Mineralium Deposita (1997) 32: 149–163
ARTICLE
H.G. Dill · H.- R. Bosse · K.- H. Henning · A. Fricke
H. Ahrendt
Mineralogical and chemical variations in hypogene
and supergene kaolin deposits in a mobile fold belt
the Central Andes of northwestern Peru
Received: 11 August 1995 / Accepted: 8 May 1996
Abstract In western Peru kaolin-alunite deposits occur
in Lower Cretaceous and Tertiary clastic, volcaniclastic
and volcanic, mostly rhyolitic, rocks. Alunites from hy-
pogene kaolin deposits yield K /Ar ages of 11.5 ± 0.7 Ma
and 13.3 ± 0.4 Ma. In addition to kaolin and alunite,
the following minerals are present: white mica, smectite,
barite, pyrophyllite, tridymite, cristobalite, a- and b-
quartz, chamosite, gibbsite, and aluminum-phosphate-
sulphate minerals (APS). APS mineralizations with
REE-bearing svanbergite and florencite originate from
supergene alteration. Woodhouseite, goyazite, crandal-
lite and pure svanbergite develop in hypogene and su-
pergene kaolin deposits. The distinction between hypo-
gene and supergene kaolinization can be made using
various element ratios in kaolin (P vs. S, Zr vs. Ti,
Cr + Nb vs. Ti + Fe, and Ce + Y + La vs. Ba + Sr).
S, Ba, and Sr are considerably enriched in kaolin during
hydrothermal alteration, whereas Cr, Nb, Ti and lan-
thanide elements are concentrated mainly during
weathering. Au and Ag become enriched during hypo-
gene kaolinization (advanced argillitization). Kaolini-
zation is associated with the evolution of the Central
Andes as follows: (1) during the Lower Cretaceous
kaolinization characterizes phases of relative tectonic
quiescence during mountain building and took place in a
miogeosynclinal back-arc basin. The kaolin-bearing se-
diments were laid down in flood plain to delta plain
environments; (2) in the magmatic arc/back-arc basin
Editorial handling: D.J. Morgan
H.G. Dill (&) · H.- R. Bosse
Federal Institute for Geosciences and Natural Resources,
P.O. Box 51 01 53, D-30631 Hannover, Germany
K.- H. Henning · A. Fricke
Ernst Moritz Arndt University, F.-L- Jahnstraße 17a,
D-17489 Greifswald, Germany
H. Ahrendt
Göttingen University, Goldschmidtstraße 3, D-37077 Göttingen,
Germany
 Springer-Verlag 1997
(eugeosyncline) kaolinization was mainly associated
with uplift and peneplanation; (3) in the magmatic arc
proper, late Miocene kaolinization of volcanic and vol-
caniclastic rocks has many features in common with the
high sulphidation epithermal Au deposits.
Introduction
Kaolinite-group minerals are extensively developed in a
wide range of lithologies (e.g. laterites, bauxites, and
altered igneous rocks) and form in various depositional
environments (e.g. tropical soils, flood plain deposits).
Examples of this type of kaolinization are widespread in
central Europe (Kromer 1980), SW England (Bristow
1977) and Italy (Moretti and Pieruccini 1968). Moreover
kaolinization may be used as an indicator of Ag or Au
mineralization in some metal deposits that occur along
convergent plate boundaries around the Pacific Ocean
and Caribbean Sea (Sawkins 1984; Mitchell 1992). The
clay deposits in western Peru permit discrimination of
hypogene and supergene kaolinization using trace ele-
ments and mineralogical data, as they display a wide
spectrum of mineralogical, geological and chemical
features typical of these two types of deposit (Fig. 1). In
the Andes they range in age from Mesozoic to Cenozoic
and may also be used to shed some light on kaoliniza-
tion as a function of evolution of a modern fold belt. At
several mining sites alunite and APS minerals [AB3
(XO4)2(OH)6 (where A = Na, K, Ca, Pb, Ba, Sr; B = Al,
Fe, Cu, Zn; and XO4 = PO4,SO4) (Scott 1987)] occur.
Since their precise mode of formation is still a matter of
debate, this study may also help in elucidating the origin
of alunite-APS mineralization (Störr et al. 1991; Li et al.
1992). In comparison with the wealth of publications
about ore deposits in the Andes, especially in Peru (Pe-
tersen 1970; Cardozo and Cedillo, 1990), research papers
on industrial minerals in this region are rare (Naranjo
et al. 1994).
150
Fig. 1 Geological map of the the Cajamarca Province (modified from
Quispe and Castro 1980) showing the kaolin deposits sampled in this
study. E Ecuador; CO Colombia; BR Brazil; B Bolivia; C Chile
Methods
Bulk samples were taken from kaolinized alteration zones in
opencast mines and shallow mines, which unfortunately seldom
expose the unaltered parent material. The samples were in-
vestigated using a combination of X-ray diffraction (XRD), scan-
ning electron microscopy (SEM), transmission electron microscopy
(TEM) and optical microscopy in order to identify relicts of the
primary minerals and to study the complex textures of supergene
and hypogene alteration. Powder samples comprising the size
fractions < 2 lm, 2 to 6.3 lm , 6.3 to 20 lm, 20 to 63 lm,
and > 63 lm and whole-rock samples were prepared for XRF
determination of trace and major elements. Oriented slides were
made of the < 2 lm fraction, after glycol treatment and heating to
550 °C for one hour, then X-rayed in the air-dry state in order to
identify and quantify the phyllosilicates. Diagnostic parameters for
identification of phyllosilicates are given by Thorez (1976) and
Weaver (1989). The determination of APS minerals using EMP,
SEM and TEM is discussed in detail by Störr et al. (1991). The K-
Ar isotopic composition of alunite was determined using the
method described by Steiger & Jäger (1977).
Geological setting
The kaolin-bearing Casma Formation was laid down during the
Late Jurassic to Early Cretaceous (Cossio 1964; Boggio 1980) and
was intruded by the tonalites and granodiorites of the coastal
batholith between 101 and 37 Ma (Pitcher and Cobbing 1985)
(Tables 1, 2). Kaolin deposits also formed by alteration of Early
Cretaceous clastic rocks belonging to the Chimu, Carhuaz and
Farrat Formations (Wilson 1963; Reyes Riviera 1980). These
clastic rocks host some anthracite-bearing coal seams and lenses of
gypsum in places, which originated from a short-term marine in-
gression in the Carhuaz Formation (Boggio 1980). The calc-alka-
line volcanic and volcaniclastic rocks of the ‘‘Volcanico Chilete’’,
‘‘Volcanico San Pablo’’ and ‘‘Volcanico Huambo’’ were emplaced
in Palaeocene to Late Miocene times and represent the main
sources of the kaolin in these formations (Audebaud et al. 1973;
Reyes Riviera 1980; Wilson 1984). In the ‘‘región de la costa’’, it is
the ‘‘Grupo Calipuy’’, which rests unconformably on the Casma
Formation, that hosts kaolin accumulations (Cossio 1964).
Results
Kaolin deposits in the ‘‘Formación Casma’’
At Chorobal, the top part of the acidic volcanic se-
quence has been altered to argillaceous material con-
sisting of illite, kaolinite and some quartz (Fig. 1, Tables
1, 2). The stope walls in the Chorobal mine are stained
with goethite, malachite and gypsum. Chorobal displays
moderately elevated contents of silver (0.6 ppm) and
mercury (0.06 ppm). Gold is below the detection limit of
0.01 ppm (Table 3).
Kaolin deposits in the ‘‘Formación Chimu’’
The kaolin deposits of ‘‘Formación Chimu’’ (Fig. 1,
Tables 1, 2) contain very fine-grained kaolinite, locally
as vermicular aggregates (Fig. 2a) and muscovite dis-
playing moire texture (Fig. 2b). The APS minerals
mainly belong to the svanbergite-woodhouseite series;
minor amounts of the gorceixite-bearing crandallite-
goyazite series are present. Pseudocubic crystals of P-
bearing alunite contain traces of Pb, Ba and Sr (Table 4).
Chemically, the deposits show many features in common
with other sediment-hosted kaolin deposits. Only U and
Ce (Angullaco 29 ppm U and 166 ppm Ce) are enriched
in these kaolin deposits.
Kaolin deposits in the ‘‘Formación Carhuaz’’
The kaolin deposits west of the Sulluscocha ‘‘laguna’’
contain kaolinite, quartz, some relict muscovite (Table 1)
 151

