Ore Geology Reviews 69 (2015) 33–56

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Ore Geology Reviews

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Kaolinization — a tool to unravel the formation and unroofing of the

Pleystein pegmatite–aplite system (SE Germany)
Harald G. Dill a,⁎, Reiner Dohrmann b, Stephan Kaufhold a, Sorin-Ionut Balaban c
a
Bundesanstalt für Geowissenschaften und Rohstoffe, D-30631 Hannover, P.O. Box 510163, Germany
b
Landesamt für Bergbau, Energie und Geologie, Stilleweg 2, D-30655 Hannover, Germany
c
Department of Earth and Planetary Sciences Birkbeck, University of London, Malet St., London WC1E 7HX, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: The Hagendorf–Pleystein Pegmatite Province, SE Germany, is known for the largest feldspar–quartz pegmatite in
Received 12 December 2014 Central Europe and renowned for its rare elements, e.g., Li, Nb, and Ta, giving rise to a spate of exotic minerals,
Received in revised form 25 January 2015 mainly phosphates. Argillaceous rocks are scarce and eclipsed by the numerous mineralogical investigations
Accepted 26 January 2015
on rare phosphates. These phosphate pegmatites are for the first time subjected to a clay mineralogical study,
Available online 28 January 2015
rendered possible by the newly discovered strongly kaolinized aplite near the Kreuzberg Quartz Pegmatite at
Keywords:
Pleystein. The supergene kaolin akin to the residual kaolin deposit at Tirschenreuth, SE Germany, was analyzed
Kaolin for its major and minor elements by XRF and micro-chemically by EMPA. Mineralogical investigations involved
Regolith XRD, IR spectroscopy, thermoanalytical studies, CEC analyses and SEM-EDX. Supergene kaolinization forms a re-
Pegmatite–aplite pository for heavy minerals critical for the interpretation of the emplacement of the Late Paleozoic pegmatites as
Ore guide well as a matrix for pegmatite-related trace elements and thereby may be used as an ore guide during exploration
SE Germany of these rare metal pegmatites. The resultant kaolin is also the protagonist in the story of exhumation and de-
struction of a pegmatite by weathering and erosion. Irrespective of the strength of kaolinization, Nb–Ta–Ti
heavy minerals can be identified in the regolith atop the host pegmatite or aplite and used for genetic interpre-
tation of the primary mineralization and the origin of the felsic intrusive. Nb–Ta solid solution series (s.s.s.) have
to be treated cautiously because of the disposition of Ta-enriched Nb–Ta oxide s.s.s. to undergo corrosion in their
tantalite lamellae more easily than in their niobium-enriched zones. Kaolinization may alter the primary Nb/Ta
ratio but not to the extent that Ta is released completely. The most strongly kaolinized new aplite is the youngest
member of a series of felsic intrusive rocks in the Pleystein pegmatite–aplite system. The supergene kaolinization
extending from the Miocene through the Pliocene can easily be correlated by “minero-stratigraphy” with the
larger Tirschenreuth kaolin deposit. The four stages established in the area furnish evidence of gradual alkalini-
zation of the meteoric pore fluids throughout the Neogene and the Quaternary. Youngest stages are found at
Tirschenreuth, the oldest regolith stage is present at Pleystein.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
The Kreuzberg quartz pegmatite is without any doubt the most out-
standing morphological expression of the Hagendorf–Pleystein Pegma-
tite Province (HPPP), SE Germany, being present as a rugged quartz reef
among the rolling hills of the Oberpfälzer Wald landscape. It was etched
into relief by chemical weathering and erosion and has now become the
symbol of the city of Pleystein (Figs. 1, 2a). The bare rock stands out
from a hillock with gentle slopes underlain by aplitic and gneissic
rocks (Fig. 2b). Unlike Hagendorf South, the largest pegmatite of this
mining district the Pleystein pegmatite has never seen any exploitation
⁎ Corresponding author.
E-mail addresses: dill@bgr.de, haralddill@web.de (H.G. Dill).
URL: http://www.hgeodill.de (H.G. Dill).
for any kind of ceramic raw materials. Although eclipsed by the neigh-
boring Hagendorf pegmatites with respect to the economic potential,
the Kreuzberg pegmatite was as attractive for mineralogists from acade-
mia and for rockhounds (Gümbel von, 1868; Scholz, 1925; Strunz et al.,
1975; Wilk, 1975; Keck, 2001; Dill and Weber, 2009) (Fig. 1). Among
the 50 minerals known from the Kreuzberg pegmatite, 25 belong to
the phosphate group, whose members from this site mainly accommo-
date Fe, Mn, Zn, Ti, Ca and Al in their structure. Kaolinite is the only
phyllosilicate apart from muscovite which has been listed in the table
of rock-forming minerals. Similar to the neighboring pegmatites and ap-
lites of the HPPP, not very much attention was drawn to this mineral in
the Kreuzberg pegmatite either and hence neither the mineralogy nor
the chemical composition of these argillaceous rocks has been investi-
gated so far. New temporary outcrops, abundant in kaolin have been
found in the Pleystein area and, hence, enabled us to perform this in-
depth study of argillization.

http://dx.doi.org/10.1016/j.oregeorev.2015.01.016
0169-1368/© 2015 Elsevier B.V. All rights reserved.
34 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56
Miesbrunn
Pegmatite-Aplite Swarm
Flossenbürg
4524/5507 Granite
Kreuzberg
Pegmatite
Trutzhofmühle
Aplite
Fig. 1. The position and geological setting of the Hagendorf–Pleystein Pegmatite Province (HPPP). a) Topographic position of the HPPP near the Czech-German Border in Germany. b) The
geological setting of the HPPP with the major pegmatites and aplites.
Geology modified from Forster (1965) and Forster and Kummer (1974).
Kaolin with its diagnostic phyllosilicate kaolinite is very widespread
in the NE-Bavarian Basement, where kaolin is still mined at
Tirschenreuth from a large residual kaolin deposit on top of one of the
late Variscan granites (Strobel, 1969; Köster, 1974, 1980; Sobanski,
1988; Kitagawa and Köster, 1991; Gilg and Frei, 1997; Störr, 2002,
2006; Dill et al., 1997, 2013, 2014a). Excluding Strobel (1969), who
pointed to a hydrothermal kaolinization in the apical parts of the
Falkenberg Granite near Tirschenreuth, all other research workers con-
cluded to a supergene alteration as the decisive process, responsible for
the large kaolin deposits in SE Germany. Shining, colorful (semi)-pre-
cious minerals, rare phosphate minerals and a variety of rare metal min-
erals are more attractive for mineralogists than the earthy group of
phyllosilicates, represented by kaolinite, although pegmatites form the
parent rock for kaolin deposits in some places elsewhere in the world
(Ribeiro Filho, 1976; Keller et al., 1980; Pirard et al., 2007). The current
study is the first detailed clay mineralogical study on pegmatite-hosted
kaolin in NE Bavaria, in an otherwise mineralogically well investigated
geological setting (Dill et al., 2008a).
In the current investigation faultbound and massive kaolin accumu-
lated in aplites of the HPPP are investigated as to its clay and non-clay
minerals. The studies aimed at three principal goals
(1) to decipher the type of kaolinization,
(2) to describe the effect of kaolinization on those primary minerals
diagnostic for the categorization of the pegmatites and aplite, re-
spectively,
(3) to constrain the physical–chemical regime under which the kao-
lin formed.
2. Field and laboratory methods
Field work included mapping and taking 50 samples at four sites in
the HPPP, the New Aplite (NA) and Kreuzberg kaolinization zone in
the town of Pleystein (Fig. 2b) as well as the sandpit Weiss and the
Hagendorf
North
Hagendorf Pegmatite
South
Pegmatite
a
N
Silbergrube Aplite Granite
Quartz vein
Acidic intrusions
Metamorphic rocks
Pegmatite+aplites
Border
Town
4536/5496
b
Trutzhofmühle Aplite (THM), both being located south of it (Fig. 3).
Bulk samples of about 3 to 5 kg were collected, screened and separated
into light and heavy minerals. The samples were taken at subcrops (cel-
lars, adits, underground storages) and form temporary outcrops and
abandoned pits. The term New Aplite (NA) was coined during the
study of pegmatites in Central Europe and is, hence, also used in this
paper (Dill, 2015). These sites allowed us to construct a vertical profile,
measuring approximately 50 m: Faultbound kaolin at Kreuzberg: 555 m
a.m.s.l., NA: 535 m a.m.s.l., sandpit Weiss: 525 to 520 m a.m.s.l., THM:
515 to 510 m a.m.s.l. For reference some samples from the kaolinized
granite at Tirschenreuth have been taken (Fig. 4) (Dill et al., 2014a).
Samples were subjected to a grain size analysis using the classical
method of sieving for routine particle size analysis and the CAMSIZER
at a more advanced level of grain size studies. The CAMSIZER® measur-
ing system is based on digital image processing. Prior to the heavy min-
eral (HM) analysis the samples were sieved and the grain size fraction
63 to 400 μm was used for follow-up HM separation. HM separation
was carried out for each sample to the grain size fractions richest in
heavy minerals (the 3–4 ∅ fraction) using sodium polytungstate of a
density of 2.9 g/cm3 (Callahan, 1987). To clarify the structural relation-
ship and help identify the pegmatitic minerals, thin sections were ex-
amined under the petrographic microscope.
XRD patterns were recorded using a Philips X'Pert PW3710 Θ-2Θ dif-
fractometer (Cu-Kα radiation generated at 40 kV and 40 mA), equipped
with a 1° divergence slit, a secondary monochromator, a point detector
and a sample changer (sample diameter 28 mm). The samples were in-
vestigated from 2° to 80° 2Θ with a step size of 0.02° 2Θ and a measuring
time of 3 s per step. For specimen preparation, the top loading technique
was used.
SEM-EDX is an important supplement to XRD. No sputter coater was
used prior to SEM-EDX analyses by means of a QUANTA 600 FEG
equipped with a GEMINI EDX system because all analyses were carried
out under low-vac-chamber conditions (1 to 10 mbar). For some
microchemical analyses we made use of the microprobe analysis.
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 35

Quartz reef of the pegmate core topped by the Kreuzberg monastery

b
Gneiss

Aplite

Pegmatite

Colluvial and alluvial deposits

1 Kaolin (numbers denote
kaolinization referred to in the text)
New Aplite
Streets
Kreuzberg
2
Monastery on top of the
quartz reef (see als Fig. 1a)

Transect shown in Fig. 6

N
100 m

Fig. 2. The quartz reef of the Kreuzberg pegmatite is the unroofed siliceous core in the center of a zoned pegmatite whose rim of alkaline feldspar has been subjected to erosion and chem-
ical weathering while the rose quartz resisted this supergene alteration. For location of the Kreuzberg pegmatite see Fig. 1. a) The morphological outward expression of the Kreuzberg
pegmatite, viewed from the Zottbach Valley towards the South. Both numbers refer to the sites of kaolinization east of the Kreuzberg pegmatite (see also Fig. 2b). b) Geological map of
the Kreuzberg pegmatite with its different zones of kaolinization. And the newly discovered aplite (“New Aplite”). 1: kaolinized aplite running through the gneiss, 2: kaolin infilling frac-
tures near the contact between the quartz reef and the marginal aplite.

