欢迎访问中国科学院大学学报,今天是

黄土-古土壤序列脂肪酸的 LC-MS/MS 检测法的建立及其在北京东灵山的应用

  • 龙雨佳 ,
  • 李玉梅
展开
  • 中国科学院大学地球与行星科学学院,地球系统数值模拟与应用全国重点实验室,北京 100049;
    中国科学院大学测试中心分子化石实验室,北京 101400

收稿日期: 2025-10-09

  修回日期: 2026-01-29

  网络出版日期: 2026-01-29

Development and Application of an LC-MS/MS Method for the Analysis of Fatty Acids in a Loess-Paleosol Sequence from Donglingshan, Beijing*

  • LONG Yujia ,
  • LI Yumei
Expand
  • State Key Laboratory of Earth System Numerical Modeling and Application, Chinese Academy of Sciences, Beijing 100049, China;
    Laboratory of Molecular Fossils of Testing Centers, University of Chinese Academy of Sciences, Beijing 101400, China

Received date: 2025-10-09

  Revised date: 2026-01-29

  Online published: 2026-01-29

Supported by

*National Natural Science Foundation of China (42077412, 41430531 and 41272207) and Fundamental Research Funds for the Central Universities (E3E40404X2)

摘要

本研究建立了一种液相色谱-串联质谱(LC-MS/MS)高灵敏度的方法,用于全新世黄土-古土壤序列中游离脂肪酸(C10 - C32)的定量分析。通过对样品制备(超声提取、硅胶柱纯化)、色谱分离、质谱参数(MRM 模式)的系统优化,对 36 种脂肪酸进行了高效的分离和定量。该方法检出限低(0.5 - 15.64 ng/mL),精密度高(RSD < 1%)。将该方法应用于北京东灵山全新世剖面,首次成功鉴定并定量了该地层中 C14:1、C15:1、C17:1 等几种单不饱和脂肪酸。这些短链单不饱和脂肪酸通常源于微生物活动,其含量的变化可能直接响应于土壤湿度与温度的变化。结合磁化率和粒度指标,系统揭示了脂肪酸组成的垂直变化规律,对古气候重建具有重要意义。结果表明,2965 - 528 cal yr BP 是东灵山全新世最温暖、最湿润的时期。本研究不仅填补了 LC-MS/MS 分析黄土脂肪酸的方法学空白,而且为高分辨率古环境重建提供了新的生物标志物指标和技术支持。

本文引用格式

龙雨佳 , 李玉梅 . 黄土-古土壤序列脂肪酸的 LC-MS/MS 检测法的建立及其在北京东灵山的应用[J]. 中国科学院大学学报, 0 : 2025065 . DOI: 10.7523/j.ucas.2026.004

Abstract

This study developed a highly sensitive method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the quantitative analysis of free fatty acids (C10 - C32) in Holocene loess-paleosol sequences. Through systematic optimization of sample preparation (ultrasonic extraction and silica gel column purification), chromatographic separation, and mass spectrometric parameters (MRM mode), 36 fatty acids were efficiently separated and quantified. The method demonstrated low detection limits (0.5 - 15.64 ng/mL) and excellent precision (RSD < 1%). Applied to a Holocene profile from Donglingshan, Beijing, the method successfully identified and quantified several monounsaturated fatty acids (e.g., C14:1, C15:1, C17:1) for the first time in such strata. These short-chain monounsaturated fatty acids typically originate from microbial activity, and changes in their content may directly respond to variations in soil moisture and temperature. Integrating magnetic susceptibility and grain-size data, the vertical variations in fatty acid composition were systematically revealed, indicating their significance for paleoclimate reconstruction. The results suggest that the period from 2965 to 528 cal yr BP was the warmest and most humid of the Holocene at Donglingshan. This research not only fills a methodological gap in LC-MS/MS analysis of loess fatty acids but also provides a new biomarker indicator and technical support for high-resolution paleoenvironmental reconstruction.

