Abstract
The Eocene is the initial stage of the Cenozoic global cooling. Compared with the abundant marine records, the continental records of Eocene are scarce. Throughout the Eocene, a series of continuous deposition of gypsum and volcanic tuff-bearing red clastic sediments have developed in the Nangqian Basin (NB). In this work, representative sediments were collected from the NB, and lipid biomarkers and compound-specific carbon isotopes of n-alkanes were analyzed. Based on the robust paleomagnetic age–depth model, from the early to the late Eocene, the compound-specific carbon isotopic compositions (δ13C23 and δ13C25) increased with the sedimentary facies changed. At the same time, the relative proportion of mid-chain length to the long-chain length homologs (Paq) decreased, and the peak carbon number (Cmax) shifted from nC21, nC22 or nC23 to nC16, nC25, nC27, or nC31. We ascribed these variations to the climate drying and water level turning high as indicated by the lithology change from fluvial to lacustrine facies and the terrestrial inputs from neighboring mountain belts in the middle–late Eocene. Moreover, we compared our n-alkane results with other records from the TP and the global sea level and marine benthic δ18O. We found that a nearly synchronous deformation and drying of the eastern TP caused by the India–Asia collision in the early Eocene was closely related to the arid conditions and topographically changed in the northern TP. The climate variations in the Eocene in the NB were mainly controlled by the global climate change and the uplift of the TP and affected by the Paratethys Sea on a long scale.
Introduction
The Eocene, which is the initial stage of the Cenozoic global climate from a “greenhouse” state to an Oligocene “icehouse” state, is considered as a “doubthouse” of global climate conditions (Zachos et al., 2008; Westerhold et al., 2020). Most of the continuous long-scale records for the Eocene paleoclimate are from ocean boreholes (; ; ; ) and marine outcrops (; ; ). In comparison with various marine records, the climate change from the evidence of lacustrine records during the Eocene, especially in the Tibetan Plateau (TP), is little known. Recently, various geochemical records from the TP have been reported. In the northeastern TP, the Eocene strata and related paleoclimate of the Xining (; ), Linxia (; ), and Qaidam basins (; Wu et al., 2021) have been reported. Based on these paleoenvironmental records, several mechanisms were formulated to interpret the environmental changes (; ; ; ; Westerhold et al., 2020). Furthermore, the Cenozoic sedimentary basins, especially the basin in the eastern Qiangtang Terrane, can provide an excellent record of the early India–Asia collision history during the Paleogene (; ; ; Xiong et al., 2020).
The Nangqian Basin (NB) (∼32–33oN, ∼96oE), in the eastern TP currently, contains a long and continuous sequence of the Eocene sediments (; ; Zhang et al., 2020). Most importantly, the NB is the intersection of the East Asian Monsoon (EAM), the Indian Monsoon (IM), and the westerlies but also the junction of the humid monsoon region in Eastern China, the arid inland region in Northwest China, and the alpine region of the TP, which is very sensitive to the changes of the environment and climate (; ). The early Cenozoic successions of gypsum and volcanic tuff-bearing red clastic sediments in the NB provide precious climatic and environmental archives (; ; Zhang et al., 2020). Many works on the Cenozoic paleoenvironment and paleoclimate of the TP have been carried out in the NB, including the lithofacies, evaporate minerals, magnetostratigraphy, pollen-spores, clay minerals, major and trace elements, clumped isotope, carbonate oxygen, and carbon isotopes, which suggest that, with the rising altitude, the climate gradually became arid and cold in the eastern TP during the Eocene (; Yuan et al., 2017; ; ; Yuan et al., 2020a; Zhang et al., 2020; Zhao et al., 2020). However, due to the lack of long sedimentary sequence and robust age constraints, the driving mechanism of the climate change is not clear.
In addition to the proxies mentioned before, lipid biomarkers originate from organisms directly, which can respond to the environment rapidly, and can be preserved in sediments stably, indicating that they preserved reliable climate records (; ; ; , , ). n-Alkanes have high abundance in organisms, which can be preserved in lacustrine sediments for millions of years, and their original isotopic signals can also be well preserved (; ; ; ; ). For example, used Paq, ACL, and δD to determine the source of sedimentary n-alkanes and study the degree of water mass restriction (open or closed) of an ancient lake basin. demonstrated a complex relationship between the isotopic composition of precipitation and the precipitation amount or East Asian summer monsoon intensity by applying the compound-specific carbon and hydrogen isotopes of terrestrial long-chain n-alkanes. applied detrital zircon U–Pb geochronology and leaf wax n-alkane δD to analyze the surface uplift history of the Hoh Xil Basin. The n-alkanes and the corresponding compound-specific isotopic compositions display the application of reconstructing the paleoclimate and paleotopography in lacustrine sediments in the TP.
