D/H ratios of fluid inclusions of Soreq cave (Israel) speleothems as a guide to the Eastern...

Ž .Chemical Geology 166 2000 183–191www.elsevier.comrlocaterchemgeo

ž /DrH ratios of fluid inclusions of Soreq cave Israel speleothemsas a guide to the Eastern Mediterranean Meteoric Line

relationships in the last 120 ky

Alan Matthews a,), Avner Ayalon b, Miryam Bar-Matthews b

a Institute of Earth Sciences, Hebrew UniÕersity of Jerusalem, Jerusalem 91904, Israelb Geological SurÕey of Israel, 30 Malchei Israel St., Jerusalem 95501, Israel

Received 17 March 1999; accepted 21 September 1999

Abstract

Ž .DrH studies of fluid inclusions of speleothems of the Soreq cave Israel are made using the method of vacuum thermalextraction. DrH measurements of present-day carbonate pool margins and waters show that the value of the vacuum

Ž .thermal extraction fractionation D sdD ydD is y30.0"1.4‰ for the Soreq cave deposits. DrHex extracted water cave water

analyses of fluid inclusions of two fossil speleothems formed during periods equivalent to glacial times suggest that theirŽ . 18isotopic compositions follow the global Meteoric Water Line MWL dD–d O relationship, compared to present-day

Ž .waters which follow the Mediterranean Meteoric Water Line MMWL trend. Two samples from interglacial periods showisotopic trends between these lines. These differences are presumed to reflect cooler less evaporative conditions in theEastern Mediterranean Sea during glacial times. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: Fluid inclusions; Speleothems; Stable isotopes; Paleoclimate

1. Introduction

The oxygen isotope composition of carbonate cavespeleothems is a powerful monitor of continental

Žpaleoclimate variation e.g., Schwarcz et al., 1976;Dorale et al., 1992; Holmgren et al., 1995; Lauritzen,

.1995; Bar-Matthews et al., 1997, 1998, 1999a,b,c .The interpretation of oxygen isotope record is basedon the carbonate paleotemperature equation, which

) Corresponding author. Tel.: q972-2-658-4913; fax: q972-2-566-2581; e-mail: [email protected]

relates the d18 O value of the carbonate to that of the

water from which the carbonate precipitated and thedeposition temperature. Studies of cave speleothemsin northern climates have shown that cave wateroxygen isotope compositions accurately reflect that

Žof the local rainfall Hendy and Wilson, 1968; Har-mon and Schwarcz, 1981; Schwarcz, 1986; Schwarcz

.and Yonge, 1983; Yonge et al., 1985 . This relation-ship does not apply in the hot Eastern Mediterraneanregion, where evaporation in the upper vadose zoneleads to isotopic fractionation between the cave andrain water and significant seasonal variation in the

18 Žd O value of the seepage water Bar-Matthews et.al., 1996, 1997, 1999a; Ayalon et al., 1998 .

0009-2541r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.Ž .PII: S0009-2541 99 00192-8

( )A. Matthews et al.rChemical Geology 166 2000 183–191184

The carbonate speleothems of the Soreq cave ofŽ .Israel Fig. 1 provide a continuous isotopic, miner-

alogical and geochemical record of the EasternMediterranean region for the last 250,000 years,covering several interglacial and glacial periodsŽBar-Matthews et al., 1997, 1998, 1999a,b,c; Ayalon

Fig. 1. The location of the Soreq cave. The cave is situatedapproximately 40 km inland of the Mediterranean Sea in Cenoma-nian dolomitic host rock.

.et al., 1999 . Potentially, climate-related data onpaleowaters of the cave can be gained from theisotopic analysis of fluid inclusions trapped withinthe carbonate speleothems at the time of their forma-tion. It is generally considered that the d

18 O of fluidinclusions is an unreliable indicator of the isotopiccomposition of the original water because fluid in-clusions may undergo post-depositional oxygen iso-

Žtope exchange with carbonate minerals Schwarcz et.al., 1976 . However, the trapped water should not

undergo post-depositional hydrogen isotope ex-change because there is no hydrogen reservoir toenable such exchange. Thus, the alternative of theanalysis of the isotopes of hydrogen DrH as aproxy for d

18 O has been explored in a number ofŽstudies Harmon et al., 1979; Yonge, 1982; Schwarcz

and Yonge, 1983; Schwarcz et al., 1976; Dennis et.al., 1997; Rowe et al., 1998 .

