AmericanMineralogist,Volume70,pages549-558,1985

distribution of nickel in hydroussilicatesfrom New Caledoniaore deposits

Heterogeneous
Ar,,lnr M,q,l.rcenunxo Gnoncps Clus
Laborstoire de Miniralogie et Cristallographie,LA CNRS 09
Uniuersitisde Paris 6 et7
4 placeJussieu75230Paris Cedex05 France
and
Lqboratoirepour I'U tilisation ilu RayonnementElectromagnitique
( LU RE),CN R5,91405OrsayFrance

Abotract
Four nickel-bearingclay mineralsfrom New-Caledoniabelongingto the lizardite-nepouite
and the kerolite-pimelite serieshave beeninvestigatedin order to study the mechanismsof
Ni-Mg substitution. Local order around Ni was determined by optical absorption spec-
troscopy and X-ray absorption spectroscopyat the Ni-K edge.Optical spectrahave been
reinterpretedthrough the Kubelka and Munk formalism which lead us to reject the optical
evidencesfor the trigonal distortion of the octahedralNi site. New data were also obtained
concerningMg-Ni ordering in theseminerals.Analysis of the ExtendedX-ray Absorption
Fine Structure(nxers)indicatesthat the intracrystallinedistribution of nickel is not random:
Ni atoms are segregatedinto discretedomains,the minimal size of which have been calcu-
lated and are interpreted differently dependingon whether the mineral belongs to the 7A
(solid state transformed)or to the 10A (solution precipitated)structure type. This departure
from ideal behavior of the Mg-Ni substitution is compared to the chemicaland structural
variationsinvolving modulatedstructures.Theseheterogeneities seemto be quite common in
low temperatureformation conditions.

Introduction other phyllosilicatesare still scarce(Brindley et al., 1979).

Nickel concentrationsresulting from the weatheringof
ultrabasic rocks under tropical conditions have been the
subject of numerousstudiesin order to understandbetter
the physico-chemicalprocesseswhich lead to these ore
bodies. Their complex mineralogy is characterizedby a
mixture of various hydrous silicates,often referred to as
"garnierites".The two main minerals(Brindley and Hang,
1913)are lizardite (serpentine)and kerolite (10A talc), the
nickeliferousend-membersof which are nepouite (Maksi-
movic, 1973;Brindley and Wan, 1975)and pimelite (Mak-
simovic, 1966; Brindley et al., 1979),respectively.Associ-
ated phasesinclude smectitesand more rarely chloritesand
sepiolites.Intimate mixing of 10A and 7A phasesis cleaily
exhibited on X-ray diffraction patterns and has been con-
firmed recently by high-resolution electron microscopy
(Uyeda et al., 1973;Pelletier, 1984).It is thereforeusually
diffrcult to obtain monomineralic phasesby mechanical
separation.
Severalstudieshave already been published concerning
optical absorption spectra of 1: 1 Ni-hydrous silicates
(Nussik, 1969; Lakshman and Reddy, 1973; Faye, 1974)
but only recently was the crystal chemistryof Ni in these
phasespreciselystudied by thesetechniques(Cervelleand
Maquet, 1982).These authors concluded that Ni2+ ions
are in 6-fold coordination and occupy sites of C." sym-
metry in lizatdite. Spectroscopicdata concerningnickel in
0m3-{04x/85/0506-0549$02.00 549
Furthermore the local order beyond the first coordination
shell is not known in any of thesephasesand limits knowl-
edgeof the substitutionprocesses in theseMg-Ni minerals.
In this paperwe presentfirst resultsof a systematicstudy
of nickel-bearingphyllosilicates(Manceau,1984)by means
of various spectroscopictechniques.Diffuse reflectanceand
K-edge absorption spectroscopies are used to obtain pre-
cise crystal chemicalparametersconcerningthe first coor-
dination shell whereasExtended X-ray Absorption Fine
Structure (nx.rns)gives data on local order at a scale of
severalangstroms.The resultsobtained on carefullyselect-
ed new-caledoniansamplesare used in discussingintra-
crystalline distribution in the two main series, namely
lizardite-nepouiteand kerolite-pimelite.
Location and characterization of the studied samples
The nickel ore depositsof New Caledoniahavebeenextensively
investigated(Trescases,1975; Troly et al., 1979; Pelletier, 1984).
Three horizons may be separatedin the alteration zone: (l) the
ultrabasicparent rock, mainly of harzburgiticcomposition;(2) the
silicated zone resulting from hydrothermal alteration of this
parent rock and consistingof primary lizardite, which was subse-
quently transformedby supergeneprocesses;(3) the lateritic zone,
mostly consistingof Fe-oxyhydroxides.Nickel-bearingclay min'
erals originate either from transformationof primary lizarditesor
from solution precipitation (neoformation) in cracks. For this
study we have selected a Mg-Fe-Ni lizardite, a pimelite and a
Mg-Ni kerolite which weresampledat Poro and Nepoui Mines in
 MANCEAU AND CALAS: DISTRIBUTION OF NICKEL IN HYDROTJS SILICA.TE9

