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Llthos, 33 (1994) 285-302

LITHOS

Large-scale silicate liquid immiscibility: a possible example from northeastern Brazil

V.P. Ferrexra a, A.N.

Sial a, J.A

Whitney b

aFederal UntversttyofPernambuco, Dept of Geology, C P 7852,Reclfe, PE, 50732-970, Brazg bUmversttyof 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 fold- belt, 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 anom- aly, 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 of an initially homogeneous magma to yield two immiscible slhcate liquids of contrasting compositions has been proposed as a possible mechanism of magmatlc differentiation since long ago Some evidence had been sug- gested, but Bowen (1928) 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, hquld immiscibility was

mostly abandoned as a plausible process of mag- matic diversification Since the early 1970's, however, interest in this process has been resurrected after the discovery of textures consisting of coexisting mafic and fel- sic components, indicative of immlsciblhty, in lunar and some terrestrial basaltic rocks (e g Roedder and Wexblen, 1970) Additionally, modern laboratory experiments on geologically significant compositions have suggested that sil- icate liquid Immiscibility could be a viable pro- cess of magmatic diversification (e g Philpotts, 1971, 1976, 1979, Roedder, 1978, 1979, Roed-

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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 pro- duction 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 cen- timeter-size segregations of felslc material

(ocelll)

in

lamprophyre

liquids

(e

g

Roedder

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 im- miscibility were described by Philpotts (1978b) This study reports field, petrographic and geo- chemical evidence that strongly suggest that hq- uid immiscibility occurred prior to emplace- ment of an ultrapotassic magma of intermediate composition to produce ultrapotassic syenite and

associated

northeastern Brazil

pyroxenlte

of the

2. Geological setting

Trmnfo

pluton,

The Trlunfo batholith is one of several elon- gate syenitlc plutons emplaced within a 200 km- long zone along the southern boundary of the Cachoelrlnha-Salgueiro foldbelt (CSF), north- east 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 fa- cies (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

'

~'°

 

[~

CRETACEOUSSEDIMENTARY

 

COVER

 

~

CACHOEIR1NHAGROUP

 

(Phylhtes Schists)

 

[~

ALGUEIROGROUP

 

(Schists Gnmsses)

eER'VA"'~

BASEMENT ROCKS

BORBOREMAPROVINCE

(Central StructuralDomoln)

I GnolssesMigmohtes)

A- Serldo

I PERALKALIC/SHOSHONITICPLUTONS

B- Cachoelnnha Solguelro

[~CALC ALKALIC PLUTONS

C Rmchodo 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 plu-

tons (modified from Sial and Ferrelra, 1990)

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

287

matlc granites of Braslhano age indicates that the Braslhano orogeny was the major tectonother- mal 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 doc- umented than the first (Brlto Neves et al., 1974, Long and Brlto Neves, 1977) More recent data (Sial et al, 1989) show that the coarsely por- phyritic Itaporanga-type granltoids (~ 80 plu- tons 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 Pnn- cesa 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 direc- tion parallel to the regional metamorphic trend Three faults cut the bathohth, locally generat- ing shear fabrics and stretching hneatlon and, at the microscopic scale, mortar texture in feld- spars and wavy extinction and polygonlzatlon of quartz Flow structures are common primary magmatlc structures and are characterized by linear, sometimes planar, orientation of pyrox- ene and K-feldspar, and alignment of pyroxe- nltlC 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,

iS predominantly composed of rocks with uni- form texture and simple mineralogy Much of the bathohth is composed of equigranular, medium- grained, leucocratlc alkali-feldspar syenltes, m which feldspar and chnopyroxene rarely exceed a few millimeters in size The predominant min- erals are perthltlC mxcrocllne and aeglrlne-au- glte, with variable amounts of quartz, sphene, apatlte, blue amphibole (formed at the expense ofpyroxene) and magnetite Brown mica is pres- ent 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 ultrapo- tasslc 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 pegma- titlC 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 cen- timeters to one meter, paralleling the flow foha- tlon 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 eu- hedral to subhedral aeglrine-auglte, sphene and apatlte Blue amphibole occurs infrequently re- placing pyroxene along rims Mxcrochne and in- terstitial 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 crystal-

line when they came in contact

Several lines of

t~

t~

L~

I

L~ I
Fig 2 (A) Pyroxenlte inclusion in the Tnunfo syenite, with sharp contacts and smooth outhnes,

