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Research ArticleREE Geochemistry of Euphrates River Turkey
Leyla Kalender and Gamze Aytimur
Department of Geological Engineering Engineering Faculty Fırat University 23119 Elazıg Turkey
Correspondence should be addressed to Leyla Kalender leylakalenderfiratedutr
Received 3 March 2016 Revised 14 April 2016 Accepted 24 April 2016
Academic Editor Stanislav Franciskovic-Bilinski
Copyright copy 2016 L Kalender and G Aytimur This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
The study area is located on the Euphrates River at 38∘41∘324810158401015840Nndash38∘141015840241010158401015840N latitude and 39∘56101584045910158401015840Endash39∘8∘134110158401015840E longitudeThe Euphrates is the longest river in Western Asia The lithological units observed from the bottom to the top are Permo-TriassicKeban Metamorphites Late Cretaceous Komurhan Ophiolites Upper Cretaceous Elazıg Magmatic Complex Middle EoceneMaden Complex and Kırkgecit Formation Upper Pliocene and Lower Eocene Seske Formation and Upper Miocene PlioceneKarabakır and Caybagı Formations Palu Formation and Holocene Euphrates River sediments The geochemical studies show that87Sr86Sr and 143Nd144Nd isotopic compositions in the Euphrates River bank sediments are 07053 07048 and 07057 and 05126540512836 and 0512775 respectively These values indicate mixing of both carbonate-rich shallow marine sediment and felsic-mafic rocks from Elazıg Magmatic Complex into the stream sediments The positive 120576Nd(0) values (035 39 and 27) are higherdownstream in the studied sediments due to weathering of the mafic volcanic rocks The chondrite NAS and UCC normalizedpatterns show that the REE compositions of the Euphrates River sediments are higher than chondrite composition but close to NASand UCC The river sediments in the tectonic zone and the weathered granodioritic rocks of the Elazıg Magmatic complex affectupstream water compositions
1 Introduction
A number of researchers have studied Nd-Sr isotopic andtrace element geochemistry of river sediments and soils astracers of clastic sources The geochemical characterizationsand Sr-Nd isotopic fingerprinting of sediments in any fluvialsystem can be done using radiogenic isotopic compositions[1ndash5] Rare earth elements (REEs) compositions have beenstudied in stream sediments [6ndash8] and in chemical weather-ing of drainage systems [9ndash12] A number of researchers havestudied REE composition of both river sediments and riverwater and discovered that heavy REE concentration is higherin the river sediments than in suspendedmatter in riverwaterThey also indicated that shale Upper Continental Crust andchondrite normalized REE patterns showed that chemicalweathering from source rocks in the continental crusterosion and terrigenous fluviatile sediment sources can bedistinguished using the REE compositions of rivers [13ndash18]Leybourne et al [19] indicated that Ce and Eu can be redoxsensitive and attributed to determination of redox conditionsYang et al [8] stated that source rock composition is a more
important factor affecting REE composition than weatheringprocesses There are fewer studies on the Euphrates RiverKalender and Bolucek [20] studied the stream sedimentsin the north Keban Dam Lake in the Eastern Anatoliandistrict and demonstrated that more REEs are transportedwith Fe and Mn rich oxides and fine size fraction sediments(eg clay minerals) via adsorption Kalender and Cicek Ucar[21] indicated that the calculated enrichment factor valuesof the heavy REE are more than those of light REE in theGeli stream sediments Geli stream is a tributary of theEuphrates River Rivers carry the weathered rock productsfrom the continents to the dam lakes natural lakes and thesea Thus this study focuses on the REE concentrations inriver bank sediments from the initial point of the EuphratesRiver (10 kilometers upstream of Keban Dam) to KarakayaDam Lake In order to evaluate distribution of REE alongthe flowing direction of the Euphrates River the sedimentsources and lithological controls were identified using UpperContinental Crust (UCC) North American Shale (NAS) andChondrite (Ch) normalized REE patterns (all average valuestaken from [8 22ndash25]) Goldstein and Jacobsen [13] studied
Hindawi Publishing CorporationJournal of ChemistryVolume 2016 Article ID 1012021 13 pageshttpdxdoiorg10115520161012021
2 Journal of Chemistry
REE compositions in river water and major rivers haveLREE enriched patterns relative to the NAS and negative Ceanomalies occur at high pH This paper firstly presents REEconcentrations and includes source rock composition of theEuphrates River sediments and waters
2 Geology
The Euphrates River is located in the Eastern Anatoliandistrict in Turkey and is located on the active tectonic zone ofthe East Anatolian fault zoneThe East Anatolian fault zone isseismically one of the most active regions in the world and islocated within the Mediterranean Earthquake Zone which isa complicated deformation area that was formed by the con-tinental collision between the African-Arabian and Eurasiancontinents These deformations involve thrust faults suturezones and active strike slip and normal faults as well as basinformations arising from these faults The Euphrates River islocated on the East Anatolian fault zone and is formed by themixing of the Karasu River and Murat River 10 kilometersupstream of the Keban Dam According to Frenken [27] theEuphrates River length is 1100 km from Palu to the Red Sea(Figures 1(a) and 1(b)) The studied sediments were sampledalong approximately 50 kilometers of the Euphrates Riverlength The main stratigraphic units found in the EuphratesRiver basin range from the Permo-Triassic Keban Meta-morphites to Plio-Quaternary Palu Formation (Figure 1(b))The Keban Metamorphites outcrop on both right and leftbanks of the Euphrates River Considering the regionalscale the Keban Metamorphites are represented by marblerecrystallized limestone calc-schist metaconglomerate andcalc-phyllite in the study area [28] Additionally in thestudy area the Upper Cretaceous Elazıg Magmatic Complexconsists of volcanic rocks (basalt andesite pillow lava daciteand volcanic breccia) subvolcanic rocks (aplite microdioriteand dolerite) and plutonic rocks (diorite tonalite gran-odiorite granite and monzonite) The magmatic rocks areoverlain by recrystallized limestone of the Permo-TriassicKeban Metamorphites [29] The Late Cretaceous KomurhanOphiolites are part of the southeast Anatolian ophiolite beltwhich are formed in a suprasubduction zone within thesouthern Neo-Tethys [30] The Komurhan Ophiolites consistof dunite layered and isotropic gabbros plagiogranite sheetdyke complex andesitic and basaltic rocks and volcanosed-imentary rocks The unit is observed in the Karakaya DamLake area (Figure 1(b)) Upper Paleocene and Lower Eocenemassive limestones are named the Seske Formation whichis characterized by interbedded clastic and carbonate rocksThe stratigraphic position of the Seske Formation indicatesthe extent of how Neo-Tethys was controlled by the tectonicand topographic features of the region during the Eocene[31 32] The Seske Formation is observed along the KarakayaDam Lake (Figure 1(b)) Middle Eocene Maden Complexis composed of basaltic and andesitic rocks and limestoneconglomerates sandstones and mudrocks (marl) [29 33ndash35] Middle Eocene Kırkgecit Formation consists of marineconglomerates marls and limestone from the bottom tothe top [36] The Alibonca Formation was deposited afterclosure of the Neo-Tethys Ocean in Mesozoic time The
unit is composed of sandy limestone and marls which areobserved in the Keban Dam Lake area [37] (Figure 1(b))UpperMiocene-Pliocene Karabakır and Caybagı Formationsconsist of sandstone mudrock marls tuff and basaltic rocks[36] The units are observed in the northeast of the KebanDam Lake (Figure 1(b)) The Caybagı Formation is named byTurkmen [38] at the Caybagı township in the east of ElazıgPliocene-Quaternary units are named the Palu Formation byKerey and Turkmen [39] The units consist of quaternaryalluvial and fluvial deposits along the level bank of the MuratRiver which is the initial point of the Euphrates River (Figures1(a) and 1(b))
3 Analytical Methods
31 Climatic Information Maximum flows of the EuphratesRiver occurred from February through April whereas min-imum flows occurred from August through October Theannual mean rainfall during that period was 372mm and theair temperature varied between 1521∘C (Elazıg) and 1631∘C(Malatya) with the highest and the lowest temperature of34∘C and minus 10 respectively between 1992 and 2001 Thecontinental climate of the Euphrates Basin is a subtropicalplateau climate (data was taken from reports by the ElazıgMeteorology Department) The Euphrates River sedimentsamples were collected in September the period of minimumflow of the Euphrates River water It is also good to takeinto consideration the effect on chemical compositions of theriver bed sediment of processes erosion of the earthrsquos surfaceThe sediment samples were taken from locations close tothe center of the river bed in consideration of the erosionalprocess and chemical composition of the river bed sediments
32 Sampling Sites In this study directing studies could notbe performed in advance of the development of sample takingmethods and suitable particle size and chemical analysismethods Ninety river sediments and water samples weretaken from the right side of the river bed along the directionof the river water flow because it is suitable for sampling ofriver bed morphology (Figure 1(b))
