Geology and Mineralogy

This document consists of 22 pages Series A.

UNITED STATES DEPARTMENT OF THE INTERIOR

GEOLOGICAL SURVEY

DATA ON THE HA1WIUM DIOXIDE CONTENT AND THE RATIO

OF HAFNIUM TO ZIRCONIUM IN MINERALS AND ROCKS

By

Michael Fleischer

March

Trace Eleiaents InTestigations Report

This preliminary report is distributed without editorial and technical reyiew for conformity -with official standards and nomenclatureo It is not for public inspection or quotation a

USGS > TEI-4,13

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CONTENTS

IntrOdUCtiOn a»o80»oeOoe»oo 0 »90o 0 oo<joe»oo»o»e9e»e»oo*i»i>»»o»*<»o 4

Hafnium and zirconium content and the ratio Hf/Zr in theearth's crust and in rocks 0 »,ooo<>«ei>BB°o.ao*.o»e.*eo«e«ao«oe 5

Hafnium and zirconium content and the ratio Hf/Zr of

Annotated bibliography & «*eoo*»««»»o*«o«».«<ie»»*«»«*o..«o» (,»<.«^ 19

TABI^ES

Page

Table 1. Estimated abundances of hafnium and zirconium inthe earth * s crust and the ratio Hf/Zr a»«<»ooo.o«.o«o 8

2 0 Hafnium and zirconium content and Hf/Zr ratio of

3« Compositions of minerals listed in tables 4 through

IK The 'hafnium and zirconium content and the Hf/Zrratio in zircon oe»o<>ai><>««i>**»»ae»<>«a*0oae<.oe»»««»o» 11

5o The hafnium and zirconium content and the Hf/Zrratio in rarieties of zircon o,»o*»e > »»a'*o»eea a .««»» 9 14

6 0 The hafnium and zirconium content and the Hf/Zrratio in zirconium oxide minerals and ores .a*.» e »** 15

7= The hafnium and zirconium content and the Hf/Zrratio in zirconium silicates aoooeoooooot.opooc,,,**,,,,,, 16

8, The hafnium and zirconium content and the Hf/Zrratio in other miscellaneous minerals ..o.^^o^oooeoao 1?

9 * ATerages of Hf/Zr ratios of minerals according to.-LOeoooooaooaooooaooocooeooooeooooeoooooooaoooo

B&TA OH THE HAFSIUM DIVIDE COIITEIT AID THE RATIO

OF HAFHIUM TO ZXRCOIIUM II JOTERAI£ AID ROCKS

By Michael Pleischer

ABSTRACT

All published data on the hafnium content and hafnium/Eirconium

ratio in minerals and rocks hare been compiled. The average ratio

If/Zr IB about 0*02 in the earth's crusts Minerals from aUtealic rocks

such as nepheline syenites hare lower Hf/Zr ratios than does zircon

from granitic rocks f Minerals from granitic pegmatites have the highest

Hf/Zr ratios ? especially some peculiar tarieties of zircon, such as

alTitej cyrtolite and aaegite ? and the rare, scandium silicate ,

thortreitite , -whl,ch is the only mineral that is reported to contain ware

hafnium than zirconium,,.

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 mth the aid of the notched-

card file on geochemistry of the U* S. Geological Surrey In addition^

the following bibliographies on zirconium were checked;

YoresSj HO E<> -and Crcocton, F* E. 3 1951 9 Zirconiumj a bibliography of unclassified literature <, Uo S^ Atomic Energy Commission, TIB*3010 S 138 p», and supplement no D 1, IT P»

Williams, G*. C ft? Baker, B* 0*5 Jr &? Holzknecht, S» Wo, aad Moody, R 0 G« 3 1950, Zirconium and ha£oium-~a bibliography» U* S. Atomic Energy Commission, NYO»1008s 256 p»

Few of the data are recent <> The methods of determination and the

authors ! own estimates of error 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 Yon Hevesy and coworkers 0

