Mineralogy and geochemical behavior of trace elements of hydrothermal alteration types in the volcanogenic massive sulfide deposits, NE Turkey

Ore Geology Reviews 48 (2012) 197–224

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Mineralogy and geochemical behavior of trace elements of hydrothermal alteration types in the volcanogenic massive sulfide deposits, NE Turkey Muazzez Çelik Karakaya a,⁎, Necati Karakaya a, Şuayip Küpeli a, Fuat Yavuz b a b

Selçuk Universitesi Muh.-Mim. Fakültesi Jeoloji Mühendisliği Bölümü, Konya, 42079, Turkey İstanbul Teknik Universitesi Maden Fakültesi Jeoloji Mühendisliği Bölümü, Ayazağa İstanbul, 34469, Turkey

a r t i c l e

i n f o

Article history: Received 8 April 2010 Received in revised form 22 March 2012 Accepted 22 March 2012 Available online 30 March 2012 Keywords: Eastern Pontides Hydrothermal alteration geochemistry Massive sulfide deposits Trace elements Turkey

a b s t r a c t Volcanogenic massive sulfide (VMS) deposits of the Eastern Pontides, Turkey, are hosted by the Maastrichtian–Eocene dacite and rhyodacite series, accompanied by lesser andesite and basalts, as well as their pyroclastic equivalents, with tholeiitic to calc-alkaline affinity. The ore mineral assemblages are chalcopyrite, sphalerite, galena, chalcocite, covellite, bornite, and tetrahedrite. Potassic-, phyllitic- (sericitic), argillic- (kaolinitic and smectitic), silicic-, propylitic- and hematitic-alteration is commonly associated with these deposits. HFSE, LILE, TRTE and REE contents show strong variability in different alteration types resulting from interaction with acid or alkaline fluids. Sample groups showed chondrite-normalized enrichment of LREE relative to HREE and sub-parallel trends, except for the hematitic- and phyllitic-alteration types. MREE are strongly depleted in the zones of most intense silicification and kaolinization. Most sample groups have strongly- to slightly-negative Eu anomalies, ranging from 0.35 to 0.88 (mean); hematitic- (1.45) and propylitic-altered rocks (1.11) have slightly- to moderately-positive anomalies. The negative Eu anomalies indicate the low temperatures of fluids (b 200 °C). In contrast, the positive Eu anomalies result from hightemperature hydrothermal conditions (>200 °C). No Ce anomaly was observed, except for phyllitic alteration where a slight positive anomaly was noted. The chondrite-normalized trace and REE patterns of the altered rocks are similar to each other, suggesting that they were derived from a common felsic source. The alteration groups formed from acid, intermediate, and alkaline hydrothermal solutions. Some transition, base and precious metals and volatile elements were clearly enriched, especially in the hematitic-, silicic-, kaoliniticand phyllitic-altered samples. The other elements exhibit different behaviors in different sample groups. REE behavior is relatively immobile in the silicic-, hematitic-, kaolinitic- and partially in moderately- and propylitic-altered rocks, based on mass-balance calculations. LILE and HFSE appear mobile in the altered sample groups, except in the propylitic-altered rocks. TRTE behave as relatively immobile in most of samples, except in some of the silicic- and phyllitic-altered rocks, and especially in the hematitic-altered samples. HFSE, most of the transition (W, Mo, Cu, and Sb) and some other trace elements (Pb, As, Hg, Bi, Se and Tl), are enriched in the hematitic-altered samples and in the some silicic-altered samples. The highest As, Bi, Mo, Se and Hg concentrations in the hematite-altered samples can be used to distinguish other alteration types and may be a useful indicator in a prospect-scale base metal exploration. © 2012 Elsevier B.V. All rights reserved.

1. Introduction The Pontide Tectonic Unit constitutes a 1500 km-long segment of the Black Sea region of northern Turkey. The unit is located within the Alpine–Himalayan chain system that encompasses the Tethyan Metallogenic Belt, a major global ore province extending from the western Mediterranean through the Carpathians, Balkans, Pontides, and Lesser Caucasus towards the Hindu Kush (Gökçe and Bozkaya, 2003; Janković, 1997).

⁎ Corresponding author. Tel.: + 90 3322410555; fax: + 90 3322410555. E-mail address: [email protected] (M.Ç. Karakaya). 0169-1368/$ – see front matter © 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.oregeorev.2012.03.007

The Pontide Tectonic Unit can be subdivided into three segments: Western, Central, and Eastern Pontides (Ketin, 1966). The Eastern Pontides lies within a larger metal rich tectonic corridor that stretches from southern Georgia and northern Armenia to Bulgaria and Romania. The Pontides region is one of the most important metallogenic provinces of Turkey. In this contribution, we address the western part of the Eastern Pontides that extends along the coast of the eastern Black Sea, north of the Northern Anatolian Fault. Copper and Zn-rich volcanogenic massive sulfide (VMS) and veintype deposits are widespread in the eastern Black Sea region of Turkey, especially in the Giresun, Rize and Artvin areas (Fig. 1). At least 400 sulfide deposits of various types and sizes are known. They are dominantly Late Cretaceous in age with reserves between 0.1 and

198

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Fig. 1. Simplified regional geological and location map of the study area (after MTA 1:500.000 scaled map).

40 Mt and of varying grades and are hosted by felsic volcanic rocks (Figs. 1 and 2, Table 1). The VMS deposits of the region are essentially similar to Kuroko-type VMS deposits in a broad sense, i.e., geologic setting, ore mineral paragenesis, alteration, lack of metamorphism (Akçay and Moon, 2001; Çağatay, 1993; Çelik et al., 1999; Çiftçi and Hagni, 2005; Çiftci et al., 2004). Çiftçi and Hagni (2005) stated that all of the VMS deposits share common host rocks, and differences between ore-mineral contents of the deposits might be realized by localized convection cells that were enriched in certain metal ions. The mineralogical and chemical properties of different types of hyrothermal alteration associated with VMS deposits in various parts of the world have been investigated by many researchers (e.g. Çağatay, 1993; Cook et al., 1990; Dubé et al., 2007; Large et al., 2001; Paulick et al., 2001; Shikazono et al., 1998, 2008). Cook et al. (1990) investigated stratiform, stratabound pyritic Cu- (Zn) sulfide ores formed via volcanic-associated hydrothermal sedimentary exhalative formation. The core of alteration zone was abnormally enriched in K relative to the surrounding rocks. The ore, located within a single stratigraphic level was enveloped by a more typical chloritic alteration zone characterized by an increasing Fe/Fe + Mg ratio away from the deposits. Large et al. (2001) suggested that an alteration box plot could be used to characterize the different alteration trends related to VMS deposits and this would assist in distinguishing syngenetic VMS-related hydrothermal alteration from regional diagenetic alteration. Paulick et al. (2001) demonstrated Na depletion and elevated Mg, S, alteration index (AI = 100 × (MgO + K2O) / (MgO + K2O + Na2O + CaO)), carbonate–chlorite–pyrite index (CCPI = 100 × (MgO + FeO) / (MgO + FeO + Na2O + K2O)), as well as higher Mo, Bi, and As with increasing proximity to ore.

The pyritic, polymetallic stratabound ores of the eastern Pontides are economically significant for Cu, Zn, Pb, Ag and Au (Çağatay, 1993). Hydrothermal alteration of the volcanic rocks by post-volcanic, acidic solutions resulted in the formation of clay minerals in both the hangingand footwalls of the ore deposits (Çağatay, 1993; Çelik et al., 1999; Karakaya and Karakaya, 2001a, b; Karakaya et al., 2005, 2007, 2011). The parent rock (PR) associated with different types of ore deposits was exposed to intense potassic- (POA), phyllitic- (PA), argillic- (kaoliniteand smectite-dominant; AAK and AAS, respectively), silicic- (SA), propylitic- (PPA) and hematitic- alteration (HA) processes. REE and high-field strength elements (HFSE; Hf, Nb, Ta, Ti, Zr and P; Saunders et al., 1980) have traditionally been accepted as rather immobile elements and are thus proposed as suitable monitors of alteration chemistry. More recent studies, however, have shown that they can be mobilized by hydrothermal processes (Jiang et al., 2003; Karakaya, 2009; Küpeli, 2010; Salvi et al., 2000). Shikazono et al. (2008) reported the geochemical behavior of rare earth elements (REE) in hydrothermally altered rocks of the Kuroko mining area, Japan, and stated that REE represented a useful geochemical index for the exploration. In the present study, we report the chemical and mineralogical effects of hydrothermal alteration on the dacitic–andesitic volcanic rocks associated with massive sulfide deposits in northeastern Turkey that were crosscut by granitoid intrusions (Figs. 1 and 2). The study was made on the alteration halos of orebodies from well-characterized examples of massive-sulfide deposits throughout the region which had not been previously determined. Geochemical investigation of VMS deposits in the Black Sea region provides information on mass transfer and element mobility during hydrothermal alteration and

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Fig. 2. Detailed geologic map of the study area, except with Murgul Mine and Ordu, Bulancak area. Modified from Kahraman et al., 1984; Keskin et al., 1998; Köprübaşı, 1992.

provides an explanation of element behaviors in different types of alteration. Studies of this type can assist exploration for hidden VMS deposits. Petrographic and geochemical analyses of major, trace, REE, HFSE, transition elements (TRTE; e.g., Co, Cr, Cu, Ni, V, Sc), Zn (Jenner, 1996) and large lithophile elements (LILE; e.g., Ba, K, Rb, Sr, Th, U, Pb, La and Ce; Schilling, 1973) are presented in this study. These data assist us to do the following: (1) define mineralogical changes undergone by the fresh rock due to hydrothermal alteration; (2) study compositional variation between the altered and parent rock and to evaluate environmental conditions during precipitation of new minerals; and (3) explain element behavior and mass transfer during fluid/rock interaction. 2. Geologic setting The geologic framework of the study area has been described elsewhere (Çağatay, 1993; Şengör and Yılmaz, 1981 and references therein) and will be only briefly reviewed here. The area comprises an extensive volcano-sedimentary sequence with an approximate thickness of 3 km. This sequence was deposited in a magmatic arc basin during northward subduction of Paleotethys oceanic crust during the Upper Jurassic–Lower Cretaceous (Fig. 3), (Çağatay, 1993; Saner, 1981; Şengör and Yılmaz, 1981). The stratigraphy is composed

mainly of Upper Cretaceous and Tertiary volcanic rocks and intruding granitic batholiths (Figs. 1 and 2). The volcanics are divided into lower basic, lower acidic, upper basic and upper acidic series. The volcanic activity resulted from an extensional regime and associated rifting and deepening of the intra-arc basins during the Upper Cretaceous after cessation of extension-related arc volcanism in the Upper Jurassic–Lower Cretaceous (Görür, 1988). The lower basic series is bimodal in character and is dominantly composed of basaltic pillow lavas and subordinate felsic lavas of tholeiitic and calc-alkaline affinity (Akçay and Moon, 2001). These units are overlain by dacitic volcanics of the Lower acidic series, which are, in turn, unconformably covered by basic and acidic series of Upper Cretaceous to Tertiary age (Akçay and Moon, 2001). The dacitic volcanics belong to distinct eruption phases and have been divided into three subtypes by Akçay and Moon: the pyrite-bearing (footwall) dacite, biotitic dacite and purple (hanging wall) dacite. The footwall dacite encloses both VMS and vein type deposits, and can be observed through the eastern Black Sea. It is generally represented by tuffs and breccia associated with lavas, and is typically highly altered. Biotite-bearing dacite is not widespread and cuts both the footwall and hanging wall dacite. It contains euhedral quartz crystals associated with biotite, and displays moderate alteration. This type can be observed locally and sometimes covers the VMS deposits; the purple color at the surface is due to the alteration. The hanging wall dacite overlies the VMS

1, 2, 6, 1, 2, 6, 1, 5, 8, 1, 2, 5, 1, 3, 7 1, 2, 6 9 1,3 3 2 3, 6 3, 6 6 1, 4 6, 11

Ref. Mining

Abandoned Abandoned Not active Active Active Abandoned Abandoned Abandoned Abandoned Abandoned Abandoned Abandoned Abandoned Abandoned Abandoned Stringers with disseminations, minor massive ore Stringers with disseminations, minor massive ore Massive, veinlets, disseminations Massive, stockworks Massive, disseminations, stockworks Massive Massive disseminations, Brecciate, massive, disseminated, stockworks Disseminations, Massive, brecciate Disseminations, massive, stockworks Disseminations, massive, stockworks Massive, stockworks, disseminations, Massive Massive, disseminations

Morphology Size (m)

85 × 700 × 1000 800 × 250 × 125 – 200 × 600 30 × 600 150 × 80 × 40 120 × 20 1000 × 60 – – – – 300 × 80 × 130 450 × 75 – Argillic, phyllic, silicification, prophyllitic Argillic, phyllic, silicification, carbonitization Silicification, hematization, prophyllitic Argillic, silicification, prophyllitic Silicification, hematization, argillic, prophyllitic Argillic, prophyllitic Argillic, phyllic prophyllitic Silicification, hematization Argillic, silicification, Silicification, hematization, prophyllitic Silicification, hematization, argillic, potassic, prophyllitic Silicification, hematization, potassic, argillic, phyllic Argillic, silicification, potassic Argillic, silicification, potassic Argillic, silicification, hematization

Alteration Ag g/t

25 – 151–204 43 7–490 – 7 77 21 96 60 2 460 50 80 0.2 – 4.2–5 0.7 0.4–6.3 0.30 0.5 0.09–4.0 2.74 0.74 0.07 0.6 – – –

Au g/t Pb %

0.05 – – 0.3 0.01–3.6 – 0.05 0.7 0.1–1.3 0.02 1.0 b 0.01 8.4 4.4 0.01 0.1 – 2 7.54 3.31 0.46 4.32 2.8 0.01–0.6 2.0 0.7–2.5 0.01 8.9 18.6 0.1

Zn % Cu %

20 8 3.9 24 2.4 1.26 0.10 5.0 – 1.4 0.1 – 10 0.5 0.2 Murgul/Damar Murgul/Çatmakaya Cerattepe Çayeli Lahanos–Şahinyuva Kutlular Killik Kızılkaya Dikmen Ağalık Karılar Karaerik Harşit Harköy İsraildere–Siyezik

1.10 0.99 4.9 5.19 4.23 2.48 1.97 3.5 0.–1.3 0.6 0.5–1.1 0.03 1.6 7.4 2.69

Ton. Mt Location

Table 1 Metal and precious element contents and some features of the VMS deposits of the investigation area.

1: DPT (2001), 2: Çağatay (1993), 3: Jica (1998), 4: http://www.maden.org.tr/resimler/ekler/cf64379eb6f29a4_ek.pdf, 5: Akçay and Moon (2001), 6: Pejatovic (1979), 7: Çiftçi and Hagni (2005), 8: Moon et al. (2001), 9: Çiftçi et al. (2005), 10: Yiğit (2006), 11: Acar (1974).

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deposits, and shows slight to strong alteration owing to fluid–rock interaction (Fig. 4). These volcanic successions host numerous VMS deposits, including Murgul, Çayeli, Kutlular, Lahanos, Ağalık, Karaerik, Killik, Kızılkaya, Şahinyuva, Karılar, Harşit, Harköy, Siyezik, İsraildere and Dikmen, as well as other minor occurrences (Figs. 1, 2 and 4). The distribution of the deposits in the Eastern Pontides indicates that the magmatic arc was located in a position close to the present day Black Sea coast during the Maastrichtian (Okay and Şahintürk, 1997). Massive or disseminated pyritic, polymetallic stratabound ore lenses associated with discordant stockwork feeder zones occur in different sites of the Dacitic series. Sulfide minerals in the deposits are mainly pyrite, chalcopyrite, sphalerite, galena, tetrahedrite–tennantite, bornite, with minor to trace covellite, marcasite, chalcocite and digenite. The orebodies are generally covered by pumiceous tuffs and dacitic tuff breccias intercalated with basalts and intruded by diabase sills and dikes (Çağatay, 1993, and references therein). Extrusion and intrusion of magma and localization of VMS mineralization were controlled mainly by the NE–SW trending block-fault systems, whereby the dacitic series has been intensely fractured and brecciated during premineralization Alpine orogenic events. These fault zones provide permeable pathways for the flow of magma and also hydrothermal fluids. The VMS deposits in the eastern Pontides consist of an upper black ore zone with galena + sphalerite + chalcopyrite + bornite which is often overlain by either barite or gypsum. Beneath the black ore zone is a yellow ore zone consisting of pyrite + chalcopyrite + sphalerite, which in turn overlies a massive pyritic layer. The massive stratabound bodies are underlain by stringer ore in highly altered felsic volcanic rocks (Çiftçi and Hagni, 2005). The alteration zones extend laterally between 350 m and 2 km from each orebody. Silicic- and hematitic-alteration zones, either interfingered with one another, or as distinct levels, are situated in the uppermost part of the deposits. The permeable vuggy-silica zone may be developed by solutions which penetrated deep into the orebodies. Illite occurrences generally occur in the footwalls of the VMS deposits, whereas smectite and kaolinite occur around or within the hanging wall. Propylitic alteration is observed immediately adjacent to the orebodies and is typified by a greenish to greenishblue coloration. Potassic alteration occurs in and around volcanic rocks intruded by granitoid batholiths and is mainly observed on the outer margins of the ore. Argillic alteration is typified by kaolinitic and smectitic alteration. Occurrences of kaolinite show an irregular areal distribution and may occur either close to, or in the outer parts of mineralization. Smectite deposition generally occurred further away from mineralization and may locally form significant concentrations as bentonite deposits. Post-mineralization tectonic uplift along pre-existing fault zones resulted in exposure of the orebearing dacitic series associated with various alteration zones under the younger volcanic cover rock series. Subsequent supergene alteration resulted in the formation of leach caps above the primary VMS orebodies. This is marked by formation of secondary minerals such as goethite, hematite limonite, malachite, azurite and gypsum/ anhydrite, locally also with accessory clay minerals and sulfates (barite, alunite and jarosite). In terms of host lithology, mineralogical composition, texture and their relatively high Au content (0–17 g/t), the eastern Black Sea VMS deposits are comparable with the Kuroko deposits of Japan (Çağatay, 1993; Çağatay and Boyle, 1977; Lambert and Sato, 1974). The Au grade is typically greater than 4 g/t in the eastern Black Sea VMS deposits, even if grade varies from deposit to deposit. Gold is notably enriched in black ores, especially in some deposits such as Cerattepe (Artvin) (Table 1). Here, the Au rich zones occur as an oxidized pod and as a siliceous zone NW of the deposit, and contain about 5 g/t Au, suggesting epithermal overprinting (Çiftehan and O'Brien, 1998).

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Fig. 3. Schematic illustration of tectonic setting of the Eastern Pontides during the Senonian to Eocene (Saner, 1981).

3. Methodology 3.1. Sampling and analysis Location, occurrence name, host lithology and types of alteration of samples are given in Table 2. Parent rock (bulk rock and clay fraction), weakly-moderately altered parent rock and other types of altered rock samples, approximately 0.5 to 1 kg in size, were collected from 95 localities near ore deposits located in the Ünye, Fatsa, Ordu, Giresun, Espiye, Tirebolu and Murgul districts (Figs. 1 and 2 and Table 2). Samples were analyzed by X-ray diffraction (XRD) and scanning electron microscopy analysis (SEM) with an energy-dispersive system (EDS). Analysis for major and minor elements and REE was done by inductively-coupled (ICP) plasma emission and ICP-mass spectroscopy (ICPMS) methods (ACME Laboratories, Canada). Mineralogical analysis of bulk-rock and clay fraction (b2 μm) samples was determined using a Rigaku D/Max 2200 PC diffractometer with CuKα radiation (λ = 1.542 Å). XRD powder diffraction determinations were performed at a scan speed of 2°/min with CuKα radiation from 2° to 70°/2θ. Glass slides with shallow cavities were filled with powders from randomly-oriented specimens. Clay minerals were identified from three XRD patterns of the clay-sized (b2 μm) fractions, each air-dried at 25 °C, ethylene-glycolated, heated at 490 °C for 4 h and extracted by the standard sedimentation technique in distilled water. Oriented preparations of the clay fractions were obtained by vacuum filtration of the clay suspension and transferred to glass plates. The size and form of submicroscopic clay minerals and their interrelations with other minerals were determined using a JSM 6400 SEM equipped with a Leo 1430 VT EDS system, operated at 20 kV.

Total abundances of the major oxides and minor elements were reported on a 0.1 g sample analyzed by ICP-emission spectrometry following a lithium metaborate/tetraborate fusion and dilute nitric acid digestion. Loss on ignition (LOI) was determined by measuring the weight difference after ignition at 1000 °C. Total carbon and sulfur analysis was performed by LECO. Rare earth and refractory elements were determined by ICPMS following a lithium metaborate/ tetraborate fusion and dilute nitric acid digestion of a 0.1 g sample. In addition, a separate 0.5 g split was digested in Aqua Regia and analyzed by ICPMS for precious and base metals. Detection limits for all major oxides were 0.01 wt.%, except Fe2O3 and LOI, which were 0.04 and 0.1 wt.%, respectively. Detection limits for trace/REE elements were: Cs, Hf, Mo, Nb, Ni, Pb, Rb, Sb, Ta, U, Zr, La and Ce, 0.1 ppm; Co and Th, 0.2 ppm; Ga, Sr and W, 0.5 ppm; As, Ba, Be, Sn and Zn, 1.0 ppm; 8.0 ppm; Tb, Tm and Lu, 0.01 ppm; Pr, Eu and Ho, 0.02 ppm; Er, 0.03; Sm, Gd, Dy and Yb, 0.05; and Nd, 0.3 ppm.

3.2. Mass-change calculations Variations in the chemical composition of hydrothermally altered rocks with respect to their equivalent fresh rock (i.e., precursor rock or unaltered host rock) can be represented using the immobile element technique reported by MacLean and Kranidiotis (1987) and MacLean (1990). Some or all of the element groups such as Al, Ti, Zr, Hf, Th, Ga, Cr, Y, and REE are thought to be relatively immobile in certain alteration systems (e.g., Karakaya, 2009; Küpeli, 2010; MacLean and Kranidiotis, 1987; Rollinson, 1993). The immobile elements show strongly positive correlation coefficients with each other in both altered and fresh rocks (MacLean, 1990).

