MM-7037/84/S3.00 + .

OO

Prediction of some weathering trends of plutonic and volcanic rocks based

on thermodynamic and kinetic considerations
H. W. NESBITT and G. M. YOUNG
Dept. of Geology, Univ. of Western Ontario, London, Ontario, Canada N6A 5B7

(Received February 6, 1984; accepted in revised form April 16, 1984)

Abstract-The exposed crust consists mainly of plagioclase (35%), quartz (20%). K-feldspar (1 I%), volcanic
glass (12%), biotite (8%), and muscovite (5%). Quartz is a resistate. thus feldspan and glass represent
approximately 75 percent of the labile minerals. The weathering characteristics of these constituents are
summarized in the context of the~~ynamic, mass balance and kinetic considerations.
Experimentaily determined release rate constants were used to predict the proportions of Ca. Na and K
released by feldspars of plutonic rocks (granites to gabbros) to weathering solutions. The chemical weathering
trends of the weathered residues, calculated from the kinetic data, conform closely to the initial trends
observed in some recent weathering profiles, demonstrating the accuracy of the predictions. Since the
weathering of feldspars is controlled by processes that should not change through geological time. the
relative release rates of Ca, Na, and K from the feldspars of granitic rocks can be calculated for future and
past episodes of continental weathering.
Experimentally determined release rate constants are not available for a wide range of volcanic glass
compositions, but the limited data indicate that compositional trends are predictable in weathering profiles
developed on volcanic rocks. The kinetic data available for rhyolitic glasses accurately predict the initial
weathering trends observed in a recent rhyolite weathering proftle.

is estimated (appendix, Table 2, column D). The com-

WEATHERING, TRANSPORTATION and deposition are
position of the exposed crust (Table 2, column E) differs
from the upper crustal estimate primarily in the pres-
three of the most important processes influencing the
ence of volcanic glass. Considering quartz, and the Fe-
properties of sediments. The physical effects of these
processes have received considerable attention as is and Ti-bearing oxides as resistates, plagioclase, potash
evident by the advances in sedimentology over the feldspar and glass constitute 75% of the exposed min-
erals readily susceptible to chemical weathering (labile
past 50 years, but less emphasis has been placed on
minerals) so that studies concerning the weathering of
the chemical aspects and particularly on the chemical
properties of elastic silicate detritus. Some early studies the exposed crust necessarily must emphasize the be-
haviour of these phases. Weathering of phyllosilicates
of siliciclastic sediments and sedimentary rocks, how-
is also important, but the amphiboles, pyroxenes and
ever, dealt with their chemistry (CLARKE, 1924) and
olivines are volumetrically small; their importance in
some of the studies of PETTIJOHN (1963) and MID
weathering of exposed crust and their cont~butions
DLETON(1960) emphasized average com~sitions, but
to sediments being pro~~onately less. Clay minerals
~nve~i~tions such as those by HIRST( 1962a,b), NANCE
accumulate primarily as muds that ultimately become
and TAYLOR (1976, 1977), and MCLENNAN et al.
lutites, the most common sedimentary rock type (PET-
(1980. 1983) are exceptional in using chemical com-
TIJOHN, 1975, p. 260). Since clays are the major al-
positions of individual samples to deduce the history
teration products of feldspars and glass, weathering
of the sedimentary rocks.
characteristics of the primary phases must be known
This paper is the first of a series presenting results
to properly interpret the chemical composition of lu-
of investigations into effects of weathering, transpor-
tites and other sedimentary rocks containing significant
tation and deposition on the bulk chemical compo-
amounts of clay minerals. An understanding of these
sition of siliciclastic sedimentary rocks. We here em-
aspects will allow the use of the chemical composition
phasize the weathering of phttonic and volcanic rocks,
of elastic sedimentary rocks to help deduce paleoen-
using thermodynamic, kinetic and mass balance con-
vironments and paleoclimates (NESBITTand YOUNG,
straints. These predicted changes are compared with
1982).
the chemical com~sitional trends observed in recent
weathering profiles in an attempt to gain a better un-
THERMODYNAMIC AND MASS
derstanding of the weathering process. The agreement BALANCE CONSIDERATIONS
suggests that future and ancient trends can be accu-
The granitic and other feldspathic rocks
rately predicted.
BLAT”~and JONES (1975, Table 3) determined that The stabilities of some common minerals in aaueous so-
approximately a quarter of the exposed crystalline rocks lution are shown on Fig. 1. Thermodynamic data are from
HELGESON (1969), NESM~ (1977). and HELGESON et al.
is intrusive (granitic), a quarter is extrusive (volcanic)
(1978). Labelled fields show the range of water compositions
and a half is metamorphic and “Precambrian”. The in which the designated minerals are thermodynamically sta-
average mineralogical composition of the upper crust ble. Minerals are not stable in waters that plot outside their
1523
1524 H W. Nesbitt and G. M. Young

i:?,.
/--

i- 3;,

*
/ ! =
+-
‘;I---,
‘4 --’
! .
t_ ;
Ru/~ i

‘ - _-&..__--112....-.-
t _.” ..:_:
FIG. I. The~~ynamic stability relations between some minerals and weathering solutrons. Waters iion;
granitic and rhyolitic {circles) and from basaltic and gabbroic terrains (squares) are taken from WFWFIi.
al. (1963. Tables 1 and 2 respectively). The dots represent waters from granitic and weathered gramtit
terrain (PACES, t972). The dotted curves denote iilite stability field, the composition of which iv
K~Al~S4-~I”~,~OH)~ where ‘n’ may vary between 0 and 1. as indicated by the numbers associated with
the straight dotted fines. The dashed lines are met&able extentions of stability field boundaries
Gib. = gibbsite; Kaoi = kaolinite; Beid = smectite (beidellite component); Pyr = pyrophyllite: MUX
= muscovite; Ab = albite; K-spar = microcline

