Metallogenesis of Precambrian SEDEX-type Barite-(Pb-Cu-Zn) deposits in the Mishu mountain, NW Iran: Constrains on the geochemistry and tectonic evolution of mineralization (original) (raw)

Abstract

The Precambrian sedimentary-volcanic sequence of Kahar Formation (KF), located in the Mishu mountain, NW Iran, hosts numerous strata-bound and stratiform Barite-(Pb-Cu-Zn) deposits. These deposits include Daryan, Shanjan, Almas, and Aralan-Pyrbala that are hosted by black shale, siltstone, and fine-grained sandstone of the KF. Available evidence such as clastic rocks, bimodal volcanism (rhyolitic and mafic flows) and geochemistry investigations shows that sedimentary host rocks of KF were formed in an extensional environment in the active continental margin. Based on petrographic studies, three different ore facies have been distinguished: 1) a stockwork (feeder) zone including five types of veins and veinlet's; 2) a massive ore consisting of barite and sulfide (galena, chalcopyrite, pyrite, sphalerite and minor tetrahedrite and tennantite) minerals, and (3) a bedded ore that includes laminated sulfides with sedimentary structures and sulfides with barite minerals. High contents of redox-sensitive elements, such as Fe, Mn, V, and U in the host rocks (KF) indicate that mineralization occured in oxic-anoxic ambient environment. The Electron Prob Micro Analyzer (EPMA) data indicate that the Se content of chalcopyrite in the bedded ore facies is higher than that in stockwork and massive ore zones, which indicate a decrease of temperature from feeder zone towards massive and bedded ores. The trace-elements distribution among the minerals from the three ore facies, indicate evidence of a submarine hydrothermal exhalative origin or SEDEX-type mineralization at the Mishu deposits (especially Co and Ni contents and Co/Ni ratios in pyrite and Zn/Cd ratios in sphalerite). The δ 34 S values of the sulfides range from +17.7 to +35.8‰ within wich the highest δ 34 S values correspond to the bedded ore (+28.7 to +35.8‰), and the lowest δ 34 S values belong to the feeder zones (+22.4 to +25.4‰) and the massive ore (+17.7 to +21.6‰). The overall range of δ 34 S suggests that sulfides were formed by the reduction of Precambrian seawater sulfate due to bacteriogenic sulfate reduction in a closed or semiclosed basin. Briefly, the sedimentary host rocks, types of mineralization (bedded, feeder, and massive ore), mineralogical pieces of evidence, along with geochemical and sulfur isotope signatures, indicate that Mishu Barite-(Pb-Cu-Zn) deposits are very similar to SEDEX-type deposits.

Figures (30)

Fig. 1. Distribution map of Ba-(Pb- Cu- Zn) deposits on the structural map of Ira; Al, Alborz zone; CIGS, Central Iranian geological and structural gradual zone; E, Eas Iran ranges; K, Kopeh-Dagh; KT, Khazar-Talesh- structural zone; L, Lut block; M, Makran zone; PB, Posht-e-Badam block; SSZ, Sanandaj-Sirjan zone; T, Tabas block TM, tertiary magmatic rocks; UD, Urumieh-Dokhtar magmatic arc; Y, Yazd block; Z, Zabol area; Za, Zagros ranges (tectonic and structural map of Iran modified afte: Aghanabati, 1998, 2004; Alavi, 1991); Location of Mishu deposits is shown with outlined rectangle in Fig. 2. (Rahimpour-Bonab and Shekarifard, 2002; Nazemi 2005; Ehya, 2012; Vazifeh, 2013; Tajeddin et al., 2012; Rajabi et al., 2012; Hashemi et al., 2014; Zarasvandi et al., 2014; Zolfi and Simmonds, 2015, Maghfouri 2017; Lotfi et al., 2017; Mirmohammadi et al., 2017).

