EconomicGeology

Vol. 57, 1962, pp. 768-784

FACIES AND TYPES OF HYDROTHERMAL ALTERATION

C. WAYNE BURNHAM

ABSTRACT

Most hydrothermallyalteredrocksare readily groupedinto two prin-

cipal facies,the argillic and phyllic (mica) facies. The argillic facies
comprisesthe propylitic,montmorillonitic,and kaolonitictypes,and the
phyllicfaciesthe muscoviticandbiotitictypes. The characteristic mineral
assemblages of the propylitictype of alterationare convenientlyrepre-
sentedon a standardACF diagram,and thoseof the other types on AKF
diagramsto which water (H) has been added.
Generallyeachtype of alterationcharacterizes a subzoneof alteration
that bearsconsistentrelationshipsto neighboringzonesand to a presumed
sourceof heat and altering fluids. These relationshipsalso are in full
accordwiththeinferredphysical-chemical requirementsof thecorrespond-
ing facies. Thus,the rocksof the outermost,
propylite,subzonegenerally
are enrichedin CaO, MgO, Na20, H9.O and CO9.. The rocksin the inter-
mediate,montmorillonite, subzoneare only slightlychangedin bulk compo-
sition, but thoseof the inner, kaolinite, subzoneare impoverishedin the
very constituentsthat have been addedto the propylite subzone. The
rocksof the innermost, phyllic,zonealsoare impoverished in CaO, MgO,
and Na9.O,but are enrichedin K9.O. However, their outer parts (mus-
covite subzone)are more impoverished in CaO, MgO, and Na9.O,than
their inner parts (biotite subzone).
The upperlimits of thermalstabilityfor the differentfaciesat 1000
barswaterpressure are fixedby thebreakdown temperatures of individual
minerals-epidoteat about460 C, kaoliniteat 400 C, andmontmorillonite
at 440 C for the argillic facies,and muscoviteat about620 C for the
phyllicfacies. Biotiteof the phyllicfaciesis stablewell into the melting
range of granitic rocks.

INTRODUCTION

Muca hasbeenwrittenabouthydrothermal alterationand the compositional

changes
inducedby it in the wallrocksof mineraldeposits, especially
in
alumino-silicatewallrocks. So much has been written and the descriptions
sovaried,in fact,thatthecasualreaderfrequentlyis bewildered
by the extreme
complexitiesandlackof uniformity,
realor apparent.Certainly
theminer-
alogyandchemistry of altered
rocksarenotassimple asmostof uswould
like,butneitheraretheyascomplexin theirprincipal
aspects
aspartof what
has beenwritten would lead us to believe. The trend until recentlyseemsto
havebeentowardgreatercomplexity
andhencegreaterconfusion,
but the
straightforward
presentation
of Creasay
(2), it is hoped,
marksa reversal
in this trend.

x Contribution
No. 61-23, Collegeof Mineral Industries,Divisionof Earth Sciences,
The
PennsylvaniaState University.
768
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 769

The confusionregardinghydrothermal alterationappearsto havearisen,

in part,because
the analytical
toolsthat wereavailable priorto about1950
wereinadequatefor thedetailedstudyof fine-grainedmineralaggregates
that
characterize
hydrothermallyalteredrocks. The polarizing microscope is a
marvelous
tool for the studyof the microscopic
featuresof rockson the scale
of a thinsection,
butit is inadequate
for determining
thebulkcomposition
of
materialsthatareasvariable in composition
overshortdistances
asarehydro-
thermallyalteredrocks.
A certainamount
of confusion
alsostemsfromourinabilitysofar to dis-
tinguishbetween
hypogene and supergeneargillicalteration.Originallyit
wasthought(5) that the kaolingroupmineralswereindicativeof supergene
acidsulfateleaching, butsincetheworkof Lovering(6), theweightof opinion
seems to haveshiftedmorestronglyin favorof a hypogene originfor theclay
mineralsin hydrothermally alteredrocks(cf. 12). It is almostcertainthat
clay minerals,especially montmorillonite, have formedduring hypogene
hydrothermal alterationin someareas,but it is equallycertainthat large
amounts of kaoliniticclayshavebeenproduced by supergene processes, notably
in severalof theporphyrycopperdeposits.
A greatdealof efforthasbeendevotedto the searchfor a key alteration
mineralor assemblage that wouldprovidea reliablegeneralguideto ore.
Asidefrom the questionable fruitfulness
of this search,it focusedattentionon
relativelyminor featuresof alterationzones--perhaps to the neglectof the
grossmineralogical and chemicalrelationships--and therebyincreased the
apparentcomplexities of the problem.
Certainly,in their minutia,hydrothermally alteredrocksare highlycom-
plex,but theyalsopossess certainfeaturesof relativelygrossaspectthat are
of suchwidespread occurrence to suggesta large measureof order and uni-
formity to hydrothermalprocesses.It doubtlesswas this sametendency
towardorder and uniformityamongstthe alterationhaloesof the porphyry
copperdepositsthat led Creasey(2) to attempta systematization of hydro-
thermalalteration. It alsois the basisof this paper,in whichan attemptis
made to systematizethe more commonalteration mineral assemblages, to
relatethemto the bulkchemical composition of the rocks,to the compositional
changes producedby hydrothermalactivity,and to the physicalenvironment
(Pa2oandT) of alteration. In attempting to systematize sucha largeamount
of information,there is muchdangerof oversimplification and overgeneraliza-
tion, but if greaterunderstandingis obtainedwithoutsacrificingaccuracy,the
risk is justified.
Part of the discussionpresentedhere is basedon a quantitativestudyof
the mineralogyand chemicalcomposition of four areasof hydrothermalalter-
ationthatwasconducted by D. W. Carpenter,S. W. Crawford,andthe writer
undergrant supportby Bear Creek Mining Company. The argumentspre-
sentedregardingthe physicalenvironmentof alterationare basedin large part
on the unpublishedresultsof experimentalwork still in progressthat is sup-
ported by grants from the National ScienceFoundation. These sourcesof
supportare gratefullyacknowledged.
770 C. WAYNE BURNHAM

