Distribution coefficients of trace elements between Merulinidae coral aragonite skeletons and seawater in the Weizhou Island, the northern South China Sea: Species and Rayleigh dependencies
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摘要: 微量元素在珊瑚文石骨骼和海水间的分配过程是控制海水中微量元素进入珊瑚骨骼的关键环节，表征该分配过程的分配系数（KD）常用于时间序列上的海水微量元素含量重建。由于缺乏珊瑚和海水的原位研究，我们对珊瑚文石骨骼与海水之间微量元素的分配行为的了解非常有限，这严重阻碍了我们对于准确的海水化学定量数据的获取。本研究中，我们选取了南海北部涠洲岛海域的两种典型的造礁石珊瑚种（网状菊花珊瑚（Goniastrea retiformis）和八重山扁脑珊瑚（Platygyra yaeyamaensis））和周围原位表层海水中的5种微量元素（Cu、Zn、Pb、Cd和Cr）进行研究，估算了这些微量元素在珊瑚文石骨骼和海水之间的分配系数。研究结果表明：各个微量元素在网状菊花珊瑚和八重山扁脑珊瑚文石骨骼和海水间的分配系数分别为3.65和3.49（Cu）；0.57和0.97（Zn）；1.06和1.42（Pb）；0.88和1.01（Cd）；0.66和0.60（Cr）。结合前人报道的各个种属珊瑚的分配系数，我们发现不同珊瑚种属Cu、Zn、Pb和Cd的KD值存在显著差异，而Cr的KD值差异则相对较小。此外，微量元素KD值还在一定程度上受到瑞利分馏的影响，该影响与KD值的大小有关。本研究为珊瑚文石骨骼和海水间分配系数提供了较为准确的KD值，为未来的珊瑚研究提供了重要的基础数据，并扩展了我们对海洋生物成因矿物晶格的化学特征的认识。Abstract: The distribution process of trace elements between coral aragonite skeletons and seawater is a key link to control the incorporating of trace elements in seawater into coral skeletons. The distribution coefficient (KD) characterizing this distribution process is often used to reconstruct the contents of trace elements in seawater in time series. Lacking of in situ research on corals and seawater, the limited knowledge related to the distribution behavior of trace elements between coral aragonite skeletons and seawater seriously hindered our acquisition of accurate chemical quantitative data on seawater. In this study we selected two typical reef-building coral species (Goniastrea retiformis and Platygyra yaeyamaensis) and five trace elements (Cu, Zn, Pb, Cd and Cr) in the surrounding in-situ surface seawater of Weizhou Island in the northern South China Sea, and estimated the distribution coefficients of these trace elements between the coral aragonite skeleton and seawater. Results revealed that the KD value of G. retiformis for Cu, Zn, Pb, Cd, Cr was 3.65, 0.57, 1.06, 0.88, 0.66 respectively; the KD value of P. yaeyamaensis was 3.49, 0.97, 1.42, 1.01, 0.60 respectively. We found a significant difference among different coral species in the KD values of Cu, Zn, Pb and Cd, but no significant difference for Cr. The results indicate that the KD values of trace elements are affected by the Rayleigh fractionation, which is related to the numerical values of KD. The study provided relatively accurate KD values for coral aragonite skeleton and seawater, represented important basic data for future research on coral reefs, and expanded our knowledge of chemical signature in biogenic lattices associated with marine organism.
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Key words:
- in situ seawater /
- Rayleigh fractionation /
- trace element /
- Merulinidae coral /
- South China Sea
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图 2 所采集涠洲岛珊瑚图片
a. 网状菊花珊瑚；b. 八重山扁脑珊瑚
Fig. 2 Coral pictures collected from Weizhou Island
a. Goniastrea retiformis; b. Platygyra yaeyamaensis
图 3 涠洲岛珊瑚文石骨骼微量元素含量（单位：μg/g）箱状图
Fig. 3 Box charts of coral trace element contents (unit: μg/g) from Weizhou Island
图 4 基于珊瑚线粒体细胞色素酶I基因序列所构建的系统发育树（a）和基于主要珊瑚种属不同微量元素KD值的聚类分析图（b）
Fig. 4 Phylogenetic tree based on cytochrome enzyme I gene sequence of coral mitochondria (a) and cluster analysis based on KD values of trace elements in main coral species (b)
图 5 涠洲岛海域不同种属珊瑚微量元素的KD值
虚线圈标记了本研究估算的珊瑚属KD值位置，数字为相对标准偏差
Fig. 5 Distribution coefficients KD of trace elements for various species of corals from the seawater in the Weizhou Island
The broken circles represent the distribution coefficients KD of Pavona corals, and the numbers are relative standard deviations
