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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
REFERENCES
Àpp1eman, D.E. and Evans, H"T. (1973): Job 9214: Indexing and least-sguares refinement of powder diffraction data. Natl. Tech. Inf.Serv., U.S. Dept. Commer., Springfield, Virginia, Document PB 2161 88.
Bancroft, G.M. and Burns, R.G. (1969): Mössbauer and absorptionspectral study of alkali amphiboles. Mineral. Soc. Amer. Spec. Pap.2, 137-148.
Borg, I.Y. (1967)z Optical properties and cell parameters in theglaucophane - riebeckite series. Cont,r. Mineral. Petrol. 15, 67-92,
Boyd, F"R. (195a): Àmphiboles. Carnegie Inst. Wash. Year Book 53,108-111.
Boyd, F.R. (1955): Àmphiboles. Carnegie Inst. Wash. Year Book 54,'11s-119.
Boyd, F.R. (1956): Àmphiboles. Carnegie Inst. llash. Year Book 55,1 98-200.
Boyd, F.R. (1959): Hydrothermal investigationResearches in Geochemistry (p.H. AbeIson, e
New York.
sod. )
f amphiboles. In. John Wiley and Sons,
Braue, W. and Seck,solid solutions a130,19-32.
H.A.t'1
(1977) z Stability of pargasite-richteritekb water vapor pressure. N. Jb. Miner. Abh.
Burns, R.G. and Greaves, C.J. (i971): Correlations of infrared and andMössbauer site population measuremenLs of actinoliLes. Amer.Mineral. 56, 2010-2033.
Cameron, K.L. ,11971\¿ Amphibole phase relations along the joinMgs.sFeg.sSiaOzz(Ou) r - Ca zl4gz.sFez.sSisOzz(0H) z. Carnegie Inst.Wash. Year Book 70, 145-'150.
Cameron, K.L. ('1975): Àn experimental study of actinolite-cummingtonitephase relations with notes on the synthesis of Fe-rich anthophyllite.Àmer. Mineral. 60, 375-390.
Cameron, M. (1970): The crystal chemistry of tremolite and richterite.À study of selected anion and cation substitutions' Ph.D.Dissertation, Virginia Polytechnic Institute and State University,BIacksburg, VÀ.
-206-
Cameron, M. and Gibbs, G.V. (197'1 ): Ref inementof two synthetic fluor-richterites. Carnegie70, 150-153.
20i
of the crystal structureInst. Wash. Year Book
Cameron, M. and Gibbs, G.V. (1973): The crystal structure and bondingof fluor-tremol-ite: a comparison with hydroxyl tremolite. Àmer.Mineral. 58, 879-888.
Cameron, M., Sueno, S., Prewitt, C.T. and Papike, J.J. (1973a): High-temperature crystal chemistry of K-fluor-richterite. Am. Geophys.Union Trans. 54, 497-498 (abstr. ).
Cameron, M., Sueno, S., Prewitt, C.T. and Papike, J.J. (1973b): High-temperature crystal chemistry of Na-fluor-richterite. Àm. Geophys.Union Trans. 54, 1230 (abstr. ).
Cameron, M., Sueno, S., Papike, J.J. and Prewitt, C.T. (1983): Hightemperature crystal chemistry of K and Na fluor-richterites. Amer.Mi neral . 68 , 924-943 ,
Carman, J.H. (1969): The study of the system NaÀlSi0q-M92Si04-Si0z-Hz0from 200 to 5000 bars and 800oc to 1100oC and its petrologicapplications. Ph.D. thesis, The Pennsylvania State University.
Carman, J.H, (97a)z Preliminary data on the P-T stability of syntheticglaucophane. Àm. Geophys. Union Trans. 55, 48'1.
Carman, J.H. and Gilbert, M.C. (1983): Experimental studies onglaucophane stability. Amer. J. Sci. 283-A , 414-431 .
Charles, R.W. 1972a)z Phase equilibria of the richterite end membersNa2CaMgsSieOzz(Oti) z and NazCaFesSieOzz(Ou) z. Carnegie Inst. Wash.Year Book 71, 506-510.
CharIes, R.W. (972b)z Physical properties of synthetic richterites.Carnegie Inst. Wash, Year Book 71, 510-513.
Charles, R.W. (1974a): Amphiboles on the join pargasite-ferropargasite.Trans. Àmer. Geophys. Union 55, 480.
Charles, R.W. (197ab): The physical properties of the Mg-Ferichterites. Àmer. Mineral. 59, 518-528.
Charles, R.W. (1975): The phase equilibria of richterite andferrorichterite. Amer. Mineral. 60, 367-374.
Charles, R.I't. (977)t The phase equilibria of intermediate compositionson the pseudobinary NazCaMgsSieOzz(oH), - NazCaFesSia0zz(0H) z. Àmer.J. Sci. 277, 594-625,
Charles, R.I.l. (1978): Synthesis and stability of hastingsite:CazNaFel*FesoSioÀ1z0zz(0H) z. Àm. Geophys. Union Trans. 59, 1217,
CharIes, R.}l. (1980): Amphiboles on lhe join pargasite-ferropargasite.Amer. Mineral. 55, 996-1001.
208
CoIvi11e, P.À., Ernst, W.G. and Gilbert, M.C. (1966): Relationshipsbetween ce11 parameters and chemical compositions of monoclinicamphiboJ.es. Àmer. Mineral. 51, 1727-1754,
Comeforo, J.E. and Kohn, J.A. (1954): Synthetic amphiboleinvestigations, I: Study of synthetic fluor-trenrolite. Àmer.Mineral. 39, 537-548.
Deer, W.4., Howie, R.A. and zussman, J. ('1963): Rock Forming Mineralsv,2, Chain Silicates. Longman, Green and Co., London, 379 p.
Drits, V.4., Goncharov, Yu.I., Àleksandrova, V.4., Khadzi, V.E. andDmitrik, A.L. (197a)z New type of strip silicate. Sov. Phys.Crystallogr. 19, 737-741.
Drits, V.À., Goncharov, Yu.I. and Khadzi, v.E. (1976): Usloviyaobrazovaniya i f iziko-kimichyeskiye svoystva tryekhryadnogolyentochnogo silikata s radikalom ISis0ru Àkad. Nauk SSSR' 1sv.,Ser. Geol. 7, 32-41 .
