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et Cosmochimica
Acla Vol.
0016-7037/90/%3.oil
+ .Gil
Copyright
0 1990Pergamon Press plc.Printed
of Geological Sciences, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 2406 I, USA
2Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 3783 1,USA
(Received April 1I, 1989; accepted in revised firm December 15, 1989)
Abstract-Phase
relations in the ice-stable field of the system NaCl-CaCl*-HZ0 have been determined
under I atm total pressure along the NaCl-HI0 and CaCl*-HZ0 binaries and along five pseudobinaries
with constant NaC1/(NaC1+CaCll) weight ratios. The results are in excellent agreement with published
data along the NaCl-HZ0 binary but show large discrepancies when compared to previous determinations
of the ice liquidus along the CaC12-H20 binary and in the NaCl-CaC&-HZ0 ternary. Eutectic temperatures
and compositions are -2 1.2OC (+O.Ol) and 23.2 wt% for the NaCl-HZ0 binary and -49.95C (50.15)
and 30.33 wt% for the Ca&-HZ0 binary. The minimum temperature reached during our experiments
in the ternary system was -34C; therefore, we do not report isotherms below -35C or the ternary
eutectic temperature.
At moderate to high salinities, isotherms cross the ice sub-field at lower total salt concentrations than
previously reported. Fluid inclusion salinities determined from previously published freezing-point data
may be in error by as much as 2 wt% total salt. In addition, NaCl/(NaCl+CaCI,) weight ratios estimated
from hydrohalite- and ice-melting temperatures may be in error by as much as 0.15.
INTRODUC-HON
EXPERIMENTAL
PROCEDURE
FLUID
INCLUSIONSARE a primary means of determining the
PTX conditions of formation or alteration of minerals. In
order to do so, compositions of fluid inclusions must be
known and phase equilibria and volumetric (PVTX) data for
the applicable fluid system must be available. Our ability to
determine compositions of inclusions has advanced significantly in recent years, owing to the development of new analytical techniques and improvements in existing techniques
which allow smaller samples to be analyzed. Similarly, there
has recently been a renewed effort to obtain PVTX data on
geologically important fluid systems over wide ranges of temperature and pressure.
Fluids from a variety of geologic environments may be
adequately represented by the simple NaCl-CaC12-HZ0 ternary system. Fluids approximated by this system are important in geothermal reservoirs, oceanic hydrothermal systems,
metamorphic environments, petroleum reservoirs, and ore
deposits of gold, copper, tin, tungsten, uranium, lead, and
zinc (WHITE, 1968, 1981; CRAWFORDet al., 1979a,b; KWAK
and TAN, 198 1; KELLY et al., 1986; ROBERT and KELLY,
1987; VANKOet al., 1988; WITT, 1988). However, the paucity
of freezing-point depression data for this and other ternary
or higher order aqueous salt systems has limited our ability
to interpret microthermometric and analytical data obtained
from fluid inclusions formed in these environments. In this
paper we describe results of an experimental study to determine the ice liquidus in the NaCl-CaCl*-HZ0 system at 1
atm total pressure and the application of these data for determining compositions of vapor-saturated, low-to-moderate
salinity (<3O wt%) fluid inclusions approximated by this
system.
* presented at PACROFl II, Second Biennial Pan-American Conference on Research on Fluid Inclusions, held in Blacksburg, VA,
January 4-7, 1989.
603
604
FIG. I. Schematic drawing of the freezing-point depression apparatus used in this study.