Major and trace elements were analyzed by X-ray fluorescence spec-
trometry (XRF) and by ICPMS (Li, Be). The chemical composition of pow-
dered samples was determined using a PANalytical Axios and a PW2400
spectrometer. Samples were prepared by mixing with a flux material
(Lithiummetaborate Spectroflux, Flux No. 100A, Alfa Aesar) and melting
into glass beads. The beads were analyzed by wavelength dispersive X-
ray fluorescence spectrometry (WD-XRF). To determine loss on ignition
(LOI) 1000 mg of sample material was heated to 1030 °C for 10 min.
The CEC was measured using the Cu-Triethylenetetramine method
(Meier and Kahr, 1999). The method was applied to the 1–2 mm fraction
with different reaction times. Standard reaction time for the powders is
2 h shaking in an end-over-end shaker. The 1–2 mm samples were addi-
tionally investigated with respect to the CEC after 48 h shaking followed
by 10 min ultrasonic treatment and finally after an additional of 72 h
shaking followed by additional 10 min ultrasonic treatment.
As some minerals may be identified much better, using their spec-
troscopic signature, infrared spectroscopy was carried out in addition
to the routine XRD. For measuring mid (MIR) infrared spectra the KBr
pellet technique (1 mg sample/200 mg KBr) was applied. Spectra
were collected on a Thermo Nicolet Nexus FTIR spectrometer (MIR
beam splitter: KBr, detector DTGS TEC; FIR beam splitter: solid sub-
strate, detector DTGS PE). The resolution was adjusted to 2 cm−1. Spec-
tra were recorded before and after drying of the pellets at 150 °C and
vacuum. Only the spectra of the dried pellets are shown.
Thermoanalytical investigations were performed using a Netzsch
409 PC thermobalance equipped with a DSC/TG sample holder linked
to a Pfeiffer Thermostar quadrupole mass spectrometer (MS). 100 mg
of powdered material previously equilibrated at 53% relative humidity
(RH) was heated from 25 to 1000 °C with a heating rate of 10 K/min.
3. Geological setting
The study area lies in the crystalline basement at the western edge of
the Bohemian Massif (Franke, 1989). The region under consideration is
mainly underlain by Precambrian paragneisses composed of biotite, sil-
limanite, cordierite, quartz, garnet and feldspar (Forster, 1965) (Figs. 1,
2). Second in abundance are acidic igneous rocks of Late Carboniferous
age. The Flossenbürg Granite, located immediately north of the HPPP,
36 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

Gneiss

Aplite
New Pegmatite
Aplite
Colluvial-alluvial-fluvial sediments
Kreuzberg
Kaolin
Pegmatite
Drainage system

Sandpit
„Weiss“
(aplite) THM
THM
Aplite
Aplite 500m

Fig. 3. Felsic intrusive rocks and kaolinization in the environs of Pleystein that were referred to in the text.

has petrographically been classified as monzogranite and was dated by
the Rb/Sr-whole rock method at 311.9 ± 2.7 Ma (Wendt et al., 1994).
The Falkenberg Granite, also called Tirschenreuth Granite in the area
where it forms the parent rock for the kaolin deposit, yielded a Rb–Sr
whole-rock isochrone conducive to an age of formation around 311 ±
4 Ma (Wendt et al., 1986). Felsic differentiates, including aplites and
pegmatites, evolved in the neighborhood of these Late Carboniferous
granites. The most renowned and abundant in Li-, Fe-, Mn and Zn phos-
phates are the pegmatites of Hagendorf North and South and the quartz
pegmatite near Pleystein (Forster et al., 1967; Mücke, 1987, 2000).
Swarms of quartz veins are bounding the Late Variscan granite province
towards the west (Fig. 1). After the Variscan orogeny, the NE Bavarian
Basement has been subjected to a strong uplift and denudation. The Me-
sozoic marine transgressions did not encroach upon the basement. Clas-
tic sediments and relics of the Cenozoic regolith were, locally, preserved
on a low-relief landscape in the basement, proper. These relic landforms
date back to the Late Mesozoic and the Early Cenozoic when subtropical
climates occurred in what is called today the “Oberpfälzer Wald”
(Borger et al., 1993). Pervasive kaolinization affected some parts of the
granitic rocks and led to some prominent kaolin deposits in the crystal-
line basement, such as at Tirschenreuth (Kitagawa and Köster, 1991). By
the end of the glacial period, channels of the present-day fluvial

4524 4526
5529 5529
Quaternary

Tertiary

Proterozoic

N Carboniferous

Not
covered
by the
official
geological
map

5524 5524
4524 4526
Fig. 4. Reference kaolin deposit at Tirschenreuth. The geological setting of the residual kaolin deposit Tirschenreuth on top of the Tirschenreuth Granite (modified from Rohrmüller, 1998)
with the River Waldnaab. Part of the official map No 6140/6141 Tirschenreuth/Treppenstein was issued by the former Geological Survey of Bavaria. The white area on the left-hand side
within the designated mining area has not yet been covered by an official geological map (Universal Mercator Projection).
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 37

2m
Colluvial scree

Fe-Mn

kao
kao
Aplite

a b

Pleystein

Sandpit
Weiss
THM Aplite
2 cm cc d

Fig. 5. Geology and lithology of aplites and kaolin deposits in the Hagendorf–Pleystein Pegmatite Province. a) The New Aplite (NA) east of the Kreuzberg quartz pegmatite shown here in a
temporary exposure at a construction site. The massive, unzoned aplite is completely altered into friable pale white kaolin down to a depth of almost 10 m. The maximum thickness of
kaolinization cannot be concluded from the present outcrops, The kaolinized aplite is intersected randomly by cm-wide fissures filled with Fe–Mn ochre (Fe–Mn). b) A fault gently dipping
towards the West constitutes the contact between the quartz forming the roof of the gallery and the aplite. The fault is filled with kaolin (kao). This flat-lying fault truncates a steeply dip-
ping fault filled with the same sort of argillaceous material (kao). Gallery underneath the Kreuzberg quartz core at Pleystein. c) A pervasively kaolinized feldspar aplite from the sandpit
Weiss south of Pleystein. d) The Trutzhofmühle Aplite (THM) with its contours marked in the field by the framed area. In the background the western outskirts of Pleystein are to be seen.
The outcrop of the THM is marked by debris which do not show any sign of kaolin when viewed with the unaided eye.

drainage systems incised into the basement rocks and took up the de-
bris of the older regolith and of lithoclasts eroded during the glacial
period.
4. Results
4.1. Lithology of the kaolin zones and their host rocks
It is possible to delineate the various lithologies and alteration zones
of the Pleystein pegmatite system by means of a large-scale under-
ground and surface mapping along a W–E transect perpendicular to
the strike of the felsic mobilizates (Figs. 2b, 6). The new aplite (NA) is
an unzoned aplite, oriented in NW–SE direction with a striking length
of approximately 300 m and measuring as much as 40 m in width
(Fig. 2b-1). It contains as major constituents kaolinite, some muscovite
and little feldspar. The term unzoned refers to a more or less homoge-
neous distribution of major and minor constituents in the pegmatite
or aplite, as it is the case with the NA. The Kreuzberg Pegmatite, a com-
posite or zoned pegmatite, however, strikingly contrasts with the NA,
being enveloped in an onion-shell-like way by different zones of aplites
and alteration zones (Fig. 6).
Colluvial debris of the surrounding gneisses was washed onto the
eroded aplite and covers the felsic intrusive rock at a thickness of
more than 1 m. In its topmost part it is completely altered into earthy
kaolin, with only some fissures randomly crossing the aplite and stand-
ing out from the pale white kaolinized aplite by their rusty brown Fe–
Mn ochre (Fig. 5a).
At about 20 m above the NA, another kaolinization has been discov-
ered in the entrance to an adit (Fig. 5b). In the past, miners drove an adit
gently dipping towards the west almost in the same direction as the NA
in search of iron just underneath the quartz core of the Kreuzberg peg-
matite (Fig. 2b). The wall rocks of the excavation are made up of aplitic
rocks resembling in their outward appearance those found in the unal-
tered NA (Fig. 5b). Argillaceous gray material forms the fault gouge at
the contact between the quartz core and the aplite and in a steeply dip-
ping fault capped by the flat-lying one (Fig. 5b). Another fault runs
through the back of the gallery. Kaolin fills the central part while the
Fe–Mn ochres developed on both sides of the fault.
Apart from this supergene kaolinization, the exocontact zone identi-
cal with the wall rocks close to the Kreuzberg pegmatite was mapped
mainly based on the study of cellars and adits along a W–E transect
through the Town of Pleystein (Fig. 6).
The sandpit “Weiss”, south of the Pleystein, lithologically resembles
the new aplite and does not provide any remarkable geomorphological
expression in the field, so that it deserves a close-up view to be
reproduced in this chapter (Fig. 5c, d). The term sandpit in a crystalline
basement might render the reader a bit confused. The pervasively al-
tered aplite which strikes perpendicular to the afore-mentioned miner-
alized structure zones was exploited as a construction raw material
which is anything but a friable quartz-feldspar grus abundant in kaolin,
similar to what has been recorded from the Pleystein new aplite and in
parts from underneath the Kreuzberg Quartz Pegmatite (Fig. 5c). The
term ‘grusy’ texture has been described by Migoń and Thomas (2002)
who applied this term as an azonal lithological term without any conno-
tation, neither to the bedrock lithology nor the way its rock-forming
minerals responded to weathering.
Considering its altitude above mean sea level (a.m.s.l.), the lowest
exposure of an aplite in the study area is located at Trutzhofmühle
38 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

quartz quartz, quartz, quartz, kaolinite

muscovite muscovite, muscovite muscovite APS minerals (P>>>>S)
alkaline feldspar alkaline feldspar alkaline feldspar kaolinite muscovite-illite
plagioclase plagioclase kaolinite ± goethite anatas
chlorite chlorite, ± chlorite Mn oxide-hydrate
± vermiculite ± quartz
± alkaline feldspar
± goethite
A B C D E

Hypogene alteration Supergene alteration (kaolinization)

gneiss
aplite massive
quartz core
eroded quartz
eroded feldspar
kaolinized
aplite

E E
B C E
A D No coverage
DE
?
B
B
?
D ?
? Kreuzberg Pegmatite ? New Aplite
? ?
0 50m 100m 150m
W E

Fig. 6. Supergene alteration superimposed onto the hypogene alteration along a W–E transect through the “Kreuzberg Pegmatite” and “New Aplite”. The distribution of alteration zone is
based on underground mapping and in the environs of the “New Aplite” based on mapping outcrops at the surface. The mineral assemblage for each zone is given in the boxes above in
decreasing order of abundance. The color is to facilitate correlation between mineral assemblage and the mapping along the transect. The number of samples for each zone used for the
analysis of clay minerals is given in Arabic numerals in squared brackets below. A: Muscovite–chlorite alteration in the gneissic wall rocks (exocontact of the Kreuzberg Pegmatite)-[5]. B:
Muscovite–chlorite–vermiculite alteration of the aplite zone (transitional zone) [6]. C: Muscovite–kaolinite–chlorite alteration of the aplite–pegmatite zone (endocontact of the Kreuzberg
Pegmatite)-[6]. D: Muscovite–kaolinite–goethite alteration of the Kreuzberg pegmatite–aplite and New aplite [10]. E: Kaolinite–APS–muscovite alteration of the Kreuzberg pegmatite–ap-
lite and New aplite [8].

