l11l

The Canadi an Mine ralo gi st

Vol. 34, pp. I I I 1-l 126 (t996)

OSCILLATORY
ZONINGIN MINERALS:
A COMMONPHENOMENON

MARK SHOREANDANTHOI{Y D. FOWLER'

Oxawa-Carleton GeoscienceCente, Depamnentof Geology,Universityof Ottawa,
140ktuis Pasteur,Ottawa,Ontario KIN 6N5

ABSTRACT

Crystalscharacterized by oscillatoryzoningshow evidencefor a quasi-cyclicalternationin the chemicalcompositionof

discretegtowth-shellsfrom tens of nanometersto tens of micrometersin thickness.Oscillatory zoning is most commonly
observedandstudiedin crystalsof magmaticplagioclase,but sensitiveimagingtechniques(e.9.,Nomarskiinterferenceconffast
microscopy,cathodoluminescence, back-scattered electronimaging,X-ray topographs)reveal its presencein many olher
minerals.Throughthe applicationof thesetechniquesand an exhaustivereview of the literature,oscillatoryzoningis shownto
occur in at least 75 rock-forming and accessoryminerals comprising most major mineral classes:silicates (hydrous and
anhydrous),sulfides,oxides,halides,carbonates, phosphates, and sulfates.Such mineral zoning is a commonbut often
well-concealed phenomenon in magmaticrocks(particularlyalkalineones),hydrothermallyalteredrocks,mineralizedrocks,
andcarbonalesequences. Mechanisms of oscillatoryzoningarediscussed, effectsof adsorptionand
includingthe less-studied
elasficstressin near-surfacegrowth-layers.Its "non-equilibrium chemistry"makesoscillatory zoning a rich subjectfor further
research.

microscopy.
Keywords:oscillatoryzoning,growthbanding,crystalgrowth,nonlineardynamics,Nomarskiinterference

Souuerc

Les cristauxzon6sde fagonoscillatoirer6sultentd'une alternationquasi-cyclique en compositionchimiqued'enveloppes

de croissancedistinctes,dont l'6paisseurvarie de dizaines de nanombtresi des dizaines de micromdtres.Le ph6nomdne
est le plus courammentobserv6et 6tudi6 dans les cristaux de plagioclasemagmatique,mais il est aussi d6velopp6dans
plusieursautresespdces,conrmeen t6moignentles techniquessensiblesde microscopiepaxcontrasted'interf6renceNomarski,
cathodoluminescence, r6partition des 6lectronsr6rodiffus6s, et images topographiquesdes rayons X. L'application de ces
techniqueset un bilan complet de la litt6rature montrent que la zonation oscillatoire a 6t6 document6epour au moins
75 mindraux principaux et accessoiresdes roches,y inclus des silicates (hydrat6sou non), sulfures, oxydes,halog6nures,
carbonates,phosphateset sulfates.Une zonationoscillatoire est corrante dans les rochesmagmatiques,rnais elle peut tre
cryptique,surtoutdansles rochesalcalines,les rochesaffect6espar une alt6rationhydrothermale,les rochesdesgltes min6raux
et les sdquencesde carbonates.Nous revoyons les m6canismesde zonation oscillatoire, et faisons allusion aux r6les de
l'adsorption et de la ddformationdlastiquedansles couchesde croissancesprds de la surface,facteursqui sont moins bien
6tudi6s.Les 6cartsde la compositionI l'dquilibre font de la zonationoscillatoireun riche sujet de recherche.

(Traduit par la R6daction)

Mots-cl4s:zonationoscillatoire,couchede croissance,croissancecristalline,dynamiquenon lin6aire,microscopieh interf6rence

Nomarski.

IN'rRoDUC'noN parallelto crystallographicplanesof low Miller indices

andhavethicknesses rangingfrom tensofnanometers
Mineralscharacterizedby oscillatoryzoningcontain to several tens of micrometers.Although the term
multiple compositionally varying growth-shells "oscillatory"is used,thefluctuationsin zonethickness
(layers,if viewedin cross-section) that are generally andcompositionneednot be regularor harmonic.The
concentration of inclusions,dislocations,andpossibly
point defects also may vary across and between
growth-layers. The zoningin magmaticplagioclase is a
commonphenomenon, so muchsothatpublicationson
r E-mail address.' afowler@acadvml.uottawa.ca the subjectdate back over a century (Rutley 1875,
tr12 THE CANADIAN MINERALOGIST

Herz 1892,Harloff 1927,Phemister1934).Its occur- small-scalegrowth mechanism(s) is responsible,and

rencein other minerals(e.9.,nepheline,augite,zircon) that theoreticalwork has focusedtoo narrowly upon
has been known for nearly as long. However, few plagioclase-meltsystems.
textbooksin mineralogytreat the topic in any detail.
We have used back-scatteredelectron (BSE) OssERvarroNs nt Mn TERALS
imaging, X-ray element maps, cathodoluminescence SHownrc Oscru.tonv Zorwqc
(CL), and Nomarski interference-contrast(NIC)
microscopyto study various minerals,and we review Methodsof obsewation
the large number of published observations of
oscillatory zoning. As will be shown, oscillatory Table 1 documentsthe presenceof oscillatory
zoning visible using the abovetechniquesis typically 2ening in numerousminerals.The data consist of
not visible using standard petrographic or routine publishedobservationsof investigatorswho haveused
microbeamanalyticaltechniques.Oscillatoryzoning is various techniques(optical microscopy,CL, NIC,
considerably more common than may generally be BSE, transmission electron microscopy, X-ray
lsalized (Table 1). In our opinion, its occurrencein topography,and ion, electron,or X-ray microprobes),
many different minerals implies that a gureralized plus our own optical, NIC, BSE, and microprobe

TABLE 1. MINERAI.S${OWINC OSCIII.ATORYZONING

r'lmls Phcpbatg Imdlifals

DimdC(3) ApatireN0) c{2) q3) B(mx@9) AesifiE c{2O

AMbN(4) l[@eda C(41)B(41) lotgm8db AO
PllubogmiE B(31) tutui&oire c{ar) qal)
Sd6d.s,slfN|l8 X@timB(22) Arsile O(2) N(7) B(14)
Clisorotatite O(40)
AsaryydbN(a) Halld6 Conbei& C(O
GaloaN(4) Diopside-l8dsbqgitc C(2) N(7)
Pyite (aL hwoitsYr.) N(4) Flqoilc O(2) q3) JadeiEB(30)
SdcibN(4) Hslite C(2) Kss{ille N(l) C{1)
Sforqudi@ N(4) trlae&iddldHodmlite B(33)
strslsite N(a) C) C(3) TuSdalg Parg8ie N(1) O(1)
Tetohedrn.t@Edre N(4) Richsile O(41)B(41)
Fertqile.hr,tositE C(t Spodm@ X(39)
H&E,hJd$dd6 Scndte-.lore[ib O(t Ilemlie C(3)

