Geochimica et Cosmochimica Acta, Vol. 58, No. 16, pp.

3425-3437, 1994
Copyright 0 1994 Elsevier Science Ltd
Pergamon Printed in the USA.All rights reserved
0016.7037/94 $6.00+ .OO

0016-7037(94)00139-l

Liquid-vapor fractionation of oxygen and hydrogen isotopes of water from the freezing to the
critical temperature

JUSKE HORITA and DAVID J. WESOLOWSKI

Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 3783l-6 110, USA

(Received October 19, 1993; accepted in revised form March 1, 1994)

Abstract-The equilibrium fractionation factors of oxygen and hydrogen isotopes between liquid water
and water vapor have been precisely determined from 25 to 350°C on the VSMOW-SLAP scale, using
three different types of apparatus with static or dynamic techniques for the sampling of water vapor. Our
results for both oxygen and hydrogen isotope fractionation factors between 25 and 100°C are in excellent
agreement with the literature (e.g., MAJOUBE, 197 1). Our results for the hydrogen isotope fractionation
factor above 100°C also agree quantitatively with the literature values of MERLIVATet al. ( 1963) and
BOTTINGA( 1968). The results for the hydrogen isotope fractionation factor obtained in this study and
from most of the literature were regressed to the equation,
lo3 In a,.,(D) = 1158.8(T3/109) - 1620.1(T2/106) + 794.84(T/103) - 161.04 + 2.9992( 109/T3),
from O’C to the critical temperature of water ( 374.1 “C) within & 1.2( 1u) (n = 157); T (K). The cross-
over temperature is 229 & 13°C ( 1u).
Our values for the oxygen isotope fractionation factor between liquid water and water vapor are,
however, at notable variance with the only dataset available above 100°C in the literature ( BOTTINGA,
1968), which is systematically higher (av. + 0.15 in lo3 In a,.,( “0)) with large errors (kO.23 in la).
Our results and most of the literature data below 100°C were regressed to the equation,
lo3 In ocl.,(‘*O) = -7.685 + 6.7123(103/T) - 1.6664( 106/T2) + 0.35041( 109/T3),
fromOto374.1”Cwithin+0.11 (lu)(n = 112); T(K).
A third water-steam isotope geothermometer, using the ratio of AsD/ As “0 given by water and steam
samples, is readily obtained from the above equations. This geothermometer is less affected by incomplete
separation of water and steam, and partial condensation of steam than those employing the oxygen and
hydrogen isotopic compositions alone.

INTRODUCTION al., 1963; MAJOUBE, 1971). The data of MAJOUBE(1971)

PHASETRANSITIONSOF water between vapor, liquid, and ice
are primary physicochemical processes, which cause varia-
tions in the oxygen and hydrogen isotope abundances of nat-
ural waters through evaporation/precipitation and boiling/
condensation cycles in the atmosphere, at the surface, and
in the upper crust of the Earth. Thus, knowledge of the oxygen
and hydrogen isotope fractionation of water among the three
phases, especially between liquid water and water vapor is
prerequisite to the use of stable isotopes as tracers of natural
waters. Several investigators ( BAERTSCHIand THURKAUF,
1960; DANSGAARD,196 1; MERLIVATet al., 1963; CRAIGet
al., 1963; CRAIG and GORDON, 1965; EHHALT and KNOTT,
1965; RENNOW, 1970; MAJOUBE, 197 1; STEWART and
FRIEDMAN, 1975; KAKIUCHI and MATSUO, 1979) have ex-
perimentally determined the equilibrium fractionation factors
of oxygen and hydrogen isotopes between liquid water and
water vapor at temperatures below 1OO”C,chiefly near room
temperature (Table 1). Several different experimental tech-
niques have been employed for collecting samples of water
vapor in isotopic equilibrium with liquid water; closed-system
liquid-vapor equilibration with static (KAKIUCHI and MA-
TSUO, 1979) or circulating air ( EHHALT and KNOTT, 1965;
RENNOW, 1970; STEWARTand FRIEDMAN, 1975), and Ray-
leigh-type slow distillation ( BAERTSCHI and THURKAUF,
1960; DANSGAARD.196 1; CRAIG et al., 1963; MERLIVAT et
3425
are the most detailed and precise, and are currently in wide
use up to about 100°C.
At temperatures above lOO”C, however, very few experi-
mental studies on the liquid-vapor fractionation of oxygen
and hydrogen isotopes are reported in the literature. MER-
LIVATet al. ( 1963) reported experimental results of hydrogen
isotope fractionation factor between liquid water and water
vapor from 1 to 350°C. Although their results for the hydro-
gen isotope fractionation appear to be precise, only a few
measurements were reported above 100°C. Equations for the
oxygen and hydrogen isotope fractionation between liquid
water and water vapor, which are largely based on data from
134 to 300°C from BOTTINGA(1968), are reported in BOT-
TINGA and CRAIG( 1968) and FRIEDMANand O’NEIL ( 1977).
KAZAHAYA( 1986) represents, to our knowledge, the only
other dataset for the liquid-vapor isotope fractionation above
100°C (Table 1) The equations based on the unpublished
data of Y. Bottinga are currently in wide use above 100°C.
The measurements reported in this paper were initiated
in order to test and validate experimental methods for de-
termining the effect of dissolved salts on oxygen and hydrogen
isotope activity ratios in brines by means of the vapor-liquid
water equilibration technique ( HORITA et al., 1993). Our
results for the hydrogen isotope fractionation factor between
liquid water and water vapor agree with the previous literature
data, but measurements of oxygen isotopes suggest possible
3426 3. Horita and D. J. Wesolowski

Table 1. Chronological list of the literature for mass-spectrometric measurements of oxygen

and hydrogen isotope fractionation factors between vapor and liquid water

Author Isotopes Temperature Method

(“C)

Baertschi and Tbilrkauf (1960) ‘*O/16O 36.6-99 distillation

Dansgaard (1961) ‘so/‘6o 4&23 distillation with N2 carrier gas

Me&vat et al. (1963) DB l-350 zloO*C, ~~tiIIation

r2WC, sampling liquid phase only

Craig et al. (1%3)b ‘sops0 2.5 distillation

Craig and Gordon (1965)

Ehhalt and Knott (1965) D/H & 1s01’60 20 circulation in closed system

Bottinga (1968, PhD thesis) D/H & “Oi”O 134-30 sampling liquid phase only

Rennow (1970) D/H 20 circulation in closed system

Majoube (1971) D/H & ‘sO/‘6O 0.75-91.6 distillation

Stewart and Friedman (1975) D/H & ‘sO/16O 19.4-27.2 circulation in closed system

Kakiuchi and Matsuo (1979) D/H & ‘*O/‘6O 10-40 static equilibration

Kazahaya (1986, PhD thesis) D/H & ‘*01“‘0 loo-335 sampling vapor phase only

a, values from 1 to 100°C were corrected in Majoube (1971)

b, more results by Horihe and Craig at 3-100°C were cited by Bottinga and Craig (1968, 1969)