immediately above the local drainage system (THM) (Fig. 3). Its outcrop
is marked in the field by rubble of quartz and aplitic rocks, based upon
which we mapped the direction of strike as NW–SE (Fig. 5d).
Both aplites in the former sandpit Weiss and at the THM are isolated
felsic intrusive dikes cutting through the monotonous paragneisses
(Forster, 1965).
As a reference type to the kaolinization currently investigated in the
environs of Pleystein, the kaolinized late Variscan granite near
Tirschenreuth was taken. A detailed description of the geology was
given in Dill et al. (2014a).
4.2. Granulometry and morphometry of kaolin
The unconsolidated earthy samples were passed through a sieve and
investigated by means of the CAMSIZER. Out of these set of samples, two
samples, one representative of kaolin on top of the aplitic parent mate-
rial and the other washed downhill from the site of weathering are illus-
trated in Fig. 7. Two samples are shown in Fig. 7 with the size
distribution described in form of cumulative grain size curve and a his-
togram. The aplitic grusy regolith that still resides on top of the aplitic
parent material shows a strikingly poorer sorting, expressed by the
graph which is more gently skewed towards the left than the kaolin il-
lustrated in Fig. 7b. The well-sorted kaolin is located downhill from
the original site of formation. Both samples also differ from each other
as to their sphericity which is calculated as the ratio of length and
width. The maximum of sphericity is represented by the globe and nu-
merically expressed by a number close to 1. A closer look at the spheric-
ity of both kaolin types shows no significant differences for the finest
fraction of kaolin particles (Table 1). Considering the opposite end of
the grain size scale gives a different picture, because of the higher angu-
larity and deviation from the globe of the in-situ kaolin. Also the
minimum of sphericity is attained at different particle sizes. Plates man-
ifested by low sphericity values are larger in the kaolin wash than in the
ins-situ kaolin (Table 1).
4.3. The heavy minerals of kaolin
Panning in the field, mineral separation using heavy liquids and
washing of kaolin in the lab revealed that the HM fraction of the kaolin
is almost negligible from the volumetric point of view, since it makes up
only less than 0.5% of the overall rock-forming minerals. A survey under
the SEM, provides a completely different picture. It shows the qualita-
tive characteristics of the HM assemblage rather variable so that they
may be used as an efficient tool for the discussion on the origin of kaolin
(see subsequent chapter). The various heavy minerals are listed in
Table 2.
4.3.1. Columbite
One of the most conspicuous minerals in the Pleystein kaolin is co-
lumbite, a complex solid-solution series (s.s.s.) of Fe, Mn, Nb and Ta,
with an ideal chemical composition of (Fe,Mn) (Nb,Ta)2O6 the mineral
grains of which are widely known from pegmatites across the Bohemian
Massif (Novák and Černý, 2001; Novák et al., 2003; Dill et al., 2008b,
2009). It cannot be overlooked by its bright color in the SEM and BSE
(back-scattered electron) images and stands out by its thin plates, local-
ly containing well-developed subdomains (Fig. 8a). This orthorhombic
oxidic mineral mostly occurs in crystals flattened to the prism faces
{01¯0}, using for labeling of the crystal morphology the Miller's indices.
Its grains are engulfed by kaolinite showing corrosion of its faces and
edges to different degrees (Fig. 8a). The Nb–Ta oxide under study is a
niobium- and iron-dominated solid solution series that most closely
corresponds to columbite-(Fe) rather than to tantalite (Linnen and
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 39

Aplic grusy regolith on top of the aplite

Aplic wash downhill of the aplite

Fig. 7. Granulometry of kaolin. The size distribution is described in form of cumulative grain size curve plotted onto a histogram. a) The aplitic grusy regolith formed immediately on top of
the aplitic parent material (autochthonous). b) The aplitic wash resulted from a combination of creeping and flowing which gave rise to some grain size sorting expressed by a conspicuous
steepening of the cumulative grain size graph (parautochthonous to allochthonous).
40 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

Table 1 to site 1, another s.s.s. among the APS mineral group has been discovered,
Morphometry of the overburden deposits on top of the newly discovered aplite at site 1 containing as major component gorceixite (up to 6.5 wt.% Ba), goyazite
(see Fig. 2b) the grain size variation of which is illustrated in Fig. 7.
a) Aplitic grusy regolith on top of the aplite.
(up to 1.9 wt.% Sr) and crandallite (up to 1.5 wt.% Ca) (Fig. 10a). This
b) Aplitic wash downhill of the aplite. APS s.s.s. is accompanied by an aluminum phosphate texturally different
from the APS mineral shown in Fig. 8c and contains Ba (3.4–3.7 wt.%)
Grain size Grain size Sphericity Sphericity
and Bi (7.5–7.8 wt.%) in significant amounts with some Ca (2.1–
Minimum Maximum Fig. 7a Fig. 7b 2.9 wt.%) (Fig. 10b). The amount of crandallite in these APS aggregates
0 63 0.829 0.821 got reduced in favor of gorceixite (Ba end member) and waylandite (Bi
63 73 0.835 0.838 end member). In the case of waylandite, the amount of iron is insufficient
73 84 0.833 0.836 (0.58 wt.% Fe) to denominate it as zairite [Bi(Fe,Al)3(PO4)2(OH)6], the fer-
84 97 0.801 0.808
97 112 0.772 0.781
ric analogue of waylandite. The latter Bi phosphate although not a very
112 129 0.749 0.759 common mineral has been described from several pegmatites across the
129 149 0.719 0.729 world (Knorring von and Mrose, 1963; Baldwin et al., 2000; Novák
149 173 0.700 0.711 et al., 2001). Waylandite was also reported together with zairite and Bi
173 200 0.670 0.683
ochre from the Kreuzberg site 2 which is located only few meters above
200 230 0.657 0.672
230 266 0.650 0.660 site 1 (Dill and Weber, 2009) (Fig. 10c). In the zairite, the Bi contents
266 307 0.640 0.648 are much higher than at site 1 attaining values of 18.8 to 28.3 wt.%,
307 355 0.643 0.645 while Bi and Fe contents range from 10.5 to 17.3 wt.% Fe. As the Fe content
355 409 0.647 0.636 goes down the Bi content may increase to 30.0 wt.% Bi and so the
409 472 0.654 0.634
472 546 0.658 0.631
waylandite end member becomes more prominent in the s.s.s. Last but
546 630 0.692 0.666 not least apatite was encountered scarcely in aggregates like a hedgehog,
630 728 0.784 0.751 made up of acicular and thin plates in the new aplite (Fig. 10d). Opposed
728 840 0.786 0.758 to many apatites from pegmatites that contain considerable amounts of
840 970 0.792 0.751
Mn and hence called manganiferous apatite, apatite from the kaolinized
970 1120 0.794 0.736
1120 1294 0.798 0.770 part of the apatite at site 1 lacks significant amounts of Mn (Schaaf
1294 1494 0.805 0.767 et al., 2008; Dill et al., 2008b, 2009). There are also phosphate-bearing
1494 1725 0.799 0.824 compounds coating on aggregates of Fe oxide– Fe oxide-hydrates and re-
1725 2000 0.794 0.824 placing the host Fe aggregates either from the margin or along grain
boundaries of hexahedral crystals (Fig. 10e). Aluminum and phosphate
show a strong positive correlation as the iron contents get significantly re-
Keppler, 1997). Its Ta ∗ 100 / (Ta + Nb) ratio varies more strongly than duced along with the increase of both elements (RAl–P = +0.75, RTi–Al =
that of the Mn ∗ 100 / (Mn + Fe) ratio but only one data point exceeds +0.34, RTi–P = +0.66). It is difficult to make a definite mineral account-
50 (Fig. 9). Both ratios diagnostic for the categorization of the colum- able for this Fe–Al–P relationship because there are too many options
bites are illustrated for all pegmatites under consideration in this with no choice between one or the other on the basis of the methods ap-
study (Fig. 9). Along-side the data array the intensity of kaolinization plied. It is likely to have cacoxenite among these phosphates. The EMPA
is given on the right-hand side and the height above mean sea level could not shed any light on these rhythmically banded aggregates of
for the outcrop of each pegmatite and aplite, respectively, on the left- Fe–Al phosphates. APS minerals mentioned above have to be ruled out
hand side. A close-up view reveals that Nb-enriched columbite forming as there were no elements such as Ca, Sr, Ba or REE detected by the EMPA.
the core of the s.s.s. is rimmed by Ta-enriched columbite-(Fe) (Fig. 8b).
The back-scattered electron images (BSE) of the corroded columbite 4.3.3. Iron–manganese–aluminum–titanium oxides
grains show a strong zonation unrivaled by the other columbite s.s.s en- Panned samples of kaolin from site 1 yielded cubes of brownish me-
countered in the Kreuzberg pegmatite and Trutzhofmühle aplite tallic luster which point to hexahedral pyrite in the heavy mineral con-
(Fig. 8d, e). Table 3 numerically proves the morphological differences centrate (Fig. 11a). As a bit of surprise, during EMPA there was not a
in the corroded columbites from the aplite at site 1. The table enables single spot of sulfur in these cubes alleged to be pyrite.
the reader to compare the mean values of the chemical composition ob- In Pleystein and in Tirschenreuth poorly crystallized Fe- and Mn
tained for three columbite grains to the chemical composition measured oxide-hydrates (“limonite”, “manganomelane”, goethite, hematite) are
at various station points in each of these mineral grains. The strongest present. At sites 1 and 2 lithiophorite has been spotted while at site 2
chemical contrast has been determined in columbite 3. Columbite is ex- cryptomelane occurs (Fig. 11b). Rhythmic layers made up of Mn and
clusive to the Hagendorf–Pleystein region. Al with traces of Co but bearing neither Si nor P this encrustation were
interpreted as a member close to todorokite.
4.3.2. Phosphates Evidence of increased amounts of Ti is furnished by increased
Phosphates are abundant in the HPPP and rare in the Tirschenreuth amounts of ilmenite, rutile, pseudorutile and anatase, the latter only at
granite, mostly as apatite (Dill et al., 2009; Dill and Weber, 2009) Tirschenreuth.
(Table 4). In the Pleystein area, the group of phosphates is mainly com-
posed of Fe-Mn phosphates of the rockbridgeite-frondelite s.s.s., Zn 4.3.4. Silicates
phosphates, e.g., schoonerite and parahopeite, and uranyl phosphates — Zircon occurs in the Pleystein and Tirschenreuth kaolin, where this
see all phosphates in Table 4. The NA is pervasively kaolinized and in transparent mineral is accompanied by schorl. Going by the morpholo-
stark contrast with regard to the phosphate assemblage in the adjacent gy of zircon that may be observed in the surrounding pegmatites, one
pegmatites (Table 5a). has to emphasize the rather different outward appearance of zircon in
In and around Pleystein, there are variable phosphate minerals the kaolin at Pleystein (Dill et al., 2012). Zirconium positively correlated
pertaining to the APS minerals (aluminum-sulfate-phosphate) sensu with Al (rAl–Zr = 0.55) and Ti (rTi–Zr = 0.60).
Dill (2001) which accommodate cations such as Ca2+, Sr2+, Ba2+, and
REE3+ in their lattice (Dill et al., 1997). At site 2 of the Kreuzberg, the 4.3.5. Sulfide
most elevated sampling site under study, the crandallite s.s.s. contains Despite the elevated Bi contents found in the phosphates there are
considerable amounts of strontium (up to 13.6 wt.% Sr) and hence, no equivalent Bi sulfides observed in the samples from the NA. At site
has to be denominated as goyazite-crandallite s.s.s. Moving downhill 2 near the Kreuzberg quartz reef, Bi sulfide (bismuthinite) marks the
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 41

Table 2
Minerals as provenance indicator (relic minerals) and the physical–chemical regime (prestage and stages I, II and III).