Droll, K. and Seck, H"À. (1976): Das system pargasit - fluorpargasitbei Ptotal = '1 kb. Fortschr . Miner . 54, 16.
Edgar, A.D. (1973): Experimental Petrology. Clarendon Press, 0xford,217p.
Ehrenberg, H. 1932)t Uber die synthese von diopsid und forsterit durchreaktion zwischen festen ausgangsstoffen und einen vergeblichenversuch der tremolite-darstel1ung. Centr. Mineral. Geol. À, 129-139,
Eitel, I,r. (1952): Synthesis of fluor-silicates of the mica andamphibole group. Proc. Internat. Symp. on the Reactivity of SoIids,Gothenburg, Sweden, 333-345.
Ernst, W.G. (1957): Àlkali amphiboles. Carnegie Inst. Wash. Year Book56,228-230.
Ernst, W.G. (1958a): Àlkali amphiboles. Carnegie Inst. Wash. Year Book57, 199-204,
Ernst, W.G. (i958b): Study of synthetic and naluraI magnesioriebeckite.Geol. Soc. Amer " , Bull. 69 , 1 56i .
Ernst, Ì'1.G. (1959); Alkali amphiboles. Carnegie Inst. Wash. Year Book58, 121-127.
Ernst, W.G. (1960): The stability relations of magnesioriebeckite.Geochin¡. Cosmochim. Acta. 19, 10-40.
Ernst, W.G. (1961): Stability relations of glaucophane. Amer" J. Sci.259, 735-765,
Ernst, W.G. (962)t Synthesis, stability relations, and occurrence ofriebeckite and riebeckite-arfvedsonite solid solutions. J. Geol. 70,689-736,
Ernst, W.G. ( 1963): Polymorphism in48, 241-260.
209
aIkaIi amphiboles. Àmer. Mineral.
Ernst, W.G. ( 1 966) : Synthesis and stability relations offerrotremolite. Amer. J. Sci. 254,37-65.
Eugster, H.P. ('1957): Heterogeneous reactions involving oxidation andreduction at high temperatures and pressures. J. Chem. Phys. 26,1760-1761,
Eugster, H.P., À1bee, À.L., Bence, 4.E., Thompson, J.B. and Waldbaum,D.R. (972'); The two-phase region and excess mixing properties ofparagonite-muscovite crystalline solutions. J. Petrol, 13, 147-179.
Fedoseev, À.0. and Chigareva, O.G. (1964): Synthetic fibrous fluorine-magnesium arfvedsonite. Àkad. Nauk SSSR Dokl. '156, 1130-1132.
Fedoseev, 4,D., Makarova, T.A. and Pivovarova, L.N. (1968a):Hydrothermal synthesis of fibrous nickel-containing amphibole andsome of its properties. Àkad. Nauk SSSR, Lzv,, Neorg. Mater. 4,796-797 .
Fedoseev, À.D., Makarova, T.4., Nesterchuk, N.I. and Sipovs(1968b): Die hydrothermalsynthese faserige amphibole ununtersuchung einiger ihrer eigenshaften. Kristal und Te95-'102.
ik
kii,ddichkn
D. P.
3,
Fedoseev, 4.D., Grigor'eva, L.F., Chigareva,(1970): Synthetic fibrous iluor-amphiboleÀmer. Mineral. 55, 854-863.
0.Gsa
. and Romanov, D.P.nd their properties.
Finger, L.W. (1969)factor calculatistrucLures. Geomanuscr ipL ) .
: RFINE. A Fortran IV computon and least-squares refinernephys. Lab. Carnegie InsL. Was
program for structureof crystal( unpubl i shed
ernth.
Forbes, W"C. ( 1 971 ) : Synthesis and stability relations of richterite,NazCaMgsSig0zz(0u) z. Àmer. Mineral. 56, 997-1004.
Gibbs, G.v. and Prewitt, C.T. ('1969): Àmphibole cation site disorder.In Int. Mineral. Àssoc. , Pap. Proc. , Fif th Gen, Ì'teet. (Cambridge,1966) " Mineralogical Society, London (abstr. ).
Gibbs, G.V", Mi11er, J.L. and She11, H.R. (962)z Synthelic fluor-magnesio-richterite. Àner. Mineral, 47, 75-82.
Gier, T.8", Cox, N.L. and young, H.S. (1964): The hydrothermalsynthesis of sodium amphiboles. Inorg. Chem. 3, 100'1-1004.
Gilbert., M.C. (1965): Synthesis and sLability relations of thehornblende, ferropargasite. Geo1. Soc. Àmer. Ànn. Mtg. Àbstr., MiamiBeach,72-73,
Gilbert, M.C. ('1966): Synthesis and stability relations of lhehornblende ferropargasite. Àmer. J. Sci. 264, 698-742,
210
Gilbert, M.C. (1969): Reconnaissance study of the stability ofamphiboles at high pressure. Carnegie Inst. Wash. Year Book 67,167-170,
Gilbert, M.C. and Popp, R.K. (1973): Properties and stability ofglaucophane at high pressure. Trans. Àmer. Geophys. Union 54, 1223,
Gilbert, M"C., Helz, R.T., Popp, R.K. and Spear, F.S. (1982):ExperimenLal studies of anrphibole stability. Mineral. Soc. Àmer.,Rev. Mineral. 98, 229-353.
Goldman, D.À. (1979): À re-evaluation of the Mössbauer spectroscopy ofcalcic amphiboles. Àmer. Mineral, 64, 109-118.
Goldman, D.À. and Rossman, G.R, (1911)z The identification of Fe2* inthe M(4) site of calcic anrphiboles. Àmer. Mineral, 62, 205-216.
Grebenshchikov, R.G., Grigor'eva, L.F., Makarova, T.A. and Romanov, D.P.(1975): Relationships between chemical compositions and structuresof synthetic amphiboles. Resumés des Communications - ConférenceInternationale sur la Physique et la Chimie des Minéraux d'AmianteUniv. Laval; Québec; 3.10, 1-11.
