FLUIDS IN THE SIILINJÄRVI CARBONATITE COMPLEX,

EASTERN FINLAND

Fluid inclusion evidence for the formation conditions

of zircon and apatite

MATTI POUTIAINEN

POUTIAINEN, MATTI. 1995. Fluids in the Siilinjärvi carbonatite complex,

eastern Finland: Fluid inclusion evidence for the formation conditions of zircon
and apatite. Bull. Geol. Soc. Finland 67, Part 1, 3-18.
In the studied zircon and apatite crystals, data recorded two different
compositional types of fluid inclusions: Type 1 H , 0 - C 0 , low salinity inclusions
(XCO, = 0.42 to 0.87; XNaCl = 0.001 to 0.005) with bulk densities of 0.73 to 0.87
g/cm3, and Type 2 H , 0 moderate salinity (XNaCl = 0.03 to 0.06) inclusions with
densities of 0.83 to 1.02 g/cm 3 . The Type 1 inclusions are not present in apatite.
In zircon, the observed fluid inclusion types occur in separate domains: around
(Type 1) and outside (Type 2) the apparent core. Fluid inclusions are further
subdivided into pseudosecondary and secondary inclusions. Using a combination
of SEM-EDS, optical characteristics and crushing-stage, various daughter and
captive minerals were identified.
The fluid inclusion data suggest that the pseudosecondary Type 1 and Type 2
inclusions in zircon and apatite were trapped during the pre-emplacement
evolution of the carbonatite at mid-crustal conditions ( P > 4 kbar, T> 625°C). The
Type 1 fluid was depleted in CO, during crystal fractionation and cooling leading
to a fluid phase enriched in water and alkalies. Fenitization was obviously
induced by these saline aqueous fluids. During emplacement of the carbonatite
to the present level, zircon phenocrysts were intensively fractured, some Type 1
inclusions were re-equilibrated, and multiphase Type 2 inclusions were trapped.
It is assumed that all these inclusions in zircon and the pseudosecondary Type 2
inclusions in apatite have a magmatic origin.
In apatite, calcite inclusions occur side-by-side with the secondary Type 2
inclusions. These calcites co-existed with the aqueous fluid during fracturing and
metamorphic re-crystallization of apatites. Probably, this metamorphic fluid also
is responsible for the transport and deposition of at least some of the calcite at low
temperatures (200-350°C).

Key words: carbonatites, fluid inclusions, zircon, apatite, microthermometry,

Siilinjärvi, Finland.

Matti Poutiainen: Department of Geology, P.O. Box 11, FIN -00014 University
of Helsinki, Finland
4 Matti Poutiainen

