Ore Geology Reviews 16 Ž2000.

41–58

Geochemical and mineralogical characteristics of Fe–Ni- and

bauxitic-laterite deposits of Greece
D.G. Eliopoulos a,) , M. Economou-Eliopoulos b
a
Institute of Geology and Mineral Exploration (IGME), 70 Messoghion Street, GR-11527 Athens, Greece
b
Section of Economic Geology and Geochemistry, Department of Geology, UniÕersity of Athens, Panepistimiolis, GR-15784 Athens, Greece

Received 4 March 1999; accepted 20 December 1999

Abstract

Contiguous vertical sample profiles from Ni-laterite deposits with in situ features ŽKastoria, Profitis Ilias, and Tsouka.
and allochthonous Ni- and bauxitic-laterite deposits in contact with basement limestone ŽNissi. and bauxitic-laterites lying
on peridotite ŽParhari. were analyzed for major, trace Žincluding Th and U., rare earth and platinum-group elements ŽREE
and PGE, respectively.. In addition, minerals with emphasis to chromite grains found as residual components in these
laterites, inherited from the ophiolitic parent rocks, were analyzed by microprobe.
Low Al 2 O 3 , TiO 2 , REE, Th and U contents are common features of the Kastoria, Bitincka and Tsouka deposits. In
contrast, elevated REE contents are present in the karst-type bauxitic- and Ni-laterite ores of Nissi and bauxitic-laterites of
Parhari. The bauxitic-laterite deposit of Nissi attains REE contents of thousands parts per million in samples from the contact
between the lowest part of the bauxitic-laterite and the footwall limestone. Highest contents of Th and U are found in the
bauxitic-laterites, with Th ranging from 4 to 28 ppm and U from 4 to 66 ppm. In general, increasing Al contents are
accompanied by elevated Ti, REE, Th and U contents at the Parhari and Nissi laterite deposits. Goethite, is the dominant
mineral in all Ni-laterite profiles studied, while boehmite co-existing with goethite is common in the bauxitic-laterites at
Nissi and Parhari. Goethite exhibits variable Al contents, while the AlrFe ratio increases towards the top of the profiles.
The PGE concentrations are generally low, ranging from less than 100 ppb to a few hundred parts per billion. The lowest
values — lower than in the bedrock — were recorded in the saprolite zone. A certain enrichment in Pt Žup to 48 ppb., Pd Ž7
ppb., and Au Ž16 ppb. is recorded in the reddish altered peridotite overlying the saprolite zone at Profitis Ilias. The Fe–Ni
ore overlying the reddish altered peridotite has the highest Os values Ž14 ppb., Ir Ž32 ppb., Ru Ž66 ppb., Rh Ž20 ppb., Pt Ž86
ppb., and Pd Ž186 ppb.. Gold contents are below 36 ppb. An increasing PtrPd ratio from 3.0 in Fe–Ni-laterites to 6.0 in
bauxitic-laterites is apparent.
Both whole rock compositions and mineral chemistry of laterites indicate that major controlling factors of the
composition of the bauxitic-laterites are the conditions during transportationrdeposition of the weathered material and
during diagenesisrmetadiagenesis stage rather than parent mafic ophiolitic rocks.

)
Corresponding author. Fax: q30-1-727-4214.
E-mail address: eliopoulos@igme.gr ŽD.G. Eliopoulos..

0169-1368r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 1 3 6 8 Ž 0 0 . 0 0 0 0 3 - 2
42 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

The comparison between the primary composition of chromite in the saprolite zone and the overlying Fe–Ni ore may
provide evidence for the discrimination between Fe–Ni ore linked to in situ weathering and ore derived by transportation to
some extent of clastic and chemical material. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Ni-laterites; bauxitic-laterites; chromite; platinum-group elements; rare earth elements; Greece

1. Introduction given and their implication to the formation of Ni-

and bauxitic-laterites is discussed.
The Fe–Ni-laterite deposits in Balkan Peninsula
are mainly found in the Mirdita–Sub-Pelagonian and
Pelagonian geotectonic zones ŽFig. 1. and are related 2. Methods of investigation
to ophiolites of Upper Jurassic to Lower Cretaceous
age. These deposits have been affected by intense
The mineralogical composition of the studied lat-
tectonism, which has created overthrusting, foliation,
erites was investigated by optical microscopy, X-ray
folding, and faulting. This has resulted in the trans-
diffraction ŽXRD; Siemens D5005 power diffrac-
portation of the laterite bodies disrupting their conti-
tometer., whole rock analysis and phase mineral
nuity and in some cases mixing them with underly-
analysis by microprobe.
ing rocks. The multistage deposition of the Fe–Ni
Major elements were determined by atomic ab-
ores, the redistribution of ore metals, the intense
sorption at the University of Athens, and minor and
tectonism and the metamorphism, which have af-
trace elements by neutron activation analysis, at
fected all the Ni-laterite deposits of Greece, have
XRA Laboratories, Canada. The lead fire-assay tech-
almost totally changed the initial mineralogical com-
nique was used for the determination of gold, plat-
position and textures of the ores. Interpretations of
inum, and palladium. The detection limit is 10 ppb
the mechanismŽs. and conditions of their genesis are
for Pt, 1 ppb for Pd, and 5 ppb for Au.
complicated. Apart from the allochthonous laterite-
Selected samples were analyzed for all PGEs ŽOs,
type there are Ni-laterite deposits which exhibit some
Ir, Ru, Rh, Pt, and Pd. plus Au at Genalysis Labora-
features of in situ laterites at their lowest part ŽAl-
tory Services, Australia, using ICPrMS after pre-
bandakis, 1980; Valeton et al., 1987; Economou-
concentration by nickel sulfide fire-assay on large
Eliopoulos et al., 1996, 1997; Tashko et al., 1996; Ž30 g. samples. The detection limits are 2 ppb for
Alevizos, 1997..
Os, Ir, Ru, Pt, and Pd, 1 ppb for Rh, and 5 ppb for
Ni-laterite deposits with in situ features, such as
Au. The SARM7 was used as standard.
those exposed in Kastoria, Profitis Ilias ŽVermion.
The electron microprobe analyses were carried
and Tsouka ŽLokris., and Ni- and bauxitic-laterite
out at the Institute of Geology and Mineral Explo-
deposits lying on basement limestone, or peridotite,
ration ŽIGME., Athens, using a JEOL Superprobe
such as those at Nissi ŽLokris. and Parhari ŽVerm-
CAMECA Camebox JSA-733 wavelength-dispersive
ion., respectively ŽFig. 1a. were investigated in the
automated system.
present study. The objective of this study are: Ža. the
whole rock analysis of laterite samples from vertical
profiles taken at the deposits listed above for major
and trace elements including Th, U, rare earth ele- 3. Characteristics of laterite deposits
ment ŽREE., and platinum-group elements ŽPGE.
and Žb. the analysis, by microprobe, of minerals with 3.1. Ni-laterite deposits
emphasis to chromite grains in laterites, which are
found as residual component inherited from the ophi- 3.1.1. Kastoria
olitic parent rocks, in an attempt to discriminate the The Kastoria Fe–Ni deposit is located in northern
Fe–Ni ores linked to in situ weathering and those Greece ŽFig. 1a., NNW of the Kastoria town, and is
derived by transportation, to some extent, of clastic developed on Upper Jurassic–Lower Cretaceous ser-
and chemical materials. These analytical data are pentinized ultramafic ophiolites of the Mirdita–Sub-
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58 43