small systematic errors in the results of BOTTINGA ( 1968)
and KAZAHAYA (1986). Their results for oxygen isotopes
above 100°C also have large scatter. Clearly, more accurate
and precise data on the oxygen and hydrogen isotope frac-
tionation factors between liquid water and water vapor above
100°C are needed for better unde~tanding of geochemical
processes involving natural waters at elevated temperatures.
In this paper, we present precise experimental results on the
oxygen and hydrogen isotope fractionation factors between
liquid water and water vapor from 25 to 35O”C, determined,
for the first time to our knowledge, on the VSMOW-SLAP
scale. Our results and those of the literature data are regressed
to single equations to cover the temperature range from the
freezing temperature (0°C) to the critical temperature of wa-
ter (374.1”C).
EXPERIMENTAL
containing liquid water to prevent water vapor from condensing (Ta-
ble 2). There must be a thermal gradient within the vapor phase, but
the temperature ofthe vapor-liquid interface, which controls the iso-
tope fractionation between the two phases, is the same as the liquid
phase. Furthermore, the uncertainty of temperature of this magnitude
(0.6-I .O”C) yields very small errors in the fractionation factors;
10.08%~ and 5 1.O%Ofor oxygen and hydrogen isotopes, respectively
( MAJOUBE, 197 I ). The temperatures of the baths were monitored
and controlled within 0.03”C by pfatinum resistance thermometers.
The equilibrium between liquid water and water vapor was reached
within several hours at 50°C (Fig. 2), and the vapor samples were
isolated from the liquid water by closing Teflon stopcocks in situ.
Amounts of water vapor recovered ranged from 3 to I1 mg. The
details of the apparatus and experimental procedure were already
presented by HORITAet al. ( 1993).
Slvcol/Water Bat!
Teflon Stopcat

In order to cover the wide range oftem~rature from 25 to 35O”C,

three different types of apparatus were employed for experiments of
liquid-vapor water equilibration.

Apparatus and Experimental Procedure

For temperatures from 25 to lOO”C, static, liquid-vapor equili- Pyrex Flask

bration vesseIs made of Pyrex glass and Teflon stopcocks were em-
ployed (Fig. 1). About 50 to 100 mL of deionized water was trans-
ferred to each vessel. After the whole vessels were evacuated at liquid
nitrogen temperature, they were immersed in a thermostated water/
ethylene glycol bath. The bath holds up to eight such vessels. The FIG. 1. Schematic diagram of the static liquid-vapor equilibration
water in each vessel was magnetically stirred. The equ~lib~um ex- apparatus used at 25- 100°C(apparatus- 1) The flask is 250 mL, and
periments were conducted at 25,50,70,90, and IW’C. The vapor the vapor samplers are 20 or 60 mL. TI is kept 0.5-l.O”C higher
samplers were maintained 0.6- 1.O”C higher than those of the &asks than r, to prevent condensation.
 T dependence of isotope fractionation factors of water 3427

Table 2. Results of the oxygen and hydrogen isotope fractionation factors (a)
determined in this study with static vapor-liquid water equilibration
method from 25 to ZOO’C

T(“C) Duration(hr) AT(OC)’ ldlna(D) SD’ ldlna(‘s0) SD’

\
ADDaratus-1 (25100°C) Vapor NUD~O bellows valve
orifice)
24.91 96 1.0 73.5, 9.w
24.91 % 1.0 73.2’ r0.2(2) 9.21’ tO.C4(2)
49.99 71 0.6 54.5, n.d.
49.99 II 0.6 56.4 1 n.d.
49.99 17 0.6 54.9 1*1.0(5) n.d.
49.99 77 0.6 56.7 1 n.d. &VCR fitting
49.99 II 0.6 55.9 n.d.
49.98 101 1.0 56.2, 1.51,
49.98 101 1.0 56.5 1t1.2(3) 7.45 I *0.06(3) *Stainles steel
7.57J (316SS)
49.98 101 1.0 54.3J
10.11 50 0.8 41.7, 6.34,
10.11 50 0.8 42.3 I 6.38 / +0.04(3)
10.11 50 0.8 42.8 1*0.4(S) 6.3Ck
70.11 50 0.8 42.3 I n.d. VCR fitting
70.11 50 0.8 42.5J n.d.
89.92 42 0.9 31.0 5.51
-Qtz cup
99.99 39 0.8 26.4 5.08, 5
99.99 39 0.8 27.5 I 5.02 I -Liquid water
99.99 39 0.8 27.4 I t0.3(4) 4.% I *0.05(4)
99.99 39 0.8 27.7J 5.023

ADDaratuS-2 (130-200°C)

129.77 31 5.0 16.2 n.d.

129.71 48 4.0 16.3 n.d.
129.66 48 3.0 11.3 3.85
149.62 92 5.0 12.4, 3.34
149.62 62 4.0 13.3’ t0.6(2) n.d.
174.60 95 3.0 7.8 2.18
174.66 45 4.0 n.d. 2.95
199.64 36 4.0 6.2, 2.29
199.64 42 4.0 5.2’ t0.7(2) n.d.
199.74 42 2.6 5.3 n.d.

# temperature gradient behveen vapor and liquid phases

* Standard deviation (lo)
n.d.-not determined

Apparatus-2 (130-200°C)

For experiments at temperatures between 130 and 2OO”C, static

liquid-vapor equilibration vessels made of stainless steel (3 16SS) were
constructed (Fig. 3a). The basic design is similar to the apparatus
used at 25- 100°C. The lower part of the vessel, which contains liquid
water, is made of two Cajon VCR stainless steel glands (3.02 cm

FIG. 3. Schematic diagram of the static liquid-vapor equilibration

apparatus used at I30-200°C (apparatus-2). (a) equilibration vessel
-6OLh ” ” a 4 a “, I
0 10 20 30 40 50 60 70 80 made of stainless steel; upper part is vapor sampler and lower part
Time (h) is for liquid water, (b) diagram of whole apparatus; temperatures of
the upper and lower parts are controlled by air and aluminum block
FIG. 2. Hydrogen isotopic equilibration of water vapor with liquid furnace, respectively, with a temperature gradient (T, - Tz = 2-
water at 5O”C, using apparatus- 1. 5°C). Vapor sample can be isolated from liquid water in situ.
3428 J. Horita and D. J. Wesolowski

o.d., 2.23 cm i.d.). The base ofthe lower gland is plugged and welded High-pressure valve
with stainless steel. The upper gland was welded to a small (0.89 cm
o.d., 0.48 cm i.d.) stainless steel VCR fitting through a stainless steel
adaptor. The upper part of the vessel, which is a vapor sampler,
consists of two Nupro bellows valves (4.4 mm orifice) with VCR
fittings. Volume of the vapor sampler is adjusted by inserting a stain-
less steel bulkhead union (5.66 cm long, 0.48 cm i.d.) between the
two valves. The lower bellows valve is finally connected to the lower
part of the vessel via a VCR fitting. Either copper or nickel gaskets
were used for all of the VCR fittings of the equilibration vessel.
leater
About IO mL of liquid water was transferred to a quartz cup inside
the equilibration vessel. The entire vessel was evacuated after freezing
the water with liquid nitrogen. The lower part of the vessel, containing
liquid water, was placed in a borehole within a 25.4 cm diameter
cylindrical aluminum block, and the upper part was exposed to air
I
(Fig. 3b). Six stainless steel vessels placed in the aluminum block
eflon bag 1
were thermally isolated in a container made of galvanized steel and
insulation. The lower parts of the six vessels were heated by the alu- 1Teflon
minum block surrounded by a heater wire, while the upper parts I
were heated by air in the container. A Teflon sheet was placed between
I
the air bath and the aluminum block in order to minimize thermal
transport. Temperatures of the upper parts of the stainless steel vessels,
Ei_lJ Pt lIneri

