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Isotopes in Environmental and Health

Studies
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The isotopic composition of

evaporating waters – review of the
historical evolution leading up to the
Craig–Gordon model
a
Joel R. Gat
a
Department of Environmental Sciences and Energy Research ,
Weizmann Institute of Science , Rehovot, Israel
Published online: 04 Mar 2008.

To cite this article: Joel R. Gat (2008) The isotopic composition of evaporating waters – review
of the historical evolution leading up to the Craig–Gordon model, Isotopes in Environmental and
Health Studies, 44:1, 5-9, DOI: 10.1080/10256010801887067

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 Isotopes in Environmental and Health Studies
Vol. 44, No. 1, March 2008, 5–9

The isotopic composition of evaporating waters – review of the

historical evolution leading up to the Craig–Gordon model
Downloaded by [University of California Santa Cruz] at 10:15 01 February 2015

JOEL R. GAT*
Department of Environmental Sciences and Energy Research, Weizmann Institute of Science,
Rehovot, Israel

(Received 21 June 20007; in final form 24 September 2007)

Attempts to explain the variations in the abundance of heavy isotopic species of water throughout the
hydrologic cycle solely by means of the classical equilibrium-fractionation processes could not be
reconciled with measured abundances of the isotopic species in residues of “evaporation systems”.
Focusing on the evaporation of surface waters, the paper follows the evolution of the concepts during
the 1950-ties and early 1960-ties leading up to the formulation of the Craig-Gordan Evaporation Model
in 1965.

Keywords: Craig-Gordon model; Evaporation; Hydrogen-2; Isotope effects; Oxygen-18; Review;

Water

The role of evaporation as the pivotal link in the hydrological cycle was recognised since
antiquity. ‘However the vapours were rising from the earth and watering all the surface of
the soil’ (Bible, Genesis 2). It was indeed a focus of interest right from the beginning of
modern scientific research, as exemplified by the amazing report of Edmund Halley in the
Philosophical Transactions of the Royal Society from the year 1694 in which the rate of
vapourisation as measured was compared to the depth of precipitation and therefore it was
concluded ‘that the sun and wind are much more the causes of evaporation than any internal
heat or agitation of the water’.
Following the discovery of the natural occurrence of the stable heavy isotopes of oxygen
[1] and of hydrogen [2] in nature, a wide spectrum of natural waters were investigated prior
to World War II, establishing the depletion of the heavy isotopes in the meteoric waters
compared to the oceans and the enrichment of the heavy isotopic species in surface waters
exposed to evaporation (reviewed by Rankama, [3]). Thode [4] showed in a few examples that
the measured values as given by Vrooman [5] indeed vindicated the expected pattern based
on the different vapour pressures of the isotopologues, namely depleted values in the vapour
and in fresh waters and enriched ones in evaporative systems, as exemplified by the value for
the Dead Sea, see table 1.

*Email: cigatj@wisemail.weizmann.ac.il

Isotopes in Environmental and Health Studies

ISSN 1025-6016 print/ISSN 1477-2639 online © 2008 Taylor & Francis
http://www.tandf.co.uk/journals
DOI: 10.1080/10256010801887067
 6 Joel R. Gat

Table 1. Sources of relative abundances of 18 O [5].

Source Relative abundance of 18 O

Freshwater Lake Ontario 1.00

Ocean water 1.009
Atmospheric water vapour over Lake Ontario 0.991
Glacier water, Lake Louise 0.977
Dead Sea water 1.020

Improved mass-spectrometric techniques by Nier [6] and McKinney et al. [7] enabled
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more precise measurement of the natural variations of abundances of both the hydrogen and
oxygen stable isotopes. Thus in the early 1950s the alumni of Urey’s ‘Chicago’ group and their
European colleagues conducted surveys of the isotope variations in the ocean domain and other
natural waters [8–11]. Results of these surveys confirmed the pattern inferred by the previous
workers, as summarized by the ‘Boato Diagrams’ [12], with depleted heavy isotopic values
in the meteoric part of the water cycle and enriched ones in evaporitic systems. Friedman [9]
noted a slight enrichment of deuterium in the ocean surface water in mid-latitudes, which he
attributed to the preferred evaporation of the light isotopologues, and a similar pattern was
noted by Dansgaard in the oceanic domain [10]. Epstein and Mayeda [8] similarly explained
enriched 18 O values in surface waters from the Florida wetlands by evaporative enrichment.
Baertschi [11] noted the linear correlation of the enrichment of the heavy oxygen isotope and
salinity in oceanic samples as expected for an evaporation process.
Craig at LaJolla then embarked on an ambitious survey of the isotopic composition of
hundreds of samples as part of his studies on geothermal waters, but as the following quotation
shows the survey confirmed the pattern previously reported but could not be explained in the
frame of an equilibrium fractionation concept:

‘Several hundred fresh water samples from all over the world were analysed for deuterium and oxygen 18 in the
course of a study of the isotopic composition of volcanic waters and steam.
. . .Heaviest values were found in East African lakes and the Nile River; lightest values in Greenland snow
and ice. For samples unaffected by extensive evaporation there is good correlation between D and O18 content,
as is expected from the theory of Rayleigh distillation. . .
. . .the waters of Borax Lake, Searles Lake, Owens Lake, Clear Lake and Lake Tahoe are affected by excessive
evaporation as described below, and thus do not follow the relationship given above.
. . .If the evaporation of water took place in such a way that the vapour leaving the system was continuously
in equilibrium with the liquid, the deuterium–oxygen-18 relationship should be such that such waters should
plot on the same line as freshly precipitated meteoric waters in a deuterium–oxygen-18 graph.
. . .However it was found that natural evaporation does not take place in this way, and in fact at ordinary
temperatures the relationship is governed by ε values of approximately –0.071 for hydrogen and –0.013 for
oxygen. Thus waters evaporated at ordinary temperatures plot on lines with a δD/δO18 slope of about 5.5, rather
than of 9 as in the equilibrium case, because the value of ε of oxygen differs by almost a factor of 2 from the
equilibrium value.
Natural evaporation was studied at Steamboat Springs, Nevada; Clear Lake and Borax Lake, California and
in East African Lakes. A δD/δ O18 ratio of from 5 to 6 was found in each case and the same ratio was obtained in
laboratory studies. No simple model molecular or diffusional distillation can adequately explain this relationship,
and the cause of this effect is not yet known’ [13].

Based on the (temperature-dependant) difference of the saturated vapour pressure of the heavy
and light isotopic species of water [14, 15] and assuming a Rayleigh-type enrichment of the
residual waters in an evaporating water body as a result, it was expected that the residues of
such systems would show rather extreme enrichment of the heavy isotopes. However, this
expectation was not realized in practice. This prompted a closer look at the process of isotope
enrichment in surface waters by both more detailed observation on natural systems and by
controlled evaporation experiments in the laboratory or on open evaporation pans. As is evident
from the following cited conclusions, there was mounting evidence for the effect of exchange
 History of the Craig–Gordon model 7

with ambient moisture in limiting the enrichment of the heavy isotopes in evaporating waters
and further evidence that non-equilibrium isotope effects also played a role.
Focusing on the first of these effects, namely the exchange with the ambient moisture, Craig,
Gordon and Horibe concluded as follows:
‘The present simple experiments have served to show that molecular exchange with atmospheric water vapor
predominates over the net isotopic effect of a simple evaporation process. It seems that the molecular exchange
rate with atmospheric water vapor may well be the most important term in the isotope balance of a natural water
body . . . We have observed such an approach to a stationary isotope state in lagoons of high evaporation’ [16].

Similarly Friedman et al. observed in studies on salt pans at the southern end of San Francisco
Bay that:
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‘it is obvious that the seawater concentrates deuterium to a small extent during evaporation. However the final
deuterium concentration in the brine is similar to that of the surface water in the vicinity. It is possible that the
sea fog that occurred almost daily during the month or so before our sampling period acted to equilibrate the
brine with the surrounding surface water’ [17].

Gonfiantini in seminal studies on evaporation of very saline systems added a further dimen-
sion to the discussion, by pointing out that the reduced thermodynamic activity of the saline
solutions also acted in the sense of reducing the enrichment of the heavy isotopic species in
the final stages of the evaporation of saline solutions. This was summarised as follows:
‘By means of simple laboratory experiments, it can be observed that NaCl saturated water and distilled water
reach different steady isotopic composition during evaporation. This fact is attributed to the different activity of
water. If activity of water changes during evaporation, as in the case of unsaturated solutions, an inversion of the
isotopic enrichment is observed’ [18].

The controlling importance of the exchange with the ambient moisture on the isotope com-
position of surface waters was confirmed independently by the tritium balance of the surface
waters during the 1960s, at a time when the high tritium levels in the atmospheric moisture
provided a reliable tracer. Pertinent studies were those of Oestlund and Berry [19] and Imbo-
den et al. [20] on Lake Tahoe; they determined that 68% of the tritium input to the lake was
the result of molecular exchange with the ambient moisture while only 32% was added by
precipitation.
Some of the early laboratory evaporation experiments were conducted into a controlled
atmosphere, e.g. by Craig, Gordon and Horibe in La Jolla [16], by Ehhalt and Knott in Heidel-
berg [21] and by Dansgaard in Copenhagen [22]. These experiments suggested a higher 18 O
fractionation than expected from the vapour pressure difference between the isotopologues, as
had indeed been hinted at before. Dansgaard showed that this effect increased at higher evap-
oration rates under larger air velocities. The role of molecular transport by diffusion through
the air column as the rate-determining step in the evaporation was then explored by conduct-
ing such experiments both in air or dry nitrogen and for comparison, in light gases such as
hydrogen [21] or helium [23]. The result seemed to confirm, based on the oxygen-18 data, that
a phase of molecular diffusion was involved in the evaporation process from an open surface,
which adds to the isotope fractionation resulting from the difference in vapour pressure (the
equilibrium isotope effect on the phase change).
Following observations on the marine lagoons in the Persian Gulf, the situation was aptly
summarised by Lloyd as follows:
‘1. Isotopic enrichment by evaporation of sea water does not occur by an equilibrium process.
2. The kinetic isotope effect and molecular exchange with atmospheric vapor noted in the fresh water
experiments of Craig et al. [16] were also found in this study.
3. The kinetic isotope effect tends to increase the rate of isotopic enrichment while the atmospheric exchange
effect tends to retard enrichment compared to an equilibrium evaporation. The significant factors in natural
environments which appear to control the isotopic enrichment rate are the salinity of the water, the atmo-
spheric humidity and the difference in isotopic composition between the initial water and the atmospheric
vapor.
 8 Joel R. Gat

