VoL. 84, NO. C8 JOURNAL OF GEOPHYSICAL RESEARCH AUGUST 20, 1979 Global Climatic Interpretation of the Deuterium-Oxygen 18 Relationship for Precipitation LILIANE MERLIVAT AND JEAN JouzeL, (CEA/DRA/SRIRMa, Centre d Etudes Nucléaires/Saclay, Bolte Postale 2, 91190, Gif-sur-Yeete, France ‘A theoretical model is derived to account for the devterium-oxygen 18 relationship messured in meteoric waters. A steady state regime is assumed for the evaporation of water at the ocean surfuce and the subsequent formation of precipitation, The ealeulations show that the deuterium and oxygen IS content in precipitation can be taken as linearly related, From the slope and the intercept (known as the ‘deuterium excess) of the 6D-§O linear rel ship for precipitation we compute the mean values on a global scale of the evaporating ocean surface temperature and the relative humidity of the air masses ‘overlying the oceans. The deuterium exces is primarly dependent on the mean relative humidity of the ar masses formed above the ocean surface, Paleoeimatie data may be obtained by this isotopic method from the analysis of old water and ice samples. A moisture deficit of te air over the ocean, equal to only 10%, in comparison to 20% for modern conditions, is deduced from the deuterium-oxygen 18 distribution measured in groundwater samples older than 30,000 years Iwtropuction It is well established that the deuterium and oxygen 18 concentrations in precipitation are linearly related. The equa- tion proposed to express this fact (see, among others, Craig [1961] and Dansgaard (1964}), while being empirical, is very well obeyed in general, This linear relationship has been of {great use in hydrogeology. On a worldwide scale it is observed that the deuterium or oxygen 18 content of precipitation is linked to the mean air temperature at the site of collection, Basically, the temper- ature-isotope relation is the result of conditions prevailing in the cloud at the time of formation of the precipitation. At the moment, observations of conditions in clouds are insufficient to formulate and subsequently check a quantitative model to account for the isotopic composition of rain. (Ona global scale the concentration of both deuterium and oxygen 18 together in precipitation is characteristic for an average climatic condition. In this article we develop a theoret- ical model to evaluate the mean sea surface temperature at the time of formation of a moist air mass and to evaluate its telative humidity. Our purpose is to obtain climatic informa- tion from an interpretation of the deuterium-oxygen 18 distri- bution in precipitation; first we look at modern precipitation and then at old groundwaters and deep ice cores. ‘THeoreTicat Mopet Let us consider the global evaporation-precipitation-runoft cycle shown in Figure 1, where dNg and dN are the net fuxes of evaporation and precipitation, 6, is the isotopic concentra- tion of the ocean (D or #0), és the isotopic concentration in the net evaporated flux, ap represents the isotopic concentra- tion in individual precipitation, dp is the weighted mean of isotopic concentration in all precipitation, and 60y is the inital isotopic concentration in moist air masses prior to alteration by precipitation. We assume also that all the water in moist air masses is precipitated, therefore ,5 Bp 8) ‘We develop first an expression for the isotopic concentra~ tion 4, in moist air and compute 4p for precipitation formed in these air masses, In the atmospheric boundary layer above the ocean surface the flux of evaporation £ is constant, We have E = dNe/dt, or E 3p 7 Mea) @ where p isthe air density, q is the specific humidity at the height z within the boundary layer, and g, is the saturated specific humidity atthe air-water interface (= = 0). In this particular case, z equals the thickness of the bound ary layer and P isthe profile coefficient at z. Previously [Merlivat and Coamtic, 1915; Merlivat, 1978a}, we have derived a general expression for the profile coefficient ©) but pr with ou © D™* ©) ‘The term u. stands for the friction velocity, and py and pr are the molecular and turbulent resistances, respectively. The term py is proportional to the ~n power of the molecular diffusivity D of water vapor in air. The term pr includes the aerodynamic parameters Equations analogous to (4), (5), and (6) can be written for each isotopic molecule; the subscript fs used for the isotopic entities, We have ‘We assume that the atmospheric system is in a steady state E_ yy, a) om for the three isotopic molecules (H, "0, HDMO, and H, "0). » a with dNg = dNp o pu Dio* ae= @ 4 = Rats 1 = Re Copyright © 1979 by the American Geophysical Union. un Re Paper