American Mineralogist, Volume 76, pages 1081-1091, I99I

Physics of aqueousphaseevolution in plutonic environments

hrrr,rp A. C.lNoBr,l
Laboratory for Mineral Deposits Research, Department of Geology, University of Maryland,
CollegePark, Maryland 20742, U.S.A.

AssrRAcr
Many mineral depositsappearto have beenformed by fluids of magmatic-hydrothermal
origin. However, the means of egressof magmatic fluids and the focusing of these fluids
into sites of alteration and mineralization are not well understood.
High Lewis numbers for HrO imply that HrO will accumulatewithin a maryinal bound-
ary layer or crystallization interval within magma chambers. Three casesare discussed:
(l) Magmatic H,O exsolution occurs at <<20o/ocrystallization (at high initial magmatic
HrO concentrationsor low pressures),inducing the rise of plumes laden with bubbles (+
crystals). (2) Magmatic HrO exsolution occurs later (at moderate initial magmatic HrO
concentrationsor moderate pressures),and vapor bubbles, trapped in an immobile crust,
form a spanningcluster at critical percolation through which the magmatic aqueousphase
can advect. (3) Vapor exsolution occurs in an immobile crust but with lower initial HrO
concentrationsor at higher pressure,so that the spanning cluster at critical percolation is
not achievedand the magmatic aqueousphaseis dispersedthrough the subsoliduscracking
front.
The likelihood of plume rise (relative to the rise of individual bubbles)can be evaluated
by calculating the characteristicrise time for individual bubbles relative to the character-
istic rise time for bubble-laden plumes. For bubbles of r s I cm, plume rise is likely.
Percolation theory indicates that a spanning cluster of the aqueousphase on a simple
three-dimensional lattice is attained when the aqueousphaseachievesa volume fraction
of iD": 0.31. Percolationis attainedfor initial magmaticHrO concentrations>l-2o/o at
0.5 kbar and >4-5o/o at2kbar. For lower HrO concentrationsand higherpressures, vapor
will be dispersed through a rather diffuse cracking front. This analysis suggeststhat or-
thomagmatic-hydrothermal fluids can be transported and focused to sites of mineral de-
position near the apical regions of magma chambers by either bubble-plume rise or ad-
vection through spanning clustersofbubbles.

INrnonucrroN: vAPoR EvoLUTroN rN
INTRUSIVE SYSTEMS
The last few decades have seen many advances in
chemical modeling of magmatic differentiation processes.
More recently, a number of studies have focused on
chemical modeling of magmatic aqueous phase exsolu-
tion. However, many of the chemical models of mag-
matic vapor evolution in ore-forming systems(Candela,
1986, 1989, 1990)ignore the physicalconstraintson the
systems that are being modeled. Whereas significant
progresshas been made in understandingore fluid chem-
istry in porphyry, skarn, and related systems,the means
of egressof the magmatic fluids from crystallizing plutons
and the mechanismsby which theseore fluids are focused
in sites of mineralization are not well understood.
The importance of orthomagmatic-hydrothermal flu-
ids in porphyry-type and skarn-type deposits has been
debated for many years in the geologicalliterature. Nor-
ton (1982) demonstratesconvincingly that nonmagmatic
HrO can be focused in regions of mineralization, with
magma bodies acting solely as heat engines.The volume
0003-o04x/9l/0708-108l $02.00
of country rock from which ore metals can be leachedby
nonmagmatic fluids is obviously much larger than the
volume of the associatedpluton. Therefore,if the country
rock is the sourceof ore substance,there is little problem
accounting for the quantity of ore metals in the anomaly.
That meteoric HrO is important in the genesisof these
deposits is not contested. Conversely, S isotope data,
summarized by Ohmoto and Rye (1979), and hydrogen
and oxygen isotope data (cf. Sheppard et al., l97l) sug-
gest that a magmatic aqueous phase may also be active
in ore formation. Further, Cl and Cu concentrations found
in fluid inclusions from porphyry copper and related de-
posits (Reynoldsand Beane, 1985; Scherkenbachet al.,
1985) may easily be accountedfor by the evolution of an
aqueous phase from arc magmas (Candelaand Holland,
1986;Candela,1989).At the Hendersondeposit,one of
the most heavily studied porphyry depositsin the world,
Carten et al. (1988) demonstratevery closelinks between
intrusions and ore zones. Differencesin the mass of ore,
intensity ofalteration, and density ofveins can be directly
correlated with primary igneousfeaturesin the associated
1 0 8I
1082 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION
stocks.Additionally, Hannah and Stein (1985),in isoto-
pic studies of the Climax group deposits, show convinc-
ingly that Pb and S were not derived from the country
rock but from the ore-relatedplutons. The intrusive com-
plexesassociatedwith the Climax, Urad-Henderson, and
Mount Emmons-Redwell porphyry Mo deposits were
emplaced in very different host rocks: Precambrian felsic
gneisses,amphibolites, and granulites at Climax; a youn-
ger Precambrian granite at Henderson; and Cretaceous
shalesand sandstoneat Mount Emmons-Redwell. These
variations in host rocks support the contention that coun-
try rocks at sites of stock emplacement played no signif-
icant chemical role in the mineralization process(Han-
nah and Stein, 1985).
Yet the hypothesis that orthomagmatic-hydrothermal
processesplay a dominant role in porphyry ore genesis
remains problematic: it fails to accountfully for the origin
of at least some of the ore constituents in porphyry de-
posits.Quoting from Carten et al. (1988):
The absenceof high temperature veins and associated
hydrothermal alteration in deep cores of stocks, the
distribution of ore about the high levels of stocks, the
orientation of veins about the apex of stocks . . . are
suggestiveof initially high concentrations of molyb-
denum and volatiles in the apex of a stock immediately
prior to the onset of significant crystallization. . . . As-
signment of molybdenum in the ore shell about the
Seriate stock to the volume of solid occupied by the
apex . . . yields concentration levels in the apical mag-
ma of approximately 13,000ppm molybdenum.
Based on these and other observations, a number of
fundamental questions may be raised with regard to the
physics of magmatic aqueous phase evolution, such as:
(1) Why do someplutonspossess focusedzonesof intense
mineralization, whereasothers do not? and (2) How can
large quantities of ore metals be brought to sites of ore
deposition, given the orthomagmatic-hydrothermal par-
adigm, when only small cupolasare intimately associated
with mineralization?
