral resources of the sea: New 

York, Elsevier, 312 p.

Millard, H. T. Jr., 1976, Determination of uranium and 

thorium in USGS standard rocks by the delayed neutron 

technique: U.S. Geological Survey Professional Paper 

840, p. 61-65.

Monget, J. M., Murray, J. W., and Mascle, J., 1976, A worldwide compilation of published multicomponent analyses 

of ferro-manganese concretions: NSF-IDOE Manganese 

Nodule Project Technical Report No. 12, August, 1976, 

127 p.

Myers, A. T., Havens, R. G., and Dunton, P. J., 1961, A 

spectrochemical method for the semiquantitative analysis 

of rocks, minerals, and ores: U.S. Geological Survey Bulletin 1084-1, p. 207-229.

Norrish, K., and Hutton, J. T., 1969, An accurate X-ray spectrographic method for the analysis of a wide range of 

geological samples: Geochimica et Cosmochimica Acta, 

v. 33, no. 4, p. 431-453.

Pearson, John S., 1975, Ocean floor mining: Park Ridge, 

N. J., Noyes Data Corp., 201 p.

Rantala, R. T. T., and Loring, D. H., 1973, New low-cost 

Teflon decomposition vessel: Atomic Absorption Newsletter, v 12, no. 4, p. 97-99.

———— 1975, Multielement analysis of silicate rocks and 

marine sediments by atomic absorption spectrophotometry: Atomic Absorption Newsletter, v. 14, no. 5, 

p. 117-120.

Stevens, S. S., 1946, On the theory of scales of measurement:

Science, v. 103, no. 2684, p. 677-680.

Sutarno, R., and Faye, G. H., 1975, A measure for assessing 

certified reference ores and related materials: Talanta, 

v. 22, no. 8, p. 675-681.
TABLES 7-33
14 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 7.—Determinations of several elements in USGS-Nod-A-1 by instrumental neutron-activation analysis by P. A.

Baedecker, U.S. Geological Survey 1

[Determinations in parts per million or in percent, as indicated, d.f., degrees of freedom; S, significant; NS, not significant; Neg., negative bottle 

variance obtained, F ratios tested at Fo.ns or the fractile in parentheses. Analytical method: Baedecker, Rowe and Steinnes (1977)]

Element 30/25

Bottle

52/1 53/18 Mean

Standard

Bottle 

(d.f. = 2)

deviation

Error 

(d.f. = 3)

F ratio

Percent

Fe _ _ _ _ 10.75 

10.98

10.86 

10.89

11.05 

10.77

10.88 Neg. 0.15 0.05 NS

Parts per million

Ba

Ce __

Co _ „ _

Cr ___ ______

Eu _ _

Gd __ __

Hf _ _ _

La ____ —

Lu _ __ _

Nd _ _ _____

Sb ______ ____

Sc ______ __

Sm _ __ _

Tb _ _ __ __

Th _ __ _

Tm __ _____

U __ __ _

Yb

1,458 

1,738 

676 

670 

2,522 

2,530 

26.4 

27.3 

4.49 

4.45 

28.1 

25.1

6.4 

6.4 

134 

129 

2.10 

2.12 

86 

83 

33.0 

34.6 

11.09 

11.36

18.5 

21.6 

4.54 

6.00 

25.4 

25.7 

.78 

1.52 

5.8 

5.5 

16.0 

17.1

1,451 

1,551 

672 

673 

2,506 

2,544 

30.7 

<67.7 

4.54 

4.52 

33.2 

32.6

6.6 

5.4 

133 

131 

2.10 

2.22 

82 

85 

33.6 

32.5 

11.10 

11.23

21.4 

21.8 

4.36 

4.81 

25.6 

25.3 

1.62 

<1.88 

6.7 

5.5 

15.9 

15.9

1,457 

1,454 

667 

651 

2,550 

2,512 

19.1 

<65.1 

4.48 

5.39 

20.8 

19.4

6.9 

5.5 

139 

129 

2.25 

2.17 

93 

83 

33.0 

34.3 

11.32 

11.27

20.8 

21.4 

5.76 

3.74 

26.4 

26.6 

2.29 

2.30 

6.5 

5.7 

15.6 

17.1

1,518 

668 

2,527 '

4.48 

26.5

6.2 

132.5 

2.16 

85.3 

33.5 

11.23

20.9

4.87 

25.8 

1.72 

5.95 

16.3

Neg. 

6.2 

Neg.

.04 

6.3

Neg. 

Neg. 

.03 

Neg. 

Neg. 

Neg.

Neg. 

Neg. 

.56

2 .77 

Neg. 

Neg.

120 

7.0 

22.2

.04 

1.4

.75 

4.6 

.06 

4.4 

.95 

.12

1.3 

1.03 

.19

3 .37 

.60 

.76

.72 NS 

2.58 NS 

.04 NS

2.74 NS 

43.4 S(0.99)

.14 NS 

.16 NS 

1.42 NS

.57 NS 

.35 NS

.55 NS

.74 NS 

.24 NS 

18.3 NS(0.99) 

9.57 NS

.37 NS 

.38 NS

1 Reston, VA 22092.
TABLES OF DATA BY ANALYSTS 15

TABLE 8.—Determination of several elements in USGS-Nod-P-1 by instrumental neutron-activation analysis by P. A.

Baedecker, U.S. Geological Survey^

[Determinations in parts per million or in percent, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios tested at FO.BS. Analytical method: Baedecker, Rowe, and Steinnes (1977)]

Element

Fe _____

Ba __ _ _

Ce ___ __ —

Co __ _-_—

CT

Eu ______

Gd ___ _

Hf ___ _

La _ _ _ _

Lu __ — —

Nd

Sb _ __ __ -

Sc — — —

Sm _ _

Tb _ _ _

Th _ _ _ _

Tm

U _ -__ _ _

Yb __ _ .

7/1

5.80

5.76

2,512

2,766

278

282 

1,789

1,802 

21.0

11.3 

6.16

6.18

26.4

25.9 

4.3

4.4 

126

121 

1.89

1.93 

106

104

49.5

50.2 

9.54

9.53 

28.3

30.9 

5.18

5.65 

17.3

16.5 

1.75

1.91

2.7

3.2 

14.2

14.2

Bottle

17/19

5.94

5.15

2,617

2,069 

288

287 

1,813

1,775 

<57.5

<57.9 

6.67

6.75

24.4

33.6 

4.2

4.4 

130

103 

1.95

1.63 

113

117 

51.5

46.4 

9.65

8.67 

29.6

30.3 

5.71

5.02 

16.3

17.2 

1.70

1.82

3.4

4.3 

14.8

11.9

48/11

I

6.03

5.85

Parts

2,519

~287

311 

1,806

1,865 

<56.0

<84.8 

6.59

7.06 

36.1

30.1

4.2

4.3

127

1.86

"ill

126 

50.1

52.9 

9.61

9.84 

31.1

32.0 

5.23

5.06 

16.8

17.7 

1.54

1.91 

3.3

4.1 

15.0

——

Mean

*ercent

5.76

per million

2,498

2,498 

289

1,808

6.57

29.4

4.3

120

1.85

112.8

50.1

9.47

30.4

5.31

17.0

1.77

3.5

13.8

Standarc

Bottle (d.f.=2)

"NJpo1

Neg.

6.5

11.4

.32

1.5

Neg.

Neg.

Neg.

5.4

Neg.

Neg.

.64

Neg.

Neg.

Neg.

.30

Neg.

1 deviation

Error 

(d.f. = 3)

0.33

2 290

9.9

29.1

.19

4.5

.10

"13.7

2 .16

6.4

2.4

.41

1.2

.35

.61

.17

.53

2 1.4

F. ratio

0.72 NS

.95 NS

1.85 NS

1.30 NS

6.44 NS

1.21 NS

.50 NS

.26 NS

.55 NS

2.40 NS

.58 NS

.98 NS

1.61 NS

.34 NS

.35 NS

.19 NS

1.64 NS

.34 NS

'Reston, VA 22092.
16 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 9.—Determinations of several elements and oxides in USGS-Nod-A-1 by John Marinenko, U.S. Geological Survey 1

[Determinations in percent. T, total; d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios tested at ^0.95 or the

fractile indicated in parentheses]

oxide

SiO2 __

AloOs

Fe2O,(T) __ 

Mg _ _

Ca

Na _ _ __

K _ _

TiO, __ _____

P2 0, _ _ __

Mn

Co ___ _____

Cu __________

Ni _ _ ____

i

3.98 

3.83 

3.32 

3.35 

15.57 

15.49 

2.80 

2.85 

11.10 

11.25 

.79 

.79 

.50 

.46 

.54 

.54 

.96 

.93 

18.35 

18.31 

.328 

.325 

.112 

.110 

.649 

.639

Bottle

2

3.92 

3.91 

2.99 

3.40 

15.40 

15.49 

2.88 

2.85 

11.38 

11.20 

.82 

.80 

.51 

.46 

.53 

.53 

.99 

1.06 

18.36 

18.41 

.334 

.326 

.112 

.114 

.653 

.644

Standard deviation

3

3.90 

3.85

3.43 

3.33 

15.49 

15.74 

2.85 

2.88 

11.10 

10.98 

.79 

.81 

.58 

.50 

.53 

.54 

.76 

1.12 

18.49 

18.50 

.323 

.323 

.112 

.112 

.650 

.654

Mean

3.90 

3.30 

15.53 

2.85 

11.17 

.80 

.50 

.53 3 

.97 

18.40 

.326 

.112 

.648

Mean -

1.82 

1.75 

10.86 

2.85 

11.17 

.80 

.50 

.32 

.42 

18.40 

.326 

.112 

.648

Bottle 

(d.f. = 2)

Neg. 

Neg. 

.03 

.01 

.10 

.006 

.02 

.004 

Neg. 

.08 

.002 

.0006 

Neg.