number 960627 5029 (0148.0227/79/009C-0627S01.003030 Fig, 1. Schematic circulation of water on a global scale Ry is the isotopic concentration in the water vapor in ther- modynamic equilibrium with the liquid at the air-water inter- face at the temperature T, of the ocean surface. If a is the isotopie separation factor between liquid and vapor at T,, we have Re = Rilo Reis the isotopic concentration in the liquid and R, stands for the isotopic concentration in the water vapor at the top z of the boundary layer. From (4) and (7) we calculate the isotopic concentration in the evaporating moisture, Ree B/E 8) In changing from the absolute isotopic concentration scale to the @ notation, calculated as the relative deviation with respect to the isotopic concentration in the liquid Rz, we obtain from (4), (7), and (8), K+ 6.) teed Se with k= 1 ~ 1y/P and b= q/qy. The term h is the relative humidity of the air mass at 2. ‘When we take into account the constraints imposed by the steady state regime on the whole water cycle (see equations (2) and (3)) we can deduce from (9) the expression of 6,, Li-k Ou" ise! (a0) kag %o 10 smooth regime e 0 2 MenuivaT ano Jouzet: DeUTERtus-OxvoeN 18 RELATIONSHIP Introducing ¢o, the relative difference between the molecular diffusivities in air for the different isotopic species, ea Dd, and using (5) and its isotopic analog, we obtain (+ e)'=1 T+ oF + r/o) a Brutsaert [1975a, 6] has developed a model for the evapora. tion of water. This model was shown to be in good agreement with observed fractionation of the isotopic species of water ‘occurring when water is evaporated and transported into the atmosphere under various laboratory (wind tunnel) conditions [Merlivat, 1978a}. In the Brutsaert model, pr and py are re lated by the following two expressions for smooth and rough ‘water-atmosphere interfaces, respectively sea dintet / iss)" net Jose)” ot In these relations,» is the kinematic air viscosity and x isthe Von Karman constant x = 0.4. The surface roughness z is computed from the wind velocity distribution of w versus 2, featint Pu Xt us Stine x" % R,, is the surface roughness Reynolds number such that tu, and 2, are not independent quantities. Charnock’s equation describes their relationship, 20 = uy2/S1.1g, g being the accel eration of gravity. We have experimentally established that Brutsaert’s equa- tion for smooth surfaces is valid for Re, < 1; when Re, > I, the equation for rough surfaces should be used. In both cases the values of k (equation (11)) can be computed as a function of the friction velocity ug. The values of ey occurring in (11) are known to be ¢p = 25.1% for deuterium and ¢p = 28.5% for oxygen 18 [Merlivat, 19786]. Figure 2 shows the numerical rough regime a u, cm/s Fig. 2. Variation ofthe kinetic fractionation factor for oxygen 18, ky, with the friction velocity or the mean wind speed atz = 10m.Menuivat aN Jouzet: DrurEnius-OxvcEN 18 RELATIONSIIP s T,% , 3. Variation of F, with the condensation temperature 7, values of & for oxygen 18. For practical purposes the mean wind speed at z = 10 m is indicated on the horizontal scele From (I1) we compute the ratio of k for deuterium and oxygen 8, ko: (odo Kaz oag In summary, we have shown that through (10) and (11), the two main equations, we can compute the isotopic content of the water vapor leaving the ocean surface. It depends on a, which is a function of sea surface temperature T,: A, the relative humidity of the air masses formed; and k, which is @ function of the wind regime in the boundary layer close to the surface of the ocean. We will discuss later the best mean value to seleet for k according to the mean wind speed regime prevailing on the ocean, We note, however, that the range of variation of k is small for a wide range of variation of u We will now calculate the isotope distribution in a moist air mass in which condensed water is in part kept within the cloud and in part removed as precipitation, ‘Weill assume that there is no mixing between the moist ait mass and the outside ai, the liquid in the cloud isin equilib- rium with the vapor, and the precipitation leaving the system has the same isotopic concentration as the liquid remaining in te cloud. With these assumptions we have dng + di, + dy = 0 da, + dic, + dy, = 0 = 0.88 na080 090 & 7% 3% T% Fig, 4. Variation of s, as « function of 7, for different values of h 5031 rr Fig. 5. Vs oO toh ition of d, asa function of where ne, 1, and np are the number of moles of vapor, liquid water in the cloud, and precipitation, respectively, while the equilibrium condition requires that le an, dnp my ‘At time ¢ the isotopic concentration in the vapor phase is equal to: From these