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Goldsmith 1982 Plagioclase
Goldsmith 1982 Plagioclase
Julrex R. Gor-osurru
Departmentof the GeophysicalSciences
The Universityof Chicago
Chicago,Illinois 60637
Abstract
Mineralogy and petrology are supplementaryand dence, attempted to explicitly define the nature of
complimentary disciplines. Much of our under- the relationship. Ramberg proposed an equilibrium
standingof the petrology and ultimately the geology between epidote and "anorthite-molecule" in the
of any portion of the earth is dependent on our plagioclase:
knowledge of the properties and characteristics of
2CaAl2Si2O8+ llzHzO = Ca2Al3Orz(OH)
minerals and of mineral interactions. The petrolo-
gist examines the minerals to help unravel the anorthite "epidote"
history of a rock; the mineralogistgains insight on + l/2Al2sio5 + 1/2sio2
mineral behavior from accumulatedinformation on kyanite quartz
the rocks. Somemineralswith limited composition-
al and structural variation have little to reveal. He then wrote a reaction in which calcic plagioclase
plus water breaks down to a more albitic plagioclase
Others, such as the feldspars,may contain a great
plus epidote,kyanite, and quartz and constructeda
deal of information, but can be complex and stub-
born in revealingtheir secrets.A voluminouslitera- theoretical curve for the equilibrium in which, with
ture on plagioclasehas not yet clearly characterized decreasingtemperature, an increasingly sodic pla-
gioclase is stable with epidote. Ramberg was fully
the phaserelations.The equilibriumpicture is over-
lain by confusion compoundedof and dominated by cognizantofthe role ofpressureand drew schemat-
kinetic factors. Furthermore,heterogeneous ic diagramsof both isobaric and isothermal surfaces
miner-
alogical reactions can be affected by the varying for the reaction. He considered this reaction rela-
energeticsof differentstructuralstates.This review tion to be a continuous one all the way from the
greenschistto the granulitefacies.
briefly covers and is restricted to the highlightsof
papers on plagioclasefeldspars in metamorphic Ramberg(1949)extended his ideas on the plagio-
rocks, and is followed by a report on an experimen- clase-epidote equilibrium to potassium-rich rocks
tal investigation that bears on plagioclase stability with orthoclaseand muscovite. A secondcontinu-
at_elevatedtemperaturesand water pressures. ous reactionoccurs:
Petrologistshave long been aware of an increase 4CaAlzSizO8+ KAlSi3Os + H2O
in anorthite content in some metamorphic rocks anorthite orthoclase
accompanying an increase in metamorphic grade
(Becke, 1913).Although earlier workers had con- + 2SiO2
? KAhSigOro(OH)z+ 2Ca2Al3SirOrz(OH)
muscovite epidote quartz
sidered a relationship between plagioclaseand epi-
dote or other Ca-rich minerals(seeChristie, 1959), Figure I is a reproduction of his (2-dimensional)
Ramberg (1943), largely on the basis of field evi- diagram.The dashedcurve, representingthe equi-
0003-004x/82/0708-0643$02.
00 il3
644 GOLDSMITH: REVIEW OF PLAGIOCLASE
I
curve, and the data clearly indicated a gradual
U
increasein the anorthitecontent of the plagioclases
F
H O M O G E N E OFUI E
SL D with increasinggrade of metamorphism.He noted
of :+ significantdeviations,however, and indicatedthat
z PLAGIOCLASE there are problems, as recognizedby Ramberg,in
its use as an index of intensityof metamorphism.In
1t ar%\ addition, Lyons noted, ". . . a great paucity of
F metamorphic plagioclase in the range of Anrr
a
An2o."
= -^\ Ramberg's (1943, 1949, 1952) deduced curves
= 1t l l
EPIDOTE lt were continuous in nature, implying an equilibrium
A
that variescontinuouslywith temperature(or meta-
z
prlllocusr
4 U
morphicgrade).A numberof field studiesin region-
(Kyonite, tl
- E9 ally metamorphosedterraneshad given some indi-
M u s c o v)i t e Y o ' r9
i
t-
cation of a rapid conversionof albite to oligoclase
U
or sodic andesineover a short distance, but it is
o
1l likely that the first clear-cutevidencefor a discon-
tl
t tinuous increase in plagioclasecomposition with
increasinggradewas describedfrom greywackesof
0 20 40 60 80 t00
C o ,A l N o ,A l the Missi series, Manitoba (Ambrose, 1936; see
Silicotes Silicotes Brown, 1962).Ambrose commented on abundant
Fig. l. ReproductionofRamberg's (1949)subsolidusdiagram epidote, and assumed that original intermediate
of the plagioclaseP epidote equilibrium, deduced in part from plagioclaseof volcanic rocks has reacted, ".