Fig. 1. Ža. Sketch map showing the Pelagonian ŽA. and Sub-Pelagonian–Mirdita ŽB. geotectonic zones of Greece, the distribution of
ophiolites and the location of the studied Fe–Ni-laterite deposits and Žb. schematic compositional variations, through vertical profiles in
representative Ni- and bauxitic-laterite deposits. Data are from Tables 1 and 2.
44 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58
Pelagonian zone. It is overlain by Tertiary molasses
ŽPlastiras, 1979; Mountrakis, 1983; Skarpelis, 1997;
Skarpelis et al., 1993.. A laterite profile exposed by
open-pit mining was sampled, since it exhibits char-
acteristics that resemble to an in situ profile. Un-
weathered peridotite is overlain by a saprolite zone,
composed of a mixture of peridotite blocks of vary-
ing sizes and different degree of weathering. Veins
of calcite, quartz, and silicate minerals, which re-
place serpentinized olivine, are abundant. Calcite is a
common mineral and occurs mostly in the form of
veinlets surrounding peridotite blocks, while quartz
is usually present as a fine-grained replacement of
serpentinized olivine and as quartz veinlets. Ni-
serpentine is also common mineral. Small amounts
of sulfide minerals and accessory chromite grains are
present.
A goethite zone, 5 m thick, consisting mainly of
goethite and hematite overlies this weathering crust.
The ground mass is fine-grained and it is composed
of a pelitic matrix Žgoethite, hematite., clastic grains
of quartz and chromite, as well as silicates ŽFe–
serpentine, talc., carbonates Žcalcite, siderite. and
Mn-oxides Žpyrolusite, lithiophorite.. Pisolitic ore, 8
m thick, overlies the pelito-morphic ore, and sedi-
ments cover the whole section.
3.1.2. Profitis Ilias (Vermion)
The Vermion ophiolites are mainly comprised of
large peridotite masses Žharzburgite, dunite and or-
thopyroxene Žopx.-dunite..
Unweathered peridotite overlain by a saprolite
zone is exposed in the area of Profitis Ilias, Vermion.
The weathering crust is overlain by a highly silici-
fied zone, which is transected by calcite veinlets,
while intense hematitization and silicification charac-
terize its upper part. The Fe–Ni ore, 5–7 m thick,
overlies this zone. The ore is pelitic at its lowest part
and becomes pisolitic towards the top.
The Fe–Ni ore is mainly comprised of goethite,
hematite, Ni-bearing chlorite, quartz, calcite and
chromite. Talc is common in the lowest part of the
ore, while illite is dominant in its upper part.
3.1.3. Tsouka (Lokris)
The Tsouka Ni-laterite deposit is characterized by
a saprolite zone, 1 m thick, followed by a pelitic–
pisolitic horizon, 4 m thick, the upper part of which
is comprised of transported material. Lower Creta-
ceous limestone layers alternating with Ni-laterite
ore are conformably overlying the mineralized hori-
zon ŽValeton et al., 1987; Alevizos, 1997;
Economou-Eliopoulos et al., 1997.. The present study
focuses on the chemical composition of the saprolite
zone and the Fe–Ni-laterite ore overlying this zone.
3.2. Bauxitic Ni-laterite deposits
3.2.1. Nissi (Lokris)
The Nissi deposits lie on karstified Jurassic lime-
stone and are conformably overlain by Lower Creta-
ceous limestone. The peculiarity of the Nissi deposits
is that they may occur either as isolated typical Ni-
or bauxitic-laterite ores or as an association of Fe–Ni
ore at the lowest part of the deposit, followed by
bauxitic-laterite towards its upper part ŽAntoniades
and Vgenopoulos, 1987; Valeton et al., 1987;
Economou-Eliopoulos et al., 1997..
The Fe–Ni-laterite ore is mainly composed of
goethite, hematite, Ni-bearing chlorite, illite, quartz,
calcite, and chromite. Boehmite, gibbsite, and kaolin-
ite are common minerals in the bauxitic-laterite.
Goethite, hematite, chromite Žusually as very small
fragments., rutile, and sulfides Žpyrite, Ni-pyrite. are
also present, whereas smectite and takovite are more
abundant towards the lowest part of the deposit.
3.2.2. Parhari (Vermion)
Although the majority of the Vermion laterites are
classified as Ni-laterites, bauxitic-laterite was lo-
cated, for first time, on pervasively serpentinized
peridotite Žopx-dunite., in a distance of less than 1
km north of the Profitis Ilias Ni-laterite deposit.
Apart from the dominant peridotites, mafic rocks
Ždiabases, microgabbros. are also present in the Par-
chari area.
The Parhari deposit is mainly comprised of
goethite, hematite, boehmite, Ni-Fe chlorite, illite,
quartz, calcite, chromite, rutile, and its alteration
product perovskite. A small amount of pyrite is also
present.
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58 45

4. Chemical composition of Ni- and bauxitic-
laterite ores
4.1. Whole rock chemistry
Representative samples from the saprolite zone
and the Fe–Ni ore, mainly through vertical profiles
from the Kastoria, Profitis Ilias and Tsouka Ni-laterite
deposits, were analyzed ŽTables 1–3..
The Fe–Ni ore of Kastoria is characterized by
low SiO 2 Ž3.45–4.5 wt.%., Al 2 O 3 Ž1.8–6.8 wt.%.,
and TiO 2 Ž0.04 wt.%. contents and wide vertical
variations of major and trace element ŽNi, Cr, Mn,
Co. contents ŽFig. 1b.. Cobalt contents range from
0.02 Žin the saprolite zone. to 0.16 wt.% Co Žin the
Fe–Ni ore. with an average value of 0.06. Man-
ganese contents range from 0.06 in the saprolite zone
to 1.70 wt.% MnO in the ferruginous zone, while the
MnOrAl 2 O 3 ratio is higher in the Kastoria Žaverage
0.73. and Profitis Ilias Ž0.11. deposits than in the
bauxitic-laterite deposits Ž0.01..
An increase of the Ti-content with increasing Al
in bauxitic- and Fe–Ni-laterites, as it is expressed by

Table 1
Chemical composition of Ni-laterite deposits through a vertical profile from the Kastoria deposit and representative samples from the
Bitincka deposit ŽAlbania.
Kastoria Bitinckaa
Saprolite zone Goethite zone Pisolitic ore Saprolite zone Fe–Ni ore
Ka-2 Ka-3 Ka-4 Ka-4b Ka-5 Ka-6 Ka-7 Ka-8 Bi50 Bi43 Bi44 Bi45
wt.%
SiO 2 58.01 51.60 36.60 22.00 3.35 3.80 4.50 4.05 26.20 6.00 7.90 5.00
Al 2 O 3 0.00 0.10 1.30 2.30 3.00 3.00 1.80 3.40 1.05 6.50 6.75 6.10
Fe 2 O 3 0.85 5.55 44.10 54.80 78.00 77.60 68.10 78.20 7.25 69.80 66.50 71.40
CaO 20.00 5.9 5.25 0.56 0.20 0.30 0.60 0.10 21.10 0.35 0.35 0.30
TiO 2 0.01 0.01 0.01 0.02 0.03 0.03 0.03 0.10 0.01 0.05 0.05 0.08
MgO 2.45 24.30 1.00 3.25 0.60 0.55 0.80 0.60 19.20 1.35 1.45 1.15
MnO 0.05 0.08 0.95 0.88 0.25 1.70 0.79 0.30 0.29 0.81 0.17 0.19
L.O.I 16.65 12.25 9.65 12.25 12.92 12.30 12.90 12.20 22.65 10.95 10.85 10.80

ppm
Ni 17 000 23 000 8500 10 500 8000 9100 7100 4400 2400 9800 13 000 7200
Cr 120 1500 16 000 23 000 20 000 15 000 23 000 17 000 3000 21 000 19 000 17 000
Co 50 180 1600 1200 330 820 420 330 150 410 2100 650
Zn - 50 - 50 250 460 370 280 390 320 - 50 410 680 310
Sc 0.6 4.6 23 41 66 280 55 42 8.9 88.8 86.2 70
La -1 -1 2 2 -1 4 3 3 1 1 1 3
Ce -3 -3 -2 -3 -3 -3 -3 -3 -3 -3 -3 27
Nd - 10 - 10 - 10 - 10 - 10 - 10 - 10 - 10 - 10 - 10 - 10 - 10
Sm - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 1.0 - 0.5 0.5 - 0.5 - 0.5 - 0.5 0.6
Eu - 0.2 - 0.2 0.4 0.5 0.3 0.3 0.3 0.6 - 0.2 - 0.2 - 0.2 0.4
Tb - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5
Yb - 0.2 - 0.2 - 0.2 - 0.2 - 0.2 - 0.2 0.3 - 0.2 - 0.2 - 0.2 - 0.2 - 0.2
Lu - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 - 0.05 0.13
Th -1 -1 -1 -1 -1 -1 -1 -1 - 0.5 - 0.5 1.9 - 0.5
U -1 -1 -1 -1 -1 -1 1.3 -1 - 0.5 - 0.5 - 0.5 0.5

ppb
Pt - 10 10 12 12 15 88 40 - 10 - 10 27 41 31
Pd -1 2 3 6 -1 -1 -1 -1 3 12 16 8
Au -5 -5 -5 -5 -5 -5 9 -5 -5 -5 -5 -5
a
Data are from Tashko et al. Ž1996..
 46
Table 2
Chemical composition of Ni- and bauxitic-laterites from Vermion, through vertical profiles
Ni-laterites from Profitis Ilias Bauxitic-laterites from Parhari Standard
Peridotite bedrock Altered peridotite Fe–Ni ore Bedrock Altered Bauxitic-laterite ore SARM7
PR-1 PR-2 PR-3 PR-4 PR-5 PR-6 W.V.4 W.V.5 W.V.6 P-peridotite P-6 P-1 P-2 P-3 P-4 P-5
wt.%

