Geochimica et Coemochimica Acta, 1973, Vol. 37, pp. 1255 to 1275.

Pergsmon
Press. Printed
inNorthern
Ireland

Au empirical Na-K-Ca geothepmomete~ for

natural waters
R. 0. FOURNIER and A. H. TRUESDELL
U.S. Geological Survey, i&n10 Park, California 94025, U.S.A.

Abstract-An empiricai method of estimating the last temperature of water-rock intem,ction

has been devised. It is based upon molar Xa, K, and Ca concentrations in natural waters from
temperature environments ranging from 4 to 34OC. The data for most geothermal waters
cluster near a straight line when plotted as the function log (P;a/K) + /3log [ 1/(C&)/Sal vs
reciprocal of absolute temperature, where /I is either 4 or $ depending upon whether the water
equilibrated above or below 100C. For most wsters tested, the method gives better results
than the N&/K methods suggested by other workers. The ratio Na/K should not be used to
estimate temperature if v(Mc,)/ilfNB is greater than 1. The Na/K values of such waters
generally yield calculated temperatures much higher than the actual temperature at which
water interacted with the rock.
A comparison of the composition of boiling hot-spring water with that obtained from a
neerby well (17OC) in Yeliowstone Park shows that continued u-sbter-rockreactions may occur
during ascent of water even though that ascent is so rapid that little or no heat is Iost to the
country rock, i.e. the water cools adiabatically. As a result of such continued reaction, waters
which dissolve additional Ca as they ascend from the taquifer to the surface will yield estimated
aquifer temperatures that tbretoo low. On the other hand, waters initially having enough Ca
to deposit calcium carbonate during ascent may yield estimated aquifer temperatures that are
too high if aqueous T\a,and K are prevented from further reaction with oountry rock owing to
armoring by calcite or silica, miner&.
The Na-K-Ca geothermometer is of particular interest to those prospecting for geothermal
energy. The method also mey be of use in interpreting compositions of fluid inclusions.

GEOTHE~~~~~TRY based upon water chemistry is of particular interest to those

involved with expIoration of sources of geothermal energy. Some of the more recent
papers devoted to the subject are by WHITE (1970), MAHON (1970), ELLIS (1970),
TONANI (1970), and FOURNIER and TRUESDELL (1970). Although many qualitative
temperature indicators have been suggested, until now only two chemical indicators
have been considered to be quantitati~~e. One is based upon the variation in solu-
bihty of quartz as a function of temperature (FOURNIER and ROWE, 1966; MANON,
1966), and the other is based upon the temperature dependence of base exchange or
partitioning of alkalies between solutions and solid phases.
Empirical curves showing the variation in natural waters of atomic Na/K
ratios vs tem~rature for temperatures below 300C have been presented in several
(WHITE, 1965, 1968, 1970; ELLIS and M&OX, 1967; ELLIS, 1969, 1970;
MEROADO, in press ; and FOURNIER and TRUESDELL, 1970). WHITE (1965) and ELLIS
(1970) both postulated that above approximately 175 to 2OOC the Na/K ratios in
most natural waters are controlled by equilibrium with albite and K-feldspar.
Over recent years, increasing evidence indicated that waters rich in Ca, such as

* Publication authorized by the Director, U.S. Geological Survey.

1266
10
1356 R. 0. FOURNIERand A. H. TRUESDELL

Mammoth Hot Springs in Yellowstone Park and the Salton Sea geothermal brines,
did not yield reasonable Na/K temperatures and that Ca content should somehow
be considered.
(In this section and those that follow, superscripts showing the ionic charge of
aqueous species, e.g. Naf, K+, Ca2+, are not shown where we are dealing with the
sum of ionic and complexed species in solution.)

Na/K GEOTHERRIOMETER
The reaction
K+ + Na-feldspar = K-feldspar + Na+, (1)
was investigated experimentally by ORVILLE (1963). HEMLEY (1967) also investi-
gated reaction (1) in the presence of muscovite and quartz. The equilibrium con-
stant, Ke,for that reaction is
K = [K-feldspar][Na+]
(2)
6 [Na-feldspar][K+]
where the square brackets denote activities of inscribed species. The variation of
the equilibrium constant as a function of temperature is given by the van% Hoff
equation,
d log K, AHO
(3)
d (l/T) = -2X%

where T is absolute temperature and AH,,, is the standard heat of reaction at given
temperature. Equation (3) allows AH(r) to be determined graphically by a plot of
log K',values, derived from experimental studies, vs 1/T. Of great importance to
this paper is the fact that the AH(r) of reaction (1) varies only slightly with tem-
perature. Because of this, a plot of log K, vs l/T yields a line with small curvature
that can be interpolated and extrapolated with more confidence than a simple K,
vs temperature plot. Once such a curve were established it would be advantageous
to use it to determine an unknown temperature of equilibration from a given value
of K,. However, it is not always possible to evaluate K, rigorously owing to un-
certainties about both the purity of the solid reactants and the activity coefficients
of the aqueous species. When the equilibration temperature is unknown, it is
impossible to evaluate K, rigorously. For practical purposes we are forced to assume
pure solid phases (unit activity by convention) and that activity coefficients for Na
and K cancel each other so that K B a molar Na/K. Unfortunately, activity coeffi-
cients for Na and K may differ widely in high temperature aqueous solutions. Even
so, when measured molal concentrations of Na and K for water-mineral reactions
are plotted as log (Na/K) vs l/T, approximately straight lines result. The empirical
curves based on natural water compositions and experimental points for the
sanjdine-high-albite series are shown as such a plot in Fig. 1. Also shown for com-
parison is the theoretical variation in K, for equation (l), derived from low-tem-
perature thermochemical data of ROBIE and WALDBAUM (1968) for microcline plus
low-albite and calculated as suggested by HEL~ESON (1969), making use of average
heat capacities (CRISS and COBBLE, 1964) for the aqueous ions computed from
absolute entropies.
 ~~~ra~~~~i~~ either of the ~~~~~~ ~~963~or ETEXLEY ~~9~~~ex~rimental data
to lower temperatures yields curves in the 100 to 300C interval with significantly
greater Ha/W:values than the ~o~~~nding theo~t~~al and empirical curves shown
in Pig. 1, CMcuIations based upon molar volumes of microline and low-albite and
partial molar volumes of aqueous NaCl and IiCI as functions of temperature and
pressure (ELLIS and MCFADDEK,1972) show that onIy a small part of this dis-
crepancy may be due to the higher pressures at which the experimental work was
perfurmed: 2000 bars for Orviflos work arzd fOOObars for Hemleys work, com-
pared to hydrostatic pressure in s column of water everywhere at its boiling point
for the theoretical curve, ~toi~hiometri~ a~t~vity-~e~~ien~s ap~ro~r~a~ to the
experimental conditions were not known. Their omission may be the main cause
for the discrepancy.
ha/K ratios of waters from geothermal bores and cold-water wells and springs
listed in Table 1 are plotted in z;ig.2. Generally, thy maximum measured in-hole
temperature is plotted. Unfortunately, the maximum measured temperature in a
drilled hole is not always the tempera,ture of the aquifer in which a given sample of
water equilibrates. W&er may enter a drilled hole through permeable channels
from a still hotter region at depth, or the aquifer may be at a Iolver temperatnre.
In the worst exampIe for chemical interpretations the water sample may be a mixture
of waters from two di%rent a*quifersat different temperatures.