INTRODUCTION U - P b zircon age of ca. 2.6 Ga ( published by the

Geological Survey of Finland 1978). The Hf and
Carbonatites are enigmatic magmatic rocks whose Sr-Pb isotopic ratios f r o m zircon plot close to the
origin has been discussed extensively (e.g., Tuttle chondritic growth curve (Patchett et al., 1981) and
and G i t t i n s , 1966; Bell, 1989). B a s e d on very close to the model bulk Earth ratio (Tilton and
experimental data, the crystallization of carbonatite Bell, 1994), respectively. This implies rapid
m a g m a is strongly dependent on the composition of intrusion of the rocks through the sialic crust to the
the co-existing fluid phase (Wy llie, 1966 and 1989). surface - probably along a large fissure - with
T h e early m a g m a t i c f e a t u r e s of c a r b o n a t i t e s , neglible contamination. The complex f o r m s a N-S
however, are easily destroyed and disturbed by r u n n i n g s u b v e r t i c a l a n d t a b u l a r b o d y in the
p o s t - m a g m a t i c re-equilibration processes (e.g., surrounding granite gneiss. It consists of glimmerite
Andersen, 1984). Thus, the early f o r m e d crystals and a series of mixedrocks together with carbonatite,
(i.e., zircon and apatite) probably carry the best carbonatite, diabase and various dike rocks (Fig.
evidence for early processes and associated fluids lb). The margins of the complex are fenitized, and
in carbonatites. Various studies on fluid inclusions fenitized granite gneiss xenoliths are found in the
in minerals f r o m carbonatites and rocks closely glimmerite-carbonatite rocks. The low metamorphic
associated with them are reported in the literature g r a d e of the g l i m m e r i t e - c a r b o n a t i t e r o c k s is
( s e e r e v i e w s by R o e d d e r , 1 9 8 4 a n d 1992). indicated by the preservation of dolomite exsolution
Compositions of fluid inclusions range from hydrous textures in calcite and the lack of carbonate-silicate
saline melts to simple gas/liquid a q u e o u s and reactions. The composition of dolomite-calcite pairs
apparently pure C O , inclusions. This paper gives a s u g g e s t s an a v e r a g e m i n i m u m e q u i l i b r a t i o n
description of fluid inclusions f o u n d in zircon and t e m p e r a t u r e of 4 5 0 ° C (Puustinen, 1974). T h e
apatite f r o m the Siilinjärvi carbonatite complex, complex was d e f o r m e d by the 1.9 Ga S vecofennian
eastern Finland. The aim is to establish their status orogeny. T h e characteristic features of the complex
(pre- to post-emplacement) during the evolution of are briefly: elongated form, age, composition of the
the complex and to characterize the PTX-conditions ultramafic phase (i.e., glimmerite), presence of
in which they formed. T o the author's knowledge, mixed rocks and the absence of rare minerals.
this is the first paper in which fluid inclusion
evidence f r o m the early phase of carbonatite m a g m a
evolution is based on a detailed study of fluid ZIRCON AND APATITE
inclusions in zircon.
Zircon phenocrysts occur mostly in the alkali
amphibole-rich parts of the glimmerite. They are
GEOLOGIC SETTING rare in the carbonatite. The zircon crystals contain
1.21% hafnium (Puustinen, 1971). They are euhedral
The geology of the Siilinjärvi carbonatite complex in form, brownish-red in colour and up to several
has been described by Puustinen ( 1 9 7 1 , 1 9 7 2 , 1 9 7 3 centimeters in the longest dimension. In ultraviolet
and 1974) and Härmälä (1981), so that only a few light, they have an orange fluoresence. In the studied
pertinent features are discussed here. It is located zircon crystal f r o m glimmerite (Fig. 2), there is an
ca. 20 k m N of the city of Kuopio, eastern Finland. apparent rounded core possibly of older zircon,
The carbonatite intruded into the southern Archean inherited either f r o m a mantle m a g m a source region
terrain (Fig. la) soon after its consolidation. The or f r o m a crustal source. T h e crystal is also
sequence of intrusion of the complex began with an intensively fractured, especially in the core region.
ultramafic phase (glimmerite). The carbonatite Apatite is not associated with any specific rock
(sövite) was emplaced, probably in several intrusion type of the glimmerite-carbonatite series. However,
phases, into pre-existing ultramafic rocks giving a the apatite content is highest in the carbonate-rich
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 5

GRANITE GNEI

DIORITE

FENITE

CARBONATITE

DIABASE

7220

6980

Sulkava

6740

2 8" 3 0 '

22° 3 0 '

Fig. 1. A. Location of the Siilinjärvi carbonatite complex in relation to the Svecofennian (SD). Archean (AD), and
to the Raahe-Ladoga tectonic zone (TZ, modified after Kinnunen, 1991). B. General geology of the complex
(modified after Puustinen, 1971).
6 Matti Poutiainen

ZIRCON ZrSi04

Fig. 2. Euhedral zircon crystal, sectioned parallel to the crystallographic c-axis, showing intense fracturing and
a rounded apparent core of possibly older zircon.

sövites. Apatite phenocrysts occur as green or METHODS

yellowish-green prisms (up to several centimeters
long), single euhedral crystals (up to 56 cm in Microthermometric measurements were made using
diameter) or as light green irregular grains and Linkam THMSG 600 programmable
grain aggregates in the glimmerite-carbonatite rocks. heating-freezing stage and L i n k a m T H 1500 high
The mineral is a cerian-type fluor-apatite, which temperature stage. Both stages were calibrated with
contains an average of 0 . 4 % lanthanides (Puusti- a set of synthetic fluid inclusion standards (see
nen, 1971). The studied apatite crystals c o m e f r o m Sterner and Bodnar, 1984). All measurements were
sövite. made on doubly-polished thin sections of 0.2 to 0.5
 Fluids in the Siilinjärvi carbonite complex, eastern Finland. Fluid inclusion evidence. 7

Table 1. Fluid inclusion characteristics.