The use of DrH ratios as a proxy for the d18 O of

water is based on the well-known correlation ofthese isotopic systems for meteoric waters. World-wide, this is represented by the global Meteoric

Ž . 18Water Line MWL relationship: dDs8d Oq10.In the present-day Eastern Mediterranean area, the

Ždeuterium excess parameter d ; defined as theexcess18 .difference dDy8d O is higher because evapora-

tion processes at the sea-surface occur into low-humidity air masses. The oxygen–hydrogen isotoperelationship is better expressed by the Mediterranean

Ž . 18Meteoric Water Line MMWL : dDs8d Oq22Ž .Gat, 1980, 1982; Gat and Carmi, 1987 . The iso-topic composition of present-day rain water abovethe Soreq cave and the cave water falls close to the

ŽMMWL with d values of 15–30‰ Ayalon etexcess.al., 1998 . In contrast, paleowaters of presumed Late

Pleistocene or Early Holocene origin in the NegevŽdesert of southern Israel and Sinai peninsula Gat,

.1980 show lower d values of about 7‰.excess

The local MWL relationship that cave watersfollowed in the past potentially provides importantconstraints on climatic conditions and the origin andstorm-tracks of the rainfall in the Eastern Mediter-ranean and Levant region. This work presents aDrH study of the fluid inclusions of the Soreq cavedeposits. Using the results of fluid inclusion DrHanalyses of modern and fossil cave deposits, weattempt a first assessment of the local MWL relation-ships that may have been followed in the past.

( )A. Matthews et al.rChemical Geology 166 2000 183–191 185

2. Analytical methods

The extraction of fluid inclusion water for DrHanalysis has been made either by crushing under

Žvacuum or by heating under vacuum thermal de-.crepitation . Low yields and poor reproducibility

Ž .Yonge, 1982; Schwarcz and Yonge, 1983 oftenlimit the former method, although Dennis et al.Ž . Ž .1997 and Rowe et al. 1998 have shown that acombination of crushing with mild heating givesreliable results. The extraction of the fluid inclusionwater in this study is made using a slight modifica-

Ž .tion of the decrepitation procedure of Yonge 1982 .Isotopic fractionation accompanies the extraction ofcalcite-bound water by the decrepitation method. The

Žvalue of this fractionation D sdD yex extracted water.dD was estimated at y22.1"3.9‰ bycave water

Ž .Yonge 1982 , but is recalibrated in this work for theSoreq cave deposits.

The vacuum line for the extraction of water forDrH analysis is based on the design of Vennemann

Ž .and O’Neil 1993 . The water was released duringthermal decomposition of 100–150 mg of 2-mm-

Ž .sized fragments about five to eight grains of thespeleothems at 9008C in a quartz tube attached to a

vacuum line. The water and carbon dioxide weretrapped at liquid nitrogen temperatures after passing

Ž .the gases over hot ca. 6008C copper oxide tore-oxidize any hydrogen formed in the heating. Theliquid nitrogen trap was replaced by alcohol slurry aty808C and the carbon dioxide pumped away. Thisprocess was repeated four times to ensure completeseparation of the carbon dioxide from the water. Theinclusion water was transferred to 12-mm diameter

ŽPyrex tube containing 40 mg of zinc shavings Bio-.geochemical Laboratories, Indiana University and

sealed. Conversion of the water to hydrogen byreduction with zinc was accomplished by heating thePyrex tube for 1 h at 5008C. This was followed byimmediate mass spectrometric analysis of the hydro-gen on the SIRA-II Mass Spectrometer at the Geo-logical Survey of Israel. Errors on the analyses ofstandard water samples are "1‰. Complete separa-tion of the carbon dioxide from the water was neces-sary; otherwise, the reduction reaction with zinc wasincomplete. It was also found that the DrH analyseswere sensitive to the amount of zinc for the small

Ž .quantities of water 0.3–0.5 mlr100 mg calcitereleased from the speleothems. Forty milligrams ofzinc gave precise results.