Badilkvie q3) Ndodltst6 Pbylhdlbalc

BnftnneO{47)
caNied& N(a) C(2) C(3) Aadndite-gmolr c{z) C(3) r(t8) Biotit O(23)
qrmie (w 'o*ng) B{8) OliviB N(7) C(42) Iipidolle C(3)
colmbile-tmlatire B(34) Tilnte q3) B(t9) MwiteC{17)
Cumdun O(2)C{3) TdDozq3) Phlog!'pibO(2) B(24)
MagnstileN(4) zirc@ NOo) c{2) c(3) B(9) MOI) Pretdb B(12)
Pwskile O(2t)
ryrochl@-ni.roti@ q2) B(U) So(d||et6 Terod|Itg
Rrdle C(2)
At@dleN(r)o(2) 'A&!rda" C(46)
Carb@s,6 Alleile C{2) B(25) Am(thmleM(32)
BpidoEO(O B(14) BcsrsirF{Ba) B(29)
Aikslle B(20) FedialyteC{O Nstselile N(1) O(2)C(3)
calcile NO) C(3) VwisitsB{43)Ql) OrlslreN(44)
DolomitcC(3) wdhlsils q48) Plasisle N(lO q2)
Cegcyi& C(3t si'Fq2) Quatz q3) M(4t
Maemile B(21) C(50) Seidim O?(13)
SidrteC(1) B(1) Ctclodura SodafteO(2)

Srtrde Bdyl o(12) c(3) x(3E)

TmalirO(2) C(3)
Anhyddeq3)
Barte q2) C(3)
Clddle CX36)M(3O

aaMs af ob@6tot O opdlsl misscoly, C: eriodolmiM, B: bd-6oanqd olec1r@foagi[& lvt eleaeM6 i@

ntcoFobe, N: N@6ti Mg@ aoftsq E0etd-ligtt ntcmfcoly, s ch@i@l geidg of etded nhsals, x Xay
topograFy.

RtM ll6stu$,2PdlliDs & Gims (rgtl),3 lrlaBhlll(1988), aRmdolr (19&]),5Palacleet al.(194/-),6b etsL
(1986).7 Clnl er df O9E6).t All@ e, aJ.(1988),9 Pacno e al, (1992),10Pidrp@0992), 11Altm8lc a aL (lgAD, U
sinrmkx & Read(19E6),13 Sdth & Bm O9S), 14Yadtey e, aL (19F1),l5 W a af. (1992),16And$@(1984),17
Royd (19q2),18Jmtwtt (191), 19Palm & Srephtr O92), 20 S@le 090), 2l Pwis O9t9), n *fr'Ils et al. (19y2),
23 KeaL (1981),24 OE,rin a 41.(19S), 25 Sl)Iem (l9l), 26 Edtss (198t, 27 R@sbo0989). 28 Tnim & &w
(19E ,29 RobiM & Orirs 0993),30 R-lc 0993), 31Nider (1981),32Haveue& Natid Oqm,33 Kawa&sts& Yua$lh
09t7),34lrhd 0987); 35PeHse (1990),3?R@drter(L969),38Gwiun a at. O90), 39Arrhir& Zrlo ($rD,40 I,hiIDot8
& GreyO94), 4l D-D.HogFtb,D6s.@, 42 SteleO99l), 43 ce! d aL (193), 44 Diqfs@ Q94!.\ 45 P@'r d 41.OqA,
&Ma1za ql. (l94o),47 s&f.Ils!a at. (t971),48 Msto & Rcr&r (1989).49phakEyA Ir@Ed 0970),50 SpofilO99t).
 OSCILLATORYZONING IN MINERAI-S
observations.We list several minerals in which
oscillatory zoning.either has not been previously
documented(e.9., kaersutite,pargasite,siderite, and
combei@, or in which NIC microscopyhas not been
previouslyusedto studythe fine detailsof suchzoning
(e.g., apatite,calcite, melilite, and nepheline).In total,
at least 75 rock-forming or accessory minerals
$lir
ffi
frjs-ig
b.
t1l3
comprising most major mineral classes(silicates,
sulfides, oxides, halides, carbonates,phosphates,and
sulfates) exhibit such zoning. It occurs in minerals
from magmatic rocks, hydrothermally altered rocks,
rocks in ore deposits,and carbonatesequences.
Oscillatoryzoningis readily observedin plagioclase
and in the clinopyroxene of alkaline rocks because
these minerals commonly occur as large euhedral
crystals that combine significant short-rangecompo-
sitional variation (i.e., growthJayers-l-10 pn in
thickness), with compositionally sensitive optical
properties.These characteristicsmake zoning clearly
visible in the optical microscope.Oscillatory26ningin
other mineralsmay be visible in thin section,although
in many instances its detection requires optimally
oriented crystals in doubly polished sectionsand the
use of a stopped-downcondenserlens. Commonly,
variations in the color or birefringence of minerals
showingoscillatory zoning arelessvisible than arethe
schlieren-likebandsthat arise from small contrastsin
the indicesofrefractionofthe growthzones.
Frc. 1. Back-scatleredelectron photomicrographs;contrast-
optimized300-secondscanson JEOL 6400SEM equipped
with JEOL solid-state detector (Carleton University).
A) Oscillatory zoning in apatite crystal in syenite
(pulaskite)from Mount Johnson,Quebec.The bulk rock
contains0.48 wt.ToP2Os,93 * l0 pg/g l,a and 199 t
20 ytglgCe.Growth zonesin the apatitecrystalvary from
{.6 wt.7o(dark) to *3,6 vt.Eo combinedl,a2O3+ CqO3
@right). Note the very small size of the unzonedcore
(-10 pm), and the asymmetrybetweengrowth layers on
equivalent crystal-faces.The image contrast has been
optimized to enhancethe zoning within the apatite.As a
cotrsequence, the gmin of kaersutiteenclosingthe apatite
crystal, which itself shows oscillatory zoning, appears
black on the image (see Fig. 2E, a photomicrographof
sirnilarly zoned crystal of kaersutite from the same
specimen).A magnetitegrain in the upperright comer of
the frame appearswhite. B) Nepheline phenocryst in
nephelinite, Oldoinyo kngai, Tanzania. The contrast
in mean atomic number is primarily due to variationsin
Fe concentration(presumablyFe3+substituting for Al).
CompareBSE resolutionto that of NIC photomicrograph
of similar crystals(Fig. 2C). C) Siderite-magnesite
crystal
in amygdule in a gabbroic dike, Montreal. The Mg/
(Mg + Fe) of the growth layersrangesfrom 0.55 (darkes0
to 0.29 (lightest). Despite the large variation of mean
atomic number in the crystal (requiring less extreme
contrastthan usedin Fig. 1A), the contrastbetweenthe
adjacent quartz, kaersutite, plagioclase and ilmenite is
barely sufficient for petrographicpuposes.
 rl14

