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Copyri&t 0 1992 Pergamon Press Ltd. Frinted in U.S.A.
(Received July 13, 199 1; accepted in revised form May 11, 1992 )
Abstract-A unified description of supergene enrichment of a porphyry copper protore is preser.ted based
on the principles of metasomatic zoning. Mathematically this formulation represents the supergene
weathering process as a moving boundary problem. A first principles approach is used to describe quan-
titatively the transport of oxygenated water through a porous host rock consisting of a Cu-bearing protore.
Mineral reaction rates are represented by kinetic rate expressions for both precipitation and dissolution.
Reaction zones containing mineral alteration products making up a leached zone, oxide zone, and en-
richment blanket propagate downward in the direction of fluid transport. The time evolution of the
system is completely determined by the governing transport equations once initial and boundary conditions
are specified, giving the composition of the unaltered host rock and infiltrating fluid entering at the surface
of the weathering column. The description provides for both fully saturated conditions and undersaturated
conditions in the presence of a water table at depth. An order of magnitude estimate of the velocity of
propagation of a redox front demonstrates that metasomatic effects become increasingly important as
the 0 content of the infiltrating water increases. Regions of higher permeability, resulting in higher fluid
flow velocities, lead to increased enrichment compared to regions of lower permeability, with reduced
flow velocities, in agreement with field observations. Results of numerical calculations suggest that the
enrichment blanket may be subdivided into three distinct zones: ( 1) an enriched zone at the top of the
blanket; (2) the middle blanket in which chemical reactions of Cu-bearing minerals are absent; and ( 3)
the nascent blanket forming the interface between the protore and middle blanket. Both the nascent and
middle blanket contain the same Cu grade as the protore. These results are in agreement with field
observations of a high Cu grade within a relatively narrow zone in the upper portion of the blanket.
Results of numerical calculations for three different scenarios are presented. The first example considers
a simplified representation of the enrichment process with chalcopyrite, covellite, and chalcocite as the
major Cu minerals. In this case chalcocite forms an enriched zone at the top of the blanket which migrates
downward increasing in width. The second and third examples differ by the presence of a water table at
depth, and include brochantite, tenorite, native Cu, and cuprite as secondary Cu minerals in addition to
the minerals used in the first example. Surprisingly, in these two examples the enriched blanket zone
does not grow indefinitely with time, but reaches a steady-state profile that is displaced rigidly in the
direction of fluid transport without changing shape. In the presence of a water table at depth, the major
enrichment occurs in the oxide zone lying above the blanket.
LIST OF SYMBOLS intrinsic reaction rate of the mth mineral (mol/L of bulk
rock/s)
designation for the ith reversibly reacting aqueous com- equilibrium constant corresponding to the mth mineral
plex equilibrium constant for the ith aqueous complex
designation for the jth primary species reaction rate constant associated with the overall reaction
affinity of the mth mineral (J mol-) of the mth mineral (mol crnm2s-l).
threshold affinity for the onset of precipitation of the total width of blanket (m)
mth mineral (J mol- ) width of leached zone (m)
concentration of the ith reversibly reacting aqueous depth of water table (m)
complex (mol L- ) designation for the mth mineral
concentration of the jth primary species (mol L- ) number of reacting minerals
inlet concentration of the Ith irreversibly reacting aqueous number of primary species
complex (mol L-l) ?I concentration of Cu in the solid phase in units of moles
concentration of 0 in air-filled pore spaces (mol L- ) per unit bulk rock volume
aqueous diffusion coefficient (cm* s-l) partial pressure of 0 (bars)
effective oxygen diffusion coefficient in air-filled pore ion activity product corresponding to the mth mineral
spaces taking into account tortuosity effects (cm s-l) gas constant
dimensionless quantity fluid-rock ratio (.I mol- K-)
initial grain size of the mth mineral (cm) surface area of the mth mineral per unit volume of bulk
oxygen fugacity (bars) rock (cm2/cm&k)
dimensionless factor appearing in the kinetic rate temperature (C)
expression for minerals time(y)
local Cu grade referenced to a REV (dimensionless) travel time of a fluid packet (xc)
reaction rate of the mth mineral (mol/L of bulk Darcy fluid velocity (m y-l)
rock/s) molar volume of the mth mineral (cm mol-)
3987
P. C. Lichtner and G. G. Biino
average fluid velocity ( m y - ) (ANDERSONet al., 1955; SCHWARTZ, 1966; GUILBERT and
velocity of the redox front associated with the mth min- PARK, 1986). This would seem to reflect the influence of
eral (m y-)
gram formula weight for the element Cu and the mth
downward, percolating, oxidizing water, rather than the
mineral (g mol-) presence of a water table. Furthermore, the top of the en-
spatial coordinate (m) richment blanket is often extremely irregular with no apparent
aqueous activity coefficients for the jth primary species similarity with the water table surface (ANDERSONet al., 1955;
and ith complex SIMMONS and FOWELLS,1966). In addition, there exist nu-
time step (y)
width of enrichment zone (m) merous accounts of existing oxidized ore bodies which appear
travel distance of a fluid packet (m) to lie below the water table ( EMMONS, 19 17; TITLEY, 1978;
time for mth mineral to dissolve completely (y) GUILBERT and PARK, 1986). TITLEY (1978) described on-
reaction index corresponding to the mth mineral going supergene enrichment below the water table at the
saturation index defined as the fraction of pore volume
Plesyumi porphyry Cu prospect in New Guinea. At the Ok
filled with fluid
stoichiometric reaction matrix for reversibly reacting Tedi deposit in New Guinea, where rainfall averages up to
aqueous complexing reactions 5 m per year, supergene ores extend well below reasonable
stoichiometric reaction matrix for mineral reactions water table levels ( GUILBERTand PARK, 1986, p. 823). The
bulk rock density (g cmm3) usual explanation given for the formation of these deposits
intrinsic rock density (g cmm3)
time for mth mineral to completely dissolve at inlet ( y) is that the level of the water table has risen since the deposits
porosity were formed.
volume fraction of the mth mineral Most likely the supergene weathering process is a combi-
initial volume fraction of the mth mineral nation of effects resulting from the presence of a partially
generalized concentration of the jth primary species saturated zone lying above the water table, as well as the
(mol L-)
generalized inlet concentration of the jth primary species influence of downward percolating oxygenated fluid. Cer-
(mol L-) tainly the presence of a water table and its fluctuations with
generalized initial concentration of thejth primary spe- time must overprint and complicate metasomatic effects
cies (mol L-) which are responsible for a continuous, downward movement
generalized flux of the jth primary species (mol
of the various alteration zones within the weathering profile
cm-* s- )
with time. The purpose of this contribution is to investigate
INTRODUCTION the contributions of these two processes to supergene enrich-
AN UNRESOLVED CONTROVERSY in understanding supergene ment of a porphyry Cu protore based on a quantitative de-
enrichment of a porphyry Cu protore is the role played by scription of fluid-rock interaction coupled to transport of sol-
the water table during the enrichment process. The accepted ute species. A unified description of supergene enrichment
view of many geologists based on extensive field observations is employed based on the principles of metasomatic zoning.
is that oxidation of sulfide minerals takes place primarily in This formulation simultaneously accounts for the effects of
a partially saturated zone lying above the water table (see the presence of a water table as well as downward percolating,
e.g., ANDERSON, 1982; BRIMHALL et al, 1985;GUILBERT oxidizing fluid enabling comparison of the extent to which
and PARK, 1986; AGUE and BRIMHALL, 1989; ALPERSand supergene enrichment takes place under fully saturated con-
BRIMHALL,1988, 1989). The enrichment process is thought ditions with enrichment in the presence of a water table.
to proceed in cycles. During the first cycle descending me- Mathematically, the supergene enrichment process is for-
teoric water oxidizes primary, Cu-bearing, sulfide minerals mulated as a moving boundary problem. The boundaries or
above the water table, transporting Cu below the water table, reaction fronts delineating different mineral assemblages be-
where it precipitates under reducing conditions. This process longing to the leached zone, oxide zone, blanket, and protore
forms a zone enriched in secondary copper sulfide minerals are determined as functions of time as part of the solution
lying below the water table, referred to as the enrichment to the governing transport equations. These reaction fronts
blanket. Oxidation continues until all sulfide minerals above propagate with time, each at its own characteristic velocity,
the water table have dissolved, leaving behind a leached zone in response to fluid flow as rainwater percolates through the
depleted in Cu. A second cycle is initiated as the water table weathering column. The presence of a water table divides
is lowered by uplift or erosion, thus continuing the oxidation the flow path into saturated and unsaturated zones. In the
process. This cyclic process of lowering of the water table unsaturated zone 0 is replenished by diffusion through air-
and subsequent oxidation may be repeated any number of filled pore spaces allowing oxidation to proceed at a much
times. The presence of the water table is considered an es- faster rate compared to the saturated zone where 0 is rapidly
sential aspect of the enrichment process, marking the bound- depleted by chemical reactions.
ary between reducing and oxidizing conditions which sepa- Exotic theories have been proposed to relate the thickness
rates the leached zone from the enriched blanket zone. The of the enrichment blanket to the water table depth. BRIMHALL
process is presumed to terminate if the water table rises above et al. ( 1985) suggested that the blanket thickness is related
the oxidized zone. A favorable climate for supergene enrich- to the height of the capillary fringe at the water table. They
ment is presumed to be semi-arid conditions with minimal argued that, as the protore is oxidized and sulfide minerals
rainfall, rather than humid conditions with plenty of rainfall. reprecipitate in the blanket, the pore size in the blanket de-
One difficulty with this interpretation is the observation creases, thereby increasing the height of the capillary fringe
that enrichment is often more pervasive in regions of higher zone and also the thickness of the enrichment blanket. AL-
permeability compared to regions of lower permeability PERS and BRIMHALL(1989) related the growth of the en-
Theory of supergene enrichment of Cu-Fe sulfide ore 3989
richment blanket to the descent ofthe water table. According in which a water table is present at a fixed depth is considered.
to the metasomatic description given here, growth of the en- The extent of enrichment and the time span required are
richment blanket is simply explained as a consequence of different for the three examples. Su~~sin~y, in the latter
downward, percolating, oxidizing meteoric water. As rain- two examples the enriched zone at the top of the blanket
water percolates through the weathering column, Cu-bearing forms a steady-state profile that is displaced rigidly in the
sulfide minerals are oxidized at the top of the enrichment direction of fluid flow.
blanket and Cu is reprecipitated at greater depth at a redox Gangue minerals are considered inert in the present cal-
trap where conditions are reducing. Each packet of fluid per- culations. This is considered to be a reasonable first approx-
colating through the weathering column displaces the position imation in spite of the fact that the hydrolysis of silicate and
of the enrichment blanket downward. A natural consequence carbonate gangue minerals is expected to buffer changes in
of the metasomatic formulation of supergene enrichment is pH resulting from sulfide oxidation, and thus affect the for-
prediction of a maximum Cu grade at the top of the enrich- mation of product minerals and the rate of enrichment of
ment blanket in agreement with field observations. Provided the blanket zone. A companion paper will investigate the
fluid entering at the top of the weathering column contains effect of gangue minerals and the presence of a descending
sufficient 0, the entire process may take place submerged water table on the supergene enrichment process ( BIINOand
below the water table. LICHTNER, 1992).