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)

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

291

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

sample

TRF-28

 

PTR-28

 

MTR-28

pomt

 

r

c

r

c

r

c

SiO 2

52 40

 

52 50

52 60

53 30

53 50

54 20

T10-~

0 20

0 50

0 20

0 40

0 40

0 20

A1203

0 60

0 40

0 20

0 50

0 40

0 60

FeOt

17 50

15 80

18

I0

14 80

15 60

12 80

MgO

7

90

9

20

8

50

10 00

10 10

11 70

CaO

15 80

 

16 50

16 40

14 70

15 70

17 60

Na20

5

10

4 60

5 00

4 40

4 30

3 30

K20

-

-

0 03

0 03

0 02

0 03

MnO

0 30

 

0 30

0 40

0 30

0 30

0 20

Total

99 80

99 80

99 73

100 13

100 32

100 63

$1

2 03

2 02

2 04

2 03

2 04

2 03

A1TM

Sum

2 03

 

2 02

2 04

2 03

2 04

2 03

AIw

0 03

0 02

0 01

0 02

0 02

0 02

Fe3+

0 33

0 34

0 34

0 29

0 28

0 20

T1

0 01

0 01

0 01

0 01

0 01

0 01

Mg

0 46

0 53

0 49

0 57

0 57

0 65

Fe2÷

0 17

0 10

0 15

0 11

0 12

0 12

Sum

1 00

1 00

1 00

1 00

1 00

1 00

Fe2+

0 07

0 07

0 10

0 07

0 10

0 08

Mn

0 01

0 01

0 01

0 01

0 01

0 01

Ca

0 66

0 68

0 61

0 67

0 64

0 71

Na

0 38

0 34

0 37

0 33

0 32

0 24

Sum

1 12

1 10

1 09

1 08

1 07

1 04

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

evidence suggest that commlnghng of these two

liquids has played a major role in the genesis of 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 plu- ton They tend to be rounded, fiat and elongate, and occur in swarms parallel to flow fohatlon and hneatlon in the syenite Pyroxenite does not oc- cur in the exposed wall rocks The inclusions are variable in size, ranging from about 0 01 to 1 m in length,

(2) Contacts are sharp with crenulated edges, which may be evidence for contrasting viscosity, (3) In some exposures, inclusions are plasti- cally folded, which indicates that both pyroxen-

lte and syenite responded plastically during intrusion, (4) The texture of the inclusion is uniformly

granular with some alignment of pyroxene crys- tals parallel to the flow fohation, (5) The mineral assemblage of the inclusions

is the

proportions of the minerals differ, (6) In most cases, the two magmas have re- tamed their identity with almost no mechanical mixing or chemical diffusion, (7) No quench textures of the inclusions are observed along the margins Moreover, apatlte is not aclcular in the pyroxenlte, but forms large euhedral crystals about the same size as those of the clinopyroxene The presence of pyroxenlte also as syn-plu-

same

as that of the host syenite, but the

292

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

Q (Wo,En,Fs)

AEGIRINE

\,Ae

Fig

from Monmoto ( 1988 ) Asterisk = syenite, square = pyroxenlte, trmngle = mixed rock

3 Compositional variation of chnopyroxenes of the Tnunfo bathohth m the Jd-Q-Ae diagram

F~elds and nomenclature

tonic and late-stage dikes argues for contempor- aneous nature of the two hqulds Most pyroxen- lte 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 con- temporaneous 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 ocel- lar-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 ba- salts 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 crys- talhzlng 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 mineral- ogy (Including aeglnne-auglte, perthltic microc- line, apatlte, sphene and nchterlte), although In different proportions In addition, pyroxene in both the inclusions and the mixed rock is com- positlonally 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 Pro- portions of ferric and ferrous iron were estimated based on the method by Robinson et al (1982)

sample

TRF-28

 

