Kahramanmaraş Dulkadiroğlu ilçesine bağlı elmalar köyü mangan yatağının jenetik incelenmesi ve Türkiye'nin jeotektonik evrimindeki yeri ve ilişkisi
Genesis investigation of manganese deposit in elmalar village, Dulkadirogullari region, Kahramanmaras, its implication and relation in Turkey's tectonic evolution
Yazar: NAŞİDE MERVE SÜTÇÜ
Danışman: PROF. DR. EMİN ÇİFTÇİ
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü / Jeoloji Mühendisliği Ana Bilim Dalı / Jeoloji Mühendisliği Bilim Dalı
Derece: Yüksek Lisans, 2019
Konu: Jeoloji Mühendisliği = Geological Engineering

Özet:
Kahramanmaraş ili Dulkadiroğulları ilçesine bağlı Elmalar köyü ve yakın çevresi inceleme alanındaki manganez yatağının jeolojik, mineralojik, petrografik özellikleri ve jeokimyasal özelliklerinin incelenmesi, kökeninin belirlenmesi ve bu yatağın bilinen diğer manganez yatakları ile karşılaştırılması yapılmıştır. Çalışma alanında yer alan litolojik birimler Üst Kretase yaşlı Koçali kompleksi (Koçali ofiyoliti ve Koçali karmaşığı), Orta-Üst Maestrihtiyen yaşlı Besni formasyonu (Keklikpınar konglomera üyesi, Sıraca marn üyesi, Elmalı kireçtaşı üyesi, Gökyalçın konglomera üyesi), Eosen-Oligosen yaşlı Midyat grubu (Ahırdağı formasyonu), Orta Miyosen yaşlı Yenicekale formasyonu (Döngele kumtaşı üyesi), Kuvaterner yaşlı yamaç molozu ve alüvyonlardan oluşmaktadır. Manganez cevherleşmesi Üst Kretase yaşlı Koçali karmaşığına ait radyolaritler arasında sinjenetik stratiform tipte ve yer yer mercek şeklinde oluşmuştur. Bölge yoğun kıvrımlanma ve kırıklanmaya maruz kalmıştır. 
Cevher numunelerinden yapılan XRD analizlerine ve cevher mikroskobisi incelemelerine göre mineral parajenezinde ana cevher olarak piroluzit, manganit, eser miktarda kriptomelan ve psilomelan; gang olarak da değişen oranlarda kuvars, kalsit ve kil mineralleri belirlenmiştir. 
Bölgeden ve Türkiye'nin önemli manganez yataklarından alınan örneklerden ayrıca ICP-AES ve ICP-MS yöntemleri kullanılarak majör, eser element ve NYE analizleri yaptırılmıştır. İnceleme alanındaki oluşumun jenezini anlamak için jeokimyasal veriler literatürde daha önce kullanılmış bazı ayırtman diyagramları yardımıyla Elmalar cevher örnekleri ile ülkemizin diğer mangan yatakları ile karşılaştırılmıştır. 
Elmalar cevherleşmesini temsil eden cevher örneklerinde Mn içerikleri %15 ila %54.03 arasında değişmektedir. Fe içeriği ise % 0.178 ila % 0.21 arasındadır. Ortalama Fe/Mn oranı ise 0.01174 olarak hesaplanmıştır. Bu değerler Fe ve Mn oluşumlarının ilgili metal taşınımı ve mineralizasyonu süreçlerinde birbirlerinden bağımsız gerçekleştiğini göstermektedir. Elmalar cevherleşmesi çok düşük Fe/Mn oranları ile deniz altı volkanizmi ile beslenmiş kimyasal sedimenter yataklara benzemektir. SiO2 içeriği ise % 59.9  ila % 72.4 arasında değişmektedir. Cevherleşme ayrıca düşük miktarlarda Al ve Ti içermektedir. Bu da cevherleşmede metal kaynağının sedimenter olmadığını önermektedir. Cevherleşmede 2360 ppm ila 11600 ppm aralığında yüksek miktarda Ba içeriği gözlenmiş olması metal kaynağı ile ilgili yorumu destekler nitelikte olup deniz altı hidrotermal etkinliği ile oluşmuş yataklara benzemektedir. Bunun yanı sıra yapılan Si-Al, Fe-(Ni+Co+Cu)×10-Mn, (Co+Ni)-(Ag+Cu+Mo+Pb+V+Zn) ayırtman diyagramlarında da örnekler hidrotermal alana düşmüş ve diyajenetik süreçlerden etkilendiği gözlenmektedir. Öte yandan Co/Zn oranı (2.3 ila 4) ile Co/Ni oranı (2.8 ila 5) olup, Ni-Zn-Co diyagramında da örneklerin çoğunluğu yüksek kobalt içeriği sebebiyle hidrojenetik alana düşmüştür.  NYE analizlerinden yapılan örümcek diyagramlarında ise negatif Ce anomalisi yatağın hidrotermal kökenli olduğunu işaret etmektedir. HNYE/ANYE oranına göre ise yatak hafif elementlerce zenginleşme göstermiş olup, bu da birincil bir zenginleşmeye işaret etmektedir. 