Pressure
7 vessel !
which contain the vapor samples, were maintained 2-5°C higher
than those of the aluminum block in order to prevent the conden- 1 Pres sure vessel
sation of water vapor (Table 2). It is unlikely that a thermal gradient
within the vapor phase interferes with the isotope fractionation at Autoclave
---__---
the liquid-vapor interface, whose temperature is controlled by the Positive-displacement pump- Furnace
aluminum block. In addition, the uncertainty due to the temperature
gradients gives small errors in the fractionation factors; <0.15%0 and FIG. 4. Schematic diagram of the dynamic liquid-vapor equilibra-
I I .5%0 for oxygen and hydrogen isotopes, respectively. Temperatures tion apparatus used at 120-350°C (apparatus-3). Water vapor in
of the aluminum block, the air bath, and the upper parts of the isotopic equilibrium with liquid water in the platinum liner was con-
vessels were monitored and controlled within O.I”C with separate tinuously removed at the sampling rates of 0.3-0.9 g/h through 0.4
platinum resistance thermometers and a thermocouple. At the end mm i.d. capillary tube, using a positive-displacement pump. Samples
of the equilibration experiments, the vapor samples were isolated of liquid water were manually collected through a capillary tube im-
from the liquid water by closing the lower bellows valve in situ via mediately after the vapor sampling.
an actuator extending to the outside of the container (Fig. 3b). Du-
ration of the liquid-vapor equilibration of these experiments ranged
from 31 to 95 h (Table 2). Based on the short equilibration time
ambient temperature. This pressure vessel was connected to a positive-
(several hours) of the apparatus-l at 50°C (Fig. 2), which has a
displacement high-pressure pump, which permitted sampling at the
geometry (orifice of valves, and distance between liquid and vapor
desired low flow rates by withdrawing water from the pressure vessel,
samples) similar to apparatus-2, these experimental times were as-
with condensed water vapor accumulating in the sampling tube and
sumed to be sufficient for the isotopic equilibration between liquid
the Teflon bag. Water vapor being continuously withdrawn from the
water and water vapor. Amounts of water vapor recovered ranged
platinum liner condensed in the platinum capillary tube, and was
from 3.5 to 10 mg.
cooled to ambient temperature by a water-cooled condenser. Samples
of condensed water vapor for isotopic analysis were collected in a
Apparutus-3 (IZO-350°C) small portion (0. I cm’) of the 0.4 mm i.d. platinum capillary tube
between two stainless-steel high-pressure valves. The temperatures
The apparatus consists of a cylindrical-shaped thin-walled (0.25 of liquid water in the liner were monitored and controlled within
mm) platinum can of about 700 cm3 internal volume, enclosed in a 0.2”C by a thermocouple placed in a thermowell in the liner. Pressures
bolted-closure stainless steel pressure vessel (ca. 900 cm3 internal monitored in the liner agreed with those of saturated water vapor at
volume) seated in a Marshall tube furnace (Fig. 4). This system was the temperatures of experiments.
designed by SIMONSON and PALMER ( 1993) for studies of the par- About 300 cm3 of helium-purged deionized water was transferred
titioning of salts ( HCl, NaCl, etc.) between brines and water vapor to the inside ofthe platinum liner. Air in the liner was displaced with
at elevated temperatures. Sampling of the vapor phase was through water vapor by heating the liner to ca. 120°C. Samples of water vapor
a platinum tube (0.8 mm o.d. and 0.4 mm i.d.), which passes through were withdrawn at 0.3-0.9 g/h. Samples of liquid water were obtained
the liner and terminates about 1 cm below the top of the liner. A immediately after a given vapor sample was taken. Two series of
second platinum tube (0.8 mm o.d. and 0.4 mm i.d.) for sampling experiments were conducted, one from 120 to 260°C and another
of the liquid phase extends to the bottom ofthe liner. A third platinum from 120 to 350°C.
tube (0.8 mm o.d. and 0.4 mm i.d.), extending to near the bottom
of the liner was used to equalize pressure between inside the liner
and the space surrounding the platinum liner in the autoclave. All Isotopic Analysis of Water
of the platinum tubes were welded to the liner with gold. Pressure
equalization across the liner was attained by transfer of liquid water For all of the liquid-vapor equilibration experiments, deionized
of identical isotopic composition in the liner to a collapsible Teflon water with 6D = -41%0 (D/H z 150 X 10m6) and 6’*0
bag in a small pressure vessel at ambient temperature with corre- = -6.7%0 ( ‘8O/‘6O z 1990 X 10m6) on the VSMOW-SLAP scale was
sponding transfer of water in the vessel to the annular space (Fig. used. Oxygen and hydrogen isotope ratios of all of the samples of
4). Samples of the liquid water in the liner were collected in an inert water vapor (3- 11 mg) were determined using the micro CO*-water
syringe attached to a platinum-core valve, which is connected to the equilibration method for oxygen isotopes ( KISHIMA and SAKAI,
capillary tube for liquid water. The sampling rates of the liquid were 1980), followed by the uranium-reduction method for hydrogen iso-
controlled manually. Samples of water vapor were collected through topes ( BIGELEISEN et al., 1952), using the same water samples. This
the first platinum capillary tube, which is then connected through a technique permits measurements of both oxygen and hydrogen iso-
length of platinum tube and high-pressure valve to a collapsible Teflon topes of single water-vapor samples of a few milligrams. For samples
bag, partially filled with water, in a third small pressure vessel at of liquid water, their 6D and 6 I80 values were determined separately
 T dependence of isotope fractionation factors of water 3429

