Contributions to 

General Geology 

1955

GEOLOGICAL SURVEY BULLETIN 1021

This bulletin was printed 

as separate chapters A-N

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1958
UNITED STATES DEPARTMENT OF THE INTERIOR 

FRED A. SEATON, Secretary

GEOLOGICAL SURVEY 

Thomas B. Nolan, Director
CONTENTS

{The letters in parentheses preceding the titles designate separately published chapters]

^ (A) Hafnium content and hafnium-zirconium ratio in minerals and rocks, 

^ by Michael Fleischer ~ -_ 1 

(B) Hawaiian volcanoes during 1952, by G. A. Macdonald 15 

4 <C) Geologic and airborne radioactivity studies in the Rock Corral area, 

San Bernardino County, California, by R. M. Moxham, G. W. 

Walker, and L. H. Baumgardner___ 109 

(D) Hawaiian volcanoes during 1953, by G. A. Macdonald and J. P. Eaton. 127 

' (B) Geology of Comb Ridge and vicinity north of San Juan River, San

Juan County, Utah, by J. D. Sears... _ __ __ _ _ _ ___ 167

<F) Ordovician and Silurian coral faunas of western United States, by 

^ Helen Duncan ____ ___ ____ __ 209

<G) Some curves from a portable differential thermal analysis unit, by

0. J. Parker, J. C. Hathaway, and P. D. Blackmon _ _ _ 237 

(H) Annotated bibliography of Alaskan Paleozoic paleontology, by J. 

k Thomas Dutro, Jr ___ _ _____ __ __ _ ___ __ __ 253

<I) Geology of Devils Tower National Monument, Wyoming, by 0. S.

Robinson _____ - _ ____ ___ . ____ - 289

< J) The problem of the Cochrane in late Pleistocene chronology, by T. N.

V. Karlstrom __ _ _ __ _ __ __ _ _ _ _ _ __ 303

4. <K) Geology of the Atomic Energy Commission Nevada proving grounds

area, Nevada, by M. S. Johnson and D. B. Hibbard ________ ___ 333

(L) Geology of the area east and southeast of Livingston, Park County,

Montana, by P. W. Richards- ____ >__. 385 

s (M) Ordovician fossils from wells in the Williston basin, eastern Montana,

by R. J. Ross, Jr_ ___ _.__ __ ___ _ __ __ __ _______ ___ 439

* (N) Geology of the Clarkdale quadrangle, Arizona, by R. E. Lehner 511
Hafnium Content and 

Hafnium-Zirconium 

Ratio in Minerals 

and Rocks

GEOLOGICAL SURVEY BULLETIN 1021 -A

Hafnium Content and

- Hafnium-Zirconium

* Ratio in Minerals 

v and Rocks

* By MICHAEL FLEISCHER

* A CONTRIBUTION TO GENERAL GEOLOGY

» GEOLOGICAL SURVEY BULLETIN 1021-A

A compilation of all published 

determinations of the hafnium dioxide 

content and the hafnium-zirconium 

ratio of minerals and rocks

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1955
UNITED STATES DEPARTMENT OF THE INTERIOR

Douglas McKay, Secretary

GEOLOGICAL SURVEY 

W. E. Wrather, Director

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

Washington 25, D. C. - Price 15 cents (paper cover)
w CONTENTS

* Page

Abstract_____-__-__-_-___-_____-_-___-___-_--_-_-_---_-_-____ 1

 * Introduction..____________________________________________________ 1

Hafnium and zirconium content and the ratio Hf/Zr in the earth's crust

and in rocks--__-_-----_--__---_-_-___-___-_--__-___---__-______ 2

., Hafnium and zirconium content and the ratio Hf/Zr of minerals.. _______ 2

Annotated bibliography.___________________________________________ 11

TABLES

TABLE 1. Estimated abundances of hafnium and zirconium in the earth's

crust and the ratio Hf/Zr________________________________ 3

2. Hafnium and zirconium content and Hf/Zr ratio of rocks______ 4

3. Composition of minerals listed in tables 4-8_______________ 4

4. The hafnium and zirconium content and the Hf/Zr ratio in

zircon______________.____________________!___________ 5

5. The hafnium and zirconium content and the Hf/Zr ratio in

varieties of zircon___________________________.__________ 7

6. The hafnium and zirconium content and the Hf/Zr ratio in

zirconium oxide minerals and ores-_______________________ 8

7. The hafnium and zirconium content and the Hf/Zr ratio in

zirconium silicates._____________________________________ 9

8. The hafnium and zirconium content and the Hf/Zr ratio in

other miscellaneous.minerals____--__________---_-_-______ 10

9. Averages of Hf/Zr ratios of minerals according to source_____ 10

nx

A CONTRIBUTION TO GENERAL GEOLOGY

HAFNIUM CONTENT AND HAFNIUM-ZIRCONIUM RATIO 

IN MINERALS AND ROCKS

By MICHAEL FLEISCHER

ABSTRACT

All published data on the hafnium content and hafnium/zirconium ratio in 

minerals and rocks have been compiled. The Hf/Zr ratio is probably about; 

0.02 in the earth's crust. Minerals from alkalic rocks such as nepheline syenites 

have lower Hf/Zr ratios than does zircon from granitic rocks. Minerals from 

granitic pegmatites have the highest Hf/Zr ratios, especially some peculiar varieties 

of zircon such as alvite, cyrtolite, and naegite, and the rare scandium silicate, 

thortveitite, which is the only mineral that is reported to contain more hafnium 

than zirconium.

INTRODUCTION

This report is a compilation of all published determinations of the 

hafnium content and the hafnium/zirconium ratio of minerals and 

rocks. The published literature has been scanned with the aid of 

the notched-card file on geochemistry of the U. S. Geological Survey. 

