Lithos 140141 (2012) 224233

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Lithos
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Boron-isotopic constraints on the petrogenesis of hematitic phyllite in the southern

Serra do Espinhao, Minas Gerais, Brazil
Alexandre Raphael Cabral a,, Michael Wiedenbeck b, Nikola Koglin c,
Bernd Lehmann a, Francisco R. de Abreu d
a

Mineral Resources, Technische Universitt Clausthal, Adolph-Roemer-Str. 2A, 38678 Clausthal-Zellerfeld, Germany
Helmholtz-Zentrum Potsdam, Deutsches GeoForschungsZentrum, Telegrafenberg C128, D-14473 Potsdam, Germany
Geodynamik und Geomaterialforschung, Julius-Maximilians-Universitt Wrzburg, Am Hubland, 97074 Wrzburg, Germany
d
Votorantim Metais, Praa Ramos de Azevedo 206, 01037-010 So Paulo-SP, Brazil
b
c

a r t i c l e

i n f o

Article history:
Received 11 May 2011
Accepted 14 January 2012
Available online 24 January 2012
Keywords:
Tourmaline
Boron isotopes
SIMS
Hematitic phylite
Southern Serra do Espinhao
Brazil

a b s t r a c t
Metasiliciclastic rocks predominate in the lower units of the Palaeo-Mesoproterozoic Espinhao Supergroup,
in the southern Serra do Espinhao, Minas Gerais, Brazil. The lower units also comprise rocks with locally
preserved igneous fabrics, but which have very unusual chemistries. These rocks, collectively known as
hematitic phyllite, are characterised by abundant ne-grained muscovite, i.e. sericite, and variable amounts
of titaniferous hematite, rutile and tourmaline. Currently, the hematitic phyllite has been interpreted as a
metamorphosed palaeosol after basaltic rocks and, as such, has been used as a palaeoclimatic indicator.
However, the lateritic nature of the hematitic phyllite cannot unambiguously be determined because of the
K metasomatism, hematitisation and tourmalinisation recorded in the hematitic phyllite and in the arenaceous country rocks. Here we report the B-isotopic and chemical compositions of tourmaline from the hematitic phyllite. Our 11B data are in the range between 15 and 4. The tourmaline compositions fall along
the povondraite"oxy-dravite" join, which denes a meta-evaporitic tourmaline trend. A meta-evaporitic B
source is constrained by the B-isotopic data as non-marine. Our model for the hematitic phyllite suggests
that B- and K-rich brines were derived from the metamorphic dewatering of non-marine evaporites. Such
brines extensively altered volcanic rocks of basaltic and rhyolitic compositions, leading to tourmalinebearing, hematitesericite assemblages of the hematitic phyllite.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The lithology referred to as hematitic phyllite, or lito hemattico,
in the southern Serra do Espinhao of Minas Gerais, Brazil, has been
used as a palaeoclimatic indicator for the deposition of siliciclastic
sediments at the base of the Palaeo-Mesoproterozoic Espinhao
Supergroup, including diamantiferous metaconglomerates of the
Sopa-Brumadinho Formation (e.g., Almeida-Abreu, 1996; AlmeidaAbreu and Renger, 2007; Knauer, 2007; Martins-Neto, 1996, 2000).
Knauer and Schrank (1993) proposed that the hematitic phyllite
represents weathered basaltic rocks, i.e., palaeosols, which were subsequently metamorphosed, and this remains the dominant interpretation. The sui generis mineralogical and chemical composition of
hematitic phyllite, which is enriched in Al2O3, Fe2O3, K2O and TiO2
in the form of muscovite, hematite and rutile, and depleted in SiO2,
MgO, CaO and Na2O, led Derby (1900a) to suggest that before

Corresponding author.
E-mail address: alexandre.cabral@tu-clausthal.de (A.R. Cabral).
0024-4937/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.lithos.2012.01.011

metamorphism it had been decomposed and leached in situ

(Derby, 1900a, p. 212).
A volcanic protolith of hematitic phyllite was recognised by previous authors mostly on the basis of petrographical observations
(e.g., Barbosa, 1951; Correns, 1932; Derby, 1899; Dussin, 2000;
Herrgesell, 1984; Moraes and Guimares, 1931; Renger, 1970).
Much of their interest in the petrogenesis of hematitic phyllite
was due to its spatial association with diamantiferous metaconglomerates of the Sopa-Brumadinho Formation. The occasional recovery of diamonds from the hematitic phyllite in the southern Serra
do Espinhao, near Diamantina, led Moraes and Guimares (1931)
to conclude that it had been the source rock for the Espinhao diamonds (see discussion in Chaves et al., 2001). Recently, the nding
of microdiamonds in a hematitic phyllite-like rock in the northern
extension of Serra do Espinhao (Chapada Diamantina) has
restored interest in the origin of hematitic phyllite (Battilani
et al., 2007). However, the original chemical composition of the hematitic phyllite near Diamantina and its equivalent in Chapada
Diamantina has been obscured by pervasive alteration involving K
and B metasomatism, which resulted in disseminations and pockets
of tourmaline in a ne-grained muscovite matrix (e.g., Correns,

A.R. Cabral et al. / Lithos 140141 (2012) 224233

1932; Derby, 1879, 1899; Herrgesell, 1984; Moraes and Guimares,

1931). The widespread tourmalinisation is at odds with the
currently accepted palaeosol model proposed by Knauer and
Schrank (1993).
Here we report the rst detailed study on the tourmaline found in
the hematitic phyllite. We present data on the mineral chemistry
of tourmaline and its B-isotopic compositions from the hematitic
phyllite near Diamantina. We also show that the tourmaline-bearing
hematitic phyllite is widespread in the southern Serra do Espinhao
(Fig. 1). Together with its potential extension to Chapada Diamantina,

225

~700 km NNE of Diamantina, our data point towards an orogen-scale

overprinting by B-rich brines.
2. Geological setting
The southern Serra do Espinhao (Derby, 1906; von Eschwege, 1822)
exposes siliciclastic metasedimentary rocks of the Espinhao Supergroup
(Almeida-Abreu and Renger, 2007; Martins-Neto, 2000; Pug, 1967; and
references therein). These rocks delineate a NS-trending intracratonic
rift basin. Rift-stage volcanism, which was coeval with the siliciclastic

Fig. 1. Distribution map of the hematitic phyllite in and south of the Diamantina area (compiled from Almeida-Abreu, 1993; Capistrano and Neto, 1980; Carvalho, 1981; Chaves
et al., 1985; Herrgesell, 1984; Luz and Neto, 1988; Marques and Dias, 1982; Pessoa and Silveira, 1987; Rudnitzki et al., 1988; Schll and Fogaa, 1981; Silva, 1988).

