Research ArticleMineralogy Geochemistry and Origin of BuyukmahalManganese Mineralization in the Artova Ophiolitic ComplexYozgat Turkey
Nursel Oumlksuumlz and Neslihan Okuyucu
Department of Geological Engineering Faculty of Engineering amp Architecture Bozok University 66100 Yozgat Turkey
Correspondence should be addressed to Nursel Oksuz nurseloksuzgmailcom
Received 13 May 2013 Revised 8 December 2013 Accepted 17 December 2013 Published 6 February 2014
Academic Editor Chengshuai Liu
Copyright copy 2014 N Oksuz and N Okuyucu 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 Artova ophiolite complex (AOC) is exposed along the northwestern and eastern margins of Yozgat area in Turkey The Mn-deposit in the Buyukmahal area is part of this ophiolite complex The deposit is in banded and lenticular forms and hosted by aradiolarite unit overlying the volcanics Pyrolusite and magnetite are the main minerals of the manganese ore in the Buyukmahal(Yozgat) areaThe gangminerals in the deposit are composed only of quartz and calcite In this studymineralogy major oxide traceelement andREE contents of Buyukmahalmanganesemineralization are evaluatedThegeochemical data indicate that Buyukmahalmineralization does not originate from a pure hydrothermal or pure hydrogenous source but from a system consisting of bothsources It is also asserted that the mineralization was first developed on a sea floor spreading center within the Alpine OphioliteSystem and then obducted as part of the AOC
1 Introduction
The Alpine Ophiolite System (AOC) is exposed along thenorthwestern and eastern margins of the Yozgat region inTurkey The Mn mineralization in the Buyukmahal is apart of this ophiolite complex The mineralization in thisarea is highly firm and generally fractured and foldeddeveloped in banded and lenticular shape and syngeneticwith radiolarite cherts Mineralizations are chiefly NW-SWtrending and small anticline structures are observed in someparts Although mineralization in the Buyukmahal area hasnot been studied Derbent and Eymir manganese depositswithin the AOC were investigated recently by Oksuz [12] These deposits were operated from time to time bylocal miners but lately none of the deposits is mined outdue to low reserve potential The Eymir manganese depositwhich is genetically linked to Buyukmahal mineralizationoccurs within radiolarite cherts of the lower Cretaceousophiolite complex [1] Major and trace element contents ofthe Eymir ore indicate that the deposit is of a hydrothermal-hydrogenous type volcano sedimentary mineralization andboth oxic and anoxic sedimentation conditions prevailed
The Derbent manganese mineralization another manganesedeposit in theYozgat region occurs as two separate ore bodies[2] Chemical data yield that hydrothermal and hydrogenous-diagenetic processes played important role in formation ofDerbent mineralization The geochemical characteristics ofthese deposits are consistent with those of several othermanganese mineralizations such as Waziristan Hazara [3]Baby Bare [4] Baft Ophiolitic melange Kerman (Iran) [5]Wakasa [6] Cayırlı [7] and Kasımaga [8] deposits Partic-ularly Waziristan (Pakistan) and Cayırlı (Turkey) depositsare regarded as hydrothermal exhalative manganese depositsoccurring on seafloor spreading centers associated withophiolite units [9 10] The Buyukmahal deposit under inves-tigation is also thought to be a hydrothermal exhalativemanganese mineralizationThe aim of this study is to discussthe mineralogical and geochemical mechanisms responsiblefor development of manganese ore in the Buyukmahal area
2 Geological Setting
Turkey comprising the border between Eurasia at the northand Gondwana at the south is an E-W elongating component
Hindawi Publishing CorporationJournal of ChemistryVolume 2014 Article ID 837972 11 pageshttpdxdoiorg1011552014837972
2 Journal of Chemistry
of the Alpine-Himalayan Orogenic zone The Alpine Oro-genic system is formed by the closure of a different branchof the Tethys Ocean During the closure of Tethys Oceancontinental parts of the Gondwana and Laurasia continentscollided Turkey as an orogenic mosaic (orogenic collage) isa part of these continental parts including remnant materialsbetween these continentals [11] The AOC is included to theAlpine Orogenic system The AOC of Upper Cretaceous ageshows a wide distribution and hosts several ore mineraliza-tions
Darmik formation of Upper Cretaceous age consistsof Boyalik limestone Akcadag sandstone and a radi-olarite member Sarimbey volcanic assemblage (spiliticbasalt andesite unit) Artova ophiolite complex (serpentineharzburgite dunite gabbro diabase chert) and Cretaceouslimestone blocks are also observed in the area Artovaophiolite complex is unconformably overlain by conglom-erate sandstone mudstone and gypsum levels of the Incikformation of terrestrial character [12] (Figure 1)
Ore bodies in the study area occur as laminated bandedand lenticular forms (Figures 2(a) 2(b) 2(c) and 2(d)) Themineralization is entirely associated with radiolarite chertsand thickness of lamina and bands is in the range of 1 to90 cm Manganese ores are quite fractured and fissured andshow an irregular structure (Figure 2(a)) Polished sectiondeterminations indicate that ore assemblage is composed ofhematite and pyrolusite whilst quartz and calcite are thegangue minerals Pyrolusite and magnetite are the mainminerals in the Buyukmahal deposit Hematite peaks wererecorded in XRD analysis but it could not be observed in oremicroscopy and Raman spectroscopy determinations
3 Material and Methods
Twenty ore samples (500 g each) were collected from theBuyukmahalmanganese depositThewhole section of the orefrom top to bottomwas sampled systematically Samples weretaken at 30 cm intervals
Powders of 12 samples under 200 mesh were analyzed atACME Laboratories Major oxide and trace element contentswere determined with ICP-ES and REEs were analyzed withthe ICP-MS method 30 g sample was powdered into 100 120583mfor geochemical analysis 05 g sample was processed in HCl-HNO