In addition, the following bibliographies on zirconium were checked:

Voress, H. E. and Croxton, F. E., 1951, Zirconium, a bibliography of unclassified

literature: U. S. Atomic Energy Commission, TID-3010, 138 p., and supp.

no. 1, 17 p. 

Williams, G. C., Baker, E. G., Jr., Holzknecht, E. W., and Moody, R. G., 1950,

Zirconium and hafnium a bibliography: U. S. Atomic Energy Commission,

NYO-1008, 236 p.

Few of the data are recent. The methods of determination and the 

estimated error of each study are given in the annotated bibliography. 

It is probable that determinations of hafnium by purely chemical 

methods or by determination of the density of the mixed oxides of 

zirconium and hafnium are of low accuracy.

Most of the determinations cited are by Hevesy and coworkers. 

Probably some samples are given more than once in the tables, as 

redeterminations were made on many of their samples. The sample 

descriptions are inadequate, so that it is not known whether two sets of 

figures for material from a given locality refer to the same sample or 

to different samples.

Most of the samples that have been analyzed have not been well 

characterized as to the t}Tpe of geological occurrence, so that only a few

320233 54 1
2 CONTRIBUTIONS TO GENERAL GEOLOGY

broad generalizations can be made as to the variation of the hafnium/ 

zirconium ratio in rocks and minerals from different types of deposits. 

New analyses of carefully selected samples of known geologic setting 

are highly desirable.

HAFNIUM AND ZIRCONIUM CONTENT AND THE RATIO 

HF/ZE IN THE EARTH'S CRUST AND IN ROCKS

Estimates of the abundances of zirconium and hafnium are assembled in table 1. It will be noted that most of the recent estimates 

are the same. The estimates for zirconium are based on the analysis 

of many samples by Hevesy and Wiirstlin (1928), but the estimates for 

hafnium are not so well established.. Very few rocks have been analyzed directly for hafnium, as shown in table 2. The estimates for 

hafnium are based largely on analyses of zirconium minerals, especially 

of zircon, as given in tables 4-8, and it is uncertain whether the different rock types have been sampled well enough to give confidence in 

the values given for the ratio Hf/Zr.

HAFNIUM AND ZIRCONIUM CONTENT AND THE RATIO 

HF/ZR OF MINERALS

The available data are given in table 4 for zircon, table 5 for alvite, 

cyrtolite, and other similar varieties of zircon, table 6 for baddeleyite 

and other zirconium oxide minerals, table 7 for zirconium silicates, 

and table 8 for miscellaneous minerals. A list of the mineral names

used in these tables is given in table 3, with the chemical formulas.

In each table, the determinations are grouped by minerals and, for 

each mineral, geographically in the order North America, South 

America, Greenland, Europe, U. S. S. R., Asia, Australia, and Africa.

As the type of deposit is not stated for many of the samples, particularly for zircon in table 4, averaging by type of deposit is not here

attempted. It should be noted that all or nearly all the samples of

alvite, cyrtolite, and otker similar varieties of Zircon, listed TH tftblft 5,

and of thortveitite and other minerals listed in table 8 are from

granitic pegmatites, whereas baddeleyite in table 6, and the zirconium

silicates, table 7, are all from nepheline syenite pegmatites or similar

alkalic rocks, The minerals from granitic pegmatites show very high

Hf/Zr ratios; those from alkalic rocks distinctly low Hf/Zr ratios.

Hevesy ^192Oa} and Hevesy aiid Jaxibison. (1£>2G) Ixo-^o g-i-^ojo. avox-o-g-os

of their own determinations; these are tabulated in table 9,

Some of the samples that have high ratios of Hf/Zr have high contents of rare earths, -uranium, and tKorium. There is not, however, a

close correlation between radioactivity and hafnium content in most

zircons.
HAFNIUM CONTENT AND HF/ZR RATIO IN MINERALS AND ROCKS 3

In view of the very high Hf/Zr ratios of the pegmatite minerals of 

tables 5 and 8, it is somewhat surprising that higher ratios are notreported for some of the zircons listed in table 4. New determinations 

of the hafnium content of zircon separated from analyzed pegmatite 

rocks, granites, granodiorites, and diorites might help to fill this gap 

in our knowledge. The Geological Survey, in the course of its work 

on the determination of geological age by analysis of zircon, has 

separated such zircon. This should be an excellent collection on 

which to determine Hf/Zr ratios.

TABLE 1. Estimated abundances of hafnium and zirconium in the earth's crust

and the ratio Hf/Zr

No.

1

2

3

4

6 

6

7

8

9

10

11

Percent by weight

ZrOa

0.030

.030

.028

.031

.030

.034

.031

.031

.035

HfOs

0. 00058

.00058

.00058

.0029

.00058

.00047

.0029

.0029

.0035

Ratio 

Hf/Zr

0.020

.020

.021

.109

.020

.016

.109

.109

.115

.034

».020

References

/

?

(

Hevesy (1925a).

Hevesy and Wurstlin (1928).

1 Quoted in Fleischer (1953) from the following: 1. Mason, 1952; 2. Rankama and Sahama,r1950; 3. Polanski, 1948; 4. Anderson, 1945; 5. Goldschmidt, 1937; 6. Fersman, 1933; 7. Schneiderhohn, 1934; 8. Berg, 1929; 

9. Olarke and Washington, 1924.

HfOs »Ratio, . 

ZrOa+HfO>
4 CONTRIBUTIONS TO GENERAL GEOLOGY

TABLE 2. Hafnium and zirconium content and Hf/Zr ratio of rocks

No.

1

2 

3

4 

5 

6 

7 

8

Material

Percent by weight

ZrOs

0.008

.019

.062

.12 

.026 .039' 

.019

HfOa

0. 0028 

. 00038 

.001 

.0001

Ratio 

Hf/Zr

0.027 

.017 

.029 

.008

References

Hevesy and Wurstlin 

(1928). 

