Geochimicn et Cosmochimico Acro Vol. 46, pp. 219 lo 287 0 Pergamon Press Ltd. 1982. Printed in U.S.A.

oOl6-7037/82/020279-lO$O3.00/0

Amorphous silica solubilities IV. Behavior in pure water and aqueous sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate solutions up to 350C
CHEN-TUNG Chemistry Division, Oak Ridge A. CHENS: National

and WILLIAM
Laboratory,

L. MARSHALL Tennessee 37830 U.S.A.

Oak Ridge,

(Received

April 23, 1981; accepted in revised form October I, 1981)

Abstract-Solubilities of amorphous silica were determined in separate aqueous solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate at temperatures up to 350C. These salts, of strong interest in hydrothermal oceanography and geothermal energy, generally ranged in concentration from zero to saturation. Solubilities in the sodium chloride solutions followed closely earlier observed decreases in sodium nitrate solutions at high temperatures. Amorphous silica solubilities were depressed most by magnesium chloride, followed by magnesium sulfate, and less by sodium chloride. As the temperature rose the relative decrease in solubility caused by added salt became smaller. Surprisingly, sodium sulfate solutions, showing little effect at 25C sharply raised the solubility as the temperature increased to 350C. Plots of the logarithms of derived activity coefficients against molalities of added salt gave approximately straight lines. These plots allow simple predictions of amorphous silica solubility in single salt solutions.

INTRODUCTION IT HAS COMMONLY been assumed by geochemists that the solubility of silica in aqueous solutions does not change greatly from that in water for low concentrations of dissolved salts (Holland, 1967; Siever, 1962; Greenberg and Price, 1957; Krauskopf, 1956; and Kitahara, 1960). Without quantitative information, silica solubility in pure water thus has been used frequently as an approximation for geochemical calculations in natural waters (Fournier and Rowe, 1966; Corliss et al., 1979; Edmond et al., 1979). Recently, the solubility of amorphous silica has been measured in aqueous sodium nitrate solutions up to six molal at temperatures from 25 to 300C (Marshall, 1980a) and in ten separate sets of aqueous salt solutions at 25C (Marshall and Warakomski, 1980). It was found in both the sodium nitrate solutions at high temperatures and the several sets of solutions at 25C that the solubility of amorphous silica decreased with increasing concentration of dissolved salt. The present study extends to temperatures of 300 and 350C solubility measurements in separate salt solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate. Solubilities in these solutions, containing the major components of seawater and other natural waters, should be of interest to geochemists and chemical oceanographers. They may be significant in evaluating silica behavior in regions of hydrothermal seawater (Corliss et al., 1979; Edmond et al., 1979).

EXPERIMENTAL

PROCEDURES

Experimental procedures were generally the same as reported in the earlier papers (Marshall, 1980a; Marshall and Warakomski, 1980). The amorphous silica used was the same as that used in the study of Marshall and Warakomski (1980). The NaCl, Na,SO,, MgCl*, and MgSO, solutions were prepared by dissolving Fisher certified grade salts in distilled water. Approximately 4 g of the amorphous silica and 30 cm3 of pure water or solution were added to each pressure vessel of 58 cm3 total volume. Hydrazine was added to NaCl and MgClz solutions to a final concentration of approximately 50 ppm to reduce corrosion of the vessel. The solid-liquid mixtures were rocked at the temperature of study for various periods before sampling. Samples of solution phase were withdrawn through the filters, capillary tubes, and valves to preweighed sample bottles filled with reagents. A
0 032

o024 l ------._.-
0020 , i t

I,

-i-l
IN.

Hz0

I
i-

t=300c

$ Oak Ridge Associated Universities Faculty Research Participant, 1980. Permanent Address: School of Oceanography, Oregon State University, Corvallis, Oregon 97331 U.S.A.
219

FIG. 1. The solubility of amorphous silica in water and in NaCl, NaNO,, Na2S04, MgCl*, and MgSO, aqueous solutions at 300C vs. duration of experiments.

