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LITHOS

Llthos, 33 (1994) 285-302

ELSEVIER

Large-scale silicate liquid immiscibility: a possible example from


northeastern Brazil
V.P. Ferrexra a, A.N. Sial a, J.A W h i t n e y b
aFederal Untverstty of Pernambuco, Dept of Geology, C P 7852, Reclfe, PE, 50732-970, Brazg
bUmverstty of Georgia, Department of Geology, 4thens, G4, 30602, US4

Received 13 July, 1993, revised and accepted 30 March, 1994

Abstract
Ultrapotasslc, peralkahc sdlca-saturated plutons (580 Ma) are widespread in the Cachoelrmha-Salguelro foldbelt, northeastern Brazil They consist of alkali-feldspar syenltes w~th pyroxemte as co-magmatlc inclusions and
syn-plutomc or late-stage dikes Pyroxemte and syemte have the same mineral phases (aeglrme-auglte, m~crocllne,
sphene, apatlte, blue amphibole, magnetite), but only m &fferent proportions Rare inclusions of a "mixed" rock
(about 60% syemte + 40% pyroxenlte m an emuls~on-hke texture) are also present Pyroxenes an the three umts
are all only slightly zoned, slhca-saturated and extremely low m A1203 (0 2-1 4%) Amphiboles are mostly K-rich
rlchterlte, characterized by high $102, low A1203 and TIO2 contents and low Mg#
The three rock types have similar REE chondme-normahzed patterns, wtth negative slopes and lack of Eu anomaly, w~th the total REE m the pyroxemte greater than that &the syemte Trace element patterns for the m~xed rock
are mtermedmte between those for the pyroxemte and syemte Major element partitioning between pyroxenlte and
syemte has the same sense as that one observed between lmmtsclble llqmds m volcanic lavas and trace element
partmonmg ~s similar to the experimentally determined partluon of lmm~soble hqmd pa~rs
The rocks have slmdar high J180 values (avg w r + 8%0SMOW,corrected from p~roxene), high lnltm187Sr/86Sr
ratios (about 0 710), and low 143Nd/144Nd(avg 0 51104)
F~eld and geochemical characteristics m&cate chemical equdlbnum among the three rock t~pes and suggest
llqmd lmm~sc~bdlty between syemte and pyroxemte, the m~xed rock representing the orlgmal magma composlt~on

1. Introduction

The separation o f an initially h o m o g e n e o u s


m a g m a to yield two immiscible slhcate liquids o f
contrasting compositions has been proposed as a
possible m e c h a n i s m o f magmatlc differentiation
since long ago Some evidence had been suggested, but Bowen ( 1 9 2 8 ) was able to show that
the features described (spheruhtes, orblcules)
were not consistent with immisclblhty After his
pioneer work on crystal-liquid fractlonation and
dlsbehef in this process, h q u l d immiscibility was

mostly a b a n d o n e d as a plausible process o f magmatic diversification


Since the early 1970's, however, interest in this
process has been resurrected after the discovery
o f textures consisting o f coexisting mafic and felsic components, indicative o f immlsciblhty, in
lunar and some terrestrial basaltic rocks (e g
R o e d d e r and Wexblen, 1970) Additionally,
m o d e r n laboratory experiments on geologically
significant compositions have suggested that silicate liquid Immiscibility could be a viable process o f magmatic diversification (e g Philpotts,
1971, 1976, 1979, Roedder, 1978, 1979, Roed-

0024-4937/94/$07 00 1994 Elsevier Science B V All rights reserved


SSD10024-4937 ( 94 )00010-Y

286

V P Ferretra et al / Ltthos 33 (1994) 285-302

der and Welblen, 1970, 1971 ) Roedder (1979)


beheves that "lmmlscibihty, rather than being
exceptional, is probably an inherent feature of
slhcate glasses including even such systems as
Na20-SIO2"
In order to play an important role in the production of large-scale volumes of two magmas,
hquld separation must occur at a relatively early
stage of differentiation of the parent magma, and
thus at relatively high temperatures In most
studied cases, however, hquld immiscibility has
been demonstrated at a microscopic scale, at late
stages of crystalhzation or in mllhmeter- or centimeter-size segregations of felslc material
( o c e l l l ) i n l a m p r o p h y r e l i q u i d s (e g R o e d d e r

and Welblen, 1970, McBlrney and Nakamura,


1974, Philpotts, 1978a, 1979, Eby, 1980) Felslc
segregations or patches in pyroxenite up to 1 m
across interpreted to have formed through immiscibility were described by Philpotts (1978b)
This study reports field, petrographic and geochemical evidence that strongly suggest that hquid immiscibility occurred prior to emplacement of an ultrapotassic magma of intermediate
composition to produce ultrapotassic syenite and

associated pyroxenlte of the Trmnfo pluton,


northeastern Brazil

2. Geological setting
The Trlunfo batholith is one of several elongate syenitlc plutons emplaced within a 200 kmlong zone along the southern boundary of the
Cachoelrlnha-Salgueiro foldbelt (CSF), northeast Brazil (Fig 1 ) The foldbelt, one of the three
segments of the Central Structural Domain of the
Borborema province (Fig 1a), is an elongate belt
of a thick flysh-type sequence of sedimentary and
volcanic rocks metamorphosed to greenschist facies (Cachoelrxnha Group) and greenschist to
amphlbohte facies (Salguelro Group) The CSF,
which developed in the Late Precambrian during
the Braslllano orogeny ( = Pan-African orogeny
in western Africa), is bounded on the north and
south by the Patos and Pernambuco hneaments,
respectively, major strlke-shp systems which are
presumed to extend for hundreds of kilometers
into what is now western Africa
The enormous volume of syn- to late-klne-