stability fields and the potential exists for the minerals and
solutions to react. These reactions are realized. The clay min-
erals are evidence. Although reactions involving silicates may
proceed slowly at ambient temperatures, they neces&iy pro-
ceed towards an equilibrium state as required by the laws of
thermodynamics. The ~~b~urn diagrams (Fig. 1)therefore
can be used to predict which minerals will react with natural
waters, to provide information about the nature of the reaction
products and to predict the directions these reactions take.
Fe&pars are the most abundant minerals in the upper
continental crnst (Table 2, column D). They are stable only
in natural waters of relatively high cation/H+ values and/or
high aqueous silica concentrations (Fig. 1). Most ofthe waters
of weathering profiles are derived from rainwater with com-
positions (Fig. 1, rectangles) well removed from the feldspar
stability field. The rainwater is made acidic by dissolution of
atmospheric CO2 and CO? derived from oxidation of organic
materiais within w~the~ng profiles. The potentmtairherefore
exists for reaction between the carbonic acidcharged rainwater
and the fetdspars. As reaction proceeds the feldapars are con-
sumed and the soiution approaches equilibrium with the feld-
spars according to Le Chatelier’s principle. The solution must
theEfore approach the stability f&d of feldspar. The precise
path fotiowed by the solution during reaction cannot be pre-
dicted without kinetic data, but the predicted reaction products
(Fig. I) are kaolinite, smectites (montmorillonites and bei-
dellites), iilites and @&site for the solution ~m~sition must
migrate through the stability fields of some or all of these
clay minerals to reach the stabiity fields of the primiu?; phases
HELGESONet al. (1969) predicted the results of reaction
of feldspars with dilute CO+harged waters using local equr.
iibrium concepts and mass balance constraints. ~Fhese cal.
culations will provide reasonable resuits only when near-equi.
librium (often metastabie) conditions prevail Krnr~c d&+
 Weathering trends sf! igneous rocks
are required to make accurate predictions. The calculations
of HELGESONet al. (1969), however, agree with the above
qualitative predictions and with available field data.
Ground waters(WHInez al., 1963; PA&S, 1972) collected
from granitic and rhyolitic (Fig. 1,circlesand dots) and from
gabbroic and basaltic terrain (Fig. I, squares) are plotted on
Fig. 1. The water data trend across the kaolinite field into
the beidellite and illite fields as predicted by HELGE~ON et
al. (1969). Kaolinite is the common weathering product of
plagioclase and other primary minerals (GRANT, 1963; GAR-
RELS,1967; GARREKS and MACKENZIE, 1967; NESBII-Iet al.,
1980). Illite is a common weathering product of granitic rocks
(GRANT,1963) and smectites are abundant secondary products
after maf~cminerals and basic rocks (PATTERSON,1971). These
observations support the calculations and interaction of
the weathering processes made by HEVXSON ef at. (f969),
but the results are still of a very general nature. Details of
many specific mineral-solution reactions are unknown and
some important minerals produced during weathering (such
as vermiculite) are not included in the calculations. The
mechanisms controlling rates of weathering reactions are also
poorly understood.
The volcanic rocks
Volcanic rocks contain both glass and minerals. The sta-
bilities of the most abundant primary minerals have been
considered. The thermodynamic properties (hence stabilities)
of only a few glasses are known, but these allow deductions
and predictions about the weathering of glass. Albite glass
can be considered a ~e~~ynamic component of glasses
(BuR~~M and DAVIS, 1974). Its stabiity in the presence of
a soiution and some common clay minerals (and crystalline
albite) is shown in Fig. 2 (albite glass data from ROBIEand
WALDBAUM,1968). The albite glass is much less stable than
its crystalline equivalent at 25°C and I bar pressure (compare
size of stability field of glass in Fig. 2 with size of crystalline
albite field in Fig. 1). The stability field of Na-smectite is
greatly expanded when glass is the primary phase. (compare
Fig. I and Fig. 2). Its enlarged stability field suggests that
smectites (montmorillonites) may be a more common weath-
ering product after glass (volcanic rocks) than after crystalline
materials provided there is no unusual kinetic behaviour.
Smectites are common after volcanic material (CRAIG and
LOUGHNAN,1964; NADEAUand REYNOLDS,198 1).
FIG. 2. Thermodynamic stability relations between some
common clay minerals and albite glass (At@)). The stability
field of crystalline albite (Ah(c)) is delineated by the dashed
boundary. Na-M = smectite as in Fig. I (Na-M equivalent
to Na-Reid).
1525
Althou~ albite glass (abfglf) stability field is much smaller
than that of crystalline albite (ab(cr)), the clay mineral fields
still separate rainwater compositions from the glass field (Fig.
2). As with mystalhne n-i&, the composition of the weathering
solutions is predicted to evolve up and across the diagram as
cations (Na, K, Ca, Mg) and aqueous silica are leached from
the solids and carbonic acid is consumed by the reactions
(pH increases). The same weathering products are predicted
to form from albite as form from albite( but their pro-
portions may be very different depending on the relative dis-
solution rates of glass and primary minerals and the rates of
formation of the secondary minerals.
Thermodynamic data for K-feldspar glass indicate that the
stability of potassic phases is essentially similar except that
the illite stability field is enlarged (instead of the smectite
field), when glass is the w~th~ng precursor. The results
suggest that Na-smectite-illite ratios in volcanic rock weath-
ering profiles may reflect Na/K values in the fresh rock.
Ground waters from volcanic terrains (Fig. I, see WHITE
et al. 1963 for analyses) are similar to waters from granitic
terrain in that they are equilibrated with the same clay minerals
(NESBI’IT,1977).
Thermodynamic and mass balance considerations
suggest that the results of weathering both volcanic
and plutonic rocks are similar. As in the case of plutonic
rocks, none of the waters derived from volcanic terrain
plots close to the stability field of the primary phase
(glass) and the same clay minerals are formed. The
proportions of secondary minerals produced should
be different as a result of differing stability fields of
clay minerals, the composition of the fresh rock and
the rates at which dissolution and secondary phase
production proceeds.
ZONATIONS AND NOMENCLATURE OF
WEATHERING PROFILES AND SOLUTIONS
Devefapment of weathering zones
GARRBLS( 1967) and HEL@SON et al. ( 1969) viewed
the weathering process as an acid-base reaction where
an acid, commonly H2C03, is neutralized by a solid
base such as a feldspar or glass to produce secondary
clay minerals and dissolved salts. Plagiocfase, K-feld-
spar, other alkali- and alkaline earth Al-silicates and
volcanic glass weather to clay minerals, the feldspars
commonly to kaolinite and illite, the mafic minerals
and glass commonly to smectites as well as the above
clays. The overall reaction is, using albite as primary
phase and kaolinite as the secondary product,
2H&O:, + ZNaAl%Oa + Hz0 - A12SirOs(OH),
carbonic albite kaolinite
acid
+ 2Na+ + 2HCO; f 4Si02 (aq). (1)
dissolved salts
An entirely analogous reaction can be obtained by
substituting other primary Al-silicates for albite and
other clay minerals such as smectite for kaolinite. For
all reactions Al is considered to be essentially insoluble,
thus remaining in solid phases. This stipulation is used
to construct Fig. 1 and it requires that the ahove re-
action be balanced as shown. From reaction ( 1), Na”/
152h H. W. Nesbrtt and G. M. Young

