海洋沉积物中
  <strong>GDGTs</strong>和长链二醇的古气候—环境指示意义研究进展

doi:10.11867/j.issn.1001-8166.2019.08.0855

地球科学进展 ›› 2019, Vol. 34 ›› Issue (8): 855 -867. doi: 10.11867/j.issn.1001-8166.2019.08.0855

海洋沉积物中 GDGTs和长链二醇的古气候—环境指示意义研究进展

陈立雷 ^1, ²(

),李凤 ^1, ²,刘健 ^1, ²

1. 自然资源部中国地质调查局青岛海洋地质研究所，山东青岛 266071
2. 青岛海洋科学与技术国家实验室海洋地质过程与环境功能实验室，山东青岛 266061

收稿日期:2019-02-28 修回日期:2019-07-14 出版日期:2019-08-10
基金资助:
有机地球化学国家重点实验室开放基金项目“东海闽浙沿岸全新世古环境;古气候演变的生物标志物记录”(SKLOG-201621);中国博士后科学基金面上项目“东海近岸全新世有机质来源及环境变化的生物标志物记录”(2018M642622)

Advances in Glycerol Dialkyl Glycerol Tetraethers and Long-Chain Alkyl Diols in the Marine Sediments: Implications for Paleoclimatic and Paleoenvironmental Changes

Lilei Chen ^1, ²( ),Feng Li ^1, ²,Jian Liu ^1, ²

1. Qingdao Institute of Marine Geology, China Geological Survey, Ministry of Natural Resources, Qingdao 266071, China
2. Laboratory for Marine Geology, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266061, China

Received:2019-02-28 Revised:2019-07-14 Online:2019-08-10 Published:2019-10-11
About author:Chen Lilei(1987-)， male， Laiyang City， Shandong Province， Postdoctoral. Research areas include quaternary sedimentary and environmental changes. E-mail： chenll@cug.edu.cn
Supported by:
the State Key Laboratory of Organic Geochemistry Open Fund “Biomarker records of the Holocene paleoenvironmental and paleoclimatic evolution along the Zhejiang-Fujian coast in the East China Sea”(SKLOG-201621);The China Postdoctoral Science Foundation Funded Project “Biomarker records from the East China Sea coast: Implications for organic matter sources and environmental changes in Holocene”(2018M642622)

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海洋沉积物中星罗棋布的脂类生物标志物分布特征，确切地记录了母源生物新陈代谢和有机组分运移转化的大量信息，常被用来重建古气候—环境变化。对利用边缘海沉积物中丰富的中心脂甘油双烷基甘油四醚（core-GDGTs）和长链二醇指示晚第四纪古气候—环境变化的研究进展进行了综述。指出厘清海洋沉积物中埋藏脂类生物标志物的“源—汇”过程是进行古气候—环境重建的前提。认为利用受早期成岩作用影响较小的多项指标可以增加重建古气候变化结果的准确性。在受大河影响显著的边缘海，可以根据海洋沉积物中core-GDGTs和长链二醇指标重建的古气候记录阐明古气候—环境变化引起的海陆联动变化机制，以期为预测未来温度和降雨变化提供可靠的技术手段及坚实的理论基础。

关键词: 甘油双烷基甘油四醚, 长链二醇, 有机质, 源—汇, 古气候重建

Lipid biomarkers widely dotted in marine sediments, as their distribution characteristics accurately record huge information on the metabolism of the original organisms and migration and transformation of these organic components, are often used to reconstruct the paleoclimatic and paleoenvironmental conditions. This paper reviewed the progress in the study of paleoclimatic-environmental changes during the late Quaternary using abundant core lipids Glycerol Dialkyl Glyceryl Tetraethers (GDGTs) and long-chain alkyl diols in marginal sea sediments. It is pointed out that clarifying the “source-sink” process of lipid biomarkers buried in marine sediments is a prerequisite for paleoclimatic-environmental reconstruction. It is believed that the use of multiple indicators that are less affected by early diagenesis can increase the accuracy of reconstructing paleoclimatic changes. In the large-river dominated marginal seas, the mechanism of land-sea climate coupling evolution stimulated by the paleoclimatic-environmental changes can be elucidated based on paleoclimatic records reconstructed from core lipids GDGTs and long-chain alkyl diols in marine sediments. It is hoped that this paper can provide reliable technical means and a solid theoretical basis for predicting future temperature and rainfall changes.

Key words: Glycerol dialkyl glycerol tetraethers, Long-chain alkyl diols, Organic matter, Source and sink, Paleoclimatic reconstruction.

中图分类号:

P736.4

图1 典型古菌isoGDGTs以及羟基化isoGDGTs和细菌brGDGTs的分子结构图及质子化后的质荷比（m/z）

Fig.1 Molecular structures of typical archaeal isoGDGTs, hydroxylated isoGDGTs and bacterial brGDGTs, and their protonated mass to charge ratio (m/z)

图2 海洋沉积物中GDGTs的提取离子色谱图（HPLC/MS）^{[

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Fig.2 The extracted ion chromatogram of GDGTs in marine sediment using high performent liquid chromatography and mass spectrometer ^{[

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图3 GeoB 12806-2孔海洋沉积物中OH-GDGTs的提取离子色谱图（HPLC-APCI-MS，安捷伦6130 MSD单四极杆质谱仪）^{[

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]}

Fig.3 HPLC-APCI-MS chromatogram generated by the Agilent 6130 MSD single quadrupole mass spectrometer in the core lipid fraction of GeoB 12806-2 ^{[