field observations. according to the familiar equation: plagioclase +
water * iron : albite + epidote * alumina *
librium of plagioclaseand epidotein the presenceof silica." He noted that water-clear albite persists
muscoviteand potash feldspar is drawn somewhat with little changethrough the biotite zone, but with
abovethe K-free equilibrium becausemuscovitein the appearanceof garnet, the anorthite content of
associationwith K-feldspar and quartz has some- the plagioclaserises abruptly from An64 to An2s-32
what lower Al-activity than kyanite. Ramberg and that epidote is greatly diminished in amount
pointed out that increasedH2O pressuredisplaces above the garnet isograd, concomitant with the
the equilibrium toward epidote, as does increasing appearanceof oligoclase.
the Fe3+/Alratio becauseof the ability of epidoteto Sincethe earlier years of the 20th century, when
incorporateFe3* in its structure. Rambergconsid- the nature of the isomorphousreplacementof Na
ered the reactions of Figure I to span a temperature and Si for Ca and Al in the plagioclasefeldspars
interval of approximately500"C, and facies,repre- became known, petrologistshad long considered
sentingtemperature,are ploted on the vertical axis. the plagioclasesto be an ideal solid solution series.
He felt that the epidote-plagioclaseequilibrium in The dogmaof one rock, one plagioclase(excluding
most quartzo-feldspathic rocks cannot registerP-Z zoning, or other non-equilibriumphenomena)pre-
conditions higher than those that would develop vailed. Chao and Taylor (1940) were the first to
Ansg-ao plus epidote,due to the low CalNa ratio in observe superstructurereflections in X-ray diffrac-
these rocks. Ramberg (1952)further extendedthe tion patterns of intermediateplagioclases,indicat-
plagioclase-epidote relations to a more complex ing structural complexities.Chao and Taylor con-
systemcontainingCaCO3and indicated that rocks sidered this as evidence against a complete solid
with the sameplagioclasecompositionsmay have solution series, although a strong hint had earlier
formed at different temperatures,dependingon the appearedwhen Taylor et al. (1934)found the c-axis
partial pressureof water. of anorthite to be twice that of albite. Kohler
Lyons (1955) plotted plagioclasecompositions (1942a,b) and Larsson (1941) were the first to
againstmetamorphicgradein the Hanover quadran- explicitly describeoptical diferences betweenpla-
gle (New Hampshire-Vermont)as a check against gioclasesofplutonic and volcanicrocks, and thus to
Ramberg's(1943)diagram. He observedthat in a differentiate high-temperature from low-tempera-
general way the separation of the plagioclase-epi- ture plagioclases.Cole et al. (1951) showed that
dote and plagioclase fields followed Ramberg's low-temperatureplagioclasefrom An3qto AnT2had
GOLDSMITH: REVIEW OF PLAGIOCLASE 645
complex superstructures.Laves (1951, 1954) re- free energy raises and flattens the plagioclase-
ported that there are plagioclasesin the composi- epidote equilibrium curve in the An35-An5sr&ng€,
tional range of approximately An5-Ar17, &rlorg reducing the temperature interval in which calcic
them peristerites,that show two phasesin "single- andesineis stable.
