American Mineralogist, Volume 76, pages211-217, 1991

Dissolution rates of plagioclase at pH : 2 and 3

Wrr-r-rau H. C.nsnv,flnNnv R. Wnsrnrcn

Geochemistry Research,Sandia National Laboratories,Albuquerque, New Mexico 87185, U.S.A.
GBoncn R. Holonnx
NSI Technology ServicesCorporation, E.P.A. Environmental ResearchLaboratory, 200 Southwest35th Street,
Corvallis, Oregon 97333, U.S.A.

Ansrru,cr
The dissolution rates of plagioclasein acids are very sensitive to the mineral composi-
tion. At pH : 2.0 and25 oC, rates range from =l x l0 15feldspar-mol/cm2/sfor albite
to greater than I x l0 r, feldspar-mol/cm2lsfor anorthite. At pH : 3.0, the respective
ratesrangefrom =3 x lQ-to feldspar-mol/cm2/sto=7 x l0-t4 feldspar-mol/cm2ls. The
relationship betweenmineral composition and dissolution rate, however, is not simple. In
order to better define such a relation at pH : 2, rateswere measuredon eight plagioclase
minerals and compared to existing data.
In general, the dissolution rates of a given plagioclasemineral estimated by different
researchersgenerally agreeto within a factor of two to five. The uncertainty is much larger
for Ca-rich minerals such as bytownite and anorthite, and reasonsfor the disag"reement
are unclear. Even with this uncertainty, however, it is apparent that dissolution rates vary
nonlinearly with composition and that the rates for the Ca-rich minerals vary more with
composition than Na-rich minerals.

INrnonucrroN last, 1984, 1985;Holdren and Speyer,1985;Caseyet al.,

1 9 8 8 ,r 9 8 9 ) .
It has long beenobservedthat mineral weatheringrates The disparity in reactivity reflects differencesin the
vary considerably with the mineral structure and com- bonding characterof Al and Si to O atoms at the mineral
position. Goldich (1938), for example, noted that silicate surface. Furthermore, becausehydrolysis reactions are
materials that dissolve slowly tend to contain a highly catalyzedby H and hydroxyl ions (Wendt, 1973), The
polymerized (e.g., tectosilicate) structure (seealso Hurd disparity in reactivity reflectsdifferencesin the acid-base
et al., 1979; Lin and Clemency, 198l). These materials properties of the exposedaluminate and silicate sites.Al
also tend to be selectivelyleachedby aqueoussolutions, is rapidly leachedfrom the surfaceoffeldspar in acid but
as there are sufficient unreactive bonds near the mineral is not detectableat near-neutraland basic pH conditions
surfaceto maintain integrity once the reactive constitu- (Caseyet al., 1988, 1989). The leaching reaction creates
ents are removed (Murata, 1943). Under certain condi- an Al-, Na-, and Ca-depletedlayer on the surfaceof some
tions, thesematerials form a thick leachedlayer adjacent plagioclaseminerals in the early stagesof a dissolution
to the aqueoussolution. Conversely,silicateswith a poor- experiment.
ly connectedfabric, such as olivine, tend to dissolve rap- This selectivehydrolysis not only affectsthe chemistry
idly and uniformly (Schott and Berner, 1985; Petit et al., of the mineral surfacebut should also be manifested in
1989) as long as the adjacent solution is undersaturated the bulk dissolution ratesofminerals, suchas plagioclase,
with respectto secondaryphases. which have a wide range in Si and Al concentrations.
Both the leaching behavior and bulk dissolution rate Plagioclase ranges in composition from albite (NaAl-
of minerals are controlled by the relative concentration SirOr) to anorthite (CaAl$irO8). This variation corre-
of reactive and unreactive sites at the mineral surface. sponds to a coupled, isostructural substitution of alumi-
Aluminate (AlO;5) sites on an aluminosilicate mineral nate (AlO;') groups andCa2'for silicate (SiO;a) groups
surface tend to be more rapidly hydrolyzed in a strong and Na".
acid than the silicate (SiO;') sites (Murata, 1943). Acid The actual variation in plagioclasedissolution rate at
treatment, for example,is usedto dealuminate zeolitesin a constant pH is poorly known, as much previous work
order to make hydrocarbon-crackingcatalysts(e.g.,Bar- was limited to a small range of mineral compositions.
rer, 1978; Man et al., 1990). Similar dealumination of Even in more comprehensive studies, however, impor-
clay has been proposed as a nonbauxitic source of AI tant variables such as the mineral surface area and purity
(Aglietta et al., 1988).Acid dealumination reactionsalso were not determined, or the solution composition was
affectthesurfaceofdissolvingfeldspars(ChouandWol- allowed to vary widely during the experiment. These