Table 1 Mineralogy and host-rock stratigraphy of the kaolin deposits studied

Host rock/Formation Deposit Mineral constituents Origin

age of formation
Abundant Common Rare

Volcanico Huambo El Guitarrero Kaolinite Quartz White mica, Ca-REE- Supergene

Upper Tertiary enriched svanbergite
Volcanico San Pablo El Sol 3/Encajon Alunite, tridymite Halloysite, Kaolinite Hypogene
Middle to Lower Cristobalite, opal CT metahalloysite barite
Tertiary Socosmayo Kaolinite, alunite Hypogene
La Providencia Kaolinite Alunite Anatase, feldspar, Supergene
Cristobalite,halloysite woodhouseite-svanbergite, Hypogene
smectite-illite m.l.
Volcanico Chilete Sangal Kaolinite Barite Alunite Hypogene
Lower Tertiary
Grupo Calipuy La Noemia Alunite, quartz, dickite Kaolinite Pyrophyllite, zunyite, topaz Hypogene
Lower Tertiary Yolanda Kaolinite, quartz Goethite Feldspar, smectite Supergene
(Hypogene)
Formacion Casma Chorobal Kaolinite, white mica Quartz Feldspar, gypsum Supergene
Lower Cretaceous Malachite, goethite (Hypogene)
Formacion Farrat Cerpac Kaolinite Quartz, white mica Supergene
Lower Cretaceous Papelillo Quartz, kaolinite White mica Supergene
Formacion Carhuaz Sulluscocha Baja Quartz Kaolinite, white mica, Supergene
Lower Cretaceous Huayllapampa chamosite
Quartz, white mica, Gibbsite,feldspar Svanbergite-florencite Supergene
Kaolinite
Formacion Chimu Cambulay Kaolinite, Quartz White mica Supergene
Lower Cretaceous Las Bateas Kaolinite Quartz, white mica P-alunite Supergene
Angullaco Kaolinite, Quartz White mica Anatase Supergene
Cahuadan Kaolinite, quartz White mica Supergene
Betty Kaolinite, quartz White mica Svanbergite -woodhouseite, Supergene
Gorceixite-bearing crandallite-
goyazite
El Alizar Kaolinite, quartz White mica Supergene
Sayopampa Kaolinite, quartz Feldspar, gypsum Supergene