226

A.R. Cabral et al. / Lithos 140141 (2012) 224233

Fig. 2. Lithostratigraphical column for the basal units of the Espinhao Supergroup in
Diamantina (e.g., Martins-Neto, 1996; Pug, 1967). The stratigraphic positioning of
the Bandeirinha Formation as part of the Espinhao Supergroup remains controversial,
but we follow Morteani et al. (2001) who distinguished the lowermost Espinhao
Supergroup from the subjacent Rio Paranas Supergroup based on the presence of
hematitetourmalinephosphate concentrations. Geochronological information from
Chemale et al. (2010) and Rosset et al. (2007).

sedimentation of the So Joo da Chapada Formation, is represented by

rocks that were extensively altered, resulting in the rock known as hematitic phyllite (Fig. 2). Magmatic zircon from the hematitic phyllite
has been dated at 1703 12 Ma (UPb, Chemale et al., 2010), conrming previous results (Dussin and Dussin, 1995; Machado et al., 1989).
The So Joo da Chapada Formation records a coarsening-upward sedimentation from a lacustrine to a deltaic to uvial setting (e.g., MartinsNeto, 2000). New geochronological data suggest a major hiatus of ca.
500 Ma between the So Joo da Chapada Formation and the overlying
Sopa-Brumadinho Formation (Chemale et al., 2010). However, hematitic
phyllite occurs as concordant bodies within the Sopa-Brumadinho
Formation (e.g., Almeida-Abreu and Renger, 2007; Knauer and
Schrank, 1993; Martins-Neto, 1996; Pug, 1967; Renger, 1970). The
Sopa-Brumadinho Formation, hosting the historically famous and economically important diamantiferous metaconglomerates, comprises
fan-deltaic and uvial quartzite and metaconglomerate that are interbedded with lacustrine pelitic rocks (e.g., Martins-Neto, 1996). The
Espinhao basin evolved to shallow-water marine sedimentation that
took place before ca. 1.10.9 Ga, when tholeiitic dykes intruded the entire Espinhao sequence (e.g., Rosset et al., 2007).
In Neoproterozoic times, large sequences of Espinhao strata were
thrust westward over Neoproterozoic rocks deposited on the So
Francisco craton, forming the Brasiliano fold-and-thrust belt that
fringes the western margin of the Araua orogen (e.g., Alkmim
et al., 2006; Uhlein et al., 1998). Metamorphic grade increases eastwards from anchimetamorphic conditions in the cratonic cover
(Schll, 1972); near Diamantina temperature and pressure conditions
of the Brasiliano tectonothermal event are constrained at 440 C and
pressure of at least 0.34 GPa (Morteani et al., 2001). Tourmaline is
ubiquitous in siliciclastic rocks of the lower units of the Espinhao Supergroup near Diamantina (Fogaa, 1997; A.R. Cabral and F.R. de
Abreu, unpublished eld observations).
3. Methods
Whole-rock samples of hematitic phyllite were pulverised using
an agate mill and were sent to Acmelabs, Vancouver, Canada, for

chemical analysis. Major elements were determined by ICP-OES

after fusion with lithium metaborate/tetraborate followed by dilute
nitric digestion. The same decomposition technique was used for
the rare-earth elements and other trace elements, which were measured by ICP-MS. An aliquot was digested in aqua regia at 95 C and
analysed by ICP-MS for Au, Ag and other metals (As, Bi, Cd, Cu, Hg,
Mo, Ni, Pb, Sb, Se, Tl and Zn). Selected samples were additionally analysed for Au, Pt and Pd by ICP-MS after re-assay fusion. Total C and S
were obtained by sample combustion combined with infrared detection (Leco). Loss on ignition (LOI) was calculated by mass difference
after ignition at 1000 C.
Boron was determined in whole-rock samples by two methods.
The rst method had sample aliquots fused with a mixture of
Na2O2 and NaOH at Acmelabs. After cooling, the resulting fused pellets were dissolved in demineralised water and HCl in a hot-water
bath; solutions were analysed for B by ICP-ES, with a detection
limit of 3 g/g. The second method, carried out at Activation Laboratories (Actlabs), Ancaster, Ontario, Canada, involved sample aliquots
that were placed in a beam of neutrons produced from a nuclear reactor. This reactor-based method measured the prompt-gamma ray
at 478 KeV using a high-purity Ge detector. The detection limit for
B is 2 g/g, which is a function of the counting time. Both methods
agreed well in samples containing b50 g/g B, but for higher
contents of B there are discrepancies of about 25% (Table 1). The
discrepancies indicate that the Na2O2NaOH-induced fusion was
incomplete.
Electron-microprobe analyses on tourmaline were performed by
a Cameca SX100 at Technische Universitt Clausthal, Germany. All
elements had their K X-ray emission lines measured at 15 kV and
15 nA with a beam diameter of 2 m. Reference materials used
were apatite (F), kaersutite (Na, Mg, Al, Si, Ca, Ti and Fe) and
MnSiO3 (Mn).
Tourmaline 11B/ 10B ratios on Au-coated thin sections were determined by secondary ion mass spectrometry (SIMS) using a Cameca
ims 6f SIMS instrument at the Helmholtz-Zentrum Potsdam. A nominally 12.5-kV, 800-pA, 16O primary beam, focused to a ~5-m diameter at the sample surface, to which a 10.0-kV secondary ion
extraction potential was applied. Distinction between the 11B + mass
station from the 1H 10B + peak was accomplished by a mass resolving
power of M/dM = 1200. In order to remove the Au coat and to
establish equilibrium sputtering conditions at the point of analysis,
a 180-second presputtering was implemented. The instrumental
mass fractionation (IMF) was calibrated using a suite of four natural
tourmaline reference materials (Dyar et al., 2001; Gonantini et al.,
2003; Tonarini et al., 2003). Individual analyses had typical measurement uncertainties of around 0.4 (1 s), but our SIMS B-isotope results are reliable to 1.9 (1 s) level as based on the repeatability
of the IMF determinations (n = 30 over three days on the four reference tourmalines). The uncertainty estimate includes the propagation
of the uncertainties in the wet chemical determinations of the compositions of the four reference tourmalines, as well as any bias from
matrix effects due to variations in tourmaline major elements.
4. Sample material
A suite of samples were collected from several localities near
Diamantina. Samples labelled BS are hematitic phyllite from the
So Joo da Chapada Formation. This study focuses on tourmaline of
the BS samples because they represent the typical hematitic phyllite
of the aforementioned unit, for which the magmatic crystallisation
age of 1.7 Ga is well established (Chemale et al., 2010; Dussin and
Dussin, 1995; Machado et al., 1989). Two polished thin sections
from samples BS-103 and BS-107-1 were selected for SIMS work.
Another suite of hematitic phyllite-like rocks, labelled DI, were
sampled from exposures of the Sopa-Brumadinho Formation in
diamond-mining areas (garimpos) between Sopa and Guinda. Two