3-H2Osolution atsim95∘C for 1 hour and then the amount
of sample was increased 10mL for the final filtering Resultsof analysis are given in Tables 1 2 and 3 In addition inorder to determine paragenesis and textural characteristicsof mineralization 10 polished sections were studied withore microscopy XRD analysis for six samples was doneat TPAO (Turkish Petroleum Corporation) laboratories ARigaku DMAX IIIC model X-Ray diffractometer with a Cutarget (2ndash70∘ 2120579) was used in the analyses Ore minerals werealso studied withThermo Scientific DXR RamanMicroscopeat the Geological Department of the Ankara UniversityThe Raman spectrums obtained were evaluated with Crys-tal Sleuth program to determine the mineral paragenesisChemical composition of pyrolusite was determined withmicroprobe analysis conducted at Montan Universitat inLeoben (Austria) The results are shown in Table 4
4 Mineralogy
Mineral paragenesis in the study area was investigated withore microscopy studies as well as XRD Raman spectroscopyand microprobe analysis for pyrolusite Results show thatpyrolusite and magnetite are the main ore minerals in theBuyukmahal area accompanied by little amount of hematiteGangue minerals are quartz and calcite Results of micro-probe analysis performed on four points in a pyrolusitecrystal are shown in Table 4
41 Pyrolusite (MnO2) It is mostly precipitated from low-
temperature hydrothermal fluids Pyrolusite is a commonalternation mineral in oxidized marine environments Pyro-lusite and magnetite forming the main components of theBuyukmahal area with a whitish yellow color are distinctwith their strong anisotropic character Pyrolusite mineralsdevelop in small veins and characteristic with anhedraland subhedral cutaways Ore microscopy and Raman spec-troscopy images of pyrolusite are shown in Figure 3 Usingthe results of microprobe analysis the structural formula ofpyrolusite (on the basis of two oxygen) is calculated asMn
169-
Fe007
-Si009
-Al002
-Ca001
O2(Table 4)
42 Magnetite (Fe3O4) Magnetite occurs as small scattered
crystals or veins Vein magnetite is observed cutting thepyrolusite (Figure 4) In single nicol magnetite is seen inbrown and gray colors and in the crossed nicols it is inanisotropic character Samples are slightly magnetic Oremicroscopy andRaman spectroscopy images ofmagnetite areshown in Figure 4
5 Geochemistry
Geochemical data are used to determine the origin ofmineralization (eg hydrothermal hydrogenous and dia-genetic) The chemical composition of Buyukmahal depositis SiO
2 8540 to 1032 wt MnO
2 6854 to 679wt and
Fe2O3 1673 to 231 wt Fe and Mn are characteristically
fractionated on precipitation from a hydrothermal solutionproducing high or lowMnFe rations in exhalative sediments[13] MnFe rations of the deposit range from 2589 to090wt (Table 1) These values are conformable with thoseof hydrothermal exhalative manganese deposits in ophioliticregions and recent submarine spreading centers [1 14 15]
The Si-Al discrimination diagram proposed by Peters[16] is used to distinguish hydrothermal from hydrogenousMn-oxide deposits Buyukmahal ore samples are almostwithin the field of hydrothermal field with only one samplewithin the field of hydrogenous deposits (Figure 5)
Ba contents of Waziristan [6] Hazara (Pakistan) [3]Binkılıc [17] Cayırlı [7] and Kasımaga (Turkey) [8] regionsare very high (415 6304 6892 1229 and 2719 resp) indi-cating a sedimentary contribution High Ba content of theBuyukmahal deposit (ave 3659) is also indicative of sedi-mentary origin Modern submarine hydrothermal Mn-oxidedeposits are more enriched in Cu Zn Ni and Co contentsin comparison to pelagic sediments However they are lower
Figure 1 Location and geology map of study area (modified from [12])
than hydrogenous deposits [13 18] Choi and Hariya [6] dis-criminated hydrogeneous deposits and submarine hydrother-mal Mn-deposits on a Ni-Zn-Co ternary diagram On thisdiagram five samples are plotted near hydrogenous fields andseven samples are close to hydrogenous field (Figure 6) InFe-(Ni + Co + Cu) lowast 10-Mn triangular diagram [9 10 19]all samples are plotted in hydrothermal and diagenetic fields
(Figure 7) Correlation data on major oxide and some traceelements contents of ore samples are given in Table 5
The correlation coefficients indicate the presence ofstrong positive relations between major oxides and varioustrace elements (Al
2O3-Fe2O3 119903 = 095 Al
2O3-TiO2 119903 =
099 TiO2-Fe2O3 119903 = 094) and the contribution of mafic
terrigenous material to the deposition environment
Figure 2 Laminated banded ((a) (b) (c)) and lenticular forms (d) in the ore bodies (mn manganese rad radiolarite)
Major oxide trace and REE geochemistry are very usefulfor understanding the formation conditions of ore depositsREE contents of 12 samples collected from the Buyukmahalmanganese mineralization are shown in Table 6
REE contents of the hydrothermal and hydrogenousferromanganese and manganese deposits differ considerablyand thus can provide great information on the genetic
processes involved in the formation of submarine man-ganese and ferromanganese ores [20ndash23] REE patterns ofthe studied deposit (Figure 8(a)) are compared with thoseof other hydrogenous and hydrothermal manganese deposits(Figure 8(b)) Results indicate that hydrogenous ferroman-ganese deposits are more enriched in REEs than theirhydrothermal equivalents Hydrogenous ferromanganese
Journal of Chemistry 5
Table2Tracee
lementscontentsof
Buyukm
ahalore(pp
m)
Sample
BaBe
Co
CsHf
Nb
RbSr
TaTh
UV
ZrMo
CuPb
ZnNi
As
Cd
SbBi
Ag
AuN1
10390
20
5632
28
23
74525
2962
05
7229
4980
926
59
4160
334
1160
2047
378
01
05
03
125
26
N2
8920
104349
29
32
152
606
1676
1187
21
3930
1319
124
2826
379
920
1992
435
01
02
05
56
05
NT1
9590
20
735
02
04
1221
3100
01
04
54
1260
175
258
12100
46
320
3410
295
01
22
01
104
50
NT2
9110
10802
1207
25
162
1311
01
1110
640
314
123
4898
153
210
4234
179
01
1001
01
24
NT3
10280
10359
1110
25
133
1840
01
1310
530
354
125
2436
202
130
4880
138
01
05
01
01
15NT4
50680
20
633
1207
23
171
6440
02
1924
1320