Inclusion type Typel Type 2

Paragenetic Pseudosecondary (1 a) Secondary ( l b ) Pseudosecondary (2a) Secondary (2b) Secondary (2c)
classification
Mineral Zircon Zircon Zircon and apatite Zircon Apatite
Phases at T r o o m H20+C02(l)+solids H20+C02(1}K:02(V) H 2 CH-vapour bubble H 2 CH-vapour H 2 CH-vapour
bubble+solids bubble
Shape Negative crystal to Rounded to negative Negative crystal to Tubular or Irregular
tubular crystal tubular irTegular
Occurrence Near the core Near the core Outside the core in Randomly With carbonate
zircon orientaded healed inclusions
fractures
Daughter (captive?) Rare apatite and other Carbonate, apatite,
minerals solids Na-K chlorides,
baryte, magnetite

m m thickness. In the temperature interval of -60 to CO,. The longest dimension of the inclusions ranges
4 0 0 ° C , t h e r e c o r d e d t e m p e r a t u r e s of p h a s e f r o m 5 to 30 jj.ni. The visually estimated volume of
transitions have a precision of +0.2 to 2.0°C, the C O , phase varies f r o m approximately 7 0 to 9 0
respectively. The crushing-stage test (see Roedder, vol.%. Pseudosecondary Type l a inclusions occur
1970) using glycerol and acidified (HCl) glycerol sparsely, oriented in small, almost regular, isolated
as a mounting medium was used in order to detect groups and show negative crystal shapes (Fig. 3a).
possible non-condensable gases and carbonate In some inclusions, hexagonal apatite (diameter
daughter minerals in aqueous inclusions. S o m e 2-5 (im) occurs as a rare daughter mineral. Secondary
fluid inclusions in zircon were cracked open to Type l b i n c l u s i o n s o c c u r e i t h e r i s o l a t e d ( F i g . 3 b ) o r
allow daughter minerals to be identified using in small groups (Fig. 3c), with rounded to negative
S E M - E D S (see e.g., Metzger et al., 1977). crystal shapes. The thin water film is sometimes
difficult to see due to the black borders of the
inclusions. Some incl usions exhibit post-entrapment
FLUID AND SOLID INCLUSIONS r e - e q u i l i b r a t i o n f e a t u r e s (i.e., d e c r e p i t a t i o n ,
fractures). N o daughter minerals were observed.
In the studied crystals, data recorded at least two Very rare multiphase Type 1 inclusions (Fig. 3d)
compositional types of fluid inclusions in zircon, with variable phase ratios were also recorded. The
only one compositional type in apatite and some inclusions of this type have an aqueous fraction
solid inclusions in both minerals. A distinction is with a CO,-liquid bubble (ca. 5 to 70 vol.%) but are
made between CO,-bearing (Type 1) and pure characterized by numerous daughter and captive
aqueous inclusions (Type 2). This classification (?) m i n e r a l s of c o l o r l e s s b i r e f r i n g e n t a n d
does not carry any genetic implications. Fluid non-birefringent solids.The inclusions occur in small
inclusions are f u r t h e r s u b d i v i d e d into groups and range in size f r o m 5 to 60 |am. T h e shape
pseudosecondary and secondary inclusions (Table is usually rounded, but some larger inclusions are
1). T h e c r i t e r i a u s e d f o r d i s t i n g u i s h i n g tubular and aligned parallel to the c-axis of the
pseudosecondary and secondary inclusions were zircon. This suggests their pseudosecondary origin.
those given by Roedder (1984). The distribution of the inclusions in zircon is
transitional between the pseudosecondary Type l a
Zircon and Type 2a inclusions. Only a f e w measurements
were carried out on this type.
Type 1. T w o or three visible phases are present at Type 2. T w o visible phases are present at room
r o o m temperature: water, liquid C O , and vapour temperature: H , 0 - r i c h aqueous liquid and vapour.
8 Matti Poutiainen

mmm
I ^
O % %

;
3 # ©

C-»»
.O-

F/g. 5. f'/uiW inclusions in zircon. A. Pseudosecondary Type la H,0-C02 inclusions. B. Secondaiy Type lb
H20-C02 inclusions. C. A group of secondary Type lb H,0-C0, inclusions. D. Multiphase Type 1 HO-CO
inclusions. E. Pseudosecondary Type 2a aqueous inclusions. F/Secondary multiphase Type 2b inclusion. The
scale bar is 50pm.