Do. 

Do. 

Do. 

Bahama (1945). 

Hevesy (1931). 

Troger (1935). 

Landergren (1935).

1

1 Spectrographic determination on a mixture of 34 granites.

2 X-ray spectroscopic determination on a mixture of 300 igneous rocks that contained 56.3 percent SiOs.

3 Spectrographic determination on ore that contained 30 percent Si02.

TABLE 3. Composition of minerals listed in tables 4~8

Mineral

Alvite i----.------

Baddeleyite-.......

Caldasite--.._... 

Catapleite.------.

Cyrtolite__.._.. 

Elpidite---------.

Eudialyte-eucolite. 

Euxenite. ..- ---.. 

Favas.- __--...

Fergusonite 

Hagatalite---.- 

Malacon.--..... 

Naegite.---.--- 

Oyamalite.-... 

Pitchblende.--. 

Polymignite. - - 

Pyrochlore.-.-. 

Rosenbuschite. 

Thalenite...--- 

Thortveitite..-. 

Wohlerite.---.. 

Yamagutilite--. Zircon---..___ 

Zirkelite-----.- 

Zirkite-----.-.

Composition

ZrSi04 containing rare earths, BeO, U, and Th.

ZrO2 .

Zirconium oxide ore, chiefly baddeleyite.

(Na2 ,Ca)ZrSi309 .2H2 0.

See alvite.

Na2 (Zr,Ti)SieOi5.3H2 0.

(Ca,Na) 5Zr2 Si6(0,OH,Cl)2o.

(Y.Ce.U) (Nb,Ta,Ti)2(0,OH)6.

Pebbles in gravel. Commonly baddeleyite, may also be

zircon.

(Y,Er) (Nb,Ta)04 . 

See alvite. 

See alvite. 

See alvite. 

See alvite.

UOjwith UCh, ThOz. 

(Ca,Fe,Y,Zr) (Nb,Ta,Ti)04 . 

(Ca,Na) (Nb,Ti) 2Oe(OH,F). 

(Ca,Na) 3 (Zr,Ti)Si2OsF. 

Y2 Si2 07. 

(Sc,Y)jSi2 07.

NaCa2 (Zr,Nb)Si!08(0,OH,F). 

See alvite. ZrSiO*.

(Ca.Fe) (Zr,Ti) 2 O5 (?). 

Commercial name for zirconium oxide ore.

1 Alvite, cyrtolite, hagatalite, malacon, naegite, oyamalite, and yamagutilite are names given to varieties 

of zircon. Some of the names are not well denned, but in general they apply to varieties of zircon that

contain appreciable water and may contain rare earths, uranium, tnorium, beryllium, and P205. Some

of this material may not be zircon.
HAFNIUM CONTENT AND HF/ZR RATIO IN MINERALS AND ROCKS 5

TABLE 4. The hafnium and zirconium content and the FIf/Zr ratio in zircon

C, Chemical separation as phosphate; D, Hf center 

 ,Hf)02; S, Spectrographic; XS, X-ray spectroscopic]

[Methods of analysis arc designated as follows: C, Chemical separation as phosphate; D, Hf content computed from density of mixed oxides (Zr,r " "

No. and locality

2. North Carolina, Henderson 

County. 

3. Do........................

4. Do... ..... .............

5. Do........... .............

7. Pennsylvania, Berks County.

9. Do'....-...- ..........

10. Do........ ...........

12. Ontario......---.-....-......

15. Brazil. ........ ------.--..---.

16. Do............ ...........

17. Do...... .............

18. Do.......... .............

19. Do......... ..........

20. Brazil, Minas Gerais1 .........

21. Brazil. Minas Gerais, Pogos 

de Caldas. 

22. Do....-.-.--. ......

23. Do.......... .............

24. Do...-............ ....

25. Do.......... .............

26. Do............ ....

27. Do - -.

28. Brazil*....... ...............

33. Do..-.,. ._- 

34. Do.. . - -..-. ..--..

35. Do.-.-.-. _ - __

36. Italy, Loncdo. _ . ...........

37. Do,- . . 

38. Italy, Novale...- - ._

40. Italy, Vicenza ... _ . _ ...

41. Do................. ......

45. Do.. .......... ...........

47. Do. . . 

49. Do -. .

50. Portusok.... __ .- ___ . ...

51. Avigait ...............

52. Schluchtsee 9 _ ...... . .....

53. Do'.,........ ...........

54. U. S. S. R. .............

55. Do........ ............

56. Do ........... .......

57. Do..... ..................

58. Do.......... .............

59. Do..... ---...... ..

60. Do......... ..............

61. Do......... ..............

62. Do ....................

63. Do...... ........... ......

64. Do..... ..................

65. Do.......... .............

66. Do ._ .

67. Do.. .......... __ ...

68. Do.... ...... .............

69. Do...... .................

70. Do.... ................

71. Do...... .................

Percent by 

weight

Zr02

2(66. 5) 

2(59.5) 

2(59.7)

63.7

64

65 

64.23

64.83

60.55 

63.05 

63.96 

65.2

HfCh

1.0

4.0

1.3

1.0

1.1 

.8 

.6

.6

1.2

1.3 

1.0

1.0

1.8

1.0

.4 

3 

.8

4

1.8 

1.1

.7

1.2 

.7

.7

.9

.7

.8

1.8

3.5 

1.0 

2.8 

1.0 

1.7

2.2

6

.2

.24

.35

.35

.5

.5

.6

.6

.6

.6

.7

.7

.7

.8

.8

1.2

1.2

1.3

Ratio 

Hf/Zr

0.016

.027 

.026 

2 (.018) 

2 (.016)

2(.011)

.023 

<.010

.008 

.015 

.010 

.023

<.014 

«.014 

<.017 

«.017 <0 

.007

.07 

.032

.021

.066 

.018 

.05 

.018

2 .035 

2.015 

2.021 

2 .026 

2.0024

Method 

of 

analysis

XS 

XS

xs 

s

D

S

s 

s 

s 

s 

s 

xs 

xs 

xs

s 

s 

s 

xs 

xs 

xs 

xs

D

c 

c 

c 

c 

c 

xs 

xs 

xs

xs

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs

D

xs 

xs 

xs 

xs 

xs 

xs xs xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs 

xs xs 

References

Hevesy and Jantzen (1925). 