Fig. 4. (A) Schematic illustration of geologic setting and hydrothermal alteration of Lahanos mine surrounding area associated with volcanogenic massive sulfide deposit. (B) Different types of dacites around the massive sulfide deposits in the Black Sea region and names for them. Modified from Akçay and Moon, 2001.

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Table 2 Location, occurrence name, host lithologies and types of alteration of samples. Sample number

Location

Alteration type

Host lithology

Occurrence name/location

K-1 K-2 K-3 K-5 K-5 K-6 K-7 K-8 K-9 K-10 K-11 K-12 K-13 K-14 K-15 K-16 K-17 K-18 K-19 K-20 K-21 K-22 K-23 K-24 K-25 K-26 K-27 K-28 K-29 K-30 K-31 K-32 K-33 K-34 K-35 K-36 K-37 K-38 K-39 K-40 K-41 K-42 K-43 K-44 K-45 K-46 K-47 K-48 K-49 K-50 K-51 K-52 K-53 K-54 K-55 K-56 K-57 K-58 K-59 K-60 K-61 K-62 K-63 K-64 K-65 K-66 K-67 K-68 K-69 K-70 K-71 K-72 K-73 K-74 K-75

73730E/22858N 81908E/26614N 74674E/28301N 80643E/22674N 88988E/31606N 73127E/32865N 72780E/23863N 73158E/23770N 74941E/29551N 74788E/29960N 80643E/22674N 88988E/31606N 91380E/30413N 80754E/19698N 80752E/25042N 51123E/52027N 74789E/29955N 746024E/3017N 87531E/38215N 87730E/38013N 87233E/36401N 89205E/37384N 88621E/37381N 50392E/41317N 76149E/28079N 76210E/27292N 76210E/27292N 73892E/21630N 73855E/21056N 91474E/32985N 73925E/21318N 76210E/28292N 76210E/28292N 74593E/29642N 80511E/29955N 74779E/22289N 75512E/18510N 77094E/17501N 74941E/29351N 74960E/29254N 77098E/16203N 74788E/29955N 74790E/29957N 80510E/22288N 74674E/28301N 75235E/21865NN 90804E/30413N Bulancak 87299E/37142N 79860E/20238NN Murgul Murgul Ordu Ordu Ordu Ordu 74096E/23422N 74956E/29520N 74951E/29524N 15934E/67971N 15934E/67971N 16200E/70209N 16200E/70209N 65766E/28345N 66542E/25279N 67740E/27120N 64669E/51360N 64702E/48728N 49353E/50680N 50528E/52368N 50024E/52077N 51174E/52576N 50429E/52272N 50429E/52272N 50413E/50094N

Parent rock Parent rock Parent rock Parent rock Parent rock Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Moderate alteration Potassic Potassic Potassic Potassic Potassic Potassic Potassic Potassic Potassic Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Silicification Hematitic Hematitic Hematitic Hematitic Hematitic Hematitic Hematitic Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Phylitic/illite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite

Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Biotite bearing dacite Biotite bearing dacite Dacite–andesite Dacite–andesite Dacite, rhyodacite Dacite–andesite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, andesite Dacite, andesite Biotitic Dacite Biotitic Dacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Quartz bearing dacite Dacite, rhyodacite Dacite, rhyodacite Dacitic–andesitic volcanites Dacitic, andesitic volcanites Dacitic, andesitic volcanites Dacitic, andesitic volcanites Quartz bearing dacite Quartz bearing dacite Quartz bearing dacite Dacite, rhyodacite Biotite bearing dacite Dacitic, andesitic volcanites Dacitic, andesitic volcanites Dacitic, andesitic volcanites Dacitic, andesitic volcanites Dacite, rhyodacite Dacitic, andesitic volcanites Dacitic, andesitic volcanites Dacite, rhyodacite Dacitic, andesitic volcanites Biotite bearing dacite Dacite–andesite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Biotite bearing dacite Dacite–andesite Dacite–andesite Dacite–andesite Dacite–andesite Dacite–andesite Dacite–andesite Mudstone–tuff Mudstone–tuff Mudstone–tuff Dacitic tuff Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite

Dikmen mine Ağalık mine Karılar mine Dikmen mine İsraildere-Siyezik mine Espiye town Şahinyuva mine Şahinyuva mine Karaerik–Karılar mine Karaerik–Karılar mine Dikmen mine İsraildere mine İsraildere mine Dikmen mine Ağalık–Dikmen mine Göbü Village Karaerik–Karılar mine Karaerik–Karılar mine Harşit mine Harşit mine Harşit–Harköy mine Harşit minemine Harşit mine Ünye town Ağalık mine Ağalık mine Ağalık mine Şahinyuva-mine Ağalık mine Harköy–Siyezik mine Şahinyuva-mine Karılar–Ağalık mine Karılar–Ağalık mine Karaerik–Karılar mine Karaerik mine Şahinyuva-mine Kızılkaya mine Kızılkaya mine Karaerik–Karılar mine Karaerik–Karılar mine Kızılkaya mine Karaerik–Karılar mine Karaerik–Karılar mine Dikmen mine Karılar–Ağalık mine Lahanos mine İsraildere mine Eriklik valley Harşit mine Dikmen mine Murgul-mine Murgul-mine Ordu-Sayaca village Ordu-Sayaca village Ordu-Sayaca village Ordu-Sayaca village Şahinyuva mine Karaerik–Karılar mine Karaerik–Karılar mine Murgul mine Murgul mine Murgul mine Murgul mine Ordu-Ulubey town Ordu-Ulubey town Ordu-Ulubey town Ordu-Kavaklar village Ordu-Kavaklar village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

203

Table 2 (continued) Sample number

Location

Alteration type

Host lithology

Occurrence name/location

K-76 K-77 K-78 K-79 K-80 K-81 K-82 K-83 K-84 K-85 K-86 K-87 K-88 K-89 K-90 K-91 K-92 K-93 K-94 K-95

50038E/51536N 50038E/51536N 49315E/50741N 49474E/51094N 49819E/51396N 50428E/52278N 48896E/52499N 78504E/34106N 72416E/27561N Bulancak 73418E/19508N 89256E/36815N 87099E/39142N Bulancak 73785E/20939N Bulancak 74070E/30262N 74765E/18845N 81882E/26720N 76843E/23021N

Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/smectite Argillic/kaolinization Argillic/kaolinization Argillic/kaolinization Argillic/kaolinization Argillic/kaolinization Argillic/kaolinization Argillic/kaolinization Propillitic alteration Propillitic alteration Propillitic alteration Propillitic alteration

Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, andesite Dacite, rhyodacite Dacite, rhyodacite Dacite, andesite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite, rhyodacite Dacite–andesite Dacite, rhyodacite Dacite, rhyodacite

Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Ordu-Göbü village Espiye town Karılar mine Bulancak–Dikmen hill Killik mine Harşit mine Harşit mine Bulancak–Dikmen hill Şahinyuva–Lahanos mine Bulancak–Dikmen hill Karaerik–Karılar mine Killik–Kızılkaya mine Ağalık mine Şahinyuva–Lahanos mine

In this study, binary correlation plots were used as a critical test for immobility of elements, and the correlation coefficients were also used as an indicator of mobility as indicated by Klammer (1997). TiO2 and Hf display a linear relationship when plotted versus one another and demonstrate the highest positive correlation coefficient (r = 0.72) in altered and their fresh rock equivalents in dacitic volcanics, with a straight line of regression passing through the origin (Fig. 5). The composition of the fresh rock was plotted on the same inclination because the ratio of these elements to each other in ore samples is very similar to that of the fresh rock, as indicated by Maclean (1988) and Maclean and Kranidiotis (1987). Thus, TiO2 was chosen as an immobile element for a single precursor system and mass changes were calculated according to Eq. (1), following MacLean (1990). All samples have been grouped according to their locations and degrees of alteration (Table 3). The parent material used in the calculations is the anhydrous parent rock. C e ¼ ½ðEa =IMa Þ  IMp −Ep

ð1Þ

where Ce is the computed element wt.%, Ea and Ep are the concentrations of the computed element in the altered and parent rock, respectively, and IMa and IMp are the concentrations of immobile elements in the altered and parent rocks, respectively. Mass gains and losses of components are equivalent to weight percent changes if the precursor mass is taken as 100 g.

The equation can be written for Al2O3 for all samples: Al2 O3 ¼

Al2 O3 altered rock  TiO2 fresh rock−Al2 O3 ðfresh rockÞ: TiO2 altered rock

ð2Þ

Using Eqs. (1) and (2), loss and/or gains of all major, trace and REE were computed. The average chemical composition of the five representative parent rock (PR) samples used in the mass calculation was that of the dacitic rocks (Table 3). 4. Results Major, trace and REE compositions of the investigated samples were analyzed; results are shown in Table 3. The mass changes in altered rocks to their fresh rock counterparts are presented numerically in Table 4 and graphically in Fig. 6. 4.1. Mineralogy and petrography of the unaltered rocks The phenocryst assemblages of the dacite and rhyodacite consist of small medium-sized (0.5–2 mm) quartz, zoned and twinned plagioclase feldspar, and locally sanidine, hornblende, biotite, sparse clinopyroxene and opaque minerals embedded in a fine-grained, glassy-microcrystalline groundmass. The groundmass comprises fine grains of plagioclase, amphibole, mica and opaque minerals. The predominant textures of the parent rock samples are microlitic

Fig. 5. Binary diagrams of average trace element concentrations (ppm) against mean TiO2 contents (wt.%) of the investigated sample groups from the Black Sea region, data from Table 2.

204

Table 3 Major (wt.%), REE elements (ppm) and chondrite-normalized ratios and some alteration indexes of samples. Sample

Moderately-altered rocks

K-2

K-3

K-4

K-5

K-6

K-7

K-8

K-9

K-10

K-11

K-12

64.80 15.03 5.1 2.75 1.17 4.4 3.28 0.58 0.12 0.09 0.013 15.00 2.40 99.77 623.0 12.30 2.20 16.40 4.50 11.00 118.60 4.00 147.40 0.70 10.70 3.50 97.00 2.10 1.20 23.10 15.90 67.00 20.00 8.60 0.10 0.30 0.20 b mdl b mdl 0.01 0.20 b mdl 159.4 23.4 30.6 62.6 7.06 26.4 4.65 0.99 4.26 0.7 3.84 0.8 2.21 0.36 2.21 0.34

72.12 13.18 2.79 1.50 1.60 3.43 2.34 0.30 0.05 0.05 bmdl 7.00 2.50 99.87 266.3 3.40 0.60 14.20 3.90 5.60 32.30 1.00 134.10 0.50 4.60 1.60 23.00 0.40 0.80 2.20 3.60 46.00 1.30 2.40 bmdl bmdl bmdl bmdl 1.00 bmdl bmdl bmdl 126.2 28.9 15.4 30.4 3.43 14.1 3.30 0.95 3.27 0.68 4.14 1.01 3.09 0.49 3.23 0.51

75.56 12.47 2.29 0.13 1.90 3.41 1.51 0.39 0.04 0.01 b mdl 5.00 2.10 99.81 365.7 0.80 1.50 12.30 3.20 5.00 31.30 1.00 162.70 4.00 3.90 0.40 17.00 0.90 1.00 25.90 188.20 18.00 1.00 15.90 b mdl 0.70 0.10 b mdl 0.90 b mdl 0.40 b mdl 105.6 21.7 14.3 28 3.21 13.6 3.10 1.00 3.05 0.59 3.35 0.72 2.19 0.35 2.30 0.35

78.00 12.66 0.72 0.78 0.56 2.78 2.05 0.21 0.04 0.03 b mdl 5.00 2.00 99.85 86.0 1.60 0.50 13.40 3.20 4.60 55.70 0.00 50.00 0.30 3.70 1.40 22.00 0.70 0.20 337.50 7.10 102.00 0.80 134.70 0.30 6.80 b mdl 0.40 3.80 0.01 b mdl b mdl 114.3 17.3 11.0 23.1 2.69 11.1 2.13 0.45 2.07 0.39 2.56 0.59 1.83 0.33 2.28 0.39

75.75 11.88 3.32 0.19 2.13 2.94 2.46 0.19 0.04 0.05 b mdl 5.00 0.90 99.86 496.7 3.00 0.80 12.30 2.90 3.80 53.90 1.00 119.50 0.30 7.80 2.00 17.00 1.30 1.40 6.00 5.70 26.00 7.30 3.30 0.10 0.20 0.10 b mdl 1.20 b mdl b mdl b mdl 97.1 22.1 16.2 32.6 3.38 13.0 2.80 0.58 2.82 0.48 3.15 0.65 2.10 0.35 2.28 0.37

61.32 13.82 4.76 3.33 2.27 1.05 3.07 0.54 0.12 0.1 0.02 15.00 9.40 99.77 554.0 11.80 2.50 15.00 4.50 10.60 101.60 3.00 88.20 0.80 10.50 2.40 93.00 2.30 2.50 26.30 6.60 65.00 18.30 b mdl 0.10 b mdl b mdl b mdl b mdl 0.02 0.10 b mdl 150.6 21.1 26.9 58.0 6.52 24.5 4.30 0.94 3.97 0.67 3.47 0.74 2.02 0.32 2.04 0.31

62.37 14.4 4.74 2.34 2.41 2.18 3.04 0.55 0.11 0.08 0.02 15.00 7.50 99.77 689.0 11.40 2.90 16.10 5.30 10.70 108.60 3.00 81.20 0.80 10.70 3.30 93.00 2.00 0.80 22.30 5.40 61.00 17.20 2.40 b mdl 0.20 0.20 b mdl b mdl b mdl b mdl b mdl 164.9 21.3 29.5 61.0 6.93 26.1 4.49 0.97 3.90 0.67 3.73 0.75 2.00 0.34 2.16 0.31

60.18 13.68 5.13 2.94 3.48 0.56 3.53 0.52 0.12 0.10 0.01 14.00 9.50 99.79 534.0 11.30 7.40 15.20 3.70 9.00 115.60 3.00 80.00 0.70 11.30 2.90 92.00 2.20 1.00 21.30 10.40 68.00 15.00 b mdl b mdl b mdl b mdl b mdl b mdl b mdl 0.20 b mdl 133.1 20.8 25.8 53.9 6.07 22.0 4.18 0.90 3.80 0.64 3.47 0.70 1.93 0.33 2.05 0.31

75.31 15.41 0.49 0.46 0.03 0.14 4.15 0.55 0.03 bmdl bmdl 12.00 3.00 99.61 2740.0 0.70 bmdl 14.40 5.70 9.20 50.80 1.00 13.40 0.60 5.60 4.00 31.00 1.30 1.20 0.40 0.80 bmdl bmdl 6.70 bmdl bmdl 0.80 bmdl 6.50 0.03 0.30 1.00 205.5 29.2 33.4 76.7 9.52 38.2 6.91 0.24 5.31 0.84 4.89 0.98 3.07 0.5 3.34 0.52

70.55 12.39 1.76 0.43 2.15 1.56 4.67 0.39 0.1 0.02 b mdl 7.00 5.70 99.76 270.0 8.00 1.10 12.20 3.30 6.10 40.70 1.00 196.50 0.30 3.60 0.90 10.00 0.90 b mdl 669.60 11.00 85.00 1.10 b mdl 0.30 b mdl b mdl b mdl 5.40 0.03 b mdl 0.70 122.4 64.3 15.5 33.2 4.45 19.3 4.86 1.47 6.18 1.24 8.85 1.96 6.02 1.01 6.15 0.94

78.00 12.66 0.72 0.78 0.56 2.78 2.05 0.21 0.04 0.03 b mdl 5.00 2.00 99.85 86.0 1.60 0.50 13.40 3.20 4.60 55.70 b mdl 50.00 0.30 3.70 1.40 22.00 0.70 0.20 337.50 7.10 102.00 0.80 134.70 0.30 6.80 b mdl 0.40 3.80 0.01 b mdl b mdl 114.3 17.3 11.0 23.1 2.69 11.1 2.13 0.45 2.07 0.39 2.56 0.59 1.83 0.33 2.28 0.39

73.95 12.67 1.40 0.32 3.18 2.96 3.43 0.18 0.05 0.03 b mdl 7.00 1.70 99.90 355.0 1.00 1.00 11.50 3.10 3.40 69.30 1.00 107.40 0.30 6.80 2.00 18.00 1.20 0.30 5.60 19.50 17.00 0.60 2.80 b mdl 0.10 0.10 b mdl 20.00 b mdl b mdl b mdl 100.3 16.8 13.6 27.6 3.00 11.3 2.26 0.60 2.23 0.42 2.76 0.62 2.08 0.31 2.30 0.38

K-13 73.75 9.61 7.39 0.25 0.06 0.07 2.59 0.12 0.03 bmdl bmdl 4.00 5.90 99.81 770.0 1.30 0.10 9.50 6.30 2.90 31.80 4.00 13.60 0.30 3.10 1.50 9.00 0.90 1.10 93.40 2.40 19.00 1.10 38.90 0.20 13.00 1.60 0.50 18.50 0.07 bmdl 0.90 241.2 17.7 10.8 25.6 3.02 11.9 2.66 0.63 2.28 0.43 3.00 0.64 2.03 0.34 2.31 0.37

K-14

K-15

67.43 12.57 3.34 1.58 2.14 2.75 1.97 0.36 0.08 0.04 b mdl 9.00 6.60 99.84 187.6 4.40 1.60 13.10 3.20 4.90 41.10 1.00 136.20 0.40 3.20 0.80 38.00 0.50 0.50 5.70 7.50 45.00 3.50 2.30 b mdl 0.10 b mdl b mdl 1.70 b mdl b mdl 0.50 111.2 22.7 13.4 26.3 3.03 12.8 2.80 0.78 2.91 0.53 3.17 0.74 2.33 0.37 2.58 0.40

73.16 11.74 0.91 0.22 0.42 3.39 3.84 0.08 b mdl 0.06 0.01 0.00 6.10 99.93 12.0 9.80 5.00 13.70 4.50 53.70 220.60 3.00 16.20 4.70 27.00 9.10 b mdl 61.70 1.40 0.90 1.60 5.00 1.10 0.60 b mdl b mdl b mdl b mdl 0.90 0.01 b mdl b mdl 111.2 25.6 37.7 68.6 6.68 20.6 3.55 0.1 3.09 0.61 3.71 0.83 2.68 0.48 3.28 0.52

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc LOI Sum Ba Co Cs Ga Hf Nb Rb Sn Sr Ta Th U V W Mo Cu Pb Zn Ni As Cd Sb Bi Ag Au Hg Tl Se Zr Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Parent rocks K-1

REE HREE MRE LRE TRTE HFSE LILE Eu* Ce* La/Yb La/Sm Gd/Yb CIA CIW K.I. AI CCPI

147.02 5.12 15.24 126.66 323.35 4176.5 28,182 0.73 1.03 9.33 4.14 1.37 54.34 61.61 28.28 51.98 50.55

84 7.32 13.35 63.33 82.90 2152.9 19,885 0.94 1.01 3.21 2.94 0.72 54.58 60.64 26.38 43.29 42.64

76.11 5.19 11.81 59.11 67.70 2630.4 13,304 1.06 0.99 4.19 2.90 0.94 54.04 57.90 21.73 23.60 32.97

60.91 4.83 8.19 47.89 468.90 1555.9 17,235 0.70 1.02 3.25 3.25 0.64 62.13 69.36 33.23 45.87 23.70

80.76 5.10 10.48 65.18 64.30 1417.7 21,126 0.67 1.06 4.79 3.64 0.88 51.30 57.70 31.87 34.33 39.39

134.7 4.69 14.09 115.92 332.03 3927.6 26,280 0.74 1.05 8.89 3.94 1.38 67.09 80.00 31.58 65.84 66.26

142.85 4.81 14.51 123.53 336.21 3959.1 26,169 0.76 1.03 9.21 4.13 1.28 57.91 66.75 30.49 53.96 57.56

126.08 4.62 13.69 107.77 303.70 3787.7 30,093 0.74 1.04 8.48 3.88 1.31 70.72 88.13 33.59 61.56 66.37

184.42 7.43 19.17 157.82 44.10 3649.2 37,301 0.13 1.04 6.74 3.04 1.13 76.61 98.18 86.82 96.44 18.13

111.13 14.12 24.56 72.45 780.70 2906.6 39,310 0.88 0.96 1.70 2.01 0.71 54.88 70.71 53.01 57.89 26.01

Potassic alteration Sample

69.47 15.87 0.36 0.07 0.20 2.21 10.39 0.12 b mdl b mdl 0.003 b mdl 1.20 99.9 24.0 11.30 0.60 16.40 5.10 69.20 173.9 4.00 18.3 5.60 27.5 3.00 0.00 82.9 1.40 0.70 7.50 3.0 0.70 0.90 b mdl b mdl 0.50 b mdl 0.70 b mdl b mdl b mdl

K-17 71.33 12.07 1.65 0.52 1.67 1.07 5.75 0.38 0.15 0.01 bmdl 11.00 5.00 99.6 259.0 12.40 1.10 15.30 3.30 6.00 53.9 1.00 164.6 0.50 3.50 1.30 10.00 68.8 0.10 1328 15.10 100.0 0.10 9.30 0.30 bmdl 0.10 0.10 bmdl 0.01 0.20 bmdl

K-18 77.28 11.47 0.82 0.06 0.23 2.90 5.24 0.09 0.02 b mdl 0.007 b mdl 1.80 99.9 24.0 18.80 2.20 12.70 4.20 33.30 161.8 2.00 18.1 3.40 20.8 1.90 0.00 120.3 1.40 0.70 7.50 3.00 0.70 0.90 b mdl b mdl 0.50 b mdl 0.70 b mdl b mdl b mdl

K-19 67.21 16.04 1.70 0.29 0.21 0.30 10.96 0.17 0.02 b mdl b mdl 3.00 2.90 99.9 650.0 1.00 2.60 12.20 3.50 10.70 194.0 2.00 37.7 1.00 31.1 3.60 22.00 9.6 b mdl 0.10 7.50 10.00 0.90 1.70 b mdl b mdl 0.20 b mdl b mdl b mdl b mdl b mdl