veins inside the silicated zone underlying the lateritic zone. The
two latter samplesare characteristicof the most abundant Ni-
containing neoformedmineralsof the garnierites.A nepouite was
also collected at Kongouhaou Mine near Thio where it occurs
together with weatheredchlorite in veins cutting the silicated as
well as the lateritic zones.
First, all sampleswere hand-pickedwith care under a binocular
microscope and homogeneousparts of the garnierites were
chosen.Then, only the pure phaseswere selectedby means of
powder X-ray diffraction, and characterizedby ScanningElectron
Microscopy (SEM) and Transmission Electron Microscopy
(TEM) associatedwith electronmicrodiffraction.Nepouite occurs
as well individualizedmacrocrystallitesof 0.2 to 1.0mm thickness
(Fig. 1a). It is made up of regularly superimposedlayers which
result in the transformation of chlorite. The internal texture of
thesecrystalliteswas revealedby TEM to be constitutedof platy
particleswhich display a mosaicstructure(Fig. lb). Becauseof the
excellentcrystallinity the X-ray diffraction patterns exhibit very
strong basal reflections.Contrary to the nepouite,the Mg-Fe-Ni
serpentineshows tiny particles of about 4O0Asize with regular
rims of a lizarditeJike mineral (Fig. tc). Kerolite and pimelite
exhibit a l0A basal reflection and their behavior with ethylene
glycol and heat treatments is characteristicof these minerals
(Brindley et al., 1977).Aft€r treatment with ethyleneglycol for 15
hours,one cannot observea definitemaximum ofthe 001 peak; in
somesamplesthe apparentbasal distanceexpandsfrom 9.36A to
about 16A whereasin others little expansionoccurs(Fig. 2). This
differencein expansivityamong samplesdependson severalpa-
rametersincluding layerchargeand stackingdisorder.
Chemical analysesby atomic absorption sp€ctroscopyare re-
ported in Table 1. The low totals of oxidesmust be attributed to
the high HrO+ content occurring in theseminerals(Brindley and
Wan, 1975;Brindley et al., 1979;Gerard and Herbillon, 1983).In
contrast with kerolite and pimelite, lizardite contains varying
amounts of iron dcpendingon its origin (Pclletier, 198a).Signifi-
cant amounts of iron (i.e., more than 1.5%) indicate a primary
(hydrothermal) origin followed by supergene transformation
whereasiron-poor phasesare neoformed(secondary)in garnier-
ites. The structural formulae were calculated assuming a total
cation chargeof 14 per unit cell for l: I phyllosilicates,and of 22
for 2:l phyllosilicates.Tetrahedral positions are filled with Si
atoms together with Al and trivalent Fe to ensurea number of
two 4-fold coordinatedatoms in TO clay mineralsand four atoms
in the TOT series.Octahedralsitesarc filled with (Mg,Ni) atoms
and with the remaining Al and Fe3+. The main featuresof these
analysesare that tetrahedralcations exc€edtwo atoms per unit
cell in the studied serpentinesand are slightly less than four in
talc-like samples.Thesedeviationshave been repeatedlypointed
out by Brindley et al. (1977, 1979)and Gerard and Herbillon
(1983).They are consistentveiththe assumptionof lizardite impu-
rities intimately mixed with 2: 1 layers in the kerolite-pimelite
seriesand with the pr€senoeof silica gelsand possibly2:l minor
phasesin the lizardite-nepouiteseries(Pelletier, 1984; Manceau,
1984).

Spcctrmcopic chsracterizetion of the Ni-site

Nickel crystal chemistry was studied by means of two
spectroscopic techniques: diffuse reflectanc€ spectroscopy
and Ni K-edge structure using synchrotron radiation. Both
Pig. l. (a) Scanningelectronmicroscopephotographsofa mac-
techniques are related in that they give the same kind of
rocrystalliteof nepouitefrom Thio. Scalemarks 50 pm. (b) Trans-
information concerning the first coordination shell, i.e., oxi-
mission electron micrograph showing a detail of the nepouite
dation state, coordination number, site distortion and layers.Scalemarks 1 pm. (c) Transmissionelectronmicrograph of
metal-ligand covalency. The determination of the actual a Mg-Fe-Ni lizardite.Scalemarks800A.
 551
MANCE,AU AND CALAS: DISTRIBLJTIONOF NICKEL IN HYDROT]SilLICATES

distortion, with significant differencesdepending on the

nickel concentration in the mineral. This site symmetry
agreeswith the structureproposedby Pavlovic and Krsta-
novic (1980)from X-ray diffraction. Our purposeis thus to
comparethe Ni-behavior in the two main hydrous silicate
familiesof the garnierites.

