Geochemistry and Mineralogy of Zincian Dolomite in the Tangedozdan area (Fereydounshahr- West of Isfahan Province)

زمین شناسی اقتصادی

Volume 17, Issue 1 - Serial Number 44, 2025, Pages 81-104   

Document Type: Research Article

DOI: 10.22067/econg.2025.1132

Author

Seyed Vahid Shahrokhi^*

Associate Professor, Department of Geology, Khorramabad Branch, Islamic Azad University, Khorramabad, Iran

Abstract

The Tangedozdan zinc and lead deposit is located 25 km northeast of Fereydounshahr and in the middle part of the Sanandaj-Sirjan zone. The rock units from old to new include greenish volcanics, calcareous sandstone, crystalline limestone, limestone to dolomitic limestone, and gray limestone belonging to the Jurassic-Cretaceous and alluviums of the Holocene time. The limestone to dolomitic limestone unit with normal contact sits on greenish volcanic and hosts zinc mineralization. The Zincian-dolomite in this area can be recognized by different amounts of zinc, smaller amounts of lead and, cadmium in its structure. In the studied area, a set of formed zinc and fewer lead ores, the most important in the exogenous part are smithsonite, hemimorphite, and cerussite, and in the endogenous part are sphalerite and, pyrite. Performing XRD analysis with the conventional method shows the presence of dolomite, smithsonite, and sphalerite. By changing the decomposition conditions, the structure parameters in Zincian-dolomites increased simultaneously with the amount of zinc, based on of this, there is a direct relationship between the zinc amount in the dolomite and the structure parameters. The study of the Zincian-dolomite sample by differential thermometry method shows the reduction of endothermic point and the zinc effect substitution in the dolomite structure. EPMA analysis of Zincian-dolomite samples show the substitution of Mg with Zn. Based on this, the replacement of dolomite by exogenous zincian-dolomite is a part of the mineralization process, and with the progress of zincian-dolomite formation and dolomitization, it eventually leads to the formation of non-sulfide zinc minerals such as smithsonite.
 
Introduction
Based on reproductive indices, the nonsulfide zinc and lead deposits are divided into two main groups, endogenous and exogenous, mineralogical characteristics, and geological characteristics (Hitzman et al., 2003). Non-sulfide zinc minerals, known as calamine, combine of exogenous zinc minerals with lead non-sulfide minerals, hydroxide cherts, and silicates (Boni and Mondillo, 2015; Luke et al., 2015; Newton, 2013). According to previous studies, the Tangedozdan zinc and lead deposit with carbonate host rock of the Mississippi Valley-type (Delavar et al., 2014) consists of exogenous non-sulfide zinc minerals (Amiri and Shahrokhi, 2023). The identification and study of zinc dolomites, considering their close relationship with non-sulfide minerals, in addition to the introduction of this collection, can be effective in broadening the exploration work and lead to an increase in accuracy
Tangedozdan area in the west of Isfahan province, 10km from Fereydounshahr city and, in the vicinity of Tangedozdan between longitudes 49˚56'30'' to 49˚57'30'' east and latitudes 32˚02' to 32˚03' north and, is located in the middle part of the Sanandaj-Sirjan zone. Rocks in 1/20000 geological map include volcanic (JK^v), sandstone (JK^s), crystalline limestone (C.L.S), limestone to dolomitic limestone (JK^l,dl) and limestone (K_l¹) belonging to the Jurassic-Cretaceous and the sediments of the Holocene time (Q^a and Q^sc) the JK^v unit is the oldest rock, consisting of Trachyandesite to andesite volcanic rocks. The JK^l,dl unit hosts mineral matter and consists of limestone to thick dolomitic limestone. It is located east of Tangedozdan with normal contact on the JK^v unit and hosts zinc carbonate mineralization.
 
Materials and methods
Chemical analysis has been done for 30 samples taken by ICP-MS method in the laboratory of the Iran Minerals Research and Processing Center. 10 samples were also analyzed by XRD in the Zarazma and Binaloud laboratory. Thermal analysis was done by DTA/TGA in the Iran Minerals Research and Processing Center laboratory.
To investigate the chemistry of the samples, 36 points were subjected to EPMA analysis in the Potsdam University Laboratory, Germany.
 
Result
In the Tangedozdan area, the most important zinc and lead minerals in the exogenous part are smithsonite, hemimorphite, and cerussite, and in the endogenous part sphalerite and to a lesser extent galena and pyrite.
In the study area, three types of dolomites can be distinguished based on the color visible in the field. The first type is dark-colored dolomite. The second type is yellow to brown, which can be due to the exogenous oxidation of Fe²⁺ in the dolomite structure (Zabinski, 1980; Motavali et al., 2019; Yang et al., 2019).
 