参考文献

[1] Mayewski P A, Rohling E E, Curt Stager J, et al.Holocene climate variability[J]. Quaternary Research, 2004, 62(3): 243-255. DOI: 10.1016/j.yqres.2004.07.001.
[2] Pye K.The nature, origin and accumulation of loess[J]. Quaternary Science Reviews, 1995, 14(7/8): 653-667. DOI: 10.1016/0277-3791(95)00047-X.
[3] An Z S, Kukla G J, Porter S C, et al.Magnetic susceptibility evidence of monsoon variation on the Loess Plateau of Central China during the last 130, 000 years[J]. Quaternary Research, 1991, 36(1): 29-36. DOI: 10.1016/0033-5894(91)90015-W.
[4] An Z S, Kutzbach J E, Prell W L, et al.Evolution of Asian monsoons and phased uplift of the Himalaya-Tibetan Plateau since Late Miocene times[J]. Nature, 2001, 411(6833): 62-66. DOI: 10.1038/35075035.
[5] Eglinton T I, Eglinton G.Molecular proxies for paleoclimatology[J]. Earth and Planetary Science Letters, 2008, 275(1/2): 1-16. DOI: 10.1016/j.epsl.2008.07.012.
[6] Eglinton G, Hamilton R J.Leaf Epicuticular Waxes: The waxy outer surfaces of most plants display a wide diversity of fine structure and chemical constituents[J]. Science, 1967, 156(3780): 1322-1335. DOI: 10.1126/science.156.3780.1322.
[7] Ficken K J, Li B, Swain D L, et al.An n-alkane proxy for the sedimentary input of submerged/floating freshwater aquatic macrophytes[J]. Organic Geochemistry, 2000, 31(7/8): 745-749. DOI: 10.1016/S0146-6380(00)00081-4.
[8] Meyers P A, Ishiwatari R.Lacustrine organic geochemistry: An overview of indicators of organic matter sources and diagenesis in lake sediments[J]. Organic Geochemistry, 1993, 20(7): 867-900. DOI: 10.1016/0146-6380(93)90100-P.
[9] Zelles L.Fatty acid patterns of phospholipids and lipopolysaccharides in the characterisation of microbial communities in soil: A review[J]. Biology and Fertility of Soils, 1999, 29(2): 111-129. DOI: 10.1007/s003740050533.
[10] Collister J W, Rieley G, Stern B, et al.Compound-specific δ 13C analyses of leaf lipids from plants with differing carbon dioxide metabolisms[J]. Organic Geochemistry, 1994, 21(6/7): 619-627. DOI: 10.1016/0146-6380(94)90008-6.
[11] Xie S C, Wang Z Y, Wang H M, et al.The occurrence of a grassy vegetation over the Chinese Loess Plateau since the last interglacier: The molecular fossil record[J]. Science in China Series D: Earth Sciences, 2002, 45(1): 53-62. DOI: 10.1007/BF02879696.
[12] Xie S C, Chen F H, Wang Z Y, et al.Lipid distributions in loess-paleosol sequences from northwest China[J]. Organic Geochemistry, 2003, 34(8): 1071-1079. DOI: 10.1016/S0146-6380(03)00083-4.
[13] Häggi C, Zech R, McIntyre C, et al. On the stratigraphic integrity of leaf-wax biomarkers in loess paleosols[J]. Biogeosciences, 2014, 11(9): 2455-2463. DOI: 10.5194/bg-11-2455-2014.
[14] Schäfer I K, Bliedtner M, Wolf D, et al.Evidence for humid conditions during the last glacial from leaf wax patterns in the loess-paleosol sequence El Paraíso, Central Spain[J]. Quaternary International, 2016, 407: 64-73. DOI: 10.1016/j.quaint.2016.01.061.
[15] Dodds E D, McCoy M R, Rea L D, et al. Gas chromatographic quantification of fatty acid methyl esters: Flame ionization detection vs. Electron impact mass spectrometry[J]. Lipids, 2005, 40(4): 419-428. DOI: 10.1007/s11745-006-1399-8.
[16] Yang K, Han X L.Lipidomics: Techniques, applications, and outcomes related to biomedical sciences[J]. Trends in Biochemical Sciences, 2016, 41(11): 954-969. DOI: 10.1016/j.tibs.2016.08.010.
[17] Quehenberger O, Armando A, Dumlao D, et al.Lipidomics analysis of essential fatty acids in macrophages[J]. Prostaglandins, Leukotrienes, and Essential Fatty Acids, 2008, 79(3/4/5): 123-129. DOI: 10.1016/j.plefa.2008.09.021.