by the uranium reduction method ( BIGELE~SEN et al., 1952) and the Table 3. Results of the oxygen and hydrogen isotope fractionation
conventional CO*-water equilibration method modified by YOSHIDA factors determined in this study with dynamicvapor-liquid
and MIZUTANI ( 1986 ). The precision of the isotopic analyses is ap- water equilibration method from 120 to 350°C
proximately +0.5%0 and ?0.05%0 ( I CT),for 6D and d “0 values, re-
spectively.
T(“C) Samplingrate&/h) ldlnar(D) SD’ ldlnar(‘80) SD’
For the isotope exchange reactions between liquid water and water
vapor. Aooaratus-3 [120-350°C)
H:*O (VI+ HJ60 (I) = H?O,,, + H:‘%, (I)
118.88 0.9 22.1, 4.53,
118.88 0.9 22.4’ t0.2(2) 4.53’ *O.c0(2)
119.18 0.4 22.5, 4.47,
HDO,,, + HzO,,, = HzQv, + HDO,,,, (2) 119.18 0.4 21.oJ *1.1(2) 4.47’ *0.00(2)
138.30 0.3 14.4, ~’ 3.58,
the oxygen and hydrogen isotope fractionation factors are defined as 138.30 0.3 14.7’ *0.2(2) 3.79 *0X(2)
159.13 0.3 9.7, 3.42,
tu,.,(‘80) = (‘~O/‘~O),/(‘~O/‘~O)” 159.13 0.4 9.8’ *0.1(2) 3.2@ iO.11(2)
159.13 0.4 11.5 n.d.
= (I + 10-%‘80,)/( 1 + 10-361*o,) (3)
199.94 0.3 5.5, 2.43,
and 199.94 0.3 4.3’ *0.X(2) 2.57) +0.10(2)
220.02 0.4 1.4, 2.12,
R,.,(D) = (D/H),/(D/H), 220.02 0.4 1.9’ +0.4(2) 2.1@ tO.Ol(2)
220.22 0.4 0.9, 1.98,
= (I + 10-36D,)/( I + 10m36D,), (4) 220.22 0.4 0s *0.2(2) 2.07’ iO.G6(2)
240.09 0.3 -1.31 1.59
where 6 is the isotopic composition expressed in the conventional 240.09 0.3 -1.4’ +0.1(Z) n.d.
delta notation in permil ( %o).Our mass spectrometer was calibrated 240.39 0.4 -2.7, 1.46,
daily against the VSMOW-SLAP scale (GONFIANTINI,1978) for both 240.39 0.4 -1.8’ t0.6(2) 1.67’ +0.1%2j
oxygen and hydrogen isotopes of water, preparing and measuring 260.05 0.5 -1.1, 1.29, ~’
samples of VSMOW and SLAP by the same methods as for the sam- 260.05 0.5 -1.Q +0.4(2) 1.39’ *0.07(Z)
260.25 0.4 -2.7, 1.29,
ples of liquid water and water vapor. The overall precision of the
260.25 0.4 -1.7’ +0.7(2) 1.35’ *0.04(2)
measured fractionation factors in this study can be evaluated based
280.20 0.4 -1.7, 1.11
on repeated measurements at the same experimental conditions (Ta-
280.20 0.4 -3.2’ +1.1(2) n.d.
bles 2 and 3). The standard deviations ( 1~) of the repeated mea-
300.24 0.4 -2.9 0.95
surements (n = 2-5) were k0. I to I .2%0 (av. &0.6%0) and kO.00 to 324.99 0.3 -4.5, 0.55,
0.15%0 (av. ?0.06%0) for values of 10) In n,.,(D) and IO3 In 324.99 0.3 -3.9’ +0.4(2) 0.67’ iO.O8(2)
cy,.,( 180), respectively (Tables 2 and 3 ) 348.62 0.4 -0.9, 0.22,
348.62 0.4 0.4’ +0.9(2) O.lQ *0.04(2)
RESULTS
* Standard deviation (1 (I)
n.d.-not determined
All of our results for oxygen and hydrogen isotope frac-
tionation factors between liquid water and water vapor are
presented in Tables 2 and 3.
MERLIVAT et al. ( 1963) are slightly, but systematically lower
than the others, even after the correction mentioned above.
Hydrogen Isotopes
The results of KAKIUCHI and MATSUO ( 1979) between 10
At temperatures below lOO”C, several investigators ( MER- and 2O”C, and our results at 25°C appear to be slightly lower
LIVAT et al., 1963: EHHALT and KNOTT, 1965; RENNOW, than those of MAJOUBE ( 197 1) and STEWART and FRIEDMAN
1970; MAJOLJBE, 1971; STEWART and FRIEDMAN, 1975; (1975). A value of EHHALT and KNOTT (1965) at 20°C is
KAKIUCHI and MATSUO, 1979) have already determined the distinctively lower than the other data. These slight discrep-
hydrogen isotope fractionation factors. However, none of ancies are probably due in part to differences in the charac-
these measurements was carried out on the VSMOW-SLAP teristics and conditions of the mass spectrometers used in
scale, the internationally recommended calibration scale for various studies as reflected in differences in the 6D values of
reporting oxygen and hydrogen isotope ratios of natural SLAP relative to VSMOW reported by many isotope labo-
compounds ( GONFIANTINI, I978 ). The purpose of our study ratories ( GONFIANTINI, 1978). The overall errors in the re-
at temperatures from 25 to 100°C was to determine both ported values of lo3 In ~l,_~(D) also differ; 20.5 ( 1CJ)( REN-
fractionation factors on the VSMOW-SLAP scale, and to NOW, 1970), & I.0 ( I a) ( MERLIVAT et al., 1963; MAJOUBE,
compare our results with the literature data. I97 I ; KAKIUCHI and MATSUO, 1979), or +2.0 ( 1U) ( EHHALT
All of the data on the hydrogen isotope fractionation factor and KNOTT, 1965; STEWART and FRIEDMAN, 1975 ). Within
between liquid water and water vapor obtained in this study these analytical errors, all of the data on the hydrogen isotope
and from the literature below 100°C are shown in Fig. 5. fractionation factor determined in this study and the litera-
Our values of IO3 In N,_,,(D) between 25 and 100°C are in ture, except for that of EHHALT and KNOTT ( 1965) at 2O”C,
good agreement with those of MERLIVAT et al. ( 1963), REN- agree quite well. Above lOO”C, we employed apparatus-2
NOW ( 1970), MAJOUBE ( 1971). STEWART and FRIEDMAN and -3 for liquid-vapor equilibration of water at 130-200°C
( 1975), and KAKIUCHI and MATSUO (1979). It should be and 120-35O”C, respectively, as described above. Using ap-
noted that the results of MERLIVAT et al. ( 1963) below 100°C paratus-3, there is some possibility that the equilibrium be-
were slightly (-4 to +5 in IO3 In PI.,) corrected in tween liquid water and water vapor was disturbed during the
MAJOUBE ( 197 1). A close examination of the data of continuous sampling of the vapor phase (i.e., continuous
IO3 In cul.,( D) between 0 and 100°C shows that those of evaporation of liquid water), thus, possibly causing a kinetic
 J. Horita and D. J. Wesolowski

,
-------Majoube (71)
Kakiuchi & Matsuo (79)
Stewart & Friedman (75)
Ehhalt & Knott (65)
Merlivat et al. (63)
Rennow (70)
This study (apparatus-l)

FIG. 5. Plot of all results of hydrogen isotope fractionation factors below IOO”C, obtained in this study and reported
in the literature. Solid line is calculated from Eqn. 5 in text.