Discussion
Based on these analyses, the main minerals are dolomite, smithsonite, sphalerite, and pyrite, secondary minerals are cerusite, hematite, quartz, barite, calcite, and rare minerals are galena, and muscovite, illite. Standard dolomite was checked and identified with cart number 036-0426 and with the help of Xpert high surplus software. Based on the Rietveld method in Maud software, two samples were analyzed and were calculated by the structure a and c parameters (Monecke et al., 2001). The selected samples have different amounts of zinc. Based on this, the lattice parameters a and c in TBA-14 sample with 2.10% zinc value are respectively a=4.8092Å and c=16.0200Å for the TBA-14 sample with 3.05% zinc value a=4.8130Å and c=16.0233 Å, and for the TBA-19 sample with 3.56% zinc, a=4.8170 Å and c=16.0310 Å were determined, respectively. The results related to pure calcite and pure dolomite. The results of differential calorimetry of two dolomite samples TBA-14 and TBA-19 from the Tangedozdan area are compared. Sample No. TBA-14 with 10.2 ppm of zinc element and the endothermic peak occurred at the approximate temperature of 503 ºC and 595 ºC, and a slight decrease of about 15% can be seen at the beginning of the peak at the temperature of 126 ºC. Also, in the TBA-19 sample, which mostly contains zinc dolomite, there are two reactive peaks at 447ºC and 509ºC, followed by two other reactive peaks at 584ºC and 674ºC. Accordingly, increasing the amount of zinc in the dolomite structure causes a decrease in the reaction point in the form of a non-linear curve, while in iron-containing samples such as Ankerite, most of the reaction curves are linear (Kulp et al., 1951). In this way and based on this test, the presence of zinc in dolomites and the formation of zincian dolomite in the Tangedozdan area can be seen. To determine the composition, type, and origin of zinc in the Tangedozdan area, three samples were selected in such a way that based on the ICP-MS analysis performed on the samples, the first type of dolomite (TBA-15) a zinc content of 82 The second type dolomite sample (TBA-14) contains 2.10 ppm, and the third type dolomite zinc sample (TBA-19) contains 3.56 ppm. The results of the EPMA analysis show that in the TBA-19 (Zincian-dolomite), in addition to calcite and dolomite, the amount of zinc element is higher than the background limit and indicates the presence of zinc in the dolomite mineral structure. Based on these studies, three types of dolomites were detected, according to which the highest amount is related to Zincian-dolomite in the TBA-19 sample, followed by TBA-14 and TBA-15 dolomite. In the TBA-16, the ratio of Zn:Mg is from 0.4 to 0.16, while in the TBA-19 Zincian-dolomite sample, this value varies from 0.39 to 1.04. Based on the studies, Zincian-dolomite can be identified in the carbonate part along with zinc and lead non-sulfide mineralization in the Tangedozdan area. Zincian-dolomite shows the most distribution along with red to orange phase 3 dolomites. Based on this, Zincian-dolomite can be seen in the exogenous phase of the oxidation zone of the Tangedozdan area. Based on this, conducting different experiments in this area indicates the presence of zinc in the dolomite structure and the formation of zincian dolomite.

Keywords

Geochemistry; Mineralogy; Zincian-dolomite; Smithsonite; Tangedozdan; Sanandaj-Sirjan zone

References

Adelpour, M. and Rostamipaydar, G., 2018. The Study of alteration, mineralization, and fluid inclusion in the Howz-e-Sefid zinc-lead deposit (Central Iran). Iranian Journal of Geology, 47(12): 19–36. (in Persian with English abstract) Retrieved January 16, 2025 from http://geology.saminatech.ir/en/Article/9609

Amiri, B. and Shahrokhi, S.V., 2017. Geochemistry and Mineralogy of Zn &Pb in Tang-e-Dozdan area (NE Feraydoonshahr-Isfahan Province). 29th Symposium of Minerallography and Mineralogy of Iran, Damghan University, Damghan, Iran.