280

C.-T. A CHEN Table I. The molal soiubility of amorphous silica in pure water at various temperatures

AND

W. L. MARSHALL

RESULTS

AND DISCUSSION

I emperaturc PC) 100 100 U.OO6.3 0.0065 0.0105 t).olos tl.ooYYs 0 0162

IS0
150 I50 200 200 200 200 250 250 250 275 275 300 JO0 700 ,350 350 150 *I!: approached **S: approached

I) 0 I 5: (I.oI ho 0 Olh 0 O?ll 0 02I8

0.02 I Y 0.024 I iJ 0235 0.0263 0 0262 il 0265 0.02Xh 0.02hS 0 0266 from under\atttrata~I1 from \uprl-\a~ urat 1t)n

for analysis of salt content h> drying at 175C. The calorimetric reagent was prepared according to Grasshoff (I 964) and Rohlmann er al. ( 1980), and consisted of 5 parts (by volume) of 2 M ammonium sulfate, 2 parts of 0.0228 M ammonium molybdate, and 2 parts of 1.5 M monochloracetic acid which was adjusted to a pH of 3.15 with NH,OH. The reagent was prepared, dispensed into the sample bottles, and weighed immediately before sampling. The analysis of dissolved silica was made spectrophotometrically as described earlier (Marshall, 1980a: Marshall and Warakomski, 1980). In order to minimize systematic experimental errors, measurements were made over different lengths of time. and saturation was approached both from undersaturation and supersaturation. It was found that the results were independent of the direction of approach. However, the transformation of amorphous silica into cristobalite and sometimes even into quartz in the salt solutions at high temperatures somewhat limited the reproducibility of our measurements. Although amorphous silica was found to be stable in pure water for over I5 days at 3OOC, it transformed into cristobalite rather rapidly in salt solutions, as observed by optical and x-ray diffraction analyses. The solubilities decreased accordingly as shown in Fig. 1. The effects of impurities, particle size, and aging (Willey, 1975, 1980; Hurd et al., 1979; Iler, 1979) were not studied. We did not attempt to determine the rate of transformation, but our limited investigation indicates that it is probably not easily reproducible. For this study, we generally limited the durations of our experiments to less than five hours when the temperature was above 250C and assumed that the measured solubilities were those for amorphous silica.

second sample was obtained

The determined molal solubilities of amorphous silica in pure water and in aqueous NaCl, Ns$O,. MgCl*, and MgS04 solutions at various temperatures up to 350C are given in Tables 1 to 5 and are plotted in Figs. 2 and 3. Also plotted in Fig. 2 are the soiubilities in water obtained from the equations of Fournier and Rowe (1977) Walther and Helgeson ( 1977). and Marshall ( 1980a). The agreement IXveri good. The solubilities in NaCl solutions (Fig. 4a, hiled triangles) are indeed similar to those in NaNO! solutions (Fig. 3a, open triangles) as expectsd (Marshall 1980a, Marshall and Warakomski, 19X0). No systematic difference can be detected within the precision of the data. Additional solubility measurements were made in NaNO, solutions using a different batch of amorphous silica. The results are given in Table h .I& plotted also in Fig. 3a (open circles). The agreement with the earlier data of Marshall (1980a) is reasonable. The 25C data of Marshall and Warakumskt are described as curves in the four parts of b LC. 1 Iar comparison. The solubilities of amorphous silica ut ha&O4 aqueous solutions are plotted in Fig 3b. Tbc solubilities decrease slightly at higher salt concentrations at 25C (Marshall and Warakomski. 1980) but re main essentially constant at 100C. The solubihties increase gradually with salt concentration at i 50C and increase sharply at temperatures above 250C Figure 3c shows the solubility values in MgCl: solutions, and they all decrease sharply at higher salt concentrations, There is indication that some crtstobalite was formed even at temperature3 below 300C in MgClr solutions. This may have contrihuted to the large scatter of the data. The reproducibility of the solubility in MgCl, solutions is thus the poorest among the four systems we studied.