D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

SiO 2 48.50 30.00 76.00 76.50 9.00 16.50 38.00 39.00 15.20 37.00 31.00 17.50 14.50 13.00 14.00 13.00
Al 2 O 3 0.50 0.20 1.20 2.20 6.70 13.00 3.80 1.80 12.50 1.00 2.00 29.00 32.70 31.90 32.00 37.4
CaO 0.30 18.60 0.40 0.50 0.50 0.40 0.30 0.70 0.38 0.50 24.00 0.80 0.80 0.60 0.90 0.90
Fe 2 O 3 18.60 7.00 15.90 14.90 71.10 58.00 42.80 31.60 58.90 11.00 7.00 36.00 36.80 32.40 39.50 33.50
TiO 2 0.10 0.10 0.10 0.10 0.10 0.24 0.10 0.10 0.11 0.10 0.10 1.28 1.70 1.65 1.69 1.15
MgO 25.90 23.20 2.10 1.60 3.00 1.90 7.40 20.00 4.65 37.00 12.80 3.60 2.40 2.10 2.70 2.10
MnO 0.24 0.11 0.23 0.18 0.97 0.61 0.41 0.33 0.62 0.10 0.31 0.37 0.41 0.24 0.36 0.26
P2 O5 0.01 0.01 0.01 0.01 0.10 0.05 0.01 0.01 0.06 0.01 0.01 0.48 0.31 0.27 0.32 0.20
L.O.I 4.50 21.10 0.90 1.20 3.30 3.50 3.40 4.50 4.45 12.50 22.70 8.30 8.20 7.00 8.20 9.70

ppm
Ni 5500 2200 4100 4700 15 000 6900 10 200 9500 7800 3100 2000 5200 5200 6400 6400 4200
Cr 5800 2500 3500 3300 21 900 12 900 11 500 11 400 11 000 3800 1900 5500 4400 3800 4100 3600
Co 300 200 200 200 1300 700 500 400 820 240 200 400 320 400 400 400
Zn 190 160 210 180 620 510 320 300 230 - 50 - 50 700 750 690 480 470
La 2 3 -1 2 18 29 19 15 170 2 2 103 115 114 117 212
Ce 3 4 -3 -3 31 62 38 20 15 4 -3 140 146 145 150 220
Nd -10 -10 -10 -10 10 20 10 10 38 -10 -10 33 35 36 39 75
Sm - 0.5 1.1 - 0.5 0.6 2.8 0.4 2.9 0.9 20 - 0.5 - 0.5 12 14 17 18 29
Eu - 0.2 0.3 - 0.2 - 0.2 0.2 2.1 0.8 1.6 6.5 - 0.2 - 0.2 1.8 2.2 2.8 3.4 4.7
Tb - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 1.4 - 0.5 - 0.5 - 0.5 1.8 2.2 2.9 6.3
Yb - 0.5 0.6 - 0.5 - 0.5 2.5 4.2 2.3 2.4 1.4 - 0.5 - 0.5 6 7 8 9 16
Lu - 0.05 0.1 - 0.05 - 0.05 0.45 0.65 0.37 0.45 5.5 - 0.05 - 0.05 1.1 1.3 1.5 1.6 2.8
Th 0.7 0.8 - 0.5 - 0.5 3.1 5.6 3.1 1.9 1.4 - 0.5 - 0.5 19 20 17 18 28
U 0.9 0.9 - 0.5 - 0.5 1.8 4.8 1.6 1.6 2.2 - 0.5 - 0.5 4.2 4 3.9 4.2 5

ppb
Os 6 4 8 8 9 3 4 4 60
Ir 32 22 20 12 28 10 19 21 74
Ru 66 52 42 28 58 18 36 40 460
Rh 20 12 7 6 9 5 11 9 250
Pt 11 -10 48 9 82 56 34 28 39 -10 -10 25 26 54 48 29 3600
Pd 5 -1 7 10 46 38 8 8 186 -1 -1 5 4 10 7 5 1600
Au -5 -5 16 -5 5 4 4 3 17 -5 -5 5 4 15 16 7 340
Table 3
Chemical composition of Ni- and bauxitic-laterites from Lokris, through vertical profiles
Ni-laterites Bauxitic-laterites Standard
Tsouka Žsaprolite zone. Nissi-2 ŽFe–Ni ore. Nissi-3 Nissi-1 SARM7
TS-1 TS-5 TS-6 TS-10 TS-11 N-11 N-14 N-16 N-22 N-36 N-2B N-C N-D N-H
wt.%

D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

SiO 2 8.50 26.80 18.40 33.00 23.00 34.00 23.50 31.20 6.48 20.90 15.90 23.10 24.10 1.85
Al 2 O 3 5.15 1.80 0.55 1.65 0.40 8.60 6.85 7.10 30.68 25.15 16.00 18.80 20.30 44.00
CaO 0.20 18.35 37.25 15.15 34.20 0.35 0.40 2.20 0.15 0.30 0.95 0.40 0.20 0.15
Fe 2 O 3 69.80 19.60 4.50 6.70 5.60 42.50 54.45 44.00 49.70 36.30 42.00 35.00 35.60 41.60
TiO 2 0.05 0.05 0.02 0.02 0.01 0.40 0.25 0.35 1.95 1.25 0.35 1.25 1.10 2.70
MgO 2.30 8.60 4.25 18.20 5.85 3.40 2.85 4.37 1.07 2.70 1.25 3.40 3.65 0.25
MnO 0.20 0.20 0.20 0.15 0.17 0.30 0.21 0.30 0.15 0.22 0.55 0.10 0.30 0.17
L.O.I 7.85 21.00 33.75 24.10 29.90 5.75 5.90 5.55 7.50 9.70 15.35 11.85 9.75 8.95

ppm
Ni 13 000 6150 2400 5850 3000 7500 7690 9000 9200 5500 40 000 27 800 27 500 1500
Cr 20 500 10 850 1800 2900 2950 20 000 24 300 25 100 10 800 5100 4500 15 100 12 000 5500
Co 450 270 110 220 92 510 570 520 340 1400 1400 430 2200 60
Zn 320 110 50 60 50 270 270 250 170 330 340 300 350 320
La 2 3 31 106 6 15 9 8 84 129 2740 172 144 56
Ce -5 -5 17 17 9 50 30 44 137 1030 292 84 126 207
Nd -10 -10 30 100 -10 10 -10 -10 65 140 2740 160 110 105
Sm - 0.5 0.8 5 17.6 0.9 2.7 1.1 1 10 29.6 404 33.7 24.3 3.6
Eu - 0.5 - 0.5 1.1 3.8 0.3 0.7 0.3 0.5 3.2 8.7 91 9.2 6.5 1.2
Tb - 0.5 - 0.5 0.5 1.2 - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 4.5 27.7 4.9 4 0.9
Yb - 0.2 0.3 0.4 1.1 - 0.2 1.2 1 0.7 7.4 20.8 27.4 14.1 20.5 3.7
Lu - 0.05 - 0.05 0.7 0.17 - 0.05 0.2 0.6 0.11 1.34 2.92 4.88 2.16 3.31 0.86
Th - 0.5 - 0.5 - 0.5 - 0.5 - 0.5 2.2 1.1 1 21 10 6 5 12 25
U - 0.5 - 0.5 1.1 2.3 - 0.5 - 0.5 - 0.5 - 0.5 16.9 6.9 46.3 66.1 13 6.9

ppb
Os 14 10 4 60
Ir 26 20 16 74
Ru 54 38 34 460
Rh 7 5 11 250
Pt -10 -10 -10 -10 -10 17 34 86 -10 12 -10 23 28 -10 3600
Pd -1 -1 -1 -1 -1 3 14 15 -1 1 3 9 30 1 1600
Au -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 -5 36 30 18 340