Amiri, B. and Shahrokhi, S.V., 2023. Ore control factors of Zinc and Lead mineralization in the Tangedozdan area (NE Fereydounshahr-Isfahan Province). Journal of ‌ Economic Geology, 15(1): 27–31. (in Persian with English abstract) https://doi.org/10.22067/econg.2023.79745.1058

Birch, W.D., 2007. Zincian dolomite from Broken Hill, New South Wales. Journal of the Geological Society of Australia, 30(1–2): 85–87. https://doi.org/10.1080/00167618308729238

Boni, M. and Large, D., 2003. Nonsulfide zinc mineralization in Europe: an overview. Economic Geology, 98(4): 715–729.  http://dx.doi.org/10.2113/98.4.715

Boni, M. and Mondillo, N., 2015. The “calamine” and the “others”: the great family of supergene nonsulfide zinc ores. Ore Geology Reviews, 67: 208–233. https://doi.org/10.1016/j.oregeorev.2014.10.025

Boni, M., Mondillo, N. and Balassone, G., 2011. Zincian dolomite: apeculiar de dolomitization case?. Geology, 39‌(2): 183–186. https://doi.org/10.1130/G31486.1

Boveiri Konari, M. and Rastad E., 2017. Nature and origin of dolomitization associated with sulphide mineralization: new insights from the Tappehsorkh Zn-Pb (-Ag-Ba) deposit, Irankuh Mining District, Iran. Geological Journal, 53(1): 1–23. https://doi.org/10.1002/gj.2875

Boveiri Konari, M., Rastad E., Mohajjel M., Nakini A. and Haghdoost M., 2016. Structure, Texture, Mineralogy and Genesis of Sulphide Ore Facies in Tappeh Sorkh Detrital-Carbonate-Hosted Zn-Pb-(Ag) Deposit, South of Esfahan. Scientific Quarterly Journal of Geosciences, 25(97): 221–236. (in Persian with English abstract) https://doi.org/10.22071/gsj.2015.41507

Choulet, F., Charles, N., Barbanson, L., Branquet, Y., Sizaret, S., Ennaciri, A., Badra, L. and Chen, Y., 2014. Non-sulfide zinc deposits of the Moroccan High Atlas: Multi-scale characterization and origin. Ore Geology Reviews, 56: 115–140. http://dx.doi.org/10.1016/j.oregeorev.2013.08.015

Delavar, S.T., Rasa, I., Lotfi, M., Borg, G., Rashidnejad Omran, N. and Afzal., P., 2014. Geological evidence and ore body facies of Tangedezdan Zn-Pb (Ag) deposit in Jurassic-Cretaceous carbonate sequence, Booeen Miandasht (Isfahan-Iran). Scientific Quarterly Journal of Geosciences, 23(91): 77–88. (in Persian with English abstract) https://doi.org/10.22071/gsj.2014.43777

Ehya, F., Lotfi, M. and Rasa, I., 2010. Emarat carbonate-hosted Zn–Pb deposit, Markazi Province, Iran: A geological, mineralogical and isotopic (S, Pb) study. Journal of Asian Earth Sciences, 37(2): 235–249. https://doi.org/10.1016/j.jseaes.2009.08.007

Fazli, S., Taghipour, B. and Lentz, D., 2018. The Zn-Pb sulfide and Pb-Zn-Ag non-sulfide Kuh-e-Surmeh ore deposit, Zagros Belt, Iran: Geologic, mineralogical, geochemical, and S isotopic constraints. Journal of Geochemical Exploration, 194: 146–166. http://dx.doi.org/10.1016/j.gexplo.2018.07.019

Gholizadeh, K., Rasa, I., Yazdi, M. and Boni, M., 2019. Mineralogy and geochemistry of Zincian-dolomite in Bahramtaj deposit, Yazd, Central Iran. Iranian Journal of Crystallography and Mineralogy, 27(4): 925–940. (in Persian with English abstract) http://dx.doi.org/10.29252/ijcm.27.4.925

Gholizadeh, K., Rasa, I., Yazdi, M. and Boni, M., 2021. Geological structures and their role in control of mineralization in Bahramtaj Lead and Zinc deposit, Yazd province, Central Iran. Researches in Earth Sciences, 12(2): 206–225. https://doi.org/10.52547/esrj.12.2.206

Goldsmith, R., Graf, D.L. and Northrup D.A., 1962. Studies in the system CaCO₃, -MgC0₃- FeCO₃: (1) phase relations; (2) a method for major element spectrochemical analyses; (3) compositions of some ferroan dolomites. The Journal of Geology, 70(6): 659–688. https://doi.org/10.1086/626865

Goldsmith, R. and Northrup, D.A., 1965. Subsolidus Phase relations in the systems CaCO₃, -MgCO₃, -CoCO₃ and CaC0₃-M&O,-NiC0₃. Journal Geology, The Journal of Geology, 73(6): 817–829. https://doi.org/10.1086/627122