Discussionof the optical absorption spectr&

mode, with BaSOa as a reference,in order to study the

powdersalready characterizedby the previous techniques'
ihe obtained reflectancemeasurementsare subsequently
transformedinto a remissionfunction
F(R): (1 - RF/2R
which is equivalent to the absorption coelficientdeduced
from the Beer-Lambertlaw (Wendlandt and Hecht' 1966)'
On a wavenumberbasis, the spectra may be frtted into
|| gaussiancomponentsin order to discusssite energiesand
a. ze to 3' ao
t3 symmetry (Men-
fossible departure from pure octahedral
Fig. 2. X-Raypowderdifrractionpatternsof keroliteand pi- dell and Morris, 1982)'
melite:behaviorwith ethyleneglycol(EG) and heattreatments' Referencefor octahedralsymmeny: nickel hexahyiltate'
CoKc radiationl" 20lmn. Optilal absorption spectrumof aqueoussolution of nickel
,uifut" i, known to be characteristicof a pure octahedral
(Burns, 1970; Cotton and Wilkinson, 1968)'We
site symmetry of nickel in lizardite was rec€ntlypublished Ni site
recordedthe spectrumof a 0.5M solution as a basis
by Cervelleand Maquet (1982)on the basisof optical ab- have
sorption spectra.These authors concluded that the octa-
hedral sites occupied by the Ni atoms exhibit a trigonal

Table 1. Chemicalanalysisandstructuralformulaeof Mg-Fo-Ni

(N),Mg-Ni kerolite(K) andpimelite(P)
lizardite(L),nepouite ments of the responsibletransitions are reported in Table
2. It is to be pointed out that the intense spin-allowed
transition at 8510 cm-1, which is directly related to the
sto2 42.20 32.50 52.7t 45.00 crystal field splitting, has a pure gaussianshape:this con-
Ar2o3 0,r5 1.43
Fe203 2.57 t,57 0.l r 0.25
Mgo 35.00 4.47 2 1 .l 0 3.04
Nlo 4,50 4 7. 5 7 14.39 38,94
Tota 1 84.42 8 7, 6 t + 88,31 87,23

st 2.06 3.79 3.82

AI 0.0I
F e (I I I ) 0.01 0.02
Tetr. 2,06 2.00 3.80 3.84

A1 0.0t 0.09
F e (I I I ) 0.09 0.07
Mc 2.55 0.41 2.26 0,38
Nl 0.18 2.14 0.83 2.66
* 3.09 3,04
oct. 2,83 2.99

----5* Fig. 3. Optical absorption spectrumof aqueousnickel sulfate'

n2l + r/zn3+ Thc absorbanceis plotted versus wavenumber(crn-l). Dott€d
New Caledonta'
L Poro' New Caledonia.
K Nepoul, ldew Caledonla.
N Thlo'
P Poro, l'leu CaLedonla' line: experimentalsPectrum.Solid line: gaussiandecomposition
and sum of the gaussiancomponents.
 552 MANCEAI] AND CALAS: DISTRIBUTIIN oF NICKEL IN HYDRIUS SILICATES