PTR-28

MTR-28

pomt

 

r

c

r

c

r

c

S10 2

52 40

52 60

56 40

56

10

55 30

55 80

TIO2

0 70

0 80

0 04

0 06

0 20

0 20

A1203

1 80

1 60

0 20

0 20

0 60

0 50

FeOt

12 70

13 00

8 90

10 00

8 90

9 70

MgO

1600

1550

1870

1760

1830

1800

CaO

6 00

6 00

5 60

5 70

6 00

5 90

Na20

5 40

5 40

5 20

5 80

4 90

5 50

K20

2 60

2 30

1 70

1 50

2 30

2 20

MnO

0 30

0 40

0 50

0 50

0 40

0 40

total

97 90

97 60

97 24

97 46

96 90

98 20

S1

7 66

7 69

8 05

8 04

7 95

7 96

AITM

0 34

0 31

-

-

0 05

0 04

Sum

8 O0

8 O0

8 05

8 04

8 O0

8 O0

A1vx

-

0 01

0 04

0 03

0 06

0 05

Cr

-

0 01

0 01

-

0 01

-

T1

0 07

-

0 01

0 02

0 02

Fe 3+

008

013

023

027

028

011

Mg

3 48

3 39

3 98

3 77

3 93

3 83

Fez+

1 37

1 46

0 75

0 92

0 70

0 99

Sum

5 00

5 00

5 00

5 00

5 00

5 00

Fe 2+

011

-

008

001

009

005

Mn

0 04

0 05

0 06

0 06

-

0 05

Ca

0 94

0 94

0 85

0 88

0 93

0 91

Na

0

91

1 01

1 01

1 05

0 98

0 99

Sum

2 00

2 00

2 00

2 00

2 00

2 00

Na

0 63

0 51

0 44

0 56

0 40

0 53

K

0 48

0 43

0 30

0 28

0 42

0 40

Sum

1 11

094

074

084

082

093

TRF= syenite, PTR = pyroxenlte, MTR = mixed rock, r=rim, c=core

pale-green cores and darker green rims The zon- ing is characterized by enrichment toward the rim in Fe 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 ae- gmne-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 high S102, lOWA120 3 and T102 contents, and low Mg/Fe* ratios (Table 2) K20 content IS rela- tively high (most values 2 wt %) filling 43-56% of total alkali in the A-site of the amphibole structure They are mostly K-rich rlchterite, ac- cording 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 ele- ment 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 concen- trations of oxides in syenite and pyroxenlte are normalized to the corresponding concentrations

294

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

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

(wt%)

 

S~O2

61

10

59 60

59 00

57 60

50 00

52 40

49 50

56 00

T102

0

59

0 46

0 41

0

65

2 20

1 80

1 50

0

34

A1203

15 40

14 90

13

10

12 80

0 78

3 30

0

75

8 60

Fe203

2 20

3

10

3 00

3 50

10 30

9 80

11 70

5 80

FeO

1 00

1 15

2 20

1 56

8 20

5 40

4

10

2 90

MgO

0

87

1 10

2

30

2

50

5 80

7 80

7 90

4

30

CaO

2

70

2 60

4 80

5 30

16 00

11 00

16 80

9 80

Na20

2 40

3 80

2 60

3 30

4

10

4 60

4 90

3 20

K20

12 80

11

60

10 40

10 70

0

32

2 20

0

23

6 50

P205

0

32

0 28

0

77

0

87

1 10

0

46

1 50

1 20

BaO

0 48

0

51

0 45

0

55

0 08

0

15

0 01

0

57

CO2

<0 05

<0 05

0 65

0

10

0 20

0 20

0 20

0 40

H20+

011

015

015

045

029

042

042

004

H20--

0

13

0

18

0

11

003

027

0

16

006

0

10

Total

100

15

99 78

99 94

99 91

100 22

100 07

99 44

99 94

al

1

16

126

186

1 33

909

301

11

10

143

d

i

82 72

78 24

71 43

67 28

7

16

17 82

3 45

46 82

q

-

-

301

-

-

or

76

12

69 32

61

88

63

21

1 90

13

07

1 37

38 71

ab

495

505

955

 