The vapour phase occupies ca. 10 vol.% of the similar to that of Type l a inclusions. N o daughter
inclusion volume. The longest dimension of the minerals were encountered. Secondary Type 2b
inclusions is 3-70 |im. The m o d e of occurrence of inclusions occur in regular planes and healed
pseudosecondary Type 2a inclusions (Fig. 3e) is fractures with tubular to rounded and irregular
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 9

in secondary Type 2b aqueous inclusions in zircon.

halite, sylvite and magnetite were identified. The

S E M - E D S produced spectra for apatite and
Na-K-chlorides are shown in Fig. 4. Usually, the
size of daughter minerals range f r o m ca. 2 to 5 um.
On some inclusion walls, non-crystalline Na-K-Cl
precipitates were recorded.
In the studied zircon crystal, the distribution of
T y p e 1 and Type 2 inclusions is shown in Fig. 5.
T h e observed fluid inclusion types occur mainly in
separate domains: around (Type 1) and outside
(Type 2) the apparent core. The Type 2b inclusions
f o r m a network of healed fractures, s o m e of which
transect the core.
Zircon contains very little solid inclusions: single
apatite crystal (diameter ca. 1 mm), calcite as
irregular inclusions and as fracture filling together
Fig. 5. Spatial relationship of Type 1 H20-C02 and with minor baryte.
Type 2 H?0 inclusions in the studied zircon crystal.

Apatite

Type 2. T w o visible phases are present at r o o m

shapes. They may contain various daughter and temperature: HL,0-rich aqueous liquid and vapour.
captive minerals (Fig. 3 f ) . Using a combination of The vapour phase occupies 5 to 10 vol.% of the
SEM-EDS, optical characteristics and i n c l u s i o n v o l u m e . P s e u d o s e c o n d a r y T y p e 2a
crushing-stage, calcite, apatite, phlogopite, baryte, inclusions are extremely rare and only t w o isolated
10 Matti Poutiainen

groups showing tubular and negative crystal shapes inclusion is dolomite (Härmälä, 1981). Calcite and
were found. The longest dimension of the inclusions opaques occur as minor inclusions.
ranges between 3 and 20 |im. No daughter minerals
were found. Thus, they are similar to Type 2a
inclusions encountered in zircon. Secondary Type MICROTHERMOMETRY
2c inclusions are associated with minute carbonate
inclusions. They are irregular in shape and have The microthermometric measurements summarized
diameters f r o m 5 to 60 jam. No daughter minerals in Table 2 are based on several polished plates m a d e
were observed. f r o m zircon and apatite. A total of 157 fluid
Solid inclusion content of apatite varies greatly. inclusions were studied in the temperature range of
It depends on the size and the degree of deformation - 1 9 6 to 1000°C. T h e r e d u c t i o n of laboratory
of the host rock. In the sheared host rock, long m i c r o t h e r m o m e t r i c d a t a w a s m a d e using the
apatite prisms contain more solid inclusions than computer program F L I N C O R (Brown, 1989).
the smaller apatite grains and grain aggregates in
the less d e f o r m e d rocks. Most of them are almost Zircon
completely devoid of any kind of inclusions (fluid
or solid). Single inclusions of carbonates occur in Type 1. Melting of the carbonic phase (T m CO,)
the apatite as rounded and elongated crystals of ca. occurred in the range of -56.6 to -57.6°C (Fig. 6a).
5 to 100 jim in size. They are oriented either with These temperatures indicate virtually pure CO,,
t h e i r l o n g e s t a x i s p a r a l l e l to t h e a p a t i t e ' s possibly with minor CH 4 or N,. Homogenization of
c r y s t a l l o g r a p h i c c - a x i s , parallel to the the carbonic phases (T h CO,) to liquid was observed
0 0 0 1 - c l e a v a g e , or m o r e or less r a n d o m l y . between +10.8 and + 27.5 °C (Fig. 6b). The clathrate
Sometimes, carbonate inclusions form a halo around melting (T m Cla) temperatures vary f r o m +8.1 to
the c-axis. The most c o m m o n carbonate solid +9.4°C (Fig. 6c), which is equivalent to 1.2 -3.7

Table 2. Microthermometric data <C°), composition and density of fluid inclusions in zircon (z) and apatite (a).