An attempt to model supergene enrichment of a porphyry
THEORETICAL APPROACH
Cu protore was presented recently by AGUE and BRIMHALL
(1989). These authors used an extremely coarse spatial res- A first principles description of supergene enrichment must
olution of the weathering profile, consisting of only four grid take into account the formation of a complicated sequence
blocks each 30 m in extent. The first two blocks represented of alteration zones, consisting of numerous secondary Cu-
the un~tumt~ zone, the third block the enrichment blanket, bearing minerals as well as many other phases, which are
and the fourth block the protore. Clearly this formulation produced during oxidation and weathering of the protore.
does not allow metasomatic effects to be investigated accu- The alteration zones advance continually downward with in-
rately and could result in a qualitatively misleading inter- creasing time in the direction of fluid flow, redistributing Cu
pretation of the enrichment process. Furthermore these au- by concentrating it at a redox trap within a blanket zone
thors used arbitrary precipitation kinetics to describe. the for- overlying the protore. The mathemati~l description of this
mation of secondary minerals, rather than using a first process is referred to as a moving boundary problem. Its so-
principles approach that allows reaction rates to vary with lution provides not only the concentrations of solute species
the chemical affinity. This is essential to account for meta- and mineral abundances as functions of time and depth, but
somatic effects during the enrichment process. also the velocities of the individual reaction fronts delimiting
In this work a first principles approach is employed in the different alteration zones. To solve the governing equa-
which the influence of metasomatic processes on supergene tions requires a mathematical algorithm which is capable of
en~chment is described quantitatively in terms of solute resolving the spatial variation of the different reactions taking
transport and chemical reaction with minerals. According to place in the weathering profile that are responsible for en-
this formulation a geochemical system evolves with time ac- richment. The thickness ofthe different alteration zones varies
cording to principles of mass conservation, kinetics, and greatly with time and depth, ranging from millimeters or less
thermodynamics. Mineral reactions are described by kinetic to hundreds of meters or more.
rate laws for both precipitation and dissolution. Transport In a first principles approach the fundamental quantities
equations are solved nume~cally using the multiple reaction entering the theory are the initial and boundary conditions
path algorithm ( LKXTNER, 1988, 1992a,b). This method is imposed on the system, and various physicochemical prop-
based on the quasi-stationary state approximation to transient erties derived from constitutive relations, contained in the
mass conservation equations which enables the governing governing equations. The initial and boundary conditions
equations to be solved over geologic time spans ( LICHTNER, specify the composition of the protore and fluid initially in
1988). Implementation of a moving grid to track each re- contact with it, and the composition of the infiltrating fluid
action front enables the development of the leached, oxide entering at the top of the weathering column. The physieo-
and enrichment zones to be followed in time with arbitrary chemical parameters include the Darcy flow velocity, diffu-
precision. sion/dispersion coefficients, porosity, permeability, mineral
Following a qualitative estimate of the rate of propagation surface areas, and kinetic and thermodynamic properties of
of a mineral redox front associated with supergene enrich- the reacting species. The composition of the infiltrating fluid
ment, three numerical examples are considered of varying may be taken simply as rainwater adjusted, if necessary, for
comptexity of the protore and secondary Cu minerals in- percolation through a soil zone at the surface. The time evo-
cluded in the calculation. In the frrst example, oxidizing water lution of the supergene weathering profile is completely de-
is allowed to percolate continuously through a chalcopyrite- termined by the governing mass transport equations from
bearing protore, fully saturated with water at all times. Sec- the initial and boundary conditions. The theory enables pre-
ondary Cu minerals are restricted to chalcocite, covellite, and diction of the evolution of leached and oxide zones and de-
bornite. The second example includes magnetite and pyrite tailed structure of the enrichment blanket with time and
in the protore in addition to chalcopyrite with secondary depth. From this result the time required to form an enrich-
minerals br~hantite, tenorite, native Cu, and cuprite as well ment blanket of a given thickness and Cu grade can be de-
as those in the first example. In the final example the situation termined.
3990 P. C. Lichtner and G. G. Biino
Continuum Theory for the aqueous complex Ai. The quantities vimand v$ refer
to the stoichiometric reaction coefficients for minerals and
Transport equations representing a time-space description
aqueous complexes, respectively. In the presence of air-filled
of the weathering profile are formulated using the continuum
pore spaces above the water table, the additional reaction
theory of mixtures ( LICHTNER, 1985 ) . In this approach mass
conservation relations describing solute transport and chem- OZ(aq)= 0%) (3)
ical reactions in a porous medium are established for a rep-
occurs between the gas and the aqueous phases, which is
resentative elemental volume (REV) of the system. A REV
assumed to be always in local equilibrium throughout the
is chosen to be smaller than the characteristic length scale of
unsaturated zone.
the phenomena being investigated, yet sufficiently large to
Examples of a selected set of mineral reactions relevant to
include many mineral grains. The spatial coordinate x, rep
describing supergene enrichment written for different sets of
resented by a point in the mathematical continuum space,
primary species are given in Table 1. The reactions for the
is associated with a REV in physical space of finite extent.
same mineral are written for different possible redox couples.
All quantities of interest which vary spatially within the sys-
All forms shown may be important at different depths and
tem, such as solute concentration, mineral modal abundance,
times during supergene enrichment of a porphyry copper
porosity, permeability, mineral surface area, Cu grade, tem-
deposit. Note the change in sign and magnitude of the stoi-
perature, and pressure, etc., are referenced to a REV. These
chiometric coefficient for H+ for the different reactions. Al-
quantities are referred to as fields, a mathematical term for
though, according to Eqn. ( 1) , the reaction of the mth mineral
any function which is defined over a region of space. Within
is formulated in terms of aqueous species and not with other
a REV the properties of the system are presumed constant.
minerals, this does not rule out the possibility of mineral-
For the field variables to have meaning, their values must be
mineral reactions taking place. In fact, the mineral reactions
independent of the size chosen for the REV within a length
as written in Eqn. ( 1) include such reactions as a special case.
scale which characterizes the system at that particular point
Nevertheless, it may be difficult to deduce the approximate
in space.
form of the overall reaction involving two or more minerals.
The use of precisely defined field variables determined over
For example, in general the stoichiometric coefficients for
a grid of REVS which span the spatial extent of the system
such an overall reaction are space and time dependent. One
may lead to definitions that are different from their conven-
advantage of the formulation given by Eqn. ( 1) is that it
tional use by geologists. One case in point is that of Cu grade,
enables prediction directly from the transport equations of
an important variable in the description of the supergene
aqueous species, which are conserved by chemical reactions,
enrichment process. In its conventional use, Cu grade is not
without the necessity of introducing any additional assump-
referenced to a REV, but rather to some arbitrary (from the
tions about the form of the reaction.
point of view of the physicochemical properties of the system)
volume of rock that need not characterize the local properties
of the system. It is defined simply as the dimensionless quan- Mass Conservation Equations
tity equal to the mass of Cu divided by the mass of rock in
which the Cu is contained. Such a definition is of little use Partial differential equations representing conservation of
in a quantitative description of supergene enrichment. Im- mass in a one-dimensional, homogeneous, partially saturated,
posing on the definition of Cu grade that it refer to a REV porous medium with porosity, 4, and saturation index, 0,
implies that it must also depend on the density of the host defined as the fraction of pore volume filled with fluid, can
rock (see Eqn. 60). This may at first be confusing to geologists be expressed in the form ( LICHTNER, I985 )
accustomed to its conventional definition, but is absolutely
essential for properly understanding the supergene enrich-
ment process. To distinguish the two definitions, the REV-
based Cu grade is referred to as the local Cu grade. Knowing for the jth primary species. In this equation x refers to the
the local Cu grade it is possible to compute the conventional depth measured from the surface of the weathering column
Cu grade, but not the reverse. Therefore, the local Cu grade and t denotes the time. The quantity \k,( x, t), referred to as
is a much more fundamental quantity. the generalized concentration (LICHTNER, 1985 ), is defined
Chemical reactions taking place within a REV are repre-
by
sented in terms of an independent set of solute species 34J,
withj= l,..., N, referred to as primary species. Hetero- *,(x2 t) = c,(x, t) + c $YCi(X, t), (5)
geneous reactions involving minerals are expressed according
to where Cj denotes the concentration of the jth primary species
and the sum is taken over all aqueous complexes labeled by
the subscript i with concentration Ci . The quantity Q,( x, t),
referred to as the generalized solute flux, is defined by
for mineral A,,, . Homogeneous reactions within the aqueous a*j<X> t,
Table 1. A number of possible different forms of mineral reactions for different sets of
primary species. The reactions differ according to the redox pair used to represent oxi-
dation. Not all possible reactions useful for describing supergene enrichment are given.
Water is considered always to be in ample abundance so that its activity may be taken as
unity and therefore the stoichiometric coefficients for Hz0 are not given in the table. The
equilibrium constants refer to standard state conditions of 25C and I bar with values
taken from the EQ3/6 data base, DATAO.CO~.R7.
describes two-phase fluid and gas transport in the unsaturated essary for describing the system including thermodynamic
zone and replaces Eqn. (4) for dissolved oxygen OZcaq).Be- and kinetic data, the Darcy flow velocity or permeability,
cause the terms involving dissolved oxygen are generally diffusivity, dispersivity, and mineral surface areas, for ex-
much smaller than those involving oxygen gas, they may be ample. The initial conditions specify the composition of the
neglected in a first approximation. However, in the neigh- unaltered host rock and the composition of the fluid initially
borhood ofthe capillary fringe where the diffusion coefficient in contact with the minerals in the rock. The initial rock
for oxygen gas rapidly decreases, it may be necessary to take composition need not be homogeneous, but could represent
both terms into account. an initially zoned rock. If a water table is present at depth,
Mass transfer equations for minerals take the form the concentration of oxygen in the air-filled pore spaces above
the water table must be specified. The boundary conditions
(8) specify the composition or flux of the infiltrating fluid at the
inlet, corresponding to the surface of the weathering column,
describing the alteration of the mth mineral, with volume and at the outlet. For pure advective transport it is not nec-
fraction &,, and molar volume vm,, with time t at a fixed essary to consider the initial fluid composition, provided it
point x along the flow path. In these equations porosity and is in equilibrium with the host rock minerals, because it is
mineral volume fraction are related by the expression pushed out of the column by the inlet fluid. In symbols these
conditions translate to
5 &?I = 1 - 4, (9) *j(O, t) = WY (11)
m=,
and
valid if total porosity can be identified with flow porosity. If
not, it may be very difficult to relate these quantities by any &(X, 0) = &, (12)
simple expression.
where qy represents the composition ofjth primary species
It is assumed in the following that local equilibrium is
in the inlet fluid, and d, represents the initial modal com-
maintained within the aqueous phase. This assumption could
position of the mth mineral in the unaltered rock.