Table 1. Coefficients
of Equation 1
a0 = -252.80766161
a, =
-4.46838599
a 2=
0.-
a3 =
-3.11224433
b,
433.18270190
bz = -232.86374780
b3 =
51.80774407
0.39937513
37.89983342
4.51383486
3.00567613
g, = -111.52366055
g, =
108.45638078
g3 =
-34.82557222
0.05251418
605
Table 2. Experimentally Determined Freezing Point Depressions (0 ,C) and Total Salinities (wt%) for
Various NaCl/(NaCl+CaCl2) Wt Ratios Shown in Parentheses at the Head of Each Pair
of Data Columns
(1.000)
e
wt%
0.00
0.00
3.08
3.40
a.45
10.48
13.11
14.25
16.46
16.78
18.57
20.18
21.80
22.80
23.34
1.84
2.03
5.42
6.98
9.22
10.27
12.49
12.86
14.91
16.91
19.17
20.64
21.48
(0.195)
(0.593)
8
0.00
1.70
;::
4.05
5.19
5.21
6.02
7.08
8.10
9.10
10.03
11.02
12.19
13.24
14.08
15.14
17.04
19.06
21.02
23.23
23.28
(0.796)
wt%
wt%
wt%
0.00
3.13
3.77
5.32
6.92
8.50
8.54
9.58
10.88
12.05
13.10
14.03
14.96
16.00
16.89
17.55
18.36
19.69
21.02
22.19
23.41
23.43
0.00
1.55
2.03
3.37
4.40
5.05
6.00
7.02
8.09
9.02
10.04
11.13
11.97
13.96
16.09
18.07
20.36
22.01
0.00
3.18
4.09
6.34
7.87
a.75
9.95
11.13
12.27
13.18
14.12
15.06
15.75
17.22
18.65
19.82
21.08
21.94
0.00
1.42
2.08
3.68
4.06
5.21
6.02
6.03
7.06
8.08
a.42
9.08
10.98
11.62
12.03
13.50
14.21
15.30
16.02
17.80
19.32
19.64
20.78
21.12
21.97
23.08
24.02
25.23
25.25
26.08
27.06
27.08
27.21
27.22
28.08
28.98
30.16
32.09
32.13
34.07
35.72
36.03
37.07
38.08
39.03
39.83
40.80
42.16
42.89
43.15
44.00
44.77
45.64
46.55
46.66
48.28
49.37
50.14
50.5 I
51.20
0.00
3.13
4.42
7.09
7.64
9.16
10.15
10.20
11.35
12.39
12.64*
13.34
14.a3*
15.46
15.72
16.77
17.31
18.04,
18.42
19.46
20.19
20.40
20.97
21.16
21.56
22.04
22.41
23.01
22.95
23.37
23.73
23.73
23.78
23.82
24.16
24.44
24.89
25.52
25.56
26.17
26.69
26.78
27.08
27.39
27.66
27.88
28.14
28.50
28.68
28.71
28.97
29.16
29.37
29.58
29.61
29.94
30.23
30.39
30.46
30.59.
(0.393)
(0.169)
Wt%
wt%
wt%
0.00
1.71
2.01
3.05
4.01
4.55
4.94
4.98
6.12
6.13
7.03
8.84
10.12
11.00
11.91
13.32
14.19
15.19
16.05
17.03
18.01
18.99
19.00
20.05
20.96
22.13
22.48
0.00
3.03
3.54
5.20
6.68
7.43
1.97
0.00
1.59
2.04
2.10
3.18
4.22
5.46
6.94
8.06
9.16
10.06
0.00
3.12
3.88
4.02
5.84
7.40
9.08
10.88
12.10
13.24
14.09
15.04
15.84
16.60
17.37
18.30
19.39
19.41
20.85
21.87
22.96
23.85
24.71
19.99
22.11
24.05
25.98
28.02
30.08
30.21
32.11
34.03
20.86
21.94
22.85
23.70
24.54
25.34
25.39
26.09
26.75
*These
:::
9.56
10.69
12.78
14.12
14.98
15.81
17.05
17.79
18.58
19.25
19.96
20.65
21.30
21.31
21.99
22.56
23.25
23.63,
data were
11.11
12.06
13.00
14.02
15.32
16.95
17.03
19.36
21.22
23.21
25.07
26.93
excluded
from
(0.000)
the renression
routine.