Ae~ording to EXLIS (f9?0), the silica method ~&LEON,1966; ~~~~~~~~ and
ROWE, 1966) of estimating temperature of underground hot water supplying a
discharging well may be better than ~~ys~ca~ measurements in the same well.
Where measured in-hole temperatures a.re not reported or are suspect, aquifer tem-
~era~ures have been estimated from the silica content of the water, silica-estimated
tempernturcs are not used exclusively in this report because some of the silica data
 1258 R. 0. FOURWER and A. H. TRUESDELL

Table 1. Chemical data for waters from known temperature environments. * Molal concentrations are given
for Na, K, and Ca

log (r;a,K) f
1035 j3 log I:t/(w/Nal
-
Ref. Ns, Ii C& tm,+ tat T )q=Gi /q=f7)q=f**
- -
CzocHosLovalcr.i~t
201 Marklin 1 1 0~000238 0000064 OO00449 3 3.62 0.73 3.17
202 Loket 2 1 0000457 ~000102 0.00166 3 3.62 0.65 3.23
205 Lokct 5 1 0000326 0000115 UG00641 4 361 0.45 297
203 V. Kamen 3 1 0~000109 0000051 0~000254 2 3.64 0.33 3.24
204 V. Kamen 4 1 0~000100 0000051 0~000210 3 3.62 0.29 3.17
206 Udoli G 1 0~00039I G~oooos9 0~00120 8 3,56 0.64 3.24
208 Marianska 8 I 0~000130 ~ooaaz6 a.00~00 8 3.56 0.71 3.42
209 Krasovice 9 1 0.000196 0,000128 0,000524 10 3.53 0.19 2.94
210 Lochousice 10 1 0~000435 0~000089 0~00190 10 3.53 0.69 3.35
EL SALVADOR
13 Ahuac~i~pan 8 2 0.210 0.0223 0,00851 228 218 2.00 0.97 0.86
ICELAND
17 Akranes 3 0.0591 0~000435 0,014o 110 109 2.62 2.13 2.23 2.54
IS &beer I 4 0.00297 0~000036 0~000047 100 2.68 1.92 2.41
20 Braiitarholt 1 4 o.ao64~ 0.0~~~2 0.000439 72 2.89 1.90 2.58
21 FXioaar G23 3 0.00298 0~000090 0~000111 102 2.67 1.62 1.71 2.25
22 Fludir 4 4 0~00324 0.000069 0.0000 18 135 2.45 1*61 1.71 1.82
25 He@1 G3 3 0~00809 0.000468 OXIOOO4O 220 212 2.03 1.24 1.20
26 H~Ilisholt I 4 0~00301 ~0~~49 0~0000~~~ 137 2.53 I.79 1.96 244
27 Hlemmiskoid I 4 0.00673 0.000095 0.000369 63 2.98 1.83 2,46
28 Husatottir 3 4 0.00604 0~000133 0.000254 i0 2.91 1.66 2.22
29 Husavik 3 0.0433 0~000803 0.00629 94 2.72 1.78 2.06
31 Hvergcrdi 03 5 0~00923 0.000691 0~000037 216 2.05 1.13 1.06
32 La&and 1 0.00309 O~OOOG2 1 0*000158 47 3.12 2.15 2.99
33 Laugarnas c;4 3 0.00270 0~000059 0~000047 136 2.44 1.66 1.80 2.20
34 Loira 0.00852 ~000107 0.00135 74 2.88 1.90 2.75
36 Namafjall 3 6 0.00578 0000716 0~000027 265 270 I.65 0.91 0.W
37 Reykir I Oa?4 18 G.0~~59 G.GO~G6 69 2.92 1.55 2.57
39 Reykjanes 3 0.518 0.0435 0.0508 225 200 2.01 1.08 0.5G
40 Iloykjanes 2 6 0.495 0.0411 0.0478 190 226 2.16 I.08 0.96
41 Keykjancs 8 6 0.36: 0.0322 0.0413 253 247 1.90 la06 0.97
42 Rcykjsvik 0~00413 O.GO~33 0~000013 155 2.52 2*03 2.01
43 Selfoss 7 4 0.00722 0~000123 0~000706 84 75 2.80 I.77 1.96 2.53
44 SPlfOss 8 4 0~00:4s 0~000130 0~000783 79 85 2.t4 1.76 1.95 2.52
45 Srltjarnarnes S-1 1 3 0.00946 0~000151 0~00151 83 79 2.81 I.$0 2.00 2.61
46 Spoestadir 1 4 ct.00343 0~000051 0~000106 74 7s 2.8s I,S3 I.98 243
JAPAN
61 Hatchobaru 1 8 0.0607 0.00739 0.000247 293 291 1.57 0.91 0*72
64 Otake 7 8 0.0368 0.30269 0~000247 216 2.05 1.14 0.99
66 otdie 8 8 0.0350 O-00276 0~000494 227 2.00 1.10 1.04
66 Otake 9 8 0.0407 0.00335 0-000307 246 193 1,09 0.96
57 Otako 10 0.0477 0.003F6 0~000502 241 l%J 1.12 1.01
Mlwco
05 Mexicsli 5 9 0,253 0.8402 0.00699 340 1.63 0,:9 0.63
66 Mesicali 8 10 0.487 0.0855 0~0180 355 1Y59 0.75 O-56
Nnw ZEAI.:WD
69 Broadlands 1 11 0.0463 0*00389 0~000115 275 234 1.82 I.08 0.86
11 0.0457 0.00537 0~000055 260 264 1% 0.93 @67
@C457 O~OOBi3 G.00~55 255 264 1.75 0.90 G+i
72 Brosdlands 3 11 0.0454 0.00454 0~000125 280 259 1.81 0.92 0.7%
73 Broadlands 4 11 0.0467 0.00558 0.0(10076 270 273 I.64 0.92 0.68
74 Broadlands 9 11 0.0404 0.00319 0~000050 292 264 1.77 0.89 0.64
75 RroadlaxIds 10 11 G+l396 0.00366 0.~00027 2SO 243 I-80 1.03 0.74
76 Broadlands 11 11 G.0443 GaxiGO @O#OlH2 271 264 l.S4 0*90 @7%
77 Broadlands 13 11 0.0426 0~00611 0~000060 258 259 I.88 0.92 0.68
79 Kawrlzu 4 12 O.Olh7 0~00143 0~000180 200 183 2.11 I.12 1.07
80 Ra\r-rrau 7A 12 O.Oli4 0~00141 0~000102 ZOO 179 2.11 I a9 1.01
81 Kawrau 7h 12 0.0398 0@0389 @~000087 2% 260 I.81 I.01 *a1
83 Kaw~rau 712 13 O~0324 WrlRl ii 0+nYlfi.i 262 I.88 1.01 0.79
 An empirical Na-K-G geothermometer for natural waters

Teble I-(Co:onkZ.)