K-20 72.52 13.38 1.77 0.23 0.17 1.44 8.42 0.20 0.07 0.09 0.009 4.00 1.50 99.8 1124 1.30 2.70 12.00 4.50 11.70 175.9 2.00 35.8 1.00 27.6 4.50 17.00 3.50 1.20 1.20 15.40 32.00 2.50 11.00 bmdl 0.30 0.20 bmdl bmdl bmdl bmdl bmdl

K-21 70.17 14.41 1.69 0.25 0.11 1.00 9.38 0.21 0.04 0.04 0.003 4.00 2.50 99.8 813.0 0.90 3.30 11.80 4.30 12.70 185.9 2.00 18.7 1.00 27.8 3.00 21.00 3.40 0.60 0.90 11.30 28.00 1.60 7.10 b mdl 0.40 0.20 b mdl b mdl b mdl 0.10 b mdl

69.46 5.07 8.89 55.5 49.20 1404.4 29,050 0.87 1.04 3.99 3.79 0.69 48.50 56.54 34.68 37.92 21.21

66.01 5.05 9.64 51.32 141.48 1101.0 22,335 0.83 1.08 3.15 2.55 0.70 76.48 97.66 87.21 95.62 74.17

72.14 5.68 10.93 55.53 105.60 2627.1 16,746 0.89 0.99 3.50 3.01 0.80 54.83 59.90 23.34 42.06 67.31

152.43 6.96 11.89 133.58 51.01 653.7 32,209 0.10 1.04 7.75 6.68 0.67 54.67 64.93 48.79 51.59 51.04

Silicic alteration K-22 64.73 16.22 1.29 1.39 1.79 2.29 5.63 0.27 0.09 0.15 0.004 5.00 5.80 99.7 1692 1.10 0.90 13.90 6.10 11.90 79.2 2.00 161.8 1.20 30.8 2.70 11.00 2.10 0.10 2.80 9.40 21.00 1.00 1.10 b mdl b mdl 0.20 b mdl b mdl b mdl b mdl b mdl

K-23 72.41 14.13 1.92 0.32 0.82 2.49 5.91 0.23 0.08 0.05 0.006 3.00 1.40 99.8 1232 1.30 1.70 12.10 5.20 11.20 164.1 2.00 75.2 1.00 25.9 3.40 19.00 2.60 0.90 1.10 4.00 29.00 2.70 13.10 b mdl 0.40 0.20 b mdl b mdl b mdl b mdl b mdl

K-24 59.56 20.72 3.51 1.55 0.02 0.15 5.88 0.74 0.13 0.01 0.004 18.00 6.80 99.7 5549 0.50 2.60 26.10 5.90 10.50 132.0 2.00 536.1 0.80 7.50 2.60 62.00 3.40 3.70 6.10 111.2 8.00 0.50 133.9 b mdl 1.40 0.50 1.30 52.70 0.19 0.80 b mdl

K-25 89.74 2.13 0.13 0.05 0.21 0.18 0.65 0.47 0.03 b mdl b mdl 2.00 6.10 99.6 2128 b mdl 0.20 1.90 4.90 12.20 4.70 164.0 68.8 0.70 0.50 0.90 0.00 9.80 0.80 3.30 135.9 6.00 b mdl 6.90 0.10 34.40 1.30 14.70 11.80 0.27 0.50 17.60

K-26 89.88 5.02 0.04 bmdl 0.01 0.11 2.62 0.10 0.03 bmdl bmdl 1.00 2.10 99.9 133.0 0.20 bmdl 3.70 3.30 5.10 19.4 11.00 53.1 0.30 0.70 0.60 0.00 4.50 0.20 2.10 28.6 2.00 bmdl 2.80 bmdl 9.30 0.50 1.20 5.40 0.14 0.20 0.50

K-27 97.75 0.61 bmdl bmdl 0.01 0.06 0.05 0.13 0.03 bmdl bmdl 7.00 1.20 99.9 470.0 bmdl bmdl bmdl 6.00 8.50 1.00 3.00 8.0 0.50 1.80 2.60 0.00 3.00 0.40 1.40 48.0 4.00 bmdl 3.50 bmdl 3.60 2.20 3.30 6.10 1.12 bmdl 6.50

K-28 85.99 7.82 1.46 0.09 0.04 0.04 1.54 0.25 0.03 b mdl b mdl 4.00 2.70 99.9 176.0 1.50 0.20 5.10 2.20 4.00 17.5 b mdl 12.2 0.30 2.40 1.20 23.00 1.40 3.40 8.00 2.40 3.00 2.00 5.10 b mdl b mdl 0.80 b mdl b mdl b mdl 0.10 2.00

K-29 82.8 3.16 0.51 0.02 0.04 0.00 0.37 4.00 0.12 b mdl b mdl 66.00 8.60 99.6 136.0 0.60 19.70 3.60 37.80 57.50 58.1 9.00 307.1 3.70 31.7 28.80 35.00 15.4 1.40 38.70 5.70 10.00 0.40 9.40 b mdl 5.60 14.00 2.20 15.70 0.33 0.80 26.60

K-30 86.1 8.52 0.28 0.59 0.03 0.04 2.34 0.10 0.02 bmdl bmdl 4.00 1.80 99.8 1245 bmdl 0.40 9.60 3.90 2.70 45.3 1.00 37.8 0.30 2.90 4.20 16.00 2.10 2.30 5.10 44.9 38.00 2.00 12.70 0.60 2.80 1.00 1.40 35.30 0.28 1.30 0.60

K-31 81.74 0.46 5.92 b mdl b mdl b mdl b mdl 2.07 0.08 b mdl b mdl 23.00 9.50 99.8 210.0 5.40 b mdl 1.10 20.70 31.00 0.30 3.00 122.1 2.20 17.7 22.60 18.00 12.7 27.90 30.50 10.0 6.00 6.30 28.50 b mdl 4.30 7.20 0.30 25.60 1.38 0.10 57.90

K-32 85.81 6.19 0.14 0.01 0.21 0.08 2.09 0.17 b mdl b mdl b mdl 6.00 4.20 99.7 543.0 44.20 b mdl 5.50 8.40 9.20 18.2 25.00 61.2 0.90 1.90 1.60 0.00 284.2 0.40 3.00 256.3 57.00 0.10 7.90 1.40 18.90 2.40 18.50 37.70 1.10 0.50 3.50

K-33 96.77 0.61 0.11 0.01 0.16 0.07 0.03 0.13 b mdl b mdl b mdl 8.00 1.70 99.6 397.0 b mdl b mdl 0.60 6.70 8.60 1.10 5.00 14.0 0.50 1.30 3.00 0.00 5.30 0.90 8.20 59.8 34.00 0.90 91.20 0.30 6.80 2.90 3.40 15.40 1.02 0.10 5.20

K-34 84.47 8.85 0.62 0.08 0.01 0.02 1.65 0.37 0.02 b mdl b mdl 7.00 3.50 99.6 223.0 4.10 2.20 17.70 2.30 4.50 99.4 1.00 4.40 0.40 5.30 1.40 132.0 64.6 2.30 15.70 16.6 4.00 0.10 3.90 b mdl 0.30 3.00 0.10 14.40 0.04 0.10 2.10

K-35

K-36

87.75 2.69 3.86 0.53 0.16 0.02 0.59 0.10 0.01 b mdl b mdl 3.00 2.90 99.0 3473 40.90 b mdl 3.80 1.20 2.60 11.5 0.00 69.5 1.60 1.60 0.90 5.00 1383 12.00 669.5 96.5 554.0 0.80 165.8 3.30 4.10 4.10 2.90 146.8 0.10 1.60 3.00

86.9 1.53 0.95 0.11 0.01 0.00 0.07 1.00 b mdl b mdl b mdl 4.00 8.80 99.6 1773 1.90 0.30 1.80 9.90 16.20 1.50 2.00 23.3 1.20 0.80 1.20 7.00 23.2 15.80 27.90 550.3 47.00 0.10 174.7 0.10 39.50 99.50 52.40 224.9 3.77 3.70 24.50

K-37 85.52 7.73 1.56 0.36 0.13 0.12 1.86 0.24 0.02 bmdl bmdl 7.00 2.30 99.9 913.6 1.30 0.20 10.70 3.00 4.60 31.5 2.00 17.2 0.40 2.40 1.60 23.00 1.30 1.70 15.80 28.5 11.00 7.30 3.50 bmdl 0.70 1.90 2.60 51.10 0.27 0.10 bmdl

K-38 83.14 10.56 0.10 0.58 0.07 1.44 1.62 0.35 b mdl b mdl b mdl 6.00 1.80 99.7 256.0 25.50 b mdl 4.00 3.00 5.00 20.9 1.00 53.2 0.60 1.30 0.40 24.00 305.4 0.30 3.40 1.00 2.00 0.20 0.70 b mdl b mdl b mdl b mdl 1.60 b mdl b mdl b mdl

K-39 90.49 4.76 0.34 0.26 0.04 0.06 1.09 0.35 0.04 bmdl bmdl 4.00 2.50 99.9 397.0 1.00 bmdl 1.90 3.90 5.90 13.0 bmdl 9.20 0.40 3.80 1.70 bmdl 0.90 3.60 7.60 106.8 4.00 2.10 7.10 bmdl 3.40 8.40 5.90 49.50 0.09 11.70 2.70

205

(continued on next page)

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc LOI Sum Ba Co Cs Ga Hf Nb Rb Sn Sr Ta Th U V W Mo Cu Pb Zn Ni As Cd Sb Bi Ag Au Hg Tl Se

K-16

60.91 4.83 8.19 47.89 468.90 1555.9 17,235 0.70 1.02 3.25 3.25 0.64 62.13 69.36 33.23 45.87 23.70

206

Table 3 (continued) Potassic alteration

Silicic alteration

K-16

K-17

K-18

K-19

K-20

K-21

K-22

K-23

K-24

K-25

K-26

K-27

K-28

K-29

K-30

K-31

K-32

K-33

K-34

K-35

K-36

K-37

K-38

K-39

Zr Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE HREE MRE LRE TRTE HFSE LILE Eu* Ce* La/Yb La/Sm Gd/Yb CIA CIW K.I. AI CCPI

141.9 28.5 37.9 67.5 6.60 21.0 3.55 0.13 3.14 0.62 3.92 0.89 2.94 0.53 3.58 0.58 152.9 7.63 12.3 133.0 36.2 941 86,550 0.13 1.03 7.14 6.72 0.62 51.6 79.9 80.7 81.3 13.5

112.1 93.7 22.5 47.8 6.27 30.4 8.70 2.40 10.5 1.93 13.25 3.01 8.69 1.15 6.89 0.9 164.4 17.6 39.8 107.0 1462 3055 48,258 0.82 0.97 2.20 1.63 1.08 55.3 71.6 63.8 69.6 24.1

111.0 20.0 30.0 54.9 5.67 18.4 3.14 0.14 2.83 0.54 3.37 0.71 2.39 0.44 3.22 0.51 126.3 6.56 10.7 109.0 71.1 779 43,769 0.15 1.01 6.28 6.01 0.62 51.5 68.8 62.2 62.9 9.76

118.4 10.1 29.2 59.1 4.96 16.0 2.25 0.38 1.62 0.27 1.40 0.37 1.14 0.20 1.47 0.27 118.6 3.08 6.29 109.3 37.0 1240 91,946 0.65 1.18 13.39 8.16 0.78 55.8 94.8 93.2 95.7 15.0

143.8 20.8 57.1 90.4 10.0 32.0 4.82 1.05 3.59 0.61 3.46 0.69 1.99 0.35 2.33 0.38 208.8 5.05 14.2 189.5 119.6 1666 71,346 0.82 0.91 16.52 7.45 1.09 53.5 83.3 82.1 84.3 16.9

145.7 19.8 50.9 86.8 9.05 28.1 4.32 0.71 3.15 0.56 3.05 0.69 1.87 0.35 2.27 0.37 192.2 4.86 12.5 174.9 76.9 1597 78,987 0.63 0.97 15.12 7.41 0.98 54.8 88.6 87.3 89.7 15.7

198.9 24.1 57.5 108.4 10.1 33.1 4.97 1.03 3.83 0.67 4.07 0.82 2.48 0.44 2.83 0.45 230.7 6.20 15.4 209.1 69.3 2230 48,775 0.77 1.08 13.70 7.28 0.96 55.7 69.8 50.7 63.2 25.3

168.1 17.3 51.2 90.0 9.09 28.7 4.38 0.89 3.21 0.54 2.95 0.6 1.77 0.30 2.12 0.33 196.1 4.52 12.6 179.0 97.2 1914 50,622 0.77 1.00 16.28 7.35 1.07 54.5 71.7 61.9 65.3 21.1

220.1 59.8 46.8 87.8 9.30 38.3 9.0 1.94 7.59 1.56 9.55 1.99 6.10 0.95 6.85 1.02 228.8 14.9 31.6 182.2 122.5 5241 55,204 0.77 1.01 4.61 3.27 0.79 76.6 98.7 77.4 97.8 45.6

192.7 24.7 2.30 2.50 0.26 1.00 0.39 0.12 1.06 0.34 3.27 0.87 2.99 0.55 3.81 0.65 20.1 8.00 6.05 6.06 11.3 3159 7738 0.61 0.78 0.41 3.71 0.20 62.2 75.9 59.6 64.2 17.8

87.4 12.7 4.90 10.2 1.23 5.40 1.18 0.23 1.43 0.31 2.23 0.50 1.60 0.29 1.86 0.28 31.6 4.03 5.88 21.7 5.30 827 21,992 0.58 1.00 1.78 2.61 0.54 62.9 96.2 95.6 95.6 1.44

196.3 45.2 2.70 6.60 0.90 4.20 1.40 0.21 2.68 0.82 7.14 1.79 6.03 0.99 7.17 1.15 43.8 15.3 14.0 14.4 12.4 1122 949 0.35 1.02 0.25 1.21 0.26 86.0 83.9 41.7 41.7 b mdl

76.8 12.6 10.4 23.0 2.86 11.3 1.88 0.36 1.39 0.30 1.95 0.43 1.35 0.22 1.51 0.24 57.2 3.32 6.31 47.6 130.4 1713 13,007 0.73 1.02 4.64 3.48 0.65 81.9 98.3 90.1 95.3 49.5

1243 77.0 128.9 267.9 29.8 108.2 14.1 2.91 5.51 1.26 10.18 2.84 11.05 2.21 17.18 3.16 605.1 33.6 36.8 534.8 198.6 25,846 3788 1.08 1.04 5.06 5.77 0.23 88.8 97.7 86.0 90.7 58.9

152.9 18.5 4.60 8.80 0.99 3.60 0.88 0.24 1.41 0.35 2.83 0.64 2.12 0.37 2.34 0.38 29.6 5.21 6.35 18.0 65.1 847 20,812 0.70 0.99 1.33 3.29 0.43 76.6 98.6 78.0 97.7 26.8

689.2 35.2 72.7 152.7 17.7 70.3 7.79 1.56 2.81 0.64 4.87 1.26 4.71 0.93 6.92 1.24 346.2 13.8 18.9 313.4 116.6 13,502 455 1.09 1.02 7.08 5.87 0.29 100.0 100.0 b mdl b mdl 100.0

272.6 56.0 4.80 10.70 1.16 6.00 2.10 0.52 3.93 1.03 8.58 2.22 7.17 1.16 8.60 1.35 59.3 18.3 18.4 22.7 110.3 1310 18,238 0.59 1.09 0.38 1.44 0.32 72.1 95.9 87.4 87.9 6.47

209.5 50.0 3.10 5.90 0.80 4.00 1.50 0.21 2.93 0.82 7.56 1.86 6.8 1.15 8.50 1.21 46.3 17.7 14.9 13.8 78.5 1005 728 0.33 0.90 0.25 1.30 0.24 80.5 72.6 11.1 14.8 54.5

89.0 9.90 5.90 8.70 1.34 5.20 1.20 0.28 1.23 0.17 1.43 0.33 1.14 0.18 1.46 0.22 28.8 3.00 4.64 21.1 162.9 2402 14,057 0.75 0.74 2.72 3.09 0.60 83.2 99.4 93.8 98.3 29.5

48.0 11.2 9.90 19.20 1.96 8.20 1.80 0.38 1.76 0.27 1.78 0.36 1.22 0.20 1.34 0.18 48.6 2.94 6.35 39.3 1273 697 8561 0.70 1.05 4.98 3.46 0.93 79.2 97.6 45.4 86.2 87.8

345.2 35.7 1.10 1.90 0.17 0.80 0.50 0.15 1.44 0.51 4.96 1.41 4.91 0.87 7.20 1.06 27.0 14.04 8.97 3.97 87.9 6368 2933 0.58 1.06 0.10 1.38 0.14 95.3 98.8 36.8 94.7 93.8

105.5 20.1 7.00 14.40 1.60 6.50 1.50 0.49 2.11 0.40 2.83 0.72 2.19 0.35 2.35 0.39 42.8 5.28 8.05 29.5 65.4 1640 16,444 0.90 1.04 2.01 2.94 0.64 76.3 94.7 75.3 89.9 49.2

108.7 5.20 1.50 3.10 0.34 1.20 0.40 0.08 0.43 0.08 0.47 0.17 0.63 0.12 1.03 0.20 9.75 1.98 1.63 6.14 61.1 2216 13,784 0.63 1.04 0.98 2.36 0.30 71.9 80.9 43.7 59.3 18.2

137.2 22.5 4.30 9.90 1.27 5.40 1.45 0.18 1.97 0.45 2.92 0.73 2.43 0.43 2.87 0.48 34.8 6.21 7.70 20.9 18.7 2420 9585 0.35 1.02 1.01 1.87 0.49 79.1 96.5 75.2 93.1 34.3

Sample

K-40

K-41

Hematitic alteration

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc LOI Sum Ba Co Cs Ga Hf Nb Rb Sn

5.93 1.34 71.75 b mdl b mdl 0.01 1.30 0.08 0.32 b mdl 0.01 2.00 17.10 97.8 9539 b mdl b mdl 14.2 1.00 1.30 4.90 b mdl

19.48 2.81 64.00 0.07 bmdl 0.01 0.72 0.11 0.13 bmdl bmdl 3.00 12.20 99.6 1316 0.20 0.20 20.1 1.30 2.30 12.40 0.00

K-42 25.96 8.33 39.53 0.44 0.02 0.05 2.06 0.44 0.06 bmdl bmdl 6.00 21.40 98.9 4984 9.70 1.00 12.5 4.30 6.80 27.90 2.00

Illitic alteration

K-43

K-44

K-45

K-46

4.14 1.07 62.06 0.11 0.05 0.00 0.08 0.03 0.01 b mdl b mdl 0.00 31.90 99.5 221 1.80 0.20 0.90 0.00 0.00 2.10 2.00

25.60 2.07 44.76 0.63 0.30 0.23 0.35 0.39 0.01 0.02 b mdl 4.00 24.30 98.9 2340 23.90 0.00 2.90 1.40 3.50 6.00 0.00

10.86 2.82 72.31 0.05 0.00 0.02 0.40 0.34 0.05 bmdl 0.01 3.00 12.50 99.4 3758 0.40 0.60 6.00 3.10 5.80 9.40 2.00

0.19 1.88 28.81 b mdl 0.18 0.02 0.45 0.56 1.00 b mdl 0.02 4.00 13.60 46.7 50,000 0.40 0.00 29.9 4.70 8.00 6.80 81.0

K-47 66.21 19.83 2.58 0.40 0.02 0.13 5.26 0.31 0.02 b mdl b mdl 11.00 5.10 99.8 746 0.40 0.20 25.6 5.50 7.10 66.0 43.0

K-48 65.91 17.71 3.37 0.65 0.10 0.13 4.50 0.56 0.14 0.01 b mdl 11.00 6.70 99.8 592 11.10 1.60 17.3 4.90 10.9 144.2 3.00

K-49 53.99 23.11 2.84 1.33 0.18 0.10 2.32 0.28 0.04 0.03 bmdl 7.00 15.60 99.8 305 0.80 1.20 20.0 6.30 14.9 49.0 3.00

K-50 47.93 24.58 9.13 1.00 0.11 0.18 6.69 0.54 0.02 0.01 b mdl 16.00 9.20 99.7 636 11.20 0.70 28.6 8.20 13.7 127.5 2.00

K-51 47.70 30.57 1.15 1.56 0.12 0.16 9.17 0.68 0.09 0.01 b mdl 23.00 8.70 99.9 830 1.40 3.20 30.4 10.3 17.5 155.1 2.00

K-52 47.75 30.98 1.39 1.55 0.02 0.16 9.19 0.70 0.03 0.01 bmdl 23.00 8.00 99.8 579 0.60 1.80 32.5 10.1 17.3 156.8 2.00

K-53 62.19 20.00 2.68 1.69 1.33 0.36 5.32 0.14 0.01 0.01 b mdl b mdl 5.47 99.2 2733 0.50 1.40 5.50 0.20 0.70 14.7 11.0

K-54 64.27 19.34 2.76 1.57 0.96 0.30 6.19 0.10 0.01 0.01 bmdl bmdl 5.10 100.6 161 0.90 1.80 2.90 0.20 0.80 17.1 0.00

K-55 66.27 16.80 2.29 1.20 0.51 0.66 6.12 0.19 0.01 0.01 b mdl b mdl 6.04 100.1 920 0.50 1.20 1.20 0.20 0.40 21.1 0.00

K-56 51.89 32.73 0.71 0.41 0.62 0.11 6.03 0.43 0.10 0.01 b mdl b mdl 6.14 99.2 2047 3.00 3.50 32.7 6.60 19.20 231.0 2.00

K-57 51.71 29.82 0.87 1.09 0.01 0.08 5.66 1.23 0.01 0.02 b mdl b mdl 9.00 99.7 1410 7.00 1.10 27.5 3.90 7.60 107.0 2.00

K-58 59.56 20.72 3.51 1.55 0.02 0.15 5.88 0.74 0.13 0.01 b mdl b mdl 7.70 100.0 5549 6.50 2.10 12.1 3.50 5.40 56.3 1.00