224

475

147

811

lc

-

-

-

0

63

-

-

-

ne

1 65

3 87

-

6 44

 

ac

6 40

9 07

8 74

10 25

28 77

28

51

-

16 89

ns

1 20

2

33

0

62

2

39

-

0 47

-

-

ks

7 96

dl-dl

4 70

5 98

7 83

13 33

31

35

30 49

-

32 67

&-hd

1 63

2

57

4

21

3 34

22

44

10 41

5

14

9

16

hy-en

-

-

1 33

-

-

4

70

0 05

0 26

hy-fs

-

-

0

82

-

-

1 84

3 26

0

12

fo

-

-

0

56

0 09

-

0 49

-

0 23

ta

-

-

0

38

-

-

0 21

-

0

12

wo

146

026

-

-

247

-

097

-

mt

061

-

1 24

001

hm

0 48

iI

1 13

0

88

0

78

1 25

4 20

3 44

-

0 65

ap

0

76

0

67

1 84

2 09

2 62

1 10

0

55

2 87

cc

-

-

149

-

046

046

-

082

TRF= syemte, PTR = pyroxemte, MTR = m~xed rock

in the mixed rock, show that except for Sl, A1 and K, all the other elements are preferably parti- tioned into the pyroxenlte This behavior is sim- ilar to that one observed by Phllpotts ( 1982 ) for ~mmlsoble hqmds 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 + A1203 )-

(FeOt + MnO +T102 + CaO + P205)

diagram

(Fig 5) analyses of syenite and pyroxenlte, which have a rather restricted compositional range, do not plot entirely within the lmmlsobll- lty field shown by Phflpotts (1982) Composi- tions of pyroxenlte fall within the lmmlsclblhty field, but composmons of syenite plot outside that, at higher concentrations of alkahs-alu- mlna-magnesla comer, due to their extreme K- enrichment Incompatible element partitioning between

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

TRF-11

TRF-28

TRF-31

PTR-02

PTR-28

MTR-28

(ppm )

Nb

< 20

24

32

34

33

20

Y

< 10

44

40

170

52

40

Rb

240

250

270

20

< 10

140

Sr

750

970

1350

740

2360

1000

Zr

27

160

142

290

250

210

Ba

5100

4000

5500

700

1070

5700

Th

nd

<15

415

<15

<15

<15

Ta

nd

<15

<15

<15

<15

<15

La

33 29

53 25

72 80

134 30

108 50

76 92

Ce

56 50

112 90

139 60

326 00

246 70

163 50

Nd

27 85

55 75

72

30

173 30

133 00

78 03

Sm

6 64

9 80

17 50

34 80

25 23

13 27

Eu

1 18

2

14

3 30

7 94

5 65

3

13

Gd

3 68

6 21

10 80

23

66

16 20

8 78

Dv

1 83

4

13

6

10

17 32

10 79

5 09

Ho

036

068

100

311

198

090

Er

0 85

1 49

2 20

7 66

4 58

2 04

Yb

0 59

1

34

1 60

6

10

3 87

1 73

Lu

0

16

0

19

0 22

0 86

0 66

0 30

REE

132 93

247 88

327 42

735 05

557 16

353 69

Eu/Eu*

0 66

0 78

0 72

0 80

0 85

0 83

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

syenite and pyroxenlte liquids, dlustrated in Fig

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 be- haved as immiscible liquids with a Sl-rlch and an

Fe-rlch melt coexisting at I 180 °C.

that the two-liquid partition coefficients (con- centration of element in basic rock/concentra- tion 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)

Watson noted

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 distri- bution among all the elements considered, ex- cept 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 Wat- son, is indicative of acidic melts being more open- structured on an atomic or molecular level rela- tive 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

o

0E

0

L~

X

0

I

o,

001

cC

\

'/

S,

A'I

I<

i

TI

\

i

Fes*

,

E

Fez* Mg

q

Co

i

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 crys- tals 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 pre- ferred partitioning of Zr into the pyroxenitic magma is indicative that suitable sites for ac- commodating 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 cllnopyrox- ene structure. Likewise in Watson's experiments, the Triunfo samples show two different groups (Fig 7) one

includes the small, highly-charged

and Zr 4+, and the other includes Sr, Ba, Mg, Ca.

cations Ti 4+

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 es- sentially ionic (E B Watson, op cit )