As a steptoward answeringtheseformidable questions,
a general,preliminary physical model has beenconstruct-
ed to account for aqueous phase evolution from felsic
magmas. The model, which is based on current physical
models of magma chambers, suggestsmeans by which
magmatic ore fluids may be scavengedfrom rather large
volumes of magma and delivered to sites of ore deposi-
tion, and it provides rationales for discriminating "pro-
ductive" from "nonproductive" plutons. Eventually,more
sophisticatedphysical models may be wedded to chemi-
cal models, such as those presentedin Candela(1986),
Candelaand Holland (1986),and Candela(1989),to pro-
vide a comprehensivemodel for the evolution of aqueous
fluids from epizonal plutons. Thus, this paper is a modest
attempt to answera portion of the question of why mag-
matic-hydrothermal mineralization occurs where it does.
The aims of this paper do not include a detailed dis-
cussion ofhow fracturing occurs in the apical regions of
magma chambers.That cupolas and apical stocksare the
foci of mineralization is not an issue. Clearly, in some
cases,the magmatic aqueousphaseis focusedtoward these
structures (given a magmatic-hydrothermal paradigm).
Knapp and Norton (198 l) show that fracturing resulting
from both magma pressureand thermal stressis initiated
in the upper regions ofa pluton. Buoyant forces resulting
from the delivery of copious amounts of fluids to these
zones ensure that repeatedfracturing will occur in these
regions(Norton and Cathles,1973).This subjecthasbeen
addressedin other works (cf. Knapp and Norton, 1981).
Rather, the mechanisms by which the aqueous phase is
brought to the upper regionsof magma chambersare the
objectsofthis study.
GrNrnlL CRYSTALLIZATIoNMoDEr,s
The primary processin the crystallization of a magma
body is the irreversible loss of heat to the surroundings.
Heat passesout of the magma at the margins of the body,
and crystallizationis localizedin theseregions.With time,
the solidus moves toward the interior of the magma
chamber, defining a moving margin.
Langmuir (1989) refers to crystallization that occurs at
the margins of a chamber as in situ and considers two
limiting casesthat are pertinent to the presentendeavor.
In Langmuir's first case,crystallization occurs at an in-
terface between solid and liquid. The degreeof crystalli-
zation as a function ofdistance varies as a steplike func-
tion near the interface. The evolved liquid is convected
away from the rather sharp solidJiquid interface because
ofa (positive or negative)changein its density upon dif-
ferentiation (Fig. l). In Langmuir's secondcase,crystal-
lization occursat the margins in a crystallization interval
offinite thickness,here defined as the region between 99
volo/oand I volo/ocrystallization, consistentwith Brandeis
and Jaupart (1987) (Fig. 2). In this case,the evolved,
residual melt within the crystallization interval is trapped
in an immobile crust or mush (Marsh, 1988a,1988b)and
does not mix with the bulk melt.
The first case is similar to the model presented by
McBirney et al. (1985) and Sparks et al. (1984) and is
applicable to systems where crystals plate (nucleate) on
the walls of a container and where rapid changesin melt
density occur with crystallization. The diference between
the density of the fractionated melt and the surrounding
less-fractionatedmelt may lead to compositionally driv-
en side wall convection, which can redistribute some of
the differentiated melt to other parts of the chamber. The
residuum may remix with the bulk melt or rise and form
a compositionally stratified cap of diferentiated magma
at the top of the chamber.
The secondcaseis a limiting caseof a model presented
for the Hawaiian lava lakes where magmatic differentia-
tion is confined mostly to crustsof solid + liquid 1+ gas),
which trap nearly all the fractionated liquid (Marsh,
1988a,1988b).Thesesystemscool mainly by conduction
(Peck et al., 1977),with convection relegatedto a rather
minor role. Experimental simulation of these systemsby
 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION
F
Fits
zp co)
o&
Y I- MECIIANICAL
CRYSTALLIZED BOUNDARY I.AYER
MAGMA
Fig. 1. A portionof a risingplumeof bubbleJaden
meltalong
the marginsof a magmachamber.
Brandeis and Marsh (1989) supports this interpretation.
Apparently, under some conditions, convection in sub-
liquidus fluids is inhibited by crystallization. Langmuir
(1989) suggeststhat the chemical trends found in some
mafic systems can be explained by chemical processes
that are intermediate betweenthe extremesof casesI and
2, with the nearJiquidus butk magma mixing with more
evolved, multiply saturatedmelts from the crystallization
interval.
Now that the basic qualitative physical models for
crystallization have been outlined, the modes of vapor
saturation in thesesystemscan be addressed.In the cool-
ing of multicomponent liquids that are in homogeneous
equilibrium, vapor saturation is the result of either a
pressuredecrease(first boiling) or the crystallization of
anhydrous phases(second,or resurgent,boiling). In the
case of second boiling, HrO saturation will either occur
aheadofthe inward-advancing solidus for all x, I or occur
late and in spatially segregatedregions (e.g., the core of
the plutonic complex), with HrO back diffusing from the
crystallization interval into the remaining body of the
liquid.
The controls on the rate of crystallization need to be
defined so that the behavior of HrO in the region of crys-
tallization can be determined. Given the importance of
conduction relative to convection, summarized above,
and the small thermal role attributed to convection for
subliquidus systems(Brandeis and Marsh, 1989) and for
systemsnot steadily heated from below (Marsh, 1988a,
1988b), a conductive model will be adopted here as the
controlling factor in heat loss. Further, aside from tran-
sient effects where nucleation phenomena dominate,
1083
l-;l MELT WTTH < 1*
CRYSTALS
w LIQUID + SOLID
m LI9UID + SOLID
+ VAPOR
cMcKrNG =-- cRYsrALLrzATroN
|
ERoNT .-.J I.-_ INTERVAL OF THICKNESS I
Fig. 2. Crosssectionof the margin of a magmachamber
traversing(from left to right):countryrock,crackedpluton,un-
crackedpluton, solidus,crystallizationinterval with liquid +
solid + aqueousfluid(s),and bulk melt. (Seetext for morede-
tails.)
magmatic systemsare probably attracted to a steadystate
characterizedby a balance between crystal growth and
heat loss to the country rocks (Brandeiset al., 1984).
