Elemental Mass Balance of the Hydrothermal Alteration Associated with the Baturappe Epithermal Silver-Base Metal Prospect, South Sulawesi, Indonesia Irzal Nur1,*, Arifudin Idrus2, Subagyo Pramumijoyo2, Agung Harijoko2, Koichiro Watanabe3, Akira Imai4, Sufriadin1, Asri Jaya HS1, Ulva Ria Irfan1 1 2 Department of Geological Engineering, Hasanuddin University, Makassar 90245, Indonesia Department of Geological Engineering, Gadjah Mada University, Yogyakarta 55281, Indonesia 3 Department of Earth Resources Engineering, Kyushu University, Fukuoka 819-0395, Japan 4 Department of Earth Science and Technology, Akita University, Akita 010-8502, Japan * Corresponding author: irzal_nur@yahoo.com Abstract The Baturappe prospect situated in southernmost part of Sulawesi island, Indonesia, is a hydrothermal mineralization district which is characterized by occurrences of epithermal silver-base metal mineralizations. The mineralizations hosted in basaltic-andesitic volcanic rocks of the late Middle-Miocene Baturappe Volcanics. This paper discusses a recent study of relationships between alteration mineralogy and whole-rock geochemistry, which focused on elemental mass balance calculation, of the hydrothermal alteration zones within the prospect. Hydrothermal alteration is zoned around the mineralizations from proximal quartz-carbonate and illite-quartz (argillic) to vein-related propylitic (epidote-chlorite-calcite) to distal-district propylitic (chlorite) alteration. Mass balance calculation indicates that in the vein-related propylitic altered zone there is a little decrease in bulk composition of the altered rock with respect to the least-altered rock. In contrast, the quartz-carbonate altered rocks show an increasing in bulk composition with respect to the least-altered rocks. The gains and losses of the major oxides and trace elements in the both alteration zones are generally consistent either with the hydrothermal alteration mineral assemblages of each alteration zone, indications of the hydrothermal alteration processes such as destruction of primary minerals and absorption of certain elements in altered minerals, and the behaviours of early metal-bearing sulphides. Keywords: Baturappe epithermal silver-base metal prospect, Indonesia, hydrothermal alteration, mass balance. Abstrak Prospek Baturappe yang terletak di ujung selatan Pulau Sulawesi, Indonesia, adalah sebuah distrik mineralisasi hidrotermal yang dicirikan dengan kehadiran mineralisasi perak-logam dasar epitermal. Mineralisasi ini terbentuk pada batuan volkanik basaltikandesitik anggota Formasi Volkanik Baturappe yang berumur akhir Miosen Tengah. Makalah ini membahas hasil studi terkini tentang hubungan antara mineralogi alterasi dan komposisi geokimia batuan, yang difokuskan pada kalkulasi kesetimbangan massa, pada zona-zona alterasi hidrotermal prospek Baturappe. Alterasi hidrotermal pada prospek Baturappe terzonasi di sekitar mineralisasi dari proksimal ke distal: zona kuarsa-karbonat dan illit-kuarsa (argilik), zona propilitik yang berhubungan genetik dengan urat termineralisasi (epidot-klorit-kasit), dan zona propilitik berskala distrik 1 (klorit). Hasil evaluasi kalkulasi kesetimbangan massa menunjukkan bahwa pada zona propilitik yang berhubungan genetik dengan urat termineralisasi terjadi sedikit penurunan komposisi kimia total pada batuan yang teralterasi dibandingkan dengan batuan ekuivalen tak-teralterasinya. Sebaliknya, batuan yang teralterasi kuarsa-karbonat mengalami peningkatan komposisi kimia total dibandingkan dengan batuan ekuivalen tak-teralterasinya. Peningkatan dan penurunan konsentrasi oksida-oksida mayor dan unsur-unsur jejak pada kedua zona alterasi tersebut secara umum