271
171
3292
361
300
3513
172
01
07
02
81
10M1
26120
20
507
22
08
26
264
3423
03
1821
860
285
59
3046
97310
259
7301
03
01
01
10M2
54080
30
1478
09
1323
183
7661
02
43
183460
651
83
4099
307
1190
2385
167
02
05
03
01
29
M3
168550
20
1346
25
20
51
466
16701
04
57
20
2600
830
101
3744
383
1280
2552
162
02
03
04
01
21
M4
7400
20
14321
01
09
1408
3212
01
26
29
9830
468
255
2331
292
1200
3427
451
03
04
02
01
79M5
33550
40
4173
1015
30
167
5120
02
47
21
3110
656
56
3728
366
1520
3200
116
02
04
04
01
29
M6
50360
50
9756
03
07
07
725528
01
1487
1830
315
159
7441
176
1280
1743
307
02
05
02
01
43
Min
7400
10359
01
04
07
08
1311
01
04
10530
175
56
2331
46
130
259
7301
02
01
01
05
Max
168550
50
14321
29
32
152
606
16701
1187
87
9830
1319
258
12100
383
1520
4880
451
03
22
05
125
79Av
e36586
23
3674
1413
39
232
4915
03
34
29
2863
547
131
4508
258
818
2804
239
02
06
02
31
28
6 Journal of Chemistry
Table3RE
Econtentsof
Buyukm
ahalore(pp
m)
Sample
LaCe
PrNd
SmEu
Gd
TbDy
Ho
ErTm
YbLu
YYHo
Ce a
nom
Dy N
Yb N
LaNN
d NN1
5090
5250
1447
6030
1114
275
1160
180
980
196
571
079
490
073
5460
2786minus034
130
164
N2
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
2587minus021
136
143
NT1
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
3154minus032
090
141
NT2
2250
1720
681
2760
427
094
339
053
260
049
129
020
117
016
640
1306minus048
144
158
NT3
1420
1770
352
1590
287
071
292
046
252
054
152
021
128
018
1270
2352minus026
128
173
NT4
1600
3030
420
1770
308
074
296
046
267
053
154
022
136
021
1330
2509minus007
128
175
M1
1310
2340
333
1350
254
061
272
043
265
053
146
021
142
021
790
1491minus009
121
188
M2
3980
3710
974
4010
781
190
792
127
734
155
445
064
406
061
4490
2897minus037
118
192
M3
4170
4270
1024
4320
835
195
874
139
786
161
487
070
438
067
4830
3000minus033
117
187
M4
2660
2360
553
2200
427
104
424
070
413
086
265
042
265
040
2320
2698minus038
101
234
M5
3780
3750
977
3990
765
183
716
116
663
131
381
055
369
054
3810
2908minus035
117
184
M6
3060
2660
650
2590
462
114
440
070
445
088
285
047
311
049
2330
2648minus039
093
229
Min
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
1306minus048
090
141
Max
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
3154minus007
144
234
Ave
2923
3255
773
3200
608
146
601
096
541
109
316
046
291
043
2876
2528minus030
119
181
Ce ano
m=log[3timesCe N
(2timesLa
N+Nd N
)]
Journal of Chemistry 7
975 905 835 765 695 625 555 485 415 345
Reference peak
Measured peak
Py
Py
Py
30120583m
Raman shift (cmminus1)
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
of the Alpine-Himalayan Orogenic zone The Alpine Oro-genic system is formed by the closure of a different branchof the Tethys Ocean During the closure of Tethys Oceancontinental parts of the Gondwana and Laurasia continentscollided Turkey as an orogenic mosaic (orogenic collage) isa part of these continental parts including remnant materialsbetween these continentals [11] The AOC is included to theAlpine Orogenic system The AOC of Upper Cretaceous ageshows a wide distribution and hosts several ore mineraliza-tions
Darmik formation of Upper Cretaceous age consistsof Boyalik limestone Akcadag sandstone and a radi-olarite member Sarimbey volcanic assemblage (spiliticbasalt andesite unit) Artova ophiolite complex (serpentineharzburgite dunite gabbro diabase chert) and Cretaceouslimestone blocks are also observed in the area Artovaophiolite complex is unconformably overlain by conglom-erate sandstone mudstone and gypsum levels of the Incikformation of terrestrial character [12] (Figure 1)
Ore bodies in the study area occur as laminated bandedand lenticular forms (Figures 2(a) 2(b) 2(c) and 2(d)) Themineralization is entirely associated with radiolarite chertsand thickness of lamina and bands is in the range of 1 to90 cm Manganese ores are quite fractured and fissured andshow an irregular structure (Figure 2(a)) Polished sectiondeterminations indicate that ore assemblage is composed ofhematite and pyrolusite whilst quartz and calcite are thegangue minerals Pyrolusite and magnetite are the mainminerals in the Buyukmahal deposit Hematite peaks wererecorded in XRD analysis but it could not be observed in oremicroscopy and Raman spectroscopy determinations
3 Material and Methods
Twenty ore samples (500 g each) were collected from theBuyukmahalmanganese depositThewhole section of the orefrom top to bottomwas sampled systematically Samples weretaken at 30 cm intervals
Powders of 12 samples under 200 mesh were analyzed atACME Laboratories Major oxide and trace element contentswere determined with ICP-ES and REEs were analyzed withthe ICP-MS method 30 g sample was powdered into 100 120583mfor geochemical analysis 05 g sample was processed in HCl-HNO
3-H2Osolution atsim95∘C for 1 hour and then the amount
of sample was increased 10mL for the final filtering Resultsof analysis are given in Tables 1 2 and 3 In addition inorder to determine paragenesis and textural characteristicsof mineralization 10 polished sections were studied withore microscopy XRD analysis for six samples was doneat TPAO (Turkish Petroleum Corporation) laboratories ARigaku DMAX IIIC model X-Ray diffractometer with a Cutarget (2ndash70∘ 2120579) was used in the analyses Ore minerals werealso studied withThermo Scientific DXR RamanMicroscopeat the Geological Department of the Ankara UniversityThe Raman spectrums obtained were evaluated with Crys-tal Sleuth program to determine the mineral paragenesisChemical composition of pyrolusite was determined withmicroprobe analysis conducted at Montan Universitat inLeoben (Austria) The results are shown in Table 4
4 Mineralogy
Mineral paragenesis in the study area was investigated withore microscopy studies as well as XRD Raman spectroscopyand microprobe analysis for pyrolusite Results show thatpyrolusite and magnetite are the main ore minerals in theBuyukmahal area accompanied by little amount of hematiteGangue minerals are quartz and calcite Results of micro-probe analysis performed on four points in a pyrolusitecrystal are shown in Table 4