0003{04xl91/0102-021l$02.00 2rr
2t2 CASEY ET AL.: DISSOLUTION RATES OF PLAGIOCLASE

TABLE1. Plagioclasecompositions by Holdren and Speyer(1987). Once prepared,the pow-

ders were treated identically.
sio, 66.83 62.89 63.74 54.71 52.34 49.45 44.97
All of the feldsparsexcept the Grass Valley anorthite
Tio, 0.00 0.00 0.01 0.05 0.07 0.03 0.01 were acquired as large crystals. These crystals were ground
Alros 19.26 21.95 23.02 27.93 29.17 32.13 34.53 and wet-sievedto isolatethe 25-7 5 rrm sizefraction. This
Fe2O3 0.04 0.05 0.09 0.28 0.31 0.40 0.31 powder was repeatedlywashedin distilled HrO and spec-
FeO 0.04 0.06 0.09 0.25 0.29 0.36 o.28
Mgo 0.01 0.01 0.04 0.23 0 . 1 4 0 . 1 4 0.02 trophotometric-grade acetonein order to remove ultra-
MnO 0.01 0.01 0.01 0.02 0.02 0.00 0.01 fine particles that cling to the larger grains. Washing re-
CaO 0 . 1 6 4 . 1 5 4.47 9.45 12.31 15.49 18.52
Nio 0.12 0.05 0.08 0.10 0.00 0.24 0 . 1 0 moves most, but not all, ultrafine particles,as determined
Naro 11.51 9.05 7.93 5.23 4.30 2.73 0.89 by scanningelectronmicroscopy.
t&o 0.11 0.35 1.43 0.93 0.30 0.12 0.o2 The anorthite was separatedfrom an anorthosite from
Note.' Separate grains within each powder were analyzed, averaged, Grass Valley, California. This material was crushed in a
and normalized to 100%. Molar Fe concentrations are divided equally
between terric and ferrous oxidation states. The average stoichiometry
steelmortar and pestle,followed by sieving to isolate the
and the total number ol analyses are includedas footnotes. In all cases, 25-75 prn size fraction. This powder was washedrepeat-
the analytical precision analysis is less than the compositionalvariation edly in distilled HrO and acetoneto remove ultrafine par-
within a singlemineral.1 : Keystonealbite:(NaoeTGoloao o2Alossi3
@Osoo),
337 analyses.2 : Mitchellcounty oligoclase:(Nao,ulG*CaoroAl,,ESirsO6@),ticles. The resulting powder consistedof a mixture of sep-
317 analyses.3 : Bancroft albite: (Nao6slcosoao.,Al,roSi.roO"*),266 anal- arate grains of mafic minerals and feldspar. Theseminerals
yses.4 : Saranac Lake andesine:(Nao16Ko6Oao6Alr anal-
$Sir soos@),294
yses. 5 : PuebloPark bytownite:(NaosKo@Cao60A11$Sireosoo),48
were sepaxatedwith a Franz Isodynamic Separator,which
anal-
yses. 6 : Crystal Bay bytownite: (Naor4GolcaoT6AllT4sirreoooo), 314 produced a nearly pure feldspar powder. Final purifica-
analyses.7 : Grass Valley anorthite:(NaoosG@Cao@Alreosi2@06@), 46 tion was accomplishedusing high-density liquids. Anor-
analyses.
thite grains were then washedwith distilled HrO and ac-
etone.
variations can lead to precipitation of secondaryminerals Feldspar compositionsand sample purity
onto the dissolving surface(seereview by Helgesonet al., The feldsparcompositionswere measuredwith an elec-
1984) or to important changesin mineral surfacechem- tron microprobe and averagecompositions are reported
istry during the experiment. in Table l The total range of measuredcompositions is
The goal of this paper is to define a relation between shown on ternary diagrams in Figure l. The diameter of
the dissolution rates and composition of plagioclasefeld- the electron beam used to analyze these sampleswas 16
spars.To achieve this goal it is necessaryto supplement rlm.