and up to 10% chamosite. At Huayllapampa, gibbsite Table 2 Geology and petrography of the host rocks
has also been identified. APS minerals rich in Ce and P
are possibly members of the solid-solution series svan- Formation Thickness of Host rock lithology
host rock series
bergite- florencite (Table 4).
Volcanico Huambo Up to 300 m Rhyolitic (?) crystal tuff
Volcanico San Pablo Up to 900 m Andesitic, dacitic and
Kaolin deposits in the ‘‘Formación Farrat’’ Rhyolitic ash and
lapilli tuffs
The Cerpac and Papelillo deposits contain kaolinite,
Volcanico Chilete Up to 800 m Latitic to trachytic ash
quartz and some illite. The kaolin is low in P, S and Ba, and lapilli tuffs (ash flow)
but relatively high in Zr, Y and Ti (Table 3).
Grupo Calipuy Up to 2000 m dacitic to rhyolitic
ignimbrites
Formación Casma 600 m to 1500 m Calcareous rocks,
Deposits in the ‘‘Grupo Calipuy’’ sandstones, claystones and
graywackes with inter-
calated andesitic lavas and
The alunite-kaolin breccia-pipe near La Noemia is the tuffs
only kaolin mineralization where, in addition to Na- and
K-alunite, kaolinite is associated with dickite (40 vol.%). Formación Farrat Up to 500m Well-bedded series of
shales and arenites
La Noemia is the only example of argillic alteration in
the study area where pyrophyllite is present; traces of Formación Carhuaz Up to 500 m Well-bedded series of
topaz and zunyite are also present. At Yolanda smectite, shales and arenites
is more abundant than kaolinite (Table 1). Chemically, Formación Chimu 80 to 600 m Well-bedded series of
the deposits of the ‘‘Volcanico Chilete’’ are intermediate carbonaceous shales and
arenites
between the kaolin-alunite deposits hosted by Tertiary
152
Fig. 2 a Vermicular aggregates of kaolinite. SEM micrograph, scale
bar 10 lm, energy dispersive X-ray spectrum, Angullaco deposit.
b Pseudohexagonal platelets of kaolinite (bottom left) and muscovite
displaying moire texture. TEM micrograph, scale bar 1 lm, Las
Bateas deposit
rocks and the kaolin deposits found in Mesozoic rocks
(Table 3).
Kaolin deposits in the ‘‘Volcanico Chilete’’
The Sangal deposit is the only kaolinite accumulation of
economic interest in the ‘‘Volcanico Chilete’’ (Fig. 1).
Cubes and pyritohedra of pyrite and locally some barite
are dispersed in a matrix of kaolinite and alunite, which
formed by alteration of pyroclastics. At a later stage of
mineralization, stockwork-like fissures were mineralized
with various modifications of kaolinite but alunite and
pyrite are absent. The Sangal deposits closely resemble
the mineralization described from the ‘‘Volcanico San
Pablo’’ with respect to mineralogy and chemical com-
position (Table 3) except for the higher Sn content.
Kaolin deposits in the ‘‘Volcanico San Pablo’’
The host rocks of the El Sol 3 (or El Encajon) and So-
cosmayo kaolin deposits are intensely brecciated and
fissured (Fig. 1). Relicts of primary components (e.g. a-
quartz, glass shards) occur in the kaolinite-alunite ma-
trix. The La Providencia opencast mine is situated on an
old peneplain truncating volcaniclastic rocks about
35 km north of Cajamarca. The loamy material beneath
the denudation surface consists of kaolinized rocks
containing zones of smectitic material up to 10 cm thick.
The rough edges of kaolinite flakes seen under TEM
suggest a low degree of crystallinity. This is supported
by the fact that halloysite and metahalloysite coexist
with kaolinite in El Sol 3 (Table.1). Alunite, which is
present in all kaolin deposits in the ‘‘Volcanico San
Pablo’’, is easily recognized by its pseudocubic habit; it
is accompanied by cristobalite, tridymite and opal-CT.
Other S-bearing minerals such as barite and woodhou-
seite-svanbergite minerals are rarer (Table 4). Other
minerals present in minor amounts are anatase and
randomly interstratified smectite-illite mixed-layer mi-
nerals with illite components up to 40%. These deposits
are significantly enriched in S, P, Ba and to a lesser
extent Pb (Table 3). Conversely, they show low Zr, Y
and Mg, except at La Providencia mine which shows
higher Ti, Mg, Ca and Fe contents than other strati-
graphically equivalent kaolinite-alunite mineralizations.
El Sol 3 stands out among the deposits because of the
abnormally high contents of Au (up to 1.05 ppm), Hg
(up to 10.37 ppm) and Ag (up to 1.08 ppm) particularly
the < 2 lm fraction. The alunite gave K /Ar dates of
11.5 ± 0.7 Ma and 13.3 ± 0.4 Ma , which support a mid-
Miocene age of formation.
Kaolin deposits in the ‘‘Volcanico Huambo’’
Near El Guitarrero, pyroclastic flow deposits fill an in-
cised palaeovalley in quartzites of the ‘‘Chimu Forma-
tion’’. Microscopic study shows that the feldspar
phenocrysts are completely altered to kaolinite, whereas
the rounded a-quartz is untouched by this argillitiza-
tion.The mineral assemblage consists of very fine-
grained (< 0.5 lm) kaolinite, some quartz and white
mica. Microanalyses of the APS minerals yielded a Ca-
and REE-enriched svanbergite (Table 4). The bulk
chemistry of the kaolinized tuff displays a fairly high
content of SiO2, Cr, V, Zr, Y, and Ti, and very low
contents of P and S (Table 3).
Discussion
Phyllosilicates
Studies by Carpenter et al. (1974) have shown that
dickite remains stable up to about 400 °C. Well-crys-
tallized, vermiform kaolinite aggregates of diagenetic
origin were detected from Angullaco using SEM
(Fig. 2a). This type of kaolinite can persist up to 375 °C
depending on the pressure (Shelley 1993). Above
this temperature it is converted into pyrophyllite
Table 3 Chemistry of the kaolin-(alunite) rocks in this study (min.-mean-max.) SiO2 to P2O5 given in wt.%, As to U given in ppm

Element A B C D E F G H
Number of samples (3) (28) (3) (3) (5) (3) (10) (12)