A.R. Cabral et al. / Lithos 140141 (2012) 224233

227

Table 1
Whole-rock analyses of hematitic phyllite near Diamantina.

SiO2 wt.%
Al2O3
Fe2O3
MgO
CaO
Na2O
K2O
TiO2
P2O5
MnO
Cr2O3
LOI
Total
C-tot
S-tot
Au ng/g
Pt
Pd
As g/g
B
Ba
Ba
Be
Bi
Co
Cs
Cu
Ga
Hf
Hg
Mo
Nb
Ni
Pb
Rb
Sb
Sc
Sn
Sr
Ta
Th
U
V
W
Zn
Zr
Y
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu

BS-107-1

BS-107-3

BS-104-4

BS-103

DI-3

DI-4

DI-5

35.01
23.17
21.92
1.34
0.02
0.19
8.57
5.43
0.05
0.02
0.01
4.00
99.73
b0.02
b0.02
2
1.6
b0.5
b0.5
40
40
404
4
b0.1
22
1.7
1.0
33
12
b0.01
b0.1
37
1.8
2.4
119
b0.1
38
2
64
2.4
12
8.1
202
2.7
2
434
64
62
146
17
70
13
3.4
13
2.0
11
2.2
6.0
0.88
5.5
0.80

36.74
24.19
18.08
1.47
b 0.01
0.17
8.60
5.26
0.68
0.02
0.01
4.50
99.73
b 0.02
b 0.02
3
4.5
b 0.5
b 0.5
20
23
534
3
b 0.1
15
1.9
0.6
32
12
b 0.01
b 0.1
35
1.9
2.2
128
b 0.1
41
3
92
2.2
11
6.2
166
4.4
2
435
65
55
127
15
64
14
3.7
15
2.4
12
2.4
6.4
0.95
5.8
0.87

35.83
21.67
22.33
1.93
0.03
0.12
8.03
5.25
0.14
0.04
0.01
4.20
99.58
0.03
b 0.02
b1
0.6
b 0.5
b 0.5
47
46
1001
5
0.1
20
2.2
2.6
28
11
b 0.01
0.1
35
6.2
8.7
101
b 0.1
40
3
75
2.0
10
8.9
127
4.5
7
431
73
98
177
25
103
20
5.3
20
2.9
15
2.9
7.7
1.1
6.3
0.89

45.70
25.37
8.56
2.30
b0.01
0.16
9.92
1.20
0.05
0.03
0.01
6.40
99.71
b0.02
b0.02
n.a.
n.a.
n.a.
b0.5
n.a.
111
612
3
0.1
6.3
5.2
0.2
28
17
b0.01
b0.1
20
0.5
4.5
162
b0.1
14
6
27
1.7
26
3.5
61
2.2
b1
628
59
83
163
20
79
13
2.9
9.9
1.8
11
2.2
6.4
0.92
6.0
0.85

43.86
27.91
7.61
2.26
0.03
0.26
9.82
1.32
0.11
0.10
0.01
5.70
98.99
0.05
b 0.02
n.a.
n.a.
n.a.
1.6
565
758
5736
12
b 0.1
18
5.5
2.7
29
31
0.01
b 0.1
32
1.7
163
163
0.4
18
6
138
2.9
27
44
284
4.7
9
1164
69
70
124
12
42
7.9
1.8
9.9
2.0
12
2.4
7.0
1.1
6.9
1.1

42.38
28.58
9.45
1.68
0.01
0.26
9.65
1.25
0.20
0.02
0.01
6.00
99.49
0.03
b 0.02
n.a.
n.a.
n.a.
b 0.5
542
711
2510
5
b 0.1
12
3.8
21
28
20
b 0.01
b 0.1
25
19
2.0
158
b 0.1
28
5
133
2.0
34
8.6
114
5.2
8
778
66
73
150
17
67
12
2.2
11
1.8
11
2.4
7.2
1.1
6.9
0.94

40.20
25.28
8.58
5.38
2.97
0.14
8.10
1.16
2.31
0.11
0.01
5.30
99.54
0.03
b0.02
n.a.
n.a.
n.a.
6.3
262
361
855
5
0.6
27
1.6
33
29
24
b0.01
0.2
27
99
12
155
0.2
19
5
67
2.3
38
26
67
4.4
56
913
142
98
213
22
83
18
3.9
21
3.6
23
4.7
13
1.9
11
1.6

Elements analysed for, but below detection limits: Ag, Cd and Tl (b0.1 g/g), and Se
(b 0.5 g/g).
Total Fe as Fe2O3; C- and S-tot = total C and S.
n.a. = not analysed.
a
Boron determined by prompt-gamma neutron activation analysis (see text).