)A ,

-i

FIG. 2. The molal solubility from 25 to 350C.

of amorphous

silica in watct

SILICA

SOLUBILITIES

IV

281

Table 2. The molal solubility of amorphous

aqueous NaCl solutions
Added Salt Cm) 11me (hr) SiO~ Solubiiity (m) Density (g cm') Added Salt (m)

silica in at various temperatures

Time (hr) sio: Solubilitl (m)

DensIt\
(g

cm)

.~
100C
16.5 U* 23.5 U 23.5 I! 23.5 U 9.5 II 19.0II 19.01: ISOT

2OO'C (continued) 0.966 I.017 1.050 1.052 I.108 I.140 I 152 4.02 4.02 4.48 5.82 6.40 4.5 s 26.5 I' 4.5 I: 26.5 U 24.0 \I 0.0102 0.0099 0.0094 0.0088 0.0077 250C 0.19 0.65 1.00 I.62 1.67 3.80 4.02 5.X2 6.5 I' 16.0I' 6.5 U 16.0U 3.5 [I 4.0 U 4.0 11 4.0 I! 0.0213 0.0200 0.0193 0.0190 0.0178 0.0162 0.0161 0.0133 300C 0.20 043 0.62 1.00 1.62 3.82 4.02 4.02 4.02 15.5u 3.5 II 3.5 U I55 II 35u 4 0 I: 40 II 4.0 II 7.0 u 0.0272 0.0262 0.0241 0.0227 0.0234 0.0207 0.0216 0.0220 0.0205 35ooc I.7 4.5 U 0.0245 0 730 0724 0.736 074x 0.770 0804 0.902 0.909 0.909 0.909 0.807 0.829 0844 0.869 0.871 0.960 0.968 I.011 I.015 I.015 I.028 1.05x 1.070

0.19 I.62 2.58 2.66 4.48 5.82 6.31

0.0061 0.0045 0.0041 0.0040 0.0048 0.0034 0.0034

0.19 0.43 0.62 0.X5 1.62 2.58 3.80 402 4.02 4.4x 5.00 5.73 5.X2 5.82 6.31

6.5 II 4.5 I' 4.5 LI 6.5 II 4.5 li 4.5 II 17.0s* 7.0 s 20.0 I' I35 11 22.5 S 22.5 S 20.0 U 53.5 Ii 53 3 I:

0.0101 0.0094 0.0094 0.0090 0.0085 0.0071 0.0071 0.0060 0.0062 0.006X 0.0056 0.0054 0.0052 0.0057 0.0056 200C

0.924 0.934 0.940 0.950 0.97x 1010 1.050 I.056 1.056 1.070 1.0x4 I.101 I.102 I.102 I.114

0.19 0.90 1.67 3.80

160 I! 16.0II 4.5 U 45s

0.0157 0.0142 0.0142 0.0103

0.x72 0.900 0.930 1.00x

*See lable

I for explanation.

Figure 3d shows the solubilities in MgS04 solutions. The experiments only covered a small concentration range because of the hydrolytic instability of MgSO, in water solutions at high temperatures (Marshall and Slusher, 1965). The data indicate that MgSO, depresses the solubility of amorphous silica. The solubility values in each salt were fitted to the following empirical equation:

(1980a), that equation used here: log so = -0.1185

for log so (25 to 300C)

is

- 1.1260 X 103/T
3.6784 X 107/T3

+ 2.3305 X lOsIT

(2)

log s = log so - Dm - Em2

(1)

where s and so are the molal solubilities in salt solutions and in pure water, respectively, M is the molality of the salt, and D and E are functions of absolute temperature,
D=a+bT+cT E=d+eT+fT (la) (lb)

where T is the absolute temperature. The parameters for Eqn. (1) for NaCl, Na2S04, MgC12, and MgS04 solutions are given in Table 7 along with the standard deviations of the fit. The parameters for Eqn. (1) without the Em2 term are also given in Table 7. The dropping of the Em2 term does not seem to significantly increase the standard deviation of the fit except for MgC12. Setchtnow (1892) originally proposed the empirical equation for the salt effect upon neutral molecules in terms of molarity (M): log S = log SO - LYM (3)

The terms a, 6, c, d, e, and fare

constants.