PRINCIPAL TYPES OF HYDROTHERMAL ALTERATION

General Statement

Thegeneralapproach takenhereto theproblemsof hydrothermalalteration

is similarto theonetakenby Creasey(2), although
therearemanydifferences
in the mannerof treatment. Creasey(2, p. 360) proposed to treat hydro-
thermallyalteredrocksas essentially
metamorphic
in natureand to sub-
dividethem into faciesof alteration,somewhatanalogousto the well-known
faciesof metamorphism. The threefaciesthusrecognized by Creasey were
calledthe "propylitic,"
"argillic,"and"potassiumsilicate"facies,andtheir
principalmineralassemblages wererepresented on standard ACF or AKF
diagrams.Thisfaciesapproach to theproblemis basedonthepremise that
alterationmineralassemblages haveformedin response to changes in the
environmentalfactorsof pressure,
temperature,
andchemical composition,
and
thatchemicalequilibrium,thoughperhaps notfullyattained, hasbeenclosely
approached
in mostcases.
An estimateof howcloselyequilibriumhasbeenapproachedin a particu-
lar casecanbeobtainedby a comparison of themodalmineralcompositionof
the rockwith the hypotheticalequilibrium mineralcomposition
calculated
fromthe bulk chemical composition. Thus,Creasey(2) plottedchemical
analyses of freshandalteredrocksfromnineporphyry copperdeposits on
AKF diagrams andfounda remarkable correspondence
between the bulk
chemical
andmodalcompositions. Theonlymajordiscrepanciesoccurred
in
rocksthatcontain
potassiumfeldspar,
muscovite,
andkaolinite,
in addition
to
quartz,
butif wateralsoisconsidered
a component,
asshown later,eventhis
assemblage
becomes
compatible.
The threefoldsubdivision
of hydrothermally
alteredrocksproposed
by
Creasey
(2) hasbeenabandoned
herein favorof a twofold
division
thatis
.noreconsonant
withtheconcept
of metamorphic
facies.Thus,themineral
assemblages of altered
rocksareheregroupedintotheargillicandphyllic
(mica)facies; theargillic
facies
corresponds
in largepartto thepropylitic
andargillicfaciesof Creasey,
butthephyllic
faciesbearsonlyslightresem-
blanceto his potassium
silicatefacies.
Bothprincipal
facies
ofhydrothermal
alteration arefurthersubdivided
into
types
accordingto predominant
mineralassociations and,hence,
accordingto
bulkchemicalcompositions.
The argillicfaciesis thussubdivided
intothe
propylitic,
montmorillonitic,
andkaolinitic types,andthephyllicfaciesinto
themuscovitic
andbiotitictypes. Eventually,
perhaps,
it will be feasible
to
distinguish
a fourth
typeofargillicalteration,
thesericitic
type,butthisshould
awaitbetterunderstanding
of the groupof minerals variouslycalledillite,
hydromuscovite,
hydromica,
andsericite (notincluding
truemuscovite). For
thepresent,
sericitic
alteration
istreatedasanextensionofthekaolinitictype.
Thehydrothermallyalteredrocks in manyareascanbereadily arranged
intotwomajorzones thatcorrespond to thetwoprincipalfacies
of alteration
(Fig.7). Moreover,
inmany
ofthese
same
areas,
it ispossible
todistinguish
subzoneswithinthemajorzones thatcorrespond
to theseveral
typesof alter-
ation. Thus,ideally
thereis,about
a givencenter
ofhydrothermal
activity,a
 F,dCIES ,dND TYPES OF HYDROTHERM,dL ,dLTER,dTION 771

succession of subzones,beginningwith the biotiticand muscoviticsubzones

of
the phyllic zone and extendingoutward throughthe kaolinitic,montmoril-
lonitic,and propyliticsubzonesof the argillic zone.