Table 2. Assignmentof absorptionbands in the visible and near- The identity of the values obtained in the kerolite-
infrared obtained by decompositionof the optical spectra with pimelite seriesdemonstratesthat the Mg-Ni substitution
gaussrancomponents processesdo not afect the nickel crystal chemistry; this
Nature of the Aqueous solutlon kerollte information is important in view of the ex.cFsevidenceof
transllion
3a2,
fron of Nl 6ulfate heterogeneous substitution in theseminerals.On the other
the tevel
hand, the marked differencein crsr values betweennep-
Energy sidth Energy oidrh
(cn')
ouite and Mg-Fe-Ni lizardite is explainedby the structur_
(cn-r)
al modification which occurs in this series at high Ni-
3 r r r {r ) contents.One of the principal characteristicsof the serpen_
8510 2484 2435
tine mineralsis a "misfit" betweenthe tetrahedraland the
trr<ol
/
13868 2338 13575 1656 octahedral sheet.The a,b parametersof the latter being
ttr"(r)
) r5L26 ll20 15377 2143 much higher than those of the tetrahedral sheet, this
16302
)
2143 17325 3750 implies a structural modification for juxtaposing thesetwo
sheets.In lizardite there exist two non-equivalentMg sites,
ftrrto) |
'Al(c)
2rE55 1461 22342 2679
which reducesthe lateral cD dimension of the octahedral
| 23900 l5s8
sheet (Krstanovic, 1968; Pavlovic and Krstanovic, 19g0;
'T (P)
I 25460 3068 25800 3tl7 Mellini, 1982).The marked differencein the crsr values
between nepouite and Mg-Fe-Ni lizardite may be ex-
plained by a structural modification ofthe octahedralsheet
leading to only one cation site and bringing about a de-
firms the octahedral(Oj point symmetry of the site. The creaseof the b parameter (Cervelle and Maquet, 19g2).
other transitionsat higher energyare rather more complex: This structural modification is possiblebecausethe Ni2+
spin-orbit coupling may act on the splitting of the 1Tr, ions are smaller than the Mg2* ions (0.77A and 0.g0A
band, as in crystalline nickel sulfates (Lakshman and respectively,Whittaker and Muntus, 1970).
Jacob, 1983).We ensuredthat the optical spectradeduced
Structure of the Ni K-edge
from reflectanccmeasurements through the remissionfunc_
tion F(R) give similar results in the caseof non-distorted The use of X-ray absorption spectra for the study of
sites(nickel-dopedmagnesiumand ammonium-magnesium chemicallyor structurally disorderedsystemshas recently
hydrous sulfates,nickel fluosilicate),mainly basedon the grown with the generalizeduse of synchrotron radiation.
pure gaussianshapeof the absorption band related to the The radiation is utilized as a powerful white-beamX-ray
crystalfield. source with various kinds of applications in mineralogy
Optical spectraof Ni-hydrous silicates.All the recorded (Calas et al., 1984).Two distinct parts of the spectracon-
spectraexhibit three absorption bandscharacteristicofsix_ tain different kinds of information: the detailedstructureof
fold coordinateddivalent nickel (Marfunin, 1979).The cor_ the K (or Z) edgeof the studiedelementand the Extended
responding remission functions may be decomposedac_ X-Ray Absorption Fine Structure (ex,us) which will be
cording to the same schemeas for the undisturbed octa_ treated in the following section.The K-edge structure and
hedral site, using gaussian components with about the energy position carry information about oxidation state.
samewidth (e.g.the kerolite spectrum:Fig. 4 and Table 2).
The disagreementwith the previous data (Cervelle and
Maquet, 1982)arisesfrom the useof the remissionfunction
insteadof the raw reflectancedata: theselatter_although
they give correct valuesof the absorptionmaxima__donot
E

z
I
F
o
z
f
u

z
o
o
o
t!
E

2g.ooo 2o.ooo t2.ooo cM-r

accuracyof the crse valuesis about *0.1 kCal/mole. The Fig. 4. Optical absorption spectntm of kerolite. The absorb_
CFSE decreases in the following order: ance is plotted versuswavenumber(crn-r). Dotted line: experi_
mental spectrum- Solid line: gaussiandecompositionand sum of
nepouite> pimelite : kerolite > lizardite. the gaussiancomponents
 gLICATES 553
MANCEAU AND CALAS: DISTRIBUTION OF NICKEL IN HYDROUS

Table 3. Crystal chemical parameters of nickel in the investigated minerals

Ni-o distance Ni-Ni disranc" Average

$to
oq=o a"ru$$ b i n" Tt:hle: : :s"e"cior nl d
i ' l ls ,h e l l dimension
of
(".-l; Kcal/nole paranete! Structural nickeliferous
X-ray
I E\AFS ExAFs EXAFS donains
diffraction
(A) ([)
fornulae
b/3

Nis0, (H^0). ,o ,
8s00
solution
Reference
2.09 2.95 t2 t2
Nio

Reference
compound 8950 3 0. 1 o t1 2.08 3.04 3,04
Ni-talc
Pimelite r.05 3.05 5,3 5.4+0,5
8950 3 0 .7 9.14 2,O65
(P)

Nepouite 2.Oa 3.06 4.j 5+0.5

9120 31.3 9,t7 J.Ub
(N)
Mg,Ni kerolite 3.05 3.05 r,7 4.7+0.5 lsA-408
8950 3 0 .7 9.15 2.07
(K)

Mg, Ni, Fe
8845 30.4 9.20 2.09 3.O7 3.05 0.4 4.9+0.5 I8A-5oA
lizardite
(L)