H”. HC03 and SiOZ (aq) increase sympatheti~i~y in
solution as weathering proceeds. As illustrated in Figs.
1 and 2 they behave as predicted in the waters fisted
by WHITE et al. (1963) and PACES ( 1972) and as pre-
dicted by HELGESON et al. (1969). Reactions of
CO,-charged solutions with K-. Ca- and Mg-bearing
Al-silicates and natural glasses can be treated and in-
terpreted in an analogous way. Natural weathering
solutions therefore evolve from low to high values of
Na’/H’, K+/H+. Ca’+/(H)+‘, Mg”‘/(H)+*, HC03 and
Si02 (aq) (Figs. 1 and 2). The mineralogy of weathering
profiles generally evolves sym~theticaiiy. Waters em-
anating from the organic zone of profiles contain
abundant carbonic acid, thus the most extensively
weathered materials, gibbsite and kaolinite, normally
occur within and just below this zone. The solutions
are progressively neutralized by reaction with solids
as they migrate through the profile towards the fresh
rock. The mineralogical assemblages and proportions
change with illites and smectites increasing in amount
towards the fresh rock, ultimately to give way to dom-
inantly primary phases. The weathering profiles and
associated waters can be classified in a manner that
reflects their genetic evolution
Dilute soil waters charged with CO2 and organic acids are
the primary agents of weathering. The acids are neutralized
by reaction with primary and some secondary minerals (in-
congruent reaction). Soil waters that do not react appreciably
with solid bases generally remain acidic displaying low Nat/
H+, K’/H’, Ca*+/(H)+*, Mg2+/(H)“‘, HCO, and SiO, (aqj
values. These waten are referred to as primirive weather&
solufions and they generally are associated with minerals,
such as gibbsite. kaolinite and quartz, that are stable in acidic
solutions. The residual weathering zone consists primarily of
these minerals and primitive weathering solutions.
Waters that have reacted to a greater extent with solid bases
are iess aggnzsive; some of their dissolved acids are neutralized
and they contain greater quantities of dissolved constituent.
The above ratios, bicarbonate and dissolved aqueous silica
are increased over the values found in primitive soil solutions.
These waters approach or achieve equilibrium with illites and
smectites, but not with gibbsite or primary minerals (excluding
quartz) and they are referred to as evolved weathering solutions
and the zone of inlermediarr wearhering contains appreciable
quantities of one or more of the mineral groups of illites.
smectites and vermiculite (Fig. 11.
Waters that achieve ~u~b~um with respect to ihl: pnrnat~~
phases such as one of the feidspars. volcanic g&s or muscovitc
{Figs. 1 and 3) are referred to as mulure weathering .co~t~trms
They are commonly associated with weathering zones whew
feldspars or glass are little altered and are abundant. the :onr’
of incipient weathering. Mature weathering solutions are not
necessarily equilibrated with respect to all priman mineral\
There is a close relationship between the vveatheriny,
solutions and the mineralogical zones in space and
time. As weathering proceeds the residuai zone en-
croaches upon the intermediate zone while the inter-
mediate zone encroaches upon the incipiently wearb
ered and fresh rock zones. The zones migrate to lowc~
fevels, one displacing the other, as a result of the m-
gration, through time, of the primitive anJ rvnivrc!
solutions to progressively greater depths.
KlNETIC CONSIDERATIONS AND RELEASE.
RATES OF CONSTITlJENTS FROM ROCKS
The precise rates of weathenng of pnmac minerals
such as feldspars can be evaluated only from kmetir-
data. To date there has been no attempt to ngorou&
apply kinetic data to weathe~ng rates or ‘iit cornpar’:-
predicted changes with those observed uz narurai
weathering profiles.
BUSENBERC~and CLEMENCY (1976). PE~KOVIC i?
al. (1976). HOLDREN and BERNER (1979~ BERNER
and HOLDREN ( 1979), and PETROVK ( 198I a,b) argue
that comminution produces defects and dtsiocations
in crystals and also produces small fragments. ali ut
which modify the apparent dissolution rates ,rf mm
erals. The studies showed, however, that in the absence
of comminution, Na, K and C’a extraction trilrn f&i-
spars obeyed a linear rate law
f‘i = A.;(*. :
where Ci is the concentration of‘ species i?i Witi’
tion at time I: Ki is the reiease rate constant And ‘:’
is a constant. Feldspars subject to ~7 ,si/lc usathenng
such as occurs during the ii-trmation UT tiprohtet,
(GRANT, 1963; NESBI’U tJ[ u!, 1980) arc iir)t i;om
minuted and their dissolution rates arc :~pzctcd I(,