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

Thus, similar behavior in the partitioning

6 2 Rare earth elements

Tnunfo syenite and pyroxenite are character- ized 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 nega- tive, 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 oppo- site case is observed here Moreover, the mixed rock, with REE concentrations between the av- erage 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 ana- lyzed at the Stable Isotope Laboratory of the De- partment of Geology, University of Georgia (USA), using fluorine as reagent Isotopic val- ues are reported in permll relative to SMOW, and displayed in Table 4 Whole-rock samples analyzed have a broad range of JlSO values, between + 1 8 and + 9 6, indicating that they cannot be primary mag- matlc 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 whole- rock/chnopyroxene J'80 fractlonatlon of +0.25%0 was assumed (Taylor et al, 1979,

1984)

The corrected isotopic compositions are re- markably uniform with a total J~80 range from

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

Na20 • K20 *

AI203+ MgO

FeOt + T)O2+

StO2

297

Fig 5 Analyses of the Tnunfo syemte and pyroxemte plotted in the S102(NazO+K20+MgO+A1203)- ( 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

L~

X

(,.)

o r'r"

I0-

OI

ool

B~

\

i

Rb

~

i

Lo

c.

s'r

T

N.

I

sm

f

z.

~

T,

~

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

~12

IK ~IO-

r~

,¢t

ox6_

z

o

-

(D

~

--~

 

.

2-

o

oo

o'~

,~

,'s

2'o

PYROXENITE /

." **~.? ~_~

Sm

Yb

"K-

M

L.U

"~

2'~

3'o

SYENITE

3'5

4'o

Fig 7 Pyroxenite/syenlte distribution coefficient vs cation charge/ionic ratio of rocks of the Trlunfo bathohth

298

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

Table 5 Oxygenisotope analyses of rocks of the Trlunfo bathohth, northeastern Brazil for pyroxene

Values in permllsMow, wr* =whole rock corrected

Sample

w r

180

Qz

K-spar

CPX

w r *~80

rock type

 

TRF-01

6 8

 

Syenite

TRF-03

5 2

 

-

-

8

1

8

3

Syenite

TRF-04

6 8

 

Syenite

TRF-05

9

1

-

95

78

80

Syenite

TRF-11

94

-

89

80

82

Syenite

TRF-13

7 9

 

-

-

7 8

8 0

S

:enlte

TRF-14

7 8

-

-

8 0

8 2

S

:enlte

TRF-18

4

1

S,enlte

 

TRF-19

3 2

 

-

2 2

6 6

6 9

S

:enlte

TRF-21

7 4

-

-

8 2

8 5

S

,enite

TRF-22

-

-

-

8 3

8 5

S

:emte

TRF-27

-

-

-

7 9

8 2

S

:enlte

TRF-31

-

-

-

8 0

8 2

S

:enite

TRF-35

9 6

 

-

7 9

8

1

S enlte

 

TRF-41

8 7

 

S

,enite

TRF-47

9 5

S

:enite

TRF-57

1 7

 

-

-12

67

69

S

:enite

PTRF-28

7 7

 

P

'roxemte (enclave)

TRF-28C

7 6

 

-

-

-

P

:oxemte

(late dike)

MTR-28

8

1

-

-

-

Mixed rock

Table 6 Rb-Sr isotope data for rocks of the Trlunfo bathohth, northeastern Brazil Except for the Trlunfo syenites, all mmal ratios were calculated assuming the same age as for the Tnunfo syenltes

Sample

Rb(ppm)

Sr(ppm)

Rb/Sr

87Rb/S6Sr

875r/86Sr

875r/86Sr),

Rock type

TRF-12

282

5

676

2

0 42

1 20891

0 71966

0 7096

Syenite

TRF-13

322 6

649

7

0

50

1 43659

0 72144

0 7095

Syenite

TRF-14

343 0

597 7

0

57

1 66006

0 72359

0 7098

Syemte

TRF-22

238

2

1401

7

0

17

0 49171

0 71383

0 7097

Syenite

TRF-25

255

5

895 2

0 28

0 82586

0 71658

0 7097

Syenite

TRF-31

371

8

1936 8

0

19

0 55539

0 71397

0 7093

Syenite

PTRF-28

7 3

3306

8

0 00

0 00637

0 71014

0 7101

Pyroxenite

Table 7 Sm-Nd isotope data for rocks of the Tnunfo bathollth, northeastern Brazil The initial 143Nd/144Ndand Nd were computed assuming a 600 Ma age, relative to a chondrltlC reservoir with present-day values of 143Nd/144Nd=0 51264 and 147Sm/