[~PHANEROZOIC~OVER

RIUNFO

t '

~'

eER'VA"'~

BORBOREMAPROVINCE
(Central StructuralDomoln)

[~

CRETACEOUSSEDIMENTARY
COVER

BASEMENT ROCKS
GnolssesMigmohtes)

A- Serldo

CACHOEIR1NHAGROUP
(Phylhtes Schists)

PERALKALIC/SHOSHONITICPLUTONS

B- Cachoelnnha Solguelro

[~

ALGUEIROGROUP
(Schists Gnmsses)

[ ~ C A L C ALKALIC PLUTONS

C Rmcho do Ponta[

Fig 1 (right) The Central structural domain m the Borborema province, northeastern Brazil (modified from Santos et al,
1984 ) (left) Slmphfied geological map of the Cachoelrlnha-Salguexro foldbelt emphasizing the main groups of granltoid plutons (modified from Sial and Ferrelra, 1990)

I P Ferretra et al /Llthos 33 (1994) 285-302

matlc granites of Braslhano age indicates that the


Braslhano orogeny was the major tectonothermal event in the Borborema province (Sial and
Ferrelra, 1990) Geochronologic data for the
Brasihano cycle in the region indicate three peaks
of thermal activity, at 700_ 20 Ma, 650-620 Ma
and 550-520 Ma, the latter two being better documented than the first (Brlto Neves et al., 1974,
Long and Brlto Neves, 1977) More recent data
(Sial et al, 1989) show that the coarsely porphyritic Itaporanga-type granltoids ( ~ 80 plutons intruding the Borborema province) were
emplaced in a time span of about 100 Ma, mainly
between 630 and 550 Ma
Within the CSF, peralkahne plutons consist of
two groups, slhca-saturated ultrapotassic alkali
feldspar syenltes to alkali-feldspar granites and
slllca-oversaturated potassic alkali feldspar
granites (Ferreira and Sial, 1986)
The former includes the Triunfo bathohth, the
Cas6, Llvramento, Duas Irm~s and Serrote do
Paulo stocks, and a large dike at Bom Nome,
which constitute the "syenltoid line" (Ferreira
and Sial, 1986), the Serra do Man bathohth and
dike sets near Terra Nova and Salguelro villages
(State of Pernambuco) and Manaira and Pnncesa Izabel villages (State of Paraiba)

3. The Triunfo batholith


The Trlunfo bathohth is the best exposed and
the freshest of the peralkahc plutons in the CSF
and constitutes the largest known ultrapotasslc
intrusion in northeast Brazil It occupies an area
of about 600 km 2, elongate in the SW-NE direction parallel to the regional metamorphic trend
Three faults cut the bathohth, locally generating shear fabrics and stretching hneatlon and, at
the microscopic scale, mortar texture in feldspars and wavy extinction and polygonlzatlon of
quartz Flow structures are common primary
magmatlc structures and are characterized by
linear, sometimes planar, orientation of pyroxene and K-feldspar, and alignment of pyroxenltlC inclusions parallel to the mineral hneatlon
In some exposures, K-feldspar is so precisely
aligned that the rock has a gnelsslc appearance
The Triunfo intrusion, in spite of its large size,

287

iS predominantly composed of rocks with uniform texture and simple mineralogy Much of the
bathohth is composed of equigranular, mediumgrained, leucocratlc alkali-feldspar syenltes, m
which feldspar and chnopyroxene rarely exceed
a few millimeters in size The predominant minerals are perthltlC mxcrocllne and aeglrlne-auglte, with variable amounts of quartz, sphene,
apatlte, blue amphibole (formed at the expense
ofpyroxene) and magnetite Brown mica is present locally
Syenite has very high K20 (up to 12 8 wt %)
and K20/Na20 ratios (up to 6 3), leading to
their classification as ultrapotasslc, as defined by
Foley et al (1987) The syenltes do not match
one of the criteria (MgO> 3 wt %) for ultrapotasslc characterization as defined by Foley et al
(1987) Nevertheless, the term ultrapotasslc ~s
maintained because Foley and co-authors also
termed ultrapotasslc the most differentiated
members (trachytes) of some ultrapotassxc
suites, which have Mg-numbers similar to those
of the Tnunfo rocks
Late-stage, finer-grained syenltlC and pegmatitlC dikes are locally found cutting the Trlunfo
syenite Despite their different grain size and dike
nature, they have the same mineralogy as the host
syenltes (K-feldspar + aegirlne-augxte)
Numerous pyroxenite inclusions occur
throughout the bathohth. Most are oval-shaped
with their lengths, which ranges from a few centimeters to one meter, paralleling the flow fohatlon of the host syenite. They have about the same
grain size as the host syenite, against which they
have sharp contacts They consist mostly of euhedral to subhedral aeglrine-auglte, sphene and
apatlte Blue amphibole occurs infrequently replacing pyroxene along rims Mxcrochne and interstitial quartz, although rare, occur in some
samples

4. Field evidence for coexisting cogenetic syenitic


and pyroxenitic liquids
The host syenite and its pyroxenitic inclusions
do not appear to have been completely crystalline when they came in contact Several lines of

t~

L~

Fig 2 (A) Pyroxenlte inclusion in the Tnunfo syenite, with sharp contacts and smooth outhnes, (B,C) syn-plutonlc pyroxemte
dikes, (D) late-stage pyroxemte dike Spikes of dike material invade the host syemte, (E) mixed rock inclusion in the syenite
showing emulsion-like texture, suggestive of its splitting into syemtlc (light) and pyroxemtlc (dark) magmas, as shown in (F)