Mineral Distribution Prestage strongly acidic Stage I strongly Stage II moderately Stage III neutral to
of minerals meteoric fluids acidic meteoric acidic to alkaline alkaline meteoric fluids
fluids meteoric fluids

(r) = relic mineral ≥23 Ma ≥4.2 Ma ≈4.2 Ma b4.2 Ma

Zircon Tirschenreuth (r) P: pH b 3
Tourmaline (schorl) Tirschenreuth (r) present
Silica (opaline material/opal CT) Tirschenreuth pH ≤ 7, pH ≤ 7, fluctuating
Pleystein fluctuating around around Eh = 0
Eh = 0 log a Al+++/(H+).3
log a Al+++/(H+).3 below 8
below 8
Quartz Tirschenreuth (r) Present
Pleystein (r)
Alkaline feldspar Tirschenreuth N pH N 7 pH N 7
Pleystein(r)
Apatite (Mn-free) Tirschenreuth (r) Present
Pleystein (r)
Ilmenite + rutile Tirschenreuth Present
Columbite-(Fe) Pleystein Present (Ta slightly
decreased during
kaolinization)
Anatas Pleystein site 1 Eh N 0 Eh N 0
Tirschenreuth
Kaolinite Pleystein N Tirschenreuth P: pH 4.5–6.5
log a SiO2(aq) −4.0
to −3.0.
T: pH 2.5–5.5
log a SiO2(aq) −4.5
to −3.0
Goyazite–crandallite-s.s.s. Pleystein site 1 HPO2−4 of −5
pH 2 to 5
log a SiO2(aq) b 1.5
Gorceixite–goyazite–crandallite-s.s.s. Pleystein site 1 HPO2−4 of −5
pH 2 to 5
log a SiO2(aq) b 1.5
Waylandite–gorceixite s.s.s. Pleystein sites 1 + 2 HPO2−4 of −5
pH 2 to 5
log a SiO2(aq) b 1.5
Waylandite–zairite s.s.s. Pleystein sites 1 + 2 HPO2−4 of −5
pH 2 to 5
log a SiO2(aq) b 1.5
Fe–Al phosphates (cacoxenite?) Pleystein site 1 HPO2−4 of −5
pH 2 to 5
log a SiO2(aq) b 1.5
Todorokite Co-bearing Pleystein site 1 Eh N 0
“Limonite”goethite, hematite Pleystein Eh N 0
Tirschenreuth
“Manganomelane”lithiophorite, Pleystein Eh N 0 Eh N 0
cryptomelane Tirschenreuth
Muscovite Tirschenreuth P: pH 6.0–12.5
Pleystein log a SiO2(aq) −6.0 to
−3.5
T: pH 5.5–11.5
log a SiO2(aq) −6.0 to
−3.5
Chlorite Tirschenreuth Chlorite group pH N 7
dependent upon the
valence state of Fe
accommodated into the
lattice of chlorite log a
Al+++/(H+).3 = 7.5
Smectite Tirschenreuth pH ≥ 8/Eh N 0

start of a series of Bi minerals, including Bi ochre or bismite, a bismuth
oxide mineral close to bismuth trioxide, and also ximengite which can-
not be proofed yet. As the only representative of the sulfides at site 1,
abundant hexahedral pyrite pseudomorphoses were panned from the
kaolin (Fig. 11a).
opal CT among the phyllosilicates of the mineral assemblage at site 1
and site 2. These tectosilicates were also encountered at Trutzhofmühle
and in the Weiss Pit (Fig. 3). Feldspar has been observed along the W–E
transect, from zones A through C, whereas quartz still persists into
zones D and E (Fig. 6).

4.4. The light minerals of kaolin

4.4.1. Tectosilicates
Alkaline feldspar, albeit strongly altered may still be spotted in small
amounts in the kaolin (Fig. 12). Silica is present as relic quartz derived
from the aplitic parent material. A few infra-red graphs also showed
4.4.2. Phyllosilicates
4.4.2.1. Zonation of the phyllosilicates in the Pleystein pegmatite–aplite sys-
tem. Phyllosilicates, including quartz and feldspar, were mapped in the
exo- and endocontact zones of the Pleystein pegmatite system and
42 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

Ta max

a b

2.56 0.44
0.37

1.06

Nb/Ta ratios

4 mm

Qtz

e d

Fig. 8. Columbite under the scanning electron microscope (SEM) and the electron microprobe (EMP). a) Plates of columbite-(Fe) with a well-developed subdomain surrounded by book-
lets and plates of kaolinite predominating the kaolin on top of the Pleystein new aplite (NA). SEM image. b) Intergrowth of Nb-enriched columbite-(Fe) in the center and Ta-enriched
columbite-(Fe) at the rim surrounded by kaolinite. Pleystein kaolinized aplite. SEM image. c) Corroded zonal columbite-(Fe) showing zones of different Nb/Ta ratios. The columbite-
(Fe) solid solution series becomes more porous in the columbite zones enriched in tantalum. BSE image. d) Uncorroded and unzoned columbite-(Fe) from the Trutzhofmühle aplite. Co-
lumbite (station points 11, 12) is intergrown with niobian rutile (station points 10, 13, 14) in a matrix of muscovite (Mus) and quartz (Qtz). BSE image. e) Uncorroded columbite-(Fe) on a
macroscopic scale in quartz from the Trutzhofmühle.

used to design the cross section of Fig. 6, which may be subdivided into
5 zones.
In the underground storage rooms belonging to the most distal zone
A tightly folded biotite–sillimanite gneisses are exposed. They are
intersected by some normal faults, but aplitic and pegmatitic bodies
are absent. Among the phyllosilicates muscovite and Fe–Mg chlorites
were identified. Zone B is called the aplite zone because of a growing
number of disharmonically folded aploids and joints filled with aplites.
Yet no coherent aplites or pegmatites were observed there. In addition
to muscovite and chlorite minor amounts of vermiculite were deter-
mined by XRD (Fig. 6). The alteration zone C adds up a considerable
amount of pegmatite veins to the stockwork-like concentration of aplite
veins and veinlets in the gneissic country rocks around the Kreuzberg
Pegmatite. As to the mineral association, only quartz, muscovite, and
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 43

60.00

50.00

40.00 Strongly
y = 2.5914x
Ta*100 /(Ta+Nb) 535 m New Aplite
Pleystein kaolinized

30.00

20.00 Very poorly

Aplite y = 1.095x
512 m Trutzhofmühle
kaolinized
Pleystein

10.00 Moderately to strongly

Pegmatite y = 0.9118x
555 m Kreuzberg kaolinized
Pleystein

0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00
Mn*100 /(Mn+Fe)

Fig. 9. The Mn ∗ 100 / (Mn + Fe) ratios plotted vs. the Ta ∗ 100 / (Nb + Ta) ratios of the strongly kaolinized newly discovered aplite (red) at Pleystein in relation to the neighboring
Kreuzberg pegmatite (blue) and the Trutzhofmühle aplite (THM). For location see Fig. 3. The trend lines and the numerical parameters to describe their inclination relative to each
other are given in the x–y plot. The vertical brackets denote the intensity of kaolinization and the figures in italics refer to the altitude above mean sea level where the felsic intrusive
rocks crop out. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

minor chlorite survived this change in the clay mineral association, spectroscopy. In the graph of Fig. 14 the four characteristic OH-
while kaolinite becomes more and more predominating towards the stretching vibrations originating from the different AlAlOH bondings
Kreuzberg Pegmatite. Compared to previous zones, in zone E, the chem- are assigned v1–v4. The v1 through v3 vibrations result from inner sur-
ical alteration has been taken to the extreme in what has been described face hydroxyls whereas v4 corresponds to inner hydroxyls.
as the "eutectic zone". The phyllosilicate mineral assemblage consists of Kaolinites with so called b-axis disorder (Russell and Fraser, 1994)
muscovite and kaolinite. lack the v2 stretching vibration and in the case of halloysite, both, v2
Zone E shows the most intensive kaolinization rife with APS min- and v3, are absent. Results obtained by IR spectroscopy confirmed,
erals (Fig. 6). only traces of kaolinite in the N63 fraction. Comparing the IR data of ka-
olin (b 63 μm fractions) of the fault gouge from site 2 to the kaolin from
4.4.2.2. Kaolin of the Kreuzberg pegmatite. The fault gouge of the the NA at site 1 reveals different degrees of crystallinity. The different
Kreuzberg pegmatite — site 2 — contained only two phyllosilicate OH-stretching spectra of both samples result from the larger illite/mus-
minerals, kaolinite plus muscovite. The latter phyllosilicate belongs to covite contents of the sample taken at site 2 and from a lower degree of
the 2M1 polytype according to the results obtained from XRD. Fraction- crystallinity of the kaolinite in this sample. The appearance or absence
ation and grain size analysis showed that kaolinite to be enriched in the or even the intensity ratio of the 3670 and 3650 cm−1 band is often con-
fine fraction (Fig. 13). The samples were also investigated by IR sidered reflecting the crystallinity (degree of structural order) of the ka-
olinite (Russell and Fraser, 1994). Accordingly, the low intensity of the
band at 3670 cm−1 indicates a lesser degree of crystallinity compared
Table 3
Chemical composition of columbite solid solution series to show the mean values in rela-
to the samples at site 2. Another applicable method to derive some in-
tion to the internal chemical zonation. The first column denotes three selected mineral formation about structural order of the kaolinites from, IR spectra was
grains of columbite and the station points used for the determination of the chemical provided by Brindley et al. (1986). These authors established an empir-
composition. ical relation of the position of v1 and the famous Hinckley index which
Mineral Mn Fe Nb Ta is determined by XRD to characterize the degree of structural order. The
v1 position of all samples ranges from 3695 to 3697 which corresponds
1/1 2.019 13.433 33.680 25.653
1/2 2.261 13.836 39.765 18.135 to a Hinckley index of 0.5 to 1.0.
1/3 2.991 12.902 35.887 22.102
Columbite 1 mean 2.424 13.390 36.444 21.963 4.4.2.3. Kaolin of the new aplite. The most intensively kaolinized part of
2/1 2.493 13.801 41.097 15.458 the pegmatite–aplite system at Pleystein, to be more precise, in the
2/2 2.259 12.942 30.610 27.980
2/3 2.044 11.782 19.128 44.290
entire Hagendorf–Pleystein Pegmatite Province, has been discovered
2/4 1.799 14.208 36.747 21.207 at site 1, the new aplite (Fig. 5a). The kaolin samples taken at outcrop
2/5 2.501 13.897 40.817 15.994 do not differ from those of site 2 by quality and contain muscovite and
Columbite 2 mean 2.219 13.326 33.680 24.986 kaolinite but by quantity. Traces of alkaline feldspar and quartz were
3/1 1.988 13.464 33.483 26.098
spotted in all XRD runs. With respect to the argillitization of the new ap-
3/2 1.724 12.368 19.443 44.172
3/3 3.164 13.888 47.056 7.378 lite, three different zones may be singled out, two marginal zones, one
3/4 1.990 13.188 31.579 27.856 facing up-hill (HD 11304734) and another down-hill (HD 11304736)
3/5 2.962 13.641 43.733 11.881 as well as a central zone (HD 11304735) (Fig. 15). The IR spectra of all
3/6 2.155 14.154 40.445 17.271 samples do not reveal significant differences. All spectra are dominated
Columbite 3 mean 2.330 13.450 35.957 22.443
by kaolinite which, according to the two well resolved bands, between
44 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

