O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Effect of Diagenesis on the Microstructure of Fossil Coral Skeletons from Atauro Island, Timor-Leste Osvaldo da Cruz Sarmentoa, Aquiles Tomas Freitasa, Bhencao Natália M.Monteiroa, Vital Cruz M. Vilanovaa, Elizario Moniza, Aniceta de Araújoa, Cornélio Cardoso Moniza, Atsuko Yamazakib a) Department of Geology and Petroleum Engineering, National University of Timor Lorosa’e, Hera-Dili, Timor-Leste b) Department of Earth and Planetary Science, Faculty of Science, Kyushu University, Fukuoka, Japan E-mail: osvaldosarmento1512@gmail.com Abstract: The diagenesis effects on carbonate sediments are possible to affect the coral proxy recording climatic variations. We report the diagenesis effect on the microstructure of fossil coral skeletons and a Tridacna shell from Pleistocene reef terraces in Atauro Island, Timor-Leste. We use three methods with observation using Feigl’s solution staining, scanning electron microscope, and thin sections. The fossil Porites coral skeletons suffer diagenetic changes, mainly growing aragonite filling pore spaces in the microstructure. On the other hand, Goniastrea coral fossil shows a minimal diagenetic alteration, even Goniastrea fossils 100ka older than Porites fossils. The fossil giant clam shell (Tridacna Gigas) from Terrace II is still well preserved very dense aragonite shell and daily band microstructure. These results suggest that the diagenetic processes accelerate not only age but also the buried environment of the fossils and microstructure of biogenic skeletons. Keyword: diagenesis, fossil coral skeleton, reef terrace, pleistocene, porites, tridacna Paleoclimate reconstruction in the tropics has emerged as an important tool for exploring the natural bounds of climate variability. Long lived, massive corals provide valuable natural archives of environment and fossil corals provide ‘windows’ into climates of the past [2, 7, 10]. The process of diagenesis in coral reef terraces refers to the precipitation of secondary aragonite or calcite in skeletal voids, or the 1. Introduction Uplifted coral reef terraces locally compose the coast of Timor and around Islands [1, 4]. Millions of hectares of coral reef dominate much of the world tropical coastline. These massive structure results from the accumulation and cementation of skeleton innumerable corals over thousands of years. 1 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Atauro Island. The highest elevation of Atauro Island is 950 m above sea level, and the coral terrace raised up to 450 m above sea level. We visited the south part, Berau and Nametan, and Acrema area in the north of the island (Fig.1A). The fieldwork conducted on coral reef terrace indicted on the Figure 1B the samples collected with special consideration from beachrock terraces, coral reef and stratigraphic relationship of the strata. Totally 20 samples were collected to assess the diagenetic effect history (Table 1). To observe the diagenesis effects, we choose the coral specimens from the outcrop of the cliff on the edge of Terrace I (~100ka) named [1]. Figure 2 shows the sketch drawing at the terraces located at south of Atauro Island (Nametan Beach). The Reef complex cover the base of the lithology is volcanic rock. At the outcrop of sampling site, facies classified three small-scale facies based on their lithology (Fig.2). The changes in sedimentation patterns might be created by minor sea level fluctuation. The older facies have been made up of lithified Grainstone including Porites fossils (ATR10-P3). The subsequent facies consist in bound stone (ATR10-C). The middle facies made up of lithic fragments and it overlies in the older facies and faunas (ATR10-P1, ATR10-P2 and ATR10-G). Fig. 1 Location of the studied area (A) and sampling points on the south of Atauro Island (B). replacement of skeletal aragonite. During this alteration, the composition of coral terrace are covered particles by transgression and regression and diagenesis effects on carbonate sediments are possible to affect the coral geochemical proxies [3, 6]. Understanding diagenetic processes is essential for carbonate sedimentology and paleoclimate studies. In this study, we observe microstructure of fossil coral skeletons and shells to examine the methods for detecting diagenesis effects and to understand the diagenetic processes depending on ages and biogenic carbonate types. 3. Method 3.1. SEM (Scanning Electron Microscope) SEM is the kind of electron microscope that produces images of a sample by scanning the surface with a focused stream of light by electrons. The technical procedure work of this machine is very complexity utility and the specially using by coral research analyses in the following steps; The firstly sample 2. Sample Site The sample sites are located in the part of north and south of Atauro Island, Timor-Leste (S08°07'45.28",E125°37'48.66",S08°18'24.94 ", E125°34'30.00"°,). The coral fringing reef uplift occurs around the volcanic rocks in 2 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Feigl’s solution staining, scanning electron microscope (SEM), and thin section. preparation, Label for each sample code, cutting sample to small portion, use SEM equipment to analyses in the microscope and take image in SEM for sample analyses with the magnification of 200 and 1000. This material of Feigl’s solution is consist such as; NaCl 100ml, 5Wt% MnSO4, 1Wt% Ag2SO4, Distilled water 94g (consist in one (1) boil), This filter to remove the remaining things, add 1-2 drops NaOH, Filter again to keep solution black coloured solution and finally analysis by Stereo Microscope Analyses. Feigl solution is one of the methods used to identified the fossil coral mineral and define the characteristics feature indicate by colour calcite is the white and aragonite is black. 