Hevcsy (1925b); Hevesy and Jantzen 

(1925). 

Hevesy and Jantzen (1923). 

Cocley and others (1953). 

Prandtl, Mayor, and Buttner (1937). 

Coolcy and others (1953). 

Do. 

Larscn, Waring, and Berman (1953). 

Do. 

Do. 

Cooley and others (1953). 

Hevesy and Wttrstlin (1928). 

Hevesy and Jantzen (1925). 

Hevesy (1925b); Hevesy and Jantzen 

(1925). 

Cooley and others (1953). 

Do. 

Do. 

Hevesy and Jantzen (1923). 

Hevesy and Jantzen (1925). 

Do. 

Do.

Prandtl, Mayer, and Buttner (1937). 

Loewenstein (1952). 

Do. 

Do. 

Do. 

Do. 

Hevesy (1925b). 

Hevesy and Jantzen (1923). 

Hevesy (1925b); Hevesy and Jantzen 

(1925). 

Hevesy (1925b); Hevesy and Jantzen 

(1923). 

Hevesy and Jantzen (1923). 

Hevesy and Jantzen (1925). 

Do. 

Hevesy (1925b). 

Hevesy and Jantzen (1925) . 

Do. 

Do. 

Do. 

Hevesy (1925b). 

Hevesy and Jantzen (1923). 

Do. 

Hevesy (1925b). 

Hevesy and Jantzen (1923). 

Hevesy (1925b). 

Hevesy and Jantzen (1923) . 

Prandtl, Mayer, and Buttner (1937). 

Hevesy and Jantzen (1923) . 

Hevesy and Wurstlln (1928). 

Do. 

Do. 

Do. 

Do. 

Borovsky and Blochln (1937b). 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do.

See footnotes at end of table. 

820233 54 2
: CONTRIBUTIONS TO GENERAL . GEOLOGY .

TABLE 4. The hafnium and zirconium content and the Hf/Zr ratio 

in zircon Continued

No. and locality

72. U. S. S. R.8... ...............

73. Do.. ..................

74. .Do.......................

75. Do...... .................

76. Do.... ...................

77. Do. ......................

78. Do.......................

79. U. S. S. R., Botogolski......

80. U. S. S. E., Kukisvurochorr. 

81. U. S. S. R., Mariupol. .......

82. U. S. S. R., Poachvumchorr. 

83. U. S. S. R., Sludyanka (with 

allanite) . 

84. U. S. S. R., upper Tulia 

River. 

85. U. S. S. R., UralMts., Ilmen 

Mts. 

86. U. S. S. R., Ural Mts., Miask. 

87. Do.:.-.-......-.....-.-.

88. U. S.S. R., Rojkow Kluitsch.

90. India.'-..... ..............

91. Do.. ..__.. ._.__.._.

92. India » _____...._ _.

93. Ceylon... ........ _____ ...

94. Do..... ..................

95. Do... ....................

96. Ceylon'........... ......:...

97. Ceylon, Walawe Ganga... _

98. Slam... .....................

99. -Do ..................

100. Korea, Chinpyong-ni. . . ....

101. Korea, Pokchm-san.....' ....

102. Taiwan, Keelung River103. Australia...................

104. Do.... ...... ............

105. Australia, Queensland- ....-

106. Tasmania......... .........

108. Do........ ..............

109. Do.... ..................

112. Nigeria. . ...................

Percent by 

weight

ZrOa

46 

44 

59

66

66

59.92 

64.22

62.3 

64

60-67

66.0 

63.4

Hf02

1.0 

.7 

.7 

1.0

.5

.8

.7

.5

. 7-1. 0

.5

1.6

.5

1.0 

1.0

5.4 

1.1

.5

.9

2.7 

1.2 

2.0

2.7

1.0

2.1

2.0

3.5

4 

.79 

1.9

4.5

1.1

3 

.9

.7

.8

2.0

2.3 

6

Ratio 

Hf/Zr

0.029 

.021 

.016

.028

.018

.10 

.020

.020 

.05 

.021

.060- 

' .067

.014 

.034 

' .025

.019

.015

Method 

of 

analysis

XS 

XS

xs 

xs 

xs 

xs 

xs

xs

xs

D

xs 

xs

xs 

xs 

s 

xs 

xs 

xs 

xs

D

xs

D

xs

xs ' xs 

xs

s

D

s 

xs

xs

xs

D

' XS

D 

D

XS

References

Borovsky and Blochin (1937a). 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Kostyleva (1946). 

Do. 

Do. 

Borovsky and Blochin (1937a). 

Kostyleva (1940).

Borovsky and Blochin (1937a). 

Prandtl, Mayor, and Buttner (1937)

Hevesy and Jantzen (1923). 

Hevesy (1925b); Hevesy and Jantzen 

(1925). 

Hevesy (1925b). 

Borovsky and Blochin (1937b). 

Cooley and others (1953). 

Hevesy and Jantzen (1923). 

Hevesy (1925b). 

Hevesy and Jantzen (1923). 

Hevesy (1925b); Hevesy and Jantzen 

(1925). 

Prandtl, Mayer, and Buttner (1937). 

Hevesy and Jantzen (1925). 