the existing data with additional experimentsso that rates Each feldspar exhibits some variation in composition
are available for a wide range of plagioclasecomposi- as measuredwith the electron probe, and the traditional
tions. The investigation is restricted to dissolution in name of some samples can be misleading. Specifically,
strongly acidic solutions where the character of the re- the Pueblo Park bytownite and the Bancroft albite are
action is relatively well understood (e.g.,Chou and Wol- labradorite and oligoclase, respectively. Much of this
last, 1985;Holdren and Speyer,1985;Caseyet al., 1988, variation in composition is attributable to microscopic
1989)and the precipitation of secondaryminerals can be mineralogic heterogeneities.Zoning, exsolution lamellae,
easily suppressed. and accessoryphasesare apparent from microscopic ex-
Marnnllrs amination of the material (seeAppendix). Although all
AND TEcHNTeuES
but one of the compositions are consistent with the per-
Preparation of samples missible range of solid solution (Fig. l), most of these
All samplesexceptthe Pueblo Park bytownite were ac- materials contain more than a single feldspar phase(Ap-
quired from Wards Natural Science Establishment, pendix). The Mitchell County andesine, for example,
Rochester,New York. The samplesand their trace min- contains exsolved potassium feldspar (Appendix), which
eralogy are described in the Appendix l.' Two samples introducesconsiderablescatterin the ternary plot of com-
of the Mitchell County oligoclaseand SaranacLake an- position (Fig. l).
desine were prepared independently. Granular samples
were independentlypreparedfrom crystalsin 1983-1984 Specific surface areas
(seeHoldren and Speyer, 1987) and as part ofthis study Specificsurfacearea of each sample was measuredpri-
in 1988. The procedures used by each researcherwere or to dissolution using a Micromeritics Digisorb 2600
similar, except that a ball mill was used to crush the ma- device. After degassingovernight at 200 oC, varying
terial in this study, rather than the disk grinder employed mixtures of N and He were adsorbed onto the powder
surface.The areaswere calculatedfrom the sorption iso-
' A copy of Appendix I may be ordered as Document AM- therm and the BET theory of area measurement (Bru-
9l-449 from the BusinessOfrce, Mineralogical Society of Amer- nauer et al., 1938). The precision and accuracy of this
ica, 1130 SeventeenthStreet NW, Suite 330, Washington, DC technique is generally better than 50/0,as determined by
20036, U.S.A. Pleaseremit $5.00 in advancefor the microfiche. repeated measurement of standards and one sample
 CASEYET AL.: DISSOLUTIONRATESOF PLAGIOCLASE 213

An
Fig. 1. Variation in Gldspar composition for each single powder as a function of the end-member compositions: albite (Ab),
anorthite (An), and orthoclase (Or). Analyses for the Keystone albite (unfilled triangle) and SaranacLake andesine (filled circle) are
shown in (A). Analyses for the Bancroft albite (filled circle) and the Crystal Bay bytownite (unfilled triangle) are shown in (B).
Analyses for the Mitchell County oligoclase (fllled circle), the Pueblo Park bytownite (unfilled triangle) and the Great Valley anorthite
(unfilled square)are shown in (C). The dashedline representsthe range offeldspar solutions (Smith, 1974).