Error 

(d.f. = 3)

0.06 

.17 

.11

.03 

.11 

.011 

.04 

.004 

.15 

.02 

.003 

.0011 

.0057

F 

ratio

0.21 NS 

.62 NS 

1.12 NS 

1.49 NS 

2.71 NS 

1.50 NS 

1.27 NS 

3.00 NS 

.20 NS 

20.2 NS(0.99) 

2.01 NS 

1.50 NS 

.98 NS

1 Reston, VA 22092. - As percent element.

Analytical methods:—SiOi>, gravimetry; ALO:>, fluorimetric analysis; Total Fe and Mn, volumetric analysis; Mg, Ca, Na, K, Co, Cu, and Ni, atomicabsorption spectvometry; and TiO^ and PsOr., spectrophotometry.
TABLES OF DATA BY ANALYSTS 17 

TABLE 10._Determinations of several elements and oxides in USGS-Nod-P-1 by John Marinenko, U.S. Geological Survey 1

[Determinations in percent. T, total; d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios tested at FO.M. Estimates of the mean, standard deviation, and F ratio c aicuated for the symmetrical data for bottles 2 and 3]

oxide

Si02 __ — _

A1203 _ _ __

Fe203 (T) ____ 

Mg __________

Ca ______ __

Na _ ___ _

K ______

Ti02 _____ _

P20S _____ __

Mn ____ __

Co _ ______

Cu _ _ __

Ni _______ _

i

14.48 

3.90 

8.23 

2.00 

2.20 

1.62

.96 

.51 

.41 

29.49 

.219 

1.20 

1.37

Bottle

2

14.45

13.82 

14.46 

3.30 

3.94 

4.02 

8.36 

8.14 

8.10 

1.98 

1.99 

1.95 

2.25 

2.21 

2.21 

1.82 

1.64 

1.63

1.04 

.97 

.98 

.52 

.50 

.52 

.43 

.42 

.22 

28.66 

29.42 

29.42 

.220 

.217 

.218 

1.19 

1.20 

1.21 

1.41 

1.39 

1.37

Standard deviation

3

14.17 i3.9a

3.44 

3.78

8.15 

8.15

1.96 

2.02

2.22 

2.14

1.74 

1.61

1.03 

.98

.52 

.50

.41 

.43

29.10 

29.04

.223 

.219

1.18 

1.19

1.41 

1.42

Mean

14.08 

3.62 

8.20 

1.99 

2.20 

1.70

1.00 

.51 

.42 

29.06 

.221 

1.19 

1.41

Mean 2

6.64 

1.97 

5.73 

1.98 

2.20 

1.68

.99 

.31 

.17 

29.19 

.220 

1.20 

1.40

Bottle 

(d.f. = l)

Neg. 

Neg. 

Neg. 

Neg. 

.02 

Neg.

Neg.

Neg. 

Neg. 

Neg. 

Neg. 

.005 

.007

Error 

(d.f. = 2)

0.34 

.36 

.11 

.03 

.04 

.11

.04 

.01 

.011 

.38 

.005 

.007 

.011

F 

ratio

0.08 NS 

.0008 NS 

.83 NS 

.03 NS 

1.25 NS 

.24 NS

0.0 NS 

0.0 NS 

.20 NS 

.006 NS 

.01 NS 

2.00 NS 

1.80 NS

1 Reston, VA 22092.

2 Average of six determinations, as the element, used for best values.

Analytical methods:—SiOs, gravimetry; AhOs, fluorimetric analysis; Total Fe and Mn, volumetric analysis; Mg, Ca, Na, K, Co, Cu, and Ni, atomicabsorption spectrometvy; andTiOs and PzQs, spectrophotometry.
18 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 11.—Determinations of U and Th in USGS-Nod-A-1 and USGS-Nod-P-1 by delayed neutron activation analysis b

H. T. Millard, Jr., and C. M. Ellis, U.S. Geological Survey1

[Determinations in parts per million, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratio tested at Fo.\

Analytical method described by H. T. Millard, Jr., 1976]

Element Bottle Mean

Standard

Bottle 

(d.f. = 2)

deviation

Error 

(d.f. = 3)

TTf

ratio

USGS-Nod-A-1

Th _ _

U _ _

17/13

24.84 

25.37 

6.84 

6.91

18/01

27.30 

35.93 

6.84 

6.97

24/32

25.79 

24.88 

6.85 

6.74

27.35 

6.86

2.71

.02

3.55

.08

2.17 NS 

1.14 NS

USGS-Nod-P-1

Th _______

U _ ________

13/12

17.80

16.47 

4.18 

4.36

22/29

15.65 

19.80 

4.36 

4.31

55/04

19.11 

17.08 

4.09

4.37

17.65 

4.28

Neg. 

Neg.

1.96 

.14

.12 NS 

.30 NS

1 Stop 424, Box 25046 DFC, Lakewood, CO 80225.

TABLE 12.—Determinations of several elements in USGS-Nod-A-1 by the National Physical Research Laboratory

[Determinations in percent, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratio tested at Fo.vs]

Element

Al _ _______

Fe _____ .___

K _

Mn_ _ __ __

Ba __

Co _____

Cu _ _ ___

Mo __ ___

Ni _ ______

Pb __________

Sr _ _ _____

Zn _ __ __

22/1

1.8 

1.3 

10.0 

9.1 

.13 

.18 

13.3 

13.4 

.32 

.21 

.30 

.31

.11 

.12 

.034 

.039 

.64 

.64 

.10 

.091 

.19 

.14 

.057 

.058

Bottle

51/12

2.0 

1.5 

10.3 

8.9 

.18 

.18 

14.6 

12.9 

.36 

.22 

.32 

.30

.11 

.11 

.038 

.034 

.64 

.63 

.094 

.094 

.20 

.16 

.061 

.059

Standard deviation

63/24

1.9

1.5 

10.3 

9.6 

.19 

.14 

14.0 

14.2 

.23 

.29 

.32 

.30

.11 

.11 

.039 

.034 

.64 

.65 

.094 

.095 

.21 

.18 

.059 

.059

Mean

1.66 

9.7 

.17 

13.7 

.27 

.31

.11 

.036 

.64 

.095 

.18 

.059

Bottle 

(d.f. = 2)

Neg.

Neg. 

Neg. 

Neg. 

Neg. 

Neg.

.000 

Neg. 

.007 

Neg. 

Neg. 

Neg.

Error 

<d.f. = 3)

0.33 

.74 

.03 

.70 

.08 

.01

.004 

.003 

.004 

.004 

.03 

.0009

F 

ratio

0.20 NS 

.17 NS 

.38 NS 

.57 NS 

.09 NS 

.11 NS

1.0 NS 

.02 NS

7.0 NS 

.08 NS 

.54 NS 

3.8 NS

1 CSIR, P.O. Box 395, Pretoria 0001, South Africa.

Analytical method:—A mixture of 20 mL HF and 10 mL concentrated HC1 was added to 1-g portions of the samples and the mixtures taken to dryness on a hotplate. This procedure was repeated. Twenty mL of 50 percent HC1 was added to the residue and evaporated to a volume of 5 mL. These 

were transferred to a 25-mL volumetric flask and made to volume with distilled water. Aliquots of these solutions were diluted to suitable concentrations for the determinations of the elements. These determinations were made using a Techtron AA5 * atomic-absorption instrument with the recommended analytical conditions.

1 Any trade names in this publication are used for descriptive purposes only and do not constitute endorsement by the U.S. Geological Survey.
TABLES OF DATA BY ANALYSTS 19

TABLE 13.—Determinations of several elements in USGS-Nod-P-1 by the National Physical Research laboratory 1

[Determinations in percent, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratio tested at Fo.es]

Element

Al

Fe ._„. _ _

K ___ ____

Mn _ _ _ __

Ba _ _

Co ___ __

Cu _____ .....

Mo _ ______

Ni __ __ _

Pb __ _

Sr __________

Zn ___ __

38/28

1.5

2.0 

5.2

5.7 

.29

.23 

25.9

25.2 

.67

.69 

.22

.22 

1.2

1.2 

.068

.068 

1.4

1.5 

.052

.053 

.099

.11 

.17

.15

Bottle

37/2

1.9

1.8 

5.2

5.2 

.29

.28

25.4

26.0 

.58

.65 

.21

.22

1.2

1.2 

.063

.058 

1.4

1.4 

.051

.053 

.11

.11

.17

.15

44/5

1.9

1.9

5.4

4.8 

.26

.35 

26.3

24.2 

.70

.73

.24

.22 

1.3

1.2 

.063

.058 

1.4

1.4 

.054

.051 

.11

.11

.15

.17

Mean

1.8

5.2

.28

25.5

.67

.22

1.2

.063

1.4

.052

.108

.16

Standard

Bottle 

(d.f. = 2)

Neg.

Neg .

Neg.

Neg.

.04

.004

.000

.004

.000

Neg .

.000

.000

deviation

Error 

(d.f. = 3)

0.21

.32

.04

.94

.03

.009

.04

.003

.04

.002

.004

.01

ratio

0.27 NS

.64 NS

.52 NS

.12 NS

4.98 NS

1.40 NS

1.00 NS

4.50 NS

1.00 NS

.71 NS

1.00 NS

(No test)

1 CSIR, P.O. Box 395, Pretoris 0001, South Africa.

Analytical method:—A mixture of 20 mL HF and 10 mL concentrated HC1 was added to 1-g portions of the samples and the mixtures taken to dryness on a hotplate. This procedure was repeated. Twenty mL of 50 percent HC1 was added to the residue and evaporated to a volume of 5 mL. These 

were transferred to a 25-mL volumetric flask and made to volume with distilled water. Aliquots of these solutions were diluted to suitable concentrations for the determinations of the elements. These determinations were made using a Techtron AA5 atomic-absorption instrument with the recommended analytical conditions.
20 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 14.—Determinations of several elements in USGS-Nod-A-1 by S. E. Calvert, Institute of Oceanographic Sciences 1

[Determinations in percent or parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative variance obtained. F ratio

tested at Fo.es]

or oxide i

Bottle

2

Standard deviation

3 Mean Bottle 

(d.f. = 2)

Error 

(d.f. = 3)

El

ratio

Percent

Si ____ __

Al ______

Fe __________

Ca __________

Mg __.____„_

K ___________

Ti _ _ _ _

P _ _______

Mn _________

CO, ___ _

Co __ _ _____

Cu _ ___ _____

Ni _ _ _____

1.45 

1.44 

2.32 

2.41 

11.24 

10.90 

11.40 

11.70 

3.27 

3.36 

.46 

.51

.29 

.30 

.57 

.62 

18.89 

18.65 

11.66 

11.70 

.44 

.39 

.18 

.18 

.60 

.57

1.20 

1.54 

2.18 

2.25 

10.78 

10.99 

11.35 

11.32 

3.11 

3.14 

.44 

.47

.29 

.30 

.58 

.59 

18.71 

18.65 

11.80 

11.55 

.37 

.34 

.19 

.18 

.57 

.52

1.35 

1.56

2.11 

2.34 

10.86 

11.12 

11.32 

11.41 

3.18 

3.11 

.51 

.50

.29 

.29 

.60 

.58 

18.56 

18.39 

11.44 

11.70 

.41 

.39 

.18 

.19 

.57 

.57

1.42 

2.27

10.98 

11.42 

3.20

.48

.29 

.59

18.64 

11.64 

.39

.18

.57

Neg. 

.04 

Neg. 

.07 

.10 

.02

Neg. 

Neg. 

.12 

Neg. 

.02 

Neg. 

.01

0.16 

.10 

.19 

.13 

.05 

.02

.006 

.02 

.12 

.15 

.02 

.006 

.02

0.16 NS

1.28 NS 

.45 NS 

1.64 NS 

9.12 NS 

2.17 NS

.5 NS 

.1 NS 

3.04 NS 

.35 NS 

3.08 NS 

.5 NS 

1.44 NS

Parts per million

As ___ _ _____

Ba _ ____ ___

Mo __ ____

Pb ___ . _

Rb __ _ _____

Sr __ __ __

Y _ _ ___ _

Zn _ __ __

Zr __ ____ .