Therefore, for all but small times, the rate of advance-
ment of the solidus is given by an expression (Jaeger,
1968)ofthe form
x:0.28.tt/2 (la)
where x is the position of the solidus (crystallization pro-
ceedsin the positive x direction) in centimeters and / is
time in seconds.(If x is recast in meters and I in years,
the constantin Eq. la is approximately16.)Equation la
assumesa constant Af : 800 "C (temperatureof crystal-
lization minus the temperature of the country rock far
from the intrusion) at the contact and assumesa fixed
melting point. However, Equation la does yield a first
order estimate of the rate of advanceof the crystallization
front. For an order-of-magnitude estimate of the thick-
nessof the crystallization interval, 1, an equation has been
extracted from Brandeis and Jaupart (1987) ofthe form
I:0.93.to31 (lb)
where 1is in centimeters and / is in seconds.Equation
lb assumesa Stephannumber (the ratio of the latent heat
of crystallization to the heat capacity of the melt times a
temperature scale for crystallization) equal to 0.55, and
crystal growth rates and nucleation rates on the order of
l0 '0 cm/s and l0 3 cm 3/s, respectively. These growth
and nucleation rates are reasonableestimatesfor the in-
terior ofpluton systems(seeBrandeisand Jaupart, 1987,
for more details on growth and nucleation ratesand back-
ground on Eq. lb). In Table l, the position of the solidus
(x) and the interval thickness(1) are given as a function
of time for a spherical chamber with a radius of I km
1084 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION

TABLE1. Solidus position,thicknessof crystallizationinterval, velocity of rise of vapor bubblesby a Stokes-likeformula

and fractionalvolumechangeas a functionof time or, more precisely, a Hadamard-Rybczynski (H-R) for-
x (meters) , (cm) AVIV x 101 t (s)
mula (Ramos, 1988). The H-R formulation accountsfor
motion in the boundary layer of the bubbles by employ-
0.89 3dl 4.5 105
ing a reduced drag coefficient, thus allowing for a more
2.8 67 9.0 106
8.9 138 17 10' rapid rise of the vapor bubbles. Bubbles of hydrosaline
28 281 36 106 fluid will rise lessrapidly, resulting in an increasein their
89 c/J 64 10e
280 1171 81 1010
population in the melt relative to bubbles of vapor. In
885 23 3.3 1011 case the bubbles may gain accessto the upper reaches
l,
Nofe: Solidus position, x (x : 0 is the original magma to country rock of the magma chamber
by H-R bubble rise or by rise of
contact),thicknessof crystallizationinterval,,, and fractionalvolumechange a plume of bubbles and liquid.
of chamber resulting from vapor exsolution as a function of time, using From the H-R formula, the characteristictime for the
Equations1a, 1b, and 20, respectively.
rise of bubbles of radius r in a chamber of characteristic
height h, containing a magma with a dynamic viscosity
(volume : 4.19 km3). This hypotheticalchamber crys- of p.r,a density differencebetween melt and vapor : Ap,
tallizesin approximately 10" s (=3000 yr). The crystal- and an accelerationdue to gravity, S, is given by
lization interval increasesin thicknessfrom a centimeter fouoo,":3'p'r'h/r2'g'Ap' (2)
scaleearly on to tens of meters near the time of complete
crystallization. F o r h : I k m , r : I c m , & r: 1 0 8p o i s e g
, : 980cm2ls,
Given this basic cooling model, the Lewis number (Ze and Ap : 2 rcm 3, a minimum bubble rise time of 1.5
= k/DH2o) for HrO (hereafter referred to simply as Le) x l0ro s is calculated.For a lower viscositymelt (p : 105
can be calculated.Ie indicates whether the rate of diffu- poise),the rise time is reducedto 1.53 x l0? s.
sion of H.O is greater or smaller than the rate of heat If the presenceof crystals or bubbles in the medium
diffusion, the main control on the rate of advance of the surrounding any given bubble is taken into account, the
crystallization front into the magma. Either HrO satura- calculated viscosity of the medium increases.The rheol-
tion is locally achieved (high fe) at the site of crystalli- ogy of crystal- and bubble-fluid mixtures has been dis-
zation (boundary zonevapor saturation)or HrO back dif- cussedby Marsh (1981),in part, in an attempt to explain
fusesinto the rest melt (low Ze). Given the rangeof HrO Daly's dichotomy of basaltic extrusionsvs. granitic intru-
diffusion coefrcientsin rhyolites(10-?to l0-8 cm'?ls)and sions. According to Marsh, basalts are rarely seen with
the thermal diffusivities found in rock systems(7 x lQ-r more than about 55 volo/ocrystals.Smith (1979)suggests
cm2ls),the Lewis numbers are orders of magnitude above that this limit constrains the eruption of silicic ash flows
unity (log Le : 3.8-4.8). This indicatesthat the rate of to those that are lessthan half crystalline. Apparently, the
diffusion of HrO into the residual melt is insignificant magma is too viscous to erupt (or in general,too viscous
relative to the rate of crystallization, and either HrO ac- to flow) if a critical crystallinity is exceeded.For granitic
cumulates in the crystallization interval or HrO accu- magma (sensu stricto), Marsh suggeststhat the critical
mulates at the crystal-melt interface. The consequences locking point may be as low as 20 volo/ocrystals.Hildreth
ofboundary zone vapor saturation will now be addressed (1981) presenteddata that support this generalproposi-
in detail. tion. Marsh and Maxey (1985) presentan equation for
the variation in the viscosity of magma as a function of
Clsn 1: vApoR SATURATToNrN A BoUNDARy the volume fraction of particles. Assuming that the vis-
LAYER DURING SIDE WALL CRYSTALLIZATION cosity risessteeplyas the proportion of crystals * bubbles
According to the models presentedby McBirney et al. (,AI)reaches20o/oby volume, their equation becomes
(1985)and Sparkset al. (1984),crystalsare plated on the : p,/ (exp 2.5' {N/II - (N/0.2)l}). (3)
lllr.otr,
magma chamber side wall as crystallizationproceeds.The
HrO concentration rises in the boundary layer until the Therefore,as the proportion ofbubbles increases,the rise
aqueous-phasebubbles nucleate and grow. The mixture time for bubbles of any given diameter will increase.