Table 4
Phosphate minerals found in the Kreuzberg pegmatite (KB) and Trutzhofmühle aplite (TM) being located next to the kaolinized new aplite at Pleystein. References: KB: Laubmann et al.
(1920), KB: Wilk (1959), KB: Dill et al. (2009), TM: Dill et al. (2006), TM: Dill et al. (2008a, 2008b).

Phosphate Chemical composition Kreuzberg New aplite Trutzhofmühle

Apatite-(MnF) (Ca,Mn,Fe)5(PO4)3(F,Cl,OH) KB TM
Autunite Ca(UO2)2(PO4)2·11H2O KB TM
Barbosalite Fe2+Fe3+2 (PO4)2(OH)2 KB
Benyacarite (H2O,K)(Mn2+,Fe2+)2(Fe3+,Ti)2 Ti[(O,F)2|(PO4)4]·14H2O KB
Beraunite Fe2+Fe3+5 (PO4)4(OH)5·4H2O KB TM
Cacoxenite (Fe,Al)25[O6|(OH)12|(PO4)17]·75 H2O KB TM
Chalcosiderite CuFe6(PO4)4(OH)8·4H2O KB
Childrenite FeAl(PO4)(OH)2·(H2O) TM
Churchite-(Y) YPO4·2(H2O) TM
Crandallite CaAl3(PO4)2(OH)5·(H2O) KB NA
Diadochite Fe2(PO4)(SO4)(OH)·6(H2O) TM
Dufrénite Ca0.5Fe2+Fe3+5[(OH)3|(PO4)2]2·2H2O KB
Ferrolaueite FeFe2(PO4)2(OH)2·8(H2O) TM
Fluellite Al2(PO4)F2(OH)·7H2O KB
Fluoroapatite Ca5(PO4)3(OH,F,Cl) KB NA TM
Frondelite Mn2+Fe3+ 4 (PO4)3(OH)5 KB TM
Gorceixite BaAl3(PO4)(PO3OH)(OH)6 NA
Gordonite MgAl2(PO4)2(OH)2·8(H2O) TM
Goyazite SrAl3(PO4)(PO3OH)(OH)6 NA
Heterosite (Fe,Mn)[PO4] KB
Hopeite Zn3(PO4)2·4H2O KB
Kolbeckite ScPO4·2(H2O) TM
Lazulite MgAl2(PO4)2(OH)2 TM
Lermontovite U(PO4)(OH)·(H2O)(?) TM
Leucophosphite KFe2(PO4)2(OH)·2(H2O) KB
Metavivianite (Fe3 − x,Fex)(PO4)2(OH)x·8x(H2O),x = 0.5 TM
Meurigite-K KFe7(PO4)5(OH)7·8(H2O) KB
Mitridatite Ca2Fe3(PO4)3O2·3(H2O) TM
Monazite (Ce,La,Nd,Th)PO4 TM
Oxiberaunite (Fe,Mn)Fe5(PO4)4O(OH)4·6(H2O) KB TM
Pachnolite NaCaAlF6·H2O KB
Parahopeite Zn3(PO4)2·4H2O KB
Petitjeanite Bi3O(OH)(PO4)2 KB
Phosphoferrite (Fe,Mn)3(PO4)2·3H2O TM
Phosphosiderite FePO4·2H2O KB TM
Rockbridgeite (Fe2+,Mn)Fe3+ 4 (PO4)3(OH)5 KB TM
Schoonerite Fe2+2Zn,Mn, Fe3+(PO4)3(OH)2·9H2O KB
Strengite Fe3+PO4·2H2O KB TM
Strunzite Mn2+Fe3+ 2 (PO4)2(OH)2·6H2O KB TM
Torbernite Cu(UO2)2(PO4)2·12H2O KB TM
Triphylite LiFePO4 KB
Triplite (Mn,Fe,Mg,Ca)2(PO4)(F,OH) KB TM
Triploidite (Mn,Fe)2(PO4)(OH) TM
Turquoise Cu(Al,Fe)6(PO4)4(OH)8·4H2O KB
Vivianite Fe3(PO4)2·8H2O KB TM
Vyacheslavite U(PO4)(OH)·2.5(H2O) TM
Wavellite Al3(PO4)2(OH,F)3·5H2O KB TM
Waylandite BiAl3(PO4)2(OH)6 KB NA
Whitmoreite Fe2+Fe3+
2 (PO4)2(OH)2·4H2O KB TM
Wolfeite (Fe,Mn)2(PO4)(OH) KB TM
Xanthoxenite Ca4Fe2(PO4)4(OH)2·3H2O KB
Zairite Bi(Fe,Al)3(PO4)2(OH)6 KB NA
Zwieselite (Fe,Mn)2(PO4)F KB

the two main OH-stretching vibrations, can be considered as well ordered.
The band at 750 cm−1 indicates the presence of muscovite (or illite) which
was not detected in the OH-stretching region because of the spectral
dominance of kaolinite. The shoulder nearby the Al–O–Si band of the clay
minerals indicates the presence of some feldspar. Quartz could not be
proved by infrared spectroscopy — the characteristic doublet at
780 + 800 cm−1 is absent, but was encountered in the XRD runs. The
DSC curves of the three samples resemble each other indicating a similar
phyllosilicate composition (Fig. 16). The curves are dominated by the ther-
mal reactions of kaolinite. Only a very weak endothermic peak of sample
11304735 indicates the presence of some swelling clay minerals in the
core zone of the aplite, a fact which has not been unraveled by the previous
methods applied to the kaolin. This is particularly evident from the mass
spectrometer curve of evolved water showing two-step-dehydration. The
pronounced endothermic reaction at about 550 °C corresponds to the
dehydroxylation of kaolinite, typically being in this range. The exothermic
peak at 983 °C corresponds to the ceramic reaction (kaolinite → mullite).
4.4.2.4. Kaolin of the Falkenberg Granite. In Fig. 17 the IR spectra of sam-
ples from the residual kaolin deposit Rappauf on top of the Falkenberg
Granite are plotted in a cumulative diagram. The IR spectra of all samples
are dominated by the bands of kaolinite, quartz, and feldspar. Sample 16-
122 also contains some chlorite. The muscovite band is mostly masked by
v4 of the kaolinite. The OH stretching region reveals the presence of well
ordered kaolinites. The presence of the v2 stretching vibration proves the
absence of b-axis disorder (Russell and Fraser, 1994). No significant differ-
ences of the crystallinity of the kaolinite of the different samples could be
detected. Using the Hinckley index sensu Brindley et al. (1986) samples
numbered 3–0.24, 6–0.47, and 9–0.79 demonstrate the best crystallinity
of kaolinite. The cation exchange capacity (CEC) was determined for
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 45

Table 5
The Fe–Al–P interrelation in hematite–goethite aggregates of the kaolinized new aplite at Pleystein.
a) Chemical composition of alteration zones with Al contents greater than 1 wt.% set alongside with the Si, Fe, Mn and P contents (in wt. %). The Fe is mainly contained in the host goethite.
b) Chemical composition of kaolinized aplites, pegmatites and granites at Pleystein and Tirschenreuth.

Al Si P Mn Fe

4.916 0.915 1.237 0.014 49.777

4.595 1.277 1.071 0.005 51.884
4.103 1.299 1.116 0.017 51.173
3.684 0.381 2.291 0.034 49.779
3.587 0.354 2.755 0.014 49.411
2.095 1.430 1.356 0.026 55.170
1.853 1.599 1.036 0.028 53.738
1.548 1.471 1.055 0.014 54.976
1.234 1.377 1.186 0.002 58.005
1.219 1.028 1.188 0.010 54.900
1.185 1.342 1.174 0.013 57.850

Locality Pleystein Tirschenreuth

West Kreuzberg East New aplite Weiss Pit

Site 2 Site 2 Site 2 Site 1

Lithology Aplite Aplite–pegmatite Aplite Aplite Aplite Primary kaolinite Altered kaolinite

wt.%
SiO2 75.78 67.62 66.17 63.16 77.36 71.80 59.84
TiO2 0.10 0.28 0.02 0.02 0.10 0.28 0.35
Al2O3 12.98 16.19 17.82 24.06 13.65 16.20 19.96
Fe2O3 1.33 2.38 4.71 1.18 0.28 1.22 2.97
MnO 0.04 0.04 1.48 0.11 0.00 0.02 0.02
MgO 0.27 0.77 0.07 0.02 0.06 0.79 3.42
CaO 0.24 0.19 0.11 0.04 0.22 0.06 0.18
Na2O 2.64 1.72 0.09 0.10 6.85 0.27 0.66
K2O 4.46 8.19 3.31 3.62 0.41 5.41 6.82
P2O5 0.38 0.36 0.32 0.13 0.13 0.07 0.11

ppm
Sc 3 6 30 8 6 5 7
V 14 33 19 6 8 12 18
Cr 17 42 11 4 4 6 10
Ni 4 8 12 13 2 7 28
Co 3 3 38 11 2 4 12
Cu 39 35 91 36 36 8 6
Zn 140 360 355 156 10 84 225
Ga 23 19 56 55 11 23 27
Rb 626 847 839 890 19 268 365
Sr 40 99 101 29 27 56 66
Y 7 13 10 8 14 19 42
Zr 40 86 20 30 211 133 169
Ta 9 13 214 33 4 4 5
Sn 14 3 69 47 3 9 13
Cs 14 18 69 44 3 15 18
Ba 247 709 301 80 17 437 601
La 14 15 55 14 14 35 48
Ce 22 30 89 17 17 64 99
Pb 18 37 15 47 71 38 30
Th 4 4 12 4 3 24 30
U 7 9 13 3 3 15 45
W 4 4 17 8 3 4 5