47
48 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

a high correlation coefficient Ž r s q0.95. ŽTable 4.
confirms previous studies ŽValeton et al., 1987..
A feature shared by bauxitic- and Ni-laterites of
Vermion and Nissi ŽLokris. is a higher SiO2 content
compared to the Kastoria, Bitincka, and Tsouka de-
posits ŽTables 1–3., which is consistent with the
presence of abundant quartz.
Nickel ranging from 4400 to 23 000 ppm exhibits
a preferred concentration in the saprolite zone of the
Kastoria deposit ŽFig. 1b.. The most common Ni-
mineral is Ni-serpentine Žaverage 30 wt.% NiO.. In
general, elevated Ni contents, ranging between 0.44
and 1.5 were recorded in the zone of the Fe–Ni ore
of the areas of Vermion and Lokris, while an enrich-
ment in Ni Ž4 wt.% Ni., Mn Ž0.55 wt.% MnO., and
Co Ž0.14 wt.% Co. was found in laterite samples
from the lowermost part of the Nissi-1 deposit ŽTa-
bles 2 and 3..
The REE contents in the Kastoria deposit are
below 10 ppm, and are comparable to these in the
Bitincka deposit in Albania ŽTable 1; Tashko et al.,
1996.. In contrast, much higher REE contents Žsome
hundreds parts per million. are present in both the
bauxitic- and the Ni-laterite karst-type deposits of
Nissi and the bauxitic ore at Parhari. Even higher
REE concentrations Žthousands parts per million.,
along with an enrichment in Ni, Co, and Mn, are
found in samples from the contact between the low-
est part of the bauxitic-laterite and the footwall
limestone at the Nissi-1 deposit, which has been
attributed to a downward mobilization and concen-
tration at the footwall limestone of these elements
ŽTables 2 and 3; Economou-Eliopoulos et al., 1997..
Since the REE in sedimentary rocks are usually
normalized to a sedimentary standard Žinstead of
chondritic normalization. we used a shale ŽPiper,
1974.. The shale-normalized REE patterns exhibit
either negative or positive anomaly of Ce ŽFig. 2.,
due probably to local redox conditions. A limited
fractionation of the REE is exemplified by the ratio
of LarLu, which is 40 and 80 for the Ni- and
bauxitic-laterites of Profitis Ilias and Parhari, respec-
tively, and 58 for the laterites of Nissi. The LarLu
ratio reaches values higher than 560 only in samples
from the contact between the lowest part of the
bauxitic-laterite of Nissi and the footwall limestone
ŽTables 2 and 3; Economou-Eliopoulos et al., 1997..
Th and U contents in the Kastoria, Bitincka, and
Tsouka Ni-laterite deposits are below 2 ppm. In
contrast, in the bauxitic-laterite of Parhari Th ranges
from 17 to 28 ppm and U is 4.5 ppm, while in the
Nissi Th ranges from 5 to 25 ppm, and U from 7 to
66 ppm ŽTables 2 and 3.. In general, increasing Al
contents are accompanied by elevated Ti, REE, and
Th contents in both the Parhari and Nissi laterite
deposits ŽTable 4..
The PGE concentrations in the saprolite zone, the
bedrocks, and the ultramafic rocks on a regional
scale are below 10 ppb Pt and 5 ppb Pd ŽTables 1–3,
Economou-Eliopoulos, 1996.. Enrichments of Pt Žup
to 48 ppb. were found in the reddish altered peri-
dotite overlying the saprolite zone at Profitis Ilias.
The highest PGE concentrations are recorded in the
overlying Fe–Ni ore and these are: 14 ppb Os, 32
ppb Ir, 66 ppb Ru, 20 ppb Rh, 86 ppb Pt and 186
ppb Pd. Gold contents are below 36 ppb ŽTables

Table 4
Correlation matrix for selected major and trace element data from Fe–Ni- and bauxitic-laterites of Greece ŽTables 1–3.
SiO 2 Al 2 O 3 Fe 2 O 3 TiO 2 MnO ÝREE Th U Pt Pd
SiO 2 1.000
Al 2 O 3 y0.175 1.000
Fe 2 O 3 y0.577 y0.672 1.000
TiO 2 y0.125 0.947 y0.682 1.000
MnO y0.262 y0.361 0.499 y0.396 1.000
ÝREE 0.145 0.606 y0.591 0.572 y0.316 1.000
Th y0.034 0.878 y0.681 0.829 y0.334 0.511 1.000
U 0.185 0.202 y0.274 0.319 y0.281 0.326 0.161 1.000
Pt y0.188 y0.232 0.341 y0.311 0.746 y0.301 y0.302 y0.226 1.000
Pd 0.005 y0.096 0.136 y0.221 0.178 y0.035 y0.221 y0.073 0.238 1.000
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58 49

Fig. 2. Shale-normalized REE patterns for the Nissi and Vermion ŽParhari. bauxitic-laterite deposits.

1–3.. Although the average Pt content Ž36 ppb Pt. in
the Parhari bauxitic-laterites is lower than that in the
Profitis Ilias Fe–Ni-laterites Ž48 ppb Pt. of the
Vermion area, it is higher than that Ž13 ppb Pt. in
karstic-type bauxitic-laterites of the Nissi ŽLokris.
area, and that Ž3 ppb Pt. in typical bauxites ŽLaskou
and Economou, 1989.. With the exception of small
chromite occurrences of the Pindos and Skyros ophi-
olites showing Pt and Pd concentrations in the order
of ppm, the average contents 44 ppb Pt and 29 ppb
Pd in the Fe–Ni-laterite ores, and the Pt and Pd
contents Žup to 88 ppb Pt and 186 ppb Pd. in certain
laterite samples ŽTables 1–3. are higher than those
Ž8 ppb Pt and 6 ppb Pd. in the majority of chromite
ores of Greece ŽEconomou-Eliopoulos, 1996.. A
preference of Pt over Pd content in bauxitic- and
Fe–Ni-laterites, the PtrPd ratio ranging from 2.9 to
6, although samples from the uppermost parts exhibit
lower Pt and Pd contents ŽTables 1–3; Economou-
Eliopoulos et al., 1996.. Also, there is a good corre-
lation between Pt and Mn Ž r s q0.75.. The chron-
drite ŽC1.-normalized PGE patterns show similar
trend and they are flat shaped ŽFig. 3. in contrast to
the negative slope of the PGE patterns for the major-

Fig. 3. Chondrite ŽC-1.-normalized PGE patterns for the Ni-laterites of Vermion ŽProfitis Ilias. and bauxitic-laterites of Nissi and Vermion
ŽParhari..
50 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

ity of the chromite ores of Greece ŽEconomou-Elio-
poulos 1996.. Given that the Cr2 O 3 content ranges
between 1.1 and 2.5 wt.% in the Fe–Ni-laterite ores
and that a significant portion of the chromiun is
hosted in silicates and other oxides apart from
chromite ŽTables 1–8., the observed Pt–Pd-enrich-
ment confirms their remobilization and re-deposition
during the laterite formation ŽBowles, 1986; Auge
and Legendre 1994..
4.2. Mineral phase chemistry
4.2.1. Chromite
Since chromite grains or fragments in laterites are
residual components inherited from the ophiolitic
parent rocks, the compositional variation of chromite
was examined. The presence of large chromite grains
with cataclastic texture is a common feature of all
Fe–Ni-laterite ores and bauxitic-laterites from the
area of Parhari ŽVermion.. Usually, chromite grains
are mylonitized, cemented by magnetite or zoned
chromite occurs as chromite cores surrounded by
small zone of ferrian–chromite and rim of magnetite.
The chromite grains found in the Nissi ŽLokris.
Fe–Ni-laterites of karstic-type are smaller than those
in the Vermion laterites. Chromite in the Nissi
ŽLokris. bauxitic-laterites occurs as very small ho-
mogeneous grains.
Alteration processes along the periphery and frac-
tures of accessory or disseminated chromite grains