konsisten, baik terhadap himpunan mineral alterasi hidrotermal yang terbentuk, indikasi-indikasi proses alterasi hidrotermal seperti destruksi mineral-mineral primer dan absorpsi unsur-unsur tertentu pada mineral-mineral teralterasi, maupun perilaku geokimia sulfida-sulfida logam pra-alterasi. Kata kunci: Baturappe epithermal silver-base metal prospect, Indonesia, hydrothermal alteration, mass balance. Introduction The Baturappe prospect is situated in Baturappe Village, Gowa Regency, South Sulawesi Province, Indonesia. It lies in the southwesternmost part of Sulawesi Island, about 50 km southeast of Makassar, the capital city of South Sulawesi Province. The prospect is characterized by occurences of epithermal silver-base metal mineralizations which are hosted in basaltic-andesitic volcanic rocks of the late Middle-Miocene Baturappe Volcanics (Nur et al., 2009). The most significant mineralization in the prospect, the Bincanai vein, contains an average grade of: Pb 17.51 %, Zn 0.35 %, Cu 0.66 %, Ag 713 g/t, and Bi 308 g/t (Nur et al., 2010, 2011a,b). Earlier works on the prospect and its vicinity included the regional geology around the area (Sukamto and Supriatna, 1982); studies of volcanism and geodynamic evolution of south Sulawesi, as well as petrology, geochemistry, and dating of the volcanics (Yuwono et al., 1985, 1988; Leterrier et al., 1990; Priadi et al., 1994; Polvé et al., 1997.); preliminary investigations of base metal mineralizations in the prospect and vicinity (Sutisna, 1990; Sukmana et al., 2002; Zulkifli et al., 2002); and occurences and distribution of significant hydrothermal ore mineralizations in the Western Sulawesi Arc in related to its tectonic setting and metallogenesis (Idrus et al., 2011). The works are generally based on regional scale studies and preliminary investigations, no detailed study has been conducted on genetic aspects of the prospect. A detailed investigation of some genetic aspects including alteration geochemistry and elemental mass balance is needed to improve understanding of the prospect. This paper discusses a recent study of relationships between alteration mineralogy and whole-rock geochemistry, which focused on elemental mass balance calculation, of the hydrothermal alteration zones within the Baturappe epithermal silver-base metal prospect. Mass balance calculation following the example of Grant (1986) were used to quantify the effects of hydrothermal alteration on the host rock. The present study allows better understanding of the behaviour (enrichment or depletion) of the elements during hydrothermal alteration processes. Geology and Mineralization Zones Regionally, the Baturappe area is situated in the southwestern part of the regional geologic map of the Ujung Pandang, Benteng and Sinjai quadrangles, Sulawesi (Sukamto 2 and Supriatna, 1982). A detailed surface geological mapping has then conducted in an area of 1000 ha to study the geological background of the mineralization in the prospect. The older rock unit broadly distributed in the study area is lava of dominantly basalt and less andesite, mostly porphyritic, with general orientations of N(80-85)oE/(18-20)oSE at the centre and east of the study area, and N120oE/65oSW at the west. Locally, blocks of volcanic breccia also exposed in the lava. Based on its lithological characteristics, this unit is interpreted as a member of lava, Tpbl (Sukamto and Supriatna, 1982) which according to K-Ar dating indicates age of 12.38 to 12.81 Ma or late Middle-Miocene (Yuwono et al., 1985; Priadi et al., 1994). The basaltic-andesitic lava which distributed from Bincanai and Ritapayung area at the west, through Bangkowa to the east, and Taloto at the south