In otler cases,CL (Marshall1988),NIC microscopy secondaryX-ray fluorescencewithin the sample

of etchedcrystals(e.g.,Pearce & Kolisnik 1990),BSE (Goldstein et al. 1992). This limit applies to a point
imaging (e.9.,Halden& Hawthorne1993),or X-ray analysis,line profile, or two-dimensionalX-ray map.
topography(e.g.,Langet al. 1991)may be requiredto Interferometricmethodssuchas NIC microscopyhave
detectzoning.Fundamentals of CL and BSE imaging $eater spatialresolutionthanthe electronmicroprobe,
are given in Marshall (1988) and Goldsteiner a/. but arequalitativein nature.
(1992), respectively.The basic principles of X-ray
topography are discussedin Lang et al. (1991): Texturesand rnicrostructures of crystals
although extremely sensitive to dislocations and showing oscillatory zoning
changesin unit-cell parameters, this techniqueis not
widely used in the Eafih sciences,being best suited The growth layers of crystals showing oscillatory
for large, highly perlect single crystals.Nomarski zoning are typically parallel to crystallographicplanes
interference-contrastmicroscopy uses optical inter- of low Miller indices,and commonlyconcentricwith
ferometry to enhancesmall variations in the surface externalmarginsof the crystal. This finding indicates
relief of a specimen.Polishingrelief emphasizes grain that such crystals maintained a euhedral shape
boundaries;zoningwithin crystalsis bestbroughtout throughoutmuch of their growth.Suchzonedcrystals
by etching highly polished surfaceswith appropriate are generally rather equant; it is considerably less
acid mixtures. Under ideal conditions (1.e., an commonfor crystalswith dendritic,acicular,or highly
unscratchedhighly reflective near-planarsurface), plate-likehabitsto exhibitsuchzoning.Oneofthe few
variationsin surfacerelief assmallas2-10 nm may be exceptionstlat we have observedis plate-like Fe-rich
resolved by NIC microscopy (Nomarski & Weill augite microphenocrystsin certain East African
1954).However,the lateralresolutionis muchpoorer nephelinites.tlightly packedmonomineralicarraysof
(300-500nm). microcrystalline fibers(e.g.,agate:Merinoet al. 1995,
Table I doesnot list every methodthat has been Heaney& Davis 1995)or dendrites(e.9.,sphalerite:
usedto detectoscillatoryzoning in a given mineral. Fowler & L'Heureux 1995) can exhibit banding
Certain well-studiedminerals (e.g., zircon, apatite) similar to oscillatoryzoning,althoughtheir mode of
have been examined with optical microscopy, growth differs from that of singlecrystals.lOscillatory
Nomarski interference-contrastmicroscopy, back- zoning is observedin crystals as small as a few tens
scattered electron imaging, cathodoluminescence, of micrometers[our own observationsof apatitein
electronmicroprobe,protonmicroprobe,secondaryion pulaskite from Mt. Johnson,Quebec,nepheline and
microprobe, X-ray topography, autoradiography, clinopyroxene in nephelinite from East Africa,
fission-trackanalysis,and so on. No singlemethodis and plagioclasein andesitefrom Montserrat;seealso
ideallysuitedfor detectingzoningin all minerals.With Vance (1962) and Cashman(1992) tor additional
back-scattered electronimaging, detectorconditions examplesofplagioclasel,to severalcentimeters in size
mustbe optimizedif very smalldifferences in themean or larger. It may be present from the center to the
atomic numberof the mineral growth-zonesare to be margin of a crystal, but oscillatory zoning in crystals
revealed.Sucha proceduremay not be compatiblewith with an unzonedcore or a monotonicallyzonedouter
routine petrographic and textural examination of margin is fairly common.This is bestdocumentedfor
specimensbecausethe 8-bit dynamic range typical plagioclase(Smith& Brown 1988),but otherminerals,
of digital images currently obtained with scanning such as diopside phenocrystsin alkaline magmatic
electronmicroscopy(SEM)(i.e.,256shadesof grey)is rocks, possesssimilar features (Thompson 1973,
rarely sufficient to show zoning within a mineral and O'Brien et al. 1988,Simonettiet al. 1996).Crystalsof
simultaneouslymaintain adequatecontrast among many minerals showing oscillatory zoning (e.g.,
the various minerals (Fig. 1). Furthermore, our plagioclase,nepheline,diopside, melilite, kaersutite)
experiencewith certainspecimensof kaersutite,augite, contain a rich assortmentof minor strucfuressuch as
and apatite has shown that weak zoning that is sieve-texturedcores, embayedfaces or rounded-off
detectableby optical or NIC methods cannot be cornerE,individual growthJayersthat vary in thickness
resolved even using carefully optimized operating on both crystallographicallyequivalent and non-
conditionsfor the SEM and the detector.Clearly, equivalentfaces,angular"unconformities"and'ocross-
potentialionic substitutionssuchas vIFe3++ ryAl = bedding" between layers, and multicored crystals
vIFe2++ IvSi would causelittle changein the
mean apparentlyformedthroughsynneusis(e.g.,Figs. 1,2;
atomicnumberof a mineral. Alldgreet al. 1981,Anderson1984,Pearce& Kolisnik
In additionto low image-contrast in someminerals 1990). Planar growth-layerscommonly cross twin
characterizedby oscillatory zoning, the spatial planesor incorporatevesiclesor foreigncrystalswith
resolutionof the BSEtechniquemay be inadequate. In little or no disruptionof subsequentlayering.
electron-microprobe analysis,the minimum volume Many of the rocks examined show oscillatory
sampledis on the order of 5-10 pm3, a fundamental zoning in more than one mineral. Our observations,
limit of resolutionimposedby electronscatteringand andtlose of otherresearchers. indicatethat suchzoned
 OSCILLATORYZONING IN MINERAI.S 1115

Frc. 2. Nomarskiinterferencecontrastmicrographsof acid-etchedcrystals,showingcharacteristicminor featuresof oscillatory

