American Mineralogist, Volume 78, pages 405-414, 1993

Formation of protectiye surface layers during silicate-mineral weatheringunder

well-leached,oxidizing conditions

Mrcrr,q.nr, ANrrroNy Ysr-spr,

Department of Geological Sciences,206Natural ScienceBuilding, Michigan State University, East Lansing, Michigan 48824, U.S.A

AssrRAcr
Formation of a protective surface layer [a layer of products through which transport
(diffusion) of aqueous reactants or products is rate-determiningl during silicate-mineral
weathering requires that (1) elementsnormally consideredimmobile (e.g.,Al, Fe) behave
conservatively;and (2) the volume ratio of product to reactantbe greaterthan one. Mineral
suitesinvolving most major rock-forming silicates(feldspars,pyroxenes,amphiboles, and
olivines) weathering to common oxides and 1:I clays are characterizedby Vo,oo< Vn*,
(V-"d/V**, < l). Protective surface layers cannot form on these minerals; instead, etch
pits and porous pseudomorphs formed by interface-controlled reactions are ubiquitous.
However, reactant-productmineral suitesinvolving almandine and spessartinegametsare
characterized by Vr^ ) V**, (V.d/V**, > l). Weathered almandine and spessartine
commonly exhibit laterally continuous, nonporous surface layers underlain by smooth,
rounded reactant-mineral surfaces.The rate-determining step during weathering in these
instancesis diffusion through the surfacela1,erof weatheringproducts. Elemental mobility
in the weathering environment and product-reactant volume ratios determine the occur-
rence ofsurface features(etch pits vs. protective surfacelayers) and associatedrate-deter-
mining mechanisms(interface- vs. transport-controlled kinetics).

IurnooucrroN eral-solution interface, (2) the reaction must occur at the

The purposeof this paper is to proposea hypothesis: interface,and (3) dissolvedproducts(e.g.,alkali or alka-
The presenceor absenceofprotective surfacelayers dur- line earth cations, aqueous silica) must leave the site of
ing natural weathering of silicate minerals and the rate- the interfacial reaction (lest they accumulateto the extent
determining mechanism of the weathering reactions are that equilibrium is attained or the reaction is otherwise
determined by the stoichiometries and molar volumes of suppressed).
reactant minerals and their weathering products. To test When a number of different reaction steps occur in
the molar volume hypothesis, product-reactant volume series,the sloweststepis rate determining. Therefore,one
ratios are calculatedfor a number of common rock-form- of two mechanismsis rate determining in the weathering
ing silicate minerals, weathering to well-crystallized sec- of silicate minerals: (1) transport control (or transport-
ondary minerals typical of thoroughly leached,oxidizing limited reaction), in which transport of aqueousreactants
weathering conditions. Volume ratios are then related to to or products from the fresh mineral surfaceis the slow
the observed distribution of etch pits and surface layers step in the reaction; or (2) surface-reaction (interface)
on naturally weatheredsilicate minerals. Fe-bearing sili- control (or interface-limited reaction), in which the rate
catesare emphasizedbecauseof the equivocal nature of of reaction is determined by processesoccurring at the
previous results regarding rate-determining mechanisms mineral-solutioninterface(Berner,1978,l98l). Eachrate-
and protective surfacelayers on these minerals. The re- determining mechanism has unique consequencesfor the
actant and product minerals investigated here are listed microscopic surface morphology of weathered mineral
in Table l. grains(Berner,1978,1981).
Surfacesof minerals dissolving by transport control are
smooth, rounded, and featureless,reflecting the unifor-
Rate-determiningmechanismsin the weathering of mity of attack on the surface(Berner, 1978, 1981).Dif-
major Fe-free rock-forming silicates fusion is the slowest form of transport (Berner, 1978,
Any mineral-HrO reaction (for example, hydrolysis of 1981);the medium through which diffusion occursmay
silicate minerals during rock weathering) requires a se- be the surrounding fluid, or a protective surfacelayer of
quenceof stepsfor the reaction to proceed.With the as- residual or secondarysolids on the surfaceofthe dissolv-
sumption that all reactants are available in excess,the ing mineral (armoring precipitate, as used by Schott and
following steps must occur (in order): (l) aqueous reac- Petit, 1987; a surface layer is protective if diffusion of
tants (e.g.,H ions or hydronium) must arrive at the min- reactants or products through it is the rate-determining
0003-o04x/93l0304-O405$02.00 405
406 VELBEL:PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING