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

known that re determinations were made on many of their samples 0 The

sample descriptions are inadequate, so that it is not possible to be

sure 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 type of geological occurrence, so that only a

few 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 geological setting

are highly desirable,,

HAFNIUM AW ZIRCONIUM CONCEIT AHD THE RATIO Hf/Zr

II IEEE EARTH'S CRUST AKB II ROCKS

Estinfetes of the abundances of zirconium and hafnium are assembled

in table l a 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 Wurstlin (13)? but the estimates for hafnium are

not so well established 0 Yery few rocks have been analyzed directly for

hafnium^ as seen in table 2« The estimates for hafnium are based

6

largely iSa analyses of sircoaium minerals , especially of zircoa, as

ia tables 4 through 8, and it is rather uneertaia whether the

rock types hare "beem sampled well enough t$ giTe conf ideaee

in the yalues giTrea for the ratio

EAMIUM Al® ZIRCOIIUM CQ!£3!E!t!I! ASP 3BE

Hf/Zr OF MUERAIB

The amilable data are giyea in table k for zirc^lai, table 5

(varieties alrite, cyrtolite, ete^), table 6 for "badiSfileyite

aad other zircotaiiam oxide aiaerals, table 7 f^r Jiircoaaium silicates,

aad table 8 for miscellaaeous miaeralSp A list of the adaeral Baaes

used ia these tables is giTea ia table 3> flth the chemical formulas*

la each table, the deteradaatioas are grouped by minerals aad, for

each mineral, geographically ia the order If&rth America, South America,

Greenland, Europe, U.S^S^*, Asia, Australia, aad Africa «

As the type of deposit is not stated for aiaay of the samples,

particularly ffcr zircm ia table k, areraging by type of deposit is not

here attea^ptede It should be noted that all or nearly all of the samples

of ̂ ircoa, variety ai?ite, etc*, of table 5? aad <sf thortveitite mad

Other minerals of table 8 are from granitic pegmatites , whereas the

bad&gleyite from Brazil, table 6, and the zirconium silicates of table 7

are all fr$m nepheli&e s3^saite pegmatites or siiailar alfcalic rocks , The

ainerals from granitic pegmatites show Tery high Hf/Zr rati#sj those

from alkalic rdcfcs distinctly low Hf/2r ratios* Heresy (7) and Eeyesy

aad Jantzea (12) hams girea averages of their -Own deterBdBatioasi these

are tabulated ia table 9,

7

Some of the samples that hare high ratios of Hf/Zr hare high

contents of rare earths, uranium, and thorium,. There is not, however,

a close correspondence between radioactivity and hafnium content in

most zircon,,

In view of the very high Hf/Zr ratios of the minerals of tables 5

and 85 it is somewhat surprising that higher ratios are not reported

for some of the zircon listed in table k» lew 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 ratio.

8

Table 1 0 -Estimated abundances of hafnium and zirconium in the earth's crust and the ratio Hf/Zr«

lOo

1

2

3

k

5

6

7

8

9

10

11

ZrQ2 Hf02 (Wto $) (¥t 0 #)

o 0 030 Oo 00058

.030 .00058

.028 .00058

0031 ,0029

0 030 0 00058

.03^ . 000^7

-,031 .0029

o031 o0029

,035 -0035

.

«, .

Ratio Hf/Zr

0,020

.020

.021

.109

,020

a Ol6

.109

.109

.115

.03^

I/ 0020

References

5

5

5

5

5

5

5

5

5

7

13

I/ Ratio HfOgZr02 H- Hf 02

1» Mason, 1952 2, Rankama and Sahama, 1950 3« Polanski, 19^8 k, Anderson ? 19^5 5» Gtoldschmidtj 1937 6 C Fersman, 1933 7. Schneiderhohn, """*' 8 0 Bergj 1929 9 B .Clarke and Washington, 192^0

Table 2 0 Hafnium and

No o Material

9

zirconium content and Hf/Zr ratio of roc

ZrQ2 Hf02 Ratio (¥t 0 %) (Wt. 5& ) Hf/Zr

1 Average ultrabasic rock 0 0008

2 Average gabbros

3 Average diorites

k Average granites

5 Rapakivi granites I/

6 Igneous rocks 2/

.019

0038

0062

.12 0 0 0028 0.02T

0 026 000038 0 01T

^ Trcs ^J!^O o

References

13

13

13

13

23

9

7 Estimated average ? eruptiverocks ,039 »001 .029 2^

8 Zinc sulfide ore,, Saxberg ?Sweden 3/ 0019 00001 o008 IT

JL/ Spectrographic determination made on a mixture of 3^- granites 2/ X-ray spectroscopic determination on a mixture of 300 igneous

rocks that contained 56o5 percent SiOgc3/ Spectrographic determination.. The ore contained 30 percent

10

Table 3« Compositions of minerals listed in tables k through 8,

Alvite I/

Baddeleyite

Caldasite Catapleite Cyrtolite I/

ElpidlteEudialyte-eucoliteEuxenite

Favas

Fergasonite

Hagatalite I/

Malacon I/

Naegite _!/

Oyamalite ~l]