Fig. 3. A schematic simplified lithostratigraphy of the Precambrian—Miocene units in the Mishu mountain, along with mineralization associated within KF

Fig. 4. The structural cross-section in the Mishu mountain (modified after Behyari et al., 2017).

Fig. 5. (a) A general view of the mineralized area in KF (Almas deposit), sedimentary host rocks of KF have thickness 1-3 km. (b) Laterally facies change of KF to rhyolite flows. (c) Alternating rhyolitic flow with KF.

Fig. 6. Field photographs of Barite-(Pb-Cu-Zn) deposits occurrences at the Mishu mountain with sedimentary - host rocks (KF). (a,b) Stratiform barite mineralization which hosts by shale and sandstone (K.F). (c) Barite mineralization in the black shale host rock (K.F). (d) Barite - sulfide mineralization in the black shale (K.f) host rocks. (e) Mineralization of barite that is deformed with the host rock.

Fig. 7. Hand specimen (a,c,d,e,f,g) and photomicrograph (b) of veins and veinlets in the stockwork ore zoe; (a) Silica-Sulfide veins and veinlets that crosscut the siltstone host rock along with silica alteration. (b) Microscopic photomicrograph of chalcopyrite (Cpy2) mineral in the stringer zone. (c) Silica- Calcite - Sulfide veins and veinlets that crosscut the black shale host rock. (d and e) angular fragments of a breccia, cemented by sulfide minerals (Cpy2 and Py). (f and g) Barite- rich veinlets that crosscut the black shale and sandstone host rocks.

Fig. 8. Hand specimen (a, b, d, f, i) and photomicrographs (c, e, g, h) of massive ore facies in the Mishu deposits. (a and b) Massive chalcopyrite (Cpyz). (c) Tetrahedrite-tennantite occurs associated with chalcopyrite; (d) Massive pyrite (Py2). (e) Replacement of pyrite (Py2) with chalcopyrite. (f) Bracciated host rock with galena (Gnz) sulfide minerals. (g and h) Pyrite and chalcopyrite are partly replaced by galena, respectively. (i) Massive sulfate (Baz) along with the presence of disseminated sulfides within the barite.

5. Geochemistry 5.1. Host rock geochemistry

Fig. 10. Hand specimen (a, b) and photomicrographs (c, d, e) of bedded ore facies in the Mishu deposits; (a and b) Bedded ore facies in barite characterized bj alternating laminations of barite and fine-grained sulfide. (c and d) Chalcopyrite (Cpy,), pyrite (Py) and galena (Gn) in the bedded ore facies; (e) Ex-solution texture of chalcopyrite with sphalerite (chalcopyrite disease).

Fig.11. Hand specimen photograph (a) and photomicrographs (b, c) of alteration in the stockwork zone. (a,b) Hydrothermal quartz veins (Silicic alteration). (c) Sericitic alteration around the stringer zone.

Fig. 12. Mineral paragenes showing the different ore stages.

Major, minor, and trace element contents of sedimentary rocks of KF. Table 1 galena and sphalerite) were analysed using 17 samples from the stockwork zone, massive and bedded ore facies. The results of the re- presentative electron microprobe analyses are shown in Tables 2-5. low. In the bedded ore facies, the galena contains Ag (avg. 0.01 wt%), Cd (avg. 0.07 wt%), Sb (avg. 0.02 wt%) and Bi (avg. 0.22 wt%). The Bi content in galena from the massive ore is higher than that from the bedded ore.

Fig. 13. (a) Classification of the Kahar sedimentary rocks based on the diagram of Herron (1998), log (Si02/Al2O3) versus log (Fe203/K20). (b) The plot of log K0, Na2O-SiO2 discrimination diagrams of Roser and Korsch (1986) for sandstone mudstone suites showing the different tectonic settings. (c) The plot of discriminant < against discriminant 1; the discriminant function diagram for sandstones (after Bhatia, 1983), showing fields for sandstones from passive continental margins oceanic island arcs, continental island arcs, and active continental margins. The Kahar sedimentary rocks plotted in the active continental margin, although tov samples plotted in the continental island arc.