SiO2 Min. 51.51 6.69 42.90 3.97 45.41 53.32 44.94 46.46
Mean 53.38 46.48 43.37 43.04 57.86 62.20 56.32 60.03
Max. 55.49 83.13 44.10 66.87 71.20 71.19 78.11 81.86
TiO2 Min. 1.42 0.11 0.08 0.23 0.66 1.16 0.76 0.13
Mean 1.43 1.53 1.13 1.15 0.91 1.32 1.46 0.70
Max. 1.44 8.09 1.88 2.77 1.30 1.63 2.22 1.06
Al2O3 Min. 29.45 5.57 36.59 23.06 18.74 16.72 13.32 7.71
Mean 30.12 27.49 37.97 32.55 27.14 23.00 28.88 24.71
Max. 30.90 38.85 39.10 41.05 37.13 30.18 37.67 34.52
Fe2O3 Min. 1.12 0.03 0.18 0.01 0.61 1.04 0.21 0.59
Mean 1.60 1.80 0.66 4.10 0.91 1.48 0.66 1.19
Max. 2.13 19.22 0.98 11.47 1.63 2.34 1.23 3.27
Na2O Min. 0.02 0.00 0.00 0.00 0.01 0.06 0.00 0.00
Mean 0.07 0.52 0.01 0.49 0.06 0.24 0.06 0.12
Max. 0.11 2.23 0.04 3.39 0.13 0.60 0.33 0.37
K2O Min. 0.31 0.01 0.02 0.02 0.14 1.25 0.24 1.47
Mean 0.59 1.51 0.03 0.79 0.89 2.59 1.39 3.84
Max. 0.78 6.24 0.04 5.24 2.13 3.40 3.76 5.35
SO3 Min. 0.001 0.001 0.063 0.001 0.001 0.001 0.001 0.001
Mean 0.001 1.010 0.350 1.298 0.014 0.019 0.037 0.058
Max. 0.001 8.284 0.898 8.926 0.066 0.055 0.070 0.493
P2O5 Min. 0.06 0.03 0.29 0.01 0.03 0.04 0.02 0.05
Mean 0.08 0.48 0.34 0.11 0.04 0.09 0.06 0.20
Max. 0.10 1.79 0.38 0.50 0.05 0.12 0.10 0.62
As Min. 1 1 1 10 1 1 1 1
Mean 6 33 11 90 14 9 13 27
Max. 15 163 32 225 22 15 30 75
Ba Min. 30 52 269 1 39 82 60 227
Mean 48 1915 5952 94 124 320 132 649
Max. 58 6411 17197 367 180 660 188 955
Sr Min. 63 43 946 1 21 71 25 71
Mean 73 1824 1125 270 73 124 109 128
Max. 83 6673 1259 1010 138 181 181 163
Ce Min. 55 1 1 1 1 40 1 1
Mean 67 83 77 10 37 92 85 5
Max. 77 248 161 37 94 121 166 32
Y Min. 33 1 1 1 1 28 1 4
Mean 36 8 9 19 14 44 29 7
Max. 38 38 19 53 34 56 39 12
153
Table 3 (Contd.)

154
Element A B C D E F G H
Number of samples (3) (28) (3) (3) (5) (3) (10) (12)

Cr Min. 39 1 1 39 24 66 49 1
Mean 54 23 6 53 47 67 75 15
Max. 65 59 17 61 77 70 105 30
V Min. 90 86 31 93 65 94 54 55
Mean 119 185 51 194 90 120 101 148
Max. 137 434 82 265 143 150 179 229
Cu Min. 8 1 1 1 6 11 1 13
Mean 20 35 5 28 19 32 13 734
Max. 28 129 14 76 34 68 37 7918
Pb Min. 19 1 16 1 1 11 22 1
Mean 24 59 16 17 11 22 34 147
Max. 29 192 16 43 24 30 72 476
Zn Min. 8 1 1 1 12 7 7 19
Mean 12 24 1 17 26 17 15 36
Max. 15 61 1 61 47 34 39 85
Zr Min. 285 42 30 20 139 231 219 78
Mean 333 390 277 177 393 302 366 127
Max. 420 2244 457 405 1087 394 813 286
Nb Min. 19 3 4 3 7 19 18 4
Mean 21 14 13 10 17 21 25 7
Max. 23 70 20 22 26 25 40 10
Sn Min. 1 1 1 1 1 1 1 1
Mean 7 15 19 11 8 17 17 9
Max. 20 132 30 41 38 28 54 3
U Min. 5 1 1 1 1 1 1 1
Mean 5 5 4 5 6 3 7 5
Max. 6 45 9 10 10 4 15 10

A: Volcanico Huambo Upper Tertiary

B: Volcanico San Pablo Middle to Lower Tertiary
C: Volcanico Chilete Lower Tertiary
D: Grupo Calipuy Lower Tertiary
E: Formacion Farrat Lower Cretaceous
F: Formacion Carhuaz Lower Cretaceous
G: Formacion Chimu Lower Cretaceous
H: Formacion Casma Lower Cretaceous
0.00 means below detection limit of RFA
 155

Table 4 Formula coefficients of APS minerals from Peruvian kaolin deposits

APS-Minerals Deposit K Ca Sr Ba La Ce Pb PO4 SO4

Svanbergite-woodhouseite Betty Min. 0.01 0.06 0.40 0.00 0.00 0.02 0.00 1.27 0.24
Number of samples 10 Mean 0.01 0.13 0.65 0.03 0.09 0.05 0.00 1.55 0.45
Max. 0.03 0.23 0.86 0.07 0.28 0.08 0.00 1.76 0.73
Gorceixite-bearing crandallite- Betty
goyazite
Number of samples 1 0.01 0.40 0.26 0.15 0.04 0.07 0.00 1.95 0.05
P alunite s.s.s. Las Bateas
Number of samples 1 0.74 0.04 0.07 0.08 0.00 0.00 0.08 0.20 1.80
Svanbergite-florencite Huayllapampa
Number of samples 2 0.05 0.16 0.54 0.01 0.06 0.16 0.02 1.76 0.24
0.09 0.10 0.42 0.00 0.01 0.27 0.02 1.67 0.33
Woodhouseite-svanbergite La Providencia Min. 0.06 0.47 0.10 0.02 0.00 0.00 0.00 0.94 0.93
Number of samples 11 Mean 0.14 0.56 0.25 0.04 0.00 0.00 0.00 0.97 1.03
Max. 0.23 0.79 0.36 0.11 0.00 0.00 0.00 1.07 1.15
Ca-REE enriched svanbergite El Guitarrero Min. 0.01 0.07 0.38 0.00 0.01 0.02 0.00 1.37 0.17
Number of samples 11 Mean 0.01 0.18 0.58 0.03 0.06 0.07 0.00 1.63 0.37
Max. 0.03 0.28 0.83 0.07 0.13 0.23 0.00 1.75 0.48