Table 5
Electron microprobe analyses of chromite grains from Fe–Ni- and bauxitic-laterites
Key: H s harzburgite, D s dunite, Crras CrrŽCr q Al., Mgras MgrŽMg q Fe 2q ..
Kastoria Bitincka
Bedrock Saprolite zone Fe–Ni ore Saprolite zone Fe–Ni ore
Sample Ka-peridotite Ka-2 Ka-3 Ka-4 Ka-5 Ka-5 Ka-6 Bi.50 Bi.50 Bi.45 Bi.44
Al 2 O 3 8.91 11.60 13.19 8.51 7.82 9.47 11.02 30.47 28.40 30.25 27.20
Cr2 O 3 61.01 57.72 57.33 60.55 60.91 59.77 58.91 39.01 41.41 38.37 41.01
Fe 2 O 3 1.22 2.08 0.51 0.61 1.31 0.39 0.48 0.51 1.16 0.37 2.67
FeO 19.20 15.29 16.59 20.89 17.56 19.14 21.02 17.07 14.95 18.65 13.72
MgO 9.02 10.71 10.11 6.56 7.01 6.03 7.02 12.80 14.02 11.61 14.61
MnO 0.25 2.02 1.93 2.27 4.80 5.11 1.82 0.23 0.21 0.37 0.20
TiO 2 0.13 0.00 0.13 0.22 0.21 0.00 0.25 0.17 0.00 0.22 0.19
NiO 0.44 0.30 0.32 0.61 0.33 0.21 0.25 0.16 0.21 0.00 0.23
Total 100.18 99.72 100.11 100.22 99.95 100.12 100.77 100.42 100.36 99.84 99.83
Crra 0.82 0.77 0.74 0.83 0.84 0.81 0.78 0.46 0.49 0.46 0.50
Mgra 0.46 0.55 0.52 0.36 0.42 0.36 0.37 0.57 0.62 0.53 0.65

Profitis Ilias Nissi-1

H D Opx-D Fe–Ni ore Bauxitic-laterite
Sample M2ŽH. M6-du S.Pa8 S.PR-1 PR-1 PR-4 PR-5 W.V.5 P-1 P-2 P-5
Al 2 O 3 20.76 10.56 28.27 13.81 15.02 26.31 18.27 10.46 14.12 26.11 12.80
Cr2 O 3 49.14 58.89 41.48 56.24 55.32 44.01 51.76 55.95 56.21 39.71 57.01
Fe 2 O 3 0.03 2.26 0.56 0.11 0.24 0.11 0.31 0.32 0.68 1.82 0.42
FeO 16.91 17.75 15.58 19.91 19.68 15.95 18.49 9.03 18.68 21.36 17.69
MgO 11.50 10.08 13.11 8.59 9.01 12.02 9.87 1.04 9.89 9.09 10.12
MnO 0.40 0.49 0.45 0.51 1.18 2.01 0.32 22.79 0.25 0.44 0.50
TiO 2 0.20 0.22 0.12 0.17 0.09 0.18 0.22 0.17 0.21 0.00 0.00
NiO 0.18 0.50 0.24 0.56 0.11 0.12 0.20 0.11 0.36 0.23 0.31
Total 99.12 100.75 99.81 99.90 100.65 100.71 99.44 99.87 100.40 98.76 98.85
Crra 0.61 0.79 0.50 0.73 0.71 0.53 0.66 0.78 0.73 0.51 0.75
Mgra 0.55 0.54 0.60 0.43 0.45 0.57 0.50 0.17 0.49 0.43 0.50
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58 51

Table 6
Electron microbrobe analyses of chromite from Fe–Ni- and bauxitic-laterites from Lokris
Tsouka Nissi-2
Saprolite zone Fe–Ni ore Fe–Ni ore
Sample TS-5 TS-6 TS-6 TS-11 TS-1 TS-1 S-1 TS-1 N-11 N-11 N-16 N-16
Al 2 O 3 19.06 26.45 25.08 26.45 26.23 37.11 31.52 28.20 7.16 36.08 15.53 24.28
Cr2 O 3 49.17 41.72 43.13 41.53 42.47 32.21 38.16 40.01 61.79 32.07 53.61 45.53
Fe 2 O 3 3.21 3.04 2.97 2.98 1.09 1.59 0.85 1.98 2.13 2.12 1.03 1.94
FeO 15.72 12.53 14.33 12.53 17.39 13.29 15.47 13.13 16.83 13.11 18.39 15.76
MgO 12.54 15.26 14.04 14.88 12.14 15.89 13.94 14.93 7.91 14.78 9.13 12.11
MnO 0.33 0.21 0.00 0.45 0.20 0.23 0.19 0.23 3.85 1.61 2.03 1.11
TiO 2 0.00 0.24 0.19 0.28 0.19 0.22 0.30 0.00 0.00 0.12 0.00 0.16
NiO 0.15 0.41 0.33 0.37 0.24 0.29 0.26 0.45 0.12 0.21 0.16 0.10
Total 100.18 99.86 100.07 99.47 99.95 100.83 100.60 98.93 99.79 100.10 99.88 100.99
Crra 0.65 0.51 0.54 0.51 0.52 0.37 0.45 0.49 0.85 0.37 0.70 0.56
Mgra 0.59 0.77 0.63 0.75 0.55 0.68 0.62 0.67 0.45 0.66 0.46 0.57

Bauxitic-laterite
Nissi-3 Nissi-1
Bottom Top
Sample N-22 N-33 N-33 N-36 N-36 N2B N2B N-C N-C N-D N-H N-H
Al 2 O 3 23.02 24.31 45.67 30.80 7.61 32.17 11.31 14.14 28.01 7.71 21.03 10.11
Cr2 O 3 46.01 41.52 21.82 39.51 62.01 35.63 58.02 56.54 41.50 62.72 48.18 59.84
Fe 2 O 3 0.65 2.65 0.55 0.22 1.39 1.22 1.21 0.43 0.69 0.59 1.51 0.68
FeO 17.42 20.91 16.43 14.31 18.61 19.01 16.32 16.78 16.18 16.86 15.16 17.65
MgO 12.04 9.11 14.21 14.01 8.01 10.88 11.04 11.11 13.02 10.28 11.76 8.93
MnO 0.41 0.31 0.41 1.21 1.91 0.61 2.09 0.38 0.30 0.89 1.60 0.54
TiO 2 0.22 0.23 0.51 0.00 0.24 0.17 0.11 0.00 0.12 0.00 0.21 0.18
NiO 0.31 0.51 0.35 0.22 0.50 0.23 0.21 0.20 0.19 0.51 0.23 0.23
Total 100.08 99.55 99.95 100.28 100.28 99.92 100.30 99.58 100.01 99.56 99.68 98.16
Crra 0.57 0.53 0.24 0.46 0.84 0.43 0.78 0.73 0.50 0.84 0.61 0.78
Mgra 0.55 0.44 0.61 0.64 0.43 0.51 0.55 0.54 0.59 0.52 0.58 0.47

have been described by Bliss and Maclean Ž1975..
Due to alteration, by Al and Mg loss to and Fe gain
from silicates, an increase of the Cra and decrease
of the Mga ratios results to a wide compositional
variation. In addition, the presence of ferrian–chro-
mite with low Mg and high Fe and Mn contents is
very common in the Fe–Ni-laterite deposits, particu-
larly in those of Kastoria and Profitis Ilias. The
higher Mn contents, in particular, in the ferrian
chromite zone of zoned chromite grains from the
Kastoria and Vermion Fe–Ni-laterite ores compared
to those in the Bitincka and Lokris deposits are
consistent with the elevated Mn contents in the
whole rock analyses ŽTables 1–6.. Analyses of
chromite cores as an accessory phase in ultramafic
parent rocks, and dispersed in bauxitic and Fe–Ni-
laterites, are often characterized by relatively low
iron content and are considered to correspond to less
altered chromite ŽTables 5 and 6.. Such grains were
selected in order to compare primary compositions.
Thus, a plot of the Cra wCrrŽCr q Al.x versus Mga
wMgrŽMg q Fe 2q .x ratio for the less altered chromite
cores, from the bedrock, highly weathered peridotite
Žsaprolite zone. and from the overlying Fe–Ni ore,
from the Kastoria and Bitincka deposits, exhibit the
most limited variation ŽFig. 4..
The primary composition of chromite in the ver-
tical profile of the Profitis Ilias Ni-laterite deposit is
52 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58

Table 7
Electron microbrobe analyses of goethite, boehmite and Ti-oxides from bauxitic- and Ni-laterites
Nissi bauxitic-laterite deposit ŽLokris.
Sample N-D N-D N-H N-H N-H N-H N-H N-22 N-22 N-22 N-36 N-36
SiO 2 0.00 0.96 0.00 0.00 0.00 0.00 1.38 1.21 2.10 0.65 0.00 0.00
Fe 2 O 3 11.65 85.30 44.56 44.22 9.88 7.76 86.71 84.21 82.26 68.52 7.82 5.75
Al 2 O 3 72.67 3.16 40.35 40.89 75.14 77.01 2.22 4.89 3.69 19.98 77.17 77.98
Cr2 O 3 0.00 0.30 0.62 0.31 0.00 0.00 0.00 0.54 1.70 1.18 0.00 0.00
TiO 2 0.41 1.96 1.35 1.68 1.00 1.49 0.00 0.88 0.19 1.56 0.28 0.00
MnO 0.38 1.07 0.26 0.33 0.43 0.00 0.45 0.31 0.19 0.00 0.00 0.41
NiO 0.00 0.00 0.00 0.39 0.00 0.29 0.00 0.88 0.45 0.99 0.23 0.00
Total 85.11 92.75 87.14 87.82 86.45 86.55 90.76 92.92 90.58 92.88 85.50 84.14

Parhari bauxitic-laterite deposit ŽVermion.