The ,4r#illic Fades

The argillic facies,as definedhere, comprisesall hydrothermalalteration
assemblages that containeither epidoteor one or more membersof the two
groupsof clay minerals,montmorillonite and kaolinite. It also includesas-
semblages that containthe poorly definedclay-micas,here calledsericite,but
owingto problemsconnected with the true identityof what has beencalled
sericitein the past,its role in this faciesschemeis not emphasized.
?ropylitizationhasreceivedconsiderably lessattentionthan other typesof
alterationmainlybecause its effectsgenerallyare lessstrikingand, at times,
difficultto distinguishfrom more normal metamorphiceffects. In nearly
everyareawherepropylitizedrockshavebeenstudied,whetherin relationto
an individualvein or to an area of intensefracturingand pervasivealteration,
they are fringefeatures. Thus, the propylitesubzoneis the outermostof the
three subzoneswithin the argillic zone of alteration.
The characteristic
mineralsof the propylitictype are shownin the ACF
diagramof Figure 1. In additionto the mineralsshown,quartz,albite,potas-
sium feldspar(orthoclase),and sericiteare possiblemembersof this type.
The hachuredlines extendingfrom "montmorillonite" to the A cornerand
from"chlorite"towardF represent
the approximate
rangein solidsolutionof
thesetwo mineralgroups.
The commonoccurrence of propylitizedvolcanicrocksdirectlyoverlying
dolomitizedlimestones (7) suggests that dolomitization
is the counterpartof
propylitizationin silicadeficientcarbonaterocks. Hence,it eventuallymight
provefeasibleto extendthepropylitictypeto includea silica-deficientsubtype.
The compositional featuresof propylitizedrocksare fully compatiblewith
their occurrence in the fringe zoneof alteration. In comparison with altered
parentrocks,they generallycontainmore CaO (calciteand epidote),MgO
(chlorite,montmorillonite and,perhaps,dolomite),andNa20 (albite), aswell
as the almostubiquitousH20 and CO2. In contrast,the inner subzones of
alteration(especiallythe kaoliniteandmuscovitesubzones)are moststrongly
leachedof CaO, MgO, and NaO. Propylitizationof mafic wallrocksmay
take place,however,without appreciableincreasein the CaO, MgO, and
NaO contents.
Epidote (or zoisite) is the only critical mineral of the silica-saturated
propylitictype; hencethe PH,-T stabilityfield of epidote (Merrin, 8, and
privatecommunication), asindicatedby curve1, Figure 5, definesthe physical
environmentof propylitization. It is noteworthythat the stability limit of
montmorillonite(9) is very closeto that of epidote,and that of iron-bearing
chlorite(15) is onlyslightlyhigher.
The PHo-T environments of propylitic,montmorillonitic, and kaolinitic
alterationare essentially
similar;hence,thereis no soundbasisfor distinguish-
ing two separatefacies,a propyliticfaciesand argillicfacies(cf. 2). There
772 C. WAYNEBURNHAM

ITE

EPIDOTE // CHLORITE

C
CALCITE
.FPENTI
TALC

I A(H)
KAOUNITE
(67/oH)

eSM

eMR ,MONTMORILLONITE
SER1CITE ( 50%H )

ecc
tDMXBU CHLOR1TE
DM

CC

MR

(>22%H)

K(H) SM
F(H )
ORTHOCLASE

FIG. 1. AND FIG. 2.

 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 773

is, however,a soundcompositional basisfor distinguishing

the threetypesof
argillicalteration. Moreover,inasmuchas the chemicalenvironmentchanges
graduallyfrom one of CaO, MgO, and Na20 fixationin the propyliticsub-
zoneto oneof CaO, MgO, and Na20 leachingin the inner part of the argillic
zone,propyliticalterationgradesalmostimperceptably
throughmontmoril-
lonitic into kaolinitic alteration.
The composition diagramfor the montmorillonitic and kaolinitictypes
(argillicfacies)is presentedin Figure2. It is indeedmuchmorecomplicated
than the standardAKF diagram(cf. 2, Figs. 2-10) becausewater (H) has
beenaddedasa fourth"component."The additionhasbeenmadesimplyby
plottingH (H20) on a coordinate perpendicular to the triangularplane,away
from the observer. In this way, distortionof the familiar AKF diagramis
avoided. The tie linesin this AKF (H) diagramare taperedsmalleraway
from the observer,toward higher water content(H).
The relationships
amongstthe severalcompatible
assemblages in the AKF
(H) diagram(Fig. 2) are morereadilyvisualizedwith the aid of Figure3.
In this diagram,A(A12Oa+ FeeOa- CaO - NaeO - KeO) is the ordinate
and I-I (I-IeO) is the abscissa. The equilibriumassemblages (compatibility
tetrahedra) of the argillic faciesare shownas small AKF diagramsextending
in a doublerow from lower left (unalteredrocks) to upper right (most in-
tenselyargillized). The row on the right representshigher statesof hydra-
tion, correspondingto higher P2o or lower temperatures,whereasthe row
on the left representslower Pl2Oor higher temperatures. The row on the
left alsois favoredby higher K20 contentsof the rocks.
The inclusionof water as an additionalcomponent is a naturalconsequence
of the basicpremisethat the variousalterationmineral assemblages found in
naturerepresenta closeapproachto equilibrium,becauseequilibriumin hydro-
thermalsystemsis determinedmainlyby water vapor pressures, temperature,
and bulk composition.Moreover,P2o can equallywell be expressed
as a
compositionalvariable (H). Water can be treated as a componentbecause
the P2o probablyremainsrelativeIy constantduring 'the developmentof a
givenfaciesor typeof alteration,eventhoughthe Pl, may be determinedby
externalfactors,suchas the pressurein a fissuresystem.
The strongestevidence,perhaps,that water shouldbe reckonedas a com-
ponentin thesehydrothermalsystemsis obtainedfrom naturally occurring
alterationassemblages.Thus, Creasey(2, pp. 336-368) describedseveral
examplesfrom the literatureof assemblages that appearedto indicatelack of
chemicalequilibrium,
but whenwateris includedas a component
(Figs. 2-4),
FIG. 1. ACF diagram of the propylitictype, argillic facies. Hachured lines
indicateapproximaterangesin compositionof phases. (Line betweenmontmoril-
lonite and kaolinite should also be hachured.)
Fx. 2. AKF(I-t) diagram of the argillic facies. Star symbol----leastaltered
parentrocks,X ----montmorillonite-bearingrocks,opencircles= kaolinRe-richrocks,
solid circles ----sericite-rich rocks, with or without kaolinite. Bu ----Butte, Montana;
CC = Chuquicamata, Chile; CD--Castle Dome, Arizona; DM-- Dixie Mine,
Colorado; FR----Front Range Mineral Belt, Colorado; MR--Morenci, Arizona;
SM--San Manuel, Arizona; and SR----Santa Rita, New Mexico. See text for
explanationand references.
774 C. WAYNE BURNHAM