Ref. Ns K Cn. tmt a

83 Kawereu 8 6 O-0362 270 261 1.84 0.98 0.64

84 Kawerctu 8 12 0.0384 285 257 1.79 0.98 @70
86 Kawersu 8 13 0.0322 0.000027 266 1.86 0.99 0.72
86 Kawerau 10 12 0.0310 0~000050 250 221 1.91 1,17 0. Y6
87 Kawerau 17 13 0.0299 0-000050 259 l-88 0.99 0.79
88 Neawha, 1 5 0.0413 0.000699 230 221 1.99 1.31 1.24
89 N;awhs 1 13 oa391 0.000723 223 2.02 1.29 1.24
91 Orakeikorako 2 14 0.0239 0~000013 260 223 Ie-GY 1.24 0%
92 Orakeikomko 3 13 0.0110 0~00103 0~000025 234 232 1% 103 O.Y2
94 Rotokaua 2 S 0.0663 0~00450 0.00125 220 217 2.03 1.17 0.94
100 Taupe 1 13 0.0554 0~00570 0~000349 256 1.89 0.99 O-83
105 Waiotapu 6 15 0.0272 0.00225 0.000225 199 2.12 1.08 0.99
106 Waiotapu 6 13 oa374 0.00396 0~000250 275 247 1.82 0.97 0.85
109 Wairakei 4/l 13 0~0%~ 0,004Ql 0~000574 220 231 2.03 1,06 0.94
110 Wairakoi 9 16 0.0517 0~00192 0.000873 192 2.13 1,43 1.35
111 Wairakoi 9 17 0.0502 0.00192 0~000823 193 2.15 1.42 1.34
112 Wairskei 20 13 0.0565 0.00523 0~000449 243 1.94 1.00 O-86
113 Wairakci 21 16 0.0487 0.00320 0~000549 197 2.13 1.18 1.12
114 Wairakei 27 18 0.0522 0.00512 0.000437 260 245 1.91 1.01 0.88
115 Wairakei 28 18 0.0522 0,00512 0~000499 253 248 1.90 1.01 0.89
116 Wairakei 41 18 0~0611 0.00440 0.0~~99 214 231 2% 1.06 @96
I.17 Waxakei 43 1S 0.0511 0.00334 O-000674 231 221 1.98 1.12 I.03
118 Wairakoi 44 5 0.0574 0.00575 0.000425 260 245 1.88 1.00 0.65
1 IQ Wairskoi 48 a 0.0522 0~00511 0.000437 245 1.93 1.01 0.88
OCEAN 19 0.453 0.00972 0~0100 4 3.61 I.67 1.45
TCBKEY
120 Kizildern KDl 20 0~0600 0.00425 0~000060 200 175 2.11 1.15 0.86
UNlTED STATeES
134 Beowawa 2 21 0.0101 0.000767 0~000020 236 231 1% I-12 1.00
137 Bradvs 2 21 0.0339 0.00166 0.00132 181 2.20 l-31 I.32
139 Casabiablo 3 21 0.0174 0-000921 175 185 2.23 1.28 1.13
2 I1 Center County Ps. 12 22 0~000044 0.000023 10 3.53 0.28 4.11
212 Center county Pa. 16 22 0~00107 11 3.52 0.23 4306
2 13centerCountyPa. 40 22 0.0~998 10 3.53 0.16 3.70
214 center county Pa. 66 22 0.00137 11 3.52 0.37 3*76
215 Center county Pa. 75 22 0.00230 10 3.53 0.71 3.76
2 16centercounty Pe. 88 22 0~00157 9 3.54 0.27 4.1 t
217 Center County Pa. 91 22 0~000565 0~000161 0.00230 11 3.52 0.55 3.11
218 Contar county Pa. 179 22 0~000143 0~000281 0~00140 11 3.52 0.71 3.93
2 19 Kettleman Hills 72
220 Kettleman Hills 12
23
23
0.5i4
0,465
0.00226
0.00427
0.0199
0~0250
wt
99
83
118
2.18@
2.56
2.41
2.04
2.20
1.88
221 Kettlom~n Hills 73 23 0.600 0.00381 0.0424 97 105 2&?J Z-20 2.04
222 Kett.leman Hills 48 23 0.283 0~00250 0.0174 100 114 2.58 Z-05 1.94
223 Kettleman Hills 74 23 0.343 0.00239 0.0247 102 112 2.60 2.16 2.05
224 Kettlem:m Hills 13 23 0.273 0~00281 0~106 109 125 2.51 1.99 2.01
225 Kottlemtura Hills 21 23 0.244 0.00192 0.0377 101 121 2.54 2.10 1.91
226 Ksttlamsn Hills 31 23 0.333 0-00299 0,111 101 116 2.57 2.05 2.05
227 Kettleman Hills 32 23 0.271 O-00203 0.0444 101 119 2.55 2.12 2.09
228 Kettleman Hills 102 23 0.308 0.00264 0~0509 100 115 2.58 2.08 2.04
229 Kettleman Hills 84 23 0.565 0.00389 0.0521 9s 110 2.61 2.16 2.03
230 K&tleman Hills I 23 0.170 0.00241 0~00254 135 143 2.40 1.85 1.67
231 Kettlemarl Hills 2 23 0.163 0~00241 0.000766 136 150 2.36 1.83 1.57
232 Kettleman Hills 5 23 0.134 0~00192 0.000766 136 134 2,46 1.85 1.52
144 Salton Sea I.I.D. 1 24 2.19 0.448 0699 340 1.63 0,69 @65
145 Saltcn SOS I.T.D. 2 26 2.31 0,422 0.719 300 I.75 O.iP 0.59
146 Seltun Sea I.I.D. 3 24 0.461 0.0320 O-0280 190 2.16 1.16 1,01
150 Stsambnst Spgs. 1 26 O-0290 0~00161 o.oooj74 186 175 2.18 1.26 1.20
151 Steemborzt. Spgs. 2 21 0.0332 0~00192 0~000167 203 2.11 I.24 I.10
165 Yello;vstono Park Y3 27 0.0129 0~000358 0~000042 178 2.23 1.56 1.45
166 Yellorvstone Park 1-4 27 0.0133 0~000460 0~0000~7 196 2.13 I.46 I.41
167 Yellowatonc Park 15 21 0.0141 0~000384 0.0110072 1O 2.26 1.56 1.49
 1260 R. 0. FOURNIER and A. H. TRUESDELL

Table I-(Co&.)

log (Na/K) +
1oq /9log [dWa)/Nal
Ref. Na K Ca tmt t*S r ,f?=oi/ /3=+ap= ;**

168 Yellowstone Park Y6 27 0.0148 0.000563 0.000250 181 2.20 1.42 1.43
169 Yellowstone Park Y8 27 0.0164 0.000563 0.000147 170 2.26 1.47 1.42
170 Yellowstone Park Y9 27 0.0117 0~000409 0~000020 196 2.13 1.45 1.32
171 Yellowstone Park Y 10 27 0~00700 0.00176 0.0112 72 2.89 0.60 2.17
172 Yollowstone Park Y13 27 0.0130 O.OOOi16 0.000037 195 2.14 1.26 1.15
U.&S .R.