portions of the study area, is identified as the host rock of the epithermal mineralizations in the prospect. At the north, the lava was intruded by a gabbroic-dioritic stock; and followed by a group of basaltic-andesitic dykes. At least 50 units of dykes with a thickness range of 8 cm to 2.5 m are cropped-out in the study area, distributed radially centered to the stock, forming a radial swarm of dyke. K-Ar dating on two samples of basalt indicate ages of 7.5 Ma and 6.99 Ma, and 7.36 Ma on gabbro (Sukamto and Supriatna, 1982). The basaltic-andesitic stock and dykes are interpreted as the mineralization-bearing rocks in the study area, which is indicated by the occurences of disseminated ore (i.e., pyrite, chalcopyrite, sphalerite, galena, covellite, magnetite, hematite) recognized in the field and microscopic observations. Due to the orientation of the dykes that are consistent to the trends of the fractures, it is interpreted that the emplacement and distribution of the dykes brought mineralization is highly controlled by geological structures (Nur et al., 2009; Figure 1). More than 20 units of quartz veins along with disseminated sulphide and sulphide stringer are distributed around the periphery of the stock in the study area, hosted in the lava and dyke units. Among these, eight significant mineralizations are distributed in four zones: Bincanai-, Baturappe-, Bangkowa- and Ritapayung zone. The mineralizations namely: Bincanai vein, Baturappe vein-1, Baturappe vein-2, Bungolo vein, Paranglambere vein (all clustered in the Baturappe zone); Bangkowa vein and Bangkowa stringer (in the Bangkowa zone); and Ritapayung dissemination (in the Ritapayung zone). The Bincanai vein and Baturappe veins are distributed and clustered along the main fault in the study area, the NW-SE trend Bincanai-Baturappe normal fault; whereas the Bangkowa- vein and stringer are hosted in NW-SE dykes. Distribution of the mineralizations and orientation of the veins are shown in Figure 1. The veins display the typical primary texture of epithermal veins: crustiform banding texture; from symmetric-, multiphase- to simple crustiform of quartz ± carbonate – sulphide (dominated by galena). In general, sulphide assemblages identified in the mineralizations indicate a range of intermediate- to high sulphidation epithermal assemblages. The sulphides include: galena, sphalerite, chalcopyrite, pyrite, tennantite, tetrahedrite, bornite, enargite, freieslebenite, and polybasite. Very fine-grained silver and bismuth minerals which occupy fractures of the early-stage minerals, were also identified by SEM-EDX analysis; the minerals include bismuthinite, cupropolybasite, jalpaite, angelaite, cuprobismutite, sorbyite, and launayite. Supergene minerals such as covellite, chalcocite, iodargyrite, anglesite, cerrusite, as well as manganese coronadite and chalcophanite were also identified. Bulk-ore chemical composition determined by XRF analysis indicates a highest grade of: Pb 17.51%, Zn 0.35%, Cu 0.66%, Ag 713 g/t, Bi 3 308 g/t for the veins, and Pb 0.11%, Zn 0.15%, Cu 5.83%, Ag 140 g/t, Bi 60 g/t for the dissemination (Nur et al., 2010, 2011a,b). 