33 Sample Preparing for Analysis The samples were takenin September when the water flow rate was low In order toprevent the existence of particles in the sediment samples thatwere too large the sampleswere sifted through sievewith holediameter of 2mm (BS10 mesh) so as to obtain the suitableparticle sizes 2 Kg of the river sediment samples was takenat 250ndash500m intervals along the Euphrates River (from 10kilometers upstream of the Keban Dam to Karakaya Dam50 kilometers) and placed into plastic bags numbered anddried at room temperature After drying the samples weresifted to different sieve dimensions in order to determine theparticle size fractions suitable for analysis (minus200mesh) In thestudy of some metals and REE concentrations in sedimentsmany researchers prefer the grain size of fine-medium sandto silt (minus74120583m) as it shows very high concentrations higherthan minus80mesh (minus180 120583m) [8 21 40 41] In order tominimizethe grain size dependencies of heavy metals concentrationsof minus75 120583m fraction representing medium fine sand to silt
Journal of Chemistry 3
Karasu River
Murat River
Euphrates River
Tigris RiverIraq
Iran
SyriaRed Sea
Black Sea
TurkeyIstanbul
Mediterranean Sea
Aege
an S
eaStudy area
N
0 500(km)
Elazığ
Jordan
Cyprus
Leba
non
38∘39
99840012
998400998400N
39∘59
99840029
998400998400E
(a)
Hazarbaba Mountain
Baskil
Goumlzeli
Karakaya Dam Lake
Keban Dam Lake
Lake Hazar
Alibonca Fm
Palu Fm
Keban Metamorphites
Maden Complex Alluvium
Keban
Ccedilaybaği Palu
N
Scale
Ccedilaybaği Fm
Plio-QuaternaryUpper Miocene-PlioceneUpper Miocene
Lower Miocene
Holocene
Thrust zone Middle EoceneMiddle Eocene
Upper Cretaceous
Koumlmuumlrhan OphiolitesJurassic Cretaceous
Permo-Triassic
Seske Fm+ +
Active fault zone(East Anatolian EAFZ)
EAFZ
Sivrice
123456
7891011
121314
10
151617
18192021
22232425
2627
282930
31323334
3536
3738
39
40
4142434445
4647484950515253
5455
5657585960
61
62
6364
65
666768 69 70 71 72 73
747576 7778
79 80 81 8283 8485
8687
8889 90
Sample sites
18
21
30
20
25
Kuzo
va
Uluov
(km)100
S
D
Gezin
Elazıg Magmatic Complex
ElazıgKovancılar
Karabakır Fm
Kırkgeccedilit Fm
(b)
Figure 1 (a) Locationmap (b) Geology map of the Euphrates River and the sampling sites (from 1 to 90 the geology map was modified fromHerece et al [26])
were used in the present study Mechanical wet sieving wasperformed to separate the minus74120583m sediment fraction fromthe bulk samples Fifteen to twenty grams of each samplewas freeze dried for 8 and 9 hours The sieved fractionswere placed in clean porcelain bowls and dried at roomtemperature
34 Chemical Analysis Elazıg Magmatic Complex includeszirconium- and titanium-bearing minerals [30] As com-monly known zirconium- and titanium-bearing mineralscontain amounts of REE This method was preferred dueto its convenience for the decomposition of the silicateminerals using HF HF is an efficient disintegration agent
4 Journal of Chemistry
Direction of drainage from Euphrates River initial point (10 kilometers upstream of Keban Dam) to Karakaya Dam
A1 A89
A87
A85
A83
A81
A79
A77
A75
A73
A71
A69
A67
A65
A63
A61
A59
A57
A55
A53
A51
A49
A47
A45
A43
A41
A39
A37
A35
A33
A31
A29
A27
A25
A23
A21
A19
A17
A15
A13
A11A9A7A5A3
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
143Nd144Nd and 87Sr86Sr
001
01
10
100Lo
g pp
m R
EE
Figure 2 Distribution of REE and the determined sample sites (A43 A61 and A89) for 87Sr86Sr and 143Nd144Nd isotopic analysis from theEuphrates River sediments
used for the decomposition of zirconium silicate and apatitesource fromgranitoids in natureThis decompositionmethodcauses the loss of silica as SiF
4and a part of titanium as
TiF4 Bulk samples were ground and sieved through 200-
mesh (about 0074mm pore size) stainless steel sieve forchemical analysis 05 g of each sediment sample was leachedwith 90mL HCl-HNO
3-HF at 95∘C for 1 hour diluted to
150mL and then analyzed by ICP-OES The extractionmethod used by Saito et al [42] was used to obtain themaximum REE concentration at 995mL 001ndash1m nitric acidaqueous solution (pH lt 4) Standard DS5 was used forthe sediment analyses The sediment samples were analyzedfor REE in Acme Analytical Laboratories Ltd Canada byInductively Coupled Plasma-Optical Emission Spectrometer(ICP-OES) The river water samples have less than 01total dissolved solids and these analyses were used by ICP-OES at BureauVeritas environmental labMaxxamAnalyticsThe isotopic measurements were made at the Middle EastTechnical University (Ankara Turkey) following the protocolof Koksal and Goncuoglu [43] TLM-ARG-RIL-02 methodswere adopted An 80mg aliquot was taken for analysis ofSr and Nd isotope ratios The samples were dissolved inbeakers in a 4mL 52 HF at 160∘C on the hotplate alongfour days The samples were dried on the hotplate using25N HCl and 2mL bis(ethylhexyl) phosphate using Bio-Rad AG50 W-X8 100ndash200 mesh and chemical seperation
of Sr ionic chromatographic columns was prepared Afterchemical separation of Sr REE fractionation was collectedusing 6N HCl Sr isotopes were measured using a single Ta-activator with Re filament and 0005NH
3PO4[44] 87Sr86Sr
ratios were corrected for mass fractionation by normalizingto 86Sr88Sr = 01194 and strontium standard (NBS 987) wasmeasured more than 2 times The chemical separation ofNd from REE was made in a teflon column using 022NHCl and 2mL bis(ethylhexyl) phosphate 143Nd144Nd datawere normalized by 146Nd144Nd = 07219 and neodymiumstandard (0511848 plusmn 5) was measured more than 2 times
4 Results
41 Nd-Sr Isotope Compositions of the Euphrates River Sedi-ments REE concentrations of the Euphrates River sedimentsfrom Keban Dam to Karakaya Dam are presented in Table 1The result of isotopic composition of the studied sedimentsand those from different origin summarized statistical val-ues and REE compositions of the Mississippi and AmazonRiver sediments are presented in Table 1 The 75120583m (200mesh) size fraction from the Euphrates River sedimentsamples (A43 A61 and A89) was analyzed for 87Sr86Sr and143Nd144Nd ratios (Figure 2 and Table 1) The study showsthat 87Sr86Sr and 143Nd144Nd isotopic compositions haverange of 07053 07048 and 07057 and 0512654 0512836
Journal of Chemistry 5
Table1Summarys
tatistic
alvaluesofRE
Efro
mEu
phratesR
iversediments
Densityv
alues(gcm3
)taken
from
Gup
taandKr
ishnamurthy[45]lowast
Sedimentsfro
mSholkovitz[46]C
alculated
120576Ndand1000Srd
atafrom
Martin
andMcC
ulloch
[4]lowastlowast
Burkee
tal[1]lowastlowastlowast
Bussy[2]lowastlowastlowastlowast
Akgul
etal[47]+
Menseletal[48]
(a)
LREE119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
HRE
E119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
La614
34159
857
608
349
Tb823
018047
033
mdashmdash
Ce
816
75344
1811
1254
707
Dy
855
063312
217
746
397
Pr677
088446
222
mdashmdash
Ho
879
017063
043
mdashmdash
Nd
700
53912
177
0564
355
Er90
6043167
120
494
217
Sm752
082405
214
mdashmdash
Tm93
2005028
017
mdashmdash
Eu524
023082
057
211
109
Yb696
029159
111
394
205
Gd
790
044
365
220
986
463
Lu98
4002023
015
047
302
Mean
593
mdashmdash
Mean
079
mdashmdash
Stdeviatio
n618
mdashmdash
Stdeviatio
n074
mdashmdash
(b)
Ther
esulto
fisotopicc
ompo
sitionof
thes
tudied
sedimentsandsomee
xamples
inthew
orld
Samplec
ode
143
Nd144
Nd
87
Sr86
Sr120576Nd(0)
1000Sr
A43
0512654
07053
035
161
A61
0512836
07048
39
1374
A89
0512775
07057
27
1317
Basaltics
oil+
0511783
0705603
226
39
Metasedsoil+
0512501
07096
46minus267
657
Metagreyw
ackes+
0512847
0705374
408
249
Sediments+
0512805
0704583
326
40
lowastlowast
Jurassic-C
retaceou
ssedim
ents
mdash0707ndash0708
mdashmdash
lowastlowastlowast
ArveR
iver
sediments
mdash0728
mdashRe
lated
toMon
t-Blanc
granite
0704
mdashCarbo
nate-richrocks
lowastlowastlowastlowast
ElazıgMagmatitesU
pper
Cretaceous
0512414ndash0
512851
0706022ndash0
708451
75Diorites
and
granites
mdash35
mdash
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
2 Journal of Chemistry
REE compositions in river water and major rivers haveLREE enriched patterns relative to the NAS and negative Ceanomalies occur at high pH This paper firstly presents REEconcentrations and includes source rock composition of theEuphrates River sediments and waters
2 Geology
The Euphrates River is located in the Eastern Anatoliandistrict in Turkey and is located on the active tectonic zone ofthe East Anatolian fault zoneThe East Anatolian fault zone isseismically one of the most active regions in the world and islocated within the Mediterranean Earthquake Zone which isa complicated deformation area that was formed by the con-tinental collision between the African-Arabian and Eurasiancontinents These deformations involve thrust faults suturezones and active strike slip and normal faults as well as basinformations arising from these faults The Euphrates River islocated on the East Anatolian fault zone and is formed by themixing of the Karasu River and Murat River 10 kilometersupstream of the Keban Dam According to Frenken [27] theEuphrates River length is 1100 km from Palu to the Red Sea(Figures 1(a) and 1(b)) The studied sediments were sampledalong approximately 50 kilometers of the Euphrates Riverlength The main stratigraphic units found in the EuphratesRiver basin range from the Permo-Triassic Keban Meta-morphites to Plio-Quaternary Palu Formation (Figure 1(b))The Keban Metamorphites outcrop on both right and leftbanks of the Euphrates River Considering the regionalscale the Keban Metamorphites are represented by marblerecrystallized limestone calc-schist metaconglomerate andcalc-phyllite in the study area [28] Additionally in thestudy area the Upper Cretaceous Elazıg Magmatic Complexconsists of volcanic rocks (basalt andesite pillow lava daciteand volcanic breccia) subvolcanic rocks (aplite microdioriteand dolerite) and plutonic rocks (diorite tonalite gran-odiorite granite and monzonite) The magmatic rocks areoverlain by recrystallized limestone of the Permo-TriassicKeban Metamorphites [29] The Late Cretaceous KomurhanOphiolites are part of the southeast Anatolian ophiolite beltwhich are formed in a suprasubduction zone within thesouthern Neo-Tethys [30] The Komurhan Ophiolites consistof dunite layered and isotropic gabbros plagiogranite sheetdyke complex andesitic and basaltic rocks and volcanosed-imentary rocks The unit is observed in the Karakaya DamLake area (Figure 1(b)) Upper Paleocene and Lower Eocenemassive limestones are named the Seske Formation whichis characterized by interbedded clastic and carbonate rocksThe stratigraphic position of the Seske Formation indicatesthe extent of how Neo-Tethys was controlled by the tectonicand topographic features of the region during the Eocene[31 32] The Seske Formation is observed along the KarakayaDam Lake (Figure 1(b)) Middle Eocene Maden Complexis composed of basaltic and andesitic rocks and limestoneconglomerates sandstones and mudrocks (marl) [29 33ndash35] Middle Eocene Kırkgecit Formation consists of marineconglomerates marls and limestone from the bottom tothe top [36] The Alibonca Formation was deposited afterclosure of the Neo-Tethys Ocean in Mesozoic time The