isotope effect; that droplets of liquid water were carried over
with the vapor phase into the capillary tube; or that during
and/or after the condensation of water vapor in the platinum
capillary tube, isotope fractionation and/or reequilibration
occurred. SIMONSON and PALMER ( 1993) and PALMER and
SIMONSON ( 1993) demonstrated that the overall partitioning
constants of HCl and NH4Cl between liquid and vapor phases,
which is more sensitive to the problems mentioned above
than the isotopic fractionation, are reproducible and invariant
with differing sampling rates from 0.5 to 2.0 g/h between
150 and 35O”C, using the same apparatus. Their results in-
dicate that the kinetic isotope fractionation at the liquid-vapor
interface, carryover of liquid droplets, and isotope fraction-
ation and/or reequilibration of the condensing water vapor
are very unlikely sources of error. In order to examine the
effect of different sampling rates of water vapor on the oxygen
and hydrogen isotope fractionation factors, we collected
samples of water vapor at two different sampling rates of 0.4
and 0.9 g/h at the lowest temperature of these experiments,
120°C. Measured values of both oxygen and hydrogen isotope
fractionation factors between liquid water and water vapor
agree well within the analytical errors (‘Table 3), suggesting
that there is very little, if any, kinetic isotope effect during
the slow evaporation of liquid water. In all of the following
experiments from 120 to 350°C, the samples of water vapor
were collected at about 0.3-0.5 g/h.
There is another line of evidence supporting the quality
of our experiments using the dynamic sampling method.
Values of both isotope fractionation factors obtained by the
two different types of apparatus with static and dynamic
sampling methods are very consistent with each other between
120 and 200°C (Tables 2 and 3; Figs. 6 and 8). This good
agreement strongly suggests that the samples of water vapor
obtained by the dynamic sampling method indeed represent
water vapor in isotope equilibrium with liquid water at the
experimental temperatures. Methods of slow distillation
similar to ours were employed over a wide range of temper-
ature in the literature (BAERTSCHI and THORKAUF, 1960,
36.6-99°C; DANSGAARD, 1961, 4 and 23°C; MERLIVAT et
al., 1963,0-60°C; CRAIG et al., 1963,2O”C; MAJOUBE 1971,
0.75-9 1.6”(Z), and their results are generally consistent with
each other as discussed before and below.
All of the results for the hydrogen isotope fractionation
factor between liquid water and water vapor obtained in this
study and from the literature are shown in Fig. 6. Our results
above 100°C are consistent with those of MERLIVAT et al.
( 1963 ) and BOTTINGA ( 1968). The data of KAzAHAyA ( 1986
and pers. commun.) are also similar to our results and those
of MERLIVAT et al. (1963) and BOTTINGA (1968), but they
are more scattered. MERLIVAT et al. ( 1963) and BOTTINCA
( 1968) collected only samples of liquid water for isotopic
analysis, and KAZAHAYA ( 1986) collected only samples of
 T dependence of isotope fractionation factors of water 343 I

Majoube (71)
Kakiuchi & Matsuo (79)
Stewart & Friedman (75)
Ehhalt & Knott (65)
Merlivat et al. (63)
Rennow (70)
Bottinga (66)
Bottinga % Craig (66)
Kazahaya (66)
This study (apparatus-l)
This study (apparatus-2)
This study (apparatus-3)
60 -

2
I
;- 50 -

CY-
0
d
40 -

-lot”““““,,“‘,‘,,‘,‘,,“,‘,“‘,“’
0 50 100 150 200 250 300 350

T (‘Cl

FIG. 6. Plot of all results of hydrogen isotope fractionation factors from 1 to 35O”C, obtained in this study and
reported in the literature. Solid line is calculated from Eqn. 5 in text.

water vapor. Then, they calculated the isotope ratios of the
corresponding samples of vapor or liquid water from isotope
mass-balance equations based on the P-V-T properties of
steam and liquid water. This approach was apparently suc-
cessful in the experiments of MERLIVAT et al. (1963) and
BOTTINGA ( 1968). The large scatter of the results of KA-
ZAHAYA ( 1986) is probably due to experimental problems
during the sampling of water vapor. He collected samples of
water vapor by expanding instantaneously the vapor phase
to a chamber of small volume through a needle valve. It was
not possible to control the sampling rate of water vapor in
this process. Problems such as isotope fractionation upon the
condensation of the water vapor due to adiabatic cooling are
suspected.
All of these data in Fig. 6 clearly demonstrate that the
hydrogen isotope fractionation factor between liquid water
and water vapor, IO3 In cr.,(D), decreases rapidly with in-
creasing temperature, and hydrogen isotope ratios of liquid
water and water vapor become indistinguishable at 220-
230% Above the crossover temperature, water vapor is more
enriched in deuterium than coexisting liquid water. Values
of lo3 In a,.,(D) reach a minimum at about 3OO”C, then,
approach again to zero at the critical temperature of water
(374.1”C).
Oxygen Isotopes
Our results for the oxygen isotope fractionation factor be-
tween liquid water and water vapor from 25 to 100°C are
also in quantitative agreement with most of the literature
data (Fig. 7). Agreement among the literature values between
0 and 100°C are also quite satisfactorily, except for those of
DANSGAARD ( 196 1) at 4 and 23”C, EHHALT and KNOTT
( 1965) at 2O”C, and of STEWART and FRIEDMAN ( 1975) at
3432 J. Horita and D. J. Wesolowski

0 -----------.Majoube (71)
v Kakiuchi & Matsuo (79)
0 Stewart % Friedman (75)
A Baertschi % Thiirkauf (60)
0 Ehhalt & Knott (65)
0 Craig & Gordon (65)
A Dansgaard (61)
----Bottinga & Craig (69)
0 This study (apparatus-l)

6-

5 -

4 “‘~‘~~~~““~‘~,~~‘~~~~‘~‘~(‘~~~~‘~~~~’~’~~”/”
0 10 20 30 40 (‘C;” 60 70 60 90 100

T
FIG. 7. Plot of all results of oxygen isotope fractionation factors below IOO”C, obtained in this study and reported
in the literature. Equation of BOTTINGAand CRAIG( 1969) is based on unpubl. data of Y. Horibe and H. Craig at 3-
IOO'C and those of BAERTSCHIand THORKAUF( 1960). Solid line is calculated from Eqn. 6.

19.4-24.4”C, which are distinctively lower than our results
and the others. Rather large (kO.3 in lo3 In a,.,( “0)) ana-
lytical errors are reported for the results of EHHALT and
KNOTT ( 1965) and of STEWART and FRIEDMAN ( 1975),
compared to the other data (fO.1 in 1u). Equations for the
oxygen isotope fractionation between liquid water and water
vapor based on unpublished data of Y. Horibe and H. Craig
between 3 and lOO”C, and those of BAERTSCHI and THUR-
KAUF ( 1960) were cited in BOTTINGA and CRAIG (1968,
1969). The two equations reported by BOTTINGA and CRAIG
(1968, 1969) differ slightly (up to 0.16 of lo3 In (Y,_“( “O)),
and the equation of BOTTINGA and CRAIG ( 1969) agrees
with that of MAJOUBE ( 197 1) within 0.19 of 10 3 In cu,.,( “0)
in the temperature range from 0 to 100°C (Fig. 7).
All of the results of oxygen isotope fractionation factor
between liquid water and water vapor to 350°C are shown
in Fig. 8. Although the results of BOTTINGA ( 1968) at 134-
300°C and of KAZAHAYA ( 1986 and pets. commun.) at 1OO-
335°C are generally consistent with each other, both datasets
have large scatter. Their values of the oxygen isotope frac-
tionation factor are systematically higher (up to ca. 0.8 of
lo3 In LY,+(“0)) than ours between 100 and 200°C. We be-
lieve that our results are more accurate than those of BOT-
TINGA ( 1968) and KAZAHAYA ( 1986), because both vapor
and liquid phases of water were sampled for isotopic analysis
in our experiments, and because our results obtained by the
two different types of apparatus agree very well in the tem-
perature range from 120 to 200°C (Figs. 6, 8). Furthermore,
the precise and accurate values of the oxygen isotope frac-
tionation factor obtained in this study and from the literature
below 100°C smoothly connect to our data above lOO”C,
rather than to those of BOTTINGA ( 1968) and KAZAHAYA
(1986).
BOTTINGA ( 1968) started his experiments of liquid-vapor
equilibration at the highest temperature (3OO”C), and suc-
cessively collected samples of liquid water with decreasing
temperature to 134°C. The isotope ratios ofthe corresponding
water vapor were then calculated from the isotope mass-bal-
ance equation. In this method, all of the errors of the isotope
analysis of the liquid water and of the isotope mass-balance
equation at high temperatures must have been accumulated
and propagated to low temperatures. At temperatures below
200°C there were very small amounts of liquid water re-
maining in the vessel, and the precision of the BrF, method
used for the 6 “0 analyses of the liquid water was ca. t0.2%0
(Y. Bottinga, pers. commun.). These are probably the reasons
for the low precision as well as systematic error in the BOT-
TINGA ( 1968 ) results of the oxygen isotope fractionation fac-
tor (Fig. 8 ). His results of the hydrogen isotope fractionation
factor are seemingly precise and accurate (Fig. 6), but this
probably reflects the fact that values of lo3 In ol,.,( D) are
small compared to the analytical error (typically f 1.O in
lu) above 200°C whereas the magnitude of lo3 In CY~_~( “0)
is still more than an order of magnitude larger than analytical
error. Because the isotopic compositions of water vapor were
obtained by isotope mass-balance in the BOTTINGA ( 1968)
 T dependence of isotope fractionation factors of water 3433