(e.g. La Noemia) (Fig. 3). Small platelets of kaolinite
together with halloysite (e.g. La Providencia) may have
formed during the incipient stages of Tertiary alteration
and the halloysite was subsequently transformed into
kaolinite, as described from modern trachytic pumice
deposits by Quantin et al. (1988). Fine-grained kaolinite
can form from various types of low temperature solu-
tions, provided the pH is low (Shelton 1964). Halloysite
and metahalloysite may reflect different stages of
weathering, diagenesis or hydrothermal alteration be-
fore altering to kaolinite at a later stage (Table 1).
Two different types of white mica were distinguished
from optical microscopy, TEM and SEM.
1. Fine-grained illite (e.g. El Guitarrero, Chorobal) in
the matrix of clastic rocks is taken to be a product of

Fig. 3 Mineral assemblage of the volcanic-hosted kaolinite- gold was . Na-K and P denote the major elements of alunite s.s.s.,
alunite deposits studied. Gold is shown in brackets since only Ba-Sr and REE-Pb denote the major elements of APS minerals
abnormally high amounts could be determined, but no carrier of
156

weathering or diagenesis of other micas. Illite asso- minerals makes it impossible to obtain a temperature
ciated with kaolinite indicates moderate weathering estimate.
conditions during which K and Mg were not fully
released from the saprolite (Nriagu 1976).
2. Large corroded platelets represent relict muscovite; Oxides and fluorine-bearing silicates
this is of detrital origin. No evidence of muscovite
resulting from hydrothermal alteration was seen. In Goethite coexisting with kaolinite in bauxites and la-
the alunite-kaolin deposits the mineralizing fluids terites indicates elevated Eh values. Gibbsite may form
must have had a pH far below 6, since muscovite was during the initial stages of weathering when alkalis, al-
no longer stable in the late stages of alteration (see kaline earth elements and silica are removed from the
plot of stability fields at 250 °C in Stoffregen and soil. Silica may subsequently have been added according
Alpers (1987)). to the following equation:
‡
Smectite reflects late-stage adjustment of the phyllo- 2 gibbsite 2 H4 SiO4 ) ‡
kaolinite 5 H2 O …†3
silicate assemblage to more alkaline conditions during Gibbsite may also form from APS minerals such as
devitrification of glass particles in the volcaniclastic crandallite as follows:
rocks. The scarcity of smectite compared with the vast
‡
amounts of kaolinite in the deposits shows that chemical crandallite 2 H ‡
‡ 3 H2 O ) …†
weathering involved predominantly acid solutions. Pyr-
ophyllite forms from kaolinite and quartz above 375 °C
‡ ‡
Ca2‡ 3 gibbsite 2 H3 PO4 … † 4

(Berman 1988); it is replaced by andalusite in a silica- The position of the phase boundary between gibbsite
saturated environment above 400 °C at Pload > 1 kbar and crandallite depends on the a
amount of REE in the
–8
(Kleemann 1986). The minimum temperature of for- system (Herold 1987). At H3 PO 4 = 10 gibbsite is
mation for the alunite-dickite-pyrophyllite paragenesis is stable at pH < 4. Its coexistence with kaolinite would
about 300 °C and the maximum about 400 °C, since imply pore solutions with a pH in the narrow range 5–6.
andalusite is absent. In reaction (1) muscovite is the Anatase is common in many supergene kaolin oc-
precursor of pyrophyllite and its formation is a function currences and probably forms from meteoric solutions
of pH and free silica in the solution: during weathering rather than during hydrothermal ac-
‡ ‡
muscovite 4 H‡ H4 SiO4 ) …†
tivity. Topaz Al2Si(F,OH)2 and zunyite Al13F4Cl
(SiO4)5(OH)4, which is a mineral not uncommon to high
‡
pyrophyllite K‡ Al3‡ 4 H2 O‡ 1
sulphur type deposits or advanced argillic alteration
zones (Bonham 1989), demonstrate that fluorine and
In the phase diagrams in the system K2O-SiO2-Al2O3- chlorine were involved in the high-temperature miner-
H2O, however, the muscovite and pyrophyllite stability alization at La Noemia.
fields are not in direct contact below 120 °C (Ben Baccar
et al. 1994; Bjorkum et al. 1993).
Chamosite is commonly found with glauconite at
Phosphate-sulphate minerals
water depths shallower than 60 m (Porrenga 1967,
Garzanti et al. 1989). Its predecessor, berthierine devel-
Elevated Sr, P, Na and K levels in some kaolin deposits
ops under anoxic, low-salinity (brackish) conditions and
(Tables 1, 3, and 4) occurs in alunite,which is a typical
is transformed into chamosite above 100 °C (Harder
product of ‘‘advanced argillic’’ alteration (Meyer and
1989). The Fe-bearing chlorite may form by the dis-
Hemley 1967). A compound sulphate-phosphate mineral
solution of kaolinite (Velde 1989):
between alunite and APS minerals occurs at Las Bateas
‡ ‡
kaolinite 2:8 Fe2‡ 3:6 H2 O ) …† (Table 1). K- and Na-alunites in these kaolin deposits
‡
1:4 chamosite 5:6 H ‡ 2 are typical hypogene minerals formed at an incipient
stage of mineralization, whereas P-rich alunite is likely
to have originated from supergene processes or during
the waning stages of hydrothermal mineralization. Ad-
The silica minerals vanced argillic alteration in which alunite and kaolinite
are the main products takes place at pH 4 – 5 (Stoffregen
Most samples studied contain primary quartz from acid and Alpers 1987). At La Noemia, where alunite is much
pyroclastic material or clastic quartz from the associated more abundant than kaolinite, the fluids were more
Cretaceous sandstone. Cristobalite, tridymite and opal- acidic than at Sangal, where the opposite is the case and
CT, which are formed during devitrification of volcanic a little barite is present. All APS minerals in clastic se-
glass, mark the waning stages of volcanic activity and dimentary rocks as well as those formed by alteration of
the beginning of hydrothermal activity. Hydrothermal volcanic material are Sr- or Ca-dominant (Tables 3, 4).
silicification becomes more intense upwards; it results Störr et al. (1991) recorded anomalously high La and Ce
from hot brines cooling or coming into contact with cold in woodhouseite from the supergene Hirschau-Schnait-
water in an aquifer. The small grain size of the silica tenbach deposits, Germany. The vein-like phosphate
 157