In the present study, the age–depth framework of the NB has been constrained by high-resolution palaeogeomagnetic records with absolute ages (; ; Zhang et al., 2020). We applied the lipid biomarker (n-alkanes) and the corresponding compound-specific carbon isotopic compositions to reflect the variations of organic matter sources and their corresponding paleoclimate conditions. Moreover, we compared our results with other records from the TP during the Eocene to discuss the possible driving mechanisms from the perspective of biological variations.
Geographic and Stratigraphic Setting
Geological Setting
The current NB, located on the border between the Qinghai Province and the Tibet Autonomous Region, is about 4,500–5,000 m (Figure 1A). The India–Asia collision formed north-eastward extrusion, which facilitated a series of contraction deformation and strike-slip faults in the eastern Tibet, including the Yushu–Nangqian thrust belt and the Jinshajiang strike-slip fault system (; Yin and Harrison, 2003; ). The NB is one of the series of narrow, elongated Paleogene basins in the Yushu–Nangqian region between the Songpan–Ganzi and Qiangtang terranes (Figures 1B,C). It is ∼80 km long in the south–north direction and ∼15 km wide in the east–west direction (; ; Yuan et al., 2020).
FIGURE 1
The NB is characterized by a continental seasonal monsoon climate today and impacted by the Asian Monsoon (mainly the Indian Monsoon) (
The Paleogene strata in the NB are characterized by prominent red beds, which contain limestone/marlite, gypsum, volcanic rock, and tuff (
Chronology
The NB contains three parts of the Paleogene deposits (
FIGURE 2

Lithofacies (A) and sedimentary facies (B) of the Paleogene sedimentary sequence in the NB. The magnetostratigraphy (C–E) is modified from the work of Zhang et al. (2020). The Ar–Ar and U–Pb ages are from the work of
Sampling and Methods
The Nangqian section is located along the Zhaqu River with a total thickness of 1050 m (Figure 1). According to lithology, a total of 67 bulk samples were selected. The 67 sediment samples were collected from 52.5 to 35 Ma in a depth interval from 0 to 1,050 m. Before collecting samples, the weathering denudation surface was knocked out with a geological hammer. Then, fresh samples were obtained and put into degreasing cloth bags for storage.
Biomarker Analyses
In this study, 22 samples were tested for biomarker analyses (Supplementary Table S1). The 22 samples are divided into two sections. There are 12 samples in the lower section (age 51.8–46.4 Ma) and 10 samples in the upper section (age 42.3–35.5 Ma).
The extraction process of biomarkers is as follows: the bulk samples were extensively cleaned to remove any possible contamination from recent organic material and crushed to fine powder larger than 100 mesh. Powdered samples (∼400 g) were weighed into pre-extracted filter paper thimbles (the filter paper was extracted using a Soxhlet extractor with DCM for 72 h previously) and Soxhlet extracted at 50°C continuously for 72 h using a Soxhlet extractor (DCM: MeOH = 9:1, v:v). The glassware used in this experiment, such as injection bottle, weighing bottle, and conical bottle, had been washed with acetone, rinsed with clean water and ultrapure water, dried in an oven, sealed with clean tinfoil, and then, burned (400°C for 5 h) in a muffle furnace previously. Tweezers and other tools were washed with DCM 2–3 times before used.
Total lipid extracts were loaded onto a solid phase extraction column (ANPEL, silica gel 500 mg). The n-alkanes were eluted with n-hexane (5–10 ml). After drying n-alkanes, 1 μL of the sample in hexane was injected into a GC–MS-QP2020NX (Shimadzus, Japan). This instrument was equipped with an Rtx-5 MS gas chromatograph which was fitted with a 30 m × 0.25 mm i. d. fused silica capillary column, coated with a film (0.25 μm) of 5% phenyl-methyl-DB-5. The carrier gas was 99.995% high purity helium, and the control mode was linear velocity. The heating program was set as follows: initially at 80°C for 2 min, rapidly increased to 210°C at a rate of 4°C/min, then increased from 210 to 295°C at a rate of 3°C/min, and held at 295°C for 20 min. The column flow rate was 1.0 ml/min, and the injection volume was 1 μL. The diversion mode showed no diversion. The MS was operated with ionization energy of 70 eV, and the temperature of ion source was 250°C. The GC–MS was tuned using perfluorotributylamine (PFTBA) and blank samples were analyzed to check the background. The interface temperature of GC–MS was 300°C. The solvent delay was set to 2 min. Both GC–MS scan and GC–MS single ion monitoring mode (SIM) were used for acquisition.