(Pueblo Park bytownite). Measured areasand uncertain- ter than 5ol0,as determined by repeatedanalysisof samples
ties are listed in Table 2. Becauseonly a small amount and standards.
of Crystal Bay bytownite was separated,the area was de- Dissolution rates were calculated by monitoring the
termined by using mixtures of Kr and He rather than concentrationsof Al, Si, Ca, and Na in the solutions (Fig.
N-He mixtures. The precision of areameasurementswith 2). Rates were calculated by linearly regressingthe con-
Kr is comparableto those made with N. The accuracyis centrations againsttime. Dissolution rates were calculat-
only within about 20010, as indicated by repeated mea- ed from the slope of these curves, and from knowledge
surement of standards. of the specificsurfacearea and composition of each min-
The exposedarea of feldspar probably did not change eral. The rates are compiled in Table 3. Data used to
significantly during the experiment and only a small frac- calculate the rates are given in Appendix l.
tion of the powder mass(typically =0.1 mass9o)was con-
sumed. The feldspar areas could not be measured after
Rnsur,rs
the experimentsbecauseof the artifacts of sample leach- The accuracyof any relation between mineral compo-
ing and drying discussedby Caseyet al. (1990). Specifi- sition and dissolution rate is limited by the abundance
cally, the leached surfacespartly separatefrom reacted and quality of data. The set of plagioclasedissolution
plagioclaseduring drying, and this separation exposesnew rates is illustrated in Figure 3, where results from this
surface area. study are comparedwith data from published sources.As
one can see,the dissolution rates vary dramatically with
Dissolution experiments mineral composition. Rates increasefrom =l x l0-t5
Batch dissolution experimentswere conducted by dis- mol/cm2ls for albite to well over I x 10-12moycm2/s for
persing each feldspar in a polyethylenebottle containing anorthite. All of these data are from experiments con-
0.010 N HCI (see Appendix). Solution volumes and ducted in HCI solutions, except possibly for the datum
massesof mineral powder are compiled in the Appendix.
The solutions were continuously agitated at 25 .C. Sam-
ples of the solution were periodically extracted from the TlsLe 2. Specificsurfaceareasof the feldsparpowders
bottles, pressedthrough a0.2 pm filter, and analyzed.The Sample Area m'zlg
samplevolumes varied between l0 and 25 ml. After sam-
Bancroft albite 0.405+ 0.03
pling, an equal volume ofunreacted background electro- Mitchell County oligoclaseno. 1 0.18+ 0.01
lyte was immediately added to the bottles to maintain a Mitchell County oligoclaseno. 2 0.645+ 0.05
constant total volume. All data are correctedfor changes Grass Valley anorthite 0.52+ 0.02
Keystone albite 0.49+ 0.05
in concentration as a result of sampling. There was neg- Pueblo Park bytownite 0.20+ 0.01
ligible drift in pH during the experiments. Crystal Bay bytownite 0.27+ O.O1
Saranac Lake andesineno. 1 0.405+ 0.03
Si concentrationswere measuredusing the Heteropoly Saranac Lake andesineno. 2 0.35+ 0.03
blue technique (American Public Health Association,
Note.'The powders range in size from 25 to 75 pm. Uncertainties(one
1970).Al concentrationwas measuredwith a DC-plasma estimatedstandard deviation)are reported from the BET r€ression (Low-
spectrophotometer.Na and Ca concentrations were de- ell, 1979) or the average of repeated measurementsof the Pueblo Park
termined by atomic absorption spectrophotometry.Pre- labradorite,whicheveris larger. The Mitchell County oligoclaseno. 2 and
the Saranac Lake andesineno. 2 were ground in 1983-1984.
cision and accuracyofthese techniquesare generallybet-
214 CASEY ET AL.: DISSOLUTION RATES OF PLAGIOCLASE

