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摘要:
有孔虫碳酸钙质壳体是海洋沉积物中普遍存在的环境记录载体之一，原位微区分析技术的发展为更进一步详细、直观地了解有孔虫壳体内微量元素的分布和变化提供了新方法，并带动了应用有孔虫壳体微区的元素含量和比值作为工具进行古环境反演相关研究的快速发展。利用电子探针 (EPMA)、激光剥蚀电感耦合等离子体质谱 (LA-ICP-MS) 并结合扫描电镜，对南海东北部陆坡区表层沉积物中的Globigerinoides ruber、Neogloboquadrina dutertrei、Pulleniatina obliquiloculata和Globorotalia inflata 4种浮游有孔虫壳体的Mg/Ca进行了原位地球化学分析。电子探针面扫描结果显示，G.ruber具有多条高Mg条带，这些周期性的条带变化可能与共生藻类有关；而N.dutertrei、P.obliquiloculata和G.inflata外部具有较厚的低Mg方解石壳。同时，LA-ICP-MS测试结果也显示出N.dutertrei、P.obliquiloculata和G.inflata的壳体中存在明显的低Mg/Ca层，而G.ruber中可见多组Mg/Ca比的高低变化，这与电子探针面扫描的结果一致。有孔虫自身的生物矿化过程会影响壳体中Mg/Ca比的分布，而污染相的存在会导致Mg/Ca测试结果的偏高。因此，认为有孔虫壳体Mg/Ca比的较大变化不仅受到周围海水温度的影响，而且还与共生藻等因素有关。此外，利用LA-ICP-MS测试可获得较为可靠的Mg/Ca比，避免了常规复杂的前处理过程，可以为今后高效、快速、高空间分辨率、低样品量的测试提供技术依据。
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关键词:
- 激光剥蚀电感耦合等离子质谱分析 /
- 电子探针 /
- Mg/Ca比 /
- 温度
Abstract:Planktonic foraminifera is one of the important materials that can provide the information of the physico-chemical environments. The development of in-situ microscopic analysis technology provides a new opportunity to carry out the detailed and intuitive understanding of the distribution and variation of trace elements in biological shells. At the same time, it also promotes the rapid development of paleoenvironmental inversion related research by using the element contents and ratios of the foraminifera shells microregion. In this paper, we used electron microprobe analysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and scanning electron microscopy (SEM) to conduct in-situ geochemical analysis of Mg/Ca in the four planktonic foraminifera shells of Globigerinoides ruber, Neogloboquadrina dutertrei, Pulleniatina obliquiloculata and Globorotalia inflata in the surface sediments of the northeastern slope of the South China Sea. The results of electron microprobe mapping showed that G.ruber had periodic bands with high Mg contents, which might be associated with symbionts. However, N.dutertrei, P.obliquiloculata and G.inflata had thicker calcite crusts with low Mg contents. The results of LA-ICP-MS also showed that there were obvious low Mg/Ca calcite crusts with of N.dutertrei, P.obliquiloculata and G.inflata, while multiple sets of Mg/Ca ratios can be seen in the shells of G. ruber, which were consistent with the results of electron microprobe mapping. The distribution of Mg/Ca ratios in shells were affected by the biomineralization process of foraminifera, and the presence of contaminants also led to higher Mg/Ca ratios. Therefore, we conclude that the large variations of Mg/Ca ratios in foraminifera shells are not only affected by the surrounding seawater temperature, but also constrained by other factors. In addition, we found that reliable Mg/Ca ratios can be obtained by the LA-ICP-MS test. The application of this method can avoid the complex pretreatment process, and provide a technical basis for efficient, fast, high spatial resolution and low sample volume testing in the future.
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Key words:
- LA-ICP-MS /
- electron microprobe analysis /
- Mg/Ca ratios /
- temperature
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表 1 DZ5重力柱状样品19 cm处的AMS14C测年数据和校正年龄
Table 1. AMS14C dating data and corrected age of the gravity core sample of DZ5 at 19 cm
深度/cm 测试材料 AMS14C年龄/aBP 日历年龄/cal.aBP 2σ范围/cal.aBP 19 G.ruber 3345±35 1162 950～1383 
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表 2 各属种不同腔室的Mn/Ca、Al/Ca平均值
Table 2. Average Mn/Ca and Al/Ca values in different chambers of each species
个体 腔室 Mn/Ca/
(mmol·mol−1)Al/Ca/
(mmol·mol−1)个体 腔室 Mn/Ca/
(mmol·mol−1)Al/Ca/
(mmol·mol−1)GR未1 F 0.17 1.62 ND未 F 0.26 3.29 − F1 0.24 3.25 − F1 0.13 2.19 − F2 0.40 7.50 − F2 0.08 1.11 平均值 − 0.27 4.12 − F3 0.08 1.73 GR未2 F 0.11 1.04 − F4 0.11 4.17 − F1 0.14 1.99 平均值 − 0.13 2.50 − F2 0.16 2.07 ND已 F 0.10 0.35 平均值 − 0.14 1.70 − F1 0.06 0.06 GR已 F 0.11 0.09 − F2 0.05 0.06 − F1 0.09 0.07 − F3 0.06 0.06 − F2 0.12 0.12 − F4 0.08 0.26 平均值 − 0.11 0.09 平均值 − 0.07 0.15 PO未 F 0.17 0.27 GI未 F 0.08 2.52 − F1 0.22 0.36 − F1 0.13 0.58 − F2 0.16 0.10 − F2 0.06 0.23 − F3 0.13 0.21 − F3 0.08 0.52 平均值 − 0.17 0.23 平均值 − 0.09 0.96 PO已 F 0.16 0.04 GI已 F 0.21 0.14 − F1 0.11 0.05 − F1 0.11 0.05 − F2 0.10 0.04 − F2 0.11 0.08 − F3 0.09 0.20 平均值 − 0.14 0.09 平均值 − 0.12 0.08
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