Heyl, A.V. and Boizon, C.N., 1962. Oxidized zinc deposits of the United States, part 1. General geology, U.S. Geology Survey, 1135-A, 52 pp. Retrieved January 16, 2025 from https://pubs.usgs.gov/bul/1135a/report.pdf

Hitzman, M.W., Reynolds, N.A., Sangster, D.F., Allen, C.R. and Carman C.E., 2003. Classification, genesis, and exploration guides for Nonsulfide Zinc deposits. Economic Geology, 98(4): 685–714. http://dx.doi.org/10.2113/98.4.685

Jazi, M.A., Karimpour, M.H. and Malekzadeh Shafaroudi, A., 2016. Crystallography, mineralogy and geochemistry of galena in Nakhlak lead mine (Esfahan). Iran Journal of Crystallography and Mineralogy, 24(1): 3–18. (in Persian with English abstract) Retrieved January 16, 2025 from http://dorl.net/dor/20.1001.1.17263689.1395.24.1.1.3

Karimpour, M.H., MalekzadehShafaroudi, A., Alaminia, Z., EsmaeiliSevieri A. and Stern C.R., 2019. New hypothesis on time and thermal gradient of subducted slab with emphasis on dolomitic and shale host rocks in formation of Pb-Zn deposits of Irankuh-Ahangaran belt. Journal of Economic Geology, 10(2): 677–706. (in Persian with English abstract) https://doi.org/10.22067/econg.v10i2.76528

Karimpour, M.H., MalekzadehShafaroudi, A., EsmaeiliSevieri, A., Shabani, S., Allaz, J.M. and Stern, C.R., 2017. Geology, mineralization, mineral chemistry, and ore fluid conditions of Irankuh Pb-Zn mining district, south of Isfahan. Journal of Economic Geology, 9(2): 267–294. (in Persian with English abstract) https://doi.org/10.22067/econg.v9i2.64930

Kulp, J.L., Kent, P. and Kerr, P.F., 1951. Thermal study of the Ca-Mg-Fe carbonate minerals. American Mineralogist, 36(9–10): 643–670. Retrieved January 16, 2025 from https://api.semanticscholar.org/CorpusID:109863578

Luke, G., Nigel, J., Cook, C., Ciobanu, L. and Benjamin, P.W., 2015. Trace and minor elements in galena: A reconnaissance LA-ICP-MS study. American Mineralogist, 100(2–3): 548–569. http://dx.doi.org/10.2138/am-2015-4862

Mandarino, J.A. and Back, M.E., 2004. Fleischer’s Glossary of Mineral Species 2004. The Canadian Mineralogist, 43(4): 1436-1437. http://dx.doi.org/10.2113/gscanmin.43.4.1436

Milliman, J.D., 1974. Marine Carbonates Part 1: Recent Sedimentary Carbonate. Springer-Verlag, Berlin, 375 pp.

Mondillo, N., Boni, M., Balassone, G. and Grist, B., 2011. In search of the lost zinc: a lesson from the Jabali (Yemen) nonsulfide zinc deposit. Journal of Geochemical Exploration, 108(3): 209-219. https://doi.org/10.1016/j.gexplo.2011.02.010

Mondillo, N., Boni, M., Balassone, G. and Villa, I., 2014. The Yanque Prospect (Peru): From Polymetallic Zn-Pb Mineralization to a Nonsulfide Deposit. Economic Geology, 109(6): 1735­1763. https://doi.org/10.2113/econgeo.109.6.1735

Mondillo, N., Wilkinson, J., Boni, M., Weiss, D. and Mathur, M., 2018. A global assessment of Zn isotope fractionation in secondary Zn minerals from sulfide and non-sulfide ore deposits and model for fractionation control. Chemical Geology, 500: 182–193. https://doi.org/10.1016/j.chemgeo.2018.09.033

Monecke, T., Kohler, S., Kleeberg, R., Herzing, P.K. and Gemmell, J.B., 2001. Quantitative phase-analysis by the Rietveld method using X-ray powder-diffraction data: Application to the study of alteration halos associated with volcanic-rock-hosted massive sulfide deposits. The Canadian Mineralogist, 39(6): 1617–1633. http://dx.doi.org/10.2113/gscanmin.39.6.1617

Motavali, K., Behzadi, M. and Yazdi, M., 2019. Geochemical evolution in Nodusahn Zn-Pb hydrothermal deposit with an emphasis on ore mineralography and sulfide analysis. Iranian Journal of Crystallography and Mineralogy, 27(1): 95–108. (in Persian with English abstract) http://dx.doi.org/10.29252/ijcm.27.1.95

Newton, T., 2013. Geochemistry of the Timberville Zn-Pb District, Rockingham County. VA. Ph.D. thesis, University of Maryland, Maryland, USA, 137 pp.

