EVÀIUATION OF AMPHIBOTE SYNTHESIS AND PRODUCT CHARACTER]ZÀTION

by

Mati Raudsepp

presenred to tr,.AulT;:i:try or Manirobain partial fulfillment of therequirements for the degree of

Doctor of Philosophyin

Geology

l^tinnipeg, Manitoba

o'Mati Raudsepp, 1984

EVALUATION OF AMPHIBOLE SYNTHESIS

AND PRODUCT CHARACTERIZATION

BY

MATI RAUDSEPP

A thesis subntitted to the Faculty of Craduate Studies ofthe u¡liversity of Manitoba in partiar fulfill¡ne¡lt of the requirernents

of the degree of

DOCTOR OF PHILOSOPHY

o 1984

Pernrissio¡r has bee¡r granred to the LIBRARy oF THE uNIVER-slrY oF MANIToBA to le'd or seil copies of trris thesis. tothe NATIONAL LIBRARY OF CANADA to microfitnr rhis

thesis ard to lend or sell copies of the film, and UNIVERSITYIvIICROFILMS to publish an abstract of this thesis.

The author reserves other publication rights, a.d neither the

thesis nor extensive extracts from it may be printed or other-wise reproduced without the author's writte¡r pernrission.

ÀBSTRACT

Synthesis products from a general survey of iron-free monoclinic amphi-

bole endmembers were characterized by powder X-ray diffraction, scanning

electron microscopy, infrared spectroscopy and Rietveld structure anaLy-

sis. Previous amphibole syntheses were reviewed and evaluated; certain

amphiboles synthesized in other studies were characterized in more de-

Lail.

Ear1y studies usually assumed on the basis of optical microscopy and

powder x-ray diffractometry that amphiboles from high-yield runs were of

the nominaL composiLion. Later studies with electron microprobe and

spectroscopic analysis showed many synthetic amphiboles to be off-compo-

sition. Furthermore, although natural amphiboles âre ordered, synthetic

amphiboles show wide degrees of long-range and short-range order, which

must be characterized for proper application of synthesis experiments.

Àmphibole synthesis and characterization in this study confirm these

findings. It is unlikely that any pure amphibole endmember has been

synthesized. Infrared spectroscopy and Rietveld structure ana).ysis of

products too meagre or fine grained for other techniques, have shown

that virtually all synthetic amphiboles deviate fron the ideal composi-

tions and show wide variation in the degree of cation ordering. These

methods should be routinely used in amphibole synthesis studies for ade-

quate characterization of run products.

IV -

ACKNO}ITEDGEMENTS

It gives me pleasure to acknowledge the support and encouragement of

A.C. Turnock, whose advice and patience contributed immeasurably Lo this

work. I thank F.C. Hawthorne for suggesting the research and for inva-

luable discussions of amphibole crystal chemistry during the study.

T.S. Ercit v¡as responsible for modifications to the Rietveld structure

analysis program and also provided helpful discussion of this part of

the work. I am grateful to W.G. Ernst who generously provided alkaliamphibole synthesis products for merciless scrutiny. F.c. Hawthorne,

J.B. westmore and D.R. veblen greatly improved the manuscript by thor-

ough and constructive examination.

v

SYMBOTS AND ABBREVIATIONS

abancamcenchlcpxcrscumdiedeneskf1foftsgh

o empty À-site91 glass

albi teanorthi teclinoamphiboleclinoenstatitechlor i tec I i nopyroxenecristobalitemagnes i o-c ummi ngt on i tediopsideeden i teenstat i teeskola i tef luor i tef or ster i tef err i -f erro-tschermak i tegehlen i te

ga rnetlayer silicatemagnesio-chromitemontepon i tenephel i neolivinepargasiteplag i oc lasequartzr ichter i tespi neltalctridymitea 1 umi no-t sc herma k i tewillemseiteunknown phase

grt1ymchrmptneolpaplqtzrispltlcLrdtswilx

v.f.g. unidentifiabless solid solution

in amphibole formula

very f ine-grained material

Solid oxygen buffersNNO Ni-NiOIW Fe-FeOIM Fe-Fe¡O¿WM FeO-FesOqMH Fe¡0¿-Fez0s

IQFrMQCCH¿FFsMCT

Fe-Si z-FezSi0¿Fe 2S i04 -Fe ¡0¿ -S iO z

graphi te*methaneFe 2Si04-FeSi0s-Fe ¡0+Cu z0-Cu0

(mi neral symbols after Kretz '1983, where appropriaLe)

- v]

CONTENTS

ABSTRACT

ÀCKNOWLEDGEMENTS

SYMBOTS ÀND ÀBBREVIATIONS

Chapter

I. INTRODUCTION

1V

v1

paqe

.t

.3tr

.6

.7

Crystal. ChemistryThe C2/n Amphibole StructureCaLion Distributions in Amphiboles

II. REVIEW OF PREVIOUS ÀMPHIBOIE SYNTHESES

Calcic-amphibolesTremol i te: ECa 2MgsSi aOz z (OH)

z

Ferro-actinolite: ¡CazFeS*SiaOzz(Ou)z .Tremolite. . "Ferro-actinolite SeriesÀctinolite-Cummingtonite SeriesF1uor-tremoliLe¡ lca2MgsSia0zzFz. ..Edenites: NaCa2MgsSizÀ1022(0u) z

Ferro-edenite: NaCazFeS+Si7A1O2z(OH)z .Fluor-edenite: NaCa2MgsSizAl0z zFzPargas ite. . . Ferro-pargasite :

NaCa z (tug,re ) o¡tsi oA1 zOz z (OH) z

Fluor-pargasite: NaCa2MgaAlSioÀlz0zzFz ..Alumino-magnesio-hornblende: rCazMg4ÀlSizÀ1Oz z(Ou) z

Fluor-a1 um i no-ma gnes i o-hornblende :ECa 2Mg4AISi zA10z zFz

Àlumino-Lschernakite: ECa2Mg3ÀlzSioÀlzOzz(OH) z

FIuor-alumino-tschermakite: rCa2MgsÀlzSisAlz0zzFzHastingsite: Naca2FeÍ*Fe3*SioAlzOzz(OH)z .Magnesio-hastingsite: NaCa2Mg4Fe3*SioÀlzOzz(OH) z .

Sodic-calcicAmphiboles .. ....Richterite: NaCaNaMgsSi aOzz (OH) z . .Potassium Richterite¡ KCaNaMg5Sis0zz(OH)z . . .Fluor-richterite: NaCaNaMgsSis0zzFz ..Magnesio-alumino-taramite¡ uNaCaNaMgsÀ1 zSi oA1 z (OH) zÀlkaliÀmphiboles ...... o.Glaucophane: lNazMgsÀl2Síe0zz(OH)z . . . . .Ferro-glaucophane: ENazpeS *Àl

zSi

II

1213'13

15171920

21

2'1

28

Crossite: lNazMgr.Riebeckite: ENa2Fe

ozz(oH)z .I s sSi e0z z (OH)

z

)2. . . . . .

Fe?isAlo.ozFe*Fel*sioozz(oH

Magnesi o-r iebeckite : rNa 2Mg3Fe I *Sí

rOz z (0H ) z

- vii -

o

r

28293030323333373739393943434445

t

3

Eckermannite ¡ NaNa zMg4AlSi eOz z (OH) z

Nyböite: NaNa 2Mg3AI zSizAlOz z (OH) z

À1ka1i Fluor-amphibolesIron-Magnesium-Manganese Amphiboles .

Sodian magnesio-cummingtonite, sodian hydro-magnesio-cummingtonite: NaMgNaMg5Si ¿Oz z (OH) z,NaNa2MgsSi s0z r (OH) (OH)

z

Sodian f luor-magnesio-cummingtonite :NaMgNaMg5Si s02 2F2

ÏII. EXPERIMENTAL METHODS

Charge PreparationStarting Materials . .Fluor-amphibole CapsuJ.esHydroxy-amphibole Capsules

Run Procedure . .

FIuor-anrphi bole SynthesesHydroxy-amphibole Syntheses

CharacterizaLion ..Optical Microscopy .

Scanning Electron Microscopy .X-ray Powder Dif fractionInfrared SpectroscopyRietveld Method of Crystal Structure Refinement

IV. ÀMPHIBOLE SYNTHESES: RESULTS

CaIcic Àmphiboles .

Tremolite: o(ca,Cd)z(Mg,Ni,Mn)sSisozz(0H)z .Eca2Mgssi sgz z (oH)

z

Substitution of Ni5 for Mg5 .Substitution of Mg¡ by MgsNi 2 .Substitution of Caz by Cdz.

Fluor-tremolite: ECazMgsSieOzzFz .EdeniLe: NaCaz(Mg,Ni ) 5SizÀlOzz(OH) z

NaCa2Mg¡SizÀ1022(Ott)z . . .Substitution of Nis for Mg5 .

,ScrIn)

NaCa 2MgaÀ1Si 6À1202 z (OH) z

Substitution of MgaÀl by ttgoCr . .Substitution of Mg4À1 by Mg¿GaSubstitution of MgaAl by MgoscSubstitution of Mg4À1 by Mgaln . . . .Substitulion of MgaAI by NiaÀl . . . .Substitution of MgaÀlSi5À12 by Mg4GaSi6Gaz . .SubstilutionofNabyK .. ..Substitution of Ca2 by Cd2 ¡ .

Fluor-pargasite: NaCazMg¡ (¡1,Cr,Ga,Sc )Si 6À1202 2F2NaCa2MgaAlSi6Alz}zzFz .. . . . . .Substitution of MgaAl by Mg4Cr . . . .Substitution of MgaÀ] by MgoGa . . . .Substitution of MgaAl by Mg¿Sc . .

45464647

47

52

70

70707374757577787879798084

B7

88888888898990909091

91Fluor-edenite: NaCa 2MgsSi 74102 2F2Pargasite: (Na,tt) (ca,Cd) z(Mg,Ni )r (AJ.,cr,Ga

sio(el,Ga)2ozz(og)z 91

9192929393939696969696969797

- vI11

Tschermakite: rCa2Mg¡ (Cr,Sc) 2Si sÀlzOzz (OH) z

Fluor-tschermakite: rCa2MgsÀlzSi oAlzOz zFzÀlumino-magnesio-hornblende: ECa 2Mg4À1Si zAlOz z (OH)

zSubstitution of Mg+ by Nia .SubstiLution of Mg4At by Mg¿ (Cr,Sc,Ti,V)

Fluor-alumi no-magnes i o-hornblende :BCazMg4ÀlSi7AI022F2 . .

Kaersutite: NaCazMg4TiSi oA12 (0+g¡1) r,Sodic-calc ic Àmphiboles

Richterite: (n,Na) (ca,Cd,Na) (ug,lli,Mn,Cu) 5

Si s0z z (0H) z .

NaCaNaMgsSi aOz z (0H) z

Subsitution of Mg5 by Ni5 . .Substitution of Mgs by Mg3Ni2 . rSubstitution of Mg5 by Mn5Substitution of Mg5 by MgaMn .Substitution of Mg5 by Mg3Mn2Substitution of Mgs by CusSubstitution of À-site Na by K

Substution of Ca by Cd . .Fluor-richterites: NaCat'ta(Mg,Mn) sSi sOzzF z,

NaCaNaMgsSi e0z zFzSubstitution of Mgs by Mg4Mn

Àlumino-winchite: ECaNaMga(A1,Cr,Sc)SirOzz(OH)z .Fluor-Àlumino-rvinchile: rCaNaMg4À1Si aOzzF z .Magnes i o-alumi no-katophor i te :

NaCaNaMga (41, cr, Sc ) Si 7À10z z (OH ) z

Àlumino-barroisiLe¡ ¡CaNaMgg (Cr,Sc ) zSiTAIOz z (OH) z

Fluor-alumino-barroisite : ¡CaNaMgsÀl zSizÀIOz zFzF luor-magnes i o-alumi no-katophor i te:

NaCaNaMga (Àl,Cr,Ga, Sc,Ti,V)Si 7A102 2F 2

NaCaNaMg aAlS i 7410 z 2F z

Substitution of Mg4Al by Mg¿(Cr,Ga,Sc,Ti,V)Magnes i o-alumi no-tarami te :

NaCaNaMg3(Cr,Sc)zSisÀlzOzz(OH)z . .Fluor-rnagnes i o-a Iumi no-tarami te :

NaCaNaMg3A]zsisÀlzOzzFz ..ÀlkaliAmphíbo1es ......

Magnesio-riebeckite¡ ENa2Mg3(Cr,Ga,Sc) zSisOzz(OH) z .Eckermann i te : NaNa 2Mg4 (À1, Cr rGa, Sc, I n ) Si sO z z (OH ) z

NaNa 2Mg4À1Si BOz z (OH) z

Substitution of Al by Ga , Ct, Sc and InFluor-eckermanni te : NaNa zMg¿ (e1,Ga, Cr, Sc, I n ) Si sOz zF zNaNa2Mg4ÀlSisOzzFz . . . . . .

Substitution of À1 by CrSubstitutionofAlbyGa .. .. ...Substitution of À1 by Sc . . . . .Substitution of A1 by In . . . r .

Nyböite: NaNazMgs(¡l,Cr,Sc,In) 2SizAlOzz(0H)z .NaNa2MgsÀ12sizÀ1022(0H)z , . . . c .Substitution of Mg3À12 by Mg¡ (Cr,Ga,Sc,In) z . .

Fluor-Nyböite: NaNa2MgsSczSizÀ10zzFz . .Iron-magnesium-manganeseAmphiboles ... ....

9898989999

99100100

10510s106

106106106

100100100102102102'103

103103103104104104104105

106

107107107107107107108108108108109109110110110110110

IX -

Sodian magnesi o-cummingtoni te :

NaMgNa (ug,tti ) sSi sOz z (OH ) z

NaMgNaMgsSi a0z z (oti) z

Substitution of NaMgNaMgs by NaNiNaNi5Sodian f luor-magnesio-cummingtonite :

NalrtgNaMgsSia0zzFz

v. DETATTED CHARACTERIZÀTION OF SYNTHETIC ÀMPHIBOLES

1101

'10

111

Infrared SpectroscopyPargasites: NaCazMg¡M3*Si oAlzOzz (OH) z

Richterites: (K,Na)caNauS*Si s0zz (OH) z

RiehteriLe: NaCaNaMg5Si a0z z (0H) z

Potassium-richteriLe: KNaCaMgsSi a0z z (0H) z .Manganese-richterite: NaCaNaMg4MnSi aOz z (OH)

z

Sodian magnesio-cummingtonites: NaMgNaMgsSi ¡Ozz (OH) z

Eckermannite ¡ NaNa 2MgaÀ1Si aOz z (OH) z

Rietveld Crystal Structure Refinement .Ref inement ResultsSome Comments on Rietveld Refinement .

Significance of the Residual Pattern . .Indexing of Synthetic Àmphibole Powder Patterns

VI. DISCUSSiON AND CONCTUSIONS

Previous Amphibole SynthesesCalcic Amphiboles . .

Tremol i teFerro-actinoliteÀctinoLiteFl uor-t remol i teEden i tesFluor-eden i tePargasite . .Fluor-pargasite rFerro-pargasite....Pargasite-richteriteHastingsiteMagnesio-hastingsite.. .. ..Miscellaneous calcic amphiboles . .

Sodic-calcic amphibolesRichlerite, ferro-richterite, fluor-richterite

Àlkaliamphiboles .. ..Glaucophane.....Riebeckites .. ..Magnesio-riebeckites . . . .Eckermannite......Nyböite......

Iron-magnesium-manganese amphiboles .Sodianrnagnesio-cummingtonites.. ..

Àmphibole Synthesis: This Study . . .CalcicÀmphiboles. .. .o

Tremolites........Edenites......Pargasites.......

111

128

128128132t3¿132132134136137138141142142

161

161161161164166167168168169169170172172174178179179183183186188188188189'189

192192192193193

x

Sodic-calc ic AmphibolesRichteritesMiscellaneous Sodic-calc ic Àmphiboles

Àlkali ÀmphibolesIron-magnesium-manganese ÀmphiboJ_es .

Sodían magnesio-cummingtonitesEvaluation of Characterization Methods Used in

StudyOptical Microscopy .Scanning ElecLron MicroscopyX-ray Powder Dif fractionInfrared SpectroscopyRietveld Crystal Structure Refinement .

Conclus i ons

Thi s

197197197198198198

198198200201201203204

REFERENCES

ÀDDITIONAL BIBTIOGRAPHY OF AMPHIBOTE SYNTHESES

Àppendi x

À. RIETVETD STRUCTURE ANATYSIS PROGRÀM DESCRIPTION

B. RIETVETD STRUCTURE ÀNÀLYSIS INPUT DÀTA

Observed Intensities

c. ÀMpHrBOtE END-MEMBER NAMES ÀND FoRMUTÀE, TEAKE (1979)

206

217

paqe

225

230

230

297

- xl -

F i qure

The C2/n amphiboLe

The C2/n amphibole

Infrared spectrum ofpargasite.

tTST OF FIGURES

structure projected onto ( 1 00 ) .

sLructure projected down Z. .

synthetic magnesio-hastingsite and

paqe

,4,4

26

83

95

1

2

3

6

4

5

Typical infrared spectra of naturalactinolite.

tremolite and

Scanning electron micrographsfluor-pargasites. .

of synthetic pargasites and

Powder X-ray diffraction pattern of scandium-pargasite.

Powder X-ray diffraction pattern of fluor-pargasite.

chromi um- f luor-Powder X-ray diffraction pattern ofpargasite. .

94

Scanning electron micrographs of syntheticfluor-eckermannites and fluor-nyböite.

fluor-pargasi te,

7, Scanning electron micrographs of synthetic richterites andsodian magnesio-cummingtonites. .

8. lnfrared spectra of pargasites

9. Infrared spectra of richlerites.

10. Infrared spectra of sodian magnesio-cummingtonite andeckermannite.

11,

12,

13.

14,

15.

101

129

133

13s

144

145

146

147Powder X-ray diffraction pattern of

Powder X-ray diffraction paLtern ofpargasite. . .,

gall i urn-f luor-pargasi te.

scandium-fluor-

16, Powder X-ray díffraction pattern of scandium-fluor-eckermannite.....

148

149

17, Powder X-ray diffraction pattern ofeckermannite. ..

- xr1

i ndi um-f luor-'1 s0

.18.

19.

Powder X-ray diffraction pattern scandium-fluor-nyböite.

Mössbauer spectrum of synthetic ferro-actinolite grown byErnst (1966).

20. Mössbauer spectrum ofbuffer.

synthetic hastingsite grown on the WM

21. Mössbauer spectra of synthetic magnesio-hastingsites grownon the CT and CCO buffers.

22. Infrared spectra of richterite, potassium richterite andsolid solution of richterite in tremolite.

23, Mössbauer spectrum of syntheticthe IW buffer. .

ferro-richterite grown on

24, Comparison of infrared spectra of synthetic and naturalglaucophanes. . .

25. Infrared spectra ofriebeckite.

synthetic riebeckite and magnesio-

26. Infrared spectra of sodian magnesio-cummingtonite and sodianhydro-magnes i o-cummi ngton i te

151

165

173

177

180

182

18s

187

191

19s

196

27. Cel1 volume versus radius of Lrivalent octahedralsynthetic pargasites.

catÍons in

1n28, Ce11 volume versus radius of trivalent octahedral cationssynthetic f luor-pargasites.

- xlt1

IIST OF TÀBLES

4

5

Table

'1 . NormaL Cation Site-assignments

2 Electron microprobe analyses ofhastingsites

3

10.

in Amphiboles

synthetic magnesio-

Synthetic amphiboles based on the sodian magnesio-cummingtonite and sodian hydro-magnesio-cummingtoniteendmember compos it ions

Synthetic amphiboles based on the sodian magnesio-cummingtonite formula

CeIl dimensions and optical properties of previouslysynthesized hydroxy-amphiboles: pure endmembercompositions

Cell dimensions and optical properties of previouslysynthesized fluor-amphiboLes: pure endmember compositions

non-

page

.6

33

48

50

53

63

66

71

75

6

7 Cell dimensions of previously synthesized amphiboles:endmember composi t ions

8. Sources and preparation of starting materials

9. Solid Oxygen Buffers

Possible cation-arrangements and hydroxyl-stretching bandassignments in anphiboles with tt(1,2,3) completelyoccupied by Mg and second cation, M . . .

Run Data: Isothermal ExperimenLs

Run Data: Non-isothermal Experiments . .

CeII Dimensions of Synthetic Amphiboles . . .

Synthetic amphibole structures refined in this sLudy . .

RefinementResults .. o. ..Selected Correlations from the Rietveld Refinement of

Indium-fIuor-eckermanniLe.. ..

11.

12,

13.

14,

15.

17,

. 8'1

112

122

124

137

138

-xIv-

139

16,

18.

19.

20.

21 .

¿¿.

140

1tr.)I JL

156

157

'160

Ce11 Dimensions Determined by Rietveld Structure Ànalyses

Atomic Positions

M(1 )- , M(2)-, u(3)-site Occupancies

Cation-anion and Cation-cation Distances

Typical Amphibole Tetrahedral Bond Lengthst

Comparison of synthetic and natural tremolite cel1dimens i ons

Ideal and observed area fractions for synthetic hastingsites23.

24.

162

175

178Octahedral site occupancies in synthetic magnesio-

hastingsites from Mössbauer data

-xv-

Chapter I

INTRODUCTION

Àmphiboles are the most complex mineral group and occur in a wide vari-

ety of igneous and metamorphic rocks. In sedimentary rocks, amphiboles

are found both as detrital and authigenic phases. Amphiboles have been

described from mafic and ultramafic nodules in mafic rocks, suggesting

that amphibole is a mantle phase. Rare occurrences of amphibole have

been noted in meteorites and in lunar rocks. The wide chemical varia-

tions within amphiboles result from the geometry of the amphibole struc-

ture. Several crystallographically unique sites are able to accommodate

virtualJ.y all major cations in the earth's crust. A comprehensive re-

view of amphibole crystal chemistry is given by Hawthorne (1981, 1983b).

Àlthough several synthetic amphiboles have been characterized by mod-

ern methods, the study of synthetic amphiboles has generally not kept

pace with advances in structural and crystal-chemical studies. Despite

a large number of experimental studies of amphibole stabílity (Gilbert

et al. 1982) and endnember syntheses (see Chapter 2), few synthetic am-

phiboles have been adequately characterized by modern methods. In the

studies of the late'1950's and early 1960's, run products were generally

examined by opticaL microscopy and powder x-ray diffracLion. The amphi-

boles were usually assumed Lo be of nominal composition, and additional

phases were ignored or considered metastabre. During the 1970's, more

sophisticated techniques (electron microprobe analysis, Mössbauer spec-

troscopy,

boles were

infrared spectroscopy) suggested

"off-composition".

2

that some synthetic amphi-

Natural and synthetic amphiboles can potentially display long-range

and short-range order/disorder that must be characterized for proper in-

terpretation of the results of synthesis experiments, particularly with

regard to thermodynamic modelling and the ínterpretation of natural oc-

currence in terms of synthesis and stability experiments. Of specific

importance here is cation order/disorder and chain-width order,/disorder.

This study was undertaken to critically assess the results of amphibole

synthesis and to more adequately characterize the products. The study

focussed on the characterization of synthetic, iron-free, monoclinic am-

phiboles with the CZ/n s|ructure because previous studies (..g. t'laresch

and Czank 1983, Veblen 1981) have shown that Fe-Mg-Mn amphiboles are not

only difficult to synthesize, but also are subject to short-range chain-

v¿idth disorder, high densities of stacking faults and other local struc-

tural disorder. The characterization of short-range structural disorder

requires high-resolution transmission electron microscopy; this tech-

nique was not available to this study but shoul-d be used to complement

future work, There is presently no evidence that such local struclural

disorder is a major problem with syntheses of calcic, sodic-calcic and

alkali amphiboles; but tittle work has been done. Mallinson et al.(1980) report evidence of chain-width disorder in nephrile. However,

Èhe nephrites are not typical calcic amphiboles; they occur in restrict-ed environment,s and have unusual physical properties. Synthetic Mg-rich

amphiboles in the system Na20 - Mgo - sioz - H2o have chain-widLh disor-

der at low synthesis temperatures (prits et aI. 1974, Drits et al. 1976,

Tateyama et al. 1 978 ) .

3

Run products were characterized by optical and scanning electron

microscopy (morphology; detection of foreign phases), X-ray diffraction(ce11 dimensions; detection of foreign phases), infrared spectroscopy

(ordering), and Rietveld stuct.ure analysis (ordering and site-occupan-

cies). These results, together with a review of previous monoclinic am-

phibole syntheses, rcere used to evaluate the problems of amphibore

synthesis and product characterization.

CRYSTAL CHEMISTBY

The standard amphibole formula may be written (Leake 1978) as

Ao-rB2C5T6022ll2

where, in natural amphiboles

À = Na, K

B = Na, Li, Ca, Mn, Fe2*, Mg

C = Mg, Fe2*, Mn, À1, Fe3*, Ti, Li

T = Si, A1

I{ = OH, F, Cl, 9-z

in this study, the following additional cation substitutions were at-tempted, with varying success:

B=Cd

C = Sc, Y, Cr, Ni, Cu, Ga, In

The classification adopted by the i.M.A. Subcommittee on AmphiboJ.es

(leake 1978), and the addendum to this report (leake and Hey 1g7g'), rvas

used. Endmembers pertinent to this study are listed in Àppendix c.

certain trivalent cation substitutions (cr, Ga, sc, ln) in the c-group

cations create new endmembers not explicitly accounted for by the clas-

sification. These compositions are named with an appropriate prefix.

o(ól

M(4)oM(4)

o

4

c

---t

-_+

0(71

0(sl

0(1) 0 (1)

o(21 o(31 0{2)

Figure 1: The C2/n amphibole structure projected onto (100). FrornHawthorne (1983b).

Figure 2: The C2/n amphibole structure projected down Z. FromHawthorne (1983b).

b

ï\E

b

For exampLe, in pargasite, NaCa2Mg4A1Si6A120 zz(OH) z,

formed by replacing all of the octahedral aluminum

NaCa2MgqScSi eAlz0z z (0H) z, is named scandium-pargasite.

the

wi th

5

amphi bole

scand i um,

Naming the monoclinic synthetic amphibole NaMgNaMgsSi sOz z (0H) z re-

quires clarification. Traditionally, this species is named "magnesio-

richterite" (..g. Gibbs et al. 1962), Gier et ar. 1964). Àccording to

Leake (978), it should be named sodian magnesio-cummingtonite (Àppendix

C). This amphibole is not sodic-calcic, its celI dimensions are more

similar to cummingtonite than richterite (particularly ß), and itsstructure may not have c2/n space-group symmetry (see chapters 4 and 5);

consequently the name sodian magnesio-cummingtonite is used here.

THE C2/M AMPHIB-Q!E STRUÇTURE

The amphibole structure (nigure 1) is based on a double-chain of corner-

linked teLrahedra that extends infiniteLy in the Z direction. pairs of

(ToOr r ) chains are linked by intermediate-size (0.53-0.83 Å) divalent

and trivalent C-group cations to form a module with I-beam cross-section

(nigure 2). The modules (I-beams) are joined in a three-dimensional ar-

ray by Iinking divalent and trivalent cations at the edges of I-beams

(r'igure 2)" These linkages are reinforced by B- and A-group cations at

the margins of the octahedral strip and in the cavity between the back-

to-back double chains.

6

EÀIION DISTRTBUTIONS IN ÀMPHIBOTES

The wide variety of cation coordinations in amphiboles, together with

the large structural compliance of some of the sites, leads to complex

site-occupancy and order-disorder relationships. Unless a synthetic anr-

phibole has been fulIy characterized with respect to its site-occupan-

cies and patterns of cation ordering, knowledge of iLs synthesis condi-

tions and physical properties is of limited use in formulating models

concerning the properties and parageneses of natural amphibotes. Table

1 summarizes the normal cation groupings in amphiboles. For a detailed

TABLE 1

NormaI Cation Site-assignments in Amphiboles

carion À M(4) M(1),M(2),M(3) T(t ),T(2)

SiÀ1Fe3*TiFe2*Mn

riCaNaK

f rom Ha¡¡thorne ( 1 983b )

review of cation ordering in amphiboles, see Hawthorne (i983b).

Chapter IIREVIEW OF PREVIOUS AMPHIBOTE SYNTHESES

Most previous amphibole syntheses have been restricted to three major

areas:

study of phase relations of endmembers and intermediate composi-

tions for geological applications.

Synthesis of amphibole asbestos for industrial applications.

synthesis of endmembers and intermediaLe compositions for crystal

chemical studies.

0f these, phase studies are most abundant in the literature surveyed

(about 50 percent). The products were generally characterized by X-ray

powder methods (ce11 dimensions) and optical properties were usually

measured. Industrial studies are next in abundance (about 30 percent).

unfortunately, these studies were generally crude, or were performed in

large-scale batches under poorly controlled conditions with commercial

viability as the most important consideration. Except in rare cases,

the products were inadequately characterized, resulting in very 1ittleuseful crystaJ.-chemical or st,ructural data. Syntheses of pure endmem-

bers and well-documented miscellaneous compositions for crystal chenical

studies are fewest in number (<20 percent) but are rich in fundamental

data.

2

3

7

IIn this chapter, previ.ous amphibole studies are reviewed. Those

studies with detailed product characterization are discussed in more de-

tail in Chapter 6. The review emphasizes those studies that contain ei-ther fundamenLal physical properties, or phase relations that are criti-cal to the future duplication of syntheses. Selected synthesis studies

not critically reviewed are included as an additional bibliography of

amphibole syntheses. cell dimensions, optical properÈies, and run con-

ditions are given in Tables 5, 6 and 7.

CÀtCI C_AMPHi BOLES

Tremolite: ¡Ca zMqsSi eOr r (OH)¿

Tuttle and England (1953) synthesized tremolite by heating mixtures of

MgO, cacO¡, and silica glass at 400oc and 1000 atm water vapour pres-

sure. Àt 500oC and the same pressure, the mixture crystallized to talc

and diopside. Experimental details and physical properties of the syn-

thetic amphibole are not given.-

Boyd (1954, 1959) determined the low-pressure stability of tremolite.

in spite of its chemical simplicity and widespread occurrence as a meta-

morphic mineral, tremolite is difficult to nucleate and pyroxene and

quartz persist nretastably, even in the presence of tremolite nuclei.

Boyd observed that with oxide and/or glass-bearing starting materials,

the probability of obtaining a perceptible amount of amphibole is about'1 in 3, for runs at temperatures between the breakdown curve and about

50o below the curve. Improved yields of amphibole were obtained with a

starting mixture of 50 percent submicroscopic tremolite and 50 percent

pyroxene and quartz. This sLrategy, however, stiIl yielded only 50 per-

cent amphibole, but larger yields vrere occasionally obLained.

9

X-ray powder diffractometer patterns (noyd 1954, 1959) show marked

pyroxene and quartz peaks. No evidence is given as to whether the am-

phibole synthesized is of tremolite composition. The cell dimensions of

this amphibole are gíven in colville et al. (1966). cell volume com-

pares well with other synthetic tremolites (lable 5), but the remaining

ce11 parameters vary.

Attempts to synthesize tremoLite at 800oC and 10 kbar from dry mix by

Gilbert (1969) produced tremolite and quartz. Reaction of this run

product with excess water at 30 kbar and 800oc produces talc, orthopy-

roxene, and quartz; no amphibole is reported. Yields and physical

properties of amphiboles are not reported.

Troll and Gilbert (972) also experienced difficulty in synthesizing

Lremolite. Yields of 85 to 95 percent were achieved only by long runs

with intermediate re-grinding. Two run schemes were used: (1) running

for 360 h at 650oC, 1 kbar, then re-running under the same conditions

for '1506 h, and Q) running tor 362 h at 775oC, 4 kbar, re-grinding and

running for 618 h under the same conditions. The 4 kbar runs are

slightly better crystallized than the 1 kbar runs. Grain size of the

largesl amphibole crystals is 10 to 15 nicrons. Cel1 dimensions are

given (rante s).

Jasmund and Schäfer (972) studied the join tremolite - alumino-

tschermakite at 1,2, and 3 kbar using gel starting materials. Àmphi-

bores grown in these experiments are only about 2 microns in size.

Yields of amphibole and proportions of other phases were not given for

runs in the endmember tremolite stability field. Cell dimensions were

10

determined for selected compositions between tremolite and tremol-

ite¡0.. "alumino-tschernakiteso (alumino-magnesio-hornblende) but lvere

not published because they do not show significant variation. Jasmund

and Schäfer (972) account for this lack of ceIl-parameter variation by

proposing that the decrease in cation-oxygen distance, from substituting

À1 for Mg in the octahedral strip, is largely balanced by the increase

in cation-oxygen disLance from the substituLion of Àl for Si in the tet-rahedral chains.

Westrich (1978) synthesized tremolite from gel prepared after the

method of Hamilton and Henderson (1958). The mixture was seeded rvith

about 5 percent natural tremolite, reacted for 45 h at 900oC and 4 kbar

water pressure, then reground and run again for 45 h. Cell dimensions

(rabte s) given for this synthetic amphibole are peculiar, especiarly g

and c. It is probable that the X-ray powder pattern was incorrectly in-

dexed. Impurity phases are reported to be less than 4 percent.

In his study of the tremolite-pargasite join, Oba (1980) grew fibrous

or acicular tremoliLe crystals up to 5 microns wide and 20 microns long

from dry mixes. According to his Table 1, 100 percent yields were not

realized; clinopyroxene at 1 kbar, and crinopyroxene plus quartz at F

kbar were present. He attributes the presence of lhese phases to me-

tastability' the result of sluggish reaction rates, and notes that theirproportions decrease with increased run length. Electron microprobe

analyses are given for coexisting amphiboles on the join, but analyses

of endmembers are not reported.

11

Jenkins (1981) suggests that synthetic tremolite is non-stoichiomet-

ric, having a Ca/(Ca+M9) ratio of about 0.88 for cations assigned to the

M(4) site. This implies that there is solid soluLion towards magnesio-

curnmingtonite. Experimental details are not given.

Hoschek (1973) synthesized tremolite for use as one of the reactants

investigation of the reaction:

Sphlogopi te+6calc i te+24quartz=3tremol i te+5K-f eldspar+H 2O+6CO 2

Gel starting materials were prepared after Hamilton and Henderson

(1968). Run conditions were 600o to 7s0oc, 4kbar, for 30 to 50 days.

Àmphibole crystals measured about .10 microns long and about 0.1 microns

thick. Refractive indices are: a=1.602(3) , r=1.628(3). Non-amphibole

phases comprised up to 2 percent of the run product.

I{ones and Dodge (1gll ) reported problems with tremolite synthesis;

all run products contained 1 to 2 percent quartz and diopside. CeIl di-mensions are given (rabte s). They note that a survey of over 1200 am-

phibole analyses from Deer et at. (1963) and Leake (1958) produced only

nine analyses in which the calculated strucLural formula contains be-

tween 1.90 and 2.10 ca, fewer than 2.10 À and B cations, and greater

than 7.80 Si. Furthermore, N. Chatterjee (pers. comm. 1971 to lJones and

Dodge) concludes that tremolite synthesized at 7500C contains 5 to .10

moJ.e percent rMgTSi¡0zz(0H)2. Because of these data and because previ-

ous workers (noyd 1959, Troll and Gilbert 1972) aLso describe difficul-ties in synthesizing tremolite, they suggest that stoichiometric trenol-

ite may not be stable above 700oC.

12

Gilbert (1969) attempted to synthesize tremolite from a dry mix at

800oC and 10 kbar. The result is amphibole plus quartz. Gilbert states

that the mix contained excess si0z. t¡either yields nor physical proper-

ties of the amphibole are given.

Ferro-actinolite: ¡ca rFel0si ror, ( oH)¿

Ernst (1966) determined the stability of ferro-actinolite in convention-

aI hydrothermal apparatus with excess water at oxygen fugacities defined

by lhe WM, IM, FMQ, NNO, and MH buffers. Starting materials comprised

reagent-grade CaO, Fe203 and Si02 corrêsponding to ferro-actinolite

stoichiometry. Hematite was reduced to metallic iron by exposure to Hz

at 6000C for one-half hour before using the mix.

Ferro-actinolite is stable only at relatively low oxygen fugacities

approximately defined by the FMQ and IM buffers. Yields of amphibole up

to 95 percent of the charge were achieved with difficulty and only by

regrinding previousJ.y crystallized lower-yield runs. Grain size aver-

aged about 0.3 x 0"3 x 5 microns. Long runs produced more amphibole

than short runs. The remainder of the products consisted of the high-

temperature and/or high-oxygen fugacity assernblages of anhydrous phases

designated as equivalent in bulk Ca-Fe-Si proportions to ferro-actinol-

i te.

Cell dimensions and mean refractive indices of 10 typical ferro-acti-nolites grown at 4060 to 5370c, 500 to 3000 bar, -23.9 to -33.6 log fO2

are given (tabte s). According to Ernst, þ decreases slightly with in-

creasing f02 and decreasing temperature. He attributes this variation,

if real, to the increase in Fe3*/îe2* ratio of ferro-actinotite at ele-

vated oxygen fugacities and low temperatures. The decrease

dius produced by the oxidation of iron could account for

octahedral strip contraction in the Y axis direction.

'13

in ionic ra-

a transverse

Tremolite. . .Eerro-actinolite Series

Hellner and Schürmann (1966) investigated the lower thermal stability of

compositions along the joín rCa2Mg5Sia0zz(OH) z - ¡CazFesSigOzz(OH) z at

about .1 kbar water pressure and 50 bars carbon dioxide pressure. Start-

ing materials consisted of CaCO¡, MgC 20a,2H2O, FezCz0¿ .2llz) and silica

9e1. Although oxygen fugacity was apparently not consistently control-

1ed during the experiments (Mueller 1967 , Hellner and Schürmann 1 967) ,

it was probably close to that of the FMQ buffer.

Yie1ds of amphibole in the amphibole stability field are not explic-

itly given; however, it is implied that they are close to 100 percent

(table 2, Hellner and Schürmann 1966). Cell dimensions were not deter-

mined but d-values for the (110) and (25'1 ) spacings are given for acti-nolites gro$In at 550oC. Amphiboles grov¡n at lower temperatures did not

produce X-ray powder patterns of sufficient quality.

Àctinol ite-CurrminqtoniLe Ser ies

Cameron (971, 1975) synthesized amphiboles along the join

!Ca2Mgz. sFez. sSi a0z z (0H) z - !M9s. sFes. sSi aOz z (OH) z. Starting materials

consisted of MgO, Fe-sponge, CaCOg, Fe203 and Corning 7940 silica glass.

Actinolite formed crystals less than 5 microns long and 0.5 microns

v¡ide. Cummingtonite crystals were larger, reaching a maximum size of

about 15 microns long and 3 microns wide. when both were present, they

14

could be distinguished optically with certainty. Ce11 parameters (table

5) are given for endmembers and for several coexisting acLinolites and

cummingtonites. Modes of amphiboles and other phases were estimated

from X-ray powder patterns. Àmounts of 5 percent of a phase indicate

that it is barely, but definitely detectabte; one percent indicates that

it is only detectable optically as scattered grains. Amphibole yields

increased at the expense of anhydrous phases when charges were rerun.

Some charges less calcic than than Àct6eCumas r,i€re converted to about 99

percent amphibole(s) in runs of 40 to 60 days.

Ca contents and Fe:Mg ratios of clinoamphiboles were estimated from

dtoo spacings and b cell dimensions, respectively. À linear determina-

tive curve of Ca versus droo was constructed (but not published) using

data from two runs; one with 99 percent cummingtonite, the other, 99

percent, actinolite. Fe contents of cummingtonite were estimated using a

determinative curve of Fe content versus b-cell dimension for the series

cummingtonite-grunerite (nlein and }laldbaum 1 967) , Fe contents of acti-nolites were estimated from a similar curve (also not published) usíng

the b cell dimension data for trernolite (royd 1gig, Colville et aI.1966), ferro-actinoliLe (Ernst 1966), and an actinolite from his own

study with ¡'e;Mg = 1. partial electron microprobe anaryses, using the

intensity ratio method described by Eugster et al. (1972), were also

used to estimate the Ca contents and Fe-Mg ratios of two actinolites and

three cumminglonites.

Because of the small grain size, precise refractive indices could ¡-¡ot

be determined for actinolite. The approximate average of a and 7 indi-ces of crystal clumps of bulk composition of 100 percent actinolite is'1.660. Refractive indices of cummingtonite are o=1.650(3), r=1.668(3).

'15

Fluor-tremol i te : ¡Ca rMo q in0rrFr

Ehrenberg (1932) unsuccessfully attempted to synthesize fluor-tremolite

by solid-state reaction from a mixture of caF2, cacog, Mgo, and sio2.

Experiments were performed at 620o, 750o and B00oc. x-ray examination

of the products showed that amphibole was absent in all runs. Run prod-

ucts included forsterite at 620oc, and forsterite plus diopside prus

fluorite at 750o and 800oC.

Grigoriev (1939) investigated the effect of 1, g, 5, and i0 percent

Alz0¡ on the optical properties of synthetic fluor-tremolite crystal-

lized from a melt starting at 14000c. He claims'100 percent yields of

amphibole, based on microscopic examination of the run products. The

results demonstrate that an increase in ALzO¡ causes a decrease in re-

fractive indices and extinction angle.

Eitel (952) noted that in the synthesis of fluor-tremolite by solid

state reaction at 1000oC, the phases formed are dependent on the fluo-

rine content of the starting mix. Increasing fluorine content from 2 to

6 atoms per formula unit íncreased the yield of amphibole. Diopside,

although always present, decreases in abundance with increasing fluo-

rine. Other phases, observed but not in all runs, include norbergite,

tridymite, CaFz, M9Fz, M9O, CaSiO¡, and CasSizOz. Specific yields are

not sLated, but were apparently not close to 100 percent. Higher yields

were obtained by melting batches at 1400oc and cooling to 12000c in 2 h,

but close to 100 percent amphibole was not achieved. physical. proper-

ties of the amphiboles grown are not given.

Boyd (1954) synthesized fluor-tremolite by solid-state

about 1000oC and 1 atm. No physical properties are given.

16

reaction at

The first well-characterized synthetic fluor-tremolite was grown by

comeforo and Kohn (1954), also reported in shell et ar. (i958). À

starting mix of MgFz, M90, finely-ground quartz and natural wollastonite

was melted at'14500c, maintained at this Lemperature for 4 h, and then

lowered at a rate of 5och-1 to 1100oC. Single crystals of fluor-tremol-

ite up to 4mm long were formed; the yield is not reported. Ànarysis of

a beneficiated sample gave the formula:

Nao. o sCa r . g lM9s. r sSi z . g o0z zFz

The slight excess of Mg is attribuLed to a small amount of glass. opti-caI properties and density are given. Cel1 dimensions were calculated

from (600), rc 12 0), (461), and (661) reflections.

Fluor-tremolite crystals suitable for single-crystal structure re-

f inement vrere grolrn by Cameron ( 1 970 ) and Cameron and Gibbs (973 ) f rom

a mix having the composition cacos'caFz'SMgo.8sio2. The charge rvas run

for 1 week at 1150oc, 1 atm; it was converted to greater than 95 percent

fluor-tremolite crystals up to 0.08 mm in size. Cell parameters vrere

calculated frorn single-crystal diffractometer dat,a.

Troll and Gilbert (1972) achieved 80 to 90 percent yields of fluor-tremol-íte with starting mixes prepared from caco¡, caFz, Mgo, and corn-

ing 7940 silica glass. Charges vrere reacted in sealed Pt capsules be-

tween 1090o and '1155oc at 1 atm f.or 20 h to 1 week with the same

equipment used by Caneron (1970)" Àlthough long runs produced larger

crystals than short runs, yields of amphibole were not increased. Non-

amphibole phases were clinopyroxene,

bal i te.

17

fluorite, and tridymite or cristo-

westrich (1978) attempted to synthesize fluor-tremolite from an an-

hydrous gel of tremolite composition. Dilute (5 percent by volume) HF

solution was added to the ge1 and the mix was reacted in a sealed

ÀgzoPdso tube at 9000c for 24 h, CelI dimensions of the resulting am-

phibole are peculiar and are not similar to any other fluor-tremolite

ceI1 parameters (taUte 6). These results may reflect experimental prob-

lems wiLh using HF as a source of fluorine, rather than the usual solidfluoride. Reaction of HF with other mix component,s, Ieading to anoma-

lous products, is suggested (cf. Manning 1978).

Edenites: NaCarMq¡SizÀlOr r (OH)¿

Boyd (1954) synthesized edenite hydrothermarly in the range g00o to

9000c and 400 to 1000 bar. Optical properties are in accord with those

of corresponding natural amphibores. No other details are given.