315 

300 

1,695 

1,680 

460 

450 

1,310 

1,315 

10 

10

1,760 

1,695 

115 

115 

880 

870 

320 

310

280 

300 

1,625 

1,645 

460 

465 

1,315 

1,315 

10 

10

1,715 

1,725 

110 

115 

865 

875 

310 

320

285 

310 

1,665 

1.715 

'465 

460 

1,325 

1,360 

10 

10

1,775 

1,700 

115 

120 

865 

885 

320 

320

298 

1,671 

460 

1,323 

10

1,728 

115 

870 

317

Neg. 

26 

2.5 

13

Neg. 

1.4 

2.9 

Neg.

14.4 

23 

5.0 

14

41 

2.9 

5.8 

5.8

.74 NS 

3.70 NS 

1.5 NS 

2.66 NS 

(No test)

.09 NS

1.5 NS 

1.5 NS 

.5 NS

3 Brook Rd., Wormley, Godalming. Surrey, GU8 5UB, England.

Analytical methods:— (1) Major elements Si to Mn, plus Co, Cu, and Ni, were determined by X-ray fluorescence on samples fused with LiaE-iO? and 

La»O.i; the method follows that of Norrish and Hutton (1969); (2) trace elements As to Zr were determined by X-ray fluorescence on powders 

pressed into discs at 15 tons; the method follows that of Anderman and Kemp (1958); (3) COa was determined gravimetrically after treating the 

sample with hot 10 percent HC1.
TABLES OF DATA BY ANALYSTS 21

TABLE 15.—Determinations of several elements in USGS-Nod-P-1 by S. E. Calvert, Institute of Oceanographic Sciences 1

[Determinations in percent or parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative variance obtained. F

ratio tested at Fo.os or the fraetile indicated in parentheses]

Element 

or oxide i

Bottle

2

Standard deviation

3 Mean Bottle 

(d.f.=2)

Error 

(d.f. = 3) ratio

Percent

Si ________

Al __________

Fe ___ — _

Ca ________

Mg _________

K _ ______

Ti __ _ _

P _ _ __

Mn ___ _ _

CO, _ ________

Co __________

Cu __ ___ __

Ni _______ ___

6.67 

6.54 

2.51 

2.53 

4.80 

4.90 

2,18 

2.12 

2.00 

2.12 

1.13 

1.14

.30 

.30 

.22 

.21 

29.66 

28.75 

1.21 

1.06 

.30 

.29 

1.02 

1.07 

1.26 

1.38

6.62 

6.62 

2.51 

2.78 

4.63 

4.62 

2.15 

2.17 

2.01 

2.19 

1.15 

1.18

.30 

.30 

.21 

.22 

29.15 

28.59 

1.91 

1.94 

.28 

.28 

1.11 

.95 

1.40 

1.11

6.74 

6.69 

2.58 

2.65 

4.83 

4.76 

2.20 

2.12 

2.17 

2.00 

1.10 

1.15

.30 

.30 

.21 

.21 

29.65 

28.59 

1.14 

1.10 

.28 

.28 

1.12 

.95 

1.34 

1.17

6.65 

2.59 

4.76 

2.16 

2.08 

1.14

.30 

.21 

29.06 

1.39 

.28 

1.04 

1.28

0.04 

Neg. 

.11 

Neg. 

Neg. 

.01

Neg. 

Neg. 

.46 

.008 

Neg. 

Neg.

0.06 

.11 

.05 

.04 

.11

.02

.006 

.61 

.06 

.004 

.10 

.14

2.20 NS 

.65 NS 

11.0 NS (0.975) 

.04 NS 

.06 NS 

1.48 NS

(No test) 

.5 NS 

.16 NS 

2 102 

9.0 NS 

.01 NS 

.13 NS

Parts per million

As _ _ _

Ba ____ _

Mo __ ___ _

Pb ____ _ ___

Rb __ __ ____

Sr _ ____ .

Y

Zn _ __ _.

Zr __ __.

40 

35 

3,405 

3,455 

820 

825 

700 

740 

20 

20

755 

745 

90 

90 

1,975 

2,010 

280 

280

50 

50 

3,500 

3,425 

825 

815 

700 

740 

20 

25

765 

745 

90 

90 

1,985 

2,010 

285 

275

25 

35 

3,460 

3,475 

835 

820 

690 

725 

20 

20

760 

740 

85 

90 

1,990 

2,015 

280 

280

39 

3,453 

823 

715 

21

751 

89 

1,998 

280

9.6 

Neg. 

Neg. 

Neg. 

.000

Neg. 

.000 

Neg. 

Neg.

4.6 

37 

7.6 

27 

2.0

12.2 

2.0 

20 

4.1

9.8 NS (0.975) 

.60 NS 

.50 NS

.14 NS 

1.0 NS

.11 NS 

1.0 NS 

.12 NS 

.0 NS

1 Brook Rd., Wormley, Godalming, Surrey, GU8 5UB, England. 

- F ratio is extremely significant.

Analytical methods:— (1) Major elements Si to Mn, plus Co, Cu, and Ni, were determined by X-ray fluorescence on samples fused with I^IkO? and 

LaaO.i; the method follows that of Norrish and Hutton (1969); (2) trace elements As to Zr were determined by X-ray fluorescence on powders pressed 

into discs at 15 tons; the method follows that of Anderman and Kemp (1958); (3) COa was determined gravimetrically after treating the sample with 

hot 10 percent HC1.
22 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 16.—Determinations of several elements in USGS-Nod-A-1 by R. T. T. Rantala, Bedford Institute of Oceanography l

[Determinations in percent or in parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained.

F ratio tested at Fo.os or the fractile indicated in parentheses]

Element 5/29

Bottle

18/15

Standard deviation

28/11 Mean Bottle 

(d.f.=2)

Error 

(d.f. = 3)

F 

ratio

Percent

Si __ _____

Al _ _ —

Fe ________

Mg — _ —

Ca ___ —

K _________

Ti _ __ __ _

Mn _________

1.98 

2.05 

2.04 

2.04 

11.20 

11.00 

2.80 

2.80 

11.00 

10.90 

.76 

.76 

.51 

.50 

.27 

.28 

17.60 

17.90

1.95 

2.15 

2.11 

2.02 

10.80 

10.90 

2.84 

2.80 

11.00 

10.90 

.80 

.77 

.52 

.52 

.27 

.29 

18.10 

17.70

1.98 

1.92

2.09 

2.06 

11.00 

11.60 

2.79 

2.79 

11.00 

11.00 

.75 

.76 

.53 

.53 

.26 

.28 

17.90 

17.60

2.005 

2.060 

11.08 

2.803 

10.97 

.767 

.518 

.275 

17.80

Neg. 

Neg. 

.13 

.01 

Neg. 

.01 

.012 

Neg. 

Neg.

0.09 

.04

.26 

.02 

.06 

.01 

.004 

.012 

.24

0.6 NS 

.43 NS 

1.49 NS 

1.75 NS 

.5 NS 

3.1 NS 

19 NS(0.99) 

.33 NS 

.26 NS

Parts per million

Ba __ ____

Be _

Co _ _______

Cr __ _______

Cu __ _ _

Li _ _ __ _

Mo _

Ni _ _

Pb _ _______

Sr _ _________

V __ _

Zn _ _

1,700 

1,680 

5.5 

5.5 

3,100 

3,170 

25 

20 

1,050 

1,050 

77 

76

460 

440 

6,300 

6,400 

798 

805 

1,680 

1,650 

578 

590 

561 

548

1,580 

1,670 

5.8 

5.8 

3,090 

3,180 

25 

25 

1,060 

1,050 

76 

76

443 

468 

6,300 

6,300 

778 

820 

1,650 

1,700 

580 

605 

565 

565

1,640 

1,740 

5.3 

5.5 

3,100 

3,130 

20 

25 

1,040 

1,060 

77 

76

465 

468 

6,200 

6,300 

778 

778 

1,660 

1,620 

590 

575 

553 

560

1,668 

5.57 

3,128 

23 

1,052 

76.3

457.3 

6,300 

792.8 

1,660 

586.3 

558.7

Neg. 

.20 

Neg. 

Neg. 

Neg. 

Neg.

Neg. 

29 

3.9 

Neg. 

Neg. 

3.6

55.5 

.08 

48 

2.9 

9.1 

.58

13.1 

58 

17.4 

28.9 

12.9 

6.0

0.91 NS 

13.0 NS (0.975) 

.12 NS 

.5 NS 

.2 NS 

.5 NS

.82 NS 

.5 NS 

1.10 NS 

.78 NS 

.35 NS 

1.71 NS

1 Dartmouth, N.S., Canada, B2Y 4A2.

Analytical method.—Samples were decomposed by acid in teflon bombs as described by Rantala and Loring (1973); the elements were determined by 

flame atomic-absorption spectrometry as described by Rantala and Loringr (1975), with slight variations due to dilutions used.
TABLES OF DATA BY ANALYSTS 23

TABLE 17.—Determinations of several elements in USGS-Nod-P-1 by R. T. T. Rantala, Bedford Institute of Oceanography 1

[Determinations in percent or in parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained.

F ratio tested at Fo.vs or the fraetile indicated in parentheses]

Element 29/23

Bottle

52/24

Standard deviation

57/10 Mean Bottle 

(d.f. = 2)

Error 

(d.f. = 3)

F 

ratio

Percent

Si ___ -

Al ___ .

Fe

Mg ______

Ca ___ .

Na — __.

K _ __ _.

Ti _ __.

Mn _ __ .

6.85

6.88 

2.42

2.38 

5.76

5.74 

1.96

1.98 

2.16

2.16 

1.63

1.64 

. _ 1.04

1.05 

.28

.29 

28.90

28.90

6.90 

6.95 

2.37 

2.45 

5.76 

5.88 

1.97 

1.99 

2.16 

2.12 

1.62 

1.65 

1.05 

1.04 

.26 

.27 

29.20 

29.40

6.85 

7.38 

2.44 

2.38 

5.94 

5.80 

1.97 

1.98 

2.18 

2.16 

1.62 

1.62 

1.04 

1.02 

.28 

.28 

29.30 

29.30

6.968 

2.407 

5.813 

1.975 

2.157 

1.630 

1.040 

.277 

29.17

Neg. 

Neg. 

.03 

Neg. 

.008 

Neg. 