Paradis, S., Keevil, H., Simandl, G. and Raudsepp, M., 2015. Carbonate-hosted non sulphide Zn-Pb Mineralization of southern British Columbia, Canada. Mineralium Deposita, 50(8): 923–951. http://dx.doi.org/10.1007/s00126-014-0565-9

Peernajmodin, H., Rastad, E. and Rajabi, A., 2018. Ore structural, textural, mineralogical and fluid inclusions studies of the Kouh-Kolangeh Zn-Pb-Ba deposit, Malayer- Isfahan metallogenic belt, South Arak, Iran. Scientific Quarterly Journal of Geosciences, 27(107): 287–303. (in Persian with English abstract) https://doi.org/10.22071/gsj.2018.63856

Rao, C.P. and Adabi, M.H., 1992. Carbonate minerals, major and minor elements and oxygen and carbon isotopes and their variation with water depth in cool, temperate carbonates, western Tasmania, Australia. Marine Geology, 103(1–3): 249–272. https://doi.org/10.1016/0025-3227(92)90019-E

Rao, C.P. and Amini, Z.Z., 1995. Faunal relationship to grain-size, mineralogy and geochemistry in recent temperate shelf carbonate, Western Tasmania, Australia. Carbonates and Evaporites, 10: 114–123.  https://doi.org/10.1007/BF03175247

Reichert, J. and Borg, G., 2008. Numerical simulation and a geochemical model of supergene carbonate-hosted nonsulphide zinc deposits. Ore Geology Reviews, 33(2): 117–133. https://doi.org/10.1016/j.oregeorev.2007.02.006

Rosenberg, E., 1967. Subsolidus relations in the system CaCO_a-MgCO_a-FeCO₃, between 350 and 550°C. American Mineralogist, 52: 787–796. Retrieved January 16, 2025 from http://www.minsocam.org/ammin/AM52/AM52_787.pdf

Siivola, J. and Schmid, R., 2007. List of Mineral Abbreviations: Recommendations by the IUGS Subcommission on the Systematics of Metamorphic Rocks: Web version 01.02.07. (Electronic Source). Retrieved January 16, 2025 from https://recordcenter.sgc.gov.co/B23/662_19MemExPl_373_Las_Acacias/Documento/pdf/Anexo1_InveRecoBibl/Siivola%20y%20Schmid%20(2007).%20List%20of%20mineral%20abbreviations.pdf

Slezak, P.R., Olivo, G.R., Oliveira, G.D. and Dardenne, M.A., 2014. Geology, mineralogy, and geochemistry of the Vazante Northern Extension zinc silicate deposit, Minas Gerais, Brazil. Ore Geology Reviews, 56: 234–257. http://dx.doi.org/10.1016/j.oregeorev.2013.06.014

Soheili, M., Jafarian, M.B. and Abdollahi, M.R., 1992. Geological map of Aligudarz Scale 1:100000. Geological Society of Iran.

Thiele, O., Alavi, M. and Assefi, R., 1967. Geological map of Golpaygan Scale 1:250000. Geological Society of Iran.

Vandeginste, V., John, C.M. and Manning, Ch., 2013. Interplay between depositional facies, diagenesis and early fracture in the Early Cretaceous Habshan Formation, Jebel Madar, Oman. Marine and Petroleum Geology, 43: 489–503. https://doi.org/10.1016/j.marpetgeo.2012.11.006

Vaziri, S.H., Fursich, F.T. and Kohansalghadimvand, N., 2012. Facies analysis and depositional environments of the Upper Cretaceous Sadr unit in the Nakhlak area, Central Iran. Revista Mexicana de Ciencias Geológicas, 29(2): 384–397. Retrieved January 16, 2025 from https://www.scielo.org.mx/scielo.php?script=sci_arttext&pid=S1026-87742012000200007

Yang, Q., Liu, W., Zhang, J., Wang, J. and Zhang, X., 2019. Formation of Pb ­Zn deposits in the Sichuan­Yunnan­ Guizhou triangle linked to the Youjiang foreland basin: Evidence from Rb­ Sr age and in situsulfur isotope analysis of the Mapping Pb­ Zn deposit in northeastern Yunnan Province, Southeast China. Ore Geology Reviews, 107: 780–800. https://doi.org/10.1016/j.oregeorev.2019.03.022

Zabinski, W., 1980. Zincian dolomite: the present state of knowledge. Mineralogia Polonica, 11: 19–32. Retrieved January 16, 2025 from http://www.mineralogia.pl/dokumenty/111.pdf