Element concentrations (wt%) for Chalcopyrite (Cpy) and Pyrite (Py) in the stockwork ore facies (A) of Mishu deposits by EPMA. Table 2 anoxic bottom waters conditions (Fig. 15a and b). However, the mo- bility of Mn is higher than Fe during hydrothermal alteration. Conse- quently, Mn may not be suitable to determine the paleoxygenation le- vels, whereas Fe is considered as a more reliable indicator. The Se content of chalcopyrite samples shows notable patterns of dis- tribution, increases from stockwork zone to bedded zones (Fig. 16). Selenium distribution is almost controlled by the temperature of pre- cipitation and solubility of Se decreases precipitously with decreasing temperature and most of Se in the system being removed out of the solution at lower temperatures. (Auclair et al., 1987). In this research, Se content of chalcopyrite samples in the bedded ore (0.09 wt%) are very higher than stringer zone (0.03 wt%) and massive zone (0.07 wt %). Therefore, due to the low temperature of the bedded ore, Se gen- erally concentrates in chalcopyrite from this zone. Based on the studies of Yamamoto (1976), Huston et al. (1995) and Simon and Essene (1996) haul of Se within hydrothermal ore-systems is largely related to the Se activity, 2S/ZSe, pH, temperature and fO2 of the hydrothermal fluid. On the other hand, based on the chemical properties, selenium is similar to sulfur. Like sulfur, Se in the natural environments may exist in both oxidation and dissociation (Yamamoto, 1976). Thus, it implies that deposition of chalcopyrite in the bedded ore of Mishu deposits has happened under high fO2 conditions. In these deposits, there are sig- nificant enrichment of Se (100 ppm and above), where this value in- dicated that Se contents similar to seafloor sulfide deposits, such as VMS and SEDEX deposits (Hannington et al., 1999b; Maslennikov et al., 2009; Revan et al., 2014). In these deposits (VMS and SEDEX), the bedded ore facies is the distal facies and formed under higher fO2 conditions (Shanks and Thurston, 2010), similar the bedded ore of the Mishu deposits. Within modern and ancient seafloor hydrothermal ee Se ee ee Ve, ee iy ee ee ae

Element concentrations (wt%) by EPMA for Chalcopyrite (Cpy), Pyrite (Py) and Galena (Gn) in the massive ore facies (B) of Mishu deposits Table 3 0.3. wt%) through bedded zone (Bi: 0.2. wt%) (Fig. 16). Fleischer (1956) reported that the content of bismuth is decreased with de- creasing temperature of formation, therefore patterns of Bi distribution in this research shows that the fluid temperature decreases from mas- sive to the bedded zone.

Element concentrations (wt%) by EPMA for Sphalerite (Sp) in the bedded ore facies (C) of Mishu deposits. Table. 5

Element concentrations (wt%) by EPMA for Chalcopyrite (Cpy), Pyrite (Py) and Galena (Gn) in the bedded ore facies (C) of Mishu deposits. Table.4

The 8°“ values of sulfide minerals in the different ore facies of Mishu deposits.