_L._._.._.. .J_ .‘. . .._.~l.. _

ill0 bt..
_. -. __ -- .---- +.f[.(]i (mgi/! ..- - -----.--_-

FIG. 3. Relationship between the Na’/H’ ratio and the concentration of bicarbonate ofthe waters plotted
in Fig. 1. Waters derived from granitic and rhyolitic terrains (circles) and basaltic and gabbroic terraIn<
(squares) are taken from WHITEef al. (1963, see Fig. caption 1). The dots are waters derived from gramt~-.
and weathered granitic terrain (PA&X 1972). See text for interpretation of trends.
 Weathering trends of igneous rocks 1527

follow a linear rate law (Eqn. 2). The release rate ratio utor of cations to weathering solutions in granitic ter-
of two species “i” and “j” is, from Eqn. (2): rain. Mineralogical and chemical studies of granitic
weathering profiles (GRANT, 1963) also show that pla-
~d~~~di~~~d~j~d~~
= Ki:Kj, (3) gioclase alters rapidly compared with K-feldspar.
hence is independent of time. BUSENBERGand CLEM- Equation (5) is rearranged to illustrate better the ac-
ENCY (1976) determined release rate constants (Ki) cordance:
and Na, Ca, and K from plagioclase and potassic feld- (Ca + Naz):Kz = 3.1:1. (6)
spar. These data are used to calculate the relative rates
The average talc-alkali granite composition is plotted
of release of Na, Ca, and K from plutonic rocks.
on Fig. 5a (dot) as is the proportion indicated by Eqn.
The average caic-alkali granite (NOCKOLDS, 1954,
(6). Extraction of these elements in the indicated ratio
Table 1) contains in its norm, 32.2 gm K-feldspar,
(Eqn. 6, Fig. 5a, open circle) necessitates that the com-
26.2 gm Ab, 5.6 gm An, and 0.8, 1.3, 1.7 gm of C,
position of the weathering residues evolves initially in
En, and Fs. Most of the granites (64 of 72) contain
the direction indicated by the arrow emanating from
biotite and 30% contain muscovite; consequently nor-
the dot. Analogous calculations have been made using
mative En, Fs and C have been combined with
average adamellite, average granodiorite, average to-
KAlS$& component to produce annite, phlogopite
naiite, and average gabbro (NOCKOLDS, 1954). The
and muscovite, leaving 29.0 gm normative K-feldspar.
predicted chemical weathering trends (Fig. Sa, arrows}
There are then, 0.103 moles of K-feldspar (Mks) and
of the five rock types are sub-parallel to the (CaO
0.122 moles plagioclase (Mpl) per 100 gm of average
+ Na20)-A&O3 boundary, indicating that Ca and Na
talc-alkali granite. The plagioclase composition is ap-
are removed in preference to K.
proximately 83 percent Ab and 17 percent An, so that
As weathering proceeds plagioclase may change
the release rate constants of Ca and Na from the pla-
composition, and thus change the ratio of Ca and Na
gioclase are 1O-‘6-~ and 10-‘5.57(Fig. 4). The release
removed from the feldspar and ultimately the direction
rate constant of K from microcline is 10-‘5~“7. The
of the weathering trend. The only circumstance where
relative release rates of these elements (considering the
this situation would not arise would be if the ratio of
number of moles of minerals present in 100 gm of
the removal rate constants equalled the ratio of Na
rock) are:
and Ca in the plagioclase, or;

log(&/kc, )= l%fxAbfxAn ) (7)

= Mpl * luc- :Mpl * KNa:Mks * Kx . (4)
where XA, and X,, are mole fractions of albite and
The proportions of Ca, Na and K extracted from the anorthite components in plagioclase. From Eqn. (7)
granite during the initial weathering stages therefore the two release rates should be equal when plagioclase
are: contains equal amounts of Ab and An. The dashed
Ca:Na:K = 0.6: 1.9: 1.O. (5)curve (Fig. 4) was calculated using this condition and
Eqn. (7), the correspondence with the experimental
Sodium constitutes two thirds of the total. GARRELS data indicating that Eqn. (7) is reasonably accurate.
( 1967) and GARRELS and MACKENZIE (1967) con- The first segments of the weathering trends (Fig 5)
cluded that plagioclase is the most important contrib- should be essentially straight as long as the two feldspars
follow their respective rate laws.

Es~j~~~ion of’& butk ~e~r~erjng rate of biotite

in granitie rocks
Most of the Fe0 in the Toorongo Granodiorite re-
sides in biotite (MARKOVICS, 1977) and its decrease
I An % - in abundance during weathering results primarily from
its oxidation to ferric iron (NESBI-IT, 1979). Since Mg
and K are retained in the secondary products of biotite
(NESBI~ et al., 1980), the oxidation of Fe(B) probably
is the best monitor of the weathering rate of the mica.
The initial removal rate of Fe0 (oxidation rate) relative
to Na20, deduced from the incipiently altered samples
of the Toorongo profile is approximately 3: 1, motar
basis (MARKOVICS,1977). Almost one half of the oc-
Abe/o -
tahedral sites of fresh biotite contain Fe and approx-
imately two thirds of a mole of biotite is weathered
FIG. 4. Relationships between Ca and Na reaction rate per mole of Fe0 oxidized. The relative degradation
constants and plagioclase composition. The dots represent
data from BUSENBERC and CLEMENCY (1976). The solid rate of biotite to Ab of plagioclase is near 1:l.
curves are fitted to the data and the dashed curve is calculated The same procedures have been applied to the
using Eqn. (8) and the kt values for Ca. Flagstaff Granodiorite (WAH~TROM, 1948) and the
 g&L&-_ --_yrt_tt..-_ . .._-.. p_~-_~~
:i
COO’
+
_’
“-.“~--__-__-~_ Y \ ~~. _,

No23 (,O- -c
2 7 ’

FIG. 5. Calculated and actual weathering trends of some crystalline rocks (molar proportions). Smai$
dots are idealized mineral compositions: PI-plagioclase; Ks-potash feldspar; Mu-muscovite: Ka--. k:+
oh&e. In Fig. Sa, the large dot is average granite, the solid square average adamellite. the solid triangk
average granodiorite the solid inverted triangle and diamond average tonalite and gabbro respectively lo
Fig. 5b, solid squares, open squares and dots are fresh and weathered materials from the Stone Mountain
Granite, the Mazaruni Granite and Toorongo Grancxiiorite profiles respectively. The calculated proportion:.
of Ca, Na and K in leachants (derived from rocks with the corresponding symbol) are plotted on Ihe
baselines of the two diagrams. The solid arrows (Fig. Sa, b) are the calculated initial trends followed hl
the leachates during the initial weathering stages. The dashed arrows mimic the advanced trends of ;h-
weathering products.