Pitchblende Polymignite Pyrochlore

Ros enbuschite

Thalenite Thortveitite

Wohlerite

Yamagutilite \J

ZirconZirkeliteZirkite

ZrSi04 containing rare earths, BeO, U, and Th

Zr02

Zirconium oxide ore, chiefly baddeleyite(Ha2?Ca)ZrSi309 °2H20See alvite

Ha2 (Zr 5 Ti)Si6Oi5 -3H20(Ga,Ma) 5Zr2Si6 (0,OH,Cl) 2O(Y 5 Ce,U)(Nb,Ta,Ti)2 (0,OH)6

Pebbles in gravel , Commonly baddeleyite, may also be zircon (T sEr)(Nb 5 Ta)04

See alvite

See alvite

See alvite

See alvite

U02 with U03 , Th02(Ca PFe s Y 3 Zr)(lb,Ta ?Ti)04(Ca 3Ia)(Fb s Ti)206 (OH,F)

(Ca,Na)3 (Zr ? Ti)Si208F

Y2S120T (Sc sY)Si207

HaCa2 (Zr 5 Nb)Si208(0,OH,F)

See alvite

ZrSi04(Ca,Fe)(Zr,Ti)205 (?)Commercial name for zirconium oxide ore

I/ Alvite ? cyrtolite, hagatalite, malacon, naegite, oyamalite ? and yamagutilite are names given to varieties of zircon« Some of the names are not veil defined, but in general they apply to varieties of zireon that contain appreciable water and may contain rare earths, uranium,, thorium, beryllium? and P20s° Some of this material may not be zireon

11

Table ^ 0 --The hafnium and zirconium content and the Hf/Zr ratio in zircon.

No.

1

2

3i*567

8910111213ill-1516171819202,1

22252k2526272829303132333^3556375839to

Locality ,Zr°2_, x (Wt. $)

ConnecticutNorth Carolina ,Henderson County

DOoDOoDOo

FloridaPennsylvania j BerksCountyOklahoma p fresh 2/ (66 ,5)Oklahoma , metamiet 2/ (59 ,5)

Do. 2/ (59-7)Oregon p Coos BayOntarioOntario , RenfrewOntario , EganvilleBrazil

Do,Do*Do, 63 o7Do,

Brazil , Minas GeraisBrazil,, Minas Gerais ,Popos de Caldas

Do 0Do 0DOoDo.Do,Do 0

Brazil p placer 6k 0GreenlandGreenland^ larsarsukAustria , Carinthia 65 France , Espailly 6^4- 023

Do 0Do»DOo 6^83

Italy p LonedoDOo

Italy , NovaleItaly , VesuviusItaly, Vieenza

Hf02 (Wt. 1

1.0

k 0 Q

1-3

1.0-

.

1.10 0 8Oo6~-

0*61*2---

1,3loO

1.0

1.81.0»..-.

Ook

5 00,8^ e1.81.10<>71*20 0 7Oo70,90.70,8

Ratio Method of References 0 Hf/Zr analysis I/

.

--

0 D Ol6«

0,027

0*02,62/(0,Ol8)2/(0 0Ol6)2/ (0.011)

0,0255/ OoOlO

««

0.008Oo015OoOlOOo023

--

--

3/ OoOi^-3/ 0.0143/ 0,0173/ 0.0173/ 0

0 0007-«

0«070,032-_

0.021---.-

XS

xsxssDS

SSSssxsxsxssssxsxsxs

xsDcccccxsxsxsxsxsxsxsxsxsxsxsxsxs

12

8, 1210k

22kk181818k1312

8, 121*.kk101212

122220202020208

108 P 128, 10

1012128

121212128

Table 4 0 ~-'The hafnium and zirconium content and the Hf/Zr ratio in zircon--Continuedo

HO. Locality (^°^}

4l Italy, Vicenza42 Norway 60^5543 Norway 9 Brevik 63* 0544 Norway 9 Frederiksvarn 6^9645 Do a 65 0246 Norway , Langesundfjord.4j Do.48 Norway 3 Larvik49 Do o5^ ,,. , y Portusok51 s Avigait52 3 Sc'ixLuchtseej

acid,53 3 Schluchtsee,

basicKJl TT Q Q PV^ UoDsDo-Ke ""