unit is composed of sandy limestone and marls which areobserved in the Keban Dam Lake area [37] (Figure 1(b))UpperMiocene-Pliocene Karabakır and Caybagı Formationsconsist of sandstone mudrock marls tuff and basaltic rocks[36] The units are observed in the northeast of the KebanDam Lake (Figure 1(b)) The Caybagı Formation is named byTurkmen [38] at the Caybagı township in the east of ElazıgPliocene-Quaternary units are named the Palu Formation byKerey and Turkmen [39] The units consist of quaternaryalluvial and fluvial deposits along the level bank of the MuratRiver which is the initial point of the Euphrates River (Figures1(a) and 1(b))
3 Analytical Methods
31 Climatic Information Maximum flows of the EuphratesRiver occurred from February through April whereas min-imum flows occurred from August through October Theannual mean rainfall during that period was 372mm and theair temperature varied between 1521∘C (Elazıg) and 1631∘C(Malatya) with the highest and the lowest temperature of34∘C and minus 10 respectively between 1992 and 2001 Thecontinental climate of the Euphrates Basin is a subtropicalplateau climate (data was taken from reports by the ElazıgMeteorology Department) The Euphrates River sedimentsamples were collected in September the period of minimumflow of the Euphrates River water It is also good to takeinto consideration the effect on chemical compositions of theriver bed sediment of processes erosion of the earthrsquos surfaceThe sediment samples were taken from locations close tothe center of the river bed in consideration of the erosionalprocess and chemical composition of the river bed sediments
32 Sampling Sites In this study directing studies could notbe performed in advance of the development of sample takingmethods and suitable particle size and chemical analysismethods Ninety river sediments and water samples weretaken from the right side of the river bed along the directionof the river water flow because it is suitable for sampling ofriver bed morphology (Figure 1(b))
33 Sample Preparing for Analysis The samples were takenin September when the water flow rate was low In order toprevent the existence of particles in the sediment samples thatwere too large the sampleswere sifted through sievewith holediameter of 2mm (BS10 mesh) so as to obtain the suitableparticle sizes 2 Kg of the river sediment samples was takenat 250ndash500m intervals along the Euphrates River (from 10kilometers upstream of the Keban Dam to Karakaya Dam50 kilometers) and placed into plastic bags numbered anddried at room temperature After drying the samples weresifted to different sieve dimensions in order to determine theparticle size fractions suitable for analysis (minus200mesh) In thestudy of some metals and REE concentrations in sedimentsmany researchers prefer the grain size of fine-medium sandto silt (minus74120583m) as it shows very high concentrations higherthan minus80mesh (minus180 120583m) [8 21 40 41] In order tominimizethe grain size dependencies of heavy metals concentrationsof minus75 120583m fraction representing medium fine sand to silt
Journal of Chemistry 3
Karasu River
Murat River
Euphrates River
Tigris RiverIraq
Iran
SyriaRed Sea
Black Sea
TurkeyIstanbul
Mediterranean Sea
Aege
an S
eaStudy area
N
0 500(km)
Elazığ
Jordan
Cyprus
Leba
non
38∘39
99840012
998400998400N
39∘59
99840029
998400998400E
(a)
Hazarbaba Mountain
Baskil
Goumlzeli
Karakaya Dam Lake
Keban Dam Lake
Lake Hazar
Alibonca Fm
Palu Fm
Keban Metamorphites
Maden Complex Alluvium
Keban
Ccedilaybaği Palu
N
Scale
Ccedilaybaği Fm
Plio-QuaternaryUpper Miocene-PlioceneUpper Miocene
Lower Miocene
Holocene
Thrust zone Middle EoceneMiddle Eocene
Upper Cretaceous
Koumlmuumlrhan OphiolitesJurassic Cretaceous
Permo-Triassic
Seske Fm+ +
Active fault zone(East Anatolian EAFZ)
EAFZ
Sivrice
123456
7891011
121314
10
151617
18192021
22232425
2627
282930
31323334
3536
3738
39
40
4142434445
4647484950515253
5455
5657585960
61
62
6364
65
666768 69 70 71 72 73
747576 7778
79 80 81 8283 8485
8687
8889 90
Sample sites
18
21
30
20
25
Kuzo
va
Uluov
(km)100
S
D
Gezin
Elazıg Magmatic Complex
ElazıgKovancılar
Karabakır Fm
Kırkgeccedilit Fm
(b)
Figure 1 (a) Locationmap (b) Geology map of the Euphrates River and the sampling sites (from 1 to 90 the geology map was modified fromHerece et al [26])
were used in the present study Mechanical wet sieving wasperformed to separate the minus74120583m sediment fraction fromthe bulk samples Fifteen to twenty grams of each samplewas freeze dried for 8 and 9 hours The sieved fractionswere placed in clean porcelain bowls and dried at roomtemperature
34 Chemical Analysis Elazıg Magmatic Complex includeszirconium- and titanium-bearing minerals [30] As com-monly known zirconium- and titanium-bearing mineralscontain amounts of REE This method was preferred dueto its convenience for the decomposition of the silicateminerals using HF HF is an efficient disintegration agent
4 Journal of Chemistry
Direction of drainage from Euphrates River initial point (10 kilometers upstream of Keban Dam) to Karakaya Dam
A1 A89
A87
A85
A83
A81
A79
A77
A75
A73
A71
A69
A67
A65
A63
A61
A59
A57
A55
A53
A51
A49
A47
A45
A43
A41
A39
A37
A35
A33
A31
A29
A27
A25
A23
A21
A19
A17
A15
A13
A11A9A7A5A3
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
143Nd144Nd and 87Sr86Sr
001
01
10
100Lo
g pp
m R
EE
Figure 2 Distribution of REE and the determined sample sites (A43 A61 and A89) for 87Sr86Sr and 143Nd144Nd isotopic analysis from theEuphrates River sediments
used for the decomposition of zirconium silicate and apatitesource fromgranitoids in natureThis decompositionmethodcauses the loss of silica as SiF
4and a part of titanium as
TiF4 Bulk samples were ground and sieved through 200-
mesh (about 0074mm pore size) stainless steel sieve forchemical analysis 05 g of each sediment sample was leachedwith 90mL HCl-HNO
3-HF at 95∘C for 1 hour diluted to
150mL and then analyzed by ICP-OES The extractionmethod used by Saito et al [42] was used to obtain themaximum REE concentration at 995mL 001ndash1m nitric acidaqueous solution (pH lt 4) Standard DS5 was used forthe sediment analyses The sediment samples were analyzedfor REE in Acme Analytical Laboratories Ltd Canada byInductively Coupled Plasma-Optical Emission Spectrometer(ICP-OES) The river water samples have less than 01total dissolved solids and these analyses were used by ICP-OES at BureauVeritas environmental labMaxxamAnalyticsThe isotopic measurements were made at the Middle EastTechnical University (Ankara Turkey) following the protocolof Koksal and Goncuoglu [43] TLM-ARG-RIL-02 methodswere adopted An 80mg aliquot was taken for analysis ofSr and Nd isotope ratios The samples were dissolved inbeakers in a 4mL 52 HF at 160∘C on the hotplate alongfour days The samples were dried on the hotplate using25N HCl and 2mL bis(ethylhexyl) phosphate using Bio-Rad AG50 W-X8 100ndash200 mesh and chemical seperation
of Sr ionic chromatographic columns was prepared Afterchemical separation of Sr REE fractionation was collectedusing 6N HCl Sr isotopes were measured using a single Ta-activator with Re filament and 0005NH
3PO4[44] 87Sr86Sr
ratios were corrected for mass fractionation by normalizingto 86Sr88Sr = 01194 and strontium standard (NBS 987) wasmeasured more than 2 times The chemical separation ofNd from REE was made in a teflon column using 022NHCl and 2mL bis(ethylhexyl) phosphate 143Nd144Nd datawere normalized by 146Nd144Nd = 07219 and neodymiumstandard (0511848 plusmn 5) was measured more than 2 times
4 Results
41 Nd-Sr Isotope Compositions of the Euphrates River Sedi-ments REE concentrations of the Euphrates River sedimentsfrom Keban Dam to Karakaya Dam are presented in Table 1The result of isotopic composition of the studied sedimentsand those from different origin summarized statistical val-ues and REE compositions of the Mississippi and AmazonRiver sediments are presented in Table 1 The 75120583m (200mesh) size fraction from the Euphrates River sedimentsamples (A43 A61 and A89) was analyzed for 87Sr86Sr and143Nd144Nd ratios (Figure 2 and Table 1) The study showsthat 87Sr86Sr and 143Nd144Nd isotopic compositions haverange of 07053 07048 and 07057 and 0512654 0512836
Journal of Chemistry 5
Table1Summarys
tatistic
alvaluesofRE
Efro
mEu
phratesR
iversediments
Densityv
alues(gcm3
)taken
from
Gup
taandKr
ishnamurthy[45]lowast
Sedimentsfro
mSholkovitz[46]C