every one of theseexamplesbecomesa compatibleassemblage.Even more

striking are the resultsof detailedstudies (unpublished)of the alteration
haloesat Bingham,Utah, Santa Rita, New Mexico, Ithaca Peak, Arizona,
and CrescentPeak, Nevada,which were madeby the writer and graduate
students
at the PennsylvaniaStateUniversity. In 617 bulk samples of altered
rocksanalyzed,261 incompatible assemblages were found, accordingto the
compatibilitydiagramsof Creasey(2, Figs. 2-10), but only two incompatible
assemblages
were found when water (H) was taken into consideration,as in

(J)Se//'Mo

,,, .2, ....... ,, ,

_ ......

Seu
K x CI
,

20
// (O)

H (MOL PERCENT
)

Fro. 3. A-H diagram of the argillic facies showingthe effect of the degreeof
leachingof CaO, MgO, and Na=O (A) and the degreeof hydration (H) on the
compatiblemineral assblages. The least altered rocks are representedby as-
semblage(O) and the mostintenselyalteredby assemblages (C) or (D) and (I)
or (). Bi = biotite, C1= chlorite, Hb = hydrobiotite,Ka = kaolinite, Mo = mont-
morillonite, Or = orthoclase,and Se = sericite.

Figures 2 to 4. Moreover, both thesesamples,which were from the zone of

supergene enrichmentat SantaRita, containedsmallamountsof kaoliniteof
suspectedsupergeneorigin.
The common minerals of the argillic facies include quartz and albite in
addition to the minerals shownin Figure 2. Quartz is almost ubiquitousin
this facies,but albiteappearsto be commononly in the propyliticand mont-
morillonitictypes. Potassium feldspar(orthoclase)is secondonly to quartz
in its frequencyof occurrence
in argillicallyalteredrocks,and like quartz,is
commonin both faciesof alteration. The only argillic-faciesassemblages in
whichorthoclase is not compatibleare assemblages (D) and (J) in Figure 3.
Assemblage(D) was not found in the 617 altered rocksanalyzedand as-
semblage(J) was found in only one.
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 775

The kaolinite2 that appearsat the A (H) cornerof Figure 2 includesall

members of thekaolincompositional groupof mineralsthatcommonly occurin
hydrothermally alteredrocks. The kaolingroupdoubtless is themostabun-
dantgroupof clayminerals in argillizedrocks,andX-ray diffraction
studiesof
the 617 alteredrocksclearlyshowthat kaoliniteis the mostcommon mineral
of this group. Henceforth,the kaolingroupmineralswill be referredto as
kaolinite.
The role of kaolinitein argillicalterationis complicated
by its dual origin.
Schwartz(12) and othershave clearlyshownthat kaoliniteis a hypogene
mineral in someareas of alteration, but there also is abundantevidencethat it
is supergene in others. Rocksfrom belowthe zoneof supergene enrichment
in the four areasof alterationstudiedrarely containmore than five percent
kaolinite. In contrast,rocksfrom thesupergene enrichedzoneat SantaRita,
New Mexico,containas muchas 60 percentkaolinite. The supergene origin
for part of the kaolinitein certainof the porphyrycopperdeposits alsohas
statistical
support,for thedepositsthatarenotablysupergene enrichedalsoare
kaolinite-rich,
whereas thosein whichsupergene enrichment is neitherintense
norwidespread (Ajo, Bagdad,Bingham, andEly) are kaolinite-poor.Hypo-
genekaolinization, on theotherhand,commonly is intensein the well-defined
vein-typedeposits, as in the outerzonesat Butte (11), at Tint,c (7), in the
ColoradoFront Range(6, 14, 1), and in manyotherdistricts.
The montmorillonite in Figure2 representsa complex groupof minerals in
whichintra-layersubstitution and cationexchange are common.The prin-
cipalintralayersubstitution in the mostcommonly occurringmontmorillonite
of the argillicfaciesis magnesium for part of the aluminum. The interlayer
(exchangeable) cationis predominantly calcium;lesscommonly it is sodium.
Themagnesium substitution
isindicated in Figure2 to extendfromtheA (H)
cornerapproximately 30 mol percenttowardF (H), but this is merelyan
estimatebasedon the informationavailable (16).
The purealuminumend-member of the montmorillonite
group(beidellite)
rarelyoccursin hydrothermallyalteredrocks. In fact, Hawkins (3) found,
in the experimental
hydrothermal alterationof naturalrocks,that montmoril-
loniteformedonly in rocksthat containedmorethan abouttwo weightper-
cent MgO; kaolinite formed, instead,in rocks that containedless than this
amount. This featureof montmorillonite stabilityappearsto be the principal
causefor the occurrenceof the montmorillonite subzone in the intermediate
part, and the kaolinite subzonein the inner part of the argillic zone of
alteration.
Sericite, as the term is used here, includesthose compositionsthat extend
from A (H) in Figure 2 ("illites") up to about 33 tool percentK (H)
("hydromica,""hydromuscovite," and "high silicasericites"),but it doesnot
includepure muscovite(maximum K20, 2M1 polytype). This separationof
the muscovite-like minerals into sericite and muscovite is based on mode of
occurrence
in hydrothermallyalteredrocks,but the distinctionbetweensericite
and muscoviteis made primarily by polytypes(17). In a few published
2 The nomenclature of the clay minerals here follows the classification of Warshaw and
Roy (16), except for a few familiar names such as "sericite."
776 C. WAYNE BURNHAM