be relaxed by incorporating a kinetic description of homo-
in the case of a water table fixed at depth, the concentration
geneous reaction rates. Such a treatment, however, is beyond
of oxygen gas at the surface of the weathering column must
the scope of the present contribution and would greatly com-
be specified. At the water table a zero flux boundary condition
plicate the set of governing equations. According to this as-
is imposed on the transport of oxygen in the gas phase. These
sumption the concentration of the ith aqueous complex is
conditions are given by the relations
related to the concentrations of primary species by the mass
action equation Co,,,,(O,t) = C&,.,> (13)
Cl = Kiy; n (r,Cj), (IO) where Coo_, denotes the concentration of oxygen at the sur-
1 face, and
corresponding to the reaction given by Eqn. (2). In this
aco2dx7 t) = o
NICHOLSON et al., 1989; MOSESand HERMAN, 1991). Un- for the reaction rate I,,,, where k,,, designates the kinetic rate
fortunately, there does not appear to exist a satisfactory rate constant, .s, represents the specific surface area, A, denotes
law for pyrite or other sulfide-bung minerals that is valid the chemical affinity for mineral J%, reacting with solute
for the fulI range of oxidation states encountered in supergene species &I according to Eqn. ( 1 ), and the coefficient fm is a
enrichment. NKHOLSON et al. ( 1988) obtained an expression constant. The affinity A,,, of the mth mineral for the overall
for the rate of pyrite oxidation under strongly oxidizing con- mineral hydrolysis reaction, as written in Eqn. ( 1 ), is pro-
ditions. Their rate law is based on adsorption of oxygen at portional to the natural logarithm of the product of the equi-
the surface of the pyrite grams and is proportional to the librium constant K,,, and the ion activity product Qm accord-
oxygen fugacity (fo). However, this rate expression is not ing to
applicable when the f% drops to sufficiently low values where
A, = -RT In K&I,,, (16)
other, more favorable, mechanisms of pyrite oxidation dom-
inate. To carry out a complete description of the supergene where the ion activity product is defined by
enrichment process, rate laws are required which encompass
the full spectrum of oxidation states and pH values found in Qm = n (Y,Kj)im, (17)
the weathering profile. Oxidation states may range from highly
oxidizing conditions to highly reducing condi~ons appro- and R and T denote the gas constant and tem~rature, re-
priate to deep groundwater in near equilibrium with pyrite. spectively. The constant fmcontrols the rate of precipitation
The pH varies from extremely acidic values resulting from far from equilibrium, where 1A,,, 1% RT, but does not greatly
oxidation of pyrite to basic values associated with equilibrium affect the rate of dissolution except for conditions close to
with silicate minerals. equilibrium. For finite fm, the reaction rate for conditions far
Fortunately, certain aspects of supergene enrichment are from ~uilib~um becomes constant for both dissolution and
insensitive to the expression for the kinetic rate law and choice p~ipi~tion. However, asf, + co, the pr~ipi~tion rate
of rate constants that are used in model calculations ( LICHT- grows indefinitely with increasing disequilibrium, a physically
NER, 1992a). Scaling properties of the kinetic mass transport unreasonable result considering that eventually the transport
equations demonstrate that the kinetic solution approaches of the reacting solute species to the surface of the mineral
its local equilibrium counterpart, given sufficient time. must become the rate limiting step. These relations can be
Quantities including solute concentrations, mineral volume expressed explicitly according to
fractions, and reaction front velocities approach values cor- k mm
S el~,IIRr > 0
responding to the local equilibrium solution with increasing
time. Thus, for example, for sufficiently large times the growth (precipitation, A,,, 4 -R T, fm + co )
of the enrichment blanket is not expected to depend sensi-
tively on the choice of kinetic rate laws and their associated Im- mmm >0
fks (18)
rate constants used in the calculations. There is, however,
(precipitation, A, $ - RT, f, < 00 )
one impo~ant proviso. This concerns the initial stages of
enrichment when protore minerals are still present over the , -k,s, < 0 dissolution, A,,, % RT).
entire flow path and reaction fronts have not had sufficient
Close to equilibrium ( 1A,,, 1 4 RT) the reaction rate is pro-
time to form. At the top of the weathering column where
portional to the chemical affinity according to the expression
conditions lead to reaction rates that are far from equilibrium,
the time required for the protore minerals to dissolve com- kms,
pletely is inversely passional to the kinetic rate constant zm= -RTcI +f,,j -%m tl-btl +RT). (19)
(see Eqn. 22). Therefore, without knowledge of the detailed
kinetic rate mechanism and surface areas of the protore min-
erals, it is not possible to predict the time required for the St&ace area
protore minerals to become completely oxidized above the In a homogeneous porous medium in which each mineral
water table. This important aspect of the problem must wait grain is ideatized as a cube, the initial specific surface area
until more accurate rate laws become available. s, of the mth mineral is related to the length of a side L&by
Given the lack of kinetic data, a simplified expression for the equation
the kinetic rate is assumed. The effects of the dependence of
the kinetic rate on such factors as pH, fox, concentration of
Fe3+, and other oxidizing species are not considered. Because Sk = $I$&. (20)
m
the rate law reduces to the local equilibrium description in
the limit as the product of the rate constant and mineral The surface area s: has units of inverse length, equal to the
surface tend to infinity, it allows departures from local equi- surface area per unit volume of buIk porous medium con-
librium to be investigated for finite rate constants. In this tained in a REV. One simple expression for the change in
sense the rate law may be considered as a pseudokinetic rate mineral surface area with reaction is the two-thirds power
law. The form of the kinetic rate law used in this study is relation of the volume fraction given by
given by the expression
(21)
1 - exp[ -A,/RT]
I, = -k,s, (15)
1 + f ; exp[ -A,/RT] based on the geometric relation of surface area to volume.
3994 P. C. Lichtner and G. G. Biino
This relation gives the correct limiting value of zero surface Generally, reaction fronts delineating the boundaries of
area when the mineral completely dissolves. However, it does the reaction zones move at different velocities proportional
not take into account the possible increase in surface area to the rate of influx of water through the weathering column.
resulting from the formation of etch pits as a consequence The corresponding reaction zones increase in width with in-
of dissolution. creasing time. However, a special class of reaction fronts exists
With the specific surface area given by Eqn. (2 1), an for which the velocity of propagation is inversely proportional
expression valid for conditions far from equilibrium can be to the fluid velocity. These fronts occur in pairs and propagate
derived for the time, TV, required for a mineral to dissolve with equal velocities. As a consequence, the reaction zone
completely at the top ofthe weathering column. Substituting enclosed by a pair of such fronts propagates with a constant
the expression for the rate obtained from Eqn. ( 18) for A, width. Such reaction zones are referred to as ghost zones
9 RT, with the surface area given by Eqn. (21), into Eqn. ( LKHTNER and BALASHOV,1992). Their width is propor-
( 8 ) and integrating yields tional to the characteristic diffusion or dispersion length of
the system, and inversely proportional to the fluid velocity.
(22) Ghost zones are predicted to occur in the enrichment blanket,
but have yet to be identified in the field. The name stems
This expression accounts for the decrease in surface area of from the property that for pure advective transport in the
the dissolving mineral with time. The factor 3 comes from limit of local chemical equilibrium their width vanishes, yet
the two-thirds power of the volume fraction in the expression the fluid composition immediately downstream from the
for the surface area. According to this relation 7, is inversely ghost remains in equilibrium with minerals in the zone in
proportional to the kinetic rate constant, initial surface area, spite of its vanishingly narrow width. It should be noted that
and the mineral molar volume, and directly proportional to the behavior of a zone as a ghost zone depends critically on
the initial volume fraction of the mineral. the equilibrium constants used to describe the minerals mak-
ing up the zone. Inasmuch as the thermodynamic data for
Cu-bearing minerals are somewhat uncertain (POTTER, 1977;
Moving boundary problem SHEAand HELZ, 1989), it is to be expected that the behavior
found here could change as more refined data becomes avail-
As already noted, a description of metasomatic alteration
able.
of a porphyry Cu protore during supergene enrichment rep-
resents mathematically a moving boundary problem. In such
problems the boundaries delineating regions of space con- Multiple Reaction Path Formulation
taining different mineral assemblages, coinciding with reac-
tion fronts, move with time. Their positions must be deter- The transport equations governing metasomatic zoning
mined as part of the solution to the problem, a characteristic for systems as complex as those involved in supergene en-
feature of the moving boundary problem. richment must be solved numerically. This represents a for-
The affinity factor, 1 - exp[ -A,/RT], appearing in the midable problem and approximations must be introduced if
numerator of Eqn. ( 15), is responsible for enabling the trans- calculations are to be carried out over geologic time spans in
port equations to describe the advance of mineral alteration reasonable amounts of computer time. The approach used
zones with time through dissolution and reprecipitation. The here is based on the multiple reaction path formulation of
ability for the reaction rate to change sign with depth is crucial mass conservation equations incorporating chemical reac-
for a description of transport-reaction processes. Without this tions ( LICHTNER,1988, 1992a,b). A reaction path in an open
factor in the kinetic rate law it would not be possible to use or closed system refers to the state of the system as it changes
a kinetic formulation to describe the propagation of reaction with reaction progress or time resulting from reaction with
zones with time. The moving boundary aspect of the trans- minerals. For a system involving fluid flow, a reaction path
port-reaction problem is taken into account in the transport may be parameterized by the travel time of a packet of fluid
equations through the reaction index [,,, defined explicitly by as it traverses the flow path. HELGESON( 1968) developed a
the relations single-reaction path formulation to describe the alteration of
minerals in a geochemical system for both open and closed
&?sx, t) systems as a function of a reaction progress variable. This
technique has found extensive application in understanding
1 if [&(x, t) > 0] or the behavior of complex geochemical systems. However, ex-
plicit incorporation of time and space is not possible. To
ZZ [&,(x, t) = 0 and A,(x, t) I A$ I 0] (23) describe the evolution of a geochemical system in both time
and space it is necessary to consider many reaction paths,
0 if c&(x, t) = 0 and A,(x,t)> 0,
with each path dependent on the preceding path through
where AZ denotes the threshold affinity, providing for su- changes in the modal composition of minerals in the host
persaturation of kinetically inhibited minerals by setting the rock.
onset for nucleation. The factor t(x, t) is unity when the The multiple reaction path formulation is based on the
mth mineral is present or when it is not present but begins quasi-stationary state approximation ( LICHTNER, 1988 ) . The
to precipitate; and zero if the fluid composition is undersat- quasi-stationary state approximation follows rigorously from
urated with respect to a mineral which is not present at depth transient mass conservation equations given by Eqn. (4) in
x and time t in the weathering column. which the term involving the partial time derivative of the
Theory of supergene enrichment of Cu-Fe sulfide ore 3995
solute concentration is neglected compared to the remaining pendent partial differential equations describing the transient
terms (LICHTNER, 1988). Thus, it is assumed that transport problem ( LICHTNER, 1988 ) . A stationary state sat-
isfies the ordinary differential equation
a\k,_O
at - . ux (X, t) = -2 ujmlm:,(X, tlzm(X, t)> (25)
m
This approximation enables time-space calculations of com- where the time t enters as a parameter referring to the state
plex, natural geochemical systems to be carried out over geo- of alteration of the host rock. This equation is subject to the
logic time spans. Its validity rests on the assumption that a boundary condition at the inlet specified by Eqn. ( 11). In
given species is much more concentrated in minerals than addition, it is necessary to specify the initial composition of
in an aqueous solution ( LICHTNER, 1988, 1991). As a con- the host rock, &,,(x, t). This quantity is obtained from the
sequence, the solute concentration rapidly becomes stationary previous reaction path, or from the unaltered host rock com-
in time compared to the time scale during which minerals position for the first reaction path. Neglecting two-phase
can be significantly altered, thus forming a stationary state. transport of fluid and air, diffusion of oxygen through the
This relation would be expected to break down for very con- unsaturated zone is represented by the stationary state equa-
centrated brines or melts. tion
1=c
In the multiple-reaction path formulation of an open sys-
tem in which advective transport of fluid takes place, each ~O*(.),m.cJm. (26)
reaction path describes the composition of a packet of fluid m
Affinity Factor
a.5 where t denotes the travel time of the fluid packet. This
DISSOLUTION
equation assumes that oxidation takes place under conditions
far from equilibrium resulting in a constant rate of oxidation.
