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Indonesian Journal on Geoscience Vol. 5 No. 2 August 2018: 179-197 INDONESIAN JOURNAL ON GEOSCIENCE Geological Agency Ministry of Energy and Mineral Resources Journal homepage: hp://ijog.geologi.esdm.go.id ISSN 2355-9314, e-ISSN 2355-9306 Geochemical Characteristics of Limestone of Wonosari-Punung Formation, Gunungkidul Regency, Yogyakarta, Indonesia Didik Dwi Atmoko, Anastasia Dewi Titisari, and Arifudin Idrus Department of Geological Engineering, Faculty of Engineering, Universitas Gadjah Mada Jln. Grafika No. 2, Bulaksumur, Yogyakarta 55281, Indonesia Corresponding author: [email protected] Manuscript received: July 6, 2017; revised: August 30, 2017; approved: April 26, 2018; available online: August 27, 2018 Abstract - A geochemical study was carried out to determine the geochemical characteristics of limestone in Wonosari- Punung Formation, and to suggest its depositional conditions and the source of rare earth elements. The study was conducted at Ponjong Area, Gunungkidul Regency, Daerah Istimewa Yogyakarta, Indonesia. White limestone which contains more abundant calcite is characterized by the highest CaO concentration. Red limestone which is associated with impure minerals such as siderite, rodochrosite, hematite, and titanite is typified by depleted CaO but higher SiO2, Fe2O3, MnO, and TiO2 concentrations. Grey limestone characterized by depleted CaO and higher MnO contents is considered to be influenced by the presence of impure minerals of manganite (Mn2O3.H2O) and/or pyrolusite (MnO2). Depletion of Sr concentration in the coloured limestone indicates that the diagenetic process increases from the white limestone to the coloured limestone. The process possibly occurred post-deposition of the limestones. The limestones show positive Mn* values (2.46 - 2.95) and authigenic U values (0.89 - 3.38) that suggest an oxidative environment. The Ce/Ce* values (0.57 - 0.80), Eu/Eu* values (1.04 - 1.88), high Y/Ho ratio, and low LaN/YbN ratio are indications that the rare earth elements in the limestones were derived from terrigenous materials. The positive Eu anomaly and enrichment of Cr and Mn of the limestones are indications of hydrothermal fluid activity taking place in the studied area. Based on the geochemical characteristics of the Punung-Wonosari limestones, the depositional environment and the source of rare earth elements of the limestones were therefore influenced by a combination of hydrothermal fluid activity with small amount of terrigenous material input and post depositional diagenetic process. Keywords: diagenetic process, rare earth elements, trace elements, oxidative condition, source of rare earth elements © IJOG - 2018. All right reserved How to cite this article: Atmoko, D.D., Titisari, A.D., and Idrus, A., 2018. Geochemical Characteristics of Limestone of Wonosari- Punung Formation, Gunungkidul Regency, Yogyakarta, Indonesia. Indonesian Journal on Geoscience, 5 (2), p.179-197. DOI: 10.17014/ijog.5.2.179-197 Introduction Punung Formation such as the development of the Miocene Wonosari-Punung Formation (Lokier, Background IJOG1999), reef facies of Wonosari-Punung Forma- Wonosari-Punung Formation is a Miocene tion (Siregar et al., 2004), sequence stratigraphy limestone formation located in the Southern and diagenesis of carbonate rocks of Wonosari- Mountain Basin. Toha et al. (1994) mentioned Punung Formation (Jauhari and Toha, 2005), that Wonosari-Punung Formation mainly consists depositional environment of carbonate rocks of of bedding and reefal limestones. Several geologi- Wonosari-Punung Formation in eastern Pacitan cal studies have been carried out on Wonosari- (Mukti et al., 2005), Punung paleoreef (Pre- AccreditedIJOG/JGI by:(Jurnal - LIPI, Geologi valid AugustIndonesia) 2016 - -Acredited August 2021 by LIPI No. 547/AU2/P2MI-LIPI/06/2013. valid 21 June 2013Indexed - 21 June by: 2016 Scopus - RISTEKDIKTI, valid May 2016 - May 2021 179 Indonesian Journal on Geoscience, Vol. 5 No. 2 August 2018: 179-197 monowati et al., 2012), and a geochemical study study, geochemical characteristics of the limestone of major oxide compound on Ponjong limestone on Wonosari-Punung limestone formation will be (Atmoko et al., 2016). Most of the previous studies determined based on geochemical elements, e.g. are based on outcrop determination, petrographic major oxide compounds (SiO2, Al2O3, Fe2O3, CaO, and paleontological analyses, except the study of MgO, K2O, Na2O, MnO, TiO2, and P2O), trace Atmoko et al. (2016) that more focused on a geo- elements (Cr, Mn, Fe, Rb, Sr, Y, Zr, Nb, Ba, La, chemical study. The studies were not emphasized Ce, and Eu), and rare earth elements contained in on limestone geochemical research of Wonosari- the Wonosari-Punung limestone. This geochemi- Punung