Prandtl, Mayer, and Buttner (1937). 

Hevesy and Jantzen (1924). '_

Hevesy (1925b). 

Kimura and Tanaka (1936). 

Do. 

Do.

Cooley and others (1953). 

Prandtl, Mayer, and Biittner (1937). 

Cooley and others (1953). 

Hevesy (1925b). 

Hevesy and Jantzen (1923).

Hevesy ana Jantzen (1925). 

Prandtl, Mayer, and Buttner (1937). 

Hevesy (1925b) ; Hevesy and Jantzon 

(1925). 

Prandtl, Mayer, and Buttner (1937). 

Do. 

Hevesy and Jantzen (1923).

' Fresh.

2 Analysis for ZrOj made on materials from the same locality similar to but not identical with the sample 

analyzed for Hf.

3 Metamict.

* Ratio, Hf02

ZrOa+HfOj

{ Placer. . '. . . .

6 Acid rocks. . ...

* Basic rocks.

s Zircon ores. . .......

B Beccarlte. . ......

NOTE. In addition to above references see Morgan and Auer (1941).
HAFNIUM CONTENT AND HF/ZR RATIO IN MINERALS AND ROCKS 7

TABLE 5. The Hafnium and zirconium content and'the Hf/Zr. 

ratio in varieties of zircon

[Varieties of zircon: (A), alvite; (C), cyrtolite; (H), hagatalite; (M), malacon; (N), naegite; (0), oyamalite; 

and (Y), yamagutilite. Methods of analysis: D, By density of oxides; XS, X-ray spcctroscopic]

No. and locality

1. United States..... .......

2. United States, Kockport, 

Mass. 

3. Do . ..................

4. United States, Bedford, 

N. Y.

7. Do .. ........ .........

8. Do ' ~ ........

9. Do......... .............

10. Do ....... . .. ...

11. (?) ....... ..........

19 O\

15. Do...... ......... .......

18. Do ............. ......

19. U. S. S. R., Ilmen Gory.... 

20. U. S. S. R., Blumovskaya..

22. Do ...................

23. U. S. S. R., Rozhkov Klucz. 

24. U. S. S. R., Zap. oleniya 

varakh. 

25. Japan, Hagata.. ____ . ...

29. Japan, Yamaguti. _ ..... ...

31. Do -. ... ...

32. Madagascar, Ahi-Kambana..

Varieties of 

zircon

(C) 

(C)

(C) 

(C)

C) 

A) 

A) 

A) 

A) 

(A) 

(A) 

(A)

(A)

88(A) 

A 

(A) 

(M) 

(M-C) 

(0) 

(C) 

(M) 

(C)

(H) 

N) 

N) 

0) 

Y) 

M) 

M 

(M)

Percent by 

weight

ZrOa

40

44

........

41.98 

41.92

62.8 

65.18

47.9 

48.4

47.82

39.7 

48.30 

49.8 

38.7 

ca.40.2

53.2

HfOa

9 

>10

17 

ca. 5

2.36 

16 

3 

8 

15 

'4.6 

4.66 

5.9

9 

5 

2.6 

10 

25.5 

26.0 

.8

1.8

2.3

 1.8

2.6

1.70

2.3 

7 

3.5 

2.2 

ca. 3.4 

7 

4 

2.0

Ratio 

Hf/Zr

0.26 '.22

.44 

'.09-. 11

.........

.13 

.13

.088 

.046

.13 

.14

.041

.066 

.17 

.08 

.065 

.097

.086

Method 

of analysis

XS 

XS

XS 

XS

XS 

XS 

XS 

XS 

XS

xs 

xs . xs

xs 

xs 

xs 

xs

D 

D

XS

xs 

xs

xs 

xs

D

References

Hevesy and Jantzen (1923). 

Hevesy and Wurstlin (1928).

Hevesy (1925b). 

Hevesy and Wurstlin (1928).

Hevesy (1931). 

Hevesy and Jantzen (1923). 

Do. 

Do. 

.Do. 

.Hevesy (1925b). 

Bedr-Chan (1925). 

Borovsky and Blochin 

(1937b). 

Hevesy and Jantzen (1923). 

Hevesy and Jantzen (1924). 

Hevesy (1925b). 

.Hevesy and Jantzen (1923). 

Prandtl and others (1937). 

Do. 

Kostyleva (1940). 

Do. 

Hevesy (1931). 

.Kostyleva (1940). 

Do. 

Kostyleva (1946).

Harada (1936). 

Hevesy and Jantzen (1923). 

Hevesy (1925b). Harada (1936). 

Do. 

Hevesy and Jantzen (1924). 

Hevesy (1925b). 

Prandtl and others (1937).

1 Ratio, HfOi

ZrOa+HfOj

8 It is stated in this reference that the oxides recovered from a large amount of these samples contained 

2.2 percent HfOj.

NOTE. In addition to the above references see Morgan and Auer (1941).
8 CONTRIBUTIONS' TO.: GENERAL GEOLOGY ;

TABLE 6. The hafnium and zirconium content and the Hf/Zr ratio in zirconium

oxide minerals and ores

[Methods of analysis: C, Chemical fractionation of phosphates; D, By density of mixed oxides; 

S, Spectrographic; XS, X-ray spectroscopic]

No.

1 

2

3 

4 

5 

6 

7 

8 

9

10 

11 

12 

13 

14 

15

16 

17 

18 

19 

20 

21

22 

23

24

Name of mineral and locality

 do--- . - 

 do.. -

 .-do---..---- -.

Baddeleyite, Brazil, fava, shell . 

Baddeleyite, Brazil, fava, core_. 

Baddeleyite, Brazil, Pocos de 

Caldas. 

--.do..... ......... ...

..... do.. ......... ... 

 do 

 do. . 