zoning.A) Stronglyzonedcrystal of diopsidein leucite-bearinglav4 Mt. Vesuvius.Sectionwas etchedfor about8 minutes
at 20oCin a concentratedIIF-HC1-<itric acid mixture. On a fine scale,zoningis irregular,andmanyepisodesof dissolution
appearindicatedby roundedcorners,embayments,and angularunconformities.This crystal is very similar to thosestudied
by Thompson(1973).Scalebar: 400 pm. B) Melilite (&ermanite) crystalsin nephelinite,Mt. Elgon, Uganda.Sectionwas
etchedfor 5 minutesat 20oCin lU%oHCl. ln addition to melilite, phenocrystsof nephelineand diopsidein this lava also
show oscillatory zoning. Scalebar: 100 pm, C) Nephelinecrystalsin nephelinite,Oldoinyo Lengai (from samesampleas
Fig. 1B). Sectionwas etchedfor 2-3 minutesat 20oCin ll%a HCl. Fine detailsof zoning are similar to thosecommonly
found in plagioclase.Areasof irregular or apparentlyunzonedgrowth are present.Oscillatory zoning is also developedin
phenocrystsand microphenocrystsof clinopyroxene,sodalite,and combeitein this lava. Scalebar: 100pm. D) Detail of a
different phenocrystofnepheline from samethin sectionas Fig. 2C. Regularzoning is sharplytruncatedby a dissolution
surface,and subsequentgrowh is extremelyirregular. This featureis only presentin one comer of the crystal, which is
-2 mm across.Scalebar: 40 pm. E) Kaersutitecrystal in pulaskite,Mt. Johnson.Sectionwas etchedfor 8-10 minutesat
20oCin a concentratedIIF-HCl-citric acid mixture.TransmittedJightmicroscopyrevealsonly broad,weak color-banding;
enhancedBSE imaging did not show *re growth zoning. Scale bar: 400 pm. F) Apatite crystal from samesampleof
pulaskite as in Fig. 2E. Section was etchedfor 30 secondsat 20oC in ll%o HCI. The crystal is partially enclosedin
magnetite(medium grey) and subsequentlyovergrown by pyrite (very light grey). Asymmerical growttt of equivalent
crystal facesis evident,and is likely due to growth that continuedafter the apatitecrystal becameattachedto magnetite.
Compareto Fig. 1A. Scalebar:40 pm.
1116 THE CANADIAN
minerals are particularly cotnmon in alkaline rocks.
For this reason, and because pristine crystals,
particularly those of easily altered minerals (e.g.,
nepheline,metlite), are best found in fresh volcanic
rocks, we examined the University of Ottawa's
collection of alkaline volcanic rocks (varying from
olivine nepheliniteto trachyte) from the East African
Rift, in addition to several samplesprovided by Dr.
Keith Bell of CarletonUniversity. We found that the
majorify (at least3 1 out of 47 phenocryst-bearinglavas
from eight volcanic centers)containphenocrystswith
oscillatory 2sning, most commonly of diopside and
nepheline.Certain of these rocks also contain other
minerals with oscillatory zoning, such as apatite,
titanite, melilite, sodalite, and combeite. Peterson
(1989)describedoscillatoryzoningin phenocrystsof
aegirine-augite,nepheline, and titanian andradite in
highly differentiated peralkaline 1"n1t"1ittes from
ShomboleVolcano, Kenya. Intrusive rocks containing
severaldifferent mineralsdisplayingoscillatoryzoning
also arefound. Using CL, Wenzel& Ramseyer(1992)
studiedoscillatory zoning in apatite,plagioclase,and
K-feldspar from a diorite-to-monzonitesequenceof
rocks.Using optical andNIC microscopy,we observed
fine1y zoned plagioclase, clinopyroxene, kaenutite,
and apatite in syenite and alkaline gabbro from Mt.
Royal and Mt. Johnson,both Monteregiancomplexes
in Quebec. In these rocks, apatite with oscillatory
2sning can be found as inclusions within magnetite,
titanite, and oscillatorily zoned crystals of kaersutite.
Asymmeftical growth-layers within apatite crystals
indicate that oscillatory zoning continued during
growth even as the apatite crystals were being
envelopedby other minerals(Frg. 1A).
Chemicalvariations in minerals
displaying oscillatory zoning
Oscillatory zoning generally does not involve
unusual compositions, but rather "normal"
compositionsthat vary over short distances.In many
rock-forming silicates, oscillatory zoning involves
substitutionof wAl for wSi, plus a coupledsubstitution
to maintainelectroneutraliry@.9.,NaSi;= CaAl in pla-
gioclase). In pyroxenes and amphiboles, more
complicatedsubstitutionsinvolving major and minor
elementsmay apply(e.9.,Thompson1973,Kawakatsu
& Yamaguchi 1987), and in accessoryminerals,
substitution involving minor or trace elementsmay
predominate.The variation in the concenfiation of
major elementswithin an oscillatorily zoned mineral
is strongly constrainedby crystal chemistry and
crystal-liquid equilibria; trace elements may show
much greater variability in concentration le.g.,
diopside:Shimizu(1990);zircon:Chakoumakos et a/.
(1987), Halden et al. (1993); titanite: Paterson&
Stephens(L992)). An extreme example is provided
by a crystal of diopside, in which Shimizu (1990)
MIN ,ERALOGIST
measuredup to 44-fold variationsin the concenfration
of Cr.
Many observationsof oscillatoryzoningshowthat it
is binary, i.e., the short-rangezoning varies between
two stable or gradually varying compositional end-
members. [The end-members may themselves be
complex solid-solutions.lTernary or higher-order
zoning hasrarely beenreportedin the literature.In the
aforementionedion-microprobestudy of an aluminian
diopside ("augite") phenocrystin an alkaline basalt,
Shimizu (1990) detected Fm-scale, large-amplitude
antithetic variation betweencompatible (Cr, Sc) and
moderately incompatible (Ii, V, Sr, Zr) elements.
This result is consistent with electron-microprobe
studiesof other casesof oscillatory zoning in igneous
clinopyroxenes (a.9.,Thompson1973).An interesting
exceptionis a dolomite crystal studiedby Fraseret al.
(1989),in which the concenfrationsof Fe, Mn, and Zn
vary independentlyof eachother.Possiblereasonsfor
this casearediscussedbelow.
In certain minerals showing oscillatory 2ening,the
growth mechanism(s)was sufficiently sensitive to
fractionatesuchgeochemicallysimilar elementsas Nb
and Ta, Mo and W, and k andHJ [e.9., columbite-
tantalite: Lahti (1987); powellite-scheelite: Palache
et al. (1944); zircon: Speer(1982)1.In contrast,in
other occurrences.levels of the rare-earth elements
vary sympatheticallywith thoseof suchgeochemically