144Nd=0

1966

Sample

Sm

Nd

1475m/144Nd

143Nd/la4Nd

eNd

 

TCHUR

TDM

(ppm)

(ppm)

 

(Ma)

(Ma)

TRF-II

4

80

25

3

0 1146

0 511504

-15

9

2104

2382

TRF-12

7 95

40

3

0 0939

0 511454

-

15

3

1756

2027

TRF-22

20 90

108 4

0 1168

0 511524

-

15

7

2124

2405

TRF-25

12 00

63

0

0 1155

0 511440

-17

2

2246

2507

PTR-54

13 20

62

8

0 1265

0 511538

-16

1

2381

2654

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

299

I000

-

 

6

4

Rubtdtum-stronttum

andsamartum-

neodymtum

tsotopes

JO0

Allquots of samples analyzed for oxygen have been used for determination of radiogenic iso- topes Rb and Sr have been analyzed at the Uni- versity of Texas, Department of Geological Sci- ences, Austin, whereas 143Nd/144Nd ratios and Sm and Nd concentrations have been deter- mined at the University Blaise Pascal, France Initial ]43Nd/144Nd ratios were computed as-

°°1 iio:i:i::

,

,

,

i

,

.

,

,

.

.

,

,

.

,

LO

Ce

NdSm

EuGd

Dy

HoEr

Yb

Fig 8 Envelopesurfacesfor rare earth elementnormahzed to chondnte,for syemteand pyroxemteand pattern for the mixedrockofthe Trlunfobathohth Normahzmgvaluesare 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

~0

a0

0730

0

725

0720

0

715

t

(87Sr/a6Sr)l

-

572

Me

suming 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 lSO- chron (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 py- roxenite 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 (07093-

0 7101 ), suggests that these values are primary

and Inherited from an unusual mantle source re- gion The parental magma had a high and unl-

-

0

709B

07tO

O 705

0 700 O0

04

oa

~2

Ja

a7Rb / 86 S r

zo

24

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 pri- marily 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/144Ndratios for the Triunfo syenite and pyroxenlte are very uni- form, lying in a narrow range from 0.510999 to 0 511086, further supportive of a co-magmatic relation of both rock types The Sm/Nd ratios are also very uniform, about 0.19, lower than the ratio for CHUR (=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 mag- mas derived from enriched mantle source, one rules out the continental crust as the source for the magma under consideration, eNd values rel- ative to a chondrltic reservoir are all strongly negative (ca - 15 to - 18), implying an old, LREE-enrlched source for these rocks There- fore, one considers that the data are suggestive of magma production within the ancient conti- nental hthospherlc mantle Nd model age, rela- tive 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 Cachoei- rlnha-Salgueiro foldbelt ultrapotassic province finds only few analogues in the world (e g Oya- woye, 1976, Corrlveau et al, 1990) as opposed to much more common younger, volcanic prov- inces (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 mineralogi- cal compositions, represented by microchne, ae- g~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 vari- ation diagrams and parallel REE patterns for these two rock types are better explained by hq- uld lmmlsclbihty This conclusion is also sup- ported by isotopic (similar, ~180, Sr and Nd) data (4) Liquid immiscibility may be a major mag- matlc process in the generation of other ultrapo- tassic syenltlC plutons along the syenito~d line in the CSF These syenites share similar character- lSt~cs to the Trlunfo syenite, m terms of petrog- raphy, mineralogy, major, trace and RE ele- ments 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 con- tam small amounts of oval-shaped, centimeter- sized 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 metaso- mattc process could be related to an Early Pro- terozoic subductlon zone, with dehydration of oceanic crust and LILE enrichment, as suggested by the trace element signatures, typical for sub- ductlon zone component

Acknowledgments

We are grateful to FINEP and CNPq Agencies

which provided funds for field work and chemi-

cal analyses We also thank Dr

versity of Texas, Austin) for the Rb-Sr isotopic analyses and Dr C Pin (University Blaise Pas- cal) for the Sm-Nd analyses Part of the micro- probe data were obtained at the North Carolina State University, Raleigh and VPF is grateful to

L E Long (Uni-

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

301

Dr R V Fodor for his assistance. An earlier ver- sxon 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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