Fig. 3. Photograph of a slab of hematitic phyllite showing aggregates of feldspar-like

laths of ne-grained muscovite (arrows).

4.1. Tourmaline-bearing samples

The hematitic phyllite of the BS sample suite consists essentially of
a ne-grained matrix of muscovite in which hematite and, subordinately, rutile are dispersed. The muscovite denes the penetrative foliation that characterises strongly deformed rocks. In less deformed
parts, tabular crystals resembling plagioclase laths can be recognised
(Fig. 3), but they were completely replaced by ne-grained muscovite,
i.e. sericite. The sericitised laths were only observed in domains lacking foliation, suggesting a pre-kinematic timing for the lath-shaped
grains. These tabular grains and their decussate arrangement were
previously described and interpreted as volcanic in origin (e.g.,
Correns, 1932; Derby, 1899; Rimann, 1931). Although our sample material has not provided any relict of feldspar in the sericitised laths,
Correns (1932) found rests of plagioclase with the least refractive
index of >1.544, indicative of at least 30 wt.% anorthite, and concluded that the hematitic phyllite would originally have been a diabase.
The hematite is titaniferous and occurs, with or without rutile, as
laths and as aggregates. The hematite laths show a range from
hematite- to rutile-dominated varieties. The hematite aggregates are
wider than the laths and locally have abundant lamellae of rutile.
The rutile lamellae in the hematite aggregates are either lenticular,
roughly parallel, or form a trellis-like fabric. Quartz is a minor component, relative to sericite and hematite, in the hematitic phyllite,
where it is mainly found as corroded grains of patchy distribution
within the sericite matrix. Monazite is sparsely disseminated as aggregates with rutile and/or hematite. Inclusions of monazite, b5 m
across, can be spotted in tourmaline. The tourmaline is thinly scattered in the hematitic phyllite, being concentrated in pockets of
b3 mm across.
Petrographically, two types of tourmaline occur in the BS sample
suite: (1) disseminated crystals; and (2) aggregates in pockets. The
disseminated tourmaline is generally found in the proximity of corroded quartz (Fig. 4a). It may show growth zones that are delineated
by hematite (Fig. 4b). The pocket tourmaline, which is coarser than
the disseminated crystals, manifests itself as aggregates without any
preferential orientation. The tourmaline pockets truncate the tectonic
foliation of the host hematitic phyllite (Fig. 4c).
5. Results

DI samples, DI-2 and DI-3, are similar to the lithology referred to as

sericitic phyllite (Silva et al., 2005), whereas sample DI-5 is a negrained greenstone. The DI samples are used for comparing their
whole-rock chemistry to the typical hematitic phyllite, i.e. the BS
samples, of the So Joo da Chapada Formation.

5.1. Whole-rock composition of hematitic phyllite

Whole-rock chemical analyses are presented in Table 1. The abundance of sericite, hematite and tourmaline that typies the hematitic
phyllite is reected in the contents of K2O, consistently tight between

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A.R. Cabral et al. / Lithos 140141 (2012) 224233

Fig. 4. a) Transmitted-light photomicrograph of hematitic phyllite. Disseminated tourmaline (arrows) occurs in the adjacencies of corroded quartz (Qz) in a ne-grained matrix of
muscovite (sample BS-103). b) Detail of the area indicated in a) under reected light. Hematite (white) is dispersed in the matrix. Arrow points to a growth zone in tourmaline
(Tur), which is delineated by ne-grained hematite (white). White spots and corresponding gures mark the location of SIMS measurements and their 11B values. c) Transmitted-light photomicrograph of pocket tourmaline (Tur) in sample BS-107-1. It comprises tourmaline-rich aggregates that truncate the tectonic foliation of the hematitic phyllite.
d) Reected-light photomicrograph of the area indicated in c), here coated with Au, to show actual SIMS spots and their respective 11B values. An individual crystal of the pocket
tourmaline may exhibit a large range of 11B values, from 8.9 to 4.0. Ms, muscovite.

8 and 10 wt.%, but variable contents of total Fe as Fe2O3, between ~8

and 22 wt.%, and B, between 23 and 758 g/g. Based on the contents
of Fe2O3 and B, the samples can be divided into two groups: (1) lowB, high-Fe hematitic phyllite, with up to ~50 g/g B and between 18
and 22 wt.% Fe2O3; (2) high-B, low-Fe hematitic phyllite, with
111758 g/g B and between 7.6 and 9.5 wt.% Fe2O3. Comparing their
Zr/Hf vs. Y/Ho ratios (Fig. 5a), both groups plot within the CHARAC
eld of Bau (1996), indicating that the overprinting sericitisation,
hematitisation and tourmalinisation did not affect the chondritic Zr/Hf
and Y/Ho ratios expected for rocks crystallised from silicate melts. For
this reason, element ratios such as Nb/Y and Zr/Ti should reect the ratios of the precursor rocks of the hematitic phyllite. The low-B, high-Fe
group of hematitic phyllite has Nb/Y and Zr/Ti ratios of a basaltic protolith, whereas those for the high-B, low-Fe group are compatible with a
rhyolitic protolith (Fig. 5b). These results agree with the petrographical
investigation of Correns (1932), who concluded that the hematitic
phyllite had derived from two rock types, quartz porphyry and diabase.
Relative depletions and enrichments in some major and trace elements are illustrated by the compositional trend of weathered basaltic
rocks because of the current genetic model for the hematitic phyllite,
which would represent weathered basaltic rocks of the opening of the
Espinhao basin (Knauer and Schrank, 1993). Our analyses, together
with additional data available in literature, dene a positive trend of
Al2O3 vs. SiO2 (Fig. 6a), which contrasts with the tighter negative
trend found in basaltic weathering proles (e.g., Nesbitt and Wilson,
1992). Also contrasting is the dispersion of hematitic phyllite on the