.005 

.010 

.22

0.22 

.04 

.08

.01 

.018 

.013 

.010 

.006 

.08

0.72 NS

.03 NS

1.27 NS 

.33 NS 

1.4 NS 

.90 NS 

1.5 NS 

6.5 NS 

16.0 NS (0.975)

Parts per million

Ba __

Be __ _

Co __ _

Cr _ ____

Cu __ _

Li _____

Mo ______

Ni _____

Pb _ _ _

Sr _ __

V _

Zn __ _

2,710

2,930 

2.8

2.6 

__ 2,240

2,260 

_ _ 20

20 

11,300

11,300 

142

142 

795

800 

_ 13,000

13,400 

428

415 

618

625 

483

490 

1,460

1,460

2,940 

2,880 

2.8 

3.0 

2,270 

2,340 

20 

20 

11,400 

11,300 

143 

140

803 

812 

13,200 

13,500 

430 

442 

628 

655 

478 

490 

1,490 

1,460

2,800 

2,910 

2.8 

2.8 

2,290 

2,280 

20 

20 

11,500 

11,400 

141 

143

785 

815 

13,400 

13,200 

442 

460 

665 

638 

470 

468 

1,470 

1,460

2,862 

2.8 

2,280 

20 

11,370 

141.8

801.7 

13,280 

436.2 

638.2 

479.8 

1,467

Neg. 

.06 

18

64 

Neg.

Neg. 

Neg. 

12 

10.4 

8.6 

Neg.

103 

.11 

30

58 

1.5

12.9 

220 

10 

15.8 

5.7 

12.9

0.38 NS 

1.5 NS

1.72 NS

3.50 NS 

.08 NS

.32 NS 

.24 NS 

4.10 NS 

1.86 NS 

5.46 NS 

.70 NS

1 Dartmouth, N.S., Canada, B2Y 4A2.

Analytical method:—Samples were decomposed by acid in teflon bombs as described by Rantala and Loring (1973); the elements were determined by 

flame atomic-absorption spectrometry, described by Rantala and Loring (1975), with slight variations due to dilutions used.
24 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 18.—Determinations of several elements in USGS-Nod-A-1 by the National Institute for Metallurgy1

[Determinations in percent, or in parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratio tested at Fo.95 or the fractile indicated in parentheses. Si through P reported as the oxide but converted to the element]

Element 9/30

Bottle

12/3

Standard deviation

36/17 Mean Bottle 

(d.f.=2)

Error 

(d.f. = 3)

F 

ratio

Percent

Si _._ __ _

Al ____ _

Fe __ _ — _

Mg _________

Ca __________

K _ _ _ _____

Ti _ ______

Mn

P _ __ _

Co _

Cu ______

Ni _ __ __

1.64 

1.68 

1.85 

1.95 

10.37 

10.31 

2.77 

2.76 

11.33 

11.31 

.35 

.42

.32 

.35

18.72 

18.61 

.64 

.59 

.278 

.282 

.108 

.106 

.624 

.616

1.56 

1.58 

1.87 

1.72 

10.25 

10.25 

2.73 

2.71 

11.28 

11.40 

.38 

.40

.32 

.30

18.62 

18.61 

.58 

.58 

.285 

.283 

.107 

.107 

.639 

.621

1.71 

1.61 

1.86 

1.94 

10.32 

10.26 

2.72 

2.72 

11.30 

11.21 

.40 

.44

.32 

.31 

18.61 

18.61 

.62 

.62 

.278 

.282 

.108 

.107 

.623 

.625

1.63 

1.86 

10.29 

2.74 

11.30 

.40

.32 

18.63 

.60 

.281 

.107 

.625

0.04 

.02 

.04 

.025 

.008 

Neg.

.008 

Neg. 

.02 

.002 

Neg. 

Neg.

0.04 

.08 

.03

.009 

.062 

.03

.015 

.04 

.02 

.002 

.0009 

.008

2.7 NS 

1.13 NS 

3.39 NS 

16.2 NS(0.99) 

1.03 NS 

.62 NS

1.50 NS 

.91 NS 

2.28 NS 

1.77 NS 

.20 NS 

.78 NS

Parts per million

Mo _ ____

Zn _ _ _

561 

561 

496

578

535

549 

579 

569

562 

635 

619 

603

567 

574

19

28

30 

34

1.80 NS 

2.32 NS

1 Private Bag X3015, Randburg, 2125, South Africa.

Analytical methods:—

1. MnO, 0.75 g of Nod-P and 1 g of Nod-A were dissolved in HC1 and HNO;i and taken to fumes with HuSO4. After cooling, water was added and the 

solutions diluted in a volumetric flask. Mn was determined on an aliquot by potentiometric titration with KMnOi.

2. SiOs, AbOn, Fe-jO;, MgO, CaO, K^O, TiOs, MnO, and PsQs were determined by X-ray fluorescence on a disc made by fusing 0.5-0.6-g samples with 

7.5 g of a flux of 10 percent LinBiCb, 51 percent NasBiO?, and 39 percent NaeCO.i.

3. For Co, Cu, Mo, Ni, and Zn, 0.4-g samples were dissolved with 10 mL HNO:i, 20 mL HF, and 3 mL HC1O4 in platinum dishes. Solutions were 

fumed to incipient dryness and 3 mL HC1 added. Solutions were warmed and 3-4 drops of HsO» added to oxidize Mn. The resulting clear solutions were transferred to volumetric flasks and diluted to the mark. Appropriate dilutions of these solutions were measured by atomic-absorption 

spectrometry.

4. The Canadian sample, CSRM-SU-1, was used as a control sample; results are listed as follows:

National Institute for Certified 

Metallurgy Value

Co _____ppm__ 568, 553, 581, 569 630

Cu ___percent— 0.845, 0.845, 0.846, 0.838 0.87

Mo _____ppm-- <40, <40, <40, <40 _____

Ni __.percent.. 1.46, 1.46, 1.45, 1.46 1.51

Zn _____ppm_- 319, 311, 304, 312 294
TABLES OF DATA BY ANALYSTS 25

TABLE 19.—Determinations of several elements in USGS-Nod-P-1 by the National Institute for Metallurgy l

[Determinations in percent, or in parts per million, as indicated, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios tested at FO.BB or the fractile indicated in parentheses. Si through P reported as the oxide but converted to the element]

Element 18/6

Bottle

24/30

Standard deviation

58/11 Mean Bottle 

(d.f. = 2)

Error 

(d.f. = 3)

F 

ratio

Percent

Si

Al _ _ _ _

Fe ________

Mg _ ___ __

Ca ___ _

K __ _

Ti __________

Mn __ _ __

P _ ___ _

Co _ _

Cu _ _ ______

Ni __ __ ___

Zn ________

6.30 

6.17 

2.55 

2.44 

5.60 

5.56 

1.88 

1.75 

2.21 

2.21 

.96 

.94

.31 

.26 

29.96 

29.91 

.22 

.20 

.200 

.202 

1.16 

1.16 

1.31 

1.32 

.148 

.147

6.37 

6.41 

2.61 

2.57 

5.60 

5.54 

1.77 

1.82 

2.20 

2.22 

.90 

.95

.31 

.31 

29.96 

29.94 

.21 

.20 

.203 

.199 

1.16 

1.15 

1.33 

1.32 

.149 

.157

6.61 

6.30 

2.66 

2.50 

5.49 

5.36 

1.82 

1.74 

2.18 

2.17 

.95 

.88

.29 

.26 

29.91 

29.90 

.20 

.19 

.201 

.200 

1.17 

1.16 

1.32 

1.32 

.148 

.158

6.36 

2.56 

5.52 

1.80 

2.20 

.93

.29 

29.93 

.20 

.201 

1.16 

1.32 

.151

0.06 

Neg. 

.075 

Neg. 

.019 

Neg.

.006 

.02 

.003 

Neg. 

.003 

.003 

Neg.

0.14 

.08 

.06

.06 

.009 

.04

.024 

.02 

.010 

.0019 

.006 

.006 

.0052

1.34 NS 

.83 NS 

4.09 NS 

.14 NS 

9.8 NS (0.975) 

.50 NS

1.15 NS 

2.10 NS 

1.16 NS

.48 NS 

1.5 NS 

1.50 NS 

.73 NS

Parts per million

Mo _ _____ 990 

1,000

980 

970

970 

980

982 10.4 7.1 5.33 NS

1 Private Bag X3015, Randburg, 2125, South Africa.

Analytical methods:—

1. For MnO, 0.75 g of Nod-P and 1 g of Nod-A were dissolved in HC1 and HNOa and taken to fumes with HsSOi. After cooling, water was added 

and the solutions diluted in a volumetric flask. Mn was determined on an aliquot by potentiometric titration with KMnO4.

2. SiOs, AhO;i, FeaO:;, MgO, CaO, K;O, TiO:;, MnO, and P°Os were determined by X-ray fluorescence on a disc made by fusing 0.5-0.6-g samples with 

7.5 g of a flux of 10 percent Li2B4O?, 51 percent Na^BiOy, and 39 percent NasCOs.

3. For Co, Cu, Mo, Ni, and Zn, 0.4 g samples were dissolved with 10 mL HNOs 20 mL HF, and 3 mL HC1O4 in platinum dishes. Solutions were fumed 

to incipient dryness and 3 mL HC1 added. Solutions were warmed and 3-4 drops of HsOa added to oxidize Mn. The resulting clear solutions were 

transferred to volumetric flasks and diluted to the mark. Appropriate dilutions of these solutions were measured by atomic-absorption spectrometry.

4. The Canadian sample, CSRM-SU-1, was used as a control sample; results are listed as follows:

National Institute for Certified 

Metallurgy Value

Co ____ppm_- 568, 553, 581, 569 630

Cu ___percent.. 0.845, 0.845, 0.846, 0.838 0.87

Mo _____ppm._ <40, <40, <40, <40 _____

Ni ___percent.. 1.46, 1.46, 1.45, 1.46 1.51

Zn _____pprn-. 319, 311, 304, 312 294
26 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 20.—Determinations of several elements in USGS-Nod-A-1 by the Institute of Geological Sciences *

[Determinations in percent. T, total; d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratio tested at Fo.ss.

Analysts: N. Cogger, chemical analysis, and Linda Ault, spectrographic analysis]

Element Metnod *

Si ___ .

Fe(T)

Mg ______

Ca _ __ .

Ca __ _.

K ____ .

Mn(T) _ .

P _ _ _ _.

Ba _ ___ .

Co

Co ___ .

Cu — _ __.

Mo __

Ni _ __

Pb

Sr ______

Tl _____

V _ _ _

Zn _ _

.__ GR __ _

.__ SA ________

._ AA _ _

._ GR _____

._ AA _ __ __

.__ FE _ _

._ PT___ _

.__ SA __ __ __

.__ ES ___ .

.__ AA _ _ .

___ SA _ _ .

___ AA

___ ES _

_ SA _ _ _.

_ AA ___ .

__ AA

__ ES _ _ .

_ ES _. _ .

_ AA _ _ .