177 Pauzhetsk 4 28 0.0429 0.00269 0~00130 195 194 2.14 1.20 1.18
182 Kamchatka 35 28 0.0141 0.000639 0.000574 174 2.24 1.34 1.42
WEST PAKISTAN
184 Shadman 27 29 0.00152 0~000128 0~00105 28 3.32 1.08 2.85
FLUID INC~~USIONS
Providencia 62-S-146 30 0.513 0.123 0.0624 ;;, II 1.66 0.62 0.62
Providencia 62-S-145 30 0.970 0.261 0.250 1.66 0.57 0.47
Provide&a 60-H-67 30 0.296 0.0639 0.170 358 1.58 0.66 0.71
Providencia 60-H-67 30 0335 0.0767 0.0749 358 1.58 0.64 0.61
Providencia 60-H-57 30 0935 0.212 0.302 365 1.57 0.64 0.57
Providencia 60-H-57 30 0.861 0.174 0.594 365 1.57 0.69 0.68
Providoncia 60-H-57 30 0.948 0.230 0.384 365 1.57 0.61 0.55
Providencia 63-R-22 30 0.352 0.0742 0.105 365 1.57 0.68 0.66
Providencia 63-R-22 30 0.365 0.0870 0.130 365 1.51 0.62 0.62
Providencia 62-S-320 30 2.77 1.19 1.43 365 1.57 0.37 0.24
Providencia 63-R-39 30 0.948 @179 0.217 290 1.78 0.72 0.62
Providencia 63-R-39 30 3.48 1.29 2.24 372 1.55 0.43 0.31

* The tabulated waters are from wells, except for the fluid inclusion waters from Providencia, Mexico.
t t, is generally the maximum measured temperature in a given well. Where a reservoir temperature is known to be different
than the maximum temperature, the reservoir temperature is given.
2 t, is temperature of last water-rock equilibration estimated from the silica content of the water.
9 Reciprocal of absolute temperature. If different t, and t, values are listed, the reciprocal oft, is given.
11Tabulated values for log (Na/K).
7 Tabulated values for log (Na/K) + j log[l/(Ca)/Na] are given only where they are less than 2.3 01 where d(Ca)/Na is
less than one.
** Tabulated values for log (Na/K) + $ log [d(Ca)/Na] are given only where they are greater than 2.0 and 2/(Ca)/Na is
greater than one.
tt The waters listed from Czechoslovakia are from wells in granitic rock. These are typical of spring waters in granitic rocks
found elsewhere, e.g. the Sierra Nevada of California described by FETH et al. (1964).
$$ Temperatures of the Kettleman Hills waters estimated from the geothermal gradient and depth of the producing zone.
@ The reciprocal of silica temperature is listed for the Kettleman Hills waters. We believe that thie is a more reliable tem-
perature than the geothermal gradient estimate.
(j11The average filling temperature is given for the fluid inclusion data.
1. PACES (1972). 16. SARBUTT(1964).
2. SI~VALDSONand CUELIAR (1970). 17. MARON (1967).
3. ARNASONand TO~IAS&N (in press). 18. MAHON (1966).
4. ARN&SSON (1970). 19. RANKAMAand SAEAMA (1950).
6. EIJ.IS (1969). 20. DO~MINCO and SAMILGIL(1970).
6. BJ +NSSON et a~?. (1970). 21. D. E. White (unpublished data).
7. ELLIS (1967). 22. LANQMUIR(1971).
8. KOGA (in press). 23. KHARAKA (1971).
9. ELLIS (1970). 24. MUIPFLER and WHITE (1969).
10. MERCADO(1967). 25. WHITE (1968).
11. BROWNE and ELLIS (1970). 26. WHITE (1964).
12. bfAHON (1962). 27. R. 0. Four&r and R. D. Barnes (unpublished data.
13. MAHON (in press). 28. VARIN et cd. (in press).
14. ELLIS (1966). 29. BARNES and CLARXE (1969).
15. i+hHON (1964). 30. RYE and HABBTY (1969).
 ,4n empirical Na-K-Ca geothermometer for natural waters 1261

a Geoiherm. grad. temp; ailfield water

A Silica temp; oil field water

z ~.~~t!pt,,p \ICo/Na -=I

. I
D Measured tBmR; G/Na z 1
f Fluid inclusion filling temp.
0 HEMLEY(1967)
D ~vrue(l963)

0
t
400 300 203 loo 50 25 0
II IiII / I I I
L 1 1 , i / 1
1.4 I.6 22 2-6 3.0 3.4
lO3/T
Fig. 2. Na/K values for natural waters vs assumed equilibration temperature.
The lower dashed line combines the empirical curves of ELLIS (1970) and WHITE
(1965, curve E). See text for details.

in Table I may not be reliable owing to variations both in analytical technique and
in sample storage and treatment procedures prior to analysis. Also, the method
and conditions of sample collection are not always specified, so that one must guess
about possible evaporative concentration of the sample owing to steam loss. A
correction for steam loss would be necessary in order to use silica to estimate under-
ground temperature. Evaporative concentrations do not affect Na/K ratios.
In Pig. 2, a line extrapolated from HEBILEYS (1967) experimental results sets
an upper limit for the Na/K data points of the natural waters. Above 200C most
points cluster close to the empirical curves of ELLIS (1970) and WHITE (1965), but
below 200C there is much more scatter. This might be attributed to disequi-
librium states of the low-temperature waters, including ocean water. However,
most Na/K values for water from oil wells at the Kettleman Hills (California) and
from drill holes in Yellowstone Park plot significantly above the empirical curve.
The Yellowstone Park waters issue from potassium-rich rocks, and it is unlikely that
the high Na/K values result entirely from disequilibrium. Some waters at higher
temperatures from other places also have relatively high Na/K values, such as No.
88 from Ngawha, New Zealand (23OC), and No. 91 from Orakeikorako, New Zealand
(260C). If one were using the empirical curves and the compositions of these New
Zealand waters to estimate subsurface temperature, the estimates would be too
low by approximately 65 and 7OC, respectively.
Sample 171 from Mammoth Hot Springs, Yellowstone Park, is particularly
noteworthy. In terms of total dissolved solids, it is the most concentrated water in
1262 R. 0. FOURNIERand A. H. TRUESDELL

the Park. The water is very rich in calcium, it deposits travertine, and has a very
low Na/K ratio. The subsurface temperature estimated from the Na/K ratio in
that water would be in excess of 400C. The temperature found by drilling leveled
off at 72OC, which is compatible both with the low silica content and high calcium
content of the water, as will be discussed later.
It is evident that a geothermometer based on the simple Na/K ratio in natural
waters must be used with extreme caution. It should be used only for waters
showing other evidences for a high temperature source, e.g. high SiO,, low Ca, etc.
Very high estimated subsurface temperatures may be obtained for waters from
low- to moderate-temperature environments. Conversely, using the empirical
curve of ELLIS (1970) and WHITE (1966), Na/K ratios of some waters may indicate
temperatures as much as 60 to 70C too low.

EFFECT OF OTHER REACTIONS

One of the main reasons for the scatter of points in Fig. 2 is that at any given
temperature the Na/K ratio depends upon the specific reaction taking place
(FOURNIER and TRUESDELL, 1970). For example, HEMLEY (1967) showed that at
the same temperature the Na/K ratios are different in solutions equilibrated with
K-feldspar and albite compared to muscovite and albite. A whole spectrum of
Na/K vs temperature curves is possible, depending upon which minerals control
solution composition.
Other cations also may have an effect upon the Na/K ratio. For instance, for a
reaction in which plagioclase alters to K-feldspar with the liberation of Na+ and
Ca2+,
Kf + Na,Ca, plagioclase + 4y quartz = K-feldspar + zNa+ + yCa2+, (4)
neglecting activity coefficients, an approximate equilibrium constant, K*, is

Nao-%)Cau
K*= K . (5)

In most natural systems the amount of Ca in solution is controlled by the solu-

bility of a calcium-bearing carbonate (generally calcite) at given conditions of tem-
perature, pH, and partial pressure of CO,. On the other hand, except for the alkali
lake environment, the amounts of aqueous Na and K are not controlled by the
solution and deposition of alkali-bearing carbonates. With this in mind it is inter-
esting to observe the distinct temperature-dependent trend obtained when log
[1/(Ca)/K] is plotted vs 103/T, as shown in Fig. 3. Except for ocean water, even
the low temperature waters follow this trend. Similarly, in Fig. 4 a plot of log
[+(Ca)/Na] vs 103/T shows a linear trend, but with more scatter of the data points.