StO
Oo = crystal Field Splitting.
S$catt = stabilization Energy.
crystal Iield

coordination numbr, site distortion and m€talJiSandco- energyon oxidation state and coordination number in Fe
valency.As the theoreticalaspectsare not preciselyknown silicatesand a comparabletr€nd in Ni silicates,the posi-
yet, it is necessaryto work by comparing the studiedsam- tion of this inflexion point suggeststhat Ni in these hy-
ples with well known referen@compounds where these drous silicatesis divalent. The splitting of the maximum
veriouseffectsmay be clearlyseparated.
The spectra were obtained at the Laboratoire pour
I'Utilisation du RayonnementSynchrotron,Orsay, France
(runn) using the radiation of the DCI storage ting (1.72
GeV). The experimentalapparatus has already been de-
scribed (Raoux et al., 1980).High spectral resolution is
obtained with a "channel-cut" monochromator using the UJ
400 reflection of silicon. Intrinsic limitations (coreJevel o
z
width) and experimentalconditions permit resolution of @
featuresseparatedby about 1.2 eY. However, becauseof tr
o
the excellentstability of the beam, it is possibleto detect (t
rD
relativeenergyshiftsas small as 0.2 eV.
Absorption K-edges of nickel in the studied clay min-
erals are shown in Figure 5 together with two reference
samples,a 0.5 M aqueous solution of nickel sulfate and
LaNiO3 (Ni3+: Crespinet al., 1983).Of the variousedge
features,only the pre-edgeregion is well known. It occurs
on the low energyside of the edgeat about 8326eV, which
is attributed to a transition of ls electronsto 3d orbitals
through a partial hybridization with the 2p oxygen ot-
bitals. Its low intensity may be partly explained by the
presenceof only two holesin the 3d-like levelsin the diva-
lent nickel (3dsion) but the predominantfact is that nickel
is in octahedralsites:the tetrahedralsymmetryis known to
enhanaesignificantly this pre-edge,as was shown in Ni- 8320 6340
containing glasses(Petiau and Calas, 1982).The first in- ENEnGY(cv)
flexion point may be usedas an indication of the oxidation Fig. 5. X-ray abeorptionrK-edgestructureof Nr in 6fold coor-
state of the metal: it shows a 3.8 eV shift towards the dinaiion: a) aqueous nickel sutfate (0.5 M); b) LaNiO3 (Ni3+)
higher energiesin the Ni3* referencevs. the aqueoussolu- from Crespin et al., 1983;c) nepouiteand Mg-Ni-Fe lizardite; d)
tions of Ni2+. Basedon the observeddependenceof edge pimeliteand Mg-Ni kerolite.
 554 MANCEAU AND CALAS: DISTRIBUTI1N oF NICKEL IN HYDR}US ,ILICA.TES

K-EDGE
STRUCTURE

(U
(J

C
not to vary much, in agreement with the conclusions ro
reachedfrom the optical spectra.Moreover, it may be con_ €
C-
cluded that neither optical nor K-edge spectraprovide evi_ o
dence for significant amounts of Ni3+. Trivalent nickel t4
would have given specific additional features on optical €
spectra. Furthermore, the oxidation state, which cin be

Energy (eV)
I s00 Be00
recent study of the Ni .'pre-edge"peak of these samples Fig. 6. Whole X-ray absorption spectrumat the Ni K-edge of
under high resolution conditions (Manceau and Calas, to nepouite showingthe edgeregion and the exAls oscillations.
be published)showedno shift of the maximum relative to
hexa-aquaNi2 + complexes in solution. The exers is basically an interference phenomenon be-
Distribution of nickel in the octahedral sheet tween the photoelectrons ejected at the absorption edge
and those which are backscattered by the various sur-
The possibility of a clustered(heterogeneous) arrange_ rounding atomic shells. It may be described by a sum of
ment of a certain type of cation in octahedral sheetsof darnped sinusoids which
depend on the pbotoelectron
phyllosilicates versus a random (homogeneous,arrange_ wavevector k
according to the relationship
ment cannot be evaluated by the previously used spec_
troscopic techniques,which are only sensitiveto the first I
/(k) :; Aj(k) sin (2kR,(k)+ /dk))
coordination shell.In contrast ExtendedX-ray Absorption K =I
Fine Structure(nnrs) which extendsto severalhundred eV
abovean absorptionedgecan give information about first, wherethe index j refersto the scatteringby the jth atomic
second,and in certain cases,more distant shells.This tech_ shell.R, is the distancebetweenthe absorberatom and the
nique is particularly suitablefor structural studiesofamor_ jth shell, ti is a phasefactor due to both the central and
phous and poorly organizedcompoundsand has beenap_ the backscatteringatoms,and A(k) is the amplitudefactor
plied to various mineralogical systems(seethe review of
Calas et al., 1984).The information obtained involves in- N.
A,ft)
r'
: -+ fj(k, n)s-2o?k2e-2Rtt
teratomic distancesbetweenthe absorbing atom and the Ri,
first coordination shells and the number and chemical where N, is the coordination number on the jth shell,
nature of neighborsin the shell; generallythe nearestand flk, a) the backscatteringamplitude function correspond-
next-nearestneighborsmay be studied and in simple sys_ ing to the atomic specieson this shell, o, is the standard
temssomeinformation may also be derivedconcerningthe deviation of the R, distances and,), the mean free path
third coordinationshell.
length of the photoelectron.
Acquisition and analysis of EXAFSspectra To ensurethe reliability of the comparisonbetweenthe
studied sampleswe have used the sameparametersin the
The experimentaltechniqueis the same as for study of analysisprocedurefor all of them. First the X-ray absorp-
edgestructure,although the spectralresolution in exers is tion background A(O) is removed from the experimental
not as important as for study of edgestructure.For com_ spectrumby substractinga Victoreen function in a region
parison purpose all the spectrawere recordedin the same beginning about 300 eV below the absorption edge.The
experimental session during dedicated runs at LURE. mean absorption A(1) of the sampleabove the edgeis ob-
Figure 6 showsthe X-ray absorption spectrumof nepouite tained by fitting a polynomial function. The sxAFsoscil-
near the Ni K-edge.One separatesthe edgeregion which lations X(E)(Fig. 7) are obtainedfrom
was studied in the previous sectionfrom the nx.cFswhich
beginsfrom about 60 eV to severalhundred eV above the r(E): (A(E)- A(1))/(A(1)
- A(o),
absorption edge.The theory of K-ex,tFSis now firmly es_ where A(E) is the experimental
absorbance.The energy
tablished (Lee et al., 1981)and a quantitative analysisof scale(E) is subsequentlyconverted
into a wavevectorscale
the experimentalspectrais thus madepossible. (k), by choosing the referenceenergy Eo at the inflexion
 MANCEAU AND CALAS: DISTRIBUTION OF NICKEL IN HYDROUSilLICATES )))