Compound-Specific δ13C Analyses
According to the preliminary results of 22 biomarkers, 23 samples were selected for the test of compound-specific carbon isotopic compositions (Supplementary Table S1). There were 12 samples in the lower section and 11 samples in the upper section. The extraction process of n-alkanes for compound-specific carbon isotopic compositions was the same as that described in Biomarker Analyses.
The test of carbon isotopic values of individual n-alkanes was finished on a GC (Agilent 6,890) coupled to an isotope ratio mass spectrometer (IRMS, Thermo Scientific MAT 253) via a combustion interface (GC Combustion Ⅲ) (Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences). High-purity helium was used as a carrier gas at 2 ml min−1. The gas chromatograph was fitted with a 30 m × 0.32 mm i. d. fused silica capillary column, coated with a film (0.25 μm). The oven temperature was programmed to be initially held at 80°C for 3 min, increased to 300°C at a rate of 3°C/min, and held for another 30 min. Individual compounds were oxidized at 940°C when flowing through an oxidation ceramic micro-reactor filled with twisted wires (NiO/CuO/Pt). Three pulses of standard pure CO2 gas, pre-calibrated against a commercial reference CO2, were injected via the GC-C III interface to the IRMS for the computation of δ13C values of sample compounds. A set of n-alkanes (n-alkane mixture type A7) with known δ13C values acquired from Indiana University were measured daily to ensure the accuracy of the machine. The standard deviation for duplicate analyses of this standard was <± 0.3‰. The δ13C values were reported with reference to the PDB standard. The resolution of hydrocarbon peaks obtained during GC–IRMS was similar to that obtained in GC–MS analysis.
Calculation of Biomarker Proxies
As for the biomarker proxies, the index of proportion of aquatic plants (Paq,
The carbon preference index (CPI) values of the extracted long-chain n-alkanes (nC26 to nC34) were calculated using a modified formula of
The average chain length (ACL) values were calculated using a modified formula of
Results
The distribution patterns of n-alkanes in the NB sediments are shown in Figure 3. The distribution of n-alkanes in the 12 samples of the lower section is mainly unimodal and maximized at nC21, nC22, or nC23. The distribution of n-alkanes in the other 10 samples of the upper section is mainly bimodal and mainly maximized at nC16, nC25, nC27, or nC31.
FIGURE 3

Distribution patterns of n-alkanes in the NB.
The Paq and CPI values of the two sections changed significantly (Figures 4B,D). In the lower section, the Paq values were between 0.72 and 0.92, with an average of 0.82. In the upper section, the Paq values were between 0.26 and 0.68, and the average value was 0.47. Meanwhile, the average value of CPI increased from the lower section to the upper section, with an average of 1.90 to an average of 2.90.
FIGURE 4

Climate and environmental proxy records of ACL (A), Paq (B), Cmax(C), CPI (D) proxies, and compound-specific carbon isotopic compositions of nC23 and nC25(E,F) in the NB. LOESS Fit (0.5 span for a, b, and d, 0.4 span for e and 0.55 span for (F). The green and yellow shaded areas mark the lower section and the upper section.
In Figures 4E,F, compound-specific carbon isotopic compositions (δ13C23 and δ13C25) were heavier in the upper section than those in the lower section. From the lower to the upper section, the average of δ13C23 changed from −34.69‰ to −30.79‰, and δ13C25 showed a similar increase from an average of −33.26‰ to an average of −28.16‰.
Discussion
Degradation Degree of n-Alkanes in the Nangqian Basin
For n-alkanes, their typical odd-to-even preference in the long-chain part suggests a low degree of degradation (
Variations in Biomarker Proxies and δ13Calk
Previous studies have shown that the mid-chain length n-alkanes are mainly from aquatic plants, such as submerged and floating plants (
In addition, n-alkanes can truly reflect the input characteristics of parent material sources (
Judging from the provenance analysis of sediments in the NB (Zhang et al., 2019), the initially accumulated sediments of the NB has changed from relatively small internal drainage networks and short main-stem rivers in this region in the Paleocene to the nearby thrust belts in the Eocene (
Evaporite minerals are also sensitive to environmental and climatic changes (
To sum up, the climate in the early and mid—late Eocene was completely different. In the early Eocene, the terrain was generally low and flat, with a humid climate and low water level. After the tectonic movements caused by the India–Asia collision, the NB and surrounding areas appeared as small intermontane sub-basins, characterized by an arid climate.
Driving Mechanisms of Eocene Climate Variations in the Eastern Tibetan Plateau
From the early to the late Eocene, the sedimentary facies and the water level recorded by compound-specific δ13C in the present study implied a notable climate transition from humid to arid conditions and a topographical change in the eastern TP.