4. In natural sea water brines the influence of atmospheric exchange predominates over the kinetic effect
throughout the evaporation while in brines produced in arid closed basins on the continent the kinetic effect
may predominate in the early stages of evaporation’ [24].

Unlike in the case of oxygen isotopes, the possible effect of the diffusion of the water iso-
topologues 1 H2 HO compared to that of 1 H2 O on the fractionation of the hydrogen isotopes
is expected to be much smaller relative to the equilibrium fractionation of these isotopes and
only the higher precision measurements later suggested a similar effect. With more precise
data at hand, Craig now summarised the situation as follows:

‘The straight line δD = 8 × δ 18 O + 10 is seen to be an adequate fit to the data, except for waters from closed
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basins in which evaporation is a dominant factor governing the isotopic relationship. The samples which fit the
dashed line at the high enrichment end of the curve represent rivers and lakes in East Africa. They fit a line
with a slope of around 5, in contrast to the slope of 8 found for most of the data. Studies of evaporation in
the laboratory . . . . show that in free evaporation at ordinary temperatures the heavy isotope enrichment ratio
δD/δ 18 O consistently follows a slope of about 5. Many of the points falling to the right of the line have a similar
slope of 5 when connected to points on the line which represent direct precipitation in the same area. . . .
It seems, therefore, that atmospheric precipitation follows a Rayleigh process at liquid–vapor equilibrium,
as first proposed by Kirschenbaum, but that the process of free evaporation at room temperature is governed by
kinetic factors’ [25].

With the above-mentioned in mind, Craig and Gordon put forward a more explicit (one dimen-
sional) evaporation model [26], based on the best that physical insights into evaporation could
provide, as a frame for quantitatively describing the process. The Craig–Gordon model [26]
follows the flux of the isotopic water molecules through both the liquid and atmospheric
boundary layers into an air layer of well-defined humidity. They initially considered the phase
transition at the liquid/air boundary to follow an equilibrium fractionation, followed by a dif-
fusive region where the transport was governed by the difference in molecular diffusivities of
the isotopic molecules in air, respectively, HDO vs. H2 O and H18 16
2 O vs. H2 O, followed by non-
fractionating region of turbulent mixing. In the absence of direct measurements, the diffusion
coefficients were calculated on the basis of classical ‘gas kinetic theory’, which predicts a
larger effect for the substitution of H18 16
2 O for H2 O than that of the deuterated molecule. Com-
parison of experimental data with the model predictions then showed discrepancies, which
they attributed to additional resistances such as an ‘accommodation coefficient’.

Craig and Gordon have shown that the rapid molecular exchange between the liquid water and atmospheric
vapour, which produces a stationary isotopic state in an evaporating liquid, is characterised by kinetic iso-
tope effects that cannot be explained simply by differences in molecular diffusion coefficients of H2 O16 ,
HDO and H2 O18 . They developed the theory of these effects in terms of diffusional models plus an interfa-
cial disequilibrium in which isotopic fractionation is also produced by differences in isotopic condensation
coefficients. The contribution of molecular diffusion to the fractionation can be calculated on the basis of
a hydrodynamically smooth surface with a fixed laminar layer or from a statistical ‘micro-eddy’ model for
a rough surface that is directly in contact with turbulent eddies. They showed that the statistical rough sur-
face model predicted the H2 O18 fractionation observed in the Craig–Gordon–Horibe experiments, but that
the HDO effects are larger than expected, so that interfacial disequilibrium provides a significant contribu-
tion to the transport resistance, but it is found that the effect is only of the order of a few percent of the
condensation resistance that can be produced by the action of certain organic monolayers on fresh-water
surfaces [23].

Another possible cause for the anomalous deuterium effect, namely diffusion in the liq-
uid boundary layer, was investigated by measuring gas invasion into the liquid. As reported
by Siegenthaler [27], the possible effect of such a mechanism, however, was also not large
enough to account for the apparent disparity. Indeed, it was only following the direct measure-
ment of the diffusion coefficients of the deuterated water molecules through air by Lillianne
Merlivat [28], which showed a larger isotope effect than given by gas kinetic theory, possibly
due to some hydrogen bonding in the gas phase, that the widespread application of the model
was launched.
 History of the Craig–Gordon model 9

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