accountsof argillic alteration, however, "hydromuscovite"and "hydromica"

have been recognized.
The X-ray diffraction analysesof more than 230 samplesof altered rocks
from SantaRita, New Mexico, revealedthat 1 Ma or 1 M (rarely 3 T) poly-
typeof "muscovite"
occurredin morethan 70 percentof the rocksthat also
contained
montmorillonite
andin nearly90 percentof thosethat alsocontained
both montmorilloniteand kaolinite. On the other hand, the 2 M1 polytype
occurredin more than 95 percentof the muscovite-bearingsamplesthat con-
tainedno clay minerals. Theseobservations are compatiblewith the results
of hydrothermal experiments by Yoder and Eugster(17) whichindicated
thatthe 1 Ma and 1 M polytypes are characteristic
of "muscovites" synthesized
at lower temperatures, and that thesepolytypescan be readilyconvertedat
highertemperatures to the2 M1 polytype. Theyalsoare compatible with the
generalobservation (cf. 4) that the common muscovite of graniticrocksand
pegmatites is the 2 M1 polytypein nearlyeverycase. Thus,it appears that
muscovite (2 Mx polytype, maximumK20) doesnotcommonly occurin rocks
of the argillicfacies,exceptin the zoneof transitionto the highertemperature
(for a given Pn2o) phyllicfacies?
Thehydrobiotite shownin Figure2 represents a seriesof compositionsthat
apparentlyextends frombiotiteto vermiculite (16), andin whichwateris
presumed to replace partor all theinterlayer
potassium. It alsoincludes the
so-called
"leached biotite,"whichprobablybelongs to thisbiotite-vermiculite
series. Mostof hydrobiotite or "leached biotite"of hydrothermally altered
rocksappears to lie closerin composition to biotite;vermiculite probably
wouldnotoccurin alteredrocksunless theywereessentially freeof potassium,
a rare situation, indeed.
The chloritein hydrothermally
alteredrockscommonly
is amesitic
in com-
position,
with moreor lessFeO in substitution for MgO and Fe2Oafor
AlcOa;hence,it generallylies closeto the point indicatedfor chloritein
Figure2. The hachured linethat extendsfromthispointtowardF (H)
represents
theapproximatepossible rangein compositionof thechlorite
group.
The chemicalcomposition of the argillic-zone rocksshowssystematic
differences
withposition
relativeto a presumedsource of heatandhydrother-
mal solutions,
whetherthe sourceis a fissureor the interiorof an intrusive
stock. The rocksof the montmorillonite
subzonegenerallyare gradationalin
compositionoutwardwiththecontiguous
propylitized
rocksor, in theabsence
of an extensive
propylitic
subzone,
with unaltered
rocks. Consequently,the
differencesin bulkcomposition between theserocksandthe unaltered parent
rocksordinarily arenotgreat. The differences become muchmoremarked,
however, onpassing inwardintothekaolinite subzone whereCaO,MgO,and
NaO arestronglyleached, andonlyHO is addedin largeamounts.
In orderto visualizebetterthe compositional
changes effectedin argillic
alteration,
selectedpublished analyses (2, 11, 14, 1) of alteredrocksand
theirunaltered parentshavebeenrecastin termsof AKF components and
plotted
inFigure2. It isclearfromthese
plots
thatargillic
alteration
follows
a This transitionzoneis represented
at SantaRita by severalrocksthat containboth1 M
and 2 Mx polytypes.
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 777

a well definedpathfrom nearthe KF (H) sideof the diagram(fresh rock)

