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/lp/de-gruyter/37-cl-of-waters-from-the-akyatan-lagoon-turkey-7UXKzfdep2
- Publisher
- de Gruyter
- Copyright
- Copyright © 2015 by the
- ISSN
- 2300-7559
- eISSN
- 2300-7559
- DOI
- 10.1515/physica-2015-0008
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Abstract
e re ort t e ir t 37Cl data or r ace ater o t e A atan la oon, T r e , ro 12 tation a led o er t e eriod 200 to 200 T e recorded ariation o 37Cl al e i airl all, ro -0 4 to 0 SM C, t o t e en iron ental condition ere i l aria le ea onall T e alinit o t e t died ater aried ro 2 8 to 9 L lot i ni icantl de art re ro t e orld Meteoric ater Line and t e vs 18 M L) it a lo e o 43 0 19 C lorine i oto e indicate a ea o iti e o ater and it alinit T i a e d e to i in correlation et een 37Cl and et een ea ater and di tinct o rce o re ater T e all read o o tained 37Cl re lt de and en anced reci ion o anal i and care l a le re aration Keywords A atan la oon, c lorine i oto e , drolo , cli ate, INTR UCTI N C lorine ta le i oto e ratio 37Cl 3 Cl) ariation are till oorl nder tood in r ace ater T i ratio onl o er all ariation and i t ere ore di ic lt to deter ine ith ood precision ith ost analytical ethods. D ane et al. 2004) st died 37Cl in aters o the Al-Khiran sa ha in K ait to ether ith their D and 18O al es. In ost recent st dies on chlorine isotopes one o t o ethods to deter ine 37Cl/35Cl ratios is sed: 1) analysis y ther al ionization ass spectro etry TIMS), hich is capa le to eas re s all antities, t it has rather lo thro hp t iao and han 1992) 2) analysis o ajor ea s enerated y electron i pact at /z 50 and 52) o chloro ethane as y isotope ratio ass spectro etry IRMS Ka ann et al. 1984). Both ethods attain a precision that is so e hat etter than 0.1 , t the second approach has a co plicated ass spectr E en a p 2004). Recently a ne ethod as de eloped in the Mass Spectro etry La oratory at UMCS L lin that is descri ed elo . The ne ethod is also ased on the ionization o chloro ethane as, t in the ionization cha er it or s ne ati e ions that are enerated on a hot etal s r ace. This leads to a si ple ass spectr , co prisin o 35Cl- and 37Cl- pea s only, and a s stantial enhance ent o the precision o the 37Cl to 0.01 . This ethod as applied to st dy the seasonal and areal ariations o chlorine isotope ratios in the A yatan la oon, T r ey, st died pre io sly y L c yer et al. 2009, 2012) or ariations o salinity and 18O- D o aters. Sta le isotopes o chlorine ay e se l in identi yin ater i in zones i the i in is si ple in nat re. or instance, a continental ater ith a distincti e 37Cl al e i in ith a sea ater ha in 37Cl close to zero. STUDY AREA The A yatan la oon 3 37 N 035 1 E) is located at the so th-eastern ed e o the Mediterranean Sea, in the Ç ro a re ion o T r ey a o t 30 2 so th o the city o Adana i s 1 and 2). The la oon s r ace is 147 and its a era e depth is 0.75 . It as or ed 10,000 years a o as a res lt o the o erlo in and sedi ent dischar e and transport ro the Seyhan and Ceyhan ri ers. The la oon eca e separated ro the sea y a thin sand arrier or ed y a e action McPherson et al. 1988). At present, the la oon recei es resh ater ro rain all and draina eirri ation canals and pro a ly d rin periods o hi h ater le els ro the Seyhan ri er and a andoned channels o the Ceyhan ri er Da tl o l 2010 K leli 2010), oth o the ha in their sprin s in the Ta r s Mo ntains Nazi et al. 1999). The Seyhan ri er has a ean dischar e o 180 3/s hich aries ro ini and a i al es o 20 3/s J ne to Octo er) and 2,250 3/s April), respecti ely McPherson et al. 1988). The a era e ri er ater co position is: 158 /L HCO3-, 48 /L Ca2 , 10 /L M 2 , 30 /L SO42-, 12 /L Na , 20 /L Cl- and 1.5 /L K ollo in eas re ents co piled y Mey ec and Ra 199 ). The la oon is connected to the sea thro h a 2 narro canal on its so theastern side and e chan es ater and sedi ents in response to tidal acti ity. Ma i tide hei ht is a o t 40 c to 0 c , e