10/6

1.72

1.70

10.92

10.90

2.90

2.90

11.02

11.02

11.08

10.98

.46

.47

18.50

18.51

.52

.53

.256

.230

.312

.312

.322

.322

.107

.112

.0527

.0534

.635

.642

.085

.087

.18

.17

.0045

.0077

.0964

.0951

.061

.063

Bottle

13/24

1.71

1.76

10.88

10.93

2.92

2.97

11.03

11.00

11.06

11.15

.45

.46

18.51

18.48

.53

.53

.260

.237

.315

.312

.321

.320

.108

.109

.0546

.0497

.635

.638

.082

.082

.18

.18

.0073

.0040

.1013

.0878

.061

.061

49/29

1.72

1.77

10.91

10.96

2.95

2.92

11.05

10.90

11.15

11.01

.46

.46

18.54

18.51

.52

.53

.204

.204

.312

.313

.322

.322

.108

.112

.0487

.0495

.633

.640

.083

.086

.17

.18

.0073

.0057

.0848

.0843

.061

.064

Mean

1.73

10.91

2.93

11.00

11.07

.46

18.51

.53

.232

.313

.322

.109

.0514

.637

.084

.177

.00608

.0916

.062

Standard deviation

Bottle 

<d.f. = 2)

Neg.

Neg.

.02

Neg.

Neg.

.003

.009

Neg.

.022

Neg.

.0008

Neg.

.0015

Neg.

.002

Neg.

Neg.

.0047

Neg.

Error 

(d.f = 3)

0.03

.03

.02

.062

.079

.006

.018

.006

.014

.0013

.0004

.003

.0020

.004

.001

.0058

.0020

.0055

.0015

F

ratio

0.72 NS

.57 NS

1.97 NS

.31 NS

.46 NS

1.5 NS

1.47 NS

.50 NS

5.86 NS

.70 NS

9.00 NS

.17 NS

2.04 NS

.15 NS

3.77 NS

.50 NS

.09 NS

2.46 NS

.54 NS

1 64/78 Gray's Inn Rd., London, WC1X 8NG, England.

2 Analytical methods:—AA, atomic-absorption spectrometry; ES, emission spectrography; 

potentiometric titrimetry; and SA, solution absorptiometry.

FE, flame-emission spectrophotometry; GR, gravimetry; PT,
TABLES OF DATA BY ANALYSTS 27

TABLE 21.—Determinations of several elements in USGS-Nod-P-1 by the Institute of Geological Sciences '

[Determinations in percent. T, total; d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained; F ratio tested at Fo.95.

Analysts: N. Cogger, chemical analysis, and Linda Ault, spectrographic analysis]

Element

Si ________

Mg __ _ __

Ca ____ _

K __ ___

Mn(T) ___

P __ _

Ba _ _ __ _

Co _ __ _

Co ______

Cu _______

Mo _____ _

Ni ___ _____

Pb _ ___ _

Sr ____ _

Tl ____ _

V _ __ _

Zn __

Method 2

_ GR _

_ SA _ ______

_ AA _____ _

_ AA ___ __

_ FE _ ___ ____

PT

_ SA __________

_ ES _ __ _ _

AA _ ______

_ SA _ ____ _

_ AA _ _ __ _

_ ES _ _ _.__

_ SA _ __ _

_ AA _ _ __

_ AA ___ __

_ ES _

. ES ________

._ AA _ _ __

25/31

6.36 

6.37 

6.06 

6.04 

2.01 

1.97 

2.20 

2.14 

1.00 

1.08 

29.80 

29.91 

.20 

.20 

.397 

.336 

.229 

.228 

.231 

.236 

1.15 

1.15 

.0706 

.0700 

1.34 

1.34 

.046 

.046

.0177 

.0140 

.0588 

.0539 

.164 

.165

Botle

57/3

6.36 

6.39 

6.05 

6.09 

2.01 

2.00 

2.26 

2.21 

1.10 

1.05 

29.95 

29.85 

.21 

.20 

.377 

.373 

.229 

.226 

.231 

.229 

1.17 

1.15 

.0678 

.0691 

1.36 

1.36 

.048 

.047

.0161 

.0155 

.0556 

.0529 

.167 

.167

Standard deviation

58/27

6.44 

6.39 

6.03 

6.03 

1.99 

2.04 

2.21 

2.16 

1.04 

1.03 

29.87 

29.81 

.20 

.20 

.383 

.377 

.226 

.226 

.231 

.229 

1.13 

1.15 

.0631 

.0664 

1.34 

1.34 

.048 

.046

.0183 

.0111 

.0557 

.0520 

.164 

.167

Mean

6.38 

6.05 

2.00 

2.20 

1.05 

29.86 

.202 

.374 

.227 

.231 

1.15 

.0678 

1.35 

.047

.09 

.0154

.0548 

.166

Bottle 

(d.f. = 2)

0.02 

.02 

Neg. 

.02 

Neg. 

Neg.

Neg. 

.0009 

.001 

.006 

.0026 

.01 

.0004

Neg. 

Neg. 

.0009

Error 

(d.f. = 3)

0.02

.02 

.03 

.04 

.039 

.065 

.004 

.025 

.0013 

.002 

.011 

.0015 

.00 

.0009

.0033 

.0027 

.0013

F 

ratio

2.40 NS 

2.40 NS 

.45 NS 

1.62 NS 

.63 NS 

.46 NS 

1.00 NS 

.15 NS 

1.90 NS 

1.48 NS 

1.50 NS 

7.41 NS 

Indet. 

1.40 NS

.08 NS 

.48 NS 

1.90 NS

1 64/78 Gray's Inn Rd., London, WC1X 8NG, England.

2 Analytical methods:—AA, atomic-absorption spectrometry; ES, emission spectrography; FE, flame-emission spectrophotometry; GR, gravimetry, PT, 

jtentiometric titrimetrv: and SA. solution absnrntiometrv.

, 

potentiometric titrimetry; and SA, solution absorptiometry.

TABLE 22.—Determinations of several elements by atomic-absorption spectrometry in USGS-Nod-A-1 and USGS-Nod-P-1

by David Piper, U.S. Geological Survey

[Determinations in percent. Data are averages of two determinations]

USGS-Nod-A-1

Element

Fe _ ____

Mn _ ____

Co _ __

Cu _ _ _

Ni ___ __

Zn _ _

35/11

10.6

17.1

.30

.088

.61

.047

Bottle

45/21

10.5 

16.9 

.30 

.087 

.61 

.044

45/24

10.7 

16.8 

.31 

.088 

.61 

.047

Average

10.6

16.9 

.30 

.088 

.61 

.046

2/15

6.49 

27.6 

.22 

1.11 

1.28 

.14

USGS-Nod-P-1

Bottle

33/11

6.31 

27.1 

.22 

1.11 

1.25 

.14

44/10

6.54 

27.3 

.22 

1.11 

1.25 

.14

Average

6.45 

27.3 

.22 

1.11 

1.26 

.14

Stop 97, 345 Middlefleld Rd., Menlo Park, CA 94025.
28 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 23.—Determinations of several elements by flame atomic-absorption spectrometry in USGS-Nod-A-1 and USGS-NodP-l by Lockhead Ocean Laboratory 1

[Determinations in percent]

USGS-Nod-A-1

Element

Fe _ _ __

Mn ___

Co __ _ _

Cu __ _

Ni _ __

4/27

10.4

17.6

.28

.11

.58

Bottle

28/21

10.3 

17.0 

.28 

.11 

.59

32/6

10.0 

17.3 

.29 

.11 

.59

Average

10.2 

17.3 

.28 

.11 

.59

26/19

5.13 

27.2 

.20 

1.12

1.24

USGS-Nod-P-l

Bottle

50/25

5.26 

26.9 

.20 

1.14 

1.26

51/26

4.74 

29.4 

.20 

1.12 

1.21

Average

5.04 

27.8 

.20 

1.13 

1.24

1 3380 North Harbor Dr., San Diego, CA 92101.

TABLE 24.—Complete analyses of USGS-Nod-A-1 by M. Saunders, Grant Institute of Geology 1

[Determinations in percent]

Oxide or 

element

Si02 ___ __

A12 03 _ _ _ __

Fe203 _ __ _

MgO ____________

CaO _ ___ __

Na2 0 ___ __ _ __

K2 0 _ _ ______

Ti02 __ _ __ __

P2 0s —— —— _ ___ -

MnO _ _ _ _

C02 _ ____

CoO _ _ _

CuO ___ __

NiO _________ _ _

Excess 0 _ __

H20+ _ ____ _

BaO _ ___ _

Cl __ __ _ __ __

MOO:, __ __

PbO __ __ __

SrO ___ _________

V2 0.-, ____________

ZnO __ __ _ _

Subtotal

Less 0=C1 _

Total _

21/21

3.91 

4.34 

15.82 

4.76 

15.70 

1.09

.55 

.47 

1.23 

23.81 

11.59 

.43

.139 

.90 

5.31

.19

.54

.062 

.100 

.203 

.108 

.082

99.23 

.12

99.11

Bottle

28/13

3.96 

4.36 

15.75 

4.75 

15.68 

1.12

.55 

.46 

1.22 

23.97 

11.56 

.44

.138 

.91 

5.30

~.20~

.54

.061 

.104 

.208 

.110 

.080

99.47 

.12

99.35

Average as

54/28

3.90 

4.35 

15.72 

4.71 

15.69 

1.12

.56 

.47 

1.21 

23.97 

11.59 

.45

.140 

.88 

5.29

.20 

.54

.060 

.107 

.197 

.110 

.080

99.24 

.12

99.12

Oxide

3.92

4.35 

15.76 

4.74 

15.69 

1.11

.55 

.47 

1.22 

23.92 

11.61 

.44

.139 

.90

-7.9 

.20

.061 

.104 

.203 

.109 

.081

Element

1.83 

3.26 

11.02 

2.86 

11.22 

.82

.46 

.28 

.53 

18.51

.34

.111 

.71 

5.30

.18

.54

.041 

.096 

.172 

.061 

.065

Method 2

C 

A 

C 

A 

G 

F

F 

C 

C 

T 

G 

A

A 

A 

T 

G 

A 

G

A 

A 

A 

A 

A

1 University of Edinburgh, West Mains Rd., Edinburgh EH9 3JW, Scotland.

2 Analytical methods:—A, atomic-absorption spectrometry; C, colorimetry; F, flame photometry; G, gravimetry; and 

T, titrimetry.