Inclusion type Type l a (z) Type l b (z) Type 2a (z) Type 2b (z) Type 2a (a) Type 2c (a)
TmC02 -57.1 to -57.6 -56.6 to -56.8
TmCla 8.1 to 8.6 9.1 to 9.4
ThC02 10.8 to 19.1 (L) 17.7 to 27.5 (L)
ThH20-C02 244 to 269 (V) 234 to 277 (V)
Te -25 to -30 -24 t o - 3 1 -30 -23 to -35
TmH20 -8.9 to-14.5 -8.7 to -12.7 -12.2 t o - 1 4 . 4 -5.5 to -11.8
ThH20 302 to 367 (L) 234 to 287 (L) 322 to 344 (L) 148 to 221 (L)
eq.wt.VoNaCl 2.8 to 3.7 1.2 to 1.8 12.7 to 18.2 12.5 to 16.6 16.1 to 18 1 8.5 to 15.8
dC02 0.78 to 0.86 0.67 to 0.80
dH20-C02 0.79 to 0.87 0.73 to 0.86
dH20 0.83 to 0.89 0.89 to 0.95 0.86 to 0.88 0.93 to 1.02
Mole fractions
X
H20 0.125 to 0.558 0.146 to 0.579 0.94 to 0.96 0.94 to 0.96 0.94 0.95 to 0.97
X
NaCl 0.002 to 0.005 0.001 to 0.004 0.04 to 0.06 0.04 to 0.06 0.06 0.03 to 0.05
^C02 0.44 to 0.87 0.42 to 0.85

TmC02 Melting of C 0 2 Te Temperature of eutectic melting

T m Cla Melting of clathrate Tm H 2 0 Melting of ice
ThC02 Homogenization of C 0 2 to liquid (L) Th H 2 0 Homogenization of H 2 0 to liquid (L)
ThH20-C02 Total homogenization of H 2 0 and C 0 2 to vapour (V) d fluid density g/cm^
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 11

eq.wt.% NaCl. Total homogenization (T h Tot) of

Typelb
the inclusions to gas was measured between 232
and 283°C (Fig. 7). ZIRCON

The pseudosecondary Type 1 a inclusions have N28 T m C0 2

lower T m C O ,V, T hC O ,2 and T mCla than the secondary J

Type l b inclusions. This indicates s o m e minor N 28 ThC02

impurities in the C O , phase, higher C 0 2 density and Typelb
Typela
slightly more saline fluid for the Type 1 a inclusions. 1 Typela 0
pT

Type 2. The apparent eutectic ( T J temperature

(i.e., first melting) was observed between -24 and y y
- 3 1 ° C (Fig. 8a). These low temperatures require H
-58 -57 56-C 10 20
other dissolved salt components (e.g., K. M g and
Ca) besides NaCl. Melting temperatures of ice
(T m ice) range between -8.7 to -14.5°C (Fig. 8b), N 25 Typeja TmCLA
corresponding to salinities f r o m 12.5to 18.2eq.wt.% Typelb

NaCl. On an average, the salinity of Type 2b

inclusions is somewhat lower than that of Type 2a
inclusions.The lack of a visible C O , phase and the
inability to nucleate clathrate phase on cooling
suggest the presence of <0.85 molal C O , or CH 4
(Hedenquist and Henley, 1985). It should be noted,
however, that in spite of the absence of free C O , , the Fig. 6. Frequency-temperature histograms of fluid
inclusion microthermometric data (zircon). A.
presence of solid carbonates as daughter minerals Carbonic phase melting temperature. B. Carbonic
in the Type 2b inclusions indicates that the fluid phase homogenization temperature. C. Clathrate
dissociation temperature.
w a s s a t u r a t e d or nearly s a t u r a t e d with ionic
c a r b o n a t e s p e c i e s at t h e t i m e of t r a p p i n g .
Homogenization ( T h H , 0 ) of the Type 2a and Type
2b inclusions to liquid took place at temperatures
f r o m 302 to 367°C and f r o m 234 to 2 8 7 ° C (Fig. 7),
respectively.