1 2 7 4 5 3 6 8 Figure 1. Geological map of the study area and distribution of significant mineralizations in the prospect: (1) Bincanai vein, (2) Ritapayung dissemination, (3) Baturappe vein-1, (4) Baturappe vein-2, (5) Bungolo vein, (6) Paranglambere vein, (7) Bangkowa vein, (8) Bangkowa stringer. Hydrothermal Alteration Zoning and Mineralogy As an introduction to discuss the relationships between the alteration mineralogy and whole-rock geochemistry, i.e., the elemental mass balance, this section briefly reviews the hydrothermal alteration zoning and mineralogy of the Baturappe prospect that have been previously reported on the earlier publications of the authors (Nur et al., 2011c,d). Zonation of hydrothermal alteration in the study area is divided on the basis of the dominant mineral assemblages and its spatial distribution relative to the mineralizations, from distal to proximal include: chlorite, epidote-chlorite-calcite, and illite-quartz and quartz-carbonate zones (Figure 2). The chlorite zone is a distal-district propylitic alteration which is characterized by a low intensity of alteration and developed on the 4 periphery of the hydrothermal system in study area. The epidote-chlorite-calcite zone is a vein-related propylitic alteration which is characterized by a higher intensity of alteration and developed proximal to the structural-controlled veins in the prospect. The illite-quartz (argillic) zone is characterized by clay mineral assemblages which distributed proximal to the related-veins at Baturappe- and Bangkowa area, and interpreted as the centre of hydrothermal activities responsible for the mineralization. The narrow and elongated distribution of the zone (Figure 2) indicates that the distribution is controlled by geological structure. The quartz-carbonate zone also distributed proximal to the relatedmineralization (the Bincanai vein and the Ritapayung dissemination), and also interpreted as the centre of the hydrothermal activities that responsible for the mineralizations. The narrow and elongated distribution of the quartz-carbonate zone around the Bincanai vein indicates that the distribution is controlled by geological structure, i.e., the BincanaiBaturappe fault (Figure 2). On the other hand, at Ritapayung, regarding the lithological host of the alteration-mineralization (volcanic breccia), the quartz-carbonate zone in this area is controlled by permeability of the host rock (Nur et al., 2011c,d). The mineral assemblages in each alteration zone is summarized in Table 1. Figure 2. Hydrothermal alteration map of the Baturappe prospect. 5 Table 1. Mineral assemblage in each hydrothermal alteration zone Hydrothermal mineral Chlorite zone Epidote-chlorite-calcite zone Illite-quartz zone Quartz-carbonate zone BC BR BK BR BK BC RP 1 to 10 7 0.5 <7 < 0.5 <1 < 200 Chlorite Epidote Calcite Quartz Sericite Albite Biotite Illite Smectite i/s c/s Kaolinite Halloysite Dolomite Siderite Pyrite Magnetite Hematite Distance to mineralization (m) District scale - Abbreviations: i/s: mixed layer illite/smectite, c/s: mixed layer chlorite/smectite; BC: Bincanai, BR: Baturappe, BK: Bangkowa, RP: Ritapayung. - Line weight indicates relative abundance. Analytical Methods In this study, the whole-rock geochemical analysis was performed by X-ray fluorescence spectrometry (XRF) and inductively coupled – mass spectrometry (ICP-MS) methods. The XRF analysis was conducted to measure the major oxides of altered and less-altered rock samples, whereas the ICP-MS analysis was conducted to measure the trace element composition of the altered and less-altered rock samples. 6 Sample preparation for the XRF analysis was performed at the Laboratory of Economic Geology, Department of Earth Resources Engineering, Kyushu University. The samples were firstly crushed and grinded, then pulverized by agate mortar, and then milled by a CMT TI-100 model of vibrating sample mill machine, and finally were pelletized using a Rigaku pressing machine to form pressed powder discs that ready to be analyzed. Before the analysis conducted, one gram of each milled samples were separated to measure their LOI (H2O) concentration. The analysis was then performed using an XRF instrument of Rigaku ZSX Primus II, which calibrated