Facies character and geochemical signature in the late Quaternary meteoric diagenetic carbonate succession at the Xisha Islands, South China Sea
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Abstract: The late Quaternary shallow-water carbonates have been altered by a variety of diagenetic processes, and further influenced by high-amplitude global and regional sea level changes. This study utilizes a new borehole drilled on the Yongxing Island, Xisha Islands to investigate meteoric diagenetic alteration in the late Quaternary shallow-water carbonates. Petrographic, mineralogical, stable isotopic and elemental data provide new insights into the meteoric diagenetic processes of the reef limestone. The results show the variation in the distribution of aragonite, high-Mg calcite (HMC) and low-Mg calcite (LMC) divides the shallow-water carbonates in Core SSZK1 into three intervals, which are Unit I (31.20–55.92 m, LMC), Unit II (18.39–31.20 m, aragonite and LMC) and Unit III (upper 18.39 m of core, aragonite, LMC and HMC). Various degrees of meteoric diagenesis exist in the identified three units. The lowermost Unit I has suffered almost complete freshwater diagenesis, whereas the overlying Units II and III have undergone incompletely meteoric diagenesis. The amount of time that limestone has been in the freshwater diagenetic environment has the largest impact on the degree of meteoric diagenesis. Approximately four intact facies/water depth cycles are recognized. The cumulative depletion of elements such as strontium (Sr), sodium (Na) and sulphur (S) caused by duplicated meteoric diagenesis in the older reef sequences are distinguished from the younger reef sequences. This study provides a new record of meteoric diagenesis, which is well reflected by whole-rock mineralogy and geochemistry.
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Figure 1. Location map of the Xisha Islands in the northern part of the South China Sea (a) and multibeam bathymetry map of the Xisha Islands (b). The bathymetry map in a has been generated by GMT software, and the data source is from https://www.ngdc.noaa.gov/mgg/bathymetry. In b, the black dot marks the Yongxing Island, and the SSZK1 borehole was drilled on the south of the Yongxing Island, Xuande Atoll.
Figure 2. Cross-section through the Xisha Platform showing the distribution of limestones and dolostones (a, adapted from Wang et al. (2018)), and integrated stratigraphic succession of Neogene rocks on the Xisha Islands showing the distribution of dolostones and limestones as well as diagenetic zones (b, adapted from Li et al. (2018)). The orange line in Fig. 1 indicates the location of the cross-section in a. In b, the stratigraphic reflectors (T20, T30, T40, T50, T60) were interpreted on seismic profiles shown by Wu et al. (2014).
Figure 3. Integrated data of late Quaternary strata of Core SSZK1: (1) chronostratigraphy based on ages come from U-Th dating results of the Well SSZK1 which propose the uppermost aeolianite facies formed after MIS 5; (2) facies; (3) variations in abundance of coral, red algae, green algae, benthic foraminifera and planktonic foraminifera; (4) vertical variations of carbonate and oxygen isotope; (5) correlation coefficients of carbonate and oxygen isotope vary in shallow-facies-dominated and deep-facies-dominated interlayer; and (6) mineralogical compositions of samples are concluded from analytical result of six samples and from the previous work in the nearby Wells XK-1 and XC-1 in the Xisha Islands (Liu et al., 1997, 2019). ARAG-aragonite, HMC- high-Mg calcite, LMC- low-Mg calcite.
Figure 4. Coral reef facies. a. Core photo of coral framestone: 1. Favia, 22.56–22.64 m; b. plane-polarized photomicrograph of coral framestone, 23.70 m; and c. plane-polarized photomicrograph of coral-debris dominated packstone, formed in the interstices between coral colonies: 1. coral fragments, 2. red algal fragments, 3. Amphistegina lobifera, and 4. micritic envelopes, 34.15 m.
Figure 5. Coral-algal reef facies. a. Plane-polarized photomicrograph of algae encrusting coral: 1. Porites, 2. Lithophyllum sp., 29.90 m; and b. plane-polarized photomicrograph of algae encrusting coral: 1. coral, 2. Lithophyllum sp., and 3. echinoid, 47.40 m.