Table 1Isotopic analyses of pools and carbonate margins from the present-day caveThe DrH analyses of the carbonate pool margins are the measured dD values.extracted water

Pool 5-9 Pool 5-7 Margin 5-9 Margin 5-718 18Ž . w x Ž . w x Ž . w x Ž . w x Ž . w x Ž . w xd O SMOW ‰ dD SMOW ‰ d O SMOW ‰ dD SMOW ‰ dD SMOW ‰ dD SMOW ‰

y4.65 y16.7 y5.35 y19.0 y51.6 y55.6y4.75 y14.3 y4.81 y18.7 y43.3 y44.4y4.24 y24.8 y4.73 y22.0 y50.7 y52.3y4.27 y16.1 y4.80 y16.7 y39.5 y44.3y4.51 y15.9 y4.66 y14.8 y44.0 y44.6y4.14 y14.6 y5.06 y16.3 y41.3 y44.3y4.36 y14.0 y4.63 y16.6 y45.1y4.22 y4.27 y14.6 y46.3y4.42 y4.54 y14.4 y37.0

y4.16 y17.2 y41.0y4.64 y16.3 y46.4y5.35 y15.2 y48.4y4.15 y16.0 y50.4y3.99 y16.3 y45.2y4.40 y12.0 y52.0

y45.4y49.8

y4.40"0.07 y16.6"1.4 y4.64"0.10 y16.4"0.6 y45.7"1.1 y47.6"2.1


Table 2dD analyses of fluid inclusions of fossil carbonateextracted water

speleothemsdD is the value of the mean isotopic analysis aftercave water

correction with D .ex

2-Z 7-23 11-23 3-35

( ) [ ]dD SMOW ‰y54.7 y55.5 y48.2 y63.4y49.4 y48.2 y48.3 y62.2y52.1 y56.6 y50.7 y68.2y49.4 y53.4 y48.5 y62.5y53.8 y50.1 y49.0 y60.2y55.4 y60.0 y40.4 y66.1y53.8 y54.4 y43.0 y73.0y56.3 y56.0 y44.6 y59.0y49.4 y48.0 y50.4 y64.0

y64.5 y59.7 y71.3y64.5 y47.0 y75.6y53.4

y52.7"0.9 y55.4"1.6 y48.2"1.5 y66.0"1.6

dDcaÕ e w at er

y22.7"1.7 y25.4"2.2 y18.2"2.0 y36.0"2.1

Fine laminae about 1.0-cm thick were separatedfor the fluid inclusion determination in fossilspeleothems. d

18 O measurements on these sampleswere made every 0.5 mm by means of a diamond

Ždrill as described in Bar-Matthews et al. 1997;.1999a .

The isotopic results are given in Tables 1 and 2.The uncertainties on mean isotopic values are re-

Ž .ported as the standard error sr6n and are propa-gated in calculations.

3. Results

3.1. Calibration of the fluid inclusion–extractionmethod

The calibration of the isotopic fractionation DexŽ .sdD ydD was achieved byextracted water cave water

measuring the DrH of fluid inclusions extractedŽ .from carbonate margins of present-day pools Fig. 2

and the DrH of the pool water. The most recentlygrown edges in contact with the water were sampled

Ž .from two pools nos. 5-7 and 5-9 . The oxygen andhydrogen isotopic compositions of the pool water

were measured over a period of 8 years in order toestablish their variability. Replicate DrH analyseswere made of the fluid inclusions. The analyticalresults are given in Table 1 and show that theisotopic compositions of the two pools overlap withinerror for both isotopes. The dD values average aty16.6"1.4‰ for pool 5-9 and y16.4"0.6‰ forpool 5-7. Oxygen isotope compositions average ataround y4.5‰ and the dD–d

18 O relationship liesclose to the MMWL, as found for present-day cave

Ž .waters Ayalon et al., 1998 .The d

18 O value of one sample of carbonate mar-Ž .gin from pool 5-9 is y5.26‰ PDB and the mean

d18 O value of 10 samples of pool margin from pool

Ž .5-7 is y5.17"0.39‰ PDB . These translate thed

18 O water values of y4.5‰ for pool 5-9 andy4.4‰ for pool 5-7 at present-day deposition condi-tions of 188C. These values are very close to themeasured mean d

18 O values of the water which arey4.40"0.07‰ for pool 5-9 and y4.64"0.10‰for pool 5-7. Thus, the carbonate margins are inoxygen isotopic equilibrium with pool waters.

Fig. 2. Photograph showing a pool and its present-day carbonatemargin at site 5. The pool margins were sampled from the thinedge in contact with the water of the pool.