291

V P Ferretra et al / Ltthos 33 (1994) 285-302

Table 1
Representative chemical compositions and mineral formulae of pyroxene of the Trlunfo bathohth, northeastern Brazil Proportions of ferric and ferrous iron were estxmated based on the method by Lmdsley and Anderson ( 1973 )
sample
pomt

SiO 2

T10-~

A1203
FeOt
MgO
CaO
Na20
K20
MnO
Total

TRF-28

PTR-28

MTR-28

52 40
0 20
0 60
17 50
7 90
15 80
5 10
0 30
99 80

52 50
0 50
0 40
15 80
9 20
16 50
4 60
0 30
99 80

52 60
0 20
0 20
18 I0
8 50
16 40
5 00
0 03
0 40
99 73

53 30
0 40
0 50
14 80
10 00
14 70
4 40
0 03
0 30
100 13

53 50
0 40
0 40
15 60
10 10
15 70
4 30
0 02
0 30
100 32

54 20
0 20
0 60
12 80
11 70
17 60
3 30
0 03
0 20
100 63

2 04

2 03

2 03

2 04

2 03

$1
A1TM
Sum

2 03
.
2 03

AIw
Fe 3+
T1
Mg
Fe 2
Sum
Fe 2+
Mn
Ca
Na
Sum

2 02
2 02

2 04
.
2 04

0 03
0 33
0 01
0 46
0 17
1 00

0 02
0 34
0 01
0 53
0 10
1 00

0 01
0 34
0 01
0 49
0 15
1 00

0 02
0 29
0 01
0 57
0 11
1 00

0 02
0 28
0 01
0 57
0 12
1 00

0 02
0 20
0 01
0 65
0 12
1 00

0 07
0 01
0 66
0 38
1 12

0 07
0 01
0 68
0 34
1 10

0 10
0 01
0 61
0 37
1 09

0 07
0 01
0 67
0 33
1 08

0 10
0 01
0 64
0 32
1 07

0 08
0 01
0 71
0 24
1 04

2 03
.

TRF = syemte, PTR = pyroxemte, MTR = mixed rock, r = rim, c = core


e v i d e n c e suggest t h a t c o m m l n g h n g o f t h e s e t w o
l i q u i d s h a s p l a y e d a m a j o r r o l e in t h e g e n e s i s o f
the Tnunfo pluton Following Vernon's (1983 )
field criteria for identifying coexisting melts, the
following can be pointed out
(1) The pyroxenlte inclusions are abundant
and uniformly distributed throughout the plut o n T h e y t e n d t o b e r o u n d e d , fiat a n d e l o n g a t e ,
a n d o c c u r in s w a r m s p a r a l l e l to flow f o h a t l o n a n d
h n e a t l o n in t h e s y e n i t e P y r o x e n i t e d o e s n o t occ u r in t h e e x p o s e d w a l l r o c k s T h e i n c l u s i o n s a r e
v a r i a b l e in size, r a n g i n g f r o m a b o u t 0 01 t o 1 m
in l e n g t h ,
( 2 ) C o n t a c t s a r e s h a r p w i t h c r e n u l a t e d edges,
which may be evidence for contrasting viscosity,
(3) In some exposures, inclusions are plastically folded, which indicates that both pyroxen-

lte a n d s y e n i t e r e s p o n d e d p l a s t i c a l l y d u r i n g
intrusion,
( 4 ) T h e t e x t u r e o f t h e i n c l u s i o n is u n i f o r m l y
g r a n u l a r w i t h s o m e a l i g n m e n t o f p y r o x e n e crystals p a r a l l e l to t h e flow f o h a t i o n ,
(5) The mineral assemblage of the inclusions
is t h e s a m e as t h a t o f t h e h o s t s y e n i t e , b u t t h e
p r o p o r t i o n s o f t h e m i n e r a l s differ,
( 6 ) I n m o s t cases, t h e t w o m a g m a s h a v e retamed their identity with almost no mechanical
mixing or chemical diffusion,
(7) No quench textures of the inclusions are
o b s e r v e d a l o n g t h e m a r g i n s M o r e o v e r , a p a t l t e is
n o t a c l c u l a r in t h e p y r o x e n l t e , b u t f o r m s large
e u h e d r a l c r y s t a l s a b o u t t h e s a m e size as t h o s e o f
the clinopyroxene
T h e p r e s e n c e o f p y r o x e n l t e also as s y n - p l u -

292

V P Ferretra et al / Llthos 33 (1994) 285-302

Q (Wo,En, Fs)

AEGIRINE
.