Integrating this equation over the time in which the fluid
packet is in contact with the mineral yields
PRECIPITATION
LOG[fo21 where C&,,, denotes the value of Co2(m)at the surface, and
6t denotes the travel time to reach the redox front from the
FIG. 1.The affinity factor 1I,,,/k,,,sm1appearing in Eqn. ( 15)applied first point of contact with the mineral zone (see Fig. 2). As-
to the reaction of chakopyrite plotted as a function of the logarithm suming oxygen is completely depleted at the redox front and
of the Ib, for two different values of the parameter f = 1 and cg.
Fixed activities aFs+ = 10e6,a~,+ = 10m6,and asot- = 10e4 are used solving for the travel time 6t yields
to obtain the curves shown in the figure. According to the figure,
dissolution of chalcopyrite is insensitive to the fs except in the im- (31)
mediate neighborhood of equilibrium.
where the subscript M indicates that the travel time is related
. *.
actimtxes aF$+ = 10w6,aw = 10w6, and aso:- = low4 are to oxidation of the mth mineral. The distance traveled by
used to obtain the curves shown in the figure. For this fluid the packet in time St:, is equal to the travel time multipli~
composition, equilibrium with chalcopyrite is reached at by the average fluid velocity v, or
log fo, = -66.025. As can be seen from the figure, for dis-
solution there is a significant change in the rate of reaction 61, = t&l, = u
G,,,,
(32)
only in the neighborhood ofequilibrium. For log _& > -65.5, k m-h
*02,,,.m
the dissolution rate is constant and equal to its value far from where the fluid velocity pi is retated to the Darcy velocity u
equilib~um. by the porosity of the porous medium according to the equa-
An immediate consequence of this result is that for the tion
rate law given by Eqn. ( 15), the fo2of the fluid does not
exert a significant control over the oxidation rate of chalco-
(33)
pyrite. This behavior can be expected for other redox-sensitive
minerals as well. Nevertheless, metasomatic effects are greatly
For a given Damy flow velocity the distance 61, is independent
reduced as the fa of the inlet Buid is diminish~. This is
of the porosity of the porous medium. The time, I%-,, required
because the distance traveled by a packet of fluid to reach
for the mineral to dissolve completely over the travel length
equilibrium with chalcopyrite is directly proportional to the
Sl,,, is given by
value of the inlet j& (see Eqn. 32). According to this result
the velocity of the chalcopyrite oxidation front goes to zero
as the oxygen content of the inlet fluid becomes zero. This (34)
analysis assumes that other oxidizing agents such as Fe3+ or
Cu2+ are not present in significant quantities. However, these Note that a factor of 3 does not occur in this expression as
species may be produced by virtue of the oxidation process compared to Eqn. (22)) because the mineral surface area is
and help to prolong oxidation after dissolved oxygen has been considered constant over the time step 87,. This is valid for
completely consumed. The full spectrum of oxidizing species sufficiently small steps and, in particular, in the limit 67, +
is taken into account in the numerical calculations presented 0 which is required below. From this result it follows that
in the next section. It turns out, however, that in spite of this the velocity of the redox front is given by
simpli~~~on good agreement is obtained between this sim-
plified description and the numerical results.
Within the saturated zone where metasomatic effects gov-
em the enrichment process, a continuous downward flow of The velocity of the front is directly proportional to the
oxygenated water results in a corresponding downward mi-
gration of the redox front. Consider oxidation of mineral &,
according to the reaction
influx of water, its oxygen content, and mineral molar vol- pressure of oxygen Po2c1, = 0.2 bars. Values for the redox
ume, and inversely proportional to the initial mineral modal front velocity and fluid-rock ratio, or equivalently the retar-
abundance and stoichiomet~c reaction coefficient ( LICHT- dation factor, are given in Table 2 for ~~~op~te, chalcocite,
NER, 199 1, 1992a,b). Remarkably, according to this result covellite, bornite, and pyrite, based on the reactions given in
the velocity ofthe oxidation front is independent of the kinetic Table 1 with oxygen as primary species. Also given in Table
rate constant and surface area of the reacting mineral. Note 2 are the time for complete dissolution of the mineral 7, at
that both the travel distance 61, and the time 67, required the surface of the weathering column and the path length 61,
to oxidize the mineral completely over the distance 61, are for equilibrium to occur. Accordingly, for a fluid packet ini-
inversely proportional to the kinetic rate constant and sutiace tially in equilib~um with the atmosphere in~ltmting into a
area. Because the redox front velocity is equal to the ratio of host rock containing 2% by volume of sulfide mineral results
the distance traveled divided by the time required for the in a redox front which propagates through the rock with a
mineral to become completely oxidized, the rate constant velocity on the order of 10s4 m y- for a Darcy flow velocity
and surface area cancel in the expression for the front velocity. of 1 m y-l. This value is larger than most erosion rates and
This result is actually very general and does not depend on would be sufficient to form an enrichment blanket 100 m
the fez vanishing at the redox front. The result is not new thick in one million years. The time for complete di~olution
and has been pointed out previously for propagation of a to occur is extremely short compared to geologic time scales
general mineral reaction front (see, e.g., LICHTNER, 1988, of typical weathering processes. The values for 7, appear to
1991). be in qualitative agreement with field observations on the
The volume of fluid necessary to oxidize the protore to a persistence of the various sulfide minerals in the weathering
given depth for fully saturated conditions can be expressed profile with the ordering: bomite > chalcopyrite > pyrite
in terms of a fluid-rock ratio. Taking the volume of rock as (C. N. Alpers, pers. commun.). This statement reflects the
the volume swept out by the redox front in time t, then the differences in mineral molar volumes and the stoichiomet~
total volume of rock reacted in time t for a cross-sectional of oxygen in the oxidation reaction, all other quantities being
area A is equal to the same.
Thus, in a fully saturated weathering column, given enough
V&,, = /II&t. (36) time and rainfall, it is possible to oxidize a sulfide-bearing
The total volume of fluid passing through the rock in the rock to significant depths. Focusing effects of fluid transport
same amount of time is equal to caused by regions of high pe~eability could enhance the
local flow velocity and therefore the rate of oxidation. Al-
Inuid= AU?. (37) though traditionally the position of the water table has been
The fluid-rock ratio is thus equal to assumed to be a major factor in the supergene enrichment
process, this analysis demonstrates that metasomatic effects
R,=-=- Vfluid @ caused by transport of Oztaql below the water table can also
(38)
V&k St be important.
which is identical to the retardation factor of the reaction
NUMERICAL CALCULATIONS
front.
For a fluid packet initially in equilibrium with the atmo- In this section predictions of the multiple reaction path
sphere it follows that description of supergene enrichment of a porphyry Cu protore
are presented. A schematic representation of the distribution
CO
oXa@= Ico2W~o2W (39)
of Cu-bearing minerals in a supergene enrichment weathering
where log KoZclf= 2.889 denotes the equilibrium constant profile is shown in Fig. 3. The weathered profile may be di-
for the reaction between oxygen gas and OZcasJ,and the partial vided into five major zones which, beginning at the surface,
erals; for example, the rate constants for calcite and plagioclase
differ by approximately seven orders of magnitude leading
to a very different behavior of concentration of the Ca ion
from the simultaneous dissolution of each mineral. Further
cuprite
difficulties are caused by redox reactions which can lead to
native copper extremely sharp reaction fronts. In the routine MPATH, the
stationary state solute transport equations are solved nu-
covellite
merically using an implicit finite-difference algorithm. Ac-
chalcocite
tivity coefficient corrections are calculated using an extended
Debye-Hilckel algorithm. Redox reactions are incorporated
chalcopyrite in MPATH in terms of actual species in solution, rather than
in terms of a hypothetical electron. This guarantees conser-
vation of electrons in the overall oxidation-reduction reaction.
Because of the sudden changes in concentration associated
with oxidation-reduction reactions, it is crucial to formulate
the finite-difference equations in terms of the logarithm of
the solute concentration, rather than the concentration itself.
In addition, an efficient adaptive step-size algorithm for ad-
vancing the solution along a streamline is essential for tracking
the solution composition across sharp reaction fronts. The
step size must be allowed both to increase or to decrease as
smooth or rapid changes in concentration are encountered
along the flow path. Thus, for example, as the fluid packet
0.2 0.6 1.0 crosses a redox front and the oxygen fugacity plummets to-
0.0 0.4 o.*,
wards zero, the step size must be altered to take into account
FIG. 3. A schematic diagram of the supergene weathering profile the different conditions on either side of the front. Before the
showing relation between the cap zone, oxide zone, enrichment blan-
fluid packet reaches the redox front large steps can be taken,
ket, and protore. The figure is adapted from field observations reported
by TITLEY( 1978 ). Only Cu-bearing minerals are included in the but as the redox front is crossed extremely short steps are
figure. Also shown is the measured Cu grade as reported by TITLEY required because of the rapidly changing concentrations of
( 1978). Note that there are two distinct chalcocite zones separated redox sensitive species across the front. Use of a variable step
by covellite. The lower chalcocite zone, also enriched in Cu, presum- size has the added advantage that it reduces significantly the
ably resulted from lowering of the water table.
total number of steps that are necessary to solve the problem.
Integrating the partial differential equations determining
are the gossan or cap zone, leached zone, oxide zone, en- the mineral modal abundances, given by Eqn. (8) or equiv-
richment blanket, and protore. Each zone is further subdi- alently Eqn. (27), requires introducing a spatial grid at which
vided into individual mineral alteration zones consisting of to store the mineral volume fractions. This is accomplished
various mineral assemblages. The protore consists of un- by using the same node points at which the stationary state
weathered gangue minerals contained in the host rock and solute transport equations are solved, associating a natural
primary Cu-bearing sulfide minerals such as chalcopyrite and spatial grid network with each stationary state. This defines
bornite. The oxide zone consists of copper oxide minerals a moving grid which changes with each stationary state. The
such as tenorite. The enrichment blanket contains secondary grid points are closely adapted to the particular sequence of
Cu minerals chalcocite, covellite, cuprite, and native Cu. Py- reaction zones which define the current state of alteration of
rite is found in both the blanket zone and protore. In Fig. 3, the host rock. The volume fractions calculated at node points
two distinct chalcocite zones are shown within the enrichment corresponding to the previous stationary state are interpolated
blanket. to the new node points of the current stationary state to carry
out the integration. In this way reaction fronts can be tracked
with time and extremely narrow reaction zones easily resolved
Numerical Algorithm MPATH
to any desired accuracy. The density of grid points is always
Calculations are carried out using the multiple-reaction chosen sufficiently fine to resolve the detailed structure of
path formulation of solute transport and mineral alteration each reaction zone, regardless of how narrow it might be.
implemented in the computer code MPATH for pure ad- This may entail using several thousand grid points.