Al2O3 vs. TiO2 diagram (Fig. 6b), where a negative distribution is

poorly dened in relation to the clear positive correlation in basaltic
weathering proles. The Zr contents of the hematitic phyllite are
constantly higher than those expected in basaltic weathering proles
(Fig. 6c). They are analogous to the Zr contents that are typically
reported from weathered alkaline ultramac rocks, from which the
hematitic phyllite is readily distinguished by its K2O and Nb contents
(Fig. 6d). As previously mentioned, one group of hematitic phyllite
has Nb/Y and Zr/Ti ratios indicative of a rhyolitic protolith.
5.2. Tourmaline composition
Compositionally, both disseminated and pocket varieties of tourmaline belong to the alkali group. Disseminated tourmaline has Mg/(Mg+
Fe) values between 0.6 and 0.8; pocket tourmaline is between 0.5 and
0.7 (Table 2). Both tourmaline types fall in the dravite eld of the X/
(X+ Na) vs. Mg/(Mg + Fe) diagram of Henry et al. (2002), where X is
the X-site vacancy (Fig. 7a). On an AlFeMg ternary diagram
(Fig. 7b), the disseminated tourmaline plots along the povondraiteoxy-dravite join, whereas the pocket tourmaline skews towards
the Fe-rich direction of the schorldravite join with dispersion parallel
to, and extending into, the povondraite"oxy-dravite" join.
Fluorine was not detected (b0.1 wt.%) in the disseminated and
pocket varieties of tourmaline. Both varieties have low contents of
TiO2, which do not exceed 1 wt.%. Titanium mostly occurs as abundant
titaniferous hematite and, subordinately, rutile in the hematitic phyllite.

A.R. Cabral et al. / Lithos 140141 (2012) 224233

Fig. 5. a) Diagram of Zr/Hf vs. Y/Ho showing the CHARAC eld of Bau (1996). b) Discrimination plot of Nb/Y vs. Zr/Ti for volcanic rocks (Pearce, 1996). Two groups of hematitic phyllite, i.e. low-B, high-Fe hematitic phyllite, and high-B, low-Fe hematitic
phyllite, plot respectively in the basaltic and rhyolitic elds.

5.3. Boron-isotopic compositions of tourmaline

SIMS measurements were performed on cores and/or rims of individual crystals of disseminated tourmaline and pocket tourmaline.
The disseminated tourmaline has 11B values that vary from 15.1
to 7.7, while the pocket tourmaline shows a 11B range from
10.9 to 4.0 (Fig. 8a, Table 3). The disseminated tourmaline has
corerim 11B values within approximately 3 (Fig. 4b). With one
exception, the pocket tourmaline also has corerim 11B values within ~ 3. The exception is a crystal of pocket tourmaline within which
the 11B values differ from 8.9 to 2.0 and 4.0 along the rim
(Fig. 4d). Overall, the 11B values of hematitic phyllite-hosted tourmaline match those from other B reservoirs, such as magmatic and
non-marine evaporitic reservoirs, but are clearly distinct from marine
evaporite (Fig. 8b).
6. Discussion
6.1. Hematitic phyllite and uid overprint
It is widely believed that the protolith of the hematitic phyllite
was an eruptive rock (e.g., Correns, 1932; Derby, 1899; Dussin,

229

2000; Herrgesell, 1984); more recently, the hematitic phyllite has

been interpreted as a metamorphosed palaeosol after basaltic rocks
(cf. Derby, 1900a; Knauer and Schrank, 1993). Analogues of such a
metamorphosed palaesol are the Tertiary FeAlTi-rich rocks in the
Bana plutono-volcanic complex, Cameroon (Kuepouo et al., 2009),
which were formed by pyrometamorphism of laterite incorporated
by basaltic magmas. Their major-element chemical composition,
though comparable in Fe, Al and Ti to the hematitic phyllite, has
very low contents of K2O. The hematitic phyllite has a remarkable enrichment in K2O in relation to the Bana palaeolaterite and other
weathering products of basaltic rocks and alkaline ultramac rocks
(Fig. 6c, d).
The palaeosol model for the hematitic phyllite requires postweathering introduction not only of K, but also of Al and Si to account
for the positive trend of Al2O3 vs. SiO2 (Fig. 6a), and of B to form tourmaline. The positive trend differs from the negative correlation of
Al2O3 vs. SiO2 recorded in modern weathering proles (e.g., Nesbitt
and Wilson, 1992; Rainbird et al., 1990). Potassium metasomatism
is common in weathering proles in continental settings and involves
the conversion of kaolinite to illite by reaction with K +-bearing pore
waters (e.g., Fedo et al., 1995; Nesbitt and Young, 1989). However,
ordinary diagenetic K metasomatism is not supposed to have added
Al and Si, and B in particular.
Geological mapping of an area about 40 km south-east of Diamantina,
near Serro (Fig. 1), has shown that tourmaline-bearing quartzite and
quartzite-hosted tourmalinite are spatially associated with hematitic
phyllite (Cabral et al., 2011). Overprinting tourmaline in quartzitic
rocks of the lower Espinhao Supergroup has been observed near
Diamantina and elsewhere in the southern Serra do Espinhao (e.g.,
Cabral et al., 2011; Correns, 1932; Guimares, 1937; Moraes and
Guimares, 1931, and references therein; A.R. Cabral and F.R. de Abreu,
unpublished data). The quartzite-hosted tourmalinite exhibits petrographical evidence that tourmaline replaced recrystallised detrital
quartz, and that titaniferous specular hematite was coeval with the formation of tourmaline (Cabral et al., 2011). These observations suggest
a regional overprint by uids bearing B, Al, Fe and Ti. The uid overprint
is manifested by quartz veins in the quartzitic rocks of the southern Serra
do Espinhao (e.g., Cabral et al., 2011; Correns, 1932; Chaves et al., 2010;
Moraes et al., 1937).
The hematitic phyllite also has remarkable contents of La and Ce
(Table 1). These LREE are mainly hosted in hydrothermal monazite,
which is intergrown with hematite and/or rutile (Derby, 1900b).
We conrm the mineralogical observations by Derby (1900b), who
noted that the hematitic phyllite and enclosing clastic rocks had experienced a new formation of monazite such as has been shown
for tourmaline (Derby, 1900b, p. 219). Other occurrences of hydrothermal monazite have been recorded in quartz veins (Chaves et al.,
2010; Derby, 1900b; see Section 6.2) and in quartzite-hosted tourmalinite (A.R. Cabral, unpublished data).
The aforementioned lines of evidence indicate that the protolith of
the hematitic phyllite underwent intense hydrothermal overprint,
which obscured its pre-metamorphic history. The K metasomatism
could even have taken place during the diagenesis of the sedimentary
pile, but a lateritic origin for the protolith of the hematitic phyllite
cannot be proven.
6.2. Nature and timing of uid overprint
The pervasive occurrence of tourmaline in the hematitic phyllite
suggests a B-bearing uid source. Insights into the nature of B reservoirs can be gained by B isotopes. Our tourmaline 11B values have
a wide range that may reect contributions from multiple sources,
such as magmatic rocks, sedimentary rocks and non-marine evaporites (Fig. 8b). Unaltered basaltic rocks have B contents of b1 g/g B
(Spivack and Edmond, 1987), which are lower than those in clastic
sediments (~ 50150 g/g B, Leeman and Sisson, 1996). Mac rocks