of bubbles and liquid will be referred to as a froth or a The characteristic time for vapor + liquid plume rise
gas emulsion, depending upon the volume percent gas. is calculatedusing the Stokesformula in a manner similar
According to Bikerman (1973), a foam has less than l0 to that usedby Marsh (1988b)to calculatethe flow time
volo/oliquid, and the liquid phaseis dominated by surface for crystal plumes. In this model, vapor bubbles accu-
rather than by bulk properties. Froth is a rather ill-de- mulate in a boundary layer. The thicknessof this bound-
fined term that will be used here to denote the region ary layer will be given by the difiirsion distance for HrO
between <10 volo/oliquid (true foams) and >90 volo/o on the time scalefor plume rise: 62= 4D*' t. The resulting
liquid (gasemulsions). Here, the term froth will include formula is then
gas emulsions. If crystals nucleate on the wall of the pq, ()
/pru-.: vq:E:iB:E:6;
chamber (as in many crystallization experiments), then
vapor bubbles will either rise separatelyor in plumes of where iD.'Ap is the density contrast between the bubble-
vapor + liquid + crystals.We can calculatethe terminal laden liquid and the bulk melt, and p is the density of the
 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION
FB RHYOLITE
11 1 TO 6 WT%ITATER
E
F
6 crystallization to approximately I kbar (=4 wt0/oHrO at
.44
Fl
m2 PLUME RISE DOMINANT
H
:-r
ca0
F INDIVIDUALBUBBLE RISE DOMINANT
at-Z
-4-3-2-10
l o g B U B B L ER A D I U S( c m )
Fig. 3. Log of the ratio of the time scaleof bubbleriseto the
time scaleof plumerise vs. bubblediameter.The blackband
indicatessolutionsto Equation4b for rhyoliteswith HrO con-
tentsbetweenI and 6 wto/0.Note that plumesrise faster(i.e.,
havesmallercharacteristic risetimes)for bubbleradii lessthan
I cm.
melt surrounding the plume. In the caseof a ..deep" epi-
zonal felsic magma (p = 2kbat,6 wtoloHrO at saturation,
depthson the order of 7-8 km), p : lQspoise(McBirney
and Murase, l97l) and D"ro : l0-? cm2ls(Delaneyand
Karsten, 198l). Characteristictimes (/","-")for the rise of
a bubbleJaden plume in a deep magma are on the order
of 3.4 x l0? s (l yr) or less.For a "shallow" magma,the
lower HrO concentrationsresult in higher viscositiesand
lower diffusivities, and plume rise times are on the order
o f 0 . 9 t o 3 . 4 x 1 0 , s ( 2 8 - 1 0 9y r ) .
In the caseof a deeperepizonal system,the plume rise
time is on the same order as the rise time for larye (r -
I cm) bubbles. However, most bubbles will have smaller
radii and therefore much longer rise times. In Figure 3,
the ratio of to"oo," to /pr,.", obtained by dividing Equation
2 by Equation 4,
: (20/ rr).fut.D*. Q,7',,
(lo,oo,./to,"-")
(4b)
is plotted vs. bubble radius (on a logJog ptot) for,D"(within
the plume) : 0.1. Over a largerangeof bubble radii, /or-.
is much smaller than lo,oo,", indicating that if vapor bub-
bles accumulate in a crystal-poor boundary layer, then
the bubble-laden liquid is apt to rise to the top of the
chamber. The density of HrO vapor is reducedupon rise
becauseof its small bulk modulus; therefore, the buoy-
ancy of a plume is further enhancedby positive feedback.
This processof bubble-laden plume flow may be a driv-
ing force for convection in some magma chambers.Com-
mon miarolitic cavities are probably the result of the de-
compressionof vapor bubblesthat were originally smaller
than the crystals growing from the same melt. The ex-
pansion of the bubbles probably results from decompres-
sion during plume rise. Granitic melts lacking miarolitic
cavities should not be interpreted as having been under-
saturatedwith HrO. Rather, those graniteswith miarolit-
1085
ic cavities may have crystallized under conditions where
the initial HrO concentration was within 80-900/oof sat-
uration. For most melts, this restricts the pressureduring
saturation), although melts with higher initial HrO con-
centrations,suchas thosefrom muscovite-bearingsources,
may possessmiarolitic cavities at much greater depths.
This boundary layer model differs from other models
(e.g.,Sparkset al. 1984;Nilson et al., 1985)by explicitly
considering the presenceof vapor bubbles in promoting
compositional side wall convection. One potentially sig-
nificant complication associatedwith this analysis is the
competition between the rate of rise of a plume and the
rate of crystal nucleation and growth due to decompres-
sion and loss of vapor. This is similar to the problem of
isothermal undercooling discussed by Westrich et al.
(1988). Presumably,plume rise will terminate when the
surrounding melt losesits fluidity. However, the system-
atics developed herein seem likely to be operative until
the plume is adiabatically pressure quenched, as dis-
cussedby Norton and Knight (1977), producing a quench
aplite or microgranite in the apical portions of the cham-
ber.
Clsn 2: vAPoR sATURATToNrN A
CRYSTALLIZATION INTERVAL
As the leading edge of the crystallization interval ad-
vances into the magma after the nucleation incubation
period, the percent crystallization at the wall steadily
climbs. Crystallization progressis given by .F,which var-
ies from I (1000/o liquid) to 0 (1000/osolid).At sometime,
dependingon the depth and the initial HrO concentration
in the melt, a critical fraction of liquid remaining (,F) is
reachedat the wall such that vapor saturation is achieved.
A new progressvariable, Z (the vapor exsolutionprogress
variable), is set equal to unity at the initiation of vapor
exsolution; Z progressestoward zero as vapor is exsolved.
As crystallization proceeds,the Z: I front advancesin-
ward behind the ,F : I front. Note that HrO-saturated
melt is confined to the crystallization interval (see Fig.