Fig. 14. Histogram of 8°‘S values of sulfides from the Mishu deposit plotted basis ore facies. stage Ht of the sulfide mineralization including stockwork and massive ore, have 8°“S values of +22.4 to +25.4%o and +17.7 to +21.6%o, respectively. Although BSR is the dominant source of ore of stage I at the Mishu deposits, but the variation of sulfur isotope compositions in stockwork and massive ore (low isotopic values) in- dicate that there is a second sulfur source involved as well. Sericite alteration found around the feeder zone, suggests high-temperature condition for this part of the deposits. Therefore, TSR can produce some reduced sulfur. At the temperature of fluid-rock interactions that exceed about 300 °C, ferrous iron in sedimentary rocks (or volcanic rocks) has the capacity to reduce seawater sulfate (Shanks et al., 1987). At the onset of hydrothermal activity, due to the high permeability of the rocks and/or the presence of syn-sedimentary fault, cold seawater in- truded into the reaction zone and after warming, climbed towards the seafloor. In this condition (high temperature), the thermochemical process led to Precambrian sulfate reduction and sulfide deposits pre- cipitated before the fluids were released to the seafloor (stockwork zone) (Ma et al., 2007). In the Mishu deposits, 5°*S values are high and the isotopic fractionation from seawater sulfate is more than 15 to 25%o, due to the presence of barite deposits along with sulfide miner- alization and contamination of sulfur isotopic compositions with barite inclusions. Similar mechanisms can describe the high 8°*S ratios of sulfides in the Mishu deposits, for example, in the Red dog SEDEX- type deposits (Kelley et al., 2004).

Fig. 15. (a,b) Fe and Mn-based paleoenvironment discriminant diagrams for sandstone samples from the KF. Fields taken from Quinby-Hunt and Wilde (1994); (a) Fe content mainly indicates anoxic sulfate reducing conditions. (b) Mn content indicates anoxic paleoconditions during sedimentation of sandstone. (c) Bivariate V/ (V + Ni) vs. V/Cr geochemical redox proxy plot (after Saez et al. 2011) for the sandstone samples from KF; most Samples plot in the anoxic field, near the boundary with the dysoxic field. V/Cr ratios close to unity for several samples suggest that the oxic—anoxic barrier is within the sediments (Jones and Manning, 1994). Field boundaries are from jones and Manning (1994) and Hoffman et al. (1998).

Fig. 17. Plot of the Co and Ni contents of pyrite from different type of ore facies in the Mishu deposits. Fields of pyrite in the various origins, after Brill (1989) and Bajwah et al. (1987), are shown for comparison. Fig. 16. Distribution of the average content of elements (wt.%) in diffrent ore facies of the Mishu deposits.

Fig. 18. Histogram of sulfur isotope analysis from sulfide minerals (Galena, Chalcopyrite and Pyrite) of Mishu deposits. Data plotted on a chronologic diagram of the average 8°4S content of marine evaporites (Horita et al. (2002), from a modified version of Claypool et al. (1980).

Comparison of features of the Barite-(Pb-Cu-Zn) deposits of Mishu mountain with principal characteristics of SEDEX deposit.

Fig. 19. Schematic genetic model of Barite-(Pb-Cu-Zn) mineralization in the KF; (a) Deposition basal sedimentary sequences (black shale, sandstone and siltstone) in an extensional setting. (b) Sedimentary rocks of KF and bimodal volcanism formed. (c) Early venting of the exhaling hydrothermal fluid on the seafloor would have led to the precipitation of an early assemblage of the fine grain size minerals (stage 1) in the bedded ore facies. (d) With continuing reduction of the water depth and increase the oxidant conditions in the basin, a large volume of barite was formed in the Misho area. (e) During this stage, compression and tectonically uplift led to deformation of KF and sulfide-sulfate mineralizations. (f) After the tectonically uplift, Mishu granites (I-type and S-type) and A-type granite have been intruded to the KF. (g) In this stage, KF, Barite-(Pb-Cu-Zn) mineralizations, and Mishu granites unconformably covered by Cambrian-Ordovician sedimentary sequence.

type mineralization for Mishu deposits. The overall range of 8°4S (+17.7 to +35.8%o) is remarkably higher than typical magmatic va- lues, suggesting that sulfides formed from the reduction of Precambrian seawater sulfate by bacteriogenic sulfate reduction in a closed or semi- closed system in the bedded ore, whereas thermochemical sulfate reduction likely played an important role in the feeder zone. The pre- sence of framboidal and laminated sulfide in the bedded ore facies supports this interpretation. Briefly, the Mishu deposits have many geologic, geochemical, types of mineralization (include feeder zone, bedded ore, and massive ore facies), and metallogenic similarities to the

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