55 DOo56 DO a

57 Do o58 DOo59 Do 060 Do o6l DOo62 DOo63 DOo64 D0 0r\^\ TTw"^Q^P HO a ^

66 Do 067 Do 9/"O

DO DO a

69 Do o70 Do »71 Do o72 UeSoSoRoj, zircon ores ^6 075 Bo* 44 074 Do 0 59°75 Do 976 Do .77 DOo78 Dof W JJvJ o ~

79 UoSeSoRo ? Botogolski80 UoSoSoRo,, Kukisvumchorr81 U 6S &S 0R op Mariupol82 U 0SoSoR<>3 Poachvumchorr 66 c

HfOg Ratio Method of (Wto %) Hf/ar analysis I/

1.8 - XS3o5 0,066 XSlob Oc01,8 XS2 08 Oo05 XSloO 0 0 0l8 XS1,7 » XSOP1 =, T^

6 0 - XS3/ Oo035 XS3/ Co 015 XSI/ Oo021 XS

3/ Oo026 XS

- 5/ 0 0 0024 XSn p - if FS\^f o &, .aaJ*-/

0 0 It "'y^c? £^ &|= ta-J ^5,0

0«55 - ' XSQ 055 - 'XS0,5 - XSO R YQ o V "" JLD

0 o 6 ~ XSOo6 - XS0.6 - XSOo6 - .XS0 *7 YQ » f " ,<SJD

0 7 Y<2 of "" AD

Oo7 - XS0,8 - XS08 > xs\y O \*S <S±A*J

1 O VC! .Ltjf,, " AD

1 0 2 » XS1 0 3 - XSi.b 0.029 xs0»7 0.021 XSOo7 0,016 XSipb - xs0^5 - xs0 08 - XSOc7 - £SOo5

OeT-laO

Oo5Io6 Oo028 XS

References

10108

108

102210151313

13

133533333333333333352222222

1515152

Table 4 W~The hafnium and zirconium content aad the Ef/Zr ratio in zircon Continued.

KO.

83

Qk

85

868788

89

909192939)4.95969798

99100101102103IQk105106107100109

110111112

Locality (ft?%)

UJ5.S.R., Sludyanka( with allanlte)

UtfStfSaR*, upper Tulia 66 .RiTer

U,S*8*Ro, Urals, IljfienMts*

UJSoSa., Urals, Mlask 59*92B®* 64*22

U*S«*S»R«>« RajfcdvKluitsch

U.S«S»R.r, YishneTjeGory

IndiaDo 0 62,3

India, placer 6k tCeylon

Do,Bo*

Ceylon , "beecariteCeylon 9 Kals-ws GangaSiam 60-67

Bo «Korea , Sinpyori 66 «0Kctrea, Htjkuslozaii 6~*>?kAustralia

B&*Australia, Queensland!Tas]i»B.iaMadagascar

SOoD0 0

Jfe,da^.scar , DiegoSuarez

Madagascar, MesatananaligeriaLocality unknown.

HfO*» Ratio Method, of « ~ (Wt* f ) Hf/Zr analysis I/ References

0-5

1,0

IpO5»41*1

0.5

0-9-~

2«71.22,0o -Tilo2.12«03,5

^ o

0.791.9-

4.5

1,13-0*90*7

0*62.02.36,

0,018

-,oao0*020

«

-0.0200,050.021

^»-»

Oa060»

0.067»

0*01^0»03^0,019

0.015

---

» n.

*

«

»

XS

BXSXS

XS

X0sXSXSJt*J«J

XBXSDXSBJB

XS,.«sBSXSXSXSD

XS1BXE

15

2

2210

8, 12

8

3k

108

108, 12

221222.11

866^

22k8

101222

8, 1222.2210

fro®, density

See also Morgan and Auer (21)

I./ Metnods of analysis are designated as C - Chemical separation as phosphate | B - Hf content 0f mixed oxides (&r,Hf)02j s - Spectrographic j XS - X-ray epectroscapic «

2/ Analysis for ZrQg Hade oaa materials frsaa the same locality siailar to "but not identical with the sample analysed, for Hf .

I/Hf 0

Table 5°~"The hafnium and zirconium content and the Hf/Zr ratio in -varieties of zircons alvite (A), cyrtolite (C), hagatalite

naegite (l) 3 oyamalite (0) s and yamagutilite

No,

125it-

5678910111215Ik1516171819202122252k

2526272829303132

Locality (w^0| }

U Q / if- \ \i/\ o Do \L J *t-O o

Uo S 0 3 Mass o ? Roskport (C)DO a (C) " ¥l-o

Uo So 3 No Yo Bedford (C)

Ontario , Parry Sound (C )Norway, Kragero (A) 34 0

Do 0 (A }Do o (A )DOo (A)DOo (A) 4la 98^ (A) 4l 092

f (A)Norway 9 G-jersted (A)Norway,, Eittero (M) 62 a 8

Do. (M) ' 65.18Norway <, Risor (A)Norway 5, southern (A) 4? 09

Do 0 (A) kQ OkUoSoSoRoo Ilmen gory (M)UoSoSoRoo Blumovskaya (M-C) ~U aS 0!SoRo 5 Karelia (C)