4). Even though the presenceof vapor bubbles reduces
the bulk density of the crystallization interval relative to
its surroundings,and although there is no critical Raleigh
number for convection in a horizontal density gradient,
a few tens of percent (by volume) of bubbles plus crystals
greatly reducethe probability of flow of the melt + vapor
* crystal mixture becauseof the increasedviscosity. In
the limiting caseof vapor saturation in a crystallization
interval, vapor bubbles are probably trapped in an im-
mobile crust. The aqueous fluid can only be removed
from the sitesofbubble nucleation through the establish-
ment of a three-dimensionalcritical percolation network
and advection ofaqueous fluids through it or by means
ofthe flow offluid through a cracking front that is likely
to form some l0- 100 "C below the solidus.
On a three-dimensional,simple cubic lattice consisting
of particles A and B (with number fractions Xo < Xu),
critical percolation is said to occur, that is, a spanning
1086 CANDELA: PHYSICS OFAQUEOUS PHASE EVOLUTION
cluster of A is formed from one end of the lattice to an-
other, when approximately 310/oof the lattice points are
occupiedby A (Sur er al., 1976 Feder, I 988). This result
was obtained by Monte Carlo simulations on a 50 x 50
x 50 grid and generalizedusing scalinglaws. Ifthe vapor-
liquid-crystal region is modeled as a simple cubic lattice
with the aqueousfluid as the potentially percolating phase,
advection of the fluid upward may be consideredpossible
when the volume fraction of the aqueous phase in the
crystallization interval reachesapproximately 0.31. The
flux of HrO at critical percolation may be low; however,
as the volume fraction increasesbeyond the critical per-
colation threshold, the advective flux (driven by buoy-
ancy and the positive pressuregradient produced by va-
por exsolution, and allowed by the ability of the melt and
the vapor to flow into the region vacated by advecting
fluid) will increaserapidly (a type of gravitationally driv-
en filter pressingofvapor).
Critical percolation begins at the wall and sweepsin-
ward behind the zone ofvapor bubble nucleation (seeFig.
4). It is followed by the solidus. The zone of percolation
occursbetweenthe solidus and a surfacecharacterizedby
the critical value of the vapor exsolution progressvari-
able (Z) at which percolation commences(2."). For an
idealized, hypothetical hemispherical magma chamber,
this zoneof percolationis a hemisphericalshellthat moves
inward and thickens with time, as doesthe crystallization
interval (Brandeis and Jaupart, 1987). The rate of in-
creaseof the volume fraction of vapor is significantly re-
ZOM OFCruTIW
PERcoKroN
f
>_ o o ""
-o
o
"'
oo
oo
>_
oo
>_ o o'
oo
>- oo
o'
"H8ffl'L L Z=l
F=Z=O
F = O.62
tl
CRYSTS+MET | 3l
BUBBLES OF AgUEOUS PrcE
Fig. 4. Detailed, idealized illustration of the production of a
spanning cluster of vapor bubbles at critical percolation. Initial Combining Equations 12 and 13 to eliminate Mi and
HrO concentration: 2.5o/o,HrO saturation : 4ol0.Under these solving for Z-, results in the expression
conditions Zcp : 0.093 and lt : 0.058. Three stagesin the
"
formation of a crystallization interval upon intrusion are shown
in the right portion of the figure: A is the leading edge of the
crystallization interval, B is the leading edgeofthe zone ofaque-
ous phase saturation, C is the magma to country rock contact, Substituting Equations l0 and 14 into the basic
D is the leading edge of the zone of percolation, and E is the equation for the system (Eq. 5) and letting M":
solidus.
tarded as V"/V,,,exceeds0.31 becauseof the upward ad-
vection of the vapor from the system.This large volume
changeis, of course,not experiencedby the whole magma
chamber but only by the hemispherical shell of percola-
tion, which is centimeters to meters thick.
Below, I present the derivation of the expression for
Z.r. ln this derivation, the volume of liquid (V,) and
volume of crystals (2.,) will be expressedas a function of
the volume of vapor (I/"). The common factor Z, will
then be removed from the right-hand side of the equation
(5)
v"".(n: v. + vt + va
(which expressesthe volume of the aqueousphase + melt
* crystal system for any given value of F) to form an
:
expressionfor V"",(F)/V., the reciprocal of which is O"
V"/V,,(F), the volume fraction of vapor in the system at
any time. Embarking on this derivation, let
(6)
F = V,/V?.
Also, assuming a constant density for the liquid during
differentiatiot, F: M,/Afi. Modeling HrO as a perfectly
incompatible substance(the presence of a few percent
hydrous minerals does not affect the substanceofthe ar-
gument), the critical F value at HrO saturation is
F = Mi/It4: Vi/Vf : C\o/CV. Q)
The vapor exsolution progress variable, Z, is unity at
vapor saturation and zero when F -- 0 at the cessationof
Z: (C$/C[o'F) or
crystallization:
F: Z,F. (8)
BecauseV*t= V? - V,,
V*'/VYxl-F' (9)
Combining Equations 6, 8, and 9 yields
v,: vo.lF z/(r - FZ)1. (10)
An expressionfor V*,may be obtained from the definition
of the density of the melt at the commencementof vapor
saturation combined with the volume form of Equation 7:
Mi: p,'F'V?. (l l)
Substituting Equation 8 into Equation 9 and combining
the result with Equation I I gives
Mi: p,'F'V-,/(l - FZ). (12)
Given the mass balanceof expressionM,: Mtf - Mt*
and the definitions Z = M'*/M'i and Cf = MV/M\,
M": (r - z)C'i.Mi. (13)
(14)
volume
p;V"
yields
 CANDELA: PHYSICS OFAQUEOUS PHASE EVOLUTION
(15)
Simplifying Equation 15, substituting the identity from
Equation 7 in the form F : C'f /C'f , and rearranging
glves
Q": V"/V",": (l + {p"/lp,(l- Z)'Ctro1y1-t.
Letting O" : 0.31 from percolation theory yields a Z
at critical percolation (Z.r) glvenby
'*:(,%-) (16)
2., car.be transformed into the critical .iqvalue, f.", (the
critical value of the crystallization progress variable at
percolation) by multiplying Equation l6 by F, yielding
F." : [Cl;o - 0.45(p"/ p,)]/ Ct;. (l 7)
The condition of -F." : 0 is a limiting caseof Equation rhyoliticsystem,bubbleJaden
17 that indicates the onset ofcritical percolation at l00o/o of the (H,O initial)/(H,O saturation) 0.8. Arrows indicate
crystallization. Setting F." : 0 in Equation 17 yields
(ff)..".: 0 . 4 5p' ,
C'i'p,
(18)
The left-hand side of Equation 18 indicates the minimum
ratio of the initial HrO concentration in the melt to the
HrO concentration at saturation, for a given total pres-
sure, at which a spanning cluster of vapor bubbles will
form. Spanning clusters will form in the crystallization
intervals of all wetter magmas (higher Cl;O)at the same
total pressure.Conversely,drier magmas at the same to-
tal pressurewill not achievea stateofcritical percolation.
