δ37Cl of waters from the Akyatan lagoon, Turkey

A N N A L E S

U N I V E R S I T A T I S M A R I A E C U R I E - S . à 2 ' 2 : S . A

L U B L I N – 3 2 L 2 N I A

V2L L;I; SECTI2 AAA 2014

į

Cl 2) :ATERS )R2M THE AKYATAN LA*22N,

TURKEY

Andrzej Pelc

, CKriVtoSKe LpcX\er

, Anne-MDrie BoderJDt

Dnd StDniVáDZ HDáDV

1_{MDVV SSectroPetr\ LDEorDtor\, InVtitXte oI PK\VicV, UMCS, 20-031 LXElin, PolDnd} 2_{LDEorDtoire de *poloJie de L\on, UMR CNRS 27, UniYerVitp L\on 1 et Ecole}

NorPDle SXSprieXre de L\on, 922 VilleXrEDnne, )rDnce

*_{CorreVSondinJ aXtKor, e-Pail VtaniVlaZKalaV#XPcVSl}

alVo at InVtitXt UniYerVitaire de )rance

ABSTRACT

:e reSort tKe IirVt į37_{Cl data Ior VXrIace ZaterV oI tKe AN\atan laJoon, TXrNe\, IroP 12}

VtationV VaPSled oYer tKe Seriod 200 to 200 TKe recorded Yariation oI į37_{Cl YalXeV iV}

Iairl\ VPall, IroP -04 to 0 Å YV SM2C, tKoXJK tKe enYironPental conditionV Zere KiJKl\ YariaEle VeaVonall\ TKe Valinit\ oI tKe VtXdied ZaterV Yaried IroP 28 to 9 JL and tKe G' vs G18_{2 Slot ViJniIicantl\ deSartXreV IroP tKe :orld Meteoric :ater Line}

:M:L) ZitK a VloSe oI 43“019 CKlorine iVotoSeV indicate a ZeaN SoVitiYe correlation EetZeen į37Cl and į' oI Zater and itV Valinit\ TKiV Pa\ Ee dXe to Pi[inJ EetZeen VeaZater and diVtinct VoXrceV oI IreVKZater TKe VPall VSread oI oEtained į37Cl reVXltV dePandV enKanced SreciVion oI anal\ViV and careIXl VaPSle SreSaration

Keywords AN\atan laJoon, cKlorine iVotoSeV, K\droloJ\, cliPate, G18_{2, G'}

INTR2'UCTI2N

CKlorine VtaEle iVotoSe ratio 37_Cl3_{Cl) YariationV are Vtill Soorl\ XnderVtood}

diIIicXlt to deterPine Zith Jood precision Zith Post analytical Pethods. DXane et al. 2004) stXdied į37_{Cl in Zaters oI the Al-Khiran saENha in KXZait toJether}

Zith their GD andG18_{O YalXes. In Post recent stXdies on chlorine isotopes one oI}

tZo Pethods to deterPine 37_Cl/35_{Cl ratios is Xsed: 1) analysis Ey therPal}

ionization Pass spectroPetry TIMS), Zhich is capaEle to PeasXre sPall TXantities, EXt it has rather loZ throXJhpXt ;iao and =hanJ 1992) 2) analysis oI Pajor EeaPs Jenerated Ey electron iPpact at P/z 50 and 52) oI chloroPethane Jas Ey isotope ratio Pass spectroPetry IRMS KaXIPann et al. 1984). Both Pethods attain a precision that is soPeZhat Eetter than “0.1Å, EXt the second approach has a coPplicated Pass spectrXP EJJenNaPp 2004).