\,Ae

Fig 3 Compositional variation of chnopyroxenes of the T n u n f o bathohth m the J d - Q - A e diagram F~elds and nomenclature
from M o n m o t o ( 19 8 8 ) Asterisk = syenite, square = pyroxenlte, trmngle = mixed rock

tonic and late-stage dikes argues for contemporaneous nature of the two hqulds Most pyroxenlte dikes are up to 4 m long and up to 20 cm wide
and within them pyroxene grains have random
orientation Generally the flow foliation of the
host syenite is oblique to the strike of the dikes
but does not cut the dike itself Locally, the dikes
are disrupted and offset, but their terminations
are smooth (Fig 2b, c) Composite dikes having
pyroxenitlc margins and coarse-grained syenltlC
cores are also common (Fig 2d) Altogether,
these field relations are suggestive of two contemporaneous liquids (e g Rogers and Bird,,
1987, Vernon, 1983)
Furthermore, a "mixed" rock found in some
exposures suggests that these two liquids had a
common parental magma This rock has an ocellar-hke texture, with spherical mihmeter-sized
syenite ocelh surrounded by pyroxenlte This
texture could be interpreted as an "emulsion", a
mixture of small irregular drops of one liquid in
the other (Fig 2e, f )
It has been noted that unmlxlng initiates with
separation of rounded globules of one phase in a

matrix of the other (Watson, 1976, Phllpotts,


1978a, Roedder, 1978, 1979) In tholentlc basalts globules of iron-rich liquid typically form in
the silica rich host The texture of the mixed rock
seems to be the reverse, with syenite globules in
a pyroxenitic matrix

5. Mineralogical evidence for liquid immiscibility


An important mineralogical consideration for
distinguishing hquld immiscibility is that crystalhzlng phases in equilibrium with one llqmd
must also be in equlllbnum with the other liquid
phase (Bowen, 1928 ) In the Trlunfo pluton both
syenite and pyroxenite have the same mineralogy (Including aeglnne-auglte, perthltic microcline, apatlte, sphene and nchterlte), although In
different proportions In addition, pyroxene in
both the inclusions and the mixed rock is compositlonally Indistinguishable from the majority
of the pyroxene in the syenite (Table 1 ) It has a
uniform pleochrolc green color, but some has

P Ferretra et al /Llthos 33 (1994) 285-302

293

Table 2
Representative chemical compositions and mineral formulae of amphiboles of the Trlunfo bathohth, northeastern Brazil Proportions of ferric and ferrous iron were estimated based on the method by Robinson et al (1982)
sample
pomt

S10 2

TIO2
A1203
FeO t
MgO
CaO
Na20
K20
MnO
total
S1
AITM
Sum
A1vx
Cr
T1
Fe 3+
Mg
Fe z+
Sum
Fe 2+
Mn
Ca
Na
Sum
Na
K
Sum

TRF-28

PTR-28

MTR-28

52 40
0 70
1 80
12 70
1600
6 00
5 40
2 60
0 30
97 90

52 60
0 80
1 60
13 00
1550
6 00
5 40
2 30
0 40
97 60

56 40
0 04
0 20
8 90
1870
5 60
5 20
1 70
0 50
97 24

56 10
0 06
0 20
10 00
1760
5 70
5 80
1 50
0 50
97 46

55 30
0 20
0 60
8 90
1830
6 00
4 90
2 30
0 40
96 90

55 80
0 20
0 50
9 70
1800
5 90
5 50
2 20
0 40
98 20

7 66
0 34
8 O0
0 07
008
3 48
1 37
5 00
011
0 04
0 94
0 91
2 00
0 63
0 48
1 11

7 69
0 31
8 O0
0 01
0 01
013
3 39
1 46
5 00
0 05
0 94
1 01
2 00
0 51
0 43
094

8 05
8 05
0 04
0 01

8 04
8 04
0 03
0 01
027
3 77
0 92
5 00
001
0 06
0 88
1 05
2 00
0 56
0 28
084

7 95
0 05
8 O0
0 06
0 01
0 02
028
3 93
0 70
5 00
009
0 93
0 98
2 00
0 40
0 42
082

7 96
0 04
8 O0
0 05
0 02
011
3 83
0 99
5 00
005
0 05
0 91
0 99
2 00
0 53
0 40
093

023
3 98
0 75
5 00
008
0 06
0 85
1 01
2 00
0 44
0 30
074

T R F = syenite, PTR = pyroxenlte, MTR = mixed rock, r = r i m , c = c o r e

pale-green cores and darker green rims The zoning is characterized by enrichment toward the rim
i n F e 3 + and Na and depletion in Ca and Mg The
pyroxene is slhca-saturated, with extremely low
A1 content (0 2-1 4%), and is a calcxc-sodlc aegmne-auglte according to Morlmoto's (1988)
nomenclature (Fig 3)
Amphibole in the three rock types is late-stage,
replaces aegmne-auglte either along rims or
cleavages and fractures It is characterized by
h i g h S102, lOW A 1 2 0 3 and T 1 0 2 contents, and low
Mg/Fe* ratios (Table 2) K20 content IS relatively h i g h (most values 2 wt %) filling 43-56%
of total alkali in the A-site of the amphibole
structure They are mostly K-rich rlchterite, according to the classification ofLeake ( 1978 )

6. Geochemical evidence for liquid immiscibility


Several geochemical lines of evidence point to
chemical equilibrium between syenite and
pyroxenite

6 1 Major and trace elements


Representative major, trace and rare earth element analyses for the Trlunfo pluton rock types
are shown in Tables 3 and 4
Major element partitioning between syenite
and pyroxenite liquids in Fig 4, where concentrations of oxides in syenite and pyroxenlte are
normalized to the corresponding concentrations

V P Ferretra et al / Ltthos 33 (1994) 285-302

294
Table 3

Representative bulk rock major element analyses and CIPW norms from rocks of the Tnunfo bathohth, northeastern Brazil
Oxide