by the fundamental parameter (FP) sensibility calibration method using 15 standards of the Geological Survey of Japan (JB-1a, JB-2, JB-3, JGb-2, JH-1, JA-1, JA-2, JA-3, JG-1a, JG-2, JG-3, JSy-1, JCh-1, JSd-2, JSd-3, JLs-1 and JMn-1) and 17 synthesized standard compounds (JA-3S, JB2-30Fe, JB2-40Fe, JB2-50Fe, JA3-20Fe, JA3-35Fe, 6elts-2, 6elts-3, AuAg-1, AuAg-2, AuAg-3, Na-rich, Ag5-BiPb, Ag9-BiPb and Ag17-BiPb). Technical specification of the analysis is, X-ray tube: Rh, voltage: 50 kV and current: 50 mA, detection limit (for the major oxides): 0.01%. Peak overlapping was examined, and overlap correction coefficients were used in the quantitative calculation in the FP sensibility calibration. The analysis was conducted at the Research Institute for Environment Sustainability (RIES) Laboratory, Kyushu University. For the ICP-MS analysis, the rest of milled samples that have been previously prepared and analyzed by the XRF method (for the major element composition) were sent to a commercial laboratory: the Actlabs (Activation Laboratories Ltd.), Canada, to be determined their trace- and rare earth element composition. Determination of 43 trace elements was then conducted by ICP-MS method, with detection limit (in ppm) as follows: Zn = 30; Cr and Ni = 20; Cu = 10; V, As and Pb = 5; Ba = 3; Sr and Mo = 2; Co, Ga, Rb, Zr and Sn = 1; Ge, Y, Ag and W = 0.5; Nb and Sb = 0.2; In, Cs, Hf and Bi = 0.1; La, Ce, Nd, Tl and Th = 0.05; Pr, Sm, Gd, Tb, Dy, Ho, Er, Yb, Ta and U = 0.01; Eu, Tm = 0.005; and Lu = 0.002 (analysis package code 4B2-research, Actlabs Service Guide 2010). To evaluate quantitatively the chemical composition changes (major and trace elements) of the host rocks of the mineralization due to hydrothermal alteration processes, the method of mass and volume change calculation (mass balance) of Gresens (1967) and its modification, the isocon diagram of Grant (1986) were applied. The Gresens’ formula for the calculation is: Xn = {[fv(gB/gA)CnB – CnA}100 where: Xn is mass gain or loss of an element between an unaltered rock (A) and its altered equivalent (B); fv is volume change factor; g is density of the rock; and Cn is concentration of an element. The equation has then rearranged by Grant (1986) to calculate the concentration changes of elements (∆C), as well as mass and volume changes (∆M and ∆V, respectively) of rocks as a results of hydrothermal alteration. The formula of the calculation is: ∆C = (MO/MA)*[(CA/CO)-1]; ∆M = [(MO/MA)-1]*100; and ∆V = (MO/MA)*[(ρA/ρO)-1]*100; where: ∆C = concentration change of elements (major oxides and trace elements) from altered rock to its unaltered equivalent (original rock), ∆M = mass change in %, ∆V = volume change in %, MO = mass of original rock, MA = mass of altered rock, CO = concentration of elements in original rock, CA = concentration of elements in altered rock, ρO = specific gravity of original rock, and ρA = concentration of elements in altered rock. Results of the calculation (elemental gains and losses) were 7 expressed in a graph where a line of iso-concentration (immobile elements) separates the enriched elements from the depleted ones. This line is called isocon. Elements plot above the reference isocon are enriched during alteration, whereas elements plot below are depleted. The gradient of the isocon is defined by ratio of the mass of original (least altered) rocks against the mass of altered rocks: MO/MA (Grant, 1986). In this study, data processing and imaging of the mass balance calculation was performed using the GEOISO software of J. Coelho (2005). Specific gravity of rock samples was measured by the buoyancy method (Archimedes principle). Elements TiO2, Zr and Y were used as immobile