606
a, =
0.00079300
al = -23.60559803
a2 =
Simonson
-14.28248382
a3 = -6.28485097
a4 =
- 1.63493939
a5 = -0.22344814
a6 =
-0.01233080
b, =
5.93722121
b, =
8.52707977
b, =
3.58341351
b, =
0.50474224
c2 =
1.46447853
c3 =
1.42997903
c$ =
0.00000000
cs =
-0.34061248
cg =
-0.08075286
unknown concentration were measured with a vibrating U-tube densimeter (Paar DMA60 and 602HP remote cell with a borosilicate
glass tube). All densities were measured at nominal temperatures of
25 and 35C. The U-tube temperature varied from 25.003 to
25.092C and from 34.970 to 35.004C for the calibration solutions
(OAKS et al., 1990) and from 25.007 to 25.097C for the solutions
of unknown concentration. The de&meter was maintained at temperature with a Neslab RTE-220 circulating bath while the sample
bottles were stored in the bath for several hours prior to each density
measurement to ensure thermal equilibrium between the tube and
the solutions. The temperatures of the circulating bath and U-tube
H2O
0 (0
X NaCl
Wt%
1.0
5.0
10.0
15.0
20.0
::oO
1.0
1.73
7.87
13.99
18.64
22.35
8.05
1.82
I .o
1.0
1.0
1.o
0.8
10.0
15.0
20.0
1.0
5.0
10.0
15.0
20.0
25.0
1.0
5.0
10.0
20.0
30.0
1.0
5.0
10.0
20.0
30.0
1.0
5.0
10.0
20.0
30.0
40.0
0.8
0.8
0.8
0.6
0.6
0.6
0.6
0.6
0.6
0.4
0.4
0.4
::t
13.98
18.44
21.97
I.92
8.24
14.00
18.26
21.60
24.33
2.02
8.45
14.04
21.24
25.83
2.12
8.68
14.10
20.90
25.40
2.22
8.92
14.18
20.56
24.84
27.89
Fl::
0.2
0.2
0.2
0.0
:::
0.0
G
+ i b,R + cT,R
,=I
+
.fRJf!w,
+ dT,X,,,
gk TuRk&ac,
+ eR3Xh,,c-l
hTuRX&t
(1)
k-l
CaCI,
o.2
0.4
O5
0.8
NaCl
NaCl
FIG. 2. Isotherms of the ice liquidus at 1 atm total pressure in the
system NaCI-CaC&-Hz0 calculated from Eqn. (2) are shown in 5C
intervals. The ice-hydrohalite and hydrohalite-halite cotectics were
constructed using data from YANATIEVA( 1946). HH = Hydrohalite
(NaCl. 2H,O), H = Halite (NaCl), 1 = Ice (H,O).
h-eezing
10 Point
20 Depression
30
40
KLT
50 )
607
l.I
This Study
Hall et al. (1988)
Potter et al. (1978)
Gibbard & Gossmann (1974)
Scatchard & Prentiss (1933)
Rodebush (1918)
. 0
+
0.30 _ *
. I
A
RESULTS
AA
and X,,
resulting
A
A
+
in the equation
W = 5 ai T: + i
i=O
,=I
bjTfx,aa + i
ck TfXhaa
(2)
k=2
where W is the total salinity in weight percent; Tf is the freezing temperature (C) divided by 10.0; and ai, bj, and ck are
the regression coefficients. Values of the regression coefficients
A*
A
A
A
____~_~_
d
A
-0
&A
--&
0.00
00
4%#a*.
0
-0.10
000
. . . . . * . . . . . . . . . . . .
5
10
15
20
25
A
x
. +
_ q
ls5
o
. . 1. . . 1
. I .
ThisStudy
Gibbard & Fong (1975)
Yanatieva (1946)
Prutton & Tower (1932)
Rodebush(1918)
Roozeboom (1889)
I .
0
x
.
0.5 -
x
0
0
+
-0.5 -
-1.0
. ..
10
20
. ..
30
. . . .
40
50
E
I
ature range even though only their five most dilute samples
along this pseudobinary were incorporated in the derivation
of Eqn. (2). The XNaCl= 0.5 1 pseudobinary data of Yanatieva,
however, show large positive deviations of as much as 1.8
wt% from our fit (Fig. 6b). When plotted on a triangular
diagram on a wt% basis our isotherms and those determined
by GIBBARDand G~SSMANN ( 1974) and GIBBARDand FONG
(1975) are nearly straight (Fig. 2). Yanatievas isotherms,
however, have substantial curvature concave toward the Hz0
apex (cf. Fig. 4.6, p. 89 in CRAWFORD,198 I). The maximum
deviation of Yanatievas data from our fit occurs roughly
along the XNacl = 0.5 pseudobinary.
DISCUSSION
Fluid inclusions thought to contain aqueous solutions of
NaCl and CaClz, as evidenced by low initial melting temperatures during microthermometric analysis of the inclusions, have generally been modeled using the freezing-point
depression data of YANATIEVA(1946). This study, however,
implies that Yanatievas reported salinities are too high by
as much as 2 wt%. For many geologic applications this salinity
difference is relatively unimportant and is often within the
o.oo/
____P_____________t_.__~_
0
-0.04L.r~I~~.-.~~~~~~~....~
0
1
2
3
4
1.0
j .,,.,,;
..,...,,...
i
'0
10
15
20
25
Freezing Point Depression ( 8 ,C)
5
FIG. 6. (a) Comparison of experimental salinities and freezingpoint depression data OfGIBBARD
and FONG( 1975)along the XNaCl
= 0.5 1 pseudobinary with salinities predicted by Eqn. (2). The five
unshaded points were incorporated in the derivation of Eqn. (2). (b)
Comparison of experimental salinities and freezing-point depression
data OfYANATIEVA
(1946) along the X,,,, = 0.5 1pseudobinary with
salinities predicted by Eqn. (2).