-8
X1 0
TABLE3. Plagioclasedissolution rates at pH : 2.0

1.5. S i l i c o n Rate (teldspar-mol/cmr/s)x 1015

6
v Sample Si Ca
Feldspar- moles 1 1 . 0 8+ 0.6 0.47 + 0.01
5 2 1 . 4 1! 0.2 2.57 + O.79
cm2
v. 3 3.62 + O.2 4.98 + 0.14
4 2 . O 5+ 1.1 2.51 + 0.87 2.53 + O.27
a
5 6.85 + 3.0 1 5 . 0a 7.5 8.46 + 0.51 8.32 + 1.20
.3 4 6 9.88 + 4.3 26.8 ! 5.7 1 5 . 8+ 0.62 1 2 . 9+ 1 . 6 3
7 1 4 . 0+ 3.3 49.2 + 4.1 42.9 + 2.08 39.5 + 3.35
e 66 o o o
8 2 1 2 . 0+ 9 5 . 0 359.0 + 174.0 425.0 + 24.9 419.0 + 28.8
1.O 1.5 io" to6 9 643.0 + 40.0 600.0 + 48.0 565.0 + 48.0 573.0 + 65.1

Seconds Note.' Uncertaintiesfor Si and Al fluxes are estimated from duplicate

-8 experiments.Uncertaintiesfor Ca and Na fluxes are from the enor of the
x1O linear regression.All uncertaintiescorrespond to one estimated standard
deviation. 1 : Keystone albite, 2 : Mitchell County oligoclaseno. 1, 3 :
Aluminum 6 MitcheffCounty oligoclase no.2,4 : Bancroft albite, 5 : Saranac Lake
" a n d e s i n en o . 1 , 6 : S a r a n a cL a k e a n d e s i n en o . 2 , 7 : P u e b l oP a r k
3.O
bytownite, 8 : Crystal Bay bytonite, I : Great Valley anorthite.
Feldspar - moleS 5,
ve .
cm'2.o
-d

,v
1.O -vt --lat
'
dissolution rates ofbytownite and anorthite. The rate of
v"
-rf _3
dissolution of the Grass Valley anorthite from this study,
for example, is approximately 75 times smaller than that
o+
o do"ro6 reported for the Pacayaanorthite by Fleer (1982) (Fig. 3).
Seconds Brady and Walther's (1989) rate for anorthite dissolution
is also considerablylower than Fleer's (1982) datum, but
Fig. 2. (a) Concentration of Si in solutionas a functionof is also higher than the rate measuredin this study for the
time. The Si concentrationsarenormalizedto the initial powder Grass Valley anorthite. Brady and Walther (1989) dis-
surfacearea,the total solutionvolume,and the compositionof
the feldspar.The resultingconcentrations solved the unnamed anorthite (Annr) at pH : 1.9. The
areplottedin unitsof
feldspar-mol/cmr. Expressed in this way,the slopeof the curve slight pH differencesamong the experiments cannot ac-
equalsthe feldspardissolutionrate in mol/cm2ls.The numbers count for such large differencesin reported rates.
correspond to thesamplesidentifiedin Table3. (b) Theconcen- The discrepancy, however, may be attributable to
trationsof Al in solutionasa functionof time. unique aspectsof Fleer's experiments. Most of the data
compiled in Figure 3 are from experimentsconductedon
granular material. The datum of Fleer (1982) is from a
from Brady and Walther (1989). A complete description batch experiment conducted on a single crystal of anor-
of this particular experiment by the original authors is in thite. She estimated the exposedsurfacearea of this crys-
preparation. tal geometrically,rather than through the sorption ofgas-
In severalexperimentseither separateminerals of sim- es onto exposed surfaces, as was done by the other
ilar composition were dissolved (e.g., the Keystone and researchers.If this crystal contained many small frac-
Amelia albites), or separateexperimentswere conducted tures, which were accessibleto the aqueoussolution but
on minerals from the samelocation (e.g.,the Crystal Bay too small to be incorporated into the areacalculation, her
bytownite). In general,the dissolution rates ofthe plagio- estimate of the dissolution rate would be anomalously
clase minerals in the approximate composition range of high. The total disagreementover anorthite dissolution
Annoto Anuoagreeto within a factor of between two and rates decreasesfrom over a factor of 100 to approxi-
five. Estimates for albite, for example, range from 1.08 mately a factor of four if Fleer's (1982) datum is exclud-
x l0 '5 to 2.5 x l0-r5 feldspar-moycm2/s.The disso- ed.
lution rate of the Keystone albite is lower than that re- The dissolution rate of the Crystal Bay bytownite re-
ported for Amelia albite at pH : 2.1 by Chou and Wol- ported by Brady and Walther (1989) is lower by almost
last (1984, 1985)but compareswell with that published a factor of ten than is reported here for the samematerial
by Knauss and Wolery (1986) for an unidentified albite. at pH : 2.0 (Fig. 3). Reasonsfor this discrepancy are
To make this comparison, data of Knauss and Wolery unclear. Although Brady and Walther (1989) conducted
(1986)were adjustedfrom 70 "Cto 25 'C usingthe stan- their experiments at sli8htly more basic conditions (pH
dard Arrhenius relation and the activation energy(8 kcal/ -- 2.15) than those employed here, the large
discrepancy
mol) measuredby Fleer (1982) for anorthite dissolution in rates cannot be attributed solely to differencesin so-
at pH 2.0. Note also that the batch dissolution rate of lution pH.
albite reported here (Table 3) compareswell with exper-
iments conductedin chemostatcells(Knaussand Wolery, DrscussroN
1986;Chou and Wollast, 1985). There are two important points to summarize from the
There is considerable disagreement,however, about the precedingsection. First, rates vary with plagioclasecom-
 CASEYET AL.: DISSOLUTIONRATESOF PLAGIOCLASE 215