These linear temperature-dependent trends throughout the entire temperature range
are contrary to the result shown in Fig. 2, where log (Na/K) values for low tempera-
ture waters depart drastically from the trend defined by the high-temperature data.
We interpret these results as follows: although absolute quantities of aqueous
Ca generally are controlled by the solubility of carbonate, Ca also enters into silicate
reactions in competition with K and Na. Therefore, the amounts of aqueous Na
and K are influenced by the aqueous Ca concentration. In general, natural waters
 An empirical Na-K-Ca geothermometer for natural waters 1263

0 Measured temp.
30
). Sllico tsmp. 0

*Geothermal gradient temp.,

20
OSilica temp; oil well Hz0
+ Fluid- inclusion temp.

5 IO

oc
I.6M)
III
1.0
400

1 Irii
I.4
r
300

16
l
200
1
2.2
I
i
2.6
1
100
I
8 I
/
30
50
I
/
25
I
34
1 I
0
1

103/T
Fig, 3. Log [1/(&)/K] vs reciprocal of absolute temperature for naturrtl waters.

3of-
Eb

o Measured temperature
0
A Silica temperature

2.0 - 0 Geothermal gradient temperature; oil well $0 k

OSilica temperature; oil well I+,0
2 i-Fluid-inclusion filling temperofure 0
0
@ ,.,1

0-

oocean

-lo 600 4 2 0

I I I I I I I
IO 14 18 22 28 30 34 36

to3/ T
Fig. 4. Log [ACNE] vs reciproaal of absolute ~0rnper~t~~ for natural waters.

contain much less K than Na. Therefore, for a given amount of reaction in response
to a change in Ca concentration, a change in aqueous K will be more evident than a
change in Na concentration, i.e. aqueous K tends to change so as to ahow any given
ratio of aqueous Ca to Na to satisfy an equilibrium expression such as equation (5).
Thus, aa expected, the correlation of K with Ca shown in Fig. 3 is better than the
correlation of Na with Ca shown in Fig. 4. However, in the low-temperature waters
shown in Fig. 4 the absolute Na concentrations are. so low that changes in Na are
evident in response to changes in Ca concentrations.
In view of the above considerations, we believe that aqueous Na-K-Ca relation-
ships generally can be explained entirely in terms of silicate reactions even though
1264 R. 0. FOURNIER and A. H. TRUESDELL

the absolute quantity of aqueous Ca is controlled by the solubility of carbonate.

Many different reactions may occur involving only aqueous Na+, K+, and Ca2+, but
all are limited to three configurations:

(x + 2y)K+ + solid = xNa+ + yCa2+ + solid (6)

(2~ - x)K+ + xNa+ + solid = yCa2+ + solid (7)
(z - 2y)K+ + yCa2+ + solid = xNa+ + solid. (9)
To facilitate comparison, equations (6), (7) and (8) can be written in terms of a
single potassium ion participating in the net reaction so that the approximate
equilibrium constant, K*, for all possible reactions can be transposed to a generalized
form,
2/G
logK* =logg+/3log=,

in which the value of p depends upon the stoichiometry of the reaction.

In formulating equation (9), the following assumptions were made : (1) excess
silica is present. In general, this is a valid assumption because quartz, chalcedony,
or cristobalite is commonly present in hydrothermally altered rocks. (2) Aluminum
is conserved in the solid phases. In actuality, this is not true because the aluminum
content of a given volume of rock commonly changes in the course of hydrothermal
alteration. However, except in rare acid waters, so little aqueous aluminum is
present compared to other cations that it can be neglected. (3) The formation of a
hydroxyl-bearing mineral on one side of an equation is balanced by the decomposition
of a hydroxyl-bearing mineral on the other side, i.e. hydrogen ions involved in
hydrolysis cancel out of the net equation. This assumption may not be valid every-
where. From a practical point of view, however, the incorporation of hydrogen ion
into an expression used for estimating subsurface temperature must be avoided.
The pH of a water ascending from a hot environment to a cooler environment
generally will change owing to continued reaction with wall-rocks, to loss of gases
such as CO, as the water boils, and to the change with temperature of dissociation
constants for various hydrogen-bearing species such as H&3,. In order to correct
for these effects, subsurface temperature and CO, partial pressure must be known.
For reactions (6) and (7), b = 2y, and for reaction (8), B = -2~. For the alkali
feldspar reaction shown in equation (l), or any reaction involving only Na- and K-
bearing minerals, j3 = 0 and equation (9) simplifies to log K* = log (Na/K). For
reactions involving only Ca- and K-bearing minerals, /3 = 1 and equation (9)
simplifies to log K* = log [2/(Ca)/K]. For any reaction in the configuration of
equation (6) in which one unit of K+ is fixed in the solid and appropriate amounts
of Na+ and Ca2+ are released, such as in equation (4), the value of /? is between 0 and
1. For reactions in the configuration of equation (7), p is greater than 1, and for
reactions in the configuration of equation (S), p is a negative number.
Figure 5 shows the distribution of data points for well waters plotted in terms of
log (Na/K) + B log [d(Ca)/Na] for p = 0, (K,, exchanged for Na,,), compared to
b = 2, (K,, + Ca,, exchanged for 3NaJ. Above lOLC, the points are more scattered
using fi = 2 than using p = 0, and the reverse is true below 100C. We reasoned
 An empirical Na-K-Ca geothermometer for natural waters 1265

olog(Na/K). p=O
t
rlog(Na/K)+2log(~/No)
5

f4

0 i .
A
No.171, p=2
3

Z-

No. 66 0

1
I I I I I I I t
IO I .4 I.8 22 2.6 3.0 3-4

103/T

Fig. 5. Distribution of data points for well waters using ,L?= 0 compare to p = 2,
plotted vs the reciprocal of absolute temperature.

that at some intermediate value of p between 0 and 2, the log K* values calculated
for most waters would fall closer to a temperature-dependent line. In order to find
an average value of B that would yield less scatter in the log K* values, we used a
subjective graphical method based upon the relations shown in Fig. 5. For example,
the log K* value for ,9 = 1 lies half way between the points for /? = 0 and @ = 2,
and the log K* value for /? = 4 lies one-fourth the distance from the ,5 = 0 to the
@ = 2 point. It is evident that the positions of some points, such as Nos. 66 and 171,
are greatly affected by changes in p, and other points, such as No. 22, are hardly
changed at all. All the corresponding pairs of data points depicted in Fig. 5 were
connected by vertical tie lines, and a slanting straight line was then drawn through
them so that it intersected the most important vertical tie lines at about the same
relative position along each tie line. (Our plot is not illustrated in this paper because
at a scale necessary for reproduction it would show only an incomprehensible jumble
of overlapping lines. The most important data points were selected on the basis
both of our estimation of the reliability of the temperature and chemical data and
upon an effort to insure widespread geographic representation,) To a great extent,
the position of the resulting line was fixed by pairs of data points with small vertical
distance between them. This line passes through the points 103/T = 1.70, log K* =
0.560and 103/T = 3.20, log K* = 3.031. Above 100C it intersects most tie lines
about one-sixth the distance from /? = 0 to @ = 2 (4 the distance from ,!l = 0 to
/? = l), so that log K* data points cluster along a linear trend when a b value of Q
is used, as shown in Fig. 6. Below lOOC, log K* values plot near a linear extension
1280 R. 0. FOURNIER and A. H. TRUESDELL

-Fluid inciusion filling temp.