Recently a neZ Pethod Zas deYeloped in the Mass SpectroPetry LaEoratory at UMCS LXElin that is descriEed EeloZ. The neZ Pethod is also Eased on the ionization oI chloroPethane Jas, EXt in the ionization chaPEer it IorPs neJatiYe ions that are Jenerated on a hot Petal sXrIace. This leads to a siPple Pass spectrXP, coPprisinJ oI 35_Cl- _and 37_Cl- _{peaNs only, and a sXEstantial}

enhancePent oI the precision oI the į37_{Cl to “0.01Å. This Pethod Zas applied}

to stXdy the seasonal and areal Yariations oI chlorine isotope ratios in the ANyatan laJoon, TXrNey, stXdied preYioXsly Ey LpcXyer et al. 2009, 2012) Ior Yariations oI salinity and į18_{O-įD oI Zaters. StaEle isotopes oI chlorine Pay Ee}

XseIXl in identiIyinJ Zater Pi[inJ zones iI the Pi[inJ is siPple in natXre. )or instance, a continental Zater Zith a distinctiYe į37_{Cl YalXe Pi[inJ Zith}

a seaZater haYinJ į37_{Cl close to zero.}

STUDY AREA

The ANyatan laJoon 3ƒ37¶N – 035ƒ1¶E) is located at the soXth-eastern edJe oI the Mediterranean Sea, in the ÇXNXroYa reJion oI TXrNey aEoXt 30 NP soXth oI the city oI Adana )iJs 1 and 2). The laJoon sXrIace is 147 NP2 and its aYeraJe depth is 0.75 P. It Zas IorPed 10,000 years aJo as a resXlt oI the oYer-IloZinJ and sediPent discharJe and transport IroP the Seyhan and Ceyhan riYers. The laJoon EecaPe separated IroP the sea Ey a thin sand Earrier IorPed Ey ZaYe action McPherson et al. 1988). At present, the laJoon receiYes IreshZater IroP rainIall and drainaJe–irriJation canals and proEaEly dXrinJ periods oI hiJh Zater leYels IroP the Seyhan riYer and aEandoned channels oI the Ceyhan riYer DaYXtlXoJlX 2010 KXleli 2010), Eoth oI theP haYinJ their sprinJs in the TaXrXs MoXntains NaziN et al. 1999). The Seyhan riYer has a Pean discharJe oI 180 P3_{/s Zhich Yaries IroP PiniPXP and Pa[iPXP YalXes}

oI 20 P3_{/s JXne to OctoEer) and 2,250 P}3_{/s April), respectiYely McPherson et}

al. 1988). The aYeraJe riYer Zater coPposition is: 158 PJ/L HCO3-, 48 PJ/L

Ca2_{, 10 PJ/L MJ}2_{, 30 PJ/L SO}

IolloZinJ PeasXrePents coPpiled Ey MeyEecN and RaJX 199). The laJoon is connected to the sea throXJh a 2 NP narroZ canal on its soXtheastern side and e[chanJes Zater and sediPents in response to tidal actiYity. Ma[iPXP tide heiJht is aEoXt 40 cP to 0 cP, e[cept in periods oI stronJ Zinds that can Jenerate a 150 cP increase in sea leYel McPherson et al. 1988). AroXnd the ANyatan laJoon, air tePperatXres ranJe IroP 9ƒC JanXary) to 28ƒC AXJXst) Zith a Pean annXal YalXe oI 19ƒC. Precipitation is Xp to 120 PP Postly occXrrinJ dXrinJ the cold season IroP NoYePEer to )eErXary, at Zhich period access to the laJoon is diIIicXlt.

FIG. 1. *eoJraphic Pap oI soXtheast TXrNey Zith the location oI the ANyatan laJoon,

FIG. 2. Satellite YieZ oI the ANyatan laJoon, TXrNey, and the location oI Zater saPplinJ

sites indicated Ey oXtlined nXPEers.

ANALYTICAL METHODS

CHLORINE ISOTOPE ANALYSIS IN :ATERS )ROM THE AKYATAN LA*OON

:ater saPples Zere deliYered in herPetically closed plastic Eottles to the laEoratory, Zhere aIter Iiltration AJCl Zas precipitated. The precipitate Zas Zashed Zith distilled Zater and dried in an oYen and then reacted Zith iodoPethane CH3I) to IorP chloroPethane CH3Cl), Zhich is the Post coPPon

Jas Xsed in chlorine isotope ratio analysis EJJenNaPp 2004). ChloroPethane is Yery conYenient Ior Pass spectroPetry as it has no PePory eIIect in YacXXP systePs and can Ee easily oEtained IroP a chlorine saPple and transIerred IroP the preparation line to the inlet systeP oI Pass spectroPeter since its PeltinJ point is í97.7 ƒC. )or CH3Cl preparation the e[chanJe reaction EetZeen the

iodoPethane CH3I) and silYer chloride AJCl) Zas applied KaXIPann et al.