distinct elementsas U and Th, and nonradiogenicPb
le.g., zircon: Chakoumakoset al. (1987), Pidgeon
(1992), Halden et al. (1993); titanite: Paterson &
Stephens(1992)1.Becauseof the potentialfor complex
multi-elementsubstitutions,the detailedinterpretation
of zoning detected by BSE requires additional,
element-specificmicro-analytical techniquessuch as
X-ray mapping.
Forrn and.preservationof chemicalzoning
Oscillatory zoning is commonly superposedupon
longer-scale,sning, either normal (i.e., the concen-
tration of less compatible elementsincreasestoward
crystal margins) or reverse. In minerals for which
detailed measurementshave been made" the short-
wavelength compositional 26ning typically has an
asymmetricalsawtoothform, with the less compatible
or lower-temperaturecomponentincreasingsmootbly
outward, followed by an abrupt retum to the higher-
temperaturecomponentat the start of the next layer
[plagioclase:Bottinga et al. (1966),Pearce& Kolisnik
(1990); diopside:Shimizu (1990); columbite:Lahti
(1987)1.Estimatesof maximum short-rangevariations
in proportion of major elementsof -5-10 mol%oin
plagioclase and clinopyroxene have primarily been
determined from electron-microprobeanalysis in
combination with an optical study (Smith & Brown
1988, Thompson 1973). Becauseof limitations of
resolutionfor the micro-analyticaltechniquesused to
 OSCILLATORY
date, the exact pattern of compositional variation
within and between individual growth-layers in
crystals showing oscillatory zoning is unclear. In a
study of oscillatory and sector zoning in authigenic
dolomite crystals, Reeder & Prosky (1986) used
transmissionelectronmicroscopyto observecompo-
sitional layering on a scale of tens of nm. Further
high-resolution studies of oscillatory zoning in
minerals by TEM, analytical electron microscopy,
electron energy-lossspectroscopy,or secondary-ion
mass spectrometrywould be useful. The precise
pattern or waveform of the compositionalzoning is
of interest becausedifferent models predict different
patterns(e.9.,Allbgre et al. 1987,Haaseet al. 1980,
Ortoleva 1990,Jamtveit 1991,L'Heureux & Fowler
1994). However, simple numerical modeling that we
havecaried out demonstrates that solid-statediffrrsion
in magmaticcrystalswill causezoning to relax toward
a lower-amplitude,sinusoidalform, regardlessof the
patternof the original zoning.Even if oneassumesthat
2eningon suchfine scalesas observedby Reeder&
Prosky (1986) could form in magmaticminerals,its
preservationwould seemunlikely. Thus the long-term
thermal evolution of the systemis an importantfactor
to bear in mind for the study of oscillatory zoning,
particularly in mineralsof magmaticrocks.
Minerals with zoning involving homovalent
substitution of low-field-strength elements such as
alkalis or alkaline earthswill be more susceptibleto
diffrrsive homogenizationthan minerals with zoning
involving chargi-compensatedryAl i= rvsi or highl
field-strengthelements.In plagioclase,calculatedrates
of homogenizationare slow enough that fine-scale
zoning is only likely to be overprintedin large malic
intrusions (Grove et al. 1984). It is likely that
preservation potential of oscillatory zoning varies
markedly arnongdifferent minerals.Zortrngin certain
minerals (e.9., plagioclase,clinopyroxene,zircon) is
preservedeven in large igneous bodies, whereas
zoningin others(e.9.,spinels,sulfidesoolivine, alkali
feldspar) appears confined to low-temperature or
rapidlygrownandcooledparageneses.
Exsolution, hydrothermal alteration, and strain-
induced recrystallization may also overprint or
eliminate fine-scale zoning. Studiesof the effects of
metamorphismor deformation on oscillatory zoning
(e.9.,Wayne & Sinha 1988,Pidgeon1992) are few.
In certain minerals, such zoning is known to survive
metamorphismto the middle to upper amphibolite
facies [e.9., plagioclase:Cannon (1966); zircon:
Patersonet al. (1992); allanite: Sorensen(1991);
xenotime:Miller er al. (1992);columbite:Cem! et al.
(1992)1.The reverse situation, i.e., the development
of oscillatory zoning during metamorphism,seems
uncommonbeyondthe specialcasesof mineralization
in skarnsandhydrothermalveins.Examplesof the few
porphyroblasticmineralsfound with oscillatoryzoning
includejadeite in blueschist(Ernst 1993),gamet in
ZONING IN MINERAI,S tttT
eclogite (Dudley 1969) and in phyllite (Anderson&
Olimpio 1,977),and plagioclasein medium-grade
schistQVlenard & Spear1996).A commonassumption
of theoretical models of oscillatory zoning is that
diffusion in the solid phaseis negligibletbroughoutthe
period of growth. This assumptionis not generallytrue
in casesof regionallymetamorphosed rocks.Because
of the paucity of data,suchrocks will not be discussed
further.
Op.rcnqs Zonntc
oF OSCILLATORY
Backgroundinfonnation
In common with most investigators,we interpret
oscillatory zoning as a primary growth-texture.The
euhedral,distinctly planar natureof the compositional
layersindicatesthat suchcrystalsmaintaineda faceted
morphologythroughoutmuch of their growth history,
with the implication that a two-dimensional layer-
spreadingmechanismof growth was operative.Many
observationsofcrystals growlng at low supersaturation
have shown that gowth parallel to partially formed
surface-layersoccursmuch more rapidly than growth
perpendicularto such layers (e.9., Baronnet 1984,
Tiller 1991a, b). Thus, although Pearce (1994)
cautioned that laterally continuous discrete gro*th-
layers do not necessarilyrepresenttime-equivalent
horizons,we considerit reasonableto assumethat they
are at leastcloseto being time-equivalent.
A model of the origin(s) of oscillatory zoning must
explain the abrupt shifts in chemical composition
within and betweengrowth-layers.The oscillationsin
chemicalcompositionareseeminglyincompatiblewith
slow, near-equilibrium growth. Such compositional
shifts appear to violate the second law of thermo-
dynamics because systems cannot spontaneously
reverse their growth composition to lower-entropy
states,given stableconditionsofgrowth. This situation
hasgiven rise to variousphysicalmodelsthat rely upon
cyclic wholesalechangesin pressureo temperature,or
bulk compositionto vary the compositionof the