Figure 6. Reef cap facies. a. Core photo of iron oxide-stained coral framestone: 1. Karst cave, 27.40–27.57 m; b. plane-polarized photomicrograph of coral framestone showing intense leaching of bioclasts, at least leached coral fragments are distinguished from their cortical coatings, formed by original intergranular porosity occlusion: 1. Porites, and 2. coral moldic pores, 28.93 m; and c. plane-polarized photomicrograph of coral framestone with coral moldic pores, 37.05 m.
Figure 7. Inner bank facies, outer bank facies and aeolinite facies. a. Plane-polarized photomicrograph of grainstone in inner bank facies, exhibiting subangular and poorly-sored bioclasts: 1. Amphistegina lessonii, 2. Globorotalia truncatulinoides, and 3. Halimeda, 23.98 m; b. plane-polarized photomicrograph of packstone in inner bank facies, exhibiting subangular and poorly-sored bioclasts: 1. Cibicidoides subhaidingerii (Parr) and 2. red algae, 32.70 m; c. cross-polarized photomicrograph of packstone in inner facies, showing the occurrence of quartz, 46.35 m; d. plane-polarized photomicrograph of grainstone in outer bank facies, showing planktonic foraminifera-rich bioclastic fragments: 1. planktonic foraminifera, 20.20 m.
Figure 8. Plane-polarized photomicrographs of products of meteoric diagenesis. a. Neomorphosed coral skeleton showing sparry calcite enclosed by microcrystalline calcite, 34.55 m. b. Micrite envelopes (red arrow), 33.20 m. c. Dissolved bioclasts, leaving molds with micrite envelope (red arrow), 42.5 m. d. Grains are connected by meniscus calcite cements causing round pore (red arrow), 32.9 m. e. Isopachous fibrous calcite fringe around grains; dissolution also occur on these early generated fibrous cements (red arrow), 25.14 m. f. Isopachous dogtooth calcite cements (red arrow), surrounding bioclasts, 47 m.
Figure 9. Cluster diagram for variables using correlation coefficient. The coefficients larger than 0.5 among these major elements means a link among the major components.
Figure 10. Vertical profile of facies and major elements variations, for symbols see legend in Fig. 3. The different colors of line titles mean different clusters of major elements.
Figure 11. Continental crust normalized major element composition (average value) for the reef facies-association, inner bank facies and aeolianite facies. Normalized values are from Taylor and McLennan (1985).
Figure 12. Dominant diagenetic environment at the uppermost 60 m depth intervals of Cores SSZK1 (a), XK-1 (b) and XC-1 (c) based on stable isotopic and mineralogical data. The previous work on Core XK-1 is from Liu et al. (2019) and Core XC-1 is from Liu et al. (1997). HMC: high-Mg calcite; LMC: low-Mg calcite.
Figure 13. The gradual decrease of S, Na2O and Sr content associated with stable isotopic values in different stage, for symbols see legend in Fig. 3. The dash line marks the ladder reduction of the average S, Na2O and Sr concentration in different depth intervals.
A1. X-ray diffraction pattern of the samples. Ar means aragonite; LH means low-Mg and high-Mg calcite; and L means low-Mg calcite.