1984, EJJenNaPp 2004). The reaction reTXires at least a 10-Iold Polar e[cess oI CH3I oYer AJCl, Zhich resXlts in a diIIicXlt pXriIication procedXre oI CH3Cl

Pethods oI chloroPethane are Xsed: i) Jas chroPatoJraphy and ii) cryoJenic separation.

In Eoth Pethods CH3I is introdXced to a preparation line Ey injection throXJh

a septXP and EecaXse oI this procedXre also soPe iPpXrities air, Zater Yapor) are adPitted to the saPple. Additionally in the aEoYe Pentioned Pethods sealinJ and sXEseTXently cracNinJ oI a saPple tXEe is needed. To eliPinate these draZEacNs a neZ triple-staJe cryoJenic procedXre Zith tZo diIIerent cryoJenic sXEstances Zas deYeloped, siPilar to the one descriEed Ey :X and SataNe 200). The Post iPportant noYelty in oXr preparation line is a neZ and siPple pipette systeP, coPprisinJ oI tZo Jlass containers separated Ey tZo stopcocNs Zith a TeIlon plXJ, Ior CH3I introdXction to the cryoJenic separation line.

Additionally Ze consideraEly siPpliIied the separation procedXre oI Eoth chloro- and iodo-Pethanes EecaXse Ze replaced the EreaN-seal tXEes Zith aPpoXles haYinJ stopcocNs Zith TeIlon plXJs. This PodiIication oI the chloroPethane pXriIication Pethod alloZed shorteninJ oI the tiPe needed Ior coPpletion oI the CH3Cl separation.

The iPproYePents oI the chloroPethane preparation techniTXe in coPEination Zith the recently deYeloped Pethod oI chlorine isotope ratio analysis Eased on neJatiYe ion Pass spectroPetry Haáas and Pelc 2009) leads to enhanced precision oI the PeasXrePents. The iPproYed Xncertainty oI sinJle į37_{Cl deterPinations Zas redXced to aEoXt “0.05Å, Zhich is iPportant in}

stXdies oI sPall natXral Yariations oI chlorine isotope ratios.

O;Y*EN AND HYDRO*EN ISOTOPE ANALYSIS O) :ATERS )ROM AKYATAN LA*OON

AliTXots oI 200 PL IroP 37 Zater saPples Zere aXtoPatically reacted at 40ƒC Zith CO₂ and H₂ in the presence oI a platinXP catalyst and analyzed XsinJ a MXltiPrepTM systeP on-line Zith a *VI IsoPriPe™ dXal-inlet isotope ratio Pass spectroPeter. ReprodXciEility oI GD and G18_{O YalXes Zas estiPated to Ee}

“1Å and “0.1Å, respectiYely, Ey norPalizinJ raZ data to the isotopic ratios oI SMO:, SLAP and *ISP international standards that Zere PeasXred alonJ Zith the saPples. Corrections oI the hydroJen and o[yJen isotope ratios caXsed Ey chanJes in the salinity-dependent Iractionation Iactors ĮCO2–H2O and ĮH2O–H2

Zere taNen into accoXnt XsinJ the eTXations deterPined Ey LpcXyer et al. 2009) and MartineaX et al. 2012).