K-59 65.40 18.73 2.48 1.08 0.01 0.05 5.57 0.63 0.03 0.01 bmdl bmdl 5.93 99.9 835 0.50 2.60 26.1 5.90 10.50 132.0 2.00

K-60 47.93 24.58 9.13 1.00 0.11 0.18 6.89 0.54 0.02 0.01 b mdl b mdl 9.20 99.6 591 11.20 0.70 28.6 8.20 13.70 127.5 2.00

K-61 37.91 25.53 14.82 0.61 0.11 0.25 6.20 0.59 0.01 0.01 bmdl bmdl 13.20 99.2 395 15.70 2.90 23.7 8.50 15.00 106.2 1.00

K-62 53.07 23.19 2.28 1.13 3.96 0.18 6.49 0.42 0.03 0.01 b mdl b mdl 9.20 100.0 523 2.60 2.90 2.7 5.80 9.30 110.1 1.00

K-63 56.53 25.04 2.78 0.93 0.20 0.20 6.79 0.54 0.01 0.01 b mdl b mdl 6.90 99.3 353 2.60 3.80 27.6 7.90 13.40 107.9 2.00

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

Sample

39.5 b mdl 5.90 0.60 55.0 1.00 523.4 1009 7244 20.0 b mdl 4802 0.30 14.80 106.7 3.20 343.2 0.73 1.80 40.7 30.3 4.90 1.80 2.30 0.26 1.10 0.28 0.10 0.66 0.11 0.75 0.18 0.51 0.08 0.56 0.08 8.8 1.23 2.08 5.46 1120 1909 27,628 48.49 98.79 0.76 0.81 2.17 4.04 0.83 48.5 98.8 99.2 99.2 98.2

7.70 0.10 2.90 0.80 56.0 2.00 56.0 1001 462.2 38.0 2.90 810 0.10 5.00 7.90 1.50 392.8 0.43 0.70 13.7 51.5 8.80 1.80 2.80 0.35 1.30 0.38 0.12 0.71 0.18 1.32 0.28 0.87 0.15 0.94 0.16 11.4 2.12 2.99 6.25 1115 1282 7781 77.93 99.42 0.75 0.85 1.29 2.98 0.54 77.9 99.4 90.0 98.8 98.9

106.7 0.50 3.80 5.00 84.0 74.30 212.0 753.4 1089 72.0 0.70 1440 0.30 31.90 49.00 35.00 1195 5.03 9.40 > 100 148.7 23.5 7.60 15.20 1.73 7.10 1.70 0.10 2.55 0.48 3.80 0.85 2.49 0.39 2.93 0.40 47.3 6.21 9.48 31.63 933 3060 23,327 79.07 98.60 0.16 1.01 1.75 2.81 0.62 79.1 98.6 80.2 97.3 95.0

9.80 b mdl 0.30 0.10 18.0 0.50 11.2 901.9 69.4 86.0 0.70 97.2 0.10 6.30 0.80 0.40 18.8 0.08 0.90 2.50 8.4 2.10 1.20 3.40 0.43 2.30 0.50 0.15 0.45 0.09 0.40 0.10 0.31 0.00 0.27 0.05 9.7 0.63 1.69 7.33 1015 232 968 92.51 92.17 1.03 1.14 3.00 1.51 1.18 92.5 92.2 33.3 79.2 99.9

66.8 0.60 0.60 0.60 68.0 466.9 37.5 5107 191.8 522.0 9.30 926.4 2.70 12.30 66.70 5.40 1284 0.30 10.40 58.9 44.0 8.20 4.80 10.50 1.11 3.90 1.00 0.23 1.20 0.21 1.43 0.28 0.86 0.14 0.89 0.12 26.7 2.01 4.35 20.3 5748 2431 5516 64.57 73.23 0.97 1.09 3.64 3.02 0.96 64.6 73.2 23.2 64.9 98.7

40.4 0.30 1.70 1.90 49.0 2.00 13.7 256.2 556.1 18.0 1.50 421.8 0.00 13.90 41.60 3.20 686.9 0.32 0.20 92.6 103.7 9.50 6.60 12.00 1.24 4.40 0.85 0.22 0.85 0.20 1.42 0.33 1.07 0.18 1.24 0.19 30.8 2.68 3.87 24.2 362 2369 7696 85.82 98.85 0.84 1.01 3.59 4.88 0.49 85.8 98.8 85.1 95.7 99.4

10,264 1.70 3.40 25.40 41.0 146.10 578.7 651.7 10,000 151.0 0.10 9129 0.70 1967.9 2000 100.0 17,030 81.30 89.00 0.00 144.4 10.7 90.3 169.0 21.0 87.6 19.40 8.99 11.17 0.95 2.68 0.51 1.14 0.18 1.34 0.19 414.4 2.85 43.7 367.9 950.8 7881 74,126 564.67 83.92 1.99 0.93 45.43 2.93 5.91 564.7 83.9 69.2 69.2 98.4

21.4 0.60 6.40 3.70 30.0 4.50 b mdl 2.30 1.10 1.00 0.50 0.80 0.00 0.00 1.50 0.00 1.6 0.00 0.00 0.00 179.1 36.9 14.5 35.8 4.13 17.2 4.40 1.31 5.20 1.02 6.71 1.36 4.24 0.70 4.79 0.77 102.1 10.50 20.0 71.6 45.2 2138 44,528 77.08 98.75 0.89 1.11 2.04 2.07 0.77 77.1 98.8 90.5 97.4 35.6

346.0 0.90 13.40 3.10 73.0 3.70 1.80 13.50 29.3 43.0 12.20 95.8 0.50 0.30 0.40 0.30 6.0 2.61 1.10 0.00 176.9 19.0 29.9 58.7 6.39 22.6 4.03 0.92 3.69 0.60 3.58 0.72 2.19 0.33 2.09 0.32 136.1 4.93 13.5 117.6 191.2 4162 38,519 78.22 97.81 0.78 1.02 9.65 4.67 1.25 78.2 97.8 83.6 95.7 46.5

27.5 1.50 38.4 4.20 20.0 3.10 0.20 1.10 20.8 30.0 1.00 2.20 0.00 0.00 0.50 0.00 b mdl 0.02 0.10 0.00 202.6 64.7 156.1 118.3 24.00 78.1 12.44 3.53 10.78 1.83 9.76 1.98 5.56 0.87 5.40 0.84 429.5 12.7 40.3 376.5 59.9 2078 19,863 89.05 97.92 0.99 0.47 19.49 7.89 1.41 89.1 97.9 59.0 92.9 63.3

61.1 1.00 9.10 3.20 38.0 76.10 77.8 1186 19.2 15.0 1.10 94.0 0.00 0.50 4.60 1.50 233.0 0.02 0.20 6.40 290.4 66.9 25.8 53.2 5.66 23.9 5.40 1.21 6.69 1.55 10.06 2.28 7.39 1.10 7.58 1.16 153.0 17.2 27.2 108.6 1267 3638 56,423 76.17 98.02 0.66 1.06 2.29 3.01 0.63 76.2 98.0 83.8 96.4 59.6

75.9 1.00 11.50 6.10 52.0 1.90 9.20 43.60 13.60 6.00 0.40 29.7 0.10 0.10 0.30 0.30 24.7 0.05 0.40 1.00 346.8 76.2 34.8 77.5 9.14 38.7 8.16 2.25 9.19 2.02 11.37 2.35 7.22 1.19 8.02 1.26 213.2 17.7 35.3 160.1 133.2 4845 77,259 75.00 98.45 0.85 1.05 2.93 2.68 0.81 75.0 98.4 83.3 97.5 22.5

15.9 1.00 10.70 2.60 65.0 4.00 4.00 1217 3.90 4.00 0.20 25.8 0.10 0.10 2.10 0.40 27.5 0.04 0.20 4.70 340.3 63.2 36.6 76.2 9.07 38.5 7.42 1.70 7.18 1.53 8.79 1.95 6.28 1.06 7.50 1.18 205.0 16.0 28.6 160.4 1310 4696 77,102 75.28 99.04 0.76 1.01 3.29 3.10 0.68 75.3 99.0 84.2 98.4 23.9

10,185 0.10 23.00 25.0 14.0 0.40 0.80 16.10 7.00 97.00 0.80 32.9 0.20 2.80 b mdl 0.10 b mdl 0.01 0.00 0.50 12.9 40.3 451.4 1879 299.3 1418 204.2 34.53 68.76 6.24 19.68 1.42 1.96 0.41 2.69 0.27 4387 5.33 334.8 4047 128.4 897 57,606 74.23 94.41 0.95 1.23 113.1 1.39 18.1 74.2 94.4 61.1 80.6 43.5

5000 b mdl 4.10 8.7 10.0 0.40 0.70 8.90 1.30 24.0 5.60 13.5 b mdl 0.10 b mdl b mdl 1.0 0.01 0.00 0.00 7.90 10.5 159.8 624.9 78.0 387.3 49.26 6.92 11.78 1.20 4.02 0.32 0.70 0.15 0.94 0.10 1325 1.89 73.5 1250 49.4 652 56,743 71.56 95.14 0.94 1.35 114.6 2.04 8.88 71.6 95.1 68.6 86.0 40.0

1839 bmdl 1.80 11.0 6.00 0.40 0.20 8.50 1.70 44.0 1.30 35.5 0.10 0.10 bmdl bmdl 0.0 0.01 0.00 0.00 7.00 17.6 20.9 121.6 28.8 190.1 39.01 6.26 13.33 1.47 6.02 0.68 1.38 0.20 1.23 0.14 431.1 2.95 66.8 361.4 60.3 1190 53,625 66.11 89.30 0.90 1.19 11.5 0.34 7.68 66.1 89.3 72.1 86.2 34.0

135.6 1.50 41.9 14.1 40.0 19.70 10.30 495.3 3101 2367 0.30 189.0 15.20 8.90 b mdl 6.00 170.9 0.61 0.60 1.90 215.7 7.00 52.7 80.2 6.49 16.5 1.91 0.28 1.10 0.22 1.32 0.23 0.85 0.17 1.20 0.23 163.4 2.45 5.06 155.9 2906 3257 55,687 82.61 98.91 0.63 1.04 29.6 17.4 0.65 82.6 98.9 84.1 89.8 15.4

19.5 0.60 3.50 1.50 231.0 18.60 1.00 13.30 2.90 6.00 0.30 7.60 b mdl b mdl 0.10 0.10 b mdl 15.00 0.01 0.10 0.00 42.8 19.2 35.5 4.76 19.3 4.70 1.56 5.19 0.94 6.02 1.40 4.30 0.66 4.46 0.70 108.7 10.1 19.8 78.8 309.3 7430 48,554 82.67 99.50 1.03 0.89 2.90 2.57 0.82 82.7 99.5 82.7 98.7 25.5

72.0 0.60 3.60 3.20 46.0 194.2 3.70 6.10 111.2 8.00 0.50 133.9 0.10 1.40 0.50 b mdl b mdl b mdl b mdl b mdl 120.3 21.3 46.8 87.8 9.30 38.3 9.00 1.94 7.59 1.56 9.55 1.99 6.10 0.95 6.85 1.02 228.8 14.9 31.6 182.2 80.78 5133 54,660 76.58 98.65 0.77 1.01 4.61 3.27 0.79 76.6 98.7 77.4 97.8 45.6

536.1 0.80 7.50 2.60 62.0 3.40 4.60 53.8 43.3 43.0 0.40 66.4 0.80 0.90 1.70 bmdl bmdl bmdl bmdl bmdl 220.1 59.8 11.8 37.6 4.63 21.1 5.20 1.01 5.27 0.91 5.96 1.27 3.85 0.53 3.66 0.56 103.4 8.60 19.6 75.1 173.4 4145 47,813 75.56 99.47 0.63 1.22 2.17 1.43 1.02 75.6 99.5 83.0 99.1 38.8

61.1 1.00 9.10 3.20 38.0 76.10 77.8 1186 19.2 15.0 1.10 94.0 0.10 0.50 4.60 b mdl b mdl b mdl b mdl b mdl 290.4 66.9 15.8 53.2 5.66 23.9 5.40 1.21 6.69 1.55 10.06 2.28 7.39 1.10 7.58 1.16 143.0 17.2 27.2 98.6 1265 3638 58,028 75.66 98.02 0.66 1.35 1.41 1.84 0.63 75.7 98.0 84.2 96.5 58.9

29.3 1.00 8.80 3.00 41.0 17.70 48.2 8392 48.6 53.0 8.20 157.8 0.10 1.50 6.50 bmdl bmdl bmdl bmdl bmdl 299.8 44.5 17.9 38.2 3.86 16.8 4.00 0.85 5.02 0.98 6.85 1.61 5.50 0.86 6.41 1.02 109.9 13.8 19.3 76.8 8524 3905 52,084 77.77 97.66 0.62 1.11 1.88 2.81 0.55 77.8 97.7 86.5 95.0 70.5

67.6 0.60 7.30 4.40 33.0 2.10 3.70 7.90 9.00 4.00 2.60 42.5 0.10 0.40 0.30 b mdl b mdl b mdl b mdl b mdl 200.7 10.2 22.5 27.6 2.95 21.4 2.30 1.15 2.11 0.40 2.28 0.46 21.22 0.17 1.09 0.20 105.8 22.7 8.7 74.5 63.8 2865 54,627 75.27 75.57 1.70 0.82 13.92 6.15 1.37 75.3 75.6 55.2 64.8 33.8

34.1 0.90 9.30 8.00 84.0 3.00 5.90 21.80 10.00 9.00 1.80 63.3 0.10 0.60 1.00 b mdl b mdl b mdl b mdl b mdl 279.3 13.3 18.6 18.6 1.97 18.7 2.30 1.11 2.95 0.55 3.00 0.55 9.35 0.21 1.48 0.23 79.6 11.3 10.5 57.9 132.9 3582 56,915 75.77 97.31 1.39 0.74 8.47 5.09 1.41 75.8 97.3 83.6 95.1 34.7

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

Sr Ta Th U V W Mo Cu Pb Zn Ni As Cd Sb Bi Ag Au Hg Tl Se Zr Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE HREE MRE LRE TRTE HFSE LILE CIA CIW Eu* Ce* La/Yb La/Sm Gd/Yb CIA CIW K.I. AI CCPI

(continued on next page)

207

208

Table 3 (continued) Smectitic alteration K-64

K-65

K-66

K-67

K-68

K-69

K-70

K-71

K-72

K-73

K-74

K-75

K-76

K-77

K-78

K-79

K-80

K-81

K-82

K-83

K-84

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc LOI Sum Ba Co Cs Ga Hf Nb Rb Sn Sr Ta Th U V W Mo Cu Pb Zn Ni As Cd Sb Bi Ag Au Hg Tl Se Zr Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE HREE

51.25 16.39 2.85 4.93 2.36 0.37 0.21 0.24 0.14 0.01 0.00 0.00 21.00 99.86 208.50 16.90 0.30 13.30 4.90 10.20 12.40 2.00 306.70 0.60 23.40 2.90 44.00 4.20 0.10 6.40 34.20 91.00 0.50 1.70 0.20 0.20 0.30 0.00 1.10 0.01 0.20 0.00 198.60 16.60 42.00 84.80 8.83 32.90 5.18 1.06 3.41 0.57 2.93 0.48 1.47 0.26 1.56 0.23 185.68 3.52

51.34 16.29 2.84 4.51 2.59 0.15 0.17 0.25 0.03 0.00 0.00 0.00 21.30 99.55 233.80 2.90 0.20 12.50 5.10 11.20 7.30 2.00 256.50 0.60 24.50 7.70 33.00 1.10 0.10 5.60 29.80 56.00 0.90 1.30 0.10 0.30 0.40 0.00 0.00 0.00 0.30 0.00 217.50 22.80 48.20 94.90 9.81 36.60 6.04 1.24 4.10 0.68 3.75 0.66 2.01 0.34 2.17 0.33 210.83 4.85

60.68 18.34 4.1 5.51 2.92 0.01 0.23 0.28 0.02 0.01 0.00 0.00 7.31 99.40 137.70 17.20 0.30 12.40 4.70 9.60 11.50 2.00 297.90 0.50 20.50 2.80 46.00 4.60 0.10 4.00 35.00 68.00 0.60 1.20 0.10 0.20 0.30 0.00 0.60 0.01 0.20 0.00 193.90 19.90 32.50 69.70 7.58 29.00 5.03 1.16 3.72 0.65 3.41 0.60 1.80 0.30 1.87 0.27 157.59 4.24

75.14 8.8 0.73 1.83 0.51 1.23 0.51 0.07 0.00 0.01 0.00 0.00 10.90 99.86 57.30 0.00 3.10 12.10 3.60 11.60 42.30 1.00 134.10 0.90 16.80 3.20 0.00 2.70 0.50 2.40 15.40 16.00 0.70 4.30 0.10 0.10 0.30 0.00 0.00 0.00 0.20 0.00 104.00 13.30 8.60 15.60 1.58 5.60 0.97 0.15 0.99 0.21 1.38 0.33 1.21 0.22 1.54 0.26 38.64 3.23

63.25 14.38 0.96 2.12 1.28 0.88 0.52 0.14 0.01 0.01 0.00 0.00 16.40 99.98 33.60 0.60 3.20 13.60 4.20 14.00 53.90 2.00 131.50 1.00 41.10 1.00 0.00 4.50 0.00 1.10 9.10 8.00 0.10 4.10 0.00 0.10 0.30 0.00 0.90 0.00 0.00 0.00 110.50 22.10 57.90 111.00 10.08 33.00 4.84 0.54 3.50 0.60 3.19 0.59 1.78 0.30 2.00 0.33 229.65 4.41

66.28 11.76 1.15 2.98 1.38 0.56 0.83 0.11 0.00 0.03 0.00 1.00 13.90 99.02 36.80 0.60 1.60 18.10 4.70 47.10 21.90 4.00 196.20 5.00 18.80 1.30 7.00 1.80 0.10 1.20 1.80 5.00 0.00 0.60 0.00 0.00 0.30 0.00 1.20 0.01 0.10 0.00 131.10 15.90 30.40 34.60 5.06 17.30 2.72 0.17 2.28 0.41 2.35 0.43 1.24 0.21 1.32 0.20 98.69 2.97

60.93 15.45 0.9 2.46 1.65 0.57 0.47 0.14 0.00 0.01 0.00 1.00 16.70 99.34 90.90 0.90 2.60 14.30 4.10 31.10 42.30 2.00 160.10 3.70 22.90 0.90 7.00 3.60 0.40 11.50 67.20 55.00 0.00 6.80 0.30 0.40 0.20 0.20 5.90 0.02 0.00 0.00 124.30 21.20 31.30 42.00 5.31 16.80 2.73 0.15 2.26 0.46 2.79 0.54 1.92 0.36 2.28 0.36 109.26 4.92

67.36 12.42 1.06 2.07 1.67 0.67 0.64 0.10 0.00 0.04 0.00 0.00 13.90 99.89 17.00 1.80 3.00 14.20 4.50 49.50 25.10 3.00 182.30 4.50 23.00 4.30 0.00 9.40 0.20 1.00 9.80 10.00 0.60 5.70 0.00 0.00 0.20 0.00 1.00 0.00 0.00 0.00 120.20 24.10 34.80 62.40 6.19 19.90 3.43 0.12 3.12 0.60 3.57 0.79 2.61 0.44 2.99 0.47 141.43 6.51

68.9 11.53 0.88 1.97 1.42 0.44 0.56 0.08 0.00 0.01 0.00 0.00 14.10 99.88 16.00 2.00 4.40 13.90 4.50 49.10 40.40 6.00 170.20 4.60 26.80 2.00 0.00 15.90 0.20 12.10 9.60 21.00 1.50 2.00 0.00 0.00 0.20 0.00 0.00 0.00 0.00 0.00 114.00 23.30 42.40 68.60 7.29 23.30 3.61 0.09 3.10 0.58 3.51 0.74 2.41 0.43 2.98 0.48 159.52 6.30

68.26 12.6 1.64 1.84 1.25 1 2.25 0.08 0.00 0.03 0.00 0.00 10.90 99.87 10.00 7.70 4.50 14.70 5.10 64.90 142.30 3.00 196.10 4.90 26.60 2.30 0.00 42.80 0.60 1.60 9.20 13.00 2.90 0.00 0.00 0.00 1.20 0.00 0.80 0.00 0.00 0.00 130.10 18.90 46.60 63.90 7.10 20.90 3.20 0.11 2.55 0.46 2.75 0.57 1.89 0.32 2.30 0.36 153.01 4.87

68.41 13.02 0.96 2.3 1.38 0.66 1.54 0.08 0.00 0.02 0.00 0.00 11.50 99.87 56.00 5.60 5.60 14.60 4.90 49.50 133.70 3.00 232.20 4.90 26.00 0.60 0.00 30.80 0.20 0.60 7.10 13.00 3.30 0.80 0.00 0.00 0.00 0.00 0.90 0.00 0.00 0.00 136.30 15.60 37.40 45.00 4.74 14.10 1.99 0.08 1.66 0.33 2.11 0.47 1.63 0.31 2.26 0.35 112.43 4.55

68.38 11.77 1.16 2.98 1.31 0.56 1.11 0.08 0.02 0.03 0.00 0.00 12.50 99.87 9.00 7.60 2.60 14.00 4.60 48.20 63.70 3.00 147.80 4.60 25.60 2.20 0.00 42.60 0.20 1.00 7.80 19.00 3.20 0.70 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 142.80 32.40 67.20 78.70 11.36 35.60 5.79 0.16 4.72 0.85 5.04 1.06 3.45 0.59 3.97 0.63 219.12 8.64

66.64 13.93 1.76 1.7 2.2 1.35 2.25 0.20 0.03 0.03 0.00 4.00 9.80 99.85 86.00 4.00 4.70 14.80 4.40 69.30 124.60 2.00 258.10 3.40 24.10 1.40 13.00 15.30 0.20 2.10 9.00 15.00 2.80 3.20 0.00 0.00 0.30 0.00 0.90 0.00 0.00 0.00 130.10 24.60 65.70 96.40 10.79 35.00 5.50 0.39 4.22 0.70 4.07 0.79 2.48 0.42 2.86 0.45 229.77 6.21