step in the alteration reaction). However, measured sili- TABLE1 . Stoichiometriccoefficientsand molarvolumesfor rock-
cate-mineraldissolution rates are too slow to be account- forming silicatemineralsand some weatheringprod-
ucts characteristicof well-leachedenvironments
ed for by aqueousdiffirsion(Berner,1978, l98l), and no
direct evidence of appreciable stoichiometrically altered Element
surfacelayershas been reported from naturally weathered Mineral (e) ne
Fe-free major rock-forming silicates.Direct examination Common rock-forming aluminum and iton silicates
of the surfacesof many naturally weathered silicates in- Anorthite At 2 100.610
Low albite Al I 100.054
stead reveals ubiquitous etch pits (crystallographically Orthoclase Al I 108283
controlled dissolution voids; seereviews by Velbel, 1986, Ferrosilite Fe2 65.941
Fe l,+l 265.88
1987; Blum and Lasaga,1987; Schott and Petit, 1987). Anthophyllite 2.9 271.68
Cummingtonite Fe
Etch pits and related featuresare produced by interface- Fayalite Fez 46.290
limited mechanisms,reflectingthe site-selectivenature of Other tock-f orming silicates
Al 2 115.43
the interfacial process(Berner, 1978, 1981; Brantley et Almandine Fe
al., 1986;LasagaandBlum,1986;SchottandPetit,1987; Spessartine AI
Mn ?
Blum and Lasaga,1987; Blum et al., 1990; Gratz eI al.,
Staurolite Fe 4 445.67
1991a, l99lb). Clay pseudomorphsafter aluminosili- AI 18
catespossessabundant porosity between clay crystallites Zoisite AI e 136.19
AI 2.16 138.146
in the pseudomorph(e.g.,Glasmann,1982;Velbel, 1983; Epidote-1 0.84
Fe
Nahon and Bocquier, 1983; Anand and Gilkes, 1984). Epidote-2 AI 2.60 137370
Diffusion through this open pore network is not likely to Fe 0.40
Oxide
be sufficiently slow to affect reaction rates at the solid- Magnetite Feo 44.528
fluid interface(e.9.,Petrovic, 1976).Interfacecontrol is Weatheling products
now favored for weathering of major rock-forming sili- Kaolinite Ar 2 99.236
Gibbsite AI 32.222
cates, including (l) qtartz, (2) feldspars, (3) Fe-free py- Goethite Fe 20.693
roxenes,amphiboles,and olivines, and (4) Fe-bearingpy- Hematite he 30.388
Lepidocrocite Fe 22.492
roxenes, amphiboles, and olivines under reducing or 19.507
Boehmite AI
extremely acidic conditions (e.g.,Wilson, 1975; Berner Diaspore AI 17.862
and Holdren, 1911, 1979;Berneret al., 1980;Schottet Bayerite AI 3 1. 1 5
AI 32.28
a l . , l 9 8 l ; V e l b e l ,1 9 8 4 b ,1 9 8 6 ,1 9 8 7 ,1 9 8 9 ;S c h o t ta n d Nordstrandite
Pyrolusite Mn 16.708
Petir, 1987;Blum et al., 1990;Gratzer al., 1991a,1991b). Ramsdellite Mn 17.838
Notej Stoichiometriesand molar volumesfor Tables 1_3 are from Smyth
Ferromagnesian-silicateweathering and Bish (1988)tor all mineralsexcept bayeriteand nordstrandite(from
The evidencefor weatheringmechanismsof Fe-bearing Maynard, 1983) and lepidocrocite(calculatedfrom unit-cellparameters
givenby Schwertmannand Taylor,1989).
pyroxenes, amphiboles, and olivines under oxidizing
conditionsis equivocal(Velbel, 1987).Although hydrous
ferric oxide precipitates form during weathering ofthese
minerals(Sieverand Woodford, 1979;Bernerand Schott, ivines in the same manner (Wilson, 1975; Grandstaff,
1982;Schottand Berner,1983,1985;Whiteet al., 1985; 1978;Delvigne et al., 1979;Nahon et al., 1982;Macaire
White and Yee, 1985) their potential diffusion-limiting et al., 1988). Mobilization of Fe by reduction in wet,
role is still not well understood. The ubiquitous occur- O-depleted soils or exceptionally acidic settingsaccounts
rence of etch pits and related features (Fig. l) on soil for only a few ofthe many natural occurrencesofetched
pyroxenes, amphiboles, and olivines favors interface- pyroxenesand amphiboles(Glasmann,1982;Anand and
controlledmechanisms(Bernerand Schott, 1982;Velbel, Gilkes. 1984).
1987).Figure I is a scanningelectronmicroscope(SEM) Boxworks (typically femrginous) comprise a rigid net-
image of a denticulated margin (also known as cocks- work of secondaryproducts that pseudomorphically pre-
comb termination and hacksaw termination) on a natu- servespyroxene and amphibole grain outlines and cleav-
rally weatheredinosilicate(hornblende),in which the teeth ages(with abundant porosity within the boxwork) even
parallel the c axis ofthe reactant chain silicate (e.g.,Ber- upon complete removal of the reactant-mineralremnants
ner et al., 1980:Bernerand Schott,1982;Velbel, 1987, (e.g.,Cleaves , 1974; Velbel,I 989;Delvigne,1983,1990).
1989,and references therein;this featureis alsocommon Densely etchedor denticulated mineral surfacesare ubiq-
on weatheredpyroxenes).This feature is also visible by uitous on most naturally weathered major rock-forming
optical petrography(e.g.,Cleaves,1974; Delvigne, 1983, silicates,even on surfacesbeneath clay coatings or oxide
1990;Velbel, 1987, 1989).Berneret al. (1980)showed and hydroxide products (e.g.,boxworks), from which the
that etch featuresreflect selectiveattack at crystal defects mineral surface is commonly separated by void (e.g.,
and dislocations;the sharp denticulationsresult from side- Cleaves,1974;Nahon and Bocquier,1983;Velbel,1989;
by-sidecoalescence of lenticular (almond-shaped)etch pits Delvigne, 1990;Nahon, l99l). This suggests that all por-
(Berneret al., 1980;Berner and Schott, 1982).Etch pits tions of the primary mineral surfaceare accessibleto flu-
(Fig. 2) and denticulated margins form on weatheredol- ids in spite ofthe precipitates.
 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING 407