samples taken along a transect perpendicular to the strike of a structure
zone in the kaolin (Table 6). It is the only site, where 14- Å phyllosilicates,
e.g. chlorite, were identified by IR spectroscopy and in addition to the well
known phyllosilicates kaolinite and muscovite, swelling 14- Å
phyllosilicates are present too. A sampling along a transect through the
open pit at a meter spacing — the precise location is kept proprietary —
gave rather moderate CEC values for the ordinary kaolin (Table 6 — nor-
mal characters) yet strikingly increased values in the dark gray altered
zone, intercalated into the residual kaolin.
4.5. The chemical composition of kaolin
The mineralogical changes during alteration of felsic magmatic
rocks are accompanied by chemical changes affecting the major
and minor elements. To assess enrichment and depletion of ele-
ments during kaolinization, both kaolins from site 1 and site 2
were normalized to the chemical composition of the aplite granite
underneath the Kreuzberg Quartz Pegmatite (Fig. 5b). Samples
from this felsic rock were taken by Müller et al. (1998) for chemical
analysis. Similarly, the average chemical composition of the
kaolinized regolith was normalized to the mean value of its parent
granite, the Falkenberg Granite, the chemical composition of which
was investigated by Wendt et al. (1986, 1994). A full overview of
the kaolinized aplites, pegmatites and granites treated in this
paper is given in Table 5b. Both types of kaolin at Pleystein are sig-
nificantly depleted in calcium and in sodium and, to a lesser extent,
in phosphate, whereas the remaining major and minor elements
plotted in the graphs of Fig. 18 were enriched relative to the parent
46 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

c
a b

c d

e hem goe
1.47

0.12

3.68 0.31

Fig. 10. Aluminum-phosphate minerals under the SEM and EMP as BSE image. a) Aggregates of APS minerals. The pseudocubic crystals clearly bear evidence of the existence of APS min-
erals, in this case a s.s.s. of gorceixite (Ba) with crandallite (Ca) and goyazite (Sr). Pleystein regolith on the new aplite. b) Aggregates of APS minerals in the kaolin of Pleystein new aplite
enriched in bismuth and barium, interpreted as a solid solution series of goyazite and waylandite. c) Isolated acicular aggregates of waylandite from the Kreuzberg site 2 at Pleystein. d)
Acicular aggregates of Mn-free apatite of secondary origin within kaolinite at Pleystein. e) Pyrite is rather vulnerable but still showing the hexahedral crystal morphology has been
completely converted into goethite and hematite denoting different stages of hydration by its different shades of white (hematite “hem”) and gray (goethite “goe”). The marginal
parts of the goethite–hematite aggregate are encrusted by aluminum phosphate which is represented by the Al/P ratios. New Aplite, Pleystein.

aplite granite. Although the overall distribution pattern of the 5. Discussion

Tirschenreuth kaolin does not greatly differ from those of Pleystein,
overall intensity of kaolinization is less striking with negative
values (depletion) less than 0.1 and enrichment factors not exceed-
ing 5 (Fig. 18). The enrichment and depletion factors oscillate
around 1.
5.1. The type and intensity of kaolinization
It is well known that, kaolin deposits are the result of two different
processes, one magmatic (hypogene) and another sedimentary
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56
b 1underneath the Kreuzberg. The kaolin types under consideration devel-
c oped under tropical and subtropical climatic conditions (Dill et al., 1997;
Fig. 11. Iron and manganese minerals. a) Panned heavy mineral concentrate of hexahedral
“pyrite crystals” which proved under EMP to be pseudomorphosed to goethite and hema-
tite to completeness at Pleystein site 1. b) Cryptomelane coating a fault plane at Pleystein
site 2. c) Platy aggregates of zircon consisting of tiny subdomains of zircon in the kaolin.
Site 1 Pleystein.
(supergene). They come into existence during the waning stages of vol-
canism, producing mainly felsic volcanic and volcaniclastic rocks affect-
ed by an acid-type alteration of epithermal deposits (Dill et al., 1995,
1997; Cravero et al., 2001; Carrillo-Rosúa et al., 2009; Marfil et al.,
2010; Kadir and Erkoyun, 2013). Mineralogically, they are characterized
by Na- and K alunites and APS minerals, where sulfate substitutes to a
great deal for phosphate in the pertinent solid solutions. A variegated
spectrum of phyllosilicates accompanies kaolinite, e.g. pyrophyllite,
dickite, smectite, and muscovite. Primary constituents or relic minerals
are the exception rather than the rule and eradicated by the
argillitization almost to completeness. All kaolinization zones in and
around Pleystein are barren as to sulfur. Even the primary pyrite, mis-
taken for the Fe disulfide on account of its well preserved hexahedra,
has completely been converted into pseudomorphoses of goethite.
Hypogene alteration around the Kreuzberg pegmatite in the
Pleystein area is characterized by a hypogene argillitisation with musco-
vite, chlorite, and minor vermiculite accompanying kaolinite but barren
as to any APS minerals. APS minerals are present in the supergene kaolin
(Fig. 6). Those APS minerals are specialized in phosphate, with all sulfur
released from the zone of kaolinization. Phosphate and sulfur in the APS
minerals become the most decisive criteria to draw to discriminate be-
tween hypogene and supergene kaolinization (Dill et al., 1997). The dis-
tribution patterns of the Pleystein kaolin sites 1 and 2 resemble each
other closely and show the same trend as the Tirschenreuth pattern
(Fig. 18). Both sites were deprived of plagioclase, in Tirschenreuth to a
lesser extent than at Pleystein, where Na2O and CaO, the major constit-
uents of plagioclase are more strongly released than at Tirschenreuth
47
ksp
mus kao
Fig. 12. Light minerals of the mineral association of the kaolinized new aplite. Potassium
feldspar present as a skeleton (ksp) is associated with booklets of kaolinite (kao) and
tiny plates of muscovite (mus). SEM micrograph.
residual kaolin deposit. Phosphate and lithium, the latter is contained in
the mica, also suffered from chemical weathering much more at Pleystein
than at Tirschenreuth. The crystallinity in Tirschenreuth does not signifi-
cantly differ from that of the new aplite at Pleystein site 1. Both kaolin
types are higher in their crystallinity than the faultbound kaolin of site
Abeysinghe and Fetherston, 1999; Goudie and Viles, 1999).
The block diagram of Fig. 19 illustrates the intensity of kaolinization
in relation to the geomorphological evolution. A diminishing infiltration
rate of meteoric waters into the paragneisses around Pleystein is
reflected in a downward decrease in kaolin. The different quantities of
kaolin between site 1 and site 2 are a mirror image of the impact of
weathering on the pegmatite of the Kreuzberg. Kaolin was washed
down-hill by fluvial erosion of the Zottbach whose river bend was
forced to evolve more and more to the east upon its incision by the
rock strength of the knob of the pegmatite counteracting the deepening
of the river bed (Fig. 19).
5.2. Relic minerals and provenance analysis
Quartz the most striking relic mineral at Pleystein forms the pinnacle of
the Kreuzberg and was dispersed in the kaolin (Fig. 2a). Feldspar from the
pegmatite is still present in the kaolin, although being strongly corroded
(Fig. 12, Table 2). The tectosilicate has mainly altered into phyllosilicates
and transported away as bed load and suspended load in the river system
(Fig. 19). Rutile and ilmenite have been derived from the pegmatites and
their immediate wall rocks and today may be discovered in the kaolin. Par-
ticularly the intergrowth of rutile and ilmenite, called “nigrine”, is common
in the drainage system around Pleystein where it has proved as a useful
tool to constrain potential target areas underlain by pegmatites (Dill
et al., 2014b). Apatite a rare constituent of kaolinized alteration zones
has been derived from the adjacent paragneisses and washed onto the
NA while at Tirschenreuth it is granite-related.
The mineral most diagnostic of the parent rocks is columbite-(Fe).
Based upon the regular trends observed in the cross plot of Fig. 9 the
NA may without any doubt be attributed to the emplacement of the
Pleystein pegmatite–aplite system. The intensity of weathering has no
bearing on the overall chemical composition of the columbite-(Fe) but
it is selective as to the Ta- and Nb-enriched lamellae of the columbite
s.s.s. Lamellae enriched in Ta are much stronger subjected to weathering
48 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56
Lin (Counts)
kaolinite
kaolinite
20
° 2 theta (Cu)
Fig. 13. XRD runs of the fault gauge from the Kreuzberg pegmatite show muscovite and kaolinite to be the only phyllosilicates and kaolinite being enriched in the b63 μm fraction.
than their neighboring niobian zones (Fig. 8). The dominance of
columbite-(Fe) and the total absence of tantalite in the stream sedi-
ments of the creeks around Pleystein may be accounted for by the
kaolinization which the columbite-(Fe) s.s.s. have gone through.
According to Aleksandrov (1963) and Linnen and Keppler (1997) the
Ta/Nb ratio increases during fractionation. The NA is the youngest mem-
ber in this consanguine succession of aplites and pegmatites which
formed the less fractioned part of the entire system. Even if the differen-
tial supergene alteration cannot be cast aside when discussing these Nb/
Ta ratios, it was not pervasive enough in this residual kaolin or residual
placer to disturb the Nb/Ta ratio to such an extent that it could no longer
be used for a genetic discussion. It has to be, however, handled with care
in fluvial placer deposits far off the source rock or multi-stage
weathering processes, both of which might lead to a selection and con-
centration of niobian columbites in favor of their Ta-enriched members
of the s.s.s.
Among the aluminum phosphates Bi-bearing phosphates do not
only contribute to the constraints of the physical-regime but they also
bridge the gap into the sulfide–arsenide mineralization in the pegma-
tite–aplite system at Pleystein. The primary mineral association at
Pleystein has bismite and native bismuth in what is called the sulfide–
arsenide association in the Hagendorf–Pleystein Pegmatite Province.
At site 1, the sulfide–arsenide association is rather poorly represented
but its former presence was confirmed by the Bi-bearing phosphates.
Aside from this conclusion, Bi is considered as rather immobile during
kaolinization and being retained in the topmost parts of the kaolinized
aplite.
5.3. Neomorphism and the physical–chemical regime
5.3.1. Zircon
The zircon crystal morphology enables the mineralogist to constrain
the physical–chemical regime of the source rocks (Fig. 11c). Considering
the outward appearance of the two types, the drastic reduction of the
prism relative to the pyramidal faces leads to an isometric crystal
shape (Dill et al., 2012). Unlike the neighboring aplites and pegmatites
at Trutzhofmühle or Hagendorf, these morphological types are totally
missing in the kaolin of the NA. A source different from those of the
< 63 µm
> 63 µm
40 60
aplites or pegmatites has to be envisaged for the sporadic zircon grains
in the NA. The pervasive chemical kaolinization atypical of the other
pegmatites and aplites in the Hagendorf–Pleystein region gave rise to
the rare case of zirconium redeposition. Zircon dissolution can take
place in weathering systems where the pH is below 3 and a naturally
high chloride concentration is available (Colin et al., 1993; Hodson,
2002). A crucial parameter is the source of Zr in newly formed phases
within the regolith. It could be mafic minerals such as amphibole
which are widespread, easily to be decomposed but low in their Zr
tenor (Duvallet et al., 1999). The second option is zircon, which is the
main host of Zr in crystalline rocks but ranks among the most stable
heavy minerals besides rutile and tourmaline. Corroded zircon does
exist and it is especially susceptible to supergene alteration as it suffers
from radiation damage (Delattre et al., 2007). This unique and rare type
of zirconium redistribution within the kaolin of site 1 is interpreted as a
relic supergene alteration under very low pH which was overprinted by
a younger supergene alteration under pH b 7, in a more mildly acidic
regime.
5.3.2. Kaolinite and aluminum phosphates
Kaolinite is the main constituent among the newly formed
phyllosilicates in the residual kaolin. In Pleystein, a mineralization far
from being called a deposit in the economic sense, its quantity is higher
than in the Tirschenreuth deposit, where quartz and feldspar are still
very widespread as relic minerals. There, the presence of feldspar be-
sides newly formed kaolinite is accountable for the industrial name or
brand “Tirschenreuther Pegmatit”. The crystallinity of the kaolin from
Tirschenreuth and Pleystein's NA is almost identical, whereas the
faultbound kaolin of the Kreuzberg is significantly lower, albeit chemi-
cally akin to the massive kaolinite from site 1. It is interpreted in
terms of an ongoing aging or kaolinite diagenesis, reflecting in the cur-
rent setting a more moderate diagenesis of obviously younger age than
that of the NA at site 1. A similar low crystallinity was determined for
kaolinite from the kaolinite in the Gehren fluorite vein, Germany, ap-
proximately 70 m below ground (unpublished data). The faultbound
kaolinite at site 2 occurs approximately 80 m to 90 m below the as-
sumed paleosurface (Fig. 19).
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 49