cept in periods o stron inds that can enerate a 150 c increase in sea le el McPherson et al. 1988). Aro nd the A yatan la oon, air te perat res ran e ro 9 C Jan ary) to 28 C A st) ith a ean ann al al e o 19 C. Precipitation is p to 120 ostly occ rrin d rin the cold season ro No e er to e r ary, at hich period access to the la oon is di ic lt. FIG. 1. eo raphic ap o so theast T r ey ith the location o the A yatan la oon, Seyhan da la e, and its catch ent asin the Ta r s Mo ntains). FIG. 2. Satellite ie o the A yatan la oon, T r ey, and the location o sites indicated y o tlined n ers. ater sa plin ANALYTICAL METHODS CHLORINE ISOTOPE ANALYSIS ATERS ROM THE AKYATAN LA OON IN ater sa ples ere deli ered in her etically closed plastic ottles to the la oratory, here a ter iltration A Cl as precipitated. The precipitate as ashed ith distilled ater and dried in an o en and then reacted ith iodo ethane CH3I) to or chloro ethane CH3Cl), hich is the ost co on as sed in chlorine isotope ratio analysis E en a p 2004). Chloro ethane is ery con enient or ass spectro etry as it has no e ory e ect in ac syste s and can e easily o tained ro a chlorine sa ple and trans erred ro the preparation line to the inlet syste o ass spectro eter since its eltin point is 97.7 C. or CH3Cl preparation the e chan e reaction et een the iodo ethane CH3I) and sil er chloride A Cl) as applied Ka ann et al. 1984, E en a p 2004). The reaction re ires at least a 10- old olar e cess o CH3I o er A Cl, hich res lts in a di ic lt p ri ication proced re o CH3Cl ro CH3I d e to their si ilarity in physical properties. So ar t o p ri ication ethods o chloro ethane are sed: i) as chro ato raphy and ii) cryo enic separation. In oth ethods CH3I is introd ced to a preparation line y injection thro h a sept and eca se o this proced re also so e i p rities air, ater apor) are ad itted to the sa ple. Additionally in the a o e entioned ethods sealin and s se ently crac in o a sa ple t e is needed. To eli inate these dra ac s a ne triple-sta e cryo enic proced re ith t o di erent cryo enic s stances as de eloped, si ilar to the one descri ed y and Sata e 200 ). The ost i portant no elty in o r preparation line is a ne and si ple pipette syste , co prisin o t o lass containers separated y t o stopcoc s ith a Te lon pl , or CH3I introd ction to the cryo enic separation line. Additionally e considera ly si pli ied the separation proced re o oth chloroand iodo- ethanes eca se e replaced the rea -seal t es ith a po les ha in stopcoc s ith Te lon pl s. This odi ication o the chloro ethane p ri ication ethod allo ed shortenin o the ti e needed or co pletion o the CH3Cl separation. The i pro e ents o the chloro ethane preparation techni e in co ination ith the recently de eloped ethod o chlorine isotope ratio analysis ased on ne ati e ion ass spectro etry Ha as and Pelc 2009) leads to enhanced precision o the eas re ents. The i pro ed ncertainty o sin le 37 Cl deter inations as red ced to a o t 0.05 , hich is i portant in st dies o s all nat ral ariations o chlorine isotope ratios. O Y EN AND HYDRO EN ISOTOPE ANALYSIS O ROM AKYATAN LA OON ATERS Ali ots o 200 L ro 37 ater sa ples ere a to atically reacted at 40 C ith CO2 and H2 in the presence o a platin catalyst and analyzed sin TM a M ltiPrep syste on-line ith a VI IsoPri eTM d al-inlet isotope ratio ass spectro eter. Reprod ci ility o D and 18O al es as esti ated to e 1 and 0.1 , respecti ely, y nor alizin ra data to the isotopic ratios o SMO , SLAP and ISP international standards that ere eas red alon ith the sa ples. Corrections o the hydro en and o y en isotope ratios ca sed y chan es in the salinity-dependent ractionation actors CO2H2O and H2OH2 ere ta en into acco nt sin the e ations deter ined y L c yer et al. 2009) and Martinea et al. 2012). RESULTS AND DISCUSSION SALINITY/ O- D RELATIONSHIPS IN AKYATAN LA OON ATERS Hydro en and o y en isotope co positions o the rac ish aters and rines ro the A yatan la oon ran e ro 48.2 to 35.8 and ro . 