toward the A (H) corner. This path also is toward increasingwater con-
tent, as shownin Figure 3, reachinghigher valuesin the kaolinitictype.
Thus, as fresh rock is exposedto the attack of hydrothermalsolutions,
underconditions of the argillicfacies,evena mild leachingof CaO, MgO, and
Na20 causes a markedshiftin bulk composition towardA(A12Oa+ Fe2Oa-
CaO- Na20- KO). The first importantalterationassemblage formed,
under conditionsof moderatetemperaturesand KO contents(granodiorite
composition)but relativelyhigh Pa2o,is that represented by diagram(A),
Figure 3, the montmorillonitic type. More extensivealterationalong this
pathleadsto assemblage (B), whichrepresents the transitionfrom the mont-
morilloniticto the kaolinitictypeandcorresponds, perhaps,to the "mixedclay
zone"of Salesand Meyer (11). Continuedalteration(leachingand hydra-
tion) generallyproducesassemblage (C), which is characteristic of the
kaolinitictype. It rarelyproceeds to assemblage (D), however,for lackof
enoughMgO at thisstageof leaching to stabilizemontmorillonite.
Alterationat somewhat highertemperatures, higherKO content(granite
composition), or lowerPa2ogenerally followsa pathapproximately as indi-
catedby the sequence of assemblages (E)-(J) in Figure3, thoughrarelyare
all assemblages in the sequence represented.In fact, alterationin certain
districtsof the ColoradoFront Range(1, 14) appearsnot to haveprogressed
beyondassemblage (G) prior to the metasomatic introduction of KO and
consequent deflection
of the pathtowardK (H) in Figure2. This effectis
illustratedin Figure2 by thetwoseriesof analyses with thesymbols FR and
DM. The FR series(1) is somewhat unusualin that the alterationsequence
is kaolinite-orthoclase-sericite,
but it is preciselythe sequence expectedupon
additionof K20 to assemblage(G), Figure 3.
Commonly, alterationin theouterpart of theargilliczoneis represented by
assemblages in the "higherhydration"sequence of Figure 3, but inwardthe
assemblages crossover verticallyinto the "lowerhydration"sequence.For
example,the biotitein fresh quartz monzoniteat Butte, Montana,was de-
scribedby Salesand Meyer (11, p. 19) as havingbeenconverted to chlorite
with montmorillonite(assemblage B, Fig. 3) in the outer part of the zoneof
alterationand thenceback to biotite with kaolinite (assemblage I, Fig. 3)
nearer the vein.
Numerousareasof hydrothermal alterationhavebeendescribed in which
the rocksof the argillicfacies,especiallythe kaolinitesubzone,passinward
towardthe vein or other sourceof hydrothermalactivityinto rocksrich in
"sericite"andquartz. This "sericite," in somecases,is truemuscovite,butin
manyothersit is sericiteas the term is usedhere. It apparentlyis concen-
tratedin thisparticularpart of the alterationhalobecause it canform either
throughtheintenseleaching of CaO,MgO, andNaO, withconsequent enrich-
ment in the residuumof AlcOa, but without introductionof KO, or through
moderateleachingand introductionof K20.
The problemof distinguishing hypogene from supergeneargillicalteration
findspartialsolution,perhaps,in the restrictedcompositional
stabilityfieldof
montmorillonite. Inasmuchas supergenealterationis largely a processof
778 C. WAYNE BURNHAM

acid sulfateleachingof alkaliesand alkalineearths,it is not likely to produce

montmorillonite(which requiresappreciable MgO) in rocksfrom whichnearly
all the MgO has been extractedby hypogeneargillic or phyllic alteration.
Thus, supergenemontmorilloniteshouldbe commononly in rocksthat have
not previouslybeenintenselyalteredby hypogenesolutions(cf. 14). On this
basis,most of the montmorillonizedrocks in the porphyry copper deposits
probablyare of hypogeneorigin.
The temperature-pressure environmentin which the critical mineralsof
the argillicfaciesare stableis shownin Figure 5. Even thoughepidote-and
montmorillonite-bearing assemblages canpersistto somewhathighertempera-
turesthan kaoliniticassemblages (curves2 and 3, Fig. 5), the widespread
occurrence of kaolinizedrockscloserto the hydrothermalsourceof heat indi-
cates that the lower temperaturelimit imposedby the kaolinite-quartz
assemblage (belowcurve3) generallyis moreimportantin determining the
physicalenvironmentof the argillicfacies.
The upperstabilitylimit of sericiteis notknownprimarilybecause it has
notyet beenascertained thatthe 1 M and1 Ma polytypes are thermodynami-
callystable(16). Its lowerwatercontentandcharacteristic modeof occur-
rencein theinnerpartof theargilliczonesuggest thatitsformation is favored
bysomewhat highertemperatures and/orlowerwaterpressures, butincreased
K20 contentcouldproducethe sameeffect.
Thus, the distributionof mineralassemblages within the argillic zoneis
moreconsonant with variationsin bulk composition than in temperature and
pressure.Thisisnotto deny,however, thattemperaturegradientscouldexist
withintheargilliczone;indeed,theywellmightbethecausefor compositional
gradientsin the hydrothermalpore fluidsand ultimatelyfor the observed
compositional
differences.

The Phyllic Facies

The phyllicfacies,as definedhere,includesthosehydrothermally
altered
rocksthat containbiotiteor muscovite,with or withoutpyrophyllite,andalusite,
topaz,andchlorite,but whichdonotcontainepidote(zoisite), montmorillonite,
or kaolinite. Thus defined, muscoviteand biotite becomecritical minerals of
the phyllicfacies,as well as the basisfor subdivision
into the muscovitic
and
biotitictypes. The majority of hydrothermallyalteredrocksthat belongto
this faciescontainabundantmuscoviteand therefore are placed in the mus-
covitictype,but in certainareas,as in the porphyrycopperdepositsat Bing-
ham,Ely, BagdadandA j o, muscovite locallyis absentand biotiteis abundant.
The mineral assemblages
of the phyllic faciesare shownin the AKF (H)
diagramof Figure4. As in Figure 2, water (H) is plottedas an additional
component in the directionperpendicular
to the AKF plane,away from the
observer. Thus, orthoclaseand andalusitelie in the AKF plane,but the other
compositions,as indicatedby the percentages in parentheses,
lie variousdis-
tancesbehindthis plane. Quartz and albitealsoare possiblemembersof all
assemblagesin thisfacies;albiteis far lesscommonthanquartz,especiallyin
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 779

the muscovitictype. Topazis a possible memberof alumina-richassemblages

in fluorine-bearing systems.
Muscoviteoccupiesa unique positionin the phyllic facies, as it and its
joins with biotite (or chlorite) and andalusiteseparatethe alterationassem-
blages that contain orthoclasefrom those that do not. The majority of
hydrothermallyaltered muscovite-bearing rocks, especiallyin the porphyry
copperdeposits.alsocontainorthoclase;therefore,their bulk compositions, as