Colville et al. (1966) synthesized edenite from a dry mix reacted at

8500c, 2 kbar for 3 days. Àmphibole yields and the presence of non-am-

phibole phases, if any, are not reported. Cell dimensions and refrac-tive indices are given (ra¡te s). The c-dimension, s,236(1s) Â is obvi-

ously in error; it is likely that the cell dimensions were not refined

correctly.

Gilbert (1969) reported edenite synthesis from oxide mix at 900oC and

20 kbar. Clinopyroxene, forsterite and traces of glass $rere present in

the run product. No yields or physical properties are given.

18

Petó (1976) reacted both gels and glasses of anhydrous edenite compo-

sition with water at 0.5, 1.0 and 2.0 kbar. certain runs after 139 to

288 h grew fine-grained, acicular crystals of amphibole presumed to be

edenite, plus diopside, forsterite, and albite. Refractive indices ß

and 7 are given. Other experiments grew abundant richteritic amphibole

plus abundant diopside and forsterite. Initially, the upper stabilitylimit of pure edenite is defined by the reaction (petö 19j6)t

4ed = 8di + 6fo + ab + 3ne + vapour

However, it seems that in the presence of diopside, forsterite, albiteand vapour, edenitic amphibole reacts with albite; Na+Si from albite re-

places Ca+41 in edenite to form richteritic amphibole and aluminous

diopside:

ed(ss) + ab = ri(ss) + di(ss) + fo

suggest that edenite is not stable at its own bulkThese experiments

composition.

Hinrichsen and Schürmann (977 ) investigated the join edenite

(HacazMg¡si7A1o2z(oH) z)...potassic-edenite (ncazr¿g¡sizÀIozz(oH)z). po-

tassium-bearing starting mixes were prepared from K20.caO.65ioz glass

plus À120s and MgO. Sodium was added as NazCOs. The amount of water

added to capsules vras kept small, generaJ.ly ress than 5 percent, in or-

der to minimize dissolution of componenLs in the vapour phase. Runs

lasted from14 to 30 days at water pressures between 0.b and 4.4 kbar,

and tenperatures between 700o and 9500C.

Hinrichsen and Schürmann (977) claim that "unequivocally" edenites

were synLhesized at 750oc and 4 kbar in the range Naroo-Na¡oKso with

yields of more than 95 percent. Àt Na25K7¡ diopside and phj.ogopite dom-

19

inated and reliable identification was impossible. pure potassic-ede-

nite was grov¡n from a single run at 750oc, 0.b kbar. This amphibole was

less than 5 percent of the run product, but x-ray and electron-micro-

scope identification was "without any doubt" according to Hinrichsen and

Schürmann. CeIl dimensions are given for pure edenite and the interme-

diate member, Na¡oKso. À rough vaLue is given for potassic-edenite,

calculated from an "extremely bad" X-ray pattern.

Greenwood (1979) was unable to synthesize '100 percent edenite. At-

tempts to duplicate the results of Colville et al-. (1966) tailed to grow

amphibole without the presence of other phases, particularly diopside

and soda montmorillonite. À11 experiments with edenite bulk composition

whether crystalline, glass, or dry mix produced only minor amphiboLe.

Amphiboles groh'n from edenite bulk composition were not characterized.

Oba (1980) reported the synthesis of edenite at 800oC and 2440 bar

water pressure. Amphibole was claimed as the only phase in the run

product besides vapour. The upper stability of edenite was determined

to be 825oC at 1 kbar. No physical properties are given.

Fer ro-eden i te: NaCa 2FeA +Si 7ÀlO2 2 (oH)¿

Colville et aI. (1966) claimed to have synthesized ferro-edenite from a

dry mix reacted at 600oc, 3 kbar for 31 days. oxygen fugacity was con-

trolled on the It't buffer. Amphibole yields, and the abundance and na-

ture of non-amphibole phases are not reported. Ce1l dimensions and re-fractive indices are given.

20

Loida and Hinrichsen (1975) synthesized edenitic hornblende and par-

gasitic hornbrende with 100 percent yields at 8000c, 4 kbar; noninal

compositions vrere Nae.5Ca2MgaAlSio.sOzz(OH), and

Nao.zscazMg¿Àrsio.zsAlr.zsozz(oH)2 respectively. ce11 dimensions are

given (ta¡te z)

FIuor-edeniLe : NaCa zMqsSir¿le"rF,z

EiteI (1952) grew fluor-amphibole by solid-state reaction at 10000C for

15 h fron mixes of fluor-edenite composition. Diopside, forsterite and

fluorite rvere present in minor amounts. Increasing the fluorine concen-

tration did not improve the yield. Fluor-amphiboles were aJ-so produced

by cooling a melt of fluor-edenite composition from 14000 to 12000C in 2

h. The crystallization of fruor-amphibore was greatly improved by in-

creasing fluorine concentration, but diopside, forsterite, fluorite,NaF, and Na-phlogopite were arso produced. The amphiboles grown in

these experiments were not characterized.

Boyd (1954) claimed to have synthesized fluor-edenite in sealed pt

tubes at abouL 1000oc and '1 atm pressure. No physical properties are

given.

Kohn and Comeforo (1955), using methods and materials similar to Co-

meforo and Kohn (1954), achieved at least 80 percent yields of fluor-e-

denite. Fractions of this material were beneficiated by heavy-1iquíd

separation until the only contaminant was about 1-2 percent clinopyrox-

ene, and about 0.5 percent others. The beneficiated material was chemi-

cally analysed and the calculated formula (including impuriLies) is:

Nao. ggCal. a+Nao. r eMg¿.zsAlo. r aSiz. I zÀ10. ea0z2Fz.s5

Cell dimensions and optical data are given (fabte 6).

21

Boron-edenite was synthesized and characterized in the same way. Itschemical formula (including impurities less Lhan 4 percent of which 3

percent is forsterite):

Nao.ssCal . szNao. I sMg¡. g zSiz. I sBo .gz}zzFz. lo

Parqasite.. .Ferro-parqasite: Naca2(Mg,Fe) ¿Àlsi eAlroz z (oH)*

Boyd (1954, 1956, 1959) determined the high-temperature stability rela-

tions of pargasite from dry starting mixes. Optical properties and celldimensions are given in cotville et ar. (1966) and Table 5. An x-ray

powder diffractogram shows a prominent peak attributed by Boyd to nephe-

line plus diopside.

Gilbert (1959) synthesized pargasite at B00oc, 10 kbar, and 900oc, 20

kbar from dry mix. clinopyroxene was also present. Reaction of parga-

site plus clinopyroxene at 800oC and 20 kbar apparently decreased the

amount of clinopyroxene, which is indicated as being netastable in the

run table. No amphibole was observed after reacting pargasite plus cli-nopyroxene between 28.2 and 38,7 kbar. physical properties and yieJ.ds

are not reported.

Gitbert (1965, 1966) studied the stability relaLions of ferro-parga-

site as a function of oxygen fugacity, temperature, and fluid pressure.

Starting materials were either dry mixesr or minerals synthesized from

these mixes. The largest crystals, 20 to 30 microns long, were obtained

at temperatures of about 800oC on the IW and WM buffers. Crystals grolrn

on the FMQ buffer at about 600oc averaged only 1 to 10 microns inlength. At oxygen fugacities defined by more oxidizing buffers, and at

lower temperatures, ferro-pargasite crystals were commonly full of in-

22

clusions of reacLion products, making them difficult to characterize.

Cell dimensions are given for ferro-pargasite synthesized on the IW, ttM,

FMQ, and NNO buffers (faUte S). X-ray powder diffraction daLa are given

for those grown on the I}l, I.lM, and FMQ buffers; cell dimensions were re-

fined in this study from these data (rabte s). viith increasing relativeoxidation, the cell volume decreases, accompanied by decreases in g and

ß dimensions. The þ and g cell dimensions do not show systematic varia-

tion. These changes suggest oxidation of some of the ferrous iron inthe octahedral strip to smaller ferric iron.

Holloway (1973) synthesized pargasite from both dry mixes and gels.

The fluid phase contained either pure H2O, or CO2 plus H2O. Varying

amounts of C02 ín the system had no apparent effect on the cell parame-

ters of pargasite. CelI dimensions are given for a pargasite grown with

pure H20 (rable s). Àmphibore yield is not stated, but pargasite was

listed as the only phase present in this run product.

Holloway and Ford (1973, 197s, i976) synthesized pargasite with 0.g7

F atoms in the half-cell (43 mol percent fluorine). Fired gel plus CaF2

were run with'10 percent by weight H2o for 5 days at 10s0oc. Amphibole

yield was about 99 percent rvith minor clinopyroxene and spinel. physi-

cal properties are not given.

Charles (1974a, 1980) synthesized pargasite in a study of amphiboles

across the join NaCa2Mg4ÀlSisÀlzOzz(OH)z - NaCazFe4AlSioAlzOzz(OH)z at 1

to 5 kbar. starting mixes were of the dry type, consisting of Mgo,

7-À1203, MgO, Si0z (cristobalite) and NazSiz0s. Pargasite yields varied

from 50 to 99 percent but cerl dimensions do not vary with yield. Non-

23

amphibole phases vlere mainly pyroxene and plagioclase. Charles (1980)

suggests that either charges with low amphibole yield are non-stoichio*

metric pargasitic amphibole with ce11 dimensions fortuitously similar tothose of purer charges, or more probabry, the amphibole is on composi-

tion. Intermediate phases were grown on MH, FMQ, ccH¿, and llt buffers.

Yields varied from 50 to 95 percent. For a given bulk composition, cel1

parameters are constant with pressure, temperature, and oxygen fugacity.

Pyroxene and ptagioclase were present in all products. Intermediate

compositions did not nucleate well; amphiboles in these runs formed only

as crystalline aggregates about 5 microns in diameter. Variation of

unit celL paramet,ers is linear with changing te/ug ratio. charles

(1980) concludes that this indicates disorder of Mg and Fe in M( 1), ttt})and M(3) sites. Ferro-pargasite crystallized r.'ith yields of 90 to 95

percent. Cell dimensions do not change with run conditions.

DrolL and Seck (976) synthesized the solid solution series pargasite

- fluor-pargasite from oxide mixes at 2 kbar according to the Lext of

the paper, but at 1 kbar according lo the title. The H20/HF ratio was

determined during long runs by means of an ion-selective t'-electrode.

Substitution of (OH) by F increased the a cell dimension from 9.81 to

9"88 in fruor-pargasite. This is contrary to other pargasite...fluor-

pargasite pairs and to experience with the same substitution in other

amphiboles, in which a decreases from the 0H to the F endmember.

Hinrichsen and Schürmann (977 ) attempted the synthesis of certain

nembers in the series NaCa 2MgaÀlSi 6À1 z0z z (OH) 2 - KCa 2MgaÀ1Si oÀl zOz z (Ott) z

from dry mixes. Pargasites were successfully synthesized only in the

composition range from NarooKo to NasoKso at temperatures from 750o to

1000oC, and pressures from 1 to 4 kbar. yields of

er than 95 percent. Cell dimensions are given

Na I ooKo and NasoKso (tables 5 and 7). Substitution

a slight increase in all celt dimensions.

24

amphibole were great-

for the compositions

of K for Na produced

Braue and Seck (977 ) studied the stability of solid solutions on

the join pargasite - richterite at 1 kbar water vapour pressure. Dry

starting mixes were used. An almost complete solid solution series on

the join was synthesized at total H2O pressure of '1 and 3 kbar and temp-

eratures of 850o and 900oC respectively. Satisfactory synthesis of am-

phibole was not possible at 850o and 900oC at 1 kbar on the composition

pa5eri5s. Àmphibole yieJ.ds were close to 100 percent at 3 kbar with mi-

nor amounts of metastable diopside, clinopyroxene and forsterite. At 1

kbar, however, experiments were complicated by a smectite phase which

persisted metastably to 950oC. This sheet silicate is characterized by

a basal reflection at 11.6 Å which expands sIowly to 14.4 Å in a hydrous

atmosphere. Treatment with organic liquids do not cause further expan-

sion. Braue and Seck (977 ) conclude that this sheet silicate is a

trioctahedral vermiculite. Reheating the 1 4,4 A phase reproduced the

11.5 Â phase, and increasing the temperature to 750oC finally yielded a

broad peak at 9 to 10 Å. Quenching immediately after initial run-up to

850oc suggests that this phase forms primarily during the heating-up

period. This conclusion is reinforced by the presence of vermiculite in

pressure*quenched runs. Conditions for the growth of this phase are ap-

parently most favourable on the bulk composition pasorisoi none was ob-

served in richterite-rich compositions. Two different amphiboles were

synthesized in this study. The first, amp I(ss), coexists v¡ith vapour

25

in the subsolidus region with minor metastable diopsidic clinopyroxene

and forsterite. The second, amp Il(ss), is produced at the solidus de-

fined by the reaction:

amp l(ss) + vapour = amp II(ss) + cpx + fo + liquid + vapour

No feldspar or nepherine were detected either optically or by x-ray dif-fraction. Cell dimensions are given for endmember pargasite and richt-erite, âs well as for intermediate amp l(ss). (tables 5 and 7). cellvolume, ê,, þ, and ß vary smoothly but show positive deviations from lin-earity. Variation in c is small compared to the standard error; it de-

creases with increasing richterite component in the solid solution.

westrich (1978) and Westrich and Holloway (1981) synthesized parga-

site from anyhydrous gel prepared after Hamilton and Henderson (1968).

The gel was crystallized hydrothermally at 12050C and 4 kbar water vap-

our pressure tor 72 h, ÀmphiboLe yield was greater than 96 percent;

cel1 dimensions are given (rabte S).

Oba (1980) synthesized pargasite in sLudy of the tremolite - parga-

site join at 1 and 5 kbar in the temperat,ure range 7500 to 1150oc.

Starting materials, method and results were discussed above in the tre-molite section. Pargasite yields are not explicitly stated but amphi-

bole is listed as the sole phase in the pargasite stability fierd. Àl-

though eleclron microprobe analyses are given for amphibole solid

solutions, no single phase endmembers ¡lere analysed. Cell dimensions

are given (table 5).

semet f972, 1973) synthesized pargasite at B00oc and 2 kbar. Except

for the infrared speclrum, no physical properties are reported. The

26

3800 3?ìCO Cm-l 3600

ACuyile-Ternrile Buf fer85trC, 2 Kb

lrrrQuorlz-Foyolite Buffer

850"C,2Kb

Porgosile800"c, 2 Kb

3660

3705

B

c

H

oH(toJ 42

Figure 3:

3705 3675

3705 72rlrrlJL__trr

38OO 37OO ¡--r 3600Cm-l

Infrared spectrum of synthetic magnesio-hastingsite andpargasite. À: magnesio-hastingsite. B: magnesio-hastingsite. C: pargasite. From SemeE (972),

27

spectrum consists of two major peaks at 3705 cm-1 (MgMgMg-oH) and 3672

cm- 1 (ugt'lgel-oH) , and a minor peak at 3642 cn- i (ugetet-oH) (nigure 3 ) .

A1 occupancy of M(1) and M(3) calculated from this spectrum is 0.23t0.05

ions per site, indentical within error to lhe ideal 0.20 ions per sitefor completely random distribution of Mg and AI among the octahedral

sites (Semet 1973).

FIuor-parqasi te: NaCa rMq¿AlSi ÂÀ1 tO. tF,

Boyd (1954) reported the first synthesis of fluor-pargasite from charg-

es sealed in Pt tubes and reacted at temperatures a little over 1000oC.

Yields were not '100 percent; fluor-amphiboLes grolrn were always mixed

with other phases.

Holloway and Ford f 973, 197s, 197G) studied the phase rel_ations of

a pargasite with 43 percent of oH at the o(3) site replaced with F. F

was added as CaFz to a fired gel. Amphibole yield was 99 percent with

minor clinopyroxene and spinel. No physical properties are given.

Dro1l and Seck f976) give lhe a-ceLl dimension of a fluor-pargasite

grov¡n during a study of lhe pargasite...fluor-pargasiLe join. No other

data were reported.

llestrich (1978) and }lestrich and Navrotsky (1981) synthesized fluor-pargasite from a gel with P added as caF2. The mix was reacted at

1000oC and 1 atm tor 24 h. Grain size of the resulting amphibole was

less than 5 microns; other phases constituted 1 Eo 2 percent of Èhe run

product. Cel1 dimensions are given (fabte 6).

28

Alumi no-maone io-hornblende: ¡Ca,Mo,À si zÀ10, , (oH)*

Boyd (1954) reported that a gLass with composition midway on the tre-molite...alumino-tschermakite join (alumino-magnesio-hornbLende) was al-most completely crystallized to amphibole at 800oC and 10 kbar pressure.

No physical properties are given.

Gilbert (1969) attempted to synthesize al-umino-magnesio-hornblende

from glass (probably the same glass as used by Boyd 1gs4) at g00o and

900oC and 10 kbar. Run products were dominantly amphibole with minor

clinopyroxene, orthopyroxene, and garnet. At 700oc and 20 kbar, less

anrphibole was produced and talc is present. No physical properties or

yields are given.

Jasmund and Schäfer (1972) apparently synthesized alumino-magnesio-

hornblende on the join tremolite...alumino-tschermakite. 100 percent

yierds are implied by symbors on the 2 and 3 kbar phase diagrams, but

the 1 kbar phase diagram appears to be in errori the symbols do not ap-

pear in the key. If the symbols are what they appear to be, the arumi-

no-magnesio-hornblende yields at 1 kbar are generally not 100 percent.

No physical properties are given. x-ray diffractograms are given for

compositions along the join but none are for run products in the amphi-

bole stability regions

Fluor-alumino-naqnesio-hornblende: !ca2Mq4Àlsi7A1o? 2F 2

Shell et aL. (1958) crystallized a melt at 1 atm with composition corre-

sponding to fluor-alumino-magnesio-hornblende. They found that with low

fluoride content, the aluminum lends to combine with calcium and siliconlo form anorthite. As fluoride content increased, ca-phtogopite grew at

29

the expense of amphiboì.e. Although amphibole was apparently present, no

estimates of abundance are given.

Àlumi no-tschermak i te : ECa rMqsAl rSi sAI r0r r (oH)¿

Àlumino-tschermakite synthesis r+as first attempted by Boyd (1954). Allhydrothermal experiments at pressures less than 2 kbar failed. At 800oC

and 10 kbar, however, a gLass of alumino-tschermakite composition was

partly crystarlized to amphibole. No physical properLies are reported.

Gilbert (969) reported the synthesis of 85 to 90 percent amphibole

from a glass of alumino-tschermakite composition at 800oC and 10 kbar.

It was tentaLively identified as tschermakite, but no supporting physi-

cal properties are given.

Jasmund and Schäfer (1972) studied the join tremolite - alumino-

tschermakite (see Tremolite section). They were unable to synthesize

amphibole on the composition of alumino-tschermakite at 3 kbar or less.

À reconnaissance run at 10 kbar also failed to yield amphibole.

The most comprehensive survey of synthetic alumino-tschermakite is by

oba ('1979), who studied lhe alumino-tschermakite - ferri-tschermakite

join at tenperatures between 750o and 1000oC at water pressures of 5 to

24 kbar. Run products were characterized by x-ray diffraction, optical

examination and by microprobe analysis for two compositions in equilib-

rium with garnet. No endnembers vrere analysed. Refractive indices and

ce11 dimensions are given. Àlthough 100 percent amphibole yields are

implied for several products in his run table, yields are not explicitlyreported. The amphiboles in equilibrium with garnet are not on composi-

30

tion; they are deficient in octahedral aluminum and contain excess mag-

nes i um.

FIuor-aLumi no-tschermak i te : ECa 'Mo

rAl, i nAl r0, ,F,

Boyd (1954) reported the synthesis of fluor-alumino-tschermakite by sol--

id state reaction in sealed pt tubes at 1000oc and 1 atm pressure. No

physical properties are given.

Shell et a1. (1958) attempted to grow fluor-alumino-tschermakite from

a me]t. No amphibole was obtained; the product was Ca-bearing rnica and

anorthite.

Hastinqsite: NaCa2Feî*Fe3*Si6À1?0, 2 (Ou)¿

CoIville et aI. (1966) claimed hastingsite synthesis at 600oc and 3 kbar

on the FMQ buffer. Run length was 31 days. Run procedure and startingmaterials were the same as those of Ernst (1960). No information ispresented concerning amphibole yield or the nature of the run product.

Cel1 dinensions and refractive indiees are given"

Malinovskiy (1966) reacted a dry mix of hastingsite composition plus

excess iron hydroxide in a neutral 10 to 12 percent solution of sodium

chloride at 5000 to 600oc and about 500 atm. Clinopyroxene is the main

product along with about 10 to 15 percent amphibole. More amphibole

crystallized from a mix with non-stoichiomelric composition,

ca0:Alz0s:si0z ='10¡22,5267,5, such a mixture, reacted in Nacl solution

rvith excess iron, produced amphibole plus magnetite. The amphibore

formed intensly pleochroic, green, acicular and elongated prisms up to 1

to 1.Smm long. A powder X-ray pattern and refractive indices are given.

31

Chemical analyses of two of the amphiboles showed that they contain 0.86

and 0.78 percent Cl respectively. The relative error in these anaLyses

is 15 percent. The amphibole composition corresponds to an intermediate

member of the hastingsite...ferro-edenite series.

Gilbert (1969) determined that hastingsite is not stable at T >650oC

at 20 kbar, or aL T >700oc at 12 kbar when oxygen fugacity was control-

led by the FFsM buffer. On the FMQ buffer, hastingsite is not stabLe

above 750oc at'12 kbar. No physical properties of the synthetic amphi-

bole are given.

Thomas f977, 1979, 1982a, 1982b) studied the upper thermal stabilityof hastingsite as a function of temperature, fluid pressure and oxygen

fugacity. Starting materials for synthesis runs comprised dry mixtures

or gels of anhydrous hastingsite composition. Run products were charac-

terized optically and by X-ray powder diffraction. Cel1 dimensions (ra-

ble 5) and Mössbauer spectra (nigure 20) are given for selected samples.

Synthetic hastingsite formed acicular grains less than 10 microns 1ong

and about 1 to 4 microns wide. Àmphibole yields in the IQF, IT{ and }lM

buffers were general.ly greater than 95 percent, but on the FMQ buffer,

yields were ]ess. Thomas (1979) is confident that the hastingsites are

on conposition because ce11 parameters are similar for all hastingsites

synthesized, proportions of breakdown phases are qualitatively similar

in all runs, and high yields from mixes of the proper stoichiometry

should be of Èhe nominal composition.

Charles (1978) studied the stability of the hastíngsite bulk composi-

tion on the IW, ccH¿, FMQ, NNo, and MH buffers. Àmphibore yields were

32

95 percent on the CCH¿ and FMQ buffers; impurities were cLinopyroxene

and plagioclase. Cell dimensions are uniform, regardless of temperature

or buffer conditions.

Maqnesi o-hast inqsi te : NaCa 2Ms4Fe 3 *Si 6Al ?02 2 (OU )¿

Semet (1970,1972,1973) and Semet and Ernst (1981) studied the stabili-ty relations and crystal chemistry of magnesio-hastingsite synthesized

from dry mixes at 850oc and 2 kbar pressure. They measured optical

properties, ce11 dimensions (tabIe 5), collected Mössbauer (Figure 2'1 )

and infrared spectra (nigure 3), and give two electron microprobe analy-

ses of the synthetic amphibole (rabte Z). Yields of 90 to 100 percent

amphibole are claimed for initial syntheses. Àt low oxygen fugacities,

however, up to 10 percent by volume of high-temperature breakdown phases

of equivalent composition was present. Àmphibole synthesized directlyfrom the dry mix is very fine grained (10 x 5 x b microns); long runs

did not produce larger crystals. Larger crystals(100 x 20 x 20 microns) were synthesized from the high-temperature as-

semblage of equivalent bulk composition. Semet notes a significant var-

iation in both colour and refractive indices with oxygen fugacity, that

is, with changes in the val-ence of iron.

Electron microprobe analyses of an amphibole grown on the CT buffer

and one grovrn on the IQF buffer show that both amphiboles are close to

theoretical magnesio-hastingsiLe bulk composition. Only the amphibole

synthesized on the cr buffer, however, conlains no ferrous iron; the

others deviale rnarkedly from the ideal composition.

33

TÀBIE 2

Electron microprobe analyses of synthetic magnesio-hastingsiLes

¿ )J

si02AI z0sFe0MgoCaONa z0Hz0

42.0811.908.39

18,3213.093.622.10

8.18.12.3.¿.

41.812,1

41 .211 .6

8.419,1t3.¿3.52.1t

5

5

9

5

1t

rom Semet (1973)1. Ideal magnesio-hastingsite,

all Fe as FeO.2, À3-1 1 T, 850 oC, 2 kbar, CT buf fer.3. À4-'11C, 8500C,2 kbar, IQF buffer.f ldeal HzO, column 1.

CoIville et al. (1966) synthesized magnesio-hastingsite on the MH

buffer at 8500C and 2 kbar. Refractive indices and cell dimensions are

given (ra¡te S). Large standard errors in the cell dimension calcula-

tions preclude useful comparison with Semet's (1973) results for the MH

buffer, although both sets of data are reasonably consistent. Because

the Mti buffer was used, this amphibole must contain some ferrous iron

and cannot be endmember magnesio-hastingsite.

SODI C-CALCI C ÀMPHI BOTES

Richterite: NaCaNaMqsSi sOz r (OH)¿

Huebner and Papike (970) synthesized the complete series of solid solu-

tions along the join NacaNaMg5sisozz(ou)2 - KCaNaMgssisozz(oH)2 from dry

mixes. Run conditions were between 7320 and 916oc., 1 and 2 kbar.

f

34

Richterite grew euhedral crystals bounded by equant to slightJ.y elongate

stubby pinacoids up to 50 microns long. Microscopic examination showed

that amphibole yierds were 98 to 100 percent; when present, other phases

were diopside and glass. CeII dimensions are given for all amphiboles

on the join (rables 5 and 7).

Cell dimensions of intermediate compositions on the join show 1it¡-edeviation from linearity between endmenbers. only runs with yields

equal to or greater than 98 percent were used Lo calculate these data.

The g, ß and ! parameters decrease markedly from potassium-richterite torichterite; b and c decrease only sIight1y.

A mix of bulk composition corresponding to potassium-ferro-richterite

was reacted at 601oc., 1 kbar on the ccHa buffer; the amphibote yield isnot given, but green and brown clinopyroxene were present. Àt these

conditions, the oxygen fugacity is approximately intermediate to that of

the FMQ and WM solid buffers. This means that Fes* must be present and

the amphibole is not on composition. Cell dimensions are given (table

5).

Makarova et al. (1971 ) synthesized richterite from alkaline media

comprising oxides, hydroxides, carbonates, and amorphous silica. Àmphi-

bole yields were 95 to 98 percent. Refractive indices are given (table

5)" Grigor'eva et g!. (1975b) give the analyzed chemical fornrula of

this richterite as:

Na 1 . s oCa r .osHo. r ¿M9¿. goSi s0zz (OH) z

Cell dimensions are also given (fabte g).

3s

Forbes (1971 ) synthesized richterite hydrothermally from a mixture of

NazCOg' CaO, MgO, and Si02. He states that carbonate-free mixes do not

differ in result from those with carbonate. Above 6500c., runs of 24 h

duration yielded 90 to 95 percent amphibole with minor unreacted mix,

forsterite and diopside; 100 percent richterite was obtained in longer

runs. Cell dimensions and optical properties are given (fable 5); celldimensions do not vary with changing pressure and temperature.

charles (1972a,b, 1974b, 197s, 1977 ) grew richterite, ferro-richter-ite and intermediate compositions on the join between the endmembers

frorn dry mixes. Oxygen fugacity was controlled in Fe-bearing runs on

the IW, !.lM, ccHa, FMQ, NNO, and MH buffers. Experiments at B00oc and'l

kbar of 2 day's duration produced 98 to 100 percent amphibole from the

endmember richterite composition. Fe-bearing amphibole grew most readi-

Iy on the IW buffer, 20 to 30 percent clinopyroxene was present in com-

positions containing more iron than Mg3Fe2 on buffers more oxidizing

than IW. For compositions Mg4Fe through Mg2Fe3, experiments on the IW

buffer at 500o to 550oC produced >95 percent amphibole with minor pyrox-

ene, olivine and g1ass. Àmphibole with MgFea composition was difficultto grovr at less than 5 kbar. End-member ferro-richterite (Type II)grew with >95 percent yield at 500o to 550oc in long runs (22 to 30

days). Minor clinopyroxene, olivine and glass nas present. Àlthough

shorter experiments (about 10 days) at higher temperatures (600o to

700oc) produced less amphibole (Type t, about 90 percent), íLs cell vol-

ume is much larger than that of the long-term product; it is probably

]ess oxidized and closer to the nominal compostion.

36

Cell dimensions and optical properties are given for representative

runs on all buffers; the parameters on the IW buffer are probably close

to the nominal composition. End-member richterite apparently has a low

stability limit with respect to pressure. Cel1 parameters trend to-

wards trenrolite with increasing pressure (Charles 1974). However, an-

phiboles containing iron show no variation in cell parameters. Chartes

(1974) examined the cell dimensions of amphiboles grown on the II^i buffer

most closely because this buffer produces the highest amphibole yields;

thus these amphiboles are closest to the nominal compositions. Parame-

ters g, g, and asinß increase almost linearly from Mg5 to MgFea, while ß

decreases; the values for b are slightly below the line for MgaFe,

Mg3Fe2 and Mg2Fe3.

Hariya and Terada (1973) synthesized amphibole with the composition

richteriteso - tremoliteso from quartz, MgO, CaCOs, and Na2SizO¡ at high

pressures. water content in the capsules was from 5 to 10 percent by

weight. Cell dimensions are given for an amphibole grown at 900oC and

29 kbar; the run table lists amphibole as the only phase in the product.

The crystals average 0.07 mm long, show no plechroism and are almost

colourless.

Braue and Seck (977 ) sLudied the stability of solid solutions on the

join pargasite-richterite at 1 kbar (see pargasite section for details).

cerl dimensions are given for the endmember richterite (tabre s).

I,lestrich (1978) claimed hydrothermal synthesis of richterite from an-

hydrous gel at 950oc and 4 kbar. The run product contains less than 4

percent non-amphibole phases. cel1 dimensions are given (rabte s); y

and a are less than those of other synthetic richterites.

37

Phillips and Rowbotham (1968) synthesized richterite from gels at

750o to 1000oC and 1 to 5 kbar. Crystals are prismatic, occasionally

twinned, and vary in size from 20 x 50 microns to 70 x 200 microns.

Cell dimensions given by Philips and Rowbotham are incorrect; they were

recalculated from the X-ray pattern using CETREF (faUte S).

Potassium Richterite: KCaNaMqsSi eOr z (OH)¿

Heubner and Papike (1970) synthesized potassium richterite in theirstudy of the richterite...potassium-richterite join. The results are

reported in the previous section.

Fluor-r ichter i te : NaCaNaMq5Si eOttFt

Eitel (1952) reacted a dry mix of fluor-richterite composition at

1000oc, 1 atm, and formed fluorine amphibole as the major phase with mi-

nor forsterite, M9F2 and caFz. In melt crystallization, increasing

fluorine concentration reduces amphibole yields and produces Na-phlogo-

pite.

Shell et al. (1958) synthesized numerous endmembers based on the

fluor-richterite bulk composition (experimental details are given in the

tremolite section). In addition to synthesizing normal fluor-richter-ite, the following substitutions were attempted: Ba, cd, co, Mn, and sr

for ca, and co, Fe, cu, Mn, Ni, and zn for Mg. Àmphibole grew from most

of these compositions, but yields were generally 1ow and they were not

characterized. Fluor-richterite yield was about B0 percent; it was

characterized by Kohn and Comeforo (1955). Beneficiated samples with

less than '1 percent impurities have chemical compositions close to the

ideal. Optical properties and celI dimensions

ray pattern are given.

38

(rable 6), and powder X-

Huebner and Papike (1970) synthesized fluor-richterite and fluor-po-

tassium-richterite endmembers at 1 atm from dry mixes sealed in pt cap-

sules. The charges were heated above the melting point to 1200oC and

then cooled to 800oc over a period of 9 days. One charge was reacted at

8180c, 2 kbar for 39 days. Àmphibole yields are not given; run products

are mainly amphibole with minor glass and diopside. CeI1 dimensions are

given (raute e).

Cameron et al. (973a, b) and Cameron et al. (1983) refined the crys-

tal structures of both of these amphiboles at room and higher tempera-

tures. Ce11 dimensions determined from Lhe single-crystal structure re-finements are slightly lower than those of Huebner and papike (1970)

(rabte g).

Cameron (1970) and Cameron and Gibbs (1971) synthesized fluor-richt-erite from a dry mix at 1 atm by cooling at soeh-1 from 1170o to i000oc.

Cell dimensions are given (raUte g). They also synthesized fluor-richt-erite with Mg/(Ug+f'e2*) = 0,67. The Fe-bearing fJ.uor-richterite 14as

cool-ed at Soch-1from 1050o to BBOoc with a metallic iron buffer. Àm-

phibole yield was less than '100 percent; the composition was determined

by electron microprobe. crystars were up to 4 mm in length. ce]l di-mensions are given (rable Z). Single-crystal structure refinements were

done on both amphiboles (see Chapter 6).

westrich (1978) craimed fruor-richterite synthesis from

gels at 10000c and 4 kbar pressure. Fluorine was added as

anhydrous

dllute (5

39

percent by voJ.ume) hydrofluoric acid. Ce11 dimensions of the amphibole

produced, however, are very different from those of other synthetic

fluor-richterites (raUte 6). FIuor-tremolite cell dírnensions given in

this study are also peculiar. These are the only fluor-amphiboles grown

with HF rather than fluoride as a fluorine source, and it is possible

that the use of HF was responsible for the anomalies (see fluor-tremol-

ite section ) .

Maqnesio-alumino-taramite: !NaCaNaMq3Al 2Si 6À1 2 (OH)¿

Phillips and Rowbotham ( 1 968 ) attempted magnesio-alumino-taramite

synthesis from gels at temperatures between 750o to'1000oC and pressures

between 1 to 5 kbar with runs 18 to 1gz h J-ong. only anthophyllite, a

talc-like mineral, and sodium-calcium montmorillonite were formed.

ALKALI ÀMPHIBOTES

Glaucophane: ¡Na rMq ¡Al rSi ¡O r r (oH )¿

Boyd (1955) reported reconnaissance runs on glaucophane bulk composition

that yielded mixtures of amphibole and albite at 750o to 825oC and b00

to 1000 bar pressure. Boyd states that this amphibole has refractive

indices, X-ray pattern, and extinction angle close to natural glauco-

phane, but the data are not given. Forsterite and enstatite, which are

expected breakdown products along with albite, r.'ere apparently absent.

Thus, the amphibole cannot be glaucophane in conposition.

From glaucophane bulk composition, Ernst /1957 ) synthesized an amphi-

bole whose upper stability limit is 20o to B0oc 1ower than that of mag-

nesio-riebeckite. High-temperature assemblages included forsterite, aI-bite, enstatite(?), liquid and vapour.

40

Ernst (1958a) presents preJ.iminary P-T stability data for amphibole

grown from the bulk composition ¡Na2Mg3Àlzsiaozz(0H) z up to 2000 bar

vapour pressure. He concludes that glaucophane is not itself a high-

pressure mineral, but can exist over a wide p-T range depending on the

bulk composition. Physical properties are not given.

Ernst (1959) ,reports the results of reconnaissance runs on the glau-

cophane composition at 6000 to 800oc and 20 to 30 kbar pressure. He

suggests that two polymorphs of glaucophane may exist because the celldimensions of this high-pressure phase are appreciably smaller than

those of the 1ow-pressure phase (Ernst 1958b). Amphibole grolrn at 7000C

and 20 kbar apparently recrystallizes at 800oC and 1000 bar to the form

with the larger unit cell. CeLL dimensions of both phases are given

(rable s) but no other experimentar results are presented.

Ernst (1951) summarized the above work and gives prevousLy unpub-

lished physical properLies and experimental technique. Two startingcompositions were used, ('1 ) NazO'3MgO.AlzO¡.8SiOz + excess HzO (glauco-

phane + vapour), and Q, NazO.3MgO.ÀlzOs.lOSiOz + excess Hzo (quartz +

glaucophane + vapour = talc + albite + vapour). Starting materials com-

prised dry mixes, glasses of the above two compositions, mixtures of

talc and Àmelia albite in proportions corresponding to composition Q)

above, and synthetic enstatile and Amelia albite in the proportion

Naz0'3M90'À120s'95i02. Amphibole yields range from less than 1 percent

of the condensed assemblage to over ?0 percent;'10 to 20 percent is typ-

ical. Grain size is about 20 to 40 microns by 1 to 3 microns. other

phases are the equivalent high-temperature assemblages (netastable).

41

Optical properties do not vary over a wide range of temperature and

pressure and amphiboJ.e grown from the equivalent high-temperature assem-

blage is indistinguishable from that grown from dry mix or g1ass. For a

temperature range of 6250 to 862oc and pressure range of 17s to 2500

bar, o varies between 1.594 and 1.596; ? varies between 1.6j8 and 1.62j,

The same set of cell dimensions reported in Ernst (1959) is given (table

5). Ernst concludes that neíther high pressure nor differential stress

is required for the stable existence of glaucophane.

Ernst (1963) presents the variation of cell dimensions of alkali am-

phiboles as a function of temperature, pressure and composition. The

composition of these amphiboles is not well-documented. only part of

the charge was crystallized to amphibole and variable amounts of the

high-temperature anhydrous assemblages of equivalent bulk composition

are present. He concLuded that gJ.aucophane occurs as two po].ymorphs,

because amphibole grown from glaucophane bulk composition at low pres-

sure has a unit cell volume more than two percent greater than natural

glaucophane, whereas that grown at high pressure had volume comparable

to that of natural glaucophane (see Chapter 6).

carman (1974) synthesized amphibole, presumed to be glaucophane, with

90 percent yield. Run conditions were B00oc at zs kbar. No physical

properties vlere given.

Gilbert and Popp f973) reported glaucophane synthesis at 7S0oc and

25 kbar. The cell dimensions of this amphibole are among the smallest

recorded for synthetic amphiboles of presumed glaucophane composition

(tabte S). They consider lhis to represent nearly fully ordered materi-

al.

42

Maresch (1973, 1974, 1977 ) reviewed the evolution of experimental

work on glaucophane. He criticized the concept of polymorphism proposed

originally by Ernst (1963) and concluded that an amphibole of gl-auco-

phane composition had never been synthesized. Maresch fg73) synthes-

ized an amphibole with greater than 80 percent yield on the glaucophane

composition; iL had cell dimensions (rabte s) which at the time were

closest to extrapolated natural iron-free glaucophane (norg 1967:

a=9.50, þ=17.67, c=5.29 Å, ß=103.720, v=864 A3). However, because ja-

deite and quartz were always present he suggested that the amphibole

composition was displaced towards anthophyllite and was not on the glau-

cophane composition. Koons (1982) examined the behaviour of amphibole

in the system

Na 20-Mg0-41 z0 g -S i0 z-H 20

and its relationships with sodium mica at high pressures. He found that

C2/m amphibole approaching glaucophane composition exists only in water

undersaturated systems. in the pressure intervaL '19 to 24 kbar at

7000c, it coexists with quartz on the glaucophane composition. Thus, itmust be displaced from the nominal glaucophane composition by substitu-

tion of NaAÀl'v for si and MgM4 MIML for NaM4 ÀrMz Koons (19g2).

Cell dimensions are given (rabte S). An electron microprobe anaLysis isgiven but it is of poor quality. Transmission electron microscopy on

this amphibole by M. Carpenter shows the amphibole to be well-crystal-rízed cL/n amphibole r,'ith B. 9 Å repeat spac ings of the ( 020 ) planes.

Rare 14 Å repeats of (020) planes were found, which are consistent with

the presence of occasional, triple-chain multipricity faults. Thus,

this amphibole has many fewer stacking defects than have been reporled

in other synthetic amphiboles (Maresch and czank 1991,1993; G. skippen,

pers. comm. lo P. Koons. ).

43

Carman and Gilbert ( 1983) investigated glaucophane stability using

geIs, oxide-carbonate mixes, and various mineral mixtures. products

were examined optically, by x-ray diffraction, and certain amphiboles

were analysed by electron microprobe. Grain sizes vrere generally less

than 10 microns. Cel1 dimensions (lab1e 5) are given for four amphi-

boles of presumed gLaucophane composition. Unfortunateì.y, the electron

microprobe analyses are unsatisfactory with totals of only 93 to 94 per-

cent; however, high yields and chemographic reasons are given to sub-

stantiate virtually nominal compositions. The cell volumes are among

Lhe lowest obtained for any synthetic alaucophane study, and the amphi-

boles are probably close to glaucophane composition.

Ferro-qlaucophane: ENa2Fel *Àl 2Si sOz 2 (OH)2

Hoffmann (1972) synthesized amphibole of presumed ferro-glaucophane com-

position from seeded runs at 500oc, 5 kbar fruid pressure with oxygen

fugacity defined by the WM buffer. Electron microprobe anayses are giv-

en to confirm nominal composition. They show that the synthetic amphi-

bole is close to endmember ferro-glaucophane in composition. Because

syntheses were done at oxygen fugacities corresponding to the WM buffer,there must be Fe3* present. cell dimensions (table 7) are given.

Crossite: ¡NarMqr . ¡Fe?1sÀlo. ezFell¡.¡Si¡Oz r (OH)¿

Koslowski and Hinrichsen (979) attempted to synthesize amphibole, in-lermediate to graucophane and riebeckite, of the composition:

lNa 2Mg r . sFe? i s¡10. ozFel I s ¡Si eOz z (OH) z

Nearl.y 100 percent arnphibole was obtained on the MH buffer at 700oc and

4 kbar H20 pressure. Cell dimensions are given (raUte z). The amount

44

and distribution of Fe2* and Fe3* were determined by Mössbauer speclros-

copy; the spectrum and details are not given.

Riebeckite : ¡Na zFeS'rel_lsi¡,Q¿ e (OH )¿

Tuttle and England (1953) report the synthesis of amphibole on the rie-beckite composition at temperatures below 610oc and in runs with less

than 3.9 percent water. No physical properties are given.

Ernst (1959, 1962) reports on the synthesis and stability relations

of riebeckite and riebeckite-arfvedsonite solid solutions at conditions

defined by the CCO, MH, NNO, FMQ, WM, IM, IÌ{ and IQF buffers. Forty-

seven sets of cell dimensions (tables 5, 7), optical properties and mi-

crometric analyses of coexisting phases are given. He shows that as ox-

ygen fugacity is decreased, the amphibole becomes more arfvedsonitic

through progressive filling of the A-site. Cel1 volumes increase from

about 912 Â3 to about 918 Å3 as the oxygen fugacity varies from condi-

tions on the MH buffer to lhose prevailing near the lower limit of mag-

netite stability. A sharp jump in volume to about 930 A3 is noted at

lower oxygen fugacities defined by the MW, IM and IW buffers. Ernst

(1962) attributes this increase to the the replacement of tetrahedral Si

by Fe3*. This is not a plausible solution; tetrahedral Fes* has not

been observed in any amphibole crystal-structure study (Hawthorne

1983b) .

45

Maqnesio-riebeckite : BNa 2MgiFet +Si Bgjj (QE)z

Ernst (1958a, 1958b, 1960) studied the stability relations of magnesio-

riebeckite at various oxygen fugacities. Cell dimensions are given for

endmember magnesio-riebeckite, but the synthesis conditions are not giv-

en for the sample used (¡¡o. 125, Tabre 5). Refinement of the x-ray pow-

der daLa given for this sample gave virtually identicaL results (No.

126, Table 5). Refinement of material provided by Ernst as part of the

present study, however, gave markedly different results; cell volumes

are consistentLy lower by about g A3 (Ho. 127-130, Table 5). Refine-

ments using Lake Toxaway quartz from the original study as an internal

standard, and BaF2 from the present study, gave essentially identical

results. The reason for this discrepancy is unknown. Àn infrared spec-

trum of material provided by Ernst (see Chapter 6) shows that the amphi-

bole grown is not magnesio-riebeckite; it is probably towards magnesio-

arfvedsonite in composition.

Ec kermann i t-e : NaNazMq¿À1Si e0r z (og)¿

Phillips and Rowbotham (1968) grew an amphibole presumed to be eckerman-

nite coexisting with a talc-like míneral frorn gels of eckermannite com-

positon al 770 to 1000oC and 1 to 5 kbar. Maximum grain size was 20x3

nicrons; length averages about 10 microns. Because of the presence of

the talc-Iike mineral, they admit that the exact composition is uncer-

tain. CelI dimensions (tab1e 5) of this amphibole are almost identical

to those of sodian magnesio-cummingtonite. Refinement of cell dimen-

sions from the powder x-ray data in their paper, however, gives very

different results (Ho. 145, Table 5). It is not known whether the celldimensions are incorrect, ot whether the wrong paltern is given. Note

that the same problem was noted with their richterite cell dimensions.