vective transport in a single spatial dimension. More details The computer code MPATH uses an extensive data base
of the code can be found in LKHTNER ( 1992b). The sta- of minerals and aqueous species equivalent to the EQ3/6
tionary state transport equations must in general be solved data base ( WOLERY, 1987). The user must select which min-
numerically. Furthermore, these equations present special erals and aqueous species to include in the calculation for
difficulties because of their mathematical stiffness. Stiffness the particular geochemical system considered. This cannot
arises when the solute concentrations are changing according be predicted by theory alone and often requires some sub-
to two or more very different length scales spanning many jective criteria on the part of the user. An option in the code
orders of magnitude. This behavior is caused by the presence allows minerals to remain supersaturated without reacting
of a wide range of kinetic rate constants of the reacting min- until a specified threshold affinity is reached. This was found
Theory of supergene enrichment of Cu-Fe sulfide ore 3999
to be essential to describe the behavior of magnetite which Ample evidence exists in the literature of deep oxygenated
became supersaturated during weathering, but is unlikely to &rids with fs near that of atmospheric conditions. FREEZE
precipitate at low temperature. and CHERRY ( 1979) present evidence that infilt~ting rain-
water may hold its charge of oxygen over long travel distances
Simplifying Assumptions depending on the soil type and minerals that are encountered
In this first step towards attempting to understand quan- along the fluid flow path. In this work it is assumed that the
titatively the supergene enrichment process formulated as a inlet water is in equilibrium with atmospheric oxygen. In-
moving boundary problem, a number of simplifying as- cluding the effects of homogeneous redox kinetics within the
sumptions are made. These include ( 1) local ~uilib~um of aqueous phase involving Hz02 as suggested by SATO ( 1960)
aqueous complexing reactions including simultaneous equi- is beyond the scope of this cont~bution.
librium of all aqueous redox couples; (2) constant concen- The main difference between the saturated and unsaturated
tration of dissolved oxygen above the water table; (3) constant zones from the point of view of oxidation-reduction reactions
porosity and permeability; (4) pure advective transport of is the variation of dissolved oxygen in the weathering profile
dissolved solute species; (5) constant temperature and pres- with depth. Above the water table replenishment of oxygen
sure of 25C and 1 bar; (6) absence of gangue minerals; (7) occurs by diffusion, and possibly by convective transport due
a soil zone is not explicitly considered; (8) a simplifi~ set to variations in barometric pressure, through air-filled pore
of Fe- and Cu-bearing minerals is used, (9) a simplified kinetic spaces. if transport of oxygen in the gas phase is sufficiently
rate law is used which does not take into account the precise rapid compared to its consumption by reaction with minerals,
form of the reaction mechanism; ( 10) the variation in surface oxidation proceeds at a constant rate of reaction governed
area is approximated by the two-thirds power of the mineral by far-from-equilibrium conditions throughout the entire
volume fraction; and ( 11) only one spatial dimension is con- unsaturated zone. By contrast, in the saturated zone the ox-
sidered. The possible effects some of these a~umptions might ygen content of the infiltrating water is not replenished, but
have on the description of supergene enrichment is considered is continuousiy depleted with depth as oxidation of sulfide
briefly. minerals takes place. A proper description of the replenish-
ment of oxygen from the atmosphere as it is consumed by
Oxygen concentration chemical reactions in the unsaturated zone requires, in prin-
There exist conflicting reports of the oxygen content of ciple, solving Eqn. (7) involving two-phase fluid transport of
near-surface water. SATO(1960f argues that the Eh of near- oxygen gas and water. This would lead far beyond the scone
surface water is buffered by H202 which is metastable. Dis- and intention of the present contribution, and it is not clear
solved oxygen is in disequilibrium with the redox state de- whether it would add much insight to understanding super-
termined by H202. SATO( 1960) does not attempt to give gene enrichment.
values for fo, or Hz02 concentrations, but assumes that the To quantify the conditions necessary for the oxygen con-
ratio of oxygen to Hz02 ranges from a value of one to 106. centration to remain constant above the water table for the
AGUEand BRIMHALL( 1989) used the value f& = 10e3, an case of diffusion through the un~turat~ zone, consider the
extremely small value, for the unsaturated zone above the solution to the stationary state transport equation,
water table. They obtained this value based on the work of
SATO ( 1960) by assuming that OZcaqjis in equilibrium with
HzOz. This would appear, however, to be a grossly incorrect
assumption. A value of & = lO-3s implies a concentration for constant reaction rate I. Aithough the effective oxygen
Of02@l) of approximately 1 atom per cubic km of fluid. Yet diffusion coefficient depends strongly on the saturation index
these authors refer to such fluid as being oxygenated and of the unsaturated zone and the tottuosity (TROEH et al.,
write oxidation reactions for pyrite and chalcopyrite involving 1982; NICHOLSONet al., 1989), these effects may be neglected
OZcaqj(see p. 16, Eqns. 8 and 9 in AGUE and BRIMHALL, for a saturation index less than about one-half. In the neigh-
1989). With such a small number of oxygen atoms it is quite borhood of the capillary fringe, D&, would be expected to
meaningless to consider chemical reactions and diffusion in- decrease dramatically. However, provided the width of the
volving Oz(asf. Of course, it is always possible to use the capillary fringe is sufficiently narrow compared to the depth
foZ as a the~~ynamic parameter, but it need not relate to of the water table, this variation should not signifi~ntly affect
the actual reaction mechanism, which is the main point of the analysis given here. The solution to this equation satisfying
this discussion. Because AGUE and BRIMHALL( 1989) were the boundary conditions
only interested in very short time spans, use of the wrong
value for the fo, did not significantly affect their calculations. co*(,)(o)= C&) (41)
It is interesting to note in passing that the metastability line and
in a pe-pH diagram for H202 with equal concentrations of
0 zcaq)and HzOz approximately coincides with the tenorite- dCo,@
(42)
cuprite phase boundary. This could give an alternative ex- dx X=,,=
planation for the observed Eh in porphyry Cu deposits if
equilibrium was achieved between these two minerals at the is given by
depth of observation. However, it would not explain similar
obviations obtained for other systems where these minerals
are not present.
4ooo P. C. Lichtner and G. G. Biino
1: 6.
column is assumed to be in equilibrium with the atmosphere
with Pogcg, = 0.2 bars and with a pH of 6. The composition
J cc 2,500 YEARS -
of the fluid entering at the top of the weathering column is
assumed to be rainwater with the composition given in Table
3. Above the water table oxygen is buffered by equilibrium
with the atmosphere, whereas below the water table, within
the fully saturated portion of the weathering column, the
fo, is determined by the subsequent water-rock interaction.
Mineral solid solutions are not considered. Surface poisoning
and armoring of minerals due to coating by product phases, F -6.
0. 1. 4. 5.
although possibly an important effect in explaining the pres- d
BET& (ME&KS)
ence of relic grains of pyrite and chalcopyrite observed in the
supergene weathering profile, are not included in the calcu- FIG. 4. Results for the oxidation of the single protore mineral
chakopyrite by infiltrating oxidizing rainwater in equilibrium with
lations. the atmosphere at the top of the weathering column for an elapsed
time of 2,500 years. Fully saturated conditions with a Darcy velocity
Oxidation of a fully saturated chalcopyrite protore of 1 m y-l are assumed in the calculation. The fo,, mineral volume
fractions, and reaction rates are shown as a function of depth. Chal-
The simplest system for investigating the supergene en- copyrite remains present in the leached zone at the top of the weath-
richment of a porphyry Cu protore is oxidation of the single ering column during this time span. See text for specification of pa-
rameters used in the calculation. Abbreviations used in the figure are
mineral chalcopyrite (CuFe!$) under fully saturated condi-
chalcopyrite, Ccp (long-dashed line); chalcocite, Cc (solid line); co-
tions. An initial volume fraction for chalcopyrite of 2% is vellite, Cv (dotted line); bomite, Bn (dashed-dotted line); pyrite, Py
used in the calculations. Secondary minerals included in the (short dashed line); and ferrihydrite, Frh (dashed-dotted line). Note
calculation are chalcocite, covellite, bornite, and pyrite. The that the pyrite and covellite dissolution rates overlap. The peak in
product of the kinetic rate constant times the surface area is the precipitation rate of chalcocite extends to 1.7 X lo- mol
L-1 s-I
taken as 5 X lo- mol cmm3 s- for all minerals. This value
is chosen arbitrarily. However, with the exception of the time
required for chalcopyrite to completely dissolve at the surface sensitive to this choice. Formation of other secondary Cu
and the width over which it dissolves, the results are not minerals such as cuprite, tenorite, brochantite, and native
Cu are suppressed in this example. Note that primary pyrite
is not included in the protore.
Table 3. The inlet fluid composition used in the cal- After a short time span of 2,500 years the supergene
culations representing rainwater in equilibrium with the weathering profile has the form shown in Fig. 4, in which
atmosphere for the subsystem Cu-Fe-S-H-O. Note that the f%, mineral volume fractions, and reaction rates are
the inlet solution is not charge balanced because it does
plotted as a function of depth. As chalcopyrite becomes ox-
idized, a sequence of alteration products is formed that di-
not represent the complete system.
vide the weathering column into a leached zone at the top
of the column, followed by a blanket zone in which secondary
species total concentration
Cu-bearing minerals precipitate, and finally the unaltered
(moles/liter)
protore. The leached zone consists of ferrihydrite and chal-
H+ 1.0 x10-s copyrite. The enrichment blanket consists of the secondary
Cl?+ 1.0 x10-s minerals pyrite, chalcocite, covellite, and bornite. Within the
Fe*+ 1.0 x10-* blanket zone the volume fraction of chalcocite exhibits a bi-
so:- 2.0 x10-s modal distribution with a maximum at the top of the en-
richment blanket. Zones of covellite and secondary pyrite
G.1) 2.52 x 1O-4
form below the first chalcocite peak. Bornite forms at the
4002 P. C. Lichtner and G. G. Biino
base of the blanket. Chalcopyrite remains present up to the nite, and pyrite, extending from the top of the upper chal-
surface of the profile where oxidation takes place by reaction cocite zone into the protore. With increasing time the chal-
with dissolved oxygen according to the approximate overall cocite zone splits into two distinct zones with the more en-
reaction riched zone occurring at the top of the blanket. The large
peak in the modal abundance of chalcocite at the top of the
CuFeS + 7/4O2 + 2Hz0 + /2Fe(OH)3(sj enrichment blanket increases with time until a maximum
+ 3/2H+ + /,Fe(OH): + 2SO:- + Cu+. value is reached, after which the chalcocite zone grows in
(47)
width at constant abundance. Bomite forms at the base of
The factor one-half is deduced from Fig. 4 noting that at the the blanket. Sandwiched between the bottom of the upper
surface of the weathering column the precipitation rate of chalcocite zone and the beginning of the lower chalcocite
ferrihydrite is approximately half the dissolution rate of chal- zone are zones of secondary pyrite and covellite which form
copyrite. According to this reaction, as oxygen is consumed, a constant plateau in the middle of the blanket in which no
the pH decreases, and Fe, Cu, and S ions are released into reaction occurs. Below the upper chalcocite zone the blanket
solution. has the same Cu concentration as in the original protore (see
With increasing time the various reaction zones evolve as Fig. 10).
shown in Fig. 5 in which the mineral volume fractions are To analyze the reactions taking place within the enrichment
plotted as a function of depth for elapsed times of 25,000, blanket, the situation is considered in detail for an elapsed
50,000, and 100,000 years. Zones corresponding to the time of 50,000 years. By this time a steady state is established
leached zone and the enrichment blanket grow with time as with the blanket and leached zones growing at constant rates.
is visible in the figures. The leached zone consists of ferri- Reaction within the enrichment blanket can be divided into
hydrite, which has a maximum modal abundance at the sur- several distinct processes involving different minerals,
face, resulting from the early oxidation of chalcopyrite, which aqueous species, and redox states of the fluid packet. It is
declines steeply with depth. The enrichment blanket consists convenient for the purpose of discussion to consider the upper
of a zoned sequence of the minerals chalcocite, covellite, bor- and lower portions of the blanket separately, defined as the
regions above and below the constant plateau in the abun-
dances of covellite and pyrite. At the top of the blanket en-
0.024 richment occurs. The lower portion of the blanket forming
(Cc 25,000YEARS -
6 ---------I the interface with the protore is referred to as the nascent
F O.OZO
3 0.016 blanket. In this region the blanket is continuously being
formed with the same Cu concentration as the protore.