Formation which was the subject of this cal characteristic of Wonosari-Punung limestone study, although studies of limestone geochemistry can be used for interpretation of its depositional are very important to understand the depositional conditions and its source of rare earth elements. condition of a limestone formation. Previous Furthermore, it is also possible for interpreting geochemical studies that have been carried out in sea level changes of the limestone depositional some places in the world and show the important environment. Therefore, this study might be use- things of geochemical research for interpretation ful for better reconstruction and understanding the of limestone depositional condition among others depositional environment of the Wonosari-Punung are oceanic chemistry of the rare earth elements Formation. This study was conducted at Ponjong (Elderfield, 1988), geochemistry of Cauvery Area, Gunungkidul Regency, Daerah Istimewa Basin, southeastern India and its implication to Yogyakarta, Indonesia (Figure 1). the provenance of limestone (Madhavaraju and Lee, 2009), rare earth elements in limestones of Geological Settings Kallankurichchi Formation, Tamil (Madhavaraju By referring to the regional geological map and Ramasamy, 1999), the source of rare earth of the Surakarta-Giritontro Quadrangle, Java, elements in carbonate strata of the Aptian-Albian scale 1:100,000 (Surono et al.,1992), the stud- Mural Formation, Mexico, related to hydrothermal ied area is composed of Semilir Formation and fluid effect (Madhavaraju and Gonzáles-León, Wonosari-Punung Formation (Figure 1a). The 2012), depositional conditions in limestone cor- Wonosari-Punung Formation consists of lime- related with paleo-redox condition, paleogeogra- stone, marly-tuffaceous limestone, conglomeratic phy and proximity to the source area (Liu et al., limestone, tuffaceous sandstone, and siltstone. 1988; German and Elderfield, 1990; Holser, 1997; It was deposited unconformably on the Semilir Northdurft et al.,2004; Lawrence and Kamber, Formation comprising tuff, dacitic pumice brec- 2006; Madhavaraju and Gonzáles-León, 2012). cia, tuffaceous sandstone, and shale (Surono et al. According to the previous geochemical studies, 1992). According to Atmoko (2016), the studied some elements such as Sr and Mn are diagenetic in- area is dominated by limestone units that belong dicators because of their widely divergent partition to the Wonosari-Punung Formation (Figures 1), coefficients, their acceptance into the carbonate and an older unit of tuffaceous sandstone-calcar- lattice, and their large compositional differences eous sandstone which distributes on north-west in marine and meteoric water (Bodine et al., 1965; and north-east of the studied area, considered to Turekian, 1972). Negative Ce anomalies preserved be a member of the Semilir Formation (Figure 1). in carbonate sediments and rocks are a strong A previous study conducted by Atmoko (2016) indication that the rocksIJOG are precipitated in an shows four types of limestone in the studied area oxide environment (Tostevin et al., 2016). Cerium composed of molluscan packstone, coralline anomalies can also be used as a potential indicator rudstone, foraminiferal grainstone, and coralline for eustatic sea-level (Chen et al., 2012). A positive framestone-bafflestone (Figure 1b). Atmoko Eu anomaly in a limestone formation is an indicator (2016) explains that the limestone in the studied of hydrothermal solutions effect on limestone (e.g. area was deposited in a reef depositional envi- German et al., 1993; Kurian et al., 2008). In this ronment and formed a reef system. Geological 180 Geochemical Characteristics of Limestone of Wonosari-Punung Formation, Gunungkidul Regency, Yogyakarta, Indonesia (D.D. Atmoko et al.) 110o34'15" E 110o46'00" E a Tomm Tmo Tms Mt. Panggung 54'00" S 54'00" S o o 7 7 D U D U D U Mt. Payung N Tmwl km 0 1 2 4 Qa Wonosari Yogyakarta 00'00" S 00'00" S o o 8 8 110o34'15" E 110o46'00" E Qa Alluvium Tmo Oyo Formation Tomm Mandalika Formation Tmwl Wonosari-Punung Formation Tms Semilir Formation Geological Structure 110o43'07" E 110o44'13" E 110o45'18" E Geological map b of Ponjong area 56'51" S 56'51" S o o N 75 75 km 0 0.25 0.5 1 Legend C: Framestone-baffelstone unit B: Foraminiferal grainstone unit A: Coralline rudstone unit Mollusk packstone unit Tuffaceous sandstone Calcareous sandstone unit Unmapped silicified limestone Unmapped andesitic breccia Dextral strike-slip fault Sinistral strike-slip fault Inferred fault Strike/Dip Sampling location 1 PLW-2A (White limestone) PLP-2B (Pink limestone) PLR-2C (Red limestone) 2 PLLG-5A (Light grey limestone) PLG-5B (Grey limestone) 56'51" S 56'51" S o o 75 75 110o43'07" E 110o44'13" E 110o45'18" E Figure 1. a. Regional geological map of the central-southern