Apatite

Type 2. T h e first melting ( T J of the inclusions was

observed between -23 and -35°C. The T m ice of the
Type 2a and Type 2c inclusions varies f r o m -12.2
to -14.4°C and f r o m -5.5 to -11.8°C (Fig. 9a),
corresponding to salinities f r o m 16.1 to 18.1 and
f r o m 8.5 to 15.8 eq.wt.% NaCl, respectively. The
T h H , 0 to liquid ranges f r o m 322 to 344°C (Type
l a ) and f r o m 148 to 2 2 F C (Type 2c, Fig. 9b).
In the apatite and zircon, the pseudosecondary
Type 2a inclusions have a similar range of salinity
and T h H , 0 , whereas the secondary T y p e 2b and Fig. 7. Frequency-temperature histogram of total fluid
homogenization temperature (Type 1) and
T y p e 2c inclusions d o not. The T y p e 2c inclusions liquid-vapour to liquid homogenization temperature of
have a clearly lower range of T h H , 0 and salinity Type 2 inclusions in zircon.
 12 Matti Poutiainen

than those of Type 2b inclusions in zircon. conducted on pseudosecondary Type 1 multiphase

T h e c o m p i l e d h o m o g e n i z a t i o n and density inclusions (Fig. 3d) in zircon. The chosen inclusions
versus salinity plots for the Type 1 and Type 2 did not contain any extremely large solid phases
inclusions in both zircon and apatite are presented which were obviously trapped. A chip (1.0x1.5
in Figs. 10 and 11. m m ) f r o m a normal doubly polished zircon plate
was used for the study. Heating was done using the
High temperature heating studies Linkam T H 1500 stage. The inclusions were heated
stepwise up to 1000°C at 5 0 and 100°C intervals
High temperature heating studies were only and held at the pre-determined temperature for
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 13

400- T n 1 1 r n 1 1 r i 1 1 r

T
h°C N156
® Type 1 o
T
yPe 2a
o/nType 2 (zircon/apatite)
^o %
o o D?P
Q, ° °
o o
O O
300-
fi °
© Oo O
o
«C Type 2 b o
'dp

Type 1ab
Bo •
200 D
& • o
ff £ D • 0
„0 $ Dn ^ ii1
• Type 2c & CQa
(apatite)

100 n 1 1 r
10 15 20
salinity wt.%NaCI equiv.

Fig. 9. Frequency-temperature histograms of ice melting (A) and liquid-vapour to liquid homogenization
temperatures (B) of pseudosecondary Type 2a and secondary Type 2c inclusions in apatite.

between ten minutes and one hour. These times are inclusions developed away f r o m the leaked
obviously insufficient for complete equilibration of inclusion.
the contents at any given temperature. Heating rates
f r o m 5 to 2°C/min were used.
The sequence of phase changes during heating is DISCUSSION OF RESULTS
given in Fig. 12. The vapour bubble disappeared at
360°C. T h e bulk of the solids dissolved before that Pressure and temperature of trapping
temperature. During further slow heating, almost
complete homogenization and sudden The composition and density relations summarized
re-crystallization on the inclusion walls occurred at in Fig. 11 were used to calculate isochores for the
970°C. Only one solid phase remained undissolved. fluid inclusions using the p r o g r a m F L I N C O R
In other inclusions, some solids disappeared between ( B r o w n , 1 9 8 9 ) . T h e r e s u l t i n g i s o c h o r e s are
580 and 680°C. W h e n cooled to r o o m temperature, illustrated in Fig. 13. T h e i s o c h o r e s f o r the
the fluid phase consisted of C O , vapour with no pseudosecondary Type 1 a and T y p e 2a inclusions
visible amount of water. Thus, preferential leakage pass through the P-T field limited by the eutectic
of water must have occurred, though there is not temperature of calcite carbonatite melt (625°C),
any visible sign of it. S o m e inclusions decrepitated and the m i n i m u m pressure (4 kbar) for the liquidus
between 600 and 700°C. A group of new minute assemblage calcite+dolomite+H,0-CO, fluid
14 Matti Poutiainen