RESULTS AND DISCUSSION

SALINITY/G18_{O-GD RELATIONSHIPS IN AKYATAN LA*OON :ATERS}

HydroJen and o[yJen isotope coPpositions oI the EracNish Zaters and Erines IroP the ANyatan laJoon ranJe IroP –48.2Å to 35.8Å and IroP –.2Å to .95Å, respectiYely LpcXyer et al. 2012). HydroJen and o[yJen isotope coPpositions oI the laJoon Zaters plot either EetZeen the tZo Iresh and Parine Zater end-PePEers or on the riJht oI the :orld Meteoric :ater Line :M:L). Models oI soXrce-Zater Pi[inJ and eYaporation Zere deYeloped Ey LpcXyer et al. 2012). In this stXdy, it is clear IroP salinity and staEle isotope coPpositions oI ANyatan laJoon Zaters that EracNish Zaters resXlt IroP Pi[inJ oI Iresh Zater IroP the Seyhan RiYer Zith Mediterranean seaZater )iJ. 1). SXch Pi[inJ, hoZeYer, is coPplicated Ey eYaporation processes, as sXJJested Ey the slope 5.43“0.19) oI the reJression line in the GD–G18_{O diaJraP Zhich is}

PXch loZer than the slope oI the :M:L Zhich is close to 8 CraiJ 191 DansJaard 194). AccordinJ to LpcXyer et al. 2012), dXrinJ Zinter and sprinJ the Zater in the laJoon is doPinated Ey Pi[inJ processes EetZeen Iresh Zaters and Mediterranean seaZater. Most saPples taNen dXrinJ the sprinJ are the resXlt oI eYapoconcentration oI EracNish Zater at Poderate tePperatXres oI 22“2ƒC. DXrinJ the sXPPer, hypersaline Zaters resXlt IroP eYaporation oI seaZater and EracNish Zaters IorPed dXrinJ sprinJ. EYaporation oYer the ANyatan laJoon reaches Xp to 7 Zt Eased on salinity PeasXrePents and operated Zith a dry relatiYe hXPidity oI 0.15 to 0.20) and hot 44“ƒC) air. These residXal Zaters are characterized Ey the hiJhest seasonal isotope enrichPent in Eoth deXteriXP and 18_{O relatiYe to VSMO:. DXrinJ the aXtXPn, Post laJoonal Zaters EecoPe}

hypersaline and are IorPed Ey eYaporation oI Zater that had isotope coPpositions and salinities close to that oI seaZater. These aXtXPnal hypersaline Zaters resXlt IroP an air hXPidity close to 0.45 and an atPospheric tePperatXre oI eYaporation oI 35“5ƒC, Zhich are responsiEle Ior Xp to 71 Zt oI eYaporation, Zith restricted isotopic enrichPent relatiYe to VSMO:.

VARIABILITY O) į37_{Cl IN :ATERS )ROM THE AKYATAN LA*OON}

The YariaEility oI the į37_{Cl YalXes is Yery diIIicXlt to discXss. The Pain}

proEleP concerns the end-PePEer YalXes. The Iresh Zater saPples had chlorine concentrations that Zere too loZ to Ee analyzed, Zhereas a saPple oI Parine Zater indicated at the EottoP oI TaEle 1) is aIIected Ey an enhanced standard deYiation oI į37_{Cl. :aters IroP the ANyatan laJoon shoZ a roXJh positiYe}

correlation EetZeen į37_{Cl and GD as shoZn in )iJ. 3. :inter saPple 200-2010}

saPple 007-11 e[hiEits the hiJhest YalXes oI 0.38 and 35.4Å, respectiYely. At Iirst siJht, Eoth į37_{Cl and GD oI Zaters increase Zhen Zater tePperatXres are}

hiJh dXrinJ the ZarP seasons sXPPer and aXtXPn), correspondinJ to the hiJhest rates oI eYaporation. MoreoYer, dXrinJ the ZarP seasons, inpXts oI IreshZater are loZest and Zater Pi[inJ is thereIore doPinated Ey the seaZater end-PePEer. This relation is, hoZeYer, distXrEed Ey tZo saPples 007-5 and 004-19) that sXJJest that Pi[inJ tooN place EetZeen seaZater and a IeZ diIIerent soXrces oI IreshZater Zith distinct į37_{Cl siJnatXres.}