Stone Mountain Granite (GRANT, 1963). The relative
weathering rates of biotite to Ab of plagioclase are
approximately 1.2:1 for both settings.
Biotite apparently weathers rapidly from granitic
rocks. Its weathering rate is perhaps slightly more rapid
than &bite component of plagioclase. GARRELs (1967)
and GARRELSand MACKENZIEf 1967) also suggested
that biotite is one of the most rapidly weathered silicate
minerals of granitic rocks. Although there is reasonable
agreement between the bulk weathering rate of biotite
from the three granitoids, the rate may be very de-
pendent upon local environmental factors and partic-
ularly to redox conditions.
Kinetic aspects of volcanic glass dissolution
and weathering of volcanic rocks
WHITE et a/. (1980) mC%Euredthe &ease rates of
Na, K, Ca, Mg and Si from vitric and crystalline rhyo-
litic tuffaceous rocks. The order of the release rates
changed with time but over an extended period each
species followed a parabolic rate law, indicating that
the rate-controlling step is different from feldspar dis”
solution. It is, however, possible that the experiments
did not proceed long enough for linear rat<%iaws tr;
prevail (WHITE, 1983). As with feldspar dissolution,
the rate law for some artificial glasses changes from
non-linear to linear after long periods (LX%\ and
DCXKXAS,196 1f. Kinetic behaviour of feldspars and
glasses possibly could be qualitatively similar. but ad-
ditional experimental studies are required tn resoive
the ambiguity.
Although the rate law governmg catton release lion;
glasses over long periods is uncertain, the ratios 01
cation release rates are independent of tlmc ss long
as the pertinent cations follow the same law, conw
quently, Eqns. (3) and (4) can be developed using both
parabolic and linear rate laws. Rate constants given
by WHITE et al. (1980. Table 4i are used with Eqn.
(3) to calculate the initial weathering trend of vitric
and crystalline tuffs. The tuff compositions {WHITE t”i
al.. Table 3) are plotted on Fig. 6 as open symbols
and the calculated trends of the leached products art-
illustrated (Fig. 6, arrows). The compositions of the*
leachants (solutions) are first calculated and, by COIP
servation of mass, the initial leachate trends (altered
t&s) are directed away from the leachant compositlon
as indicated by the arrows (Fig. 61. The inittal trends
 Weathering trends of igneous rocks 1529

FIG. 6. Calculated trends for the Rainier Mesa vitric tuff (Fig. 6a) and the crystalline tuff
(Fig. 6b). The solid symbols represent the compositions of weathering solutions calculated
from the kinetic data of WHITE et al. (1980).