Sample P-1 P-1 P-2 P-2 P-2 P-2 P-2 P-2 P-3 P-5 P-5 P-5 P-6 P-6 P-6
SiO 2 0.46 0.00 0.56 0.00 0.00 0.00 0.00 0.00 0.00 0.54 0.34 0.00 0.63 0.91 0.76
Fe 2 O 3 87.04 17.84 88.06 19.69 14.86 10.38 3.51 0.68 22.99 88.79 83.10 12.97 3.53 4.49 7.89
Al 2 O 3 0.77 65.68 0.00 64.04 68.71 73.81 82.05 84.17 59.27 0.00 2.03 71.32 0.00 0.21 0.31
Cr2 O 3 0.31 0.00 0.19 0.00 0.28 0.58 0.00 0.00 0.00 0.00 0.30 0.00 0.00 0.00 0.00
TiO 2 1.31 1.36 0.39 1.68 1.52 0.81 0.41 0.00 2.48 0.98 5.10 0.97 91.78 87.38 57.17
MnO 0.18 0.00 0.10 0.12 0.00 0.00 0.00 0.00 0.10 0.34 0.23 0.08 0.00 0.19 0.00
NiO 0.00 0.25 0.57 0.00 0.00 0.28 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CaO 0.73 3.10 29.21
V5 O5 2.34 3.35 4.25
Total 90.07 85.13 89.87 85.41 85.37 85.86 85.97 84.85 84.84 90.65 91.10 85.34 99.01 99.63 99.59

Ni-laterite deposits
Kastoria Bitincka Profitis Ilias ŽVermion.
Sample Ka-5 Ka-6 Ka-7 Bi.45 Bi.45 PR-5 PR-6 PR-6 PR-6
SiO 2 2.19 1.87 1.80 0.50 0.72 0.94 0.84 0.67 1.03
Fe 2 O 3 74.40 70.98 74.65 89.56 88.78 87.23 88.92 87.23 86.20
Al 2 O 3 2.48 2.02 2.58 0.00 0.78 1.17 0.00 1.08 0.98
Cr2 O 3 1.46 0.78 3.68 0.00 0.29 1.03 0.49 0.80 0.90
TiO 2 0.00 0.00 0.00 0.00 0.24 0.63 0.30 0.24 0.69
MnO 2.22 1.50 0.55 0.16 0.00 0.42 0.12 0.00 0.87
NiO 1.46 0.70 0.99 0.44 0.00 0.00 0.00 0.00 0.00
Total 84.21 77.85 84.25 90.66 90.81 91.42 90.67 90.02 90.67

high-Al ŽCra s 0.53. and shows limited chemical
variation, although ferrian chromite is commonly
depleted in Al, Mg and enriched in Cr, Fe and Mn
resulting high Cra values ŽTable 5.. In contrast,
there is a wide variation in the primary composition
of chromite ŽCra ranges from 0.4 to 0.8. through a
vertical profile in the bauxitic-laterite, which is com-
parable to the composition of the chromite in the
ultramafic rocks of the region, such as harzburgites,
dunites and opx-bearing dunites ŽTable 5.. This vari-
ation extends further to higher Cra and lower Mga
values in ferrian chromite ŽFig. 4b.. Similarly, the
compositional variation of chromite is wide in the
Ni- and bauxitic-laterites from Nissi, in contrast to
that in the Tsouka Ni-laterite deposit ŽFig. 4c..
Therefore, a comparison between the primary com-
position of chromite seems to provide valuable in-
sights for the discrimination between Fe–Ni ores
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58 53

Table 8
Electron microprobe analyses of silicate minerals from Fe–Ni- and bauxitic-laterites
Fe–Ni-laterites
Kastoria Profitis Ilias
Sample Ka-1 Ka-2 Ka-2 PR-5 W.V.5.1 W.V.5.2 W.V.5.3
Mineral Serpentine Talc Chlorite
SiO 2 38.71 43.13 40.51 60.81 25.95 30.52 29.35
Al 2 O 3 0.75 0.00 0.17 0.00 11.31 14.64 14.51
Cr2 O 3 0.00 0.00 0.55 0.00 1.15 0.00 1.45
FeO 40.27 0.46 5.99 3.09 18.96 7.61 30.35
MgO 2.81 10.47 32.56 30.39 15.35 18.35 4.86
MnO 0.42 0.00 0.09 0.00 0.00 0.95 0.99
TiO 2 0.00 0.00 0.00 0.00 0.00 0.00 0.00
NiO 1.62 30.27 3.15 0.71 11.72 12.12 2.61
Total 84.58 84.33 83.02 95.00 84.44 84.19 84.12

Bauxitic-laterites
Parhari Nissi-1
Sample Pa-2 Pa-3 N-C.1 N-C.2 N-C.3 N-C.4 N-D.1 N-D.2 N-32 N-36.1 N-36.2
Mineral Chlorite Fe-chlorite
SiO 2 20.57 18.02 34.81 25.82 34.64 32.21 32.58 30.98 30.46 23.67 30.14
Al 2 O 3 25.85 22.22 33.79 24.58 29.99 27.18 27.58 25.71 25.89 22.56 29.62
Cr2 O 3 0.23 0.38 0.00 0.68 0.35 0.00 0.73 0.39 0.95 0.25 0.00
FeO 34.08 38.71 11.08 29.53 10.41 11.88 9.89 10.95 12.39 34.87 15.97
MgO 1.99 2.77 3.22 0.00 4.52 5.95 4.48 5.52 5.11 1.24 4.34
MnO 0.25 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.19 0.18 0.00
TiO 2 0.48 0.72 0.76 0.00 0.00 0.72 0.21 0.00 1.02 0.74 0.98
NiO 1.22 1.36 0.15 4.24 4.59 6.43 9.38 10.17 7.87 1.53 3.58
Total 84.67 84.40 83.81 84.85 84.50 84.37 84.85 83.72 83.88 85.04 84.63