ct)
l!

x
tu
o
UJ
N
J

tr
o
z

Fig. 7. Normalizednx*s of the nepouite.Normalized ln(Ig/I) is plotted versusphoton energy(eV).

point of the Ni K-edge (Eo: 8340 eV)' A Fourier trans- SECOND SHELL
form is performedon the function k'xft). As the shapeof
the windows used for computing this Fourier transform
may strongly influenceit, we usedconstanttransformation
a flat window in the range 3.7A-1-ll.2l-r
"onditionr, 1
endedon both sidesby a cosinefunction of 0.5A- width.
The magnitudeof this Fourier transform concerning the
four mineralsstudiedin the previoussectionis reported in
Figure 8, together with the Ni-talc (willemseite)as a refer-
encecompound whoseMg analog has a well known struc- z
ture (Rayner and Brown, 1973). It is possible to get the o
contribution of a definite shell to the nxlrs by backtrans- -
o
forming the correspondingpeak on the Fourier transform tr
into the k-space.Figure 9a shows the damped sinusoid o
obtained by backtransformingthe secondpeak of the wil- o
lemseite.The interatomic distancesare calculatedby using
theoreticalphaseshifts r/(k) (Teo and Lee, 1980).The valid-
ity of these phaseshifts was confirmed by studying crys-
talline references,namely willemseiteand bunsenite(NiO).
On account of the agreementof the ExAFsdata with the
actual Ni-O and Ni-Ni distancesin thesccompounds,the
accuracyof the distancemeasurementsis estimatedto be
0.02A; a relative precisionof about 0.01A may be attained
by comparing spectra studied under identical treatment
conditions.
The first peak of the Fourier transform (Fig. 8) is as-
sigrredto the oxygencoordination shell: the corresponding
Ni-O distancesare reported in Table 3. They confirm the
octahedralsite of nickel in all the studiedcompounds'The
secondpeak correspondsto the next nearestneighbors,Ni'
Fe or Mg. It is assignedto the Ni-Ni distancein NiO and
Ni-talc, but we must discussin more detail the chemical Fig. 8. Comparisonof the partial distribution function (Fourier
nature of the atoms constituting this shell for the minerals transformmoduluscurve)of the ExAFsspectraat the Ni K-edgeof
which havea more complexcomposition. five Ni-bearing clay minerals.
 556 MANCEAU AND CALAS: DISTRIBU.TrcN oF NIjKEL
Fig. 9. Fourier filtered contribution of the secondshell (dotted
line) and the correspondingcalculatedcurve (solid line) basedon
theoreticalphaseshift and backscatteredamplitude valuesof Teo
and Lee (1980):a) nepouite:6 Ni neighborsat 3.06A; b) Ni_talc:
Ni atoms are surroundedby 6 Ni neighborsat 3.04A;c) the same
sampleas d), but calculationsare performed by assuming6 Mg
neighborsat 3.07A: the fit is clearly unacceptable;d) Mg-Fe-Ni
lizatdite:4.4 Ni neighborsat 3.06A.
Euidence for heterogeneous distribution of nickel
The nickel end members of the two series under investi_
gation are characterized by a second shell constituted onlv
IN HYDR)T]S ilLICATES
by Ni atoms. As b/3 is equal to the metal-metal distance,
the Ni-Ni distanceswhich are calculatedby nx.lrs analysis
are comparedto the bl3 valuesobtained by X-ray difrac-
tion from the 06.33reflectionin Table 3. The good agree-
ment betweenboth techniquesconfirms the validity of our
analysis.
The study of mineralsof low Ni-content is more diflicult
to perform becausesome assumptionsmust be made con-
cerning the constitution of the secondshell around Ni as
the phaseshifts ry'(k)dependon the chemicalnature of the
backscatteringatom. We performedtwo calculations,first
by assuming that all the atoms of the second shell are
transition elements(Ni and Fe have similar backscattering
phases and amplitudes and cannot be distinguished by
ExAFs),then by assumingonly Mg atoms in this shell.The
structural constraint is given by X-ray diffraction of these
minerals which shows that the b parameterand thus the
cation--cationdistancesare close in the kerolite-pimelite
and in the nepouite-lizarditeseries(Table 3). This may be
explainedby the similar ionic radii of Mg and Ni (0.80A
and O.77 A, respectively).
The fact that the interatomic distance is well defined
allows us to overcome the indetermination about the
nature of the secondnearestneighbors.This is true because
the distancedeterminedby rx.lrs variesdependingon the
type of backscatteringatom, and inverselyit is possibleto