predicted for both vitric and bone t&S are similar compositional changes accompanying the
to trends predicted for the granitic rocks. weathering of ~anodiorites and gabbros
Plagioclase, potash feldspar and quartz are by far
COMPARISON OF PREDICI’ED TRENDS WITH
RECENT WEATHERING TRENDS
the most abundant ofgranitic minerals(Table 2). Since
the first two minerals contain most of the Ca, Na and
Compositional changes accompanying the K in true granites, application of the experimental
weathering of granites kinetic data to these rocks is reasonable. Their appli-
cation to adamellites, granodiorites and particularly
The kinetic studies of BUSENBERGand CLEMENCY to tonalites and gabbros is problematic because po-
( 1976) are applicable to granites for they contain ap tassium resides in biotite as well as K-feldspar.
proximately equal weight proportions of quartz, pla- The Toorongogranodioriieweatheringpro&e. MARKOV~CS
giociase and K-feldspar but only smah amounts of (1977), NESBIT~(1979) and NESBI~ et al. (1980) studied
other minerals. Since quartz contains no aIkaIis or the Toorongo granodiorite in east-central Victoria, Austraha.
alkaline earths, the relative leaching rates of Na, Ca The bulk chemical compositions of materials from the profile
and K from the feldspars should be predictable from are shown on Fig. 5b (dots). The fresh granodiorite plots very
close to the average granodiorite of NOCKOLDS ( 1954). The
the kinetic studies. initial weathering trend predicted for the Toorongo profile is
illustrated (Fig. 5b, arrow) and the slope is similar to that
The Stone Mountain profile. GRANT (1963) documented calculated for Nockolds’ average granodiorite. The experi-
mineralogical changes accompanying weathering of the Stone mental data Of BUSENBERG and CLEMENCY(1976) were used
Mountain Granite near Atlanta, Georgia in the U.S.A. The to calculate the trends. Agreement between the observed and
rock is an adamellite or quartz monzonite and has undergone predicted trends indicates that weathering trends of inter-
weathering in a moist warm climate. The molar quantities mediate and probably gabbroic rocks can be accurately pre-
of the minerals have been calculated and are plotted on Fig. dicted.
Sb (solid squares). CaO and Nap reside only in ph&clase It is surprising that the predicted trends mimic the actual
(An,*) and the bulk of KzO resides in microdine (GRANT, data of granodiorites considering the biotite and K-feldspar
1963). The proportion of CaO, soda and potash predicted to contents of these rocks. There is. however, a reason for the
be extracted from the granite is. using molar proportions and a~ment. The reactivity and quantity of plagioclase in these
the appropriate rate constants (Fig. 4); rocks result in weathering solutions con~ning abundant Ca
and Na compared with K. The weathering solutions therefore
(Ca + Na,):K, = 3.7:1 .O. (8) plot close. to the (Ca f Na) apex of fig. 5b and the fresh
granodiorites and gabbros plot close to the plagioclase com-
position (Fig. 5b). The compositions of the granodioritic and
The predicted weathering trend is shown by the solid arrow
gabbroic weathering products therefore evolve along trends
on the extreme right of Fig. 5b. The solid squares represent
subparallel and close to the (CaO + Na20)-A1203 sideline.
the actual compositions of the residues.
There is little l&O in these rocks and only if potash resided
The Mazaruni profile. LEVERING (1959) quotes chemical
in a mineral that were at least an order of magnitude more
analyses of a granite and its saprolitic weathering products
reactive than plagioclase or biotite would the weathering so-
from a quarry in Guyana in northern South America. The
lutions contain much potassium.
data am plotted on Fig. 5b (open squares). The initial weath-
ering trend for the granite is calculated in the same way as
was the Stone Mountain weathering trend. The predicted (Ca Compositional changes accompanying the
+ NazO):K, value is 3.0: I.0 (normative plagioclase, Anis,
weathering of volcanic rocks
= 0.108 moles; normative microcline 0.087 moles). The pre-
dicted initial weathering trend for the Mazaruni profile (Fig.
5b, solid middle arrow) closely follows the observed trend Kinetic data of WHITE et al. (I 980) are applicable
(Fig. Sb, open squares), indicating that the laboratory kinetic to the weathering of some volcanic rocks, but there is
studies are applicable to weathering of feldspars in granites. need for much more kinetic data. In its absence, a
1530 H. W. Nesbrtt and G. M.
more empirical approach is adopted. As with the crys-
talline rocks, the weathering trends predicted using the
data of WHITE et al. (Fig. 6) are subparallel to the
(CaO + NarO)-A1203 boundary. Since the available
kinetic data and the thermodynamic and mass balance
relations suggest that feldspathic crystalline rocks and
glassy rocks weather in a grossly similar way, the
weathering trends developed on volcanic rocks of ba-
saltic through rhyoiitic composition are predicted to
be similar to the crystalline rocks of equivalent com-
position; the weathering trends are sub-parailei to the
(CaO + Na20)-A&O, boundary.
The Baynton basalt projle. The Baynton profile (central
Victoria, Australia) is developed on continental basalts to a
depth of one to two metres (WILSON, 1978). The fresh rock
(Fig 7) plots well below the feldspar join indicating appreciable
normative clinop~oxene which plots at the lower Left apex.
Proportionately, it contains little &O and necessarily plots
very close to the (CaO + NarO)-A1203boundary. Accordingly,
the weathering products evolve along the boundary because
only soda and lime are available to solutions in any quantity.
Other basaltic profiles (CRAIG and LDUGHNAN, 1964; PAT-
TEWN. 1971)fohow a virtuatfy identical path, att Confotmmg
to the weathering trend predicted for their plutonic com-
positional equivalent, gabbro (Fig 5). Them is some curvature
of the trend (Fig. 7) during the incipient weathering stage
and detailed study of a second profile confirmed the initially
enhanced leaching of patash (WILSON.1978). Lack of kinetic
data prevents prediction of weathering trends on basal&
The Bumbo Latite projile. CRAIG and LOUGHNAN (1964)
report analyses of a recent profile developed on the Bumbo
Latite (Kiama, NSW, Au&f. The h-e& iatite and its weathering
products are plotted on Fig. 7 and as with plutonic rocks of
intermediate composition, the weathering trend is subparallel
to the (CaO + Na20)-A120, boundary. Although the trend
FIG. 7. Weathering trends observed in some recent profiles
developed on volcanic rocks. The dots represent the trend
produced over the Baynton Basalt (Australia), the circles the
trend produced by weathering ofthe Kiama Latite (Australia)
and the squares represent the weathering trend produced on
the Tai MO Shan rhyolite porphyry (Hong Kong).
Young
isgrossly similar to crystalline rocks ofequivalent composmon.
it is somewhat more complex in that there may be curvature
of the trend as indicated by the most highly weathered mn-
terials. Additional data are required to confirm that the cur-
vature is real and that it results from weathering and noi
from introduction of foreign materials at the top oftheprofile.
The Tai h4o Shun rhyolite porphyry profile. 7’ht: fresh por-
phyry and its weathering products (BROCK, 1943)are plotted
in Fig. 7 (squares). The initial trend is sub-parallel to the
(CaO + Na20)-A1203 boundary and is similar to the trends
for the vitric and crystalline rhyolite tuff (Fig. 6) calculated
using the kinetic data OfWHITE c‘f al. f 1980) and 10the trends
observed over granitic rocks (Fig, Sb). The profile devefoped
on the rhyolite porphyry evolves as predicted fintroductor-1
remarks to this section) and profiles on even more siliceou\
rhyoiites are anticipated to evolve rn a similar fashron
The compositional trends observed tn weathenng
prohles developed on basaltic through rhyolitic vci!-
canic rocks are similar to those deveioped over crya-
t&line rocks of equivalent composition. but some o!
the volcanic rock trends seem complicated in deta11
Some display curvature which is not apparent in pro-
files developed on crystalline rocks. The differences
may be due to the mixture of glassy and irystaliirte
materials in volcanic rocks and a resulting change
through time, of the dominanr mechanism of leaching
of elements from the rocks. Alternatively, the curvature
may be due to drastic changes in the proportions OE’
elements available to solutions as weathenng proceeds
and modifies the composition of the volcanic materials
TRENDS PRODUCED DURING ADVANCES
WEATHERING STAGES
The initial weathering trends of igneous rocks are
subparallel to the (Na20 + CaO)-Al$& boundary, prt’
marily because removal rates of Na and Ca from pla-
giocfase or glass generally are greater than the removai
rate of K from microcline or glass. Kaoinnite. illitc
and smectite are common clays produced during
weathering of primary phases. They are stable in ir:-
termediate zones and portions of some advanced zones
of weathering where solutions are aggressive (Fig. i :_
hence their presence shouId have little e&et on tht
proportions of Na, Ca, and K extracted from incipient
and intermediate weathering zones. The initial weath-
ering trends (Fig. 5a) eventually curve as the propor~
tions of feldspars change (resulting from diflerential
feldspar weathering). The trends are affected dramar-
ically when one of the feldspars is almost completei!
destroyed for isotated), hence curvature 1%most an-
parent as the initial weathering trend approaches 3
boundary of the triangle (Fig. Sa). When plagioclm
disappears first, as is likely, the weathered materials
would contain kaolinite, illite and K-feldspar and the
bulk composition of the material therefore piots close
to the l&O-Alz03 boundary. Subsequent weathering
then would result in removal of K first from the potassrc
minerals (Na and Ca already removed) so that the
remaining K-feldspar, followed by illite, is converted
to aluminous phases such as kaolinite (and gibbsite in
extreme weathering conditions). These predictions as-
sume that potassium is more susceptible tc leachmg
 Weathering trends of igneous rocks 1531