Grebenshchikov, R.G., Romanov, D.P., Sipovskii, D.P. and Kosulina, G.I.(197a)z Structure of a germanate hydroxyamphibole. ZhurnalPrikladnoi Khimi í 47 , 1905-19'10.
Greenwood, H.J. (1953): The synthesis and stability of anthophyllite.J. Petrol. 4, 31 7-35'1 .
Greenwood, H.J. (979)z Thermodynamic properties of edenite. InCurrent Research, Part B, Geological Survey of Canada, Paper 79-18,36s-370.
Gr igor'eva, tSynthesi sf luoramphi213, 1 087-
Er
andbo1109
, Krupenikova, Z.Y, and Romanov, D.P. (1973a):some properties of silicate and germanate
es of the richterite series. Àkad. Nauk SSSR, Dokl.0.
Grigor'eva, L.F., Romanov, D.P. and Gileva, K.G. (1973b)¡ Untersuchungdes zusammenhangs zwischen chemischer zusammensetzung und strukturrhombischer und monokliner fluoramphibole. Kristall und Technik 8,415-424.
Grigor'eva, L.F., Mikirticheva, G.À. and Gileva, K.G. (1975b): Kineticsand mechanism of formation of fibrous fluoramphiboles by solid statereactions in the SiOz - MgO - MgFz - Na2O system. Resumés desCommunications - Conférence Internationale sur Ia Physique et laChimie des Minéraux drAmiante Univ. Laval; Québec; 4,15, 1-9.
Grigoriev, D.P. (1939): Experimental investigation of the effect ofalumina on the optical properties of tremolite. Comptes Rendus(oollady) 0e t'Academie des sciences d 1'uRss 23, 71-73.
211
Hamilton, D.L. and Henderson, C.M.B. (1968): The preparation ofsilicate compositions by a gelling method. Mineral. Mag. 36,832-838.
Hariya, Y. and Terada, S. (1973): Stability of richterites.-tremolites.solid solutions at high pressures and possible presence of sodiumcalcic amphibole under upper mantle conditions. Earth and Planet.sc i . Lett. 1 8, 72-7 6.
Hawthorne, F.C. (1975)¡ The crystal chenristry of the amphiboles. V. Thestructure and chemistry of arfvedsonite. Can. Mineral. 14, 346-356.
Hawthorne, F.C. (1981): Crystal chemistry of the amphiboles. Mineral.Soc. Àmer., Rev.Mineral. 9À, 103-139.
Hawthorne, F.C. (1983a): Quantitative characterizalion of site-occupancies in ninerals. Amer. Mineral. 68, 287-306,
Hawthorne, F.C. ( 1 983b) :Mineral , 21 , 173-180.
The crystal chemistry of the amphiboles: Can.
Hawthorne, F.C. and Grundy, H.D. (1978): The crystal chemistry of theamphiboles. VII. The crystal chemistry and site chemistry ofpotassian ferri-taramite. Can. Mineral. 16, 53-62.
Hawthorne, F.C., Raudsepp, M., Williams, B.t. and Hartman, J.S. (198a):Characterization of cation ordering in synthetic amphiboles byRietveld structure refinement and 27À1 and 2ssi I'lAs NMR spectroscopy.GÀC/MAC Program with Abstracts 9, p,72.
Hel1ner, E. and Schürmann, K. (1966); Stability of metamorphicarnphiboles: the tremolite-ferroactinolite series. J. GeoI . 74,322-331.
Hellner, E. and Schürmann, K. (967)¿ Stability of metamorphicamphiboles: the tremolite - ferroactinolite series: a reply. J.Geol. 76, 351 .
Hinrichsen, Th. and Schürmann, K. (977)z Experimental investigationson the Ha/x substitution in edenites and pargasites. N. Jb. Miner.Abh.130,12-18,
Hoffmann, C. (1972)z Natural and synthetic ferroglaucophane. Contr.Mineral. and Petrol. 34, 135-149.
Holloway, J.R. (1973): The system pargasite-HzO-COz: a model formelting of a hydrous nineral with a mixed-volatile fluid - I.Experinental results to I kbar. Geochim. Cosmochim. Àcta 37,651 -666.
Holloway, J.R. and Ford, C.E. (1973): The effect of fluorine onhornblende: fluid-absent melting of R-OH pargasite to 35 kbars.Trans. Amer. Geophys. Union 54, 479.
212
HoIloway, J.R. and Ford, C.E. (1975): FIuid-absent melting of thefluoro-hydroxy amphibole pargasite to 35 kilobars. Earth. Planet.sci. Lettr . 25, 44-48.
Holloway, J.R. and Ford, C.E. (1976): FIuid absent melting of fluoro-hydroxy pargasite at pressures up to 3skb. Prog. in Exp. Petrol. 3,284-285, N.E"R.C., London.
Hoschek, G. (1973): Die reaktion pJ-ogopit + calcit + guarz = tremolit +
kalifeldspat H20 + C02. Contr. Mineral. Petrol. 39, 231-237,
Huebner, J.S. (1971 ): Buffering techniques for hydrostatic systems atelevated pressures. In Research techniques for high pressure and andhigh lemperature (C.C. Ulmer, ed.). Springer-VerIag, New York.
Huebner, J.S. and Papike, J.J. (1970): Synthesis and crystal. chemistryof sodium-potassium richterite, (Na,K)llacaugsSisOzz(oH,F) z: À rnodelfor amphiboles. Àmer. Mineral. 55, 1973-1992,
Jasmund, K. and Schäfer, R. (1972)z Experimentelle bestimmung der P-T-stabilitatsbereiche in der mischkristallereihe tremolite -tschermakit. Contr. Mineral. Petrol, 34, 101-115.
Jenkins, D.M. (1981): Dehydration boundary of synthetic tremolite inthe presence of forsterite. Geol. Soc. Amer. Ànn. Mtg., Àbstr. withPrograms 1 3, 480.