41 Pyrolusite (MnO2) It is mostly precipitated from low-
temperature hydrothermal fluids Pyrolusite is a commonalternation mineral in oxidized marine environments Pyro-lusite and magnetite forming the main components of theBuyukmahal area with a whitish yellow color are distinctwith their strong anisotropic character Pyrolusite mineralsdevelop in small veins and characteristic with anhedraland subhedral cutaways Ore microscopy and Raman spec-troscopy images of pyrolusite are shown in Figure 3 Usingthe results of microprobe analysis the structural formula ofpyrolusite (on the basis of two oxygen) is calculated asMn
169-
Fe007
-Si009
-Al002
-Ca001
O2(Table 4)
42 Magnetite (Fe3O4) Magnetite occurs as small scattered
crystals or veins Vein magnetite is observed cutting thepyrolusite (Figure 4) In single nicol magnetite is seen inbrown and gray colors and in the crossed nicols it is inanisotropic character Samples are slightly magnetic Oremicroscopy andRaman spectroscopy images ofmagnetite areshown in Figure 4
5 Geochemistry
Geochemical data are used to determine the origin ofmineralization (eg hydrothermal hydrogenous and dia-genetic) The chemical composition of Buyukmahal depositis SiO
2 8540 to 1032 wt MnO
2 6854 to 679wt and
Fe2O3 1673 to 231 wt Fe and Mn are characteristically
fractionated on precipitation from a hydrothermal solutionproducing high or lowMnFe rations in exhalative sediments[13] MnFe rations of the deposit range from 2589 to090wt (Table 1) These values are conformable with thoseof hydrothermal exhalative manganese deposits in ophioliticregions and recent submarine spreading centers [1 14 15]
The Si-Al discrimination diagram proposed by Peters[16] is used to distinguish hydrothermal from hydrogenousMn-oxide deposits Buyukmahal ore samples are almostwithin the field of hydrothermal field with only one samplewithin the field of hydrogenous deposits (Figure 5)
Ba contents of Waziristan [6] Hazara (Pakistan) [3]Binkılıc [17] Cayırlı [7] and Kasımaga (Turkey) [8] regionsare very high (415 6304 6892 1229 and 2719 resp) indi-cating a sedimentary contribution High Ba content of theBuyukmahal deposit (ave 3659) is also indicative of sedi-mentary origin Modern submarine hydrothermal Mn-oxidedeposits are more enriched in Cu Zn Ni and Co contentsin comparison to pelagic sediments However they are lower
Figure 1 Location and geology map of study area (modified from [12])
than hydrogenous deposits [13 18] Choi and Hariya [6] dis-criminated hydrogeneous deposits and submarine hydrother-mal Mn-deposits on a Ni-Zn-Co ternary diagram On thisdiagram five samples are plotted near hydrogenous fields andseven samples are close to hydrogenous field (Figure 6) InFe-(Ni + Co + Cu) lowast 10-Mn triangular diagram [9 10 19]all samples are plotted in hydrothermal and diagenetic fields
(Figure 7) Correlation data on major oxide and some traceelements contents of ore samples are given in Table 5
The correlation coefficients indicate the presence ofstrong positive relations between major oxides and varioustrace elements (Al
2O3-Fe2O3 119903 = 095 Al
2O3-TiO2 119903 =
099 TiO2-Fe2O3 119903 = 094) and the contribution of mafic
terrigenous material to the deposition environment
Figure 2 Laminated banded ((a) (b) (c)) and lenticular forms (d) in the ore bodies (mn manganese rad radiolarite)
Major oxide trace and REE geochemistry are very usefulfor understanding the formation conditions of ore depositsREE contents of 12 samples collected from the Buyukmahalmanganese mineralization are shown in Table 6
REE contents of the hydrothermal and hydrogenousferromanganese and manganese deposits differ considerablyand thus can provide great information on the genetic
processes involved in the formation of submarine man-ganese and ferromanganese ores [20ndash23] REE patterns ofthe studied deposit (Figure 8(a)) are compared with thoseof other hydrogenous and hydrothermal manganese deposits(Figure 8(b)) Results indicate that hydrogenous ferroman-ganese deposits are more enriched in REEs than theirhydrothermal equivalents Hydrogenous ferromanganese
Journal of Chemistry 5
Table2Tracee
lementscontentsof
Buyukm
ahalore(pp
m)
Sample
BaBe
Co
CsHf
Nb
RbSr
TaTh
UV
ZrMo
CuPb
ZnNi
As
Cd
SbBi
Ag
AuN1
10390
20
5632
28
23
74525
2962
05
7229
4980
926
59
4160
334
1160
2047
378
01
05
03
125
26
N2
8920
104349
29
32
152
606
1676
1187
21
3930
1319
124
2826
379
920
1992
435
01
02
05
56
05
NT1
9590
20
735
02
04
1221
3100
01
04
54
1260
175
258
12100
46
320
3410
295
01
22
01
104
50
NT2
9110
10802
1207
25
162
1311
01
1110
640
314
123
4898
153
210
4234
179
01
1001
01
24
NT3
10280
10359
1110
25
133
1840
01
1310
530
354
125
2436
202
130
4880
138
01
05
01
01
15NT4
50680
20
633
1207
23
171
6440
02
1924
1320
271
171
3292
361
300
3513
172
01
07
02
81
10M1
26120
20
507
22
08
26
264
3423
03
1821
860
285
59
3046
97310
259
7301
03
01
01
10M2
54080
30
1478
09
1323
183
7661
02
43
183460
651
83
4099
307
1190
2385
167
02
05
03
01
29
M3
168550
20
1346
25
20
51
466
16701
04
57
20
2600
830
101
3744
383
1280
2552
162
02
03
04
01
21
M4
7400
20
14321
01
09
1408
3212
01
26
29
9830
468
255
2331
292
1200
3427
451
03
04
02
01
79M5
33550
40
4173
1015
30
167
5120
02
47
21
3110
656
56
3728
366
1520
3200
116
02
04
04
01
29
M6
50360
50
9756
03
07
07
725528
01
1487
1830
315
159
7441
176
1280
1743
307
02
05
02
01
43
Min
7400
10359
01
04
07
08
1311
01
04
10530
175
56
2331
46
130
259
7301
02
01
01
05
Max
168550
50
14321
29
32
152
606
16701
1187
87
9830
1319
258
12100
383
1520
4880
451
03
22
05
125
79Av
e36586
23
3674
1413
39
232
4915
03
34
29
2863
547
131
4508
258
818
2804
239
02
06
02
31
28
6 Journal of Chemistry
Table3RE
Econtentsof
Buyukm
ahalore(pp
m)
Sample
LaCe
PrNd
SmEu
Gd
TbDy
Ho
ErTm
YbLu
YYHo
Ce a
nom
Dy N
Yb N
LaNN
d NN1
5090
5250
1447
6030
1114
275
1160
180
980
196
571
079
490
073
5460
2786minus034
130
164
N2
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
2587minus021
136
143
NT1
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
3154minus032
090
141
NT2
2250
1720
681
2760
427
094
339
053
260
049
129
020
117
016
640