Since we have few data points at 35OC, only the current data between 100 and 300C and the previous 25C data of Marshall and Warakomski (1980) were fitted. Further, since our pure water data agree well with the equation reported by Marshall

where S and So are the molar solubilities of the amorphous silica in salt and in water, respectively, and D (where the prime in this paper indicates use of molarity) is a function of temperature similar to Eqn. (la). Since density data were available only for

282

C.-T A. CHEN AND W. L. MARSHALL Table 3. The molal solubility of amorphous

Na2S0, solutions silica in aqueous at various temperatures

the NaCl and Na&.I, aqueous solutions (Hilbcrt, 1979; Khaibullin and Borisov, 1966; Khaibullin and Novikov, 1973) the amorphous silica solubility data in these two salts were fitted to Eqn. (3) The parameters are given in Table 8. PIlso given in Table 8 are the parameters for an EM term similar to that in Eqn. (lb). The addition of an EM term does not seem to improve the fit significantly.
Activity coefJicients

The activity coefficients for dissolved silica can be defined as so/s, based on either molality or molarity (Robinson and Stokes, 1968; Marshall, 1980b). Thus the activity coefficients are related to the salt concentrations as follows: log y = Drn +
logy = Em (1)

DM

+ EM.

(5)

The logarithm of molal activity coefficients (log y) in NaCI, Na,SO,, MgC&, and MgSO, solutions are plotted against molality in Fig. 4 using the six parameters given in Table 7. It shows clearly in Fig.

4 that the dissolved silica acttvrty coeffictrnts tn aill four solutions increase with salt concentrations at 25C. The activity coefficients decrease with increabing temperature. For those in NaSO,, the values 01 log 7 become negative at temperatures higher iir:irl IOOC. It must be noted, however, that the calculated values of log y or log y are based on the soluhility of amorphous silica, which may be fully hydrated. Quartz might be expected to show different behavior and accordingly provide different values for acrivity coefficients as defined here. It was demonstrated (Marshall. IYXOb) that tog ,P plotted against molarity of added salt produced straight line relationships. However, this behavrot cannot be proved at high temperatures from the prcsent measurements due to the large scatter of the data. Furthermore, high temperature density dat:l were only available for NaCl and Na2S0, and the log ; values were calculated for these two salts only. The values obtained using the parameters given tn Table 8 for the three parameter equation are plotted m Fig. 5. The values for logy increase with increasing Nat ! concentration but decrease with increasing temper-

SILICA

SOLUBILITIES

IV
I - H,O __ / ./ /ffl I / / I C

283

I k7) i_
_

I A IN

( NaCl-

I Hz0

O.05 (6)

I IN No,SO, 1 __^

I 300 ,275

STD.

DEV.

IN NoNO,o A

<

H,O
c

PRESENT VALUES PAST VALUES

0.04

t
0 \ 2 3 (NaCI II _ I( I ( 4 OR NaNO# II 5 6 7 8

iI

II

I
- Hz0

I 0 I 0 I t I 2

(c)

25

IN MgCI,

I 3

I 4

NazSO,/m I 0.02 0.02 I I I I IN MgS04I Hz0

OO!

n -0

4 Mg$/m

0
in aqueous

2 MgSQ,/m

FIG. 3. The modal solubility solutions, 25-300C.

of amorphous

silica

NaCI,

Na2S0,,

MgC1>. and

MgSO,

ature. That is, the extent of salting out decreases when the temperature of the solution is raised. In NaSO, solutions, however, silica is salted out at lower temperatures but salted in at higher temperatures.

Table 4. The mold solubility of amorphous sihca in aqueous MgCIl solutions at various &mperatures
Added Sal1 cm) _~. 1 .oO

100C
2351; 235 951 190 I I 0.003h4 0 00247 II 00039 0.00041 0.50 1 00 I (10 I so I 50 0 00x43 0.007 0 004: 000412 0 0032h 0 002 I x 0 00 I32 0 00 I I 7 0.000x 0 000x9 I 1 .oo I 00 I .oo 2 OS 2 05 2 05 5 I 5 I 11.0141 0.0 I24 0 0 I3 1 0 0107 0.00940 0.0095h 0.009hY 0.0072 0 004.37 I 0 5 I 0 I 0 I 5 1.5 2 05 2.05 ?.Xh 5 ( 0 027h 0.024Y O.OZh I I).O??Y 0 020 I 0 0201 tt 0177 0 0194 0 00744 IO 2.W 6 0