Kempe, D.R.C. (1969): The ce11 parameters of the arfvedsonite-eckermannite series, with observations on the MgO and total ironcontent of amphiboles. Mineral. Mag. 37, 317-332,
Klein, C. and Watdbaum, D.R. (1967)¡ X-ray crystal]ographic propertiesof the cummingtonite - grunerite series. J. Geol, 75, 379-392,
Kohn, J.À. and Comeforo, J.E. (1955): Synthetic asbestosinvestigations, II: X-ray and other data on synthetic fluor-richterite, -edenite, and -boron edenite. Àmer. Minera1.40,410-421 ,
Koons, P.O. (1982): À experimental investigation of the behaviour ofamphibole in the system NazO - MgO - À120s - SiOz - HzO at highpressures. Contr. Mineral. Petrol . 79, 258-267 .
Koslowski, T. and Hinrichsen, Th. (1979): Synthesis, properties andupper thermal stability of a glaucophane - riebeckite mixed crystal.N. Jb. Miner. Mh., 1979, 357-362.
Kretz, R" (1983): Symbols for rock-forming minerals. Àmer. Mineral.68,277-279.
Leake, B.E. (1968); A catalog of analyzed calciferous andsubcalciferous amphiboles together with their nomenclalure andassociated minerals. Geol. Soc. Amer. Spec. Pap. 98.
213
Leake, B.E. (1978)¡ Nomenclature of amphiboles. Can. Mineral. 16,501 -520.
Leake, B.E. and Hey, M.H. (1979): Addendum to the nomenclature ofamphiboles. Mineral. Mag. 42, 561-563.
Loida, A. and Hinrichsen, Th. (1975): Synthese und stabilitatgranulitischer amphibole. N. Jb. Miner. Mh., 1975, 45-47.
Makarova, T.À., Korytkova, E.N. and Fedoseev, À.D. (1971): Herstellungfaseriger amphibole bei hohen temperaturen un drucken. 824-826,
Makarova, T.4., Fedoseev, 4.D., Sipovskii, D.P. and Nesterchuk, N.I.(1972) z Fibrous amphibole formation conditions during hydrothermalsynthesis. Eksperimental'nye Issledovaniya Mineraloobrazovaniya vSukhikh Okisnykh i Silikatnykh Sistemakh, Moscow, USSR, "Nauka";1972; 153-'157.
Malinovskiy, I.Yu. (1966): Hydrothermal synthesis of amphibole of theferroedenite - ferrohastingsite series. Akad. Nauk SSSR, Dokl.170,1 64-1 66 .
Mallinson, L.G., Jefferson, D.4., Thomas, J.M. and Hutchison, J.t.(1980): The internal structure of nephrite: experimental andcomputational evidence for the coexistence of multiple-chainsilicates with an amphibole host. Phil. Trans. Royal Soc. London295, 537-552.
Manning, D.A.C. (1978): Experimental problems encountered in theaddition of fluorine to sLarting materials in the system Qz-Àb-Or.Prog. in Exp. Petrol. 4, 46-48, N.E.R.C., London.
Maresch, W.V. (1973): New data on the synthesis and stability relationsof gtaucophane. Earth PIanet. Sci. Lett, 20, 385-390.
Marebch, W.V. (1974): Neuen Daten zur Stabilitat und "Polymorphie" dessynthetischen Glaukophans. Fortschr. Mineral. 51, 30-31.
Maresch, W.V. (977)z Experimental studies on glaucophane: an analysisof present knowledge. Tectonophys. 43, 109-125.
Maresch, W.V. and Czank, M. (1981)¡ Crystal chemistry of synthetic Mn-anthophyllite: are synthetic amphiboles suitable for stabilitystudies. Terra cognita, Spring, i98'1 , 89.
Maresch, W.V. and Czank, M. (1983): Phase characterization ofamphiboles on the join Mn'*Mgr-xSiaOzz(09) z. Àmer. Mineral.7 44-753 ,
synthet ic68,
Maresch, !{.v. and Langer, K. (1976): Synthesis, lattice constants andOH-valence vibrations of an orthorhombic amphibole with excess 0H inthe systen Li2O-M9O-SiOz-H20. Contr. Mineral. Petrol. 56, 27-34,
214
MuelIer, R"F. (1967): Stability of metamorphic arnphiboles: thetremolite - ferroactinolite series: a discussion. J. Geol-.76,234-236.
Nesterchuk, N.I., Makarova, T.À. and Fedoseev,4.D. (1968):Hydrothermal synthesis of a fibrous Na-Co amphibole. Àkad. NaukSSSR, Dokl. 179 , 106-'107.
Oba, T. (1978): Phase relations of ca2MgsÀlzSioAlz0zz(oti) z -Ca2MgsFez3*SioÄlzOzz(OH)z join at high pressure - the stability oftschermakite -. J. Fac. Sci. Hokkaido Univ., Ser. IV, 18, 339-350.
Oba, T. (1980): Phase relations on the tremolite - pargasite join.Contr. Mineral. PetroL 7l, 24'l-256,
Papike, J.J., Ross, M. and Clarke, J.R. (1969): Crystal-chemicalcharacterízaLíon of clinoamphiboles based on five new structurerefinements. Mineral. Soc. Àmer. Spec. Pap. 2, 117-136.
Petö, P. (1976)¡ Synthesis and stability of edenitic hornblende. Prog.in Exp. Petrol. 3, 27-28, N.E.R.C., London.
Phillips, R. and Rowbotham, g. ('1966): Studies on synthetic alka1iamphiboles. Papers and Proceedings of the Fifth GeneralMeeting,I .M.À., Cambridge, 249-254.
Prewitt, C.T. (1963): Crystal structure of two synthetic amphiboles.Geol. Soc . Àmer . Ànn. Mtg. New York, 'l 324-1 33À.
Raudsepp, M., Hawthorne, F.C. and Turnock, A.C. (198a): Derivation ofsite-occupancies in synthetic pyroxenes and amphiboles by Rietveldstructure refinement. Geol. Soc. Àmer. Abstracts with Programs 16,No. 6.
Raudsepp, M., Turnock, À.C. and Hawthorne,characterization of viRs* analogues ofcAC/MÀc Program with ebstracts 7, p.75.
F.C. (1982): Synthesis andpargasite and eckermannite.
Ribbe, P.H. and Prunier, Jr., À.R. (1977)z Stereochemical systematicsof ordered Cz/c silicate pyroxenes. Àmer. Mineral. 62, 710-720.
Rietveld, H.M. (1967): Line profiles of neutron powder-diffractionpeaks for structure refinement. Àcta Cryst, 22, 151-152.