1306minus048
144
158
NT3
1420
1770
352
1590
287
071
292
046
252
054
152
021
128
018
1270
2352minus026
128
173
NT4
1600
3030
420
1770
308
074
296
046
267
053
154
022
136
021
1330
2509minus007
128
175
M1
1310
2340
333
1350
254
061
272
043
265
053
146
021
142
021
790
1491minus009
121
188
M2
3980
3710
974
4010
781
190
792
127
734
155
445
064
406
061
4490
2897minus037
118
192
M3
4170
4270
1024
4320
835
195
874
139
786
161
487
070
438
067
4830
3000minus033
117
187
M4
2660
2360
553
2200
427
104
424
070
413
086
265
042
265
040
2320
2698minus038
101
234
M5
3780
3750
977
3990
765
183
716
116
663
131
381
055
369
054
3810
2908minus035
117
184
M6
3060
2660
650
2590
462
114
440
070
445
088
285
047
311
049
2330
2648minus039
093
229
Min
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
1306minus048
090
141
Max
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
3154minus007
144
234
Ave
2923
3255
773
3200
608
146
601
096
541
109
316
046
291
043
2876
2528minus030
119
181
Ce ano
m=log[3timesCe N
(2timesLa
N+Nd N
)]
Journal of Chemistry 7
975 905 835 765 695 625 555 485 415 345
Reference peak
Measured peak
Py
Py
Py
30120583m
Raman shift (cmminus1)
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Figure 1 Location and geology map of study area (modified from [12])
than hydrogenous deposits [13 18] Choi and Hariya [6] dis-criminated hydrogeneous deposits and submarine hydrother-mal Mn-deposits on a Ni-Zn-Co ternary diagram On thisdiagram five samples are plotted near hydrogenous fields andseven samples are close to hydrogenous field (Figure 6) InFe-(Ni + Co + Cu) lowast 10-Mn triangular diagram [9 10 19]all samples are plotted in hydrothermal and diagenetic fields
(Figure 7) Correlation data on major oxide and some traceelements contents of ore samples are given in Table 5
The correlation coefficients indicate the presence ofstrong positive relations between major oxides and varioustrace elements (Al
2O3-Fe2O3 119903 = 095 Al
2O3-TiO2 119903 =
099 TiO2-Fe2O3 119903 = 094) and the contribution of mafic
terrigenous material to the deposition environment
Figure 2 Laminated banded ((a) (b) (c)) and lenticular forms (d) in the ore bodies (mn manganese rad radiolarite)
Major oxide trace and REE geochemistry are very usefulfor understanding the formation conditions of ore depositsREE contents of 12 samples collected from the Buyukmahalmanganese mineralization are shown in Table 6
REE contents of the hydrothermal and hydrogenousferromanganese and manganese deposits differ considerablyand thus can provide great information on the genetic
processes involved in the formation of submarine man-ganese and ferromanganese ores [20ndash23] REE patterns ofthe studied deposit (Figure 8(a)) are compared with thoseof other hydrogenous and hydrothermal manganese deposits(Figure 8(b)) Results indicate that hydrogenous ferroman-ganese deposits are more enriched in REEs than theirhydrothermal equivalents Hydrogenous ferromanganese
Journal of Chemistry 5
Table2Tracee
lementscontentsof
Buyukm
ahalore(pp
m)
Sample
BaBe
Co
CsHf
Nb
RbSr
TaTh
UV
ZrMo
CuPb
ZnNi
As
Cd
SbBi
Ag
AuN1
10390
20
5632
28
23
74525
2962
05
7229
4980
926
59
4160
334
1160
2047
378
01
05
03
125
26
N2
8920
104349
29
32
152
606
1676
1187
21
3930
1319
124
2826
379
920
1992
435
01
02
05
56
05
NT1
9590
20
735
02
04
1221
3100
01
04
54
1260
175
258
12100
46
320
3410
295
01
22
01
104
50
NT2
9110
10802
1207
25
162
1311
01
1110
640
314
123
4898
153
210
4234
179
01
1001
01
24
NT3
10280
10359
1110
25
133
1840
01
1310
530
354
125
2436
202
130
4880
138
01
05
01
01
15NT4
50680
20
633
1207
23
171
6440
02
1924
1320
271
171
3292
361
300
3513
172
01
07
02
81
10M1
26120
20
507
22
08
26
264
3423
03
1821
860
285
59
3046
97310
259
7301
03
01
01
10M2
54080
30
1478
09
1323
183
7661
02
43
183460
651
83
4099
307
1190
2385
167
02
05
03
01
29
M3
168550
20
1346
25
20
51
466
16701
04
57
20
2600
830
101
3744
383
1280
2552
162
02
03
04
01
21
M4
7400
20
14321
01
09
1408
3212
01
26
29
9830
468
255
2331
292
1200
3427
451
03
04
02
01
79M5
33550
40
4173
1015
30
167
5120
02
47
21
3110
656
56
3728
366
1520
3200
116
02
04
04
01
29
M6
50360
50
9756
03
07
07
725528
01
1487
1830
315
159
7441
176
1280
1743
307
02
05
02
01
43
Min
7400
10359
01
04
07
08
1311
01
04
10530
175
56
2331
46
130
259
7301
02
01
01
05
Max
168550
50
14321
29
32
152
606
16701
1187
87
9830
1319
258
12100
383
1520
4880
451
03
22
05
125
79Av
e36586
23
3674
1413
39
232
4915
03
34
29
2863
547
131
4508
258
818
2804
239
02
06
02
31
28
6 Journal of Chemistry
Table3RE
Econtentsof
Buyukm
ahalore(pp
m)
Sample
LaCe
PrNd
SmEu
Gd
TbDy
Ho
ErTm
YbLu
YYHo
Ce a
nom
Dy N
Yb N
LaNN
d NN1
5090
5250
1447
6030
1114
275
1160
180
980
196
571
079
490
073
5460
2786minus034
130
164
N2
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
2587minus021
136
143
NT1
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
3154minus032
090
141
NT2
2250
1720
681
2760
427
094
339
053
260
049
129
020
117
016
640
1306minus048
144
158
NT3
1420
1770
352
1590
287
071
292
046
252
054
152
021
128
018
1270
2352minus026
128
173
NT4
1600
3030
420
1770
308
074
296
046
267
053
154
022
136
021
1330
2509minus007
128
175
M1
1310
2340
333
1350
254
061
272
043
265
053
146
021
142
021
790
1491minus009
121
188
M2
3980
3710
974
4010
781
190
792
127
734
155
445
064
406
061
4490
2897minus037
118
192
M3
4170
4270
1024
4320
835
195
874
139
786
161
487
070
438
067
4830
3000minus033
117
187
M4
2660
2360
553
2200
427
104
424
070
413
086
265
042
265
040
2320
2698minus038
101
234
M5
3780
3750
977
3990
765
183
716
116
663
131
381
055
369
054
3810
2908minus035
117
184
M6
3060
2660
650
2590
462
114
440
070
445
088
285
047
311
049
2330
2648minus039
093
229
Min
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
1306minus048
090
141
Max
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
3154minus007
144
234
Ave
2923
3255
773
3200
608
146
601
096
541
109
316
046
291
043
2876
2528minus030
119
181
Ce ano
m=log[3timesCe N
(2timesLa
N+Nd N
)]
Journal of Chemistry 7
975 905 835 765 695 625 555 485 415 345
Reference peak
Measured peak
Py
Py
Py
30120583m