2 to .95 , respecti ely L c yer et al. 2012). Hydro en and o y en isotope co positions o the la oon aters plot either et een the t o resh and arine ater end- e ers or on the ri ht o the orld Meteoric ater Line M L). Models o so rce- ater i in and e aporation ere de eloped y L c yer et al. 2012). In this st dy, it is clear ro salinity and sta le isotope co positions o A yatan la oon aters that rac ish aters res lt ro i in o resh ater ro the Seyhan Ri er ith Mediterranean sea ater i . 1). S ch i in , ho e er, is co plicated y e aporation processes, as s ested y the slope 5.43 0.19) o the re ression line in the D 18O dia ra hich is ch lo er than the slope o the M L hich is close to 8 Crai 19 1 Dans aard 19 4). Accordin to L c yer et al. 2012), d rin inter and sprin the ater in the la oon is do inated y i in processes et een resh aters and Mediterranean sea ater. Most sa ples ta en d rin the sprin are the res lt o e apoconcentration o rac ish ater at oderate te perat res o 22 2 C. D rin the s er, hypersaline aters res lt ro e aporation o sea ater and rac ish aters or ed d rin sprin . E aporation o er the A yatan la oon reaches p to 7 t ased on salinity eas re ents and operated ith a dry relati e h idity o 0.15 to 0.20) and hot 44 C) air. These resid al aters are characterized y the hi hest seasonal isotope enrich ent in oth de teri and 18O relati e to VSMO . D rin the a t n, ost la oonal aters eco e hypersaline and are or ed y e aporation o ater that had isotope co positions and salinities close to that o sea ater. These a t nal hypersaline aters res lt ro an air h idity close to 0.45 and an at ospheric te perat re o e aporation o 35 5 C, hich are responsi le or p to 71 t o e aporation, ith restricted isotopic enrich ent relati e to VSMO . VARIABILITY O Cl IN ATERS ROM THE AKYATAN LA OON The aria ility o the 37Cl al es is ery di ic lt to disc ss. The ain pro le concerns the end- e er al es. The resh ater sa ples had chlorine concentrations that ere too lo to e analyzed, hereas a sa ple o arine ater indicated at the otto o Ta le 1) is a ected y an enhanced standard de iation o 37Cl. aters ro the A yatan la oon sho a ro h positi e correlation et een 37Cl and D as sho n in i . 3. inter sa ple 200 -2010 37 has oth lo Cl and D o -0.55 and -34.8 , respecti ely, hile s er sa ple 0 07-11 e hi its the hi hest al es o 0.38 and 35.4 , respecti ely. At irst si ht, oth 37Cl and D o aters increase hen ater te perat res are hi h d rin the ar seasons s er and a t n), correspondin to the hi hest rates o e aporation. Moreo er, d rin the ar seasons, inp ts o resh ater are lo est and ater i in is there ore do inated y the sea ater end- e er. This relation is, ho e er, dist r ed y t o sa ples 0 07-5 and 0 04-19) that s est that i in too place et een sea ater and a e di erent so rces o resh ater ith distinct 37Cl si nat res. This hypothesis is s pported y the co ple relations o ser ed et een 37 Cl and salinity S in i . 4. Lo salinity aters ha e distinct 37Cl al es and the hi hest 37Cl al e hich is o nd in a sa ple ith a hi h salinity does not correspond ith sa ples ith e en hi her salinities hich ha e 37Cl al es close to 0 . T o processes are responsi le or 37Cl aria ility in aters ro the A yatan la oon. The irst is i in et een sea ater, di erent so rces o resh ater local rain and the Seyhan Ri er) and rac ish aters inherited ro earlier seasons. As sea ater contains a o t a tho sand ti es ore chlorine than the Seyhan Ri er, 37Cl aria ility can only e o ser ed i reser oirs ha e hi hly contrasted chlorine isotope co positions. The second process is ater e aporation that concentrates the hea iest chlorine isotope in the resid al ater. TABLE 1. Analytical data ro Sa ple no. Sta- Sa plin tion date L c yer et al. 2012) alon ater te p. ( C) 18.0 28.0 27.7 15.0 29.7 32.3 25.7 32.2 23.0 30.0 34.8 25.5 Air te p. ( C) pH Salinity ith O (H2O) ( ) SMO -0. 4 -3.28 -4.15 -4.70 1.2 - .23 2.59 -1.52 -1.93 2.80 . 