Elmalar manganez cevherleşmesi metal kaynağı olarak hidrotermal kökenli olup Üst Kretase yaşlı radyolaritleri ile arakatmanlı, sinjenetik ve stratiform oluşmuş olmalıdır. Yatağın jeokimyasal incelemesine bakıldığında deniz suyu etkisine oluşum sonrasında da maruz kaldığı düşünülmektedir. Yatağın oluşumu, Fe ve Mn iyonlarını taşıyan denizaltı volkanizmi kökenli eksalatif akışkanların deniz tabanına yayılması sonucu kimyasal sedimenter olarak çökelmesi ile gerçekleştir. Eh-pH davranış farkı sebebiyle Mn iyonları çözeltide göreli olarak daha uzun kalıp, Fe'den daha uzağa taşınmış ve radyolaritler ile eş zamanlı olarak (sinjenetik) spilitik bazaltların üzerine konkardan olarak yerleşmiştir. 
Elmalar mangan cevherleşmesi denizaltı volkanizmi kaynaklı eksalasyon ürünü mangan yataklarına dahil olup, volkanojenik sedimenter kökenli bir yataktır. Bitlis-Zagros sütürü boyunca özellikle Cu ve Fe cevherleşmeleri ile uzaysal ve zamansal ilişkili olarak bir çok zuhurun varlığı bilinmektedir. Elmalar cevherleşmesi bu kenet kuşağının KB'sında, Kilis cevherleşmesi ise GD'sunda yer alan örnekler olarak kabul edilebilir.

Abstract:
Study area is located in Elmalar region that is in Dulkadiroğlu country is a village in Kahramanmaraş province, and in its near surroundings in Southeast Anatolia. Study area is 18 km far away from Kahramanmaraş. In this study, geological, mineralogical, petrographic characteristics, and geochemical features of the study area has been investigated. The objective of this study is to explain the genesis of the deposit through comparing it with other occurrences of Turkey.
Southeast Anatolia from South to North are divided into three tectonic units which are Arabian Platform, Zone of Imbrication and Nappe Region. There are two deformation that are known through the orogenic evolution. The first one is the settlement of the ophiolite nappes on the Arabian plate in the Upper Cretaceous and the second one is happened in between Eosen and Miocene. In the first deformation, the first ophiolite nappes were settled on the Arabian platform during the Maestrichtian period, and the Koçali complex and the Kızıldağ ophiolite were also a product of this period. Ophiolitic community in Southeast Anatolia extends from Hakkari Cilo to Hatay Kızıldağ and are exposed over an arc of approximately east-west trending. Manganese deposits are located in intermediate layers of the unit consisting of spilitic basalt and radiolarites in Koçali Formation. Lithologies exposed in the study area from old to young are Upper Cretaceous aged Koçali Complex (Koçali ophiolite, Koçali melange), Middle-Upper Maestrichtian aged Besni formation (Keklikpınar conglomerate member, Sıraca marl member, Elmalı limestone member, Gökyalçın conglomerate member), Eocene-Oligocene aged Midyat group (Ahırdağı formation), Middle Miocene aged Yenicekale formation (Döngele limestone member), Quarternary aged slope debris and alluviums.
Manganese deposits can occur in almost all geomorphological and tectonic environments in ocean basins with one or more of the following four processes which are hydrogenetic, hydrothermal, diagenetic, replacement of rocks and sediments. Manganese deposits of Turkey are divided into four groups according to their formation, their chemical properties, their mineralogy, their age and wall rock relations. They are radiolarian chert hosted, black shale hosted, volcanic arc hosted, Trakya basin manganese deposits. 