Raman shift (cmminus1)
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Figure 2 Laminated banded ((a) (b) (c)) and lenticular forms (d) in the ore bodies (mn manganese rad radiolarite)
Major oxide trace and REE geochemistry are very usefulfor understanding the formation conditions of ore depositsREE contents of 12 samples collected from the Buyukmahalmanganese mineralization are shown in Table 6
REE contents of the hydrothermal and hydrogenousferromanganese and manganese deposits differ considerablyand thus can provide great information on the genetic
processes involved in the formation of submarine man-ganese and ferromanganese ores [20ndash23] REE patterns ofthe studied deposit (Figure 8(a)) are compared with thoseof other hydrogenous and hydrothermal manganese deposits(Figure 8(b)) Results indicate that hydrogenous ferroman-ganese deposits are more enriched in REEs than theirhydrothermal equivalents Hydrogenous ferromanganese
Journal of Chemistry 5
Table2Tracee
lementscontentsof
Buyukm
ahalore(pp
m)
Sample
BaBe
Co
CsHf
Nb
RbSr
TaTh
UV
ZrMo
CuPb
ZnNi
As
Cd
SbBi
Ag
AuN1
10390
20
5632
28
23
74525
2962
05
7229
4980
926
59
4160
334
1160
2047
378
01
05
03
125
26
N2
8920
104349
29
32
152
606
1676
1187
21
3930
1319
124
2826
379
920
1992
435
01
02
05
56
05
NT1
9590
20
735
02
04
1221
3100
01
04
54
1260
175
258
12100
46
320
3410
295
01
22
01
104
50
NT2
9110
10802
1207
25
162
1311
01
1110
640
314
123
4898
153
210
4234
179
01
1001
01
24
NT3
10280
10359
1110
25
133
1840
01
1310
530
354
125
2436
202
130
4880
138
01
05
01
01
15NT4
50680
20
633
1207
23
171
6440
02
1924
1320
271
171
3292
361
300
3513
172
01
07
02
81
10M1
26120
20
507
22
08
26
264
3423
03
1821
860
285
59
3046
97310
259
7301
03
01
01
10M2
54080
30
1478
09
1323
183
7661
02
43
183460
651
83
4099
307
1190
2385
167
02
05
03
01
29
M3
168550
20
1346
25
20
51
466
16701
04
57
20
2600
830
101
3744
383
1280
2552
162
02
03
04
01
21
M4
7400
20
14321
01
09
1408
3212
01
26
29
9830
468
255
2331
292
1200
3427
451
03
04
02
01
79M5
33550
40
4173
1015
30
167
5120
02
47
21
3110
656
56
3728
366
1520
3200
116
02
04
04
01
29
M6
50360
50
9756
03
07
07
725528
01
1487
1830
315
159
7441
176
1280
1743
307
02
05
02
01
43
Min
7400
10359
01
04
07
08
1311
01
04
10530
175
56
2331
46
130
259
7301
02
01
01
05
Max
168550
50
14321
29
32
152
606
16701
1187
87
9830
1319
258
12100
383
1520
4880
451
03
22
05
125
79Av
e36586
23
3674
1413
39
232
4915
03
34
29
2863
547
131
4508
258
818
2804
239
02
06
02
31
28
6 Journal of Chemistry
Table3RE
Econtentsof
Buyukm
ahalore(pp
m)
Sample
LaCe
PrNd
SmEu
Gd
TbDy
Ho
ErTm
YbLu
YYHo
Ce a
nom
Dy N
Yb N
LaNN
d NN1
5090
5250
1447
6030
1114
275
1160
180
980
196
571
079
490
073
5460
2786minus034
130
164
N2
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
2587minus021
136
143
NT1
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
3154minus032
090
141
NT2
2250
1720
681
2760
427
094
339
053
260
049
129
020
117
016
640
1306minus048
144
158
NT3
1420
1770
352
1590
287
071
292
046
252
054
152
021
128
018
1270
2352minus026
128
173
NT4
1600
3030
420
1770
308
074
296
046
267
053
154
022
136
021
1330
2509minus007
128
175
M1
1310
2340
333
1350
254
061
272
043
265
053
146
021
142
021
790
1491minus009
121
188
M2
3980
3710
974
4010
781
190
792
127
734
155
445
064
406
061
4490
2897minus037
118
192
M3
4170
4270
1024
4320
835
195
874
139
786
161
487
070
438
067
4830
3000minus033
117
187
M4
2660
2360
553
2200
427
104
424
070
413
086
265
042
265
040
2320
2698minus038
101
234
M5
3780
3750
977
3990
765
183
716
116
663
131
381
055
369
054
3810
2908minus035
117
184
M6
3060
2660
650
2590
462
114
440
070
445
088
285
047
311
049
2330
2648minus039
093
229
Min
430
490
122
590
096
020
087
013
064
013
037
006
046
008
410
1306minus048
090
141
Max
5330
7710
1739
7200
1544
376
1515
248
1359
264
740
104
648
089
6830
3154minus007
144
234
Ave
2923
3255
773
3200
608
146
601
096
541
109
316
046
291
043
2876
2528minus030
119
181
Ce ano
m=log[3timesCe N
(2timesLa
N+Nd N
)]
Journal of Chemistry 7
975 905 835 765 695 625 555 485 415 345
Reference peak
Measured peak
Py
Py
Py
30120583m
Raman shift (cmminus1)
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Figure 3 Ore microscopy and Raman spectroscopy images ofpyrolusite
deposits show positive Ce anomaly but hydrothermal fer-romanganese deposits are characteristic with negative Ceanomaly [22ndash24] All samples of the Buyukmahal manganesemineralization show strong negative Ce anomalies whichresemble the pattern of typical submarine hydrothermaldeposits (Figure 8(a)) However the Ce anomaly depends onthe temperature of the fluid the proximity to the hydrother-mal source and redox conditions [23 25 26] Eu also showsnegative anomaly in all samples indicating contaminationfrom the continental crust andor sediment contribution viadehydration [27]
In hydrothermal solutions LaNNdN ratio is 30ndash74 (aver-age 45) and DyNYbN ratio is 06ndash21 (average 12) Theseratios inMn-oxide crusts are 27ndash43 and 04ndash12 respectively[4] These rations in hydrogenous deposits are 090ndash150and 03ndash191 respectively [24] The ranges of LaNNdN andDyNYbN ratios for the Buyukmahal manganese mineraliza-tion are 141ndash234 (average 182) and 090ndash144 (average 118)(Table 6) These values imply that Buyukmahal mineraliza-tion might be a hydrogenous deposit
YHo ratios in the area range from 1306 to 3154 (average2505) High YHo ratios are indicative of multienvironmentsfor the mineral deposition In this respect both deep marineenvironments and terrigenous materials may be effective forprecipitation [30]
Data computed with the formula of Ceanom = log [3 timesCeN(2 times LaN + NdN)] also yield information on the originof mineralization For example in the case of Ceanom gt minus01Ce is said to be enriched which reflects an anoxic characterfor the water body of sedimentation If Ceanom lt minus01 there is
a negative Ce anomaly which indicates an oxic nature for thewater body of sedimentation [31] Ce anomalies in all samplesat Buyukmahal are found to be Ceanom lt minus01 indicating anoxic character for the sedimentation environment