Caldasite, Brazil, Pocos de 

Caldas. 

 do , 

 do 

Zirkite ore, Brazil ..............

Baddeleyite, Colorado (sic) J

Polymignite, Norway, Frederiksvarn.

Percent by 

weight

ZrOj

97.1 

97.7 

92.42 

91.12 

59 

74 

59 

74

73.2 

92.1

28.71

29.11 

51.7 

51.89

HfOs

1.8 

1.2 

.7 

2 

.5 

.5 

1 

1

2.1 

1.1 

1.4

.9

.6 

1.2 

1

Ratio 

Hf/Zr

0.021 

.014 

.009 

.025 

.010 

.008 

.019 

.015 

.013

.017 

.017 

'.002 

1.024 

1.022

1.034 

1.041 

.012 

.068 

.010 

.036

.024 

.026 

.022

Method 

of 

analysis

XS 

XS

xs 

xs 

xs 

xs 

xs

xs

s

D

c 

c 

c 

c 

c

c 

c

s 

s 

s 

xs

xs 

xs 

xs

References

Hevesy and Jantzen (1923). 

Hevesy (1925b). 

Do. 

Hevesy and Jantzen (1923) . 

Hevesy (1925b). 

Do. 

Hevesy and Jantzen (1923) .

Do.

Cooley and others (1953).

Prandtl and others (1937) . 

Loewenstein (1952). 

Do. 

Do. 

Do. 

Do.

Do. 

Do. 

Cooley and others (1953). 

Do. 

Do. 

Hevesy and Jantzen (1923; 

1924). 

.Hevesy (1925b). 

Hevesy and Jantzen (1924) . 

Hevesy (1925b).

HfOa ' Ratio'Zr02+Hf02

2 Baddeleyite is not known from Colorado, U. S. A.
TABLE 7. The hafnium and zirconium content and the Hf/Zr ratio in zirconium 

silicates, analyzed by X-ray spectroscopic methods

No.

1 

2 

3 

4

5 

6

7

8 

9

10

11 

12

13 

14 

15

16 

17 

18 

19 

20

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

31 

32 

33 

34

35 

36 

37

Name of mineral and locality

Catapleite, Greenland. _ . .......

Do.... ....................

Catapleite. U. S. S. R., upper 

Tulia Eiver. 

Oatapleitc, U. S. S. R.... ........

Do. 

Catapleite, U. S. S. R., Pereval 

Lopar. 1

Eudialyte, Greenland, Narsarsuk. 

Do........ ...................

Do.... ....................

Eudialyte, Greenland, Kangerdluarsuk.

Eudialyte, Norway, Barkevik. . . . 

Eudialyte, U. S. S. R., Kola 

Peninsula. 

Do.. ................ ... ...

Do... ................ ... ..

Do..... ......... ....... ...

Do..... ............. ......

Eudialyte, altered, U. S. S. R., 

Poach vumchorr.i 

Eudialyte, U. S. S. R. ...........

Do..... ...................

Do.. .. ---------------

Do. .... ... ......

Do..... ....... ............

Do...... .....................

Do.. ... .... .... .... ...

Do..... ... ..... ...... .... ....

Do. .... ... ... .... . ..... ..

Do..-- .- ... .... . ....

Do... ... ..... ... ...... ..

Elpidite, Greenland, Narsarsuk... 

Elpidite, Greenland, Narsarsuk ... 

Rosenbuschite, Norway, Langesund. 

Wohlerite, Norway, Langesund... 

Do..-- ...-... .........

Wohlerite, Norway, Barkevik _ __

Percent by weight

ZrOj

30.65 

31.53 

31.52 

30.5

14.30 

12-16

12-16

12-20 

14.32

14.47 

12.21 

13

19 

13

30

13.5 

2.0 

2.7

20.1 

20.28 

19.80

17.55

15.61

HfOa

0.2 

.3 

.3 

.6

.35

.1

.19 

.2

.6

.2 

.17

.7 

.2 

.2

.3 

.3

.1

.4

.12 

.12 

.12 

.2

.1

.06

.35

.12

.06

.06

.06

.4 

.2 

.3

.7

.5

Ratio 

Hf/Zr

0.007 

.011 

.011 

.023

.015 

.014- 

.019 

.042- 

.057 

.019 

.014

.055 

.019 

.017

.018 

.026 

2.021

.015

.010 

.069 

.051

.023 

.011 

.017

.046 

2.031 

.037

References

Hevesy and Jantzen (1923). 

Hevesy (1925b). 

Do. 

Borovsky and Blochin (1937a).

Borovsky and Blochin (1937b) 

Do. 

Kostyleva (1940).

Hevesy and Jantzen (1923). 

Hevesy and Jantzen (1924).

Do.

Hevesy (1925b). 

Do.

Hevesy and Jantzen (1923). 

Hevesy (1925b). 

Borovsky and Blochin (1937a).

Do. 

Do.

Hevesy and Wilrstlin (1928). 

Hevesy (1925b). 

Kostyleva (1940).

Borovsky and Blochin (1937b). 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Do. 

Hevesy and Jantzen (1924). 

Hevesy (1925b). 

Do.

Hevesy and Jantzen (1923) . Hevesy and Wurstlin (1928). 

Hevesy (1925b) .

'Method of analysis not given. 

'Ratio,
10 CONTRIBUTIONS TO GENERAL GEOLOGY

TABLE 8. The hafnium and zirconium content and the Hf/Zr ratio in other 

miscellaneous minerals, all analyzed by X-ray spectroscopic methods

No.

1 

2 

3 

4 

5

6 

7 

8 

9 

10 

11 

12

Name of mineral and locality

Thortveitite, Norway, Iveland... 

Do 

Do. . 

Thortveitite, Norway, Unneland. 

Thortveitite, Madagascar, Befanamo. 

Do . 