Fig.2. Etchpits on naturallyweathered olivinefrom a slight-

Fig. l. Denticulatedmargin on naturallyweatheredhorn- ly weatheredcorestonein spheroidallyweatheredbasaltnear
blende,formed by side-by-sidecoalescence of lenticular(al- SchofieldBarracks,Oahu,Hawaii. Note both individual etch
mond-shaped) etchpits. Sampleis from a weatheredcorestone pits and spatialarraysof overlappingpits. In orderto minimize
developed on theCarrollKnob Complex,in theBlueRidgenear preparation artifacts(Cremeens et al., 1987),no chemicalor
Otto, North Carolina(Velbel,1989).Scanningelectronphoto- mechanical pretreatment wasemployed;thedustadheringto the
micrograph;scalebar is 10 ;rm long. surfaceconsistsofnatural finesproducedandredistributeddur-
ing sampleshippingandstorage. Scanning electronphotomicro-
graph;scalebar is 10pm long.

Garnet weathering
Studies of naturally weathered almandine garnet by Scanning electron microscope (Fig. a) and X-ray dif-
Stoopset al. (1979),Parisotet al. (1983),Embrechrsand fraction fiRD) observationsshow that the limonite con-
Stoops(1982), and Velbel (1984a)provide considerable sists of radially oriented fibrous intergrowths of gibbsite
evidence that almandine weathers by a transport-con- and goethite that formed by centripetal replacement of
trolled (diffusionlimited) mechanism in oxidizing weath- garnet (Velbel, 1984a1- Graham et al., 1989b,report he-
ering environmentssuch as saprolite(Velbel, 1984a).In matite as the femrginous product in their material). Etch
many soils, almandine surfacesare directly exposed to pits are absent. Diffusion (transport) of reactants and
soil solutions(Velbel, 1984a;Ghabru et al., 1989; Gra- products through the gibbsite-goethitelayer is the rate-
ham et al., 1989a).Thesegrainsexhibit numerouswell- determining step in the weathering of almandine in the
formed etch pits (Fig. 3), indicating interface-control of oxidizing environment of the saprolite (Velbel, 1984a).
garnetweatheringin theseweatheringenvironments (Vel- Both coated and uncoated almandine grains can occur in
bel, 1984a).However, in many lateritic and saprolitic the same soil (Graham et al., 1989a);garnetsthat were
regoliths, layers of limonite replace garnet. The replace- partially weathered in saprolites have thick coatings of
ment begins at grain boundaries and internal fractures limonite and persist in soils, whereas garnets that by-
traversing the garnet, and the replacement front evolves passedthe coating-forming, saprolitic stageof weathering
from the original grain boundary toward the grain or frag- (i.e., were removed to soils directly from fresh outcrops)
ment center, a texture known as centripetal replacement weathermuch more readily @mbrechtsand Stoops,1982).
(Parisotet al., 1983;Velbel, 1984a).The resultingprod- These observationsfurther attest to the protective nature
ucts occur as layers of uniform thickness (Stoops et al., of the coatings.Similar featureson manganiferousgarnets
1979;Embrechtsand Stoops,1982;Parisotet al., 1983; (Nahon et al., 1984, 1985; Perseil and Grandin, 1985)
Velbel, 1984a).In thin section,the contact betweenthe suggestthat similar weathering mechanisms prevail in
garnet surface and the layer of weathering products is these instancesas well. These findings are significant be-
sharp and smooth, and garnet subgrain corners (e.g., at causethey include the first direct evidence that a protec-
the junctions of fractures)are commonly visibly rounded tive surface layer exists on any naturally weathered sili-
beneath the layers. catemineral (Velbel. 1984a.1987).
408 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING

Fig. 3. Etch pits on naturallyweatheredalmandinegarnet. Fig. 4. Outersurfaceof limonite(gibbsiteand goethite)sur-