alculated
120576Ndand1000Srd
atafrom
Martin
andMcC
ulloch
[4]lowastlowast
Burkee
tal[1]lowastlowastlowast
Bussy[2]lowastlowastlowastlowast
Akgul
etal[47]+
Menseletal[48]
(a)
LREE119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
HRE
E119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
La614
34159
857
608
349
Tb823
018047
033
mdashmdash
Ce
816
75344
1811
1254
707
Dy
855
063312
217
746
397
Pr677
088446
222
mdashmdash
Ho
879
017063
043
mdashmdash
Nd
700
53912
177
0564
355
Er90
6043167
120
494
217
Sm752
082405
214
mdashmdash
Tm93
2005028
017
mdashmdash
Eu524
023082
057
211
109
Yb696
029159
111
394
205
Gd
790
044
365
220
986
463
Lu98
4002023
015
047
302
Mean
593
mdashmdash
Mean
079
mdashmdash
Stdeviatio
n618
mdashmdash
Stdeviatio
n074
mdashmdash
(b)
Ther
esulto
fisotopicc
ompo
sitionof
thes
tudied
sedimentsandsomee
xamples
inthew
orld
Samplec
ode
143
Nd144
Nd
87
Sr86
Sr120576Nd(0)
1000Sr
A43
0512654
07053
035
161
A61
0512836
07048
39
1374
A89
0512775
07057
27
1317
Basaltics
oil+
0511783
0705603
226
39
Metasedsoil+
0512501
07096
46minus267
657
Metagreyw
ackes+
0512847
0705374
408
249
Sediments+
0512805
0704583
326
40
lowastlowast
Jurassic-C
retaceou
ssedim
ents
mdash0707ndash0708
mdashmdash
lowastlowastlowast
ArveR
iver
sediments
mdash0728
mdashRe
lated
toMon
t-Blanc
granite
0704
mdashCarbo
nate-richrocks
lowastlowastlowastlowast
ElazıgMagmatitesU
pper
Cretaceous
0512414ndash0
512851
0706022ndash0
708451
75Diorites
and
granites
mdash35
mdash
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
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Carbohydrate Chemistry
International Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 3
Karasu River
Murat River
Euphrates River
Tigris RiverIraq
Iran
SyriaRed Sea
Black Sea
TurkeyIstanbul
Mediterranean Sea
Aege
an S
eaStudy area
N
0 500(km)
Elazığ
Jordan
Cyprus
Leba
non
38∘39
99840012
998400998400N
39∘59
99840029
998400998400E
(a)
Hazarbaba Mountain
Baskil
Goumlzeli
Karakaya Dam Lake
Keban Dam Lake
Lake Hazar
Alibonca Fm
Palu Fm
Keban Metamorphites
Maden Complex Alluvium
Keban
Ccedilaybaği Palu
N
Scale
Ccedilaybaği Fm
Plio-QuaternaryUpper Miocene-PlioceneUpper Miocene
Lower Miocene
Holocene
Thrust zone Middle EoceneMiddle Eocene
Upper Cretaceous
Koumlmuumlrhan OphiolitesJurassic Cretaceous
Permo-Triassic
Seske Fm+ +
Active fault zone(East Anatolian EAFZ)
EAFZ
Sivrice
123456
7891011
121314
10
151617
18192021
22232425
2627
282930
31323334
3536
3738
39
40
4142434445
4647484950515253
5455
5657585960
61
62
6364
65
666768 69 70 71 72 73
747576 7778
79 80 81 8283 8485
8687
8889 90
Sample sites
18
21
30
20
25
Kuzo
va
Uluov
(km)100
S
D
Gezin
Elazıg Magmatic Complex
ElazıgKovancılar
Karabakır Fm
Kırkgeccedilit Fm
(b)
Figure 1 (a) Locationmap (b) Geology map of the Euphrates River and the sampling sites (from 1 to 90 the geology map was modified fromHerece et al [26])
were used in the present study Mechanical wet sieving wasperformed to separate the minus74120583m sediment fraction fromthe bulk samples Fifteen to twenty grams of each samplewas freeze dried for 8 and 9 hours The sieved fractionswere placed in clean porcelain bowls and dried at roomtemperature
34 Chemical Analysis Elazıg Magmatic Complex includeszirconium- and titanium-bearing minerals [30] As com-monly known zirconium- and titanium-bearing mineralscontain amounts of REE This method was preferred dueto its convenience for the decomposition of the silicateminerals using HF HF is an efficient disintegration agent
4 Journal of Chemistry
Direction of drainage from Euphrates River initial point (10 kilometers upstream of Keban Dam) to Karakaya Dam
A1 A89
A87
A85
A83
A81
A79
A77
A75
A73
A71
A69
A67
A65
A63
A61
A59
A57
A55
A53
A51
A49
A47
A45
A43
A41
A39
A37
A35
A33
A31
A29
A27
A25
A23
A21
A19
A17
A15
A13
A11A9A7A5A3
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
143Nd144Nd and 87Sr86Sr
001
01
10
100Lo
g pp
m R
EE
Figure 2 Distribution of REE and the determined sample sites (A43 A61 and A89) for 87Sr86Sr and 143Nd144Nd isotopic analysis from theEuphrates River sediments
used for the decomposition of zirconium silicate and apatitesource fromgranitoids in natureThis decompositionmethodcauses the loss of silica as SiF
4and a part of titanium as
TiF4 Bulk samples were ground and sieved through 200-
mesh (about 0074mm pore size) stainless steel sieve forchemical analysis 05 g of each sediment sample was leachedwith 90mL HCl-HNO
3-HF at 95∘C for 1 hour diluted to
150mL and then analyzed by ICP-OES The extractionmethod used by Saito et al [42] was used to obtain themaximum REE concentration at 995mL 001ndash1m nitric acidaqueous solution (pH lt 4) Standard DS5 was used forthe sediment analyses The sediment samples were analyzedfor REE in Acme Analytical Laboratories Ltd Canada byInductively Coupled Plasma-Optical Emission Spectrometer(ICP-OES) The river water samples have less than 01total dissolved solids and these analyses were used by ICP-OES at BureauVeritas environmental labMaxxamAnalyticsThe isotopic measurements were made at the Middle EastTechnical University (Ankara Turkey) following the protocolof Koksal and Goncuoglu [43] TLM-ARG-RIL-02 methodswere adopted An 80mg aliquot was taken for analysis ofSr and Nd isotope ratios The samples were dissolved inbeakers in a 4mL 52 HF at 160∘C on the hotplate alongfour days The samples were dried on the hotplate using25N HCl and 2mL bis(ethylhexyl) phosphate using Bio-Rad AG50 W-X8 100ndash200 mesh and chemical seperation
of Sr ionic chromatographic columns was prepared Afterchemical separation of Sr REE fractionation was collectedusing 6N HCl Sr isotopes were measured using a single Ta-activator with Re filament and 0005NH
3PO4[44] 87Sr86Sr
ratios were corrected for mass fractionation by normalizingto 86Sr88Sr = 01194 and strontium standard (NBS 987) wasmeasured more than 2 times The chemical separation ofNd from REE was made in a teflon column using 022NHCl and 2mL bis(ethylhexyl) phosphate 143Nd144Nd datawere normalized by 146Nd144Nd = 07219 and neodymiumstandard (0511848 plusmn 5) was measured more than 2 times
4 Results
41 Nd-Sr Isotope Compositions of the Euphrates River Sedi-ments REE concentrations of the Euphrates River sedimentsfrom Keban Dam to Karakaya Dam are presented in Table 1The result of isotopic composition of the studied sedimentsand those from different origin summarized statistical val-ues and REE compositions of the Mississippi and AmazonRiver sediments are presented in Table 1 The 75120583m (200mesh) size fraction from the Euphrates River sedimentsamples (A43 A61 and A89) was analyzed for 87Sr86Sr and143Nd144Nd ratios (Figure 2 and Table 1) The study showsthat 87Sr86Sr and 143Nd144Nd isotopic compositions haverange of 07053 07048 and 07057 and 0512654 0512836
Journal of Chemistry 5
Table1Summarys
tatistic
alvaluesofRE
Efro
mEu
phratesR
iversediments
Densityv
alues(gcm3
)taken
from
Gup
taandKr
ishnamurthy[45]lowast
Sedimentsfro
mSholkovitz[46]C
alculated
120576Ndand1000Srd
atafrom
Martin
andMcC
ulloch
[4]lowastlowast
Burkee
tal[1]lowastlowastlowast
Bussy[2]lowastlowastlowastlowast
Akgul
etal[47]+
Menseletal[48]
(a)
LREE119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
HRE
E119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
La614
34159
857
608
349
Tb823
018047
033
mdashmdash
Ce
816
75344
1811
1254
707
Dy
855
063312
217
746
397
Pr677
088446
222
mdashmdash
Ho
879
017063
043
mdashmdash
Nd
700
53912
177
0564
355
Er90
6043167
120
494
217
Sm752
082405
214
mdashmdash
Tm93
2005028
017
mdashmdash
Eu524
023082
057
211
109
Yb696
029159
111
394
205
Gd
790
044
365
220
986
463
Lu98
4002023
015
047
302
Mean
593
mdashmdash
Mean
079
mdashmdash
Stdeviatio
n618
mdashmdash
Stdeviatio
n074
mdashmdash
(b)
Ther
esulto
fisotopicc
ompo
sitionof
thes
tudied
sedimentsandsomee
xamples
inthew
orld
Samplec
ode
143
Nd144
Nd
87
Sr86
Sr120576Nd(0)
1000Sr
A43
0512654
07053
035
161
A61
0512836
07048
39
1374
A89
0512775
07057
27
1317
Basaltics
oil+
0511783
0705603
226
39
Metasedsoil+
0512501
07096
46minus267
657
Metagreyw
ackes+
0512847
0705374
408
249
Sediments+
0512805
0704583
326
40
lowastlowast
Jurassic-C
retaceou
ssedim
ents
mdash0707ndash0708
mdashmdash
lowastlowastlowast
ArveR
iver
sediments
mdash0728
mdashRe
lated
toMon
t-Blanc
granite
0704
mdashCarbo
nate-richrocks
lowastlowastlowastlowast
ElazıgMagmatitesU
pper
Cretaceous
0512414ndash0
512851
0706022ndash0
708451
75Diorites
and
granites
mdash35
mdash
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
4 Journal of Chemistry
Direction of drainage from Euphrates River initial point (10 kilometers upstream of Keban Dam) to Karakaya Dam
A1 A89
A87
A85
A83
A81
A79
A77
A75
A73
A71
A69
A67
A65
A63
A61
A59
A57
A55
A53
A51
A49
A47
A45
A43
A41
A39
A37
A35
A33
A31
A29
A27
A25
A23
A21
A19
A17
A15
A13
A11A9A7A5A3
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
143Nd144Nd and 87Sr86Sr
001
01
10
100Lo
g pp
m R
EE
Figure 2 Distribution of REE and the determined sample sites (A43 A61 and A89) for 87Sr86Sr and 143Nd144Nd isotopic analysis from theEuphrates River sediments
used for the decomposition of zirconium silicate and apatitesource fromgranitoids in natureThis decompositionmethodcauses the loss of silica as SiF
4and a part of titanium as
TiF4 Bulk samples were ground and sieved through 200-
mesh (about 0074mm pore size) stainless steel sieve forchemical analysis 05 g of each sediment sample was leachedwith 90mL HCl-HNO
3-HF at 95∘C for 1 hour diluted to