mineralization from the Nuba Mts., Sudan, which

formed from meteoric low temperature solutions, con-
tains mainly sulphate-poor crandallite (up to 2.1% SO3)
(Dill et al. 1991). In conclusion, PO43) may replace
SO42) in APS minerals and alunite formed from me-
teoric fluids or low temperature solutions during su-
pergene alteration. Elevated REE suggest formation of
APS minerals by weathering. There is evidence that in
some alunite-silica-kaolinite mineralizations a high-
temperature assemblage (P-free alunite) was overprinted
by lower temperature, supergene assemblages (Table 1).
Ba in barite was supplied by hydrothermal solutions and
scavenged from the mineralizing fluids when the S con-
tent was high and K low a way similar to that operative
in some kaolinitic alteration zones in high-sulphate Au
deposits (Siddeley and Araneda 1990). If this early de-
pletion in SO42) did not occur, K could react with SO42)
to form alunite, in which bivalent Ba may substitute for
K, or enter APS minerals at a later stage. Gypsum is a
true supergene product resulting from oxidation of
pyrite or Cu sulphides.

Distinction between hypogene and supergene

kaolinization on the basis of chemical composition

P2O5 versus SO3

Fig. 4a,b Cross plot illustrating the chemical composition of the
These hypogene kaolin deposits are rich in S and P due kaolin a P2O5 vs. SO3; b Zr vs. TiO2
to the presence of alunite and some APS minerals
(Fig. 4a). The P2O5 content rises with degree of super-
gene alteration (e.g. Chorobal).

Zr versus TiO2

Zr is very immobile under near-atmospheric conditions

and is an indicator of either the degree of weathering the
source area has undergone or the amount of reworking
the sediment has undergone. Ti on the other hand may
be concentrated in the form of anatase by hydrothermal
fluids (Yau et al. 1987). The Zr and Ti data at Yolanda
and Sulluscocha point to pervasive weathering and re-
working; the presence of chamosite supports this
(Fig. 4b, Table 1) as does an enrichment in zircon
commonly found in linear terrigenous shoreline sands
and backshore beach placers (Peterson et al. 1987).
Fig. 5 Zr / TiO2 vs. Nb / Y (Winchester and Floyd 1977) to
demonstrate mobilization of the immobile elements Zr and/or
Zr / TiO2 versus Nb / Y TiO2 during kaolinization in volcanic and volcaniclastic rocks. The
letters denote host rock petrography as listed in Table 2. The shaft
Zr, Nb, Y. and Ti have been considered to be immobile of the arrow gives the rock type as concluded from modal analysis;
during various petrological processes and, thus, are arrow head and solid dot give the type of the kaolinized rock using
chemical parameters
widely used to distinguish the various types of volcanic
rocks (e.g. Winchester and Floyd 1977) with respect to
their geotectonic setting (Pearce 1980). Samples used drothermally altered to such an extent that the parent
throughout these studies mostly contain mineral as- material can no longer be recognized. If a bivariate plot
semblages recrystallized in the greenschist facies or hy- of the so-called immobile elements (Fig. 5) is used to
158
classify the parent rock then one obtains a more basic
volcanic rock than with modal analysis (Table 2). The
results obtained from the Zr / TiO2 vs. Nb / Y (Fig. 5)
and Zr versus TiO2 plots (Fig. 4b) suggest that Ti is
released from its primary host minerals (e.g. biotite)
during hypogene and supergene kaolinization. Super-
gene concentration of Ti, however, is considerably more
efficient than the equivalent process during hydro-
thermal alteration, so that Ti can be used to distinguish
supergene from hypogene kaolinization (Steinwede
1990).
Cr + Nb versus Ti + Fe
Cr may substitute for tetravalent Ti in TiO2 modifica-
tions and for trivalent Fe in goethite during supergene
kaolinization (Köster 1974). Nb is known to be con-
centrated in Ti minerals as well, due to the similar ionic
radii. Samples from pure supergene kaolin deposits
contain high Cr and Nb, whereas these elements are
very low in hypogene deposits (Fig. 6a). The striking
contrast between hypogene and supergene kaolin de-
posits in this diagram is due to the fact that these two
elements, which under near ambient conditions are ex-
tremely insoluble, are coupled (Wagman et al. 1982). Cr
Fig. 6 Plot illustrating the chemical composition of kaolin miner-
alization (for legend see Fig. 4) a Cr + Nb vs. Ti + Fe b
Ce + Y + La vs. Ba + Sr
only forms soluble species below pH 4 –5-depending on
the activity of Cr (10–4 to 10–6)- and above pH 13.5.
Hydrothermal kaolin deposits in which alunite coexists
with kaolinite probably require pH < 4; such a low
pH is not attained in supergene environments. This may
explain why supergene deposits are rich in Cr and Nb.
Furthermore Zr / TiO2 vs. Nb / Y shows only moderate
variation in the Nb / Y ratio, since Nb is almost im-
mobile during weathering (Fig. 5).
Ce+Y+La versus Ba+Sr and Pb
Ba and Sr may substitute for each other and are mainly
found in barite, which occurs in hypogene deposits
(Table 1). Conversely, Ce, Y and La are considerably
enriched during bauxitization and supergene kaoliniza-
tion (Maksimovic and Panto 1983). Not surprisingly, the
hypogene deposits show abnormally high Ba + Sr,
whereas the samples collected from supergene kaolin
deposits cluster at a very high level of REE, e.g. at
Sulluscocha (Fig. 6b). This is corroborated by the tri-
angular plot, where La + Ce represent florencite,
Ba + Sr goyazite and gorceixite, and Pb plumbo-
gummite (Stoffregen and Alpers 1987; Störr et al. 1991).
Plumbogummite was not detected in any of the deposits.
Pb does not substitute for other cations in the APS
minerals but can replace Ba in barite (Fig. 7). REE are
mobilized during weathering but reprecipitate within the
weathering zone (Burt 1989). Pb is derived from de-
composition of K-feldspar in the bedrock; however, it is
very low in the weathering zone.
Ore mineralization and chemical composition
Base metals were not enriched during kaolinization. The
only exception to this is Cu. A disseminated Cu miner-
alization, visible as coatings of malachite, is responsible
Fig. 7 Triangular plot of Ce + Y + La vs. Ba + Sr vs. Pb (mean)
(for legend see Fig. 4)