0 Majoube (71)
V Kakiuchi & Matsuo (79)
D Stewart & Friedman (75)
Baertschi & Thiirkauf (60)
Ehhalt & Knott (65)
Craig & Gordon (65)
Dansgaard (6 1)
- - -Bottinga (66)
Kazahaya (66)
This study (apparatus-l)
This study (apparatus-Z)
This study (apparatus-3)

6-

-0 50 100 150 200 250 300 350

'I'(OC)
FIG.8.Plot of all results of oxygen isotope fractionation factors from 0.75 to 35O”C, obtained in this study and
reported in the literature. Solid line is calcutated from Eqn. 6 in tent.

experiments, any possible systematic erron in his calculations 1979, IO-4O’C) were regressed to a single equation as a func-
were more pronounced in oxygen isotopes than in hydrogen tion oftemperature, lo3 In CU,.~(D)=f( T), from the freezing
isotopes. In the case of the results of KAZAHAYA ( 1986) ex- temperature (0°C) to the critical temperature of water
perimental problems during the sampling of water vapor are (374.1 “C). The results of EHHALT and KNOTT ( 1965) at
suspected as for the data of the hydrogen isotope fractionation ZO”C, and of KAZAHAYA (1986) at lOO-335“C were not
factor (Fig. 6 ). included in the regression, because of their systematic and/
or large random errors, as discussed above. It was found that
DISCUSSION equations with a form in a common use in stable isotope
geochemistry, f( T) = T-” (n = 0, 1, 2, 3 . . .), cannot sat-
Regression to Single Equations isfactorily fit the large number (n = 157) of data from 0 to
350°C with a crossover, and that terms of T” (n = I, 2,
Hydrogen isotopes
3 . .) should be added to the equation. A function with the
Results of the hydrogen isotope fractionation factor be- form ( CI+ h/ r3) was found to explain over 99% of the vari-
tween liquid water and water vapor obtained in this study ance. However, T3, T2, and T terms in decreasing order of
from 25 to 35O”C, and from the literature ( MERLIVAT et al., importance were needed to fit all of the data over the entire
1963, 0-350°C; BOT-IINGA, 1968,134-300°C;RENNOW, temperature range from 0 to 35O’C within experimental error.
1970, at 20°C; MAJOUBE, 197 I, 0.75-9 I .6”C; STEWART and Since the equation 1O’ln mrV(D) =f( T) should have a min-
FRIEDMAN, 1975, 19.4-27.2”C; KAKNJCHI and MATSUO, imum value around 300°C, and there are only a few meas-
3434 J. Horita and D. J. Wesolowski
urements above 3OO"C, these few data points have large le-
verage for determining the shape of the equation above
300°C. This large leverage resulted in positive values of the
fitted equations, lo3 In (Y,_“(D)=f( T), at temperatures near
the critical temperature (374.1 “C). As temperature ap-
proaches the critical temperature (374.1 "C), the fractionation
factor, a,.,(D), must approach unity. Thus, we introduced
a boundary condition of IO3 In (Yf_,(D)crit= f( 374.1 “C)
= 0. Then, all of the data were satisfactorily regressed to the
equation
IO3 In cu,.,(D) = 1158.8( T3/109) - 1620.1(7’*/ 106)
+ 794.84( T/103) - 161.04 + 2.9992( 109/T3),
(5)
within f1.2 (la) (n = t57); T(K). Differences between
measured values of IO3 In LY,+( D) from the literature and in
this study, and values calculated using Eqn. 5 are shown in
Fig. 9. This equation yields a crossover temperature of 229
+ 13°C (lo), and a minimum lo3 In (YI+(D) value of -3.6
at 303°C. Equation 5 gives values of the hydrogen isotope
fractionation factor very close (within 1.O in lo3 In L~I_“( D))
to those of MAJOUBE( 1971), which are the largest dataset
below 100°C (Fig. 5 ) . The equation by BOTTINGA and CRAIG
( 1968) for temperatures from 134 to 300°C yields slightly
larger ( 1.0-I .4 in IO3 In a,.,(D)) and slightly smaller ( 1.O in
IO3 In (Y,.“(D)) values than Eqn. 5 at 140-17O*C, and at
250-27O”C, respectively, with a crossover tem~rature of
223°C and a minimum IO3 ln LX,(D) value of -4.3 at 293°C
(Fig. 6).
Oxygen isotopes
Results of the oxygen isotope fractionation factor by
DANSGAARD( 1961) at 4 and 23*C, EHHALT and KNOTT
( 1965) at 2O”C, and STEWART and FRIEDMAN ( 1975) at
19.4-24.4”C, were not included in the dataset for regression
A Merlivat et al.
0 EhhaIt & Knott
0 ,---...Majoube (71)
n 0 Stewart & Friedman (75)
4-
:
- 0
%Z I I
r3 -6 I , I ,
0 50 100
FIG. 9. Deviation plot of experimental results of
calculated values using Eqn. 5 in text. The data reported by EHHALT and KNOR ( 1965) and KAZAHAYA ( 1986) were
not used in the derivation of Eqn. 5, but are shown for comparison.
to a single equation, because they are distinctively lower than
the others (Fig. 7). It was also shown that the data of BOT-
TINGA ( 1968) at 134-300’C and KAZAHAYA ( 1986) at IOO-
335’C have both systematic and large random errors (Fig.
8). Thus, our results from 25 to 350°C and those of BAERT-
SCHI and THURKAUF (1960) 36.6-99”C, CRAIG and GOR-
DON ( 1965) at 20°C MAJOUBE( 1971) 0.7.5-91.6”C, and of
KAKIUCHIand MATSUO ( 1979) lo-40°C were regressed, with
a boundary condition of lo3 In a,.,( ‘80)cnt = fl374.l”C)
= 0, to the equation
lo3 In cu,.,(‘“O) = -7.685 + 6.7123( I03/T)
- 1.6664( 106/T2) + 0.350411 109/T3), (6)
within to.11 (1~) (n = 112); T(K). A function with the
form (a + b/ T')was found to explain 99.9% of the variance,
but the additional terms were needed to fit all of the data
within experimental error. An equation without the boundary
condition is very similar to the above equation, except for
yielding a small positive value (0.06) of lo3 In c+.,( “0) at
the critical temperature ( 374.1 “C). Differences between
measured values of lo3 In fyl+(‘*O) from the literature and
in this study, and values calculated using Eqn. 6 are shown
in Fig. 10. Equation 6 and that of MAJOUBE ( 197 1) agree
within 0.07 of lo3 In (Y,+(“0) at temperatures below 90°C
(Figs. 7, 10). Two equations for the oxygen isotope fmction-
ation factor were reported by BOTTINGA ( 1968; also, Y. BOT-
TINGA, pers. commun. in FRIEDMAN and O’NEIL, 1977) at
temperatures between 134 and 300°C. The two equations,
which are very similar to each other, give systematically higher
($0.14 and +O. 12 in average) values of lo3 In a,.,( ‘*O) than
those of Eqn. 6, with large errors (kO.23 in 1g) (Figs. 8, IO).
Water-Steam Isotope G~thermometer
Boiling and phase separation of an ascending hot water/
steam body in a geothermal field are major processes con-
V Kakiuchi & Matsuo (79)
0 Kazahaya (86)
l This study apparatus-l)
8 This study apparatus-2
+ This study i apparatus-3 1
1,,
, , I,, , , , , I,, , , ,
150 200 250 300 350
‘I’ (‘C>
IO'In a&“(D) in this study and from the literature, From the
 T dependence of isotope fractionation factors of water 3435