or inert elements (e.g., Mauk and Simpson, 2007) when input the data to the software. Result and Discussion In this study, four samples around the Bincanai vein were selected to be evaluated. The selection of the samples is because around the Bincanai vein a systematic sampling was conducted from proximal to distal site of the vein. The samples include: WBC.2B, WBC.2C and WBC.2D which were collected respectively 1 m, 2 m, and 3 m from the vein. These samples represent altered rocks which according to their alteration mineral assemblages (Table 1), the first two samples represent the quartz-carbonate zone and the rest represents the epidote-chlorite-calcite zone or vein-related propylitic. For the leastaltered rock, sample BCFW.1 that was taken relatively far from the vein (10 m) is selected. From the mineral assemblage identified by microscopic observation, this sample is relatively weak altered compared to the other three samples. Chemically, the sample also generally has a lower content of H2O, Cu, Zn and Pb relative to the other three samples (Table 2). Thus, beside consider the relative distance from the mineralization, the alteration mineral assemblage and chemical composition are also considered to select the least altered and altered rocks in this evaluation. Whole-rock chemical composition of the samples are listed in Table 2, and the results of mass balance calculation, the isocon diagram of the three pairs of least-altered and altered rocks (BCFW.1 vs WBC.2D, BCFW.1 vs WBC.2C, and BCFW.1 vs WBC.2B) including their enrichment-depletion diagram of selected elements are respectively shown in Figure 3, 4, 5. The gradient of isocons and results of mass and volume change calculations are attached in each isocon diagram (Figure 3.A, 4.A, 5.A). The propylitic altered rock (sample WBC.2D) indicates a little decrease in bulk composition with respect to the least-altered rock. This is expressed by the slight negative value of their mass and volume changes, -0.95% and -8.75%, respectively (Figure 3.A). K2O and Rb are strongly enriched with enrichment factors of 0.52 and 0.60, respectively, and Ba is slightly added with factor of 0.07 (Figure 3.B). The strong enrichment of K 2O may related to the presence of illite and sericite; these secondary minerals are identified in the samples of propylitic altered rock around the Bincanai vein. The addition of Rb and Ba indicates that the elements are probably absorbed in altered plagioclase and sericite (Idrus et al., 2009). MgO also moderately enriched with enrichment factor of 0.25 (Figure 3.A), which may related to the abundance of clinochlore in the sample (13.61 wt.% from semi-quantitative XRD result, Nur et al., 2011c,d). CaO is slightly depleted (depletion factor of 0.20). The depletion of CaO in propylitic alteration has been reported by Idrus et al. (2009), which may indicates that replacement of the calcic plagioclase rims is more intense than the formation of Ca-bearing hydrothermal minerals such as calcite and 8 epidote in the rocks. The depletions of Na2O, Sr and V reflect destruction of plagioclase during the alteration. The strong gain of Cu and slight to moderate gain of Zn indicate a high abundance of early copper- and zinc-bearing sulphides. Whereas the strong depletions of Pb and Bi suggest that lead- and bismuth-bearing sulphides are still not well developed in this alteration zone. Other elements such as MnO and Cs are enriched, whereas Zr, In and Sn are depleted (Figure 3). In contrast, the quartz-carbonate altered rocks (WBC.2C and WBC.2B) show an increasing in bulk composition with respect to the least-altered rock. This is expressed by the positive values of their mass and volume