230

A.R. Cabral et al. / Lithos 140141 (2012) 224233

Fig. 6. Correlation plots of (a) Al2O3 vs. SiO2, (b) Al2O3 vs. TiO2, (c) K2O vs. Zr and (d) K2O vs. Nb for the hematitic phyllite in comparison with modern weathered products of basaltic
rocks (Nesbitt and Wilson, 1992) and/or alkaline ultramac rocks (Cornelius et al., 2005).

are therefore an unlikely source of the B required for the observed

widespread occurrence of tourmaline.
Tourmaline is also widely distributed in the arenaceous rocks in
the lower sequences of the Espinhao Supergroup, where it occurs
as tourmalinite and tourmaline-bearing quartzite. Tourmaline 11B
values from tourmalinite and quartzite vary from ~1 to 10.4
11B (Cabral et al., 2011) and fall within the range of tourmaline
11B values from the hematitic phyllite (Fig. 8a, Table 3). This similarity in 11B values suggests that tourmaline from hematitic phyllite,
from quartzite-hosted tourmalinite and quartzite have a common
source. The amount of B required for the overprinting tourmaline
on a regional scale seems inconsistent with the local clastic sediments
being the sole source of the required B.
The hematitic phyllite-hosted tourmaline has compositions that plot,
on an AlFeMg ternary diagram (Fig. 7b), along the povondraiteoxy-

dravite trend. This compositional trend is characteristic of B-rich

brines of evaporitic origin (Henry et al., 2008). Our 11B data, together with the regional tourmalinisation, are consistent with a nonmarine evaporitic B source. Lacustrine evaporitic brines may have
high concentrations of K and B (e.g., Eugster, 1980; Warren, 2010).
Continental evaporites have not yet been recognised in the southern
Serra do Espinhao, but a lacustrine evaporitic source is compatible
with the fan-deltaic depositional setting of the Sopa-Brumadinho
Formation (e.g., Martins-Neto, 1996).
Both the BS and DI samples, from the So Joo da Chapada Formation (~ 1.7 Ga) and the overlying Sopa-Brumadinho Formation
(~1.2 Ga), respectively, display similar enrichments in B and K, suggesting that the BK metasomatism post-dated the ca. 500-Ma
hiatus proposed by Chemale et al. (2010). The hematitic phyllite and
metasedimentary rocks of the Espinhao Supergroup have a tectonic

Table 2
Electron-microprobe analyses of disseminated tourmaline (115) and pocket tourmaline (1630) from hematitic phyllite.
wt.%

10.69
36.57
30.78
0.47
7.62
0.07
8.47
0.91
2.17
b 0.04
97.74

10.43 10.84
35.64 36.70
28.32 35.46
0.67 b 0.13
10.28
3.42
0.14 b 0.05
7.88
8.17
0.40
0.46
2.42
2.19
b 0.04 b 0.04
96.18 97.24

5.946
5.899
0.057
1.036
0.009
2.052
0.158
0.685

5.942
5.564
0.085
1.433
0.020
1.958
0.071
0.783

5.887
6.702

0.19
0.66

0.16
0.58

0.26
0.81

0.459
1.953
0.079
0.682

10

10.53 10.73
36.13 37.26
30.03 30.86
0.26 b0.16
8.73
7.17
0.07
0.13
7.92
8.65
0.35
0.12
2.61
2.57
0.08 b0.04
96.72 97.49
5.962
5.841
0.032
1.205
0.010
1.949
0.062
0.834
0.017
0.09
0.62

6.034
5.890
0.971
0.018
2.088
0.021
0.805
0.18
0.68

11

12

10.71 10.65
37.09 36.32
31.36 30.87
0.11 b 0.15
7.36
8.41
b 0.05
0.08
8.17
8.09
0.29
0.20
2.71
2.58
0.07 b 0.04
97.88 97.20
6.016
5.995
0.014
0.999
1.977
0.050
0.851
0.015
0.09
0.66