; 0.012
E o.M%
3
p 0.004 Upper blanket
0.000
At the top of the enrichment blanket, the pH, pe, solute
0.024
50,000YEARS concentrations, and mineral reaction rates and volume frac-
H 0.020 ----mm- tions of chalcocite, covellite, and pyrite are shown in Fig. 6
t; /r CCP plotted as a function of depth corresponding to 50,000 years.
4 0.016
cd I The points labeled A-B-C-D-D-E-F-G-H appearing in Figs.
a 0.012
6 to 11 are referred to in what follows to describe the path
3
3 0.008 of a fluid packet traversing the supergene weathering profile.
p 0.004 Point A refers to the inlet, points B-C-D-D-E-F-G to the
0.000
chalcocite zone in the upper part of the blanket, and point
H refers to the protore. At point B chalcocite begins to dissolve
0.024 at its upstream boundary. Dissolved oxygen is depleted com-
z i-l 100,000YEARS
Y 0.020
pletely from solution at point C. However, oxidation of chal-
l-l
5 cocite continues at a constant rate until point D, where equi-
4: 0.016
E librium with chalcocite is reached. At the downstream end
; 0.012 of the chalcocite zone, chalcocite precipitates as the covellite
5 0.008 zone is encountered at point D and covellite dissolves. Point
$ 0.004. Frh E labels the point of the onset of pyrite dissolution. Note that
the fluid compositions at points D and D are identical. At
0.000
0. 10. 40. 50. point F the reaction rates of chalcocite, covellite, and pyrite
DEP4P;I(MEkRS) rapidly plummet to zero with an accompanied drop in the
FIG. 5. Mineral volume fractions plotted as a function of depth pe. Reaction stops at point G, which denotes the plateau
for times ranging up to 100,000 years for the same set of parameters region in the middle of the blanket.
used in Fig. 4. Two separate zones of chalcocite are formed. Secondary Dissolution of chalcocite in the upper blanket (B-C-D)
pyrite and covellite occur between the upper chalcocite zone, and
the chalcopyrite zone representing the protore. The bomite zone
takes place in two distinct stages. In the first stage (B-C),
propagates without changing shape (see Fig. 9). Zones of this type chalcocite is oxidized by dissolved oxygen. The reaction can
are referred to as ghost zones (LICHTNER and BALASHOV,1992). be expressed in the approximate form
Theory of supergene enrichment of Cu-Fe sulfide ore 4003
/T)+/
5 0.020
of the above reactions. This simple behavior is also a con-
4 0.016
sequence of the lack of any significant aqueous complexes
2 0.012
involving SO:-.
E
w 0.008
j Along segment D-D the fluid packet remains in equilib-
3 0.004
rium with chalcocite, and no further change in the concen-
B O.Ooo6.0 7.0 10.0 11.0 tration of aqueous species occurs. At point E the fluid packet
encounters covellite which begins to dissolve, causing chal-
FIG. 6. The pH, pe, solute concentrations, and mineral reaction cocite to precipitate. Within the zone of chalcocite precipi-
rates and volume fractions in the upper portion of the enrichment tation marked by segment D-E-F-G, two distinct regions with
blanket plotted as a function of depth corresponding to an elapsed reactions involving the minerals covellite and pyrite occur.
time of 50,000 years. The points labeled B-C-D-D-E-F-G are dis- An approximate overall reaction for covellite + chalcocite,
cussed in the text. The same set of parameters are used as in Fig. 4.
In spite of the linear drop in the fe across the upper chalcocite zone along segment D-E can be written as
(labeled B-C-D), the dissolution rate of chalcopyrite is constant with
&US + 2(5 - 4a)Cu+ + 4((~ - 1)H20 + Cu2S
depth until equilibrium is obtained. In the bottom two figures the
solid line refers to chalcocite, the dotted line to covellite, and the + (8 - 7~u)Cu*+ + ((Y- l)SO:- + 8((u - l)H+, (50)
short dashed line to pyrite. Note that the pyrite and covellite disso-
lution rates overlap along segment E-F. The units for solute concen- where the coefficient (YN 1.02, as estimated from Fig. 6 by
tration are 10m4mol L- of aqueous solution, and for reaction rate
comparing the absolute values of the rates of covellite and
IO-* mol L- s-l of bulk porous rock.
chalcocite. The reaction covellite + pyrite + chalcocite, along
segment E-F-G, can be written in the unique form
Cu2S + 5/202c8j
+ a(t)H + + a( t)Cu2+
CuS + FeS2 + 7/4C~+ + 3/2H20 - */&u2S
+ (2 - a(t))CuOH+ + SO:-, (48)
+ Fe + 3/&SO:- + 3H+, (51)
in which the reaction cofficient a( t) is a function of the travel
time t. The coefficient a( f) varies between 0 and 2 depending which is in good agreement with the calculated relative rates
on the degree of complexing of Cu*+ to form CuOH+. Initially of chalcocite, pyrite, and covellite, and consistent with the
the fluid has a pH of 6 with Cu 2+as the dominant Cu species drop in pH shown in Fig. 6. According to the latter reaction
in solution. As chalcocite begins to dissolve the value of the the Cu in solution is completely depleted by precipitation of
coefficient a( 0) is close to two, and the pH rises sharply from chalcocite at point F in the profile in agreement with Fig. 6,
its initial value of 6 to a maximum value of approximately caused by the redox trap formed by oxidation of pyrite.
8.3 as shown in Fig. 6. However, as the pH continues to By contrast, the concentrations of both SO:- and Fe+
increase, the coefficient a (t) decreases becoming approxi- increase.
mately zero and the pH becomes roughly constant with fur- Both reactions given by Eqns. (50) and (5 1) result in an
ther dissolution of chalcocite. With oxygen still present in increase in Cu grade. The migration and growth of the en-
solution, the dominant Cu species is CuOH+. riched portion of the blanket, consisting of the upper chal-
When all dissolved oxygen in the fluid packet has been cocite zone, occurs by two distinct mechanisms. First of all,
depleted, as indicated by point C in the figure, the second Cu is recycled within this zone as chalcocite is dissolved at
stage of chalcocite dissolution (C-D) begins. In this case, ox- its upstream boundary and reprecipitated at its downstream
idation of chalcocite continues to occur by reduction of Cu*+ , boundary. Precipitation of chalcocite first occurs when the
4004 P. C. Lichtner and G. G. Biino
::
F --.v----------_
4.
Note that the secondary minerals covellite and pyrite are DEPTH (ME%RS)
formed earlier at the base of the blanket by dissolution of FIG. 7. Mineral reaction rates in the lower portion ofthe enrichment
chalcopyrite where a separate zone of bornite also forms (see blanket and protore plotted as a function of depth corresponding to
Fig. 7). This region is referred to as the nascent blanket zone an elapsed time of 50,000 years. The mineral reactions conserve Cu.
because it refers to the region where the blanket is continu- The same conditions are used as in Fig. 4. Also shown are the pH
(solid line) and pe (dashed line).
ously forming from the protore. The dissolution of covellite
and pyrite in the upper blanket, leading to simultaneous pre-
cipitation of chalcocite, couples the upper and lower blanket
zones and results in a continuous growth of the chalcocite transported away by the aqueous solution. Thus, the vertical
zone with time. The dissolution of chalcocite at its upper weathering column is closed with respect to Cu, but open
boundary and reprecipitation lower in the blanket results in with respect to Fe and S.
the gradual downward displacement of the chalcocite zone A number of distinct reactions occur in the lower blanket
in the direction of fluid flow visible in Fig. 5. This is a char- at the interface between the protore and blanket which may
acteristic feature of all reaction zones subject to advective be represented schematically according to
transport of fluid. cc -t Py + cv, (52a)
ccp + cc + Py + cv, (52b)
Nascent blanket
ccp + cv + cc + Py, (52~)
Reaction does not take place along segment G (see Fig. 7)
which separates the upper and lower parts of the blanket. In Ccp + Bn + Cc + Cv, (52d)
this region the mineral volume fractions of covellite and pyrite Ccp + Bn + Py. (52e)
form a constant plateau referred to as the middle blanket.
Deeper in the enrichment blanket a third region of reaction These reactions correspond to increasing depth within the
occurs labeled by the points G-H. At the upper part of this lower blanket. These reactions conserve Cu and therefore
region covellite precipitates internally over a wide zone as preserve the Cu grade of the protore. Their net result is the
pyrite and chalcocite dissolve as shown in Fig. 7. Still deeper transformation of chalcopyrite into covellite and pyrite. The
in the profile chalcocite and pyrite precipitate as chalcopyrite region over which these reactions take place is referred to as
dissolves. A jump in the rates of chalcocite, pyrite, and co- the nascent blanket.
vellite occur as bornite dissolves at its upstream boundary. In the nascent blanket, alteration zones containing pyrite,
Covellite stops reacting just before bornite begins to precip- covellite, chalcocite, and bomite are formed. These processes
itate. As bornite continues to precipitate chalcocite stops re- all require some form of sulfate reduction. Although ther-
acting. Finally the packet of fluid approaches equilibrium modynamically feasible, sulfate-reducing reactions most likely
with minerals pyrite, bornite, and chalcopyrite as pyrite and do not take place in nature at ambient temperatures without
bomite precipitate, driven by the dissolution of chalcopyrite. the help of sulfate-reducing bacteria. A hypothetical overall
Dissolution of chalcopyrite is the ultimate source of Cu that reaction describing the direct transformation of chalcopyrite
is later deposited at the top of the enrichment blanket in the to covellite can be written in the form
form of chalcocite. Covellite acts as an intermediary for the
2H+ + CuFeSZ + CuS + HZScaq)+ Fe*+, (53)
concentration of Cu at the top of the blanket.
The concentrations of dominant aqueous species are shown which conserves Cu and does not require sulfate reduction.
in Fig. 8. In contrast to Cu, which is greatly depleted from To investigate reactions in the lower blanket, disallowing sul-
solution as a consequence of the low solubilities of copper fate reduction, would require relaxing the condition of ho-
sulfide minerals under reducing conditions, Fe and S are mogeneous equilibrium in the aqueous phase. This is beyond
Theory of supergene enrichment of G-Fe sulfide ore 4005
r
surface of the weathered profile after an elapsed time of ap-
proximately 8,600 years. This time is in agreement with Eqn.
_.-..
(
(22), based on the rate expression for conditions far from
2W
I
equilibrium, which results in the estimate presented in Table
.-__ sof
---___
2:
--____
.......... 7ccP = 3 e N 8,600 years, (56)
*.* c CCP
.... ;-y
*..* using the values vcc,, = 42.83 cm3 mol-, $ccp = 0.02, and
.....*
__-- kccdiccp = 5 X lo-l5 mol cme3 s-. At this time, although
._ the altered profile is only 6 m deep, distinct zones of ferri-
0. 5. 10. 15. 25.
hydrite, chalcocite, bomite, covellite, and pyrite have formed.
DEPTH (METEFS)
With increasing time the width of the alteration zone in-
FIG. 8. Concentration of the dominant aqueous species plotted creases. Eventually a steady state is established where the
on a linear scale as a function of depth for an elapsed time of 50,000 various reaction zones propagate with constant velocities
years for the same conditions in Fig. 4. The weathering column is
closed with respect to Cu, but not to Fe or S. without changing their maximum modal abundance as they
increase in width. An exception is the mineral bomite, which
+3-a-p
SO:- + PFeS2 + CusFeS4
4
+ ((Y - ,6 - l)Fe2+ + (p - LY+ 3)H20. (54)
The coefficients cy and p are related to the relative rates of
precipitation of pyrite and bomite, and dissolution of chal-
copyrite by
1, 1,
(55)
=1,=11,,,1.