for the elevated base metal contents in the Chorobal
kaolin (Table 3 see H). The moderately high Ag and Au
levels in the < 2 lm kaolin fraction from El Sol 3 are
probably due to absorption of these elements by phyl-
losilicates in the alteration zone, as no carriers of ‘‘in-
visible gold’’ or gold minerals have been noted in the
Peruvian kaolin deposits. Although commercial gold
concentrations have not yet been discovered at El Sol 3,
the low Au content lends support to its assignment to
the high sulphidation type of Au deposit, which is
widespread in other parts of the cordillera of North and
South America (Davidson and Mpodozis 1991; Stoffre-
gen and Alpers 1987; Sillitoe 1991; White 1991; Co-
lumba and Cunningham 1993).
Sediment-hosted and volcanic-hosted kaolin deposits:
a function of the evolution of the Andean fold belt
Between Jurassic and Recent times, during which sub-
duction of oceanic lithosphere has taken place (Frutos
1990; Sheffels 1990), three different geotectonic en-
vironments favourable for kaolinization may be deli-
neated in the Peruvian Andes (Fig. 8a): back arc
(miogeosynclinal), magmatic arc/back arc (eugeo-
synclinal), and magmatic arc.
Fig. 8a Diagrammatic representation of the mobile fold belt of
the Central Andes during the Mesozoic according to Frutos (1990).
Casma denotes the area where kaolin deposits of the Casma
Fm. evolved. B denotes the position of the cross section of Fig
8b; b Cross section through the Cretaceous sedimentary rocks on
the western limb of the Marañon Anticline (stratigraphy after
Benavides-Cacaeres 1956). The squares refer to the type localities of
kaolin deposits of a Chimu; b Carhuaz; c Farrat Formations.
Lithology: stippled, sandstone, arkose, conglomerate; hatched
claystone; bricks calcareous rocks
159
Back arc (miogeosynclinal) environment
The section through the western flank of the Marañon
Anticline shows the Valangian to Aptian continental
clastic sequences becoming more argillaceous towards
the centre of the back arc basin with thin calcareous
intercalations indicating minor marine incursions (Be-
navides-Caceres 1956; Wilson 1963)-(Fig. 8b, Santa
Fm.). Angular unconformities subdivide these sequences
(Fig. 8b- e.g. between the Chimu and Goyllarisquisga
Formations). Sites of supergene argillitization in the
Chimu Fm. are proximal to the Marañon Anticline
(Figs.1, 8b, 9). The short distance between the source
area and the Chimu Formation depocentre guaranteed a
continuous supply of unstable minerals such as feldspar
and mica. Abundance in Ce, Y and U points to an acidic
source rock. Local angular unconformities truncating
the Chimu Formation provide evidence that kaoliniza-
tion kept pace with erosion and uplift. Sedimentological
features observed during this study and others recorded
by Wilson (1963) and Boggio (1980) suggest that sedi-
ments of the Chimu Formation may have been laid
down in a mixed-load fluvial environment with kaoli-
nitic overbank fines. P-rich alunite and APS minerals
formed in backswamps where the moderately low pH of
the pore solution favoured the formation of kaolinite
(Alpers et al. 1992; Morgan 1993). Booklets of kaolinite
strongly suggest in-situ formation of the phyllosilicates
during early diagenesis.
Cryptocrystalline goethite between the detrital quartz
grains demonstrates that palaeosols developed on the
unconformities. This sort of kaolinization resembles the
china clay deposits of central Europe, which are typical
of a stable tectonic environment (Kromer 1980).
Consequently, the deposition of the Chimu sediments
and their kaolinization mark phases of relative tectonic
quiescence during the orogeny of the Central Andes.
Kaolin from Cerpac and Papellilo (Figs. 1, 9, Table 1)
accumulated in a suspended-load fluvial environment
under lower energy conditions than the kaolin deposits
of the Chimu Formation. The presence of chamosite at
Sulluscocha strongly suggests nearshore marine re-
deposition of kaolin. It is the most distal supergene
kaolin deposit relative to the Marañon Anticline. The
gibbsite at Huayallapampa is explained in terms of low
pH and extremely low aH3PO4, which may cause APS
minerals to be replaced by Al(OH)3. Such a low pH may
be caused by organic acids (Diessel 1992), common on a
delta plain (Boyd et al. 1992).
Magmatic arc/back arc (eugeosynclinal)
The Casma Group has been assigned to a back arc
geotectonic setting (Atherton et al. 1983), with the main
period of subsidence during Albian and Neocomian
times (Guevara 1978). Between the Late Cretaceous and
Palaeocene the strata were intruded by the Coastal
Batholith (Pitcher and Cobbing 1985). The region was
160
then uplifted, peneplained and covered by a thick se-
quence of volcanic rocks known as the Calipuy Group
(Vidal 1987). Primary Pb, Zn and Cu sulphide miner-
alization in the igneous rocks at Chorobal was subse-
quently converted into an argillic mineralization. Initial
stages of kaolinization at Chorobal are structurally
controlled and similar in appearance to that described as
hypogene kaolinization from the Variscan granites of
Cornwall (Bristow 1977). The driving forces for the
large-scale kaolinization, however, are inferred to be
uplift and peneplanation previous to the extrusion of the
subaerial Calipuy Volcanics at 41 Ma in this region
(Noble et al. 1979). Supergene kaolinization occurred in
the aftermath of compressive deformation of the Incaic
phase at about 40 Ma.
Magmatic arc
Uplift and peneplanation were followed during the late
Tertiary by subaerial volcanic activity characterized by
the subsidence of caldera and the deposition of extensive
pyroclastic and volcanic rocks with the ‘‘Grupo Cali-
puy’’ at the base (Noble et al. 1979; Mc Kee and Noble