A Baertschi & Thiirkauf (60) 0 Stewart & Friedman (75)

A Dansgaard (61) V Kakiuchi & Matsuo (79)
El Craig & Gordon (65) 0 Kazahaya (66)
0 Ehhalt & Knott (65) 0 This study (apparatus-l)
0 ----Bottinga (66) n This study (apparatus-2)
0 ...........bfajoube (7 1) + This study (apparatus-3)
l.o,p~s~,~~r~,~~ II,I I I I ,I I I ,I 1 I 8, I1 a 1,

0.6

0.4

0.2

0.0

-0.2

-0.4

-0.6

-0.6

-1.0
0 50 100 150 200 250 300 350
T(‘C)
FIG.10. Deviation plot of experimental results of IO3 In (Y,_J‘*O) in this study and from the literature, from the
calculated values using Eqn. 6 in text. The data reported by DANSGAARD (1961), EHHALT and KNOTT (1965),
BOTTINGA(1968),STEWART and FRIEDMAN (1975). and KUAHAYA (1986)were not used in the derivation of Eqn.
6, but are shown for comparison.

trolling the isotopic composition of geothermal waters. In Thus, the value of A6D/A6’*0 depends not only on tem-
some geothermal systems, both steam and liquid water can perature, but also on the isotopic composition of natural wa-
be collected, and their oxygen and hydrogen isotopic com- ter. Assuming RI = RVSMOW,Eqn. 8 can be reduced to
positions could be used to calculate reservoir temperatures
ASD/Ad’*O = (1 - a,.“(D)-I)/( 1 - cu,.,(“O)-I). (9)
within k3-lO”C, using Eqns. 5 and 6. However, it is difficult
to collect samples of water and steam without contamination The value of AbD/A6”0 was calculated from Eqns. 5, 6,
of steam and water, respectively. In addition, cooling of steam and 9 from 0 to 35O”C, and are shown in Fig. 11. The value
after the phase separation may cause condensation of steam, is about 8 near room temperature, which is the typical value
resulting in isotopic fractionation. For these reasons, tem-
peratures calculated from oxygen and hydrogen isotopes of
the water-steam geothermometer are often discordant (MI-
ZUTANI, 1972; TRUESDELL and HULSTON, 1980), and lower
than those of measured well-head temperatures ( MIZUTANI,
1972). Although the oxygen isotope geothermometer is, in
principle, more precise than the hydrogen isotope geother-
mometer due to its higher sensitivity to temperature, es-
pecially above 200°C (Figs. 6, 8), incomplete separation of
steam and water, and the condensation of steam give rise to
a larger systematic error for the oxygen isotope geothermom-
eter.
A third water-steam isotope geothermometer employs the
slope in the 6D-6 “0 diagram, given by the ratio of differences
in oxygen and hydrogen isotopic compositions of water and
steam samples ( GIGGENBACH, 197 1; TRUESDELL and HULS-
TON, 1980):

A?jD/A6’*0 = (6D, - SD,)/(S”O, - 6’*0,). (7)