0.2
0.;
609
brines
0.6
0.6
NaCl
NaCl
FIG. 7. (a) An example of the difference in XNaQthat results from modelling hydrohalite- and ice-melting temperatures
from YANATIEVA'S
(1946) data and ours. For an inclusion in which hydrohalite melts at -25C in the presence of ice,
solution, and vapor, XNaCl= 0.53 from Yanatievas data versus 0.70 from our data. Dash-dot curve is Yanatievas
-25C isotherm and light solid curve is our -25C isotherm. Dashed lines are the pseudobinaries corresponding to
the respective X,,, . The ice (I), hydrohalite (HH), and halite (H) fields are labeled in Fig. 7b. (b) Geothermal brine
(open circles) and fluid inclusion (stippled ovoid regions) compositions from the Salton Sea Geothermal System,
California. The lightly stippled regions M and N represent fluid inclusion compositions modelled using Yanatievas
data. The dark stippled regions M and N represent reinterpretation of the data in M and N using Eqn. (2) and
Yanatievas compositional results for the ice-hydrohalite cotectic. Because the geothermal brine compositions have
been plotted with KC1 combined with NaCl on a wt% equivalent basis, their total salinities have been exaggerated.
REFERENCES
CRAWFORDM. L. (198 1) Phase equilibria in aqueous fluid inclusions.
In Fluid Inclusions: Applications to Petrology (eds. L. S. HOLL~STER
and M. L. CRAWFORD),Vol. 6, pp. 75-97. Mineralogical ~ssociation of Canada.
CRAWFORD M. L., FILERJ., and WOOD C. (1979a) Saline fluid inclusions associated with retrograde metamorphism. Bull. Mineral.
102,562-568.
610
RODEBUSH
W. H. (I 9 18) The freezing points of concentrated solutions
and the free energy of solution of salts. .I Amcr (hem. Sac 40,
1204-1213.
ROOZEBOOM
H. W. B. (1889) Experimentelle und theoretische Studien iiber die Gleichgewichtsbedingungen zwischen festen und
fliissigen Verbindungen von Wasser mit Salzen, besonders mit dem
Chlorcalcium. % PhJ:s. Chemie 4, 3 l-65 (in German).
SAN DIEGOGASAND ELECTRIC
(1980) Final Report DOE/ET/28443TI. Geothermal Loop Experimental Facility, Contract No. DEAC03-76ET28443.
US Dept. of Energy, pp. 8.98-X. 107.
SCATCHARDG. and PRENTISSS. S. (1933) The freezing points of
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and bromides. J .Amer. Chcm Sot. 55, 4355-4362.
STERNERS. M., HALL.D. L.. and BODNARR. J. (1988) Synthetic
fluid inclusions. V. Solubility relations in the system NaCI-KCIHZ0 under vapor-saturated conditions. Geochim. Cbonochim. Actu
52,989-1005.
THOMPSONJ. M. and FO~JRNIERR. 0. (1988) Chemistry and geothermometry of brine produced from the Salton Sea Scientific Drill
Hole, Imperial Valley. California. J. Geoph_w. Rex 93, I3,16513,173.
VANKOD. A., BODNARR. J.. and STERNERS. M. (1988) Synthetic
fluid inclusions: VIII. Vapor-saturated halite solubility in part of
the system NaCI-CaC12-H20, with application to fluid inclusions
from oceanic hydrothermal systems. Geochim. Cosmochim. Actu
52,245 1-2456.
WHITED. E. (1968)Environments of generation of some base-metal
ore deposits. Econ. Geol. 63, 301-335.
WHITE D. E. (198 I) Active geothermal systems and hydrothermal
ore deposits. Econ. Geol. 75th Anniversary Vol., 392-423.
WILLIAMSA. E. (I 986) Data on production horizons in six geothermal
wells in the Salton Sea Geothermal Field. Data Transfer Package
86/I, Contract No. E5 12-08300, US Dept. of Energy, 28 p.
WITT W. K. (1988) Evolution of high-temperature hydrothermal
fluids associated with greisenization and feldspathic alteration of
a tin-mineralized granite, Northeast Queensland. Ecun. Geol. 83,
3 10-334.
YANATIEVA0. K. (1946) Polythermal solubilities in the systems
CaCl*-MgCll-H20 and CaC12-NaCI-H20. Zhur. Prikl Khim. 19,
709-722 (in Russian).