Table 1. Results of X-ray diffraction (XRD) analyses in samples
Depth/m Aragonite/% High-Mg calcite/% Low-Mg calcite/% 2.00 54.7 23.5 21.8 18.39 76.4 0 23.6 27.80 43.6 0 56.4 31.20 0 0 100.0 43.80 0 0 100.0 53.65 0 0 100.0 
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Table 2. Descriptive statistics of major elements analysis results in reef facies-association, inner bank facies and aeolianite facies in comparison with the continental crust
Al2O3 CaO Fe2O3 MgO K2O SiO2 Na2O TiO2 MnO P2O5 S Reef facies-association Average 0.019 54.850 0.016 0.522 0.009 0.355 0.151 0.002 0.003 0.044 0.224 Max 0.144 55.561 0.102 0.980 0.034 2.115 0.512 0.006 0.005 0.183 0.006 Min 0.001 53.795 0.003 0.227 0.004 0.116 0.031 0.001 0.001 0.008 0.053 Inner bank facies Average 0.050 54.164 0.039 0.561 0.019 1.183 0.187 0.003 0.003 0.063 0.342 Max 0.300 55.380 0.166 0.889 0.094 9.736 0.667 0.008 0.005 0.183 0.014 Min 0.010 49.054 0.009 0.298 0.007 0.139 0.075 0.001 0.001 0.008 0.063 Aeolianite facies Average 0.046 51.798 0.039 1.973 0.015 0.258 0.494 0.002 0.003 0.109 0.340 Max 0.400 52.897 0.219 2.634 0.057 1.764 0.633 0.013 0.006 1.770 0.165 Min 0.016 49.901 0.009 0.725 0.010 0.081 0.363 0.001 0.002 0.035 0.266 Continental crust 15.040 5.390 6.170 3.670 2.580 61.710 3.180 0.670 0.090 0.170 –
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Table 3. The correlations of main elements in SSZK1 carbonate profile
Al2O3 CaO Fe2O3 MgO K2O SiO2 Na2O TiO2 MnO P2O5 S Sr Al2O3 1 CaO –0.34 1 Fe2O3 0.57 –0.43 1 MgO 0.08 –0.88 0.17 1 K2O 0.79 –0.48 0.68 0.09 1 SiO2 0.52 –0.21 0.53 0.15 0.82 1 Na2O 0.15 –0.88 0.26 0.75 0.26 –0.07 1 TiO2 0.90 –0.24 0.52 0.02 0.76 0.50 0.06 1 MnO 0.15 –0.21 0.30 0.23 0.23 0.14 0.09 0.13 1 P2O5 0.63 –0.30 0.22 0.19 0.42 0.16 0.16 0.58 0.02 1 S 0.07 –0.87 0.20 0.82 0.14 –0.19 0.98 –0.01 0.09 0.11 1 Sr 0.09 –0.75 0.21 0.61 0.15 –0.17 0.93 0.02 –0.02 0.10 0.92 1 Note: Correlation coefficients larger than 0.5 (P<0.01, n=138) are marked by bold numbers.
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Table 4. 230Th dating results for corals from Core SSZK1, Yongxing Island
Depth/m [U]/10–6 234U/238U 234U/238U (initial) 230Th/238U 230Th/232Th Age/a BP Error (2σ) 7.21 0.816 1.147 1.149 0.047 3 59.4 4 239 246 13.47 2.450 1.141 1.144 0.082 1 7 090.3 8 114 190 18.39 2.490 1.126 1.153 0.539 0 1 178.8 69 795 274 24.30 2.946 1.121 1.155 0.630 0 2 886.6 88 094 349 30.11 1.028 1.110 1.214 1.010 0 709.8 236 524 2 131 42.52 0.891 1.104 1.260 1.083 0 710.0 329 184 5 601 44.89 1.279 1.097 1.294 1.102 0 1 456.1 392 344 9 658 55.92 1.000 1.087 1.337 1.107 0 1 227.7 479 636 19 388 Note: The unreliable dating results are marked by bold numbers.
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A1. Detection limit of the analytical method
Element Analytical method Detection limit CaO XRF 0.032 2 (10–2) MgO XRF 0.003 0 (10–2) Al2O3 XRF 0.002 7 (10–2) Fe2O3 XRF 0.002 7 (10–2) Na2O XRF 0.040 2 (10–2) SiO2 XRF 0.004 0 (10–2) K2O XRF 0.002 2 (10–2) P2O5 XRF 0.000 9 (10–2) MnO XRF 0.002 3 (10–4) TiO2 XRF 0.001 0 (10–2) S XRF 0.000 6 (10–2) Sr ICP-MS 1.000 0 (10–6)
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