The DrH analyses of the fluid inclusions in thecarbonate pool margins are also given in Table 1 asthe measured d D values. Bothextracted water

speleothems show similar mean isotopic composi-tions: y45.7"1.1‰ for 5-9 and y47.6"2.1‰ for

Ž .5-7. Thus, as found by Yonge 1982 , there is a cleardepletion in the isotopic composition of the fluidinclusion relative to the parent water. The corre-sponding values of D are y29.1"1.8‰ for poolex

5-9 and y31.2"2.1‰ for pool 5-7. These twoindependent determinations yield a weighted meanvalue of D sy30.0"1.4‰. This is lower thanex

the value of y22.1"3.9‰ determined by YongeŽ .1982 . The different D values may be the conse-ex

Žquence of the heating temperature Yonge used

.7008C , but may also reflect slight variation in thebehavior of different cave deposits.

3.2. DrH 18Or16O relations of fossil speleothems

Isotopic measurements were made on four fossilspeleothem samples. The variation of d

18 O with timefor the last 140,000 years for Soreq cave speleothems

Žhas been presented by Bar-Matthews et al. 1999b;.c . A portion of this variation, covering the last

120,000 years, is illustrated in Fig. 3. More detaileddiagrams, showing the variations of d

18 O in the timeranges of the speleothems lamina on which the DrHmeasurements were made, are also given in Fig. 3.The sample choice was governed by several consid-

18 ŽFig. 3. Graphs showing the secular variation of d O with time in the Soreq cave for the last 120 ky taken from Bar-Matthews et al.,.1999b,c and the periods from which the samples were taken. The four inset graphs are enlargements of the detail in the main graph,

showing the d18 O variations in the studied samples.


Ž .erations: i to cover time intervals characterized bydifferent d

18 O values indicative of different climaticŽ .conditions; ii choice of samples that were detrital-

free to avoid DrH contamination by clays andŽ .hydroxides; iii the resolution of the sampling for

Ž . 18 Ž .DrH 1 cm compared to d O 0.5 mm analysesfavored samples showing relatively small d

18 O varia-tion. The d

18 O and d13C values of the four fossil

samples and their paleoclimate interpretation wereŽsummarized by Bar-Matthews et al. 1997; 1998;

.1999a; b; c .

3.2.1. 2-ZStalagmite mean d

18 O s y5.52 " 0.27‰ —covering the 4.0–4.5 ka time interval, with climaticconditions similar to present-day. The estimated tem-

Žperature of deposition is 18–208C Bar-Matthews et.al., 1997 .

3.2.2. 7-23Stalagmite mean d

18 O s y2.83 " 0.26‰ —from the 22–23 ka interval, equivalent to the end ofthe last glacial. This period is characterized by thehighest d

18 O values observed in the last 120 ka.Ž .Colder temperatures ;10–148C and lower average

annual rainfall occurred relative to the present-dayŽ .Bar-Matthews et al., 1997, 1999a .

3.2.3. 11-23Stalagmite average d

18 Osy3.97"0.16‰ —covering the 73–74 ka interval, equivalent to glacial

Ž .period stage 4 with estimated temperatures of 14–188C.

3.2.4. 3-35Stalagmite mean d

18 O s y6.96 " 0.22‰ —covering the 105–108 ka. This sample has the lowestd

18 O values of the 120-ka period and was formedŽduring warm and wet climatic conditions Bar-Mat-

.thews et al., 1999b,c with an estimated temperatureof 16–208C.

The measured DrH analyses of the fluid inclu-sions extracted from these speleothems are given inTable 2 and plotted as histograms in Fig. 4. The dDvalues show distributions similar to those found forthe present-day pool margins. The dD valuescave water

corrected for D are given at the bottom of Table 2ex

Fig. 4. Histograms showing the ranges of measured dDextracted

values of the four fossil speleothem samples studied in thiswater

work.

and show a variation of almost 20‰ from y18.2"

2.0‰ to y36.0"2.1‰.