changes, +15.56% and +6.09% respectively for sample WBC.2C, and +20.93% and +33.87% respectively for sample WBC.2D (Figure 4 and 5). SiO2, CaO and FeO are enriched which explains the development of quartz and carbonate calcite and siderite in this alteration zone. The enrichment of FeO (0.11 in WBC.2C and 0.16 in WBC.2B) may also related to the occurrence of chamosite in the alteration zone. K2O, Rb, Cr and Ba are moderately to strongly enriched with the average enrichment factors for the two samples are 1.22, 2.99, 1.11 and 0.46, respectively (Figure 4.B and 5.B). The strong enrichment of K2O may related to the presence of illite and sericite in the samples (Table 1). The addition of Rb and Ba indicates that the elements are probably absorbed in altered plagioclase and sericite (Idrus et al., 2009); this may also explains the addition of Cr in the samples. MgO is slightly enriched in sample WBC.2B, with enrichment factor of 0.29 (Figure 5.B), which may related to the presence of clinochlore in the sample; result of semi-quantitative XRD indicates proporsion of 25.28 wt.% (Nur et al., 2011c,d). The depletions of Na2O and Sr reflect destruction of plagioclase during the alteration. The moderate to strong gains of Zn, As, Ag and Pb are respectively indicate a high abundance of early zinc-, arsenic-, silver- and lead-bearing sulphides in this inner zone of alteration. Cu and Bi are depleted in sample WBC.2C, but are then enriched in the more proximal sample, WBC.2B, which may explains that copper- and bismuth-bearing sulphides are more developed in the more proximal zone (to the vein). Other elements such as MnO, V, Ni, Y, Zr, Sb, Cs, Ce and U are enriched, whereas In and Sn are depleted (Figure 4 and 5). 9 Table 2. Whole-rock geochemical data of the four samples Sample code Sample type Alteration zone BCFW.1 Andesite Least-altered WBC.2B Andesite Quartz-carbonate WBC.2C Andesite Quartz-carbonate WBC.2D Basalt Epidote-chlorite-calcite (vein-related propylitic) MnO MgO CaO Na2O K2 O P 2 O5 H2 O Total 49.14 1.04 15.28 9.50 0.20 6.54 8.07 3.15 2.45 0.40 3.66 99.43 44.67 0.86 13.28 9.13 0.36 6.97 8.53 1.85 4.20 0.37 9.47 99.69 47.33 0.90 13.63 9.13 0.25 6.08 7.33 2.46 5.01 0.39 7.23 99.74 48.51 1.05 15.35 9.35 0.26 8.26 7.18 2.21 3.77 0.37 3.00 99.31 Trace elements (ppm) V Cr Co Ni Cu Zn Ga Ge As Rb Sr Y Zr Nb Mo Ag In Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Bi Th U 254 70 32 20 100 80 17 1.3 <5 57 729 22.2 104 5.5 <2 < 0.5 0.1 3 < 0.2 0.5 540 17.7 36.1 4.78 20.2 4.82 1.45 4.55 0.73 4.09 0.78 2.17 0.32 2.09 0.362 2.4 0.55 < 0.5 0.42 21 0.2 4.65 1.74 237 130 28 40 130 200 16 1 11 112 407 21 96 4.8 <2 0.6 < 0.1 2 33.4 4.7 592 16.7 34.9 4.64 19.4 4.86 1.45 4.43 0.69 3.88 0.73 2.06 0.302 1.99 0.319 2.2 0.5 < 0.5 0.51 29 0.2 4.84 2.16 229 120 26 30 50 160 15 1 <5 129 554 22 98 4.4 <2 < 0.5 < 0.1 2 4.7 3.3 748 17.8 37 4.89 20.5 5.07 1.46 4.75 0.73 4.13 0.79 2.23 0.326 2.05 0.311 2.2 0.46 < 0.5 0.55 42 0.1 5.22 2.27 246 70 32 20 190 90 16 1.3 <5 92 679 21.7 99 5 <2 < 0.5 < 0.1 2 < 0.2 1.4 583 17 35.5 4.64 19.5 4.77 1.47 4.52 0.72 4 0.76 2.15 0.322 2.05 0.318 2.3 0.45 < 0.5 0.4 13 0.1 4.52 1.71 Major elements (%) SiO2 TiO2 Al2O3 FeO 10 30 Cu (A) K2O Vein-related propylitic altered rock (WBC.2D) SiO2 Zr Ba Sr V Tl Rb Zn Ni MnO As Ce Hf La Er W Al2O3 Ga Co Yb Tm Nd P2O5 Y Cr Lu Na2O Sn Pb U Cs TiO2 Ge Sb Mo CaO Ho Sm Th Nb DyPr Tb Ag In Ta H2O MgO Eu FeO Bi Isocon gradient: 0.92 Mass change: -0.95% Volume change: -8.75% 0 Concentration change (∆C) 0 1.0 30 Least-altered rock (BCFW.1) (B) BCFW.1 vs WBC.2D 0.5 0 -0.5 -1.0 SiO2 FeO MgO CaO Na2O K2O V Cr Co Cu Zn As Rb Sr Y Zr Mo Ag Sn Ba Pb Bi Figure 3. A. Isocon diagram of sample BCFW.1 (least-altered rock) vs WBC.2D (veinrelated propylitic altered rock); major oxides in wt.