150mL and then analyzed by ICP-OES The extractionmethod used by Saito et al [42] was used to obtain themaximum REE concentration at 995mL 001ndash1m nitric acidaqueous solution (pH lt 4) Standard DS5 was used forthe sediment analyses The sediment samples were analyzedfor REE in Acme Analytical Laboratories Ltd Canada byInductively Coupled Plasma-Optical Emission Spectrometer(ICP-OES) The river water samples have less than 01total dissolved solids and these analyses were used by ICP-OES at BureauVeritas environmental labMaxxamAnalyticsThe isotopic measurements were made at the Middle EastTechnical University (Ankara Turkey) following the protocolof Koksal and Goncuoglu [43] TLM-ARG-RIL-02 methodswere adopted An 80mg aliquot was taken for analysis ofSr and Nd isotope ratios The samples were dissolved inbeakers in a 4mL 52 HF at 160∘C on the hotplate alongfour days The samples were dried on the hotplate using25N HCl and 2mL bis(ethylhexyl) phosphate using Bio-Rad AG50 W-X8 100ndash200 mesh and chemical seperation
of Sr ionic chromatographic columns was prepared Afterchemical separation of Sr REE fractionation was collectedusing 6N HCl Sr isotopes were measured using a single Ta-activator with Re filament and 0005NH
3PO4[44] 87Sr86Sr
ratios were corrected for mass fractionation by normalizingto 86Sr88Sr = 01194 and strontium standard (NBS 987) wasmeasured more than 2 times The chemical separation ofNd from REE was made in a teflon column using 022NHCl and 2mL bis(ethylhexyl) phosphate 143Nd144Nd datawere normalized by 146Nd144Nd = 07219 and neodymiumstandard (0511848 plusmn 5) was measured more than 2 times
4 Results
41 Nd-Sr Isotope Compositions of the Euphrates River Sedi-ments REE concentrations of the Euphrates River sedimentsfrom Keban Dam to Karakaya Dam are presented in Table 1The result of isotopic composition of the studied sedimentsand those from different origin summarized statistical val-ues and REE compositions of the Mississippi and AmazonRiver sediments are presented in Table 1 The 75120583m (200mesh) size fraction from the Euphrates River sedimentsamples (A43 A61 and A89) was analyzed for 87Sr86Sr and143Nd144Nd ratios (Figure 2 and Table 1) The study showsthat 87Sr86Sr and 143Nd144Nd isotopic compositions haverange of 07053 07048 and 07057 and 0512654 0512836
Journal of Chemistry 5
Table1Summarys
tatistic
alvaluesofRE
Efro
mEu
phratesR
iversediments
Densityv
alues(gcm3
)taken
from
Gup
taandKr
ishnamurthy[45]lowast
Sedimentsfro
mSholkovitz[46]C
alculated
120576Ndand1000Srd
atafrom
Martin
andMcC
ulloch
[4]lowastlowast
Burkee
tal[1]lowastlowastlowast
Bussy[2]lowastlowastlowastlowast
Akgul
etal[47]+
Menseletal[48]
(a)
LREE119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
HRE
E119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
La614
34159
857
608
349
Tb823
018047
033
mdashmdash
Ce
816
75344
1811
1254
707
Dy
855
063312
217
746
397
Pr677
088446
222
mdashmdash
Ho
879
017063
043
mdashmdash
Nd
700
53912
177
0564
355
Er90
6043167
120
494
217
Sm752
082405
214
mdashmdash
Tm93
2005028
017
mdashmdash
Eu524
023082
057
211
109
Yb696
029159
111
394
205
Gd
790
044
365
220
986
463
Lu98
4002023
015
047
302
Mean
593
mdashmdash
Mean
079
mdashmdash
Stdeviatio
n618
mdashmdash
Stdeviatio
n074
mdashmdash
(b)
Ther
esulto
fisotopicc
ompo
sitionof
thes
tudied
sedimentsandsomee
xamples
inthew
orld
Samplec
ode
143
Nd144
Nd
87
Sr86
Sr120576Nd(0)
1000Sr
A43
0512654
07053
035
161
A61
0512836
07048
39
1374
A89
0512775
07057
27
1317
Basaltics
oil+
0511783
0705603
226
39
Metasedsoil+
0512501
07096
46minus267
657
Metagreyw
ackes+
0512847
0705374
408
249
Sediments+
0512805
0704583
326
40
lowastlowast
Jurassic-C
retaceou
ssedim
ents
mdash0707ndash0708
mdashmdash
lowastlowastlowast
ArveR
iver
sediments
mdash0728
mdashRe
lated
toMon
t-Blanc
granite
0704
mdashCarbo
nate-richrocks
lowastlowastlowastlowast
ElazıgMagmatitesU
pper
Cretaceous
0512414ndash0
512851
0706022ndash0
708451
75Diorites
and
granites
mdash35
mdash
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
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Carbohydrate Chemistry
International Journal of
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Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 5
Table1Summarys
tatistic
alvaluesofRE
Efro
mEu
phratesR
iversediments
Densityv
alues(gcm3
)taken
from
Gup
taandKr
ishnamurthy[45]lowast
Sedimentsfro
mSholkovitz[46]C
alculated
120576Ndand1000Srd
atafrom
Martin
andMcC
ulloch
[4]lowastlowast
Burkee
tal[1]lowastlowastlowast
Bussy[2]lowastlowastlowastlowast
Akgul
etal[47]+
Menseletal[48]
(a)
LREE119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
HRE
E119873=90
Density
Maxm
in
values
Euph
rates
River(pp
m)lowast
Mississippi
River
lowast
Amazon
River
La614
34159
857
608
349
Tb823
018047
033
mdashmdash
Ce
816
75344
1811
1254
707
Dy
855
063312
217
746
397
Pr677
088446
222
mdashmdash
Ho
879
017063
043
mdashmdash
Nd
700
53912
177
0564
355
Er90
6043167
120
494
217
Sm752
082405
214
mdashmdash
Tm93
2005028
017
mdashmdash
Eu524
023082
057
211
109
Yb696
029159
111
394
205
Gd
790
044
365
220
986
463
Lu98
4002023
015
047
302
Mean
593
mdashmdash
Mean
079
mdashmdash
Stdeviatio
n618
mdashmdash
Stdeviatio
n074
mdashmdash
(b)
Ther
esulto
fisotopicc
ompo
sitionof
thes
tudied
sedimentsandsomee
xamples
inthew
orld
Samplec
ode
143
Nd144
Nd
87
Sr86
Sr120576Nd(0)
1000Sr
A43
0512654
07053
035
161
A61
0512836
07048
39
1374
A89
0512775
07057
27
1317
Basaltics
oil+
0511783
0705603
226
39
Metasedsoil+
0512501
07096
46minus267
657
Metagreyw
ackes+
0512847
0705374
408
249
Sediments+
0512805
0704583
326
40
lowastlowast
Jurassic-C
retaceou
ssedim
ents
mdash0707ndash0708
mdashmdash
lowastlowastlowast
ArveR
iver
sediments
mdash0728
mdashRe
lated
toMon
t-Blanc
granite
0704
mdashCarbo
nate-richrocks
lowastlowastlowastlowast
ElazıgMagmatitesU
pper
Cretaceous
0512414ndash0
512851
0706022ndash0
708451
75Diorites
and
granites
mdash35
mdash
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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CatalystsJournal of
6 Journal of Chemistry
and 0512775 respectively 120576Nd (0) values were calculatedusing
120576Nd (0) =143Nd144Nd (Measured)
0512636
minus 1 times 104 (1)
(see [48 49])The calculated 120576Nd (0) values have range of 035 39
and 27 Table 1 shows the result of the radiogenic isotopecompositions in the Euphrates River sediments 87Sr86Sr and143Nd144Nd and calculated 120576Nd (0) data of the sedimentsfrom different origins The isotope compositions ratios of143Nd144Nd and 87Sr86Sr in the Euphrates River sedimentssuggest that the REE pattern of river sediments changes sys-tematically with the compositions of the rocks in the drainagearea The range of 87Sr86Sr ratios found in the EuphratesRiver sedimentsmay be explained usingmetagreywackes andsediments (0705374 0704835 and 0704583 resp) accord-ing to Table 1 The calculated 1000Sr ratios are 161 (A43)1317 (A61) and 1374 (A89) and Nd values are 598 (A43)645 (A61) and 840 (A89) ppm while La concentrations are98 (A43) 78 (A61) and 45 (A89) ppmThe comparison with1000Sr and La values indicated that the weathering of felsicigneous rocks decreases downstream of the Euphrates Riverwhile it increases in the mafic igneous rocks
42 REE Results of the Euphrates River Sediments Largevariations are observed in the distribution of the REE in theEuphrates River sediments (Table 1) La concentrations rangefrom34 to 159 ppmwhile Lu concentrations range from002to 023 ppmThe concentrations of the light REE are 75 timeshigher than heavy REE concentrations Ce concentrationsrange from 75 to 344 ppm Figure 2 plots indicate thatthe concentrations of La and Ce are the highest along theflowing direction of the Euphrates River The concentrationsof the REE at the A37 sample site decrease because of thenext thrust zone Thus the circulation of mixing waterspossibly influenced the concentrations of REE in the studiedriver sediments The REE plots for the Euphrates Riversediments in this study exhibit a small degree of variationThe abundance of the REE in the river sediments is probablydue to themineralogic characterizations of the regional rocksFigure 2 plots can be explained to mean that the variationsof the light REE along the flowing direction are higher untilA51 sample site except for A34 A35 A36 and A37 sites Theheavy REE concentrations increase from A51 sample site toA90 because of the mineralogic characterizations of maficvolcanic and metaophiolitic rocks
43 REE Results of the Euphrates River Water REE concen-trations of the Euphrates Riverwaters are presented inTable 3The Amazon Indus Mississippi and Ohio Rivers waterdata from Goldstein and Jacobsen [13] are also presented inTable 3 La concentrations have range from 002 to 263 ppband Ce concentrations have range from 012 to 543 ppb Thehighest Ce and La values in the water samples are observed atthe A34 site and Pr Sm Gd Dy Er and Yb have the highestvalues 007 007 007 006 003 and 003 ppb respectively at
the same site However the lowest Ce and La concentrationsin the studied sediments were observed at the same site Theresults indicate that the circulation of mixing water alongthe tectonic zones can be a much more important factor onthe absolute abundance of the REE in river sediments thanweathering of the regional rocks
5 Discussion