70.73 11.08 1.2 1.83 1.85 0.59 1.28 0.11 0.00 0.02 0.00 2.00 11.20 99.88 40.00 2.70 3.70 12.00 4.60 44.80 83.20 2.00 262.30 3.40 19.00 0.50 12.00 8.40 0.20 2.30 6.60 16.00 2.30 1.60 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 133.50 19.50 39.70 56.50 6.22 19.80 3.07 0.19 2.66 0.48 2.89 0.61 1.98 0.37 2.47 0.39 137.33 5.21

64.58 13.11 1.17 3.18 1.79 0.42 0.79 0.11 0.00 0.06 0.00 1.00 14.60 99.85 36.00 2.30 2.40 14.40 5.80 50.60 34.00 3.00 152.80 4.60 24.50 0.30 0.00 8.90 0.00 1.40 9.70 22.00 2.20 1.90 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 159.10 27.60 44.60 90.50 7.24 22.60 3.87 0.23 3.37 0.66 4.03 0.87 3.00 0.54 3.81 0.61 185.93 7.96

66.19 14.62 1.19 2.28 1.19 1.82 2.36 0.10 0.02 0.02 0.00 1.00 10.10 99.89 21.00 3.80 1.40 16.60 5.80 47.00 37.70 4.00 87.10 4.70 26.40 2.70 0.00 22.80 0.30 1.50 4.60 13.00 2.00 1.30 0.00 0.00 0.00 0.00 2.50 0.00 0.00 0.00 123.20 23.80 43.30 71.10 7.08 22.00 3.53 0.14 3.07 0.58 3.66 0.75 2.50 0.43 3.00 0.46 161.60 6.39

65.21 13.35 1.17 3.05 1.45 0.44 1.01 0.09 0.02 0.03 0.00 0.00 14.00 99.85 31.00 4.10 3.80 15.50 5.40 46.90 89.60 4.00 119.10 5.10 28.70 8.60 9.00 14.90 0.00 2.60 6.10 16.00 2.60 5.50 0.00 0.00 0.20 0.00 2.70 0.00 0.00 0.00 142.70 29.50 46.90 47.00 7.68 22.40 3.28 0.14 2.91 0.58 3.80 0.84 2.79 0.47 3.06 0.48 142.33 6.80

68.04 12.92 0.9 2.18 1.36 0.6 1.29 0.08 0.02 0.02 0.00 0.00 12.50 99.88 20.00 5.70 4.70 14.50 5.00 46.10 103.80 4.00 208.20 4.90 24.80 0.60 0.00 43.10 0.20 1.20 8.50 12.00 2.80 0.00 0.00 0.00 0.00 0.00 3.30 0.00 0.00 0.00 129.70 14.50 37.50 50.00 5.05 14.40 1.96 0.08 1.56 0.31 1.96 0.43 1.47 0.27 1.95 0.32 117.26 4.01

71.99 10.39 0.64 0.6 0.24 2.88 3.27 0.06 0.03 0.00 0.00 0.00 9.80 99.87 247.00 4.20 3.20 7.60 5.10 94.40 236.10 2.00 84.00 3.90 26.10 0.80 0.00 19.60 0.20 0.60 7.10 13.00 0.40 1.20 0.00 0.00 0.30 0.00 2.10 0.00 0.00 0.00 133.80 38.40 72.80 197.70 12.40 37.50 6.48 0.19 5.41 0.97 5.96 1.21 3.99 0.63 4.21 0.64 350.09 9.47

70.35 15.42 1.25 4.43 2.11 0.1 0.19 0.04 0.01 0.01 0.00 0.00 5.96 99.87 814.80 1.50 4.00 14.20 2.80 9.00 23.20 2.00 208.30 0.50 11.70 3.00 6.00 0.70 0.00 2.80 25.90 26.00 2.10 2.30 0.00 0.40 0.40 0.00 0.00 0.00 0.10 0.50 89.90 23.50 20.50 42.40 4.79 17.50 3.57 0.51 3.24 0.61 3.70 0.74 2.16 0.35 2.28 0.35 102.70 5.14

61.53 13.73 2.93 1.03 2.69 1.56 1.87 0.47 0.03 0.05 0.00 11.00 14.00 99.88 223.00 3.70 1.30 12.80 4.00 6.40 45.00 1.00 199.90 0.50 4.30 0.90 32.00 0.60 0.00 4.60 3.40 12.00 0.40 0.50 0.00 0.00 0.00 0.00 0.70 0.01 0.00 0.00 136.10 17.90 14.30 29.70 3.79 14.80 3.29 0.94 3.27 0.54 3.09 0.62 1.77 0.29 1.99 0.31 78.70 4.36

M.Ç. Karakaya et al. / Ore Geology Reviews 48 (2012) 197–224

Sample

MRE LRE TRTE HFSE LILE Eu* Ce* La/Yb La/Sm Gd/Yb CIA CIW K.I. AI CCPI

13.63 168.53 172.48 2264.1 2373.8 0.82 1.06 18.15 5.10 1.55 91.90 93.09 2.67 65.31 93.06

16.47 189.51 118.93 1864.1 2019.3 0.81 1.05 14.98 5.02 1.34 96.01 97.06 2.29 63.07 95.83

14.57 138.78 135.80 1974.6 2447.7 0.88 1.07 11.72 4.06 1.41 98.49 99.82 2.65 66.21 97.56

4.03 31.38 21.84 539.8 4514.8 0.50 1.02 3.76 5.58 0.46 77.36 74.89 12.50 57.35 59.53

13.26 211.98 9.80 1012.6 4648.3 0.43 1.11 19.52 7.52 1.24 76.92 83.24 10.83 55.00 68.75

8.36 87.36 14.80 847.4 7199.5 0.22 0.67 15.53 7.03 1.22 86.60 86.45 14.43 66.26 74.82

8.93 95.41 102.77 1002.5 4320.1 0.20 0.78 9.26 7.21 0.70 91.44 89.17 9.13 56.89 76.36

11.63 123.29 27.08 778.2 5612.6 0.12 1.02 7.85 6.38 0.74 87.37 84.92 12.67 53.66 70.50

11.63 141.59 36.60 651.8 4960.9 0.09 0.94 9.59 7.39 0.74 89.66 88.84 12.76 57.63 74.03

9.64 138.5 25.20 684.6 19,117 0.13 0.85 13.66 9.16 0.79 75.54 79.29 35.49 64.51 51.71

6.64 101.24 22.50 675.2 13,284 0.14 0.81 11.16 11.82 0.52 82.55 85.70 26.19 65.31 59.71

17.62 192.86 30.80 767.1 9541.1 0.10 0.69 11.41 7.30 0.84 79.45 86.46 18.62 68.62 71.26

15.67 207.89 40.90 1537.1 19,253 0.26 0.87 15.49 7.51 1.05 66.95 75.82 30.00 52.67 49.01

9.90 122.22 37.30 845.8 11,082 0.22 0.87 10.84 8.13 0.76 82.46 85.09 23.06 56.04 61.84

13.03 164.94 28.90 879.6 6862.9 0.21 1.21 7.89 7.25 0.63 89.45 90.46 12.78 64.24 78.24

Kaolinitic alteration

11.73 143.48 21.30 867.5 19,817 0.14 0.98 9.73 7.72 0.73 65.60 73.92 30.85 60.65 45.36

11.55 123.98 34.30 826.9 8718.8 0.15 0.60 10.33 8.99 0.67 84.01 90.22 16.97 68.24 74.43

6.30 106.95 21.70 752.6 11,118 0.15 0.87 12.97 12.04 0.57 79.31 86.74 23.76 63.90 61.97

20.22 320.4 18.20 727.8 27,825 0.10 1.58 11.66 7.07 0.91 54.59 66.75 46.78 55.36 16.78

12.37 85.19 38.40 385.6 2688.8 0.49 1.03 6.06 3.61 1.01 96.65 97.91 2.78 95.10

11.75 62.59 63.70 3095.6 16,017 0.94 0.97 4.84 2.73 1.16 65.73 72.79 26.15 67.64 53.60

Propylitic alteration

K-85

K-86

K-87

K-88

K-89

K-90

K-91

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc LOI Sum Ba Co Cs Ga Hf Nb Rb Sn Sr Ta Th U V W Mo Cu Pb Zn Ni As Cd Sb Bi Ag Au Hg Tl Se Zr Y

50.64 38.60 1.50 b mdl 0.23 b mdl 0.10 0.40 0.10 0.01 b mdl 22.00 10.46 99.29 114.9 b mdl 0.50 24.50 0.50 0.60 5.00 1.00 435.5 b mdl 2.80 1.40 48.0 0.60 0.10 3.10 4.50 1.00 0.20 12.50 b mdl 1.10 1.40 0.20 1.90 0.08 0.10 b mdl 15.60 1.40

52.72 29.33 1.76 0.04 0.01 0.01 0.21 0.78 b mdl b mdl b mdl 23.00 14.20 99.51 3979 1.70 b mdl 34.00 12.80 19.60 5.20 2.00 78.4 1.20 7.70 0.90 69.0 117.4 16.90 459.10 511.20 603.00 0.20 235.30 3.60 50.60 35.00 3.10 119.90 0.83 10.60 16.20 1230.0 46.60

57.26 33.26 0.19 0.12 0.16 0.05 0.06 1.38 0.15 b mdl 0.01 15.00 8.80 99.85 488.2 0.90 1.20 35.30 8.60 29.40 5.20 4.00 41.1 3.10 66.40 1.40 11.0 12.70 0.50 166.30 30.60 256.00 1.40 37.90 1.50 2.40 0.20 b mdl 1.00 0.09 0.20 0.70 201.70 13.70

48.93 37.86 b mdl b mdl 0.17 b mdl 0.32 0.31 b mdl b mdl b mdl b mdl 11.97 99.56 182.0 2.10 0.20 103.50 2.40 6.90 b mdl 12.00 5872.4 0.40 23.40 2.20 257.0 11.60 0.70 1.10 42.20 b mdl 0.40 8.20 b mdl 1.30 0.50 b mdl b mdl 0.04 b mdl b mdl 98.90 1.30

52.54 33.58 b mdl b mdl 0.17 b mdl 1.40 1.08 b mdl 0.14 b mdl b mdl 10.57 99.48 156.7 b mdl 0.10 30.90 8.20 20.60 b mdl 8.00 4808.9 1.10 39.40 2.60 83.0 7.80 0.30 1.00 5.70 1.00 0.30 5.70 b mdl 0.50 0.30 b mdl 1.30 0.04 b mdl 0.00 316.10 7.50

45.90 29.28 4.84 1.08 0.01 0.12 6.84 1.48 0.04 0.00 b mdl 24.00 9.80 99.69 2559 5.20 0.60 19.00 5.90 10.70 71.40 1.00 111.6 0.70 7.00 1.70 22.0 28.70 104.30 17.30 284.00 6.00 0.20 175.80 b mdl 1.80 36.00 0.90 97.50 0.20 5.80 27.10 609.70 109.00

54.06 31.93 0.76 b mdl 0.03 b mdl 2.87 0.45 b mdl 0.32 b mdl 20.00 8.73 99.14 1075 b mdl 1.80 14.80 1.30 1.70 25.60 b mdl 2264.9 0.10 18.70 3.10 128.0 0.80 1.10 3.80 12.20 5.00 0.30 21.30 b mdl 4.10 2.50 0.30 1.90 0.02 3.00 0.60 33.00 3.10

K-92 66.43 13.60 4.03 3.20 1.42 2.45 2.79 0.46 0.11 0.16 b mdl 10.00 5.30 99.87 155.0 4.50 0.80 13.50 2.60 4.30 36.40 1.00 34.5 0.30 2.50 0.90 44.0 0.30 0.40 1.30 4.20 81.00 0.70 b mdl b mdl b mdl b mdl b mdl 1.20 b mdl b mdl b mdl 95.90 23.10

K-93

K-94

K-95

STD*

DL

46.41 15.93 13.32 6.12 5.94 3.97 0.34 0.83 0.09 0.12 b mdl 38.00 6.70 99.78 78.0 37.60 2.30 16.50 1.30 1.70 8.50 b mdl 324.6 b mdl 0.70 0.20 327.0 0.20 0.90 126.30 4.20 78.00 26.00 3.40 0.10 0.20 0.10 0.10 2.60 b mdl b mdl b mdl 38.80 19.90

40.88 16.24 8.22 4.16 8.73 1.29 0.88 0.68 0.13 0.11 b mdl 25.00 18.50 99.83 25.7 25.50 0.70 16.00 1.80 2.40 16.50 b mdl 193.0 0.20 1.40 0.40 235.0 0.20 0.90 13.80 3.80 84.00 18.50 4.40 0.10 0.20 0.10 0.00 2.10 b mdl b mdl b mdl 63.40 18.50

50.39 20.30 7.77 5.12 4.43 5.97 0.29 0.54 0.14 0.12 0.01 18.00 4.70 99.78 99.8 23.70 b mdl 18.80 2.80 3.90 2.50 b mdl 419.1 0.40 5.40 0.20 102.0 0.90 0.20 1.40 1.00 51.00 17.60 b mdl b mdl b mdl b mdl b mdl 0.90 b mdl b mdl b mdl 108.30 11.60

58.04 14.14 7.61 3.33 6.38 3.68 2.16 0.69 0.82 0.39 0.55 25.00 1.90 99.70 497.0 27.20 6.90 17.20 9.60 21.20 28.20 15.00 406.80 7.20 10.30 16.40 207.00 14.80 19.10 106.9 65.90 385.0 53.20 53.40 5.80 3.30 4.40 0.70 51.00 0.20 4.30 3.70 284.9 31.50

0.01 0.01 0.04 0.01 0.01 0.01 0.01 0.01 0.01 0.002 0.1 0.01 0.02 1.00 0.20 0.10 0.50 0.10 0.10 0.10 0.50 0.10 0.20 0.10 8.00 0.10 0.10 0.10 0.10 0.02 0.30 0.05 0.02 0.05 0.01 0.05 0.02 0.03 0.01 0.05 0.01 0.10 0.10

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Sample

210

Table 3 (continued) Kaolinitic alteration

Propylitic alteration

K-85

K-86

K-87

K-88

K-89

K-90

K-91

K-92

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu REE HREE MRE LRE TRTE HFSE LILE Eu* Ce* La/Yb La/Sm Gd/Yb CIA CIW K.I. AI CCPI

6.20 15.60 1.95 9.20 1.66 0.28 0.63 0.05 0.22 0.04 0.12 0.02 0.14 0.03 36.14 0.31 2.88 32.95 74.3 2851 1401 0.89 1.08 29.86 2.35 3.19 99.72 100.0 30.3 40.56 82.87

7.00 26.10 2.14 10.20 4.50 1.68 6.70 1.43 12.51 2.89 10.71 2.13 18.60 2.83 109.42 34.27 29.71 45.44 1156 5940 6333 1.00 1.62 0.25 0.98 0.26 99.18 99.89 77.78 11.90 88.02

45.90 96.30 10.57 35.10 4.80 0.80 2.84 0.48 2.48 0.42 1.21 0.20 1.26 0.20 202.56 2.87 11.82 187.9 484.8 9171 1178 0.71 1.05 24.56 6.02 1.60 99.76 99.73 15.38 84.75 88.57

56.80 73.50 5.61 14.80 1.67 0.23 0.57 0.05 0.19 0.03 0.13 0.02 0.16 0.03 153.79 0.34 2.74 150.7 260.6 1967 8836 0.77 0.99 239.34 21.39 2.52 99.09 99.51 65.31 51.55 73.81

62.50 125.50 12.19 39.30 4.39 0.70 1.56 0.21 1.14 0.20 0.78 0.12 0.95 0.14 249.68 1.99 8.20 239.49 85.3 6821 16,699 0.87 1.09 44.35 8.96 1.16 95.68 100.00 89.17 46.15

2.40 5.70 0.68 3.60 2.60 0.63 6.94 1.82 14.15 3.68 12.34 2.01 14.79 2.42 73.76 31.56 29.82 12.38 88.4 9674 59,823 0.48 1.07 0.11 0.58 0.33 79.56 99.27 84.97 98.20 46.00

35.80 83.60 10.23 48.00 9.32 1.59 3.37 0.23 0.62 0.06 0.19 0.05 0.34 0.05 193.45 0.63 15.19 177.63 150.8 2767 27,264 0.93 1.05 70.99 2.42 7.02 91.13 99.83 98.97 98.29 20.80

12.20 23.90 2.65 12.40 2.80 0.91 2.95 0.56 3.54 0.79 2.43 0.37 2.47 0.40 68.37 5.67 11.55 51.15 141.5 3341 23,409 1.03 1.01 3.33 2.74 0.85 59.21 62.78 28.30 54.35 61.10

K-93 3.70 9.00 1.35 7.00 2.10 0.89 2.74 0.49 3.40 0.70 2.19 0.32 2.00 0.31 36.19 4.82 10.32 21.05 639.7 5410 3245 1.21 0.97 1.25 1.11 0.97 54.25 54.94 2.08 39.46 81.85

K-94 7.10 16.20 2.04 9.60 2.60 0.91 2.90 0.52 3.03 0.64 1.93 0.28 1.70 0.27 49.72 4.18 10.60 34.94 408.6 4712 7554 1.08 1.02 2.82 1.72 1.21 75.75 79.28 5.84 37.82 76.63

K-95 14.80 27.90 2.86 11.00 2.50 0.81 2.20 0.36 2.20 0.44 1.22 0.18 1.15 0.18 67.80 2.73 8.51 56.56 254.8 3964 2950 1.13 1.03 8.68 3.72 1.36 53.20 53.17 1.83 34.22 67.31

STD* 12.10 27.30 3.41 13.90 2.91 0.86 2.91 0.51 2.98 0.61 1.84 0.28 1.77 0.27

DL 1.00 0.10 0.02 0.3 0.05 0.02 0.05 0.01 0.05 0.02 0.03 0.01 0.05 0.01

Note: chemical alteration (CIA), chemical weathering (CIW), alteration (AI), chlorite–carbonate–pyrite (CCPI), potassium (KI) ındexes; mdl: below detection limit; mdl: minimum detection limit; STD*: standard for major and trace, and refractory elements are SO-18 and DS7, respectively.

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porphyritic, hyalomicrolitic porphyritic, glomeroporphyric and felsitic. Plagioclase phenocrysts contain the lowest anorthite content in the dacite (An32–35) and rhyodacite (An22–26). Subhedral to euhedral plagioclase is the most common phenocryst phase and some of these crystals exceed 1 mm in the long dimension. The plagioclase phenocrysts often show normal or oscillatory zoning. Two types of plagioclase are found together; the first type is quite clear and characterized by normal zoning, whereas the second type is marked by a sieve-like or dusty texture in the core or rim. Euhedral to subhedral phenocrysts of quartz are strongly corroded and embayed. 4.2. Mineralogy and petrography and of the altered rocks Late Cretaceous volcanic host rocks were subjected to intense potassic, phyllic (sericitic), argillic (kaolinitic and smectitic), silicic, propylitic and hematitic alteration processes during fluid–rock interaction related to VMS mineralization. The parent rock and moderately-altered rocks are gray to dark-gray in color. The main minerals and anorthite content of the moderately-altered rocks are, however, similar to the parent rocks. The moderately-altered rocks contain hornblende and subhedral biotite, both of which are dark brown in natural light, and have been replaced and surrounded by a dark halo of Fe-oxyhydroxides. Opacite pseudomorphs have formed and replacement by oxides has occurred. The matrix is typically glassy (colorless, variably devitrified) and locally displays flowbanded textures with fine-grained plagioclase crystallites. Propylitic alteration, observed as carbonatization and chloritization, is almost always associated with sericitic alteration. The main constituents of the alteration are calcite, epidote, zeosite, albite and chlorite which are observed as interstitial coarse crystals (Fig. 7). Replacement of the anorthite-rich zones of plagioclase by calcite is observed. Hornblende and biotite are first chloritized, and then carbonatized starting from the central parts of the grains. Chloritization of the mafic constituents formed as a by-product of sericitic alteration; MgO is supplied from these minerals. Phyllitic-altered samples are composed mainly of illite and subordinate kaolinite and quartz. Quartz phenocrysts are rounded and corroded, and the corrosion pores filled by clay minerals. Some corrosion features suggest replacement of quartz phenocrysts. Kaolinite, alunite, quartz and disseminated pyrite are the main components of the argillic alteration. Locally, alunite is associated with gypsum. Smectite (mainly montmorillonite) was observed in different colors, including purple, white, and pale green. Smectite is sometimes pure or associated with one or two minerals e.g., with quartz and/or silica polymorphs and clay minerals, and forms economic bentonite deposits in different regions, e.g. Ünye, Göbü, Ulubey, Fatsa, Kumru, etc. (Çelik et al., 1999; Karakaya and Karakaya, 2001a,b; Karakaya et al., 2011, Fig. 2). Original fragments of volcanoclastic material, which are generally volcanic glass, have been altered to montmorillonite. The bentonite deposits contain about 0–10% non-clay minerals, such as biotite, opal-CT, cristobalite and pyrite (Fig. 8A). Hematitic alteration, developed in the upper part of pyrite-rich orebodies, is represented by the presence of hematite, goethite, jarosite and, rarely, barite (Fig. 8A). Potassic alteration is characterized by mineral assemblages of orthoclase, sanidine, quartz and biotite. Orthoclase is typically a green color and difficult to distinguish from adularia via XRD alone (Fig. 8A). The low-K illite samples contain smectitic layers and the crystallinity of these illites is poorer than the high-K illites. The reflection of low-K illites is broad and shows an asymmetry towards the low angle side, with prominent higher order at 5.04, 3.33, 2.57 and 1.99 Å in air-dried samples. The 10.20 Å reflection of the low-K illites shows overlapping of 12 Å reflections (Fig. 8A, B). The illite exhibits dioctahedral type with a d (060) value of 1.496 Å and its behavior after glycol treatments is the same.