Rietveld, H.M. (1969): A profile refinement method for nuclear andmagnetic structures. J. ÀppI. Cryst. 2, 65-71.
Rowbotham, G. and Farmer, V.C. (973)z The effect of "4" site occupancyon the hydroxyl slretching frequency in clinoamphiboles. Contr.Mineral. Petrol. 38, 147-149,
Schairer, J.F. (1959): Phase equilibria with particular reference tosilicate syslems. In Physicochemical Measurements at HighTemperatures (,¡.0. Bockris, ed. ). Butterworths, London.
215
Schairer, J,F. and Bowen, N.L. (1955): The system KzO - AlzOs - SiOz.Amer. J. Sci. 245, 193-204.
Schreyer, W. and Seifert, F. (1968): Synthetic amphibol-es in the systemNa20-Mg0-Si02-Hz0 and their significance for the chemistry of naturalamphiboles. Papers and Proceedings of Lhe Fifth General Meeting1966, I.M.À., Cambridge, 23-24,
Semet, M. (1970): Stability relations of the amphibolemagnesiohastingsite. Àmer. Mineral. 55, 311-312 (¡bstr. ) .
SemeL, M. (1972): Stability relations and crystal chemistry nof theamphibole magnesiohast ings i te, NaCa zMg¿Fe
3 *Si oAl zO z z (OH ), ph.¡.
Dissertation, Univ. of California, Los Angeles, 216 p,
Semet, M. (1973): A crystaÌ-chemical study of syntheticmagnesiohastingsite. Àmer. Mineral. 58, 480-494.
Semet, M. and Ernst, W.G. (1981): Experimental stabiJ.ity relations ofthe hornblende magnesiohastingsite. Geol. Soc. Àmer. 8u11. Pt. II,27 4-358 ,
She11, H.R., Comeforo, J.R. and Eitel, ll. (1958):investigations: synthesi.s of fluor-anphibolesBureau of Mines, 4517, 35 pp.
Synthetic amphibolefrom meIts. U.S.
Strens, R.G.J. (97a) z The common chainIn The Infrared Spectra of Minerals (
Mineralogical Society, London.
ibbon, and ring silicates.. Farmer, ed. ) .
,tv.c
Tateyama, H,, Susumu, S. and Sudo, T. (1978): Synthesis and crystalstructure of a triple chain silicate, Na2Mg¿Sis0t e(0H) z. Contr.Miner. Petrol. 66, 149-156.
Thomas, W.M. (977)z Preliminary stability relations of the hornblendehastingsite, and the effect of Fe3* for aluminum replacement inamphiboles. Àmer. Geophys. Union Trans. 58, 1244 (¡bstr.).
Thomas, W.M. (979)z Stability relations of the amphibole hasLingsite,NaCa2MgaFe3*SioAlzOzz(oH)2. Ph.D Dissertation, Univ. of California,Los Àngeles, 183p.
Thomas, W.M. (1982a): Stability relations of the amphibole hastingsite.Àmer. J. Sci. 282, 136-164.
Thomas, I.t"M. (1982b) ¡
hastingsites, andamphiboles. Àmer.
Thompson, J.B. (1981):of the biopyriboles.
sTFe Mössbauer spectra of natural and syntheticimplications for peak assignments in calcicMineral, 67, 558-567.
Àn introduction to the mineralogy and petrologyMineral. Soc. Amer., Rev. Mineral. 9À, 141-188.
Tro11, G. and Gilbert, M.C, (1912)¿ Fluorine-hydroxyl substitution intremolile. Àmer. Mineral, 57, 1386-1403.
216
Troll, G. and Gilbert, M.C, (197Al' t Fluorine-hydroxyl substitution intremolite. Trans. Àmer. Geophys. Union 55, 481.
Tuttle, 0.F. (19a9): Turo pressure vessels for silicate-water studies.Geol. Soc. Àmer. BuI1. 60, 1727,
Tuttle, 0.F. and Engl-and, J.L. (1953): Stability relatíons of theamphiboles. Carnegie Inst. Wash. Year Book 52, 62'64.
Veblen, D.R. (198'1): Non-classicat pyriboles and polysomatic reactionsin biopyriboles. Mineral. Soc. Àmer., Rev. Mineral. 94, 189-236.
virgo, D. (1972a)'. Preliminary fiLting of sTFe Móssbauer spectra ofsynthetic Mg-Fe richterites. Carnegie Inst. Wash. Year Book 71,51 3-51 6.
Westrich, H.R. ('1978): Fluoride-hydroxyl exchange in several hydrousminerals. Ph.D. Thesis, Arizona State University, Àrizona.
Westrich, H.R. and Ho1loway, J.R. ('1981 ) : ExperimentaJ. dehydration ofpargasite and calculation of its entropy and Gibbs energy. Àmer. J.Sci. 281,922-934.
Westrich, H.R. and Navrotsky, A. (1981): Some thermodynamic propertiesof fluorapatite, fluorpargasite, and fluorphlogopite. Amer. J. Sci.281, 1091-1103.
Wiles, D.B. and Young, R.A. (1981): À new compuler programanalysis of X-ray powder diffraction patterns. J. Àppl.1 49-1 51 .
for RietveldCryst , 14,
Witte, P. ('1976): Obere thermische stabiJ.itatsgrenzen von synthetischernagnesiorichteritenphasen. Fortschr. Miner . 54, 105-106.
I.titte, P., Langer, K., Seifert, F. and Schreyer, I.l. (1969):Synthetische amphibole mit OH-uberschuss im system Na20-Mg0-Si0z-H20"Naturwiss. 56, 414-415,
llones, D.R. and Dodge, F.C.},I. (977) z The stability of phlogopite inthe presence of quartz and diopside. In Thermodynanrics in Geology(p.C. Fraser, ed.). D. Reidel Publ. Co., Dordrecht-HolIand,229-247 .