6 Discussions and Conclusions
The AOC of Upper Cretaceous age is located along thenorthwestern and eastern margins in Yozgat (Turkey) and
8 Journal of Chemistry
Table 4 Composition of pyrolusite (pr) samples of Buyukmahal ore
(a)
Si Ti Al Fe Mn Mg Ca Na K Ba Ag Znpr48 261 008 061 326 7571 009 060 000 005 025 000 000pr49 226 010 043 270 8048 004 055 006 005 095 001 006pr50 152 019 042 300 7490 008 049 003 009 020 002 006pr51 232 008 059 302 7644 006 040 005 016 032 002 000Ave 218 011 051 299 7688 007 051 003 009 043 001 003
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
is included to the Alpine Orogenic system Mineralizationin the Buyukmahal area observed in banded and lenticularforms occurs in a close associationwith radiolarite cherts andis intensely affected by the tectonism
Based on the results of major and trace element datamineralization in the study area was probably formed fromhydrothermal solutions associated with a sea floor spreadingcenter However ore minerals at Buyukmahal were not
HydrothermalFe Mn
Diagenetic
Hydrogenous
50
5050
(Ni + Co + Cu) times 10
Figure 7 Fe-(Ni + Co + Cu) times 10-Mn discrimination diagram [910 19]
precipitated entirely from a purely hydrothermal or purelyhydrogenous fluid but certainly from a mixture of thesetwo For instance Ti is generally immobile in hydrothermalsolutions and could be a measure of clastic input [32] Thegood correlation observed between Al
2O3and TiO
2(119903 =
099) can be attributed to the mixing of detrital materialsduring precipitation [6]
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Ba Co Rb Sr U Zr Mo Cu Pb Zn Ni As Bi AgBa 100 minus019 026 098 000 016 minus021 minus008 039 037 minus017 minus034 037 minus027Co 100 minus019 minus014 045 014 037 minus010 018 059 minus012 071 016 minus012Rb 100 021 minus033 085 minus057 minus037 054 023 minus042 018 069 030Sr 100 001 016 minus017 minus006 042 044 minus016 minus030 039 minus022U 100 minus027 042 067 minus035 025 minus029 036 minus014 017Zr 100 minus041 minus040 072 054 minus028 042 090 016Mo 100 047 minus032 minus022 039 050 minus037 019Cu 100 minus061 minus013 002 012 minus032 038Pb 100 060 002 018 083 004Zn 100 minus032 031 072 minus017Ni 100 minus005 minus026 minus003As 100 027 042Bi 100 005Ag 100070 and higher values and minus070 and lower values specify the presence of possitive or negative corelation coefficients
1
10
100
1000
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Sam
ple
cond
rite
(a)
Hydrothermal
Hydrogenous
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
REE
cond
rite
1000
100
10
1
(b)
Figure 8 (a) Chondrite normalized REE diagram for ore samples (normalization values are from Evensen et al [28]) (b) REE diagramshowing hydrogenous [29] and hydrothermal [29] fields
10 Journal of Chemistry
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
Fe compounds (less stable than Mn) precipitate prox-imal parts whilst Mn compounds precipitate distal partsof hydrothermal vents along the sea floor spreading cen-ters [33 34] Eh andor pH of the hydrothermal solutionalso exert controls on the precipitation of Mn and Fe andtheir compounds [34ndash37] Mn is more mobile relative toFe during low Eh andor pH conditions The fractionationof Mn compounds from Fe compounds suggests a spatialvariation in Eh andor pH [34] Considering Fe and Mnconcentrations of the mineralization in the study area it canbe asserted that Buyukmahal deposit was formed from ahydrothermal source in addition considering the high Fecontent mineralization might be formed in a proximal siteof the hydrothermal vent
Although mineralization at Buyukmahal is of a hydro-thermal type it does not originate from a pure hydrothermalor pure hydrogenous source Geochemical data support asystem contributed from both sources The mineralizationwas developed on a sea floor spreading center within theAlpin Ophiolite system and then obducted as part of theAOC
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
Acknowledgments
This study constitutes a part of MS degree thesis of NeslihanOkuyucu The Scientific and Technical Research Council ofTurkey (TUBITAK Project no 109Y167) and the Bozok Uni-versity (Grant no BFFM2009-06) are greatly acknowledgedfor financial support Dr Ibrahim Uysal is kindly appreciatedfor his help in EMP analysisThe authors also thank ProfessorYusuf K Kadıoglu and Cumhur O Kılıc for the Ramanspectroscopy analysis
References
[1] N Oksuz ldquoGeochemical characteristics of the Eymir (Sorgun-Yozgat) manganese deposit Turkeyrdquo Journal of Rare Earths vol29 no 3 pp 287ndash296 2011
[2] N Oksuz ldquoGeochemistry and the origin of manganese min-eralizations in Derbent (Yozgat) Regionrdquo Bulletin of the EarthSciences Application and Research Centre of Hacettepe Universitvol 32 no 3 pp 213ndash234 2011
[3] M Tahir Shah andC JMoon ldquoManganese and ferromanganeseores from different tectonic settings in the NW HimalayasPakistanrdquo Journal of Asian Earth Sciences vol 29 no 2-3 pp455ndash465 2007
[4] C E Fitzgerald and K M Gillis ldquoHydrothermal manganeseoxide deposits from Baby Bare seamount in the NortheastPacific Oceanrdquo Marine Geology vol 225 no 1ndash4 pp 145ndash1562006
[5] K Heshmatbehzadi and J Shahabpour ldquoMetallogeny of man-ganese and ferromanganese ores in baft ophiolitic MelangeKerman Iranrdquo Australian Journal of Basic and Applied Sciencesvol 4 no 2 pp 302ndash313 2010
[6] J H Choi and Y Hariya ldquoGeochemistry and depositional envi-ronment of Mn oxide deposits in the Tokoro Belt northeasternHokkaido Japanrdquo Economic Geology vol 87 no 5 pp 1265ndash1274 1992
[7] A Karakus B Yavuz and S Koc ldquoMineralogy and major-traceelement geochemistry of the Haymana manganese mineraliza-tions Ankara Turkeyrdquo Geochemistry International vol 48 no10 pp 1014ndash1027 2010
[8] S Koc O Ozmen and N Oksuz ldquoGeochemistry characteristicof kasimaga (Keskin-Kırıkkale) manganese oxide mineraliza-tionsrdquo Mineral Research and Exploration Magazine vol 122 p107 2000