crystal" X-ray photographs.Laves estimated the Brown (1962)presentedan excellentreview and
compositionsof the exsolvedphasesto be approxi- clarification of the subject of peristerite unmixing in
mately Ane and An3s. Gay and Smith (1955)con- the plagioclasesand related metamorphic and facies
firmed this observation,and refined the estimation series.His summaryof the field observationsindi-
of composition of the two phases as An3*2 and cated that the rate of increasein the composition of
Anzt=z.Thisregion of compositionwas termed the the most basicplagioclasewith increasingmetamor-
"peristeritegap". Additional crystallographicwork phic grade is continuous or nearly so in rocks of the
and refinement was done by Ribbe (1960, 1962), andalusite-sillimanite type and perhaps in the low-
Brown (1960),and Fleet and Ribbe (1965). pressureintermediatetype. A jump occursbetween
Christie(1959)pointed out the significanceof the about An7 and about An26in the kyanite-sillimanite
peristeritegap in low-temperatureplagioclases,and type and the high-pressureintermediatetype, and in
that as a consequenceRamberg'ssmoothunbroken the jadeite-glaucophane type only albite seems to
curve needed modification. He also assumedan exist. He mentionedthat the relation betweengar-
immiscibility gap in the intermediateregion delin- net and the discontinuityin plagioclasecomposition
eatedby Cole et al. (1951)in the low-temperature is not clear; there is an implication that reactions
plagioclases.On the basis of the discontinuitypro- involving garnet and other Ca-rich phases may or
ducedby the peristeritephenomenon,Christie stat- may not be important in this connection.Sen (1963)
ed that the plagioclaseepidote thermometer was pointed out that not all plagioclases unmix, thus
useless. breaksin compositionare not always present, and
At this sametime de Waard (1959)publishedon at any rate are of no avail in delineating metamor-
basicand pelitic schistsof the Usu massifin Timor phic facies. Demarcationmust be made on empiri-
and noted changesin the An content of the plagio- cal grounds based on petrographic observations,
clasesover relatively short distances,reflecting a and checkedagainstother independentevidenceof
successionof narrow zones of metamorphism.He faciestransitions,such as reactionsinvolved in the
found the frequency of occurrence of plagioclase metamorphicprocess.
betweenAn5 and An2sto be remarkablylow, partic- Kretz (1963) restated Ramberg's (1943, 1949,
ularly in the basic schists.He was almost certainly 1952)emphasison the fact that by the nature of
unaware of the evidence of a peristerite gap, and their compositions plagioclase-epidotereactions
suggestedthat the abrupt change is coupled to the must involve one or more additional phases,and
formation of garnet in pelites and hornblende in that knowledge of the reactions is essential to an
basic rocks. The papers by Christie (1959)and de understandingof plagioclasethermometry. Through
Waard (1959)set off a small flurry of activity in the the use of some simplifying assumptions,Kretz
early 1960'son the nicetiesof the plagioclasecom- derived equations to interrelate the composition of
positional problem from two points of view: (a) plagioclase,temperature,pressure,chemicalpoten-
faciesboundaries,and (b) crystal-chemicalaspects. tial of HzO and the composition of the other solid
From this point until the presentthere have been solutionsthat take place in six univariant universal
numerousfield observations,a number of interpre- reactions,three of which were consideredby Ram-
tive papers, rather few experimentalstudies, and berg:
many crystallographicinvestigations,all related to
the plagioclases,and directly or indirectly, to their epidote * muscovite + quartz
P anorthite * potashfeldspar + H2O (l)
behavior in metamorphic and low-temperature en-
vironments.Someof the earlier interpretivepapers epidote + kyanite + quartz
<= anorthite + H2O (2)
are by Rutland (1961,1962),Christie (1962),Noble
(1962),Sen (1963)and Kretz (1963).Noble (1962) epidote + CO2
summarizedthe previous field and theoretical work a anorthite * calcite + H2O (3)
relative to the peristeritegap and presenteda fur- epidote * chlorite + quartz
ther refinement of the Ramberg-Christie diagrams. ? actinolite * anorthite + H2O (4)
He also consideredthe effect of intermediatemeta- epidote actinolite + quartz
*
stable plagioclases,suggestingthat the increased e anorthite + calcic pyroxene + H2O (5)
GOLDSMITH: REVIEW OF PLAGIOCLASE
tents converge to Anla in the central part of the verse zoning, even three-fold zoning, in epidote-
highesttemperature(garnet)zone, Tsuji cautioned bearing, amphibole-freerocks of the eastern Alps.
againstthe use of a presumedperisterite gap as the The plagioclasecores are commonly 0-6VoAn, with
sole explanation,pointing out the possibility of a 14-19%An in the rims. CompositionsbetweenAn5
reaction at the boundary between the epidote am- and An15 are rare, presumably representing the
phibolite and the amphibolite facies where albite, peristerite gap. Plagioclasesmore calcic than An35
chlorite, and actinolite react to form a componentof are also rare. Only calcite-free or low-calcite rocks
amphibole that enriches the plagioclasein Ca. were studied,as the An-contentof the plagioclaseis
Crawford (1966) studied two suites of regionally significantly increased in rocks with greater than
metamorphosedsemi-peliticschistsfrom Vermont 20Vo carbonate. They noted that the presence of
and New Zealand in order to investigate the para- margarite may also influence the Ca-content of the
genesisof low-temperatureplagioclase.On the ba- plagioclase,as indicated by Ackermand and Mor-
sis of coexisting albite and oligoclase,and taking teani (1973).In epidote-containingrocks, they call
into consideration reactions to produce different upon the peristerite gap plus an ill-defined two-
associatedCa-rich phases, Crawford outlined a stage metamorphic process with increasing tem-
peristerite solvus with a vertical albite limb and a peraturesto accountfor the feldsparcompositions.