Young, R.A. (1980): Structural analysis from X-ray powder diffractionpatterns with the Rietveld method. Symposium on Accuracy ín PowderDiffraction, National Bureau of Standards, Gaithersburg, MD, 143-163,
Young, R.A. and tliles, D.B. (1981)¡ Àpplication of the Rietveld methodfor structure refinement with powder diffraction data. Àdvances inX-ray Analysis 24, 1-23,
ÀDDITIONAL BIBLIOGRÀPHY OF ÀMPHIBOIE SYNTHESES
À11en, J.C., Boettcher, À.L. & Marland, G.andesite and basalt: I. Stability as aMineral. 60, 1069-1085.
( 1 975) : Amphiboles infunction of P-T-f02. Àmer.
Ànderson, À.T. (1980): Significance of hornblende in calc-alkalineandesites and basalts. Àmer. Mineral. 65,837-85'1.
Bowen, N.L. and Schairer, J.F. (1935): Grunerite from Rockport,Massachusetts, and a series of synthetic fluor-amphiboles. Àmer.Mineral , 20, 543-551 .
Cawthorn, R.G. ('1976a): Melting relations in part of the system CaO-Mg0-4120¡-Si0z-NazO-Hz0 under Skb pressure. J. Petrol, 17, 44-72.
Cawthorn, R.G. ('1976b): Some chemical controls on igneous amphibolecompositions. Geochim. Cosmochim. Àcta. 40,'13'19-1328.
Cawthorn R.G., Curran, E.B. and Arculus R.J. (1973): A petrogeneticmodel for the origin of the calc-alkaline suite of Grenada, LesserAntilles. J. Petrol, 14, 327-337,
Chao, P. (1973): Fibrous a1kali amphiboles at high temperatures andhigh pressures. Geochimia 2, 1 1 3-'1 30 .
Chernosky, J.V. (1976): The stability of anthophyllite - a reevaluationbased on nelv experimental data. Amer. Mineral, 61, 1145-1'155.
Chernosky, J.V. and Àutio, t.K. (1979): The stabilily of anthophyllitein the presence of quartz. Àmer. Mineral. 64, 294-303.
Chernosky, J.V., Day, H.W. and Caruso, t.J. (1982): R phase diagram forMg-anthophyllite. Trans. Àmer. Geophys. Union 63, '1'151.
Chigareva, O.G. and Grigor'yeva, L.F. (1970): Synthesis of fluor-asbestos from natural talc. Àkad. Nauk SSSR, Dokl. 195, 1194-1196,
Chigareva, 0.G., Grum-grzhimailo, S.V. and Fedoseev, À.0. (1959):Spectrophotometric study of synthetic fibrous fluor-amphiboles. Zap.vses. Mineral. Obshchest. 98, 96-101 (in Russ.).
Christophe-Michel-Lévy, M. (1957): Premiers stades du metamorphismearLificiel d'une dolomie siliceuse: formalion de tremoliLe et dediopside. 8u11. Soc. franç. Minéra1. Crist. 80, 297-302.
Ðay, H.W. and Ha1bach, H. (1979): The stability field of anthophyllite:the effect of experimental uncertainty on permissible phase diagramtopologies. Àmer. Mineral, 64, 809-823.
-217-
218
Eitel, }l. ( 1 925) : Die experimentellen hiLfsmittel zur mineraJ.syntheseunter hohen drucken und hohen temperaturen. Fortschr. Min. Krist.Petr. 10, 157-186.
Espig, H. (1962)z Beilrag zur synthese asbestartiger und einigeranderer silikate. Silikattechn. 13, 131-137.
Fedoseev, 4.D., Grigor'eva, L.F. and Chigareva, 0.G. (1966): Diesynthese faserige silikate unter thermische bedingungen. KristalTechnik 1, 231-236.
Fonarev, V.I. (1976): Equilibrium in the association of orthopyroxene,cummingtoni.te, magnetite and quartz over t.he pressure range of 1000to 5000 kg/cnz in the presence of NNO buffer. Akad. Nauk. SSSn.Dokl. 228 , 1441-1444,
Forbes, W.C. (1971b): Synthesis of grunerite, FeTSisOzz(Ou) z. NaturePhys. Sci.232,109.
Forbes, W.C , (1977) z Stability relations of grunerite, FezSi aOz z (0H) z.Àmer. J. Sci. 277, 735-749.
Gilbert, M.C. and Briggs, D.F. (197a): Comparison of the stabilities of0H- and F-potassic richterites - preliminary report. Trans. Amer.Geophys. Union 55, 480-481.
Gilbert, M.C. and 1ro11, G. 1197a)z A comparison of the stabilities of0H- and F-tremolite. Int. Mineral. Assoc. 9th General Meeting,Berlin and Regensberg, Germany, Collected Abstracts, 84.
Goncharov, Yu.I. (1977)z Phase formation in the system NaF - MgFz - MgO- SiOz at 400 - 1200oC.. Isvestiya Akademii Nauk SSSR,Neorgan i schesk i e Mater ialy .1
3 , 452 -459 .
Goncharov, Yu.I. and Kovalenko, V.S. (1973): On the mechanism offormation of amphibole asbestos. Geokhimiya t 782-786.
Goncharov, Yu., Balitskii, V.S., Khadzhi, I.P. and Popova, N.P. (97a) ¿
Replacement of phlogopite by amphibole asbestos of the ecermannite -arfvedsonite series in alkaline hydrothermal solutions. VsesoyuznogomineralogicheskcAo obshchesta zapski 103, 716-718.
Grebenshchikov, R"G., Sipovskii, D.P. and Makarova, T.A. (1976):Comparative assessment of conditions for formation of silicate andgermanate amphiboles under hydrothermal conditions. Akad. Nauk.SSSR, !2v., Neorg. Mater, 12, 963-965.
Grigoriev, D.P. (1935)¡ Uber die kristallisation von hornblende undglimmer aus kunstlichen silikatschmelzen. Centr. Mineral. Geol. 4,117 -123 ,
Grigoriev, D.P. and Iskul1, E.W. (1937)¡ The regeneration of amphibolesfrom their melts at normal pressure. Amer. Mineral. 22, 169-177.
Greenwood, H.J. (1963): TheJ. Petrol. 4, 317-351.
219
synthesis and stability of anthophyllite.
Greenwood, H.J. (1971): Ànthophyllite. Corrections and comments on itsstability. Amer. J. Sci.270t 151-154.