46

NyÞöi te ; NaNa 2Mq3Àl,si zAIo? 2 (oH),

Phillips and Rowbotham (1968) tailed to grow amphibole on the nybôite

composition at 750 to 1000oC and 1 to 5 kbar. Sodic montmorillonite was

the only phase.

Carman and Gilbert (1983) synthesized amphiboles apparently near ny-

böite in composition with yields of about 90 percent. Syntheses were

performed at 900 and 980oc, and 25 and 33.6 kbar respectively. cell di-mensions are given (rabte 5); note, however, that the bulk composition

of No, 147 was that of glaucophane, while that of No, 146 was nyböite.

À1kaIi Fl-uor- hi bol-es

Syntheses of alkali fluor-amphiboles are rare. Eitel fgSZ) attempted

to synthesize fluor-eckermannite in the sotid state at '1000 to 1100oC,

but 100 percent yields were not obtained. Crystallization from a melt

also produced extraneous phases in addition to amphibore. physicat

properties are not given. Shell et aI. (1958) reacted a fluor-eckerman-

nite composition in the solid state at 1010oC and obtained fluor-amphi-

boIe, forsterite, clinoenstatite, MgFz and g1ass. physical properties

of the amphibole are not given.

Fedoseev and Chigareva f964) reacted a mix of magnesio-fluor-arfved-

sonite with excess NaF and NaCl plus sawdust and obtained close to 100

percent amphibole. Optical properties are given.

47

r RON-MAGNEST UM-MÀNGANESE AMPHr BorES

.Edtan magnes i o:cummi nqton i te, ggdi an . hydro-maqnes i o-cummi nqton i te :

!,lal'lgN¿¡MqsSi a0r r (oH)¿, t'¡aHar¡lqsSi Â02 r (OHI@E-

Gier e'! al. (1964) synthesized a variety of amphiboles based on the

sodian magnesio-cummingtionite and sodian hydro-magnesio-cummingtonite

compositions (tabte ¡). Starting materials were prepared from solutions

of 1 M MgCl2, 2 M NazSiO3, colloidal silica, and 1 M NaF (for fluor-am-

phibole). substitutions for Mg were accomplished by repracing Mgcl2

h'ith CoCl2 or NiCl2. The resulting gels were crystallized in sealed pt

capsules. Products comprised denseLy intertangled fibers with diameters

of 0.1 to 3 microns and lengths up to 10 cm. À11 products were analyzed

by X-ray powder diffractometry, but only the powder pattern and.cell di-mensions for the sodian hydro-magnesio-cummingtonite are given (rable

5). The ß-angle is the same; the other parameters are smaller and give

a volume that is 1.2 percent less than that given by Gier et aI. (1964).

structural studies of the co-amphibole (no. 3, Table 3) and the sodian

fluor-magnesio-cummingtonite (no. 5, Tabre 3) by prewitt (1963) and

Gibbs and Prewitt (1968) show that co occupies rhe M(1), M(2), M(3) and

M(4) sites in sample No. 3, and that both amphiboles deviate somewhat

from their ideal compositions. Cell dimensions are given in prewiLt

(1963) for the Co-bearing amphibole and the fluor-amphibole (raUte s).

Schreyer and Seifert (1968) synthesized amphiboles in the system Na20

- MgO - SiOz - HzO at compositions on and between the endmembers

Na2Mgosi aoz z (oH) 2 and Na4Mg4si aOzo (oH) z (OH) z. The endmembers were not

characterized except for stability. NazMgosi soz z (oH) z melts incongr-

uently at 965t20oC and 1 kbar water pressure to forsterite, an osunil-

ite-type phase, and liquid, whereas solid solutions towards the Na-rich

48

TABTE 3

Synthetic amphiboles based cn the sodian magnesio-cummingtonite andsodian hydro-magnesio-cummingtonite endmember conpoãitions

No. Chemical Formula Run ConditionsT( "c) P(atm) t (n)

I

2

3

4

Na 2. 5Hr . sMgsSi e0z z (OU) z

Na 2. 2He. oMgo. eMg sSi s0z z (OH) z

Na z. ¿ qHo. z sCoo. ¿CosSi aOz z (OH) z

Na 2. 2He. zMgs. oCoz. sSi s0z z (0H) z

Na I . z ¿Ho. s sMgo. zMgsSi aOzz-(Fr.zz)(oH)o.z¡

700700575700700

30003000200030003000

6

6

6

6

6

Gier et al. 1964

endmember melt at successively lower temperatures. Àt 770t10oC, the Na-

rich endmember melts to less Na-rich amphibores prus riquid. It is not

1ike1y, however, that the Na-rich endmernber was actually synthesized.

Four sodium atoms in the formula unit imply that a sodium atom must oc-

cupy at least one of the M(1), M(2) or M(3) sites; sodium occupancy of

the octahedral strip has not been documented by structure studies (ttaw-

thorne 1 983b) .

Nesterchuk et aI. (1968) synthesized a Co-rich analogue of sodian

magnesio-curnmingtonite with formula (by chemical analysis) :

Naz. o sHo. z ¡Cos. ¿ sFeð lo 6Siz. s aOzz (OH) z

High yields (98 percent) were obtained by the co-precipitation method,

in which a solution of CoSOq was added in small amounts to a solution of

Na2Si03'9H20 with continuous stirring. The resulting suspension of

fine, dispersed particles was placed in a platinum crucible and reacted

in an autoclave at 3000 to 500oc, and at pressures of about 900 atm.

Run lengths varied between 10 and 168 h. The

phibole formed a pink, matted, fibrous mass with

4 mm long and 4 to 5 microns thick.

49

synthetic Co-bearing am-

individual fibers up to

Fedoseev et al. (1968a) synthesized a Ni analogue of sodian magnesi-

o-cummingtonite with formula (by chemical analysis):

Na z. s sNi s. o sSi a0z z (0H) z

Best results were obtained from starting materials comprising NaOH,

NiCl2 and Si0z in proportion to the amphibole stoichiometry governed by

the reaction:

14Na0H + 6Niclz + 8sio2 = Na2Niosiaozz(oH) z + 12Nacl

Solutions of the calculated amounts of NaOH and NiCIz were mixed with

finely pulverízed, amorphous sioz, and reacted at 450o to 5000c at pres-

sures near 900 atm. The product consisted of a green, fibrous mass of

amphibole with fibers up to 4 mm 10ng and 0.015 to 0.1 microns thick.Refractive indices were measured. Àttempts to refine the cell dimen-

sions from the given x-ray powder data as part of this study faiJ.ed; the

refinement did not yield reasonable values. It seems that Lhe published

powder data are in error.

Fedoseev et al. (1968b) reported synthesis of sodian magnesio-cum-

mingtonite, and nickel and cobalt analogues using similar techniques as

in Nesterchuk et aI. (1968) and Fedoseev et aI. (1969a). The resultsfor the Ni- and Co-amphiboles are the same data that were reported inNesterchuk et aI" (1968) and Fedoseev et al. (1968a). x-ray powder data

for the sodian magnesio-cummingtonite of formula (by chemical analysis):

Na z. s zlHo. zsFeE i o zMgs. s e Si sOz z (OH) z

are given.

50

witte et aL. (1969) synthesized sodian magnesio-cummingtonite from

glass of composition NazO'6MgO,BSiOz at 750o Lo 7700C and 1 kbar water

pressure. Run lengths varied from 47 to 1.19 h. They also grew

Na3Mgssie0zr(oH)(ott)2 f rom glass of composition Na 20,2tttgo.4sioz at 500o

to 600oC at 2 kbar water pressure. Run lengths varied from 44 to'117 h.

cell dimensions are given for both endmembers (rab1e s).

Makarova et al. (1971) synthesized amphiboles based on the sodian

magnesio-cummingtonite formula h'ith all or part of the Mg replaced by

Co2* or Ni2* (raUte ¿). Syntheses were done in alkaline media, similar

to the methods used by Nesterchuk et al. (1968) and Fedoseev et al.(1968a, b). Optical properties are given. Ce]1 dimensions (raUte S)

and more precise chemical formulae (rable 4) for these amphiboles were

TÀBLE 4

Synthetic amphiboles based on the sodian magnesio-cummingtonite formula

No, Formula Synthes i sT("c)

D.P(")

I

23

Naz. s zCal .osHo. I ¿Mg¡. sosis0zz(0H) zNaz. osHo" zgCoSl¡¿FeElooSiz. s aO zz(Otl) zNaz. o sNi 3i o sSi sOzz (OH)

z

770-8 0 07 40-7 60I 00-82 0

1 '180

1 0751200

Maka rova et al. f 971)formulae from Grigor'eva et al. (197S)

compiled by Grigor'eva et al. (197s). Makarova et al. (1972) report-

ed the synthesis of Mn-bearing sodian magnesio-cummingtonite with for-muLa (by chemical analysis):

Naz. ¡ zMnl . r eMg¡. ¿+Sí s0zz(0H) z

51

The other syntheses presented in this paper, sodian

magnesio-cummingtonite, Ni analogue and co analogue, are the same ones

described earlier (Fedoseev et al. 1968a, b, NesLerchuk et al. 1968).

No physical properties are gíven.

Grebenshchíkov et aI. (974) synthesized sodian magnesio-cummingto-

nites with two different habits depending on synLhesis conditions. Àt

450o to 5500C and pressures above 750 atm under conditions of low NaoH

concentrations, Iong fibers were grov¡n. At 350o to 450oc and 250 to 750

atm with higher NaOH concentrations, "aveniform" or "bundle aggregates"

of amphibole were formed. CeIl dimensions are given in Table 5 for the

two varieties.

t{itte (1976) studied the stability of the endmembers sodian magnesÍo-

cummingtonite, NaMgNaMgssi eoz z (OH) z, and sodian hydro-magnesio-cumming-

tonite in the system Nazo - Mgo - sio2 - Hzo. The Na-poor endmember

becomes stable at 750oc, 350 bar and at 850oc, s50 bar. It breaks down

at 955oC, 800 bar to forsterite + Na2Mg5Si r zOso + melt + HzO. Àbove 800

bar water pressure, it reacts to forsterite + enstatite melt + HzO at

990oc, 1 kbar, and 1'130oc, 5 kbar. The Na-rich hydro-endmember displays

a significantly lower thermal stability. It becomes stable at 550oC and

'150 bar; between the points 61Ooc, 250 bar and 6130c, 300 bar it reacts

to amphibole solid solution + Na2MgzSioOrs + melt + HzO, and above 300

bar only to amphibole solid solution + nelt + Hzo. sodian hydro-magne-

sio-cummingtonite melts at 580oC, 5 kbar water pressure.

52

Sodian f luor-maqnesio-cumminqtonite: NaMqNaMqsSi ¡Or zFz

Gibbs e! al. U962) synthesized sodian fluor-magnesio-cummingtonite both

from a melt and by pneumatolysis from batch compositions containing ex-

cess fluoride. The product contained mostly acicular amphibole; the

identity of other phases is not stated. Reagent grade NaF and Na2co3,

technical grade MgO and MgFz and -200 mesh quartz (99.9 percent SiO2)

were reacted in sealed graphite or pt crucibles at 12500c. Àfter 2 h,

the temperature was lowered to below the solidus at 10och-1. Chemical

analysis of the producL shows good agreement with the nominal composi-

tion; cerl dimensions and opLical data are given (table 6). singre

crystal data are consistent with the space group IZ/n.

Fedoseev et al. (1970) and Grigor'eva et al. (1973a,b) give cell di-mensions and optical properties of sodian fJ.uor-magnesio-cummingtonites

(fa¡te 0). other syntheses by these workers of amphiboles based on this

endmember composit,ion were not reviewed in detail; cell dimensions are

given in Tab1e 5. Miscellaneous syntheses by others of amphiboles based

on this endmember composition are listed in the additional bibliooranhv

of amphibole syntheses.

53

TABLE 5

ce11 dimensions and optical properties of previousry synthesizedhydroxy-amphiboles: pure endnember conpositions

A. Cell Dimensions

Ref .T a (Å) b (Å) c (Å) ß (") V (43)

e.833(s)e.801 (3)e.828(3)9.822(2)9.873(10)s.814(6)

1 8.05418.07 (

1 8.0s91 8.05s18,0271 8.063

18.35(2)18.31(2)18.33 ( 2 )18,31(2)18.32(2)18.3e (2 )18.3s(2)18.36 (2 )18.3s(2)18.34(2)18.34(2)

NaCa 2Mg17.986(17)17 .946(s)17.94(3)

Calcic AmphibolesTremol i te

ECa 2MgsSi aOz z (OH

5.268(45.284(25.27 6(35.277 (2s.250(75.275(3

Ferro-actinolite

.31

.32

.28

.30

.30

.30

.30

.30

Pargas Í teaÀlSisÀIz0zz(

s.255(8)s.282 ( s )5.279(3)

104,s2(7 )

104.3s(3)104.70(3)104.63Q)104.30(1s)104.65(s)

905. 3

905.4905.890s.4905.4904,6

937.5 ( 20 )940.7937,6q?q ¿

941 ,4938. 1

939.0938.7937 ,7937.5938.2

t

)

1

2

34

5

6

55

55555

5555

(e)3)(6)(5)(6)(12)

10)3)4)4)8)7)

¡cazFeS*si6o22 0H)z1)

I

1

1

1

1

I

1

I

1

1

(

(

(

(

(

(

(

(

(

(

(

(

1

8.o

10.11.12,13.14.15.16.17,

.98

.96

.97,97

q?

.959898989B

97

99

9

99

9

99

9

99

1

1

1

1

1

1

1

I

1

1

1

.30

.32

.29

104.4(1)104,7 (1)104.6(1)104.7 (1)104.7(1)104.4(1)104.6(1)104.3(1)104.5(1)104.5(1)104.5(1)

105.25(e)1 04.40 ( 2s )

¿

105.30(i4)105.67(3)105"s0(5)

e11.4(2)8ee.8(10)

(20 )(20 )

Q0)Q0)(20 )(20 )(20 )

Q0)(20)Qo')

18,19,

9.911(11)9.8s3(15)

21 .22,23.

9.906(10)9.914(3)9.896 ( 2 )

Eden i teNaCa 2Mg5Si zAl0z z (0H)

z17.e51(22) 5.310(5)18.00s(11) s.236(15)

20, 9.999( 1 0)

Ferro-eden i teNaCa 2Fe3

*Si 7A10z z (OH)

z18.217(11) 5.314(14) 105.50(17) s32.8 ( 30 )

OH

lRef. corresponds to references aL end of table.

904.7 (19)904.9(7)903.2 ( 3 )

54

Ref . a (Å) b (Å) c (Å) ßo v (Å3)

24,25,26.a'l

28.îo30.31.3¿.33.34.35.36.

37,38.39.40.41 ,42,43.44.45.

e.e05(s)e.890 ( 2 )9"8'19 .87 4(4)e.888(s)e"8e1(4)e.8e0 ( 3 )e.891 (8)e.Bes(2)e.887 ( s )e"8e3(2)e.8ee ( 2 )e.8e2(1)

17.9560)17.930(s)

5 .27 6(1)5,27 4(3)

17.904(10)17 .943(7 )

17 .e32(6)17.93s(6)17.953/22)17.93e(s)17,940(14)17 .941 (5)17.946ß)17 .941 (2)

s.278 ( 3 )5.280(3)5.275(4)5,277 (2)s.280(10)s.280(2)5.271 (6)5 .27 6(1)5.278 ( 1 )s ,277 (1)

10s.70(2)105.54(2)

105.43(4)105.55(2)105.s0(7)10s.53(2)10s.63(12)105.s7(3)10s.52(7)105.55(1)10s.s8(1)105.ss(2)

899.4(902.5(901.5(901.9(e02.8 (

902.8 (

900.9(902,1 (

903.1 (

902.2(

928.8(4)928.8(4)928,5927 .0924.7925,4926.7 (2)925,1s23.1 (2)

930 "

934.933.932,933.930.934.935.933.932.932,

903.4901.1

(4)(4)

8)s)6)4)10)3)e)2)2)3)

Ferro-pargas ÍNaCa zFe I

-A1S i oAl zO.330

t

2

te2

(OH

.9s3

. 9583)7)

5

55

55

55

55

9

9

9

9

9

99

9

9

54

)

)

)

)

2

3

2

(

(

I

1

1

I

(

(

(

18,152(18. 14e (

18.14(218.13(218.13(218.13Q

,328/2.33(1).33 (1 ).33 (1 ).34(1).326(1.324(2.334 ( 1

si teoAlz0zz(0H)z.325,325.321.318.322,321.334.340.325.329.323

2

105,27'1 05. 30

?

5

)

)

)

)

2

2

¿

.95

.94

.90o1

.952, 938.890

1 05.105.1 05.1 05.1 0s.

3(2(1(1(3018.128(4)

18.11e(6)18.123(4)

10s.221 05. 08

stinHa I1

555

555555

55

46.Ã.1

48,49.50"þt.52.53.54.55.55,

9.979(27e"e90(4)

10.003(2)10.001(3)10.003(2)9.e57(8)9.e84(2)9.ee6(1)9"994('1 )e.95s(1 )

s.997 (2)

NaCa z'18.

1 5218,21318.i8418. 1 9118.18118.18418,16218.18118,17 418.19618.179

Magnesio-hastingsiteNaCa 2MgaFe 3 *Si

641 2O z z (0u )17 .982(30) 5.289( 1 1 )18.0i5(9) 5.282(3)18.025(g) 5,290(4)18.029(4) 5,293r)

27) 105"20(34)103.2s(3)10s.33(2)105.31 (2)10s.33(2)1 05. 1 3 ( 1 )

10s.2s(3)105.2s(3)105.33(2)10s.09(2)10s.34(2)

2

105.61(1210s.43(4)105.43(4)10s.43(1)

Fefr*Fee*5(63 )(10)(4)(3)(2)(2)(4)(3)(4)(2)(5)

3I

1

I

1

3

321

1

ßl6n)8(e)5(218(2)5Q)1(2)6(5)4(s)1(3)7 (2)e(3)

57,58"59.60.

9.92s(1s)9.928(2)9.s30(5)9.e33(2)

e09.1 (260)910.7 (8 )

912.0 ( 10 )

913.0 ( 5 )

55

Ref . a (Å) b (Â) c (Å) ôt)

o v (Å3)

61,62.63.

e.e32Q)e.933(1)e.e26(s)

18.015(4)18.028(3)18.029(9)

.297 (1

.297 (4

Tscherma k i terca2MgsÀlzsioÀ1z0zz

105.43(2)105.44Q\10s.46(5)

912,914 ,

913.

t

104.e3Q)105.51(2)105.43(3)10s.21 (4)104.96(4)

89s.4897.3896. s896,2899.9

.289(155

5

s.294(1s.28s ( 35.283(35.290(35.326(3

2(3)3(3)7(8)

(s(sQ(s(e

OH64.65.66.67,68.

"90.89"87

9 .7 49(4)9.843(3)e.83e(2)9,822(4)9 .7 42(4)

69. 9.770(4)

171717

17 .95

17 ,95

Ferri-tschermakite!Ca 2Mg rFel +Si oÀl zOz z (Og)

z18.02(1 ) s.30e(3) 10s.14(3)

Sodic-calc ic amphibolesRichter i te

NaCaNaMgsSi a0z z (OH) z

I

1

1

I

1

70.71,1)73,74.75.76,77,78.1q

80.81.

81a .

82,83.

9 .e82(7 )

10.003 (1 )

17.978(5)17.978Q)17.e80(4)17.976(4)17.982(2)17.984,7)18.003(8)18.001(9)17 .975(4)17 .979(4)17.9s8(3)17 .978(5)18.10(1)

Ferro-r ichter i teNaCaNaFeA *Si

sOz z (0H) z18.223(6) 5.298(5)1 8.238 (4 ) s.308 ( 1 )

103.73(12)103.92(2)

936.2(10)940.0(7)

e.eoe(1)e.8ee ( 2 )e.e02(1)s.e01(2)e.e03(1)9.884(7)e.8e3 ( 3 )9.896(s)9.854(4)9.e07 Q)9.892(s)9.e01(3)9 .7 4(1)

2)1)3)3)1)6)4)6)6)¿ì10)3)

s.268(15.269(15 .269 (1s ,270 (15.267 (1s.268 ( 35.268(25.270(35.266Q5.269(15.263Q5.269rs.2e(1)

104,22(3)104,22(2)104.22(2)104.20(2)104.23Q',)104.07(B)104.23(3)104.33(5)104.18(s)104 -)t( )\'104.28(3)104.20Q)104,12

e02.60 )

909. I908.6909.4909.4909,2907 .7909. 5909.6904. 3qnq Á

906. 0909.3905

921.4(s)84. 10.049(2)

Potassium-richteriteKCaNaMg5Si e0z z (OH) z17.988(3) 5.272(1) 104.80(1 )

Potass i um-f er ro-r ichter i teKCaNaFeS *Si

aOz z (Ori ) z18.201o) 5.2e0Q) 104.53(3)8s. 10.172(3) 948.2(4)

56

Ref . a (Å) b (Å) c (Å) ß (") v (Å3)

ÀIka1i amphibolesGlaucophane

rNa 2Mg 3AI 2Si a0z z (OH) z

86.87.88.89.90.91,92.93.q¿

95.96.q?

98.99.

100.101 .102.103.104.'1 05.1 06.107 .1 08.109.110.111.112.1'13.114 .115.116.117 .119.119.

a.120.121 .122.123.

9 ,719.649 .717 (2)9 .619(7 )e .7 42(1)e.703(5)9.783(5)q 7?

9 ,719.759.669.789,7 6q11

9.819,749.699,669.709.679,769.719,739.699.649.669.699.619. 599.619,73

17 ,9217 "7117 .922(317.682(117 .921 (317 .928(617.860(717 ,9117 ,9217 ,9117.7417 ,8218.0117 .9217 ,9317.8317 ,9017.8317 ,8617.8317 .9017.73

17 .7517 .7717 .7117, 9017 ,9817.694,12)17.700(5)17 ,7 0117 ,697 (13)17.700(5)17.6e0(10)17.6e4(5)

5,27s. 285 ,271 (1)5.292(5)5.269 ( 1 )

5,272(2)5.27 4(2)5.275.275.275.285,29

102.51 03.7102.64(1)103.44(8)102.71(1)102.57 ß)103.31(4)102,8102 ,6102,9103.7103.6103.5'103.0

103.1102,6103.1103.6102.7103.0102.5103.7'103.7

103.7103.7103.7103.7103.6103.4.103.8

102.8103.4103.58(7)10s.s0(2)103.71 03.531 03.50i 03.57103,42

89s. 3

875.889s. 7 (

875.4 (

897.3 (

895. 0 (

896.6 (

89689689887889789689889989sI9'1878I9'1883899883888882875877879877878873896893868.5(10)870.4 ( 3 )

)

3

)

)

)

2

9,1

4

4

Ë

L

tr

5. 2B5,275.255.275.255. 285. 285.275,28s. 285"285.27s.29s. 305. 285.275.255.293(4)5.291Q)5.2765.284(s)5.291(2)5.290(2)5.281(2)

870.9867 ,4870,4869.2867 ,7

27¿5

17.8017 "7417.7017,7017 ,72

q1

9.59.59.5

240(6)57(3)98

(g(s(q(e

9.540(8)9.ss7(3)e.5ss(3)9.s47(3)

57

Ref . a (Å) b (Å) c (Å) ß (") V (43)

125.126.127 .128.129,130.

9.799.794(3)9.7 42(1)9,745(4)9.761(5)e.693 ( 1 )

1 02.8102.93 (4)103.38(2)103.40(s)103.43(6)103.19(1)

908. 6908. 9

899. 9900. s900.7896.4

124. 9. 586 ( 3 )

Ferro-glaucophanerNa zFe 3

*¡l ,Si aO z z (0H ) z17.89(3) s.317(3)

Magnesio-riebeckiterNa 2Mg¡Fel *Si

s0z z (OH) z18.02 5 "2818.023(6) s.283(1 )

17 .e45Q) s.2e1 (1 )17 .943(7 ) s. 294 (3 )

17.e28(8) 5.291 (3)17 .953Q) 5. 2e0 ( 1 )

RiebeckiteBNazFeS -rel *si

soz z (og) z18.06 5.33

18.082(10) 5.331 (4)18.07 5.331 8.08 5. 3418.05 s.331 8. 0s s.3318.06 5.3418.07 5.3318.09 5.3318.08 5.331 8.04 5. 3418.09 s.33.18. 08 5.33

Ec kermann i teNaNa 2Mg4À1Si s0z z (OH)

z17.89211) 5.284(6)17.889(7) 5.270Q)

103.75(1) 894.9Q',)

3

2

5

61

131.132.IJJ.134,13s.136.137 ,

1 38.139.1 40.141 .142 ,143.

1 03.103.103.'1 03.103.103.'103.

103.

9,749.739(6)9.739.729.72q 7?

9 ,719.739.7 49,739.739,749,75

e.652(4)9.649Q)

103.3103.30(6)

913.i913,7 (

911 ,7913.7910.9911 .7912.1912.0913.3912.8912.3914 ,3914.0

898.6(8)88e. 6 (4 )

7

1

1

1

030303

2

2?

4

2

44

4

54

4

144 .145.

146 .147 ,

e.7 62(6)9.67s ( 3 )

103.17(49)102.73ß)

148 .149 .1 50.

9.735(7)9.70(1)e.68(1)

877.0(8)877.0(5)

wybö i reNaNa 2MgsÀl zSi 7À102 z (0H) z

17.681 (1 1 ) 5.290(3) 103.7317.699Q) s.286(6) 103.73

I ron-magnes i um-manganese amphi bolesSodian magnes i o-cummi ngton i te

NaMgNaMg5Sie0zz(0H)z17.911(11) 5.279(4) 102.59(s)18.01 (1 ) 5.28(2) i03.03(8)18.06(1) 5.30(s) 104.90(17)

898.38ee(5)8e5(10)

58

Ref . a (A) b (Å) c (Å) ß (") v (Ä3)

Mi scellaneous composit ions151 .152,1 53.1 54.

9.89e"866(5)e.832 ( s )e.6s0 ( 5 )

18.0s 5.2817 .997 (6) 5.274(3)18.088(2) 5.29e(5)17.920Q) 5.270(s)

103103.03(4)103.0(2)102.eQ)

918912,3918.2888.3

B. Optical Properties

Ref . a ,'t Z^cav. at7

1"2,1

8.o

10.11"t¿.13.14,15.tb.

19,20,21,23.36.37"38.39.40.41.42,46,51.52,53.

1 .6011 .605

1.6251 ,528

tt

?Ê,

1 .621 (3)1.700(3)1 ,6241,617

1.634(3)1 .726(3)1 .6451 "636

1.58e(3)1 .68e (3 )

1.688(3)1.6e0(3)1.6e1(3)1.688(3)1.68e(3)1.690(3)1.688(3)1.5e1(3)1.68e(3)

1.624(3)

1.715(5)1.700Q)1.6e8Q)1 .698 (2 )1 .699(2)1 ,7021.6e8(3)1.6s2(2)1.6e2(2)

1.713(3)1.71s(3)1.715(3)1.71s(3)1 "7281,722(3)1.712ß)1,712(3)

222427

59

Ref . a T av. at'l Z^c

54.55.57.58.60.62.63.64.65.66.67.68.69,70,72.?o

80.81a.82.84.91 .

120,

.697 (3)

.6e8(3)

.652

.642(4)

.6s0(5)

.654(4)

.657(3)

.640

.639

.640,642.643.642.602(2).604(s).603(2)

1"723ß)1.725ß)1 .66s1.653(4)1,662(4',)1.66e(4)1 ,672(4)'1 . 6541 .6541 .6531 ,6521 .6551 .6611.620ß)1.622(3)1.624(3)1"624(3)1.61s1,710(4)1,629(2)1,6201 .620

16Q)

1s(2)

I

1

1

1

1

1

1

1

1

1

1

1

1

1

I

I

1

I

1

1

1

1

17

502(3)5006e0(5)604(3)595602

24252525

'10

5Q)

Co1ville et aI. (1966): synthesized by Boyd (1959)TroLl and Gilbert (1972)t 650oC, 1.01 kbai, 1966 hTroll and Gilbert (1972)t 775oC, 4.06 kbar, 9BO hoba (1980): g00oc, .t kbarWestrich (1978): 900oC, 4 kbar, 45 h, rerun 45 h

1

2?

4

567

I9

Wones and Dodge (1977)z 770oC, 2 kbar, 166 hErnst (1966)¡ 528oC, 3 kbar, 733 h, -1og fO2=11.9Ernst (1966): 4700C, 3 kbar, 989 h, -fog tOi=26.AErnst (1966): 452oC, 1 kbar, 984 h, -toõ fOr=27,UErnst (1966): 437oC, 2.98 kbar, 840 h, llog fOr=29.,Ernst (1966): 406oC, 2 kbar, 1604 h, -Iog iOr=jg.gErnst (1966): 537oc, 3 kbar, 475 h, -1og tor=27,tErnst (1966): 516oC, 3 kbar,502 h, *log fO2=29.UErnst ( 1 966 ) : 503 oC, 2 kbar, 820 h, -lóg fO z=29 .1Ernst ('1966): 459oc, 1 kbar, 903 h, -Ioõ tor=31 ,nErnst (1966): 420oC, 0.5 kbar, 1125 h, llog fO2=33.,Ernst (1966): average of No. 8-16 this tabÍeHinrichsen and Schürmann (977)z 7S0oC, 4 kbar9oluiJlu * ¿. (1966): 8s0oc, 2 kbar, 3 days9oluille g! al. (1966): 6000C, 3 kbar, 31 dãys, rW bufferColyille ç! ql. (1966): synthesized by Boyd (1954, 1956, 1959)Holloway (1973)¿ 1002oC, 1.24 kbar, 1ó3 h-

10.11.12,13.14,15.16.17,18.19.20.21,22.

60

23.24.25,26.2',7.

28,29,30.31.32.33.34,35.36.37.38.39.40.41 .42.43,

44,

45.

(1e80)(1e80)(1s80)(1e80)(1s80)(1s80)(1s80)(1s80)(1s80)(1980)(1e80)(1e66)(1e66)(1s66)(1e66)(1e66)

333 h330 h330 h330 h330 h336 h331 h

i eldi eId

oba (1980): 950oc, 5 kbarT.testrich (1978), westrich and Holloway (1981): 12050c, 4kbar , 72 hBraue and Seck (1977 )

Droll and Seck (1976)Hinrichsen and Schürmann (1977],CharlesCharlesCha r lesCharlesCharlesCharlesCharlesCha r lesCharlesCharlesCharlesG i lbertG í lbertGilbertGilbertGi lbert

: 750oC, 2

: 750oC, 2

: 750oC, 2

: 750oC, 5 kbar, 527 h Iiii1

i

vvvvvvvv

=95=95=80=85=90=60=95=99

eIdeldeldeldeldeld

tabl eMQ buf fer, yield=9Oe"CH¿ buffer, yield=90eoufferuf fer

750 0c

750 0c

850 0c

8500c: average: 600[, 2

: 700[. 2

: average: average

690 0c,

680 0c,

680 0c,

690 0c,

: 850oC, 2 k: 8500C, 2 k

2

2

1

1

kbar,kbar,kbar,kbar,kbar ,kbar,kbar,

No. 28kbar,kbar,(4 run(4 run

-35368368s),s),

thi sh, Fh,crl,IbI,lMb

cell dimensions refined in this study fron X-ray powderdata (cilbert 1966, Table 2, No. ÀI1)Gilbert (1966): 683oC, 1021 bar, 517 h, WM buffer,cell dimensions refined in this study from X-ray powderdata (Gilbert 1966, Table 2, No. HI8)Gilbert (1966): 6400c, 1989 bar, 408 h, FMQ buffer,cell dimensions refined in this study from X-ray powderdata (Gilbert 1966, Table 2, No. ÀF4)Co1ville qt al. (1966): 600oC, 3 kbar, FMO, 31 daysCharles (1978)

: average (4 runs), FMQ buffer: single run, NNO buffer: 847oC, 2014 bar, 81 h, II^I buffer,

600oC, 3 kbar, I8F buffer600oC, 3 kbar, Iti buffer600oC, 3 kbar, WM buffer660oC, 3 kbar, FMQ buffer, ME3

46.47.48. Thomas49. Thomas50. Thomas5'1 . Thomas52. Thomas53. Thomas54. Thomas55. Thomas56. Thomas57. CoIvill58. Semet (

(

(

(

(

(

(

(

(

(

À

1

1

1

1

1

1

7

7

7

7

(

1979)1979')197 9)1979)1979)1979)1979)1979)1982a

3 kbar, IQF buffer, MI33 kbar, IW buffer, MH323 kbar, WM buffer, MF323 kbar, FMQ buffer, ME3

bar, MFI buffer, av. obar, CT buffer, av. o

40221

3

39

fer, 3 daysof8

: 680oC, 3 kbar, WM bufferet al. (1966)¡ 850oC, 2 kbar, MH buf

59.60.61 ,62.63.64.55.66.67.

SemetSemetSemetSemetSemetOba (

Oba (

Oba (

Oba (

973')973)973')973)973)973)8):8):8)¡8)¡

9100c850 0c

8500C850 0C

850oC,2 kbar, IQF buffer, av.850oC, 2 kbar, WM buffer, av. o850oC, 2 kbar, FMQ buffer, av.850oC, 2 kbar, NNO buffer, av.

f5of 10of3t6f. 12

r5 t(b10 kb12 kb'1 5 kbar, +cpx+grt+qtz

19191919

bt

68.69.70,71.72,'t774.75,76.77,78,79,

80.

81.

83.

81a .

82.

Oba (1978):Oba (1978):Forbes (1971) t

Braue and SeckCharles ( 1 974bCharles (1974bCharles ( 1 974bCharles (1974bCharles (1974bCharles (1974bWestrich (1978Huebner and Pa

850oc, 20 kb850oC, 20 kbar, no buffer

850-950oC, 100-750 bar(1977)z 1030oC, -1 kb: 800-850oC, 1 kbar, av. of 4: 700oC, '1 kbar , 72 h: 800oc, 2 kbar, 48 h: 700oC, 5 kbar, 119 h: 600oC, 7 kbar, 456 h: 5'10oC, 10 kbar, 600 h: 950oc, 4 kbar , 72 hike (1970): 760-916oC, 1-2 kbar, 3.5 h - 56 days

av. of. 7

)

)

)

)

)

)

)

p

84.85.86.87,88.

Phillips and Rowbotham (1966): 750-1000"C, 1-5 kbar, 1g-192 h.Note that these cell dimensions are incorrect, see No. g1

Phillips and Rowbotham (1966): same as No. 91. ceil. dimensionsrefined in this study from x-ray powder data in their Table 1.9.tig9r'ey?-+ +1._{19751. Synrhesized by Makarova er at. (197i)Charles (197ab): 500-530oc, 5-iO lbar, S3S-lZl h, ail õI 3,

I9l buf ferCharles (197ab): 600-70OoC, 5-7 kbar, 1ZO-216 h, av. of 2,

IW buf ferHuebner and Papike (1970): 732-916oC, .1-2 kbar, 3.5 h-56 daysHuebner and Papike ('1970): 601oC, 1 kbar, CCHq bufferErnst (1959, '1961): 800o, 1 kbar, "glaucophane I"Ernst (1959): 800o, 20 kbar, "g1aucóphane II"Ernst (1961, 1963): ce11 dimensions iefined in this study fromx-ray powder data in Ernst (196'1), Table 5, Ernst (1953); Table 1,same sample.as No. 86, this table, "glaucophane I"Ernst (1963): cell dimensions refineã in tÈis study from x-raypowder daLa in Ernst (1963), Table 5, same sampre ãs No. Bj, itistable; "glaucophane II "Ernst (1963)¡ Run No. GM-1 obtained f rom I,i.G. Ernst, same as No. 95this tabre,.cel1 dimensions refined in this study, ;'glaucophane I"Ernst 19ü ): Run No. G-119 obtained f rom w.G. Einsti asl"c,- l-.egkbar, i0 h, ce}1 dimensions refíned in this study, "glaucopúane II"Ernst (1961, 1963): Run No. c-'134 obtained from w.c.-nrnst; 603"c;4.6 kbar, 1092 h, same as No. 97, this table, ceIl dimensiónsrefined in this study; "glaucophane I"Ernst (1963): 815oC, 1 kbar, 1920 h, glassErnst (1963): 835oC, 1.19 kbar, 37 h,-mixErnst (1963): 760oC, 2 kbar, 221 h, glassErnst (1963): 294oC, 4.6 kbar, 1460 h, mixErnst (1953): 603oc , 4.6 kbar, '1092 h, 91assErnst (1963): 4030c, 4.?S kbar , 1414 h,

-mix

Ernst (1963): 680oC, 10 kbar, SZ h, mixErnst (1963 ) : 796o_C, 10 kbar, I h, glassErnst ( 1963 ) ¡ 63'1

oC, 10.4 kbar, 1 S h, glassErnst ( 1 963 ) : 521 oc , 11 ,1 kbar, 4 h,

-giass

Ernst (1963): 600oC, 12.4 kbar, 72 h,-mixErnst (1963): 797oC, 12.8 kbar, 6 h, glass

89.

90.

91,

92,

93.94,95.96,97,98.99.

100.101.102,103.1 04.

62

118. Maresch (1973): 700oC,2119. cilbert and popp (1973):

I kbar, 6 h, glasskbar, 47 h, mix7 kbar, 20 h, mix7 kbar, 18 h, mixkbar, '13 h, mixkbar, 3? h, mix, No. GC-1kbar, 20 h, mixkbar, 13 h, mix, No. GC-zkbar, 6 h, glass9 kbar, 1095 h, gì.aucophane I3 kbar, 5 h, glaucophane Ikbar, 241 h, glaucophane II

9 kbar, 1097 h, glaucophane III kbar, "amphibole 2"750oc, 25 kb

13.1516,16.17202025302.920,0.52.9

105.1 06.107 ,1 08.1 09.110.111.112 ,'113.

114,1'15.116,117 ,

Ern stErnstErn stErn stErnstErn stErnstErn stErn stErnstErn stErnstErn st

(1e63):(1963):(1963):(1e63):(1e63):(1e63):(1e63):(1e63):(1e63):(1e63):(1e63):(1e63):(1e63):

6970c,750 0c,

7 50 0c,

800 0c,

690 0c,

700 0c,

900 0c,

700 0c,

599 0c,

2960c,7130c,500 0c,

3 50 0c,

Koons ( 1 982 ) : 700 oC, 25 kbar, 1 52 hcarman and Gilbert (tgg¡): No.4100, g00oc, 35 kbar, 16 hCarman and Gilbert (1983): No.G31, 750oC, 2b kbar, 0.S hCarman and Gilbert (1983): No.G35, 750oC, 25 kbar, 24 hCarman and Gilbert (1983)¡ No.4i26, g'15oc, 25 kbar, 24 hHoffmann (972)z I500oC, 5 kbar, 4 weeks, WM bufferErnst (1960): no conditions givenErnst (1950): refined in thiã study from X-ray powder datain his Table 13 (data for No. 125 used by ernãt)Ernst (1960): refined in this study from data corrected onrun R-129 provided by W.G. Ernst using BaF2 as internalstandard. 802oC, 1950 bar, 5 hErnst ('1960)¡ refined in this study from data colrected onrun R-129 provided by w.G. Ernst using Toxaway qtz as internalstandard. Compare with No. 127, 126, 125Ernst (1960): refined in this study from data colrected onrun R-101 provided by tI.G. Ernst. 8760e, 730 bar, 119 hErnst (1960): refined in this study from data colrected onrun R-130 provided by W.G. Ernst. B0BoC, 500 bar, 1g hErnst f962): No, 12, his Tabte 10, 40BoC, 2 kbar , 161 hErnst (1962)z refined in this study from data colrected on runHR-54-8 provided by lr.G. Ernst. Same as No. 13143. Ernst (1962), Table 10Phillips and Rowbotham (1968): 770-1000oC, 1-5 kbar, 1g-92 h.Note that these ceIl dimensions are incorrect, see No. 14SPhillips and Rowbotham (1968): refined in this study from x-rayX*ray powder data in their Table 1; same sample as ño. 144.Carman and Gilbert (1983): 980oC, 33.6 kbar,- Z0 hCarman and Gilbert (1983): 9000C, 25,0 kbar, 30 hi,titte et al. (1969): 750-770oC, 1 kbar, 4Z-119 hGrebenschikov et a1. (97a)z 450-5500C, >7S0 atmGrebenschikov et a1. (97a)t 350-450oC, 2S0*7S0 atmGier et al. (196.4)J Na2.5Hl. sMgsSisOzrlou)r, 700õð, 3000 atm, 6 hr,¡iLte É.ê!. (1969): Na3Mg5SisOzr(OH)(OH)2, 500-600oc, 2 kbar, 44-Prewitt (1963) : Na zHzCoS*SieOzz(ott) z

131.132,

1 33-1144

"

119a120,121,122,123,124,125.126,

'l

I2

54

'154. Prewitt ( 1963 ) : Na zHzMgsSi aOz zFz

2

I

9

0

2

3

h71

1461471481491501 s'1

152153

63

TÀBIE 6

ce11 dimensions and.opticar properties of previousry synthesizedfluor-amphiboles¡ pure endmember compositións-

A. CeIl Dimensions

Ref . a (Å) b (Å) c (Å) nt)

o v (43)

Fluor-tremol i tenCa 2MgsSi s0z zFz

1

2

34

5

9.787 ( 3 )

e.781(s)9.783 ( 3 )9.777 (4)9 .87 6(7 )

104 ,44(2)104.52(8)104.s2(3)104.50(3)106.10(s)

898.1898.0898.8897.5891.9

18.004(2)18.007(4)18.016(4)18.013(6)18.007(11)

17 .957 (418.019(817.963Q17.963(217.963ß17.968(3

s.263Q)5.267 (6)s.268 ( 3 )5.265Q)5,220(6)

5

5

6

7

Fluor-pargasiteNaCa 2MgaAlSi 641 zO z zF z17.922(9) s.284(3) 105.73(8) 898.7(6)6

7

I9

e.8s8(s)9. 88

9.847 ( 5 )e.807(5)

9.8239. 6s39.8349.8269"8289.824

104.83(8)104.45(8)

90s,2898. 0

900.3An? ¿

901.1900.3900.3900.6

FI uor -eden i teNaCa2Mg5SiTÀ1022F218.004(4) 5.282rc)

17 .9s7 (4) 5.266(6)

Fluor-richteriteNaCaNaMg5Si s0z

10.11.12.'13.

14,15.

F6

I1

1

1

I

)

)

)

)

)

)

5I1

1

1

3

(

(

(

(

(

(

5.2685.2445.2625.2635.2625.263

1 04.331 03.37104,21104.23104,24104.22

(8)(1\(1)(1)(1)(1)

(5)Q)(2)Q)(4)

16"17,

g.g4gQ')9.953(1)

Potass i um-f luor-r i chter i teKCaNaMg5Sis0zzFz

17 .977 (4) 5.267 (1)17 .981(2) 5.264(1)

104.80(2)104.81(1)

e10.6(3)e10.8(2)

18.19"20"21 ,

9.677 (5)e.65(1)9. 6ge.67 (1)

Sodian f luor-magnes i o-cummington i teNaMgNaMg5Si 602 2F 217.914(e) s.274ß) 102.9s(s)

17.921) 5.26(1) 102.74(8)17.92 5,27 102.9217.e2(1) 5.27(1) 103.00(8)

891 .01887(2)8918e0(5)

64

Ref . a (Å) b (Å) (Å) ß (") v (Å3)

UE

tr

L

trJ.

tr

tr

E

tr

5.5.

1)i)1)1)1)1)i)1)1)1)1)i)1)

(1)(1)(1)(1)(1)(1)(1)(1)(1)(1)(1)(1)(1)

Mi scellaneous sitionsompo26r22.

23,24,25.26.27,28.29,30.31.32,33.34.

.65

.61,67.69.70.71.51.55.68,70,72

17 .91(17 .92(17 ,96(17. 98 (

17 ,94(17 ,97 (

17.86 (

17 ,87 (

17.93 (

17 .92(17 ,94(17.89 (

17.90(

9

9

9

9

9

99

9

9

99

9

9

262626262628272627262626

6568

)

)

)

)

)

)

)

)

)

)

)

)

)

I

1

1

1

1

1

1

I

1

1

I

1

102.70(8)102.81(8)102.84(8)102.88(8)102.87(8)103.57(8)104.08(8)104.00(8)102.53(8)102.75(8)102.67 (8)102.63(8)103.00(8)

887 (2883(2891 (28e3(2892(2892(2870(2873(2890(s892(s895(s887(s888(s

B. Optical Properties

Het. a ß ''l Z^c

7

2a8.9.