A(H)
ANDALUSITE
PYROP HYLLI TE
{DO%H)
TOPAZ

MUSCOVITE
(40%H)
MR

MI

ISM
,,j CHLORITE
L
. S ( 40%H )
SM

EL AJ
BI ')('MR
eEL
q3/
AJ

)(-CC SM
SR
EL BI
K(HI EL F(H)
ORTHOCLASE

FIG. 4. AKF (H) diagramof the phyllicfacies. Hachuredlinesrepresentthe

approximaterange in compositionof phases. Star symbol- least altered rocks
and solid circles-- altered rocks. AJ = Ajo, Arizona; BA = Bagdad,Ariiona;
BI ----Bingham,Utah; CC --- Chuquicamata, Chile; CD -- Castle Dome, Arizona;
EL----Ely, Nevada; MR--Morenci, Arizona; SM = San Manuel, Arizona; and
SR = Santa Rita, New Mexico. See text for references.

shownin Figure4, lie ontheKF sideof themuscovite-chlorite

join. In some
areas,however,
notably wherephyllicalteration
hasbeensuperimposed
onan
earlierintense
argillic
alteration
without
introduction
ofI(.O,thebulkcompo-
sitions
oftherockslieveryclose tothemuscovite-chlorite
joinandrarelythey
containpyrophylliteor andalusite.In the presence
of muchfluorine,altera-
tion commonlyis veryintenseandproduces greisenrich in topaz,muscovite
and quartz.
780 C. WAYNE BURNHAM

The biotitictypeof alterationgenerallyis mineralogically

simple,consisting
chieflyof biotite,orthoclase,and quartz, with more or lesschlorite,muscovite,
andalbite. It mergeswith the mineralfaciesof unalteredgraniticrocksand,
at times, is difficultto recognizeas a productof hydrothermalalteration.

800

700
600

00

4OO

5 PH20
(BARS)

15

12

o el
le lee

ee

I i
i 214 I8

FIG. 5. PH2o-Tcurvesthat mark the approximate upperlimit of stabilityfor

certain alterationmineral assemblages.Curve 1 = epidotedecomposition, curve
2 -- kaolinite-quartzreaction,curve3 = montmorillonite
breakdown,curve4 -- iron-
bearingchloritebreakdown,curve5: muscovite-quartz reaction,and curve6 = be-
ginning of melting of granite.
Fie. 6. Relationshipbetween the K20 and CaO contentsof hydrothermally
alteredquartzmonzoniteporphyryat Bingham,Utah. Samplestaken on 400-foot
grid pattern and analyzedby X-ray fluorescence
methods.

Ordinarilybothbiotiteand orthoclase are more abundantand plagioclase is

lessabundantand morealbiticthan in the unalteredparentrocks.
The chemicaleffectsof phyllicalterationshowa continuitywith the effects
producedin the kaolinitictype. The intenseleachingof CaO, MgO, and
NaeO persistin rocksof the muscovitic type,but thereis a markedslackening
in the intensityof MgO and NaO leachingin the biotitictype. This is due
primarily to the fixing of MgO in biotite and NaeO in albite. Most of the
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 781

CaO is removedfromintenselybiotitizedrocks,however,andaccounts largely

for the shiftin bulk compositionawayfrom the KF (H) sideof Figure 4.
Potashmetasomatism, weak to moderatein the inner part of the argillic
zone,locallyis very intensein the phylliczone,especially the biotitesubzone,
as illustratedby certainof the analysesplottedin Figure 4. Thus, intensely
alteredporphyryin the phylliczoneat Bingham,Utah, not uncommonly con-
tains 13-14 weightpercentK20 (Fig. 6), whereas"fresh" porphyrycontains
only about 4.2 percent. Where K20 is added in moderateamountsto in-
tenselyalteredrocks,muscovitemay accommodate most of the addition,but
where added in large amounts,hydrothermalorthoclaseis predominant.
Concomitant with intenseKO metasomatism, CaO is stronglyleachedfrom
the rocks,resultingin the inverserelationshipbetweenr20 and CaO shown
in Figure 6. This relationship,expressedas the KeO/CaO ratio, provides
a very sensitiveindicatorfor the detectionof phyllic and argillic alteration
(excludingpropylitization).
The characteristic mineralassemblages of the phyllicfaciesare stableover
a wide rangeof temperatures and pressures, as indicatedin Figure 5, curves
5 and 6. Biotite, althoughstableto higher temperaturesthan muscovite,is
morereadilyattackedat the lowertemperatures of the argilliefaciesand com-
monlyis convertedthereto hydrobiotite, chlorite,or sericite. Muscovite,on
theotherhand,rarelyis affectedby lowertemperature solutions andgenerally
persistsas the 2 M polytypeinto the zoneof weathering.
Pyrophylliteandandalusite are stablein hydrothermal environments only
abovethestabilitylimit of kaolinire(curve3, Fig. 5); hence,the occurrence of
oneor theotherin phyllic-facies rocksindicates that a certainminimumtem-
perature,at a givenpressure,wasexceeded.Unfortunately,neitherof these
mineralsis sufficientlywidespreadin occurrencein altered rocksto be very
usefulin this respect(cf. 13).
The PH2o-Tcurve for the reactioninvolvingmuscoviteand quartz (curve
5) fixesthe uppertemperaturelimit for the muscovitic
type. At temperatures
abovethis curve,only biotitictype assemblagesoccur. The mostcommonof
theseassemblages, the orthoclase-biotite-quartz-albite
assemblage,also is the
normalprimaryphaseassemblage to crystallizefromhydrousgraniticmagmas.
Biotitictypealteration,therefore,
constitutes
a connectinglink,mineralogically,
chemically,and physically,betweenmagmaticcrystallization and hydrothermal
alteration.
Rocksof the phyllicfacies,becauseof their highertemperaturenature,are
susceptible
to retrogradeargillicalterationduringthe waningstagesof hydro-
thermalactivity. This retrogradealterationrarelyappearsto be intense,but
might accountin large part for the chloritizationand leachingof biotite,as
well as kaolinizationof both the micasand orthoclase(cf. 10).
The compositional
changes producedby phyllicalterationfollowdifferent
pathsthroughthe AKF (H) diagram(Fig. 4), depending upon the tem-
peratureand pressureconditionsof alterationand the intensityof r20
metasomatism.Where phyllic alterationof the muscovitictype has been
superimposedon an intenseargillicalteration,the path extendswell toward
782 . WAYNE BURNHAM