TRF-01

TRF-I 1

TRF-28

TRF-31

PTR-02

PTR-11

PTR-28

MTR-28

61 10
0 59
15 40
2 20
1 00
0 87
2 70
2 40
12 80
0 32
0 48
< 0 05
011
0 13
100 15

59 60
0 46
14 90
3 10
1 15
1 10
2 60
3 80
11 60
0 28
0 51
< 0 05
015
0 18
99 78

59 00
0 41
13 10
3 00
2 20
2 30
4 80
2 60
10 40
0 77
0 45
0 65
015
0 11
99 94

57 60
0 65
12 80
3 50
1 56
2 50
5 30
3 30
10 70
0 87
0 55
0 10
045
003
99 91

50 00
2 20
0 78
10 30
8 20
5 80
16 00
4 10
0 32
1 10
0 08
0 20
029
027
100 22

52 40
1 80
3 30
9 80
5 40
7 80
11 00
4 60
2 20
0 46
0 15
0 20
042
0 16
100 07

49 50
1 50
0 75
11 70
4 10
7 90
16 80
4 90
0 23
1 50
0 01
0 20
042
006
99 44

56 00
0 34
8 60
5 80
2 90
4 30
9 80
3 20
6 50
1 20
0 57
0 40
004
0 10
99 94

1 16
82 72
76 12
495
1 65
6 40
1 20
.
4 70
1 63
146
.
.

126
78 24
69 32
505
3 87
9 07
2 33

186
71 43

1 33
67 28

301
17 82

61 88
955
8 74
0 62
.
7 83
4 21
1 33
0 82
0 56
0 38
.
.

63 21

909
7 16
301
1 90
224
.
28 77
-

11 10
3 45
1 37
147
.
7 96
5 14
0 05
3 26
097
1 24
0 48

143
46 82
38 71
811
-

(wt%)
S~O2
T102
A1203
Fe203
FeO
MgO
CaO
Na20
K20
P205
BaO
CO2
H20+

H20-Total
al
d i
q
or
ab
lc
ne
ac

ns
ks
dl-dl
&-hd

hy-en
hy-fs
fo
ta
wo
mt

hm
iI
ap
cc

.
5 98
2 57
026
.

.
.

0
6
10
2
.
13
3
0
-

63
44
25
39

13 07
475
.

.
28 51
0 47

.
33
34

09

31 35
22 44
247
061

30 49
10 41
4 70
1 84
0 49
0 21
-

16 89
32 67
9 16
0 26
0 12
0 23
0 12
001

1 13

0 88

0 78

1 25

4 20

3 44

0 65

0 76
-

0 67
-

1 84
149

2 09
-

2 62
046

1 10
046

0 55
-

2 87
082

T R F = syemte, PTR = pyroxemte, M T R = m~xed rock

in the mixed rock, show that except for Sl, A1 and


K, all the other elements are preferably partitioned into the pyroxenlte This behavior is similar to that one observed by Phllpotts ( 1982 ) for
~mmlsoble h q m d s in volcamc rocks, except for
sodium, which in the present study partitioned
into the mafic (pyroxenltlC) material, tied up to
the aegmne-auglte crystals
In the SIO2- (Na20 + K20 + MgO + A 1 2 0 3 ) (FeOt + MnO +T102 + CaO + P205)
diagram

(Fig 5) analyses of syenite and pyroxenlte,


have a rather restricted compositional
range, do not plot entirely within the lmmlsoblllty field shown by Phflpotts (1982) Compositions of pyroxenlte fall within the lmmlsclblhty
field, but composmons of syenite plot outside
that, at higher concentrations of alkahs-alumlna-magnesla comer, due to their extreme Kenrichment
Incompatible element partitioning between
which

V P Ferretra et al / Ltthos 33 (1994) 285-302

295

Table 4
Representative bulk rock trace element analyses of rocks from the Trlunfo bathohth, northeastern Brazd
Element
( ppm )

TRF-11

TRF-28

TRF-31

PTR-02

PTR-28

MTR-28

Nb
Y
Rb
Sr
Zr
Ba
Th
Ta
La
Ce
Nd
Sm
Eu
Gd
Dv
Ho
Er
Yb
Lu
REE
Eu/Eu*

< 20
< 10
240
750
27
5100
nd
nd
33 29
56 50
27 85
6 64
1 18
3 68
1 83
036
0 85
0 59
0 16
132 93
0 66

24
44
250
970
160
4000
<15
<15
53 25
112 90
55 75
9 80
2 14
6 21
4 13
068
1 49
1 34
0 19
247 88
0 78

32
40
270
1350
142
5500
415
<15
72 80
139 60
72 30
17 50
3 30
10 80
6 10
100
2 20
1 60
0 22
327 42
0 72

34
170
20
740
290
700
<15
<15
134 30
326 00
173 30
34 80
7 94
23 66
17 32
311
7 66
6 10
0 86
735 05
0 80

33
52
< 10
2360
250
1070
<15
<15
108 50
246 70
133 00
25 23
5 65
16 20
10 79
198
4 58
3 87
0 66
557 16
0 85

20
40
140
1000
210
5700
<15
<15
76 92
163 50
78 03
13 27
3 13
8 78
5 09
090
2 04
1 73
0 30
353 69
0 83