Do - 

Do 

Percent by weight

ZrO.

1.2

2 

.8 

2.2

2.0 

1.3

2.8 

2.90

HfOa

2.0

.5 

1.1 

1.8

3.2 

1.0 

.13 

ca .1 

Tr.

Ratio 

Hf/Zr

1.9 

1.20 

.29 

1.6 

.94

1.8 

.88 

.26 

ca.04

1,019 1.06- 

.06

References

Hevesy and Jantzen (1924) . Hevesy and Wiirstlin (1928). 

Hevesy (1925b). 

Hevesy and Jantzen (1924).. 

Do.

Do. 

Hevesy (1925b). 

Hevesy and Wiirstlin (1928).. 

Hevesy and Jantzen (1924) . 

Hevesy (1925b). 

Hevesy and Wiirstlin (1928). 

Do.

i Ratio, 

HfOa

ZrOz+HfOs

TABLE 9. Averages of Hf/Zr ratios of minerals according to source 

[Data from Hevesy (1925a) and Hevesy and Jantzen (1925)]

Mineral Table no.i Ratio 

Hf/Zr

Nepheline syenite minerals

Baddeleyite ________________________________________

Elpidite- . . .. 

Eudialyte.. _______________________________________ -----

Polymigmte. - _ _ - . . .- - - -

Rosenbuschite.. _____________________________ 

Wohlerite _____ ..... ............... _ ....... ____ .... ___ ...... _

Zircon.. _______ . ___ .... __ i. __ _. ___ _ ., _ .. __ .....

6

6

7

7

7

6

7

7

4

0.014

.008

.011

.011

.011

.023

.017

.034

.017

Granitic minerals

Alvite. ... .- ....... . . -

Malacon- _______ _ .._..-- __________ _ -___ _. ________ _ ___ _ ._ ___-----_-

Thortveitite.. _ __ ... __ .-_. __ ___-. __ _-____---.__ __ .-...__ __ ____ __ _.-

5

5

8

.13

.46

.46

.57

i The table numbers refer to this report.
HAFNIUM CONTENT AND HF/ZR RATIO IN MINERALS AND ROCKS 11

j

r* ANNOTATED BIBLIOGRAPHY

Bedr-Chem, Safder, 1925, Analyse des Alvits: Zeitschr. anorg. allg. Chemie,

v. 144, p. 304-306.

_ An X-ray spectroscopic analysis by Jantzen is given for a sample of alvite, 

locality not stated.

Borovsky, I. B., and Blochin, M. A., 1937a, Definition of hafnium in zirconium 

)» minerals of the U. S. S. R.: Acad. sci. U. R. S. S. Bull., Se>. g6ol., p. 185-193.

[Russian with English summary.]

/ X-ray spectroscopic analyses are given of 14 samples. The accuracy of the 

analyses was not known as no pure zirconium was available, but analyses of 

similar mixtures of tantalum and tungsten were accurate within about 11 percent.

 1937b, The analysis of minerals by the X-ray spectroscopic method: Acad.

^ sci. U. R. S. S. Bull., Se"r. ge"ol., p. 929. [Russian with English summary.]

Analyses are given of 31 samples. The accuracy is estimated to be within

* about 10 percent.

« Cooley, R. A., Martin, A. V., Feldman, C., and Gillespie, J., 1953, The hafnium 

to zirconium abundance ratio and specific radioactivity of some'ores: Acta

* * - geochim. et cosmochim., v. 3, p. 30-33.

^ Hafnium and zirconium were separated chemically from ores and their ratio 

was determined spectrographically for 14 samples by the porous cup method. 

4 The abundance ratios are believed to be accurate to ±5'percent.

Fleischer, Michael, 1953, Recent estimates of the abundances of the elements in

the earth's crust: U. S. Geol. Survey Circ. 285, 7 p. 

^ A compilation.

A Harada, Zyunpei, 1936, Chemische analysenresultate japanischen Mineralien 

[Chemical analyses of Japanese minerals]: Hokkaido Imp. Univ. Fac. Sci. 

"*f Jour., Ser. 4 Geol. and Mineral, v. 3, p. 221-362.

Six analyses of the hafnium content of minerals are quoted. See especially 

pages 296-299.

k

Hevesy, Georg v., 1925a, Chemical and physical properties of hafnium. Dis- 

> covery and properties of hafnium: Chem. Rev., v. 2, p. 1-41.

A review. Averages are given for the HfOz/Zr02 ratio of minerals.

 1925b, Recherches sur les proprie'te's du hafnium [Research on the prop-

* erties of hafnium]: K. danske vidensk. Selsk., Math. fys. Medd. 6, no. 7, 149 p. 

A detailed review, which gives many determinations of the ZrOa and HfOa 

content of minerals.

 1931, Chemistry and geochemistry of the titanium group: Chem. Soc.

London Jour., p. 1-16. 

A review.

Hevesy, Georg v., and Jantzen, V. T., 1923, The hafnium content of zirconium 

ores: Chem. Soc. London Jour., v. 123, p. 3218-3223; the same paper was 

published in Zeitschr. anorg. allg. Chemie, v. 133, p. 113-118, 1924. 

X-ray spectroscopic analyses, with tantalum as internal indicator, are given

for 31 samples.
12 CONTRIBUTIONS TO GENERAL GEOLOGY

Hevesy, Georg v., and Jantzen, V. T., 1924, Hafnium content of zirconium ores:

Chem. News, v. 128, p. 341-342. 

X-ray spectroscopic analyses are given for 13 samples.

 1925, The hafnium content of zirconium ores: Chem. News, v. 130,

p. 179-180.

X-ray spectroscopic analyses are given for 20 zircon samples for which radioactivity, helium content, and specific gravity had previously been determined. There 

was no direct relationship between the radioactivity and the hafnium content.