10.'18

.

19.20,21,¿¿.23.24.25.26.27,28.29.30.31.32.33.34,

1.s81(1)1.581.60s(2)1.588(2)1.603(2)1.s76(1)1 .577 (2)1 ,577 (2)1 .577 (2)1.605(2)1 .597 (2)1 ,607 (2)1 ,604(2)1 .603 (2 )1.612(2)1.608(2)1.623Q)1.582Q)1 . s80 ( 2 )

1.603(2)1.585(2)1.590(2)

1 .617 e)1.s98(2)1.614(2)1 . s89( 1 )1.s89(2)

1.5e3(2) .602(2),61,624.60s.6¿¿,59s. 596.596. 596.618.618,616.612.610.620.618. 630.594. 596.615. s99. s99

1

1

1

1

1

1

1

1

I

1

1

1

1

1

1

1

1

1

1

1

1

1

(2)Q)Q)(1)(2)Q)(2)Q)Q)Q)Q)Q)(2)QTQ')(2)Q)Q)Q)Q)

211618122211 .412121216251720162320

1212121012

65

rbö hatm

, Cameron and Gibbs (1973): '1 '1 50 oc, '1 atm

REFERENCES1. Cameron (1971)2, Comeforo and K3. Troll and Gilb4. Troll and Gilb5. Westrich (19786. Westrich (19787. Droll and Seck8. Kohn and Comef9. Kohn and Comef

10. Kohn and Comef

ohn (195a): 1450oert (1972)z 1142'ert (1972) z 1132o): 9000C, 1 atm,): '10000C, 1 atm,

(1e7 6 )oro (1955)oro (1955)oro (1955)

,11

'1 00 0c,tohh

5och-1atmr 29atm,71

c 2h,c, 1

c, 1

24h24h

39 daysatm, 9 daysatm, 9 days

1170-1000oc, '1 atm, 5och- 1

atm, 9 daysatm, 9 days

1. westrich (1978): 1000oC, 4 kbar2. Huebner and Papike (1970): 818oC, 2 kbar3. Huebner and Papike (1970): 1244-791oC, j4. Huebner and Papike (1970): 1132-843oC, 1

5. cameron (1970), cameron and Gibbs (97i)6. Huebner and Papike (1970): 1244-791oCt 1

7. Huebner and Papike (1970):'1'131-843oC, 1

8. Gibbs et aI. (1962)9. Fedoseev et al. ( 1 970 )0. Grigor'eva et aI. (1973a)1 . Grigor'eva et al. ( 1 973b)2-29, Fedoseev et aI. (1970)

22. Na2Mg5NiSisO22F223. NazMgs. ¡Cuo. sSi sOzzFz24. Na2Mg5CoSieOzzFz25. Na zMgt. aZnt.¿Si aOz zFz26. Na2Mg5MnSiaOzzFz27. Na2CdMgsSis0zzFz28. Na z. sMgsCrE I sSi aOz zFz

1

I

1

1

1

1

I

1

1

2

2

¿

9. Na3MgaFe5*Si6022F24. Grigor'eva et al " ( 1 973b)0. Li r . sNao. sMgs. sSi sOz zFz

3'1 . tio. sNa 1 . 5Mg5Si eOz zF z

32. ti r. oMn t.z\4g+.zSieOz r. sFz. I33. tír.sCao. rgMgs zSir)r,.eFz.o34. ti I . sCao. sMgoSi aOzzF z

230-3

3

66

TABTE 7

cell dimensions of previously synthesized amphiboles: non-endmembercompositions

Ref . a (Å) b (Â) c (Á) ß (") v (Å3)

1

2

3

4tr

67

I9

01

9.8929.8699.8539.8549.8369.8359.8619.8369.8839,8469.836

(s(s(t0(s(o(s(s(q(s(s

ÀctinoliterCa 2Mg z . sFe z . sS i e0 z z (OH ) 2

18 .1e1 (12) 5.2es ( 3 )18.184(16) s.301(4)18.18s(13) s.294(s)18.i93(20) 5.294(2)18.193(20) 5.295(4)18.189(23) 5.294(4)18.206 (e ) 5.2e8Q)18.19s(9) 5.29sQ)18.209(10) 5.230(3)18.1e2(e) 5.28e(3)18.17s(16) s.295(10)

104.6s(s)104.39(7)104.44(8)104.44(4)104.4s(7)104.25(8)104.52(3)104.38(4)104.s6(5)104.33(5)104.38(11)

i soz z (oH) z

10s.43(4)105.35(3)105.31 (3)105.12(3)10s.05(4)104.89(4)1ñÂ" 1?. 1)\,v¡.rv\&/

104.s6(1)104.42(1)

921.e/7)921.4(10)918.6(10)e17.8(e)917.s(11)e18.0(10)920.8 ( s )917.8(s)923.0(6)91 7.8 (5 )917.0(14)

12.13.14,15.16,17,18.19.20,

21 ,

.899(3,90212.903(2

903.4 (

904.5(905. s (

906. 9 (

908.2 (

907 .9(oño ^/909. 6 (

908.e(

9

9

99

9

9

99

9

,904.90s.903.904.906.902

NaCa 2Mg a

PargasÀ1S i 6À1 2

17.9ss(s17.973(s17 .98s(417 ,991(51 8.006 ( si8.002(s18"000(417.994(217 .984(3

ite-ricozz(ou)

hterite joinz -NaCaNaMg s S

5.273Q)5.270Q)5 .271 (2)5.272(3)s,273(1)s.26e(2)a -?11 ( 1\s .271 (1)s"269(1 )

2

2

4

21

1

(

(

(

(

(

(

43

3

4

45J

21

PargasiÈic hornblendel{ao. zsCaz.oMg¿ :oÀlr .oSi6. zsÀl r,t sOzz(OH)e.87eQ) 18.012(7) 5.264(7) -lo5.lei 2

4) 904.1(13)

22.23.24,

pargasite.NaCa 2Mg aÀ1S i oÀ1 z0 z z9"904(1) 17.98e(s)

9.915(3) 18.031 (7)9.930(5) 18.i04(6)

. ferro-pargasite join0H) z-NaCa zrel -¡lsi

oÀI z05.291 (2) 1 0s.45s.301(3) 10s.40s.320(2) 10s.27

zz(ou) zQ) e08.6 (s )(1) 913.6(10)(1) e22.6ß)

Potassium-pargasiteKo. ¡oNao. soCa2MgaÀ1Si oÀ1 zOz z (OH)

z17,924(10) s.288(3) 105.54(4)2s. 9.901 (4) 904.1 (8 )

67

Ref. a (Ä) b (Å) c (Å) t)o V (43)

26. 9.933(6)

27, 9.851(4)

Potassium-edeniteKo. soNao. ¡oCazMgsSi 74102 z (0H)

z18.028(18) 5.327(3) 10s.34(8)

EdeniLic hornblendeNae" 5Ca2.oMg+.oÀlr.oSio. sAI r. sOzz(OH) z18.009(16) 5.294(6) 10s.06(6)

91e.e(1)

906.e(i5)

Tschermaki te. . . f err i-tschermak i te joini 6À120 zzØu) z

10s.61 (2)105.23(4)10s.16(4)105.02(4)

e01.0(3)e0s.5 ( 3 )e01.6(s)902.4(3)

914 ,591 9.6926.7932,7

28.29.30.31.

rca 2Mg ¡À1 zS i oÀ1 z09.874(3) 17 "91(19.887 (3 ) 17 .94(19.761 (6) 17.99(19.763(4) 18.01(1

NaCaNaMgsSi a0z z9.917(2) 18.020(s)e.935(2) 18.063(3)9.962(s) 18.122(6)e.980(7) 18.180(7)

zz(otl) z- sFel*SrCa 2Mg5.291(s.294(s.319(5.312(

Richterite. . . ferro-richterite(oH)z-¡¡acaNaFeB -si,

1

4

55

joinozz(oH)04.13(5132.

)')34.35.

5 .277 (1 )5.284Q)s.292(2)5.2s7 (5)

'i 04.08 (51 04.07 ( 3103.97(3

3

63

9

36. 9.85

Cross i teENa2Mg r . sFe I I s¡to. ozFel I ¡ sSi eOz z (OH)

z18.03 5.33 103.4 s19(12)

Ri ebeck i te-ar f vedson i teENa 2Fe 3

.ne I *Si

aO z z (OH ) z-NaNa zFe lFe 3 *Si sO2

1 8.09 5. 32 1 03.318.08 5"33 103.318.07 5.33 .103.3

18.07 5.33 103.318.06 5"33 103.31 8.06 s. 33 1 03.318.07 5.34 103.418.03 s.33 103.318.07 5.33 103.418.10 5.30 103.21 9.07 5. 33 1 03.4'18.05 5.33 103.418.07 5.33 103.418.06 5.34 103.4'19.06 5.33 103.51 8.05 5. 33 103.418.08 5.33 103.41g .22 5. 3'1 102 ,918.10 5.33 103.31g .23 5 . 31 102 ,g

z (oH) ,37.38.39.40.41 .42.43,44.45.46.47.48.49.50.51 .52,53.54.55.56.

9.769. 759.769"759,759,759,749.739,7 49.789.779,769,7 69,769.759,7 49,759,829.839.85

914.3914 .1914 ,491 3.0913.09'1 3.6913.1910.091 3.3914.591s. s914 ,1914 ,6915.09'13.3911,4914 ,2926.1922,1929.0

68

Ref . a (Å) b (Å) c (Å) ß (") v (Å3)

5't .58.59"60.61,62,63"64"65"66.67"68.69,70.71.

9. 849 .809.919. 909.889,879. 889,919"899.829.829.839.879.859.87

5 "325.325.315.32s.315.315.305.315.315. 325.32s.335.325.325.31

923.5920.9929.8931.5931.4928,9930.5933.3929.8923,5920,8922,0928.4924.6930.5

18.1318.15'18.i418.1618.2118. 1818,2318,2118. 1618. 1418.13'18.09

18"1618.1318.22

Richterite... pota ss iz(oH)z-

J

555

um-r ichKCaNaMg,272(1).270r).26e(1).268(1)

103.3103.0103.2103. 0103.1103.0'103.

1

103.1'103.

1

103,2103,2103.3103.2103.3103. 1

terite joinsSi ¿02 z (gtt) z

104 .7 4 (1)104.65Q)104.s6(3)104.42(5)

91 9.8 (3917.8 (3915,5Q912,7 (3

NaCaNaMg5Sig 0z1)2)6)3)

1)73.74,'7 Ê.

10.030(1)10.009(3)s.e83Q)9.948(2)

17 .98617 ,9841 7.98017 .981

76.

Fluor-richteriteNa(Nao. s rCao. ¿sFeo, oo) r(lutgo. sgFeo. s z ) sSi z .t sOzzp ze.846Q) 18.01e(3) s.zt+(s) ìo¿.es(l i- s06.e(6)

REFERENCES1-11. Cameron (1975)

. 559 oc, ( 1 00r'eO/Feo+MqO )( 1 00neo/neo+Msó)( 1 00neo/reO+Mso)( 100re0,/reO+MgO)( 1 00neor/reO+MgO )(100r'eOr/¡'eO+MgO)( 1 00neo/neo+MsO )( 1 0 0neor/l'eO+MgO )( '1 00neo/reo+Mgo )( 1 00neo/neO+MgO)

( 1 0Oneo/reO+MgO )

. 5050c

. 550 0c

. 5920c

. 603 0c

. 6650c

. 5560c

. 65'1 0c

. 505 0c

.5500c

.6500c

kbar,kbar,kbar,kbar,kbar,kbar,kbar,kbar,kbar,kbar,kbar,

738-1 00,1 6E-50 ,'17D-50,

1 8c-s0 ,1 58-50,43C-50,38c-80,53D-80 ,92D-90,528-90 ,61 B-1 00,(977)

8(4)(6)(¿ )(6)0)(8 )'(3)(3)

446463949485Js05449

4

1

2¿

4

5

67

I9

0

1

02

3

4

5

6

¿

2

2

2

2

2

2

2

2

22

(3)(3)3(6)

'1

1

12-21

1

1

1

1

Braue and Seckpas¡ri1spaseri2ppaTeri3ppa6eriaepa5eri5e

69

17, paaeri6s18. pasorizo'19. pa2erise20. palerise

21. toida and Hinrichsen (1975): 800oC, 4 kb22-24. Charles (1980)

22. l4gsPe , av. of 1 023. MgzEpzt av. of 624. MgFe3, av. of 4

25, Hinrichsen and Schürmann ,1977)z 7S0oc, 4 kb26. Hinrichsen and Schürmann (1977)t 7S0oC, 4 kb27, toida and Hinrichsen (1975): 800oC, 4 kb28-31.oba (1978)

28.29,30.31.

32-35.

tsgoftslo, B50oC,t5zoftsso, I50oC,tsoofLs¿0, 850oC,ts5efts5s, 8500C,Char les (97 4)

2kb2kb2kb2kb

IW buf fer, IW buf fer, IW buf ferIW buf fer

32. FeMga, av. o33. Fe2Mg3, av.34. Fe3Mg2, av.35. FeaMg, av. o

t 7,of. 7

of5f 3,

36. Koslowski and Hinrichsen (1979):37-71. Ernst (1962)72-75. Heubner and papike (1970)

72. Ko.sz5r âV, of.273. Ko. z s, av. of 374, Ko.sor âV. of 375. Ko.zs, av. of 3

76. Cameron (1970), Cameron and Gibbs

7000C, 4 kbar

(1971 ): i 050-880oC, 5och- r , .1 atm

Chapler III

EXPERIMENTÀI METHODS

CHÀRGE PRE TION

Ëtartilq Materials

Dry mixtures of appropriate anhydrous amphibole stoichiometry and solidoxygen-buffer materials were prepared from commercial reagent-grade ox-

ides and other compounds. Source chemicals and procedures for mix-corn-

ponent preparation are given in Tabte B.

After weighing out components, the mixture was blended by hand for 5

minutes and then ground in a powered alumina mortar under alcohol for at

least t hour. The thoroughly ground mix was again blended by hand forabout 5 minutes and dried overnight at 4000 to 1000oc, depending on the

stability of the components. Prior to use, the mixes were stored tight-Iy capped in a desiccator over Mg(CtOo)r.

Ànhydrous ge1s, prepared gravimetrically according to the method of

Hamilton and Henderson (1969), were used for certain pargasite, alumino_

magnesio-hornblende, edenite, and alumino-winchite compositions. Compo-

nents required in addilion to those for dry mixes are also listed in Ta-

ble 8.

71

TABTE 8

Sources and preparation of starting materials

Component Source Trea tment

Mgo

sÍ0 2

Z-41 z0s

Ca0

Na z0

Na z0

Kz0

CaF z

NaF

cd0

GeOz

Ni0

Sc z0g

Crz0s

Corning Fused SilicaCode 7940

e1 (oH) g

Fisher tot 765051

Fisher Lot 754056

CaC0 g

Fisher Lot 740807

Na zSi z0s

Na zCOsFisher Lot 751625

KHCo3Fisher tot 794339

Fisher LoE 787317

Fisher Lot 775169

CdC0sFisher Lot 734756

Matheson, Coleman &

8e11, tot 101"110

Fisher Lol 730777

À1fa Lot 081380

Fisher Lol 724579

Cleaned in aqua regia.Washed in distilled HzO.Dried to constant weightat .1

000 oC.

Heated at 900oC, 48 h.

Dried at 1000oC toconstant weight.

Decarbonated to constantweight before weighing,or added to mix as CaCOsmix decarbonated at 1000

,o c

Prepared after Schairerand Bowen (1955). oried at200oC for 3 h.

Added as carbonate.decarbonated at 700oC

Mix

Added as carbonate. Mixdecarbonated at 7000C.

Dried at 8000C, 24 h.

Dried at 400oC, 24 h.

none, used as is

dried at 4000, 24 h,

none, used as is

dried 400o, 24 h

none, used as is

72

Tab]e I (continued)

Component Source Treatment

CuO

'Jzoz

Ti z0¡

Ti02

Ga z0g

Inz0s

Mn0

Li z0

Fe203

Fe

À1

Si02

Alfa Lot 032681

À1fa Lot 081778

Fisher Lot 795530

Àldrich tot 1097

Johnson MattheyLot 582934

Cu20, Baker andÀdamson Lot T318J

MnC0¡Fisher tot 700983

Li zCO¡Fisher Lot 75427'1

Fisher LoL 766122

Fe-metal powderBaker Lot 25598

si04 (CzHs ) ¿

Fisher tot 780760

none, used as is

none, used as is

none, used as is

dried at 4000C, 24 h

dried at 400oC, 24 h

heated in air at 400oCfor 48 h

none, used as is, added asca rbonate

none, used as is, added asca rbonate

none,

none,

used as is

standardized as inEdgar f 973)

Mg

used as is

Additional components for gels

Mg-meta1 powder none, used as isFisher Lot 794121

À1-metal powderFisher Lot 763574

none, used as is

17'

Eluor-amphibole Capsules

In most fluor-amphibole synthesis experiments, 4 mm o.d., 3.7F mm i.d.Pt tubes 22 to 23 mm long were used to contain the charge. The tubing

was cleaned prior to use by boiling it in concentrated HCI and 14as an-

ealed at red heat in a gas flame for a few seconds. Àfter one end was

crimped flat and welded shut with an electric arc welder , 20 Lo 40 mg of

dried mix of appropriate fluor-amphibole stoichiometry were packed into

the capsule, filling about one-fifth to one-quarter of it. The remain-

der of the tube was then flattened to expeJ. air and sealed by welding.

During the second weld, the lower portion of the capsule containing the

charge was immersed in ice-water to prevent volatilization of 1ow-me1t-

ing point components.

Several fluor-amphibole runs vlere attempted in large-bore (5 mm) Àu

capsules. Àu tubing apparently softens at temperatures about 1000C be-

low its melting point, and capsule failure was freguent due to internal

gas pressure. In successful runs, fluorine reaction with the Au capsule

inner wall did not seem to be significant, and run products were not

measurably different from those reacted in pt capsules.

satisfactory results were not obtained using large-volume (>l g)

charges in unsealed Pt crucibles similiar in configuration to runs by

westrich (1978). A Pt crucible containing the charge rvas covered with

Pt foil, folded over the edge. This crucible was placed into a larger

crucible hatf-fiIled with car'2 and also covered rvilh foil. Because of

uncontrollable amounts of fluorine leakage, high amphibole yields were

rare and results could not be consistently reproduced. When successful,

however, this method has the advantage of producing large amounts of

product for characterization.

74

HydrplLv-amph i boI e Çapsules

In hydroxy-amphibole experiments, about 30 to 90 mg of charge corre-

sponding to the appropriate anydrous amphibole composition, plus s to 20

percent doubly distilled and de-ionized water were loaded into capsules

prepared in the same way as for fluor-amphibole syntheses. tthen ele-ments of variable oxidation state were not present, 4,5 or 5.0 mm o.d.,4.1 or 4.75 mm i.d. Àu tubes 25 to 35 mm long were used to contain the

charge. In order to fit the pressure vessel bore with less risk of jam-

ming, the ends were crimped in a tricorn configuration with a drillchuck, rather than flat-crimped, before welding.

For runs requiring oxygen fugacity control, two methods were em-

ployed. First, if an approxirnate oxygen fugacity corresponding to the

NNO buffer was suitabre, the charge rras simply loaded into 4 mm o.d.,3.75 mm i.d. Pt tubes 25 mm long and run with the pressure vessel wall(contains Ni and NiO) and H20 pressure medium reaction as the bufferingagent. second, for precise oxygen fugacity control, the standard

double-capsule solid-buffering techniques developed by Eugster (1957)

and reviewed by Huebner (1971) were used. Inner capsules were 3 mm o.d.

2.5 mm i.d. Pt or ÀgTopdso tubes 20 mm long; the outer capsules were

5 mm o.d., 4.75 mm i.d. Au tubes 3s mm rong. Buffer reactions and ab-

breviations are listed in Table 9; source chemicals and preparation of

buffer materials are given in Table B.

75

TÀBLE 9

SoIid Oxygen Buffers

2Cu z0cuprite

4Fe ¡0¿magnet i te

2Ninickel

2Fei ron

* 0z

4Cu0tenor i te

6Fe z0 ¡hemat i te

2Ni0bunsen i te

2Fe0wüst i te

CT

MH

NNO

Ill

+

+

+

0z

0z

0z

RUN PROCEDURE

Fluor-amphi bole Syntheses

Fluor-amphibole synthesis experiments at one atmosphere pressure were

conducted in verLical quenching furnaces similar to those described by

Schairer (1959). Two types of furnace designs, both wound h'ith ptooRh¿o

wire on mullite cores 30.5 cm long, were used: one with an inner tube

diameter of 23 mm, the other with a 44 mn inner tube. up to four charg-

es in Pt or Àu capsules vrere simultaneously reacted in the smaller fur-naces by suspending them on a pt wire at the hot spot. Quenching at the

end of a run v¡as accomplished by releasing the suspension wire and aI-lowing the capsules lo drop into a container of cold, distilled water

located below the open lower end of lhe furnace tube. The larger fur-nace allowed the simultaneous reaction of up to 20 capsules packed into

an alumina crucible. The crucible was positioned at the hot spot with a

ceramic pedesÈal inserted from the boLtom of the furnace tube. Runs

were guenched either with a blast of coId, compressed air after 1owering

76

the crucible-pedestal assembly, or by removing the crucible and dumping

the capsules into cold, distilled water. Distitled water was used so

that if capsules cracked during guenching, the run product was not con*

taminated and could be salvaged by drying.

Temperatures were measured with ceramic insulated, bare-wire pt-

PtezRhrg thermocouples (rype n). In singJ.e-capsule runs, the measuring

junction was placed as close as possible to the middle of that part of

the capsule containing the charge; in multiple-capsule runsf the junc-

tion was located at the centre of the capsule bundle. Thermoelectric

potentials were measured with a Tinsley Type 3184-D potentiometer reada-

ble to 5 microvolts. A reference junction in the thermocouple circuitwas maintained at 0oC by an ice-water bath. Thermocouples were not cal-ibrated for each run, but simil-ar calibrated circuits used in this labo-

ratory are consistently within 3 degrees of the melting point of copper

(1084.90c).

Temperature during runs in the smaLler furnaces t+as maintained within

5 degrees of the set value by home-nade, proportionar-type temperature

controllers. The large-bore furnace was equiped with a Theall Engineer-

ing Company Model TP-2000 Thermocouple Temperature Programmer. In addi-

tion to precise isothermal proportional control rvithin 1 degree or less

of the set value, experinents could be performed at linear cooling rates

of 0o to 1ooc hr-1.

77

Hvdroxv- hibole Svnt heses

Hydroxy-amphiboles were synthesized between 600o and 800oC, 1 and 3 kbar

water pressure with conventional hydrothermal eguipment. Co1d-seal

pressure vessels with 6.4 mm bores, similar in design to that of Tuttle( 1949 ) , v¡ere machined f rom Rene 4.1 al.loy and measured between 20 and

30.5 cm in length, and between 25 and 32 mm in diameter. stainl_ess

steel or graphite filler rods were used to nrinimize fluid volume inside

vessels and to prevent convection in the pressure medium. I,iater pres-

sure rias applied with a hand-operated pump.

Experiments up to 3 kbar at '1000oc were performed in LECO Temp-pres

TzM (Ti-Zr-Mo ÀlIoy) pressure vessels 30.5 cm long and 25 mm in diameter

with water-coored head nuts. Àrgon pressure was appJ.ied with an air-driven stainless steel diaphragm pump to 2 kbar and then boosted to 3

kbar with a hand-operated pressure inLensifier.

Pressure vessers were heated in nichrome-element, tubular, split-typefurnaces. Temperature was maintained during runs by one of several

tlrpes of temperature eontrollers: Theall Engineering company Model

Tc-1000 with zero-sH'itching, time proportioning controJ.; sirect M.K.2

Silicon-controlled Rectifier proportional type; and West Corporation

Gardsman on-off type controller.

Temperalures during runs were monitored by stainless steel-sheathed,

M90-insulated, chronel-Àlumel thermocouples (rype tt) inserted into ex-

ternal wells drilled in the bottoms of the pressure vessels. The depth

of the wells vlas appropriate to position lhe thermocouple Èip about 5 mm

away from, and approximately opposite to, the centre of a 2s mm sample

capsuLe. The actual temperature inside the vessel was previously cali-

78

brated against the external thermocouple using an internal thermocouple

and dummy capsule and fi11er rod, during simurated runs at 1 atm.

Thermoelectric potentials were measured with a Leeds and Northrup

8690-2 Millivolt Potentiometer readable to 0.01 mv. A reference junc-

tion in the thermocouple circuit was maintained at 0oC by an ice-water

bath. Thermocouples were not calibrated for each run. Random checks

using the thermal pause method and NaCl resulted in freezing-point val-ues within 2 degrees of an acceptable value of 800.4oC. Temperature un-

certainty in these experiments lras approxinrately t10oC.

Pressures vrere measured on 10 cm (1400 bar) and 18 cm (5500 bar) esh-

croft Maxisafe bourdon-tube gauges, cal-ibrated at the factory. The giv-en uncertainty was 10.5 percent of the full-scare reading.

Pressure vessel-s tvere quenched under pressure by opening the furnace,

removing the vessel to an adjacent metal support, and blasting it with a

jet of co1d, compressed air for about 1 minute. Immersion in cold water

followed immediately¡ fresh cold water vras continuously added to the

bath while warm water was removed, to make the quench as quick as possi-

ble. The pressure vessel usuaÌly reached room temperature in less than

5 minutes.

CHÀ I ZATION

Optical Microscopy

Capsules were weighed before and immediately after runs to check forweight gains or losses that would indicate capsule leaks. The capsule

was then examined under a binocular microscope for external signs of

79

leakage, especially if post-run and pre-run weights were not similar.Àfter opening, the product was checked for contamination by leaks, signs

of reaction with capsule material, texture and grain size. A smal] por-

tion of the product was gently crushed and mounted on a gJ.ass slide with

piccolyte (refractive index 1,52) under a cover glass for viewing at

higher power with a polarizing microscope.

Scanninq Electron Microscopv

À major block to the characterization of run products is their very finegrain size, which makes optical examination difficult and often useless

in identifying phases other than amphiboLe. Furthermore, phases of poor

crystallinity or very low abundance do not register, or are overlapped

by major phases in X-ray diffraction patterns. Scanning electron mi-

croscopy offers much greater useful magnification and superior resolu-

tion to optical methods, allowing phases of different or complex mor-

phologies to be readily distinguished i.n most cases. Magnifications of

2000 to 20000x are the most useful for examining typical run products in

detail, but lor+ magnifications in the optical microscopy range ('100 to

500x) are also important in documenting the overall characteristics.

X-reI Powder Diffraction

X-ray powder diffractograms were routinely taken for all run products at

fast scanning speed (30oze min-1). These allowed for quick evaluation

of the amphibole yield and of the nature and approximate concentrations

of non-amphibole phases. subsequently, all runs with high yierds of am-

phibole were scanned at slow speed (0.6o2e min-1) for cell dimension de-

termination and to obtain accurate d-spacings for identification of non-

amphibole phases.

80

Powder diffractograms were obtained on a Philips Automated powder

Diffractometer System Pl.t1710 using monochromatized Cu radiation (CuKa,

waveLength=1.5418 Å). The finely-ground amphibole run product and a

small amount of BaF2 rv€r€ blended thoroughly by grinding gentJ.y under

alcohol. The mixture lvas spread on a glass slide with alcohol to form a

thin (0.01 mm), uniform smear. The BaFz (a = 6.19860(5) Å) was cali-brated against Si (HsS Standard Reference Material 540a, a=5.43083(4)

Å). Àmphibole peaks were indexed by comparison to published patterns of

amphiboles with known structure and composition. OnIy those reflections

that could be unambiguously indexed and did not overlap significantlywith neighbouring peaks were used in celL dimension calculations. These

requirements restricted usable amphibole reflections to 10 Lo 12, be-

tween 9o and 4502ø CeIl dimensions were refined using the CETREF program

of Appleman and Evans (1973),

_I nf rared Spectroscopv

High-resolution infrared spectra of minerals containing hydroxyl groups,

such as amphiboles, exhibit fine structure that is sensitive to the ca-

tion occupancies of the M(1) and M(3) sites (Hawthorne 19g3a, b). In

binary solid-solutions, there are eight possible ways of distributingLwo different cations over the three M-sites coordinating each hydroxyl.

In amphiboles, however, the three M-sites coordinating the hydroxyl are

in a pseudotrigonal arrangement that inLroduces an accidental degeneracy

to some bands and reduces the number of resolvable bands to four. In

endmembers, 2M(1)+M(3) configurations around each hydroxyl are identi-caJ-, and a single, sharp hydroxyJ.-stretching band results (Figure 4a).

Figure 4 displays typical natural amphibole spectra collected in this

81

study under the same experimental conditions as the synthetic amphibole

spectra. Note the sharp, narrow peaks with band v¡idths between 6 cm-1

and 9 cfr-1, values typical for other naturaL amphibole spectra (Strens

1974). of particular interest is the peak shape of the single MgMgMg

stretching band in the tremolite spectrum (Figure 4A). The shape corre-

sponds to that of a markedly skewed gaussian distribution. Figure 48

shows a typical natural actinorite spectrum with Mg and Fe as the pre-

dominant octahedral cations. Table '10 shows the possible cation ar-

rangements and hydroxyl-stretching band assignments in amphiboles with

M(1,2,3) sites completely occupied by Mg and a another different cation,

TÀBLE 1 O

Possible cation-arrangements and hydroxyl-stretching band assignments inamphiboles with M(l,2,3) compreteJ.y occupied by Mg ánd second ãation, M

M(1) M(1) M(3) rq(1)+u(3)1 M(1)=M(3)z

Mg

M9

MgM

M

M

Mg

M

Mo"2M

MgM9

Mg

M

M

M

Mo--f

MgM

Mg

M

Mg

M

M

À

B'Bt t

Bttc'ct t

ct t

D

À

B

B

B

cccD

lidea1 band ascally distinc

zband assignmeaccidental detrigonal arra

signment for crystallographi-t configurationsnts for configurations withgeneracy due to pseudo-ngement

(from HawLhorne 1983b)

M Interpretation of ternary and more complex solid solutions is diffi-

82

cult because the number of fine-structure bands becomes very J-arge. For

example, there would be ten hydroxyl-stretching bands in a three-compo-

nent solid solution, and twenty in a four-component solid solution.

High-resolution (2.0 cm-1) infrared spectra of hydroxy-amphiboles in

the fundamental o-H stretching region (3600-3800 cm-1) were recorded on

a Nicolet Fourier transform interferomelric infrared spectrophotometer,

Model MX-1, equipped with a Nicolet 1280 computer for signal processing.

The sample chamber 'oas

purged '+ith dry nitrogen before and during spec-

trum collection. Frequency measurements were calibrated internallyagainst a He/ne laser and are accurate to 0.0'1 cm-1 according to the

manufacturer.

Powdered sampres were prepared by grinding '1 to 1 2 ng of. amphibore by

hand in an alumina mortar with ethanol until the grain size rvas gener-

ally less than 2 microns. This vlas achieved quickly because most of the

synthetic amphiboles were less than 2 microns in grain size initially.Àfter drying to evaporate the ethanol, lhe sampte was mixed with KBr,

either by hand grinding in an alumina mortar¡ or in a dentist's amalga-

mator (wig-r,-nug). This mixture rvas dried under vacuum at 12soc and

then was pressed in an evacuated, heated (about 90oc) die into a 13 mm

pel1et.

83

A

B

3 BO3 603 +o 3 zo3 oo3 BO3 603 r*0 3 zo3 TI Tì

I.JAVENUÌIIBEtrS

Figure 4: Typical infrared spectra of naturalÀ: Tremolite, Gouverneur, New york.Net Lake Àrea, 0ntario.

tremolite and actinolite.B: Actinolite, Setting

84

Rietveld Method of Crystal Structure Refinement

The Rietveld method (Rietveld 1967,1969) uses the whole powder diffrac-tion pattern to characterize the structure of the material examined.

The structure parameters of the mineral, atomic coordinaLes, site-occu-

pancies and thermal parameters, together with various experimental pa-

rameters affecting the pattern, are refined by least-sguares procedures

to minimize the difference between the whole calculated and observed

patterns.

X-ray intensity data were collected on a Philips Àutomated Diffrac-tion System PW'l710 equipped with graphite crystaL monochromator for CuKo

radiation. Beam divergence was controlled with an automatic divergence

slit so that a constant area (approximately 1.9 cmz) of the specimen was

irradiated throughout the scanning range. Intensities were measured at

0,02o2e steps with counting times of either I or 16 s per step; scanning

ranges were between 8o and 73o2e.

Specimens were ground with ethanol in an alumina mortar for aL least

5 minutes and loaded into either an aluminum holder with a glass insert

to support the powderr ot into a HF-etched depression in a glass slide.The slurry was worked with a probe so that it was evenly distributed and

dried with its surface precisely flush with the top of the holder.

Grain size was generally less than s microns with some grains up to

20 microns long. À11 specinens analysed exhibit prismatic to acicular

habits, but sEM photographs (Figure 5, 6) suggested that preferred ori-entation was apparently not severe in mosl samples and special precau-

tions were nof taken lo eliminare it during sample preparation. Àt-

tempts by other workers (e.g. young and t.liles 1 981 ) to minimize

preferred orientation by mixing the specimen with an

ground glass did not significantly improve refinements.

85

equal amount of

Structures vrere refined using a sIíght1y modified version of the pro-

gram DBW 2.9 (wiles and Young 1981). The features of this program are

summarized in Appendix À. Refinements were done in three stages.

First, the scale factor, cefl parameters and zero-point were refined

wi.th atomic positions, site-occupancies and isotropic temperature fac-

tors for individual atoms fixed at estimated values approximately cor-

rect for amphiboles. in this stage, a background model based on inspec-

tion was used; other profile parameters were estimated either from the

intensity data or from pubrished work, and were not refined. In the

second stage, the half-width parameters, peak asymmetry parameter and

preferred orientation parameter were included in the refinement. In ad-

dition, the background was refined as a second order polynomial function

in 20. Because most of the amphibole diffraction pattern above about

26o2ø consists entirely of severery overlapped peaks, background mod-

elling is difficult. ÀLtempts to nodel the background by extrapolation

between areas of low intensity between peaks failed above 2Go2ê. In the

third stage, the remaining structural parameters were added to the re-

finement and the background model function v¡as expanded to the third or-der. Background refinen¡ents at higher orders failed to converge. pa-

rameter shifts in the final cycle of refinement were generally less than

0. 1 to 0.2 sigma.

Best refinement results (lowest R-factors) were obtained with the l,tod

2 Lorenzian profile function (Appendix a. ) and by refining the overall

isotropic temperature factor.

86

Complete refinement of a typicat amphibole structure requires the si-nultaneous refinernent of 45 to 50 parameters. In order to decrease com-

puting time the refinements were performed at 0.O4o2A steps rather than

at the collected interval of 0.02o. The results were essentially iden-

tical; standard errors were slightly larger at the larger step.

Chapter IV

ÀMPHIBOtE SYNTHESES: RESULTS

This chapter describes and evaluates the results of all endmember amphi-

bole syntheses and isomorphic substitutions in these endmembers that

were attempted during this study. Because the chief aim of the synthes-

es vias to grow pure amphiboles for crystal-chemical characterization,

run products were initially examined only for amphibore yield. subseq-

uently, products with high amphibole yields (>80 percent) were document-

ed in detail. Experimental conditions and products for each run are or-ganized according to nominal starting composition in Tables 11 and 12.

In the run products that were examined in detaiL, only those phases that

could be identified unambiguousry from powder x-ray patterns, or rarely,optically, are listed under "products. " Thus, in complex, multi-phase

run products, some low-abundance phases may have been masked in the X-

ray powder patterns by the intense reflections of high-abundance phases.

Runs with >80 percent amphibole are marked with an asterisk in the run

number (e.g. PÀA'1*). Low-yield or amphibole-absent run products are de-

scribed only by the approximate amphibole mode under "products." In the

text, results are summarized by principal amphibole group with headings

showing all attempted substitutions collectively in the ideal endmember

formula. Products were identified and characterized according to the

method outlined in Chapter 3. CeIl dimensions for amphiboles from high-

yield runs are given in Table 13.

-87-

88

EÀILCIC AMPHIBOLES

Tremol i te : o ( Ca, Cd )¿(t'tg, [L,t',tn ) sS i aOzz ( OH )¿

ECa 2MgsSi a0z z (0H) z

Runs of up to 18 days duration on the endmember tremolite conposition at

200 to 35oc below its 1 kbar stability limit (noyd 19s4,19s9) failed to

grow perceptible amphibole. Both experiments were performed at simitar

temperatures, at 1 kbar, but gave different results. The short run ß32

h) comprised abundanL diopside and three metastably coexisting silicapolymorphs: low-quartz, low-cristobalite and tridymite. Cristobalitewas the most abundant; quartz was the least abundant. In the rong run

(44s h), the peaks in the x-ray powder pattern are better formed and

sharper than in the short run. tow-quartz is the only sirica phase;

other phases are the same. Weak reflections corresponding to enstatitewere observed. Às tremolite is a common constituent of marbles, run

TR-B'1 þ¡as attempted on the bulk tremolite composition using a startingmix comprising CaCOs, M9CO3 and Corning 7940 silica glass. Modest

amounts of amphibole (less than 20 percent) were formed. The presence

of abundant C02 apparently encourages tremolite growth.

Substitution of Ni5 for Mg5

Replacement of Mgs by Ni5 yielded about 10 to 20 percent very pale

green, weakly pleochroic, acicular amphibore averaging about 4 unr in

length. No attempt was nade to contror oxygen fugacity. The presence

of Ni in the product suggests that oxygen fugacities were close to thatof the NNO buffer; NiO reflections, however, were not detected in the

x-ray powder pattern. The most abundant phase r{as pale green, prisnat-

ic Ni-diopside with cell dimensions (a=9.7409(g), b=g.g96(1 ),

89

c=5.236(3), ß=105 .78(2) , V=436 .6Q) ) similar to those f or caNisi 206 giv-

en in Ribbe and Prunier (1977 ) (a=9 ,737 , b=8.899, g=5 .231, ß=105.9,

v=435.9), and three silica polymorphs, low-quartz, low-cristobalite and

tridymite. CrisLobalite was most abundant of the silica phases in the 1

kbar run, whereas quartz was most abundant in the 2 kbar run. Willem-

seite occurred ín abundance in the 2 kbar run with a strong, sharp basal

reflection in the x-ray powder pattern (d=9.42 Å,) but was only detected

optically in the 1 kbar run. Cell dimensions of the nickel amphibole

were calculated (raUtei:lg).

Substitution of Mg5 by Mg3Ni2

Replacement of Mg5 by Mg3Ni2 resulted in higher amphibole yield (30 to40 percent). Other phases were similar to the Ni5 Íurì composition.

CeI1 dimensions of the Mg3Ni2 amphibole (taUte 1¡) are consistent with

the simple replacement of 2Mg by 2Ni in the octahedral strip. Because

the ionic radius of Ni (0.69 Â) is smaller than that of Mg (0.72 Ð, the

cell volume of the MgsNiz amphibole should be slightly smaller than that

of endmember tremolite. Note, however, the large increase in the a-pa-

raneter.

Substitution of Ca2 by Cd2

Tremolite synthesis with Ca in the M(4) site replaced by Cd was not suc-

cessful. Àbout 30 percent clinoamphibole was obtained whose cell dimen-

sions are more like cummingtonite than tremolite. The presence of

monteponite (cdo) suggests that the amphiboJ.e has Iittle, if any, cd.

90

FIuor-tremol ite ¡Ca oMo ^ i ^0, "F,

Neither isothermal (Table 11) nor non-isothermal experiments (raUte lz)yielded close to 100 percent amphibole. Best yields were about 70 Lo g0

percent. Isothermal experiments produced prismatic crystals up to 0.05

mm in length; in non-isothermal runs, spectacular crys¡als up to 1.0 mm

were routinely obtained. In spite of this large contrast in growth hab-

it, cell dimensions of these amphiboles r+ere almost identical (raUte l¡)and are very similar to those determined by previous workers (rabte e)

who claimed yields as high as 95 percent.

High yields of amphibole resulted only from sLarting mixes v¡ith SiOz

added as Corning 7940 silica glass. Furthermore, yields were higher ifCaCOs was decarbonated after mixing with the other components, rather

than before. During decarbonation, the mix partiaJ-ly crystallized to

diopside and MgsFz(SiO4)2. ÀpparentJ.y such a mixture promotes amphibole

nucleation and growth. Prior to this discovery, fluor-tremolite mixes

were prepared with dehydrated HzSíO¡'nH2O or cristobalite instead of

silica glass. Runs with these mixes failed to produce significantamounts of amphibole; products were dominated by tridymite, quartz,

diopside and fluorite.

Edenite¡ NaCa2 (Lq,Ni ) sSizÀIOr z (OH)¿

NaCa 2Mg5Si 7À102 z (0H ) z

Edenite was not synthesized. À11 runs produced <5 percenl amphibole

with abundant clinopyroxene, forsterite, plagioclase and traces of

quartz. À layer silicale ("1y'' in Table 11) with basal spacing about

11.2 Ã vras present in all runs. AIso present vras an unidentified phase

rr'ith prominent x-ray peaks corresponding to d-spacings of

Å. Dry mixes and gel-s yielded identical results.

91

2.60 and 2,43

Substitution of Ni5 for Mg5

Replacement of Mg5 by Ni5 in the edenite formula resulted in increased

amphibole yierds (30 to 40 percent). other phases were the same, or Ni-

bearing equivalents of phases in endmember edenite runs.

Fluor-edeni te : NðlêrMqsSi zÀ1Oz rF :

FIuor-edenite syntheses v¡ere generally successful. Àt l-east 90 percent

yields were obtained from starting mixes prepared with silica glass; as

for fluor-tremolite, mixes prepared with HzSiO¡.nH20 did not grow sig-nificant amphibole. Largest crystals (up to i to 2 mm in length) were

obtained in non-isothermal runs.

Parqasite¡ (na,¡t) (ca,cd)¿(ug,ni )4(el,cr,Þ,Sc.,In) sie (¡l,ca) rOr, (OH)¿

NaCa 2MgaÀ1Si 6À1 z0z z (OH) z

Pargasite synthesized readily with yields of B0 to 95 percent. Best re-

sults were obtained at 800 to 900oc and 2 to 3 kb. pargasite formed

clear, colourless prisms up to 40 microns rong and g microns wide. Run

length had littre effect on grain size and yield; runs of.2s h and 1126

h had similar yields, grain size and infrared spectra (see Chapter 5).

Amphibole yields were similar in syntheses from dry mixes as opposed togels, but crystals grown from gels were more acicular in habit. Gehle-

nite, however, $¡as a prominent ninor phase in runs with ge1s. cell di-mensions (tabte ig) of these pargasiles are consistent with one another

and agree well with previous work (rabte S).

92

Substitution of Mg4Al by t¿goCr

Substitution of Cr for octahedral Al reduced amphibole yields to about

80 percent. chromium-pargasite formed pale green, slightly pleochroic

prisms up to 24 microns l-ong and 1 to 2 microns wide. overall grain

size is finer than pargasite, and crystals tend to be more acicular inhabit. Abundant eskolaite (CrzO¡) in aI1 runs suggests that the amphi-

bole is not on composition; the amounts of Cr in clinopyroxene and spi-nel are uncertain. Cell dimensions (taUte l¡) of three typical runs

were similar with cell volumes 4 to 6,{3 larger than pargasite. The in-crease in vorume is due almost entirely to an increase in b, suggesting

that substantial amounts of Cr have replaced Al in the octahedral strip.

Substitution of Mg4À1 by MgaGa

Poor amphibole yields (20 to 30 percent) were obtained at 1 kbar and

temperatures less than 800oC; the run product was mostly clinopyroxene

with minor plagioclase, forsterite, nepheline and three different layer

silicates with basar spacings of i4.8, i2.2 and 9.9 Å. Raising eitherthe pressure Lo 2 kbar or the temperature above 800oC, increased amphi-

bole yields to more than 90 percent. Àmphibole formed clear, colourless

crystals up to 15 microns long and 2 to 4 microns wide. Layer silicateswere not present. The amphibole grolvn at 75Boc, 1 kbar, has cell dimen-

sions lhat are edenitic in character, rather than pargasitic (lower q,

ß, higher b). Apparently little Ga, if any, y¡as incorporated into the

octahedral sites. At 817oc,2,1 kbar, the cell dimensions of the amphi-

bole are very similar lo those of Cr-pargasites (rable 13). Because the

ionic radii of Cr (0.615 Å) and Ga (0.620 Å) in octahedral coordination

are almost identical, this similarity probably reflects the sane degree

of- cr/Ga substitution for AI in these amphiboles. Ga not

probably replaces À1 in pl-agioclase or, where present, in

cates.