Notes:—Both dried nodule samples rapidly absorbed moisture during weighing. When exposed to the atmosphere 

overnight. Nod-A-1 absorbed between 11 and 13 percent H2O and Nod-P-1, between 8 and 10 percent H2O. Inconsistent data were obtained for HaO+ by two methods, andthe results are reported as an approximate value.
TABLES OF DATA BY ANALYSTS 29

TABLE 25.—Complete analyses of USGS-Nod-P-1 by M, Saunders, Grant Institute of Geology

[Determinations in percent]

Oxide or

element

Si02 _______ -

A1203 _ - ________

FesOa ___________

MgO ____________

CaO ___ ____

Na20

KL,0 __ ____ ____

Ti02 _ _ _ ____

P205 _ __ _____

MnO _ _ _____

C02 _ __ ________

CoO __ __ _____

CuO ___ ___ _

NiO _

Excess 0 _ __

H20+ ________ _

BaO _ _ ______

Cl _ _ __________

Mo03 _ _ ___

PbO __ __ _____

SrO ___ _ _

VoOs

ZnO

Subtotal _ _

Less 0=C1 _ _

Total _ ___

31/2

14.61 

5.12 

8.50 

3.29 

2.91 

2.21

1.23 

.48 

.48 

38.64 

.69 

.32

1.71 

1.98 

8.42

.33 

.15

.113 

.058 

.091 

.092 

.208

99.83 

.03

99.80

Bottle

1/5

14.60 

5.19 

8.48 

3.32 

2.87 

2.26

1.21

.47 

.48 

38.67 

.77 

.34

1.70 

2.01 

8.40

.32 

.14

.113 

.060 

.086 

.094 

.210

99.99 

.03

99.96

Average as

47/15

14.63 

5.12 

8.41 

3.27 

2.91 

2.23

1.21 

.46 

.48 

38.65 

.82 

.34

1.66 

1.99 

8.42

.32 

.14

.108 

.057 

.090 

.095 

.213

99.82 

.03

99.79

Oxide

14.61 

5.14

8.46 

3.29 

2.90 

2.23

1.22 

.47 

.48 

38.65 

.76 

.33

1.69 

1.99

~8.2 

.32

.111 

.058 

.089 

.094 

.210

Element

6.82 

3.85 

5.91 

1.98 

2.07 

1.65

1.01 

.28 

.21 

29.92

.26

1.35 

1.56 

8.41

T2~9~~ 

.14

.074 

.054 

.075 

.053 

.169

Method 2

G 

A 

C 

A 

A 

F

F 

C 

C 

T 

G 

A

A 

A 

T 

G 

A 

C

A

A 

A 

A 

A

1 University of Edinburgh, West Mains Rd., Edinburgh EH9 3JW, Scotland.

- Analytical methods:—A, atomic-absorption spectrometry; C, colorimetry; F, flame photometry; G, gravimetry; and 

T, titrimetry.
30 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 26.—Determinations of several elements in USGS-Nod-A-1 by David Felix, Ocean Mining Laboratory 1

[Determinations in percent or in parts per million, as indicated. Data for day 1 for all elements are not included in the analysis of variance. S, 

significant; NS, not significant; VS, very significant (calculated F > Fo.ons). Means and F ratios from the analysis of variance for the complete 

sets of three data on days 2 and 3. Degrees of freedom for mean sums of squares: bottles, 2; days, 1; and residual (error), 2. F ratios tested at 

Fo.ss or the fractile indicated in parentheses. For any element except Pb, the upper mean is for all data and the lower is for the six data used in 

the analysis of variance and for best values]

Element Day

Bottle

Mean

F ratio

Bottles Days

Percent

Al _______ 1____ 1.78 1.84 1.81 1.96

2____ 2.14 2.00 2.00 2.04

3____ 2.03 2.04 2.01

Fe _______ 1____ 11.2 11.3 11.2 11.38

2____ 11.1 11.2 11.2 11.43

3____ 11.6 12.0 11.6

Mn ______ 1____ 18.2 18.5 18.5 17.84

2____ 18.0 19.0 18.2 17.57

3____ 16.8 16.8 16.6

Co _______ 1____ .330 .329 .329

2____ .337 .340 .338

3____ .336 .334 .333

Cu _______ 1____ .10 .11 .11

2____ .11 .12 .11

3____ .11 .11 .11

Ni _______ 1____ .67 .68 .67

2____ .66 .65 .65

3____ .66 .66 .66

	lion

Cr _______ 1____ 13 14 13 20.8

2____ 21 22 22 24.5

3____ 28 26 28

Mo 2 ______ 1____ 420 420 420 425.6

2____ 430 430 440 428.3

3____ 420 420 430

Pb 2 ______ ____ 1,260 1,280 1,260 1,267

V 2 _______ 1____ 850 870 850 830.0

2____ 800 800 800 816.6

3____ 830 840 830

Zn 2 ______ 1____ 630 620 600 600.0

2____ 600 620 590 591.7

3____ 580 580 580

.3340

.3363

.110

.112

.662

.657

1 NS 

2.0 NS 

1.82 NS 

1 NS 

(No test) 

1 NS

16.54 NS (0.99) 

16.0 NS(0.99) 

32.65 8(0.995) 

30.5 8(0.995)

(No test) 

11.45 NS (0.99)

Parts per million

1 NS

4.19 NS 

(No test) 

3.08 NS

2.71 NS

160.9 VS

13.44 NS (0.99)

(No test) 

73.19 VS

11.29 NS (0.99)

'Kennecott Exploration, Inc., 3377 Carmel Mt. Rd., San Diego, CA 92121. 

2 Data for element converted from percent, and nonsignificant zero added.

Analytical method:—1-g portions of the dried samples were digested in teflon beakers with hot HC1, HC1O4, and HF to form dense perchloric fumes. 

After making to volume, appropriate dilutions were made to bring concentrations of each metal to its optimum range for atomic absorption. Determinations were made without background corrections on a Perkin-Elmer model 305 atomic-absorption unit. In-house standards and analyzed samples, 

plus standards prepared from spectrographic-quality metals, were used to bracket the unknowns. Calibration curves were not used.
TABLES OF DATA BY ANALYSTS 31

TABLE 27.—Determinations of several elements in USGS-Nod-P-1 by David Felix, Ocean Mining Laboratory 1

[Determinations in percent, or in parts per million, as indicated. Data for day 1 and the second listed determination for day 3 for all elements are 

not included in the analysis of variance. S, significant; NS, not significant; VS, very significant (calculated F > Fo.ms). Means and F ratios from 

the analysis of variance for the complete sets of three data on days 2 and 3. Degrees of freedom for mean sums of squares: bottles, 2; days, 1; 

and residual (error), 2. F ratios tested at Fo.vs or the fractOe indicated in parentheses. For any element except Pb, the upper mean is for all data 

and the lower is for the six data used in the analysis of variance and for best values.]

i

Bottle

2

F ratio

3 Bottles Days

Percent

Al

Fe ___ .

Mn _ .

Co _ __.

Cu _ _ _.

Ni _______

_ 1 _ _ _

2_ __ _

3

3__

__ 1_

2_ __ _

3_ _ _

3 __ _

. _ 1

2 _ _ .

3_ _ .

3

1_ _ _.

2 _

3 _ _ .

3 _ _.

1

2 __ .

3 _ _.

3 __ _.

._ _ 1

2_ _ _.

3

3

2.45

2.40

3.54

6.2

6.8

6.0

30.4

27.4

30.4

.236

.242

.241

1.17

1.14

1.18

1.41

1.37

1.39

2.39

3.26

3.14

6.8

6.0

5.9

27.6

30.3

30.3

.238

.243

.239

1.14

1.18

1.18

1.37

1.40

1.40

2.42

2.40

3.37

6.1

7.2

6.0

30.2

27.5

30.0

.240

.240

.242

1.17

1.14

1.17

1.40

1.38

1.38

2.819

2.893 1.13 NS

6.33

6.47 <1 NS

29.34

28.87 <1 NS

.2401

.2410 <1 NS

1.163

1.158 <1 NS

1.388

1.382 1.3 NS

158 NS (0.995)

49 NS(0.99)

320 VS (0.995)

1.75 NS

100.5 NS (0.995)

3.42 NS

Parts per million

Cr _

Mo 2

Pb 2

V 2

Zn 2 __ _

1

2 _

3

3 _

1 _

2_ _

3 _ __

3 _ _

__ 2

3_

3 _ _

__ 1 _

2

3

3 ___

__ 1

2

3_ _

3

30

19

16

700

650

670

650

740

590

650

700

1,670

1,620

1,640

19

16

17

650

670

680

640

790

730

650

690

750

1,620

1,630

1,660

18

19

16

720

650

660

640

730

590

630

720

1,660

1,600

1,640

18.9

17.5 » (No test)

672.2

658.3 <1 NS

698.3 <1 NS

663.3

673.3 <1 NS

1,638

1,625 <1 NS

3 (No test)

24.47 NS (0.975)

30.25 NS (0.975)

27.0 NS (0.975)

6.97 NS

1 Kennecott Exploration, Inc., 3377 Carmel Mt. Rd., San Diego, CA 92121.

2 Data for element converted from percent, and nonsignificant zero added.

3 All variation in the analysis of variance due to days.

Analytical method:—1-g portions of the dried samples were digested in teflon beakers with hot HC1, HClO-i, and HF to form dense perchloric fumes. 

After making to volume, appropriate dilutions were made to bring concentrations of each metal to its optimum range for atomic absorption. Determinations were made without background corrections on a Perkin-Elmer model 305 atomic-absorption unit. In-house standards and analyzed samples, 

plus standards prepared from spectrographic-quality metals, were used to bracket the unknowns. Calibration curves were not used.
32 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 28.—Determinations of several elements in USGS-Nod-A-1 by atomic-absorption spectrometry by Wayne Mountjoy,

James G. Crock, and George Riddle, U.S. Geological Survey *

[Determinations in percent or in parts per million, as indicated. Alkalies, alkaline earths, and iron were determined by Mountjoy, and other elements by Crock and Riddle, d.f., degrees of freedom; NS, not significant. F ratios tested at Fo.ss or the fractile indicated in parentheses]

Element

FP

Mg _________

Ca _ _

Na ___ _ .

K __

Cu _ _ __ .

Ni __________

Ag __________

Cd __. __ .

Li ___ _ .

Pb __________

Rb 2 __ _ _.

Sr — __ _.

Zn _____ __ .

Run

. 1 __ _

2 _ __

. 1

2 __

. 1

2

. 1_

2

. 1-

2_ _

. 1

2 _

. 1

2

1

2 __ __

1

2_ _ _

1

2

. 1 _

2_ _ _

. 1 _

2 _

. 1

2 _ _

l

10.8

11.0

2.90

2.91

11.2

11.0

.77

.79

.518

.507

.1070

.1070

.5690

.5720

6

6

72

71

845

850

9

12

1,510

1,490

590

588

Bottle

2

10.9

11.0

2.90

2.91

11.1

11.1

.79

.79

.508

.513

.1060

.1090

.5800

.5750

7

7

72

72

855

855

9

13

1,500

1,500

608

590

3

Percent

10.8

10.8

2.87

2.87

11.0

11.1

.79

.77

.511

.503

.1070

.1070

.5600

.5750

Parts per million

7

6

72

73

845

855

10

13

1,500

1,500

593

597

Mean

10.88

2.893

11.08

.783

.510

.1072

.5718

^K

6.5

72

850.8

11

1,500

594.3

F

Bottle 

(2 d.f.)