When liquid water and water vapor are in isotopic equilib- 0 50 100 150 200 250 300 350
rium, the above equation can be written as T('C)
FIG.1I. ValueofAaD/ A6 “0 defined by liquid and vapor water
(1 - ~,-~(D)-‘)(R,lRvs~ow)~ in isotopic equilibrium as a function of temperature, calculated from
A6D’A6’80
=(1 - 01~_“(‘80)-1)(R,/RVSMoW)o_,*~ (8) Eqns. 5, 6, and 9 in text.
3436 J. Horita and D. J. Wesolowski
observed for meteoric waters (CRAIG, 196 I ). The value de-
creases with increasing temperature, due to a rapid decrease
in the value of the hydrogen isotope f~ctionation factor
compared to the oxygen isotope fractionation factor (Figs.
6, 8). The sign of AsD/As “0 changes at about 229°C be-
cause of the crossover of the hydrogen isotope fractionation
factor, and the value keeps decreasing. The Value of AsD/
A$‘*0 calculated using equations reported by BoTTlr\iCi~
( 1968, also Y. BOITINGA, pers. ~ommun. in FRIEDMANand
O’NEIL, 1977) differs slightly (Fig. I 1). The value of AsD/
A6”O calculated using Eqns. 5, 6, and 9 in Fig. 1 I can be
expressed by a simple equation,
AfiD/A6’80 = ( 1 _- a,.,( D)-I)/( 1 -- oc,.,( “0)-‘)
= -186s(T3/109)+ 171.1(~z/lo~)
- 84.03( T/ 103) + 22.65,
from 0 to 350°C within 0.05. Incomplete separation ofwater
and steam, and partial condensation of steam upon cooling
tend to slightly increase the value of AsD/ A&‘*O, thus yielding
a minimum tempe~ture of the phase separation in the cal-
culation. However, these effects on the calculated tempera-
tures are smaller than on those obtained from values of A8D
and A6180 alone. For example, from the isotopic data of
water and steam collected at Otake geothermal field, Japan,
reported by MIZUTANI ( 1972), discordant temperatures of
63- 125°C and 103- 140°C for the phase separation can be
obtained from the oxygen and hydrogen isotope ratios, re-
spectively. Values of A&D/As “0 give nearly constant tem-
peratures of 140- 153 + 1O”C, which are only slightly higher
than the measured steam temperature ( 136°C). It should be
noted that errors in the value of AsD/ A&‘*0 increase with
increasing temperature due to a rapid increase of the errors
in the oxygen and hydrogen isotope fractionation factors rel-
ative to the absolute values of the two fractionation factors
(Fig. 1I ). Thus, the water-steam isotope geothermometer
using the value of A&D/ A8 I80 should be limited to temper-
atures less than about 250°C.
CONCLUSION
Experimental measurements of the oxygen and hydrogen
isotopic compositions of coexisting liquid water and water
vapor have been performed from 2.5 to 350°C using three
different types of apparatus with static or dynamic techniques
for the sampling of water vapor. Our results for the oxygen
and hydrogen isotope fractionation factors determined
the VSMOW-SLAP scale agree well with most of the literature
data below 100°C (i.e., MAJOUBE, 197 1). For the hydrogen
isotope fractionation factor, the agreement between our data
and those of MERUVAT et al. ( 1963) and BOTTINGA ( 1968)
is quite satisfactory also above 100°C. However, the data of
the oxygen isotope fractionation factor reported by BOTTINGA
( 1968) and KAZAHAYA ( 1986) above 100°C have large ran-
dom error with slight systematic error. Two sets of equations
for the oxygen and hydrogen isotope fractionation factors,
which cover different temperature ranges, are currently in
wide use; one for the tem~rature range from 0 to 100°C by
MAJOUBE ( 197 1) and another for the temperature range from
130 to 3OO”C, based on the BOTTINGA ( 1968) data. New
single equations for the oxygen and hydrogen isotope frac-
tionation factors between liquid water and water vapor, based
on our results and most of the literature data, are presented
to cover temperatures from the freezing temperature (0°C)
to the critical temperature of water (374.1 “C).
rfclinott,~f~~~~Li.~-Thanks are due to R. W. Carter and D. A. Palmer
for making possible the experiments using apparatus-3. We also thank
D. R. Cole for his support and insightful advice throughout the course
of this study. Reviews by Y. Bottinga, R. Gonfiantini, and
M. K. Stewart were helpful. K. Kazahaya provided us with his un-
published data. This study was supported by the Geoscience Program
of the Office of Basic Energy Sciences and the Geothermal Technology
Program of the Office of Energy Efficiency and Renewable Energy,
US Department of Energy (DOE), under contract number DE-ACOS-
( 10) 84OR2 1400 with Martin Marietta Energy Systems. Inc. The senior
author participated in the US DOE Postdoctoral Research Associates
Program at Oak Ridge National Laboratory administered by Oak
Ridge Associated Universities.
~dit(~ri(ll jl~~dli77~: B. E. Taylor
REFERENCES
BAERTSCHIP. and TH~RKAUF M. ( 1960) Isotopic-effekt ftir die
trennung der saue~toff-isoto~n I60 und I80 hei der rektifikation
von leichtem und schwerem wasser. H&. Chirn, Actri 43, 80-89.
BIGELEISEN J., PERLMANM. L., and PROSSERH. C. (1952) Con-
version of hydrogenic materials to hydrogen for isotopic analysis.
Anul. Chern. 24, 1356-1357.
BOTTINCAY. (1968) Isotopic fractionation in the system: calcite-
graphite-carbon dioxide-methane-hydrogen-water. Ph.D. disser-
tation. Univ. California San Diego.
BOTTINGAY. and CRAIG H. ( 1968) High temperature liquid-va~r
fractionation factors for H20-HDO-H2’“0. EOS 49, 356-357.
BOTTINGAY. and CRAIG H. ( 1969) Oxygen isotope fractionation
between CO2 and water, and the isotopic composition of marine
atmospheric C02. Earth Pluwn Ski. Lett. 5, 285-295.
CRAIG H. ( 1961) Isotopic variations in meteoric waters. Science 133,
1702-1703.
CRAIG H. and GORGONL. I. ( 1965) Deuterium and oxygen-l 8 vari-
ations in the ocean and the marine atmosphere. in Sfablr I.st~o~~.s
in Owano~ruphic Studio and Puie(~ter~~~rafztrev (ed. E. TON-
GIOR~X),pp. 9-l 30. Lab. Geologia Nucleare.
CRAIG H.. GORGON L. I., and HORIBEY. ( 1963) Isotope exchange
effects in the evaporation ofwater: I. Low-temperature experimental
results. J. Gcophns. Re.s. 68, 50795087.
DANSGAARDW. ( 196 I ) The isotopic composition of natural waters
with special reference to the Greenland ice cap. 1!-&&.cftn Gr~~~~[~
165, l-120.
EHHALTD. and KNOTT K. ( 1965) Kinetische isotopentrennung bei
on
der verdampfung von wasser. TCNUS17, 389-397.
FRIEDMAN1. and O’NEIL J. R. ( 1977) Comoilation of stable isotone
fractionation factors of geochemical interest. USGS Pro/: P&cr
440-k%;, Fig. 8.
GIGGENBACHW. ( 1971) isotopic composition of waters of the
Broadlands geothermal field. Beet, ~~u~ff~d J. Sci. 14, 959-970.
GONFIANTINIR. ( 1978) Standards for stable isotope measurements
in natural compounds. Nutuw 271, 534-536.
HORITAJ.. WESOLOWSKI 1). J., and COLED. R. ( 199.3)The activity-
composition relationship of oxygen and hydrogen isotopes in
aqueous salt solutions: 1. Vapor-liquid water equilibration of single
salt solutions from 50 to 100°C. Gc0chim. Cosmochim. Actu 57,
2797-28 i 7.
KAKI~ICHIM. and MATSCOS. ( 1979) Direct measurements of D/
 T dependence of isotope fractionation factors of water
H and ‘8O/16O fractionation factors between vapor and liquid
water in the temperature range from IO to 40°C. Geochem. J. 13,
307-3 1 I.
KAZAHAYA K. ( 1986) Chemical and isotopic studies on hydrothermal
solutions. Ph.D. dissertation, Tokyo Inst. Technology.
KISHIMA N. and SAKAI H. ( 1980) dxygen-18 and deuterium deter-
mination on a single water sample of a few milligrams. Anal. Chem.
52,356-358.
MAJOUBEM. ( 1971) Fractionnement en oxyg;ne 18 et en deutkrium
entre l’eau et sa vapeur. J. Chim. Phys. 68, 1423-1436.
MERLIVATL., BOTTERR., and NIEF G. ( 1963) Fractionnement iso-
topique au tours de la distillation de I’eau. J. Chim. Phys. 60,56-
59.
MIZUTANIY. (1972) Isotopic composition and underground tem-
perature of the Otake geothermal water, Kyushu, Japan. Geochem.
J. 6, 67-13.
PALMERD. A. and SIMONSONJ. M. ( 1993) Volatility ofammonium
3437
chloride over aqueous solutions to high temperatures. J. Chem.
Eng. Data 38,465-414.
RENNOWM. ( 1970) Gleichgewichts- und kinetische trennfaktoren
bei der verdunstung von wasser. Staatsexamensarbeit, Univ. Hei-
delberg.
SIMONSON J. M. and PALMERD. A. ( 1993) Liquid-vapor partitioning
of HCl(aq) to 350°C. Geochim. Cosmochim. Acta 51, l-7.
STEWARTM. K. and FRIEDMANI. ( 1975) Deuterium fractionation
between aqueous salt solutions and water vapor. J. Geophvs. Re.y.
80,3812-3818.
TRUESDELLA. H. and HULSTONJ. R. ( 1980) Isotopic evidence on
environments of geothermal systems. In Handbook gf Environ-
mental Isotope Geochemistry: The Terrestrial Environment A (ed.
P. FRITZ and J. Ch. FONTES), pp. 179-226. Elsevier.
YOSHIDAN. and MIZUTANIY. ( 1986) Preparation of carbon dioxide
for oxygen- I8 determination of water by use of a plastic syringe.
Anal. Chem. 58, 1273-1275.