3.3. Thin Section Analyses Thin sections made for all samples at National University of East Timor, Faculty Engineering sciences and Technology department geology and Petroleum. There are nineteen sample for thin sections made by corals sample found in outcrop (ATR1ATR10, ATR10-C, ATR10-T, ATR10-G, and ATR-M1 until ATR-M3). These thin sections used to verify the mineralogy of the corals, examine the growth banding, and assess diagenetic changes, cementation, and alteration of microstructure fossil coral skeleton. Fig. 2 Stratigraphy column in the field and sketch or drawing coral terrace at outcrop in the field. Examination of the samples in this manner allowed microscale assessment of the fabrics and determination of any diagenesis that had affected in the fossil corals microstructure. In this study, we use SEM; Phenom G2 pure installed in KIKAI institute for Coral Reef Sciences, Japan. SEM images were taken under the following conditions: a 7.8 nm pixel resolution; voltage, 5 kV; and exposure time, 8 s. 4. Result The coral reef terrace in Acrema North of Atauro Island exhibits variable degrees of skeletal preservation. Although mostly devoid of cement, some corals from in this local contain minor amounts of fibrous and/or finely crystalline cement in some of their pores. Other corals in this area as South of Atauro Island (Nametan) with well preserved and another portion have altered, the external skeletons extensively replaced by coarse 3.2. Feigl’s Solution Staining There are two ways for examination in laboratory to determine the mineral composition for each sample. To examine the diagenesis effects on fossil coral skeletons and Tridacna shells, we observe the samples using 3 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) particles (Fig.3). Although these corals have recrystallized, most pores are open and contain only minor finely crystalline cement. Massive coral reef limestone in reef flat zone, beach conglomerate deposit is well rounded, and carbonate cemented. Bioturbated muds and sand in the back reef often with fossil mollusks (Tridacna), much of the limestone sequence forms a series of terrace level, where presents, the reef crest facies mark the highest elevation of each terrace. The terrace often has a thin regressive beach conglomerate deposit overlying the reef and sediment facies. The limestone surface weathers to pale grey and is hard cavernous. The development of a limestone terrace corresponds to sea-level high, with the oldest terrace occurring at the highest elevation. Table 1 Details of Coral Sample list, Fieldwork in Atauro Island Calcite or effect diagenesis rating. Sample Name ATR1 Latitude Longitude -8.129244444 125.63018 33 ATR2 -8.128938889 125.62978 06 ATR3 -8.303847222 125.56311 39 ATR4 -8.304377778 125.56257 78 ATR5 -8.305138889 125.56195 ATR6 -8.305302778 ATR7 -8.305547222 ATR8 -8.304736111 125.56145 ATR9 -8.305077778 125.56145 ATR10-G -8.306927778 125.575 125.56209 17 125.56198 61 Sampling Location Acrema (Atauro_nor th) Acrema (Atauro_No rth) Nametan (Atauro_So uth) Nametan (Atauro_So uth) Atauro_Sou th Atauro_Sou th Atauro_Sou th Nametan Beach Nametan Beach Nametan (Atauro_So uth) 4 Genus (Sampl e type) Sample Field size Terrace ((X,Y,Z Outcrop cm)) (Coral) 11.11.2 0 (Coral) 9.5.13 Goniast rea sp. 15.6.5 (Tridac na) 14.1 Tridacn a Gigas Porites sp. Porites sp. Porites sp. Porites sp. Goniast rea sp. Age Terrace (chapel& Veeh 1978) - - IIIa 230Ka II 200Ka I 100Ka 7.14.3 15.5.10 12.8.11 11.9.9 9.11.5 30.21.1 5 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Tridacn a 28.22 Porites sp. 16.13.1 1 Porites sp. 30.14.1 4 Porites sp. 23.29.1 0 (Coral) 14.30.6 Nametan Beach Porites sp. 9.7.8 125.575 Nametan Beach (Coral) 8.8.3 125.575 Nametan Beach (Coral) 16.19.5 ATR10-T -8.306927778 125.575 ATR10P1 -8.306927778 125.575 ATR10P2 -8.306927778 125.575 ATR10P3 -8.306927778 125.575 ATR10-C -8.306927778 125.575 -8.306927778 125.575 -8.306927778 -8.306927778 ATR MODER N1 ATR MODER N2 ATR MODER N3 Nametan (Atauro_So uth) Nametan (Atauro_So uth) Nametan (Atauro_So uth) Nametan (Atauro_So uth) Nametan (Atauro_So uth) Fossil porites corals (ATR10-P1, ATR10P2) of the terrace I are investigated by SEM image, stained Feigl’s solution, and thin section to observe on the fossil coral microstructure with diagenesis changes. On SEM images of the fossil Porites specimen, ATR10-P1, on Figure 3 (b,c), fiber-like crystals are growing on theca wall as secondary aragonite. On thin section image of coral skeleton (e,d), microstructure of theca wall and dissepiment are altered. SEM images of another Porites coral fossil (g,h), ATR10P2, shows that theca wall has smooth surface, however, high magnification