93

in amphibole

layer sili-

Substitution of MgaÀl by tutgosc

Sc-pargasite synthesized readily but yields v¡ere never more than about

90 percent. Amphibole formed c1ear, colourress crystals up to 1.1 mi-

crons long and 1 to 2 microns wide (rigure 5). sczo¡ rvas a minor phase

in ali- run products, indicating that the amphibole was off-composition.

Cell dimensions (ra¡te 1¡) show that the amount of Sc in octahedral

sites is high; the cell volume of sc-pargasite is about '1b Ås larger

than that of pargasite.

Substitution of Mg4ÀL by MgaIn

About 90 percent yields of amphibole were obtained in 2 kbar runs. Am-

phibole formed pale yellow, faintly pleochroic crystals up to I microns

long and 1 micron wide. Àlthough the cell volume of this amphibole (ta-

ble'13) is about 9 Å3 larger than that of pargasite, it is 6 A3 smaller

than that of Sc-pargasite, indicating only partial substitutíon of Infor À1 in the octahedral strip. Furthermore, all run products contained

unreacted In z0s.

Substitution of MgaÀl by Ni¿Àl

Two runs were attempled with Ni4 substituted for Mga, one with no oxygen

fugacity control, the other on the cr buffer. Àmphibore yields were

about '10 percent in both runs.

94

Figure 5: Scanning electron micrographs of synthetic pargasites andfluor-pargasites. A: scandium-pargasite (Scpe-¡S,6). B:fluor-pargasite (r'p¡-¡ur). C: chromium-fIuor-pargasite(rcrp¡-e3a). D: gall.ium-f1uor-pargasite (rcapÀ-¡5a).Numbers in parentheses correspond to run numbers in Table 11.Scale bar represents '1 micron.

95

Figure 6: scanning electron micrographs of synthetic fluor-pargasite,fluor-eckermannites and fluor-nyböite. À: scandiurnlfluorlpargasite (rscp¡-el). B: scanãium-f1uor-eckermannite(rscnc-¡1 ). C: indium-fluor-eckermannite (r'lnnc-¡t i. D:scandium-f1uor-nyböite (nscHy-¡3). Numbers in parenthesescorrespond to run numbers in Tab1e 1 1 . scare bár represents1 micron. Àrrow in B points to layer silicates.

96

Substitution of Mg¿ÀISi6À12 by Mg4GaSísGaz

Replacement of both octahedral and tetrahedral A1 by Ga was unsuccess-

ful; amphibole yields were less than 10 percent. Ga apparently does not

assume tetrahedral coordination in pargasite.

Substitution of Na by K

Repracement of Na in the À-site by K was not accomplished;

yielded less than 10 percent amphibole.

both runs

SubsLitution of Caz by Cdz

No significant amphibole was produced.

FLuor-parqasite: NaCarMq¿ (À1,CrrGa,Sc )Si eÀlrOr rF,

NaCa 2Mg4À1Si 641 zOzzF z

All runs on the fluor-pargasite mix prepared with Corning silica glass

as Si0z source yieloed >90 percent amphibole. Mixes prepared with

Hzsi0s'nHz0 failed to grow amphibole. Fluor-pargasite formed clear,

colourless crystals up to 16 microns long and 4 microns wide in isother-

mal runs (figure 5). Non-isothermal runs produced large crystals be-

lween 0.02 and 1 mm in length. In both types of experiments, products

were similar except for minor fluorite in non-isothermal experiments.

Cell dimensions of amphiboles with either cooling history are similar(ra¡te l:).

Substitution of MgaÀl by lutgoÇr

Às in Cr-hydroxy*pargasite, Cr substitution reduced yields to about B0

percent in isothermal runs. Little amphibole was formed in the singj.e

97

non-isothermal run. cr-fIuor-pargasite formed pale green, slightrypleochroic, blocky to prismatic crystals up to'18 microns long and 6 mi-

crons wide (nigure 5). cell votume is 3 to 4 A3 1arger than that of

fluor-pargasite. This increase is due mainly to an increase in b, sug-

gesting Cr occupancy in the octahedral. strip.

Substitution of MgaAI by MgaGa

Ga-fluor-pargasite formed about 85 to 90 percent blocky to prismatic,

clear, colourless crystaJ-s up to 14 microns long and 5 microns wide in

isothermal experiments (r'igure 5). Larger crystars to 0.S mm 1ong were

formed in non-isothermal runs. Cell dimensions were not affected by run

history and are sirnilar in both runs. The ceII dimensions of an isoth-ermal run analysed by the Rietveld method are systematically larger than

the other two; it may have more Ga substituted for Àl than Lhe other two

(see Chapter 5).

Substitution of Mg4À1 by MgrSc

Sc-fluor-pargasite formed about 85 to 95 percent blocky to prismatic,

grains up to 23 microns long and 5 to'16 microns wide. Figure 6 shows

the wide variation in morphology. The single non-isothermal run greÍr

crystals up to 0.5 mm in lengLh but yielded only about 7E percent amphi-

bole. The cell volume is about 20 Å3 rarger than that of fluor-parga-

site which, suggests that nost of the octahedral À1 was replaced by Sc.

NoLe that the volume of scandium-fluor-pargasite is larger by about i Å3

than that of scandium-pargasite. Às the vorume of hydroxy-amphibote

should be larger than that of its fluorine analogue, it is probable that

the scandium-pargasite has a lower Sc-occupancy than the fluor-scandium-

pargasite (see Chapter 5).

98

Tschermakite: ¡CazMq: (Cr,Sc) zSi eAlzOz r (OH)*

syntheses on the endmember tschermakite composition (Mgselz) were not

attempted because previous work clearly shows that this amphibole does

not grow at low pressures (see Chapter 2). Replacenent of octahedral A1

by either cr or sc also did not yield amphibole at 1 kbar; both run

products were dominated by cJ.inopyroxene and anorthiLe.

Eluor-tschermakite: ECa2Mq3Al 2Si 6Al202 2F2

Runs on the fluor-Lschernakite composition also failed to grow amphi-

bole. Products were dominated by anorthite, clinopyroxene and cristo-balite.

Àlumino-maqnesio-hornblende: ËCazMq4ÀlSizAlO2 2 (OH)¿

Àbundant amphibole on this composition was difficult to synthesize. Àt,

or near'1 kbar pressure, amphibore yierds varied between 10 and 30 per-

cent; the remainder of the products was mainly clinopyroxene and anorth-

ite. Àt 2 to 3 kbar, yields improved but did not exceed about 55 per-

cent. Forsterite was present in aIJ runs and at temperatures above

830oc coexisted metastably with quartz. Talc, and rarely chorite, ap-

peared below 720oc. Talc was also present in a run (Hg-¡g, Table 1 1 )

which was aborted after 2 h at 840oc and 2.5 kbar because of a pressure

leak. This experiment suggests that tarc formed earJ.y in the run-up

stage and reacted out at high temperature. Àmphibole in these runs

formed clear, colourless prisms ress than 10 microns long and 0.5 mi-

crons wide. No significant differences in products were observed in

runs with ge1 starting mixes as compared to dry mixes, except that the

former tended to be not as well crystallized. Grinding run products and

99

rerunning increased neither the yield nor the grain size (g¡-nl, TabJ.e

11). Cell dimensions (ra¡te 1¡) of amphiboles grown on the alumino-mag-

nesio-hornblende composition are intermediate to those of synthetic tre-molite and tschermakite (fabte S). Because there is no cation in this

composition that can occupy the A-site, and other cation substitutions

are limited by charge balance to the stoichionretric formuLa, these am-

phiboles are probably close to the nominal composition, in spite of low

yields. Àny minor deviations from the nominal composítion would be most

likeIy the result of magnesio-cummingtonite solid solution.

Substitution of Mga by Nia

Runs in Àu capsuì.es without any attempt to control oxygen fugacity

failed to produced amphibole. Run products were mainJ.y clinopyroxene,

anorthite, quartz, Ni and minor oLivine. on the MH buffer, however,

about 10 to 20 percent amphibole was present along with abundant willern-

seite, clinopyroxene, anorthite, quartz and traces of olivine.

Substitution of Mg4AI by Mga(Cr,Sc,Ti,V)

High amphibore yields were not achieved by substituting cr, Ga ,sc, Ti

or V for octahedral À1. Amphibole yields varied from less than 5 to 60

percent. Highest yields were achieved in the 3 kbar runs.

Fl uo lumi no-maones i o- rnblende: ¡CarMq¿ÀlSizÀ10r rF,-âr

Fluor-alumino-magnesio-hornblende rlas also difficult to synthesize.

Mixes prepared with Hzsios.nHzo failed to grow more than about 20 per-

cent amphibole. Low-cristobalite and anorthite were the major phases in

these runs. Runs with mixes prepared from Corning 7940 silica glass

100

yielded up to about 60 to 70 percent c1ear, colourless, prismatic amphi-

bole crystals less than 5 to 10 microns long. Highest yields were ob-

tained in cold-sea1 hydrothermal vessels pressurized to 3 kbar with ¡r.Non-isothermal runs grew large crystals (up to 0.5 mm) of both clinopy-

roxene and amphibole. Amphibole yields in these runs did not exceed 50

to 60 percent.

KaersuLite: NaCa rMq¿TiSi sÀl r (O+OH)z¿

Runs on the kaersutite composition failed to grow amphibole.

SODIC-CÀLCT C ÀMPHT BOTES

Richter i te: (n,na) (Ca,Cd,Na) (¡¿g,¡ti,t'ln,Cu)r Si ¡Or, (OH)¿

NaCaNaMgsSi e0z z (OH) z

Richterite was synthesized readily with greater than 95 percent yield.

Minor diopside was the only other phase identified in the run product.

Richterite formed clear, colourress prisms up to 35 microns long and.1l

microns wide (rigure 7). Ce11 dimensions (rabte 13) of synthetic richt-erite grolrn in this study are virtually identical to those of Heubner

and Papike (1970) and Charles (1974) (ra¡fe S).

Subsitution of Mgs by I'ii s

Replacing Mgs by Nis also yielded about 95 percent amphibole. Runs were

performed in Àu capsules rlithout attempting to control oxygen fugacity.

Reducing conditions were implied by the presence of metallic Ni in the

run products. clinopyroxene was rare, but the presence of Ni suggests

that the amphibole contains less than SNi. Nickel-richterite formed

pale green, slightly plechroicr âcicular crystals up to 35 microns long

101

Figure 7: scanning electron micrographs of synthetic richterites andsodian magnesio-cummingtonites. À: KNaCaMgsSi aOz z (0H)

z(nnc-¡l ) . B. NaCaNaMgaMnsi s0z z (oH) a (ugalanRc-À2 t. c;NaMgNaMg¡Si a0z z (0H)z (Mgnc-e1) . D: NaNiñaNi sSi aOz z (oH)z(HiugnC-eZ). Numbers in parentheses correspond to runnumbers in Table '11. Scale bar represent,s 1 micron.

and 3 microns wide.

that of richterite,

M9 by Ni.

102

The cell volume (taUte l3) is about 7 Ar less than

which is consistent with substantial replacement of

Substitution of Mg¡ by Mg3Ni2

Richterite r+ith this composition grew with yiel-ds slightly below that of

richterite and Ni-richterite: about 90 percent. It formed pale green,

slightly pleochroic, acicular crystals up to 25 microns rong and 4 mi-

crons wide but not as acicular as the Ni-endmember. In addition to am-

phibole, clinopyroxene and metallíc Ni were present; excess Ni indicates

that there must be less than 3Ni in the octahedral strip. The cell vol-ume (ta¡te lg) is about 3 Â3 less than that of richterite and about 3 Å3

larger than that of endmember Ni-richterite.

Subst i tut i on of Mg ¡ by ttn s

Attempts to grow richterite with all Mg replaced by Mn failed both in

unbuffered runs and in runs on the NNO buffer. tess than s percent am-

phibole was observed.

Substitution of Mgs by Mg4Mn

Greater than 95 percent yields of amphibole resulted from both unbuf-

fered runs and from runs on the NNO buffer. Mn-bearing richterileformed very pale yellow-pink, prismatic crystals up to 1g microns rong

and 7 microns wide. The crystals are not as we]l formed as richteriteand exhibit a much larger variation in grain size (rigure 7). The cellvolume (ra¡te l3) is I Å3 larger than that of richterite, evidence forMn occupancy. Clinopyroxene was the only other phase detected in the

run product.

Substitution of Mgs by Mg3Mn2

Runs on this compositition produced about

physical properties essentially identical totion. Cell volume increased Lo 920.G A3 in

content. This increase, however, is less

richterite to Mg4Mn composition, suggesting

in this amphibole and that it is, therefore,

103

90 percent amphibole with

those of the Mg4Mn composi-

response to the higher Mn-

than half the increase from

that there is less than 2Mn

not on composition.

Substitution of Mgs by Cus

No amphibole was grown on thís composition.

abundant cuprorivaite (CaCuSi ¿Ol o ) , tenorite

The run product comprised

(cuo) and minor chlorile.

Substitution of ¡-site Na by K

Virtually '100 percent amphibole was grovrn on this composition; no other

phases were detected. K-richteriLe formed clear, colourless, short and

stubby to prismatic crystals up to 20 microns long (rigure 7). The celldimensions (raUte 1¡) are essentially identicaL to those of Huebner and

Papike f 970) (raUte S).

Substution of Ca by Cd

Substitution of Ca by Cd yielded about 95 percent clinoamphibole but

with cell dimensions (ra¡te lg) unlike those of a1l other richterites.Note especially the low a, ß, and ! paramelers that are similar to sodi-

an magnesio-cummingtonites (rables 13, 5). Furthernore, the infrared

spectrum of this amphibole is identical to that of sodian magnesio-cum-

mingtonite (see Chapter 5). Àlthough it would seem unlikely that thisamphiboLe contains Cd, Do Cd-bearing phases were detected either opti-caJ.ly or by powder X-ray diffractometry.

104

ELuor-richterites¡ NeCaNa(U9,Mn) sSi ¡Oz zFz

NaCaNaMgsSi a0z zFz

Fluor-richterite mixes prepared with HzSiO¡.nHzO as the siLica source

did not yield significant amphibole. Mixes prepared rvith Corning 7940

silica glass grew up to 90 percent amphibole, the remainder being clino-pyroxene and forsterite. FLuor-richterite crystals were very-finegrained (<.10 microns) and blocky to prismatic in habit. The cell volume

is about 10 Å3 less than that of richterite; an amount consistent wilh

most hydroxy-/fluor-amphibole cell differences except for pargasites

(see Chapter 6). Non-isothermal runs produced similar results except

for grain sizes up to 0.5 mm.

Substitution of Mgs by Mg4Mn

Àmphibole yield was about 95 percent, the remainder being clinopyroxene.

Mn-bearing fruor-richterite formed pale-yelrow, stubby prisms up to 30

microns long and.13 microns wide. The cell volume (ra¡te l¡) is about.11 A3 less than that of the hydroxy-analogue; this is comparable lo the

10 Å3 difference between fluor-richterite and richterite.

Àlumino-winchite: ¡CaNaMq¿ (À1,Cr,Sc )Si rOr, (OH)¿

Alumino-winchiLe could not be synthesized at pressures near 1 kbar, ei-ther from dry mixes or geIs. No more than 20 Lo 30 percent clinoamphi-

bole was grown under these conditions. crinopyroxene, plagioclase and

quartz and/or cristobalite dominated run products. Substitution of Cr

for octahedral Àl was also unsuccessful; Sc substitution yielded up to40 to 50 percent amphibole, but not enough for adequate characteriza-

tion.

105

E I u o r_-A I um i n o-w i n c h i t e : ¡llaNaMq 4 À.I S i s g22F 2

t'luor-alumino-winchite synthesis attempts were no more successful than

experiments on the hydroxy-equivalent compositions. Unlike previously

discussed fluor:amphiboles, the nature of the starting mix 9¡as irrele-vant to the results. Similarly poor yieJ-ds obtained from mixes prepared

with HzsiOs'nHzo or corning 7940 sirica glass. some improvement inyield was obtained when CaCOs was decarbonated along with other mix com-

ponents rather than before mixing; amphibole yields increased from nilto about 20 to 30 percent. Best yields (about 40 to 50 percent) were

obtained in non-isothermal runs, but not sufficient for adequate charac-

terization.

Maqnes i o-alumi no-katophor i te : NacaNaMq ¿ (À1, cr, sc ) s i, Alo ", (oH )¿

Poor yields were obtained for aLl magnesio-alumino-katophorite composi-

Lions. Substitution of Cr and Sc for octahedrat À1 increased yields to

about 40 percent.

Alumino-barroisite: IÇêNêMag (e¡,Sc) rSirAIOr, (OH)¿

Àttempts to grow alumino-barroisite with octahedral ÀI replaced by Cr or

Sc failed to produce more than about 5 to 10 percent amphibole. Runs on

the endmember alumino-barroisite composition were not attempted because

the aluminous endmembers of previous sodic-calcic anrphibole syntheses

had been more difficult to grow than cr- or sc-bearing ones.

106

!' I uor -g l um i n o-ba r r o i s i t e : ¡!êNalvlq 3 Àl 2 S i 7 ÀlO 2 2 F 2

Both isothermal and non-isothermal experiments on the fluor-alumino-bar-

roisite composition failed to grow detectabl-e amphibole.

Fl- es1 -kaNaCaNaMq ¿ À1, Cr rGa, Sc , Ti ,V SizÀ10zrFr

NaCaNaMg aAlS i zAI0 z zF z

Fluor-magnesio-alumino-katophorite syntheses produced amphibole yieldsbetween 20 and 80 percent; highest yields were in non-isothermal runs.

The ubiquitous presence of abundant accessory phases, however, showed

that the amphiboles grown are considerably off-composition and not suit-able for characterization.

Substitution of MgaAl by Mg¿(Cr,Ga,Sc,Ti,V)

Although yields between 60 and 80 percent were obtained for amphiboles

grown with these substitutions for octahedral 41, the presence of phases

containing cr, Gã, sc, Ti and v indicate that the amphiboles are not of

the nominaJ. compositions.

Maqnesio-alumino-taramite: NacaNaMqs (cr,sc ) rsi ¡Àl ror r (o¡l)¿

Runs with Cr and Sc replacing octahedral Al in the magnesio-alumino-tar-

amite formula were unsuccessful; only 20 to 30 percent amphibole was

grolrn.

Fl-uor qnesio-alumino- tarami te:

Runs on the fluor-magnesio-alumin

more than about 5 percent amphibo

107

NaCaNaMq¡Al rSi nÀI r0r rFz

o-taramite composition failed to yield

1e.

AtKALi ÀMPHIBOTES

Maqnes i o- i ebec k i l-a. IN&ì,lqs (Cr,Ga, Sc ) rSi ¡Oz r (OH)¿

Àttempts to grow amphibole by replacing Fe!* with cr, Ga or sc failed.Àmphibole yields were less than 30 or 40 percent. sc-mix gave the high-

est yields.

Ec ke ann i te : NaNazMg¿ (Al,CrrGarSc,In)Si sOzz(Ou),

NaNa 2Mg4À1Si a0z z (OH) z

Runs on the endmember eckermannite composition grew virtually 100 per-

cent clear, colourless amphibole crystars up to 35 microns long and 10

microns wide. No other phases were observed in the powder x-ray pat-tern. The cell dimensions (taUte l¡) of this amphibole are very close

to those of sodian magnesio-cummingtonite, which suggests that it was

synthesized, rather than eckermannite. Furthermore, the infrared spec-

trum of this amphibote is almost identical to that of sodian magnesio-

cummingtonite (see chapter s). This means that the amphibole is AI-free, but no Àl-bearing phases v¡ere detected.

Substitution of À1 by Ga , CÊ, Sc and In

Runs on the eckermannite composition with the above substitutions forthe octahedral À1 grew beLween s0 and 85 percent amphibole. None of

these amphíboles, however, was suitable for detailed characterization

because of the presence of other phases with Ga, cr, sc and In as con-

sLituents which implied that the amphiboles are off-composition.

108

Fluor-ec k ermannite: NaNa 2Mq4 (AL,Ga, Cr,Sc, I n )Si s0z rF r

NaNa 2Mg 4À1S i a0 z zF z

Isothermal runs on the fluor-eckermannite endmember composition grew

greater than 90 percent amphibole with ninor albite, forsterite and lay-

er silicate with basal spacing of about 9.54 Å. This amphiboLe formed

c1ear, colourless, prismatic to acicular crystals up to 15 microns J.ong

and 1 to 3 microns wide. Non-isothermal runs gave lower yields (about

80 percent) with nepheline and NaF in addition to albite, forsterite and

layer silicate. The cell volume (raute 1g) is 10.5 A3 less than the hy-

droxy equivalent, an amount typical of the difference between fluor- and

hydroxy-amphiboles. However, these ce11 parameters are very similar tothose of sodian magnesio-fIuor-cummingtonite and it is unlikely that the

amphibole is actually fluor-eckermannite.

Substitution of Al by Cr

Greater than 90 percent of pale green, prismatic amphibole with crystals

up to 10 microns long and 3 microns wide were obtained. However, the

presence of magnesio-chromite and eskolaite argue against complete sub-

stilution of À1 by Cr. The cell dimensions (rable 13) are unlike those

of sodian magnesio-fluor-cummingtonite; note especially larger a and ß.

Àlthought the volumes are similar, the amphibole is probably intermedi-

ate in composition belween chromium-fluor-eckermannite and sodian magne-

s i o-f luor-cummi ngton i te.

Substitution of Al by Ga

Runs on this composition yielded greater than 90 percent, c]ear, colour-

less amphibole with acicular crystals up to 30 microns rong and 4 mi-

109

crons wide. The only other phase detected was a layer siticate with ba-

sal- spacing of about 9.66 Å. The cell parameters (rable 13) are closerin magnitude to those of sodian magnesio-fluor-cummingtonite than the

cr-bearing variety, but the slightly larger a, ß and vorume suggest thatminor Ga was incorporated during growth.

Substitution of À1 by Sc

Yie1ds of more than 95 percent were obtained in isothermal runs withprobable traces of NaScSizOsi non-isothermal runs also grew clinoensta-tite and forsteriLe. The amphibole was extremely fibrous with individu-al fibres greater than 100 microns long and only about 2 microns in di-ameter. scanning electron micrographs (rigure 6) do not show the

fibrous character because the fibers are very brittle and break easilyinto shorter Lengths. The cell volume (ra¡te 1g) is 1s to.16 Ä3 1arger

than that of chromium-f1uor-eckermannite which, along with the very highyield, suggests that Sc substitution was essentialJ.y complete (see Chap-

ter 5 for occupancies). The remaining cel1 parameters, most importantlyß, are analogous to those of natural eckermannites (cf. Kempe .1969).

Substitution of A1 by In

Essentially 100 percent amphibole was obtained in these runs; no otherphases were detected. indium-fluor-eckermannite forned cl-ear, colour-less, prismatic crystals up lo 25 microns long and 4 microns wide (r,ig-

ure 6). cell dimensions are typically like those of natural eckerman-

nites (cf. Kempe 1969). Detailed occupancies are given in chapter 5.

110

NvböLLe: NeNa:]&r(Al,cr, 9c, In ) rSi zÀ1or r (oH)¿

NaNa 2Mg3À1 2Si zAl0z z (0U) z

Runs on the nyböite endmember composition failed to grow amphibole.

This probably reflects the fact that nyböite is only stable at high

pressures (Carman and Gilbert 1983).

Substitution of Mg3AIz by Mgs(CrrGa,Sc,In) z

Runs with these compositions grew between 40 and 80 percent amphibole,

but the low yields and presence of phases containing cr, Ga, sc and In

demonstrate that these amphiboles are considerably off-composition. Àt-

tempts to grow nyböite with both octahedral and tetrahedral Àl replaced

by Ga failed completely.

Fluor-Nvböite¡ NaNarMq¡Sc rSizÀ1Or zF r

These runs yielded greater than 90 percent amphibole with minor Na-

ScSi206. Scandium-fluor-nybóite generally formed clear, colourless, ex-

tremely fibrous crystals up to 100 microns long and about'1 micron wide;

more prismatic crystals measuring about 40 microns long and 10 microns

wide are also present (nigure 6).

I RON-MÀGNESI UM_MANGÀNESE ÀMPHI BOLES

sodian maqnesio-cumminqtonite: NaMqNa (Mg,Ni ) ssi ¡oz r (ott)¿'

NaMgNaMg5Si aOz z (0u) z

Sodian magnesio-cummingtonite grorvs readily with yields greater than 9E

percenL. The only other phase detected in the run product was forster-ite. These amphiboles form clear, colourless, extremely acicular crys-

taI up Lo 18 microns long, but generally 1ess than 1 or z microns wide

111

(nigure 7). ceIl dimensions (tab1e 13) compare well with those of sodi-

an magnesio-cummingtonite grown by l,iitte et aI. (1969) but are markedly

different from those by Grebenschikov et aI. (1975) "

Substitution of NaMgNaMgs by NaNiNaNi¡

This substituLion in the endmember sodian magnesio-cummingtonite formula

yielded about 50 to 60 percent amphibote in runs on the CT buffer. The

remainder of the run was willemseite. The amphibole formed pale amber,

extremely fibrous needles less than 30 microns long and 1ess than'l mi-

crons wide (rigure 7). The celI volume (ra¡te l3) is abouL 7 Å3 less

than that of endmember sodian magnesio-cummingtonite; this is the same

as the difference in cell volumes of richterite and Ni-richterite. Un-

buffered runs did not grow amphibole; the products consisted of abundant

willemseite, Ni and quartz.

sodian f luor-maqnesio-cumminqtonite: NaMgNaMq¡si ¡oz rFr

Isothermal runs on this composition produced only about 30 to 40 percent

amphibole; the run product was dominated by cristobalite and minor cli-noenslatite and tridymite. Non-isothermal runs yieLded up to about 70

percent amphibole with abundant clinoenstatite and minor cristobaliteand tridymite. The cel1 dimensions (table 13) are different from those

of Gibbs et al. (962)¡ in particular the volume is smaller. It isprobable that the amphibole grovrn is off-composition.

112

TÀBLE 1 1

Run Data: Isothermal Experiments

Run Number T(de9)

Pt(bar) (h)

Productsl

Si I icate Hydroxy-anrphibolesCalcic Amphibolesrca2MgsSi sgz z (ott)z

1 000 332 fli+qtz+crs+trd+en?1 000 445 di+gtz+en

Mq3Ni2rR-À1 783 2000

CdTR-A2 742 1 000

ECa zNi sSi sgz z (OH) z68 Nidi+crs+qtz+trd+cam+Ni+wi1

25 Nidi+crs+qtz+trd+cam+¡i+pi1

rCa 2MgsNi zSi s0z z (OH)z51 MgNidi+qtz+cam+Ni+¡1"

!Cd2MgsSi a0z z (0H) z91 gtz+cum+fo+en+mpt+tlc

TR-A1TR-À5

NiTR-A1NiTR_À2

ED-A1GED-À-1GED_À2GED-À4

NiED-À1

PA-Ä1 *PÀ-A2*PÀ_À2A*

795810

793801

1 0002000

770803811820

1 0001 00020001 000

NaCa 2Mg5Si 7À102 z (0H) z

!7 cpx+fo+p1+gtz+cam+ly+?9? cpx+fo+pl+qtz+cam+li+?y cpx+fo+pl+qtz+cam+ly+?67 cpx+fo+pI+qtz+cam+li+?

PA-A8B'K

782

890840500

92386586s923890840590

400

PÀ-A3*PA-À4*PÀ-À5*PÀ-À6xPÀ-A7*PÀ-A8*PÀ-A8À*

NaCa "Ni .S i .Àl n^ ^ lôHì ^_JE_ r--_v¿¿\v.., ¿

1 000 26 cpx+cam+Iy+ol+pl+?

NaCa 2MgaAlSi e Àl z0z z (0H) z'1000 155 cam+cpx+f s+pIine+spl?

1-2kbar 384 cam+cÞx+fo+pt+ne+sbt?1 000 891 cam+cÞx+fs*þl*ne*sþl?

(p¡-ee produãt rerun)1 000 52 cam+spx+fs+pl+ne+spl?1 000 381 cam+cÞx+fq*þl*ne*sþl?1 000 381 cam+sþ¡+¡e+þl+ne+sþI?1 000 sZ cam+cpx+f6*þI*ne*sþl?1 000 1 55 cam+cþ¡+¡e+þ]+ne+sþI?1-2k 384 cam+cþ¡+¡s*þl*ne*9î,1 000 891 cam+gþx+¡s*þl*ne*ih

(pe-¡g produãt rerún)1 000 891 cam+spx1¡e+pl+ne+gh

(pe-¡g produðt rerún)1000 1126 cam+cpi+fe+pl+ne+9h+spl?PA-À9* 801

113

Run Number T(deg)

Pt(bar) (h)

Produc t s

PÀ-À1 0*PÀ-À1 1 *PÀ_A1 2*GPA-Ai *GPÀ_A2XGPÀ-À2a*

GPA-A3*GPA-A4*

NiPA-A1

N i PA-A2

ScPA-A1 *ScPA-A'1a*

ScPÀ-À2*ScPA-À4*ScPA-45*ScPÀ-46*

CrPÀ-À'1*

CrPA-À2*

CrPA-À3*CrPA-44*

CrPA-À5*

GaPÀ-À1GaPA-À2*GaPA-À3*

I nPA-A,1I nPA-À2I nPÀ-À4

895895

1 0001 000

148148

801917842935838930

1 0001 10020001 000'1000

i 000

1126472527

52565

cam+cpx+ f 9+p1+ne+spl ?

cam+cpx+ f e+p1+ne+gh+spI ?

cam+cpx+ f o+pl +gh+spI ?

cam+gh+cpx+ f o+ne+spl ?

cam+gh+cpx+ f o+ne+spl ?

cam+gh+cpx+f o+ne+sp1 ?

(gP.o.-.o.e product:mix=1 :'1 )

cam+gh+cpx+ f o+ne+spl ?

cam+gh+cpx+ f o+ne+spI ?

868

796

Naca 2Ni 4A1si e Àl zOz z (OH) z

2000 1 0 cpx+pl+Hi+cam+qtz+wi1+ol+spl ?+1Y

1 000 47 cpx+p1+qtz+cam+v¡i 1+oI+spI?+Iy (cr butter)

NaCa 2Mg¿CrSi e Àl zOz z (0H) z

1 000 40 cam+cpx+e5[+fe+]y+pl+ne+sp1 ?

2000 24 cam+esk+cpx+pI+fo+ne+Pl+spl ?

3000 45 cam+cpx+esk+spl+fo+pl+ne1 000 70 cam+esk+cpx+p1+fo+spl+ne

+ly21 00 73 cam+esk+cpx+p1+fo+spI+ne

+ly

820840

NaCa 2Mg4ScSi oAl z0z z (OH ) z

1 000 40 cam+cpx+Sc 203+fs+¡s+pI+?2000 25 cam+cpx+Sc zO¡+fo+ns+pl+?

(ScP¡-e1 product regroundand rerun )

2000 25 cam+cpx+Sc 203+fe+¡s+pl+?3000 45 cam+cpx+Sc zO¡+fo+ns+pl+?2000 '70 cam+cpx+Sc 203+fe+¡s+pl+?2000 70 cam+cpx+Sc z0s+fo+ns+pl+?

820

845

90s846

83i

840905834830

758846817

NaCa zMg¿GaSi oÀt zOz z (OH) z'1000 49 cpx+pI+cam+f o+ne+Iy1 000 7O cam+cpx+pl+fe+¡s+Iy?21OO 73 cam+cpx+fo+pl?+ne?+1y?

NaCa zug¿InSi oA1 z0z z (OH) z

1 000 48 cpx+cam+gh+fo+Inz0¡1 900 52 cam+cpx+gh+fo+Inz0¡2000 73 cam+cpx+gh+fo+In z0s

8'1 0

755838

114

Run Number T(deg)

Pt(bar ) (ir

Produc t s

Ga3PA-À1 779NaCa zMg¿GaSi 6Ga zOz z (OH) z'1000 49 <.1Oeo cam

KCa 2Mg4AlSi sAI z0z z (OH) z

1000 68 <10eo cam2000 22 <10eo cam

NaCdzMg¿AISi 6AI zOz z (OH) z.1000 49 (Seo cam

rCa 2MgsSc zSi oÀ1 zOz z (0H) z

1000 69 Oeo côrì

ECazMgsCrzSie ÀlzO zz(OH) z

1000 9'1 Oeo cam

KPÀ-A1KPA-À2

CdPA-A'1

ScTS-À1

CrTS-À1

HB-A1HB_À2HB-A3HB-A4HB-A6HB-À7HB_À8HB-A9HB-A1 O

HB-A1 2

HB-A1 3

HB-À1 4

HB-À1 5

HB-81

GHB-A'1GHB-À2GHB-À3GHB-À4GHB-A5GHB_A6GHB-A7GHB_À8GHB-À9GHB-À.10

NiHB-A1NiHB-À2NiHB-A3

1 0001 0001 0001 000i 0001 0001 000250030003000200020003s001 000

798930803803705705600811780812

1 000'1000'1000

1 0001 000i 0001 000200 0

12003 000

835830

7s8

768

792

782748726696835766780840804715764743679775

¡Ca zMg4À1si 7À102 z (oH) z'158 cpx+an+cam+en+f o147 cpx+an+cam+en+fo238 cpx+an+cam+en+fo234 cpx+an+cam+en+fo136 cpx+an+ca¡+s¡+fe+qtz1 60 cpx+an+can+en+fo47 cpx+an+ca¡¡+s¡+fg+qtz2 cpx+an+cam+en+f9+q¡z+t1c ?

38 cpx+an+cam+en+fo71 cpx+an+cam+en+fo+t1c?

141 enx+an+cam+en+fO141 cpx+an+cam+en+fo74 cpx+an+cam+tlc+chl?

1 65 cpx+an+cam+en+fo(g¡-¡1,42 reground, rerun)

48 cpx+an+cam+en+fo65 cpx+an+cam+en+fo+qtz

1 35 cpx+an+cam+en+fo1 35 cpx+an+cam+en+fo123 cpx+an+cam+en+fo123 cpx+an+cam+en+fo724 cpx+an+cam+en+fo42 cpx+an+cam+en+fo47 cpx+an+cam+en+fo20 cpx+an+cam+en+fo

sCa zNi ¡À1Si zÀ10z z (Ott) z

1 000 68 cpx+an+qtz+Ni+ol1 000 25 cpx+an+qtz+Ni+ol1100 43 cpx+an+wil+qtz+cam+ol (t'ttt buf ter)

793801790

115

Run Number T(deg)

PI( bar ) (h)

Produc t s

ScHB-À1ScHB-À2

GaHB-À'1

CrHB-41CrHB-À2

TiHB-À'1

VHB_A1VHB_A2

KR-À1KR-A2

RC-A1 *RC-A2*

MnRC-À1MnRC-42

Mg4MnRC-À'1*Mg4MnRC-42

Mg3Mn2Rc-À1 *Mg3l,tn2RC-¡2't

768850

'1000

3000

rca 2Mg4scSi zÀ1oz z (0H) z

69 20-30eo cam24 20-30e" cam

NiRC-À1 * 800

Mg3Ni2RC-A1 * 852

rCa 2Mg4GaSi zAl0z z (OH) z

3000 60 40-50e" cam

rCa 2Mg4Crsi zÀ102 z (0H ) z

1000 91 <10eo cam3000 46 30-40eo cam

Eca 2Mg4TiSi zAI0z z (Ou) z

3000 48 20-30e. cam

Eca2Mg4vSi7Al0z z (OH) z

3kb 58 <5eo cam3kb 68 50-60% cam

NaCa zMg¿TiSi 6À1 z (o+oH ) z ¡1000 41 Oeo câm2000 49 Oeo cârr

Sodic-calc ic ÀmphibolesNaCaNaMgsSi s0z z (OH) z

1 000 50 cam+cpx1 000 50 cam+cpx

NaeaNaNi sSi a0z a (0U) z

1 000 30 cam+Ni+cpx

NaCaNaMg¡Ni zSi e0z z (OH) z'1000 29 cam+Ni+cpx

NaCaNaMnsSi sOz z (OH) z'1000 165 (Seo cam

1000 194 (Seo cam

NaCaNaMgaMnSi aOz z (0H) z

1 000 29 cam+cpx1 000 '103 cam+cpx

NaCaNaMg3Mn zSi a0z z (0H) z

1'100 24 cam+cpx1000 103 cam+cpx (t{HO butf er )

804

792854

695810

804

783792

852790

903903

479608

854790

116

Run Number Pt(ba r ) (ir

Produc tsT(deg)

CuRC-À1 742

KRC-À1 * 865

CaMgRC-À1 796

cdRc-A1 80s

NaCaNaCusSi sOz z (0H) z

1 000 26 CaCuSi ¿Or o+CuO+chl?(cr butier)

KCaNaMgsSisOzz(OH) z'1000 93 cam

Na (NaCao. sMgo. s )l,IgsSi s0z z (oH) z

1 000 64 cam+cpx?

NaCdNaMgsSi sOz z (OU) z

1000 70 carn+?

EcaNaMg4Alsi B0z z (OH) z

1000 54 20-30e" cam1000 101 20-30Po cam1000 41 <Seo cânì1075 67 20-30eo cam1000 64 <10eo cam1000 41 <Seo cânì1 000 164 <Seo cam750 26 <Seo câm

1075 67 <10eo cam

ECaNaMg4AlSi sOz z (0H) z

1000 91 40-50eo cam

¡CaNaMg+ÀtSi Boz z (Ou) a

1 000 69 <10eo cam

NaCaNaMgaÀlsizÀl0z z (0U) z

1200 48 5-10% cam1200 96 1 0-20% cam

NaCaNaMgaScSizAl0z z (0H) z

1000 69 30-40eo cam

NaCaNaMgaCrSi zAlO zz(Oll) z

1000 69 30-40% carn

NaCaNaMgsSc zSi sÀl zOz z (0H) z

1000 69 20-30eo cam

NaCaNaMg gCr zS i oÀl zO z z ( Ott ) z

1000 91 20-30eo cam

I^tc-A1lrc-À2wc-À3I.tc-À5GWC-À1GWC-À3GI^¡C-À4GtlC-45GWC-À6

ScVIC-41

CrWC-À1

KÀ_À1KÀ_À2

ScKÀ-41

CrKÀ_41

ScTÀ-À1

800707866800800866706762800

760

690

889755

782

782

798

CrTA-41 797

117

Run Number T(deg)

Pt( bar ) (h)

Products

ScBA-À1

CrBÀ-4,1

ScRB-A'1ScRB-42

CrRB-A1CrRB-À2

GaRB-41

EC-A1EC-81EC-À2

ScEC-À'lScEC-42

CrEC-À1CrEC-42

GaEC-À2GaEC-43

I nEC-À1

'1000

1 000

798

797

rCaNaMg¡Sc zSizÀ102 z (0H) z

1000 69 5-'10eo cam

¡CaNaMg ¡Cr zSi zÀlO z z (0u ) z

1000 91 5-10e" cam

Àlkali amphibolestrNa 2Mg¡Sc zSi e0z z (OH ) z

1 000 53 5-1 0% cam1 000 97 40-50% cam

690765

690777

738

775817790

nNa 2MgsCr zSi eOz z (OH) z

53 <Seo cam100 20-30eo carn

718860

718850

rNa 2MgsGa zSi eOz z (OH) z

1000 79 (Seo cêrn

NaNa2MgqAlSi aoz z (OH) z

1 000 47 cam2000 95 cam1 000 144 cam

NaNa 2Mg ¿ ScS i s01 000 43 40-501 000 51 40-50

N¡N¡ ^Mn,crqi .ô^ ^ lnu) ^9ea1\v.tt ¿

1000 43 70-80eo cam1 000 4 70-80% cam

zz(9oC9oC

zz(9oCo-^1L

OH

am

am

769790

800

NaNa 2Mg 4GaS i e01 300 49 80-901 000 144 80-90

0H)zam

am

NaNa 2MgaInSi sOz z (0H) z

1400 45 80-90% cam

118

Run Number PT(bar) (h)

Produc t sT(deg)

I nNY-41 783

Ga3NY-41 738

MgRC-À1

NaNa 2Mg ¡Àl zSi zAlOz z (0H ) z

1000 43 Oeo cam

NaNa 2Mg¡Sc zSi zAl0z z (0U ) z

1000 50 40-60eo can1380 45 50-70eo cam

NaNa 2Mg¡Cr zSi 7AJ.O2 z (Oti ) z1000 91 70-80eo cam1000 50 70-80eo cam2000 51 70-80e" cam

NaNa 2Mg gIn zSi zAl0z z (OH ) z'1000 16 60-80% carn

NaNiNaNi 5Si s0z z (0H) z

1000 24 cam+wi1 (cT buffer)1 000 48 wil+qtz+Ni

Si licate Fluor-amphibolesealeie Amphiboles- __''r---

ECa2MgsSia0zzFz1 70 cam+di+fI+trd+en+crs1 1 68 cam+di+fl+trd+en+crs1 1 30 cpx+trd+en+f1+fo

NaCa 2Mg sS i zA10 z zF z

3

NY-À1

ScNY-A 1

ScNY-À3

CrNY-41CrNY-42CrNY-43

NiMgRC-À1NiMgRc-À2

FTR-H1 ;2FTR-H3;4FTR-H5

FED-A1FED-A2FED-A3FED-À4FED-À5FED-À7FED-À9FED-B5X

718

700790

690700800

NaNa 2Mg sGa zSi zGaOz z (OH ) z'1000 79 Oeo cam

I ron-magnes i um-nanganese Àmphi bolesNaMgNaMgsSi s0z z (OH) z

806 1 000 46 can+fo

1143113711ss

806787

120211 481107't 041

9991161880938

1

1

1

1

I

1

1

1

1 g1+v. f .9.g1+v. f . g91+crs+cp¡+pI+f 1+v. f . g.cpx+c r s+pI+f l+cam?+g1

J 2

I

2 5

42 cpx+crs+pl+q¿m+fl+gI12 gl+v. f .9.

1 58 crs+cpx+p1+f1+cam120 g¿¡+fs+pl+cpx

119

Run Number PI(bar) (tr

ProductsT(deg)

FPA-A'1FPA-A2FPÀ-A3FPA-À6FPA-B-1FPA-B2FPA-85FPÀ-BUtFPA-NMR

FScPA-A1 *FScPÀ-A3a*FScPÀ-À3b*FScPÀ-À3c*

FGaPÀ-41 *FGaPA-À3a*FGaPÀ-À3b*FGaPA-À3c*

FCrPÀ-À1 *FCrPÀ-A3a*FCrPA-À3b*FCrPA-À3c*

FTS-A1FTS-À2

FHB-À1FHB-À2FHB-À3FHB-A4FHB-A5FHB-A6FHB-B'1FHB-B4

120411511256880

1 0801 080

93810001 000

NaCa 2Mg aAIS i 6À1 zO z zF z

1 1 91+p1+cpx1 4'1 gl+pI+cpx'1 3.3 g1+v. f . g.1 1 58 pl+f1+cpx+ne+fo?+spl?1 '185 cam+cpx+pl+¡s+f e+5pl J1 185 cam+cpx+pl+¡e+fe+5plJ1 120 cam+cpx+pl+spl+ne+fo1 48 cam+cpx+pl+5pl+¡s+fe1 63 cam+cpx+p1+sp1+ne+fo

NaCa 2Mg a ScS i oAl zO z zF z

1 7'1 cam+cpx+fo+ne?1 75 cam+cpx+fo+ne?1 75 cam+cpx+fo+ne?1 75 cam+cpx+fo+ne?

NaCa 2MgaGaSi e Al zOzzF z

1 7 1 cam+p1+fo+cpx1 90 cam+pl+fo+cpx1 90 s¿m+p1+fo+cpx1 90 cam+p1+fo+cpx

NaCa 2MgaCrSi e A1 zOzzF z

1 71 cam+mchr+pl+cpx+fo1 90 cam+mchr+pl+cpx+fo1 90 cam+mchr+p1+cpx+fo1 90 eam+mehr+BJ+enx+fo

rCa 2MgsAl zSi eÀl z0z zF z

1 25 Oeo cânì'1 158 Oeo cam

lca2Mg4A1SizÀ10zzFz5 50% gl+v.2 20% gl+v.I <10eo gl+v1 60e, gl+v.