equations we derive an equation for Ry, and after logarithmic differentiation we obtain dy _ (a= Ndty ~ ny de R im a, and hence for the precipitation, Re | (@= Ndty =m dee , dee Re Tip + az @ Rewriting the last equation in terms of & mz (mass of the liquid), and m, (mixing ratio of the air mass at the time 2), we get ap T+ oe If no liquid wate is kept within the cloud (m, = 0) and if is constant (da/a = 0), equation (12) becomes a Rayleigh distillation equation. If all the iquid is kept in the cloud, the integrated form of (12) becomes identical to the relation de- ea = 1) diy + ms dae ams + ami) (2) TABLE |. Parameter Values home OS Ake dae 05 0 868OBT TS 292 06 64 28 DS 07 3 638288 08 B21 1078107 09 Sul S40 196 53 og BIS, 1B BT 107 os SBT 1075032 scribing the isotope distribution in a hailstorm [Jouzel et al., 1975). ‘We think that an interesting feature of the model we have developed is that it takes into account the presence of liquid in various proportions inside the clouds. DEUTERIUN-OXYGEN 18 RELATIONSHIP FOR THE PRECIPITATION We have one equation (equation (12)) for HDO and H,'*0. In the following, the equilibrium isotopic separation factors are called « and 8 for deuterium and oxygen 18, respectively, ‘The two equations giving the variation of GPp and Ps, are linked by a relationship depending on m,, mz, a and B, i.» the physical conditions prevailing in the cloud (my, mz, and the condensation temperature). Observations have shown that the deuterium and oxygen 18 contents in meteoric watersare linearly related (Craig, 1961), Py = 8 Puy + 10 (13a) or, according to Dansgaard [1964], using mean isotopic weigh- ted values for precipitation, Po = (8.1 £0.1) APmo + (11 1) (136) To compare the empirical equations (equations (13a) and (136)) with our model, we obtain, from the two versions of (12) (HDO and H,"0), equation (14), giving @Pp as a func- tion of Pia; daPo daPa T+ 8P a ata = din + de | TH OP ame tam) ‘ari, + am) BIB = 1) ding + me dB Bem, + Sm.) Now we examine which values of the physical parameters contained in (14) will result in the observed linear relationship between Pp and 4Pu (equations (13a) and (136). Equation (14) is the basic relationship for calculating the values of Pp and Pup at different stages of the condensation process in the moist air mass. This is done via a step by step rhumerical integration, starting at the point @P, (@Pi.y 2P.%) fon the curve @Pp = f(@Pm), with 4P,, and 2Pi%o being the isotopic concentrations in the initial precipitation, From such calculations, done with reasonable values for the physical pa- rameters entering (14), as will be discussed in the next para~ graph, we conclude that Pp and Puy are linearly related for condensation temperatures ranging from T; to ~20°C (lower limit assumed for the condensation of water vapor to liquid in the air mass) and that the tangent with slope s to the curve Pp = {(@P%), (equation (14)) changes very little in going from T; to ~20°C, such that s; = s and the intercept d of this tangent with the y axis is very close to a. Before going further we discuss now the computation of the coordinates aP,, and 4P."> of point Py. At point Pi, s = s, d= dy a = a8 = Band T= 7, In general, (ay = 14 4Po 8 la~1) 5" TF BP a @ BS (15a) where rode) (ete a)/ (e+ 5) (156) Menuivar AND JoUzet: DEUTERIUN-OXYGEN 18 RELATIONSHIP and a= oercemy= (140%) / (1+ 0 P being the total air pressure. The equilibrium between the condensed phase and the water vapor at point P, requires that for deuterium, 1+ 6P,,= all + a%,) (15e) (160) and for oxygen 18, 1+ aim = Bill + eV) To evaluate 2%, and @Vs%o, see (10). Using (16a), (166), and (15a), we obtain that at point P,, (166) i, with L = Lhe, ke, ht) Shy T= kolt Since the numerical values of kp and kwp are small (<10~, the factor L is always close to unity (I < L < 1,001), The factor G, (equation (17)) equals unity because at point P,, mz, = 0. In our model, water at the sea-atmosphere interface evapo- rates at temperature Tz and causes a relative humidity hin an air mass situated directly above the water surface. When this air mass is displaced vertically and cools, condensation of water vapor causes the first liquid to be formed at 7; and P. Assuming a standard atmosphere with AT/Az = ~6.5°C/km, T, and P, can be calculated when 7, and A are known. With (158) the function value F, can be evaluated because « and are known as functions of temperature [Majoube, 1971) In Figure 3 we have plotted F, versus T;, 7; ranging from 8°C to 25°C, corresponding to Te = 20°C for h = 0.6 and T. = 30°C for k= 0.85. In the range of conditions, closely resembling natural conditions, F, varies from 0.98 to 1.02. This means that s, (equation (17), L = I