The manganese mineralization in the Elmalar region occurs as alternating layers with radiolarites sitting on the spilitic basalts of  Koçali complex of Upper Cretaceous age. The mineralization is concordant, stratiform, and may form lensial bodies in places. Quartz and calcite veined spilitic basalts can be used as a guide. In the field, mudstone, clay stone, spilitic basalt and limestone complex mass is overthrusted by the radiolarite and ore mass. The radiolarite and mineralization were pushed below the complex by faulting (to the older unit). The mineralization is mostly observed as syngenetic stratiform type, irregular lenses in places. The beds were intensely folded and fractured due to post-formational tectonic events. Anticline and synclines are frequently observed in the study area and mineralization is conformable with these structures. 
Ore and wall rock samples taken from the study area  and the ore samples taken from important manganese deposits of Turkey are analyized by X-ray diffraction method. According to XRD analysis, main ore minerals are mainly pyrolusite, manganite and less quantity of criptomelane, psilomelane and the gangue minerals including quartz, calcite and clay minerals according to mineral paragenesis of the study area. 
In the study area, 13 samples representing the main lithologies and ore were taken. Polished section samples were prepared and examined by an ore microscope. Pyrolusite is generally seen in low temperature hydrothermal deposits. Pyrolusite is the replacement product of manganese oxides like manganite and ramsdellite. Manganite, pyrolusite, psilomelane and cryptomelan are characteristic minerals of supergene conditions and are formed by oxidation of primary manganese minerals. In the mudstone wallrock thin sections, calcite vein cut the matrix formed of silt and clay. Vein thickness of the calcite is 0.06 on average. Quartz fenocrystals are generally founded in the thin sections as anhedral grains. In one of the mudstone thin sections, manganese oxide were observed as cementing material. In the some of the mudstone thin sections, round radyolarian particules and trace to minor manganese oxide were seen. The size of the radiolarian clasts with cellular structure varies from 0.3 mm to 0.7 mm. It is observed that manganese oxides filled in the spaces left from the radiolarians. In clayey limestone thin section, the clayey and abundant carbonate-containing matrix was cut by late-stage calcite veins. The thickness of the calcite vein is 0.25 mm on average. Radiolaria fossils were also observed in the same thin section. The pyrolusites appear to be gray under plane polarized light. It has a strong pleochroism, its color varies between gray and dark gray. Manganite, psilomelane, braunite show parallel extinction and strong anisotropy. In the pyrolusite polished sections, coarse grained quartz with intergranular space filled by manganese oxides by mainly pyrolusite were observed. The manganese oxide mineral observed in the polished sections is predominantly subhedral and anhedral pyrolusite up to 100 micron in size. Banded texture were observed in some of the sections. It was observed that intergranular spaces filled by manganese oxide was mainly pyrolusite. Coarse grained pyrolusite shows cracks and fractures as a result of post formational tectonic effects. Anhedral massive fine-grained pyrolusite and carbonate veins that cut the pyrolusite were also commonly observed indicating late stage carbonate precipitation that are healing these fractures. The interlayers were filled with the same carbonate matrix. Overgrowing coarse grained pyrolusite onto fine grained pyrolusite and psilomelane in between pyrolusite and quartz contact are also observed as lens, prismatic crystals.
Ore samples were taken from the study area and from the important manganese deposits of Turkey (e.g., Binkılıç, Tavas, Dursunbey ve Kilis). Then, major and trace element analyzes were performed in the ALS Labs (İzmir-Gaziemir) employing ICP-MS and ICP-AES methods. To compare the results, geochemical data, ternary and scatter diagrams were utilized. Mn, Fe, Al, Ti and Si elements play an important role in investigating the genesis of manganese deposits. Mn contents of ore samples taken from manganese deposition of Elmalar area vary by at least 15% at most 54.03 (average 33.82%). Fe / Mn ratio was determined as 0.01174. Fe/Mn ratio is a useful parameter for understanding the genesis of a manganese deposit. The hydrothermal deposits associated with active ocean spreading centers show low Fe/Mn ratios. These values indicate that Fe and Mn formations are independent from each other in the related metal transport and mineralization processes. The mineralization of Elmalar manganese is similar to chemical sedimentary deposits fed by submarine volcanism with very low Fe / Mn ratios. Bonnatti et. all, 1972 was stated that the ratio of Fe/Mn was in the wider range than the hydrothermal in the hydrogenetic deposits which are 0.1> Fe/Mn> 10. The percentage of SiO2 is between 72.4 and 59.9. High SiO2 content is also seen as a parameter for hydrothermal deposits.  But some of the silica may be supplied by radiolarite. Thus, it is cautiously interpreted. The low Fe / Mn ratio and the manganese oxides (pyrolusite) deposits indicate areas away from the spreading center (distal sites). It is known that iron is the first dissolving element, that manganese can remain in solution for longer periods of time under oxidative conditions, and the pH value must be changed slowly and regularly to remove iron and manganese from each other. The reason for the high Al and Ti content is stated to be the sedimentary contribution. Toth (1980) used the Si-Al diagram to distinguish between hydrothermal and sedimentary deposits. This diagram is generated for the Elmalar deposit and because of the low Al content and the high Si content, the deposit plots in the hydrothermal area on this diagram.  This suggests that the metal source in the mineralization is not sedimentary. The high amount of Ba content observed in the mineralization in the range of 2360 ppm to 11600 ppm supports the interpretation of the metal source and is similar to the deposits formed by underwater hydrothermal activity.