DMeasured temp.
~Silico temp.
*011 well water. geothermui
gradient temp.
AOit weli water, silica temp.
qMeasured temp., p = 4/3

Fig. 6. Suggested curve for geothemometry of natural waters. The two dashed
lines show f 15*C and - 15% with respect to the middle curve. Superimposed
am the data points for the well waters listed in Table 1. See text for details.

of this line when b = 4 is used. [Previously @'OBRNIER and TRUESDELL, 1971),

we suggested a line with a slightly diEerent slope and the use of p = 8 for low-
temperature environments. Additional data acquired recently have caused us to
change our original curve.] Most data points fall within about & 15 to 3UC of this
line. An exception is in the 5 to 15OC region, where many points plot either above or
below the curve. In this temperature interval, the points that faI1 below the curve
are generally for waters from granitic rocks, and the points above the curve are for
waters from limestones and dolomites. The scatter of points may reflect departures
frum chemical equilibrium and/or different net reactions taking place in rocks of
greatly different compositions.
For @ = Q, the net reaction is

K+ f solid + iCa2+ + $??a+ + solid,

and for ,!? = s, the net reaction is

K+ + $Na+ + solid F+ @a2+ + solid.

We do not mean to imply that all reactions above 100C in hot-spring systems have
the stoichiometry of equation (10)or that all reactions in the weathering environ-
ment have the stoichiometry of equation (I 1). However, it appears that the combined
/3 = 6 and /! = + straight-line curve may serve as a useful reference for geother-
momet,ryof manywaters. It should be particularly useful for waters in which the silica
geothermometer of FCNJRWIERand ROWE (1966) is ambiguous, i.e. high-siliea values
may be due to equilibria with quartz at high temperatures deep underground or to
metastable equilibrium with amorphous silica at low temperatures near or at the
surface. Neither the SO, nor the Na-K-Ca geothormometers are reliable for acid
suIfate-rich waters that contain little chloride.
 An empirical Na-K-Ca geothermometer for natural waters 1267

In considering equations (10) and (ll), it should be remembered that a net re-
action cannot be deduced only from the composition of water flowing from a rock
or only from the mineralogy of an alteration assemblage. One must know either the
change in composition of water as it flows through a given volume of rock or the
change in bulk composition of that given volume of rock in response to water-rock
reactions. In the real situation, new Na- and Ca-bearing minerals may form con-
currently with decomposition of other Na- and Ca-bearing minerals. If, during this
alteration, there is a net decrease in Na and Ca in the solid phases per given volume
of original rock, then the new Na- and Ca-bearing minerals cancel out of the net
equation.
Equation (10) is entirely consistent with the usual changes in bulk chemistry of
igneous rocks that result from hydrothermal alteration associated with ore deposition.
Generally, progressing from fresh to more altered rock, there is first a progressive
leaching of Na and Ca with simultaneous fixation of K. Potassium is removed from
the rock only after Na and Ca are essentially depleted. The situation in regard to
equation (11) and the weathering environment is less clear cut. Most chemical
studies ofweathered rocks give only the composition of the least and most weathered
portions of rock with little regard for the bulk chemistry of the main portion of
intermediate weathered material. The situation is further complicated by seasonal
fluctuations in water tables and a tendency toward non-equilibrium conditions as
rates of reaction decrease with decreasing temperature.

Na-K-Ca GEOTHERMOMETER
We suggest that Fig. 6 may be used to estimate temperature of last rock-water
equilibration as follows: (1) express the concentrations of dissolved species in units
of molality. (2) Using molality values, calculate log [2/(Ca)/Na]. If this number is
negative, calculate log K* for p = $, and use Fig. 6 to estimate temperature. (3) If
log d(Ca)/Na is positive, calculate log K* for /3 = $, and determine whether the
temperature estimated from Fig. 6 is greater or less than 10GC. If greater than
lOOC, recalculate log K* using ,5 = 4, and use that value to estimate the tempera-
ture. Otherwise, use /I = $ to estimate the temperature.
Table 2 lists subsurface temperatures estimated by the silica (FOURRIER and
ROWE, 1966), log (Na/K) (Fig. 1) and log (Na/K) + /? log [d(Ca)/Na] (Fig. 6)
methods using compositions of hot-spring waters from several regions where
reservoir temperatures are known in nearby drill holes. Obviously, no single method
works best for all waters. However, the silica method and calcium-corrected method
(Fig. 6) are better than either the ELLIS (197( ) or extrapolated experimental
(HENLEY, 1967) curves for most waters. In comparing the results shown in Table 3,
it should be remembered that hot-spring waters may come from aquifers or reser-
voirs at more shallow depths or lower temperatures or both than the main reservoir
supplying a given geothermal well. Thus, some of the low estimated temperatures,
compared to measured temperatures in drill holes, may be real in the sense that
shallow aquifers or reservoirs do exist at the lower temperatures. This is in con-
trast to a situation in which water compositions change either by continued water-
rock reaction or by mixing with near-surface water during travel from a deep
reservoir to the surface.
Table 2. Subsurface temperatures estimated from hot-spring water compositions for areas where temperatures are known in nearby wells.