The results suggest that the tectonic zone is an importantfactor in controlling the abundance of the REE concentra-tions in the Euphrates River sediments Moreover the studyindicates that the REE compositions are dependent uponthe type (subtropical climatic influences water circulationriverbed morphology and secular variation) of weatheredregional rocks The comparison of 87Sr86Sr compositions ofthe Euphrates River sediments with those from basaltic soiland metasedimentary soil from Sholkovitz [46] in Table 1shows that the studied sediments have basaltic and meta-greywackes characterization (Figure 3) Bussy [2] obtained0728 for 87Sr86Sr ratio in the Arve River sediments whichare related to theMont-Blanc granites (Table 1) However thisstudy reveals that 87Sr86Sr ratio in carbonate-rich rocks is0704 The lower 87Sr86Sr ratios (07053 07048 and 07057obtained for the sample sites A43 A61 and A89 resp)from river sediments in the Keban Dam Lake area down-stream of the contact between the Permo-Triassic shallowmarine metasediments and the Upper Cretaceous magmaticcrystalline complex of the Elazıg Magmatic Complex arecaused by mixing of the two sources 143Nd144Nd isotopiccompositions in the studied river sediments determined haverange values of 0512650 51283640 and 512775 (Table 1) andthe values are similar to the composition of metagreywackes143Nd144Nd isotopic composition ratios have range values0512414 to 0512851 for granodiorites in Upper CretaceousElazıg Magmatites [47] (Table 1)These comparisons indicatethat the weathered felsic igneous rocks in the river sedimentsare greater at the A43 sample site because of Upper Creta-ceous granitic rocks from Elazıg Magmatic Complex than atthe A61 and A89 sample sites These sites have weatheredbasaltic igneous rocks compositions due to Upper Creta-ceous basic volcanic rocks of the Elazıg Magmatic ComplexFigure 3 shows that neodymium isotope ratios in the NewEngland fold belt change from positive 120576Nd (0) values intertiary basalt to negative values in granitoids andmetapeliticrocks [48] The positive 120576Nd (0) values reflected the con-tribution of the isotope compositions in the downstreamsediments due to weathering of the basic volcanic rocksThus regional and local studies indicate that the EuphratesRiver sediments have different isotope composition due tomixing of different weathered source rocks (eg Permo-Triassic Keban Metamorphites and Upper Cretaceous ElazıgMagmatic Complex granodioritic and basic volcanic rocks)The Euphrates River sediments have the lowest average REEconcentrations while the Mississippi and Amazon Riversediments yield the highest values Table 1 shows that theaverage LREE (La Ce Nd Eu and Gd) and HREE (Dy ErYb and Lu) compositions of the Euphrates River sediments
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 7
1
10
100Lo
g La
LaNASLaUCCLaCh
010
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(a)
010
100
Log
Ce
CeNASCeUCCCeCh
10
1
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(b)
PrNASPrUCCPrCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89010
1
10
100
Log
Pr
(c)
NdNASNdUCCNdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
010
1
10
100
Log
Nd
(d)
Log
Sm
SmNASSmUCCSmCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(e)
Log
Eu
EuNASEuUCCEuCh
010
1
10
100
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89
(f)
GdNASGdUCCGdCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
100
Log
Gd
(g)
Figure 3 Normalized patterns of the LREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a) La(b) Ce (c) Pr (d) Ndlowast (119873 = 50) (e) Sm (f) Eu and (g) Gd normalized patterns
are lower by 833 to 363 and 3952 to 1834 times compared tothe REE compositions of the Mississippi River and AmazonRiver REE compositions The researchers indicated that thelight and middle REE enrichment in river sediments may
be related to apatite-rich rocks [52 53] However Kalenderand Cicek Ucar [21] suggested that the calculated enrichmentfactor values of the heavy REE are more than those for thelight REE in the tributaries of the Euphrates River sediments
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
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Advances in
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
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Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Chemistry
Table 2 North American Shale (NAS) upper continental crust (UCC) and chondrite (Ch) from Yang et al [8] Condie [22] Taylor et al[23] and Sholkovitz [50 51] and normalized REE summary statistical values (ppm) in Euphrates River sediments lowastObaje et al [18]
LREE Mean St dev lowastNigerian Gora River HREE Mean St dev lowastNigerian Gora RiverLaNAS 028 008 mdash TbNAS 039 011 mdashLaUCC 029 009 mdash TbUCC 052 015 mdashLaCh 2677 808 3976 TbCh 651 185 mdashCeNAS 027 009 mdash DyNAS 052 013 mdashCeUCC 028 009 mdash DyUCC 062 015 mdashCeCh 2012 634 1796 DyCh 723 178 mdashPrNAS 029 009 mdash HoNAS 042 010 mdashPrUCC 031 010 mdash HoUCC 053 013 mdashPrCh 1710 546 mdash HoCh 574 141 mdashNdNAS 028 006 mdash ErNAS 042 010 mdashNdUCC 030 006 mdash ErUCC 052 013 mdashNdCh 1426 297 1896 ErCh 573 139 mdashSmNAS 038 011 mdash TmNAS 035 009 mdashSmUCC 048 014 mdash TmUCC 051 014 mdashSmCh 1020 300 mdash TmCh 522 141 mdashEuNAS 048 012 mdash YbNAS 036 009 mdashEuUCC 065 017 mdash YbUCC 051 012 mdashEuCh 770 198 40462 YbCh 618 147 2552GdNAS 045 012 mdash LuNAS 033 009 mdashGdUCC 058 016 mdash LuUCC 047 012 mdashGdCh 735 198 5850 LuCh 468 123 mdash
Table 3 REE concentrations in river water in ppb The AmazonIndus Mississippi and Ohio Rivers data from Goldstein andJacobsen [13]
LREE119873 = 90
River water Dissolved loadEuphrates Amazon Indus Mississippi Ohio
La 025 0074 00029 0020 00063Ce 054 021 00024 0010 0010Pr 004 mdash mdash mdash mdashNd 018 013 00032 0020 0011Sm 004 0034 000071 0004 00025Eu lt001 0008 000022 0001 00006Gd 004 mdash 0050 mdash mdashTb lt001 mdash mdash mdash mdashDy 004 0031 0036 00075 0006Ho lt001 mdash mdash mdash mdashEr 002 0016 0017 00065 0005Tm lt001 mdash mdash mdashYb 02 0015 00014 mdash 00036Lu lt001 mdash 00021 mdash 00006
due to Fe-Mn oxyhydroxide adsorption capacity for HREElinked to the basic volcanic rocks source of HREE Yanget al [8] stated that zircon contributes to the bulk HREEsin sediments because of the relatively high abundance ofHREEs in zircon The lithologic units along the EuphratesRiver bed contribute to the bulk of LREEs concentrations
as a result of apatite-rich zircon-poor Upper Cretaceousgranodiorites LaYb mean ratio of 772 in the studied sedi-ment samples indicated high erosional rate because La maybe removed from crustal source via weathering process andthis is in agreement with the finding of Obaje et al [18]The distribution trend of REE along the flowing directionof the Euphrates River at some of the sample locationsA32 A33 A34 A35 and A36 indicates that the thrustzone between Upper Cretaceous Elazıg Magmatic Complexand Permo-Triassic Keban Metamorphites influences thedecreasing REE composition in the river sediments dueto mixing water circulation Average LREE concentrationsupstream have higher-than-average HREE concentrationcompared to downstream ones due to the shallow marinemetasediments and felsic magmatic rocks (Permo-TriassicKeban Metamorphites felsic rocks from Upper CretaceousElazıg Magmatites) upstream However the basic volcanicrocks (Maden Complex and Komurhan metaophiolites) areobserved downstream along the Euphrates River flowingdirection Obaje et al [18] and Ramesh et al [54] stated thatpositiveCe anomalies are related to the formation ofCe4+ andCe hydroxides and terrigenous input and diagenetic condi-tionsThe positive Ce anomalies may indicate hydromorphicdistribution of the REE in river sediments According to someresearchers Eu anomalies have less contribution from felsicmagmatic rock weatheringThe negative Eu anomalies (lt001detection limit) indicate that the REE compositions in theriver sediments more or less contribute to felsic magmaticrock weathering compared with terrigenous input and basicmagmatic rock weathering Lower river flowing velocity may
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 9
be responsible for REE homogenous REE distribution inagreement with Obaje et al [18] The average chondritenormalized values indicate LREE and HREE enrichmentand their summarized statistical values range from 2677 to735 and 723 to 468 respectively (Table 2) The chondritenormalized patterns illustrate that the REE compositionof the Euphrates River sediments differs from chondritecomposition but also the REE enrichment is close to NASand UCC The REE normalized values of the NigerianGora River from Obaje et al [18] are shown in Table 3The CeCh value is higher (2015) in the Euphrates Riversediments than theNigerianGoraRiver sediments (1796) dueto sulfide-rich mineralization in the studied area especiallyKeban polymetallic mine deposit Ramesh et al [54] revealedthat the positive Ce anomalies indicate terrigenous inputdepositional environment and diagenetic conditions due tothe formation of Ce4+ and stable Ce hydroxides Accordingto Nielsen et al [55] Tl and Ce may be controlled by resid-ual sulfide and clinopyroxene respectively during mantlemelting due to their highly different ionic charges and radiiLuo et al [56] indicated that while the adsorption abilityof REE decreases on colloidal particles from light (La) toheavy (Lu) the complexes of REE with carbonate increaseand also the larger colloidal particles have stronger abilityto adsorb Ce from weathering of granitic rocks Howeverboth LREE andHREE concentrations are lower thanNAS andUCC (Figures 4 and 5) LREE patterns show that Sm and Eupatterns are closer to 1 and Gd pattern is higher than 1 LaCe Pr and Nd (Figures 4(a) 4(b) 4(c) 4(d) 4(e) 4(f) and4(g)) GdYbNAS andUCC ratio gt1 indicates that apatite fromgranodioritic rocks had contributed to the river sedimentREE compositions [57ndash61] According to Leybourne andJohannesson [60] Eu is mobilized during hydromorphictransport compared to SmandGdHowever the study revealsthat SmandEu aremobilizedmore compared toGdThusGdenrichment was observed in the river sediments HoweverHREE patterns enrichment is relative to chondrite but HREENAS and UCC normalized patterns are observed to be closeto 1 (Figures 5(a) 5(b) 5(c) 5(d) 5(e) 5(f) and 5(g)) All ofthe river sediment REE compositions that display enrichmentare relative to chondrite REE composition