DOo (G?U^SdSaRo;, Rozhkov .Klue.^ (M) -U 0S 0-SoRon Zap oleninyavarakt (C) 47^82

Japan,, Hagata (.1) 39-7Japan,, Mino (l) 48 30Japan,, laegi (N) 4-9 0 8Japan 3 Gyama (0) 38 JJapan 3 Yamagutl (Y) ca 0 4o 0 2Madagascar (M)

Doo (M) 55 02Madagascar ;, Ahi-Iambana (M) -

Hf02 Ratio (Wt» ^) Hf/Zr

9 0 0 026>10» 2/ 0^22,17 o Qokk

ca 0 5 0 Oo09-2/ OollP ^6 ""

f, o ̂ U -

16 0 0 0 ,543 &8.

15 o

4 06 Ool?k 066 0»155.99 05o Oo088?.o6 0^046

J.,V o °

3/ 5o5 Ool55/ 6oO Ool4

0 0 81,82»5Io82 e 6

Io70 O d *04l2.3 0<,0667o Ool73o5 0 0082,2 0.065

cQi^ok 0<>0977oi 0 0 0 0862aO

Method of analysis I/

XSXSXSXS

XSXSXSXSXSXSXSXSXSXSXSXSDD--XS-,

-.

.XSXS--XSXSD

References

1015813

91010101081310118

10222215159

1515

166

10866118

22

See also Morgan and Auer (2,1)

I/ Methods of analysis? D - By density of oxides; XS scopie e

2/ Ratio HfOg

-ray spectre-

^ It is stated in 'the same reference (22) that the oxides recoTered from a large amount of these samples contained 2*2 percent

15

Table 6 0 ~~The hafnium and zirconium content and the Hf/Zr ratio in zirconium oxide minerals and ores 0

No*

1234567

8

9

10111213

1415

161718192021

222324

Name and locality /_.. 2^\^ W w o yu /

Baddeleyite, Brazil 97 0 1DOo 97o7

Baddeleyite , Brazil,, fava 92 0 42DOo 91ol2Do. 59 0Doo 74 »

Baddeleyite , Brazil, fava,shell 59 ,

Baddeleyite , Brazil,, fava pcore 74 o

Baddeleyite , Brazil yPQ^OS de Caldas

Do IDo, 73=2DOo 92.1

Fava,, Brazil 9 Ppcos deCaldas

Do 0Caldasite. Brazil, Pocos de > -' f Caldas

DO a

DOoZirkite ore,, BrazilBaddeleyite 3 Colorado J/ZrOg reagentPolymignite , Norway 9 Frederiksvarn 28 0 71

DOc 29 0 11Zirkelite 3 Brazil 51° 7Zirkelite, Ceylon 51=89

Hf02 Ratio Method of . (Wt. %) Hf/Zr analysis I/ References

1, 0 8 Oo021Io2 OaOl4

Oa7 0.0092 0 Oo025Oo5 0»0100.5 OoQ08

1» Oo019

1» 0 0 015

0,0132 alol 0 0 0171 0 4 0,017

2/ Oo0022/ Oo024

2/ Oo0222/ 0 0 034"2. / Oo04l

0 00120,068OoOlO

0^9 Oo036Oo6 0=024Io2 Oo0261 0 Oo022

XSxsxsxsxsxs

xs

xs

sDcc

cc

cccsss

xsxsxsxs

1088

1088

10

10

4222020

2020

202,0204k4

10, 118

118

_!/ Methods of analysis? C - Chemical fractionation of phosphates y D - By density of mixed oxides; S - Spectrographic; XS - X-ray speetroscopie.

, . HfOg £-,/ Kacio ff-Ytf) j_ IIT'P'O

3/ Baddeleyite is not kno¥n to occur in Colorado,, U 0SJU

16

Table ft The hafnium and zirconium content and the Hf/Zr ratio in zirconium silicates 0

Zr02 Hf02 Ratio Method of No a Name and locality /w+ .at\ /Uf, v\ rr-p/W a-nni-vR-fQ i / References

\ W u o TO / ^wuo/0/ Hi, j z_|X CUiClJUjyDJUb JL^

1

234

561

89

10

1,112

131,k

15

1617181920

2122232,425262728295031

Catapleite, Greenland 30 065 0*2 Oo007DOo 31°53 Oo3 OoOll

Catapleite, Norway 31° 52 Oo3 OoOllCatapleite, UJSeSoR*,upper Tulia RiTer 30 0 5 0 06 Q«Q23Catapleite, U 0S e S 0R 0 - Oo35