(Cation concentrations are in moles per liter of water)

EL SALVADOR
Ahuaehapan, spg. No. 3* 63 0.00120 0.0181 0.00146 183 1.09 0.28 1.18 228 175 227 295 208
ICELAND
Reykjaneat 99 0~0564 0.623 0.427 644 I.16 -0.42 1.02 226-2531111 232 209 276 232
NEW ZEALAND
Broadlands, spg. No. I$ 0~0000649 0.0374 0~00210 338 1.25 0 1.25 260_2851It/ 209 229 187 250 200
Broadlands, spg. No. 4$ 75 0000699 0.0187 0~000818 280 1.36 0.15 1.41 260-285 1111 204 160 220 179
Kawerau, spg. No. 4$ 0.0000250 0.0173 0.00136 240 1.11 -0.54 0.93 200-2851111 180 192 222 286 246
Ngawha, Jubilee Bath$ 48 0.000195 0.0361 0.00161 178 1.35 -0.41 1.21 230 172 166 222 20;
Orakeikorako. spg. No. 983 0.0000624 0.0122 0~00107 280 1.05 -0.19 0.90 260 180 204 237 305 237
Rotokawa, spg. No. S$ 0.000209 0.0431 0.00261 340 1.22 -0.44 l-07 220 201 218 193 256 225
Taupe, spg. No. 511 82 0.000349 0.0175 0.00118 260 1.17 0.03 1.18 204-25611 t/ 108 208 270 208
Taupe. Kitchen spg.1) 76 0.000274 0.0176 0~00120 235 1.17 -@03 1.16 204-25611 II 190 208 270 211
Waiotapu, spg. No. 202 0.000225 0.0196 0.000563 380 1.54 -0.12 1.50 275 208 227 125 184 168
Waiotapu, spg. No. 64$ 0.000873 0.0531 0.00409 490 1.11 -0.30 1.01 275 225 240 222 286 232
Wairskei, spg. No. 97$ 0.00112 0*0289 0.00174 235 1.22 0.07 1.24 260 179 191 103 256 201
TURKEY
Kizilderer( 100 0~0000299 0.0548 0.00320 185 1.23 - 1.00 0.90 200 105 190 253 253
UNITED STATES
BBOWaWe** 0~0000175 00105 O.OOOi42 444 1.12 -0.36 1.00 236 230 258 220 284 236
Steamboat Springs, spg. No. 27tt 0*000299 0.0307 0.00192 317 1.20 -0.25 1.12 186 197 213 200 262 217
Steamboat Springs, spg,. No. SO$$ 60 0000399 0.0277 0.00156 220 1.25 -0.14 1.50 186 186 187 250 168
Yellowstone Park, Mammoth Termme@ 74 COO856 0.00566 0~00143 52 0.60 1.22 2.23 72 7277 436 533 96
Yellowstone Park, Ojo Caliente Spg.@ 05 0.0000275 0.0138 O~OOOP35 245 1.77 - 0.42 1.63 174 176 91 162 152
Yellowstone Park, spg. by Y5 drillhole@j 92 0~00000098 0.0157 0.000233 210 1.83 -0.69 I.60 170 172 84 144 153
Yellowstone Park, spg. at Porcelain Terrace@ 95 0~0000774 0,0183 0.00187 692 0.99 -0.32 0.88 over 240 249 261 326 256
Yellowstone Park, spg. by I-13 drillhole@ 95 0.0000192 0.0148 0.000486 280 1.48 - 0.62 1.27 205 189 204 135 196 X06
Yeftowstone Park, Spouter spg.@ 92 0~0000175 0.0183 0.000486 309 1-58 --064 1.37 over I70 195 118 17.5 184

* SIGVALDSON and CUELLAR (1970). t BJBRNSSON et al. (1970). $ MAHON (1970). 3 ELLIS and MAEON (1964). 11S ARDUTT (1964). 7 DOMINGO and SAMIL~IL
{lg70). ** \THITE (1964). $t BR.ANNOCK et al. (1948). $$ D. E. \%ite (unpublished data). 43 R. 0. Four&r (on~ublishcd data). /\I1Range of temperatures
reported for producing zones in different drill holes. fiy Solubility of chalcedony used instead of quarts (unpublished data of Fournierad Rowe).
 An empirical Na-K-Ca geothermometer for natural waters 1269

Table 3. Composition (parts per million) of hot spring YF 392 in Yellow-

stone National Park compared with the composition of water from the
nearby Y-5 drill hole.
(Roberta Barnes, analyst)

1 2 3 4

T(C) 170 92 (boiling)

SiO, 210
PH 6.7 8.44
ca 2.9 3.38 0.4 7.25
fifg 0.10 0.12 0.005 20.0
Xia 324 377 360 0.90
K I5 I7 9.1 1.65
Li 3.1 3.6 3.2 0.97
NH, 0.21 0.24 to.1
HCO,* 423 493 467 0.91
SO, 15 17 16 0.94
Cl 234 273 268 0.87
F 19 22 25 0.76
B 2.4 2.8 2.8 0.86

1. LVater collected in a stainless steel bottle (FOURNIER and MORGAN-

STERN, 1971) from 75 m deep in the Y-5 drill hole, Yellowstone Park. The
hole is 164 m deep and penetrated just one aquifer at a depth of 76 m and
temperature of 17OC.
2. Calculated composition of water from the Y-5 drill hole after loss
of 14.2 per cent water through adiabatic cooling and separation of the
resulting steam, but no loss of dissolved constituents.
3. Composition of hot spring YF 392.
4. Ratios of constituents in aquifer to constituents in the hot-spring
water. If the aquifer water cooled entirely adiabatically from 170 to
92C, without loss or gain of dissolved constituents, the ratios would be
0.86.
* Total alkalinity expressed as HCO,-.

In many places, significant water-rock reaction occurs during the upward

movement of an increment of water from a reservoir to the surface. Table 3 com-
pares the composition of water in a hot spring with that in the reservoir feeding that
spring. The reservoir was found 76 m deep with a temperature of 170%. It is a
highly fractured zone in otherwise impermeable ash-flow tuff. The fractured zone
may be stratigraphically controlled, possibly caused by a discontinuity in the cooling
history of the ash-flow tuff (L. J. I?. Muffler, oral communication, 1972). Water in
tl e spring, 30 m distant from the drill hole, is boiling and flows at an estimated rate
of 20 liters per minute. Taking the silica content, 210 ppm, of the hot-spring water
and assuming cooling entirely by adiabatic processes as the water moves from the
reservoir to the surface, a reservoir temperature of 172% is estimated by the method
of FOURKIER and ROWE (19GG). This is in excellent agreement with the measured
reservoir temperature of 170C. Therefore, it appears that an assumption of adia-
batic cooling is good. The ratio of chloride in the deep water to that in the hot-spring
water also supports this assumption (see Table 3, column 4). In order for the water
to cool adiabatically (without loss of heat by conduction), the water must have risen
1270 R. 0. FO~JRNIER
and A. H. TRUESDELL

to the surface relatively quickly. Yet, a great deal ofwater-rock reaction has occurred
during the ascent, as shown by the decrease in calcium and potassium, instead of the
expected increase. Thus, we can expect that the Na-K-Ca geothermometer will
commonly yield temperatures lower than the reservoir temperature because of con-
tinued reaction with wallrocks at lower temperatures during ascent. In the example
just described, the reservoir temperature estimated from the Na-K-Ca content of
spring YF 393 is 153C, 17% less than the actual temperature. In a few hot spring
systems, such continued reaction may be minimal because the channelways are
lined with non-reactive silica (FOURNIER and TRUESDELL, 1970).

EFFECT OF pH
When a water emerges from a spring or well, its hydrogen ion activity may be
over an order of magnitude different from the original hydrogen ion activity of that
water at depth. Furthermore, the original pH at depth can be calculated only if
subsurface temperature and partial pressures of gases such as CO, are known.
Therefore, as previously noted, hydrogen ion cannot be incorporated into an expres-
sion used for estimating subsurface temperature. In formulating our empirical
expression relating water composition to subsurface equilibration temperature we
have assumed, for practical purposes, that hydrogen ions do not enter into the
reaction. This is equivalent to saying that, although several different simultaneous
reactions may be taking place, one reaction can be written in which the solid products
and reactants undergo a change in Na, K and Ca, but not hydrogen ion. Such a
reaction will define a Na-K-Ca relationship, such as equation (9), which is inde-
pendent of other simultaneous reactions in which hydrogen ion does participate.
The fact that the data points shown in Fig. 6 show so good a correlation with tem-
perature suggests that this is generally the case.
For situations in which hydrogen ion does enter into the net reaction equations
similar to (6), (7), and (8) may be formulated :

1+2--x
K+ + zH+ + solid = xNa + ~ Ca2+ + solid (10)

1+x+2
Kf + xNa + zH+ + solid = 2 Ca2+ + solid (11)
x-l-z
Ca2+ + zH+ + solid = xNa + solid.