TRF = syenite, PTR = pyroxenlte, MTR = mixed rock

syenite and pyroxenlte l i q u i d s , dlustrated i n F i g


6, indicates that except for those elements tied to
the structure of K-feldspar in the syenite (Ba, Rb,
K). all the other indicated elements show higher
concentrations in the pyroxenlte
The partitioning of trace and minor elements
between two silicate hquids is not as well known
as those for crystal-liquid equlhbrium during
crystallization and melting processes Only few
studies about the behavior of some elements of
geological Interest are available (e g Watson,
1975, 1976, Ryerson and Hess, 1978) Watson
(1976) performed experiments at 1 atm using
mechanical mixtures of sihca glass, synthetic
leuclte and fayahte These compositions behaved as immiscible liquids with a Sl-rlch and an
Fe-rlch melt coexisting at I 180 C. Watson noted
that the two-liquid partition coefficients (concentration of element in basic rock/concentration In acidic liquid) has a linear relationship
with respect to cation charge/ionic ratios for large
divalent and trivalent elements
The distribution coefficients for the Triunfo
pluton (element ratio of pyroxenite to syenite)

as a function of the cation charge/ionic size is


shown in Fig 7, using, for example, data for rocks
at site 28 (samples TRF-28 and PTR-28, Table
4) The relationship is similar to that observed
in Watson's experiments, yields a linear distribution among all the elements considered, except for the small, highly charged cation P There
is also a systematic enrichment in the syenite with
increasing size of the alkaline earth elements Mg,
Ca, Sr, Ba (distribution coefficients 3 4, 3 5, 2 4
and 0 26, respectively), which according to Watson, is indicative of acidic melts being more openstructured on an atomic or molecular level relative to basic melts Ba is more enriched in the
syenltlC hquld, probably accommodated in the
structure of K-feldspar The heavier rare earth
elements (Lu, Yb) are partitioned more strongly
toward the basic (pyroxenltlC) melt than are the
lighter rare earth elements (La, Ce)
P and Zr are preferably partitioned toward the
basic liquid, a behavior also observed by Watson
in his experiments The degree of partitioning,
however, IS lower in the Trlunfo pluton Lower
coefficient for P may reflect the slow diffusion of

296

I P Ferrelra et al / Llthos 33 (1994) 285-302

Thus, similar behavior in the partitioning of


trace elements between baslc/felslc liquids In
Watson's experiments and in the Trlunfo pluton,
is compatible with thermo-chemical equilibrium
between the syenite and pyroxenite, which makes
immiscibility a tenable process for the origin of
these two end-members

o
0E

cC

6 2 Rare earth elements

'/

0
L~
X

o,

001

S,

A'I

I<

TI

Fes* Fez* Mg

Co

No

Fig 4 Major element concentrations (oxides in wt %) in


syenite (circle) and pyroxenlte (asterisk) normalized to the
corresponding concentrations in the mixed rock, from site 28
(samples TRF-28, PTR-28 and MTR-28, Table 3 )

this cation in molten sihcate, or could be that


some of the P in the syenite was in apatite crystals at the same time the two hquid coexisted
(Apatite can occur included in pyroxene crystals
and its modal amount as well as whole rock P205
contents are highly variable m different samples
from both pyroxenite and syenite ) The preferred partitioning of Zr into the pyroxenitic
magma is indicative that suitable sites for accommodating this cation are found in the basic
melt The absence of zircon from both syenite
and pyroxenite leads to the assumption that any
available Zr is probably tied to the cllnopyroxene structure.
Likewise in Watson's experiments, the Triunfo
samples show two different groups (Fig 7) one
includes the small, highly-charged cations Ti 4+
and Zr 4+, and the other includes Sr, Ba, Mg, Ca.
La, Sm, Lu, Eu, Ce, Yb, Rb. This division into
two groups represents different types of site in
the melt The upper trend represents cations
whose bonding with oxygen is partially covalent
and the second, cations whose bonding are essentially ionic (E B Watson, op cit )

Tnunfo syenite and pyroxenite are characterized by overall enrichment in REE relative to
chondrlte abundance, with greater enrichment in
the pyroxenlte (up to about 1000 ppm) relative
to syenite (up to 370 ppm) They have similar
chondrite-normahzed REE patterns with negative, almost parallel slopes, laclong significant Eu
anomaly (Fig 8) The REE data further refute
any model involving fractlonatlon or partial
melting, which, in either case, yields increasing
enrichment in more felslc members The opposite case is observed here Moreover, the mixed
rock, with REE concentrations between the average concentrations of the two end-members,
has a general pattern similar to the patterns for
the other rocks, which is compatible with
unmlxing

6 3 Oxygen tsotopes
Whole rock and mineral separates were analyzed at the Stable Isotope Laboratory of the Department of Geology, University of Georgia
(USA), using fluorine as reagent Isotopic values are reported in permll relative to SMOW, and
displayed in Table 4
Whole-rock samples analyzed have a broad
range of JlS O values, between + 1 8 and + 9 6,
indicating that they cannot be primary magmatlc values In order to estimate the original
isotopic values, the j180 of chnopyroxene was
used, because in the absence of modal quartz, this
phase is one of the most resistant minerals to '80
exchange To calculate magmatic values, a wholerock/chnopyroxene J ' 8 0
fractlonatlon of
+0.25%0 was assumed (Taylor et al, 1979,
1984)
The corrected isotopic compositions are remarkably uniform with a total J~80 range from

V P Ferrelra et al / Llthos 33 (1994) 285-302

297

FeOt + T)O2+

Na20 K20 *

StO2

AI203 + MgO

Fig 5 Analyses of the T n u n f o syemte and pyroxemte plotted in the S 1 0 2 ( N a z O + K 2 0 + M g O + A 1 2 0 3 ) ( FeO t + ZlO2 + CaO + P205 ) (wt %) diagram The immiscibility field is from Roedder ( 195 l, in Phllpotts, 1982 ), for the system
fayahte-leuclte-sxhca circle = syenite, dot = pyroxenxte
I0-

~12
~IOIK

L~
X

r~

(,.)
o
r'r"

,t
OI

ox6_

." **~.? ~_~

~......--~

(D

Sm

Yb
"K-

L.U
M "~

2-

ool

B~ Rb

Lo c.

s'r N. sm z.