图 6 涠洲岛海域网状菊花珊瑚和八重山扁脑珊瑚珊瑚微量元素KD值的平均值及标准偏差对比
Fig. 6 Comparison of distribution coefficients KD of trace elements for Goniastrea retiformis and Platygyra yaeyamaensis from the seawater in the Weizhou Island
表 1 本研究采集的涠洲岛珊瑚文石骨骼微量元素含量（单位：μg/g）
Tab. 1 The contents of trace elements (unit: μg/g) in coral skeletons collected in Weizhou Island
珊瑚种类 位置 珊瑚采集点位 Cu Zn Pb Cd Cr 网状菊花珊瑚 （Goniastrea retiformis） W1 W1-1 3.40 197.40 1.08 0.11 0.35 W3 W3-1a 3.33 6.71 1.37 0.14 0.49 W3-2 2.60 5.63 0.69 0.12 0.90 W3-1b 3.69 12.87 1.51 0.29 0.51 八重山扁脑珊瑚（Platygyra yaeyamaensis） W4 W4-2 1.45 5.26 0.85 0.05 0.28 W5 W5-2 3.49 12.52 6.52 0.12 0.92 W5-1 2.56 6.41 4.80 0.04 0.38 W6 W6-1 3.89 10.29 1.21 0.12 0.68 注：斜体为移除的异常值。 
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表 2 南海不同海域珊瑚骨骼微量元素平均含量（单位：μg/g）
Tab. 2 Average content of trace elements in coral skeletons in the Souch China Sea (unit: μg/g)
位置 珊瑚种类 Cu Zn Pb Cd Cr 参考文献 广西涠洲岛 网状菊花珊瑚（Goniastrea retiformis） 3.11 6.17 1.05 0.12 0.58 本研究 八重山扁脑珊瑚（Platygyra yaeyamaensis） 3.02 9.47 1.19 0.08 0.55 本研究 广西涠洲岛 澄黄滨珊瑚（Porites lutea） 2.70 19.23 1.58 0.09 0.72 文献[29] 帛琉腔星珊瑚（Coelastrea palauensis） 3.74 27.71 1.52 0.16 0.98 文献[29] 十字牡丹珊瑚 （Pavona decussata） 2.52 17.6 2.51 0.15 0.54 文献[29] 西沙永兴岛 帛琉腔星珊瑚（Coelastrea palauensis） 2.34 21.11 − 0.09 − 文献[30] 鹿角杯形珊瑚（Pocillopora damicornis） 3.81 26.41 − 0.14 − 文献[30] 西沙永兴岛 澄黄滨珊瑚（Porites lutea） 1.27 2.56 0.36 0.0025 0.30 文献[31] 广东大亚湾 澄黄滨珊瑚（Porites lutea） 11.7 16.9 1.02 0.10 1.08 文献[32] 小角刺柄珊瑚（Hydnophora microconos） 7.71 3.74 1.84 − − 文献[33] 马来西亚沙巴 标准盘星珊瑚 （Favia speciosa） 8.72 4.69 1.79 − − 文献[33] 团块滨珊瑚（Porites lobata） 6.97 4.12 1.37 − − 文献[33] 注：“−”代表无数据。
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表 3 从涠洲岛采集的海水pH、SST（单位：℃）、表层海水盐度（SSS）和溶解微量元素含量（单位：μg/L），以及基于高分辨率珊瑚数据的调整系数[21]
Tab. 3 The pH, SST (unit: °C), surface sea salinity (SSS) and the contents (unit: μg/L) of dissolved trace elements of the seawater samples collected from Weizhou Island, as well as the adjustment coefficients based on the high resolution coral data [21]
位置 pH SST SSS Cu Zn Pb Cd Cr W1-1 8.42 27.6 32.0 0.96 10.66 0.92 0.11 0.90 W1-2 8.46 27.8 31.9 1.16 11.53 0.52 0.12 0.92 W3-1 8.37 27.1 32.6 0.93 8.41 0.69 0.068 0.70 W3-2 8.39 27.3 32.5 1.01 8.03 0.80 0.07 0.79 W4-1 8.88 27.3 32.2 0.40 3.25 0.19 0.021 0.67 W4-2 8.93 27.4 32.7 0.41 3.92 0.24 0.024 0.70 W5-1 8.45 27.2 32.4 0.88 4.83 0.24 0.046 0.58 W5-2 8.59 27.6 32.8 1.05 5.75 0.56 0.05 0.66 W6-1 8.43 27.6 31.9 0.55 8.35 1.23 0.042 0.99 W6-2 8.46 27.8 32.0 0.60 8.9 1.62 0.046 1.00 平均值 8.53 27.5 32.3 0.82 7.23 0.65 0.051 0.79 一类海水水质标准 5 20 1 1 50 调整系数 0.85 0.61 0.63 0.38 0.80
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表 4 涠洲岛两种珊瑚中微量元素的分配系数及其他珊瑚种属参考值对比
Tab. 4 The comparison of calculated distribution coefficients for trace metals among two species of corals from Weizhou Island and reference values of other coral species
珊瑚物种 位置 Cu Zn Pb Cd Cr 本研究 网状菊花珊瑚（Goniastrea retiformis） W1-1 4.32 − 1.06 0.55 0.45 W3-1 3.65 0.59 1.50 0.90 0.66 W3-2 2.84 0.56 0.70 0.88 1.18 平均值 3.60 0.57 1.08 0.78 0.76 中值 3.65 0.57 1.06 0.88 0.66 八重山扁脑珊瑚（Platygyra yaeyamaensis） W3-1 3.49 0.96 1.42 − 0.60 W4-2 3.55 0.97 2.64 1.01 0.38 W5-1 3.48 1.42 − 0.75 1.06 W5-2 3.22 1.52 − 1.01 1.27 W6-1 6.40 0.80 0.66 1.13 0.58 平均值 4.03 1.13 1.58 0.98 0.78 中值 3.49 0.97 1.42 1.01 0.60 参考值 澄黄滨珊瑚（Porites lutea）[21] 2.70 1.76 1.11 0.60 0.53 帛琉腔星珊瑚（Coelastrea palauensis）[21] 4.40 1.35 1.09 0.99 0.58 十字牡丹珊瑚（Pavona decussata）[21] 3.04 1.21 1.93 1.24 0.59 柱状牡丹珊瑚（Pavona clavus） 0.36[17] 0.7～1.3[19], 1 [7, 12], 0.76[20] 脑珊瑚（Pseudodiploria strigosa） 1[7] 2.3[12]
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