211

Kaolinite is found in minor or trace quantities within the halo of the vein system, associated with K-feldspar, 10 Å micas and quartz in most of the investigated deposits, e.g. Lahanos, Harşit, Killik, and Karaerik (Fig. 2). No other phyllosilicates were found and the glycol solvation allows us to discard the presence of expandable clay minerals (I/Sm inter-layers or smectites). Among the sulfate minerals, only gypsum and jarosite were identified and alunite was detected in subordinate quantities. The crystallinity of kaolinite is generally poor, with XRD patterns typically showing broad d (001) reflections, often with a distinct asymmetry towards the low-angle side. A broad d (002) reflection and disordered, continuous reflection were observed. Ca-bentonite contains kaolinite, albite and silica polymorphs (i.e., quartz and opal-CT). Their XRD peaks are at 7.25, 3.34 and 4.12 and 4.04 Å, respectively, with the latter the more intense of the two. The basal spacing (001) of the untreated Ca-montmorillonite is between 14.40 and 15.12 Å. Second, third, fourth and fifth order basal spacing can be identified in the XRD patterns of the untreated and glycolated samples; in the heated samples, only the first-, second- and thirdorder spacing are present (Fig. 8C). The glycolation of Ca-bentonite caused a shift of the smectite peak from 14.40 to 17.25 Å. The absence of mixed-layer illite–smectite minerals is inferred from the width of the 17 Å peak (ethylene glycol-solvated) and the existence of rational d-spacing of the remaining basal reflections. Heating at 490 °C results in a collapsed smectite peak at 10.32 and 9.90 Å.

4.3. Chemical features The parent rock samples are poor in Mg and Fe and contain between 4.83 and 7.68 wt.% (Na2O + K2O). In the moderately-altered samples, Mg is poor and Fe is partially enriched. SiO2 and Al2O3 are major components of all sample groups (Table 3). SiO2 in the silicicalteration (87.66wt.%) and Fe2O3 (54.75wt.%) in the hematiticalteration are higher than in the other sample groups. TiO2, except for a few samples from the silicic and kaolinitic alteration, is also b1.0 wt.% while MnO and P2O5 concentrations are lower by 1.0 wt.% or than the detection limit in all samples. The degree of weathering can be calculated using the chemical index of weathering, CIA = [(Al2O3) / (Al2O3 + CaO* + Na2O + K2O)] × 100, where the values are expressed as molar proportions, and CaO* is the amount of CaO incorporated in the silicate fraction of the rock (Nesbitt and Young, 1982, 1984). Bulk compositions of profile materials are portrayed on an A–CN–K diagram (Fig. 9; Nesbitt and Young, 1984). Moderately-altered samples have a mean CIA of 61.55 and are slightly enriched in REE (except Eu) if compared to the parent rock. REE patterns of the kaolinitic-, smectitic-, silicic-, phyllitic- and hematitic-altered samples with CIA values of 95.45, 88.81, 79.74, 76.74 and 72.74, respectively, are distinct from one another. The hematitic-altered samples show different behaviors and generally plot in the CN corner of the diagram, e.g., samples K-30 to K-36. The CIA value of potassic- (56.58) and propylitic-altered samples (60.60) are similar to the parent rock and moderately-altered rocks. The parent rock and moderately-altered samples, and some smectiticaltered samples, are located in the same area of the A–CN–K diagram; potassic-altered samples follow a nearly parallel trend to the CN–K line. The phyllitic-, kaolinitic-, two samples of moderately-altered, and hematitic-altered samples are located on the AK-line and near or on the A-corner. The smectitic-altered samples are situated on the A– CN-line, and hematitic-altered samples are located at the CN-corner (Fig. 9). The alteration facies of the ore deposits in the NE Black Sea region can be separated into mineralogical and geochemical components using the concentrations of MgO, Fe2O3, K2O, Na2O and CaO (i.e., alteration box plot; Large et al., 2001; Fig. 10). The alteration index (Ishikawa et al., 1976) quantifies Ca and Na depletion and enrichment relative to Mg and K. The carbonate–chlorite–pyrite index (Large

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Table 4 Mass gain and losses (g. ppm) of the altered rocks (based on 100 g of average fresh rock composition and constant TiO2).

PR MPR POA SA HA PA AAS AAK PPA

PR MPR POA SA HA PA AAS AAK PPA

SiO2

Al2O3

Fe2O3

MgO

CaO

74.7 26.0 52.2 70.7 − 48.1 − 16.2 155.5 − 45.9 − 44.6

13.3 4.3 12.1 − 5.44 − 7.77 8.5 30.7 6.2 − 3.9

2.90 1.45 − 0.58 − 1.47 192.6 0.46 1.24 − 2.36 1.47

1.09 0.22 − 0.51 − 0.73 − 0.75 0.12 7.66 − 1.05 1.46

1.50 0.39 − 0.69 − 1.36 − 1.37 − 0.81 3.47 − 1.43 1.16

As

Cd

Sb

Bi

Ag

Au

Hg

Tl

Se

Zr

Y

33.7 − 2.3 − 19.2 31.4 4534 14.2 − 26.1 − 6.5 − 32.8

0.10 0.02 − 0.07 1.03 0.72 0.71 − 0.02 0.18 − 0.08

1.63 2.76 − 1.36 9.34 198 − 0.57 − 1.34 2.47 − 1.59

0.08 0.41 0.50 5.87 263 0.82 0.80 3.8 − 0.06

0.08 0.11 − 0.01 7.36 16.9 0.30 − 0.06 0.20 − 0.07

1.41 8.71 1.80 65.1 2283 17.2 2.40 9.8 − 0.51

0.00 0.02 0.01 0.78 8.5 0.37 0.00 0.08 0.00

0.12 − 0.09 − 0.04 1.56 12.8 − 0.02 0.02 1.07 − 0.12

0.00 0.39 0.00 6.12

123 79 126 120 − 18.8 5.6 315 16 − 76

23.1 9.8 22.7 18.9 − 6.9 9.3 54.9 − 15.1 − 12.7

Na2O 3.46 − 0.28 − 0.18 − 3.27 − 3.41 − 3.20 − 0.61 − 3.45 − 1.50

K2O

TiO2

P2O5

MnO

Cr2O3

LOI

Sc

Ba

Co

Cs

Ga

Hf

2.38 2.02 11.47 − 0.19 − 0.77 3.46 1.57 − 1.70 − 1.67

0.34 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.06 0.01 0.02 − 0.03 0.31 − 0.03 − 0.01 − 0.04 0.01

0.05 0.01 0.01 − 0.04 − 0.04 − 0.04 0.02 − 0.01 0.03

0.00 0.00 0.01 0.00 0.01 0.00 0.00 0.00 0.00

99.83 34.14 73.85 58.16 130.7 − 7.81 199.6 − 49.7 − 47.6

7.55 1.00 − 2.19 0.61 − 3.07 − 3.39 − 5.98 − 2.12 4.17

375.0 202.2 897 1256 12,100 670 152.9 140 − 319.4

4.31 4.64 9.43 13.28 2.85 − 1.43 8.67 − 3.67 7.32

1.14 2.04 2.31 − 0.75 − 0.53 0.60 10.17 − 0.79 − 0.67

14.00 4.38 10.44 − 6.16 10.20 0.24 32.83 12.21 − 4.83

3.61 2.56 4.51 3.62 − 0.93 0.17 11.89 − 1.37 − 2.33

La

Ce

Pr

Nd

Sm

Eu

Gd

17.9 13.4 54.4 − 7.8 − 3.8 104.6 121.1 0.6 − 12.0

36.06 26.07 93.55 − 15.6 − 8.50 403.6 199.8 − 2.78 − 24.3

4.03 8.28 27.46 − 5.97 − 1.46 301.4 59.61 − 3.60 − 10.0

15.96 1.41 4.12 − 0.89 0.01 43.05 9.14 − 1.06 − 1.81

3.26 − 0.03 0.33 − 0.32 0.40 7.0 0.11 − 0.38 − 0.31

0.81 1.16 3.13 0.10 − 0.19 13.56 7.20 − 1.81 − 1.62

0.56 0.20 2.0 0.00

36.1 2.69 9.08 − 1.65 − 0.69 61.8 19.6 − 0.7 − 2.7

Note: PR: parent rock, MPR: moderately-altered rock, POA: potassic alteration, SA: silicic alteration, HA: hematitic alteration, PA: phyllic alteration, AAS, AAK: argillic alteration for smectite and kaolinite, respectively, PPA: propylitic alteration.

et al., 2001; Fig. 11) measures total alkali depletion relative to Mg and Fe enrichment associated with chlorite and pyrite alteration. Correlation coefficients were calculated for whole rock samples and different altered-rock groups (Table 5). Al2O3 shows slightly negative or no correlation with all major oxides in the moderately-, kaolinitic- and potassic-altered samples, but shows strong positive correlation with some major oxides, notably MgO and K2O in the kaolinitic-, phyllitic- and hematitic-altered samples. Similar behavior was observed for some of the less mobile elements, such as Zr, Ti, Ta, Nb and Y. TiO2 and Fe2O3 relations are clearly different in various rock groups. The correlations in the sample suites, therefore show different features (Tables 5 and 6). TiO2 displays a strong positive correlation with P, Zr, Nb and Hf in the parent rock, hematitic- and silicic-altered samples (Table 6). HFSE show strong positive correlations (r = 1.0– 0.80) with LREE and some MREE in the rock suites, and a moderately positive correlation (r = 0.79–0.60) in the kaolinitic- and potassicaltered samples. TiO2, HFSE, REE and TRTE present a strong or moderately negative correlation with SiO2 in nearly all sample groups, except for smectite-altered samples. TiO2 and HFSE show strong positive correlations with metallic and precious elements in the potassic-altered samples, and HFSE and REE display a strong positive correlation with the same elements in the hematitic-altered samples. TiO2, HFSE and TRTE display similar behavior to the elements in the propylitic-altered samples (Table 6). According to the mass-balance calculations, SiO2 is strongly depleted in the hematitic-, kaolinitic- and propylitic-altered sample suites, but is enriched in the smectitic-, silicic-, potassic- and moderately-altered samples (Table 4, Fig. 6). Magnesium and Ca appear to have been partially leached out of the system during hematitic-, silicic-, kaolinitic- and potassic-alteration, and accumulated during generation of the smectitic-, propylitic- and moderatelyaltered samples. Notably, gain of Mg and loss of Ca is recognized in the propylitic-altered samples. Na and K are completely lost mass in the silicic-, hematitic-, kaolinitic- and propylitic-altered samples. In the other alteration types, except potassic and moderately-altered samples, Na is depleted, whereas K is enriched. Phosphorus, Mn and Cr are enriched in the potassic-, moderately- and propylitic-altered samples, but depleted in phyllitic- and kaolinitic-altered samples. In the hematitic-, silicic- and smectitic-altered samples, Na and K display different behaviors. Zirconium and Y are enriched in the

potassic-, silicic-, moderately-, smectitic-, phyllitic- altered samples, but depleted in the hematite- and propylitic-altered samples. In contrast, Zr is enriched, but Y is depleted in the kaolinitic-altered samples. Rubidium and Sr show almost immobile behavior in the complete altered rock groups whereas Ba is enriched in all alteration rock suites. Mass gains for LILE are recognized, especially in the potassic-, phyllitic-, moderately-, smectitic- and hematitic-altered samples, but are lost in the kaolinitic- and propylitic-altered samples. In addition, LILE behaved in an immobile way only in the silicic-altered products. HREE and MREE are accumulated during the potassic-, silicic-, moderately-, phyllitic, and smectitic processes; they are leached out of the system during the kaolinitic and propylitic processes, but show nearly immobile behavior during hematitisation. LREE appear to be almost immobile in the silicic-, hematitic- and kaolinitic-altered sample groups; they are, however, enriched in the phyllitic-, smectitic-, potassic- and moderately-altered types, but depleted in the propylitic-altered samples. HFSE mass gains are seen in the hematitic-, smectitic-, potassic-, and moderately-altered samples but lost mass in the phyllitic, kaolinitic, and propylitic products. Total REE concentrations in the samples range from 55.5 ppm to 495.6 ppm. HREE concentrations are generally lower than the LREE and MREE. The TRTE concentration is higher for hematitic-altered samples and lower for smectitic-altered samples. TRTE, HFSE and LILE concentrations are clearly low in the smectitic-altered rocks; HFSE concentrations are high in the kaolinitic-altered samples. Concentrations of the REE are high in the kaolinitic-, smectitic-, potassic- and phyllitic-altered samples, and very low in the propylitic-altered samples (Table 3, Fig. 12A). REE concentration is generally enriched in the altered groups, with the exception of propylitic- and hematitic-altered samples. TRTE are also mainly enriched in altered sample groups, especially in the phyllitic- and hematitic-altered samples, but depleted in the smectitic-altered samples and, to some extent, silicic-altered samples. HFSE are clearly leached in the smectitic-altered samples but accumulated in the other sample groups. LILE is obviously enriched in the potassic- and phyllitic- and slightly enriched in the moderately- and hematitic-altered samples. Other trace elements (W, Mo, As, Cd, Sb, Bi, Au, Ag, Hg and Tl) are strongly enriched in the hematitic-, and kaolinitic-altered samples and moderately in the silicic- and phyllitic-altered samples (Fig. 12B).

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213

Nb

Rb

Sn

Sr

Ta

Th

U

V

W

Mo

Cu

Pb

Zn

6.12 20.08 41.26 3.87 − 1.60 1.08 136.2 − 1.24 − 4.24

59.55 82.85 223.7 − 26.0 − 41.9 10.8 193.4 − 53.3 − 49.5

1.43 1.68 2.67 14.41 9.37 3.89 8.24 1.24 − 1.24

125 − 23 − 14 − 62.8 836 2584 478 1320 4.8

1.18 1.06 3.03 − 0.13 − 0.82 − 0.64 10.41 − 0.85 − 1.04

6.27 9.77 37.65 − 2.77 0.13 6.34 72.04 4.59 − 4.70

1.82 3.52 3.33 1.64 2.17 7.27 6.14 − 0.69 − 1.55

35.92 0.47 − 15.2 − 16.7 79.92 − 4.14 − 18.3 33.18 51.3

1.10 23.95 86.84 379.5 80.70 12.95 54.21 9.95 − 0.86

0.94 0.34 0.79 4.21 441.00 8.4 − 0.28 3.82 − 0.63

80.55 52.5 53.6 80.53 3254.00 361.0 − 70.9 − 44.5 − 65.4

45.00 − 36.4 − 23.7 76.87 5774.00 112.0 1.64 6.1 − 43.2

52.86 − 3.27 − 19.22 99.79 204.5 90.0 16.37 − 5.3 − 11.27

Ho

Er

Tm

Yb

Lu

REE

HREE

MRE

LRE

TRTE

HFSE

2.33 0.20 0.42 0.51 − 0.17 0.10 0.94 − 0.16 − 0.22

0.38 1.4 2.9 3.86 − 0.59 0.7 6.4 − 0.7 − 1.45

2.5 0.2 0.5 0.6 − 0.1 0.1 1.0 − 0.1 − 0.2

0.40 58.03 203.1 − 20.2 − 16.6 943.8 441.3 − 14.6 − 58.3

91.6 3.0 6.2 7.9 − 1.35 2.8 13.8 − 2.1 − 3.1

5.6 4.7 12 2.8 − 0.8 70 27 − 6.0 − 6.2

12.1 50.4 184 −31 − 14 871 400.1 − 6.51 − 49.0

73.9 72.7 58.2 169 3573 424 − 80 − 43 − 22

206 137 269 1.49 1337 − 121 409 − 163 − 45.4

Tb 3.16 0.22 0.57 0.21 − 0.10 1.32 1.34 − 0.37 − 0.30

Dy 0.58 1.58 3.56 2.93 − 0.75 4.44 8.07 − 1.97 − 1.75

3.48 0.34 0.76 0.80 − 0.15 0.34 1.61 − 0.43 − 0.40

0.77 1.12 2.39 2.96 − 0.50 1.87 5.38 − 1.12 − 1.22

Chondrite-normalized REE values of all sample groups show LREEenrichment, HREE-depletion and nearly flat HREE patterns (Fig. 12A). Parent rocks are characterized by REE patterns with moderately steep negative slopes (La/Yb = 4.79) and a considerably negative Eu anomaly (Eu/Eu*CN = 0.82) (Fig. 12A, Table 3). Moderatelypropylitic-, -potassic- and -smectitic-altered sample patterns are similar to that of the parent rock, with the exception of the propylitic subgroup, which displays a positive Eu anomaly (Eu/Eu*CN = 1.11). Kaolinitic- and silicic-altered samples show a concave-shaped pattern with a clearly negative Eu anomaly (Eu/Eu*CN = 0.75, 0.74, respectively). In addition, hematitic- and phyllitic-altered samples display some differentiation with respect to the other sample groups, e.g., phyllitic-altered samples are much more enriched in LREE and somewhat enriched in MREE, whereas hematitic-altered samples are more depleted in HREE compared to the chondrite, with a moderately positive Eu anomaly (Eu/Eu*CN = 1.57). Cerium anomalies, denoted as Ce/Ce*, are defined as the ratio of Ce content normalized to chondrite CeN and calculated as (Ce/Ce*) = CeCN / (LaCN × PrCN)1/2. Slightly positive Ce anomalies were observed in the parent rock, potassic-, moderately- silicic-, phyllitic-, kaolinitic- and propylitic-altered samples. The hematitic- and smectitic-altered samples displayed slightly negative anomalies (Ce/Ce* from 0.81 to 1.14 and 0.60 to 1.58, respectively; Table 3). The lowest REE fractionation, described by the La/YbCN ratio, is found in the silicic-altered samples (2.4), in contrast to the highest REE fractionation which is seen in the smectitic-altered samples (11.49). LREE fractionation, characterized by the (La/Sm)CN ratio, ranges from 1.93 (in PA) to 6.79 (in the smectiticaltered samples). HREE fractionation, given as (Gd/Yb)CN ratio, varies from 0.31 in the smectitic-altered samples to 1.68 in the phylliticaltered samples (Table 3). Some sample groups, e.g., the silicic-, kaolinitic, and partially smectitic-altered samples, show lower (Gd/ Yb)CN than the other sample groups. Therefore, their HREE patterns are characterized by an upward slope (Fig. 12A). SiO2, MgO, and MnO are enriched in highly-altered rock. Alkali loss appears to also be an important expression of alteration for the area. Argillic alteration, e.g., kaolinite-altered samples, dominated by sulfate minerals (mainly alunite and partly jarosite and natroalunite) also occurs. Jarosite occurrences are generally observed close to hematization and are superimposed on the alunite occurrences. The K2O index (KI=K2O/(K2O+Na2O+MgO+CaO)∗100; Shikazono et al., 2008) has a strong- to moderately-negative correlation

Ni 6.20 − 0.96 − 4.11 − 4.30 − 2.32 − 3.68 − 0.37 − 6.00 1.69 LILE 2435 17,041 96,417 − 366 12,293 32,226 14,078 − 12,713 − 14,272

with Eu/Eu* [Eucn/(Smcn × Gdcn) − 1/2] in the parent rock and propyliticand smectitic-altered samples, but the correlation between the K2O index and Eu/Eu* is not clear in other sample groups. The correlation between LREE/REE and Eu/Eu* is moderately positive in the hematitic-, silicic- and moderately-altered samples, and moderately negative in the parent rock, kaolinitic- and potassic-altered rocks.

5. Data interpretation The overlapping of 10 Å reflections of the low-K illite with 12 Å reflections indicates an illite–smectite inter-stratification, and the illite appears to be the 1M polytype. The high-K illite does not show any inter-stratification and is therefore the 2 M polytype. The crystallinity of 2 M illite is better than the 1 M polytype. The increase in crystallinity is related to the K2O content. Smectite, rarely including opal-CT and kaolinite, is typical of argillic alteration. Asymmetry of the basal reflections in the smectites suggests minor mixed-layering; the d060-value is 1.49 to 1.50 Å, indicating a di-octahedral character typical of montmorillonite and beidellite (Wilson, 1987). The characteristics of the main diffraction peaks of the feldspar minerals in the K-6 and K-9 samples (grading to 3.30 and 3.27 Å, in the 201 plane diffracting around 4.22 Å) are in correspondence with those of the orthoclase subgroup, following the criteria of Moore and Reynolds (1997), suggesting the presence of high-potassium feldspar. Macroscopic observations allow us to recognize the presence of adularia in these samples. Two types of adularia can be distinguished. The first type of adularia is Na-rich (2.21 wt.% Na2O), contains traces of Ba (24 ppm), and occurs replacing plagioclase. The second type is Na-poor (0.30 wt.% Na2O), but richer in Ba than the first type (650 ppm), and occurs in the fine-grained quartz veinlets. Ca was detected below 0.20% in both samples. The SiO2 content of the parent rock samples varies from 64.80 to 75.75 wt.%, which is within the range typical for fresh, modern felsic volcanites (Le Maitre et al., 1989). Increasing intensity of alteration is coupled with a gradual decrease in Na2O and K2O in some sample groups, e.g., moderately-, silicic-, hematitic-, smectitic- and kaoliniticaltered samples, culminating in intensely altered dacites/rhyolites with b0.3 wt.% (Na2O + K2O). The moderately-altered samples contain between 2.66 and 7.23 wt.% (Na2O + K2O) and SiO2 content ranges from 60.18 to 78.00 wt.%, except for a single sample.

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Fig. 6. Mass changes of major elements and of total TRTE, REE, HFS and LIL (ppm) elements of the investigated samples. Mass gains and losses of components are equivalent to weight percent changes if the precursor mass is taken as 100 g. The error bars correspond to the standard deviation. Abbreviations were given in Table. 4.

Therefore, the moderately-altered samples are dacite, rhyolite and andesite (Le Maitre et al., 1989). Despite some differences in major element content, all the slightly and moderately altered parent rocks (PR and MPR, respectively) and other sample suites are characterized by rhyolite/dacite, andesite, and rhyolite compositions. Three kaolinitic-altered samples plotted on andesite/basalt or sub-alkaline basalt area in the Nb/Y vs. Zr/TiO2 diagram of Winchester and Floyd (1977). The Zr/TiO2 vs. Nb/Yb diagram shows that the potassic-altered samples have lower Nb/Yb ratios than the parent rocks and moderately silicic- and phylliticaltered samples, whereas most of the kaolinitic-altered samples exhibit depletion in Zr/TiO2 ratio relative to the abovementioned sample groups. However, Nb/Yb ratios of the smectitic-altered samples are higher than those of the other sample groups (Fig. 13). These elements, commonly accepted as relatively immobile, showed different ratios in various alteration types; this may relate to their dissimilar behaviors. Loss of alkalis and earth alkalis (CaO, MgO, Na2O and K2Owt.%) and gain of sesquioxides (Al2O3, TiO2wt.%), in addition to increasing H2O, as reflected by loss-on-ignition (LOI) indicate progressive alteration of the parent rock. Primary Ca-, Na- and K-bearing silicates are leached during weathering, and are replaced by newly-formed Al-rich clay minerals and sulfates, so that the proportion of Al2O3 to CaO* + Na2O + K2O increases in the weathered products.

