Journal of Economic Geology (Sep 2023)
Petrogenesis and Geochemistry of REE of Intrusive Rocks, Skarn Zone, and Iron Ore of Shotorsang, Northwest of Neyshabour
Abstract
Shotorsang iron skarn is located in 60 km northwest of Neyshabour (Khorasan Razavi, Iran) in Quchan-Sabzevar magmatic belt. Subvolcanic intrusion rocks have intruded into Cretaceous limestones and created skarnization. These rocks are divided into syenite porphyry and granodiorite porphyry based on their geochemical characteristics. They are I type oxidizing, metaluminous, and tectonic. Setting of the subvolcanic rocks are the subduction zone of the continental margin (VAG). Comparing the mineralization potential of the subvolcanic rocks of this area based on the use of the graph of SiO2 against K2O, MgO, Na2O+K2O, and Ni-V shows that they are fertile in terms of the formation of Fe and Cu skarn. Syenite porphyry is the origin of this mineralization, and magnesium in skarn is taken from hydrothermal fluid. The diagram of Eu/Eu*, Ce/Ce*, (Pr/Yb)n ratios also confirms the presence of meteoric water in the formation of the skarn zone. The primary fluid, which has a positive anomaly of Ce/Ce* and Eu/Eu* had acidic and oxidant conditions and high temperature, and formed pyroxene skarn. A part of magnetite mineralization is formed in this zone, and in this condition, the highest amount of REE entered the pyroxene skarn zone and diluted the fluid in terms of REE. This issue has led to a sharp decrease in the amount of REE in the mineralization zone. Negative Ce/Ce* and Eu/Eu* anomalies indicate alkaline conditions with less concentrated REE content, consistent with chlorite skarn. The highest amount of Fe mineralization is formed in this zone. Introduction Shotorsang iron skarn is located in 60 km northwest of Neyshabour (Khorasan Razavi, Iran) in Quchan-Sabzevar magmatic belt. Subvolcanic intrusion rocks have intruded into Cretaceous limestones and created skarnization (Amini and Khannazer, 2000(. This study found that at least four subvolcanic intrusion rocks are present in this region: Granodiorite porphyry, biotite syenite porphyry, quartz syenite porphyry, and quartz diorite to monzodiorite porphyry. These are divided into syenite porphyry and granodiorite porphyry based on the geochemical characteristics. Material and methods About 90 samples were collected for laboratory investigations of petrogenesis studies. Moreover, 25 samples were selected to be analyzed using the XRF and ICP-MS methods. Laboratory studies were carried out in Ferdowsi University of Mashhad and samples were analyzed in Acme and Zarazma laboratories. Results Subvolcanic rocks are I-type oxidizing, metaluminous, and tectonic. Setting of the subvolcanic rocks are the subduction zone of the continental margin (VAG). Moreover, some samples have been placed at the border of syn-collision due to high Rb, which is the result of high potassium. Enrichment of LILE elements such as K, Cs, Ba, Rb and incompatible elements that behave similar to them like Th compared to HFSE elements is observed in all samples compared to the primitive mantle. Enrichment of LILE relative to HFSE indicates magma related to subduction zones. The Sr element shows opposite behavior compared to the LILE elements. This issue can be justified by the high amount of CaO in magnetite ore (from 0.3% to more than 3.5%), because the two elements are similar in terms of chemical properties. Comparing the mineralization potential of the subvolcanic rocks of this area using the graph of SiO2 against K2O, MgO, Na2O+K2O, and Ni-V shows that they are fertile in terms of the formation of Fe and Cu skarn Meinert, 1995(. For igneous rocks, it was confirmed that the amount of Rb increases during the fractionation and crystallization processes (Meinert, 1995 (. Granitoids with potential for iron skarn have lower Rb (39 ppm). This amount is 103 ppm for copper skarn and 69 ppm for gold skarn. The amount of Rb content for all granitoids of Shotorsang area is 80 ppm. Considering the connection of these granitoids with iron skarn in this area, the high Rb content can be justified by crustal contamination of these rocks (Martin-Izard et al., 2000). Moreover, it can be mixing of a mafic magma with a felsic magma at a shallow depth. The amounts of V and Ni in iron skarn deposits are the highest; that is, 152 and 35 ppm, respectively. Ni and V for Shotorsang syenite porphyry group are 16 and 82, respectively and for Shotorsang granodiorite porphyry are 20 and 48, respectively. These values are lower than the global average of iron skarn. In general, the high amount of Rb and the low amount of Ni and V confirm the hypothesis that the magma has been fractionated and contaminated with crust. If the amount of Rb as well as the amount of Ni and V increase, the mixing of a magma derived from the mantle or a mafic magma with a highly fractionated magma would seem to be a more acceptable hypothesis (Meinert, 1995). Therefore, according to what was stated about the tectonic setting and the cases mentioned above, as well as the process of changes in the spider diagram of the rare earth elements of the studied area, it can be expected that the fluid forming the iron skarn of this region has undergone magmatic fractionation and been contaminated with crust. (La/Yb)n, (La/Sm)n and (Gd/Yb)n ratios were used to evaluate the separation degree between REEs. (La/Yb)n determines the degree of separation between LREE and HREE (Aubert et al., 2001; Yusoff et al., 2013), while the other two ratios are used to determine the degree of separation between LREE and MREE, and between MREE and HREE, respectively (Yusoff et al., 2013). These ratios vary for (La/Yb)n from 1.12 to 1.69, for (La/Sm)n from 6.7 to 40.72, and for (Gd/Yb)n from 0.89 to 4.22. As it is known, during the skarnization process, the highest degree of separation has occurred between LREE and HREE (up to about 70 times) and the lowest degree of separation has also occurred between MREE and HREE. The highest value of these ratios is in the mineralization zone, which indicates that the highest amount of separation of REE elements has taken place in this zone. Syenite porphyry is the origin of this mineralization, and magnesium in skarn is taken from hydrothermal fluid. Discussion The diagram of Eu/Eu*, Ce/Ce*, (Pr/Yb)n ratios confirms the presence of meteoric water in the formation of the skarn zone (Kato, 1999). The primary fluid, which has a positive anomaly of Ce/Ce* and Eu/Eu*, had acidic and oxidant conditions and high temperature and formed pyroxene skarn. A part of magnetite mineralization is formed in this zone, and in this condition, the highest amount of REE entered in pyroxene skarn zone and diluted the fluid in terms of REE. This issue has led to a sharp decrease in the amount of REE in the mineralization zone. Negative Ce/Ce* and Eu/Eu* anomalies indicate alkaline conditions (Meinert, 1995) with less concentrated REE content, consistent with chlorite skarn. The highest amount of Fe mineralization is formed in this zone. Acknowledgements The authors are grateful for the cooperation of the employees of the Shotorsang iron ore mine, especially Mr. Qotbi.
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