Hevesy, Georg v., and Wlirstlin, K., 1928, Ueber das Hausfigskeitverhaltnis 

Zirkonium/Hafnium und Niob/Tantal [The abundance ratios zirconium/ 

hafnium and niobium/tantalum]: Zeitschr. physikal. Chemie, v. 139A, 

p. 605-614. 

Previous work is summarized and some new determinations are given.

Kimura, Kenjiro, and Tanaka, Kazuo, 1936, The chemical analysis of zircon from 

Chinpyong-ni and Pokchin-san, Korea, with a supplement on the hafnium 

Content in Japanese zirconium minerals: Chem. Soc. Japan Jour., v. 57, 

p. 1205-1207.

Analyses by the X-ray spectroscopic method are given for zircon associated 

with graphite, sphene, scapolite, and phlogopite at Chinpyong-ni, Korea, and 

from nepheline syenite at Pokchin-san, Korea. The ratio HfOz/ZrO^ is given 

for one other zircon sample and for five unusual zircon samples (naegite type).

Kostyleva, E. E., 1940, The geochemistry of hafnium in the U. S. S. R.: Trudy 

Inst. Geol. Nauk no. 39; Mineral.-Geokhim. Ser. 8, p. 41-47 [Russian with 

English summary]; Chem. Abs., v. 37, p. 6607 (1943). . 

Previous work is summarized and some new determinations of HfOa are given.

1946, The metamict state of minerals of the zircon group [in Russian]:

Fersman Memorial Vol., Acad. sci. U. R. S. S., p. 27-35. 

All analysis Of CyrtOlite from.Zap, Qleniya varakh, Karelia, is given.

Landergren, Sture, 1935, Bidrag till kannedomen om vara sulfidmalmers geokemi 

[Contribution to the knowledge of our sulfide ores]: Geol. foren. Forh., 

v. 57, p. 62G-626.

Spectrographic analysis of zinc sulfide ore from Saxberg containing about 11

percent Zn, 3O percent SiO2 , gave Zr 14O g/ton, Hf 1 g/ton.

Larsen, E. S., Jr., Waring, C. L., and Berman, Joseph, 1953, Zoned zircon from

Oklahoma: Am. Mineralogist, v. 38, p. 1118-1125.

Spectrographic analyses were made on fresh and metamict zircon from pegmatite

in granite. The fresh zircon contained O.9 percent Hf; 2 samples consisting chiefly

of metamict zircon contained 0.7 and 0.5 percent Hf. Chemical analysis of similar fresh zircon gave 67.6 percent Zr02 a + HfOi, of similar metamict material

gave 60.3 percent ZrO2 + HfO2 .

Lee, O. I., 1928, Mineralogy of hafnium: Chem. Rev., v. 5, p. 17-37.

A re vie-! r, in which Hevesy's determinations are quoted.
HAFNIUM CONTENT AND HF/ZR RATIO IN MINERALS'AND ROCKS 13

Spectrographic analyses are given, in terms of the relative intensities, of a pair 

of Hf-Zr lines. The results are as follows:

No.

1

2

4

5

6

7

8

9

10

11

12

Mineral 

....-do 1 ---... ---------

-.-do. ----------------

.....do i - - -..-

..... do" -- 

-..-do'-- ---------.

 ..do' ._...- --.

Locality

^lellen Wis

... -do... ... .. .. ........ .........

..-..do----------- - .......... ....................

. .-.do ... ........ ........ ............ ..........

Bedford, N. Y... ...-... ... ........ ... 

Ratio intensity 

Hf/Zr

0.52

.41

KQ

(2 )

.45

.30

.25

.53

.26

.51

.42

.70

1 In granite.

' Trace of hafnium.

Loewenstein, Walter, 1952, Estudos sdbre as propriedades quimicas dos minerals 

de zirconio da regiao de POC.OS da Caldas, Minas Gerais [Chemical properties of zirconium from Pogos da Caldas, Minas Gerais]: Univ. Sao Paulo, Fac. 

fil., cieng. e letras Bol. 147, Mineral, no. 9, p. 41-74.

Chemical analyses of 12 samples of zircon and baddeleyite were made by fractional precipitation as phosphate.

Morgan, J. H., and Auer, M. L., 1941, Optical, spectrographic, and radioactivity

studies of zircon: Am. Jour. Sci., v. 239, p. 305-311.

As no determinations of the absolute content of zirconium and hafnium were 

made, these can be related to the determinations given in tables 4 and 5 only if 

no. 10 above is assumed to contain about 5 percent HfC>2 (table 5). If so, the 

zircon samples listed above have remarkably high hafnium content.

Prandtl, Wilhelm, Mayer, Georg, and Biittner, Leonhard, 1937, Uber die Trennung von Hafnium und Zirkonium. II. Die Rolle der Phosphorsaure in der 

Chemie des Zirkoniums [The separation of hafnium and zirconium. II. 

The role of phosphoric acid in the chemistry of zirconium]: Zeitschr. anorg. 

allg. Chemie, v. 230, p. 419-426. 

Analyses by the determination of the density of the mixed oxides, (Zr,Hf)Oj,

are given for 14 samples.

Sahama, T. G., 1945, On the chemistry of the east Fennoscandian rapakivi

granites: Comm. g6ol. Finlande Bull. 136, p. 15-67.

Spectrographic analysis of a standard mixture of 54 rapakivi granites gave 

0.12 percent Zr02 , 0.0028 percent Hf02 .

Tro'ger, E., 1935, Der Gehalt an selteneren Elementen bei Eruptivgesteinen 

[The content of rare elements in eruptive rocks]: Chemie der Erde, v. 9, 

p. 286-310. 

Eruptive rocks are estimated to contain on the average 0.039 percent ZrOj,

0.001 percent Hf02 .

O