1 0061073107 3

1 073

1 0061 0001 0001 000

1 0061 0001 0001 000

'1151

880

1 14811071 0411204

999880845938

I

1

1

1

I

1

30001

f .9.f.g..f.9.f.g.

2.3.

1

421s840

120

c rS+an+f 1+cpx+cam+gtzc r S+an+f 1+cpx+cam+qtzs¿¡+qtz+an+cpx+f1s¿¡+gtz+an+cpx+ f l

120

Run Number Pt(bar ) (tr

Produc t sT(des)

FMg4l"lnRC-À2* 1035

Sodic-calc ic AmphibolesNaCaNaMgsSi s0z zFz

1 46 Oeo cam1 138 <5eo cam1 92 Oeo cam1 1 88 cam+cpx+fo1 120 cam+cpx+fo

NaCaNaMgqMnSi sQzzF z

1 44 cam+cpx

rCaNaMg¿À1Si a0z zF z

1 147 40-50% cam1 1 38 1 0-20% cam1 1 08 Oeo cânì1 '163 Oeo cam1 24 5- 1 Oeo cam1 188 20-30eo cam1 120 10-20eo cam

NaCaNaMgaÀ1Si zÀ102 zF zj jq7 s¿¡+fl+g11 1 38 crs+pl+cpx+fl+cam1 1 63 s¿m+p1+f1+crsj 215 s¿rn+fl+gI

NaCaNaMg q ScS i zÀ10 z zF z

1 71 60-80eo cân

NaCaNaMg aGaS i z À10 z zF z

1 71 50-70eo cam

NaCaNaMg a CrSi zÀ10 z zF z

1 71 50-70eo cam

NaCaNaMgaTiSi zÀ102 zF z

1 7'1 50-70eo câm

NaCaNaMg aVS i z À10 z zF z

1 71 50-70% cam

NaCaNaMg gÀI zS i eÀ1 z0 z zF z

46 Oeo cänì12 Oeo cânì

136 <Seo cârn120 <Seo câm

FRC-A1FRC-À2FRC-À3FRC-81 *FRC-85

FWC-À2FWC-À3FWC-C1FWC-C2FI^IC-81FT'IC_82FWC-88

FKA-A2FKA-À3FKA-À4FKA-A5

FTÀ-À1FTÀ-À2FTÀ-A4FTÀ-À8

1'153900

11521 055

938

1102904

11511 02111071 0s5

938

1102904

1 0201072

FScK.À-À1 1006

FGaKÀ-À'1 1006

FCrKA-À'1 1006

FTiKA-A1 1 006

FVKA-A1 1 006

11s31 109

900938

121

Run Number T(deg)

Pt(bar) (h)

Pr oduc t s

FCrEC-À1t' 938

¡CaNaMg sÀl zS i zA10 z zF z

1 46 Oeo cam1 66 Oeo cânì1 1 38 <5eo câfir

Àlkal i emphiboJ.esNaNa 2Mg 4ÀlS i s0 z zF z

120 cam+ab+fo+]y ( 9.5120 cam+ab+fo+ly ( 9.5

NaNa zMg¿ScSi a0z zF z

1 120 cam1 90 cam

NaNa2Mg4GaSi s0z zF1 120 cam+ly ( 9.61 90 cam+Iy ( 9.6

NaNa 2Mg q CrS i e0 z zF z

1 120 cam+gtz+mchr+esk

NaNa2Mg¿InSia0zzFz'1 45 cam1 90 cam

NaNa 2Mg g Sc zS i zÀ10 z zF z

1 120 cam+NaScSi z0o1 90 eam+NaScSi rOn

FBÀ_A1FBÀ-A2FBÀ-À3

FEC-À',1*FEC_A2*

FScEC-À1 *F ScEC-À3*

FGaEC-41 *FGaEC-À3*

FI nEC-À1 *FI nEC-43*

FScNY-42*FSeNY-43*

11531109904

938938

9381 000

9381 000

9851 000

9381 000

4 A)4 Å)

2

6 Å)6Å)

I ron-magnes i um-manganese Àmphi boles

NaMgNaMgsSi s0z zFzMgFRC-A4 909 1 46 crs+cam+cen+trd

NoteslEntries in this column include either phases identifiedin run products, or approximate amphibole mode.

122

TABTE '12

Run Data: Non-isothermal Experiments

Run Number Pt(bar ) (h) (

ProductsT(deg) degrlh )

Rate

FTR-H6FTR-H7

FED_À8FED-81 *

FPA_A4FPÀ-À5FPA_83

FPÀ_84

FPA-87

FScPA-À2

FGaPÀ-À2

FCrPÀ-À2

FTS-À4

FRC-83

Flrc-86FWC-E7

1239- 816 1

1193- 799 1

1 1 96-1 0s8 1

1239- 816 1

1 1 64-1 1091 1 96-1 0581239- 816

,1

1

1

FIuor -amph i bolesCaIcic-amphiboles

ECazMgsSis0zzFz332 1.30 cam+di+trd+en308 1 .30 cam+di+trd+en

NaCa2MgsSizAl0zzFz1q7 0.94 crs+cpx+p1+fl+cam332 1.30 s¿¡+fe+pL+cpx+crs

NaCazMgaÀlSis0zzFz12 4.58 gl+pl+cpx

147 0.94 g1+p1+cpx+sp1?332 1.28 g¿m+pl+fI+cpx+spl

+ f o+ne308 1 .30 s¿¡+pl+f1+cpx+spl

+ f o+ne382 1,12 s¿¡+pI+f1+cpx+sp]

+ f o+ne

1193- 799 1

1273- 844 1

NaCa 2MgaScSi oAI zOzzF z1273- 844 1 382 1,12 can+cpx+ns+f6+fl+91

1273- 844

1273- 844

NaCa 2MgaGaSi sÀ1 zOzzF z

1 382 1,12 q¿m+fe+pl+sp¡+fl+91

NaCa zMg¿CrSi sAl zOzzF z

1 382 1.12 cpx+mchr+fq+pl+cam+ne

1193- 799ECa zMgsAl zSi sAl zOzzF z

1 308 1 .30 Oeo cânì

EcaNaMg4AlSi 80332 1 .30308 1 .28

Sodic-calc ic ÀmphibolesNaCaNaMgsSis0zzFz

1239- 816 1 332 1,28 cam+cpx+fo

zzF z

40-50e"40-50e"

camcam

1239- 816 1

1193- 799 1

123

Run Number T P t Rate Pr oduc t s(deg) (bar) (h) (aeg/h)

FKA-À'13FKA_A-16

FScKA-42

FGaKÀ-42

FT i KA_A2

FBA_À4FBA-À5

FEC-À3

FScEC-À2*

MgFRC-À1MgFRC-À5MgFRC-46

1239- 8161193- 799

1239- 8161193- 799

1273- 844

1273- 844

NaCaNaMg ¿ ScS i z 410 z zF z

1273- 844 1 382 1 .12 50-70eo cam

NaCaNaMg ¿GaS i zÀ10 z zF z

1273- 844 1 382 1.12 50-70so cam

NaCaNaMg 4Ti S i z Àl-0 z zF z

1273- 844 1 382 1 ,12 50-70eo cam

NaCaNaMg aAlS i z Al0 z zF z

1 332 1 ,28 60-80e" cam1 308 '1 .30 60-80e" can

¡CaNaMg sAl zS i z À10 z z1 332 1 ,28 oeo

1 308 1 .30 oeo

Al kal i -amphi bolesNaNa 2Mg 4AIS i e0 z zF z

1 3BZ 1,12 cam+fo+ab+ne+NaF+ly(9.59 Å)

NaNazMg¿ScSie0zzF¿1 382 1 ,12 cam+fo+cen+NaScSi z0o

I ron-magnes i um-manganese Àmphi boles

F 2

camcam

1240- 962 1

1239- 816 1

1193- 799 1

NaMgNaMgsSis0z:Fz47 6.40 cam+cen+crs+trd

332 1 .30 cam+cen+crs+trd308 1 .30 cam+cen+crs+trd

124

TABLE 1 3

Cell Dimensions of Synthetic Àmphiboles

Run No. a (Å) b (Å) c (Å) ß (") v (Å3)

aCa

9.820(4) 18.012(10

Calcic AmphibolesTremol i te

zNi sSi aOz z (OH) z

) s.2s3(3) 104.82(6) 8e8.3(5)NiTRÀ1

Mg3Ni 2TR-A1

CdTR-A2

FTR-H1 ,2FTR-H6

FED-81

cDÀ-À?À

PÀ-À8ÀPA-À2ÀPA_A-10

CrPÀ-À3CrPÀ-À4CrPÀ-45

GaPÀ-À1GaPÀ-42GaPÀ-À3

ScPÀ-À5ScPÀ-46ScPa-À5,6R

ECa 2MgsNi zSi sOz z (Ou) z

9.882Q) 18.032(4) 5.271(2) 104.58(3) 903.1(2)

¡CdzMgsSi sOz z (Ou)z9.666(13) 18.071(24) 5.290(8) 102.91/12) 900.7(1s)

9.7q?

77 (4)78(1)

897.898.

FIuor-tremol i te¡CazMgsSia0zzFz

18.006(7) s.268(3) 104.48(5)18.013(2) s.2665(7) 104.47(1)

FIuor -eden i teNaCazMgsSi tAIOzzFz

9.827Qt 17.943(3) 5.285(2) 10s.11(3) 899.7(3)

Parga s i teNaCa zMgqÀ1Si oAI zOz z (OH) z

e(s)2(1)

J

3

3

2

2

3

2

q qn¿l?l9.907(3)e "8e4(2)e.8e7 Q)

1? q¿1lql17.929(6)17.948(5)17 .946(4)

6 ?R1

5.2825.2805.284

e.s14(2)s. e17 (3 )9.90e(2)

9"849(2)9,923ß')9.910(4)

NaCa 2Mg¿CrSi oÀ1 zOz z (OH) z

17.993(4) s.28s(1 ) 105.44(2)17.998(6) 5,287(2) 105.41(2)17.98e(s) 5.285(2) 10s.42Q)

Naca zMg4GaSi oAl zoz z (OH) z

17.9s3(4) 5.297(1't 105.1717 .973(5) 5.292(1) 1 05.4917.976o) 5.289{.2) 10s.54

)\ 10q E¿l?)2') 105. 51 (2 )1) 105.s0(2)1 ) 105.s1 (2)

qn¿ n

904.0903.5904.4

908.7909.8908,2

903.9 (

g0g. 7 (

907.9(

2

3

3

2

2?

NaCa 2MgaScSi oÀ1 z0z z (0H ) z

9.e42ß, 18.101(5) 5.297(1|\ 10s.37(2) 919.2(3)9.944Q) 18.096(5) 5.298(1) 105.39(2) 919,2(319.9404(8) 18.094(2) 5.2983(4) 105.367(s) 918.89

t¿5

Run No. a (Å) b (Å) c (,{) ß (") v (Å3)

NaCa 2Mga I nSi eAl zOz z (OH) z

inPA-À4 9.937(3) 18.030(4) s.289Q) 105.s4(2) 912.9(3)

FPANMR

FPÀ-BULFPÀ-BUtRFPÀ-84FPÀ-85

FCrPA-À1FCrPA-À3FCrPA-A3R

FGaPÀ-À'1FGaPÀ-42FGaPA-A3R

e.830 ( 4 )e.827 ( 3 )e.8281 (8)s.818(3)e.820 ( 3 )

NaCa zMg ¿ CrS i 641 20 2 2F 2

9.834(3) 17.971(5) 5.286(1 ) 10s.07(2) 902.1 (3)9.845(8) 18.005(13) s.284(4) 105.06(6) 904.4(7)9.8397(6) 17.977(1) 5.2916(3) 10s.105(4) 903.68

FIuor-pargas i teNaCa 2Mg4A1Si oÀ1 zOzzî z

17.919(6) s.2e4Q) 10s.16(3) e00.0(31''t .927(7) 5.293(2) 10s.19(3) 899.8(417 .932Q) 5,2942(4) 1 05. 1 72(5) 900. 5217.9290) 5.295(2) 105.27(4) 899.2(417.931(s) 5.293Q) 105.20(3) 899.4(3

NaCa2Mg4GaSi oÀl zOzzF z

17.951 (4) 5.2e6r) 10s.16(2) 903.5(2)17.945(4) 5.299r) 10s.2s(2) 903.9(2)17.968(1) 5.3028(3) 10s.198(3) 906.s8

9.846(2)9.852 ( 3 )9.8597 ( 6 )

FScPÀ-À1FScPÀ-3AR

s.881(2)9.884s(4)

Na18.'145'18.

1 s6

Caz(4)5(e

MgaScSi6À12022F2s.317(1) 105.17Q) 920.1Q)

) s.g18s(2) 10s.215(3) 9?1.04

HB_A3

RC-À1

KRC-À1

CaMgRC-À1

NiRC-A1

9.770(4)

9.902(1 )

10.048(2)

9.843 ( 4 )

Eca 2Mg4ÀlSi zAloz z (og) z

18.039(4) 5.278Q) 104.62(5)

Sodic-calc ic amphibolesRichter i te

NaCaNaMg5SisOzz(0H) z

17.980(3) s.2683(8) 104.21(1)

KCaNaMg¡Si sOz z (0t¡) z

17.990(3) 5.2733(9) 104.84(1 )

Na (NaCao. sM9o. s )MgsSi sOz z (oH) z

17.959(6) 5.275Q) 103.68(4)

e00.0(4)

e0e.3(2)

s21 .sQ)

e06.0(4)

(oH)z104.00(3) 917.3(3)

NaCaNaMgsNi zSi aOz z (OH) z

M93Ni 2RcA'1 9.894 ( 3 ) 17 .962ß) 5,264(2) 1 04 .29 ( 3 )

NaCaNaNí sSi s0z z (Ott) z

9.882(1) 17.e44Q) 5.2579(7) 104.76(1) 902.8(1)

e06.4 ( 3 )

NaCaNaMg4MnSiM94MnRC-A2 9,920ß) 18.058(5) 5,278(

a0z z

i)

126

Run No. a (Å) b (Å) c (Å) ß (") v (Å3)

NaCaNaMg3Mn 25i e0z z (OH) z

Ms3Mn2RCA2 9.927(3) 18.088(s) 5.282(1, 103.91 (3) 920.5(3)

FIuor-richteriteNaCaNaMg¡Si e0z zFz

FRC-A1 9 .820Q) 17 .964(4) 5.2s8 ( 1 ) 104.11 (2) 899.6 (2 )

NaCaNaMg ¿MnS i s0 z zF z

FM94MnRCÀ2 9.835(3) 18.040(5) s.26s(1) 104.10(3) 906.0(3)

cdRc-A 1

EC_81

FEC-A1

FGaEC-À1

FCTEC-41

EcnEa-À1¡ suuv ¡¡ I

FSCEC_A2PSCEC-À3R

FI nEC-A1FI nEC-A3R

o aralr\¿ôvþJ\-t

9.826Q)9"8383(4)

NaNa 2Mg 4 S1a n¿q/q\ q ?ar v a v ¿e \ v,

18.047(4) 5.2918.0629/2) 5.29

NaCdNaMg5Si aOz z (0H) z

9.749(4) 17.946(4) 5.271(1) 102.70Q) 899.7(3)

Àlkali nmphibolesEc kermann i te

NaNa 2Mg4AIsi a0z z (OH) z

9.710Q) 17 .927 (3) 5.270(1) 102.67 (1) 897 .'r (2)

NaNa zMg¿AlSi eOz zF z

9.6s4(4) 17.902(6) 5.262(1) 102.72(2) 887.2ß)

NaNa zMg ¿GaS i e0 z zF z

9.683(2) 17.89s(4) 5.2637(8) 102.95(1 ) 888.9(2)

NaNa 2Mg 4 CrS i s0 z zF z

9.716Q) 17.817(3) 5.2740(7) 103.58(1) 887.s(2)

cSie111\1(1)26Q

ozzE z1^? Ê,Ll)\ Arl ?12\rwv.v¡\!, ¿t t.J\¿l

103.63(2) e11.8(3)) 103.652Q) 913,97

NaNazMg¿InSis0zzFze.84s(3) 18.081(8) 5.293Q) 103.4e(3) el6.2(4)9 .8526Q) 18.0967 ( 7 ) 5.2927 Q) 103.521(2) 917 . s3

NaNa 2Mg sSc zSi zÀ102 zF z

FScNY-À2 9"839(3) 18.160(7) 5.330(3) 103.9s(4) 924.2(5)FScNY-A3R 9.8467(5) 18.164(1 ) s.3403(3) 103.986(3) 926.83

M9RC-Al

I ron-magnes i um-manganese Àmphi bolesSodian magnesio-cummingtonite

NaMgNaMg5Si a0z z (Ott)z9.740Q) 17.934(3) 5.2700(8)'102.60(1) 898.4 ( 2 )

NaNiNaNi sSi s0z z (OH) z

NiMsRc-À1 9.737(3) 17.891 (6) 5.254(2) 103,21(4) 891.0(4)

127

Run No. a (Å) b (A) c (,{) ß (") v (43)

Sodian f luor-magnesio-cummingtoniteNaMgNaMgsSis0zzFz

M9FRC-ÀS 9.648(3) 17.914(5) 5.264(3) 102.68(5) 887.6(s)

Chapter V

DETÀILED CHÀRACTERIZATION OF SYNTHETIC ÀMPHIBOTES

INFRARED SPECTROSCOPV

Parqasites: NaCarMq¿M3 *Si eÀl r0z r (OH)¿

I nf rared spectra of synthetic pargasites with l',t3 *=À1, Cr, Ga and Sc are

presented in Figure 8. For the ordered case, in which the M(2) site oc-

cupancy is 0.SMg+Q.5M3* and the M('1,3) sites are occupied solely by Mg,

the spectrum should consist of a single band corresponding to the MgMgMg

configuration. The spectrum of pargasite (M3*=Àl), however, consists of

two major bands at 3709 cm-1 and 3676 cr-1 , and a poorly resolved shoul-

der at about 3645 cm-1. Because the sample is from a high-yield run and

is therefore close to of lhe nominal composition, the two major bands

were assigned to the MgMgMg (¡) and MgMgÀl (B) configurations respec-

t i vel v ¡ná l-he mi nar hend trl thc M.rÀl Àl lC) nnnf i nrrr¡l inn rTlha D-h¡nÂ:vòee¿v¡¡r ve¡¡e,

corresponding to lhe A1À1Al configuration, is absent" Band width is

about 25 to 33 cm-r, which is considerably larger lhan typical values of

about 6 cm-1 for natural amphibole spectra (Strens 1974),

Frequency shifts (relative to the MgMgMg band) of bands involving À1

are -33 and -65 cm-1 for the MgMgAl and MgÀ1AI configurations, respec-

tively. Strens (974) showed lhat the frequency shifts of individual

bands are a function of the electronegativiLies of the bonded cations

according to the approximale relationship:

Av=35n (xmg-xs ) cm- 1

L29

sMsMs

MgMgAl

MgMgCr

MgMgGe

MgMgSc

PErga6ltePA-A 1 O

Chromlum-pargaslt€GrPA-A 5

Gelllum-pargaslt€GaPA-42

Scandlum-pargaslt€ScPA-A 5.6

20 o03 3 3 o 3 0?D

'JÊVENUIlBEÊS

o3 3

Fiqure 8¡ Infrared spectra of pargasites

130

where 0<n<3 is the number of Mg ions replaced in any one Mgs(OH)2 c1us-

Ler, and Xmg and Xs are the Allred-Rochow electronegativities of Mg and

the substituent cation respectively. This gives a frequency shift of -9

cm-1 for the MgMgAI band relative to MgMgMg, which is significantly dif-

ferent from the observed shíft of -33 cm-1. Clear1y, the magnitude of

the frequency shift is not a simple function of electronegativity. Fur-

thermore, because the frequency shifts given by Strens f974) were de-

termined mainly from configurations involving Mg and divalent cations,

the shifts calculated for trivalent cations are underestimated. Semet

(973) also records the frequency shift of the MgMgÀI band in the syn-

thetic pargasite spectrum as -33 cm-1, identical to this study.

Infrared spectra of chromium-pargasite, gallium-pargasite, and scan-

dium-pargasiLe from this study, and magnesio-hastingsite (Semet 1972,

1973) all have shoulders near 3676 cn-1 corresponding to the MgMgAI con-

figuration (Figures 3, 8). These spectra suggest that synthetic parga-

sites (M3*=cr, Ga or Sc) and magnesio-hastingsite (M3*=Fe) are not of

the nominal compositions but contain minor octahedral À1. The magic an-

gIe spinning nuclear magnetic resonance (t't¡S Nt"tR) spectrum of scandium-

fluor-pargasite supports this conclusion; the octahedral to tetrahedral

AI ratio is 95:5 (Hawthorne et al 1984).

This discrepancy between the nominal composition and Èhe composition

of the synthetic amphiboles is reflected in the speclrun of chromium-

pargasite (M3*=Cr), which consists of major bands at 3710 cm-1 and 3659

cfiì-1 , a shoulder at 3674 cr- 1, and at least I minor bands or shoulders

(rigure 8), suggestíng that configurations other than those due simply

to Mg, Cr and Àl in amphibole are present. The two major bands were

131

assigned to MgMgMg and MgMgCr configurations; the shoulder at 3674 cm-1

is probably due to the MgMgAl configuration. Minor bands at lower fre-

quencies, although of low probability, coul-d result from one or more of

configurations MgAlAI, ÀlÀ141, MgÀlCr, MgCrCr, ÀIAICr, ÀlCrCr or CrCrCr.

Bands with frequencies between 3710 cm-1 and 3674 cm-1 are puzzling be-

cause they cannot be due to any configurations involving Mg, Cr or À1 in

amphibole. The presence of nrinor layer silicates in the run product,

however, ilây account for some of these bands. In addition, a shoulder

at about 3715 cm-1on the high-freguency side of the MgMgMg band points

to the splitLing of this band and cannot be explained in terms of the

C2/n anphibole structure.

Gallium-pargasite (M3*=Ga) spectra exhibit sirnilar anomalies. Bands

at 3706 cffi-1, 3676 cm-1 and 3665 cm-1 were assigned to the MgMgMg,

MgMgÀL and MgMgGa configurations, respectively. Minor bands and shoul-

ders at lower freguencies are the result of Lhe other normal Mg, Ga and

Al configurations. The MgMgMg band has a shoulder at abouL 3711 cm-1i

this is at a frequency shift of +5 cr-1, identical to a simiLar shouLder

in the chromium-pargasite spectrum. No fine structure was resolved be-

tween the MgMgMg and MgMgÀl peaks as in the chromium-pargasite spectrum.

In contrast to chromium- and gallium-pargasites, the scandium-parga-

site (M3*=Sc) spectrum is straightforward. The three major bands at

3711 cfi-1, 3679 cm-1and 3673 cm-1 were assigned to the MgMgMg, MgMgAl

and MgMgSc configurations, respectively.

132

RLchterites: (¡,Na)qaNaMß*si ¡oz r (oH)*

Richterite: NaCaNaMg5Si eOz z (0H) z

The infrared spectrum of synthetic richterite (nigure 9) is typical of

endmember amphibole having llg as the sole octahedral cation. It con-

sists of a single, sharp band at 3729 cn-lcorresponding to the MgMgMg

configuration. A barely resolved tremolite-like peak occurs at about

3673 cm-1, suggesting that this richterite is slightly off-composition.

This spectrum is almost identical to that of Rowbotham and Farmer (1973)

except that their tremolite peak is more intense. Band h'idth is 21

cnì-1 , about 3 times wider than in typical natural amphiboles (Strens

1974).

Potassium-richterite: KNaCaMgsSi sOz z (OH) z

The spectrum of potassium-richterite is almost identical to that of

richterite except that the MgMgMg peak is shifted +3 cm-1 to 3732 cm-1

and the tremolite-lile peak at about 3670 cm-1 is more intense. Band

width is about 18 cm-1. The magnilude of the MgMgMg band frequency

shift is consistent with that of typical values of +3 cm-1due to K sub-

stitution for Na in the À site (Hawthorne 1983b). Às for richterite,

the band at 3670 cm-1 suggests limited solid solution towards tremolite

and consequent deviation from the nominal composition.

Manganese-richterite: NaCaNaMgAMnSi s0z z (0H) z

The spectrum of richterite with M3*=Mg+Mn consisLs of a single band at

3729 cn-1. A slight swellíng at the base of the peak on the low-fre-

quency side may represent the contribution from another band. Il is not

like1y, however, that this represents the MgMgMn band, because the fre-

rlchterltes

MgMgMg

tremolite

MgMgMg

133

KCaNaMg

KRC-A 1

5

NaCaNaMg

RC-A 1,25

I NaCaNaMOOMn

M94MnRC-42

Mg3Mn2 RG-42

NaGaNaMgaMn,

38ürr :ir¡o :lal J7+3 3i¿t-l ,¡2r:¡ -ìÈß! 3ÈtjtJ :f-,ç t-l 3É,¿O

r.J Ê V t- l{ U lY B i. t'ì :ì

Figure 9: Infrared spectra of richterites.

quency shift is only about -22 cn-1. Most probably,

of the skewed gaussian peak shape (see Figure 44.).

be virtualJ.y all ordered into the M(2) site. Band

wider than richteriLe (23 cm-1 versus 21 cm-1).

134

it is an artefact

Àpparently, Mn must

width is slightly

The spectrum of richterite with M3*=Mg3Mnz is similar, consisting of

a single band at 3725 cm-1. Band width is 23 cm-1and there is a slight

swelling at the base of the peak at about 3707 cm-1 (see arrow, Figure

9). The spectrum suggests that most, if not all, of the Mn is ordered

into the M(2) site. Note that the MgMgMg band shifts to lower frequen-

cies by 4 cm-1 f rom endmember richteriLe to richterite with 2t"tn. The

reason for this shift is unknown. Both spectra of the manganese-richt-

erites also show minor tremolite-like peaks at about 3673 cm-1.

Sodian maqnesio-cumminqtonites: NaMqNaMqsSi eOr r (OH)¿

Idea1ly, the sodian magnesio-cummingtonite spectrum should consist of a

single, sharp, hydroxyl-stretching band corresponding to the MgMgMg con-

f inrrrat i nn - The nhsprr-rpd snp¡trum lF iortre 10 ) - however . consi sts of twO¡ ¿>v¿ t vv v¡Jev e¡ e¡.r v Y u- f

major absorbances: a single, well-resolved band at 376 cfr-1, and a

broader band that could possibly result from three closely overlapping

components. Between these two groups, there is also a weak shoulder at

about 3729 cm-1. This spectrum, with the exception of additional fine

structure, is virtually identical to that of Maresch and Langer (976)

who observed lwo bands at 3739 cm-1 and 3716 cm-1 (nigure 264). The

higher frequency band is about twice as wide as the other band, and it

is possible that the fine-structure seen in this study is not resolved

in their spectrum.

13s

sod¡an magnes¡o-cummingtoni te

MsRC-A 1

'eckermannlte"

EC-A2

:dritl .¡ )g¡ i ittr -r l'* ¡ .¡i ¿t J i ür-rr.llì V i-NtiMtJt..rì:ì

J b ¿ltì

Figure 10: Infrared spectra of sodian magnesio-cummingtonite andeckermannite.

136

Because the octahedral sites in sodian magnesio-cummingtonite must be

occupied sole1y by Mg, all bands in the spectrum must be from MgMgMg

configurations. The presence of more than one band implies the exis-

tence of more than one hydroxyl environment, not possible in space group

Cz/n. Maresch and Langer ,1976) assign a band at 3727 cn- 1 to OH-va-

lence vibrations in SiOH groups in lhe amphibole (rigure 26):

NaNa2MgsSi a0z r (oH) (0H) z

They do not account for the other bands (see Chapter 6). The origin of

the other bands is stilL unknown. Precession photographs (Hawthorne

1984, pers. comm.) show reflections with h+k=2n+1 suggesting that sodi-

an magnesio-cummingtonite is primitive rather than C-centered. Until

the crystal structure is known, the spectrum cannot be interpreted wilh

certainty.

Ec ke rmann i te : NaNa 2Mq4Àlsi ao2, (oH)¿

The spectrum of the synthetic amphibole grovrn on the eckermannite compo-

sition is of interest because it is virtually identical to that of sodi-

an nagnesio-cummingtonite (nigure 10). It consists of a sin91e, well-

resolved band at 37'16 cm-1 and a group of bands between 3739 cm-1 and

3754 cm-1. Thus, this amphibole cannot be eckermannite, a conclusion

reached earlier from cell dimensions (taUte 1¡).

137

BIETVEID E¡I$IÀ! STRUCTURE REFINEMENT

The Rietveld method (Rietveld 1967,1969) uses the whole powder diffrac-

tion pattern to characterize the structure of the material examined.

The structure parameters of the mineral, atomic coordinates, site-occu-

pancies and thermal parameters, together with various experimental pa-

rameters affecting the pattern, are refined by least-squares procedures

to minimize the difference between the whole calculated and observed

TÀBIE 1 4

Synthetic amphibole structures refined in this study

Name Nominal Composition fRun Number(s)

1 ) Scandium pargasite2) FJ.uor-pargas i te3 ) Chromium-f luor-pargasi te¿ ) cattium-f luor-pargasite5 ) Scandium-f luor-pargasi te6) Scandium-f luor-eckermannite7 ) I ndium-f luor-eckermanniteo\ ô-^-r:..- r1..^- ---L.i.:!^Q I ÞLCrr¡UI Uilr"-rJ-UU! ¡lyU\,rJ, LC

NaCa 2MgaScSi oÀl z0z z (OH) z

NaCa 2Mg4À1Si oÀ1 zOzzF z

NaCa zMgqCrSi oÀ1 zOzzF z

NaCa 2Mg ¿GaS i sÀl z0 z zF z

NaCa zMg¿ScSi e À1 zOzzF z

NaNa 2Mg4ScSi s0z zF z

NaNa2MgaInSie0zzFzlr-Ìt- lrà ô- ô: Âl^ F¡rcr¡\c1 2¡'¡9 3ùL 2 Jr 7 ^LV Z 21 2

ScPÀ-À5, 6FPÀ-BUtFCrPÀ-À3a , b, cFGaPA-À3a, b, cFScPA-À3a , b, cFScEC-À3a, b, cFI nEC-A3a, b, cFõ-rrrr rr^ L -rùU¡l¡ öJd¡U¡L

fTable 11, Chapter 4

patterns.

The strucLures of eight amphiboles synthesized in this study vrere re-

fined with the Rietveld method (tabte 1¿). Raw intensity data is listed

in Appendix B. Results of all structure refinements are summarized in

Tab1es 15, 16, 18, 19 and 20. Calculated and observed powder diffrac-

tion patterns are given in Figures 11 to 18.

138

Ref inemen_t Results

CeI1 dimensíons derived from the refinements are given in Table '16.

In general, they are up to an order of magnitude more precise than those

derived from normal least-sguares refinement of powder diffraction data

(raUte '1:). I^lith the exception of gallium-f luor-pargasite, ceI1 dirnen-

sions are identical within 2- or 3-sigma for both methods of determina-

TÀBLE 1 5

Refinement Results

No. t Sca1e B P Asym Zero Rexp Rp Rwp Rb

1

¿

3

4567

I

0.00264(4) 1

0. 00642 ( 9 ) 20.00427 (6) 2

0.00610(7) 1

0.00s33(s) 1

0.00753(8) 1

0.004s9(5) 1

0.00717(8) 1

0.15(1) 0

0.14(1) 1

0.07(1) 1

0.04(1) 1

0.15(1) 1

0.0e(1) 1

0.05(1) 2

0.28(1) 0

.8(

.2(

.0(

.t¿

)

)

)

97

7

I

.78

.4(0.0270.0760.0720,1270.0610.1150.0970.107

,7.60.23,23

I)

)

9I7

7

6

Q(zQ(z(l(l(l(l

4,462,903.392.792,952,572.782.68

'16.3

rþ.J14 .7IJ.J1a 1

11.3'1 0.812,8

14.51 3.913. 912.211 .19,9

10.211,2

0

7

5

6¿

2

5

.46

.l I

1)

.1(

.39

.20

.37

.09

5992280373 98

tNo. corresponds to numbers in Table 14, B is the overall Lemperaturefactor, P is the preferred orientation parameter, Àsym is the asymmetryparameter , Zero is the zeropoint correction, Rexp is the statisticallyexpected value for Rwp, Rp is R-pattern, Rwp is the R-weighted patternRb is R-Bragg (see Àppendix A for details).

tion when obtained for identical samples.

Àtomic positions are given in Table 18. Cation-anion and cation-ca-

tion distances (faUte ZO) were calculated using the RFINE program (rin-

ger 1969). Typical ranges of natural and synthetic amphibole !etrahe-

dral bond lengths are given in Tab1e 21. Mean tetrahedral bond lengths

139

TÀBLE 1 7

Selected Correlations from the Rielveld Refinement ofI ndi um-f luor-ec kermann i te

I z

000T

4

1

51

-0(7-oQ-0(6-î(2

-0.02-0.36-0.33-0 ,47

0

0.02-0. 16

0.14

-0.45-0.28-0.24-0.35

are a good test of the refinement results because they are well known

from single-crystal structure studies and are not as variable as other

cation-anion distances. Inspection of Table 20 shows that individual

tetrahedral bond lengths exhibit extreme ranges of variation that are

inconsistent with single-crystal structure data for both pargasites and

aIkali amphiboles. Mean tetrahedral bond Lengths are better behaved and

are reasonable, except for gallium-fluor-pargasite (4) in which <T(2)-o>

;- *,,^f. 1-,ã^F +Lâñ zrrrl{ l-n:. }Liõ .i a na} l.i L^lrr rra-.i^+.i ^^ l- i-t.i.,;¡-¡Þ ¡¡¡uv¡¡ ¡qtygr u¡¡g¡¡ -¡ \ r, v- I L¡¡rÞ ¿J ¡¡vu ¿¡^sr.I . Yqt¿qL¡vr¡ ¿¡¡ ¿¡tu¡v¡u

ua1 <M-0> with mean ionic radii of constituent octahedral cations is not

consistent with trends for single-crystal structures (Hawthorne '1983b).

Hawthorne (1984, pers. comm.) suggesls that the existence of a pseu-

do-glide paralle1 to c in arnphiboles is responsible for the incorrect

atomic distances because the T(1) and T(2) telrahedra are pseudo-symme-

trically related and atomic positions are highly correlated during re-

finement (rabte lZ). This supposition is supported by Rietveld struc-

lure refinemenLs of synthet.íc P2t/c clinopyroxenes by Raudsepp et al.(1984). Telrahedral bond lengths vlere variable beyond reasonable ex-

140

TÀBLE 1 6

Cell Dimensions Determined by Rietveld Structure Ànalyses

No"t a (Å) b (Å) c (Å) ß (") v (Å3)

1

2J45

67

I

9.9398 ( 7 )e .8284(7 )

9.8401 (s)9.8598 ( s )9.88s1 ( 4 )e.838s ( 3 )9.8528 ( 3 )

9.846s ( 4 )

18.0s3(2)17.931(1)17.978(1)17,9682(9)18.1s67(8)18.0636(6)18.0970(6)18.1643(8)

.2982(4

.2936(4

.2914(3,3026ß.3185(2.2927 (2

"292s(2.3401 (3

1 05.363 ( 5

10s.169(4105.100(3105.197 (2105.214Q1 03. 6s'1 ( 2

103.521 (2103.98s(3

918.78900.40903.76906. 57921,11914.04917 .60926.79

tNumbers correspond to numbers in Table 14

tremes, but siLe-occupancies determined for the same material by Möss-

bauer spectroscopy vrere statistically identical to those determined from

the Rietveld refinement. As with the amphiboles, the tetrahedra are

highly correlated due to the occurence of pseudo C-centring in Lhe P2t/c

structure. To test the validity of this conjecture, the structure of a

natural olivine was refined by the Rietveld method with the same experi-

mental technique that was used for the synthetic amphibole refinements

(L. Groat and F.C. Hawthorne, unpublished data). In addition, a single-

cryslal structure of the olivine was refined as a check on the Rietveld

method. R-f actors f or the Rietveld ref inement were Rp=12,41 , Rwp='13.2't

and Rexp=4,75, comparable with values from the amphibole refinemenLs.

Bond lengths and site-occupancies were statistically identical for both

methods. This suggests that site-occupancies in the amphiboles are

fairly accurate. Synthetic amphibole site-occupancies are given in Ta-

b1e 19. All negative values differ from zero by less Èhan 3-sigma, and

141

than 1 .000may be

may be

regarded as zero; corresponding occupancies greater

interpreted to be 1.000.

Spme Comments on RiqLve.ld Ref inement

In general, powder struct,ure refinements of these synthelic amphiboles

are comparable with most refinemenfs in the literature (voung 1980).

Rietveld refinement is still a technique undergoing rapid development,

and several aspects are currently not satisfactory:

1. The peak profile function currently used in all Rietveld routines

does not adequately model the observed peak shape. Difference

plots in Figures 11 to '18 show consistent sinusoidal fluctuations

that reflect poor fits at the peak base. These are best observed

for the (020) and (110) peaks between 9.5 and 10.6o20.

2. The single refinable asymmetry parameter does not adequately mod-

eI peak asymmetry over the entire 20 range. Best results (lowest

Rwp's) were obtained by refining the asynmetry parameter only be-

1^,, -L^..! t10,)ô. -^Í:-:-^ !L,: ^ ---^*-!^- G^- !L^ --L^l ^ c^!!-<ÿ9W Clr.tvUL ¿L LV¡ lgrrllrll9 LrrJ.Ð P(rrdr¡lE;Ls! r\r¿ L¡¡g vY¡¡vJtr pdLLtrlr¡

gave higher R-values.

3. All of the samples, except indium-fluor-eckermannite (8) contain

up to 10 percent extraneous phases that contribute to the overall

pattern. Peaks due to phases other than amphibole are marked by

arrows in Figures 1'1 to 18. These correspond to phases other

than amphibole ]isted in Table 11. The refinement program alIows

regions of extraneous intensity to be excluded, but extra inten-

sity under amphibole peaks cannot be excluded in this way; this

raises the R-factors significantly.

142

Significance of the Residual Pattern

The residual pattern that remains when the observed diffraction pattern

is subtracted from the calculated pattern (Figures 1'1 to 18) is valuable

because it comprises the diffraction patterns of phases other than an-

phibole in the run product. In the whole pattern, the scattering con-

tribution of these phases are partly or completely masked by the intense

amphibole pattern; this may lead to the false assumption that the arnphi-

bole yíe1d is near '100 percent.

With the current profile function, the interpretation of the residual

pattern is not straightforward because the diffraction patterns of ex-

traneous phases are mixed with residual intensity derived from inade-

quate peak-shape models. The residual pattern of indium-fluor-eckerman-

nite (figure 17) cont,ains only contributions from inadequate peak-shape

modelling, and the run product may be confidently interpreted to be es-

sentially '100 percent amphibole. À11 of the other residual patterns

contain obvious contributions from non-amphibole phases, not all of

..'L;^L --^ ^L,,i ^,,è Í'^ñ rL^ ,.,L^l ^ *-rr^¡¡¡ñ¡¡¡U¡¡ q!ç vVv¡VUP llVlll Ll¡ç Wl¡t/¿g ÀJAULglt¡Ð.

Indexing of Synthetic Àmphibole Powder Patterns

Use of the Rietveld method ensures that the amphibole pattern is cor-

rectly indexed, and that non-amphibole peaks are not indexed as amphi-

bole peaks. This is of more importance than one would initially think,

as several published patterns have incorrect indexing and wrong cell di-

mensions as a result of this.

143

CapLtþn: ErgÈreS Powder X-¡ey Dif fraction Patterns.

Figures 1.1 to 18 show the results of Rietveld structure refinements with

graphite-crystal monochromatized CuKol and CuKoz X-ray data collected in

0.04"20 steps in the range 8 Lo 72o2e, Open squares are the observed

data, the solid line is the calculated pattern, the vertical bars below

the pattern represent all possible Bragg reflections and the arrovls

point to non-amphibole reflections. The residual pattern obtained by

subtracting the observed and calculated patterns is shown at the bottom.

1 1 ro '18.

rtroçFlfl

'uo€OrrDFt

xI

Fl0,

o,FIhlhlq'c¡rÈ

oJ'EÞ,ct.cl'(Dhl5oRi

(,lc)9'Þgr

CãI\t

o,Ftro9'Ut

rffD

1.0

0"5

0.0

0.0

1ngoL

o

(toÉ,

5Þ

10 15 20 25 30 35 U0 U5 50 55 60 65 70"20

I iltIilt ilIIiltf I]illfrlt Itiltl]il ililltilil]ill ]illllfl]lt ilillll llilllllllilI il ilil 1I lt lil

Scandium-pargas¡te

IIeI

a

Iå

I

I I I

-rI:---- III--Ift-tt- _-EE

_æ

IG- EE

--EITæ----æ

o.=(t,(úo(!o'Io5E

Þ

--l¡ éoo!!'+D

+D

+

't 45(DNoOl--LN(oOcolJltnOU

I

LNJC]

:fLr)cnOcoU

Iôj

Oc\-l

LN

O

c)LN

OC

].

,tilsuelul o^ltBlou

OO

O

122 Pow

der x-ray diffraction pattern of fluor-pargasite.F

i gure

- I-------- III:fI- !-GI!=IIæ=E

I----- :æææ-æI

s f

!Þo.o

3

>+

È.ôood.

3

Þ

o= g,oooCLIo=IE.3Eo-co

D+

"

D+

146(DN0O|..-

LNCO

cl(DaLNOLNLN:fOfLNCD

OcnLNC\J

OC\I

LJ-)

O

OIJ

LNclcf

Á¡¡suetu! o^ltE

laH ?cf

Figure 13:

Pow

der X-ray diffraction pattern of chrom

ium-fIuor-

pargasite.

I- :-= :-=I----- I-: I- t-I=-=-IE=æ-IæII==

=-===

o.=(t,(!oG

'oIo:IEJõa

l-rú€ètrÞÞÞ

147@({ocft--

LN@c)aUI

LNOu')

LN=clfU)

c.)

C]

arì

LNc!cfC\

Uî

Cf

cfLN

OO

. ,{usuolul e^ltE

louC

]OO

142 Pow

der X-ray diffraction pattern of galliun-fluor-pargasite.

FÍ gure

I:::-:!=---- EæE--- I-----¡--æ_-- E----=

o.=U'

(r,o(úoIo:IE.=Ec(úoCN

D+

e.s

148(DNoclÈ-

tn(oOLOtnu)clLNLN=f

O3LOcnOcr)

UI

CU

OC\I

LNO

OOcl

LNO

r{¡¡suelul a^llBleU

O

Figure 15:

Pow

der X-ray diffraction pattern

pargasiÈe.

c)

of scandium-fIuor-

0.5

=otro

åç

o:qt

ofr

F{

rocFtlD

Oì

oÌúc!o7r4(Do,Ftoãño,ÞX:'tP. Flft o,(D<

o,ttrItÈt!,c¡rl

oJÌt9,rtcflDFl

=oñat,c)ÞÞo,Çj

IHIPcoFl

I

1.0

0.0

0.0

Þ(o10 15 20 25 30 35 q0 45 50 55 60 65 1002ø

illl ll lll II Illlll llrf,ilillll]tßillt iltfiilrüililil]ilililt ililil1ililllliii[llliiHIii[¡tilt]I

Scandium-f luor-eckermannite

501

o({oOt-r

UI

CO

O(9LNaOtnLJ^)jOjU

Ic.)

OcoLNCU

Oc!u-)

O

OOLNO

OÁ

¡¡euelul a^ttBleU

?O

Figure 17:

Pow

der x-ray diffraction pattern of indium-fluor-

ec kermann i te .