Sampleis from shallowhorizonsofsoil developedon the Pre- facelayerformedby centripetalreplacement duringweathering
cambrianCoweetaGroup,in the Blue RidgenearOtto, North ofalmandinegarnet.Cross-sectional viewsthroughsurfacelayer
Carolina(Velbel,1984a).Scanningelectronphotomicrograph; showthat it consistsof radially orientedgibbsiteand goethite
scalebar is l0 pm long. andprovideadditionalevidenceofcentripetalreplacement (Vel-
bel, 1984a).Notetheabsence ofshrinkagecracksor othervoids,
despitedesiccationduring samplestorageand preparationfor
Unansweredquestions SEM.Sampleis from deepweatheringprofile(saprolite)devel-
1. It is now generallyacceptedthat a protective surface opedon Precambrian TallulahFallsFormationin theBlueRidge
layer does not form on naturally weathered pyroxenes nearOtto, North Carolina(Velbel,1984a).Scanning electron
and amphiboles(Bernerand Schott, 1982;Velbel, 1987). photomicrograph; scalebar is 10pm long.
Does a nonprotective surfacelayer of secondaryminerals
form on weatheredferromagnesiansilicates,which is too criterion statesthat thick oxide layers that form on re-
actant metal during oxidation are adherent and pore free
thin, too porous, or otherwise unable to be transport lim-
(i.e., protective, in that diffusion through them is rate
iting, but still compositionally altered (Bernerand Schott,
I 982)? determining)if Vr/V,(where Zois the volume of product
2. Why do thick protective surfacelayers not form onand V, is the volume of reactant) > I (Kubaschewskiand
naturally weathered pyroxenes, amphiboles, or olivines Hopkins, 1962; Hauffe, 1965).By analogywith the Pil-
(Bernerand Schott, 1982; Velbel, 1984b, 1987, 1989), ling-Bedworth rule, the potential for any primary rock-
whereassuch layers do appear to form on Fe- and Mn- forming silicate mineral to form a protective surfacelayer
bearing garnets(at least under certain conditions; Stoops
during weathering may be estimated by calculating the
etal., 1979;'Embrechtsand Stoops,1982; Parisot et al., volume of secondary minerals that would form from a
1 9 8 3 ;V e l b e l , 1 9 8 4 a , 1 9 8 7 N given volume of reactant, if one assumesconservative
; ahon et al., 1984,19851
Perseiland Grandin, 1985)? behavior of the least mobile elements.A protective sur-
3. What combination of mineralogical factors of the facelayer can form only if geochemicalconditions permit
primary mineral (e.g., structure or major-element com- conservativebehavior of elementslike Al, Fe, or Mn, and
position) and geochemical(e.g.,redox, leaching, acidity)if V,/V, > l. If product-forming elementsbehave non-
conditions in the weathering environment determine the conservatively (e.9., because of chelates enhancing the
circumstancesunder which a potentially protective sur- solubility of otherwise immobile elementssuch as Al, or
face layer can form during silicate-mineral weathering? weathering under reducing conditions, mobilizing Fe or
Mn), or if V,/ V, < I , formation of a sufficient volume of
Mnrnoos products to result in a continuous, uninterrupted layer of
The approach used here is analogous to the Pilling- products capable of occluding primary-mineral surface
Bedworth rule, widely used by metallurgists to explain area is impossible, and the surfaceis vulnerable to direct
and predict the corrosion of metals (e.g., Kubaschewski atlack, with interfaceJimited kinetics. Etched, product-
and Hopkins,1962; Hauffe, 1965).The Pilling-Bedworth poor surfacesresult.
 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING 409