growing crystal. The interpretation of oscillatory
zoning then becomesstraightforward:the composition
of each layer was controlled by the local (P,TJ)
environment at the time of growth. Satisfactory
explanationsfor such large-scalerepetitive changes
have, however, proved elusive. Many recent
investigatorsexplain the growth as being due to non-
linearities causedby coupling of growth parameters
such that chemical variations spontaneouslyarise.
Indeed, these types of systems,which are termed
'ochemicaloscillators", are now well recognized in
chemistry (Gray & Scott 1990). Theoretical models
of oscillatoryzoning(Sibleyet al. L976,Haaseet al.
1980,Alldgre et al. 1981,Ortoleva1990,L"Heureux
1993,L'Heureux& Fowler 1994)havemainlyfocused
on plagioclase,with someauthorseven consideringit
1118 THE CANADL{N MINERALOGIST
to be a phenomenonrestricted to that mineral (e.9.,
Alldgre et al. l98l).
The presenceof inclusions,cross-bedded growth
layers, resorbedsurfaces,etc., in crystals that have
oscillatory zoning signifies that the causative
mechanismis robust, becausesuch perturbationsin
crystal substratesor local conditions of growth com-
monly have little effect on subsequentgrowth-layers.
[This is additional evidence for a layer-spreading
mechanism of growth.l From our observationsof
oscillatory zoning in severaldifferent mineralswithin
the same rock, we infer that such zoning does not
require exceptionalphysical or chemicalconditionsto
form.
Mechanismsof oscillatory zoning
in mngmaticminerals
Explanations of oscillatory zoning fall into two
broad genetic categories. Extrinsic mechanisms
involve physical or chemicalchangeswithin the bulk
systemthatarepartiallyor wholly independent oflocal
crystallization,such as crystal settling, large-scale
convection,fluid mixing, reservoirreplenishment,elc.
In comparison,proposed intrinsic mechanismslink
crystal growth to purely local phenomena.Primarily,
these involve coupling between the rate of crystal
growth and solute diffrrsion through the crystal-melt
boundary layer. Intermiftent small-scale boundary-
layer convection, buildup and relaxation of elastic
strain due to cell-parametermismatch in zoned
growth-layers,and cyclic "poisoning" by adsorbed
growth-inhibiting ions are also mechanismsthat have
beenmentionedin the literature.
Extrinsic mechanisms(magmatic)
Bowen(1928)suggested thatcrystalsof plagioclase
characterizedby oscillatory zoning were advected
throughout a convecting magma in a chamber,and
differences in temperature,pressure,or chemical
composition within the chamber were reflected in
the composition of the plagioclasegrowth-layers,
assumedto be in equilibrium with the local melt. This
modelremainswidely quoted(e.9.,Singeret al. 1995).
Wiebe(1968)suggested thatpoorcorrelationof zoning
among crystalswas due to late convectivemixing of
different batchesof phenocrysts.Plagioclasecrystals
have densitiesrelatively close to tfiose of common
silicate melts, suchthat their suspensionand retention
are feasible in convecting calc-alkaline or tholeiitic
magmas.However,onewould expectdenserminerals
(e.g., zircon,trtartrte,pyrochlore,andradite,aegirine)to
settleout rapidly, particularly in low-viscosity alkaline
or carbonatitic magmas. In addition, textures
suggestiveof large-scaleconvection (e.g., modal
layering or preferred orientation of minerals) are
commonlyabsentin intrusiverocks,including many in
which mineralsshow oscillatory zoning. Unequivocal
evidence of magmatic convection (e,9., direct
measurements of fluctuations in flow or temperature)
has not yet been obtained, such that it remains an
untested(albeit physically plausible)phenomenon.
Phemister(1934)proposedthat cyclic changesof
dissolvedvolatile species(largely HrO) led to changes
in the composition of the liquidus plagioclase.
Although volatiles can be rapidly exsolved from
magmasat low pressures,and geothermalphenomena
such as geysersare commonly periodic on a short
time-scale,changesin the concentrationof dissolved
HrO at higherpressurewill be bufferedby its solubility
and rate of diffrrsive transport.The dehydration(i.e.,
exsolution,vesiculation,and volatile loss) of a batch
of magma would appearin most casesto be an
irreversible process.It is also unclear how P(H2O)
would significantly affect the compositionof zircon,
pyrochloreand titanite. As wellothis explanationfails
to account for occurrencesof oscillatory zoning in
clinopyroxenein anhydrouslunar basalt (Thompson
1973), plagioclasein (typically H2O-undersafurated)
mid-ocean ridge basalt (Allbgre et al. L98l), and
minerals in pegmatites crystallized from closed-
Vstem, volatile-rich derivative liquid (Lahti 1987,
Cem! et al. 1992).
knportantly, such extrinsic models fail to explain
critical observations, such as tenfold (or greater)
variations in the concentrationof trace elementsin
certain minerals, or the decouplingof geochemically
similar elementsin accessoryminerals.The presence
of oscillatory zoning in a broad range of minerals in
magmaticrocks ranging from mid-ocean-ridgebasalt
to carbonatite implies that some form of general
growth-mechanismis responsible.It has long been
noted (Greenwood& McTaggart1957,Wiebe 1968)
that fine oscillatory layers in plagioclasecannot be
correlatedamongcrystals.On a slightly smallerscale,
we have observedsharply different patternsofzoning
in apatite crystals from Monteregian syenites,even
among crystals of similar size enclosedin a single
amphiboleor magnetitehost-crystal.This is a strong
argument against a simple extrinsic mechanism of
oscillatory zoning.
Intrinsib mechanisms(magmatic)
Many proposedintrinsic mechanismsinvoke feed-
back betweencrystal growth and solute diffrrsion or
surface effects as a source of nonlinearity in the
crystal-growthkinetics. In essence,a growing crystal
is surrdundedby a (narrow) boundary layer that is
depletedin growth constituentswith respectto bulk
liquid; the interplay of chemical diffirsion, thermal
diffirsidn, and rates of crystal growth may lead to
oscillatory (or cyclic) growth-rates and patterns of
chemicalzoning within crystals.Although qualitative
suggestionsalong theselines were long ago proposed
 OSCILLATORYZONING IN MINERATS 1119