from K-feldspar and illite than is Al from the clay is not determined by the plagioclase dissolution rate.
minerals. The assumption seems reasonable and the The experimental data, however, are used here to ac-
curately predict the relative release rates of Na + Ca
proposed reactions are feasible (Fig. 1) in that kaolinite
is stable in acidic weathering solutions associated with and K from weathering profiles. Our conclusion is that
the advanced stages of weathering. These mineralogical feldspar dissolution does control relative release rates
changes are observed at Stone Mountain (GRANT, of these metals. The apparent discrepancy between
1963). The com~ition~ our results, using the experimental data of Busenberg
trends (Figs. 5 and 6) there-
fore move towards the AlzOs apex after encountering and Clemency, and the findings of PA&S (1983) can
the A120s-KzO boundary. The actual weathering trends be resolved if the process causing the low Na release
from the Stone Mountain, Mazaruni, Toorongo and rates from basins affects, in an identical way, the three
Tao MO Shan Rhyolite profiles follow both predicted metals. PACES( 1983) suggests that the surfaces of pla-
initial and advanced weathering trends and terminate gioclase are old with few defects or other active sites
close to the A&O3 apex. compared with the laboratory material. If this expla-
nation holds for plagioclase, it must hold for potash
DISCUSSION AND CONCLUSIONS feldspar; the effects on both minerals would have to
be quantitatively similar to account for our successful
Fe&pars and volcanic glass are of prime importance prediction of weathering trends using the experimental
in any consideration of the weathering process of ex- data. A simple alternative explanation is suggested by
posed crust. The~~ynamic principles and kinetic PAISES( 1983). The low release rate of Na from drainage
data allow prediction of the paths followed by rain- basins may result from dilution of waters that have
water-derived solutions during reactions with crustal weathered feldspars, by waters moving rapidly through
rocks. Weathering solutions evolve from the gibbsite the regolith where clay minerals dominate and porosity
field, through the kaolinite, illite and smectite fields (and possibly permeability) is high (GRANT, 1963).
to that of feldspar and/or glass where reactions cease. The second possibility must occur but it remains to
Experimental studies of feldspar leaching by COz- document its magnitude.
charged waters show that, in the absence of commi- Before it is decided that plagioclase dissolution is
nution, Na, K and Ca extracted from feldspar-s obey the process controlling the removal rate of Na from
a linear rate law. Knowledge of release rate constants drainage basins, more detailed studies including the
permits calculation of relative rates of dissolution of relative removal rates of at least Na, Ca and K, are
Ca, Na and K from feldspars in plutonic rocks of required. Our results indicate that the ratios of Na,
varied composition. The few experimental kinetic Ca and K removed during in situ weathering are con-
studies are inconclusive regarding the rate law gov- trolled p~ma~ly by the ratio of the two feldspars in
erning release of Ca, Na and K from vitric materials, the parent rock and the relative release rates of the
but the trends predicted from the parabolic rate law cations from the respective feldspars. There is no as-
data of WHITE et al. (1980) conform to the trend ob- surance that the cations, once released to solution,
served in the Tai MO Shan Rhyolite Porphyry. There remain entirely as dissolved constituents. Materials,
is good correspondence between these theoretical and and particularly secondary products within regolith,
experimental results and chemical data from modem colluvium and alluvium, may react with some or all
weathering profiles when plotted as molecular pro- of these cations retarding and perhaps grossly modi-
portions on an A&03, (CaO + NazO), KzO diagram. fying their relative release rates from a drainage basin.
The early stages of weathering are character&d by Additional studies, similar to that OfPAeES (1983) but
depletion in CaO and NaZO and KzO along a straight including additional elements, are required to remove
line sub-parallel to the (CaO + Na20)-A1203 join. The these ambiguities.
late or advanced stage of w~the~ng shows depletion Some comments are required concerning the effects
in KzO as the com~sition of the leached rocks ag of temperature (hence climate) on the predicted
proaches that of kaolinite and/or gibbsite. weathering trends. Temperature variations do not aI%ct
Thermodynamic stability of minerals, experimental geometric aspects of the activity diagrams (Fig. 1) and
kinetic data, and compositional data from weathering affect quantitative aspects in only minor ways. Gen-
solutions and profiles are in accordance, providing a erally, the fields of the hydrous phases shrink, with
framework for interpretation of compositional changes increased temperature, towards the lower left comer
accompanying the weathering of plutonic and volcanic of each diagram but none of the stability fields dis-
rocks. The information is particularly useful for the appears or even diminishes greatly over the temper-
interpretation of ancient weathering profiles. ature range 0 to 50 degrees C. The deductions drawn
PA&S (1983) demonstrates that the bulk removal from these diagrams (constructed for 25 degrees C)
rate of Na from drainage basins is much lower (by a therefore hold for all conditions under which chemical
factor of approx. 100) than is suggested by the ‘weath- weathering would occur. The effects of temperature
ering rates’ of plagioclase (BUSE~ER~ and CLEMENCY, on kinetics of reactions can be assess& using the Ar-
1976). There can be many reasons for the apparent rhenius equation. Increased tem~mtu~ increase re-
discrepancy (PA&, 1983), including the possibility action rate; chemical weathering would be more rapid
that the bulk release rate of Na from drainage basins in the torrid zone than in the temperate or frigid zone.
1532 H. W. Nesbttt and G. M. Young
If the chemical weathering mechanisms are dependent
upon temperature with different mechanisms operating
in specific temperature ranges, then few predictions
can be made. There is, however, no positive evidence
to suggest that temperature affects the mechanisms of
chemical weathering reactions. We conclude that tem-
peratures affect rates of weathering primarily, and from
both equilibrium thermodynamic and kinetic view-
points, the qualitative aspects of weathering do not
change greatly; the same weathering products are pro-
duced from the same parent materials, but the pro-
portions of secondary products and their rates of pro-
duction are affected by temperature, hence climate.
Thermodynamic stability of minerals, experimental
kinetic data, and compositional data from weathering
solutions and protiles are in accordance, providing a
framework for interpretation of compositional changes
accompanying the weathering of common feldspathic
and volcanic rocks. The framework can be used to
interpret the chemical trends of recent weathering pro-
files, to predict changes in profiles to be produced in
the future and particularly to understand and interpret
weathering trends produced in the past. The infor-
mation also helps to decipher the climatic regimes
influencing the composition of sediments and sedi-
mentary rocks (NESBITT and YOUNG 1982).
Acknowledgements-We thank S. McLennan and A. J. R.
White for stimulating discussions. They helped to clarify nu-
merous aspects of the study and the former offered many
helpful suggestions for improvement of the text. S. R. Taylor
and S. McLennan provided the encouragement and the stim-
ulus to publish the results. Grants from NSERC of Canada
to each of the authors provided the financial support, for
which we are very grateful.
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 Weathering trends of ignizous rocks 1533