-10 -11

-11 -12
log {Rate} tos {Rate}
-12 -13

-13 -14

6
-14 4 + -15
rL F---a+
.5 o
IC
-15 -16
o 20 40 60 80 100 40 60 80

{molepercent}
Anorthite { molepercent}
Anorthite
Fig. 3. Specifrcdissolutionratesof plagioclase samplesas a Fig-4. Dissolutionratesof plagioclase asa function
samples
functionof compositionin pH : 2.0 solutions.The numbers of mole percentanorthitein pH : 3.0 solutions.SampleC is
correspondto tho samplesidentified in Table 3. Ratesare re- from Chouand Wollast(1984),sampleH is from Holdrenand
portedasfeldspar-moVcm2/s asdetermined by Si fluxes.Sample Speyer(1985,1987),andsampleA is from AmrheinandSuarez
C corresponds to the Amelia albite(Chouand Wollast,1985). ( I 988).
SampleF corresponds to thePacayaanorthite(Fleer,unpublished
data).SampleK is an unidentifiedalbite describedby Knauss
and Wolery(1986).Samplesidentifiedwith a B correspondto trend of the logarithms of rate vs. composition is not
an unidentifiedanorthite of compositionAno, and the Crystal constant, but increasesin slope with increasedCa and Al
Bay bytownite (Patrick Brady, personalcommunication).The content (Fig. 3). Although the data are scattered,the rates
curve is an empirical correlationbetweendissolutionrate and apparently increasemore rapidly for the calcic minerals
feldsparcomposition.
than they do for minerals in the composition range Anoo
to Anro-ro.This relation is apparent even if Fleer's (1982)
datum is excluded from the set of data. To verify this
position by a factor of well over 103.The large difference relation, additional dissolution rates are compiled from
in dissolution rate of very sodic and very calcic plagio- experimentsat pH : 3 and are shown in Figure 4.
clase has been pointed out before (Lasaga, 1983; Brady As in the casefor experimentsat pH : 2, ralesincrease
and Walther, 1989).The new data presentedhere for pla- with anorthite content. The total variation in rates with
gioclaseminerals of intermediate composition, however, mineral composition is, however, not as pronounced as
add much detail to the relation (Fie. 3). in the more acidic solution (Fig. 3). The relation between
Second,this wide variation in rate is much larger than the logarithm of dissolution rate and mineral composi-
the uncertainty surrounding any singlecomposition. Dis- tion is nonlinear, however,just as was observedat pH :
solution rates of a single plagioclasecomposition from 2 (Fig.3). The dissolution rates of plagioclasein the ap-
different investigators generally agreeto within a factor proximate composition range Anoo to An,oo vary more
of approximately 2 to 5 for minerals in the approximate dramatically with composition than plagioclasein the ap-
composition rangeAn00to Anuo.The disagreementis much proximate composition range Anooto Anoo.The relation
larger for more Ca-rich plagioclase,and additional data between plagioclasedissolution rate and mineral com-
are critically neededon these compositions. position is, ofcourse, heavily influenced by the few data
An empirical correlation of dissolution rate with min- for calcic compositions. The following empirical corre-
eral composition in pH : 2 solutions is given by: lation describesthe distribution ofrates:
log,o[R(X)]: -14.7484 - 0.0135083x X log,o[R(X)]: -15.023 - 0.001131x X
+ 0 . 0 0 0 5 0 5 2 3 x8 l G . (l) + 0.0003176x l3 (2\