With increasingpressure,the density of the aqueousphase
increasesmore rapidly than the solubility of HrO in the
melt, resulting in an increasein the minimum CLolCf for
which a spanningcluster of vapor bubbles will form with-
in a crystallization interval (seeFig. 5). At magma pres-
sures equal to or greater than approximately 1.7 kbar,
critical percolation is not achievedat any initial HrO con-
centration. If itr lies between I and 0, then significant
amounts of fluid "can be removed and concentratedbefore
the solidus isotherm sweepsthrough the system.If f." is
negative, critical percolation is never achieved, and HrO
is probably pumped out ofthe systemthrough the crack-
ing front; this is discussedin the next section ofthis pa-
per.
The approach taken here, essentiallya "modified mass
balance approach" coupled with a phenomenological
physical model rooted in elementary percolation theory,
obviously neglectssome effects,such as the spatial dis-
tribution of bubbles on a small scaleand nucleation con-
trol of bubble size distribution. However, these parame-
ters are likely to affect the particular values ofF." or 2."
I 087
z
tr
1
p PLUME RISE
0.9
F
V)
0.8
0.7
N 0.6
H
0.5
0.4
NO PERC
-l 0.3
0.2
F
z 0.1
C\l
0
o . 20 . 4 0 . 6 0 . 8 r
t.2 1.4 1.6 1.8 2
PRESSURE(kbar)
Fig. 5. The curvedline indicates,for a given pressure,the
minimumratioof theinitial magmaticHrO concentration to the
magmaticHrO concentration at saturation[(HrO initial)/(H.O
saturation)lat which a spanningclusterof vapor bubbleswill
allow the upwardadvectionof magmaticHrO. Further,in a
plumeriseis expected for values
:
regionsof graphfavoringlarge-scale upwardtransportof the
magmaticaqueousphase.
or the specificrelationship betweenpermeability and po-
rosity of the crystallization interval, rather than the con-
ceptual featuresof the physical model.
Given this concept ofcritical percolation, advection of
the aqueousphase occurs as porous media flow through
the spanningcluster of vapor bubbles.An illustrative cal-
culation can be performed by using data on the relation-
ship of permeability to porosity for obsidian reported in
Eichelbergeret al. (1986).At a porosity of 37o/o, the ob-
sidian exhibited a permeability on the order of k : l0 ''z
cm2, the lowest permeability measuredin their study. At
higher porosities (up to 74o/o),the permeability climbed
to almost k : l0 8 cm'. Therefore, calculationsfrom this
study provide a minimum estimate for the fluid flux of
an upwardly aqueousphase. The estimate is most accu-
rate for porosities close to the iD"ofthe original spanning
cluster. Given kinematic viscosities for the aqueous phase
on the order of l0 3 cm2ls at 800 'C and I kbar (Norton
and Knight, 1977), a Darcy fluid flux can be calculated
from the equation Q: (Wv)'(Ap/h). After the spanning
cluster ofvapor bubbles is achieved, the pressureat any
point in the column of vapor will be lessthan that in the
adjacentmelt by a factor of Lp : g'h' Lp, whereg : the
acceleration due to gravity, h: characteristicheight of
the magma chamber, and Ap = 2 g'cm-3 is the difference
in density between the melt and vapor. In this case,
(le)
Q: (Wv)'s'Ap.
This calculation yields a minimum value of Q: t0-u t'
em 2/s, which is comparable to the largest fluid fluxes
1088 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION

calculated in the convective systems surrounding mag- the overpressureproduced in a magma chamber, neglect-
ma-hydrothermal systems (Norton, 1982). Obviously, ing shear deformation of the roof and neglecting volume
these fluxes are sufficient to deliver significant amounts changesresulting from crystallization (asidefrom second
of fluid to upper portions of a magma chamber. boiling), can be obtained using the coefficient for com-
At this point, the effect of the chlorinity of the magma pressibility of the magma. Taking 0 = l0 5bars-r and AP
and the associatedaqueousphasemay be addressed.When ,v 10'zbarsfor pure tensile failure yields d'V/V = LP'A
the magmatic aqueous fluid composition is in the two- = l0 3,suggestingthat failure of the chamber occurswith
phaseregion of the systemNaCl-HrO for pressuresbelow a whole-chamberfractional volume increaseon the order
approximately 1.4 kbar at 800 "C (Bodnar et al., 1985), of 0. l. This result is in good agreementwith the more
some fraction of hydrosaline fluid (with a density on the sophisticatedanalysisofTait et al. (1989), who suggest
order of unity) will be present. As a result of its lower that failure occurs with fractional changesin volume of
density, one might expect the vapor to be fractionated 0.2 - 0.8 x l0 3. Inspection of Table I suggeststhat
relative to the hydrosaline fluid, although both will rise failure occurs early (after about I yr) and continues
to the top of the chamber. The vapor may, however, rise throughout much of the crystallization history of the
faster. Whereas the hydrosaline fluid is buoyant within magma chamber. The whole-chamber volume changes
the confines of the magmatic system (p-r, > pnyarosarinenuia), are on the same order as those required to fracture the
it is not buoyant within the surrounding geothermal sys- roof zone of the chamber.