According to Fig. 7, the value for (YN 5 and fi N 22/7,in which
0.0 0.2 0.4 0.6 0.8 1.0
case the coefficient of HZ!&,) is approximately zero. This
reaction results in an increase in pH and concentration of
Fe+, and a decrease in the concentration of SO:- in agree-
ment with Fig. 8. Therefore, this reaction, although ther-
modynamically feasible, requires the reduction of sulfate to
proceed. Note that dissolved oxygen does not occur in this
reaction and thus is not involved in oxidation ofchalcopyrite
deep in the supergene weathering profile. A different situation
occurs when chalcopyrite first dissolves at the surface of the
weathered profile, in which case dissolved oxygen is respon-
. 2 u.4 0.6 ".X
sible for oxidizing chalcopyrite according to Eqn. (47). TIME (YEARS) *lo5
The rate of formation of the enrichment blanket can be
FIG. 9. The positions of the reaction zone boundaries for (a) chal-
estimated from Fig. 9a,b, and c, where the positions of the cocite, (b) ferrihydrite, covellite, and pyrite and (c) bomite, plotted
reaction zone boundaries for (a) chalcocite, (b) ferrihydrite, as a function of time along with the dissolution front of chalcopyrite
covellite, and pyrite, and (c) bomite are plotted as a function for the same conditions as in Fig. 4.
4006 P. C. Lichtner and G. G. Biino
width of a ghost zone approaches zero. To compute the width DEPTH (METERS)
of the ghost zone accurately, it is necessary to take into ac- FIG. 10. Copper concentration in the solid phase in units of mol
count diffusive or dispersive transport in addition to advec- cme3 of bulk porous medium plotted as a function ofdepth at different
times indicated in the figure. Enrichment in Cu occurs only at the
tion. top of the blanket. The Cu concentration remains constant with in-
The chalcopyrite oxidation front advances at a rate of ap- creasing depth.
proximately uccp - 4.4 X 10m4 m y- corresponding to a
Darcy fluid velocity of 1 m y-' . This boundary represents
the position of the base of the enrichment blanket and the width. They referred to this zone as an incipient zone of
beginning of the protore. The upper boundaries of the pyrite enrichment. According to the calculations presented here
and covellite precipitation fronts are parallel to the chalco- it now becomes clear that what BRIMHALLet al. ( 1985) were
pyrite dissolution front representing coherent waves. Simi- actually observing was the enrichment peak at the top of the
larly, the lower pyrite and covellite dissolution fronts are also blanket, followed by the middle blanket and nascent zone
parallel representing coherent waves. The top of the enrich- where Cu is conserved. The actual bottom of the blanket
ment blanket coincides with the upper boundary of the chal- would be difficult if not impossible to determine based on
cocite zone. After chalcocite splits into two distinct zones, measurements of Cu grade alone.
for times greater than approximately 5 X lo4 years, four re- It is interesting to compare the calculated ratio of the width
action fronts can be identified with the approximate respective of the enriched portion of the blanket to the width of the
velocities, from top to bottom, of II:; - 1.4 X 10m4, 02~ leached zone with field observations. From the reaction front
- 2.0 x 10-4, $2 - 3.2 X 10e4, and u?~ - 4.4 X 10m4m velocities listed above one finds
Y-I. The enrichment blanket grows with time according to
L,
- 3 x 10-4t,
Lb = (UQ,- ug,',')t - = (59)
(57) ub
with t in years and the width of the blanket Lb in meters. where & denotes the width of the enrichment peak defined
Therefore, according to these results, a blanket 300 m thick by the positions of the upper chalcocite reaction fronts. This
is formed after an elapsed time of IO6 years. The ratio of the value lies within the range of values reported by BRIMHALL
width of total leached zone to the width of the blanket is et al. ( 1985) of 1.5 to 4 derived from extensive field obser-
approximately equal to vations. Certainly there are a number of uncertainties in the
calculated value. The presence of a water table at depth is
Ll U'd,'
-=
(58)
not taken into account, nor is the influence of gangue min-
_ ug = 0.5.
Lb vcc, erals; and a simplified set of Cu minerals is used in the cal-
culation.
Thus, the blanket grows approximately twice as fast as the
In the supergene enrichment process, reaction zones occur
leached zone. This estimate is determined by the positions
in the leached zone, oxide zone, and the enrichment blanket.
of mineral reaction zones and need not reflect a significant
A measure of Cu enrichment within each reaction zone is
change in Cu grade. However, it is difficult to identify the
provided by the quantity ~Vc,(x, t) representing the concen-
base of the blanket from field observations based on Cu assay
tration of Cu contained in the solid phase, referenced to a
and density data because of the constancy in Cu grade across
representative elemental volume (REV), as a function of
the protore interface.
time and depth according to the expression
According to the results shown in Fig. 9a,b,c, the blanket
may be further divided into subzones consisting of the Cu-
bearing minerals chalcocite, covellite, and bomite. The upper NC(X,t) = 5 ~C,mcz4m(X,
l?l=,
t). (60)
portion of the blanket is enriched in Cu, whereas the lower
portion has Cu content identical to that of the protore itself The quantity NcU has units of moles of Cu per unit volume
(see Fig. 10). BRIMHALLet al. ( 1985) identified the bottom of bulk rock. This quantity should not be confused with the
of the blanket zone with a significant change in Cu grade. local Cu grade 9(x, t), also referenced to a REV, which
They noted the existence of a deeper zone with a mineralogy reflects changes in density of the host rock as it becomes
distinct from the protore, but with no significant increase in altered. The local Cu grade 9 (x, t) is defined as the weight
Cu grade. However, they did not attempt to determine its percent of Cu contained in the solid phase associated with
Theory of supergene enrichment of Cu-Fe sulfide ore 4007
wc~cu(x, t)
0(x, t) = (61)
Pb(X, t)
where Pb( x, t) denotes the bulk rock density defined in terms
of mineral volume fractions by the equation
0.0
Pb(X,t) = 5 ~,~;'&I(~,~), (62)
WI=,
-5.0
and W, and WcU refer to the gram formula weight of the \
H&J \\ py
mth mineral and elemental Cu, respectively. The bulk density ,\
Pb is related to the intrinsic rock density, pr, by the porosity -10.0
0.0 2.0 4.0 6.0 8.0 10.0
according to the expression
PH
Pb(X, 1) = 11 - d'(X,t)lk%(X, t). (63)
20.0
II ' '
Accordingly, the local Cu grade is a function of the porosity
and intrinsic rock density, as well as the concentration of Cu
15.0
in the solid phase. To appreciate the distinction between 9
and .NcU consider, for example, the weathering process in
10.0
which the number of moles of Cu contained in a represen-
tative sample of rock remains constant, but the porosity of
the rock is increased as feldspar minerals making up the B 5.0
gangue component of the rock become altered to clay min-
erals. Then, the local Cu grade, 9, must increase according 0.0
to Eqn. (6 I), whereas the Cu concentration, JV~,, as defined
above, remains the same.
-5.0
Conservation of Cu within the weathering column requires
that the integral of Nc,(x, t) over depth be conserved:
I. -10.0
0.0 2.0 4.0 6.0 8.0 10.0
Nc,(x, t)dx = constant, (64)
s0 PH
where L denotes the depth ofthe weathering column. In such FIG.Il.Activity diagrams as functions of pe-pH showing the re-
cases the system is closed with respect to Cu. This formulation action paths corresponding, from left to right, to times 2500, 5000,
and 25,000 years. After 25,000 years a steady state is reached and
takes into account only flow in the vertical direction. Copper the paths coincide. (a) is balanced on Fe and (b) is balanced on Cu.
has been observed to be lost from the vertical weathering To construct the figures it is assumed that the activity of SOi- is
column due to lateral fluxes ( BRIMHALL et al., 1985; ALPERS IO- and the activities of K+, Fe*+, Fe+, Cu+, and Cu2+ are equal
and BRIMHALL, 1989). to 10w4. Note that the reaction paths are calculated including only
chalcopyrite, covellite, bomite, and chalcocite as Cu-bearing minerals.
The concentration of Cu in the solid phase is plotted as a
The abbreviation Jar designates jarosite.
function of depth in Fig. 10 for different times using Eqn.
(60). Because gangue minerals are not included in the cal-
culation, it is not possible to compute the local Cu grade. As of two distinct chalcocite zones separated by covellite obtained
can be seen from the figure, enrichment occurs at the top of in the numerical calculations is a consequence of the wedge-
the blanket resulting from precipitation of chalcocite. How- shaped stability field of covellite. Along the segment E-F-G-
ever, in the lower portion of the blanket the Cu concentration H, chalcocite precipitates, dissolves, and again precipitates
is constant and equal to its value in the protore. This is a as covellite precipitates and chalcopyrite dissolves. According
consequence of the mineral-mineral replacement reactions to the figure, for times greater than several thousand years
occurring in the nascent blanket which conserve Cu. The Cu the reaction path shifts to higher pH values as pyrite com-
concentration in this region consists of contributions from pletely dissolves at the top of the blanket. To properly account
covellite, bornite, and the lower chalcocite zone. The zone for the path in this case it is necessary to introduce additional
of enrichment at the top of the blanket grows continuously Cu minerals into the calculation as is done in the next section.
with increasing time as noted above.
The reaction path of the fluid packet is plotted on a pe- Chalcopyrite-pyrite-magnetite protore
pH activity diagram shown in Fig. 1 la balanced on Fe and
Fig. 1lb balanced on Cu. The thick solid curves denote re- A somewhat more realistic protore consisting of 2% chal-
action paths corresponding, from left to right, to times of copyrite, 4% pyrite, and 2% magnetite is considered in this
2500, 5000, and 25,000 years. After 25,000 years the system section including the influence of the Cu-bearing minerals
reaches a steady state and the paths coincide. The formation tenorite ( CuO), cuprite ( CuzO), native copper (Cu), and
4008 P. C. Lichtner and G. G. Biino
d ME
a Ok02
0.000
0.018 a0 a.5 9.0 9.5 10.0 105 11.0
~~.~~~~~I
11.0 1l.S 12.0 12.5 13.0 13.5 14.0
DEPTH (METERS)
FIG. 13. Enlargement of the top of the enrichment blanket showing
the mineral volume fractions as a function of depth for the same
conditions as in Fig. 5. The minerals brochantite, native Cu, cuprite,
and chalcocite form ghost zones which propagate without changing
shape after approximately Z~,~ years have elapsed. Note that the
same horizontal and vertical scales are used in each figure.
0.05 pletely dissolved over the entire flow path, even throughout
the protore, contrary to observations. This could be due to
Frh their use of a rate law valid for conditions far from equilibrium
which does not take into account the affinity factor enabling
the rate to vanish at equilibrium. In the calculations presented
w 0.02 here, magnetite became supersaturated, and precipitation had
Ls
to be suppressed by incorporating a nucleation barrier in the
3 0.01
kinetic rate law.