image suggests some portion covered by secondary aragonite crystals. Fiegl’s solution stained specimens Beach - shows small part of calcite and almost part surrounded by aragonite. Thin section images (l, m) show the texture on theca wall, dissepiment, and septa is surrounded by secondary aragonite crystals. Fossil coral skeleton, Goniastrea sp. (ATR3) from Terrace IIIa is investigated by SEM (Figure 4 (b, c)). The skeletal dissepiment and theca wall structure are smooth and well preserved. Fiegl’s solution stains whole part of aragonite skeleton (d). The thin section image also suggests theca wall and 5 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Fig. 3 Figure 4. Observation on ATR10-P1 and ATR10-P2 sample from Terrace I. The SEM images on the surface of ATR10-P1 with a magnifying power of 200 (b) and 1000 (c). The polarized image of thin section (d, e). The SEM images on the surface of ATR10-P2 with a magnifying power of 200 (g) and 1000 (h). The coral skeleton stained by Feigl’s solution shows distinguish the part of aragonite (stained gray) and calcite (stained white) (k). The polarized image of thin section (l, m). dissepiment structure is well preserved. The SEM images of fossil Tridacna shell (ATR5) have no secondary crytals (Fig. 5b, 5c). The fine growt lines are observed on thin section images (Fig. 5d, 5e). 6 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) Fig. 4 Observation on ATR3 sample. The SEM images on the surface of skeletons dissepiment observed with a magnifying power of 200 (b) and 1000 (c). The coral skeleton stained by Feigl solution shows distinguish the part of aragonite (stained gray to yellow) and calcite (stained white) in between the theca walls and dissepiment (d). The polarized image of thin section (e, f) indicated the diagenesis dissepiment and theca wall well preserved. Fig. 5 Observation on ATR5 sample. The SEM images on the surface of skeletons observed with a magnifying power of 200 (b) and 1000 (c). The coral skeleton stained by Feigl solution shows distinguish the part of aragonite (stained gray ) and calcite (stained blue) in between surface skeleton (d). The polarized image of thin section (e) well preserved. 7 O. C. Sarmento et al. / TAJST—Vol. 3 (2020) section and scanning electron microscopy to detect diagenesis changes). Diagenesis, even at low levels, has the potential to distort the primary chemistry of coralline aragonite. Detecting and avoiding diagenesis is of utmost importance to coral paleoclimate research, and thin section analysis should play an essential role in that endeavor. 5. Outlook The coral reef framework and associated around Atauro Island provide a remarkably favorable for marine cement (figure 2). Marine cementation and diagenetic effect alter fossil coral manifest as secondary aragonite or calcite crystal filling inter-skeletal pore spaces [7, 9, 11]. Quaternary uplifted of marine terraces in Atauro Island form by the combined effects of sea-level change (caused primarily by changing glacial ice volume) and tectonic uplift on coastlines [1, 4]. Atauro Island is suitable to understand the diagenesis processes on coral and shell species in different ages. This study examines the utility of three ways methods, SEM analysis, Feigl’s solution, and thin section. The combination of these three ways will provide detailed information about diagenetic effects on biogenic carbonate. The Porites and Goniastrea corals, and Tridacna shell from Terraces I and Terraces IIIa around southern Atauro Island are compared in terms of the diagenesis effect on their microstructure (Figs. 3,4,5). The fossil Porites samples (ATR10-P1, ATR10-P2) are more influenced by diagenesis than the fossil Goniastrea samples (ATR3) (fig.4). Fossil Goniastrea samples (ATR3) shows minimal evidence of physical diagenetic alteration (fig.4). These results might be responsible for 1) coral microstructure such as pore spaces and complex, and 2) the buried environment of fossils. Diagenesis results in mineral phases, secondary aragonite, or calcite, depending on the zone [5, 8]. The growth of secondary aragonite on the coral skeletal structure typically occurs within marine phreatic and marine vadose zones. Secondary calcite, growing on the skeletal structure or replacing the original organic aragonite, occurs during subaerial exposure in the marine or freshwater vadose zones or can occur in freshwater phreatic environments. Finally, we aware that this research paper was not perfect, including its fossil coral skeleton and among others, so we hope to have appropriate cooperation with the readers to be able and successfully of article paper in the adjacent future research. Acknowledgement The authors are thankful for this research was made possible by funding from JICA CADEFEST Project Phase II for providing financial support. We are deeply indebted to numerous colleagues from the Kyushu University. We are thankful for KIKAI institute for providing SEM facilities to carry out this work. The fossil giant clam shell (Tridacna Gigas) from Terrace II is still well preserved very dense aragonite shell and daily band microstructure. Feigl’s solution is instant methods for detecting the diagenesis process. 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