for plagioclase(Harloff 1927), zircon (Brammall & aqueous solutions. Explanations proposed for
Harwood 1923), aufi" apatite (Groves & Mourand oscillatoryzoningin thesecrystalscanalsobe divided
1929), the prevalling opinion then was that a stable into extrinsic (e.9., changein solution composition,
steadystatewould rapidly establishitself, with crystal pressure,or temperature)and intrinsic mechanisms
growth constrainedby chemicalor thermal diffusion. (e.9., adsorptionof growth inhibitors).It is difftcult
At any rate, the physical parametersrequiredfor such to isolatethe causesof oscillatoryzoningin minerals
modeling (species diffusivities, pm-scale mineral formed in chemicallyopen aqueoussystems.Such
compositions, partitioncoefficients,etc.) were poorly minerals grow from relatively dilute solutions,
known, and the application of nonlinear differential requiringthatpore-or vein-fillingfluids be exchanged
equationsremainedunexploreduntil the mid-1970s. or recharged manytimesduringmineralizingepisodes.
Pearce(1994) has summarizeda number of recent Nevertheless,evidence is mounting that intrinsic
models(Sibleyer al. 1976,Haaseet al. 1980,Alldgre mechanismsmay play a significantrole, particularly at
et al. 1987, Loomis 1982, Simakin 1983, Ghiorso the microscopicscalein carbonate andsphalerite.
1987,Pearce1993,Wang & Merino 1993).We refer
readersto this review, but add specific comments Extrinsic mechanisms (aqueous)
regardingthe modelof Loomis(1982).
A possible consequenceof a rejected-solute Meyers (1974, 1978) postulatedan extrinsic
boundarylayer aroundcrystals[largely ignoredexcept mechanismthat relatesfine-scalezoning in carbonate
by Loomis(1982),who emphasized therole of rejected rocks to paleohydrogeology.Alternating cathodo-
H2Ol, is the formation of small-scaleconvection luminescentand nonluminescent zonesin diagenetic
currents.Generally,the rejectedsoluteand undepleted carbonate cements were interpreted to be due to
bulk solution will have contrastingdensities.The fluctuations in the concentrationof Fe and Mn.
potential effectsof cyclic gravity-driven separationof Accordingly,the bandsweremodeledto haveformed
crystalandliquid,or depletedandbulk solution,cannot in responseto fluctuating redox conditionsduring
be summarily discounted:for example,convective meteoricdiagenesis. Correlationof similar sequences
instabilitiescausedby as little as 5 ppm Ag or Sn of bandshasled to the conceptof "carbonatecement
can disrupt the gowth of extremelypure Pb crystals stratigraphy"',wherein widely distributedbands are
(Tiller 1991b). However, oscillatory zoning is correlated,andinterpretedto haveformedasa result of
observedin variousmineralswith crystal sizesas small bulk changesin fluid over the scaleof 102-105km2
as 10-30 pm. The smallsizeof suchcrystals,coupled (Meyers 1991).Correlationsare made by matching
with the typically slow rates of crystallizationin "unique" aspectsof samplesfrom the samesequence
geologicalsystems(seebelow), shouldhave allowed or, if correlationsare not uniqueat the fine scale,by
chemical diffusion to reduce density variations "lumping packagesof zoned sequences"(Goldstein
betweendepletedand bulk liquid to a very low level, 1991). Temporal relationshipsare deducedthrough
particularly in the case of growth of accessory stratigraphy,cross-cuttingrelationships,and oxygen
minerals. Therefore, we do not consider boundary- isotopevariationsin cements.
Iayer convection to be a particularly promising At a detailedlevel, Machel & Burton (1991)
mechanismfor the formation of oscillatory zoning. proposedthat concentriczoningin carbonateminerals
Nonlinearmodelsof oscillatoryzoningnotreviewed couldbe dividedinto fwo types:cyclic andoscillatory.
by Pearce(1994) include tfiose of Jamweit (1991), They definedcyclic zoning as a set of two or more
Wang & Merino (1992), L'Heureux (1993), and intensitiesin cathodoluminescence color that occur
L'Heureux & Fowler (1994). L'Heureux (1993) repetitively,and characterized oscillatoryzoningas a
and L'Heureux & Fowler (1994) proposed subsetof cyclic zoningin which zonesof two distinct
constitutionalundercoolingas a mechanismusing intensitiesin color, rarely more than a few pm wide,
experimentallydeterminedgrowth-ratesof plagioclase oscillate.Cyclic zoningconsistingof only fwo zones
and a major componentpartition-coefficient modified canbe difficult to distinguishfrom oscillatoryzoning,
after Lasaga(1982).Oscillatorybehaviorwas found exceptthat color intensitiesof the former"correspond
for geologicallyreasonableconditions without the to zones that are less regular and have dissimilar
need for an arbitrary term to accountfor dissipation thicknessesin comparisonto those of oscillatory
in the growth equation.The mechanismis generally zonation".[Machel & Burton (1991) also statedthat
applicable,but requires well-characterizedgrowth oscillatoryzoning shouldbe avoidedfor conelation
ratesof minerals.[The modelsof Jamweit(1991)and purposes becauseindividualzonescannotbe correlated
Wang & Merino (1992) are summarizedin the next amongadjacentcrystals.l
section.l Evidenceconsistentwith an external control of
oscillatory zoning is present in other minerals
hning in mineralsgrownf'romaqueoussolution of diageneticor hydrothermalorigin. For example,
we noted earlier that Fraser et al. (1989) measured
Manv of the minerals listed in Table I srew from independentvariationsin the concentrationsof Mn, Fe,
tr20 TIIE CANADIAN MINERALOGIST
andZn in oscillatorily zoneddolomite [cf the diopside
crystal studied by Shimizu (1990)1.Becausethese
divalent cationsare all slightly larger (andpresumably
less compatible in dolomite) than Mg, correlated
variationsin their concentrationsmight be expectedif
an inhinsic-type mechanismof zoning had operated.
Episodic flow of fluid during hydrothermal
mineralizationhas been postulated(Cathles& Smith
1983,Sibson1987,Fowler& Anderson1991,Yardley
et al. 1991.,Jamweit et al. L993), and long hiatuses
may separateperiods of rapid crystallization. These
episodes may be responsible for coarse, cm-scale
banding within Mississippi-Valley-typeore deposits,
as opposedto fine-scalebandingthat is interpretedto
be due to crystal-growth dynamics (Fowler &
L'Heureux 1996).In hydrothermalwgs and veins,
medium to coarsegrowth-bands(tens of micrometers
to millimeters thick) have been conelated among
separatecrystalsof tourmaline(Dietrich 1985),apatite
(Knutsonet al. 1985),beryl (Grazianiet al. 1990),and
prehnite and epidote (Yardley et al. l99l). Such
minerals may well have grown in large (tens to
hundredsof meters in dimension) but hydraulically
continuoussystems.
Geographically extensive correlations appear
reasonablewhere applied in a very general fashion,
such as where correlationsinvolve a small numberof
broad growth-bandswithin similar-sized authigenic
crystalsin little-deforrnedsedimentaryformations.The
correlationof individual pm.-scalegrowth-bandsover
distancesof tens of kilometers (e.9., McLimans et al.
1980) is much more problematic,and may be based
more upon the nafiral tendencyto seek patterns in
"noisy' datathan uponthe presenceof truly correlated
growth-bands,such as would be shown by a series
convolution or signal analysis (e.9., Fowler &
L'Heureux 1996). Moreover, it is possiblethat in
some cases,correlationsare due to phaselocking of
chemicaloscillators(whereinchemicalreactionsoccur
synchronouslyover localized regions owing to feed-
back effects: Gray & Scott 1990) and not to external
controls. Oscillatory chemical reactions do not
intrinsically require large variations in fluid tempera-
fure, pressuren or composition(Gray & Scott 1990).
Extremelyfine, laterally continuousoscillatory zoning
is present in sphalerite in many veins that show
textural evidenceof open-spacegrowth, with only a
limited number of discrete events (e.g., brecciation
or change of mineral assemblage).We have
investigated sub-pm zoning of Ag, Sn, and Sb in
decimeter-thicksphaleriteveinsfrom British Columbia
(studiedby Beaudoin1991).Attributingeachof these
tens or hundredsof thousandsof layers to an event
of episodicflow, such as a crack-sealcycle, may not
be necessary,if one considers that similar zoning
can be producedin mineralsgrown in isothermalgels
or unstirredsolutions@eederet al. l99},Puuis et al.
199D.
Intrinsic mechnnisms(aqueous
)
Reeder& Paquette (1989)showedthatsectorzoning
in naturalcalcite commonlyinvolvesthe elementsMg,
Mn, Fe, and Sr. They replicated sector zoning in
syntheticcalcite, and demonstatedthat incorporation
of Mn2+in the solution influencesthe relative growth-
rate of different crystallographicforns. Reder et al.
(1990) induced oscillatory zoning in calcite from
Mn-doped aqueous solutions. The zoning arose
spontaneously,and from isothermalsolutionswherein
the chemicalcompositionwas not changed.Wang &
Merino (1992)mathematicallymodeledthe adsorption
and desorptionof Mn2+ions in calcite growing from
solution. By considering the interaction of the
electrical chargeof the calcite surface(controlled by
pH and equilibrium involving carbonatespecies)with
Ca2+and Mn2+ adsorption,they obtained oscillatory
behavior for certain combinations of growth para-
meters.The applicationof this mechanismto the case
of magmaticmineralswould be difficult.