tem. For example,given that cold ground HrO has a den-
sity on the order of unity, vapor-saturated hydrosaline CnrlrroN oF THE MAGMATIc vAPOR-DTSPERSE
SYSTEM: THE LACK OF CRITICAL PERCOLATION
liquids with salinities greaterthan 500/oNaCl (at 500 bars
pressureand temperaturesgreaterthan approximately 550 According to Knapp and Norton (1981), thermal
"C) will not be buoyant within the hydrothermal system. stressesgeneratedby the cooling of a pluton causerock
(The interestedreaderis referred to Henley and McNabb, failure by brittte fracture. Fracture permeability develops
1978, especiallyFig. 4 therein, for further considerations adjacent to the magma-rock interface under conditions
of this type.) The hydrosaline fluid will tend to pond in where the igneous rock fails. Norton and Taylor (1979)
the crystal mush near the roof, possibly creating a stable, modeled fracturing in the Skaergaardsystemby assuming
stratified deepbrine zone (cf. Henley and McNabb, 1978). that the pluton fractured when the temperaturedecreased
This may account for the trapping of hydrosaline fluids to 50 "C below the solidus. For porphyry copper systems,
as opposed to vapor in inclusions in magmatic minerals Norton (1982)has useda figureof 100'C below the sol-
in the upper reachesofplutonic complexes(Frezzotti and idus for magma-inducedfracturing in already-crystallized
Ghezzo,1989). portions of the pluton. This latter figure is supported by
Although the crystallizing magma experiencesvolume stress-straincalculations for the no-strain case;with rea-
increaseson the order of 45o/o[the relative volume change, sonable values for Poisson's ratio, the elastic constant,
'C
AV/V = (V" - VJ/V,, is equal to 0.45 when Q" = l/"/ and thermal expansion,AZ on the order of 100 yields
(V" + V-t t V^^,) is equal to 0.311,the volume of the effective stresseson the order of 102bars, which is on the
crystallization interval is rather restricted (see Table l). same order as the tensile strength of many rocks. In cases
The total volume increase of the magma chamber is where the critical Z of percolation is outside the domain
therefore rather modest. The value of AV/V can be cal- of the Z variable in a real system (i.e., negative values of
culated by considering vapor evolution to occur rn a Z.r),the accumulatedaqueousphasewill remain in pores,
sphericalshell bounded by the solidus (at x) and the lead- vesicles, or miarolitic cavities until provided egress
ing edge of the crystallization interval (at x + I) at any through the cracking front and entrained in the meteoric
time such that HrO flow. Even though thesepacketsof fluid may advect
upward toward the zone of mineralization, the fluid ex-
A V / V \ - ^ * : 0 . 4 5 . [ ( l- x ) ' - ( l -x- 4 ' 1 Q 0 ) periencesa rather rapid decreasein temperatureupon rise
for a magma chamber with a radius of I km. The A,V/V and may be diluted by adjacent nonmagmatic fluids (cf.
is tabulated in Table l. Norton and Knight, 1977). This is clearly different from
It is not the purpose of this paper to provide a model the percolation case wherein fluid advects through the
for the fracturing of plutons; however, the crystallization melt under quasi-isothermalconditions to a localized, al-
and vapor saturation model presented here does allow beit downward migrating region. Becauseof the acceler-
for the fracturing of a magma chamber by magma pres- ated cooling and dilution of the magmatic fluids upon
sure, and this will be discussed briefly. Given tensile transport in the absenceof critical percolation, this mech-
strengthsofroofrocks on the order of I 00 bars (cf. Suppe, anism is likely to result in scatteredshowsof mineraliza-
1985),a Mohr circle analysiswith a combination Grif- tion rather than centralized zones of intense alteration
fith-Coulomb failure envelopesuggeststhat pure tension- and mineral deposition. This will be termed a magmatic
al failure is indicated for magma overpressures(AP) on vapor-dispersesystembecauseegressofthe fluid through
the same order as the tensile strength,with a Mohr circle the cracking front results in a much more heavily dis-
radius of approximately AP. A crude approximation of persedzone of metasomatism from magmatic HrO.
 CANDELA: PHYSICS OF AQUEOUS PHASE EVOLUTION 1089

DrscussroN matic volatile phase(s) under supersolidus conditions

would be by a highly tortuous rise of individual vapor
This paper has described two possible processesby bubbles through a crystal-choked immobile crust within
which magmatic aqueousfluids may be delivered to the the crystallization interval. In this case, bubble rise is
upper regions of felsic magma chambers. Both mecha- likely to experiencea much greater drag force than that
nisms, plume rise and critical percolation, may be oper- accountedfor by either Stokesor Hadamard-Rybczynski
ative in nature depending on the conditions prevailing drag coefficients.Most likely, this would result in a va-
upon crystallizalion. Further, a synthesiswill be present- por-disperse system with little focusing of the flow of
ed that unites the two models presentedin this paper (i.e., magmaticHrO.
the formation of a crystallization interval with melt Therefore, boundary-layer second boiling in systems
"locked in" vs. side wall compositional convection) with high Ie numbers at a variety of Cl;oand pressures
through the processofvapor exsolution. The critical fac- spans the range between systems allowing side wall
tor determining the behavior of a given system, within (plume) fractionation at high C!0 and low pressure,on
the framework of the models presentedin this paper, ls one hand, and those resulting in low-mobility rest melt
the rate of changeof the density of the crystal-melt-vapor + upwardly percolatingvapor at lower Cl;Oand high pres-
systemas crystallization proceeds.This rate is controlled sures,on the other hand. The observablecharacteristics
by the timing of vapor evolution (which, in turn, is con- of thesecaseswill reflect the mode of vapor transport. In
trolled by Ctf /Ctg and by the densityof the aqueousphase the caseof plume rise, the quenching of the plumes will
(which, in turn, is controlled dominantly by pressureand result in aplites, miarolitic granites, and porphyries with
to a lesserextent by temperature).For magmaswith high fine-grainedgroundmass.Zones ofintense alteration and
values of Ctf /C,i (note that the maximum value for this mineralization may surround thesebodies. In the caseof
ratio is unity under equilibrium conditions), vapor satu- advection through a spanning cluster, hydrothermal al-
ration occurs early (at high F values), and significant teration may be centeredon the apical region of the plu-
buoyancy is achieved at relatively low viscosity (crystal- ton, but strong textural variation is not expected.In the
linity). In this case,plumes may rise from a subvertical caseof the vapor-dispersesystem, alteration and miner-
border zone. Given that the probability of eruption of a alizalion will be dispersed throughout a large volume.
granitic melt is significantly decreasedfor crystallization When present, concentratedzones will be small in vol-
greater Ihan 20o/o,vapor evolution probably must occur ume and not necessarilyconcentratedin apical regions.