5.931
5.941
1.148
0.011
1.970
0.035
0.817
0.15
0.63

13

14

10.58
36.62
29.81
0.45
8.63
b 0.06
8.05
0.54
2.34
0.05
97.08

10.59 10.61 10.57 10.72 10.49 10.63 10.52 10.52 10.45 10.46 10.47 10.45 10.60 10.53 10.50 10.62 10.50
35.93 36.26 35.43 36.28 35.38 35.26 35.02 35.29 35.34 35.26 35.33 35.31 35.52 35.10 34.99 35.73 35.08
29.14 30.27 32.52 32.41 31.37 33.46 32.07 31.36 30.70 30.49 30.87 31.44 31.48 31.80 31.89 32.62 31.42
0.27
0.44
0.24
0.34
0.31
0.20 b 0.22
0.20
0.67
0.67
0.66
0.22
0.55
0.23 0.21 b 0.20
0.32
9.71
8.13
8.45
6.59
9.98
6.46
9.41 10.40
9.17 10.98
9.84
9.51
6.88
9.58 9.56
9.11
9.84
0.10 b0.06
0.06
0.08
0.06
0.05
0.06 b 0.06
0.08
0.08
0.07
0.05 b 0.06
0.07 0.07 b 0.06
0.06
8.56
8.40
6.84
8.18
6.40
7.66
6.73
6.48
7.00
6.27
6.62
6.49
8.49
6.75 6.60
6.60
6.72
0.23
0.56
0.09
0.64
0.08
0.15
0.08
0.09
0.31
0.13
0.30
0.06
0.94 b 0.05 0.07
0.07
0.06
2.72
2.40
2.40
2.11
2.55
2.02
2.68
2.59
2.23
2.47
2.28
2.44
2.15
2.67 2.49
2.84
2.94
0.05
0.07 b0.04
0.05 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 b 0.04 0.04 b 0.04
0.05
97.29 97.14 96.59 97.38 96.60 95.88 96.56 96.93 95.95 96.81 96.43 95.96 96.60 96.72 96.42 97.58 96.99

6.015
5.772
0.055
1.186
1.972
0.095
0.746
0.010
0.17
0.62

15

5.895
5.633
0.033
1.332
0.013
2.094
0.041
0.864
0.010
0.09
0.61

B2O3 calculated using stoichiometric constraints (Henry et al., 2008).

Total Fe as FeO; X = X-site vacancy.

5.940
5.842
0.054
1.114
2.050
0.099
0.762
0.014
0.14
0.65

16

5.825
6.300
0.029
1.161
0.008
1.677
0.015
0.763
0.22
0.59

17

5.884
6.194
0.041
0.893
0.010
1.977
0.112
0.663
0.010
0.24
0.69

18

19

20

5.864
6.127
0.038
1.383
0.008
1.580
0.014
0.818

5.767
6.450
0.025
0.884
0.007
1.867
0.026
0.639

5.787
6.246
1.301
0.009
1.658
0.014
0.858

0.17
0.53

0.34
0.68

0.13
0.56

21

5.833
6.109
0.025
1.437

22

23

24

25

26

27

5.858
5.970
0.083
1.525
0.011
1.553
0.024
0.795

5.865
6.039
0.082
1.366
0.010
1.638
0.052
0.734

5.872
6.162
0.027
1.322
0.007
1.609
0.010
0.786

5.826
6.086
0.067
0.944

1.596
0.016
0.831

5.876
6.017
0.084
1.275
0.011
1.737
0.056
0.718

5.793
6.186
0.029
1.322
0.010
2.076 1.660
0.165
0.683 0.855

0.16
0.53

0.24
0.58

0.19
0.50

0.23
0.55

0.21
0.55

0.18 0.15
0.69 0.56

28

5.792
6.221
0.026
1.323
0.010
1.628
0.012
0.798
0.008
0.19
0.55

29

5.850
6.293
1.246
1.610
0.012
0.901
0.09
0.56

30

5.805
6.127
0.040
1.362
0.009
1.658
0.010
0.944
0.010
0.04
0.55

231

Fig. 7. a) Diagram of Mg/(Mg + Fe) vs. X/(X + Na) for classication of tourmaline species (Henry et al., 2002), where X is the X-site vacancy. Symbols as in b). b) Upper portion of an AlFeMg ternary diagram for tourmaline from hematitic phyllite near
Diamantina, Minas Gerais (Table 2). Magnesium-rich tourmaline, ~ 2.0 atoms of Mg
per formula unit, plots near the oxy-dravitepovondraite join, which is characteristic
of meta-evaporitic tourmaline (Henry et al., 2008).

foliation that records the ~0.6-Ga Brasiliano orogeny (e.g., Alkmim

et al., 2006; Uhlein et al., 1998). The regional tectonic foliation is
cross-cut by monazite-bearing quartz veins (Chaves et al., 2010;
Derby, 1900b). Quartz-vein monazite from a locality near Diamantina
has a UPb age of 458 3 Ma (Chaves et al., 2010). We envisage that
metamorphic uids acquired high concentrations of K and B from a
continental evaporitic source. Such uids altered basaltic and rhyolitic
rocks that were deformed during the Brasiliano tectonics, generating
the hematitic phyllite with disseminated, syntectonic tourmaline.
The pocket tourmaline, which truncates the tectonic foliation of the
host hematitic phyllite, represents a late-tectonic tourmaline generation of Brasiliano age.

6.3. Isotopic heterogeneity

One crystal of pocket tourmaline has heterogeneous 11B values,

with a variation from 8.9 to 4.0 11B along the rim (Fig. 4d).
This isotopic variation is unlikely to result from an analytical artefact
because two measurements immediately adjacent to each other gave
reproducible results, i.e., 2.0 and 4.0 11B. A few explanations for
this local isotopic heterogeneity of the pocket tourmaline could be
put forward, such as temperature-dependent B-isotopic fractionation,
Rayleigh fractionation and multiple sources of uid (e.g., Jiang et al.,
1999; Marschall et al., 2009; Meyer et al., 2008; Pal et al., 2010).
However, more data are needed in order to substantiate the isotopic
heterogeneity and then to condently discuss its causes.