AI increases as a result of plagioclase destruction or epidote, chlorite, calcite, muscovite/illite and orthoclase formation. A combination of the two indices in the box plot enables discrimination of the main alteration assemblages and distinguishes unaltered or weaklyaltered samples representing background composition group samples from those which experienced more intense hydrothermal alteration (Paulick et al., 2001). The coefficient between elements shows important discrepancies between the different rock groups. Different correlation coefficients may relate to the differential mobility of these elements under changing conditions of chemical alteration—i.e., pH, temperature, Eh (redox potential), and types and concentration of ion complexes (SO42 −, Cl −, F−, CO32 −, etc.). TiO2 correlates with some elements in the HFSE group, e.g., P, Zr, Hf, Nb and Ta, which are mostly conserved during the alteration. 6. Discussion It can be inferred that the hydrothermal pulses were caused by distinct periods of post-volcanic activity and changing water/rock interactions by comparing petrographic and geochemical properties of altered and fresh rocks. The propylitic-altered rocks contain epidote, chlorite, albite and carbonate minerals (mainly calcite) formed from the destruction of feldspar and biotite. This mineral

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215

Fig. 7. Photomicrographs (crossed nicols, except left side of K-95) of typical dacite and rhyodacite in the PR and MPR, and also POA, SA and PPA samples, which include albite (Ab), biotite (Bt), calcite (Cal), epidote (Ep), quartz (Qz), plagioclase (Pl) and chlorite (Chl) phenocryts (abbreviation from Whitney and Evans, 2010). Various alteration types such as albitization, chloritization, epidotization, sossuritization, carbonatization, argillitization and silicification have been developed by effecting hydrothermal processes during fluid– rock interaction (PR: parent rocks, MPR: moderately-, POA: potassic-, SA: silicic-, PPA: propylitic-, HA: hematitic, AAS: smectitic, AAK: kaolinitic, PA: phyllitic-altered rocks).

paragenesis represents propylitic alteration at high temperature, in excess of about 200 °C (Inoue, 1993). Not including pumpellyite in the paragenesis of the alteration indicates that the fugacity of CO2 is significantly high (Inoue and Utada, 1991). Hydrothermal carbonate alteration is common in volcanic-hosted massive sulfide deposits and has been described in several deposits (Galley et al., 1993; Paulick et al., 2001; Shikazono et al., 1998, 2008). It has also been observed in modern, submarine hydrothermal systems (Goodfellow et al., 1993). In general, oxidizing conditions and low temperatures (b100 to 200 °C) are inferred from carbonate alteration (Paulick et al., 2001).

The calcareous alteration may be formed at early to middle stages of alteration. K-feldspar (mainly orthoclase), magnesian biotite and some quartz are typical of the potassic-altered rocks, which often show complex overprinting relationships with the mottled alteration facies. The formation of feldspar rather than sericite suggested that the pH of the hydrothermal fluids increased from acidic in the central parts of the hydrothermal alteration system to near-neutral on its fringes (Paulick, et al., 2001). The authors stated that the potassic alteration facies were observed locally on the fringes of the footwall alteration

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Fig. 8. (A): X-ray diffraction pattern of random powder patterns of studied bulk samples showing the main reflections (Å) and minerals identified in some samples. B: barite; G: goethite, H: hematite; J: Jarosite; I: illite, K: kaolinite S: smectite, Qz: quartz, Op-CT: opal-CT and O: orthoclase. B, C: X-ray diffraction pattern of b2 μm fraction oriented in natural condition, after heated at 490 °C and solvated in ethylene glycol atmosphere illite (B) and smectite (C) samples.

zones of the Thalanga VMS deposits. In the study area, potassic alteration zone is also observed in the outer parts of the alteration system, as well as in the Kuroko deposits in Japan (Shirozo, 1974) and Que River deposits (McGoldrick and Large, 1992), and inferred that this type of alteration took place under relatively low temperature conditions and low fluid/rock ratios (Paulick et al., 2001). Argillic alteration is classified into two alteration groups: kaolinitic- and smectitic-alteration. The kaolitic-altered rocks also contain some sulfates, mainly alunite and some jarosite, and rare

occurrences of natroalunite. Jarosite occurrences are generally observed close to hematitisation and are superimposed on alunite; textural evidence suggests a supergene origin of these minerals. Leached caps are characterized by a variety of iron oxide-sulfate minerals, especially goethite, hematite and jarosite, with clays and barite. Some of these are shown in Fig. 8A and also include alunite, gypsum, jarosite, kaolinite, opal, quartz and scorodite. Leach caps are typically highly oxidized with red, orange-yellow, and pink hues due to the weathered and altered Fe-minerals present.

Fig. 9. Triangular Al2O3–(CaO* + Na2O)–K2O plot diagram (Nesbitt and Young, 1982) of investigated samples. The predicted weathering trends are more or less parallel to the Al2O3–CaO* + Na2O line, suggesting that loss of K is less than CaO and Na2O. CaO* = mole CaO-(mole P2O5 × 10 / 3). Ka: kaolinite, Gb: gibbsite, Chl: chlorite, other abbreviations were given in Fig. 7.

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Fig. 10. Slightly altered dacite is relatively MgO and Fe2O3 poor, containing 1.07 to 2.84 wt.% (Na2O + CaO). The composition of moderately- to intensely altered rock groups indicates that hydrothermal alteration is dominated by processes such as destruction of primary feldspar, sericitization, chloritization, and pyritization leading to Na2O loss and elevated Na2O + MgO. A combination of carbonate alteration and chloritization is inferred to have formed the hydrothermal precursor to disseminated plagioclase, hornblende and biotite alteration. Albite-altered hanging wall dacite has high Na2O concentration and plots to the right of slightly altered dacite. See Fig. 9 for legend and Fig. 7 for abbreviations.

Hydrothermal hematitic alteration developed at the uppermost part of the VMS mineralization was overprinted by weathering processes evidenced by red to orange colored earthy goethite, limonite, jarosite, and secondary hematite, malachite, and azurite assemblages. By reaction with a strongly acidic primary solution (rich in SO42 −), the acidic to intermediate rocks were almost entirely altered to quartz + opal ± cristobalite along high-percolation zones. Alunite is accepted as of supergene origin in the high-sulfidation alteration type (Hayba et al., 1985; Heald et al., 1987). Studies by Rye et al. (1992) reveal the possibility for alunite generation from oxidation of H2S on the top of the boiling part of high-sulfidation systems. The resulting strongly acidic solutions contain mainly aluminum (besides silicon and other elements) and cause extensive alteration to silica mineral + jarosite/alunite in adjacent rocks, when the pH of the solution are high (pH = 4 to 5), kaolinite precipitated with or without alunite. The presence of alunite as a characteristic mineral phase in such low temperature hydrothermal facies indicates a high sulfate ion activity in hydrothermal solution (Knight, 1977). A change from alunite to jarosite indicates a change from Al to Fe 3 + in the sulfate-mineral structure, probably reflecting a decrease in the solubility of Al relative to Fe 3 + and a decrease in pH.

217

Alteration of volcanic rocks is characterized by different element behaviors in different alteration types, except for the immobile elements, e.g., Ti, P, Mn and Cr. Strong Si and Fe enrichment and severe leaching of major oxides, particularly Na2O, CaO and MgO in the silicic-, moderately- and hematitic-altered rocks, are related to the nature of the alteration types near the orebodies (Table 4). K2O is usually enriched in the potassic-, phyllitic- and moderately-altered rocks. Therefore, a progressive increase in the K/Na ratios was observed towards the potassic and phyllitic zones. K, Rb, Ba, Sr and REE (especially LREE) were enriched in the phyllitic (generally at the footwall) and Ca, Na and Mn were depleted relative to other samples, especially in hanging wall samples (silicic and hematitic). This process must be acidic and requires oxidizing environment conditions because Si was removed by an alkaline solution. On the other hand, the silica gain, or loss, in altered rocks and the alkaline or alkaline-earth element leaching from the system indicate that the acidic and basic conditions alternated during the alteration processes. High-temperature acid solution has the potential to leach most rock-forming elements, e.g., Na, K, Mg, and Ca, which are formed in mineral assemblages in the parent rock. The very aggressive acidic solutions produced kaolinite, alunite and jarosite, in addition to silica. Native sulfur, alunite, and pyrite are major constituent mineral characteristic of acidic alteration (Inoue, 1993). The moderately- and smectitic-altered samples are predominant in the depletion of only Na2O, the other alteration types are also characterized by enrichment of the other elements, especially Si and Al. CaO is strongly enriched in the smectitic-altered samples in relation to the composition of the bentonites. Also, the similarity of the element behavior of the moderately- and smectitic-altered samples explain that the two rock groups originated from nearly same parent rock or process. The most important mass-loss was developed during kaolinitic-alteration. The other elements were leached out of the system, when Al could be volumetrically enriched. In general, the component Al2O3 is conventionally considered to be conserved in rocks during hydrothermal alteration because of its low solubility in moderately acidic solutions. However, if the pH of the solution is extremely low (b4 at 20 °C), Al2O3 is more easily dissolved in the solution, whereas SiO2 is relatively insoluble (Inoue, 1993). The addition of SiO2 to the hydrothermal solutions causes alteration of feldspar to kaolinite. This type of alteration by extremely acidic solutions has also been reported in many hydrothermal systems related to sulfur deposits (Inoue, 1993). Whereas silica polymorphs, gypsum, black-ore minerals, kaolinite, and alunite form under strongly acidic conditions, illite and montmorillonite form under weakly acidic and weakly

Fig. 11. The various alteration facies at the eastern Black Sea can be discriminated geochemically in the alteration box-plot (Large et al., 2001). Separate fields are occupied by the data from slightly altered dacite, intense iron oxide-rich mineral alteration, argillic, propylitic, silicic, potassic and intense calcareous alteration. Samples of quartz-K-feldspar alteration facies plot in the lower right-hand corner defining a trend toward the composition of K-feldspar. Hanging-wall, slightly- to moderately-altered dacite and rhyodacite plotted to the left of the box for least altered dacite. Samples from the intense altered section plot above the diagonal line, separate analyses showing geochemical characteristics reflecting the effects of hydrothermal alteration from samples representing background composition. See Fig. 9 for legend.

218

Table 5 Correlation coefficients between analyzed elements in the investigated samples. Na2O K2O

1.0 −0.1 1.0 −0.8 − 0.4 −0.2 0.3 −0.1 0.1 0.0 0.1 0.1 0.4 0.0 0.1 −0.5 − 0.1 −0.1 0.2 −0.2 − 0.1 −0.1 0.4 −0.4 − 0.2 0.0 0.0 0.1 0.0 0.2 0.0 0.2 0.0 0.1 0.3 −0.4 − 0.1 0.2 0.0 0.1 0.3 −0.1 − 0.2 −0.4 0.3 −0.4 − 0.2 −0.5 − 0.2 −0.2 0.0 −0.2 0.1 −0.1 0.0 0.1 0.1 0.1 0.3 0.0 0.1 0.2 0.2 −0.1 0.3 0.0 0.1 −0.4 − 0.1 −0.1 0.1 −0.1 0.3 SiO2 Al2O3

1.0 0.1 − 0.1 0.0 0.6 0.2 0.0 − 0.1 0.4 0.0 − 0.2 0.1 0.2 − 0.1 0.0 0.0 − 0.2 0.2 − 0.1 − 0.1 − 0.1 0.5 − 0.2 − 0.2 − 0.2 0.0 − 0.2 − 0.1 0.0 − 0.1 − 0.1 0.0 Na2O

1.0 − 0.2 − 0.1 − 0.2 − 0.2 − 0.1 0.3 − 0.1 0.1 − 0.1 0.3 0.0 − 0.2 − 0.2 − 0.3 − 0.3 0.1 − 0.3 − 0.3 0.0 0.2 0.5 0.5 0.2 0.1 0.1 − 0.2 − 0.3 − 0.2 − 0.2 − 0.2 − 0.2 0.5 0.0 − 0.1 Fe2O3

1.0 0.8 0.4 −0.2 −0.1 0.0 0.6 0.0 0.1 −0.2 0.3 0.1 −0.2 0.1 −0.1 0.0 0.1 0.1 −0.2 0.4 −0.2 −0.2 −0.1 0.6 −0.2 −0.2 −0.1 0.0 −0.2 −0.1 0.0 −0.1 −0.1 −0.3 MgO

1.0 0.5 − 0.2 0.0 0.1 0.7 0.1 0.2 − 0.1 0.4 0.1 − 0.2 0.0 − 0.1 0.0 0.0 0.0 − 0.2 0.5 − 0.1 − 0.1 0.0 0.7 − 0.2 − 0.2 − 0.2 − 0.1 − 0.2 − 0.1 − 0.1 − 0.1 0.0 − 0.3 CaO

TiO2

P2O5

MnO Cr2O3 Sc

1.0 0.0 1.0 − 0.1 0.2 1.0 0.0 0.0 0.1 1.0 0.1 0.2 0.5 0.3 1.0 0.1 0.9 0.1 0.2 0.2 1.0 − 0.1 0.0 0.9 −0.1 0.4 0.0 − 0.1 0.0 0.0 0.3 0.0 0.2 0.0 0.5 − 0.1 0.1 0.2 0.4 0.0 0.8 0.0 −0.2 0.1 0.6 0.0 0.0 − 0.2 −0.1 −0.1 −0.1 0.8 − 0.1 − 0.1 0.1 0.1 0.0 − 0.1 0.0 0.9 −0.1 0.4 0.0 0.0 0.0 − 0.2 −0.1 −0.1 −0.2 0.1 0.1 − 0.1 0.0 0.0 −0.1 0.0 0.6 0.5 −0.1 0.3 0.4 0.0 0.3 0.2 0.4 0.2 0.6 0.0 0.0 0.1 −0.1 0.0 0.0 − 0.1 0.0 0.9 −0.1 0.3 −0.1 − 0.2 0.0 0.1 0.0 0.0 0.1 − 0.1 0.1 0.1 0.6 0.4 0.3 − 0.2 0.0 0.0 −0.2 −0.1 0.0 0.0 0.7 0.0 −0.2 0.0 0.6 0.4 0.4 − 0.1 −0.2 −0.1 0.4 0.2 0.5 0.3 0.0 0.2 0.3 0.2 0.6 − 0.1 −0.2 −0.1 0.5 0.3 0.4 0.4 −0.1 0.1 0.4 0.1 0.4 0.3 0.0 0.3 0.2 − 0.1 0.0 0.1 −0.1 0.0 0.1 0.0 1.0 0.3 0.0 0.3 0.8 0.9 0.0 0.2 0.0 0.2 0.1 K2O TiO2 P2O5 MnO Cr2O3 Sc

Ba

Co

Cs

Hf

Nb

Rb

Sr

Ta

Th

U

V

Cu

Pb

Zn

Ni

Cd

Zr

Y

REE

HREE MREE LREE TRTE HFSE LILE

1.0 −0.1 −0.1 0.0 −0.1 −0.1 1.0 −0.1 −0.2 0.5 0.0 0.1 0.9 0.2 −0.1 0.2 0.0 −0.1 0.3 0.0 0.4 0.2 0.2 0.2 0.3 Ba

1.0 −0.1 −0.2 −0.1 −0.1 −0.1 −0.1 −0.2 −0.2 0.4 0.2 −0.1 0.4 0.5 0.4 −0.1 0.0 −0.2 −0.1 −0.1 −0.2 0.3 0.0 −0.1 Co

1.0 0.6 0.5 0.4 −0.1 0.4 0.4 0.5 0.0 −0.2 −0.1 −0.2 0.0 −0.2 0.4 0.2 0.6 0.3 0.2 0.6 −0.2 0.5 0.0 Cs

1.0 0.3 0.0 0.0 0.2 0.3 0.7 −0.1 −0.1 −0.1 0.0 −0.1 0.0 0.9 0.5 0.7 0.7 0.5 0.6 −0.1 0.8 0.0 Hf

1.0 0.4 0.0 0.9 0.6 0.2 −0.3 −0.2 −0.1 −0.2 −0.2 −0.1 0.2 0.1 0.5 0.1 0.1 0.5 −0.2 0.0 0.0 Nb

1.0 −0.1 0.3 0.4 0.0 −0.1 −0.2 −0.2 −0.3 −0.1 −0.3 0.0 0.2 0.3 0.0 0.2 0.3 −0.2 −0.1 0.7 Rb

1.0 0.0 − 0.1 0.5 0.0 0.1 0.8 0.1 0.0 0.1 0.0 − 0.1 0.3 − 0.1 0.4 0.3 0.1 0.2 0.2 Sr

1.0 0.6 0.2 − 0.4 − 0.2 − 0.1 − 0.1 − 0.2 − 0.1 0.1 0.0 0.4 0.0 0.0 0.4 − 0.2 − 0.1 0.0 Ta

1.0 0.2 − 0.3 − 0.2 − 0.1 − 0.1 − 0.2 − 0.1 0.1 0.0 0.6 0.0 0.1 0.6 − 0.3 0.1 0.1 Th

1.0 − 0.1 0.0 0.4 − 0.1 − 0.1 − 0.1 0.5 0.2 0.7 0.3 0.5 0.7 0.0 0.7 0.1 U

1.0 0.1 0.0 0.1 0.7 0.0 −0.1 −0.1 −0.2 −0.1 0.0 −0.2 0.2 0.3 0.0 V

1.0 0.2 0.6 0.0 0.5 −0.1 0.0 −0.1 0.0 0.0 −0.1 1.0 0.0 0.0 Cu

1.0 0.1 −0.1 0.1 0.0 −0.1 0.1 −0.1 0.2 0.1 0.2 0.1 0.2 Pb

1.0 0.1 1.0 0.2 −0.1 −0.1 0.1 0.1 −0.1 0.7 0.1 −0.2 Zn

1.0 0.0 −0.1 −0.2 −0.1 −0.2 −0.1 −0.1 0.1 0.1 −0.2 Ni

1.0 0.3 0.0 −0.1 0.2 0.1 −0.1 0.6 0.1 −0.1 Cd

1.0 0.5 0.5 0.8 0.5 0.4 0.0 0.7 0.0 Zr

1.0 0.4 1.0 0.9 0.4 1.0 0.8 0.7 0.7 0.3 1.0 0.2 0.0 −0.1 0.0 0.4 0.5 0.6 0.3 0.2 0.2 Y REE HREE

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SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO Cr2O3 Sc Ba Co Cs Hf Nb Rb Sr Ta Th U V Cu Pb Zn Ni Cd Zr Y REE HREE MRE LRE TRTE HFSE LILE

SiO2 Al2O3 Fe2O3 MgO CaO

1.0 0.6 0.0 0.5 0.4 MRE

1.0 −0.1 0.5 0.2 LRE

1.0 0.1 1.0 0.0 0.0 1.0 TRTE HFSE LILE

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alkaline conditions (Wirsching et al., 1990). However, the more abundant silica leaching during the kaolinite formation in the kaolinitic-altered samples may indicate that alteration solutions were acidic at the early stage of alteration but later became progressively more alkaline as alkaline and alkaline-earth elements dissolved. Al2O3, SiO2, and H2O are major components of acidic hydrothermal solutions. During the intensive acid-type alteration, significant SiO2 enrichment of the smectitic-altered samples and medium to strong depletions of the other major element oxides (Fe, Mg, Na and Ca) were observed (Table 4). The presence of alunite and, more rarely, jarosite in the alteration facies indicates strongly sulfuric-acidic solutions (pH = 2–4) (Ossaka et al., 1987; Wirsching et al., 1990). The potassic-altered rocks have strong K-enrichment, a considerable amount of Si-enrichment and moderate Al-enrichment, as well as Ca, Fe, Mg and Na depletion. This finding is in contrast to the element trends of the propylitic group, except for Na, which is consistent with properties of potassic alteration (Velde, 1985). Fe and Mg were enriched in some rock groups (moderately-, phyllitic-, smectitic- and propylitic-altered sample), suggesting that they are fixed, newly-formed minerals (e.g., hematite, goethite, lepidocrosite, jarosite, epidote, and chlorite) under alteration conditions. On the other hand, Ca was preserved in several sample groups, whereas Na was also leached out of the system during all types of alteration. This trend may be explained by the higher activity of Na in alteration conditions and newly formed Ca-bearing minerals, e.g., Ca-smectite, epidote, and gypsum. Sulfates, such as alunites and jarosites, are very common in a supergene environment and appear at the top of a deposit in an oxidizing environment and in acid pH systems throughout a deposit, whereas smectites form at low temperatures and usually with an alkaline pH. CIA for all feldspars is 50, and mafic minerals biotite, hornblende, and pyroxenes have CIA values of 50–55, 10–30, and 0–10, respectively; consequently, all weathered feldspar-bearing, granitic rocks have CIA values close to 50 (Nesbitt and Markovics, 1997). Parent rock, potassic- (except K-14), most of propylitic- and half of the moderately-altered rocks plot close to the feldspar join (the line joining plagioclase and K-feldspar compositions), indicating that feldspars are the most abundant aluminous minerals of the samples. In most of the silicic-altered rocks, CIA values are between 62 and 100, reflecting a dearth of feldspar. The phyllitic-altered rocks, represented by illitic samples, plot higher on the diagram, reflecting the increased proportion of clay minerals compared with feldspars. The most weathered samples plot at 66 to 89 wt.% A12O3, generated by the alteration process, which caused destruction of primary feldspar, formation of hydrothermal phyllosilicates, and precipitation of disseminated pyrite. There is an inflection in the weathering trend as the composition approaches the A–K line, whereas the smectiticaltered samples are located at, or near, the A–CN line. The kaoliniticaltered samples situated on A–K line and close to the A corner have CIA values between 80 and 99.8, except K-83. Nesbitt and Markovics (1997) indicated that secondary clay minerals, such as kaolinite, gibbsite and chlorite have CIA values of 100, and illite and smectite have values of 70–85. At this point, all Ca and Na have effectively been leached from the materials (i.e., all plagioclase is destroyed). The inflection towards the A apex represents weathering of the remaining K-feldspar. The increasing CIA values in the investigated samples reflect the destruction of primary minerals as well as provide information on the degree of chemical weathering and predicting weathering tendency. According to CIA values on the A–K–CN diagram, the investigated samples show three different weathering trends. The smectitic-, kaolinitic-, phyllitic-, silicic- and hematiticaltered samples suffered from intense alteration. The degree of alteration of the parent rock, partially moderately-, potassic and propylitic-altered samples is lower than that of the other sample groups. And also, the investigated samples showed different