7 2.09 eas red D (H2O) ( ) SMO 1.2 -24.9 -14.5 -34.8 3.5 -47.3 17.3 4.3 -11.8 15.7 35.4 10.8 Cl. 200 -13 0 04-5 0 07-2 200 -10 0 04-21 0 07-5 AMB0 07200 0 04-19 0 07-7 AMB-11 03-11-200 04-27-200 07-07-200 03-11-200 05-03-200 07-07-200 10-08-2005 07-07-200 NBS ( /L) scale 15.5 8.00 32.0 30.0 34. 17.0 25.2 28.0 28.8 30.2 18.0 21.4 25.2 29.1 9.10 8.13 8.00 9.03 8.03 8.24 8.32 8.58 8.78 9.03 8.32 14.0 12.1 15.0 25.0 2.8 4.0 17.4 25.0 34.0 50.3 44.0 Cl ( ) SMOC 0.0 0.0 -0.12 -0.55 0.08 -0.20 0.1 -0.17 -0.14 -0.38 0.38 -0.15 03-04-200 05-03-200 07-07-200 10-08-2005 0 04-17 AMB-18 0 07-11 AMB-22 MS -2 13 18 18 22 A 04-29-200 10-09-2005 07-08-200 10-13-200 10-11-200 2 .0 24.5 32. 2 .0 n.a. 30.0 2 . 2 . 31.0 n.a. 8.40 8.43 7.98 8.40 n.a. 0.1 , n.a. -0.13 -0.0 0.00 0.07 0.0* not a aila le *Standard de iation FIG. 3. A plot o sa ple. Cl in SMOC ith respect to D ( VSMO ) o analyzed ater FIG. 4. A plot o Cl in SMOC ers s salinity in /L. CONCLUSIONS e ha e o nd oth te poral and spatial aria ility o 37Cl in the analyzed aters. A ea positi e correlation as o nd et een 37Cl and D o ater and its salinity. This ay indicate a i in et een sea ater and distinct so rces o resh ater (local rain and the Seyhan Ri er and i in ith rac ish aters inherited ro the or er seasons). The o erall spread o o tained 37Cl res lts is relati ely narro , ro 0.38 to -0.55 , hich de ands enhanced precision o analysis and care l sa ple preparation. RE ERENCES 1. 2. 3. 4. Crai , H. (19 1) Isotopic variations in meteoric waters. Science 133, 1702-1708. Dans aard, . (19 4) Stable isotopes in precipitation. Tell s 16, 43 -4 8. Da tl o l O.I., Sec in ., Kalat D.G., Yil az T., Ers C.B. (2010) Speciation and implications of heavy metal content in surface sediments of Akyatan lagoon Turkey. Desalination 260, 189-210. D ane M.J., Al- a el 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), Jo rnal o A rican Earth Sciences 40, 49- 0. E en a p H. (2004) Chapter 28, in: P. de Groot (ed.) Handbook of Stable Isotopes, Else ier. . Ha as S, Pelc A (2009) New isotope ratio mass spectrometric method of precise 37 Cl determinations. Rapid Co . in Mass Spectro . 23, 10 1-10 4. 7. K leli T (2010) Quantitiative analysis of shoreline changes at the Mediterranean Coast in Turkey. En ir. Monitor. Assess 167, 387-397. 8. L c yer C., Boder at A.-M., Martinea ., o rel ., G r z K. and Nazi A. (2012) Water sources, mixing and evaporation in the Akyatan lagoon, Turkey. Est arine, Coastal and Shel Science 115, 200-209. 9. L c yer, C., Gardien, V., Ri a dier, T., o rel, ., Martinea , ., Cros, A. (2009) Oxygen isotope fractionation and equilibration kinetics between CO2 and H2O as a function of salinity of aqueous solutions. Che ical Geolo y 264, 122-12 . 10. MacPherson N, Cittolin G, Coo H, Besi tepe 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. A aila le as a PD le at the ollo in URL : http:// . ao.or /docrep/ ield/003/S8479E/S8479E00.ht 11. Martinea , ., o rel, ., Boder at, A.-M., L c yer, C. (2012) D/H equilibrium fractionation between H O and H as a function of the salinity of aqueous 12. 13. 14. 15. 1 . solutions. Che ical Geolo y 291, 23 -240. Mey ec M., Ra A. (199 ) River discharges to the oceans: an assessment of suspended, major ions and nutrients. GEMS/EAP, 245 pp. Nazi A., E ans G., G r z K. (1999) Sedimentology and palaeontology with special reference to the ostracoda fauna of Akyatan lagoon (Adana SE Turkey). Geoso nd 35, 127-147. Pelc A., Ha as S. (2008) Negative ion source for chlorine isotope ratio measurements. Rapid Co nications in Mass Spectro etry 22, 3977-3982. J., Sata e H. (200 ) Purification of CH3Cl from CH3I using cold trap with 37 Cl measurements, Analytica Chi . Acta 555, sealed 2,2,4-trimeth 41-4 . iao Y.K., han C.G. (1992) High precision of isotopic measurement of chlorine by thermal ionization mass spectrometry of theCs2Cl+ ion. Int. J. Mass Spectro . Ion Proc. 116, 183-192.
Journal
Annales UMCS, Physica – de Gruyter
Published: Mar 1, 2015