A.R. Cabral et al. / Lithos 140141 (2012) 224233

B2O3
10.51 10.66 10.85 10.68 10.74
36.26 36.71 37.20 36.33 36.72
SiO2
29.70 29.28 33.19 30.67 32.13
Al2O3
0.96
0.28 b0.15
0.33 b 0.15
TiO2
FeO
7.77
9.66
5.01
8.15
5.90
MnO
b 0.06
0.10 b0.06 b0.06 b 0.06
MgO
8.19
8.32
8.84
8.45
8.83
CaO
1.88
0.24
0.13
0.56
0.29
1.84
2.54
2.36
2.43
2.38
Na2O
0.05
0.05 b0.04
0.04
0.06
K2O
Total
97.17 97.84 97.57 97.63 97.06
Atomic proportions based on T + Z + Y = 15 cations
Si
5.998 5.985 5.956 5.915 5.943
Al
5.789 5.626 6.264 5.886 6.128
Ti
0.120 0.035
0.041
Fe (total)
1.075 1.317 0.671 1.109 0.799
Mn
0.014
Mg
2.019 2.023 2.109 2.050 2.130
Ca
0.334 0.043 0.022 0.097 0.050
Na
0.589 0.802 0.734 0.768 0.748
K
0.011 0.010
0.009 0.012
X/(X+Na)
0.10
0.15
0.25
0.14
0.20
Mg/(Mg+Fe)
0.65
0.61
0.76
0.65
0.73

232

A.R. Cabral et al. / Lithos 140141 (2012) 224233

Table 3
Boron-isotopic compositions of disseminated tourmaline (upper half, 113) and pocket
tourmaline, p (lower half).
Table 2

Tourmaline

Spot location

11B ()

1 s

1
2

3
4

5
6

7
9
10

12
13

16

17

18
19
20
21
22
23
24
25
26
27

Grain #1

Core
Margin
Between 1 and 2
Core
Margin
Margin
Core
Margin
Margin
Core
Core
Core
Core
Core
Core
Core
Margin
Core
Core
Margin
Margin
Margin
Core
Margin
Core
Core
Core
Core
Margin
Core
Margin
Core
Margin

12.0
11.5
13.8
9.0
12.0
12.3
15.1
12.5
12.0
12.5
11.8
8.7
9.0
7.7
9.5
8.2
7.1
6.6
7.6
4.0
2.0
8.9
8.7
10.9
5.4
6.9
5.1
6.4
7.4
7.4
8.9
6.1
8.7

0.34
0.32
0.31
0.33
0.39
0.35
0.36
0.38
0.38
0.35
0.36
0.37
0.34
0.34
0.32
0.33
0.34
0.31
0.36
0.35
0.36
0.36
0.31
0.33
0.33
0.38
0.35
0.36
0.33
0.33
0.31
0.41
0.31

Grain #2

Grain #3

Grain
Grain
Grain
Grain
Grain
Grain
Grain
Grain
Grain

#4
#5
#6
#7
#8
#9
#1 p
#2 p
#3 p

Grain #4 p
Grain
Grain
Grain
Grain

#5 p
#6 p
#7 p
#8 p

Grain #9 p
Grain #10 p

Fig. 8. a) Histogram of our tourmaline 11B results from hematitic phyllite near
Diamantina (Table 3). The range of tourmaline 11B values from quartzite-hosted
tourmalinite and tourmaline-bearing quartzite of the Sopa-Brumadinho Formation is
also shown for comparison (Cabral et al., 2011). b) Ranges for 11B in selected reservoirs (Barth, 1993).

Numbers in the left column refer to electron-microprobe analyses in Table 2. The stated
uncertainty reects the analytical stability of the individual analysis. The total uncertainty for all analyses is estimated at 1.9 (1 s), as based on the observed repeatability
on our suite of four tourmaline reference materials.

7. Conclusion

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(regio mediana central da Serra do Espinhao meridional), in: Almeida-Abreu,
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Brasil. PhD thesis, Universitt Freiburg.
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and aqueous systems: evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect.
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mineral chemistry and tourmaline B isotopes of the Crrego Bom Sucesso area,
southern Serra do Espinhao, Minas Gerais, Brazil: Implications for AuPdPt exploration in quartzitic terrain. Journal of Geochemical Exploration 110, 260277.
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(Projeto Mapeamento Geolgico do Espinhao Meridional, SE-23-Z-A-III-INE).
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Geolgico do Espinhao Meridional, SE-23-Z-A-VI-2NO). Diamantina, DNPM/CPRM/
CGE, Rel. Int., 48 pp.
Chaves, M.L.S.C., Dossin, I.A., Uhlein, A., Alvarenga, C.J.S., 1985. Relatrio geolgico da
Quadrcula de Sopa, 1:25.000 (Projeto Mapeamento Geolgico do Espinhao
Meridional, SE-23-Z-A-III-2SO). Diamantina, DNPM/CPRM/CGE, Rel. Int., 62 pp.
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Espinhao Range (Minas Gerais, Brazil) and their redistribution through the geologic record. Journal of South American Earth Sciences 14, 277289.

Tourmaline is widespread in the hematitic phyllite and arenaceous

rocks of the lower units of the Espinhao Supergroup in the southern
Serra do Espinhao. We have constrained the origin of the overprinting
tourmaline in the hematitic phyllite by means of tourmaline B-isotopic
and chemical data, which suggest a non-marine evaporitic B source. Our
study cannot prove the current palaeosol model for the hematitic phyllite, rather it points toward the presence of evaporites where they are
not otherwise obvious in the rock record. We interpret the hematitic
phyllite as the metasomatic alteration of basaltic and rhyolitic rocks
by metamorphic B-bearing brines of continental evaporitic origin.
Acknowledgements
We gratefully acknowledge three anonymous reviewers for their
constructive and detailed comments, which greatly improved the
manuscript. Dr. Marco Scambelluri is thanked for his careful editorial
handling. This study beneted from a Deutsche Forschungsgemeinschaft (DFG) research grant (LE 578/29-1).
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