In Equation l, X representsthe mole percent anorthite where all variables are as previously defined. AII of the
in the plagioclaseand R (X) is the dissolution rate in feld- exp€riments used to compile Figure 4 were conducted in
spar-mol/cm'zls(Fig. 3). All data shown in Figure 3 are HCI solutions.
included in this regression,including Fleer's (1982) esti- It is not surprising that the rates ofdissolution ofpla-
mate of the anorthite dissolution rate. No statistical sig- gioclasevary so dramatically and nonlinearly with com-
nificance is assignedto this nonlinear regression,and the position. The structure of albite contains an extensive
correlation is heavily weighted by the datum of Fleer framework of linked silicate tetrahedra which are resis-
(1982). The regressionis shown as a bold, nearly contin- tant to hydrolysis relative to the aluminate sites. Con-
uous line in Figure 3. versely, silicate tetrahedra in ordered anorthite are iso-
An important feature of the data is that dissolution lated from one another by aluminate groups. In contrast
rates of calcic plagioclaseare apparently more sensitive to albite, selective hydrolysis of the Al from anorthite
to variations in composition than sodic materials. The completely disrupts the structure.
216 CASEY ET AL.: DISSOLUTION RATES OF PLAGIOCLASE

The relationship between dissolution rate and mineral nessofthe leachedlayer is controlled by the solution and
composition is likely to vary with the solution composi- mineral compositions. In any case, the overall rate of
tion. As noted by Wendt (1973), the pH-dependenceof dissolution is controlled by the rate of destruction of the
hydrolysis rates in simple solutions is controlled by the silicate framework, and these kinetics can be described
acid-basepropertiesof the important bonds (seealso Bales with an approximately zero-order rate law. Thus rates of
and Morgan, 1985; Carroll-Webb and Walther, 1988; dissolution become nearly constant with time after the
Blum and Lasaga, 1988). Other sorbed ligands can also early stagesof an experiment.
promote hydrolysis rates(Amrhein and Suarez,1988)and Mineralogic heterogeneities,however, influence con-
the relationships shown in Figures 3 and 4 are not ap- siderably the measured rate of dissolution. Ca-rich pla-
propriate for solutions containing ligands, such as fluo- gioclasedissolves many times more rapidly than either
ride ion or certain organic acids, which changethe char- Na- or K-rich feldspar (compare the rates compiled in
acter of hydrolysis from proton-promoted dissolution. Figure 3 with that reported for potassium feldspar by
Sorption ofthese ions onto a hydrolyzing bond enhances Holdren and Speyer,1985).Most plagioclasesamplesused
the rate and may also modify the relation between dis- in this study contain fine-grained intergrowths of two
solution rate and mineral composition. Of the data com- feldspar minerals, or are zoned in composition. The Ban-
piled in Figure 3, only Knauss and Wolery (1986) em- croft albite, for example, is antiperthitic (Appendix).
ployed a potentially catalytic solute (biphthalate) in their Likewise, the Mitchell County oligoclase contains an
experiment. The close agreement between Knauss and exsolved K-rich feldspar and exhibits a wide range in
Wolery's rate estimate and those of other investigators composition (Fie. l). The net dissolution rate is different
suggeststhat the biphthalate did not affect their result. than would be measuredon homogeneousmaterial with
Many potential factors may accountfor the uncertainty the same nominal composition.
of a factor of approximately two to five for minerals in Regular variations in the dissolution rate with time can
the composition rangeAnooto Anuo.Any singlebatch rate also lead to uncertainties in the rate estimate. Rates de-
measurement,for example,is only reproducibleto within creasewith time in the early stagesof an experiment by