Jamtveit(1991) proposednon-idealsolid solution
betweenmineral end-membersto explain oscillatory
zoning in grossular-andraditegamet in skarns. An
important point, allowing a damping term in the
growth-rateequationusedby the author,is that strain
within growth-layers should occur owing to the
different unit-cell dimensions of andradite and
grossular(-5.5 Vodifferencein volume).In a study of
oscillatory2eningin syntheticbarite--celestite crystals,
Putnis er al. (1992) also noted that substantialelastic
strain energy would occur owing to the significantly
different unit-cell dimensionsof the two solid-solution
end-members(-I2.7 Vodtfferencein volume).This is
a general phenomenonthat is readily applicable to
minerals of any origin. Briefly, if the equilibrium
composition (based on the P, T, X of the growth
solution) of a crystallizing phasediffers from that of
the crystal substratealready present, then interplay
betweenchemical potential energy and elastic strain
energy could arise even in ideal solid-solutions.A
necessarycondition for this mechanism is that a
minimal amount of crystal-liquid re-equilibration
occur; in other words, the ratio of the crystal
growth-rateto the rate of chen'licaldiffrrsionwithin the
near-surfacelayersmust be large.
Ir4PLIcATroNs
ANDCoNcLUSIoNS
Favoredmtchanismsof growth
In our opinion, the gleat concentration of
researchon the albite-anorthite system has delayed
investigationinto a number of potentially significant
mechanismsof oscillatory zoning. Plagioclase-melt
systemshavebeenintensively studied,and the effects
of changing temperature, P(H2O), and bulk or
boundary-layermelt compositionare well known. The
 OSCILLATORYZONING IN MINERALS
same cannot be said of chemically more complex
minerals such as clinopyroxenes, amphiboles, and
tourmaline.The unusuallysmall variation (<17o)of the
molar volume of plagioclasefrom albite to anorthite
meansthat little elasticstrainenergyis associatedv/ith
zoning in plagioclase,but this is not generallytrue of
other solid-solutions.In addition, plagioclasegxowth
canbe modeledwith soriresuccessby consideringo4ly
the concentrationof major speciessuchas Na, Ca d,l,
and Si. Thus the role of adsorbedions of improper
chargeor radius, alone or in charge-coupledsubstifu-
tions, has beenlargely neglectedin numericalmodels
of oscillatoryzoning,with the exceptionofthe work of
Wang & Merino (1992). The presenceof oscillatory
zoning in minerals that are nearly compositionally
invariant suchasquartz(Pemyet al. 1992)or diamortd
(Lang et al. l99l), cannotbe explainedby fluctuating
ratios of major constituentspeciesin a boundarylayer.
Impurities are likely incorporatedinto suchcrystalsin
an organizedmannermore consistentwith adsorption-
controlledgrowth.
Adsorption of minor or'tace constituentshas been
proposedas d mechanismfor sectorzoning in crystals
gtown from magmas (DpwO 1977) and aqueous
solution (Reeder & Glams 1987), and may be
applicableto;oscillatory zoniqg as well. [These fwo
types of zoning oc0ur together in a number of
minerals.l The large shore,ilnge i'ariations in trace-
element concentrationin soine cases of oscillatory
zoning in crystals seenq. ,to require some form of
disequilibrium partitioning (e.9., Shimizu 1990).
Adsorption is likely to be a less effective inhibitor of
growth in magmasthan it is in low-temperaturedilute
solutions or very pure melts (Baronnet 1984, Tiller
l99la), owing to both the exponentialdependenceon
temperatureof attachmentand detachmentkinetics
(Tiller 1991a)andincreasedsolid-solutionin minerals
at high temperatures, This is not to saythat sucheffects
arenegligiblein igneoussystems.For examplq Beattie
(1994) used a combination of elastic theqry with a
simpfe ionic model of a crystal to successfullymodel
equilibrium olivine-melt partition coefficients by
estimating the lattice-strain energy associatedwith
substitutionalcations.The possible connectionto the
previously mentionedwork of Jamtveit (1991) is
clear. [n many minerals showing oscillatory zoning,
substantial short-rangetensional and compressional
forces must exist within growth layers. Carefully
conftolled experimentson, semiconductorcrystals of
simple compositionhave detnonstratedthat short- and
medium-rangeelastic stresses associated,with
differences in ionic size, considerably affect the
selectionof incorporatedspecies(e.9.,Tiller l99lUb).
A similar argumentcan be made for the electrostatic
forces associatedwith adsorbed ions of incorrect
charge.
In light of the variety of minerals that show
oscillatory zoning and the wide range of their
LL2I
conditionsof formation, we suggestthat suchzoning,
ratherthanbeing pathological(cf Alldgre et al. l98l),
may be a normal result of crystal growth undercertain
circumstances.What those circumstancesmay be is
presently unknowtr, but nature and experimental
igneous petrology hold some clues. Alldgre el a/.
(1981) suggestedthat synthetic plagioclaserarely
showsoscillatory zoning becauseofthe short duration
'of
and larger undercooling experimental runs
(compared to natural crystallization). The typical
absenceof such zoning in experimentalchargesmay
thusplacean upperlimit on growth ratesof plagioclase
and clinopyroxeneof -lFlo m/s. Order-of-magnitude
lower liririts (-10-tl n/s) can be estimatedfrom
limescalesof diffirsive re-equilibration (Grove et al.
1984),crystal-sizedistributions(Cashman1990,L992,
Resmini & Marsh 1995),'heatfluxes from magma
bodies (Brandeis& Jaupart1987), and other galcula-
tions of rirean residence-timesof batchesof magma,
such as uranium decay-seriesdisequilibria (Volpe &
Hammond 1991). In qualitative terms, oscillatory
zoning is'favored by moderatelyrapid growth, on the
order of 10-ll to 10-13m/s for commonrock-forming
magmatic silicates, and proportionately less for
accessoryminerals of smaller size. Clearly, fower
constraintsexist on the growth rates of crystals in
aqueopssystems.
Areasof future research
One reason for the profusion of proposed
mechanismsfor oscillatory zoning is that research
has largely been theoretical, or concentratedon
observatiqnson plagioclase.To our knowledge, no
comprehensivestudy of oscillatory zoning has been
attempted.Such a study would ideally include the
examination of natural occlurences, experimental
synthesis,andtheoreticalmodeling.
Very few of the many published observationsof
oscillatory zoning have been made at the important
10.-100nm scale. hoperly oriented thin foils of
crystalp qhowing oscillatory zoning could give key
information if studied with the transmissionelectron
microscope'combined with energy-dispersionmicro-
analysis.Minerals of igneousorigin would have to be
carefully selectedin order to minimize the "smearing"
effect of prolonged solid-state diffusion at high
temperatures;for this reason,minetalsof hydiothermal
origin might be more suitablefor suchq study.
Experimentalsynthesishas been perhapsthe least
explored approachto the study of oscillatory zoning
(and iq thus possibly the most promising). Very few
controlled experimentshave produced oscillatory
zciningiinminerals,exceptionsbeing Mn-dopedcalcite
(Rcrderet q\.1990)andcelestite-barite solid-solutions
@utnisi et q.l. 1992). However, a number of other
experimentShave produced such 26ning in non-
systematicfashion [e.9., spinel: Wang & McFarlane
rt22 THE CANADIAN
(1968),plagioclase:Lofgren (1980)"majoritegarnet:
Katoet al. (1988),phlogopite: Sun& Baronnet(1989),
ruby: Hughes(1990),diamond:Lang et al. (1991)1.
Carryingout a silicatecrystalllzationexperimentwith
a durationof severalmonthsor yearsposesnumerous
technicaldifficulties. A morepractical alternativeis to
grow carbonate,sulfate, molybdate, tungstate, or
sulfidecrystalsin isothermalgelsor aqueoussolutions
dopedwith minor or trace levels of impurities(e.9.,
Putniset al. 1992). Abanery of suchexperimentswith
different concentrations of reagentand dopants,and
different growth-rates,could readily be carried out
in order to investigatekey factors underlying the
formationof oscillatoryzoningin crystals,including,
one would hope, some factors also relevant to
magmaticcrystals.
Oscillatoryzoning occursin at least 75 different
minerals, ranging in origin from phenocrystsin
magmatic rocks to cementsin sandstone,Further
investigations areneededbothto fully characterize the
details of the zoning found in minerals and to
understandthe underlyingmechanism(s)of growth.
Such an understandingwill be requiredin order to
determinethe significancethat oscillatoryzoningmay
havein determiningthe historyof the hostrocks.
ACKNOWLEDGEMENTS
Financial supportfor this study was provided by a
Natural Sciencesand EngineeringResearchCouncil
(NSERC)scholarshipto M.S. and researchgrant to
A.D.F. The authorsthank Glenn Poirier and Peter
Jonesfor electronmicroprobeandSEM assistance, and
Don Hogarth,Ralph Kretz and Dolores Durant for
readingvariousversionsof the manuscript.Reviews
by B. Jamtveit and E. Merino and editorial and
scientificsuggestionsby R.F. Martin andR.A. Mason
are gratefully acknowledged.
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741-753.
ALLEGRE, C.J., PRovosr, A. & Jaupanr, C. (1981):
Oscillatory zoning: a pathological case of crystal growth.
Nature 294,223-228.
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