This hypothesis is sXpported Ey the coPple[ relations oEserYed EetZeen į37_{Cl and salinity S in )iJ. 4. LoZ salinity Zaters haYe distinct į}37_{Cl YalXes and}

the hiJhest į37_{Cl YalXe Zhich is IoXnd in a saPple Zith a hiJh salinity does not}

correspond Zith saPples Zith eYen hiJher salinities Zhich haYe į37_{Cl YalXes}

close to 0Å. TZo processes are responsiEle Ior į37_{Cl YariaEility in Zaters IroP}

the ANyatan laJoon. The Iirst is Pi[inJ EetZeen seaZater, diIIerent soXrces oI IreshZater local rain and the Seyhan RiYer) and EracNish Zaters inherited IroP earlier seasons. As seaZater contains aEoXt a thoXsand tiPes Pore chlorine than the Seyhan RiYer, į37_{Cl YariaEility can only Ee oEserYed iI reserYoirs haYe}

hiJhly contrasted chlorine isotope coPpositions. The second process is Zater eYaporation that concentrates the heaYiest chlorine isotope in the residXal Zater.

TABLE 1. Analytical data IroP LpcXyer et al. 2012) alonJ Zith PeasXred į37_Cl.

SaPple no. Sta-tion SaPplinJ date :ater tePp. Air tePp. pH Salinity į18_O (H2O) įD (H2O) į37 Cl (ƒC) (ƒC) NBS scale (J/L) (Å) SMO: (Å) SMO: (Å) SMOC 200-13 1 03-11-200 18.0 15.5 8.00 32.0 -0.4 1.2 0.0 004-5 1 04-27-200 28.0 30.0 9.10 14.0 -3.28 -24.9 0.0 007-2 2 07-07-200 27.7 34. 8.13 12.1 -4.15 -14.5 -0.12 200-10 4 03-11-200 15.0 17.0 8.00 15.0 -4.70 -34.8 -0.55 004-21 5 05-03-200 29.7 25.2 9.03 25.0 1.2 3.5 0.08 007-5 5 07-07-200 32.3 28.0 8.03 2.8 -.23 -47.3 -0.20 AMB-  10-08-2005 25.7 28.8 8.24 4.0 2.59 17.3 0.1 007-  07-07-200 32.2 30.2 8.32 17.4 -1.52 4.3 -0.17 200- 7 03-04-200 23.0 18.0 8.58 25.0 -1.93 -11.8 -0.14 004-19 7 05-03-200 30.0 21.4 8.78 34.0 2.80 15.7 -0.38 007-7 8 07-07-200 34.8 25.2 9.03 50.3 .7 35.4 0.38 AMB-11 11 10-08-2005 25.5 29.1 8.32 44.0 2.09 10.8 -0.15

004-17 13 04-29-200 2.0 30.0 8.40 24.0 1.70 9.1 -0.13

AMB-18 18 10-09-2005 24.5 2. 8.43 90.0 4.23 25.5 -0.0

007-11 18 07-08-200 32. 2. 7.98 40.8 4.47 29.7 0.00

AMB-22 22 10-13-200 2.0 31.0 8.40 95.0 4.21 20.0 0.07

MS:-2 A 10-11-200 n.a. n.a. n.a. 38.0 1.54 11.3 0.0*

*Standard deYiation 0.1Å, n.a. not aYailaEle

FIG. 3. A plot oI į37_{Cl in Å SMOC Zith respect to įD (Å VSMO:) oI analyzed Zater}

saPple.             :LQWHU 6SULQJ 6XPPHU $XWXPQ 0HGLWHUUDQHDQVHDZDWHU δ'Æ9602:

FIG. 4. A plot oI į37_{Cl in Å SMOC YersXs salinity in J/L.}

CONCLUSIONS

:e haYe IoXnd Eoth tePporal and spatial YariaEility oI į37_{Cl in the analyzed}

Zaters. A ZeaN positiYe correlation Zas IoXnd EetZeen į37_{Cl and įD oI Zater}

and its salinity. This Pay indicate a Pi[inJ EetZeen seaZater and distinct soXrces oI IreshZater (local rain and the Seyhan RiYer and Pi[inJ Zith EracNish Zaters inherited IroP the IorPer seasons). The oYerall spread oI oEtained į37Cl resXlts is relatiYely narroZ, IroP 0.38 to -0.55 Å, Zhich dePands enhanced precision oI analysis and careIXl saPple preparation.

