Geological, geochemical and microthermometric characteristics of the Hakkari region Zn-Pb deposits, SE Turkey
Graphical abstract
Trace element associations (As, Se, Hg, Tl, Mn and Sb), fluid inclusion (Th from 165 to 289 °C; salinity from 1 to 22% equiv. NaCl) and isotope data indicate that the Hakkari Zn-Pb province were formed as synsedimentary processes associated with feeder systems during the initiation of the Triassic rifting in as a vent-proximal SEDEX-type.
Introduction
The Tethyan Metallogenic Belt (TMB) stretches for over 12,000 km from Europe through Turkey to Pakistan, Tibet, China and Southeast Asia (Reynolds and Large, 2010, Richards, 2015) and hosts a wide diversity of metallic mineral deposits. In western part of TMB, the Turkish section contains three main Pb-Zn region that are temporally and spatially distinct (Yiğit, 2009, Hanilçi et al., 2019). The eastern Pontide Pb-Zn ± Cu province was related to Late Cretaceous arc magmatism, the western Anatolian Pb-Zn ± Cu ± Au ± Ag province was related to Oligocene to Miocene arc magmatism. The third province, in the Tauride-Anatolide Tectonic unit, contains carbonate-hosted Pb-Zn ± Ba ± F deposits (Fig. 1a).
Sediment-hosted Pb-Zn deposits are generally classified as “clastic-dominated (CD), sedimentary exhalative (SEDEX)” and “Mississippi Valley-type (MVT) deposits (Leach et al., 2010). The SEDEX deposits occur in the shale, sandstone, siltstone and/or carbonates of clastic sedimentary sequences, often with a distinct stratiform character. The tectonic settings of the SEDEX deposits are interpreted to be passive margin, back arc, continental rifts and sag basins (Goodfellow, 2004, Goodfellow and Lydon, 2007, Leach et al., 2010). In contrast, the MVT Pb-Zn deposits occur in passive margin platform carbonates (e.g. Leach and Sangster, 1993, Bradley and Leach, 2003).
Sediment-hosted Zn-Pb deposits of the Taurides-Anatolides tectonic unit (Şengör and Yılmaz, 1981) occur within passive margin carbonate rocks. Most of these deposits were identified as Mississippi Valley Type (MVT), e.g. the deposits in Hadım-Bozkır and Aladağ–Zamantı provinces, based on their geological setting, ore-wall rock relationships, formation temperature and the isotope geochemistry data (Alp, 1976, Hanilçi and Öztürk, 2005, Hanilçi and Öztürk, 2011). However, although carbonates occur in the Horzum region the Pb-Zn deposits are defined as carbonate replacement (CRD) type, because of the relatively high formation temperature (avg. 235 °C) and the presence of bornite, arsenopyrite and argentite in paragenesis (Hanilçi et al., 2019).
In the southeast corner of Turkey, between Hakkari and Çukurca, there are important Zn-Pb deposits within the passive margin carbonates of the Arabian Platform. The geological setting of these Zn-Pb deposits was determined by Hanilçi and Öztürk (2008) and the mineralogy of the non-sulfide ores by Santoro et al. (2013). In last decade, the region has seen extensive mining activity and 1.1 million tons of ore has been extracted by underground and open pit mining. This activity has facilitated detailed field observation, especially in the mineralized zones, and detailed geochemical analysis of the primary sulfides and their oxidation products. The aims of this study is to define the ore forming process, deposit type, and to propose a formation model for the Zn-Pb deposits of Hakkari region in relation to the evolution of the Tethyan Ocean in this region. The required information will come from ore textures, ore-host rock relationships, ore and isotope (S, Pb) geochemistry, chemistry and microthermometric measurements of fluid inclusions.