linked with the in situ weathering and those derived
by transportation to some extent of clastic and chem-
ical material.
4.2.2. Ti-oxides
The Ti-bearing minerals consisting of nearly pure
TiO 2 phase corresponding to rutile, and a Ti–Ca
phase the chemical composition of which ŽTable 7.
approaches iron perovskite are occasionally found
only in the bauxitic-laterites of Nissi ŽLokris. and
Parhari ŽVermion.. Rutiles are probably clastic
grains, while perovskite occurs surrounded rutile and
forms replacement textures ŽChristidis et al., 1998..
4.2.3. Matrix
Nickel is mainly hosted in chlorite Žboth Mg- and
Fe-rich., the Fe-rich serpentine Žcronstedtite., espe-
cially in the Kastoria deposit ŽTable 8., and in
goethite ŽTable 7., all being components of the
matrix. In addition, the matrix shows a significant Cr
content, up to 3.68 wt.% Cr2 O 3 . Due to the very fine
grain size of components in the matrix, in particular
the clay minerals, usually the electron microprobe
analysis represent the composition of a mixed aggre-
gate rather than pure mineral phases. Nevertheless,
the Fe-dominant composition of these mixed aggre-
gates obtained by electron microprobe analysis ŽTa-
ble 7. coupled with microscopic examination and
XRD examination indicate that goethite and hematite
are the main minerals, and that apart from Cr fixed
in the clastic grains of chromite, the matrix contains
an additional amount of Cr and Ti.
Boehmite co-existing with goethite is common in
the bauxitic-laterites from both Nissi and Parhari.
54 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58
Fig. 4. Compositional fields showing the variation of CrrŽCr q Al. versus MgrŽMg q Fe 2q . in the studied Ni- and bauxitic-laterite
deposits.
Moreover, goethite exhibits variable proportions of
Al Žsubstitution of Al 3q for Fe 3q ., as it has shown
by Schwertmann Ž1983., with the AlrFe ratio in-
creasing towards the top of the profiles, and accom-
modate significant amount of Ni, Cr, and Mn ŽTable
7..
5. Discussion
Generally, it has been accepted that ultramafic
masses have undergone strong weathering, producing
laterite covers, to an extent depending upon the
climatic conditions and the topographic situation
ŽGolightly, 1981.. The primary source of nickel is
forsteritic olivine, which typically contains 0.3 to 0.4
wt.% Ni, as well as serpentinite. Elements may be
leached ŽMg, Si, Ca., enriched by supergene pro-
cesses ŽNi, Mn, Co, Zn, Y., or residually concen-
trated ŽFe, Cr, Al, Ti. ŽGolightly, 1981; Schellmann,
1989..
The mafic–ultramafic rocks in the Balkan Penin-
sula are ophiolite complexes Žof Upper Jurassic–
Lower Cretaceous age., which are found in a variety
of tectonic settings, the most typical being marginal
basins ŽPearce et al. 1984.. Subsequent to their em-
placement, many of those ophiolites were exposed to
extensive weathering that resulted in formation of
laterite crusts. During the continental stage which
followed the emergence of the Lower Cretaceous,
the laterite deposits which had been formed were
eroded and their erosion products were transported
and re-deposited in new sites forming secondary
sedimentary Fe–Ni deposits, in one or more stages
ŽAlbandakis, 1980; Valeton et al., 1987.. Some
weathering was younger, as shown by the Tertiary
molassic cover in Kastoria and Bitinka ŽMountrakis,
1983; Tashko et al., 1996..
In a comparison of the studied Ni-laterites of
northern and central Greece and the neighboring
deposits in Albania, there are some common features
between the Bitincka deposit ŽAlbania. and the Kas-
toria, Tsouka, and Profitis Ilias deposits in Greece
ŽFig. 1.: Ža. they have serpentinized peridotite as
bedrock, overlain by a saprolite zone Žaffected by
intense tectonism., which in turn is overlain by a
ferruginous zone, Žb. low Al 2 O 3 , TiO 2 and REE
contents, Žc. low Pt, Pd, and Au contents, but higher
Pt andror Pd contents than in bauxites, and Žd. a
preference of Pt over Pd Žaverage PtrPd ratio is 2.9.,
while samples from the uppermost part exhibit lower
Pt and Pd contents ŽTables 1–6; Tashko et al., 1996;
Economou-Eliopoulos et al., I996, 1997.. A limited
compositional variation of chromite grains within
saprolite zone and the overlying Fe–Ni ore of the
Bitincka, Kastoria, and Tsouka deposits is apparent
ŽFig. 4.. With respect to the source and the condi-
tions during the formation of the weathering crusts,
the transportation and re-deposition of Ni-laterites,
the chromite, which is a major clastic component,
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58
and the concentration process of the trace elements
in laterites were considered.
5.1. Implications of the chromite for the origin of Ni-
and bauxitic-laterites
Although the size of the chromite grains in the
bauxitic-laterites at Parhari ŽVermion. found on ser-
pentinites is comparable to that of the neighboring
Fe–Ni-laterites, usually the grain size of chromite in
Fe–Ni-laterites are larger than that in bauxitic-
laterites of karstic-type. The longer distance of trans-
portationrdeposition, in the case of the Lokris de-
posits of karstic-type Žtheir basement are Triassic
limestones. compared to those found on peridotites
is apparent. The very small grain size of chromite in
the Nissi-3 bauxitic-laterites may represent frag-
ments of the large chromite grains Žcomponents of
parent peridotites. probably caused during a long
distance transportation.
The compositional variation of accessory chromite
grains within the peridotite of the saprolite zone, and
the chromite grains in the overlying Fe–Ni ore is
very limited in the Kastoria, Bitincka, Profitis Ilias,
and Tsouka deposits, although compositions range
from high-Al to high-Cr ŽTables 5 and 6; Fig. 4..
The difference in the composition of chromite within
each deposit Žhigh-Cr or high-Al. is probably related
to the parent ultramafic rock type, such as harzbur-
gite, dunite, and opx-bearing dunite in the case of
Vermion ŽTable 4.. The homogeneous composition
of chromite through vertical laterite profiles may be
related to either homogeneous composition of the
ultramafic parent rocks on a regional scale or to in
situ weathering followed by re-deposition of clastic
and chemical components at the upper parts by
transportation within limited distance. For example,
the composition of less altered chromite from the
Kastoria deposit ŽCra 0.78. is comparable to that of
the bedrock ŽCra 0.77. and the saprolite zone ŽCra
0.74., while that from the Bitincka deposit ŽCra
0.50. is comparable to that of the saprolite zone
ŽCra 0.46.. The chromite composition from the
Profitis Ilias ŽVermion. Fe–Ni-laterite deposit is sim-
ilar to that of opx-bearing dunite, whereas the com-
positional variation of chromite from the Parhari
bauxitic-laterite ŽVermion. is comparable to that of
55
chromite in dunite and opx-bearing dunites ŽTable
5.. In general, the wide variation in the primary
composition of chromite grains in Ni-laterites is
consistent with contribution of clastic and chemical
material from various ultramafic rock types. These
rock types are members of ophiolite complexes, as it
is well exemplified by laterites lying on karstified
limestones of Jurassic age Nissi-2 and bauxitic-
laterites Nissi-1 and -3 ŽTables 5 and 6..
5.2. Major factors controlling the composition of
laterites
The majority of Fe–Ni-laterites in Greece are
allochthonous, even those lying on a weathering
crust, their pissolitic ore which overlies the in situ
zone has been effected by the sedimentary processes
and may contain clastic and chemical material from
various rock types. The bauxitic-laterites in Lokris
and Vermion are allochthonous. Apart from chromite
occurring as a residual component of the laterites,
rutile grains surrounding by its alteration products,
like perovskite, ŽChristidis et al., 1998., are also
present in bauxitic-laterite, but they are rare. Never-
theless, the presence of clastic Ti-bearing minerals in
bauxitic-laterites from Vermion and Lokris, show a
contribution from mafic rocks, as it has been sug-
gested in previous studies ŽVeleton et al., 1987.. It is
consistent with he presence of mafic rocks Ždiabase
and gabbros. in the Parhari area, although peridotites
are the dominant ophiolitic rocks. However, the sig-
nificant average Ti contents in goethite and boehmite
Ž1.16 wt.% TiO 2 . indicate that they host major por-
tion of the whole Ti content ranging between 1.1 and
2.7 wt.% TiO 2 in the bauxitic-laterites ŽTables 2 and
3.. In addition, major portion of the Al occurs as a
substitution for iron in goethite and chlorite ŽTables
7 and 8., while the excellent correlation between
Al 2 O 3 and TiO 2 ŽTable 4. confirm earlier studies
ŽValeton et al., 1987..
Al and Ti, which are relatively immobile, show
fairly constant Al 2 O 3rTiO 2 ratios Ž0.01. in the