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alteration degree and types based on the AI, KI, CIW and CCCP indexes. The different weathering trends, types and alteration degree of the sample groups may have resulted from a series of complex processes, probably influenced by a variety of factors, fluctuations in hydrothermal solutions, changes in fluid temperature and composition, variable fluid/rock ratios, and interaction of the hydrothermal fluids with ambient sea water. Na2O to CIW, CIA and CCPI relationships are strongly to moderately negative (r= −0.89, r = −0.71 and r = −0.62, respectively). CIA to CCPI indices show strong to moderately positive correlations in the smectitic- (r = 0.95), potassic- (r= 0.90), hematitic- (r= 0.84), silicic(r= 0.72) and phyllitic-altered samples (r = 0.65), and moderately negative in the parent rock (r = −0.68). The CIA to CCPI indices display no relationship in the moderately-, kaolinitic- and propylitic-altered samples. These results indicate that the indices can potentially be used for Na2O depletion and defining hematitic alteration due to HFSE. During hydrothermal alteration, the investigated rocks showed similar behaviors. All REE were enriched relative to chondrite, and enrichment ratios for LREE are higher than those for HREE. Moreover, HREE signatures of all sample groups are nearly flat, which indicates that the investigated samples were derived from felsic source rocks (Fig. 12A). Sub-parallel trends of the chondrite-normalized REE patterns may have resulted from low fluid/rock ratios and/or coherent REE behavior, consistent with secondary mineral assemblages that contain epidote and albite. The presence of epidote and albite is generally assumed to be a marker of low permeability and low fluid/rock ratios (Browne, 1978). In samples exhibiting the subparallel tendency, parent rock textures were more preserved than in other samples, and various secondary mineral assemblages imply that the fluid/rock ratios were low. As evidenced by the pseudomorphous replacement of the mineral phases of the parent rock, it is probable that hydrothermal alteration was developed as iso-volumetrically in weakly-altered, but not in more highly-altered samples owing to their original texture and mineral composition was almost lost during the alteration. The similarity of REE patterns of the sample groups originating from alteration by alkaline and acid solutions points to that fact the shape of the REE trend depends principally on the fluid/rock ratios and mineralogy (Hopf, 1993). The pH and temperature of the fluids may be indirectly influenced by mineral stability. The similarity between altered sample groups and parent rock may indicate that the REE are retained in the alteration products due to the low alteration intensity, or that secondary phases were able to accommodate all the REE released from parent rock during alteration, except in the cases of phyllitic and hematitic alteration. Moreover, REE could probably be taken up by suitable host minerals, e.g., illite. It is known that illite can act as a sink for REE (Alderton et al., 1980; Palacios et al., 1986). However, all REE liberated from the parent rock cannot be held in the hematitic-altered rocks. The concave trends of the silicic- and kaolinitic-altered samples could have resulted from selective middle REE fractionation and higher fluid/rock ratios. On the other hand, CO2 quantity in the fluid is an important agent in geothermal systems in which concave patterns are developed. Under hydrothermal conditions, carbonate (CO32 −) and bicarbonate (HCO3−) ligands are thought to form stable complexes with the REE (REECO3+ and REEHCO32 +) and those involving the HREE are generally considered to be more stable (Cantrell and Bryne, 1987; Wood, 1990). REE are transported in solution as carbonate complexes and the contrasting stabilities of LREE and HREE complexes is the reason for HREE fractionation evidenced by concave trends. The lack of HREE fractionation in propylitic-altered samples, which contain abundant calcite, may result from a lowering of the activity of HCO3− during boiling, resulting in breakdown of carbonate complexes and a release of HREE. These HREE may then incorporate into the calcite (McLennan and Taylor, 1991). Most of the sample groups have strong to slightly negative Eu anomalies, ranging from 0.35 (smectitic) to 0.88 (mean), whereas

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Table 6 Summary of correlation coefficients among analyzed elements. Rock suites

Parent rock samples

Element Positive

TiO2 REE

HFSE TRTE

Potassic-altered samples

Hematic-altered samples

Al, Na, P, Sc, Cs, Hf, Nb, V, Zr, REE, LREE MREE, HFSE Al, Fe, Mg, Na, K, Ti, P, U, Mn, Sc, Ba, Co, Cs, Ga, V, Hf, Nb, Rb, Th, W, Ni, Zr, LREE, Gd, REE, LILE Al, Na, P, Sc, Co, Cs, Hf, Nb, V, Zr, LREE, Gd, REE, MREE Cu, Zn, As, Cd, Sb,

Fe, Mg, Ba, Co, Ga, Si Sr, W, Ni, Eu, Tb Si

Fe, Mg, Ba, Rb, Th, W, Ni, Eu, Tb

Rock suites

Element Positive 0.79–0.60

TiO2

Fe, Sc, HFSE

V, Eu

Cu, Sb, As

REE

LREE, MREE

Y, HREE

Si

Cu, Sb, As, Lu

HFSE

Fe, Ti, V, Eu

Ca, Sc, TRTE

Ca, Sr

Mo, Eu, Tb, Y, HREE, MREE Ta, Nb, W As,Sb,Ag Au

TRTE

V, Zn

TiO2

P, Sc, Cs, Hf, Nb, Sr, U, Ta, Th, Zr, LREE, MREE, REE, HFSE Ti, P, Sc, Cs, Hf,Nb, U,Sr,Ta,Th,Zr,Lu Ti, P,Sc,Cs,Hf, Nb,Sr,Ta,Th,U Zr, Lu, LREE, MREE W, Cu, Cd Fe, Sc, Co, Mo, Cu, Ni, As, Cd, Sb, Bi, Ag, Au, TRTE, HFSE Hf, Nb, Ta Zr, LREE

Al, Fe, Ca, P, Cr, Si Pb, Cd, Zr, Eu, HFSE Y,HREE, Gd, Er, Tm, Yb

Smectitic-altered samples

REE

LREE

K, Ba, U, Gd, LILE

HFSE

Ti, P, Sc, V

Al, Mg, Ni, Ga

Si

TRTE TiO2

Cu, Zn, Cd, Y Fe, Mg, Sc, Ba, Ga, Sr, V, Pb, As, Sb, Ag, Au, Hg, Tl, Sm, Eu

Eu, Dy, Ho Al, P, Mo, Zr, Y, Nd, LREE, MREE

Si, Th

U Na, Tb

REE

Zr, LREE

Mg, Mn, Ba, HFSE

W

Si, K, Co, Nb

REE

HFSE

Fe, Mg, P, Sc, Ba, Ga, Sr,V, Pb, As, Sb, Ag, Au, Hg, Tl, Sm, Eu Cu, Zn, Cd, Y, Gd, Dy Ho, Er, MREE

Al, Zr, Y, Gd, Tb, Dy, MREE, HREE P, Sm, Eu, Tb, Tm, Yb, Ho, REE

Si, Th

Na, K, Nb, Rb, Sr, V Cr, U, Ni, Bi, La, Ce, LREE, LILE

HFSE

TiO2

Cd, Ba, W, Hg, HFSE

Al

REE

Ta, Th, LREE, MREE

Ca, Mn, Tb

HFSE

Ti, Sc, Ba, V, Hg

Al

TRTE

Cu

Na, W, Mo, Ag Au

TiO2

Hf, Nb, Ta, Zr, HFSE

Fe

Al, Ca

REE

P, Cr, Sr, Ta, U, Mo, Pb, As, Sb, Bi, Au, Ag, Hg, Tl, LILE, HFSE Ti, P, Cr, Ba, Hf, Nb, Sr, Ta, U, Mo, Pb, As, Sb, Bi, Ag, Hg, LREE, MREE, LILE Ca, Na, Mn, Co, W, Zn, Ni, Cd

Cr, Cs, Ba, Sr, U, Sb,Bi,Au,Ag,Hg,Tl, LREE, LILE Ti, Ga, Hf, Nb

Fe

Si, Mg, Cs

Ga, Zr

Fe

Si

TRTE

Cs, Ga,Th, Zr

Si

Cu, Sb, Lu

Al, Mg, P, Ga, Ni

HFSE

Negative − 1–0.7

1–0.80

Sc, V, HFSE

TRTE

Phyllitic-altered samples

0.79–0.60

Rb, Th

Na, Sr, As, Cd, Sb, Ag, Au Ag, Au, Ta, W, As, Sb

Silicic altered samples

REE HFSE

TRTE Propylitic-altered TiO2 samples

TRTE

Si, Ca, Ta, Th,U, Kaolinitic-altered TiO2 Pb,Zr La,Ce,LREE samples Ti, Cr, Sc, Ba, V, REE Co, Hg, HFSE, LILE Si, Fe, Ca, Ta HFSE Th,U,Zr, REE Si, U TRTE

Hf, W, Cu, Zn, Cd, Sb Ag, Hg, Eu

Si, Cs, Nb, Th, Ta,Ni

Si

Y, MREE, HREE

Cs, Nb, Ta,Th, V K, Cs, Nb, Rb, Ta, W, LILE Si

Si, LILE Si, LILE

Mn,Ba,As Mg, Ca, Cs

Si, P, Ba, W, LILE

Fe, Ti, Sc,V Co,Mo,Cu, Ni, Mg, Ca As, Cd, Sb, Bi, Ag, Au, TRTE Fe, Mg, Ti, Sc,V, Co, Mo, Cu, Ca Ni, As, Cd,Sb, Bi, Au, Ag, Cs, HFSE Na, HFSE Mg, K, Cr, Co, Rb, Y, LILE Nb, Ta, Th, Ni, LREE Si, Ga, Hf Na, Ti

− 0.6–0.4

Mg, Co, Nb, Ta, Y, REE Ba, Ga, Pb, As, Sm

Si, Hf, Nb, Th, U, Zr, Ta, REE LREE, LILE Fe, Ti, Sc,V Co, Cs, Ag, Au, Mo, Cu, Ni, As, Cd, Sb, Bi Si, K, Mn Ba, Hf, U Nb, Ta, Zr, LREE, LILE Si, K, Hf, Nb, Ta, Zr, LREE

P, Rb, W

Pb, Zn, Eu, Dy

Th P, Mn, Ba

Mn, Sr

Al, Ca

Sc, Sr

Fe, Mn, V

Al, Mn, V U

Al, Fe, Mn, Ca, Na, K, P, Cs, Rb, Sr, LILE

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Moderately-altered TiO2 samples

Negative − 1–0.7 − 0.6–0.4

1–0.80

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Fig. 12. (A) Chondrite-normalized REE pattern of the investigated sample groups (normalization values from Boynton, 1984). (B) Chondrite-normalized trace elements and REE diagram of sample groups (normalization values from Sun and McDonough, 1989). Data are from Table 2; abbreviations as in Fig. 7.

hematitic- (1.50) and propylitic-altered samples (1.11) have slightly to moderately positive anomalies (Fig. 12A). Eu depletion may result from the dissolution of Eu-rich mineral phases by hydrothermal fluids (Lewis et al., 1997). Hydrothermal fluids may preferentially leach Eu relative to the other REE at temperatures above 250 °C (Bau, 1991; Sverjensky, 1984). The Eu anomalies occur parallel to depletion in Na2O and CaO, suggesting that they developed at least partially in response to weathering of plagioclase, where most of the Eu is hosted and indicating felsic source rocks (Fig. 12A). The positive Eu* anomaly of propylitic- and hematitic-altered samples may be explained by alteration of plagioclase in the parent rock. Positive Eu anomalies have also been observed in some hydrothermal ore deposits (e.g., Palacios et al., 1986), in hydrothermal fluids from mid-ocean ridges (e.g., Klinkhammer et al., 1994) and ferrugineous chert, barite and hydrothermally altered dacite just above orebody of Kuroko deposits. And also, a negative Eu anomaly was reported in hydrothermally

altered footwall dacite of the Kuroko deposits (Shikazono et al., 2008). Klinkhammer et al. (1994) suggested that partitioning of REE 3 + and Eu 2 + is dominated by the chemical substitution for Ca 2 + and Sr 2 +, respectively, in plagioclase during the transition from An-rich plagioclase to Ab-rich hydrothermal plagioclase. The Sr 2 + content of most of the propylitic-altered samples is higher than that of the parent rock and of the moderately-altered samples. This situation may indicate that Eu 2 + was retained in hydrothermal albite or taken up by suitable hosts in the altered rock (Kamineni, 1986). Eu can be divalent under reducing conditions, and very reducing water contains Eu 2 +. These conditions are also suitable for the occurrence of calcite in the propylitic-altered samples formed from parent rock. The positive and negative Eu anomaly of different alteration types may have been originated from by selective leaching of Eu from feldspar in the parent rock due to the interaction of ascending hydrothermal solution. Some authors have indicated that leaching of REE3 + is pH dependant; lower

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Fig. 13. Nomenclature of unaltered and altered samples according to SiO2 vs. Zr/TiO2 contents on the diagram of Winchester and Floyd (1977), abbreviations as in Fig. 7.

pH favors REE3 + mobility and higher pH can induce precipitation (Aubert et al., 2001; Moore, 1998; Terkado and Fujitani, 1998). The positive and nearly positive Eu anomalies may be related to ore mineralization while strongly negative Eu anomaly may be related to the late stage mineralization processes. Therefore positive Eu anomalies can be partially used proximity of ore-bearing rocks. Almost the entire sample suite shows no Ce anomaly, except for the phyllitic-altered samples, which have weak positive anomalies. Ce is only fractionated from other rare earth elements owing to the formation of Ce 4 + under highly oxidizing conditions: the other REE remain trivalent (Braun et al., 1990; Class and la Roex, 2008). Such conditions do not occur in the deep mantle but can occur in nearsurface environments, notably under the oxidizing conditions in seawater. In oxic conditions, Ce is less readily dissolved in seawater; thus, oxic seawater is more depleted with respect to Ce, whereas oxic sediments are more enhanced with respect to Ce. Conversely, in suboxic seawater, Ce included in sediments is mobilized so that Ce is released into the water column, resulting in a less negative to a positive anomaly in seawater (DeBaar, 1991; DeBaar et al., 1985, 1988; Sholkovitz and Schneider, 1991). Almost all of HFSE, with the exception of TiO2, clearly display mobile behavior (Table 4, Fig. 12), even if HFSE are generally considered as conservative elements in most geologic settings (e.g., Jiang et al., 2005). HFSE exhibit similar chemical properties. There are two alternative suggestions concerning HFSE mobility during magmatic, metamorphic and hydrothermal processes. One line of reasoning suggests that HFSE are immobile (e.g., Corfu and Davis, 1991; Floyd and Winchester, 1978). Other authors have proposed that they are mobile to some extent, and under certain circumstances (e.g., Jiang, 2000; Jiang et al., 2005; Karakaya, 2009; Nesbitt et al., 1999). HFSE mobility may relate to a number of factors, including P–T conditions. HFSE solubility is largely enhanced with increasing pressure and temperature as well as highly alkaline (8–12) or acidic (b4) pH conditions (Barnes and O'Neil, 1969; Van Baalen, 1993; Veyland et al., 2000). HFSE contents of all of the samples are partially depleted or enriched relative to chondrite, except P, and exhibit similar patterns, suggesting that they all originated from same source rock. HFSE contents of all of the samples are partially depleted in the hematitic- and propyliticaltered samples and enriched in the other sample groups compared to the parent rocks (Table 4, Fig. 12). Previously, HFSE were thought to have been immobile or to have conservative behaviors during hydrothermal alteration processes (e.g., Jiang, 2000; Jiang et al., 2003; Rollinson, 1993; Salvi et al., 2000); however, our sample groups exhibit

various features in different alteration types, possibly related to changing environmental conditions. Pyrite and/or chalcopyrite in the deposits are associated with gypsum, which is taken as evidence for the alteration of pyrite in the supergene alteration zone located at the uppermost parts of the deposit. Alteration of such minerals under acidic conditions could provide a sulfur source for formation of alunite and jarosite; alunite formation requires acid conditions and high sulfate activity. In volcanic rocks, which are reduced below the hematite– magnetite oxygen buffer, the presence of alunite indicates high H2S activity if the fluid contained greater than 0.001 m total sulfur when the temperature of the fluid was 300 °C (Knight, 1977). This fact greatly enhances the likelihood that alunite-producing fluids also produced high total sulfur mineralization at depth. If the volcanic rocks above a porphyry pluton are more oxidized than the pluton, the fluid will oxidize as it migrates upward. Most of the transition metals (W, Mo, Cu, and Sb), base and precious metals (Ag and Au) and volatile elements are enriched in the hematitic- and silicic-altered samples. The concentration of Mo, Bi and Sb are typically b1 ppm in the parent rock and moderatelyaltered samples. Elevated values are, however, found in the phyllitic(generally observed in the footwall), as well as in the hematiticaltered samples. The highest As, Bi, Mo, Se and Hg concentrations in the hematitic-altered samples can be used to distinguish other alteration types and may be useful in prospect-scale base metal exploration. The high concentration of the abovementioned elements of the silicic- and hematitic-alteration zones, situated in the uppermost part of the deposits, may be useful geochemical indicators of proximity to blind ore deposits. In the study area, there are economic and good examples of VMS deposits and some precious metals (e.g., Au, Ag) of Turkey. They have been mining by underground operation due to the ore mineralization exposed beneath by younger volcanics and covered by thick alteration envelopes. Because the ore deposits do not outcrop on the surface, it is not possible to determine the ore mineralization, so it is most important to prospect the mineralization by means of chemical and mineralogical characteristics of the alteration zones. Especially, phyllitic zones rich in illite are associated with ore mineralization and are formed mainly in footwalls of the VMS deposits, and laterally pass to K-poor illite and illite–smectite. Increasing of illite crystallinity and K2O content indicates that increasing of temperature may be action of hydrothermal solution. The propylitic zones are typically greenish-blue colored and are found at the nearest area of the ore deposits while potassic-alteration is observed at the mainly outer part of the ore. So, determination of the alteration zones can be used as proximity marker of orebodies and

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drilling programs for the VMS deposits. And also, major and trace including rare-earth element behaviors in different types of alteration zones can be used for discovering unknown VMS and other economic deposits and for interpreting hydrothermal system. 7. Conclusions The tectonically controlled fossil VMS deposits in the eastern Black Sea region are hosted by hydrothermally-altered peripheral zones in the Senonian Dacitic series. The similar REE patterns, with LREE enrichment relative to HREE, and significantly negative Eu anomalies of the hydrothermal alteration products were derived from a common source rock and their origin is felsic. The strong variability of HFSE, LILE, TRTE, and REE concentrations of the sample suites probably indicates different degrees of alteration and different fluid/rock ratios in the weathered materials. Negative Eu anomalies are reduced in almost all of the altered rock groups, with exception of the propylitic- and hematitic-altered samples, probably because of the presence of Eu 2 + under reducing hydrothermal conditions. The positive Eu anomalies in all other types resulted from high-temperature hydrothermal conditions (>200 °C). HFSE and most of the transition metals (W, Mo, Cu, Sb), base and precious metals (Ag and Au), and some elements (e.g., Pb, As, Hg, Bi, Se and Tl) are enriched in the hematitic-, and somewhat enriched in the silicic-altered samples (Table 3). The highest As, Bi, Mo, Se and Hg concentrations are found in the hematitic-altered samples and can be used to distinguish other alteration types and can be used as pathfinder elements for prospection. The mineral enrichments in these types of alteration may be particularly important where large areas of alteration must be evaluated and where mineralization is blind to surface. Mass-balance calculations show that REE are relatively immobile in the silicic-, hematitic-, kaolinitic-, and fairly immobile in the moderately- and propylitic-altered samples. LILE are mobile in all altered samples, as well as HFSE, except in the propylitic-altered samples. TRTE are also relatively immobile in most of the samples; it is slightly mobile in the silicic- and phyllitic- and especially mobile in the hematitic-altered samples. The eastern Black Sea region has valuable resources not only VMS but also some precious metals at the present and future. However almost all of them were covered intense alteration haloes. So, discovering additional deposits in the ore province may be possible by using mineralogical data and chemical pathfinder elements presented here. Acknowledgments This investigation was made possible through the partial financial support of TUBITAK (The Scientific and Technical Research Council of Turkey with project no. YDABÇAG-139 and 103Y016). The authors are indebted to the two anonymous reviewers for their comments. Finally we thank Nigel J. Cook for his careful editorial input and constructive suggestions which improved the quality of the manuscript. References Acar, E., 1974. The importance in terms of trace elements of some the copper–lead–zinc mines of Giresun region within eastern Black Sea province. Min. Res. Explor. Bull. 82, 136–147. Akçay, M., Moon, C.J., 2001. Geochemistry of pyrite-bearing- and purple dacites in north-eastern Turkey: a new exploration tool for the Kuroko type deposits. In: Piestrzyski, A. (Ed.), Mineral Deposits at the Beginning of the 21st Century. Krakow, Poland, pp. 210–213. Alderton, D.H.M., Pearce, J.A., Potts, P.J., 1980. Rare element mobility during granite alteration: evidence from southwest England. Earth Planet. Sci. Lett. 49, 149–165. Aubert, D., Stille, P., Probst, A., 2001. REE fractionation during granite weathering and removal by waters and suspended loads: Sr and Nd isotopic evidence. Geochim. Cosmochim. Acta 64, 1827–1841.

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