% and elements in ppm. B. Enrichment-depletion diagram of the sample pair. 11 30 Ce (A) SiO2 Zr Ba Quartz-carbonate altered rock (WBC.2C) Zn Rb Cr V P2O5 Cs Y Tm Lu Na2O As La Hf U Er MnO Yb W Ga Al2O3 Co Pb Ni Sr Nd Sn Cu Eu FeO Mo CaO Ge MgO K2O Th Tb Ho TiO2 Gd Nb Tl Dy In Ta H2O Sb Bi Isocon gradient: 0.92 Mass change:+15.56% Volume change: +6.09% 0 Concentration change (∆C) 0 2.0 30 Least-altered rock (BCFW.1) (B) BCFW.1 vs WBC.2C 1.5 1.0 0.5 0 -0.5 -1.0 SiO2 FeO MgO CaO Na2O K2O V Cr Co Cu Zn As Rb Sr Y Zr Mo Ag Sn Ba Pb Bi Figure 4. A. Isocon diagram of sample BCFW.1 (least-altered rock) vs WBC.2C (quartzcarbonate altered rock); major oxides in wt.% and elements in ppm. B. Enrichmentdepletion diagram of the sample pair. 12 30 (A) Ba K2O Pb Zr SiO2 Quartz-carbonate altered rock (WBC.2B) Zn Rb V Cu Cr P2O5 MnO Y Nd Lu Tm Ni Sb U W Yb Al2O3 Ce Er Co La Ga Hf Sr Sn Na2O Bi As Eu H2O CaO Cs FeO Mo MgO Th Ho Gd Ag Nb TiO2 Dy Tb Tl Ta In Ge Isocon gradient:1.11 Mass change:+20.93% Volume change: +33.87% 0 Concentration change (∆C) 0 5.0 30 Least-altered rock (BCFW.1) (B) BCFW.1 vs WBC.2B 4.0 3.0 2.0 1.0 0 -1.0 SiO2 FeO MgO CaO Na2O K2O V Cr Co Cu Zn As Rb Sr Y Zr Mo Ag Sn Ba Pb Bi Figure 5. A. Isocon diagram of sample BCFW.1 (least-altered rock) vs WBC.2B (quartzcarbonate altered rock); major oxides in wt.% and elements in ppm. B. Enrichmentdepletion diagram of the sample pair. Conclusion Mass balance calculation indicates that in the vein-related propylitic altered zone there is a little decrease in bulk composition of the altered rock with respect to the leastaltered rock; the mass and volume changes is -0.95% and -8.75%, respectively. In contrast, the quartz-carbonate altered rocks show an increasing in bulk composition with respect to the least-altered rocks, which expressed by the positive values of their mass and volume changes, +15.56% to +20.93% and +6.09% to +33.87%, respectively. The gains and losses of the major oxides and trace elements in the both alteration zones are generally consistent either with the hydrothermal alteration mineral assemblages of each alteration zone, indications of the hydrothermal alteration processes such as destruction of primary minerals and absorption of certain elements in altered minerals, and the behaviours of early metal-bearing sulphides. 13 Acknowledgments This paper is a section of the first author’s dissertation completed at the Graduate Program of Geological Engineering, Faculty of Engineering, Gadjah Mada University, Yogyakarta, Indonesia. The authors are very thankful to the management of PT. Sungai Berlian Bhakti Mining for the permission to collect field data for the study. The authors also wish to express honest gratitude to Dr. Ryohei Takahashi and Mr. Naohiro Goto, respectively for the guidance and assistance in conducting XRF analysis at Kyushu University. Sincere gratitude also directed to the Directorate of Higher Education, Department of National Education, Indonesia for the grant of Hibah Disertasi Doktor 2010 that made possible for the authors to send samples to be analyzed by ICP-MS method at the Actlabs, Canada. This study was made possible through the long-term scholarship of the Fellowship Doctoral Degree Program, Hasanuddin University Engineering Faculty Development Project under JBIC (Japan Bank International Cooperation) Loan No.IP-541. The manuscript improvements from reviewers are gratefully acknowledged. References Grant, J.A., 1986. The isocon diagram – a simple solution to Gresens’ equation for metasomatic alteration. Economic Geology, 81, 1976-1982. 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