Grigor'eva, L,F., Makarova, T.À. and Korytkova, E.N. ('1975):Sinteticheskie amfibilovye asbesty, Izd. Nauka., Leningrad, 253 p.
Hamich, M. and Seck, H.À. (1974)t Synthese und phasenbeziehungen Ti-haltiger pargasiLe. Fortschr. Miner. 51, 18-19.
HeIz, R.T. (1973): Phase relations of basalts in their melting range atP HzO = 5 kb as function of oxygen fugacity. Part I. Mafic phases.J. Petrol, 14, 249-302,
Hel-2, R.T. (1975): PhaseatPH20=5kb. Part1 39-1 93.
relations of basalts inII. MeIt compositions.
their melting rangesJ. Petro.L. ll,
Helz, R.T. (1979): Àlka1i exchange between hornblende and melt¡ a
temperature-sensitive reaction. Amer. Mineral, 64, 953-965.
Hinrichsen, Th. (1967): Uber den stabilitatsbereich der Mg-Fez*-Àl-Mischkristallreihe rhombisher hornblenden. Teil I: Hydrothermaleuntersuchungen der anthophyll i t-f erroanthophyll i t-mi schkr i stallre ihe.N. Jb. Miner. Mh, 1967, 257-270.
Hinrichsen, Th. (1968)¡ Hydrothermal investigations and stabilityrelations of synthetic Aedrites. In IMA Papers and Proceedings,Fifth General Meeting, 1965, Cambridge, 243-248.
Hinrichsen, Th. (1968): Uber den stabilitatsbereich der Mg-Fez*-41-Mischkristalle rhombischer hornblenden. Teil I: Hydrothermaleuntersuchungen der magnesium-eisen-mischkristallreihen von gedriten.N. Jb. Miner. Mh. 1968, 41-57,
Hinrichsen, Th. (1974): Upper stability of orthorhombic amphiboles inthe system MgO-Fe0-4120¡-Si0z-H20. IMA Meeting, West Berlin,Collected Abs., 86.
Hinrichsen, Th. (977)z 0rthorhombic amphiboles: Breakdown product ofthe reaction pycnochloríte + quartz. N. Jb. Miner. Àbh. 130, 33-38.
Hotloway, J.R. (1975): Fluid-absent melting of the fluoro-hydroxyamphibole pargasite to 35 kilobars. Earth Planet. Sci. Lett, 25,44-48.
Iiyama, J.T. (1953): Synthese hydrolhermale a 750 C, 1000 bars dans lasysteme Na20-Mg0-À1203-Sí0 z-HzO d'amphiboles orthorhombiques etmonocliniques. Compt. Rend. Àcad. Sci. Paris 256,966-967,
Kadzhi, I.P., Drits, v.À., Yarotskii, v.G. and Dimitrik, A.L. (1979):Novaya polimorfiaya raznovidost voloknistykh ftoramfibolovMgzSiaOzzFz. Nov. Dannye Miner. SSSR 28, 153-162,
KaIinin, D"V. and Deniskina, N.D. (1975):hydrothermale Methoden ihrer Gewinnung,Synthesereaktionen und Eigenschaf ten.Part C, C296, 111-1 19.
220
Synthetische Amphibolasbeste :
die Kinetik derFreiburger Forschungshef te,
KaLinin, D.V. and Ripinen, O.I. (197a)z Synthesis of fibrousfluoramphibole in salt melts. Eksperimental'nye Issledovaniya poMineralogii ¡¡ovosibirsk, USSR, Akad. Nauk SSSR, Sib. 0td., Inst.Geol. Geof iz. ; 197 4 , 55-57.
Kichang, NA (1982): Amphibole stability relations in the system edeniteand edenite + 4Quartz. Trans. Amer. Geophys. Union 63, .115'1
.
Kiseleva, I.À. (1966): Hydrothermal synthesis of ferruginous hornblendeand actinolite from acid chloride solutions. Àkad. Nauk SSSR, Dokl.171 , 177-180.
Koenigsberger, J. (927) z Experimentelle hilfsmittel der hydrothermalensyihese bei hohen temperaturen und drucken. Fortschr. Min. Krist.11, 41-48.
Kiseleva, I.À. (1968): Dependence of ferroactinolite-hedenbergiteequilibrium on temperaLure and the activity of calcium. Geokhim. No.1, 37-45.
Koltermann, M. (1965): Der thermische zerfall des anthophyllits und diebildung von fluor-anthophyllit und norbergit bei der reakLion vonmagnesiumsilikaten mit NaF, LiF und HF. N. Jb. Miner. Mh, 1975,17 6-184,
Kopp, o.c. (1967): Synthesis of grunerite and other phases in thesystem SiO2-NaOH-Fe-HzO. Amer. Mineral, 52, 1681-1688.
Korytkova, E.N. and Makarova, T.À, (1972)t Experimental investigationof the hydrothermal alteration of olivine in connection with theformation of asbestos. Geokh. No. 11, 1416-1420.
Korytkova, 8.N., Fedoseyev, À.D. and Makarova, T.A. (1968): Synthesisót fibrous arnphibole by hydrothermal recrystallization of olivine.Akad. Nauk SSSR, Dokl, 182, 1396-1398.
Korytkova, 8.N., Makarova, T.NÀ. and Grebenshchikov, R
Hydrothermal crystallization of fibrous amphibolesIzvestiya Àkademia Nauk SSSR, Neorganicheskie Mater1 898-1 900.
.Gfria
. (1978):om talcs.ly 14,
Korytkova, 8.N., Makarova, T.À. and Nesterchuk, N.I. (1975): Study ofhydrothermal reaclions of the amphibole synthesis in connection withtlre genesis of asbestos. Resumås des Communications - ConférenceInteinationale sur la Physique et la Chimie des Minéraux d'ÀmianteUniv. Laval; Québec i 4.14, 1-10.
Kushiro, I. (1970): Stability of amphibole and phlogopite in lhe uppermantle. Carnegie Inst. I'lash. Year Book 68 , 245-247.