The Pilling-Bedworth rule appearsto be important for common secondaryminerals (e.g.,gibbsite, goethite, ka-
reaction products in which diffusion of matter is from the olinite, lepidocrocite) around itself. At best, a fraction of
outer surface of the product toward the metal-product the original grain volume is occupiedby weatheringprod-
interface (Kubaschewskiand Hopkins, 1962; also, From- ucts. Void ratios (one minus the value shown in Table 2)
hold, 1976), a geometry preciselyanalogousto the ob- for any individual reactant-product pair involving Fe-
served centripetal garnet replacement textures (e.g.,Vel- and A1- end-membersof common rock-forming silicates
bel, 1984a,1987).Reactant-productmolar volumeshave rangefrom 1.4 to 88.6 vol0/0.Void ratios are even higher
also been used in investigations of rate-determining if Al or Fe are mobilized. These void ratios are sufrcient
mechanismsof weathering,hydrothermal alteration, and to render the products ineffective as barriers to transport
pseudomorphous replacement of Ti minerals that are ofaqueous reactantsor products (assumingthe void space
natural analogues for ceramic high-level radioactive is interconnected).
wasteforms(Hollabaughet al., 1989; Vance and Doern, Most other oxide and oxyhydroxide products of weath-
l 989). ering, both common (hematite, boehmite, diaspore) and
The total number of moles of a given element (e) in uncommon (bayerite) have molar volumes lower per Al
any arbitrary volume of reactant or product mineral is or Fe than gibbsite or goethite (Table l; Smyth and Bish,
given by I 988; Maynard, I 983), so product-reactantvolume ratios
will be lower for these products and void ratios will be
n",V,
.m. -:e...t ' -
I/o
( l ) higher than the values indicated in Table 2 for goethite
and gibbsite. These minerals are even less likely to form
where m".,: total number of moles of elemente in min- protective surface layers on common rock-forming sili-
eral i, n".,: stoichiometric coefficientof element e in min- catesthan are gibbsite and goethite.Even uncommon sec-
erali, V,: volume of mineral i, ar'd, V?: molar volume ondary minerals with larger molar volumes per Fe or Al
of mineral l. (e.g.,nordstrandite)cannot occur in sufficientvolumes,if
Writing two such equations (one for i : reactant min- Al and Fe behave conservatively. The molar volume of
eral, r, and the other for I : product mineral, p), setting nordstrandite is only 0.2o/ogreaterthan that of gibbsite,
tfi.., : ffi"* (that is, conserving element e, letting all of and nordstrandite is rare as a weathering product (May-
element e presentin the reactantmineral be incorporated n a r d , 1 9 8 3 ) .
into the product mineral), combining the equations for Feldspars,pyroxenes,amphiboles, and olivines cannot
reactant and product minerals, and rearranging,gives form protective surface layers of common weathering
products under wellleached, oxidizing conditions (Table
Vo- n"'Vf;
-n: (2) 2) and should all exhibit site-selective dissolution and
i*A etch pits under all circumstances(i.e., whether Fe and Al
where Vo/V, is the volume of product mineral produced behaveconservatively or not). This is consistentwith the
per unit volume of reactantmineral, if elemente is con- literature on natural weathering of these minerals, on
served. which etch pits and related features are ubiquitous, and
Molar volumes and stoichiometric coefficientsfor re- apparently protective coatings have never been reported
actant and product minerals summarized in Table I are (Wilson, 1975;Bernerand Holdren, 1977, 1979;Berner
taken directly from the compilations of Smyth and Bish et a1.,1980;BernerandSchott,1982;Velbel,1984b,1986,
(1988)and Maynard (1983),or calculatedfrom unit-cell 1 9 8 7 , 1 9 8 9 ) .
parametersreportedby Schwertmannand Taylor (1989). Table 3 showsproduct-reactantvolume ratios for some
lesscommon silicates.If Al, Fe, and Mn are conserved,
certain combinations of weatheringproducts [e.g.,alman-
Rnsur,rs dine - iron oxyhydroxide (goethite or lepidocrocite) +
The calculated values of the product-reactant volume aluminum hydroxide (gibbsite or bayerite or nordstran-
ratio for common rock-forming silicate minerals weath- dite)l have VJV, > l These reactant-product combina-
ered under thoroughly leached oxidizing conditions are tions could form protective surface layers. Such appar-
shown in Table 2. The maximum possible volume of ently protective layersoccur on some naturally weathered
aluminous secondaryminerals that can be formed from almandine(e.g.,gibbsite + goethite,Fig. 4; Stoopset al.,
common feldspars is from anorthite. Among ferromag- 1979;Embrechtsand Stoops,1982;Parisotet al., 1983;
nesian silicates, Fe end-members form the maximum Velbel, 1984a,1987)and spessartine (Nahon et al., 1984,
possiblevolume ofproduct. IfFe behavesconservatively, 1985;Perseiland Grandin, 1985;Velbel, 1987).
any real pyroxene, amphibole, or olivine with lesserFe2+ Combinations of products that include aluminum oxy-
components in solid solution will form a lesservolume hydroxides (boehmite, diaspore) or iron oxides (hema-
of ferruginous product than the amount shown in Ta- tite) form product assemblageswith too little solid vol-
ble 2. ume to form protective surface layers on garnets(Vr/V,
Under well-leached,oxidizing conditions,no common < l; Table 3). Therefore, the factors that determine the
rock-forming silicate mineral contains enough Fe or Al specific secondary mineral formed in any particular
to form a thick, nonporous, protective surface layer of weathering environment will also control, through the
410 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING

molar-volumerelationshipsfor com-
TreLe2. Reactant-product mineral relations of that product, the rate-determlnlng
mon rock-forminosilicateminerals mechanism of garnet weathering. However, drawing
Element mechanistic inferences from product mineral relations
Reactant ' product conserved Vr,.alV,""o alone (without information on textural relationships, for
Anorthite- gibbsite AI 0 640 example, centripetal replacementtextures) is hazardous.
Low atbite - gibbsite AI 0.322 For instance, hematite is believed to form from alman-
Orthoclase- gibbsite AI 0.298 dine in at least some weathering profiles (Graham et al.,
Anorthite- kaolinite AI 0.986
Low albite- kaolinite AI 0 496 1989b).If almandineweathereddirectly to hematite,the
Orthoclase- kaolinite AI 0 458 calculations here suggestthat the hematite-bearingprod-
Ferrosilite- goethite Fe 0.628
Anthophyllite- goethite Fe 0 . 11 4 uct cannot have acted as a protective surfacelayer, even
Cummingtonite- goethite Fe 0.175 in combination with gibbsite (for products : gibbsite +
Fayalite - goethite Fe 0.894 hematiteand reactant: almandine,V,/V,:0.953; Table
Ferrosilite- lepidocrocite FC 0.682
Anthophyllite' lepidocrocite Fe o 124 3). However, if the hematite formed by dehydration of
Cummingtonite . lepidocrocite Fe 0.190 earlier formed goethite or lepidocrocite, the weathering
Fayalite - lepidocrocite Fe 0.972 product layer or pseudomorph will presently consist of

TaeLe3. Reactant-productmolar-volumerelationshipsfor some less common rockJormingsilicateminerals

Reactant - oroduct Elementconserved Ve,"olv,.".,

Almandine- goethite Fe 0.538

Almandine- gibbsite AI 0 558
A L M A N D I N E- G O E T H I T E+ G I B B S I T E 1.096
Almandine- leoidocrocite Fe 0.585
A L M A N D I N E- L E P I D O C R O C I T+E G I B B S I T E 1. 1 4 3
Almandine' bayerite AI 0 540
'| 078
A L M A N D I N E- G O E T H I T E+ B A Y E R I T E
A L M A N D I N E- L E P I D O C F O C I T+E B A Y E R I T E 1.125
Almandine- nordstrandite U.55Y
A L M A N D I N E. G O E T H I T E+ N O R D S T R A N D I T E 1 097
A L M A N D I N E- L E P I D O C R O C I T+E N O R D S T R A N D I T E 1.144
Almandine' hematite Fe 0.395
Almandine- boehmite AI 0.338
Almandine- diasDore AI 0.310
Almandine- goethite+ boehmite 0.876
Almandine- goethite+ diaspore 0.848
A l m a n d i n e ' h e m a t i t e+ g i b b s i t e 0.953
Almandine- leoidocrocite+ boehmite 0 923
Almandine- lepidocrocite+ diaspore 0.895
Spessartine- gibbsite AI 0.547
Spessartine- pyrolusite Mn 0.425
Spessartine- gibbsite+ pyrolusite 0.972
Spessartine- ramsdellite Mn 0.454
'| 001
SPESSARTINE - G I B B S I T E+ R A M S D E L L I T E
Soessartine- kaolinite AI 0.842
S P E S S A R T I N E . K A O L I N I T E+ P Y R O L U S I T E 1.267
S P E S S A R T I N E ' K A O L I N I T E+ R A M S D E L L I T E 1.296
Staurotite- goethite Fe 0 186
STAUROLITE ' GIBBSITE AI 1.301
STAUROLITE- BAYERITE AI 1.258
STAUROLITE. NORDSTRANDITE AI 1.304
Staurolite - leoidocrocite Fe 0.202
Staurolite' hematite Fe 0.136
Staurolite- boehmite AI 0.788
Staurolite- boehmite+ lepidocrocite 0.990
Staurolite- boehmite+ goethite 0.s74
Staurolite- diasoore AI 0.721
Zoisite- gibbsite AI 0.710
Z O I S I T E- K A O L I N I T E AI 1.09
Epidote-1- gibbsite AI 0.504
Epidote-1- kaolinite AI o776
Epidote-1- goethite Fe 0 126
Epidote-1- kaolinite+ goethite 0.902
Epidote-2 - gibbsite AI 0.610
Epidote-2- kaolinite AI 0.939
Epidote-2 ' goethite Fe 0.060
n ooo
Epidote-2- kaolinite+ goethite
MAGNETITE. HEMATITE(MARTITE) Fe 1.O2

Notei Capitalizedentries are those reactant-productassemblagesthat exceed the Pilling-Bedworthcriterion,favoring formation of protective surface
layersand diffusionlimitedreactions
 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING 4tr