determine its type by knowledge of the. actual distance.
Distancedeterminationis made by consideringthe contri-
bution of one shell to the whole ExAFsspectrumby back-
transformingthe correspondingpeak in the real spaceinto
the k space(Fig. 9b) and calculatingthe zerosof this func-
tion. If we use the ExAlsformula as definedabove,a theo-
retical curve may be calculatedby adjustingthree parame-
ters: the number and nature of the surroundingatoms(this
latter affectsboth phaseshift and amplitudevalues)and the
correspondinginter-atomic distances.Only the latter two
are used for distance calculation as they determine the
zeros of the sine function. The Debye-Waller parameter
was fixed to 0.09A,the value determinedfor the relerence
compound.A good agreementis found betweenthe experi-
mental and calculated curves (Fig. 9b and 9d) by taking
nickel (or iron) as the backscatteringatom and the Ni-
(Ni,Fe) distancesdeterminedfrom XRD (3.05-3.06A).On
the contrary, it is not possibleto get a correct fit by con-
sidering a secondshell only composedby Mg atoms (Fig.
9c) unlessthe Ni-Mg distanceis set at the unrealisticvalue
of 3.13A. Since nickel is essentiallysurrounded by heavy
atomsevenin clay mineralsof low (Fe,Ni)content,we have
evidencefor the heterogeneouscharacter of the substitu-
tion of Mg by transition elements.
Estimation of the size of the Ni-enriched qreas
As the nature of the atoms presenton one coordination
shell is known, it is possibleto get their number from the
amplitude of the correspondingExArs.The backscattering
amplitude of nickel was calculated from the theoretical
values of Teo and Lee (1980)and found to be valid bv
 MANCEAU AND CALAS: DISTRIBUTION OF NICKEL IN HYDROUSilLICATES
analysisof the willemseiteas a referencecompoundfor the
clay minerals we investigated.The number of Ni second
neighborsfound by ExAFsin Ni end-membersnepouiteand
pimelite is in good agreementwith the structural formulae
(Table 3). In the phasesof low-(Ni,Fe) content it must be
noticed that the secondpeak has a similar intensity as for
the referencecompounds,which indicatesthe presenceof
predominant(Ni,Fe) atoms on the secondshell.It must be
noticed that the differencebetweenthe backscattererphase
of Mg and Ni is about z; thereforethe presenceof some
Mg atoms together with Ni atoms on the secondcoordi-
nation shell would tend to decreasethe amplitude of the
wave backscattered by the surrounding atoms. EXAFS
cannot separatethe contributions of heavy atoms from the
light ones, as the A(k) function varies almost linearly in
both casesin this energy range. Apparent values are 4.4
* 0.5and4.2+0.5 Ni(Fe) atoms for lizarditeand kerolite
respectively.If we take into account the phaseopposition
which existsbetweenNi and the Mg atoms which complete
to six neighborsthis secondshell we obtain the respective
valuesof 4.9+0.5 and 4.7*0.5. Thesevaluesmust be com-
pared to thoseestimatedfrom the structural formulae,0.38
in lizardite and 1.66in kerolite. We have thus additional
evidencefor the non-random distribution of nickel in the
octahedrallayer of theseminerals.
The comparison betweenthe number of Ni(Fe) neigh-
bors calculatedfrom structural formulae and measuredby
ExAFSmay be interpreted quantitatively to estimate the
averagesizeof the areaswhich are Ni( + Fe)-enriched.If we
assumethat these latter have a circular shape and are
devoid of Mg atoms, only the atoms at the boundariesof
theseregionshave Mg as neighbors.In this hypothesiswe
get averagediametersof between204 (i.e.,2 cell units) and
60A in Mg-Fe-Ni lizardite and between 15A and 4OA in
Mg-Ni kerolite. In a model assuminga circular shapeof
these segregatedareas,it must be noticed that the mean
number of Ni atoms surrounding a central atom increases
faster for the small dimensionsthan for the larger ones.
Consequentlythese calculationsare no_t?gllqreF for the
large dimensions.If Mg atoms are pr€sentinside theseen-
riched areas,the dimensionsobtained are significantly in-
creased.Therefore the averagevalues given above corre-
spond to an lower limit; the upper limit cannot be esti-
mated but may lead to a whole layer. Furthermore,as we
haveonly accessto spatiallyaveragedvalues,a distribution
of thesedimensionscannot be excluded.
Discussion