10h N58 APATITE TmH20

T y p e 2c

5-
Type 2a

11 n p m i pi 11 F ] 11111 I I I I ' I —I —I 1 1—I—I 1 J I —I—I 1

-15 -14 -13 -12 -11 -10 -9 -8 -7 -6 °C - 5

15-
N58

10-
APATITE

5-
T y p e 2a
Type 2c

n i i i- 1
' ' ' I ' ' ' I
100 200 3 0 0 Th°C

Fig. 10. Diagram showing homogenization temperature (TJ versus salinity in Type 1 and Type 2 inclusions of
both zircon and apatite. Salinity of Type 2 inclusions decreases with decrease in Th, corresponding to
pseudosecondary (2a) and secondary (2b and 2c) inclusions.

I I
• Type 1a
1.1 - • Type 1b
a Type 2a
a Type 2b
1.0- 0 T y p e 2 a c (apatite)
o„o „ o

0.9- ° ° - J
0.8- n S • ff S A AAA!
A

^E • ••
0.7- O)
•o
0.6 H -

salinity wt.% NaCI equiv.

i i i i l i 1 i 1 1 1 1 1 1 1 1 1 1 1
5 10 15

Fig. 11. Diagram showing fluid density versus salinity derived from the microthermometric data presented in
Figs. 6-9. Density of Type 2 inclusions in both zircon and apatite increases with decrease in salinity,
corresponding to pseudosecondary (2a) and secondary (2b and 2c) inclusions.
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 15

Fig. 12.
A 0.05 mm F Heating study
of multiphase
Type 1
inclusion in
zircon. The
sequence of
phase
dm^^^^^^ C 02 Iq 02V changes
C02 drawn at
different
dm 27°Q -73°C temperatures
(A-J), has
been

B G reproduced
from images
captured by a
Mitsubishi
video copy
processor.
Abbreviations:
Iq
C02 i c ^ l ^ C 0 2 v cp= captive
mineral, dm=
* dm daughter
mineral, lq=
225°C -59°C liquid, v=
vapour, rs=
re-crystallized
C H solid, s=
solid.

fluid ^taj— ^ C02lq vj^l» - ^ C02v

dm
360°C -56.6° C
D 1

C02 V

860°C 17°C
E J

Jib*
fluid^^
970°C 19°C
16 Matti Poutiainen

Fig. 13. P-Tdiagram showing

sets of isochores for the Type 1
and Type 2 pseudosecondary
(la and 2a) and secondary (2b
and 2c) inclusions encountered
in zircon and apatite. A P-T
field limited by the carbonatite
eutectic (625°C) and the
minimum pressure (4 kbar)for
the liquidus assemblage
calcite+dolomite +Hß-C02
(Wyllie, 1966), is shown for
reference (see text for further
explanation).

(Wyllie, 1966). In zircon and apatite, the isochores the carbonatite at mid-crustal conditions (P > 4
of the T y p e 2a inclusions fall within the same kbar, T > 625°C). This is also supported by the high
sector. N o n e of the isochores cross the P-T field of liquidus temperature (970°C) of multiphase Type 1
the final, obviously shallow crustal emplacement of inclusions in zircon. The m i n i m u m pressure of 4
the carbonatite (1 to 2 kbar) at temperatures above kbar would correspond to a crustal depth of at least
the experimental solidus (625°C). The fluid inclusion 14 km. Fluid inclusion e v i d e n c e f o r the Fen
data thus suggest that the pseudosecondary Type 1 a carbonatite complex (Norway) also demonstrates
and Type 2a inclusions in zircon and apatite were the mid-crustal origin for the apatite (Andersen,
trapped during the pre-emplacement evolution of 1986). Haapala (1980) obtained evidence for high
 Fluids in the Siilinjärvi earbonite complex, eastern Finland. Fluid inclusion evidence... 17