[18] Fu X Y, Anderson M, Wang Y, et al.LC-MS/MS-MRM-based targeted metabolomics for quantitative analysis of polyunsaturated fatty acids and oxylipins[M]//High-Throughput Metabolomics. New York, NY: Springer New York, 2019: 107-120. DOI: 10.1007/978-1-4939-9236-2_7.
[19] Medina J, Borreggine R, Teav T, et al.Omic-scale high-throughput quantitative LC-MS/MS approach for circulatory lipid phenotyping in clinical research[J]. Analytical Chemistry, 2023, 95(6): 3168-3179. DOI: 10.1021/acs.analchem.2c02598.
[20] Ali N, Shen C D, Ding P, et al.AMS measurements of 10Be and 14C in loess profile at Donglingshan, Beijing[J]. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2010, 268(7/8): 1054-1057. DOI: 10.1016/j.nimb.2009.10.096.
[21] Shi M R, Wang G A, Guo Z T, et al.Continuous measurements in North China and culture experiments reveal the potential of leaf n-alkane carbon isotopes in paleoclimate studies[J]. Global and Planetary Change, 2023, 228: 104206. DOI: 10.1016/j.gloplacha.2023.104206.
[22] Zhong Y Z, Dubois N, Xiong J G, et al.Jet transitions caused multiple abrupt droughts in the Asian summer monsoon margin during Holocene times[J]. Palaeogeography, Palaeoclimatology, Palaeoecology, 2022, 601: 111106. DOI: 10.1016/j.palaeo.2022.111106.
[23] Della Corte A, Chitarrini G, Di Gangi I M, et al. A rapid LC-MS/MS method for quantitative profiling of fatty acids, sterols, glycerolipids, glycerophospholipids and sphingolipids in grapes[J]. Talanta, 2015, 140: 52-61. DOI: 10.1016/j.talanta.2015.03.003.
[24] Zhou L P, Oldfield F, Wintle A G, et al.Partly pedogenic origin of magnetic variations in Chinese loess[J]. Nature, 1990, 346(6286): 737-739. DOI: 10.1038/346737a0.
[25] Heller F, Tung-sheng L. Palaeoclimatic and sedimentary history from magnetic susceptibility of loess in China[J]. Geophysical Research Letters, 1986, 13(11): 1169-1172. DOI: 10.1029/GL013i011p01169.
[26] Zimmerman A R, Canuel E A.A geochemical record of eutrophication and Anoxia in Chesapeake Bay sediments: Anthropogenic influence on organic matter composition[J]. Marine Chemistry, 2000, 69(1/2): 117-137. DOI: 10.1016/S0304-4203(99)00100-0.
[27] Meyers P A.Applications of organic geochemistry to paleolimnological reconstructions: A summary of examples from the Laurentian Great Lakes[J]. Organic Geochemistry, 2003, 34(2): 261-289. DOI: 10.1016/S0146-6380(02)00168-7.
[28] An Z S, Porter S C, Kutzbach J E, et al.Asynchronous Holocene optimum of the East Asian monsoon[J]. Quaternary Science Reviews, 2000, 19(8): 743-762. DOI: 10.1016/S0277-3791(99)00031-1.
[29] Gu Y S, Huang X Y, Zhang W G, et al.Red Palaeosols development in response to the enhanced east Asia summer monsoon since the mid-Pleistocene in South China: Evidence derived from magnetic properties and molecular fossil records[J]. Journal of Earth Science, 2013, 24(3): 382-396. DOI: 10.1007/s12583-013-0331-4.
[30] Zou L, Sun M Y, Guo L D.Temporal variations of organic carbon inputs into the upper Yukon River: Evidence from fatty acids and their stable carbon isotopic compositions in dissolved, colloidal and particulate phases[J]. Organic Geochemistry, 2006, 37(8): 944-956. DOI: 10.1016/j.orggeochem.2006.04.002.
[31] Zhang Z H, Zhao M X, Eglinton G, et al.Leaf wax lipids as paleovegetational and paleoenvironmental proxies for the Chinese Loess Plateau over the last 170kyr[J]. Quaternary Science Reviews, 2006, 25(5/6): 575-594. DOI: 10.1016/j.quascirev.2005.03.009.