SiO stretching
silictaes

kaolinite
muscovite
kaolinite /
kaolinite

muscovite
kaolinite
v1

3700 cm-1
v2 < 63 µm

v3 v4 > 63 µm

3900 3400 2900 2400 1900 1400 900 400

-1
wavenumber [cm ]
relative absorbance

Kaolin Low crystallinity

< 63 µm
cm-1
3650 cm-1

Site(<63µm)
10910351 2
3670

High crystallinity

Kaolin
< 63 µm
Site (<63µm)
11304734 1

4000 3900 3800 3700 3600 3500 3400 3300 3200 3100 3000
wavenumber [cm -1]

Fig. 14. IR spectra of the Pleystein kaolin. The inset on the top right illustrates the relative abundance of kaolinite in the various grain-size fraction the main plot reveals different degrees of
crystallinity for kaolinite at site 2 (Kreuzberg Pegmatite) and site 1 (new aplite). The four characteristic OH-stretching vibrations originating from the different AlAlOH bondings are
assigned v1–v4.
SiO silicates
relative absorbance

kaolinite
kaolinite

feldspar
muscovite/illite

11304736 (<63µm)

11304735 (<63µm)

11304734 (<63µm)
3900 3400 2900 2400 1900 1400 900 400
wavenumber [cm -1]

Fig. 15. IR spectra of the various argillitization zones of the new aplite at site 1, Pleystein. a) marginal zone facing up-hill — HD 11304734. b) central zone — HD 11304735. c) marginal zone
facing down-hill — HD 11304736.
50 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56
1.5
1.0
0.5
[µV/mg]
0.0
0 100 200 300 400
-0.5
water
-1.0
-1.5
Fig. 16. DSC curves of the b63 μm fractions of kaolin from site 1, the new aplite at Pleystein. The inset shows the mass spectrometer curve of water (evolved gas analysis).
Considering the physico-chemical calculations in Fig. 20a, the stabil-
ity field of kaolinite from the sampling sites at Tirschenreuth is indica-
tive of a pH in the range 2.5 to 5.5. The log a SiO2(aq) varies in a narrow
range from −4.5 to −3.0. As no newly formed phosphates were identi-
fied at that site the activity of HPO−4 has not been considered throughout
calculation. Neither gibbsite nor pyrophyllite was identified in the sam-
ples. The stability field of kaolinite spreads the pH range 2.5–5.5. At
Pleystein small amounts of Al-phosphates occur and therefore a moder-
ately higher log activity of HPO2− 4 of −5 has to be assumed in this cal-
culation and the entire stability field of kaolinite shifts to the pH range
4.5–6 (Fig. 20b). Sulfate often substituting for phosphate in these solid
solutions series is absent from this kaolinization so that alunite-group
minerals and minerals of the woodhouseite series are not expected
(Fig. 6-P → S). The conditions during which the Al phosphates at
Pleystein came into existence can be described as to the pH by the
range 2 to 5. As to the silica content, they can tolerate a log a SiO2(aq) of
up to 1.5. The log a SiO2(aq) at Pleystein varies in a narrow range from
−4.0 to −3.0. In both cases the conversion of K feldspar into kaolinite
did not take place by a direct replacement of the tectosilicate but
worked its way through an intermediate phase, muscovite.
5.3.3. Muscovite and silica
At Tirschenreuth the muscovite developed in the pH range 5.5–11.5
and at Pleystein in the range 6–12.5 (Fig. 20a, b). The log a SiO2(aq) varies
in a wider range from −6.0 to −3.5 at Tirschenreuth and Pleystein. Al-
kaline feldspar is stable above pH 7 in both sites. Below the feldspar
decomposed into muscovite and kaolinite.
Silcretes may be found at different scales associated with kaolin,
from fragments mixed up with the argillaceous matrix to isolated cob-
bles and boulders (Summerfield, 1983b). Newly formed silica or
silcretes are common to both sites under study in NE Bavaria and their
formation was modeled using a log a Al3 +/H+3 -pH diagram to show
the alteration of silica (quartz) → kaolinite → chlorite (daphnite,
chamosite) at Pleystein at 25 °C and Tirschenreuth using the dissolved
species as log aFe2 + = − 4, log aMg2 + = − 4. As the pH drops below
pH 7 and log a Al+++/(H+).3 is below 8, silica precipitates in the
kaolinized alteration zone.
5.3.4. Chlorite and smectite
At a pH N 7 at various ratios of log a Al+++/(H+).3 chlorite can appear
(Fig. 20c). Due to the lack of talc (minnesotaite), chlorite is assumed to
have formed from kaolinite when the meteoric solutions turned more
alkaline rather than from silica. The fourth phyllosilicate in the kaolin
recrystallisation
mullite
dehydroxylation
kaolinite
500 600 700 800 900 1000 1100 1200
HD-11304734
HD-11304735
HD-11304736
T [°C]
associations in both sites under study is a Fe-bearing species of smectite
which developed at pH N 8 from muscovite or K feldspar (Fig. 20d). The
cation exchange capacity (CEC) determined for samples from the
Rappauf kaolin mine, taken along a transect perpendicular to the strike
of a structure zone in the kaolin, points to a smectitisation postdating
the formation of the residual kaolin (Table 6).
5.3.5. Iron-, manganese and titanium oxide/hydrates
The redox conditions are assumed to be above Eh N 0, owing to the
overall presence of various oxidic Mn, Fe and Ti compounds (Table 2).
Of these oxidic minerals, only cryptomelane offers an opportunity to
chronologically constrain the age of formation of the host kaolin,
owing to its K contents. So far only once, K/Ar dating of this Mn minerals
has been performed for this region in NE Bavaria suggesting a supergene
alteration of the adjacent Hagendorf-South Pegmatite at 4.20 ± 0.33 Ma
(cryptomelane I) and at 0.87 ± 0.04 for cryptomelane II (Dill et al.,
2010a, 2010b). Further radiometric dating using secondary uranium
minerals yielded for the torbernite from the same deposit at Hagendorf
an age of 4.55 Ma and for autunite–torbernite from the nearby
Flossenbürg Granite of 3.99 Ma (Dill et al., 2010a, 2010b). Based upon
that, there is compelling evidence for a supergene alteration during
the Early Pliocene, affecting granites and pegmatites in the region alike.
5.4. Chronology, weathering and climate
Fine-tuning of the stratigraphy of chemical weathering allowed for a
fourfold subdivision, applicable to the large residual kaolin deposits at
Tirschenreuth as well as to the pegmatites and aplites of the
Hagendorf–Pleystein Pegmatite Province (Table 2). The deepest part
of this zone of chemical weathering has been well preserved in the
Pleystein area where the quartz pinnacle of the “pegmatite ruin” of
the Kreuzberg pegmatite is the most striking example of the interface
between the crystalline parent rocks and the regolith (Fig. 19). The
weathering profile at Pleystein is only patchily preserved as a result of
the fluvial incision into the old peneplain (paleosurface). Upon deepen-
ing of its river bed, a great deal of the regolith that evolved on the aplites
has been eroded, in the case of Trutzhofmühle almost to completeness
(Fig. 19-THM). The latter aplite suffered most strongly from the inten-
sive erosion along the cut banks of the river. The fluvial dynamic was
slightly better and, hence, more favorable for the preservation of the
weathering mantle on top of the Weiss sandpit. It lies on the passage
from a cut bank to a slip bank of a meander belt. In contrast to the
sites mentioned previously, sites 1 and 2 are found in a much better
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56 51

0.600
3_0.24
7_0.51
9_0.79
11_101
0.500 13_109
6_0.47
16_122
relave absorbance
0.400

0.300

0.200

0.100
3800 3750 3700 3650 3600 3550 3500
wavenummber [cm-1]

1.600 3_0.24
7_0.51
9_0.79
1.400 11_101
13_109
6_0.47
1.200 16_122
relave absorbance

1.000

0.800

0.600

0.400

0.200

0.000
1400 1300 1200 1100 1000 900 800 700 600 500 400
wavenummber [cm-1]

Fig. 17. IR spectra from various sites in the residual kaolin deposit Rappauf on top of the Falkenberg Granite south of Tirschenreuth (see Fig. 4 for location).

Table 6 position, as far as the preservation of the regolith is concerned. They are
Cation ion exchange capacity (CEC) of kaolin samples from the Rappauf ka- located on the slip bank where the regolith was less strongly affected by
olin deposit at Tirschenreuth. The samples were taken at a meter-spacing the latter erosion and the apron of colluvial debris got only slightly
perpendicular to the strike of a darker alteration zone within the pale gray
reworked in the course of fluvial incision (Fig. 19).
kaolin. The samples taken from this younger alteration zone are marked by
bold-faced letters.