The Fe- (Ni + Co + Cu) × 10-Mn diagram proposed by Bonatti (1972), distinguishes between hydrogenetic and exhalative hydrothermal ferrous manganese deposits. Co, Cu, Ni and Zn are reported to be depleted in hydrothermal deposits according to hydrogenetic deposits. In this diagram, intensive hydrothermal and diagenetic effects on Elmalar manganese deposits were observed. The manganese deposits of hydrothermal origin are indicated in the previous studies showing that they are enriched in the elements of As, B, Ba, Be, Ge, Pb, Sb, Sr, Tl and W. The elemental association of Ba, Cu, Li, Mo, Pb, Sb, Sr, V, Zn was interpreted as a descriptive symptom of hydrothermal deposits. According to Ni-Zn-Co hydrothermal and hydrogenetic discrimination diagram by forwarded by Choi and Hariya (1992), the hydrogenetic and hydrothermal effects were observed together in manganese mineralization of Elmalar. From the trace elements (Ni, Cu, Co) used to construct the diagram, Ni and Cu indicates the hydrothermal origin and, the Co indicates the hydrogenetic origin.  Co/Zn ratio is interpreted as the discrimination indicator between hydrothermal and hydrogenetic deposits that is stated Co/Zn 0.15 for hydrothermal and 2.5 for hydrogenetic deposits. According to Co+Ni-Ag+Cu+Mo+Pb+V+Zn diyagram by Nicholson (1992), samples plot in the hydrothermal area. 
The slow-forming hydrogenetic Fe-Mn deposits are characterized by a strong positive Ce anomaly. In the submarine hydrothermal deposits containing metal, Ce shows a negative anomaly and it is stated that it contains less REE than the hydrogenetic deposits. Elmalar manganese deposit is similar to submarine hydrothermal deposits with showing negative Ce anomaly and low total REE content. In the case of Tavas and Kilis manganese deposits, Ce gives a positive anomaly and resembles hydrogenetic deposits. However, Kilis did not show a strong positive Ce anomaly in the manganese sample, such as Tavas, and the total REE contents were very low compared to the other analyzed deposits and the known hydrogenetic manganese deposits in the world. Negative Ce anomaly was observed in Binkılıç, Dursunbey and Trabzon samples. The LREE / HREE ratio of the Elmalar deposits is 16.12 and the light elements are enriched. As mentioned in the Oksuz (2011), the light rare earth elements indicate the primary enrichment in the Mn oxidation process.
Elmalar manganese deposit is hydrothermal in origin as metal source intercalated with Upper Cretaceous radiolarites should be formed syngenetically and as stratiform layers. When the geochemical data of the deposits is considered, it is thought that it was also exposed to sea water after the formation. Formation of the deposit is due to the precipitation as submarine volcanism bearing Fe and Mn ions carried out by chemical sedimentary precipitation as a result of the exhalatation of fluids to the sea floor. Due to the difference in Eh-pH behavior, Mn ions remain relatively longer in solution and be able to move farther away than Fe ions and are concordantly deposited on (syngenetic) spilitic basalts simultaneously with radiolarites. Elmalar manganese mineralization is exhalation product caused by submarine volcanismi thus it can also be considered as a volcanogenic sedimentary deposit. The presence of many occurrences is known along the Bitlis-Zagros suture, especially in terms of spatial and temporal relationship with Cu and Fe mineralizations. Elmalar mineralization can be considered as examples in NW and Kilis mineralization in SE of this suture belt.