~ T,

Fig 6 Element concentrations in syemte (circle) and pyroxenite (asterisk) normalized to the corresponding concentrations in the mixed rock, from site 28 (samples TRF-28,
PTR28 and MTR-28, Table 4)

o
oo

o'~

,~

,'s

2'o

2'~

3'o

3'5

4'o

PYROXENITE / S Y E N I T E

Fig 7 Pyroxenite/syenlte distribution coefficient vs cation


charge/ionic ratio of rocks of the Trlunfo bathohth

V P Ferretra et al / Ltthos 33 (1994) 285-302

298
Table 5

Oxygenisotope analyses o f rocks o f the T r l u n f o

b a t h o h t h , n o r t h e a s t e r n Brazil Values in permllsMow, wr* = w h o l e rock corrected

for pyroxene
Sample

w r 180

Qz

K-spar

TRF-01
TRF-03
TRF-04
TRF-05
TRF-11
TRF-13
TRF-14
TRF-18
TRF-19
TRF-21
TRF-22
TRF-27
TRF-31
TRF-35
TRF-41
TRF-47
TRF-57
PTRF-28
TRF-28C
MTR-28

6 8
52
6 8
9 1
94
79
78
4 1
32
74
9 6
8 7
9 5
17
7 7
76
8 1

.
.
.
-

.
.
.

.
.

.
.

8 3

78
80
7 8
80

80
82
80
82

6
8
8
7
8
7

6
8
8
8
8
8

Syenite
Syenite
Syenite
Syenite
Syenite
S :enlte
S :enlte
S,enlte
S :enlte
S ,enite
S :emte
S :enlte
S :enite
S enlte
S ,enite
S :enite
S :enite
P 'roxemte (enclave)
P : o x e m t e (late dike)
M i x e d rock

2 2
.
.

.
.

-12
.

8 1

rock type

95
89
.

w r *~80

CPX

6
2
3
9
0
9

9
5
5
2
2
1

67

69

Table 6
R b - S r isotope data for rocks o f t h e T r l u n f o b a t h o h t h , n o r t h e a s t e r n Brazil Except for the T r l u n f o syenites, all m m a l ratios were
calculated a s s u m i n g t h e s a m e age as for the T n u n f o syenltes
Sample

Rb(ppm)

Sr(ppm)

Rb/Sr

87Rb/S6Sr

875r/86Sr

875r/86Sr),

Rock type

TRF-12
TRF-13
TRF-14
TRF-22
TRF-25
TRF-31
PTRF-28

282
322
343
238
255
371
7

676
649
597
1401
895
1936
3306

0
0
0
0
0
0
0

1 20891
1 43659
1 66006
0 49171
0 82586
0 55539
0 00637

0
0
0
0
0
0
0

0
0
0
0
0
0
0

Syenite
Syenite
Syemte
Syenite
Syenite
Syenite
Pyroxenite

5
6
0
2
5
8
3

2
7
7
7
2
8
8

42
50
57
17
28
19
00

71966
72144
72359
71383
71658
71397
71014

7096
7095
7098
7097
7097
7093
7101

Table 7
S m - N d isotope d a t a for rocks o f t h e T n u n f o bathollth, n o r t h e a s t e r n Brazil T h e initial 143Nd/144Nda n d N d were c o m p u t e d
a s s u m i n g a 600 M a age, relative to a chondrltlC reservoir with present-day values o f 143Nd/144Nd=0 51264 a n d 147Sm/
144Nd=0 1966
Sample

Sm
(ppm)

Nd
(ppm)

1475m/144Nd

143Nd/la4Nd

eNd

TRF-II
TRF-12
TRF-22
TRF-25
PTR-54

4
7
20
12
13

25
40
108
63
62

0
0
0
0
0

0
0
0
0
0

-15
- 15
- 15
-17
-16

80
95
90
00
20

3
3
4
0
8

1146
0939
1168
1155
1265

511504
511454
511524
511440
511538

9
3
7
2
1

TCHUR
(Ma)

TDM
(Ma)

2104
1756
2124
2246
2381

2382
2027
2405
2507
2654

299

V P Ferretra et al I Llthos 33 (1994) 285-302


I000

6 4 Rubtdtum-stronttum
n e o d y m t u m tsotopes

Allquots of samples analyzed for oxygen have


been used for determination of radiogenic isotopes Rb and Sr have been analyzed at the University of Texas, Department of Geological Sciences, Austin, whereas 143Nd/144Nd ratios and
Sm and Nd concentrations have been determined at the University Blaise Pascal, France
Initial ]43Nd/144Nd ratios were computed assuming an age of 600 Ma and compared to the
chondrxte reservoir (CHUR) Results are shown
in Tables 5, 6 and 7, respectively for Rb-Sr and
Sm-Nd isotopes
A six-point whole-rock Rb-Sr lsochron, with a
correlation coefficient r of 0 999, was obtained
for the Trlunfo syenite, giving an age = 583 _+ 12
Ma. A pyroxenite inclusion lies on the same lSOchron (Fig 9). Its initial 87Sr/86Sr at 583 Ma is
0 7101, approximately the same initial ratio of
the syenite ]sochron (0.7097) Together, the pyroxenite and syenite data yield an age of 572 Ma
and initial 87Sr/86Sr ratio = 0 7098
The small variation of initial 87Sr/g6Sr ratios
obtained for the Triunfo pluton ( 0 7 0 9 3 0 7101 ), suggests that these values are primary
and Inherited from an unusual mantle source region The parental magma had a high and unl-