-II*= III:III--- II------- I=a--

-Ü-I=:

0)

=cc(!EoxooIo:tIE.3!c

@

}Ît

roCFtfD

'rto€o,lDFf

XI

Èl0,

o,rlrñtslocrrl-

oJ

'õa,rtrrrDnÞ

oc¡oJO¡

É¿

IHI

CoFl

IÞ

tto:rflD

1.0

0.5

0.0

:øÊo

so:sotr

0.0

(rt

10 15 20 25 30 35 U0 rl5 50 55 60 65 -70"29

ilil il illl lil t[ il ililill[ll|¡ilüilllilililt illlltillilil|flnifiiiltitilrüii1]fi]itFlllril

Scandium-f luor-nyböite

I

152

TABLE '18

Àtomic PosÍtÍons

À. Pargasites

(1) Q) (3) (4) (5)

0(1 )

0(2)

0(3 )

0(4)

0(s )

0(6)

r(1 )

0.107 (1 )

0

0.716(4)

0.0e5(1 )

0

0.704 ( 3 )

1)(5)2)

1)Q)1)

1)(s)2)

2)(6)3)

2)(6)3)

1)(3)1)

2)(6)3)

x0y0z0BO

x0y0z0BO

vz0BO

x0y0z0BO

x0y0z0B1x0y0z0B1

y0z0BO

.127 (1)

.0970(4)

.223ß)

.80

0.117(1)0.0901 (6)0.214(2)

0.107('1 )

0.0862(5)0.21eQ)

.101(2)

.1758(7)

.722ß)

.80

0.103(1) 0.103(1)0.0884(6) 0.0919(7)0.207 Q) 0.197 (2)

0.127(1) 0.123(1) 0.104(1) 0.119(0.1702(6) 0.170s(6) 0.1683(6) 0.16980 .7 42ß) 0 .7 42(2) 0 .731 (2) 0 .724(

x 0.101 (2 )

0

.698(4)

.80

x 0.283 ( 1 )

0.339 ( 2 )0

0.276 ( s )

0.334 ( 2 )

00.27 4(4)

0.347 ( 1 )

0

0.293 ( 3 )

0. 103 (2 )

0

0.718(3)

0.oee(1 )

0

0.710(2)

.345(1)

.2489(6)

.7 67 (4)

.80

.352(1 )

.13ee(6)

.099(3)

.10

0.351 ( 1 )

0.1389(4)0.117 Q)

.343 (

.1134

.640 (

.10

0. 339 (0. 1 0950.61 1 (

0.334(0. 1 1370.59s(

0.340 (

0.1 0970. s91 (

0.340(1 )

0.1160(4)0.607 Q)

x 0,339(2)0(7) y 0

z 0"293(s)B '1 .20

0.340 ('1 )0

0.276(3)

0.36s(1) 0.357(1) 0.3s3(1) 0.3s8(1)0 .2482(6) 0 .2467 (6) 0 .24s0 (5 ) 0 .2447 (4')0.791(4) 0.794(3) 0.782(3) 0.787(2)

0.352(2) 0.3s9(2) 0.350(1 )

0.1386(s) 0.1367(s) 0.1388(5)0 .122(3) 0 .122(31 0 . 1 0s (2 )

.0827 (4)

.302(2)

.40

0.274(0.08360.296(

0.27511) 0.286(1) 0.282(0.0834(3) 0.0859(3) 0.08410.293(1) 0.298(1) 0.298(

1s3

(1) Q) (3) (4) (s)

r(2 )

x00000M(1 ) y 0.0868(6) 0.0e13(6) 0.08e3(5) 0.0884(s) 0.0883(4)

z 1/z 1/z i/z 1/2 1/2B 0.60

M(2 )

00c000.1740(s) 0.1804(6) 0.17s1(s) 0.1767(4) 0.1762ß)

000000. 60

M(3 )

x00000M(4) y 0.2808(4) 0.2776(5) 0.2770ß) 0.2781(3) 0.2794ß)

z 1/z 1/z i/2 1/2 i/2B 0.90

.285(

.1681

.807 (

"40

0.298(10.1719(0.813(1

.296r

.1725(

.814 ( 1

.28s(1

.1 703 (

.806 ( 1

.292(,1692.809 (

1)Q)1)

)o3) 0)o

)o3) 0)o

)o3) 0)o

l)(3)z)

x0y0z0BO

0

0

00. 60

vzB

vzB

0

0

0

0

0

0

0

0

0

00

0

A

x0v 1/2z0B 2"30

0.027(3) 0.033(3)1/2 1/2

0.01i('10) 0.036(2)

0.028Q)1/2

0.041(7)

0.03s ( 2 )

1/20.048(s)

omN i1

27

4

5

a1 CompositionsScandium pargasite: NaCa2Mg4ScSi oÀlzOz z (OH) z

Fluor-pargasite: NaCa2MgaAlSi 641202 2F2Chromium-f luor-pargasite : NaCa2t'tg4CrSi oÀ1 zOz zFzGallium-f luor-pargasite: NaCazMg4GaSi 5À1 202 2F2Scandium-f luor-pargasite: NaCa2MgaScSi oÀ1 zOz zF z

154

B. À1ka1i emphiboles

(6) (7) (8)

0(1 )

0(2 )

0(3)0.0e8 ( 1 )

0

0.704(2)

0.0e8(2)0

0.713(3)

1)(5)2)

1)(4)2)

(4)Q)1)

1)(s)2)

0

)o0

1)(4)2)

1)(¿2)

(4)(211)

1)(4)2)

(4)Q)1)

x0y0z0BO

x0y0z0BO

vz0BO

x0y0z0BO

x0y0z0B1x0y0z0B1

x0y0z0BO

.112(1)

.0887 ( 4 )

.212(2')

.80

0.122(0.08580.219(

0.10s(0. 091 20.213(

,124(,1647. 73'1 (

.80

0.122(1) 0.126(1 )

0.1639(5) 0.1677(5)0.732(2) 0.724(2)

X 0.101(1)0

.705(2)

.80

0(4)

0(5 )

0(6)

r(1 )

.3se(1)

.2449ß)

.794(2)

.80

.346(1 )

,1264(4).081(2).'10

0.348 (

0 .127 1

0. 073 (

0.340(1)0.1313(s)0.083(2)

.344(1)

.1183(4)

.577 (2)

.'1 0

0.338(0,11710. 568 (

.34s(

.1162

.s9s(

0.354(1) 0.357(1)0.2438(4) 0.2461(4)0.789121 0.787 (2)

x 0.340(1)0(7) y 0

z 0.309(2)B 1.20

0.338(1)0

0.299(3)

0.340 ( 1 )

0

0.311(3)

.2804

.0837

.28s(

.40

0.28310. 08380.285 (

0.28310. 08440. 284 (

I trËIJJ

(6) (7) (8)

r(2 )

M(1 )

0000.0890(3) 0.0870(4) 0.0870(4)

1/2 1/z 1/20.60

x000M(2) y 0.1823(3) 0.1821Q) 0.1802(3)

2000B 0.60

M(3 )

M(4 )

0000.2751(4) 0.2751 (5) 0.2792(5)

i/2 i/2 1/z0. 90

(5)Q)1)

x0y0z0BO

0

0

0

.2910

.1682

.79s (

.40

0.2889(5) 0.2889(s)0.1677 Q) 0.1664(2)0.793(1) 0.805(1)

X

vÁ

B

x

vzB

x

vzB

0

0

0

0

0

0

0.60

A

x 0.036(2)v 1/2z 0.066 (4 )B 2.3

0.040 ( 2 )1/2

0.061(4)

0.04s(2)1/2

0.070(4)

om(

(

(

N 1n6)7)8)

a1 CompositionsScandium-f luor-eckermannite¡ NaNa 2Mg4ScSi aOzzF z

Indiunr-f luor-eckermannite: NaNa zMgsInSi sOz zFzScandi um-f luor-nyböi te : NaNa 2Mg 3 Sc zSi zAlO z zF z

156

TÀBIE 1 9

M(1 )- , I4(2)-, tu(3)-site occupancies

(1) Scandium pargasiteM(1) Ms 1.023(25)M(2) Me 0.771(23)M(3 ) Ms 0.812(29)

Q) Fluor-pargasiteM(1 ) Mg 1-xM(2 ) Mg 1-yM(3) Mg 1-z

(3) Chromium-fIuor-pargasiteM(1) Me 1.014(12)M(2) Ms 0.890(14)M(3) Ms 1.015(20)

(4 ) Gallium-fIuoM(1) MsM(2) MsM(3) Ms

(5) Scandium-fluor-pargasiteM(1 ) Ms 0.983(14) Scr[(2) Ms 0.ss4(15) ScM(3) Ms 0.986(20) Sc

(6) Scandium-fluor-eckernanniteM(1 ) Ms 0.968(12) Scvt?) M9 0.524(12) scM(3) Ms 1.032(16) Sc

0, Indiun-fluor-eckermanniLeMg

Mg

M9

(8) Scandium-fluor-nyböiteM(1 ) MsTlQt. Mg

M(3) Ms

Ga -0.026(8)Ga 0.112(8)Ga 0. 036 ( 1 2 )

0.017(14)0.446(16)0.014(20)

0.034(12)0 .47 6(12')0.032(16)

1.004(2)0.4e8 ( 2 )1 .012(4')

In -0.004(2)In 0.502(4)In -0.008(4)

0.932(14)0.104(16)1.0s2(20)

sss

c 0.068(14)c 0.896(16)c -0.052(20)

Sc -0.023Q4)Sc 0.229Q3)Sc 0.188(29)

Cr -0,014(12)Cr 0.110(14)Cr 0.020 ( 20 )

iI1

vL

AÀÀ

r-pargas i te1.026(8)0.888(8)0.964r2)

M(1yiQM(3

157

TABLE 20

Cation-anion and Cation-cation Distances

A. Pargasites

(1) (2) (3) (4) (5)

TTTT

-0(1-0(5-o(6-0(7

TQ,_oQr(2)-0(4r(2)-0(sr(2)-0(6

1.5i41 ,7561,8171 ,602

1,6241,6641,6871,657

1 ,6491,6761.6471,662

1 .6081.6431 .5671 .648

1,6621 .6561 .6931 .660

<r ( '1 )-0> 1 .672 '1 .658 1 .659 1 ,617 1 .668

1,7731.6fi1 .5991 .534

1.6281 .553'1 .6861.654

.494,7 06.666

1 ,7241 ,5211 .6461 ,759

1.6451 .5371 .6821 .605

.6391

1

i,1

<T(2)-0>

M(1)-0(1)M(1)-0(2)M(1 )-0( 3 )

<M( .1 )-0>

2,1422.0882,004

2.078 2.087

2.0591.9952,199

2.3202.103

2.043 2.054

-1 .629 1 .630 T-626 1 .663 ß1

x2x2x2

x2x2x2

x2x2x2x2

2.0642.0862 ,111

2,1321 .9882.010

2.0492.0642,048

2.0402.047

2.1082.1052.082

m

2,0702,012

2.1322.025

2.0692,031

M(2)M(2)M(2)

-o(1-oQ-0 (4

2.0912. 0851 .963

1 .9482. 0532.086

2,0431 ,9672,129

2.0542,1112.118

<M( 2 ) -0>

M(3)-0(1) x4M(3)-0(3) x2

<M( 3 )-0>

t¡ãa 2.046 uozg 2.060 mj

2.248 2.042 2,096 2.056

2,3202 ,4102.6592.693

2,4622.3242,6192.726

2.4422.3932,6242.688

2.4042.3782,6812.684

2,4562,3692.6342,631

2.0s1

M(4)-0(2M(4)-0(4M(4)-0(5M( 4 )-0 (6

<M( 4 )-0> 2.521 2.533 2.537 2,537 2,523

1s8

(1) (2) (3) (4) (s)

M(1M(1M(1M(1t4QM(2

)-tq(1))-u(2))-u( 3 )

)-u(¿ )

)-u(3 )

)-u(¿ )

3.1413.0833"0803,5123.1483.280

3.27 43 "0923,1123.3413.2353.169

3.2113.0633.09s3.3743.1483,218

3,1773.0903"091? ¿nq

3.1753,217

3.2063.1013.10s3.4703.1993.2s3

-rQ-r(2-r(1

TTT

3"0823 . 05'12.993

3.1083. 0602.998

3. 1403.0392.999

3.0943.0153.087

3.1033.0s13.054

omN i1

2

3

4

5

al CompositionsScandium pargasite: NaCazMg+ScSi eAlzOz z (OH)

z

Fiuor-pargasite: NaCa2MgaÀ1Si 6À1 202 2F2Chromium-fluor-pargasite: NaCa zMg4CrSi 6A1 202 2F 2

Gallium-f luor-pargasite: NaCa 2MgaGaSi oÀ1 zOz zF z

Scandium-f luor-pargasite ¡ NaCa zMg¿ScSi 6À1 202 2F2

1s9

B. AIkali emphiboles

(6) 0) (8)

r(1)-0(1r(1)-0(5r(1)-0(6r(1)-0(7

r(2)-0(2r(2)-0(4r(2)-0(5r(2)-0(6

M(1)-0(1M(1 )-0(2M(1)-0(3

1 .6131 ,5821 ,6s11.6i5

1 .5491.6171 .5881 ,607

1.7121.5741 .7241 ,626

<T ( .1 )-0>

<M( 3 )-0>

1 ,615 1 .590 '1 .6s9

<T(2)-0>

<M( 1 )-0>

<M(2)-0>

x2x2x2

x4x2

1,610 1.605 1.s98

1 .5951 .539r.bbl

'1 .643

'1 .5991.5221 .6341 .666

1 ,6461.5711.5811 .595

2 "0792.0392.057

2.1172.0492 "024

2,0422.0952.047

2.1802 .1082"033

2.2722,0911.OBB

1 .099l. t552.073

2, 0s8 2,063 2,061

x2x2x2

M(2 )-0 ( 1

M,2)-oQM(2)-0(4

x2x2x2x2

2,107 2,150 2.109

3)-0(1)3)-0(3)

M

M

M

M

M

M

2 .1122,038

2.1302.023

2,1302.001

2"087 2.084 2,087

4)-oQ)4)-0(4)4)-0(5)4)-0(6)

2.5032 "3442.9652"555

2.5122.3572.9822,595

2,5182.3662.8962.565

<M(4)-0> 2,592 2,612 2,586

160

(8)

(1)-M(1)( 1 )-M(2 )( 1 )-M(3 )( 1 )-M(4 )(2)-M(3)(2)-M(4)

M

M

M

M

M

M

TTT

3.2153,1373.0963.3623.2933.133

3 .1493.1573.0793.4043.2953.136

3.1613.1623. 1033 .4913.2733.219

1

1

I

-r(2_TQ-r(1

3.0853.0283,024

3,0793.0243.033

3.1242.9983.066

Nomi n(6)(7)(8)

aI CompositionsScandium-f luor-eckermannite¡ NaNazMg¿ScSi sOzzF z

Indium-fluor-eckermannite: NaNazMg¿InSi s0z zFzScandi um-f luor-nyböi te : NaNa 2Mg 3Sc zSi zÀ10 z zF z

TÀBLE 21

Typical Àmphibole Tetrahedral Bond Lengthsf

Min Max Mean

TTTT

(

(

(

(

îQ) -oQr(2)-0(4r(2)-0(5r( 2 ) -0(6

1)-0(1)1)-0(s)1)-0(6)1)-0(7)

'1 .580'1 .6'1 31 .5501 .590

1 .6901 "7301.7101,670

1 .638'1 . 6611.6521.637

<T('1 )-0>

<T(2)-0>

1.610 1.681 1.64'l

1 .6081 .5721.s801 .600

1 ,7201 .6501.6761.704

1.633'1 . 6011,6431.659

1,620 1.670 1,634

fCalculated from data in Appendix D,Hawthorne (1983b).

(6) (7)

Chapter VI

DISCUSSION ÀND CONCTUSIONS

The discussion embraces three majcr themes:

What was learned from a critical evaluation of previous amphibole

syntheses and how detailed characterization of these amphiboles,

when accomplished, clearly demonstrates the need for such analy-

ses as a routine part of A_11 synthesis experiments.

I.lhat was learned f rom amphibole syntheses during this study, par-

ticularly the importance of sophisticated characterization of run

products.

General conclusions about synthetic amphibofes, especially cation

ordering, and how synthetic amphiboles differ significantly from

natural amphiboles. The need for caution in applying the results

of amphibole synthesis experiments to natural amphibole is empha-

s i zed.

PREVIOUS AMPHIBOTE SYNTHESES

Calc ic Àmph i boles

Tremol i te

All tremolite syntheses have been difficutt, requiring runs from several

hundred to over a thousand hours. In spite of these lengthy runs, many

with intermediate regrinding of charges, yields are generally poor, be-

tween 50 and 85-95 percent. Six synthetic tremolites have been charac*

1

2

J

161

162

terized by celI dimensions (Table 5, No. 1,2,3,4,5 and 6). 0f these,

No. 5, grown by Westrich (1978), is suspect, having a and c parameters

much higher and lower respectively, than the others. Although yields

are variable, the ceI1 dimensions are remarkably similar and bracket

those of natural tremolite characterized by Papike et al. (1969) (rabte

22). The nalural amphibole was characterized by single-crystal struc-

TABTE 22

Comparison of synthetic and natural tremolite cell dimensions

21

9.801 -9.83318 .054-'18. 075.268-5.284

1 04.35-1 04.70904.6-905.8

1. Natural tremolite, Papike et a1. (1969)2, Synthetic tremolite, range from Table 5

ture refinement and is close to ideal tremolite in composition.

Tro1l and Gilbert lglZ) argued that their tremolite was "on composi-

tion" for three reasons:

With the tremolite bulk composition, the only possible solid so-

lution component is nagnesio-anthophyllite/magnesio-cummingto-

nite, EMgTSisOzz(OH)r, nith ce]l volume 1756 A3 for the synthetic

endmember (Greenwood 1963). Solutions containing magnesio-anÈho-

phyllite should trend towards lower volumes because one*haIf the

ab

Dt)

v

e.818(s)18.047(8)5.275 ( 3 )

104.66(s)904.2 ( 6 )

1

163

cel1 volume of magnesio-anthophyl-lite is only 878 Å3 compared to

the average of 905"6 Å3 for tremolites grown in these experi-

ments. Because thís cell volume is comparable to those of other

tremolite synLheses, Troll and Gilbert conclude that their syn-

thetic tremolite is "nearly" stoichiometric.

The proportions of the breakdown phases remain nearly constant

whether an amphibole is present or not.

Published analyses of natural tremolites at the time of the study

(Table 5, Troll and Gilbert (972)), show no evidence of solution

towa rds ma gnes i o-anthophyl 1 i te/ma gne s i o-c ummi n gton i te .

Troll and Gilbert (1972) point out that the analysis of this natural

tremolite shows no evidence of solid solution towards magnesio-antho-

phyllite,/magnesio-cummingtonite. However, it has an excess of 0.08 oc-

tahedral cations and a deficiency of Ca (1.86) (napike et al. 1969). Àt

least minor solid solution towards magnesio-anthophyllite/magnesio-cum-

mingtonite is suggested. This reinforces the argument of Jenkins (1981)

that synthetic tremolite may be non-stoichiometric, having a Ca,/(Ca+t"tg)

ratio of about 0.88. Furthermore, N. Chatterjee (pers. comm, 1971 lo

Wones and Dodge) concluded that tremolite synthesized at 750oC contains

5 to 10 mole percent EMgzSiaOzz(OH)2. Goldman and Rossman (977 ) and

Goldman (979) present evidence from electronic absorption and Mössbauer

spectroscopy for Fe2* in the M(4) site of calcic amphiboLes; by analogy,

Mg could also occupy the M(4) site in tremolite.

It is likely that stoichiometric trenolite has never been synthes-

ized, and the possibility of magnesio-anthophyllite/magnesio-cummingto*

nite component in synthetic tremolite is än experimental difficulty that

2

3

164

has not been adequately resolved. Although synthetic tremolite run

products are very fine-grained and cannot be readily characterized by

electron microprobe or single-crystaf structure analysis, it is essen-

tial that this synthesis problem is overcome in future tremolite stud-

ies; these techniques are the only ones presently available to determine

M(4) site-occupancies in tremolite.

Ferro-actinolite

Ferro-actinolite provides an ideal example of

tal chemical characterization. Ernst ( 1 966)

actinolite to be on composition because:

the value of proper crys-

considers synthetic ferro-

1, Phases of anhydrous condensed assemblages for the ferro-actinol-

ite bulk composition are present in the same relative propor-

tions, regardless of amphibole yields.

2. Optical and X-ray properties do not depend on the amphibole

y i eld.

3. Mean indices of refraction and ß cell angles indicate that the

syntheLic ferro-actinolite does not represent solid solution with

gruner i te .

These arguments for nominal composition are similar to those advanced by

Troll and Gilbert (972) in their tremolite study, and indeed, by most

other synthesis studies. That these arguments are inadequate rvas shown

by Burns and Greaves f971) who examined the Mössbauer spectrum of one

of these ferro-actinolites (rigure i9). If the amphibole were of the

nominal composition, the spectrum should consist of three Fe2* doublets

wíth intensity ratios 2 2221, eorresponding to Fe2* at M('1 ), M(2) and

165

¡

YltOClfY (mm./¡rc.)

F i gure 19: Mössbauer sErnst ( 1 956

pec).

trum of synthetic ferro-actinolite grown bySpectrum fron Burns and Greaves (1971),

166

M(3) respectively. This is not the case. Burns and Greaves (1971 ) pro-

pose that the doublet with the smallest quadrupole splitting is due to

Fe2* at u(4); this assignment is supported by electron absorption spec-

tra examined by Goldman and Rossman (1977), The remaining doublets are

assigned to Fe2* at M(1) and at M(2)+¡¡(3). These results show that fer-

ro-actinolite grown by Ernst (1966) is off composition and contains some

grunerite component in solid solution.

Àctinolite

Cameron f975) apparently synthesized actinolite midway on the tremol-

ite...ferro-actinolite join. The run product contained minor magnesio-

cummingtonite, clinopyroxene and quartz, but the ceI1 volume (¡lo. 1, Ta-

ble 7) of 921.9(7) Å3 is essentially identical to that calculated from

average synthetic tremolite and ferro-actinolite ß21.8 Å3) in Table 5.

The amount of magnesio-cummingtonite solid solution, if any, could not

be determined from the relatively imprecise electron microprobe analyses

given. In view of the probability of magnesio-anthophyllite/magnesio-

cummingtonite solid solution in synthetic tremolite, demonstrated grun-

erite solid solution in ferro-actinolite and the cel1 volume exactly

half-way between the endmembers with solid solution, this actinolite

probably contains cummingtonite in solid solution as we11. Mössbauer,

infrared and electronic absorption spectra would have been invaluable

here lo investigate the occupancies of the M(i-3) sites, and especially

lhe M(4) sile.

167

FIuor-t remol i te

Fluor-tremolite apparently grows readily, compared lo tremolite, and

most studies report yields of 95 to 100 percent in isothermal runs.

Grain size is generally large enough for single-crystal structure analy-

sis, particularly in non-isothermal experiments, where crystals up to 4

mm in length have been grown (Comeforo and Kohn 1954). Cameron (971)

and Cameron and Gibbs (1973) refined the crystal structure of fluor-tre-

molite from a run with greater than 95 percent amphibole. The cell di-

mensions of this fluor-tremolite are essentially identical to those of

other studies (tab1e 6) except for Westrich (1978). It was pointed out

in Chapter 2 that fluor-amphiboles grown in his study with HF in the mix

give anomalous results and should be disregarded. The average cell vol-

ume of fluor-Lremolite (898.i Â3), calculated from the data in Table 6

is 7.2 Å3 less than that of tremolite (905.3 A3).

UnIike hydroxy-tremolite, fluor-tremolite grows readily with high

yields, either in the solid state or from melts. Furthermore, the large

crystals would be ideal for highly-precise single crystal structure re-

finement wiLh the bulk-composition restrained by electron microprobe

analysis of the crystal used to collect the X-ray dala. Unfortunately,

the existing structure refinement (Cameron 1971, Cameron and Gibbs 1973)

used assumed cation site-populations, and lhus the possibility of magne-

sio-anthophyJ.lite/magnesio-cummingtonite solid solution vras not re-

solved.

168

Eden i tes

Although edenite synLhesis was claimed by Boyd ('1954), neither his ede-

nite nor any subsequent synthetic amphibole of this composition has been

adequately documented. Edenite synthesized by Colville et aI. (1966)

has a c celI dimension that is not reasonable for any amphibole. Fur-

thermore, the cell volume is lower than that expected for edenite. Col-

ville et aI. (1966) aLso synthesized ferro-edenite and give cell dimen-

sions; the cell volume is 33 Å3 larger than the volume of their edenite.

One of these sets of data must be wrong. In the absence of other data,

it is not possible to evaluate the validity of these results. Hinri-

chsen and Schürmann (1977 ) claim "unequivocalJ-y" edenites synthesized in

the range Naroo to NasoK¡0. The ce1I dimensions of their endmember ede-

nite meet expectations based on the parameters of tremolite and parga-

site, but definitive characterization is lacking. Greenwood's (1979)

exhaustive attempts to synthesize edenite trom a variety of starting ma-

terials nret with failure, as did experiments in this study. In view of

these results, âDy amphiboles synthesized on the edenite composition in

the future must be characterized in detail.

Fluor-eden i te

Kohn and Comeforo ('1955) give the only cell dimensions of fluor-edenite,

determined on a run product that was beneficiated with respect to amphi-

bole. The chemical analysis of this amphibole (plus 1-2 percent contam-

inants) shows it to contain Na in the M(4) site and octahedrat À1; thus,

it is off composition. The cell volume is 6,2 A3 less than that of ede-

nite grown by Hinrichsen and Schürmann (1977l,. It is unlikely that pure

fluor-edenite has been synthesized.

169

Pargasite

Àlthough about a dozen, comprehensive studies of the physical. properties

and phase relations of pargasite and ferro-pargasite have been completed

in the past 30 years, surprisingly, none have characterized these amphi-

boles except by optics and cell parameter refinement. Semet (1972,

1973), however, examined the infrared spectrum of pargasite in his study

of magnesio-hastingsite and showed that Mg and Àl were completely disor-

dered among the M(1), M(2) and M(3) sites. No cell dimensions were giv-

en. All pargasite studies generally give consistent results. The fif-

teen sets of ceII dimensions (raUle S) vary only between about 0.2 and

0.6 percent. Oba (1980) gave electron-microprobe analyses of coexisting

amphibo).es on the join tremolite-pargasite but neglected the endmembers.

Hinrichsen and Schúrmann 11977 ) claim !o have synthesized pargasite with

haLf of the A-site Na repJ-aced by K. The ceII volume of lhis amphibole

(tabte Z) is about 5 Å3 greater than that of pargasite. Differences in

ce11 volume between arnphiboles with A-sites completely filled with ei-

ther Na or K are in the range I to .1 2 A3 , which supports Hinrichsen and

Schürmann's (977 ) claim. There is no direct evidence to support any

claim of pure pargasite synthesis. It seems that most pargasite

syntheses have yielded amphibole close to pargasite in composition, buL

the presence of both octahedral and tetrahedral À1 requires careful doc-

umentation of their distribution.

Fluor-pa rgas i te

In contrast to abundant pargasite syntheses, there are only three stud-

ies of endmember fluor-pargasite. of these, one (westrich 1978, West-

rich and Navrotsky 1981) reports cel1 dimensions. Note that the differ-

170

ence in cell volume between fl-uor-pargasite and pargasite is only about

4 Å3, in marked contrast to all other hydroxy-/fluor-amphibole pairs,

which differ by about 7 lo 1'1 Å3. This fact is puzzling and requires

careful documentation of the actual composition of synthetic amphiboles

claimed to be fluor-pargasite, to determine whether this is a fundamen-

tal crystal chemical property of pargasite...fluor-pargasite or simply a

reflection of deviation from nominal composition during synthesis.

Ferro-pargasite

Charles (1974a, 1980) synLhesized pargasites across the join pargasiLe -

ferro-pargasite at oxygen fugacities defined by the IW, CCHa, FMQ and MH

buffers. There are sone problems with the results of this study, which

are probably related to changes in Lhe oxidation state of iron. Charles

(1980) states that for a given bulk composition, ce1I parameters do not

change within 2-sigma wiLh changes in oxygen fugacity. Data Lo support

this claim are given for amphiboles grown on the CCH¡ and FMQ buffers.

Inspection of cell dimensions in his Table 3, however, shows ranges in

cell volume of 4.7, 5.8 and 4.1 Å3 for the MgsFe, M92Fe2 and MgFe3 com-

positions respectively. These are outside the 2-sigma range, even for

the few volumes with high standard errors. There is no definite trend

in volume with oxygen fugacity, but surprisingly, volunes are generally

higher at higher oxygen fugacities. This is contrary to the expected

trend to lower volumes as ferrous iron is oxidized to smaller ferric

iron. Charles (1980) states that the ceII dimensions do not vary with

amphibole yield down to about 60 percent; however, amphiboles from 50

percent runs differ from high-yield runs up to about 5 Å3" Cell dimen-

sions of ferro-pargasites synlhesized on FMQ and CCHa buffers are essen-

171

tially identical and are also very similar to those of Gilbert (1966)

grolrn on the IW buffer" Charles (1980) concludes that Mg and Fez* are

disordered among the M('1), M(2) and M(3) sites because cell dimensions

vary linearly with composition.

Gilbert (1966) noted that the cell volume of ferro-pargasíte de-

creased with increasing oxygen fugacity and suggested that this trend

reflected the oxidation of octahedral Fe2* to Fe3*. He proposes that

this reaction could be accounted for either by solid solution towards

hastingsite or by the formation of oxyamphiboJ.e. 0f the four sets of

celI dimensions given in his study (tab1e 5), No. 39 is probably the

best; the other samples contain Fe3*. No.'s 43,44, and 45 are refine-

ments of X-ray powder data (Gilbert 1966, Table 2) done during this

study of ferro-pargasites grov¡n on the IW, WM and FMQ buffers respec-

tively. Cell volumes from these refinements are about 2 A3 less than

those of comparable samples refined by Gilbert (1966). The reason for

this discrepancy is not known, but since the differences are consistent-

ly towards smaller cell dimensions for refinements in the present study,

differences between internal standards are the probable cause.

These two studies on the pargasite...ferro-pargasite join serve to

underline the problems created by not characterizing synthetic amphi-

boles of complex compositon, par!icularly if cations of variable oxida-

tion state are present. Àlthough the conclusions of these studies, es-

pecially with respect to the broader aspects of stability relations, are

probably va1id, the crystal chemical implications are obscure in the ab-

sence of further characterization. Spectroscopic methods, combined with

either Rietveld or single-erystal strueture refinement, would provide

direct evidence

reasoning about

and obviate

the nature of

172

the need for circuitous crystal chemical

the octahedral and M(4) site-occupancies.

Pargasite-richterite

Braue and Seck (1977) studied the pargasite-richterite join with the in-

teresting result that ce11 dirnension variation between the two endmem-

bers show positive deviations from linearity. The deviations cannot be

explained on the basis of cation sizes and site occupancies, especially

as synthetic pargasite infrared spectra (Semet 1972, 1973¡ this study)

show that Mg and Al are randomly distributed among the octahedral sites.

Rietveld structure analyses of the intermediate compositions could re-

veal any structural reasons for these trends.

Hastingsite

Hastingsites synthesed by Thomas (977, 1979, 1982a, 1982b) were charac-

terized by Mössbauer spectroscopy and are ideal examples of the value of

detailed run-product characterization. Thomas f972, 1982b) collected

57Fe Mössbauer spectra for six of the products. He assumes that because

the hastingsites are close to nominal composition, the M('1), M(2) and

M(3) sites are entirely filled with iron and the M(4) site has little or

no iron, Four doublets are assigned to the spectra, three for oclahe-

dral ferrous iron and one for octahedral ferric iron (nigure 20). Thom-

as (1982b) shows that observed fractional areas of the three ferrous

doublets are inconsistent with predicted completely ordered (all Fe3* in

M(2) ), completely disordered (Fe3* over M( 1,2,3)l , or indeed, witl¡ in-

termediate configurations (table 23). In spite of the anomalous area

fractions in these spectra, the total ferrous intensity is well account-

173

v

202 Mössbauer spectrum of synthetic hastingsite grown on the WM

buffer. Note that the AÀ', BB', CC' and DD' peakintensities depart from the ideal ratios 22121t1. FronThomas (1982).

2

¿

f¡J(J2É&othÊa

t-2f¡'¡Uf¡¡À

F i gure

174

ed for by the three ferrous doublets, and te3*/(Fe2*+Fe3*) ratios were

calculated from the ratios of the ferrous doublet areas to those of the

ferric doublets (taUte Z¡). Hastingsites crystal-lized on the I0F, IW

and WM buffers carry considerably less than the 20 percent Fe3* of lhe

ideal formula; the two samples (ME339, M8340) crystallized on the IW

buffer and then annealed on the FMQ buffer are close Lo 20 percent. Ta-

ble 23 shows that the Fe3*/Fe2* ratio is a function of oxygen fugacity.

This is also clearly reflected in Lhe cell dimensions of these samples;

cell volumes of hastingsites synlhesized on the IW and iQF buffers are 2

to 5 Å3 larger than those grown or annealed on more oxidizing buffers.

Note that this range is comparable to the range in volumes of amphiboles

grown on the pargasite...ferro-pargasite join by Charles (1974a, 1980)

who claimed that similar volume differences did not reflect changes with

oxygen fugacity. Àn alternate peak assignment of two ferrous doublets

and one ferric doublet was statistically not as good as the four doublet

fit. However, the inner ferrous doublet has a constant area fraction of

about 0.20, a value consistent þ¡ith all Fe&b38e. ordered into the M(2)

site. The results of this study show the value of detailed characteri-

zation, particularly when cations of variable oxidation state are in-

volved. It is unfortunate that infrared spectra were not collected;

these could have substantiated the assertion that Fe3* is ordered into

M(2).

Magnesi o-hast ings i te

Semet (1970, 1972, 1973) and Semet and Ernst (1981) characterized syn-

thetic magnesio-hastingsite with both Mössbauer and infrared spectrosco-

py. Four-doublet fits to Méssbauer speetra (nigure 2'1) of magnesio-has-

175

TABLE 23

Idea] and observed area fractions for synthetic hastingsites

Sample

IdeaJ area

Orderedl

fractions

Di sordered 2

Observed areafractions

0.10.10.10.10.1

2

.18

.18

.18

3

.28

.28

.28

1

0.40 0

0.40 0

0.40 0

0.40 0

0.40 0

0"40 0

2

.20 0

.20 0

.20 0

.20 0

.20 0

.20 0

4

0,120,120,120.190.220,12

1

0.3s 0

0.35 0

0.35 0

0.32 0

0.31 0

0.3s 0

3

0. 350. 350.350,320.310. 3s

4

0.12u.l¿0.120.190.220,12

1

0. 540. 500.480.490.420.47

2

0.230.260.270.220.260. 28

4

0.120.120,120.190,220.12

3

0.11M1322( rQr ) 3

MH321 ( r}l)MF323 (I^lM)

M8339 ( 4 )

M8340(lW)4F193 (liM)

.21

.18

.28

. tb

.16

.18

3

3

0

1

3

(from Thomas 1982b)

lThe four columns refer to Fe2*zThe four columns refer to Fe2*Fe3 * in all- sites.

3Buffer used during run.4Synthesized on IWi annealed on

1nin

M

M

3

3

M

M

anan

d M(2),d M(2),

and Fe3* in M(2).and the sum of

IQF.

tingsites synthesized on the most-oxidizing buffers show that the major

contribution of Fe3* to Lhe total absorption is by the M(2) site; only

minor unresolved absorption of Fe3* is attributed to Fe3* in the M(1)

and M(3) sites. Two remaíning doublets are assigned to Fe2*: an unre-

solved absorption from Fe2* in the M(1) and M(3) sites and another from

Fe2* in the M(2) site. Area ratios of these peaks differ markedly from

those calculated for random distribution of either Fe2* or Fe3* in the

octahedral sites. Fe3* strongly prefers the M(2) site, whereas Fe2*

prefers M(1) and M(3). Octahedral site occupancies of these synthetic

magnesio-hastingsites as determined from the Mössbauer data are summa-

rized in Table 24. NoLe that on the most oxidizing buffer (Cr), only

Fe3* is present, but on the CCO buffer, significant Fe2* is present.

176

The percentage of Fe3* varies from about 13 percent on the IQF buffer Lo

100 percent on the CT buffer. Thus, the rut*/Fez* ratio is a function

of oxygen fugacity, and the synthetic magnesio-hastingsites are signifi-

canLly off-composition at fower oxygen fugacities.

Infrared spectra of synthetic magnesio-hastingsite show two major

peaks and several minor ones (rigure 3). The spectrum of amphibole

grolrn on the CT buffer has two major peaks, one at 3705 cm-1 (tugUgt'lg-Ott)

and the other at 3660 cm-1 (ugugne3*-oH)i on the IQF buffer, the lower

energy peak is shif ted to 3675 cm-1 (t'tgugnez*-OH). Minor peaks in both

spectra between 362.1 and 3645 cm-1 probably represent (l¿gFe2rFez*-oH),

(ugne2*Fe3*-oH) and (tugne3*Fe3*-oH) groups. Evidence from infrared

spectra of pargasites synthesized in the present study (see Chapter 5)

with transition metals substituted for octahedral À1, suggests that some

octahedral À1 is generally present. The rough bulge at about 3670 cm-1

in the spectrum of magnesio-hastingsite synthesized on the CT buffer

(nigure 3) may also reflect the presence of minor amounLs of Àl in the

M(1) and M(3) sites. Ratios of peak areas representing occupancies of

Mg, Fez* and Fes* in the M('1) and M(3) sites compare favourably with the

ratios calculated from the Mössbauer spectra.

These results clearly show the necessity of detailed characterization

of complex synthetic amphiboles. Mössbauer spectra show that only mag-

nesio-hastingsite grown on the CT buffer contains no Fe2*, and thus, is

probabl-y close to the nominal composition. In addition, the strong

preference of Fe3* for the M(2) site is c1ear. Infrared spectra suppor!

the Mössbauer data and point to the possibility of A1 in M(1) and M(3)

sites.

17'l

¡.00

90

Þt!N

JCE

=Go1¡¿JÞCEE(.fz.

zOL)

-t 0VELOCITY

ItN t{11l5EC

¡,E

Ëltô,É.

Figure 21: Mössbauer spectra of synthetic magnesio-hastingsites grownon the CT and CCO buffers. A: CT buffer, no Fe2* present.B: CCO buffer, considerable Fe2* present. From Semet(1e73).

I

III

I¡II

IIII

A

\Êþcilv ¡n mm/sêcrelotiui lo rrt Fe57

A

B

178

0ctahedral site occupancies

TÀBLE 24

in synthetic magnesio-hastingsites fromMössbauer data

BufferM(1),M(3)

Fe2*Mg Fe3*M(2 )

Fe2* Fe3*Mg

I9F(av. )

cc0CTIQF to CTCT to iQF

0,790.870.850.780 .84

0. 070.1s0.22

0 .810.700.730.830.73

0.070.270.270.170.'17

0,210.06

0.120,03

0,16 0. 09

Miscellaneous cafcic amphiboles

Other calcic amphibole synLhesis studies are few in number and generally

lack detailed characterization (see Chapter 2). Oba (1978) attempted to

characterize amphiboles on the alumino-tschermakite - ferri-tschermakite

join by electron micropobe analysis. Unfortunately, only certain amphi-

boles in equilibrium with garnet were analysed; these are not on compo-

sition. Cell dimensions (table 5) are given for endmember tschermakite

and ferri-tschermakite, as well as for certain intermediate composi-

tions. Yields of 100 percent are claimed for many of these, but no sup-

porting evidence is given.

The paucily of other calcic amphibole studies probably reflecÈs the

experimental intractibility of these amphiboles with vacant À-sites. It

was noted above that tremolite grows only with difficulty, requiring

long run times and intermediate regrinding and rerunning of products.

Other calcic amphiboles with vacant ¡-sites either are stable at only

very high pressures or apparently groyr exlremely s1owly.

179

Sodic-calc ic amphiboles

Richterite, ferro-richterite, fluor-richterite

Both richterite and fluor-richterite synthesize very readiJ.y and all

studies report close to 100 percent yields. CeLl dimensions of al-L

richterites and fluor-richterites are closely consistent between differ-

ent studies with two exceptions. Richterite (Ho. 78, Table 5) and

fluor-richterite (Ho. , Tab1e 6) synthesized by Westrich (1978) are

markedly different. Certain other amphiboles grovrn in this study have

been shown also to have anomalous properties; apparently there are ex-

perimental problems with these syntheses and the results should be used

with caution. In addition, the cell dimensions of richterite (no. 80,

Table 5) given by Phillips and Rowbotham (1968) are apparently in error.

Refinement of their powder X-ray data during the presenl study gave re-

sults (¡¡o.81, Table 5) consisLent with others. CeI1 parameters vary in

an acceptably linear way for compositions on the join richterite and

ferro-richterite (Huebner and Papike 1970), suggesting that the amphi-

boles are very close to the nominal compositions. Potassium-ferro-

richterite grown on the CCH¡ buffer in the same study, however, probably

contains Fe3* and is, therefore, not on composition.

Although it seems that richterites synthesize readily on the nominal

composition, infrared spectra of lhese amphiboles show otherwise. Row-

botham and Farmer (1973) exanined the infrared spectrum of richterite

grown by Phillíps and Rowbotham (1968), and observed that instead of a

single band corresponding lo the MgMgMg configuration, an additional

peak was present (figure 22). This peak corresponds lo the tremoliLe

MgMgMg configuration, which is well developed in the spectrun of lhe

Figure 22:

180

Infrared spectra of richterite, potassiun richterite andsolid solution of richterite in tremolite. À: solidsolution of richterite in tremolite. B: richterite. C:potassium-richteriÈe. Note the weak tremolite peaks aE 3672óm-1 in the richterite and potassium-richterite spectra.From Rowbotham and Farmer (1973).

(oct

o¡(rl

ANaR 25TR 75

Noc1 B

NaR!1m

(\l(ocl

cKR

'1 81

richteritezs - tremolitez s solid solution (nigure 22). Rowbotham and

Farmer (i973) conclude that the richterite is deficient in A-site ca-

tions. They aLso examined the infrared spectrum of potassium-richterite

(rigure 22) provided by (and apparently synthesized by) B. velde. The

spectrum consists of a major band at 3734 cm-lwhich was assigned to the

MgMgMg configuration. In addition to this normal band, however, an ad-

ditional weak band at 3672 cff-1 , corresponding to tremolite solid solu-

tion, indicates Lhat the amphibole deviates from the nominal composi-

tion.

Mössbauer spectra (virgo 1972) demonstrate that Fe3* (nigure 23) is

present in alI of the Fe-bearing richterites grown by Charles (1972a,

b) . The ferro-richterite with the large ceIl but low yield (rype I )

that is closest to the extrapolated trends of all the cell parameters

contains about 5 percent Fe3*; the other (Type II) with smaller cell but

higher yield contains about 10 percent Fe3*. This is surprising in

light of the fact that these amphiboles were grovrn on the IW buffer.

Sing1e-crystaJ. structure analysis of Fe-bearing fluor-richterite with

Mgrl(ug+r'e)=0.58 (electron microprobe analysis) shows that Fe2* prefers

M(2) relative to M(1 ) and M(3), and that the Fe/Mg ratios in M(1) and

M(3) are similar (Cameron 1970, Cameron and Gibbs 1971'). Charge balance

considerations are given as evidence for little or no Fe3* (Cameron

1970) " Cel1 contents caLculated from the analysis indicate a deficiency

of Ca relative to the ideal formula and an excess of octahedral cationsi

excess Fe is assigned to the M(4) site. Because the amphibole yield was

less than 100 percent, it would have been instructive to know lhe nomi-

nal composition (not given) and to compare it to the actual composition

as determined by electron microprobe.

182

-.02r

ót5

a a6

t6

.0

dl

-.80 .00 .80

VELOCITY

I

2.10 320

mm/sec

a

r.ó0

.2

z9ùÉoØ!o

t-zzoØl¡JÉ

35.¡ ü

J¿Id

1

¿

ò

t

I

5

295

375

I

I

-¡ o0 -3.20 -2.rO -ló0 ¡.00

Figure 23: Mössbauer spectrum of synthetíc ferro-richterite grown on

the IW buffãr. Note the presence of Fe3*. From virgo(1972).

183

À1ka1i amphi boles

Glaucophane

The results of glaucophane synthesis by Ernst (1957, '1958, 1959, 1961,

1963) and the subsequent attempLs to explain them provide an outstanding

case study of the need for detailed characterizalion of synthetic amphi-

boles. Ernst (1961) assumes that the amphibole grorln is glaucophane be-

cause:

Long runs yield more amphibole than short runs.

Relative proportions, deduced by comparison with X-ray standards

and by micrometric analyses, of metastable phases in the amphi-

bole stabiiity field are unaffected by the amount of amphibole

present and are in the same proportion at temperatures in excess

of the amphibole stability fie1d.

Refractive indices and d-spacings of the amphibole show no meas-

urable variation with the amount obtained and are independent of

the starting material.

Ernst (1963) proposed that glaucophane occurs as two polymorphs: one

with large volume - glaucophane I, the other with small volume - glauco-

phane II. Ernst reached this conclusion because amphibole grown from

glaucophane bulk composilion at Iow pressure has a unit cell volume more

than Lwo percent greater than that of natural glaucophane, while that

grovrn at high pressure has volume comparable to natural glaucophane. He

was puzzled by the lack of difference in optical properties of the as-

sumed polymorphs: glaucophane I has o=1.595, ß= 1.620, extinction angle

10o; glaucophane II has a=1.596, ß =1,620, extinction angle 10o. Ac-

cording to the Gladstone-Dale relationship, the denser polymorph should

1

2

3

184

that of glauco-have a mean

phane I, if

index of refraction about 0.013 greater than

Lhe cornpositions are identical.