2.00 NS

16.0 NS

<1 NS

<1 NS

<1 NS

1.78 NS

1.05 NS

<1 NS

1.0 NS

2.32 NS

2.94 NS

f Nn f-pq-M

<1 NS

ratio

Run 

(1 d.f.)

4.00 NS

(No test)

<1 NS

(No test)

<1 NS

1.21 NS

<1 NS

<1 NS

"Wrt fpaf

3.04 NS

98 NS(0.99)

<1 NS

<1 NS

1 Stop 928, Box 25046 DFC, Lakewood, CO 80225.

2 Determinations near the limit of estimation of the method.
TABLES OF DATA BY ANALYSTS 33

TABLE 29.—Determinations of several elements in USGS-Nod-P-1 by atomic-absorption spectrometry by Wayne Mount]oy,

James G. Crock, and George Riddle, U.S. Geological Survey 1

[Determinations in percent or in parts per million, as indicated. Alkalies, alkaline earths, and iron were determined by Mountjoy, and other elements by Crock and Riddle, d.f., degrees of freedom; NS, not significant. F ratios tested at Fo.ss or the fractile indicated in parentheses]

Element

Fe

Mg _________

Ca _

Na __ __ _.

K ______

Cu _ _

Ni _ _ _ _.

Ag __________

Cd _ _ __.

Li ___ _.

Pb __________

Rb _____ .

Sr _ __ __.

Zn __ __ _.

. 1 _ _

2 _

1-

2

. 1

2

. 1 _

2

. 1

2

1

2 _ _

. 1

2 _ __

1

2 _

. 1 _

2 __

. 1 _

2 _ _

_ 1

2

1

2 __ _

. 1

2 __ _

i

5.82

5.87

2.01

1.99

2.17

2.20

1.62

1.61

1.08

1.04

1.08

1.08

1.25

1.25

22

22

139

138

485

490

22

24

655

660

1.580

1,590

Bottle

2

5.80

5.84

2.01

2.01

2.20

2.19

1.62

1.62

1.08

1.04

1.08

1.08

1.21

1.23

22

23

139

136

480

495

24

24

655

660

1,570

1,600

3

Percent

5.81

5.93

2.01

1 2.00

2.20

2.21

1.60

1.61

1.07

1.04

1.06

1.08

1.26

1.26

Parts per million

23

22

139

134

490

490

21

23

645

660

1,600

1,600

Mean

5.845

2.005

2.195

1.613

1.058

1.077

1.243

<5

22.3

137.5

488.3

23.0

655.8

1,590

F

Bottle 

(2 d.f.)

1,2 NS

1.0 NS

1.0 NS

2.0 NS

<1 NS

2.0 NS

7.13 NS

(No test)

1.0 NS

<1 NS

3.08 NS

<1 NS

1.29 NS

ratio

Run 

(1 d.f.)

7.3 NS

3.0 NS

<1 NS

(No test)

100.5 NS (0.995)

2.0 NS

<1 NS

(No test)

6.75 NS

2.24 NS

4.15 NS

6.23 NS

2.29 NS

Stop 928, Box 25046 DFC, Lakewood, CO 80225.
34 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 30.—Chemical determinations of several constituents in USGS-Nod-A-1 by Sarah T. Neil, U.S. Geological Survey l

[Determinations in percent. Data, except those for F, Cl, S, Ni, Co, and Cu, were reported as oxides on sample portions not dried. All data were 

calculated to the dry basis by the individual determinations of HaO— (at 105°C), given in parentheses as the last entries in the table. Oxides were 

then converted to elements by gravimetric factors, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios 

tested at Fo.os]

or oxide

Si __________

Al _ ___ _

Fe ___ _ ____

Mg _________

Ca __ ____

Na _ __ _ __

K

H£ 0+ _ _____

Ti _ _ __

P __ ______

C02 ___ _____

F ____ _

Cl __ ________

S _____ __ _

Mn _ _____

Ni ____ __

Co __________

Cu _ ______

(H20-) _____

14/32

1.66

1.72 

1.94

1.97 

10.99

10.99 

2.86

2.92 

11.28

11.30

.88

.88 

.51

.50 

8.26

8.37 

.37

.38 

.53

.53 

11.80

12.09 

.10

.10 

.42

.44 

.40

.39 

18.03

17.80 

.65

.66 

.35

.33 

.12

.12 

(13.45)

(13.35)

Bottle

33/15

1.66

1.68 

1.90

1.90 

11.09

10.99 

2.92

2.93 

11.27

11.26 

.88

.87 

.49

.49 

8.29

8.40 

.38

.38 

.54

.53 

12.12

12.06 

.10

.10 

.41

.45 

.45

.43 

18.17

18.31 

.65

.65 

.34

.34 

.10

.12 

(14.12)

(14.02)

38/10

1.71

1.69 

1.90

1.96 

10.99

11.00 

2.91

2.90 

11.31

11.26

.87

.92

.49

.53 

8.38

8.41 

.38

.38 

.54

.54 

12.18

12.14 

.10

.10

.42

.42 

.39

.35 

18.21

18.24 

.65

.66 

.34

.35 

.12

.10 

(13.82)

(13.79)

Mean

1.69

1.93

11.01

2.91

11.28

.88

.50

8.35

.38

.54

12.07

.10

.43

.40

18.13

.65

.34

.11

Standard

Bottle 

(d.f.=2)

Neg.

0.02

Neg.

N^p1

Neg.

Neg.

Neg.

N^P*

.00

.00

.07

N^p1

.03

.17

N^p1

Neg.

Neg.

deviation

Error 

(d.f. = 3)

0.03

.03

.04

.03

.02

.02

.02

.06

.00

.00

.12

09

.02

.11

.01

.01

.01

F

ratio

0.64 NS

2.02 NS

.90 NS

.97 NS

.70 NS

.50 NS

.76 NS

.78 NS

1.00 NS

3.00 NS

1.62 NS

fNn tA«H

.20 NS

7.19 NS

5.50 NS

.50 NS

.20 NS

.50 NS

1 Menlo Park, CA 94025.

Analytical methods:—

Gravimetry: Total H»O (Penfield); HiO—; SiO-; AhO.i (weighed as A1PCU); CaO (weighed as CaCO:i); i»lKO (weighed as MgaPaO); and total S 

(weighed as BaSOO.

Other methods: Na»O and K:;O, by flame photometry; TiOa, by spectrophotometry with Tiron; PaOs by spectrophotometry with molybdovanadate method; 

Ni, Co, and Cu, by atomic-absorption spectrometry; total Fe, by spectrophotometry with orthophenanthroline; F, by F- electrode; Cl, by spectrophotometry using Fe(CNS):i; COa, as total C, by combustion with Leco WR-12; and total Mn, volumetrically with sodium bismuthate.
TABLES OF DATA BY ANALYSTS 35 

TABLE 31.—Chemical determinations of several constituents in USGS-Nod-P-1 by Sarah T. Neil, U.S. Geological Survey 1

[Determinations in percent. Data, except those for F, Cl, S, Ni, Co, and Cu, were reported as oxides on sample portions not dried. All data were 

calculated to the dry basis by the individual determinations of HaO— (at 105°C), given in parentheses as the last entries in the table. Oxides were 

then converted to elements by gravimetric factors, d.f., degrees of freedom; NS, not significant; Neg., negative bottle variance obtained. F ratios 

tested at Fo.95 or the fractile indicated in parentheses.]

Element 

or oxide

Si __ _____

Al ____ __

Fe _ __ ____

Mg __ _ __

Ca __________

Na . _______

K __ _ ___

H2 0+ _ _ __

Ti _________

P _ __ ____

CO. _________

F __ _____

Cl __________

S _ ________

Mn __ ______

Ni __________

Co __ ___ _

Cu __ ______

(H.O-) _ ____

'Menlo Park, CA 

Analytical methods:- 

Gravimetry: Total

21/10

6.60 

6.56 

2.47 

2.48 

5.95 

5.95 

2.04 

2.08 

2.26 

2.27 

1.74 

1.72

1.06 

1.04 

8.47 

8.47 

.36 

.36 

.20 

.20 

.81 

.81 

.04 

.03

.17 

.11 

.20 

.20 

29.78 

29.67 

1.35 

1.37 

.25 

.25 

1.18 

1.18 

(6.70) 

(6.70)

94025. 

H2O (Penfield);

Bottle

23/3

6.57 

6.55 

2.47 

2.43 

5.95 

5.92 

2.03 

2.06 

2.26 

2.32 

1.73 

1.73

1.05 

1.04 

8.59 

8.53 

.38 

.36 

.21 

.22 

.83 

.84 

.03 

.04

.10 

.12 

.20 

.17 

29.79 

29.88 

1.40 

1.37 

.25 

.26 

1.15 

1.20 

(7.19) 

(7.25)

H»O— ; SiOa; Ahl

36/8

6.56 

6.55 

2.48 

2.49 

5.97 

5.94 

2.06 

2.18 

2.37 

2.40 

1.72 

1.74

1.04 

1.05 

8.62 

8.72 

.37 

.37 

.21 

.21 

.80 

.85 

.03 

.04

.12 

.11 

.20 

.22 

29.74 

29.58 

1.37 

1.38 

.24 

.24 

1.19 

1.15 

(6.39) 

(6.29)

3:s ( weighed as

Mean

6.57 

2.47 

5.95 

2.08 

2.31 

1.73

1.05 

8.57 

.37 

.21 

.82 

.04

.12 

.20 

29.74 

1.37 

.25 

1.18

A1PCM; CaO

Standard deviation

Bottle 

(d.f. = 2)

0.00 

.01

Neg. 

.01 

.06 

Neg.

Neg. 

.09 

.00 

.01 

Neg. 

Neg.

Neg. 

.01 

.06 

.01 

.01 

Neg.

(weighed as CaCOs); MgO

Error 

(d.f. = 3)

0.02

.02 

.02 

.05 

.03 

.01

.01 

.05 

.01 

.00 

.02 

.01

.03 

.01 

.09 

.02 

.00 

.03

( weighed

— F

ratio

1.00 NS 

2.17 NS 

.72 NS 

1.12 NS 

10.46 NS (0.975) 

.00 NS

.17 NS 

8.85 NS 

1.00 NS 

7.00 NS 

.73 NS 

.00 NS

.76 NS 

1.46 NS 

2.05 NS 

1.36 NS 

7.00 NS 

.07 NS

as MgsPaO?); and total £

(weighed as BaSOi).