Section snippets
Geological setting
The geology of the Hakkari region consists of Palaeozoic and Mesozoic age carbonates and clastic rocks that were deposited on a passive margin on the southern edge of the Arabian microplate. The ophiolitic mélange of the Cretaceous, Yüksekova Complex (Perinçek, 1990) was obducted over these basement units during the Eocene to the Miocene (Fig. 1b). During this period the basement units were folded and thrusted producing the present day steep mountainous terrain. Sedimentary basement rocks
Zn-Pb deposits and their occurrence
The Hakkari region Zn-Pb deposits are found both as concordant (the Meskantepe, Karakaya, and Üzümcü), and discordant (Kurşuntepe and Akkaya) types. The concordant ore bodies are located in the northern part of the region and have a synsedimentary stratiform character but were subsequently subjected to strong orogenic deformation and are now folded. They occur within late Triassic limestone and limestone shale alternations and locally exhibit a reaction contact with the hanging wall limestone
Methods
The mineralogical composition of both oxide-carbonate and sulfide Zn-Pb ores was investigated by petrographic examination of polished sections and by XRD (X-Ray Diffraction). The XRD studies were performed in the Istanbul University-Cerrahpasa, Department of Geological Engineering, with a Rigaku D/Max-2200 model instrument using a Cu Kα tube with settings of 40 kV, 20 mA and 2 thetas. The minerals were identified using the database from the Jade 6.5 software. The geochemical analysis was
Ore mineralogy and petrography
The Zn-Pb deposits in the Hakkari province are primarily “non-sulfide” zinc deposits whose characteristics can be used to distinguish a number of sub-types (e.g., Heyl and Bozion, 1962, Large, 2001, Hitzman et al., 2003, Boni and Large, 2003). However, primary sulfide ore zones (Figs. 5 c, d, 7b) have been preserved from oxidation within the non-sulfide ore in some of the deposits (Meskantepe, Üzümcü, Kurşuntepe and partly in the Karakaya deposits). These sulfide ore zones are very important in
Ore geochemistry
The minor and trace element concentrations of non-sulfide (NSO) and sulfide ore (SO) samples from the Karakaya and Meskantepe deposits are summarized in Table 1. The low Mg content (<1%) of both ore types reflects that the dolomitization, common in MVT type deposits, did not occur. Wide ranges of Fe (from 4 to 32%), Zn (from 4 to 47%) and Pb (from 0.5 to 28%) in the NSO zones (Table 1) indicate the variability of oxidation conditions laterally and vertically though the ore zones during
Sulfur and lead isotopes
Sulfur isotope analysis was performed on 39 samples (19 sphalerite, 12 galena and 8 pyrite) from seven different Zn-Pb deposits/mineralization in the Hakkari province (Table 2). While most of the galena samples were collected from the oxide carbonate ore zone, the sphalerite and pyrite were collected from the primary sulfide ore lenses (Fig. 5c, d; 7e) that were preserved in the oxide-carbonate ore zones. δ34SCDT values are between −3.43‰ and 5.13‰ (avg. 0.99‰) for galena, −1.46‰ and 3.98‰
Fluid inclusion studies
Fluid inclusion studies were measured in suitable transparent minerals that occur with the primary sulfides. Measurements were undertaken in quartz from the Üzümcü and Meskantepe deposits (Fig. 13a–d), quartz, barite and calcite from the Karakaya deposit (Table 4; Fig. 13e, f) and honey coloured sphalerite (Fig. 14g) and quartz from the vein-type ore zone of the Kurşuntepe deposit.
Microthermometry was performed on primary (P) and pseudeosecondary (PS) fluid inclusions, which could be observed
Tectonic setting and ore formation
Zn-Pb mineralization in the Hakkari region is located in a 6 km thick sedimentary rock package as shown in Fig. 1b. These sediments were deposited on the passive continent margin of the southern edge of Gondwana during the early Palaeozoic to the late Mesozoic. No magmatic rocks are present in these sediments in the Hakkari region. The underlying rock units of the Palaeozoic are the Derik formation, which consist of a thick volcano-sedimentary unit >2 km thick. This formation can be observed
Conclusion
The Zn-Pb deposits in the Hakkari region were developed within the late Triassic shale intercalated carbonated rocks deposited on the passive continental margin of the Arabian plate. Three different types of mineralization are observed in the region, which are (i) synsedimentary, (ii) sub-seafloor replacement and (iii) the vein-type which occurs in the feeder zones. Synsedimentary and sub-seafloor replacement type deposits have 10’s of km of lateral continuity. The mineralization has been
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper
Acknowledgements
The authors thank to Fatih Turan (GÖK-FA Company-Turkey), Karakaya Mining Company (Turkey), Ölmez Mining Company (Turkey) for their sharing unpublished company reports and logistic supports during the field study, Çavuş Altunbulak (Geological Eng.) for the discussing the Üzümcü deposit data, and the anonymous reviewers, and the editors Franco Pirajno and İbrahim Uysal for their valuable suggestions that help to improve this paper.
This paper was supported by İÜ-BAP (YADOP-37096; BEK-03506) and
References (107)
- et al.
Phase relations and adiabats in boiling seafloor geothermal systems
Earth Planet. Sci. Lett.
(1985) Revised equation and table for determining the freezing point depression of H2O-NaCl solutions
Geochem. Cosmochem. Acta
(1993)- et al.
Fluid inclusions in hydrothermal ore deposits
- et al.
Trace and minor elements in sphalerite: a LA-ICPMS study
Geochim. Cosmochim. Acta
(2009) Sulfur-rich sediments
- et al.
Gypsiferous carbonates at Honaz Dağı (Denizli): first documentation of Triassic gypsum in western Turkey and its tectonic significance
J. Asian Earth Sci.
(2008) - et al.
Neoproterozoic continental arc volcanism at the northern edge of the Arabian Plate, SE Turkey
Precambr. Res.
(2015) - et al.
The isotopic abundance and content of sulphur in meteorites
Geochim. Cosmochim. Acta
(1966) - et al.
Products and distinguishing criteria of bacterial and thermochemical sulfate reduction
Appl. Geochem.