[9] E Bonatti T Kraemer and H Rydell ldquoClassification andgenesis of submarine iron-manganese depositsrdquo in Ferroman-ganese Deposits on the Ocean Flor International Decade onOcean Exploration D Horn Ed pp 149ndash166 National ScienceFoundation Washington DC USA 1972
[10] D A Crerar J Namson M S Chyi L Williams and I MFeigenson ldquoManganiferous cherts of the Fransiscan assem-blage I General geology ancient and modern analogues andimplications for hydrothermal convection at oceanic spreadingcentersrdquo Economic Geology vol 77 pp 519ndash540 1982
[11] AOkay andOTuysuz ldquoTethyan sutures of northernTurkeyrdquo inTheMediterranean Basins Tertiary ExtensionWithin the AlpineOrogen B Durand L Jolivet F Horvath and M Serrane Edsvol 156 pp 475ndash515 Geological Society London UK 1999
[12] A E AkcayMDonmezHKara A F Yergok andK Esenturkldquo1100 000 scale geologicalmaps of Turkey Yozgat-I33 threaderrdquoMTA Ankara vol 80 pp 1ndash16 2007
[13] M T Shah and A Khan ldquoGeochemistry and origin of Mn-deposits in theWaziristan ophiolite complex northWaziristanPakistanrdquoMineraliumDeposita vol 34 no 7 pp 697ndash704 1999
[14] X Jiancheng S Weidong D Jianguo et al ldquoGeochemical stud-ies on Permian manganese deposits in Guichi eastern ChinaImplications for their origin and formative environmentsrdquoJournal of Asian Earth Science vol 74 pp 155ndash166 2013
[15] A Sasmaz B Turkyilmaz N Ozturk et al ldquoGeology and geo-chemistry of middle eocene maden complex ferromanganesedeposits from Elazıg-Malatya Region Eastern Turkeyrdquo OreGeology Reviews vol 56 pp 352ndash372 2014
[16] T Peters ldquoGeochemistry of manganese-bearing cherts associ-ated with Alpine ophiolites and the Hawasina formations inOmanrdquoMarine Geology vol 84 no 3-4 pp 229ndash238 1988
[17] A H Gultekin ldquoGeochemistry and origin of the OligoceneBinkılıc manganese deposit Thrace basin Turkeyrdquo TurkishJournal of Earth Sciences vol 7 p 11 1998
[18] D S Cronan ldquoUnderwater mineralsrdquo Academic Press LondonUK 1980
[19] J R Hein S S Marjorie and L M Gein ldquoCentral Pasificcobalt rich ferromanganese crusts Historical perspective andregional variabilityrdquo in Geology and Offshore Mineral Resourcesof the Central Pasific Basin SircumPasific Council for Energy andMineral Resources B H Keating and B R Balton Eds vol 14of Earth science series Springer New York NY USA 1992
[20] J R Toth ldquoDeposition of submarine crusts rich in manganeseand ironrdquo Geological Society of America Bulletin vol 91 no 1pp 44ndash54 1980
[21] D E Ruhlin andRMOwen ldquoThe rare earth element geochem-istry of hydrothermal sediments from the East Pacific Riseexamination of a seawater scavenging mechanismrdquo Geochimicaet Cosmochimica Acta vol 50 no 3 pp 393ndash400 1986
Journal of Chemistry 11
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
[22] J DWonder P G Spry and K EWindom ldquoGeochemistry andorigin of manganese-rich rocks related to iron-formation andsulfide deposits western Georgiardquo Economic Geology vol 83no 5 pp 1070ndash1081 1988
[23] J R Hein A Kochinsky P Halbach et al ldquoIron andmanganeseoxide mineralization in the Pacificrdquo in Manganese Mineraliza-tion Geochemistry and Mineralogy of Terrestrial and MarineDeposits K Nicholson J R Hein B Buhn and S DasguptaEds vol 119 pp 123ndash138 Geological Society London UK 1997
[24] H Elderfield C J Hawkesworth M J Greaves and S ECalvert ldquoRare earth element geochemistry of oceanic ferro-manganese nodules and associated sedimentsrdquo Geochimica etCosmochimica Acta vol 45 no 4 pp 513ndash528 1981
[25] N Clauer P Stille C Bonnot-Courtois and W S Moore ldquoNd-Sr isotopic and REE constraints on the genesis of hydrothermalmanganese crusts in the Galapagosrdquo Nature vol 311 no 5988pp 743ndash745 1984
[26] J R Hein Y Hsueh-Wen S H Gunn A E Gibbs and WChung-ho ldquoComposition and origin of hydrothermal iron-stones from central Pacific seamountsrdquo Geochimica et Cosmo-chimica Acta vol 58 no 1 pp 179ndash189 1994
[27] S S Sun and W F McDonough ldquoChemical and isotopic sys-tematics of oceanic basalts implications formantle compositionand processesrdquo inMagmatism in Ocean Basins A D Saundersand M J Norry Eds pp 313ndash345 Geological Society LondonUK 1989
[28] N M Evensen P J Hamilton and R K OrsquoNions ldquoRare-earthabundances in chondritic meteoritesrdquoGeochimica et Cosmochi-mica Acta vol 42 no 8 pp 1199ndash1212 1978
[29] U Von Stackelberg ldquoGrowth history of manganese nodules andcrusts of the Peru BasinrdquoGeological Society vol 119 pp 153ndash1761997
[30] J Nayan J Rongfen andW ZiyuPermain Palaeogeography andGeochemical Environment in Lower Yangtze Region PetroleumIndustry Press Beijing China 1994
[31] J Wright H Schrader andW T Holser ldquoPaleoredox variationsin ancient oceans recorded by rare earth elements in fossilapatiterdquo Geochimica et Cosmochimica Acta vol 51 no 3 pp631ndash644 1987
[32] R Sugisaki ldquoRelation between chemical composition andsedimentation rate of Pacific ocean-floor sediments depositedsince the middle Cretaceous basic evidence for chemicalconstraints on depositional environments of ancient sediments(plate tectonic orogenic model)rdquo Journal of Geology vol 92 no3 pp 235ndash259 1984
[33] AG Panagos and S PVaranavas ldquoOn the genesis of someman-ganese deposits from eastern Greecerdquo Syngenesis and Epigenesisin the Formation of Mineral Deposits pp 553ndash561 1984
[34] S Roy ldquoEnvironments and processes of manganese depositionrdquoEconomic Geology vol 87 no 5 pp 1218ndash1236 1992
[35] K B Krauskopf ldquoSeparation of manganese from iron in sedi-mentary processesrdquo Geochimica et Cosmochimica Acta vol 12no 1-2 pp 61ndash84 1957
[36] J D Hem ldquoChemical factors that influence that influence theavailability of iron and manganese in aqueous systemsrdquo Geo-logical Society of America Bulletin vol 83 pp 443ndash450 1972
[37] L Frakes and B Bolton ldquoEffects of ocean chemistry sealevel and climate on the formation of primary sedimentarymanganese ore depositsrdquo Economic Geology vol 87 no 5 pp1207ndash1217 1992