Heats of solution
The logarithms of amorphous silica molal solubilities in NaCl, Na2S04, MgC12, and MgS04 solutions at selected molalities, calculated from Eqn. (I), with the six parameters, are plotted against l/(T/K) in Fig. 6. The solubilities in a solution of constant salt molality increase with increasing temperature in all four salts. The plots for NaCl, MgC!&, and MgS04 solutions show that the solubility is lower at higher salt concentration and that the effect of salt concentration becomes smaller at higher temperatures. Conversely, Na,SO, enhances amorphous silica solubility, particularly at the higher temperatures. The salt effect for Na2S04 accordingly becomes larger instead of smaller at high temperatures. The approximate values for the molal heat of solution of amorphous silica to form saturated solutions (AH) in NaCI, Na2S04, MgC12, and MgSOs solutions can be calculated from the vant Hoff equation (Robinson and Stokes, 1968) a In s/d(l/T)

2.05 3 32 5.64

15ooc 0.50 I 00 I .50 2 05 2.75 3.35 3 .m 5 h4 5.15 7 0 20 0 I 725 s* 20 0 I 72 5 s 20 0 I I3 5 11 20.0 535 175s 200C 0 50 1.00 I 00 I-50 I 50 1.50 2k5 IX5 45 45 265 24.0 lh5 2h5 x5 430 \I I I I 1 s II l I I I I

95 5 I

2.05 2.60 3.X0 4.60 4.60 5 75

24 0 1 24 0 (1

0.00335
0 0032x 0 001x4

= -AH/R

(6)

284

C.-T. A. CHEN

AND

W. L. MARSHALL

-A- STD.

DEV.

A-?+

STD. DEV .. %

FIG. 4. Log y for solubility of amorphous solutions vs. salt molaiity at 25 to 300C.

silica

in aqueous

NaCI,

Na,SO,,

MgCI:, and MgSO,

calculated

where R is the gas constant. Average values of Ul from Eqn. (6) over the range ol 100 tcj 300C are plotted against salt concentration rn Fig. 7. The values all fall within the range of 2.X to 3.6 kcal mol.-. It should be noted that Eqn. (6) is strictly valid only at constant pressure whereas our solubility data were obtained at the vapor pressure of the salt solutions. Because of this discrepancy and because of the scatter of the data, LIH values plotted in Fig. 7 should be considered as approximate at bebt.
CONCLUSIONS

v
Z> /n x 2 j h

>

.i>T,/

5;~ i.--~_~~

rbl INNO,S~~, *^ //;;;__11_1

,y
___ li.

-- _--__

---___.

,
. ..

N $ _,,<,

_.._

:-.F ,

l...
\ 1 T 573 !?bV %. \~,

_
. i

Solubilities of amorphous silica were measured in aqueous NaCl, Na2S04, MgC&, and MgS04 solutions over the range of 100 to 300C at various salt molalities. The results substantiate the earlier prediction of Marshall (1980a) and Marshall and Warm akomski (1980) that the solubilities in NaNO., solutions would closely resemble those in NaCl solukms.
__.._._..-__._. _... _.--..

J 02 ~---I L

-~~ ,
hocSSa **

1.

Logy for solubility of amorphous silica in qucoua NaCl(a) and NazSOd(b) solutions vs. salt concentration imolarity) at 25 to 3OOC.
5.

-___ I-IG.

SILICA SOLUBILITIES
Table 5. The molal solubility of amorphous silica in aqueous MgSOl solutions at various temperatures
Added Salt cm) 1 ime lbr) 50: Solubilq (m) Added Salt (m) Time (hr) sio: Solubilit> (m)

IV

285

Table 6. The molal solubility of amorphous silica in aqueous NaNOp solutions for comparison with previous measurements (MARSHALL, 1980a)
Added NaNO, (m) 100 6.3 SiO: Solublllty (m)

IOOOC 0.06 0.64 I 00 I .20 1.31 I 92 2.21 3.61 70.0 70.0 h6.0 66.0 IX.0 9.5 9.5 95s 150C I75 53.5 95.5 17.5 535 95.5 17.5 s II II s I: I 5 0.009x4 0.00937 0 00939 0.0095x 0.0095x 0 00993 0.00872 0 OOXhO 0.0 I3 0013 I!* II ll U I; I: s* 0.00602 0.00560 0.00489 0.00433 0.00502 0.00463 0.00354 0 00372 0.06 0.1 I 0.11 0.1 1.00 I .20 I .39