goethite-rich profiles of Kastoria, Bitincka, and
Tsouka, while the TiO 2rAl 2 O 3 ratios in bauxititic
laterites of Vermion and Lokris range between 0.05
and 0.06 ŽTables 1 and 3.. They appear to be residu-
ally concentrated in about the same relative propor-
56 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58
tions as occur in parent ophiolitic ultramafic rock
ŽTiO 2rAl 2 O 3 ratio ; 0.05. ŽGolightly, 1981; Schell-
mann, 1989..
5.2.1. Significance of the REE and PGE concentra-
tions
In general, increasing Al contents are accompa-
nied by elevated REE, Th and U contents ŽTables
1–3. confirming that they share similar conditions
during their leaching, transport and deposition ŽVale-
ton et al., 1987; Maksimovic and Panto, 1991.. Their
level and inter-element relationships indicate very
good positive correlation between Al, REE, Ti, and
Th ŽTable 4. and their association mostly with
bauxitic-laterites Žaverage ÝREEs 503 ppm. and to
a lesser degree with Fe–Ni-laterites of karstic-type,
like Lokris Žaverage ÝREEs 145 ppm. or those of
Vermion Žaverage ÝREEs 113 ppm., whereas in
the Fe–Ni-laterites with in situ features, like the
Kastoria, Bitincka, and Tsouka deposits, the ÝREE
content is - 10 ppm. The strong positive inter-ele-
ment correlation among REE ŽEconomou-Eliopoulos
et al., 1997. and the average high La content Ž188
ppm. in unaltered serpentinites of Greece ŽValeton et
al., 1987. may provide evidence that serpentinized
peridotites may be a potential for REE enrichment
and a link between source rocks and bauxitic-laterites.
Assuming that there is a transition from al-
lochthonous Fe–Ni- to bauxitic-laterites, the well-
pronounced REE, U- and Th-enrichment may have
been effected by the conditions of transport and
depositionrre-deposition of the weathered material.
A low Eh environment during the formation and the
post-diagenesis stage of the bauxitic-laterites is sug-
gested by the lack or rare presence of ferrian chromite
surrounding the chromite grains ŽTable 6. and the
presence of chamosite ŽMucke, 1994.. The impor-
tance of controls by organic compounds has been
emphasized for leaching, transport, and deposition of
REE, Th, and U ŽWood, 1996..
In contrast, the PGE level is higher in Fe–Ni-
laterites than in bauxitic-laterites ŽTables 1–3.. Pri-
mary PGE mineralization in ophiolite complexes is
mostly associated with chromite andror sulfides. In
small chromite occurring from the base of the cumu-
late series andror the uppermost part of the mantle
sequence, near the Moho of ophiolites, the concen-
trations of Pt and Pd located are in the order of parts
per million, but the average Pt and Pd content Ž8 and
6 ppb, respectively. in the majority of chromite ores
of Greece is low ŽAuge and Maurizot 1995; Auge et
al., 1995; Economou-Eliopoulos 1996.. Thus, the
average contents of Pt and Pd in Fe–Ni-laterites Ž44
and 29 ppb, respectively., reaching values up to 88
ppb Pt and 186 ppb Pd in certain samples ŽTables
1–3. are higher than those in the majority of chromi-
tites in Greece ŽEconomou-Eliopoulos, 1996..
It is well known that lateritic weathering strongly
affects primary PGE mineralization, and leads to the
dissolution and transport of PGE, resulting in the
formation of new minerals, in particular, Pt–Fe ox-
ides ŽBowles, 1986; Wood and Vlassopoulos, 1990;
Auge and Legendre 1994; Auge et al., 1995.. Bowles
et al., Ž1994, 1995. indicated possible mechanisms of
solution, transport, and precipitation and that organic
compounds could provide a potential means of their
transport. In addition, the common presence of Pt-
and Pd-oxides in the Vourinos ŽGaruti and Zaccarini,
1997. and Pindos ŽPrichard et al., unpublished data.
ophiolite complexes of Greece confirm that the pri-
mary Pt–Pd minerals are easily weatherable phases.
Pt and Pd can be taken into solution, leached from
rocks under oxidizing conditions, and subsequently
precipitated in a reducing environment, such as in
sedimentary rich in organic matter ŽBaranger and
Disnar, 1991; Bowles et al., 1995; Salpeteur et al.,
1995.. With the exception of one sample of Fe–Ni-
laterite from Vermion showing 186 ppb Pd, the Pt
concentrations are much higher than Pd. Although
the PGE level is lower in bauxitic- than in Fe–Ni-
laterites, they exhibit PGE patterns with a similar
trend ŽFig. 3., the average PtrPd ratios range from
2.9 in Fe–Ni-laterite deposits with in situ features
ŽKastoria, Bitincka, and Tsouka., 3.2 in al-
lochthonous deposits ŽNissi. to 6 in bauxititic lat-
erites ŽParhari and Nissi. ŽTables 1–3.. The observed
decoupling between Pt and Pd in allochthonous lat-
erites, as is exemplified by the variation of the
PtrPd ratio and the PGE patterns ŽFig. 3a. may be
related to difference in their solubility and conditions
during transportation and re-deposition. Although
further study is required in order to define Pt–Pd-
minerals in laterites of Greece, investigations on the
W. Andriamena area, Madagascar ŽSalpeteur et al.,
1995. and Ora Banda Sill, W. Australia ŽGrey et al.,
1996. indicated that Pt mobility is higher that Pd,
 D.G. Eliopoulos, M. Economou-Eliopoulosr Ore Geology ReÕiews 16 (2000) 41–58
and that most Pt and small proportion of the Pd are
associated with secondary Fe-oxides. Furthermore,
Grey et al. Ž1996. concluded that Pd is only slowly
released during weathering, becoming incorporated
into Al-rich goethite.
Considering the inter-element correlation with
PGE, the only good correlation is that between Pt
and Mn Ž r s q0.75.. Given the relatively high mo-
bilization of Mn and Fe under reducing conditions
Žlow Eh. and low pH ŽNorton, 1973., and the Pt–Mn
good positive correlation, the lower Mn, Fe, and Pt
contents in bauxitic- than in Fe–Ni-laterites ŽTables
1–3. may reflect more reducing deposition environ-
ment, probably due to the presence of abundant
organic matter, in the former than in the latter.
Moreover, the presence of Fe-chlorite Žchamosite.,
the absence or very small rim of ferrian–chromite
surrounding chromite grains, coupled with the com-
mon presence of sulfides, even in small amounts, are
also compatible with reduced to weakly oxidized
conditions during and after the diagenesis stage of
the bauxitic-laterites.
Therefore, although the composition of the al-
lochthonous Fe–Ni- and bauxitic-laterites has been
effected by sedimentary processes and various source
rocks, the compilation of present and literature data
indicate that major controlling factors of the compo-
sition of the bauxitic-laterites are the conditions dur-
ing transportation, depositionrre-deposition of the
weathered material rather than parent mafic ophi-
olitic rocks.
6. Conclusions
Ž1. Very low contents of Al 2 O 3 , Ž4.5 wt.%.,
TiO2, Ž0.04 wt.%., REE Ž- 10 ppm., U Ž1 ppm., Th
Ž0.05 ppm. and PtrPd ratio Ž2.9. are common fea-
tures of the Fe–Ni-laterite deposits of Kastoria, Bit-
incka and Tsouka deposits. Furthermore, increasing
average Al 2 O 3 Žfrom 7.5 to 30.2 wt.%., TiO 2 , Žfrom
0.33 to 1.5 wt.%., REE Žfrom 145 to 503 ppm., U
Žfrom 7.5 to 13 ppm. and PtrPd ratio Žfrom 3.2 to 6.
from the allochthonous Fe–Ni- to bauxitic-laterites,
respectively, may reflect a transition of the former to
the latter.
Ž2. The good correlation between Pt and Mn
Ž r s q0.75. in laterites, the elevated values of the
57
PtrPd ratio in bauxitic-laterites, coupled with the
presence of Al-goethite coexisting with boehmite,
Fe-chlorite Žchamosite. and the very small rim of
ferrian–chromite surrounding chromite grains in
bauxitic-laterites, suggest more reduced conditions
during their deposition, diagenesis, and post-diagene-
sis stage than those of allochthonous laterites.
Ž3. Whole rock compositions and mineral chem-
istry within bauxitic-laterites indicate that major fac-
tors controlling their composition are the conditions
during transportation, re-deposition of the compo-
nents and their diagenesis–post-diagenesis stage, and,
to a lesser extent, contribution from mafic ophiolitic
rocks.
Ž4. The comparison between the primary compo-
sition of chromite in the saprolite zone and the
overlying Fe–Ni ore may provide evidence for the
discrimination between Fe–Ni ore linked to in situ
weathering and ore derived by transportation to some
extent of clastic and chemical material.
Acknowledgements
This research is part of an EUrBRITE EURAM
III Project ŽContract No. BE 1117 CT95-0052. enti-
tled ‘‘Integrated Technologies for Minerals Explo-
ration: Pilot Project for Nickel Ore Deposits’’. The
financial support is greatly acknowledged. Dr. G.
Economou and Mr. I. Katsikis of IGME are thanked
for their assistance with the electron probe micro-
analyses. Many thanks are also expressed to two
anonymous reviewers of this journal for their con-
structive criticism and suggestions.
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