at .iq values greater than 0.8 for this mechanism to be The discussionin this paper is predicated on the con-
operative. This effect is obviously enhanced at lower dition that HrO is characterizedby large Ze numbers in
pressuresbecauseof the effect of reduced pressure on magmatic systems. There may, however, be magmatic
density and, hence, buoyancy. Here, side wall crystalli- systems(still not well studied) that possessrelatively low
zation is seen as a special case of the crystallization in- viscosities and high diffusivities. London (1986) and
terval-percolation model, where Clf is sufficiently high London et al. (1989)have discussedthe effectsofincreas-
and pressuresufficiently low that the presenceofbubbles ing Li, B, P, F, and H on crystallization and vapor exso-
at low crystallinity on the inner (leading) edgeof the in- lution in pegmatitic systems.In melts with anomalously
terval induces plume rise. This might result if, for ex- large concentrations of these elements, it is possible to
ample, a magma with few crystals and 3 wto/oHrO in- generatemelts with low viscosity, high diffusivity, and
truded to a depth of approximately l 9 km (equilibrium greatly enhanced HrO solubility. This combination of
H,O solubility equal to approximately 3 wto/o).Under lowered l,e numbers and elevated HrO solubilities could
these conditions, a few percent crystallization would in- result in a significant delay in vapor saturation in these
duce vapor bubble formation and plume rise. If, how- magmas, and vapor saturation might occur only in re-
ever, this same magma were to intrude to a depth of 3.5 stricted portions of an intrusion. The style and texture of
to 4 km, then the first bubbles may not form until ap- crystallization and the style of vapor evolution would be
proximately 25o/ocrystallization occurred. The high vis- very differentin suchsystems.London et al. (1989)have
cosities realized in felsic systemswith greater than 20o/o pointed out that the increase of the structure-breaking
crystals (Marsh, 198l) might preclude plume rise under componentsLi, B, P, F, and H in felsic systemsmay lead
theseconditions. However, critical percolationis achieved to a reduction in nucleation rates offeldspar as the short-
at F :0.2 (i.e., after 800/ocrystallization);in this some- rangestructureof the melt deviatessignificantly from tec-
what deepercase,the delivery ofvapor to the apical por- tosilicate-likeunits. The reduction in nucleationrate leads
tions of a chamber would be by advection through a to the production of pegmatitic textures. These systems
spanning cluster of vapor bubbles. This percolation in- may evolve a vapor only from restricted portions of the
terval sweepsinward and downward with time through magma chamber.
the chamber. If this same initial magma were to crystal-
lize at a greater depth (e.g., greater than 7-8 km), then CoNcr-usroNs
both plume rise and critical percolation would be pre- Simple physical analysis of the crystallization of felsic
cluded. The only means of egressavailable for the mag- magmas in light of recent studies of magma dynamics
1090 CANDELA:PHYSICSOF AQUEOUSPHASEEVOLUTION
suggeststhat the achievementof critical percolation with-
in a crystallization interval is possible if the initial H,O
concentration of the magma is above a minimum value
for a given pressure (Fig. 5) and if the system is at a
pressureof lessthan 2kbar. Fracturing by secondboiling
is consistentwith this model, and aqueousfluids will ad-
vect to the apical portions of magmaswithout experienc-
ing significant cooling or mixing with meteoric or other
HrO. In systems with high enough HrO concentrations
for a given intrusion pressure or in caseswhere crystal
nucleation occurs dominantly along the walls of the
chamber, plumes of bubbleJaden melt may raft to the
top of the magmachamber.Thesebuoyantly rising plumes
may erupt, yielding permeablefroths (Eichelbergeret al.,
1986),or may form apophyses,dikes, or lift cupolasby
virtue of their buoyancy. These models account for the
delivery of magmatic aqueous fluid from large portions
of magma chambers to the upper portions where miner-
alized zones are formed. This may explain how large
amounts of magmatic vapor, charged with mineralizing
agentssuch as Mo or Cu are focused into small regions,
yielding large concentrationsof ore metals that appear to
be genetically related to small apical stocks, such as at
the Henderson mine and related deposits.Therefore, sys-
tems that are capableof delivering largevolumes of vapor
to apical regions by plume flow or advection through
spanning clusters possessa greater probability of devel-
oping into productive systems.Plumes rising to the top
of a chamber may be pressurequenched,resulting in the
crystallization of the vapor + melt mixture with time.
The final product might be an aplite (London et al., 1989)
consistingof an intimate mixture of igneousmaterial (e.g.,
quartzand feldspar)and hydrothermal material (e.g.,mo-
lybdenite), as is found in the upper regions of a number
of silicic plutons (Ohlander, 1985).Someof theseoccur-
rencesexhibit little alteration, as if only a small degreeof
cooling in the presenceofaqueous fluids occurred before
the aqueousphasewas driven from the pluton. However,
the molybdenite in these systems has precipitated at a
high enough temperature to result in its incorporation in
the aplitic granites. This is consistent with the high-pre-
cipitation temperaturesfound for molybdenite in volca-
nic gases(Bernardet al., 1990).
In systemsthat are relatively dry or deep and achieve
neither critical percolation nor plume rise, the magmatic
aqueousphaseis apt to be releasedfrom the pluton in a
more dispersedstate, resulting in diffuse zones of meta-
somatism and mineralization. Disseminated molybde-
nite (Whalen, 1980)and scheeliteor wolframite probably
mark the incipient cooling and dilution of dispersedmag-
matic fluid and may characteize, at least in some cases,
the nonproductive system.
AcxNowr,nocMENTS
Discussionsover the lasr few yearswith Chip (C.E.) ksher and Frank
Spera inspired me to write this paper. Steve Lynton, Phil Piccoli, and
Tom Williams are thanked for later discussions.A lengthy discussionwith
Bruce Marsh in December 1988at the University of Maryland concerning
crystallization, probability, and rheology was enlightening. Further com-
ments by Steve Lynton, Dennis Bird, and an anonymous reviewer have
greatly improved the manuscript. Special thanks to Barbara ke for help
with the figures. Mary Ostrowski and A. kdbetter are thanked for pro-
viding additional inspiration. Of course, all errors in this paper are the
responsibility of the author. The support of NSF grants EAR-8706198
and EAR-9004154 and the Magma Energy Project of DOE is gratefully
acknowledged.
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