Infrared spectra of Lhree synthetic amphiboles of nominally glauco-

phane composition were collected on material generously supplied by W.G.

Ernst (nigure 24). CeII dimensions and synthesis conditions of these

samples are given in Tab1e 6). The spectrum of "glaucophane I " (Figure

24C, sample GM-1, Ernst 1963) is similar to that of sodian magnesio-cum-

mingtonite (nigure 10C), as are its cell dimensions (¡lo. 90 and 95, Ta-

b1e 5). Comparison of the spectrum of GM-1 to the natural ferro-glauco-

phane spectrum (nigure 24D), shows clearly that this amphibole cannot be

glaucophane. This confirms the proposal of Maresch (1973 , 1977 ) ttrat

"glaucophane I" is "magnesiorichterite" (sodian magnesio-cummingtonite)

and not a 1ow-pressure, high-temperature polymorph of glaucophane. Fur-

thermore, it supports the contention of Carman (1969) who argued that

"glaucophane I" is a persodic amphibole remote from the glaucophane com-

position. It also argues against the suggestion that "glaucophane I" is

an amphibole near nyböite ("miyashiroite") and eckermannite (Thompson

'1981, Carman and Gilbert 1983). Thonpson (1981 ) does point out, how-

ever, that a sodian magnesio-cummingtonite component cannot be ruled out

ent i rely .

The spectra of samples GC-2 and GC-1 (nigures 24À and B, Nos. .1'12 and

110 in Table 5) are of poor quality, but it is obvious that these amphi-

boles also cannoÈ be endmember glaucophane (cf. natural ferro-glauco-

phane, Figure 24D) " Both spectra comprise two distinct groups of bands;

one is centered at about 3664 cn-1, the other is near 3723 cm-1. The

band at 3664 cm-lcorresponds exactly to the MgMgMg configuration in the

185

A

B

Dc

.r ir.o .: iq rr 3'/ zo : )oo 368o -lÉi6o :l6ti tl-

-rÄla-- ið'rro ìÈsthf'ì VFNUI'1Btr PS

Fiqure 24: Comparison of infrared spectra of synthetic and natural;iñ;;;h;;"t. À¡ svnth;tic glaucophane I¡ (Gc-2' ErnstÌ;Ëãi."ì;--;tnli¡etiå slaucopñane Ii (Gc-1' nrnst 1963)'

C: synthetic alaucophane í (cv-j, Ernst 1963) ' p: nâturalfãrro-9tauèophane (Piednont, Italy)'

185

natural gl-aucophane and it is likely that it is the same in the synthet-

ic amphiboles. The other band group is very poorly resolved, but itrepresents a frequency shift of about +59 cflì-1, placing it in the fre-

quency range of amphiboles with full Na-occupancy in the A-site. These

specLra suggest that the samples, both designated as "glaucophane II" by

Ernst (1963), are probably amphiboles intermediate in composition be-

tween glaucophane and eckermannite, or perhaps nyböite. Indeed, their

cell dinensions are very similar to those of nyböites grown by Carman

and Gilbert (1983). The interpretation of these three infrared spectra

establishes r,rithout doubt that neither "glaucophane I" nor "glaucophane

II" can be endmember glaucophane and contributes substantially to the

case for routine characterization of all synthetic amphiboles with spec-

troscopic methods.

Riebeckites

In contrast to the glaucophane studies, riebeckite syntheses (Ernst

1962) seem to have been reasonably successful. The infrared spectrum

(r'igure 25) of riebeckite (sample HR-54-8, Ernst'1962, No. 131 in Table

5 ) consists of a single, sharp band at 3618 cm-1and a very weak band

at about 3673 cm-1. The origin of the weak band at 3673 cm-'muy be due

to mÌnor Na-occupancy in the À-site, indicating minor solid solution to-

wards eckermannite. It would have been instructive to see if this peak

increases in intensity in the riebeckite-arfvedsonitic amphiboles. Band

width of the 3618 cm-1 peak ís between 6 to 7 cm-t which is rernarkably

narrow for synthetic amphibole. It is not clear whether or not the rnain

band is solely due to an Fe2*Fe2*Fe2* component, or whether or not there

are additional components due to configurations involving Fe3*, as there

is no definitive evidence on the relative effecLs of Fe2* and Fe3*.

't87

A

B

BO3 603 tro 3 ?o3 003 803 603 qo 3 -n:¿LJ J

l^lÊVENUIlBERS

Figure 25: Infrared spectra of synthetic riebeckite and magnesio-riebeckite. À: riebãckite (Hn-s¿-e, Ernst 1962). B:magnesio-riebeckite (n-10'1 , Ernst 1960 ) .

a o0

188

Magnesio-riebeckites

Magnesio-riebeckite syntheses (Ernst 1960) apparently failed to grorv am-

phiboles on Lhis composition. The infrared spectrum (nigure 25) of nrag-

nesio-riebeckite (sample R-10'1, Ernst 1960, No. 129 ín Tab1e 5) is of

poor quality, but it is obvious that this amphibole cannot be of the

nominal composition. Bands al 3667 cffi-1, 3549 cm-1 and 3629 cn- 1 were

assigned to the MgMgMg, MgMgFe3* and MgFe3*Fe3* configurations respec-

tively, after Bancroft and Burns (1969). The band at 3655 cm-1may be

due to the configuration MgMgFe2*. The poorly resolved, complex group

of bands around 3724 cn- I is probabJ-y the result of frequency shifts

caused by Na-occupancy of the À-site, indicating substantial solid solu-

tion towards magnesio-arfvedsonite. Thus, the amphibole is off-composi-

tion.

Ec kermann i te

It is unlikely that eckermannite has been synthesized. Ce11 dimensions

(rabte S) of the amphibole grorvn by Phillips and Rowbotham (1968), Íe-

gardless of which set is correct (see Chapler 2), are more like those of

sodian magnesio-cummingtonite. Attempts in the present study to grow

eckermannite under similar conditions to Phillips and Rowbotharn (1968)

grew amphiboles with infrared spectra similar to sodian magnesio-cum-

mingtonite (r'igure 10).

Nybói te

The results of Carman and Gilbert (1983), who claim nyböite synthesis,

are difficult to evaluate. The high-pressure, vapour deficient stabili-

ty and the ce1l dimensions are consistent with amphibole of this compo-

189

sition, but further characterization is necessary. Furthermore, one of

the two amphiboles with published cell dimensions vlas grown from start-

ing maLerial of glaucophane composition.

I ron-magnes i um-manganese amph i boles

Sodian magnesio-cummingtoni tes

Amphibole syntheses based on the sodian magnesio-cummingtonite commposi-

tion and equivalent fluor-amphiboles have been popular, but relatively

little characterization of the nature of these amþhiboles has been done

(see Chapter 2). This is surprising because existing information

strongly suggests that the structure is not Cz/n. T,titte et aI. (1969)

examined the infrared spectrum of sodian hydro-magnesio-cummingtonite;

it shows a band at 842 cm-lthat is absent from the spectrum of sodian

magnesio-cummingtonite. They propose that this band corresponds to the

Si-O-H bending frequency in SiOH groups. À portion of this spectrum be-

tween 3600 and 3800 cm-1 is shown in Maresch and Langer (976) along

with the spectrum of sodian magnesio-cummingtonite (nigure 26), They

suggest that the additional 0H can only substitute for oxygen at the

o(1), o(2) or O(4) sites, thus forming SiOH groups. Because 0(4) is

highly underbonded relative to O('1) and O(2), they conclude that 0(4) is

the likely site for the additional OH. The infrared spectrum (figure

26) displays an extra O-H stretching band at 3727 cn-lwhich they attri-

bute to OH-valence vibratíons in SiOH groups.

The spectrum of sodian magnesio-cummingtonite has two well resolved

bands. The presence of two MgMgMg-OH stretching bands suggests that so-

dian magnesio-cummingtonite crystallizes in a space group other than

'1 90

C2/n. It is not likety that the splitting of the MgMgMg-OH stretching

band is due to chain-width disorder because the relative areas of the

bands are always similar in both the specimens synthesized in this study

and in those synthesized by others. If one of the bands were due to a

chain-width modification phase, variation in chain-width disorder with

different synthesis conditions should cause changes in the relative band

areas. Furthermore, precession photographs of sodian magnesio-cumming-

tonite (Hawthorne 1984, pers. comm.) show reflections with h+k=2n+'1 sug-

gesting that it is primitive, rather than C-centered.

191

A

3800 3700

wavenumbers

3600

Figure 26: Infrared spectra of sodian magnesio-cummingtonite and sodianhydro-magnesio-cummingtonite À: sodian magnesio-cummingtonite. B: sodian hydro-nragnesio-cunmingtonite.From Máresch and Langer (1976r,

192

ÀMPHIBOIE SINTHEÊ]-å: THIS STUÐI

Calcic Àmphiboles

TremoI i tes

Attempts in this study to grow tremolite confirm the difficulties ex-

perienced by previous workers. Substitution of Ni for Mg yielded more

encouraging results, but lack of appreciable amphibole yields reflect

the general reluctance of A-site empty calcic amphiboles to crystallize.

Cd substitution for Ca failed also, as it did for pargasite and richter-

ite. It seems both from previous work and this study that synthesis of

pg trernolite-based endmembers, suitable for deLailed characterization,

is not possible with current techniques.

In contrast, fluor-tremolite grows fairly readily, but the optimistic

claims of previous workers of easy growth were not seen in this study.

More than 80 percent yields rì'ere never obtained, either isothermally or

in non-isothermal experiments. The large crystals grovrn in non-isother-

ma1 experinents, however, have the advantage of being suitable for de-

tailed characterization by any method and show promise for future stud-

ies. Cell dimensions (ta¡le lg) of fluor-tremolites grovrn in this study

are identical to high-qualily cel1 dimensions (rable 6) from other stud-

ies. This is remarkable, considering that yields are at least 20 per-

cent lower than those of some of the previous studies. Thus, it seems

that because of the simple composition of fluor-lremolite lack of 100

percent yields is not critical to achieving synthetic amphibole of êp-

parently nominal composition. There sti1l may be minor solid solution

towards magnesio-cummingtoniter âs noted in the previous sectíon, that

is not detected by celI variation.

193

Eden i tes

Àttempts to synthesize edenite suffered the same difficulties as in ear-

lier studies. In view of these problems, careful consideration of syn-

thetic products grown on this composition is advised. Fluor-edenite

grew with yields of 90 percent or more, and yielded amphibole with plau-

sible fluor-edenite celt dimensions. Fluor-edenite differs from fluor-

pargasite by J.acking octahedral À1 and having only one tetrahedral A1;

the M(4) and A site contents are the same. Thus,3, ß, and V should be

about the same in both amphiboles, b should be Larger and g smaller.

These predictions are supported by the cel1 dimensions of fluor-edenite

and fluor-pargasite synthesized in this study (ra¡te lg). The cell vol-

ume based on comparison of resuLts on edentite grown by Hinrichsen and

Schürmann (1966) is too small, but with the possibility of solid solu-

tion between tremolite and edenite, further characterization is re-

quired. Fluor-edenite ceI1 dimensions given by Kohn and Comeforo (1955)

(raUle 6) seem to be those of a more sodic amphibole with composition

between fluor-edenite and fluor-richLerite; note especially the lower ß

and higher V.

Pargasites

Much effort was expended on pargasite synthesis, not only because of the

apparent success of previous work, but also because this composition is

intrinsically interesting with respect to Al ordering in the tetrahedral

sites and M3* ordering in the octahedral sites. Endmember pargasite

synthesizes readily, but yíelds are never quite 100 percent. Cell di-

mensíons (table 13) are consistent r+ith previous studies (rable 5).

Substitution of Cr, Ga, Sc and In for ocÈahedral A1 reduced yields to

194

about 80 to 90 percent. Variation in cell volume with the radius of the

octahedral cation (nigure 27) did not give an acceptably Iinear trend,

indicating that complete substitution of Cr, Ga and Sc for Al in the oc-

tahedral strip did not occur (naudsepp et aI. 1982). This deviation

from the nominal conposition is well documented in the infrared spectra

of this series (Chapter 5), r+hich all showed MgMgÀI bands in addition to

Mg-M3* configurations. Site-occupancies (rable 19) from the Rietveld

structure refinement of the scandium-pargasite showed that the composi-

tion of the octahedral cations, in terms of Mg and Sc scattering, is

Mg¿. s sSco. o s. The octahedral Àl content therefore is about 0.35 cations

p.f.u. Furthermore, Sc has the ordering pattern M(2)>M(3) and avoids

M(1). Endmember pargasite shows completely random distribution of Mg

and AI over the octahedral sites from infrared spectrum analysis. 0r-

dering in the Ga and Cr pargasites has not been confirmed by structure

analysis but the infrared spectra suggest at least partial ordering.

Results of fluor-pargasite syntheses largely paral1el lhose of hy-

droxy-pargasites except for higher yields of the scandium-fluor-parga-

site compared to scandium-pargasite. Variation of cell volume with tri-valent octahedral cation radius is also not acceplably linear but is

improved over hydroxy-pargasites (rigure 28). The complete series of

Ga, Cr and Sc substitutions for octahedral À1 was characterized by Riet-

veld structure refinement to determine cation ordering among the octahe-

dral sites. Rietveld structure analysis is particularly useful for

fJ.uor-amphiboles because of the inapplicability of infrared spectroscopy

in the hydroxl-stretching region. Site-occupancies (tabte 1g) show that

chromium-fluor-pargasite and gallium-fluor-pargasite are def icient in Cr

'19s

^

920

910

PARGASITES

Cr Ga Fe

r3+ (Å

vcoo

900AI Sc

)

Figure 27: CelI volume versus radius of trivalent octahedral cations insynthetic pargasites. Solid circles are syntheticpãrgasites gròwn in this study; solid triangle is magnesio-hastingsite fron Semet 1972, 1973.

O

A

¡

r<v

196

FLUOR-PARGASITES920

910

AI Ga Cr

r3+ (Sc

Cell volume versus radius of trivalent octahedral cations insynthet ic f luor-pargasites.

900

)A

nìgure 28:

AV(Sc-Al)=25 A/

oo

t

and Ga respectivly, compared to the nominal composition,

dium-fluor-pargasite has nearly the ideal Sc-content.

M3* cations are almost completely ordered into M(2).

197

but that scan-

Furthermore, the

Sod i c:çalc i c A¡phi lqleg

Richterites

Syntheses of amphiboles based on the richterite composition confirmed

aIl aspects of previous studies. Richterites and fluor-richterites grow

readily and with yields usually greater than 95 percent. infrared spec-

tra of endmember richterites and Mn-bearing richterites (rigure 9)

showed limited, but definite, solid solution with tremolite for both the

Na and K endmembers, confirming the conclusions of Rowbotham and Farmer

(1973). In view of the confused sLate of Mn ordering information in am-

phiboles (Hawthorne 1983b), the infrared spectra of the Mn-bearing

richterites (figure 9) revealed the important result that Mn is appar-

ently completely ordered into the M(2) site. Hawthorne (976) and Haw-

thorne and Grundy (1978) attempted to derive Mn-site preferences in sod-

ic-calcic amphiboles on the basis of mean bond lengths at the M(1), M(2)

and M(3) sites. They observed the preference M(3)>M(1)=M(2), but their

results were highly speculative. These spectra also showed tremolite-

like peaks, indicating some solid solution towards tremolite.

Miscellaneous Sodic-calcic Amphiboles

Syntheses on other sodic-calcic amphibole compositions were generally

unsuccessful for the purpose of detailed characterization. These re-

sults paralleI, ât least in part, the lendency of A-site empty calcic

amphiboles !o be extremely difficult to synthesize at low pressures.

198

À1ka1 i Àmphi boles

Previous studies show most alkali amphiboles to have high-pressure sta-

bility fields and it is not surprising that attempts to grow nyböite

failed. Eckermannite syntheses were also disappointing. Infrared spec-

tra (nigure 10) of hydroxy-eckermannite and ce11 dimensions of fluor-

eckermannite (raUte g) clearly show that amphiboles similar to sodian

magnesio-cummingtonite were grown. It is unlikely that eckermannite

ever has been synthesized.

I ron-masnes i um-manganese Amphi boles

Sodian magnesio-cummi ngton ites

Synthesis results with this interesting composition paral1e1 those of

previous studies and emphasize the need for very detailed and careful

documentation of these amphiboles. Infrared spectra (nigure 10) show

clearly that there are aL least two different hydroxyl-stretching envi-

ronments. This confirms the previous speculations of Witte et al.(1969) and Maresch and Langer (1976). Furthermore, preliminary single-

crystal structure studies in progress (Hawthorne, unpublished data) con-

firm that the space group is not C2/n, but is primitive.

EVÀIUATION OF CHÀBÀEIE¡]¿ÀT]IN METHODS USED IN THIS STUDY

Optical Micrpsc_opy

Optical examination of synthesis products has been a routine part of

previous amphibole syntheses. In this study, all synthesis products

were routinely examined with both a low-power binocular microscope, and

at high power with a polarizing microscope. Low-power examination of

unopened capsules is critical in documenting Ieaks. In hydroxy-amphi-

199

boLe experiments, the vapour phase was generally between 5 lo 20 weight

percent of charges weighing 30 to 90 mg; leaks were readily detected by

weight loss during pre-experiment heating tests or during the experi-

ment. In fluor-amphibole syntheses, however, the vapour phase is only

about 4 percent of charges weighing between 20 to 40 mg; partial losses

through hairline cracks and defective welds are not easily detected even

with precise weighing. This problen is generally compounded by Pt loss

from the capsule during high-temperature runs. Examination of the

opened capsule interior reveals any evidence of reaction with the

charge, a rare occurence with Pt and Àu capsules and runs of the compo-

sition used. Low-power examination of the charge shovrs whether differ-

entiation occurred during the run and is important in documenLing the

generaJ. physical properties of the products (colour, morphology, grain-

size).

Àfter low-power examination, a representative portion of the product

is generalty crushed and nounted on a gl-ass slide with a suitable medium

for observation at high-power with a standard polarizing petrographic

microscope. This has been a standard characLerization techníque in sta-

bility studies, particularly in liquidus experiments, where it is neces-

sary to identify small amounts of glass or minor phases. Refractive in-

dices can be measured and modal anatysis of the run products is, in

principle, a possibilty.

Unfortunately these methods are inadequate as a practical characteri-

zation technique in the synlhesis of pure minerals for crysLal-chemical

characterization. Synthesis products are generally too fine-grained to

be ídentified optically and measurement of refractive indices is diffi-

200

cult, if not impossibte in some cases. Minor phases can be unambiguous-

ly identified only if their optical properties are significantly differ-

ent from the primary product; accurate modal analyses also are difficult

for this reason. Furthermore, standard optical lechniques are not fast

enough for rapid characterization of large numbers of products, as in

this study,

The difficulty in using optical methods in this type of study is well

illustrated by the problems in glaucophane synthesis by Ernst (1961,

1963). Although Ernst measured refractive indices and the products were

modally analysed, the amphiboles synLhesized in these studies were later

shown to be off-composition (Maresch 1977¡ this study). According to

the Gladstone-Dale rule the denser polymorph should have had a mean re-

fractive index approximately 0.013 greater than glaucophane I (Ernst

1963). Thus Ernst's interpretation of two glaucophane polymorphs of the

same composition but of different densities could not have been correct.

Optical methods in the present study were found to be of limited use in

product characterization. They are most valuable for deciding whether a

particular synthesis product is of sufficiently high yield and quality

for more detailed characterization.

Scanni¡g Electron

Scanning electron

terization of run

imaged with this

may be present in

detected in X-ray

Mi c rosc opy

microscopy has much potential in the initial charac-

products. Extremely fine-grained products are readily

technique and the presence of extraneous phases that

amounts too small or of inadequate crystallinity to be

powder diffraction patterns' are observable. Note the

201

abundant layer silicates mixed with fibrous amphibole in Figure 7D.

More ímportantly, Figure 68 (arrow) shows a few flakes of layer silicate

which were observed neither optically nor in the X-ray powder diffrac-

tion pattern. Inspection of other synthesis products in Figures 5, 6

and 7 also reveals traces of layer silicates, some of which were ob-

served in X-ray diffraction patterns but not optically.

Other silicates (pyroxenes, olivines, feldspars), although obviously

present in X-ray powder patterns, could not be positively identified in

scanning electron micrographs. Semi-quantitative energy dispersive

spectroscopic capability would have been invaluable in the idenLifica-

tion of these important phases.

X-rav Powder Diffraction

Conventional X-ray powder diffractometry continues to be important for

the identification of phases greater than a few percent, and in the

rough estimation of their abundances. In addition, precise ceIl dimen-

sions are readily calculated by least-squares refinement and the lattice

spacings of extraneous phases can be determined. The usefulness of this

method is decreased if synthesis phases are poorly crystalline (degraded

peak intensity and shape), if their abundances are less than 4 or 5 per-

cent, or if severe overlap of several phases occurs.

Infrared Spectroscopy

Infrared spectroscopy is a rapid and versatile technique in the charac*

terization of order-disorder in sythetic rninerals. Synthetic systems do

not contain large numbers of minor components and spectra are generally

202

simpler to interpret than natural ones. In amphibole studies, infrared

spectra in the hydroxyl-stretching region are the most important; order-

ing of M(1) and M(3) cations may be characterized with high sensitivity.

Furthermore, the 0-H stretching spectrum can reveal the presence of ex-

traneous phases conLaining the hydroxyl group such as layer silicates,

which are common in many run products. Deviations from nominal composi-

tion can also be revealed with sensitivity. For example, the common

presence of small peaks near 3673 cm-1 in the infrared spectra of syn-

thetic richterites (rigure 9) indicates a frequency shift in the MgMgMg-

0H stretching band to lower frequencies due to the presence of vacant

À-sites. Although infrared spectra in the 0-H stretching region should

be sensitive to chain-width and other local structural disorder, this

possibility was not pursued in this study.

Synthetic pargasite spectra illustrate the application of this method

to both problems of cation ordering and stoichiometry. It was shown in

Chapter 5 that endmember pargasite has an essentially random distribu-

tion of Mg and À1 over the M(1,2,3) sites. The spectra of pargasites

with M3+=Gâ¡ Cr and Sc all have shoulders corresponding to the MgMgÀl-OH

configuration showing that they are off-composition, containing minor

amounts of octahedral À1. Layer silicates in the chromium-pargasite run

product that were reflected in the X-ray diffraction pattern (raUte 1l)

are also evident in the infrared spectrum as fine-structure between 3674

cm-1 and 3710 cm-1. The presence of substantial MgMgM3*-0H configura-

tions in the spectra of Cr-, Ga- and Sc-substituted compositions sug-

gests that these pargasites are at least partially disordered.

203

EspecialJ.y important is t.he very small amount (Iess than 5 mg) of ma-

terial reguired. The sensitivity of infrared spectra to small varia-

tions in nominal compositions and the ability to detect order-disorder

phenomena in these amphiboles is clear evidence that this method should

be used routinely to characterize synthetic amphiboles.

Rietveld Crystal Structure Re f i nement

The Rietveld structure analysis method represents a significant advance

in the detailed characterization of amphibole synthesis products. A1-

though it has potential to refine the entire structure, problems in this

study during refinement h'ith certain highly-correlated positional param-

eters in the tetrahedral chaíns (see Chapter 5) tinited the method to

deriving accurate site-occupancies. The infrared spectrum of scandium-

pargasiLe showed that Sc was present in either the M(1) or M(3) sites,

or both; Rietveld analysis results showed that Sc-occupancy in the M(1)

site was negligible, it having the ordering pattern M(2)>M(3)>>M(1)-0.

Furthermore, the Rietveld results allowed the calculation of the defi-

ciency in Sc-occupancy (0.354) and therefore the amount of Àl-occupancy

in octahedral coodination (0.21) as suggested by the infrared spectrum.

The Rietveld method is particularly useful in characterizing fluor-am-

phiboles for which the infrared method in the o-H stretching region is

not applicable. Six of the seven fluor-amphibole structures refined

(No.'s 3-8, Table 14) in this study showed that these amphiboles have

partial to complete ordering of Mg and the M3*-cation in the octahedral

strip. No ordering information was derived for fluor-pargasite (Ho. 2,

Table 14) because there is insufficient con!rast in the scattering povr-

ers of Mg and 41.

204

In addition to the above, the Rietveld method has other advantages

over conventional X-ray powder diffractometry. Cell dimensions calcu-

lated during the refinement are up to an order of magnitude more precise

than those by least-squares methods based on measurement of peak cen-

troids in normal diffractometer scans. This improvement stems from the

fact that in the Rietveld refinement, the peak positions are calculated

from the whole peak profile, which takes into account any machine aber-

rations affecting its shape. In addition, the residuaL pattern from the

subtraction of the observed diffraction pattern from the calculated pat-

tern, contains the diffraction patterns of phases other than amphiboles.

In the whole pattern, scattering from these phases is often partly to

completely masked by the dominant amphibole pattern. Preliminary re-

sults with this method during the present study show that this technique

has considerable potential for detailed characterization of synthesis

products.

CONCTUSIONS

The present study has underlined the importance of detailed characteri-

zation of amphibole syntheses. Not only is it important to the crystal-

chemical study of pure endmembers, but is also critical for modelling of

petrologic systems, especially if thermodynamic properties are measured.

Furthermore, with the increasing availability of high-resolution trans-

mission electron microscopy, it is obvious already from preliminary work

that this lechnique must also be added in order to study chain disorder

and other defects.

are

205

In summary, the most salient conclusions resulting from this study

it is unLikely that a pu¡e amphibole endmember has ever been syn-

thesized either previousLy, or in this study.

Because virtually all synthetic amphiboles are off-composition,

they must be completely characterized before crystal-chemical or

petrologic ínterpretations are made.

The usefulness of infrared spectroscopy and the relatively recent

Rietveld powder structure method for detailed characterization

have been demonstrated in Lhis study. Although problems in the

refinement of chain silicates were not entirely overcome, the

site-occupancies h'ere invaluable in documenting ordering in

fLuor-amphiboles" The development of a better profile function

should lead to better results.

Because of the significant differences in cation ordering between

natural and synthetic amphiboles, and the possibility of chain-

width dísorder, high densities of stacking faults or other struc-

tural disorder, this study has emphasized the importance of de-

tailed characterization in documenting these differences. This

is critical in appLying the results of synthesis and stability

studies to natural amphiboles; the interpretation is usually not

simply one of analogy, but of contrast.

2

J

4

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Popp, R.K., Gilbert, M.C. and Craig¡ J.R. (977b1 ¡ Stability of Fe-Mgamphiboles with respect to sulfur fugacity. Àmer. Mineral. 52,1 3-30.

Ravior, E. and Hinrichsen, Th. (1975): Upper stability of syntheticanthophyllite mixed crystals. N. Jb. Miner. Mh. , 1975, 162-166,

t.tô

A.J. ( 1 970) ¡ Stability of porassicYear Book 68, 231-233.

222

Romanov, D.P., Koval-ev, G.I. and Grigor'eva, L.F. (1973): X-rayinvestigation and identification of sythetic fibrous amphibole.Rentgenograf iya Mineral'nogo Syr'ya, No. 9 , 32-37 ,

Saito, H. ('1952): Hydrothermal treatment of synthetic asbestos. i.Treatment of Lhe ystem 2NaF.CaO.3Mg0,Fez0¡'8Si0z. J. Chem. Soc.Japan, Ind. Chem. Sect. 55, 415-417,

Saito, H. (1952): Suitable proportion of raw material for syntheticasbestos. I. Suitable range of alkali oxide. J. Chem. Soc. Japan,Ind. Chem. Sect. 55, 703-705.

Saito, H" (1953): Hydrothermal treatments of synthetic asbestos. II.Treatments of crystals without calcium oxide. J. Chem. Soc. Japan,Ind. Chem. Sect. 56, 235-236,

Saito, H. (1953): Suitable proportion of raw material- for syntheticasbestos. II. SuiLable amount range of fluoride. J. Chem. Soc.Japan, Ind. Chem. Sect. 56, 585-587.

Saito, H. (195a): Hydrothermal treatment of synthetic asbestos. vII.Investigation of Lhe composition range of fusing mixture byvolatilization of fluorine. J. Chem. Soc. Japan, Ind. Chem. Sect.57 , 488-490.

Saito, H. (1954): Synthesis of asbestos of the amphibole group. J.Japan. Chem. 8, 626-635.

Saito, H. (1956): Influence of reduction of ferric oxide in syntheticfluor-amphibole on crystallinity. Kogyo Kagaku Zasshi 59,1309-1312.

Saito, H. (1963): Isomorphic substitution of fluor-richterite. KogyoKagaku Zasshi 66, 18-21 .

Saito, H. and Àmemiya, Y. (1961)¡ Separation of crystals from syntheticfluor-arfvedsonite mass by hydrothermal treatment. Kogyo KagakuZasshi 64 , 1 54'1-1 543.

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223

Saito, H. and Yamai, I. (1968): Synthetic fluorine-containing asbestos.XXIII. Synthesis of fluorine-containing asbestos in the vapour phase.Kogyo Kagaku Zasshi 71, 824-827,

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224

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Àppendix À

RIETVELD STRUCTURE ÀNÀLYSIS PROGRÀM DESCRIPTION

The basic DBt.t 2.9 progran of tliles and Young (1981) was slight).y modi-

fied to convert intensities collected with an automatic divergence slit

to corresponding fixed-slit intensities using lhe reLationship (etritips

Operating Manual: Automatic Divergence Slit pwl 386/50),

r f=[d rc.20268)ta /tsin ( 1 1 .1 60+0.8778eo ) -0.1 9355]

where If=intensity for fixed slit,

slit and d=divergence of fixed slitIa=intensity measured with automatic

( in degrees).

This program performs Rietveld (1961, 1969) analysis on x-ray powder

diffraction data collected on a B-20 diffractometer operated in step

scanning mode. It features single-pass operation and built-in direct

applicability with all space groups and with all atoms for which the re-

quired scattering factors are Listed in the I nter tional Tab1es for

x-ray Crvstalloqraphv (1974) as coefficients of an exponential. series

generating the X-ray scattering factors, plus anomalous scattering cor-

rections as appropriate.

The Newton-Raphson method is used to minimize the quantity

U = T*, lr, (o)-yr (c) I 2

where y¿ (o) is the

fraction pattern,

by

intensity observed at the

y¿ (c) is that calculated,

ith step in the powder dif-

and the weight w¿ is given

-225-

226

wi = 1/(y¿ +y¿¡ )

where y¿6 is the background intensity at the ith step.

The cal.culated counts y, (c) are determined by summing the contribu-

tions from neighbouring Bragg reflections plus the background as

y¿ (c ) = Slpn LK I F,( | 2c {ae, n ) nn *y,6 (c )

where S is a scale factor, L*=Lorenz and poLarization factors for the

Kth Bragg reflection, FK=SIructure factorr P*=multipJ.icity factor,

P*=preferred orientation function (currently only for platy habit as

exp(ea2) where P*is the ref inable parameter and o is the acute angJ.e

between the scattering vector and the normal to the crystailite), 0¿x is

the the Bragg angle for the Kth reflection, K=h,k,J,, the indices identi-

fying the Bragg reflection for which each of the above is evaLuated, and

G(40¿K )=G(20¿ -2eK) is the reflection profile function g(40¿¡1 ) multiplied

by an asymmetry function a(Ae¿6) given by

a (40¿n ) =1 -[À( signA0¡x ) ( 2ae ix) 2/tan06

The background model may be obtained from the function

y¿6 (c)=Bo+3r (20) +Bz(28) 2+B¡ (2e) 3+B¡ (20)a+Bs (2e) 5

or from an operater-supplied table of background intensities, or from

linear interpolation between operator--selected points in the pattern.

Current.ly availabl.e prof ile functions

d¡ .- atn 2(2€- 2o*)' Gau.slan d-ÆH* -li- ;^n-

*1 ì/[t+c, 1ze'-zo*)')' l{od I Lorentzlôn qI_'K -Hil- 2 Hr

include

l7t+c, (20.,-20*)'?-Hi.-

I 7.[ t+C, (2er- 20*)'? ì''s

T---

lôrentzlàn

Hod ? Lorentzlan

where H is the fuli-width at

and C14(223-1).

221

hal.f-maximum, C.=41n2, Ct=4, C:=4(212-1)

H is approximated by

H2=Utan20 +VtanQ +W

where U,V and W are constants for a particular X-ray pattern

Three quantitative criteria of calculated to observed pattern fit are

given ("R-factors"):

Rg

¡ I I("obsl) - l(calc) |

¡ t('obs')

Rp

r I Y.i(obs) - (l/c).Y1(càlc) I

r vr(obs)

I r,. f Y',(obs) - (l/c) v',(catc) I 2

l@t/2

RHp

(n-p) t/2R

exP r w., I Yr(obs) I

Of these, the R"rp is the most important for following the progress of a

refinement because its numerator is the quantity being minimized. In

the R-Bragg expression, the symbol "I(obs)" is placed in quotation marks

because it is not actua).ly observed" It is calculated by allocating the

actually observed intensities l¿ (o) to Bragg intensities, "I(obs)", ol-l

the basis of the calculated intensities I (c) after Rietveld (1969). In

the expression for Rexp, n is the number of observations and p

number of variable paraneLers during refinement.

228

is the

The following parameLers can be refined simultaneously in the least-

squares ref inement:

1. lattice

2. atom posLions (x,y,z)

3. isotropic or anisotropic Lemperature

4, atomic site occupancy

5. profile U,V,W and asymmetry

6. preferred orientation

7, background function

8. 2ê-zero correction

9. overal scale (one for each phase)

i0. overall istropic t.emperature factor

factors

Required input information includes

initial values of all variable parameters

step-scan data in equal increments in 20

20 Iimits and excluded regions in the data

wavelengths

background spec i f ication

space group symbol

chemical symbol and valence of each atom

number of phases

profile function choice

1

¿

3

4

5

6

7

I9

229

profile cut-off (in units of H )

preferred orientaLion vector for each phase

termination control: either number of cycles or 'Eps' value in

which case the run terminates when the shifts <Eps. for all pa-

rameters.

relaxation factors for the shifts (separately specified for four

different groups of parameters)

output controls

10.

11.

I .'tt¿.

13.

The output includes identifiers of the refinement conditions and

subject so that a given run can be reconstructed unambiguously

adjustable-parameter final values, last shift, and standard devi-

ations

R-weighted pattern, R-pattern, R-Bragg and 'expected' R-weighLed

pattern

The following user selected printouts are available

reflection list for each phase

corrected dat,a 1ist, with w values

observed and calculated intensities

correlation matrix

I i ne-pr i nter pJ-ot

off-line plot (".g. CalComp or Versatec)

I

¿

3

¿

3

4

5

6

Appendix B

RiETVEID STRUCTURE ANATYSIS INPUT DATA

OBSERVED INTENSITIES

This appendix contains t,he observed intensities used as input for Riet-

veld structure analysis. The figures in brackets after the amphibole

name are the starting 20 value, step size in o2 0, and final 20 value.

Entries in the table read across, in the input format 8(F7.0,1X).

226225232215210257239258232249259229235246285261318286355455536764

'1 0961260

750520473523665799

12982101'10s4

22224623920326021719721322423224624224426027927332735035s467546735

1 '1s8

1207669488470527646874

1 4431 984889

Scandium-pargasite (8.00, 0.01, 72.00)217 192 213 239 253234 234 236 207 236222 228 22'1 234 217204 253 242 224 238222 230 220 212 241226 235 234 229 231222 223 198 207 240238 222 249 235 200255 23"1 260 233 255231 243 225 221 244229 240 253 238 257235 231 240 265 270224 231 258 259 259248 258 244 267 258283 262 303 254 279317 286 300 288 276318 317 301 316 333370 351 339 334 368347 427 416 398 396468 480 488 511 546607 605 588 64s 6777'16 833 904 901 957

1178 1243 1242 1220 129511'13 1093 '1034 933 862623 594 576 578 51 I471 507 500 459 484474 472 478 482 51 6

580 540 547 565 583650 691 703 710 773922 953 1018 1109 1178

1 535 1 584 1 685 1 858 18921 945 1 857 1664 1484 1424741 668 589 51 3 496

236199221225220198220244¿¿ba1)LJ¿

2572562852602602823'1 0

363444507701939

1292809537453503561835

116120671 184

441

-230-

231

382298261276243219238235230259224257214233227215221216239220207249224245250225225222247210235221224231201208¿¿>2292363022322s8215230244242232236253263239213233245278

373252¿53236277232228250226252226223226206214207236205227245205228218230209221242219259234251226244271215238¿l>262206245239216233227247248221231236235213264213250253

388277306265253243211267234250236258242250241228219219256222224'185

215221227¿3ba1É.

240214¿3¿239219243209235235209245213239251'198

222210228233245273222217204216231214232

334284247244233)2724027024122524023923221419',7

227252245240254220216229252218228216250221205247245209236240260217231233248254227216239246248230243248249220233235238244

318272270237247236214217217262234251246242244254237230239229245238230241234199240229232253232221227220228224¿¿ö231252230236247242228239222239224253240229246221234235

321300264222245244246255258242222255245250232209237234208245221215243251230243238231239246275240211237246233¿+t¿s6239217226216222244237224220253247250¿¿¿232223221240

290260259261244239235230246245254229221215255212224236228234220234222256231263261263241260242241265233207239¿¿*2332562402402082082022442s3222238236217227235247246226

318273268258240212277203247255255237220225224217¿5¿241238222219209237224211251228231227244233217241238213219ô1Ê¿JJ

212217241204210213234245250247204209231253242227245235

232

23724121122523824623424924222023724023426022726423324423726823623426224228528s299307369515574402349333329392557

'1002

1 8591328

558382369362384336292242293272275255285333370

254242250224224242232221230207238231244237232243221230254228223213260236238273274313414541585370321298338406555

11111 843'1 1'1 5

50s3813353863693'1 3

28630128928729126s3'1 5

329387

248250242244240242227227227260280253240245243225226251220244243279249220255254265311401573550441329315376448665

117I18181019

472367355390352317254289276273260296302316369

257230245250232243¿¿5222242235224208¿3t2s8227238256235237¿b¿240264255240240257298326378589s3338230s322370455661

1 345'1780

8804723533743653623012732802722792632s6280307407

221228230237266270233247247218230237264218246224230273267203251278234258230290291310426579492373315322372471747

146417 48806459326321389358289256248244261265249272335429

22224124622523622421122522724423224522923522223124623525426523922626026826224530s328444596475364304319357482768

'1 5941 647

7384403733573413403'1 3

257299284279291288309341464

256270228241243216?)g2292282432692342662492502342642612242642382002662322562512723344775 5'1

448370294341395503910

1 6361527

664397329359378314281¿5¿264279251267279314360452

2332432432252172762312602402522342332452182312592712552322302342482402542612552463824975904443 5'1

31934139753s

102116641 346

621392360375387329288257273282282260277325332486

233

s061 0011 98620641159

6443603593¿t28227128324934937732329333139355255936432231727631130s290304365372379450607763735892900632512609883

1 455'1535

976518362312302325275291312321313

537117 821061987

97750s4053653182752452772933283773493423323875245744122983'1 0

285290290286293336410369470597795718972925609508633964

1 s381525885478365318277313309286284320303

584124022011 83394350836936729328725427629233640333331532442657952739133032930630529131633s3393s8412433617730778878890601504659

i 00115291520857456391321328319283303326317298

3261263224617 18

827472349340298301298¿t3291366375288309314418s36575353269291303306283288294352374346465673741800

1014818s6ss10653

1 0551 5951 404738436354293347324297304298334332

6941 37522941 5407864543933572902892992733013483353172783634855845013572972743073012922903073643463995317026908149998'145'11473680

117 9

17 131286

6704 5'1

34430830030332s287302333342

7071 s3623651 417

67047838334229927428726528538034129531336445762547036'1

303287284267295289309357371420559684771865995765s39553719

120716'181239

628399330310306289281263299308349

8251 68923061293

6804353993172932852452683173543112823073605215694393273052972633023123123453453944435417707108729'13709489s09783

132416121143bt5360317284318267283269308300332

89'71 805217 01 188

6453803483'1 5

3072872863'l I3183503222873343705'14570462349275¿63282313281337298344387446573755717876907627543s63860

1 3s31 6301 081

5593363173032793032883352903'1 1

348

234

368371398348308299298321308317304288J tð33330332929631437939s4134665r5s09487s305947139s6

1 60031'156467830649112235116787s742856

1 633399768753¿t¿26411224

649604575559498545674827

11271 638

341426402320283270302327312302288305307288282303323302347366459525522526465525629694943

17 31

33877 001830s47 9721571138

723772913

1 89444 50688 s50242268'1080

649579571570508584686871

117 6177 0

3204053833113393013192903012963133242763333073s1313325335390439504469498484554621795

1 053171138 317 49977 15421'7191s1 034786754942

1947498769574631207 6

9226525725435394995777159'13

12441 869

364390353301318302300333268303301310311320309306325342388420486527499496502542643749

1 0801 98842367 917736337861 68s1 039775I0'1

1012222453 57578342481 8568455535595s0543s3s577692941

12232101

3624173532882983212923373023043223123362873113283163783374264714905'145045215s3608841

1 1772054477 080'12695634 681618994763804

1116248757 43666537841 695

833579612610530522598735

101413'192206

3854'1 3

348308289292282306322299304293323302302314339351379420478466s30475485556672892

120823394 9888302643630981 437946713846

1260284361 04637735721 537

848593613553533s19592731995

137 62404

391384364316281258272285267292314304297320330345332355348422455488475507556576657882

1 353249856778207583328811375857779809

135231 5863 93597231791 41175356'1

630584490514624839

1 1091 5062611

36338531s30'7275308318345303268297312300332345327341358367414497494483535498s6166690'1

1 38828796098I 364549625091297

867776872

142235s06541567 627841 306

70557''Ì554554524528561752

107 7

1 5842915

235

3 0487 0240336594424091 088

780611559597789

1 398265022241145

689594631624911

11411 186

90s817

1230231 44692807 27 13740331795

92072',1

804748674560679807

1432297934673051343328 51

19271 188

9409129s9

1328253250 9458933920

344 381 34

1 00s6534'121381 028

787686614593785

'1609

259421291 069

6926536036768s3

12061175

891817

12722453507 68037687 036081 56'1

821767768687667577659917

157 43052337 0309 1

331 5278417961247972929994

147 32695560958 39380 1

38 6684 53941 648 57'1853

1 033723617621638834

1 699272519979356306126486419s6

1182117 6886852

'1408

283256 34I 56764383257'1453

772715703706651s90677920

1 666325432'7 6

31 0s329327 01

1 69811 469148s8981

1 556310257 1753643645

41 539121917 3440 3

17 43927727548601578

10261 84827 181782877671623640721910

11391094896921

1 43028426017844 0602228961 396

767770718704588599704

10281879331 I333231 99331 425071624'1 069

916897

1 0881687332358 5051 863602

47879694I 5633822154791s6966s3562531986

199226991 640

864636588592737992

11501 003896936

1 631322865408250s60 5

2570I ¿5¿733702786717s92606719

114221903305323531 173327242715241032

911899

118517 663667604251 053 280

5299'10044

790 0340 1

147 6

838662572558673

1i 0922302738'1498

762650646636804

101312181012863933

17 22358370387963527 1

2338110679474176866960860s780

1 0982300337 1

323633 07320424131 4271 034889899

121418973927620348363123

58 5810292716929901294

839676622563648

1 183235024731 420746683667631744

1 0491273

944876994

1929392672857732473021911 00377978072569763'1

621783

1 331243735273077326131 0821601 30s

91984993s

12382060438 56046459531 30

640710269670527781170

824642611542715

1324250124151227

711658619500812

'1087

1212982862

1 0962052428577307 4304250201 01005

6907947056446076s6832

1 341277534433067333s303620s2127 6

970915985

1222223547 40598742243240

236

331 4439842923552497 59247096i8374503228361 6461128924818715676666652690749

10231 551335466427B 08578833602019153518s842210 281284777 642860'1 3481 050857966

1 0451236172020121 460

827s39516659

1 0331 4131107765s80647938

337 4463542183 s6'1

527397 62

'10902

803047 032 5901 5981013874766696687660710702788

1 0081 64538057 08277 06545932041 850'1488

197 6481 3

1 08981247 1

681 1

268912411 030

943972

1 00112211 8861 96512947515'1 6

562692

11 41'1380

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ÀMPHIBOLE END-MEMBER NAMES ÀND

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FoRÌ.fuLÀE, LEÀKE ( 1 978 )

Trlt SODIC-CAtClC At',lPHI80LtSi tilO HttlEER NAHESAND €ilo I{EI{8ER FORHULAE

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fomuìa

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