4. Discussion

The application of the fluid inclusion dD valuesfocuses on the local MWL relationships that mayhave operated in the past. The MMWL and globalMWL relationships are plotted in Fig. 5 on a graph


Fig. 5. dD vs. d18 O plot of the isotopic compositions of waters

Žmeasured in this study. The dD values shown by black dots.within a shaded area whose height represents the "1d error are

Žthe dD values in Table 2 i.e., are converted fromcave water. 18measured values using the D parameter . d O values areex

Ž .calculated see text for details . The different black dots within theŽ .shaded areas reflect the various temperatures at 28C intervals for

which the d18 O values are calculated. The MMWL and global

MWL are shown for reference. The open circles show the mea-sured isotopic compositions of present-day cave waters. The iso-topic compositions of the two present-day pool samples are takenfrom Table 1.

of dD vs. d18 O. The range of isotopic compositions

of present-day cave waters is shown on the graphand can be seen to be distributed around the MMWL.The isotopic compositions of pool water 5-7 and 5-9fall within this array and close to the MMWL.

In order to determine the local MWL relationshipin the past, it is necessary to independently estimatethe d

18 O of the fossil water. This is done by calculat-ing the water composition from the mean d

18 O val-ues of the speleothems using the carbonate paleotem-

Ž .perature equation O’Neil et al., 1969 and the previ-ously given temperature estimates. This calculationyields a range of cave water d

18 O values, which areplotted in Fig. 5 against the dD values givencave water

in Table 2. All samples plot to the right of theMMWL and to the right of the majority of the datapoints of present-day cave waters, i.e., the four fossilsamples have lower d values than generallyexcess

found in present-day rainfall and cave water.The samples showing the most marked shifts

away from the MMWL are 11-23 and 7-23. Sample11-23 plots close to the global MWL and 7-23 onthis line or slightly to its right. Both samples formed

at times when glaciation occurred in the northerncontinents. Sample 11-23 was formed at the begin-ning of glacial stage 4, and sample 7-23 was de-posited close to the peak of the last glacial maximumwhen amounts of rainfall precipitation were lower inthe Eastern Mediterranean region and temperatureswere at their coolest in the last 120 ka. The highd

18 O values of the speleothems of this period couldreflect either an isotopically heavier Mediterranean

Žsea vapor source e.g., Vergnaud Grazzini et al.,.1986; Frumkin et al., 1999 andror colder sea sur-

face temperatures during the last glacial maximumŽGat and Carmi, 1987; Charles et al., 1994; Bar-Mat-

.thews et al., 1999a,c . The close proximity of sample7-23 to the global MWL indicates that there was farless evaporation above the Mediterranean Sea at theend of the glacial period. Speleothems 3-35 and 2-Zplot between the MMWL and global MWL lines.These samples were formed during interglacial con-ditions in warmer and wetter climate and most prob-ably, the effect of the Mediterranean Sea on theevaporation processes was more similar to that ofpresent-day. The data suggest that the d value isexcess

strongly offset towards the MWL at the time of mostŽ .intense glacial conditions sample 7-23 , but that

under milder conditions, this offset is less.

5. Conclusions

This research has shown that the DrH analysesof water fluid inclusions in fossil carbonatespeleothems can provide significant data on the pale-owaters, provided the analytical method for the ther-mal extraction of hydrogen is calibrated using thepresent-day cave system. The value of the vacuum

Žthermal extraction fractionation D sdDex extracted water.ydD is y30.2"1.4‰ for the Soreq cavecave water

deposits. The isotopic compositions of present-dayrainfall and cave waters in the Soreq cave plot alongthe trend of the MMWL dD–d

18 O relationship. Incontrast, the dD values of two speleothemcave water

samples formed during colder climatic conditionssuggest that cave waters had d values that wereexcess

closer to those of the global MWL. This shift awayfrom the MMWL is particularly marked in a sampledeposited at the time of the last glacial maximum.


Lower sea-surface and atmospheric temperaturesduring the last glacial maximum were the mostprobable causal factors for this difference relative tothe present-day. Two samples from interglacial peri-ods show isotopic trends between the MMWL andglobal MWL. Future work will concentrate on devel-oping a more detailed understanding of the secularvariations of fluid inclusion DrH and carbonated

18 O values.

Acknowledgements

This research was supported by grants from TheIsrael Science Foundation founded by The Academyof Sciences and Humanities and the Belfer Founda-tion. Reviews by Drs. P. Dennis and H.P. Schwarczwere very much appreciated. We express our grati-tude to Ami Peled from the Nature Protection Au-thority at the Soreq cave for his generous help, andto Bettina Schilman, Anton Vax and Iris Zohar for

[ ]help with the isotopic analyses. MB

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