150C (continued)
95.5 53.5 53.5 95.5 13.5 13.5 II U u II II u 0.00864 0.00859 0.00847 0.00x5x 0.00834 0 00864 0 00870

l(C)

I .39
I 57 1.92 2.27

95 5 u

150 200 250

300

6.3 6.3 2. I
4.7

0.0026 0.0049 0.0090

0.01 I9 0.0219

200C 24.0 24.0 24.0 24.0 U U I! I 0.015x 0.0153 0015X 00159

250C 5.0 5.0 I I 0 0205 0.0210 0.02

53 5 1

0 0 I3

5 0 If

II

The solubilities increase with increasing for all salt solutions of constant molality values decrease at constant temperature

temperature studied. The with higher

salt concentration in NaCl, MgC12, and MgS04 solutions. However, in Na2S04 solutions the salt decreases the solubility at lower temperatures but increases the solubility at higher temperatures. The average heats of solution for amorphous silica are calculated. In the next paper (Marshall and Chen, 1982), solubilities of amorphous silica in aqueous mixtures of the above salts will be presented to show agreement with values calculated by additivity behavior through the use of Eqn. (4) for each separate salt.

300

200

150

(00

25

300

200

(50

100

25

I
IN N&-H20

I
IN Na2S04Hz0

(0)

I[ I
STD. DEV. (4 4 %I

Cd)

IN MgS04-

Hz0

STD. DEV. (5.7%) STD DEV. (17 %I

15

2.0

2.5 [I/T/K)] x 103

3.0

3.5

f.5

2.0

2.5 [(/(T/K)] x 403

3.0

3.5

1/(T/K) at several constant

FIG. 6. Log s of amorphous silica molalities

in aqueous of salt.

NaCl,

Na,SO+

MgCI,, and MgSO, solutions

vs.

286

C.-T. A. CHEN AND W. L. MARSHALL Table 7. Parameters for eqn. (1) describing the effect of salt on the solubihty of amorphous silica (based on molality)

I Oa

104b _... ~~~

IO.
3.0504
---8 7442 X.6X03 - I!648 -6.3309 -16.324 29.828 78 i?(

102d

04e

1o7t

I .x754 0.31949 0.54372 0 7087 3.3566 4.462 I

7.510x -9.6086

--4.5052 4 6982 20x44 3 X692 -0.83X5

0
3 1961 0 -0.6 I449 0 -2 7712 0 35.959

-1.x951 0

I 2489
0 --0 4324 0 15.729

779x

-28.740 59.306

Table 8. Parameters for eqn. (3) describing the effect of salt on the solubility of amorphous silica (based on molarity)

104b

101

lO*d

104c

1r17t

I .660X I .4541 I 7876 I .42 19

-2.1527 14.4395 15 6444 17.194

0 2OXX 20.7965 -26.5615 --32.254

0 8.6272 0 I .6986

0 --4.6569 0 3.23X6

0 5.8764 0 h 5) 2rt

Acknowledgements-We wish to acknowledge the stimulating discussions with E. G. Bohlmann, R. H. Busey, F. W. Dickson, D. C. Hurd, R. E. Mesmer, and M. T. Naney. R. H. Busey and R. E. Mesmer prepared the standard silica solution and R. L. Sherman performed the xray diffraction analyses. C.-T. A. Chen acknowledges the leave granted by the School of Oceanography, Oregon State University. We also appreciate the excellent comments of the journal reviewers, D. A. Crerar and J. D. Rimstidt. Research sponsored by the Division of Engineering, Mathematical and Geosciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract W7405-eng-26 with Union Carbide Corporation and by Oak Ridge Associated Universities (ORAU) for DOE

REFERENCES
E 5

L_-

.i

~1..

i..__

..i_.__

FIG. 7. Average heat of solution (100-3OOC) of amorphous silica in aqueous NaCI, MgCI,, Na2S04, and MgSO+ solutions vs. salt molality.

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