Other methods: Na°O and KaO, by flame photometry; TiO2, by spectrophotometry with Tiron; P2Os by spectrophotometry with molybdovanadate method; 

Ni, Co, and Cu, by atomic-absorption spectrometry; total Fe, by spectrophotometry with orthophenanthroline; F, by F~ electrode; Cl, by spectrophotometry using Fe(CNS):-.; CO2, as total C, by combustion with Leco WR-12; and total Mn, volumetrically with sodium bismuthate.
36 USGS ROCK STANDARDS: MANGANESE NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 32.—Averages of determinations of elements

[Averages in percent or in parts per million as indicated. Averages are indicated by the table number and the number of determinations (w) for

surviving the selection process

Table No. .. __ .

Element

Si ____ __ __

Al _ _ _

FP

Mg _____ ____

Ca __ __ _ ____

Ca - _ ____

Na

K _ _ ___

Ti ____ _ _

Mn _______

P _ _ _ _

Co ___ _ _ _

Co - ________

Cu __ _ ___

Ni __________

C02 _________

H2 0+ ___ _

AcAc

Rn

Be _____ -

Cd ____ _

Ce _ _ _ —

Cl __ _

Cr __ _ _ _

Eu _ _

Gd _ _ _ _

Hf _ ______

La __ _ _

Li __ ____

Lu _ _____

Mo _ _ —

Nd __ — _

Pb _ — __

Rb ___ _ _

Sb ___ ___

Sc ___ _

Sm _ _ _

Sr _ __

Tb — ______

Th __________

Tl _________

Tm _________

U _ _____

V _ _ _ __

Y

Yb _ _____

Zn __ _______

Zr

7 28 9 22

n—6 w=6 w=6 w=3

Percent

_.._ _ _ __ _ _ 1.82 _ _

1.75

10.88 10.88 10.86 10.6

_ _ 2.89 2.85 _ __

__ _ _ 11.08 11.17

_ _ _ .78 .80 _ —

__ __ .510 .50 _____

_ _ _ __ .32

18.40 16.9

_ _ _ _ .42

.2527 _ _ .326 .30

.1072 .112 .088

.5718 .648 .61

Parts per million

_________ <5 _____ _____

1,518 _ _ __ _ —

6.5

668 _ _ _

] 25.9 _ _ __

4.48 _ _ _ __

26.5

6.2 _ _ _

132.5

_ ____ 72 __ _

2.16

85.3 _

851

__ _ 11 __ _ _

33.5 _____ __ _ __ _____

11.23 _____ _ _ _ __ _

20.9 _ __

1,500

4.87 _ _ __ _ __

25.8 _ _ __ _____

'1.72 _ _ _ ____

5.95 _ __ _ __

16.3 _ _ ____

594 __ 46o

11 12 14

n = G n = 6 wrr6

__ __ __ 1.42

1.7 2.27

_ _ 9.7 10.98

_ ___ 3.20

11.42

.17 .48

_ _ _ _ __ .29

13.7 18.64

__ _ __ _ .59

.31 .39

.11 .18

.64 .57

11.64

298

2,7oo 1,671

36o 460

95o 1,323

- _ _ __ 10

l,8oo 1,728

27.35 _ __ _______

6.86

59o 870

1 Average of four. - Average of three.
AVERAGES FOR USGS-NOD-A-1 BY ALL ANALYSTS 37 

in USGS-Nod-A-1 by all contributing analysts

each average. Lower case letter "o" indicates nonsignificant zeros added to values for trace-element averages. Bold-faced numbers indicate averages 

and estimates calculated from them]

Si __ -

Al

Fe

Mg __ ___

Ca

Ca _ __.

Na

K __ ___

Ti _______

Mn ____

P

Co ____ .

Co ____

Cu _ _

Ni ______

C02 __ _

H20+

Ag __ _

As

Ba _ _ _

Be __ _

Cd

Ce __ _

Cl _____

Cr _ __ _

Eu _ ___

Gd ______

Hf _ _

La ______

Li ___ _

Lu _

Mo _ _

Nd _ __ .

Pb ___ .

Rb _ __.

Sb ___ .

Sc _ __.

Sm

Sr __ _.

Tb _ .

Th __ _ .

Tl

Tm _ _ .

U ___ .

V

Y _ __ .

Yb __ .

Zn ___ .

Zr _ _ .

16 18 20 24 26 23 30

n = G n = G n = G n = 3 n = G n = 3 n = 6

Percent

2.00 1.63 1.73 1.83 _ _ _ 1.69

2.06 1.86 _ 3.26 2.04 _ 1.93

11.08 10.29 10.91 11.02 11.4 10.2 11.01

2.80 2.74 2.93 2.86 _ _ 2.91

10.97 11.30 11.00 11.22 __ _ _ __ 11.28

_ _ _ _ — _ 11.07 ____ _____

.77 __ .82 _ _ .88

.52 .40 .46 .46 _ __ .50

.28 .32 .28 _ __ .38

17.80 18.63 18.51 18.51 17.6 17.3 18.13

.60 .53 .53 _ _ .54

.3128 .281 .313 .34 .336 .28 .34

322

.1052 .107 .109 .111 .112 .11 .11

.6300 .625 .637 .71 .657 .59 .65

11.61 _ _ 12.07

~7.9 _ 8.35

_ __ _ _ __ __ ____ 5.30 ___ __ _ _ _ _

Parts per million

1,668 __ 2,32o l,8oo _ _

5.6 __ _ ____-_- __ ___

23 _ __ __ 24 _

76.3 _ _ _ ____ _ _ _ _ __ _

457 567 514 41o 428

793 _ 84o 96o * 1,267 _ _ __ _

1,660 _ l,77o l,72o _ _ _ ____

._ —— — — _ _ 61 _ __ __ __ ___ __ _ _______

586 916 610 817 __ __ __

559 574 62o 65o 592 _ _ _ _

"Best"

value

1.78

2.05

10.93

2.87

11.03

.775

.50

.32

18.54

.60

.311

.11

.636

1,670

448

846

1,748

770

587
38 USGS ROCK STANDARDS: MANGANESE-NODULE SAMPLES USGS-NOD-A-1, USGS-NOD-P-1

TABLE 33.—Averages of determinations of elements in

[Averages in percent or in parts per million as indicated. Averages are indicated by the table number and the number of determinations (n) for

surviving the selection process

Table No. _______

Element

Si AI

Fe

Mg _ _

Ca __ __ __

Na — _ ______

K _

Ti _ _ _

Mn __ —

p

Co __ ____

Co _ _ __ _

Cu _ _

Ni __ ___

C02 _ _____

H20+ _______

Ag __________

As _ —

Ba _ - _

BP

Cd __ __ —

Ce _ _____

Cl _ _ __

Cr _ __ __

Eu _ _

Gd __ __ _ _

Hf __ __ __

La _ ____ _-

Li __ __ __

Lu __ __ _

Mo _ _ _ _

Nd _ _

Pb _ _ —

Rb — _ ____

Sb _____ __

Sc _ __ _

Sm_ __ __

Sr _ _ _____

Tb _ — __

Th _ ____

Tl ____ .__

Tm _ _ _ __

U _ _ _

V _ — _ _

Y _ __ _ __

Yb — -_ ——

Zn

Zr

8

n = 6

5.76

.1808

1 2,498

289

~15

6.57

29.4

4.3 '120

1 1 gg

112.8

50.1

9.47

30.4

5.31

17.0

1.77

3.5

J 13.8

29 10 22

n = 6 n = 6 n = 3

Percent

6.64 __ _

1.97 ___

5.84 5.73 6.45

2.00 1.98

2.20 2.20 - -

1.61 1.68

1.06 .99

_ __ _ .31

__ _ 29.19 27.3

.17

.220 .22

1.08 1.20 1.11

1.24 1.40 1.26

Parts per million

<5 _____ _____

22.3

137.5

488 __ _ __

23 __

656 _ _ _____

1,590 _ ____

11 13 15

n = 6 n = 6 n = 6

__ _ _ 6.65

_ _ 1.8 2.59

5.2 4.76

_ __ _ 2.08

2.16

.28 1.14

_ _ _ .30

_ _ 25.5 29.06

__ .21

.22 .28

1.2 1.04

_ _ 1.4 1.28

_ __ _ __ 1.39

39

6,7oo 3,453

63o 823

_ _ 52o 715

_ _ _ __ 21

_ _ l,08o 751

17.65 ____ _______

4.28 __ _

_____ 89

_ _ l,6oo 1,998

_ _ _ 280

1 Average of four.
AVERAGES FOR USGS-NOD-P-1 BY ALL ANALYSTS 39 

USGS-Nod-P-1 by all contributing analysts

each average. Lower case letter "o" indicates nonsignificant zeros added to values for trace-element averages. Bold-faced numbers indicate averages 

and estimates calculated from them]

Si _ __ _

Al

Fe ______

Mg _

Ca _ ___

TVTa

K _ __ _

Ti _ _____

Mn _______

P ______

Co _______

Co _ _____

Cu _ _

Ni _ ___

C02 ______

H2 0+ ____

Excess 0 _

Ag _______

Ac

Ba _ _—

Be _____

Cd _______

Ce

Cl __ __ __

Cr _____

Eu _ ___

Gd _______

Hf __ ____

La _ __

Li __ ___

Lu _

Mo _ _

Nd -

Pb ______

Rb __ _ _

Sb _ __ __

Sc _ ___

Sm _ _

Sr - _____

Tb _ __

Th __ __

Tl _____

Tm _ _ __

U _ ______

V _ _____

Y ___ _

Yb ______

Zn ______

Zr _______

17 19

n=6 n = 6

6.97 6.36

2.41 2.56

5.81 5.52

1.98 1.80

2.16 2.20

1.63 _ _

1.04 .93

.28 .29

29.17 29.93

_ _ .20

.2280 .201

1.137 1.16

1.328 1.32

2,862

2.8

20

142

802 982

436

638 _ _

480

1,467 l,51o

21 25 27

nr=6 n = 3 n = 6

Percent

6.38 6.82

__ _ 3.85 2.89

6.05 5.91 6.47

2.00 1.98

2.20 2.07 - ____

1.65

1.05 1.01 _ _

_ __ _ .28 __ _

29.86 29.92 28.87

.20 .21

.227 .26 .241

231

1.15 1.35 1.16

1.35 1.56 1.38

.76

~8.2 _ __ _

8.41 ___ _

Parts per million

3,74o 2,9oo

_ _ l,4oo

17.5

678 74o 658

47o 54o 698

~900 75o

154

548 53o 673

l,66o l,69o 1,625

23 31

n=3 n=6

6.57

2.47

5.04 5.95

_ _ 2.08

2.31

1.73

1.05

_ _ .37

27.8 29.74

.21

.20 .25

1.13 1.18

1.24 1.37

.82

8.57

l,2oo

"Best"

value

6.51

9 *»*»

5.78

1 44

214

1.64

1.05

.30

29.14

OA

.224

1.15

1.34

3,350

762

555

680

570

1,595

a U.S. GOVERNMENT PRINTING OFFICE: 1980 O—311-344/81