K++ 2 (12)
The corresponding approximate equilibrium constant, I<**, for each of these re-
actions is :

logK** &log; -log; +(I f.2 4)logH NW

(13)

log R*" = -xlog~-log;+(l +z+x)log~

d/(C4
(14)

log K** = (15)

 An empirical Na-K-C& geothermometer for natural waters 1271

Equations (13) and (15)are identical, except that x is larger in (15) than in (13).
For better comparison with equation (Q), equations (13) and (14) may be recast,
respectively, into the following forms :

d(Ca) d(Ca)
log K** = log N; + (1 - 2)log Na + 2 log H

2/(Ca) 2/(Ca)
log K** = log ; + (1 + x) log Na + ZlogH. (17)

Equations (16) and (17) are similar to equation (9) except for the additional term
z log[2/(Ca)/H]. As yet, we have not evaluated whether addition of this term would
increase or decrease the scatter of points shown in Fig. 6.

EFFECT OF CARBON DIOXIDE

At a constant partial pressure of CO, the stability of calcite decreases as tem-
perature increases. Depending upon pH relationships, the solubility of calcite may
either increase or decrease as the partial pressure of CO, increases. Where pH is
controlled or buffered by silicate hydrolysis reaction, an increase in Yco, decreases
the amount. of Ca in solution, thus decreasing the solubility of calcite. On the other
hand, where pH may decrease in response to an increase in P,,, the solubility of
calcite also will increase as Pco, is increased. In general, silicate reactions will
control pH deep in hot spring systems where temperatures are high and rates of
reaction are rapid. On the other hand, in cooler environments where high partial
pressures of CO, exist pH is likely to be controlled by carbonate equilibria. In any
event, the important consideration is the amount of aqueous Ca in the water.
High aqueous Ca contents require smaller Na/K ratios according to equation (9).
This accounts for the very low Na/K values in Ca-rich waters, such as those at
Mammoth hot springs, Yellowstone Park, and, in fact, most other travertine-
depositing thermal waters. For CO,-rich or Ca,,-rich environments, the Na-K-Ca
geothermometer will give good results provided that calcium carbonate was not
deposited after the water left the reservoir. Where calcium carbonate has been
deposited, the Na-K-Ca geothermometer may give anomalously high temperatures.

EXPERIMENTAL RESULTS
A few experimental results with little or no CO, present bear upon the empirical
geothermometer presented in this paper. The most significant are some experiments
by J. J. Hemley (oral communication, 1971) conducted at 1000 bars and 300 and
5OOC in which chloride solutions were equilibrated with mixtures of K-feldspar
plus andesine. The resulting solutions were analyzed for Na, K, and Ca. The
analytical results are plotted in Fig. 7. The log (Na/K) values plot far below the
empirical Na/K curve from ELLIS (1970)and WHITE (1965, curve E) and the experi-
mental curves for albite plus K-feldspar (HEMLEY, 1967; ORVILLE,1963).When the
B = $ correction is applied, however, the data plot very close to the empirical
@ = + curve derived from natural water compositions. This experimental work
was not taken into account when the /3 = 6 empirical curve was drawn.
One of us (Fournier) has carried out some experiments at temperatures below
300C, and the results of these are also plotted in Fig. 7. In two experiments, basalt
11
1272 R. 0. FOURNIERand A. H. TRUESDELL

K-fe1d.t andesine

altered to clinop-
tilolite(Fournier. unpub.)

Elasalt(Fournier, unpub.)

qNa/K alb. + K-feld.(ORVILLE. 1963)

C
600 500 400 300 200 100
I
I I I I I I I I
lb 14 l-8 22 2.6
103/ T

Fig. 7. Comparison of experimental and empirical results. The dashed line is

the Na/K empirical curve combined from ELLIS(1970) and WHITE(1965, curve E).
The lower solid line is the empirical p = & curve from Fig. 6 of this paper.

was dissolved in pure water at 200 for 30 days and at 194C for 37 days, and the
resulting solutions were chemically analyzed. Again the data fall on or close to the
empirical curve for /l = 4. Similar results also were obtained at 200C when clinop-
tilolite-rich rock was reacted with 0.05 m NaCl for 13 days. In another group of
experiments clinoptilolite-rich rock was dissolved at 150C for 13 days; one part
was reacted with 0.05 m NaCI, and a second part was reacted with a 50: 50 mixture
of NaCl plus KC1 (0.09 m total chloride). Base exchange occurred and the resulting
solutions approached each other in composition. The data bracket the empirical
b = g curve, but plotted as Na/K are far off the empirical curves of ELLIS (1970)
and WHITE (in press).
Additional experimental work will be necessary to calibrate the Na-K-Ca geo-
thermometer and to understand its implications. However, the initial agreement
between experimental results and the empirical curve is very encouraging.

CoNCLUsIoNs
The ratio Na/K should be used for geothermometry with great caution, and
preferably only for near-neutral and alkaline waters that do not deposit travertine
and/or waters with log [2/(Ca)/N a ] 1ess than 0.5. In Table 3 it is evident that some
waters give better results when referred to the ELLIS (1970) curve, and others give
better results when referred to the extrapolated experimental curve of HEMLEP
(1967).
Much of this ambiguity is removed when a correction is made for the calcium
content of the water. The function, log (Na/K) + @ log [2/(Ca)/Na], appears to
work well for most geothermal waters when /3 is assumed to be i or +, according to
the criteria in a preceding section. However, in some places the net rock-water
 An empirical Na-K-Ca geothermometer for natural waters 193

reaction may be such that /? is greatly different than our assumed value. If this is
true, our calcium correction method may fail to yield the correct temperature.
All water composition geothermometers may be adversely affected by con-
tinued water-rock reaction as the waters ascend and cool. Waters that initially have
little calcium will generally yield low estimated aquifer temperatures owing to con-
tinued water-rock reaction during ascent. However, waters initially CO,- and
calcium-rich may yield high estimated subsurface temperatures owing to the rapid
deposition of calcium carbonate and slower reactions invoking Na and K.
Another obvious problem is mixing of deep water with shallow water of different
composition. If the shallow water is very dilute relative to the deep water, mixing
will have little effect upon Na/K ratios. Such mixing will, however, have an effect
upon the calcium-corrected geothermometer because the square root of calcium is
involved in the calculation. But, if the original calcium concentration is small
relative to sodium, mixing may have little effect.
The NrlrK-Ca geothermometer also may be of use in interpreting compositions
of fluid inclusions trapped in minerals. Chemical data for fluid inclusions from
Providencia, Mexico (RYE and HAFFTY, 1969) are plotted vs filling temperature in
Figs. 2 and 6. In Fig. 2, if the Providencia Na/K data are referred to the experi-
mental curve defined by the work of HEMLEY (1967) and ORVILLE (1963), tempera-
tures of 500 to 700C are suggested (Fig. 2). If the data are referred to the empirical
curve of ELLIS (1970), temperatures of 400 to 500C are suggested (Fig. 2). In
contrast, if the chemical data are referred to the calcium-corrected curve of Fig. 6,
temperatures of 300 to 375C are suggested; this temperature interval is in reasonable
agreement with the range in filling temperatures.

Acknowledgenaents-The manuscript was reviewed by L. J. P. MUFFLER, D. E. WHITE, G. K.

CZA~NSKE, A. J. ELLIS, and TOMAS PACES. We wish to acknowledge their many helpful com-
ments and suggestions. We are particularly grateful to J. J. HEMLEY for allowing us to use his
unpublished experimental data in our Fig. 7.

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