(1995) - et al.
Ore facies, mineral chemical and fluid inclusion characteristics of the Hossein-Abad and Western Haft-Savaran sediment-hosted Zn-Pb deposits, Arak Mining District, Iran
Ore Geol. Rev.
(2018)
Tectonic, magmatic, and metallogenic evolution of the Tethyan orogeny: from subduction to collision
Ore Geol. Rev.
Upper palaeozoic subduction/accretion processes in the closure of palaeotethys: evidence from the Chios Melange (E Greece), The Karaburun Melange (W Turkey) and the Teke Dere Unit (SW Turkey)
Sed. Geol.
The Hakkari nonsulfide Zn–Pb deposit in the context of other nonsulfide Zn–Pb deposits in the Tethyan Metallogenic Belt of Turkey
Ore Geol. Rev.
Tethyan evolution of Turkey: a plate tectonic approach
Tectonophysics
HokieFlincs_H2O-NaCl: a Microsoft Excel spreadsheet for interpreting microthermometric data from fluid inclusions based on the PVTX properties of H2O-NaCl
Comput. Geosci.
Temperature, density and buoyancy fluxes in Bblack smoker plumes, and the criterion for buoyancy reversal
Earth Planet Sci. Lett.
Fluid inclusions in hydrothermal ore deposits
Lithos
Çukurca-Köprülü-Yığınlı (Hakkari ili) alanının jeolojisi ve hidrokarbon olanakları
A Fluid Inclusion and Stable Isotope Study of the Tom Ba-Pb-Zn Deposit, Yukon Territory, Canada
Econ. Geol.
Emerald mineralization in Colombia: fluid chemistry and the role of brine mixing
Miner. Deposita
Constraints on the origins of fluids forming Irish Zn-Pb-Ba deposits: evidence from the composition of fluid inclusions
Econ. Geol.
Fluid mixing during ore deposition at the Tynagh base-meatl deposit, Ireland
Eur. J. Mineral.
Nonsulfide zinc mineralization in europe: an overview
Econ. Geol.
Sulfur and oxygen isotope compositions of Upper Triassic sulfates from northern Apennines (Italy): paleogeographic and hydrogeochemical implications
Geol. Acta
Role of lithospheric flexure and plate convergence in the genesis of some Appalachian zinc deposits
U.S. Geol. Surv. Bull.
Tectonic controls of Mississippi Valley-Type lead-zinc mineralization in orogenic forelands
Mineral. Deposita
Die Zink-Blei-vererzungen des Aladag-Giebietes/TÜRKEI mit betrachtungen zur palaokastentwicklung
Metal sources in mineral deposits and crustal rocks of ecuador (1°N - 4°S): a lead isotope synthesis
Econ. Geol.
The importance of oxidized brines for the formation of Australian Proterozoic stratiform sediment-hosted Pb-Zn (Sedex) deposits
Econ. Geol.
Magmatic evolution of Quaternary mafic magmas at Long Valley Caldera and the Devils Postpile, California: effects of crustal contamination on lithospheric mantle-derived melts
J. Geophys. Res.
Reconstraction of the Red Dog Zn-Pb-Ba orebody, Alaska: implications for the vent environment during the mineralizing event, Canada
J. Earth Sci.
Development of an oblique subduction zone tectonic evolution of the Tethys Suture zone in Southeast Turkey
Int. Geol. Rev.
Tracing ancient fluid flow pathways: a study of the lower carboniferous base metal Orefield in Ireland
The genesis of Irish-type Zn–Pb deposits: Characterisation and origin of the principal ore fluid
Bacteria were responsible for the magnitude of the world-class hydrothermal base metal sulfide orebody at Navan, Ireland
Econ. Geol.
Geochemistry, mineralogy, and geology of the Jason Pb-Zn deposits, Macmillan Pass, Yukon, Canada
Econ. Geol.
The sulfur cycle
Thermochemical sulfate reduction: a review
J. Therm. Anal.
Geology, genesis and exploration of SEDEX deposits, with emphasis on the Selwyn Basin, Canada. Sediment-hosted lead-zinc sulphide deposits - attributes and models of some major deposits In India, Australia and Canada
Gelology and genesis of stratiform sediment-hosted (SEDEX) zinc-lead-silver sulphide deposits
Sedimentary exhalative (SEDEX) deposits
The effect of salinity on the maximum thermal gradient of a hydrothermal system at hydrostatic pressure
Econ. Geol.
Mississippi valley type Zn-Pb deposits in the Aladağlar-Zamantı (Eastern Taurus) region: Ayraklı and Denizovası Zn-Pb deposits, Turkey
İstanbul Earth Sci. Rev.
Hakkari region Zn-Pb deposits: preliminary evidence for their geological features and formation
Geochemical/isotopic evolution of Pb––Zn deposits in the Central and Eastern Taurides, Turkey
Int. Geol. Rev.
Carbonate-hosted Pb-Zn deposits of Turkey
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