and G; = 1) depends to a good approximation only on a and 6, which is @ well-known obser vation. In Figure 4 we have plotted s, as @ function of 7, for various values of fh, using the Majoube [1971] equations for a and 8 The intercept d, is given by dy = 6P,,— S:8Pim (18) land can be calculated while using (10), (16), and (17). Com puted values of d; are plotted in Figure $ versus h for three different values of 7,, with k as for a smooth surface model and uy = 20cm/s. Obviously, d, depends very weakly on Te Once the initial conditions at point P; are calculated, 6Po ‘and Pip can be computed for different stages of the com densation process in the ascending and travelling air masses. For the sake of demonstration, Table 1 shows the velues ofs and d as well as the values of 5 and dy for T. = 25°C. Parameter m, indicates the percentage of liquid water kept within the cloud, The values given in the table have beet calculated for an isobaric process after the condensation his started. No differences for the values of s and d are found if P/dT = 5 mbar/°C and 10 mbar/°C. ‘We conclude from these numerical examples thatthe deute rium-oxygen 18 relationship measured for precipitation semMERLIVAT AND JoUzEL: DEUTERIUN-OXVGEN 18 RELATIONSIHP TABLE 2, Values of Deuterium Excess tS eel ae atin oe eg Ye BRS RB Ba in en plesin nature depends mainly on the physical characteristics of the sir masses at the origin of the precipitation. INTERPRETATION OF THE EQUATION 8Pp = s@Pay +d In geochemistry, d is commonly called the deuterium excess. ‘The relations (10), (16), and (17), (18) show that d depends on the values of Te, h, and the kinetic fractionation factors ko and Joy (Figure 2). In a study of the global circulation of water vapor in the atmosphere, Erikson and Bolin (1964) write that more than 95% of the ocean surface is smooth. We will thus consider the expressions of kp and ku in the smooth surface model of evaporation to check the dependency of d on the aerodynamic conditions at the surface of the ocean. The values ‘ofd listed in the Table 2 have been calculated for T. = 25°C. We observe that d is only slightly dependent on the wind regime in a likely occurring natural range of variation. Figure Sshows a weak dependency of d on Zz. Values of d are at first fixed by the initial relative humidity of the air masses giving the precipitation, The data shown in Figure 5 are en important result of this study. Through the results shown in Figures 4 and 5, the inter- pretation of the parameters of (13a) and (136) is straight- forward in terms of mean evaporation temperature at the ocean surface and mean relative humidity of the air masses formed. Using (13a), we derive h = 81% and T, = 26°C, while (12b) gives h = 79.5% (41.5%) and Ty = 25.4°C (£2.2°), The isotopic method allows a precise determination of h but appears less sensitive for Discussion The value T, = 254°C seems quite reasonable, since the main sources of water vapor over ocean areas are the sub- tropics and the trade wind belts between latitudes 10° and 2S°N and 10° and 25°S. Mean sea surface temperatures for these latitude ranges are found in the book of Sverdrup etal {1946}. A rough computation of a weighted mean temperature, {aking into account the relative areas of the three oceans, gives trvalue of 247°C, This figure isin reasonable agreement with the value of T, = 25.4°C (42.2°) that we have derived We have no direct way to discuss the value off, The isotopic rethod does not allow us to draw conclusions about the aerodynamic regime at the ocean surface because the kinetic fractionation factors depend only very weakly on the wind 5033 speed values. For this reason the knowledge of 7; and h does not provide information about the evaporation rate at the ‘ocean surface. For T. = 254°C and A = 0.795 we have £ = 0.23U, where E is given in meters of water per year and U(= = 10) is given in ‘meters per second. With our model we can derive paleoclimatic data from the isotopic analysis of old water samples. Sonntag et al. [1979] report for Sahara groundwaters older than 20,000 years a deuterium excess calculated asd = 2D ~ 8 mp, equal to Sto ‘Our model indicates that this corresponds to paleohumidity of the air over the ocean of 90% in comparison to 80%, as computed for modern conditions. Obviously, more experimental data are needed before we can determine a general climatic trend for the last ice age. After we have checked that our theoretical model can be extended toward lower cloud temperatures when solid precipi- tation is formed we will investigate the deuterium-oxygen 18 distribution in ice samples accumulated in Antarctica. 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