RE)ERENCES

1. CraiJ, H. (191) Isotopic variations in meteoric waters. Science 133, 1702-1708. 2. DansJaard, :. (194) Stable isotopes in precipitation. TellXs 16, 43-48.

3. DaYXtlXoJlX O.I., SecNin *., Kalat D.G., YilPaz T., ErsX C.B. (2010) Speciation and implications of heavy metal content in surface sediments of Akyatan lagoon – Turkey. Desalination 260, 189-210.

4. DXane M.J., Al-=aPel A., Eastoe C.J. (2004) Stable isotope (chlorine, hydrogen and oxygen), geochemical and field evidence for continental fluid flow vectors in the Al-Khiran Sabkha (Kuwait), JoXrnal oI AIrican Earth Sciences 40, 49-0.

            :LQWHU 6SULQJ 6XPPHU $XWXPQ 0HGLWHUUDQHDQVHDZDWHU 6DOLQLW\J/

5. EJJenNaPp H. (2004) Chapter 28, in: P. de Groot (ed.) Handbook of Stable Isotopes, ElseYier.

. Haáas S, Pelc A (2009) New isotope ratio mass spectrometric method of precise

G37_{Cl determinations. Rapid CoPP. in Mass SpectroP. 23, 101-104.}

7. KXleli T (2010) Quantitiative analysis of shoreline changes at the Mediterranean Coast in Turkey. EnYir. Monitor. Assess 167, 387-397.

8. LpcXyer C., BoderJat A.-M., MartineaX )., )oXrel )., GrEz K.and NaziN A. (2012) Water sources, mixing and evaporation in the Akyatan lagoon, Turkey. EstXarine, Coastal and ShelI Science 115, 200-209.

9. LpcXyer, C., Gardien, V., RiJaXdier, T., )oXrel, )., MartineaX, )., Cros, A. (2009) Oxygen isotope fractionation and equilibration kinetics between CO2 and H2O as a function of salinity of aqueous solutions. ChePical GeoloJy 264, 122-12. 10. MacPherson N, Cittolin G, CooN H, BesiNtepe S. (1998) The farming of sea bass,

sea bream, and shrimp in Iskenderun Bay, Turkey. Food and Agriculture Organization of the United Nations (FAO) report. AYailaEle as a PD) ¿le at the IolloZinJ URL : http://ZZZ.Iao.orJ/docrep/Iield/003/S8479E/S8479E00.htP 11. MartineaX, )., )oXrel, )., BoderJat, A.-M., LpcXyer, C. (2012) D/H equilibrium

fractionation between H

2O and H2 as a function of the salinity of aqueous

solutions. ChePical GeoloJy 291, 23-240.

12. MeyEecN M., RaJX A. (199) River discharges to the oceans: an assessment of suspended, major ions and nutrients. GEMS/EAP, 245 pp.

13. NaziN A., EYans G., GrEz K. (1999) Sedimentology and palaeontology with special reference to the ostracoda fauna of Akyatan lagoon (Adana – SE Turkey). GeosoXnd 35, 127-147.

14. Pelc A., Haáas S. (2008) Negative ion source for chlorine isotope ratio measurements. Rapid CoPPXnications in Mass SpectroPetry 22, 3977-3982. 15. :X J., SataNe H. (200) Purification of CH3Cl from CH3I using cold trap with

sealed 2,2,4-trimeth\OSHQWDQHIRUį37_{Cl measurements, Analytica ChiP. Acta 555,}

41-4.

1. ;iao Y.K., =hanJ C.G. (1992) High precision of isotopic measurement of chlorine by thermal ionization mass spectrometry of theCs2Cl+ ion. Int. J. Mass SpectroP.