Sample number Cu2+/CEC (meq/100 g) 5.4.1. Prestage

1 0.47
2 0.81
3 0.47
4 0.71
5 0.81
6 2.06
7 17.75
8 1.28
9 1.15
The prestage of kaolinization is marked by an aggressive chemical
weathering whereby even zircon was attacked. Resultant silcretes, albe-
it on a microscopical scale, developed under semiarid conditions with
dryer (period of solution more alkaline) and wetter seasons (period of
redeposition — see pH in Table 2) (Summerfield, 1983a, 1983b). Fluctu-
ating groundwater levels have played a decisive role in its precipitation.
They were recorded from Paleogene beds in Great Britain (Ullyott et al.,
2004), from Neogene beds of the Cologne Embayment, Germany, and
52 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

100.00
Kaolin
New Aplite
10.00

Sample/aplite granite
1.00

0.10

0.01

100.00 Kaolin
Kreuzberg
10.00 Pegmate
Sample/aplite granite

1.00

0.10

0.01

100.00 Kaolin
Falkenberg
Sample/ Falkenberg Granite

10.00 Granite

1.00

0.10

0.01

Fig. 18. Enrichment and depletion of kaolin relative to its parent rocks at Pleystein and Tirschenreuth. a) New aplite normalized to the aplite granite underneath the Kreuzberg Quartz
Pegmatite. Standard: Müller et al. (1998). b) Faultbound (gauche) kaolin normalized to the aplite granite underneath the Kreuzberg Quartz Pegmatite. Standard: Müller et al. (1998).
c) Kaolin regolith normalized to the average chemical composition of the Falkenberg granite. Standard: Wendt et al. (1986, 1994).

recent sites of precipitation in Australia (Thiry, 1991; Radtke and
Bruckner, 1991; Wopfner, 1997). The nearest site within the NE Bavar-
ian Basement investigated for its widespread occurrence of silcretes is
situated near Stegenwaldhaus north of the kaolin deposits under
study. Cryptomelane associated with this site with silcretes and kaolin
was subjected to K/Ar dating and yielded an age of ≥ 23 Ma (Aquita-
nian-Early Miocene) (Dill and Wemmer, 2012). A late Early Cretaceous
to Mid-Miocene age of kaolinization age is indicated also by the isotope
method and fits the mineralogical observations made in this area (Gilg,
2000).
5.4.2. Stage 1
Kaolinization during stage 1 of the supergene alteration is accountable
for the majority of kaolinite well preserved as kaolin in the sampling sites
at Pleystein and mined from the residual kaolin deposit at Tirschenreuth,
where the prestage cannot be claimed to exist. There are various options
to discuss the absence of this prestage at Tirschenreuth. Mining in the
open pits there has not yet reached the level close to the interface with
the unaltered parent rock to prove its existence. Another possibility to
keep in mind is the paleoclimatic regime which was not suitable there
to produce such a supergene alteration. And last but not least the geo-
morphological processes might have been detrimental to the preserva-
tion of this kaolin prestage, in that deep erosion during the initial phase
of weathering has denudated the remnants of what is called here
prestage. Generally, the presence of kaolinite in weathering profiles
may be used as an argument for warm and humid climatic conditions
of the tropics, but it has to be noted that both minerals occur also in
more temperate morphoclimatic zones of the extra-tropical parts on
the globe (Bouchard and Jolicoeur, 2000). In the Hagendorf–Pleystein Re-
gion and the Flossenbürg Granite Complex, being located immediately
north of the Hagendorf–Pleystein study area, several chronological stud-
ies on the supergene alteration lend support to a strong chemical
weathering around 4.2 Ma (Dill et al., 2010a, 2010b). Chronological
data were obtained by dating cryptomelane and uranyl phosphates. Ox-
idic manganese compounds are present in the kaolin at Pleystein, but
uranyl phosphates did not develop there (Table 2). Presumably, the age
of kaolinization evolved earlier than the precipitation of the afore-
mentioned supergene minerals (Fig. 19). The physical–chemical regime
is dominated by acidic meteoric pore fluids percolating through a regolith
totally deprived of sulfides. This is also true as to the phosphate minerals
 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56
Fig. 19. Three dimensional view of the kaolinization at outcrop in the present-day geomorphology around Pleystein. The lithologies and sites mentioned in the text are given: site 1: New
Aplite, site 2: Kreuzberg Quartz Pegmatite, Weiss Pit: aplite, THM: Trutzhofmühle Aplite. The numbers in the rectangular boxes denote the age of kaolinization.
which the Hagendorf–Pleystein Pegmatite Province is renowned for, such
as Fe–Mn phosphates, Zn phosphates or the rare Ti phosphate (Table 4).
The question still awaits an answer. Did the new aplite lack these phos-
phates or were these minerals more vulnerable to weathering, wiped
out by the pervasive chemical weathering? The aluminum phosphates
are indicative of a preexisting primary sulfide mineralization with its sul-
fides totally converted into waylandite-zairite s.s.s. The latter solid-
solution series has been observed in the new aplite, devoid of Fe–Mn
phosphates, Zn phosphates and Ti phosphate and in the Kreuzberg peg-
matite where all these phosphates are still present besides waylandite-
zairite s.s.s. Unlike the Kreuzberg Pegmatite, the new aplite did not
have these precursor phosphates and is representative of a reduced rare
metal assemblage.
5.4.3. Stages 2 and 3
Stage 2 is characterized by the presence of newly formed white mica
and sporadic silica. Moderately acidic to alkaline meteoric fluids are as-
sumed to have created these minerals within the kaolinitic regolith.
White mica is closely associated in time and space with the kaolinite
so that its appearance within the regolith was not very late and assigned
an early Pliocene age of formation (Table 2, Fig. 19). The gradual change
from acidic to more alkaline solutions is backed also by the presence of
heavy minerals and phyllosilicates sensitive to supergene alteration and
observed outside the Hagendorf–Pleystein Pegmatite Province.
Stage 3 is the youngest alteration stage to be mapped in the kaolin
on top of the NE Bavarian Basement, yet not represented in the kaolin
recorded from the sites at Pleystein but only at Tirschenreuth, where
14- Å phyllosilicate, e.g., chlorite, smectite and mixed-layer minerals
came into being at the passage from the Late Pliocene into the Quaterna-
ry. The mineralogical changes along the present-day drainage system
53
manifest moderate weathering conditions resulting in leaching losses
of some base cations such as K+.
6. Conclusions
Supergene kaolinization produced a repository for heavy minerals
critical for the interpretation of the origin of pegmatites and as such
may be used as an ore guide and last but not least is the protagonist in
the story of exhumation and destruction of a pegmatite. Reading the ka-
olin means deciphering the productive and destructive part of a pegma-
tite, which the Pleystein pegmatite ruin is a classical example of.
Irrespective of the strength of kaolinization, Nb–Ta–Ti heavy min-
erals can still be identified in the regolith atop the host pegmatite or ap-
lite and used for genetic interpretation of the primary mineralization
and the origin of the felsic intrusive. While oxidic Ti minerals are rather
resistant to weathering and “nigrine” aggregates (intergrowth of rutile
and ilmenite) can even be cast as a shelter to minerals more susceptible
to chemical weathering, oxidic Nb–Ta s.s.s. have to be treated more cau-
tiously because of the disposition of Ta-enriched Nb–Ta oxide s.s.s. to
undergo corrosion more easily in their tantalite lamellae than in the
niobium-enriched zones of columbite. This supergene alteration has
modified the Nb/Ta ratio in the columbite group minerals, it has, how-
ever, not blurred the Nb–Ta ratio in the columbite-(Fe) beyond its appli-
cability for genetic interpretation. Therefore based upon the Nb/Ta ratio,
the most strongly kaolinized new aplite is the youngest member of the
Pleystein pegmatite–aplite system (Fig. 9).
The Pleystein pegmatite–aplite system is the most pervasively altered
and most deeply eroded felsic complex in the Hagendorf–Pleystein prov-
ince providing a regolith of kaolin more than 50 m thick (Figs. 2a, 19).
54 H.G. Dill et al. / Ore Geology Reviews 69 (2015) 33–56

0 0

–1 –1

–2 Clinoptil-K –2 Clinoptil-K

–3 Pyrophyllite –3
Pyrophyllite

log a SiO2(aq)
log a SiO2(aq)

–4 Kaolinite –4 Kaolinite
Maximum Microcline Maximum Microcline
–5 Muscovite –5 Muscovite
AlH2 PO++
4
–6 +++ –6
Al Berlinite Kalsilite
Kalsilite –7
–7
Gibbsite Gibbsite
–8 –8

–9 –9
25°C 25°C
–10 –10
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
a pH b pH

9 -
–3.5
Chamosite 7A
Kaolinite –3.6 Clinoptil-K
8
- –3.7
Daphnite 14A
–3.8 Maximum Microcline
log ratio Al+++/H+^3

7
Phengite
log a SiO2(aq)
–3.9
Kaolinite
6
–4
Saponite-Mg
–4.1
5
Quartz Muscovite
Minnesotaite –4.2
4 Greenalite
–4.3

–4.4
3
Gibbsite
–4.5
25°C 25°C
2 –4.6
c 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 d 6 6.5 7 7.5 8 8.5 9
pH pH

Fig. 20. Log activity versus pH diagrams of the supergene kaolinization in the NE Bavarian Basement. Assumed concentrations of dissolved species are given below in mol/l. a) Log a SiO2 (aq)
-pH diagram to show the alteration of K feldspar (microcline) → muscovite → kaolinite at 25 °C at Tirschenreuth, using the dissolved species as log aK = −2. b) Log a SiO2 (aq) -pH diagram
to show the alteration of K feldspar (microcline) → muscovite → kaolinite → Al phosphate (berlinite) at Pleystein at 25 °C using the dissolved species as log aK = −3, log aHPO4− = −5.
Physical–chemical basis Brookins (1987). c) Log a Al3+/H+3 -pH diagram to show the alteration of silica (quartz) → kaolinite → chlorite (daphnite, chamosite) at Pleystein at 25 °C using
the dissolved species as log aFe2+ = −4, log aMg2+ = −4. Physical–chemical basis Brookins (1987). d) Log a SiO2 (aq) -pH diagram to show the alteration of K feldspar (microcline) → mus-
covite → kaolinite → smectite group minerals (Mg saponite) at Pleystein at 25 °C using the dissolved species as log aK+ = −3, log aMg2+ = −3. Physical–chemical basis Brookins (1987).

The kaolinization extending from the Miocene through the Pliocene,
older stages cannot be ruled out, is a residual kaolin, without any evi-
dence of a hydrothermal input. The larger Tirschenreuth kaolin deposit
can easily be correlated (Table 2, Figs. 2, 4).
The four stages furnish evidence of gradual alkalinizations of the me-
teoric pore fluids throughout the Neogene and the Quaternary (Table 2).
Even if kaolinization does not provide us with another type of eco-
nomic residual kaolin deposit like Tirschenreuth, owing to the moderate
size of pegmatites at outcrop, kaolin is a favorable tool for the genetic
and applied parts of economic geology. In reference to the latter one, ka-
olin can give us a precise answer about the shape and size of a pegma-
tite–aplite system at subcrop considering all aspects of its unroofing
story (Fig. 19).
Acknowledgements
Chemical analyses were carried out in the XRF laboratory of BGR
(Federal Institute for Geosciences and Natural Resources, Hannover)
by F. Korte. The preparation of samples and SEM analyses were per-
formed by D. Klosa. D. Weck has carried out the XRD analyses. H. Hein
performed the IR analyses, while N. Schleuning determined the CEC.
The analyses in the electron microprobe laboratory of BGR were carried
out by C. Wöhrl. We acknowledge with thanks their contribution to this
study. We express our gratitude to an anonymous reviewer for his help-
ful comments to a first draft of our paper. We also extend our gratitude
to F. Pirajno for his editorial handling as editor-in-chief of ORE GEOLOGY
REVIEWS and his comments made to our paper.
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