this factor (Table 3). Furthermore, rates estimated from as much as a factor of ten as the particularly reactive sites
batch experiments ofshort duration difer depending upon dissolve (e.g.,Holdren and Berner, 19791,Holdren and
which element is examined. Rates calculatedfrom the Al Speyer,1985;Knaussand Wolery, 1986).Such a period
flux, for example, are larger than rates calculated from of enhancedreactivity is apparent in Figure 2 as anom-
the Si flux (Table 3). alously rapid increasesin Si concentration in the first 0.5
The uncertainty that arisesfrom this nonstoichiometric x 106s ofeach experiment. Subsequentchangesin con-
dissolution is too small to influence dramatically the re- centration are approximately constant (Fig. 2), and it is
lation between rate and composition shown in Figure 3. these data that are used to calculatethe dissolution rate.
In fact, both Knauss and Wolery (1986) and Chou and Holdren and Speyer(1985), however, also show that the
Wollast (1985) establishedstoichiometric dissolution in rates decreaseslowly with time over many hundreds of
their chemostat experimentsand their rates differ signif- hours of reaction. All of the data compiled in Figure 3
icantly. The discrepancymust be attributed either to dif- are from experiments that lasted severalhundred hours.
ferencesin the experimental design,or to inherent differ- Subtletiesof sample preparation can also causerates to
encesin the reactivities of the two albites.Note, however, vary by factors ofbetween two and five. Egglestonet al.
that the results of Knauss and Wolery (1986) compare (1989), for example,found that diopside dissolution rates
well with the rate estimate for the Keystone albite. Stoi- decreasedfor several months after the mineral powder
chiometric dissolution was not achievedin this batch ex- was initially prepared. They attributed the decreasein
penment. rate with time to slow recrystallization of the damaged
The nonstoichiometric dissolution arises becauseAl, mineral surfacesto a relatively undamagedstate. A sim-
Na, and Ca dissolve more rapidly from the plagioclase ilar mechanism may explain the duplicate experiments
structure than Si in the early stagesof an experiment. The on separatelypreparedsamplesofSaranac Lake andesine
differencein rate disappearswith time as a leachedlayer and the Mitchell County oligoclase (Table 3). The dis-
of constant thicknessdevelopson the mineral surface.At solution rates ofthe duplicatesvary by factors ofapprox-
this stage, the difiirsive flux of Al through the leached imately two in each case.One clear distinction between
layer is constant and proportional to the rate of destruc- thesematerials is the time that elapsedsincepreparation.
tion of the residual silicate framework (Chou and Wol- The slowly dissolving material was prepared 4-5 yr ear-
last, 1984). lier than the more rapidly dissolving material.
There have been no studies to date documenting the The essentialpoint is, however, that the variation in
time required to reach a leachedlayer of constant thick- rate for any single plagioclasesample is small relative to
ness for plagioclase minerals at pH : 2. The ratio of the entire variation in rate with composition. Many po-
dissolved substancesreleasedfrom the mineral cannot be tential factors can causerates to vary by a factor of be-
trusted, since these fluxes may reflect the dissolution of tween two and five besidesthose listed above. Thus the
trace impurities and exsolvedphases.The ultimate thick- relation between the plagioclase dissolution rates and
 CASEY ET AL.: DISSOLUTION RATES OF PLAGIOCLASE 217

mineral composition derived above is meaningful. This Fleer, V.N. (1982) The dissolution kinetics of anorthite and synthetic
relation will be improved, of course, as additional data strontium feldspar in aqueous solutions at temperatures below 100 eC:
With applications to the goologicaldisposal ofradioactive nuclear wasles,
are acquired.
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