5J Tenorite does not appear until more than 100,000 years
0.00
0. 5. IO. 1s. 20. 25.
have elapsed after pyrite has completely dissolved at the sur-
DEPTH (METERS)
face allowing the pH to increase. The tenor&e zone grows
FIG. 12. Volume fractions of primary and secondary minerals for with increasing time and is slightly more enriched in copper
enrichment of an initial host rock consisting of pyrite (Py f, magnetite than the protore. Tenorite together with ferrihydrite form the
(Mag), and chalcopyrite (Ccp) plotted as a function of depth for
oxide zone near the surface. Zones of chalcocite and bornite
elapsed times of 100,000, 200,000, and 300,000 years for otherwise
the same conditions used in Fig. 5. The extent of alteration is sig- form in the nascent blanket.
nificantly less in this case due to the competition for oxygen among The cluster of minerals brochantite, native Cu, cuprite,
the three primary minerals. A greater concentration of ferrihydrite and chalcocite appearing at the top of the blanket all form
occurs in the leached zone in this case as a consequence of oxidation ghost zones. This becomes apparent in Fig. 13 where a detail
of primary protore minerals magnetite and pyrite. The abbreviations
used in the figure are bornite (Bn), brochantite (Bet), chalcocite of the top of the blanket is shown for the same times as in
(Cc), chalcopyrite (Ccp), covellite (Cv), copper (Cu), cuprite (Cpr), Fig. 12. Each profile is drawn to the same horizontal and
ferrihydrite (Frhf, pyrite (Py), and tenor&e (Tnr). vertical scale to aid visual comparison. After approximately
Theory of supergene enrichment of Cu-Fe sulfide ore 4009
0.08. , ,
200,000 years have elapsed there is no noticeable change in
$iE
the volume fraction profiles of the ghost zone minerals. Thus,
these zones propagate without changing shape by either
growing in width or increasing in modal abundance. Con-
sequently these zones do not become further enriched in Cu
with increasing time as was the case for chalcocite in the
previous example. This has the interesting consequence that
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
the enrichment peak in Cu at the top of the blanket propagates 0.08, _ , ,
without changing shape after a steady state is established as 0.07 100,000 YEARS
d 0.06 t I i
shown in Fig. 14 where the Cu concentration in the solid
phase is plotted as a function of depth for the indicated times.
Thus, in this case a maximum enrichment grade is reached
in spatial extent. The peak in Cu concentration is made up
of the ghost zone minerals shown in the previous figure. Minor
enrichment is present in the tenor&e zone which grows in 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
0.08
I
width with time.
As long as pyrite is still present at the top of the enrichment
blanket, the pH remains low and Cu minerals such as tenorite,
brochantite, native Cu, and cuprite are not able to form. In
this case chalcocite is the dominant mineral in the enriched
zone, which grows continuously with time. However, as soon
as pyrite has completely dissolved at the top of the blanket, 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
the pH increases and a more complicated structure of the 0.08, , ,
0.07
enrichment profile results. Chalcocite is now relegated to a
I-.~~~,~~~
6 0.06
narrow ghost zone which migrates downward without in- 4 0.05
creasing in Cu concentration. With increasing time the only g 0.04
Fig. 16a, with an enlargement of the region from 50 to 7.5 m . 0.10 100,000 YEARS
shown in Fig. 16b, for times ranging from 25,000 to 500,000 u
* 0.08
years. The sharp drop in pH observed in the figure is due to cc
cr, 0.06
the presence of pyrite. 0j 0.04
An enlargement of the region below the water table ex-
* 0.02
tending to the middle blanket is shown in Fig. 17 for times
0.00
up to 150,000 years, and in Fig. 18 from 200,000 to 500,000 SO.0 52.0 54.0 56.0 S&B 60.0 62.0 64.0 66.0
E 0.06
8.0
2 0.04
64 g 0.02
7.0
O.tiO
SO.0 52.0 54.0 56.0 58.0 60.0 62.0 64.0 66.0
6.0
DEPTH (METERS)
FIG. 17. The effect of a water table at a fixed depth of 50 m on
supergene enrichment. Mineral modal abundances are plotted as a
function of depth for the indicated times. The blanket zone forms
below the water table with a sharp enrichment at the top ofthe blanket.
0.09
portant that oxygen is present at the top of the blanket in
0.08
6 0.07 order to produce other oxidizing species that can be trans-
+ 0.06 ported in solution to react with the protore and continue the
g 0.05
. 0.04 oxidation process. For a fixed position of the water table, the
first stage lasts for only a very short period of time compared
0.004
0.000
I?
I : 4 4
to the second stage, which may go on indefinitely. The final
structure of the supergene enrichment blanket is shown sche-
50.0 55.0 60.0 65.0 70.0 75.0 59.059.560.060.561.061.562.0
2
0.09
0.08
0.06
* 0.07
I T"F:: . 3WO@)YF.ARSj
, 0.020 .
o,o16 1
,
py/ AC1
,_ matically in Fig. 20. It may be divided into three zones: an
enriched zone, middle blanket, and nascent blanket. Enrich-
ment takes place primarily in the oxide zone and at the top
Pv j 0.012F Pnr / J of the blanket in the enrichment zone with minor enrichment
extending downward into the middle blanket. The nascent
zone refers to the bottom of the blanket. This zone is being
continually formed directly from the protore as long as water
60.0
50.0 55.0 62.062.563.063.5
64.064.565.0 is percolating through the weathering column. At the inter-
faces between the middle and nascent blanket, and nascent
blanket and protore, chemical reactions conserve Cu in the
solid phase and no enrichment occurs, but merely transfor-
mation to a different mineral assemblage.
According to the results of the calculations, the main effects
of the presence of a water table at depth are the formation of
a highly enriched oxide zone and a much larger blanket zone.
50.0 55.0 60.0 65.0 70.0 75.0 66.0665 67.0675 60.060.569.0
0.09 0.020 However, the enrichment peak at the top of the blanket is
O.OR 500,600 YEARS comparable to the case with the water table at the surface.
1 0.07 0.016
u
4 0.06
Tnr$
0.012
p? 0.05 PY
p 0.04
0.000
0
-1 0.03
> 0.02 0.004
0.01
0.00 0.000
50.0 55.0 60.0 65.0 70.0 75.0 69.069.570.070.571.071.5
72.0
DEPTH (METERS) DEPTH (METERS)
FIG. 18. An enlargement of mineral volume fractions at the top
of the enrichment blanket for the same conditions as in the previous
figure. The minerals native Cu, cuprite, and chalcocite form ghost
2sTm
zones which propagate without changing shape after approximately
400,000 years have elapsed.
years, and 71 m at 500,000 years. The width of the peak .o.01050~o55.0 60.0 65.0 70.0
300,000 YEARS
75.0
ZONE
involving fluctuations in the level of the water table and a
metasomatic origin of the field observations. For example,
TITLEY ( 1978) reported a second chalcocite zone that was
also enriched in Cu (see Fig. 3) and therefore can best be
explained as resulting from lowering the water table.
One ofthe main assumptions in the calculations presented
here is that of local homogeneous equilibrium within the
aqueous phase and in particular the stipulation of overall
redox equilibrium between aqueous sulfur species. For this
to occur in natural systems requires the presence of sulfate-
reducing bacteria. Sulfate reduction takes place in the cal-
culations in the lower blanket, resulting in the precipitation
of pyrite, bomite, and chalcocite. Of the minerals considered
in this study, only covellite is able to precipitate under re-
ducing conditions without the necessity of sulfate reduction
taking place. Covellite is also the dominant mineral, other
than pyrite, in the middle blanket. To what extent the inhi-
bition of sulfate reduction in the lower blanket influences
the upper blanket is difficult to surmise without actually car-
rying out the calculation. Qualitatively, the results are not
expected to differ greatly from the present calculations. For
example, it can be expected that the reaction front velocities
in the upper blanket may be increased somewhat owing to
less pyrite being present.
It would appear from the calculations that a favorable sit- EVANS H. T., JR. ( 1981) Copper coordination in low chalcocite and
djurleite and other copper-rich sulfides. Amer. Mineral. 66, 807-
uation for formation of a highly enriched blanket is the pres-
818.
ence of a deep water table in agreement with the general FREEZER. A. and CHERRYJ. A. ( 1979) Groundwater. Prentice-Hall.
behavior of supergene enrichment deduced from field obser- GUILBERTJ. M. and PARKC. F. ( 1986) The Geology ofOre Deposits.
vations. A descending water table can be expected to lead to W. H. Freeman.
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chemical processes involving minerals and aqueous solutions: I.
1992). In the absence of a water table, enrichment still occurs, Thermodynamic relations. Geochim. Cosmochim. Acta 32, 853-
but at a much slower rate. Including secondary copper-oxide 877.
minerals in the calculation leads to formation of a steady LICHTNERP. C. ( 1985) Continuum model for simultaneous chemical
state in which the peak in Cu concentration at the top of the reactions and mass transport in hydrothermal systems. Geochim.
enrichment blanket propagates rigidly downward with time Cosmochim. Acta 49,779-800.
LICHTNERP. C. ( 1988) The quasi-stationary state approximation to
with no further increase in Cu concentration. This is a con- coupled mass transport and fluid-rock interaction in a porous me-
sequence of higher pH conditions resulting in the formation dium. Geochim. Cosmochim. Acta 52, 143-165.
of so-called ghost zones, consisting of minerals brochantite, LICHTNERP. C. ( 199 1) The quasi-stationary state approximation to
chalcocite, cuprite, and native Cu, which propagate without fluid-rock reaction: Local equilibrium revisited. In Advances in
Physical Geochemistry (ed. J. GANGULY), Vol. 8, pp. 452-560.
changing shape and thus do not lead to increased enrichment. LICHTNERP. C. (1992a) Scaling properties of time-space kinetic
Incorporating pyrite with chalcopyrite in the protore for fully mass transport equations and the local equilibrium limit. Amer.
saturated conditions leads to a slower rate of enrichment due J. Sci. (submitted).
to the depletion of oxygen in the infiltrating fluid by oxidation LICHTNERP. C. ( 1992b) Time-space continuum description of fluid-
rock interaction in permeable media. Water Resources Rex (sub-
of pyrite.
mitted).
In order to carry out detailed comparisons with field ob- LICHTNERP. C. and BALASHOVV. N. ( 1992) Metasomatic zoning:
servations of individual porphyry Cu deposits, it is necessary Appearance of ghost zones in limit of pure advective mass transport.
to include the presence ofgangue minerals in the calculation. Geochim. Cosmochim. Acta (in press).
Gangue minerals can alter the pH within the weathering pro- LICHTNERP. C. and WABERN. ( 1992) Redox front geochemistry
and weathering: Theory with application to the Osamu Utsumi
file, thereby affecting the sequence of alteration minerals in uranium mine, Pocos de Caldas, Brazil. J. Geochem. Exp. (in
the blanket, the presence of ghost zones, and the degree of press).
enrichment. MCKIBBENM. A. and BARNESH. L. ( 1986) Oxidation of pyrite in
low temperature acidic solutions: Rate laws and surface textures.
Acknowledgments-Extensive reviews by Charlie Alpers, Jim John- Geochim. Cosmochim. Acta 50, 1509-1520.
son, and Ron Nicholson, and editorial assistance from Scott Wood, MOSESC. 0. and HERMANJ. S. ( 199 I ) Pyrite oxidation at circum-
added significantly to the content of the manuscript, and we are neutral pH. Geochim. Cosmochim. Acta 55, 47 l-482.
grateful for their comments. MOSES C.O., NORDSTROM D.K.,HERMAN J.S.,and MILLS A.L.
( 1987) Aqueous pyrite oxidation by dissolved oxygen and by ferric
iron. Geochim. Cosmochim. Acta 51, 1561-1571.
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Pyrite oxidation in carbonate-buffered solution: I. Experimental
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