Treue 4. Texturaland kineticconsequencesof elementalmobilityand product-reactantmolar-volumeratios

lmmobileelementsconserved? No (removed) Yes Yes
Product-reactantvolume ratio Any value vplv, < 1 VJV, > 1
Surface morphologyof relict pr,- 1. Bare grain surface 1. Product-poorgrain surface 1. Protective surface layer
mary mineralgrain 2. Etch pits 2. Etch pits 2. Smooth rounded reactant
mineral surface
Rate-determining
mechanism Interface-limited Interfacelimited TransportJimited
Examples(see text for refer- Feldspar,amphibole,pyroxene, Feldspar,amphibole,pyroxene, Almandinegarnetand spessar-
ences) olivine,garnetweatheredin olivineweatheredin saprolite tine garnet weathered in sap-
the presence of organrc che- underoxidizingconditions roliteunderoxidizingcondi-
latingagents(in soils)or un- tions
der reducingconditions*
Texture produced by complete Moldicdissolutionvoid Porous pseudomorph Solid pseudomorph
destruction of primary mineral
Demonstratedor possible exam- Pyroxene,amphiboleunder Fe- Limoniteor clay boxwork after Limoniteor manganeseoxide
ples (referencesbelow) mobileconditionst,-t pyroxeneor amphibolet nodules after garnet+
'Also, numerousexamplesof intrastratallydissolveddetritalsilicates(e
-. Glasmann,1982; Anand and Gilkes,1984. 9., feldspars,heavy minerals)in sandstones

t Basham,1974; Cleaves,1974; Delvigne,1983, 1990; Velbel,1989.

f Velbel,1984a,1987; Nahonet al , 1984, 1985; Perseiland Grandin,1985.

hematite, but its precursor(goethiteor lepidocrocite)may Drscussron

still have acted as a protective surfacelayer. Only textural
evidencein samplesthat preserveremnant reactant gar- Three sets of mineralogical (product-reactant molar-
net and its contact relationships with the product will volume ratios) and environmental conditions can be
reveal the pathway of hematite formation and the rate- identified. Each set results in a specific rate-determining
determining role of the product in such instances.In the mechanism and associatedsuite of surface features on
absenceof information from replacement textures, the partially weathered relics of primary (reactant) mineral
present mineral relations alone of a product assemblage grains (Table 4).
with Vo/V, < I are not sufficient criteria for dismissing l. Removal of Al, Fe, or Mn causesthe formation of
the protective surface-layerhypothesis,or for confirming porous pseudomorphs(in the caseof partial removal of
that the product itself was not rate determining. the least mobile elements) or primary mineral surfaces
Nonconservative behavior of potential coating-form- completelydevoid of any weatheringproducts (in the case
ing Al and Fe (Velbel, 1984a) causesetching of grain of complete removal), interface-controlled reaction ki-
surfaceson some occurrencesof naturally weathered al- netics, and etch pits. Any aluminosilicate or ferromag-
mandine (e.g., Embrechts and Stoops, 1982; Velbel, nesian silicate mineral (including almandine garnet and
1984a, 1987; Graham et al., 1989a).If Al and Fe are presumably other minerals like those listed in Table 3)
removed by inorganic complex-forming anions or organ- can exhibit these features under conditions favoring re-
ic chelating agents in shallow soil solutions (or in the moval of the key elements.
burial diagenetic environment; Hansley, 1987; Salvino 2. A chemical environment favoring Al, Fe, and Mn
and Velbel, 1989), by exceptional acidity in the weath- conservation, operating on a reactant-product mineral
ering environment, or by reduction of Fe in wet, O-de- suite characterizedby V, < V, (V,/V, < l) results in po-
pleted soils, the protective surfacelayer cannot form, and rous pseudomorphs,interface control, and etch pits.
site-selective,interfacelimited attack on the garnet sur- The ubiquity of etch pits and interface-controlled re-
face forms etch pits (Fig. 3; Velbel, 1984a, 1987).Inter- action kinetics on naturally weathered feldspars,pyrox-
mediate cases are also possible; for example, limonite enes,amphiboles,and olivines(e.g.,Figs. l, 2), weathered
(gibbsite-goethite)septa sometimespreservegarnet grain to common oxides, oxyhydroxides,hydroxides,and l: I
boundaries and fracturesbut surround voids from which clays, can be explained by either ofthe above scenarios.
garnethas apparentlybeenremoved(Stoopsetal.,1979; 3. A reactant-productmineral suite charactenzedby Vo
Embrechtsand Stoops,1982;Parisotet al., 1983;Velbel, > V, (V"/V, > l) weathering in a chemical environment
1984a,1987).Thesemight be due either to solid-solution favoring Al, Fe, or Mn conservation results in the for-
effectsor multistage weathering. If the actual garnet con- mation of a protective surfacelayer with smooth, round-
tains insufficient almandine or spessartine component ed surfaceson the reactant-mineralgrain beneaththe pro-
(relative to the end-member values shown in Table 3) for tective surfacelayer and transport-controlled kinetics. Of
the product/reactant ratio to exceedunity, then a porous all the silicate minerals examined to date, only almandine
pseudomorph forms, even if Al and Fe are conseryed. and spessartinegarnetshave ratios greaterthan unity un-
Alternatively, if an early, Al- and Fe-conservingstageis der normal leaching conditions, and then only for certain
followed by a stagein which Al and Fe are mobile, similar combinations of products. This scenarioaccountsfor ob-
textures might result. served features of weathered almandine and spessartine
4t2 VELBEL: PROTECTIVE SURFACE LAYERS IN SILICATE WEATHERING