slopingoligoclaselimb, at pressureson the order of Frey and Orville (1974)studied a margarite-bear-
5-7 kbar. The solvus maximum occurs at about ing black shalefrom the central Swiss Alps with the
450-500"C (corresponding to the almandine-stau- following unusual features:
rolite isogradsin the Vermont area) and spansthe 1) The first plagioclase to appear in the lower-
plagioclasecompositionsAnl to An2aatlower tem- gradegreenschistfaciesis not albite,but oligo-
peratures. clase-andesine(-An:o).
Cooper(1972)followed progressivemineralogical 2) The An-content commonly remains constant
changes in metabasic rocks of a Barrovian-type with increasingmetamorphicgrade.
series,from greenschistto amphibolitefaciesin the 3) Some rocks at the transition from the green-
southern Alps of New Zealand. This area is the schist to the amphibolite facies show unusual-
sameas that studied by Evans (1964)and Crawford ly high An-contents (up to Anzo). Graphical
(1966).As did Crawford, Cooper used coexisting analysis of the system CaO-Na2O-AlzOr-
compositionsof albite and oligoclasethrough the SiO2-H2O-COz(with SiO2, H2O, and CO2 in
garnet zone to outline the form of the peristerite excess)with the phasespyrophillite, parago-
solvus.At the oligoclaseisogradethe compositions nite, margarite, zoisite, calcite, and plagio-
are An6-1 and An23-25.In Vermont the calcium clase satisfactorily explains the variable com-
mineral participating in the development of oligo- positional nature of the plagioclase and addi-
clase is a carbonate, in New Zealand, epidote. tionally points to the importance of certain
Cooper noted that oligoclase first appears as thin specific reactions under varying conditions of
discontinuousrims around an albite nucleus at the P-T-X in controlling the composition of the
garnet-oligoclase-hornblendeisograd, and although feldspar.
oligoclaseis soon in evidenceas individual grains, The importance of the Fe content of epidote and
zoned grain relationships persist throughout the the oxidation potential on the composition of the
garnet zone. With increasing metamorphic grade associatedplagioclasewas discussedby Hormann
through the garnet zone oligoclase increases in and Raith (1973),who investigatedthe Fe3+content
amount, becoming more sodic in composition, of epidotes in a metamorphic series from Tyrol,
while albite decreases,becomingmore calcic. Coo- Austria. Fe3* in epidote as well as the oxidation
per stated that true amphibolite facies status is ratio (Fe3+ x 100/Fe3++ Fe2*1 decreasesfrom
attained by the final disappearanceof albite at the greenschist to almandine-amphibolite facies. Re-
secondoligoclaseisograd, either by the complete dox reactionswere suggestedthat account for ob-
replacementof albite coresby oligoclase,or (proba- served mineral assemblagesand that may explain
bly simultaneously)by the rise of sodic plagioclase the increaseof An-contentof coexistingplagioclase
above An1s, presumably due to closure of the with increasing metamorphic grade. The impor-
peristeritesolvus. tanceof oxidation and of the value of P66,/Pq,s was
Morteani and Raase(1974)found abrupt changes also consideredby Rambaldi (1973).
in plagioclasecompositions,seen especiallyas re- E. Wenk (1962)observedthat the An content of
GOLDSMITH: REVIEW OF PLAGIOCLASE
Wenk, E., Wenk, H.-R., Glauser,A' and Schwander,H. (1975) Wenk, H.-R. (1979b)An albite-anorthiteassemblagein low-
Intergrqwth of andesine and labradorite in marbles of the grade amphibolite facies rocks. American Mineralogist, 64,
central Alps. Contributions to Mineralogy and petrology, 53, l2g4_l2gg-
3ll-326.
Wenk, H.-R. (1979a)Superstructure variation in metamorphic Manuscript received, September 16, IggI;
plagioclase.AmericanMineralogist,64,71-76. acceptedforpublication,Marchg, 19g2.