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表1 应用于古气候—环境重建的四醚酯和长链二醇主要指标

Table 1 Main indicators for tetraether esters and long-chain alkyl diols used in paleoclimate and paleoenvironmental

指标	公式	指示意义	参考文献
BIT	BIT = $G D G T - I a + G D G T - I I a + [G D G T - I I I a] G D G T - I a + G D G T - I I a + G D G T - I I I a + [C r e n a r c h a e o l]$	陆源和海源有机质的相对丰度	[ 20 ]
TEX₈₆	TEX₈₆ = $G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′] G D G T - 1 + G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′]$	海水温度	[ 21 ]
TEX $86 H$ 和TEX $86 L$	TEX $86 L$ = log ( $G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′] G D G T - 1 + G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′]$ ) TEX $86 L$ = log ( $G D G T - 2 G D G T - 1 + G D G T - 2 + G D G T - 3$ )	海水温度	[ 22 ]
RI-OH 和RI-OH′	RI-OH = $O H - G D G T - 1 + 2 × O H - G D G T - 2 O H - G D G T - 1 + O H - G D G T - 2$ RI-OH′ = $O H - G D G T - 1 + 2 × O H - G D G T - 2 O H - G D G T - 0 + O H - G D G T - 1 + O H - G D G T - 2$	海水表层温度	[ 17 ]
CBT	CBT =-log( $G D G T - I b + G D G T - I I b G D G T - I a + G D G T - I I a$ )	大气年平均温度和pH	[ 23 ]
MBT	MBT = $G D G T - I a + G D G T - I b + [G D G T - I c] ∑ [a l l ? b r G D G T s]$	pH	[ 23 ]
DI	DI 1 = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,14 - d i o l s) + C 30 1,15 - d i o l$ 或 DI 2 = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,13 - d i o l s) + (C 28 + C 30 1,14 - d i o l s)$	营养盐状况	[ 6 , 24 ]
LDI	LDI = $C 30 1,15 - d i o l C 28 1,13 - d i o l + C 30 1,13 - d i o l + C 30 1,15 - d i o l$	海水表层温度	[ 25 ]
DCI	DCI = $C 30 1,14 - d i o l C 28 + C 30 1,14 - d i o l s$	海水表层温度	[ 24 ]
DSI	DSI = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,14 - d i o l s) + (C 28 : 1 + C 30 : 1 1,14 - d i o l s)$	海水表层温度	[ 24 ]

表1 应用于古气候—环境重建的四醚酯和长链二醇主要指标

Table 1 Main indicators for tetraether esters and long-chain alkyl diols used in paleoclimate and paleoenvironmental

指标	公式	指示意义	参考文献
BIT	BIT = $G D G T - I a + G D G T - I I a + [G D G T - I I I a] G D G T - I a + G D G T - I I a + G D G T - I I I a + [C r e n a r c h a e o l]$	陆源和海源有机质的相对丰度	[ 20 ]
TEX₈₆	TEX₈₆ = $G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′] G D G T - 1 + G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′]$	海水温度	[ 21 ]
TEX $86 H$ 和TEX $86 L$	TEX $86 L$ = log ( $G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′] G D G T - 1 + G D G T - 2 + G D G T - 3 + [C r e n a r c h a e o l ′]$ ) TEX $86 L$ = log ( $G D G T - 2 G D G T - 1 + G D G T - 2 + G D G T - 3$ )	海水温度	[ 22 ]
RI-OH 和RI-OH′	RI-OH = $O H - G D G T - 1 + 2 × O H - G D G T - 2 O H - G D G T - 1 + O H - G D G T - 2$ RI-OH′ = $O H - G D G T - 1 + 2 × O H - G D G T - 2 O H - G D G T - 0 + O H - G D G T - 1 + O H - G D G T - 2$	海水表层温度	[ 17 ]
CBT	CBT =-log( $G D G T - I b + G D G T - I I b G D G T - I a + G D G T - I I a$ )	大气年平均温度和pH	[ 23 ]
MBT	MBT = $G D G T - I a + G D G T - I b + [G D G T - I c] ∑ [a l l ? b r G D G T s]$	pH	[ 23 ]
DI	DI 1 = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,14 - d i o l s) + C 30 1,15 - d i o l$ 或 DI 2 = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,13 - d i o l s) + (C 28 + C 30 1,14 - d i o l s)$	营养盐状况	[ 6 , 24 ]
LDI	LDI = $C 30 1,15 - d i o l C 28 1,13 - d i o l + C 30 1,13 - d i o l + C 30 1,15 - d i o l$	海水表层温度	[ 25 ]
DCI	DCI = $C 30 1,14 - d i o l C 28 + C 30 1,14 - d i o l s$	海水表层温度	[ 24 ]
DSI	DSI = $C 28 + C 30 1,14 - d i o l s (C 28 + C 30 1,14 - d i o l s) + (C 28 : 1 + C 30 : 1 1,14 - d i o l s)$	海水表层温度	[ 24 ]

图4 长链二醇的分子结构图及对应长链二醇硅烷衍生物的特征离子质荷比（m/z）

Fig.4 Molecular structures of long-chain alkyl diols and mass-to-charge ratio (m/z) of the characteristic ions corresponding to the long-chain diol silylated derivative

图5 海洋沉积物中长链二醇的提取离子色谱图（GC/MS） $①$

Fig.5 The extracted ion chromatogram of long-chain alkyl diols in marine sediment using gas chromatography and mass spectrometer $①$

图5 海洋沉积物中长链二醇的提取离子色谱图（GC/MS） $①$

Fig.5 The extracted ion chromatogram of long-chain alkyl diols in marine sediment using gas chromatography and mass spectrometer $①$

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