DOa - Ool

Cataple its , U S ,S 0R 0 ,Pereval Lopar ea 0 Q«3

Eudialyte, Greenland 1^ 0 30 0«19 0=0.15Eudialyfce , Greenland,,larsarsuk . 12- 16 Q 02 0»Q1^-

0^019DOo 12- 16 0 0 6 OeOte"'

DOo 12-20 0.2 Oo019Eudialyt-e , G-reenland,Kanger dluarsui l^-»32 Ool7 OoOl^

ludialyte, Norway 1^ 0^7 0 0 7 0 0 055Eudialyte, lorway.Barkevik 12 021 0 02 0*019Eudialyte, UeS 9S eRo, KolaPeninsula 13 0 Oo2 0 0 017

Dc,> 19 o OoJ OoOlSDo 0 13 0»3 Oo026DOo - 2/Oo021DOo - Ool ~~ -

Eudialyte p U &SoS 0R 0 ,Poachvumchorr, altered 30 Oo4 Oo015

Eudialyte, UoS 0S 0R 9 13 =5 Ool2 0*010DOc. 2 aO Ool2 0 0069DQ O 2,7 0»12 Oo051T\.^ f\ O JJO o "° U e>G, =

DOo OolBOo - 0,06DOo - 0.35Do 0 - Ool2DOo » Oo06Do 0 - 0*06DOe - Oo06

XSXSxs

xsxsxs

-xs

xs

xs

xs

xsxs

xs

xsxsxsxsxs

-xsxsxsxsxsxsxsxsxsxsxs

1088

233

1510

11

11

8

810

8

222138

1533333333333

Elpidite, Greenland,Narsarsuk 20 0 1 0<A OoG2°5 XS 11

Table To--The hafnium and zirconium content and the Ef/Zr ratio in zirconium silicates =Continued 0

*,.

33

3^

35

363T

Name and locality , §*\ WlJ o f) )

Elpidite, Greenlandp. Narsarsuk 20o28Rosenbusehitep Norway,,Langesund 19 «80

Wohlerite, Norway,,Lange sund IT » 55

DOoWohlerite, Norway,Barkevik 15.61

I/ Method of analysis; XS - X-ray2/ Ef02

10 Zr02 + Hf02

Table 80- -The hafnium and zirconium

Hf02 Ratio (Wt. %) Ef/Zr

0*2 OoQll

0«3 0.017

0=7 0 00^6- 2/0 o 031

Oo5 Oo03T

spectrosaopic .

content and the

Method of analysis _!/

XS

XS

XSXS

XS

Ef/Zr ratio

References

8

8

1013

8

in other miscellaneous minerals 0

No*

1

2345

6T89101112

Zr02 Name and locality ( lll+ «r\

\ p¥ C; o y<3 /

Thortvettite , Norway ?Iveland . 1. 0 2

DOoDo,, 2«

Thortvei.tite , Norway3Unneland 0.8Thortveitdte , Madagascar^Befanamo 2 0 2

DOo 2oOBo. 1.3

Thalenite ? Sweden , Osterby - -Pyrochlorej, Sweden , Alno 2 0 8 ca

Do e 2o90PitchblendeFergusonite and eujcenite

Hf02 Ratio (Wt 0 <j>) Ef/Zr

2 00 1,92/0 o 20

0=5 0<>29

1.1 1.06

1.8 0.9^3o2 1.81.0 Oo880»13 0 0 26C^ "I r^i^i C) (fj/1-

tr2/0 o 0192/0.05-

Method of analysis I/

XSXSXS

XS

XSXSXSXSXSXSXSXS

References

11138

11

1111813118

1313

0.06

I,/ Method of analysis 2 XS - X-ray spectroseopia,

Zr02 + Hf02

18

Table 9"--Averages of Hf/Zr ratios of minerals according to source (Data of Hevesy and Jantzen P 7 and 12),

Hepheline syenite minerals

Mineral

BaddeleyiteBaddeleyite 9 faTasCatapleiteElpiditeEudialytePolymigniteBo seribus chiteWohleriteZircon

See table no 0

66777677k

Hf/Zr

0,0140,008OoOll0.0110,0110,0250.0170«05^0 e 017

Granitic minerals

AlviteCyrtolite BfelaconlaeglteThortreitite

0 C 08

AOTOTATED BIBLIOGRAPHY

1

Bedr-Chan, Safder^ 1925? Analyse des Alvitss Zeitschr* anorg* allgem c Chenu, v e iMi-, PO 304-5Q6o