JO0

1 iio:i:i::
,

LO

Ce

NdSm

EuGd

Dy

HoEr

Yb

Fig 8 Envelopesurfacesfor rare earth elementnormahzed


to chondnte, for syemteand pyroxemteand pattern for the
mixed rock of the Trlunfo bathohth Normahzmgvalues are
from Evensenet al (1978)
+ 8 0 to + 8 5%o. Such a narrow range of~180 is
compatible with a common magmatlc origin for
the units of the bathohth

t
0730

572

andsamartum-

Me

(87Sr/a6Sr)l

709B

0 725

0720

~0
a0

715

07tO

O 705

0 700

O0

04

oa

~2

Ja

zo

24

a7Rb / 86 S r
Fig 9 Rb-Sr lsochronfor syemtesandpyroxenlte(Y-axissample) oftheTrmnfobathohth

300

V P Ferrewa et al / Ltthos 33 (1994) 285-302

form 87Sr/86Sr ratio, around 0 710, based primarily on the pyroxenite samples, which have
higher Mg number, CaO and Sr contents (i e
least susceptible to Sr isotopic contamination)
At 583 Ma lmtial 143Nd/144Nd ratios for the
Triunfo syenite and pyroxenlte are very uniform, lying in a narrow range from 0.510999 to
0 511086, further supportive of a co-magmatic
relation of both rock types The S m / N d ratios
are also very uniform, about 0.19, lower than the
ratio for C H U R ( = 0 31, DePaolo, 1988), and
compatible with a LILE-enrlched source
Regarding that (a) pyroxenlte magmas are
usually believed to be mantle derived, (b) the
presence of mica pyroxenlte xenohths in these
syenltes (Ferrelra and Sial, 1994) originated
from the mantle source, as elsewhere (e g Lloyd
et al, 1987), and that (c) most authors (e g
Foley et al, 1987) consider ultrapotassic magmas derived from enriched mantle source, one
rules out the continental crust as the source for
the magma under consideration, eNd values relative to a chondrltic reservoir are all strongly
negative (ca - 15 to - 18), implying an old,
LREE-enrlched source for these rocks Therefore, one considers that the data are suggestive
of magma production within the ancient continental hthospherlc mantle Nd model age, relative to chondnt~c reservoir, averages 2 1 Ga, and
thus indicates an Early Proterozolc age for the
generation of the old, enriched-mantle domain

7. Discussions and conclusions


The main conclusions of the study are
(1) The plutonic, Late Proterozolc Cachoeirlnha-Salgueiro foldbelt ultrapotassic province
finds only few analogues in the world (e g Oyawoye, 1976, Corrlveau et al, 1990) as opposed
to much more common younger, volcanic provinces (e g Foley et al., 1987)
(2) Alkah feldspar syenltes and pyroxenltes in
the Trlunfo bathohth, the largest of the plutons
in the CSF, show basically the same mineralogical compositions, represented by microchne, aeg~rlne-augate, sphene, apatite and magnetite, an
assemblage that attests to crystalhzatlon under

high oxygen fugaclty and chemical equlhbrlum


between that two rock types
(3) Several chemical characteristics of the
syenlte-pyroxenlte association do not support
crystal fractionation as the main mechanism
governing their formation Linear trends in variation diagrams and parallel REE patterns for
these two rock types are better explained by hquld lmmlsclbihty This conclusion is also supported by isotopic (similar, ~180, Sr and Nd)
data
(4) Liquid immiscibility may be a major magmatlc process in the generation of other ultrapotassic syenltlC plutons along the syenito~d line in
the CSF These syenites share similar characterlSt~cs to the Trlunfo syenite, m terms of petrography, mineralogy, major, trace and RE elements and isotopic signatures (Ferrelra, 1991)
Some degree of crustal contamination occurred,
particularly for some narrow (up to 300 m wide)
plutons, which may have been more susceptible
to crustal interactions These syenltes also contam small amounts of oval-shaped, centimetersized pyroxenitic Inclusions, which may also have
formed by liquid immiscibility Study of the
Trlunfo pluton indicates that this process was
much more common than previously supposed,
dunng Late Precambrlan times in th~s part of
Brazil
(5) The existence of a metasomatlzed mantle
source is invoked to explain the chemical and
isotopic signatures of these rocks The metasomattc process could be related to an Early Proterozoic subductlon zone, with dehydration of
oceanic crust and LILE enrichment, as suggested
by the trace element signatures, typical for subductlon zone component
Acknowledgments
We are grateful to FINEP and CNPq Agencies
which provided funds for field work and chemical analyses We also thank Dr L E Long (University of Texas, Austin) for the Rb-Sr isotopic
analyses and Dr C Pin (University Blaise Pascal) for the S m - N d analyses Part of the microprobe data were obtained at the North Carolina
State University, Raleigh and VPF is grateful to

V P Ferretra et al / Llthos 33 (1994) 285-302

Dr R V Fodor for his assistance. An earlier versxon of the manuscript was reviewed by Dr L
Anderson, and substantial improvement was
made as a result of the thoughtful criticism of Dr.
A R Philpotts

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