221
richterite.Kushiro,Carneg
and ErlankInst. Wash
Lambert, I.B. and Wyllie, P.J. (1968): Stability of hornblende and amodel for the low velocity zone. Nature 219, 1240-1241,
Ludke, W. (1933): Methodisches zur synthese von silikaten mitleichtfluchtigen substanzen unter stationaren bedingungen. Fortschr.Min. Krist. Petr. 18, 29-31,
Makarova, T.A. and Pivovarova, L.N. (97'l) t Hydrothermal synthesis ofmanganese fibrous amphiboles. Zhurnal Prikladnoi Khimii (f,eningrad)50, 2562-2564.
Makarova, T.À., Nesterchuk, N.I., and Korytkova, E.N. (977)z Study ofthe mechanism of amphibole formation under hydrothermal conditions.Vsesoyuznogo mineral.ogicheskogo obshchestva zapiski 106, 241-242,
Malinovskiy, I.Yu. (1967): Hydrothermal synthesis of iron cordierite inexperiments on the synthesis of ferrohastingsite. Doklady ÀkademiaNauk SSSR '173, 893-894.
Metz, P. and Winkler, H.G.F. (196a): Experimentelle untersuchung derdiopsidbildung aus tremolit, calcit und quarz. Naturwiss. 151, 460.
Muller-Fabian, B. (977)t Statistische untersuchungen zum waschstum undhabitus von fluor-amphibol-kristallen in oxid-fluorid-gemengen.Kristall und Technik 12, 1149-1155.
Mysen, B.O. and Boettcher, À.L, (1976)z Melting of a hydrous mantle:III. Phase relations of garnet websterite + HzO at high pressuresand temperatures. J. Petrol. 17, 1-14,
Obata, M. and Thompson, À.8. (1981)¡ Àmphibole and chlorite in maficand ultramafic rocks in the lower crust and upper mantle. À
theoretical approach. Contr. Miner. Petrol, 7'1, 74-81,
Popp, R"K., Gilbert, M.C. and Craig, J.R. (197*): Effect of oxygenfugacity on the stability of Fe-Mg amphiboles. Trans. Àm. Geophys.Union **, 1200,
Popp, R.K., Gilbert, M.C. and Craig, J.R. ('1976): Synthesis and x-rayproperties of Fe-Mg orthoamphiboles. Àmer. Mineral, 61, 1267-1279.
Popp, R.K., Gilbert, M.C. and Craig, J.R. (977a)z Stability of Fe-Mgamphiboles with respect to oxygen fugacity. Àmer. Mineral. 62, 1-12,
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.
Saito, H. and Ogasawara, K. (1959): Synthesis of various types offluoramphibole by isomorphic substitution. Kogyo Kagaku Zasshi 62,97 6-978 .
Saito, H. and Ogasawara, K. (1959): Synthesis of various types offluoramphibole by isomorphic substitution. Kogyo Kagaku Zasshi 62,97 6-978 .
Saito, H. and Takusagawa, N. (1965): Synthetic asbestos. XXI. Synthesisof fluornanganese - richterite asbestos by sintering nethod. KogyoKagaku Zasshi 68, 2347-2351.
Saito, H. and Yamai, I. (1968)¡ Synthetic asbestos. xxlI. Synthesis ofasbestiform crystals by gas-phase reaction using double crucibles.Kogyo Kagaku Zasshi 71, 354-357.
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,
Scheumann, K.H. and Ludke, W. ( 1 933 ) :niederen drucken. Ber. Verhandl.273-278,
Uber hornblendesynthesen beisachs Àkad. wiss. teipzig 85,
Schürmann, K. (1968): Synthesis and stability field of cummingtonite.Papers and Proceedings of the Fifth General Meeting 1966, I.M.À.,Cambridge, 255-260.
Schürmann, K. (1967)z Hydrothermale experimentelle untersuchungen anmetamorphen monoklinen hornblenden. Teil i: Zur stabilitat dercummingtonite. N. Jb. Miner. Mh. , 1967 t 270-283,
Sipovskii, D.P", Grebenshchikov, R.G. and Makarova, T.Achemical compound: f ibrous amphibole-like gernanate.Nauk SSSR 205, 404-406.
Takusagawâ, N. and Sailo, H.composition glass-ceramicKyokai Shi 80, 201-211,
(1972) z NewDokl. Akad.
(19721t MicrostrucLure of fluor-richteritehaving high mechanical strength. Yogyo
Shiebold, E. ( 1 958 ) : Röntgenograf ische feinstrukturuntersuchungen annatürlichen und synthetischen asbestarten. Wiss. Z. HochschuleSchwermaschinenbau 2,
Shishelova, T.I., Tchilikanova, L.V. and Tchaikina, E.A. (1981 ): X-rayinvestigation of cobalt amphibole asbestos. Twelfth InternationalCongress of Crystallography, Collected Àbstracts, C-154.
Spear, F.S. (1981): An experimental study of hornblende stability andcompositional variability in amphibolite. Amer. J. Sci. 281,697-731,
Takusagawâ, N. and SaiLo, H. (1970): Cryslallization in fluorrichteritecomposition glass. IV. Effect of glassy phase separation onnucleation in fluorrichterite composition glass. Yogyo Kyokai Shi78, 411-420.
Takusagawâ, N. and Saito, H. (971)t Studies on the heat treatment offluor-richterite composition glass for obtaining the polycrystallinemateriaL having high mechanical strength. Yogyo Kyokai Shi 79,377 -386,
Takusagawâ, N. and Saito, H. (972)z Relation between microstructureand mechanical strength of crystallized glasses having the chemicalconposition of fluor-richterite containing aluminum. Yogyo Kyokaishi 80, 365-374,
Widmark, E.T, (1974): An edenite forming reaction: hydrothermalexperiments. N. Jb. Miner. Mh., 1974, 323-329.
224
Yagi, K. , Hariya, Y" , Onuma,relation of kaersutite. J33'1-342,
K. and Fukushima, N. (1975): Stability. Fac. Sci. Hokkaido Univ., Ser. IV, 16,
Sci.ïen, E. (971)z Comments on the thermodynamic constants and
hydrothermal stability relations of anthophyllite. Àmer. J.270, '136-150.
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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Gl aucophane
Ferro-g I aucophane
Hagnesio-riebeckì te
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lla gnes i o- a rf vedsoni te
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Ferro-¿ ì umi no- tschemòk i te
Aì Lrmi no-magnes i o-hornb ì ende
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fomuìa
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