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Univ. Vie. Aust. 55 pp. SiOz 66.0 66.4 64.93 65.4
TiOn 0.6 0.52 0.6
Al203 16.0 1::; 14.63 14.7
APPENDIX Fe203 1.5 1.36 1.4
Fe0 4.51 2.75 2.8
THE CHEMICAL AND MINERALOGICAL W?O 2.3 ::: 2.24 2.2
COMPOSITION OF THE UPPER CRUST CaO 3.5 3.8 4.12 4.0
Nat0 3.8 3.6 3.46 3.5
K20 3.3 3.3 3.10 3.2
The response of rocks to weathering is determined largely P205 0.18 0.15 0.16
by their mineralogical and bulk chemical compositions. Data Others 0.7 2.37 1.8
concerning the average compositions of the upper crust are
essential to an appreciation of weathering reactions. The av- A Average upper ctust estimated by
erage composition of the earth’s upper continental crust (Table Taylor and McLennan (1981).
B Average upper crust estimated by
1, column A) is reasonably well established (TAYLOR and Wedepohl (1969, Table 7-10).
MCLENNAN,1981; SHAWef al., 1967, 1976; EADE and FAH- C Average Canadian Precambrian
RIG, 197 1) but the average mineralogical composition (Table Shield estimate (Shaw et al.,
2, column A) is not well known. WEDEPOHL(1969, p. 247- 1967) _
248) estimated the average chemical (Table 1, column 8) and D Average upper continental crust
estimated using data from Blatt
mineralogical (Table 2, column A) upper crustal composition and Jones (1975) and data in
using only data from plutonic rocks.The chemical estimate columns i3 and C.
of WEDEKxiL (1969) is similar to others, but the mineralogical ’ Total iron given as FeO.
1534 H. W. Nesbitt and G. M. Young

Tabie 2. Average mlneraioglcal t:ompos~tlo~~ OL without knowing the percentage volatdes the ahovc c;alcu.
crustal rocks (~01.8) lations can not be made. Fortunately. the close correspondence
._-- _---__.-- _-. .__,_____.~
_ _.
A R i: i; E between the columns A and C (Table 1) suggests that there
would be no great diBrence between our mineraIogical avemge
Quartz 21.0 25.4 24.42 23.2 20.3 (Table 2, columns D and E) and the average rticufated ifthc
PldCYiOClaSe 41.0 39.2.5 34.25 19.9 34.q results of Taylor and McLennan could have been used
Gl& 0.0 0.0 '3.0 0.0 :2.5 The extrusive rocks (BLATT and JONES. 1972).which ii:
Orthoclase 21.0 4.5' 8 .6 12.9 11.2
Biotite 4.0 i5.29 11.23 8.7 7.6 elude voluminous amounts of plateau basalts, must be CWP
Muscovite 0.0 9.77 7.61. 5.0 4.4 sidered when determining the mineralogical compositlon t-4
Chlorite 0.0 0.c ?.?i 1 .2 i.3 the exposeu’continental crust. The only additional phase w
Amphiboles 6.0 O.c, j.0 2.I L.8 be considered is the glass of volcanic rocks. There are ni.
Pyroxenes 4.0 0 . ij ‘1.i : .4 : .z
Olivines 0.6 0. c ii . I: !7. 2 3. ;I known estimates of the proponion of @ass to cn;stals zn rt‘
Oxides 2.c ?..?7 i.3- L.6 I.4 cently extruded rocks, but if only half is glass. then glass
Others 0 .5 4: 4.7 3.0 &,<I represents 12% to 13% of the exposed crystalline rocks, smct:
---- _.- -.-. --_ -.- __-_ - a quarter of the exposed crystalline rocks arc extrusive (BLA ~1
Average mineralogical composition of upper
continental crust as estimated by Wedepoh:
and JONES. 1975, Table 3). The proportions of mmerals III
(1969, Table 7-11). the exposed crystalline crust (including glass) arc given in
Mesonorm of the Canadia;: Shield !Shaw et A, Table 2 (column E). Glass is the third most abundant phax
1967). and more important than potash feldspar. It probably makes
Mesonorm of the Canadian Shleid modified t:, a signi~cant cont~bution to sediments and mav well affect
include chlorite (see appendix:.
Estimated average mineralogical composition their compositions substantialt~.
of the upper continental crust. See appendix The estimate (Table 2. column E) assumes <he densinca
for details of the calculation. of the glass and intrusive rocks are similar. [f lhe average
Estimated averaqe composition of the
exposed crust. -See the appendix for details
glass composition is more mafic than average upper crust
of the calculation. (Table 2, column D), as it may be b> inclusion of large amounts
of basatt, the proportions of ma& minerals given in column
E would be shghtiy’less than listed and the leucocratic minerais
would be propo~ionateiy greater. The amount ofglass would
Mclennan. A better mineralogical estimate probably could remain the same. Since the mafzc minerals are already Lowe
be obtained if the above calculations were begun with the this correction would be small and probably WI Justified
average chemical composition of Taylor and McLennan, but considering the other approximations made.