[32] Wiesenberg G L B, Schwarzbauer J, Schmidt M W I, et al. Source and turnover of organic matter in agricultural soils derived from n-alkane/n-carboxylic acid compositions and C-isotope signatures[J]. Organic Geochemistry, 2004, 35(11/12): 1371-1393. DOI: 10.1016/j.orggeochem.2004.03.009.
[33] Matsuda H, Koyama T.Early diagenesis of fatty acids in lacustrine sediments: I. Identification and distribution of fatty acids in recent sediment from a freshwater lake[J]. Geochimica et Cosmochimica Acta, 1977, 41(6): 777-783. DOI: 10.1016/0016-7037(77)90048-5.
[34] Gunstone F D .Fatty acid and lipid chemistry[M].Springer US,1996. DOI: org/10.1007/978-1-4615-4131-8
[35] Sinsabaugh R L, Shah J J F, Findlay S G, et al. Scaling microbial biomass, metabolism and resource supply[J]. Biogeochemistry, 2015, 122(2): 175-190. DOI: 10.1007/s10533-014-0058-z.
[36] Han C H, Wang Z L, Si G C, et al.Increased precipitation accelerates soil organic matter turnover associated with microbial community composition in topsoil of alpine grassland on the eastern Tibetan Plateau[J]. Canadian Journal of Microbiology, 2017, 63(10): 811-821. DOI: 10.1139/cjm-2017-0157.
[37] Matsuda H, Koyama T.Early diagenesis of fatty acids in lacustrine sediments: II. A statistical approach to changes in fatty acid composition from recent sediments and some source materials[J]. Geochimica et Cosmochimica Acta, 1977, 41(12): 1825-1834. DOI: 10.1016/0016-7037(77)90214-9.
[38] Yang H, Ding W H, Xie S C.Distribution of microbial fatty acids and fatty alcohols in soils from an altitude transect of Mt. Jianfengling in Hainan, China: Implication for paleoaltimetry and paleotemperature reconstruction[J]. Science China Earth Sciences, 2014, 57(5): 999-1012. DOI: 10.1007/s11430-013-4729-8.
[39] Maher B A, Thompson R.Paleorainfall reconstructions from pedogenic magnetic susceptibility variations in the Chinese loess and paleosols[J]. Quaternary Research, 1995, 44(3): 383-391. DOI: 10.1006/qres.1995.1083.
[40] Maher B A, Thompson R. Mineral magnetic record of the Chinese loess and paleosols[J]. Geology, 1991, 19(1): 3-6. DOI: 10.1130/0091-7613(1991)019<0003: MMROTC>2.3.CO;2.
[41] Liu T S.Loess and the Environment[M]. Beijing: China Ocean Press,1985,1-412.
[42] Sun D H, Bloemendal J, Rea D K, et al.Grain-size distribution function of polymodal sediments in hydraulic and aeolian environments, and numerical partitioning of the sedimentary components[J]. Sedimentary Geology, 2002, 152(3/4): 263-277. DOI: 10.1016/S0037-0738(02)00082-9.
[43] Újvári G, Kok J F, Varga G, et al.The physics of wind-blown loess: Implications for grain size proxy interpretations in Quaternary paleoclimate studies[J]. Earth-Science Reviews, 2016, 154: 247-278. DOI: 10.1016/j.earscirev.2016.01.006.
[44] An Z S, Wu G X, Li J P, et al.Global monsoon dynamics and climate change[J]. Annual Review of Earth and Planetary Sciences, 2015, 43: 29-77. DOI: 10.1146/annurev-earth-060313-054623.
[45] Lu H Y,An Z S.The Paleoclimatic Significance of Loess Grain-Size Composition on the Loess Plateau[J].Science in China(Series D: Earth Sciences),1998(03): 278-283. DOI: 10.1007/BF02878745.
[46] Shepard F P.Nomenclature based on sand-silt-clay ratios[J]. Journal of Sedimentary Research, 1954, 24(3): 151-158. DOI: 10.1306/D4269774-2B26-11D7-8648000102C1865D.
[47] Wang Z D, Huang C C, Zhou Y L, et al.Characteristics of Holocene Loess-Palaeosol Particle Size Composition and Paleoclimatic Significance in East Guanzhong, Shaanxi Province[J]. Advances in Earth Science, 2018, 33(03): 293-304. DOI: 10.11867/j.issn.1001-8166.2018.03.0293
文章导航

/