A (H) beforecurvingtoward muscovitecomposition.Where phyllicaltera-

tion has been initiated at higher temperaturesand argillic alterationis weak
or absent,the path extendsa shorterdistancetoward A (H) beforecurving
toward the AK (H) side or, if K20 metasomatismhas been intense,toward
K (H). Where phyllic alterationof the biotitic type at higher temperatures

25W 20W 15W lOW 5W 0 5E IOE 15E 20E 25E 30E 35E 40E

5S

lOS

15S

20S

25S'

3OS

35S

40S

ALTE AP
45S

50S
Argillic
Focies .hyllic
Foci

55S
muo,,,c
type type

monoril Ionific Wofific

60S
type

Fro. 7. Generalizedalteration map, Santa Rita, New Mexico. Grid interval

is 500 feet; Samplestakenon 250-footgrid pattern,July 1956.

hasbeenaccompanied
by intenseK20 metasomatism,
asis commonly
the case,
thepathcurvesdirectlyfromthefreshrocktowardI((H).

ttYDROTHERMAL ALTERATION AT SANTA RITA, NEW MEXICO

The alterationpatternin the SouthPit area of the Chino mine, Santa

Rita, New Mexico is presentedin Figure 7 as an illustrationof the proposed
faciesclassification
of hydrothermalalteration. It is basedon the X-ray
analysis
of morethan230samples
takenona 250-foot
gridpatternandcon-
sistsof a central area of argillic-faciesrocksthat is flanked on the east and
westby phyllic-facies
rocks.
 FACIES AND TYPES OF HYDROTHERMAL ALTERATION 783

Most of the argillic alteration is of the kaolinitic type and much of it

probablyis supergene in origin. Areas of montmorillonitic-typealteration
are indicatedby stippling. Similarly,exceptfor a few smallpatchesof
biotitic-type
alterationin the easternpart of the maparea,mostof the phyllic
alteration is of the muscovitictype.
The distributionof alteration facies with respectto the mine area in
Figure 7 suggests that a major part of the ore is associated
with argillicalter-
ation. This appearsto be true, in general,althoughlarge amountsof ore
occur 500 feet or more from the argillic zone, within the phyllic zone of
alteration.

I)ROTI-IER^r, ^r, TER^XXON ^NI) XE OCCURRENCE OF ORE

One of the principalobjectivesin the numerousstudiesof hydrothermally

altered rocks has been to establishcriteria, based on certain features of the
altered rocks, that would be of general use in guiding the searchfor ore.
Althoughthis objectivenot alwayshas beenachieved,certain featureshave
proven useful as guidesto ore in somedistricts. Unfortunately,they have
not provenas usefulwhen appliedto the searchfor ores elsewhere.
The evidenceis overwhelmingthat hydrothermalalterationand ore for-
mation are geneticallyrelated processes,but apparentlyonly to the extent
that both are hydrothermalprocesses.There are very few hydrothermalore
depositsthat lack associatedwallrock alteration,but there are many areasof
hydrothermalalterationthat are essentiallybarrenof ore deposits. Moreover,
rocksof a certainfaciesor type of alterationare ore-bearingin one area and
barren in another.
The almostubiquitousassociation of alterationwith ore, but not always
ore with alteration,is readily explainedin terms of the conditionsimposed
by each phenomenonon a hydrothermalsystem. Hydrothermal alteration
is dependentmainly on the presence,under certain conditions,of hydro-
thermal solutions,whereasthe occurrenceof ore is dependent,in addition,on
the availabilityof the ore constituents.Thus, the availability of ore con-
stituentsis the principalfactor in determiningwhethera particulararea of
hydrothermally alteredrocksis barrenor metallized.
The main inferenceto be drawn from this conclusionwith respectto the
explorationfor hydrothermal oresis that the mostreliableguideto ore in
hydrothermally alteredrocksstill is the valuablemetalcontentof the rocks,
themselves.Beyondthis, many factorsmust be taken into consideration,
includingthe type of alteration,and the prospects
are dim that hydrothermal
wallrockalteration,in itself,will ever constitutea really reliableguideto ore.
COLLEGEOF MINERAL INDUSTRIES,
PENNSYLVANIASTATEUNIVERSITY,
UNIVERSITY PARK, PA.,
March 27, 1962
REFERENCES

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copper deposits: Ecoa. Gv.o..,v. 54, p. 351-373.
784 . WAYNE BURNHAM

3. Hawkins, D. B., 1961, Experimental hydrothermal studies bearing on rock weathering and
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