1982). The supergene and hypogene kaolinization of
‘‘Volcanicos Calipuy’’, ‘‘Chilete’’, ‘‘San Pablo’’ and
‘‘Huambo’’ may have been caused by this volcanic ac-
tivity. The kaolin-alunite deposits are shown in Fig. 9 in
an idealized volcanic edifice and hydrothermal alteration
and mineralizing system reflecting different stages of
hypogene and supergene kaolinization. The deepest level
of erosion of a diatreme-maar system is preserved in the
La Noemia K-Na alunite-kaolinite deposit. Hydro-
thermal solutions produced in the ignimbrites led to the
formation of replacement ores containing dickite and
pyrophyllite at temperatures of as much as 400 °C
(Fig. 3), which is held to be the maximum temperature
of formation of the alunite-kaolinite mineralization.
Fluid inclusion studies of the Rodalquilar gold alunite
deposit, Spain, by Arribas et al. (1995) yielded tem-
peratures of formation for the advanced argillic zone
between 220 °C to 330 °C. The brecciated texture of the
volcaniclastic bedrocks and the many agglomerates
among pyroclastic deposits suggest explosive venting
(La Noemia). F and Cl contained in topaz and zunyite
contributed to this explosive activity. The La Noemia
alunite-dickite-pyrophyllite mineralization is inter-
preted, on the basis of its circular structure and the
brecciation of the pyroclastic country rocks, in terms of
diatreme formation. This diatreme was probably pro-
duced by phreatomagmatic processes as discussed by
Sheridan and Wohletz (1981) and Fisher and Schmincke
(1984). The Yolanda kaolin deposit formed at the mar-
gin of the diatreme where hydrothermal alteration in-
terfingers with weathering (supergene/hypogene near-
vent facies). The hypogene kaolinization at Sangal,
which is younger than the alunite-kaolinite mineraliza-
tion at La Noemia, formed below 300 °C (Table 1).
This assumption is based on the absence of pyrophyllite
and dickite. Studies by Steele et al. (1995) showed that
advanced argillic assemblages with dickite and APS
minerals formed at temperatures of between 120 °C and
280 °C and a pH < 6. As the magma had been depleted
in Cl and F, and to a lesser extent H2S (low-alunite
mineralization), no breccias or pipelike structures
formed in this distal vent facies. During eruption of the
‘‘Volcanico San Pablo’’, the depositional environment
may have been an ephemeral lake filled with massive to
crudely bedded sand-sized and well-bedded ash-lapilli
tuffs. Evidence is based on the hillocks and the tableland
which are made up of gently dipping layers of subaerial
siliceous sinter containing alunite, cristobalite, opal CT
and tridymite as well as the smectite-silica-kaolin asso-
ciation. The temperature of formation is difficult to as-
certain but is lower than at La Noemia. The Socosmayo
deposit is closest to the feeder channels (kaolinite-alu-
nite). Outwards the hypogene, high-alunite mineraliza-
tion of Socosmayo gives way via low-alunite
mineralization at El Sol 3 to mineral assemblages rich in
smectite and halloysite at the margin of the shallow
ephemeral lakes (La Providencia). The APS minerals at
La Providencia resulted from supergene repho-
sphatization of alunite under increased aH3PO4 and
rising pH, which overprinted the primary high sulphi-
dation-type mineralization (hot-spring facies deposited
in a maar lake). An ancient peneplain which forms the
top of the La Providencia mineralization suggests that,
like the near-vent facies of the Yolanda deposit, this
mineralization was subject to chemical weathering
(Fig. 9). The El Guitarrero kaolin deposit originated by
chemical weathering of a pyroclastic flow deposit and its
texture may be interpreted in terms of a palaeosol or
saprolite. Precipitation of REE-enriched APS minerals
took place during supergene alteration which was
stronger than in La Providencia (post-maar facies sa-
prolite). The El Sol 3, Socosmayo and Sangal kaolin
deposits formed at the shallowest erosion level of the
‘‘high sulphidation epithermal deposits’’, which is mid-
Miocene in age. In La Joya , Bolivia, alunite from a
dacite gives an age of 13.6 ± 0.5 Ma (Ludington et al.
1992). A mid-Miocene age is also suggested for the
alunite-kaolinite mineralization which was discovered in
the late stage Au-Ag mineral assemblage of Kharma Sb
vein-type deposit, Bolivia (Dill et al. 1995). The high
sulphidation epithermal deposits from Chile are also
Miocene in age (Sillitoe 1991). Although Cu and Au are
only minor constituents in the alunite-kaolin deposits
studied here, the pattern of alteration observed closely
resembles high-sulphidation Cu-Au mineralization in
the Nansatsu District, Japan (Hedenquist et al. 1994).
c
Fig. 9a Diagrammatic representation of wall rock alteration and
lithology of the volcanic-hosted kaolin-deposits referred to in the text
(not to scale); b diagrammatic representation of the palaeogeography
and lithology of the sediment- hosted kaolin-deposits referred to in the
text (not to scale)
161
162

Acknowledgements We are indebted to U. Siewers and J. Lodziak Dill HG, Weiser T, Bernhardt IR, Riera Kilibarda C (1995) The
who performed the chemical analyses (at the laboratories of the composite gold-antimony vein deposit at Kharma (Bolivia).
Federal Institute for Geosciences and Natural Resources, Hann- Econ Geol 90: 51–66
over). H. Rösch and I. Meyer kindly carried out the XRD analyses Fisher RV, Schmincke H-U (1984) Pyroclastic rocks. Springer,
for this study. Fluid inclusion studies and laser-raman spectroscopy Heidelberg New York Berlin
were performed by C. Reutel. We are also indebted to D. Noble Frutos J (1990) The Andes Cordillera: a synthesis of the geological
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