REE compositions of the Euphrates River water werecompared with REE in dissolved load of Amazon IndusMississippi and Ohio River waters from Goldstein andJacobsen [13] (Table 3) Figure 6 indicates that the REEcompositions of the Euphrates River water are higher thanREE compositions in the dissolved load compared of theAmazon Indus Mississippi and Ohio Rivers However theREE patterns of the Euphrates River water were similar toREE in dissolved load in the Amazon Indus Mississippiand Ohio River waters Yb content in the Indus River wateris higher while Ce content in the Mississippi River wateris lower than in the Euphrates River water According toGoldstein and Jacobsen [13] high Yb values in suspendedmaterials may be derived from older rocks Goldberg et al[62] indicated that Ce depletion in river waters in a highpH environment may be related to the result of preferentialremoval of Ce4+ onto Fe-Mn oxide coatings of particles
This indicates that suspendedmaterials load in the EuphratesRiver water is probably more than in the Mississippi Ohioand Indus River waters Ce anomalies are calculated using thefollowing equation
Celowast =3CeNAS
(2LaNAS +NdNAS)(2)
from [13] where
Celowast = 3 times 0000024 (2 times 0000015 + 0000020) = 116 (3)
As shown positive Ce anomalies (Celowast gt 1) support the factthat Cemay be fixed on the clay at pH gt 7 Also the calculated(LaYb)NAS values in the Euphrates River water and sedimentare 0098 and 077 It is apparent that both Euphrates Riverwaters and sediments have heavier REE composition thanlight REE according to NAS normalized patterns
6 Conclusions
(1)This paper indicates that a contribution from a third com-ponent can change the isotopic composition of the studiedsediments (a) Permo-Triassic carbonate-rich metasedimentsand (b) felsic magmatic and (c) mafic volcanic rocks fromUpper Cretaceous Elazıg Magmatic Complex
(2) The study indicates that the Euphrates River averageLREE (La Ce Nd Eu and Gd) and HREE (Dy Er Yb andLu) compositions have lower range values from 833 to 363and 3952 to 1834 times less than Mississippi River REE andAmazon River sediment compositions respectively
(3) This paper revealed that the Euphrates River hashigher LREE than HREE concentrations and also in thethrust zone which is close to the Euphrates River bed there islow REE composition due to fast water circulation
(4) Average LREE concentrations upstream in theEuphrates River are higher than average HREE concentra-tions downstream due to felsic magmatic rocks
(5) LaYb ratio (772) indicates high erosion rate and Lamay have been added from crustal sources via weatheringprocesses
(6) The positive Ce and La anomalies indicate both ter-rigenous input and contribution of the oxidative compoundsfrom sulfide-rich mineralization in the Euphrates River bedsediments
(7) The chondrite NAS and UCC normalized patternsshow that the REE compositions of the Euphrates Riversediments differ from chondrite but are similar to NAS andUCC
(8)The Sm and Eu patterns are close to 1 and Gd patternis higher than 1 (gt1) and also GdYbNAS andUCC ratio greaterthan 1 indicates that the source of REE may be apatite-richgranodioritic rocks which are from the Elazıg MagmaticComplex Also terrigenous sediments and lithological con-trol are more effective on the Euphrates River sediment REEcompositions
(9) The Euphrates River waters have the highest com-position values for both LREE and HREE in comparison tothe other basic river waters (the Amazon Indus Ohio and
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
10 Journal of Chemistry
010
1
10Lo
g Tb
TbNASTbUCCTbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(a)
DyChDyUCCDyNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
010
1
10
Log
Dy
(b)
010
1
10
HoNAS
HoChHoUCC
Log
Ho
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(c)
010
1
10
ErNASErUCCErCh
Log
Er
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(d)
010
1
10
Log
Tm
TmNASTmUCCTmCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(e)
001
010
1
10
Log
Yb
YbNASYbUCCYbCh
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985(f)
001
010
1
10
Log
Lu
LuChLuUCCLuNAS
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 8985
(g)
Figure 4 Normalized patterns of the HREE average concentrations (119873 = 90) of Euphrates River sediments in the NAS UCC and Ch (a)Tb (b) Dy (c) Ho (d) Er (e) Tm (f) Yb and (g) Lu normalized patterns
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 11
Euphrates River sedimentsc
c
c
c
BasaltMetasedimentary rocksBasaltic soil compositeBasaltic soil
Metased soil compositeMetased soilReservoir sedimentNamol River sediment fertilizer
New Englandgranitoids
Metapelitic rocks
Metagreywackes
120576Nd
(0)
minus10
minus5
0
5
10
05122
05126
05130
143N
d144N
d
0708 0712 0716070487Sr86Sr
Figure 5 Diagram of Nd versus Sr isotopic composition in rocksoil and sediment samples from Martin and McCulloch [4] Linesconnect rock and soil samples taken from the same localityOutlinedfields show isotopic compositions of the New England granitoidsmetapelitic rocks and metagraywackes from the New England foldbelt [49]
1
01
001
0001
00001
Log
wat
er co
mpo
sitio
n
EuphratesAmazon
IndusMississippi
Ohio
Ce Nd Sm Eu Dy Er Yb LuLa
Figure 6 Distribution of REE in the Euphrates River waters andthe Amazon Indus Mississippi and Ohio River waters data fromGoldstein and Jacobsen [13]
Mississippi River waters) due to regional felsic and maficlithological units Due to circulation of mixing water REEconcentrations increase in the river water but decrease in theriver sediments
Competing Interests
The authors declare that there are no competing interestsregarding the publication of this paper
Acknowledgments
The authors would like to thank FUBAP for the researchsupport (Project no MF 1426)
References
[1] WH Burke R E Denison E A Hetherington R B KoepnickH F Nelson and J B Otto ldquoVariation of seawater 87Sr86Srthroughout Phanerozoic timerdquo Geology vol 10 no 10 pp 516ndash519 1982
[2] J F V R Bussy ldquoPetrogenese des enclaves microgrenuesassociees aux granitoides calco-alcalins exemple des massifsvarisque du Mont-Blanc (Alpes occidentales) et Miocene duMonte Capanne (Ile drsquoElbe Italie)rdquo Memoires de Geologie(Lausanne) vol 7 p 309 1990
[3] F X Gingele and P De Deckker ldquoLate Quaternary fluctuationsof palaeoproductivity in the Murray Canyons area SouthAustralian continental marginrdquo Palaeogeography Palaeoclima-tology Palaeoecology vol 220 no 3-4 pp 361ndash373 2005
[4] C E Martin and M T McCulloch ldquoNd-Sr isotopic andtrace element geochemistry of river sediments and soils in afertilized catchment New South Wales Australiardquo Geochimicaet Cosmochimica Acta vol 63 no 2 pp 287ndash305 1999
[5] M Revel-Rolland F Arnaud E Chapron et al ldquoSr and Nd iso-topes as tracers of clastic sources in Lake Le Bourget sediment(NW Alps France) during the Little Ice Age palaeohydrologyimplicationsrdquo Chemical Geology vol 224 no 4 pp 183ndash2002005
[6] R L Cullers T Barrett R Carlson and B Robinson ldquoRare-earth element and mineralogic changes in Holocene soil andstream sediment a case study in theWet Mountains ColoradoUSArdquo Chemical Geology vol 63 no 3-4 pp 275ndash297 1987
[7] W Zhu M Kennedy E W B de Leer H Zhou and G J F RAlaerts ldquoDistribution and modelling of rare earth elements inChinese river sedimentsrdquo Science of the Total Environment vol204 no 3 pp 233ndash243 1997
[8] S Y Yang H S Jung M S Choi and C X Li ldquoThe rareearth element compositions of the Changjiang (Yangtze) andHuanghe (Yellow) river sedimentsrdquo Earth and Planetary ScienceLetters vol 201 no 2 pp 407ndash419 2002
[9] H W Nesbitt ldquoMobility and fractionation of rare earth ele-ments duringweathering of a granodioriterdquoNature vol 279 pp206ndash210 1979
[10] J-J Braun J Viers B Dupre M Polve J Ndam and J-PMuller ldquoSolidliquid REE fractionation in the lateritic systemof Goyoum East Cameroon the implication for the presentdynamics of the soil covers of the humid tropical regionsrdquoGeochimica et Cosmochimica Acta vol 62 no 2 pp 273ndash2991998
[11] B Rasmussen and J E Glover ldquoDiagenesis of low-mobilityelements (Ti REEs Th) and solid bitumen envelopes in Per-mian Kennedy Group sandstone western Australiardquo Journal ofSedimentary Research vol 64 pp 572ndash583 1994
[12] R H Meade and R S Parker ldquoSediment in the rivers of theUnited Staterdquo inUS Geological SurveyWater Supply Paper vol2275 pp 49ndash60 1985
[13] S J Goldstein and S B Jacobsen ldquoRare earth elements in riverwatersrdquo Earth and Planetary Science Letters vol 89 no 1 pp35ndash47 1988
[14] D G Brookins ldquoAqueous geochemistry of rare earth elementsrdquoin Geochemistry and Mineralogy of Rare Earth Elements B R
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
12 Journal of Chemistry
Lipin and G A McKay Eds vol 21 chapter 8 pp 201ndash226Mineralogical Society of America 1989
[15] H Elderfield R Upstill-Goddard and E R Sholkovitz ldquoTherare earth elements in rivers estuaries and coastal seas and theirsignificance to the composition of ocean watersrdquo Geochimica etCosmochimica Acta vol 54 no 4 pp 971ndash991 1990
[16] K H Johannesson D L Hawkins Jr and A Cortes ldquoDoArchean chemical sediments record ancient seawater rare earthelement patternsrdquo Geochimica et Cosmochimica Acta vol 70no 4 pp 871ndash890 2006
[17] I Hossain K K Roy P K BiswasM AlamMMoniruzzamanand F Deeba ldquoGeochemical characteristics of Holocene sedi-ments from Chuadanga district Bangladesh implications forweathering climate redox conditions provenance and tectonicsettingrdquoChinese Journal of Geochemistry vol 33 no 4 pp 336ndash350 2014
