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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
225
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
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).
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).
228
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.
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.
229
230
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).
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
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).
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
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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