The data presentedin this study permit discussionof the and the existenceof distinct Mg- and Ni-octahedrallayers
nickel distribution within the two most abundant Ni-
containingseriesof the garnierites.
Ni-Mg cation ordering in the kerolite-pimelite series
Two types of structural configurations may be con- mechanisms,which certainly play an important role in the
sidered:(l) Ni and Mg can be clusteredwithin the octa- processesof supergeneenrichmentof nickel. In summary,
hedral sheetor (2) different types of Ni{Fe) sheetscan be the most important result of this study is the discoveryof a
irregularly distributedin the phyllosilicatestructure.In this heterogeneous
latter model the 2: 1 phyllosilicates
of the garnieriteswould
557
essentiallyconsistof mixtures of kerolite and pimelite at a
scaleof severallayers.This hypothesiscannot be excluded
as it would not be detectedby XRD, whereasthe optical
spectraof both phasesare identical.
Ni-Mg cation ordering in the lizardite-nepouite
series
The two-cation ordering schemesdescribedpreviously
cannot apply to this series,as the coexistenceof Ni- and
MgJayers in the lizardite would give optical spectrasimilar
to that of nepouite.The marked differencebetweenboth
spectraleadsto rejectionof this hypothesis.Data available
point to the existenceof Ni-rich areasof small dimensions
without any structural reorganizationas it is observedin
the nepouite.This discussionrefers to the crystallinity of
theseminerals.From the TEM studiesand the presenceof
a strong 06.33 reflection,we deducethat there is a good
crystallinity of the samples in the ob planes, with a
200-300Alength ofcoherence.The Ni-containing areasare
smallerthan that value.
Conclusion
Few data exist on the actual mechanismsof atomic sub-
stitution in minerals. In the case of ions with the same
valence,the condition of equality of chargesand of ionic
radii is not suffrcientto imply the existenceof ideal solid
solutionsin minerals.The chemicalheterogeneityat a scale
of several angstromsthat we report in Ni-clay minerals
may be compared to the chemical variations bringing
about modulated structuresshown under high resolution
conditions in some minerals and alloys (Buseck and
Cowley, 1983).However as ExAFSis not basedon any as-
sumption concerningthe periodic characterof the chemical
heterogeneities, we have no information about that param-
eter and it is unlikely that they could be imagedby rnrru.
The structural problem is the correlation between both
scalesof observation of these heterogeneities, the middle
range order between 5 and 15A being until now impossible
to attain directly either with techniquessuch as nxens(be-
causeof the limited mean free path of the photoelectrons)
or with imaging techniques.However, the existenceof
chemicalheterogeneitycould be related to the growth con-
ditions, with the possibleinfluenceof disequilibrium con-
ditions. The distinct behavior of 10A and 7A minerals
pointed out in this study refersalso to distinct geological
formation conditions. The lizardite is derived from the
transformationof primary serpentinesby a Ni-enrichment
and a subsequentMg loss.In contrast, the mineralsof the
kerolite-pimelite seriesare solution precipitated products
can be correlated to this distinct formation process.The
comparison of Ni-crystal chemistry among minerals
formed under various weatheringconditions could lead to
a better comprehension of heterogeneoussubstitution
distribution of Ni (i.e.,a clustering)in the
octahedral sheet ofhydrous Ni layer silicates.
 558 MANCEAU AND CALAS: DISTRIBUTI1N oF NICKEL IN HYDR\IIS SILI1ATES
Acknowledgments
The authorswishto thankM. GilbertTroly and MM. Esterle,
Bernard Pelletierand Bernard Escande(Soci6t6M6tallurgiqueLe
Nickel, SLN) who helped us in the knowledgeof the New Cale-
donian ore depositsand provided facilities during the sampling.
We are also grateful to L.u.R.E.for the Synchrotron Radiation
facilities,Mrs. MadeleineGandais and M. Claude Guillemin for
TEM studiesand Mrs. H6ldne Vacheyfor the chemicalanalyses.
We thank Mrs. JacquelinePetiau and MM. Gerard Bocquier,G.
E. Brown, Bernard Cervelleand Michel Semetfor their kind ad-
vices.This work is supported by MST/MRI grant, Valorisation
desRessources du Sous-Sol,
ContractN.82D-O8ll.
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