[18] S O Obaje I A Akpoborie F C Ugbe and A OnugbaldquoRare earth and trace elements distribution in sediments ofRiver Gora Minna Area North-Central Nigeria implicationfor provenancerdquo Earth Science Research vol 4 no 1 pp 103ndash112 2015
[19] M I LeybourneW D Goodfellow D R Boyle and GM HallldquoRapid development of negative Ce anomalies in surface watersand contrasting REE patterns in groundwaters associated withZn-Pbmassive sulphide depositsrdquoAppliedGeochemistry vol 15no 6 pp 695ndash723 2000
[20] L Kalender and L Bolucek ldquoMajor and trace elemet contam-ination of groundwaters stream sediments and plants of theabandonedmines inKeban district (Elazıg) of EasternAnatoliaTurkeyrdquo in Proceedings of the 57th Geological Congress of Turkeyp 187 MTA Culture Sites Ankara Turkey March 2004
[21] L Kalender and S Cicek Ucar ldquoAssessment of metal contam-ination in sediments in the tributaries of the Euphrates Riverusing pollution indices and the determination of the pollutionsourcerdquo Turkey Journal of Geochemical Exploration vol 134 pp73ndash84 2013
[22] K C Condie ldquoAnother look at REEs in shalesrdquo Geochimica etCosmochimica Acta vol 55 no 9 pp 2527ndash2531 1991
[23] S R Taylor S M McLennan R L Armstrong and J TarneyldquoThe composition and evolution of the continental crust rareearth element evidence from sedimentary rocksrdquo PhilosophicalTransactions of the Royal Society A Mathematical Physical andEngineering Sciences vol 301 no 1461 pp 381ndash399 1981
[24] S R Taylor SMMcLennan andM TMcCulloch ldquoGeochem-istry of loess continental crustal composition and crustalmodelagesrdquoGeochimica et Cosmochimica Acta vol 47 no 11 pp 1897ndash1905 1983
[25] S R Taylor Solar System Evolution Cambridge UniversityPress Cambridge UK 1992
[26] E Herece E Akay O Kucumen andM Sarıaslan ldquoGeology ofElazıg-Sivrice-Palu areardquo Report MTA 9634 1992
[27] K Frenken ldquoIrrigation in the Middle East region in figuresrdquoWater Reports 34 FAO Rome Italy 2009 AQUASTAT Survey2008
[28] L Kalender and S Hanelci ldquoGeneral features of copper miner-alization in the eastern Euphrates Keban-Elazıg area TurkeyrdquoJournal Geological Society of India vol 64 pp 655ndash665 2004
[29] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquo inProceedings of the Symposium for the 25th Anniversary of EarthSciences at Hacettepe University Ankara Turkey November1993
[30] M Beyarslan and F Bingol ldquoUltramafics and mafic bodies incumulates of ispendere and komurhan ophiolites (SE AnatolianBelt Turkey)rdquoTurkish Journal of Science and Technology vol 51no 1 pp 19ndash36 2010
[31] M Turan E Aksoy and A F Bingol ldquoThe characterizationsof the east Taurus geodynamic evolution in the Elazig areardquoUniversity of Firat Sciences and Engineering Bulletin vol 72 pp1ndash23 1995 (abstract in Engilish)
[32] I Turkmen M Inceoz E Aksoy and M Kaya ldquoNew findingson Eocene stratigraphy and paleogeography of Elazg areardquoBulletin of the Earth Sciences Application and Research Centreof Hacettepe University vol 24 pp 81ndash95 2001
[33] D Perincek and H Kozlu ldquoStratigraphy and structural relationof the units in the Afsin-Elbistan-Dogansehir Regionrdquo inProceedings of the International Symposium on the Geology ofthe Taurus Belt O Tekeli and C Goncuoglu Eds pp 181ndash198 Mineral Research amp Exploration Institute Ankara Turkey1984
[34] O Sungurlu D Perincek G Kut et al ldquoGeology of the ElazıgHazar and Palu areardquo The General Directorate of PetroleumAffairs vol 29 pp 83ndash191 1985 (Turkish)
[35] Y Yılmaz E Yigitbas and S CGenc ldquoOphiolitic andmetamor-phic assemblages of Southeast Anatolia and their significance inthe geological evolution of the orogenic beltrdquo Tectonics vol 12no 5 pp 1280ndash1297 1993
[36] M Turan and A F Bingol ldquoTectono-stratigraphic character-izations of between Kovancılar and Baskil (Elazıg) areardquo inProceedings of the Ahmet Acar Geology Symposium CukurovaUniversity pp 213ndash217 Adana Turkey 1991 (Turkish)
[37] I Turkmen E Aksoy S Kurum B Akgul and M InceozldquoLower Miocene volcanism of Arguvan-Arapgir (Malatya)region and their significance in the regional stratigraphyrdquoGeosound vol 32 pp 103ndash115 1998 (abstract in English)
[38] I Turkmen ldquoStratigraphy and sedimentological features ofCaybagı Formation (Upper Miocene-Pliocene) in the easternElazigrdquo Bulletin of Turkish Geological Society vol 34 no 5 pp45ndash53 1991
[39] E Kerey and I Turkmen ldquoSedimentological aspects of PaluFormation (Pliocene-Quaternary) The east of Elazıg TurkeyrdquoGeological Bulletin of Turkey vol 34 pp 21ndash26 1991
[40] F Ackermann ldquoA procedure for correcting the grain size effectin heavy metal analyses of estuarine and coastal sedimentsrdquoEnvironmental Technology Letters vol 1 no 11 pp 518ndash5271980
[41] L Kalender and C Bolucek ldquoEnvironmental impact anddrainage geochemistry in the vicinity of the Harput Pb-Zn-Cuveins Elazıg SE Turkeyrdquo Turkish Journal of Eath Sciences vol16 pp 241ndash255 2007
[42] S Saito O Ohno S Igarashi T Kato and H YamaguchildquoSeparation and recycling for rare earth elements by homoge-neous liquid-liquid extraction (HoLLE) using a pH-responsivefluorine-based surfactantrdquo Metals vol 5 no 3 pp 1543ndash15522015
[43] S Koksal and M C Goncuoglu ldquoSr and Nd isotopic character-istics of some S I and a type granitoids from central anatoliardquoTurkish Journal of Earth Sciences vol 17 pp 111ndash127 2008
[44] I Raczek K P Jochum and A W Hofmann ldquoNeodymiumand strontium isotope data forUSGS referencematerials BCR-1BCR-2 BHVO-1 BHVO-2 AGV-1 AGV-2 GSP-1 GSP-2 andeight MPI-DING reference glasses Geostandards NewsletterrdquoThe Journal of Geostandards and Geoanalysis vol 27 pp 173ndash179 2003
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 13
[45] C K Gupta and N Krishnamurthy Metallurgy of Rare EarthsCRC Press 2005
[46] E R Sholkovitz ldquoThe aquatic chemistry of rare earth elementsin rivers and estuariesrdquo Aquatic Geochemistry vol 1 no 1 pp1ndash34 1995
[47] B Akgul M Akgul M Satır and A Sagıroglu ldquoGeochronol-ogy and ısotope geochemistry of the Upper CretaceousElazıgMagmatites in Eastern Anatolia (Turkey) implications forpetrogenesis and tectonic evolutionrdquo in Proceedings of the45th Anniversary Geology Symposium p 21 Trabzon TurkeyOctober 2010
[48] H D Mensel M T McCulloch and B W Chappell ldquoThe NewEngland Batholith constraints on its derivation fromNd and Srisotopic studies of granitoids and country rocksrdquo Geochimica etCosmochimica Acta vol 49 no 2 pp 369ndash384 1985
[49] W F McDonough M T McCulloch and S S Sun ldquoIsotopicand geochemical systematics in Tertiary-Recent basalts fromsoutheastern Australia and implications for the evolution ofthe sub-continental lithosphererdquo Geochimica et CosmochimicaActa vol 49 no 10 pp 2051ndash2067 1985
[50] E R Sholkovitz ldquoRare earth elements in the sediments of theNorth Atlantic Ocean Amazon Delta and East China Seareinterpretation of terrigenous input patterns to the oceansrdquoAmerican Journal of Science vol 288 no 3 pp 236ndash281 1988
[51] E R Sholkovitz ldquoChemical evolution of rare earth elementsfractionation between colloidal and solution phases of filteredriver waterrdquo Earth and Planetary Science Letters vol 114 no 1pp 77ndash84 1992
[52] J F Banfield and R A Eggleton ldquoApatite replacement andrare earth mobilization fractionation and fixation duringweatheringrdquo Clays amp Clay Minerals vol 37 no 2 pp 113ndash1271989
[53] R E Hannigan and E R Sholkovitz ldquoThe development of mid-dle rare earth element enrichments in freshwaters weatheringof phosphate mineralsrdquo Chemical Geology vol 175 no 3-4 pp495ndash508 2001
[54] R Ramesh A Ramanathan S Ramesh R Purvaja and VSubramanian ldquoDistribution of rare earth elements and heavymetals in the surficial sediments of theHimalayan river systemrdquoGeochemical Journal vol 34 no 4 pp 295ndash319 2000
[55] S G Nielsen C T A Lee Shimizu and N M Behn ldquoThesulfur abundance of the mantle deduced from trace elementratiosrdquo in Proceedings of the 24th Goldschmidt Meeting p 1814Sacramento Calif USA June 2014
[56] J Luo Y Hu Y Shen J Hu and H Ji ldquoEffects of colloidalparticle size on the geochemical characteristics of REE inthe water in southern Jiangxi province Chinardquo EnvironmentalEarth Sciences vol 75 no 1 article 81 17 pages 2016
[57] G N Hanson ldquoRare earth elements in petrogenetic studiesof igneous systemsrdquo Annual Review of Earth and PlanetarySciences vol 8 no 1 pp 371ndash406 1980
[58] L P Gromet and L T Silver ldquoRare earth element distributionsamong minerals in a granodiorite and their petrogenetic impli-cationsrdquo Geochimica et Cosmochimica Acta vol 47 no 5 pp925ndash939 1983
[59] J Hermann ldquoAllanite thorium and light rare earth elementcarrier in subducted crustrdquo Chemical Geology vol 192 no 3-4pp 289ndash306 2002
[60] M I Leybourne and K H Johannesson ldquoRare earth elements(REE) and yttrium in streamwaters stream sediments and FendashMn oxyhydroxides fractionation speciation and controls over
REE + Y patterns in the surface environmentrdquo Geochimica etCosmochimica Acta vol 72 no 24 pp 5962ndash5983 2008
[61] MMishra and S Sen ldquoProvenance tectonic setting and source-area weathering of Mesoproterozoic Kaimur Group VindhyanSupergroup Central Indiardquo Geologica Acta vol 10 no 3 pp243ndash253 2012
[62] E D Goldberg M Koide R A Schmitt and R H SmithldquoRare-earth distributions in the marine environmentrdquo Journalof Geophysical Research vol 68 no 14 pp 4209ndash4217 1963
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
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