P-T conditions (ca. 4.5 kbar and 600°C) for the However, apatite and calcite may co-crystallize
apatite f r o m the Sokli carbonatite. over a wide range of temperatures and pressures,
The Type 1 H , 0 - C 0 , inclusions pre-date the a n d t h e y m a y a l s o c o - e x i s t w i t h l i q u i d at
Type 2 aqueous inclusions, as indicated by their temperatures below 600°C. There is also a possibility
m o d e of occurrence in zircon. This implies a change that this temperature range (i.e., 300 to 420°C)
in fluid composition. According to experimental refers to the post-crystallization re-equilibration
data (Wyllie, 1966), a fluid phase in equilibrium c o n d i t i o n s of a p a t i t e d u r i n g t h e r e g i o n a l
with a cooling carbonatite melt crystallizing solid metamorphism ca. 1.9 Ga ago. Late-stage fluorine
carbonates would be greatly enriched in water and hydroxyl exchange may have occurred at low
(98-99% H , 0 at the C a C 0 5 - M g C 0 r H , 0 eutectic). metamorphic temperatures with an aqueous fluid,
This explains the lack of Type 1 inclusions in mainly affecting the mica.
apatite. Furthermore, apatite crystallized later than Single crystals and trails of calcite inclusions
zircon. T h e occurrence of minute apatite daughter completely sealed within the apatites are thought to
crystal in some of the Type 1 H , O C O , inclusions result f r o m the trapping of already precipitated
indicates beginning of apatite crystallization before crystals of calcite. They often occur side-by-side
c a l c i t e . D u r i n g t h e e a r l y s t a g e of c r y s t a l with the secondary Type 2c aqueous inclusions in
fractionation, multiphase Type 1 inclusions were the same apatite crystal. It is concluded f r o m these
trapped in zircon. They represent heterogeneous observations that these calcites co-existed with the
trapping of crystallized solids and enclosing fluid. aqueous fluid during fracturing and re-crystallization
Apatite and calcite co-exist in the secondary T y p e of the apatites. This fluid may also be responsible
2b inclusions. They were trapped during for the transport and deposition of at least s o m e of
emplacement of the carbonatite into the pre-existing the calcite. Malinin and Dernov-Pegarev (1974)
glimmerite, causing intense fracturing of zircon showed that appreciable quantities of calcite can be
and re-equilibration of some Type l a inclusions transported by alkali-carbonate solutions, even at
(now Type l b ) . Thus, during crystal fractionation low temperatures (200-350°C). Unfortunately, it
and subsequent compositional change in the cooling was not possible to obtain direct fluid inclusion
carbonatite m a g m a , the Type 1 fluid was depleted evidence for the formation conditions of calcite.
in C O , and enriched in water and alkalies (i.e., Obviously, these secondary T y p e 2c inclusions in
towards higher salinity). The alkalies were apatite have a metamorphic origin.
partitioned into the aqueous phase interacting with R e - c r y s t a l l i z a t i o n of a p a t i t e t o g r a n u l a r
the carbonatite melt b e c a u s e of their higher aggregates took place either during emplacement
solubilities in water. Fenitization of the country of the m a g m a to their present position, or more
rock and the country rock xenoliths was obviously probably during the later m e t a m o r p h i s m . This
induced by these saline aqueous fluids.This is together with deformation would explain the scarcity
supported by the presence of Type 2 inclusions. It of fluid inclusions in apatite.
is assumed that all these inclusions in zircon and the
very f e w pseudosecondary inclusions in apatite
have a magmatic origin. ACKNOWLEDGEMENTS: I wish to thank H. Kauppi-
Phlogopite-apatite geothermometer (Stormer and nen for providing the zircon samples and especially O.
Härmälä for guiding me in the Siilinjärvi open pit andfor
C a r m i c h a e l , 1971) yields a crystallization help in locating additional proper apatite samples for the
temperature range of ca. 300 to 4 2 0 ° C for the study. Excellent polished sections were prepared by L.
apatite, calculated f r o m the chemical composition Rämö. lam grateful also to J. Juhanoja of the Department
of apatite and phlogopite f r o m glimmerite (Puusti- of Electronmicroscopy for his genereous technical help
with the SEM-EDS. P. Salonsaari assisted me in the
nen, 1971). This temperature range is well below
geothermometric calculations of apatite. The paper also
the experimental eutectic temperature of 635°C for benefited from reviews by S. Lindblom, K. A. Kinnunen
the system c a l c i t e + a p a t i t e + H , 0 (Biggar, 1969). and I. Haapala.

2 21442
18 Matti Poutiainen

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