garnets(and probably staurolite and some epidote group determining mechanisms(transport-control by protective
minerals; seebelow). surfacelayersvs. site-selectiveinterface-limited reactions
The bulk volumetric calculationsand presumedkinetic that produceetch pits) among major mineral groups,under
consequencespresentedhere, although intended to relate various conditions of conservative or nonconservative
to morphologicalfeaturesvisible at petrographicand SEM behavior of key elements. The product-reactant volume
scales,may also be correlated with smaller scalefeatures. ratio is always less than unity for common rock-forming
Reactant-productmineral suitescharacteizedherc by Vo/ silicates(feldspars,pyroxenes,amphiboles, and olivines)
V, < | include those (e.g., feldspar to clay) for which weathered under thoroughly leached, oxidizing condi-
HRTEM studies suggestincoherent structural relation- tions, even for Fe- and Al-rich end-members.This ex-
ships between reactant minerals and their alteration plains why etch pits are ubiquitous and why protective
products, and open, porous, amorphous intermediates surfacelayers of secondaryminerals are not observedon
between the reactant mineral and crystalline clay prod- the common silicates.The product-reactantvolume ratio
ucts (Eggleton and Buseck, 1980; Eggleton and Smith, is greaterthan one for mineral pairs involving almandine
1983; Eggleton, 1986; Tazaki, 1986; Tazaki and Fyfe, and spessartinegarnets and many common weathering
1987a, 1987b;Banfield and Eggleton,1990).Such open products. These volume relationships explain why rate-
fabrics would probably not inhibit transport of solutesto determining, protective surface layers form on Fe- and
or from the fresh mineral surface (Eggletonand Buseck, Mn-bearing garnets (at least under chemical conditions
1980;Eggletonand Smith, 1983;Eggleton,1986).Thus, favoring conservative behavior of Al, Fe, and Mn), and,
the same compositional and structural (volumetric) attri- further, why in the absenceof such chemical conditions,
butes that influence product abundances,porosities, and protective surfacelayers cannot form, resulting in inter-
transport properties at the micrometer scalemay also be facelimited dissolution and etching. Product-reactant
related to those same properties at the nanometer scale volume ratios, transport properties of the products, and
as well. geochemicalconditions that determine the solubility of
The same sets of conditions also relate to specific tex- Al, Fe, and Mn explain the distribution of rate-determin-
tural features resulting from complete alteration of the ing mechanismsand the associatedetch pits and protec-
reactant mineral. These textures are also summarized in tive surfacelayerson naturally weatheredsilicateminerals.
Table 4. Table 4 includes examples of textures from the
lateritic, bauxitic, saprolitic profiles discussedhere,as well AcxNowlnncMENTS
as examplesfrom burial diagenesisof sandstones. I am grateful to Joe D. McKee for asking the critical question at the
The hypothesisthat product-reactantmolar volume ra- right time; Fabrice Colin, Jean Delvigne, Bruno Boulang6,Eduard Bard,
tios predict rate-determining mechanismscan be further Jean-Dominique Meunier, Daniel B Nahon, Alain Baronnet, Enrique
tested.Under Al-conservativeconditions (e.g.,weather- Merino, Duncan F Sibley, and David T Long for useful discussionsof
mineral replacementtextures;Alex E Blum, Robert A Bemer, SusanL.
ing in the vadosezone, below the soil zone where organic
Brantley, Danrel B. Nahon, and Scott Argast for their encouragingand
chelating agentsmight mobilize Al), naturally weathered supportive comments; Danita S. Brandt for penetrating and too-often
staurolite should form a protective surface layer of alu- underappreciatededitorial comments; Eric J Esseneand SusanL Brant-
minous hydroxide weathering products (gibbsite, bayer- ley for their provocative and thorough reviews of the manuscript; and
ite, or nordstrandite)but not of aluminous oxyhydroxides Robert B Gordon for introducing me to the Pilling-Bedworth rule and
the literature on corrosion. Alan S Pooley ofthe Yale PeabodyMuseum
(boehmite or diaspore), whether Fe behaves conserva-
facilitated the scanningelectron photomicrography.This paper was writ-
tively or not (Table 3). Zoisite can form protective surface ten during my sabbaticalleave at the Department of Geology,University
layers of kaolinite, but layers consisting of aluminum hy- ofCincinnati, and revisedduring a visit to the Laboratoire de G6osciences
droxides or aluminum oxyhydroxides will not be protec- de I'Environnement, Universit6 d'Aix-Marseilles III I am grateful to my
colleaguesat both theseinstitutions for their hospitality Initial research
tive (Table 3). Although neither of the two specific epi-
on this project was supportedby NSF grants EAR 80-078I 5 and BSR 85-
dote samplesincluded in the compilation of Smyth and 14328.
Bish (1988) contains sufficientAl * Fe to form protective
surfacelayers,epidote even slightly more aluminous than
RnnnnnNcns CITED
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