An X-ray spectroscopic analysis by Jantzen is given for a sample of alvite s locality not stated 0

Borovsky, I. B 0 , and Blochin, M. A OJ 1937a ? Definition of hafnium inzirconium minerals of the U 0 S* So R 0 s Bull, acado scio U 0 R 0 S» So, Ser 0 ge'olsj p c 185-193 (Russian with English summary)

X-ray spectroscopic analyses are given of 1^- samples Theaccuracy of the analyses was not known, as no pure Zr was available, "butanalyses of similar mixtures of tantalum and tungsten were accurate withinabout 11 percent 0

Borovsky, ! B e? and Blochin ? M O A 09 193Tb ? The analysis of minerals "by the X-ray spectroscopic methods Bull,, acado scio U e R 0 So S 0? S6r e ge3lo s p 0 929-956 (Russian with English summary).

Analyses are given of Jl samples. The accuray is estimated tobe about 10 percent.

k

Cooley, Ro A oy Jfartin s A. V 09 Feldnjan ? Cc, and Gillespie s J OJ 1953? The hafnium to zirconium abundance ratio and specific radioactivity of some ores? Geochim 0 et Cosmochim* Acta 9 v 0 3j P« 3Q-55<>

Hafnium and zirconium were separated chemically from ores andt-heir ratio was determined spectrographically for 1^ samples by theporous cup methodo The abundance ratios are believed to be accurate to+ 5 percento

Fleischer, Michael, 1953? Recent estimates of the abundances of the elements in the earth's crusts U 0 S* Geol 0 Survey Circular 285, 7 PP«

A compilationo

Ha.rada 3 Zyunpei 5 193^.? Chemische analysenresultate japanischen Mineralien(Chemical analyses of Japanese minerals)? Hokkaido Imp 9 Univ 0 Fac. Sci 0 Jouroj Ser 0 k Geolo and Mineral , Vo 3, p 0 221-362, especially p 0 296-299,

Six analyses of the Hf content of minerals are quoted,,

7

Eevesy, Georg v 0 <, 1925a5, Chemical and physical properties of hafnium 0Discovery and properties of hafniums Chem. Reviews, v 0 2 S p 0 l-^-l.

A review o Averages are given for the HfOs/ZrOg ratio of minerals.

20

8

Hevesy, Georg v,, 1925b, Recherches sur les proprietes du hafnium(Researches on the properties of hafnium) °0 Ko danske vidensk, selsko, Matlu-fyso Meddo 6, no 0 7, 1^9 p.

A detailed review, which gives many determinations of the Zr02and Hf02 content of minerals 0

Hevesy, Georg v 0 , 1931, Chemistry and geochemistry of the titanium group : Chenio Soc» London Jour 0 , p» l-l6 0

A review

10

Hevesy, Georg v oj, and Jantzen, Vc T 0 , 1923, The hafnium content of zirconium ores: Chem. Soe* London Jour 0 , v» 123, P« 3218-3223; the same paper was published In Zeitschr. anorg* allgem. Chem» , v«> 133? P» 113

X~ray spectroscoplc analyses ? ¥ith tantalum as internal Indicator, are given for 31 samples ,

11

Hevesy, Georg v 0 , and Jantzen, V 0 T., 192^, Hafnium content of zirconium oress Chem 0 Hews, v» 128, p 0 3^-1-" 3^-2 .

X-ray spectroscopic analyses are given for 13 samples

.12

Hevesy, Georg v., and Jantzen, V 0 T., 1925, The hafnium content of zirconium ores i Chemo News, v* 130, p» 179-l80 e

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,,

15

Hevesy , Georg v», and Wurstlin, K*, 1928, Ueber das Haufigskeitverhaltnis zirkonium/hafnium and niob/tantal; (The abundance ratios zirconium/ hafnium and niob ium/ tantalum ); Zeitschr, physical, Chemie,, v

Previous work is summarized and some new determinations are given o

Kimura, Kenjiro, and Tanaka, Kazuo, 1936, Analysis of zircon from Synpyori and from Hukusinzan., Korea Hafnium content of zirconium minerals of Japans Chenu Soc, Japan Jour», v 0 57? P- 1190°" 119^ «

This paper was not available in translation, but the resultswere obtained from Harada (6) 0

21

15

Kostyleva s E. E», 19^-0, The geochemistry of hafnium in the U« S Trudy Ins to Geol, Hauk no e 39; Miner al»-Geokhim 0 Ser 0 8, p (Russian -with English summary); Chem, Abs os v» 37? P° 6607

Previous work is summarized and some new exterminations ofare given

16

Kbstyleva, Eo £» 9 19^6" , The metamict state of minerals of the zircongroup (in Russian)? Fersman Memorial Yol^ Acado Sei 0 U e R 0 S 0 So, Po 27-35 .

An analysis of cyrtolite from Zap 0 Oleniya varalda, Karelia , isgiven.

17

Landergren, Sture, 1935 » Bidrag till kannedomen om Yara sulfidmalmersgeokemi (Contribution to the knowledge of our sulfide ores)s Geol* foren0 Forh 8? v e 57 , p 0 626-636

Spectrographie analysis of zinc sulfide ore from Saxbergcontaining about 11 percent Zn 3 30 percent SiOs ? gave Zr 1^0 g/ton, Hf 1 g/ton,

18

Larsen, E 0 S 0? Jr 0? Waring^, C e L 05 and Bermanc, Joseph^ 1953 5 Zoned zirconfrom Oklahoma? Am 0 Mineral «, v» 38, p 0 Hl8-1125o

Spectrographie analyses were made on fresh and metamict zircon from pegmatite in granite 0 The fresh zircon contained 0«,9 percent Hf; 2 samples consisting chiefly of metamict zircon contained Oo7 and 0 05 percent Hf <* Chemical analysis of similar fresh zircon gave 67*6 percent

f HfOg, of similar metamict material gave 60o3 percent ZrOa +

19

Lee , Oo I., 19285 Mineralogy of hafniums Chem* Re views , v 0 5» P« 17-3T A review in which Hevesy's determinations are quotedo

Loewensteinj, Walter, 1952, Estudos sobre as Propriedades quimicas dos minerais de z'irconio da regiab de Pocos de Caldas 3 Minas Gerais 0

ical properties of zirconium from Pocos da Caldas, Minas Gerais) Sab Paula, Fac» fll 0 , cienc 0 e letras Bol 0 1^7 s Mineral» no 0 9?

p a 4l~7^ eChemical analyses of 12 samples of zircon and baddeleyite were

made by fractional, precipitation as phosphate.

22

21

Morgan, J 0 H 0 , and Auer, M 0 Lo 5 19^-1 > Optical, spectrographic, andrad.ioactI.Tity studies of zircons Am, Jour. Sci 0 , v 0 239? P- 305-311'

Spectrographic analyses are given, in terms of the relative intensities, of a pair of Hf-Zr lines. The results are as follows;

Ratio intensityHf/Zr_______

1» Zircon, granite, Minnesota2o Zircon, granite. New Jersey, Andover5o Zircon, granite, Wisconsin, Mellenk-o Zlreon, Wisconsin, Wausau5 » Zircon, granite, Manitoba, Oxford House6. Do*To Do*8 0 Do.9° Malacon, Colorado, Cheyenne Canyon

10o Cyrtolite, New York, Bedford1,1 o Malaeon, Ontario, Hybla12c Alvite s Norway, Helle

Hf trace 0,^5 0,30 0,250.530 0 260,51 OA2

As no determinations of the absolute content of zirconium and hafnium were made, these can be related to the determinations given in tables k- and 5 only if no 0 10 above is assumed to contain about 5 percent Ef02 (table 5). If so, the zircon samples listed above have remarkably high hafnium contento

Prandtl, Wilhelm, Mayer, Georg, and Buttner, Leonhard, 1937? fiber dieTrenaung von Hafnium imd Zirkonium> II 0 Die Rolle der Phosphorsaure in der Chemie des Zirkoniums. (The separation of hafnium and zirconium, II o The role of phosphoric acid in the chemistry of zirconium, ) s Zeitschr 0 anorgo allgem e Chem0 , v«. 230, p 8 ^19-^26 0

Analyses by the determination of the density of the mixed oxides,(Zr«,Hf)02j are given for l4 samples ,

23

Sahama, T 0 Go, 19^5, On the chemistry of the east Fennoscandian rapakivi granite ss Comm» g^ol, Finlande Bull, 136, p P 15-67=

Spectrographic analysis of a standard mixture of 5^ granites gave 0..12 percent ZrOa, 0 0 0028 percent

Troger, E 0 , 1955, Der Gehalt an selteneran Elementen bei Eruptivgesteinen (The content of rare elements in eruptive rocks )'0 Chemie der Erde, v 0 9, PO 286-310o

Eruptive rocks are estimated to contain on the average 0*039percent ZrOg, 0.001 percent