Previous studies have indicated that three main forcing mechanisms, including the uplift of the Tibetan Plateau, the retreat or incursion of the Paratethys Sea, and global cooling, may be responsible for the change (
The global cooling could be a first-order control in the NB beyond the impact of the India–Asia collision and the retreat or incursion of the Paratethys Sea. The global cooling reduced evaporation from the sea and thus the water vapor flux to the air (
FIGURE 5

Summarized paleoclimatic records of the Eocene in the Tibetan Plateau. (A) sedimentary facies in the Nangqian Basin (this study); (B) red and blue dots and corresponding fitted curve (0.4 span for nC23 and 0.55 span for nC25) indicating the δ13C of mid-chain alkanes nC23 and nC25 from the Nangqian Basin (this study), and the δ13C values averaged over the three long-chain alkanes nC27, nC29 and nC31 from the Qaidam Basin (
FIGURE 6

(A) Sedimentary facies in the Nangqian Basin (this study); (B) red and blue dots and the corresponding fitted curve indicating the δ13C of mid-chain alkanes nC23 and nC25 from the Nangqian Basin (this study); (C) global sea level curve (
Exploring the past topography is essential for disentangling the complex interactions between orography and climate (
A vast shallow epicontinental sea extended across Eurasia and was well-connected to the Western Tethys before it retreated westward and became isolated as the Paratethys Sea during the Paleogene (
In general, our observations recorded a significant change in sedimentary facies from braided river facies to brackish lake facies in the early-mid Eocene in the eastern TP. At the same time, the compound-specific carbon isotopic compositions of n-alkane (δ13C23 and δ13C25) recorded the rise of the lake level. In the mid–late Eocene in the NB, the terrestrial input in the sediments increased, which corresponded to the climate drying and topographic change at this time. In comparison with three main driving mechanisms, our records were consistent with global climate changes, related closely with the India–Asia collision in the early Eocene, and the relevance with Paratethys Sea needs further study. We claim that the climate variations in the Eocene in the study area were mainly controlled by the global climate change and the uplift of the Tibetan Plateau, but the impact of the Tethys Sea cannot be ignored.
Conclusion
We applied the n-alkanes and the compound-specific carbon isotopic compositions in the NB to reflect the paleoclimate conditions in the eastern Tibet Plateau. From our multi-proxy records, we came to the conclusion that the NB underwent rapid drying from the early to the mid–late Eocene. The compound-specific carbon isotopic compositions (δ13C23 and δ13C25) were affected by the water level deepening and showed a rapid positive. From the n-alkene records in the NB, the type of aquatic organism in the Eocene lacustrine sequence had an evident change from submerged and floating plants to emergent and terrestrial plants, responding to climate drying and orographic uplifting. Meanwhile, the lithofacies changed from the braided river, alluvial fan, and ephemeral shallow pond/lake environment to a semi-brackish lake in a distal floodplain and finally to playa mudflat and saline lake environments. We regard the change of multi-proxy records by n-alkenes consistent with the sedimentary facies change and aridity in the NB and responded synchronously in the northern TP, which was mainly controlled by the global cooling and the uplift of the Tibetan Plateau and affected by the Paratethys Sea on a long scale.
Statements
Data availability statement
The original contributions presented in the study are included in the Supplementary Material, further inquiries can be directed to the corresponding authors.
Author contributions
JW: participation in the whole work and drafting of the article; YW, GW, and ZW: perception and design and final approval of the version to be published; and WH, TZ, XM, PZ, HM, XY, SL, and LL: data analysis.
Funding
This work was supported by the National Natural Science Foundation of China (grant numbers 41831176), the Second Tibetan Plateau Scientifc Expedition and Research (STEP) Program (grant number 2019QZKK0707), the Strategic Priority Research Program of CAS (grant numbers XDB26000000), the National Natural Science Foundation of China (grant numbers 41902028, 41972030, 42072038 and 41888101), the National Key R and D Program of China (grant number 2017YFA0604803), the CAS “Light of West China” Program and the Youth Innovation Promotion Association CAS (No. 2021425).
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Publisher’s note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors, and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/feart.2022.849041/full#supplementary-material
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Summary
Keywords
Nangqian Basin, Eastern Tibet Plateau, organic geochemistry, Eocene, lacustrine sediments
Citation
Wei J, Wang Y, Wang G, Wei Z, He W, Zhang T, Ma X, Zhang P, Ma H, Yu X, Li S and Li L (2022) Biomarker Records From Eocene Lacustrine Sequence in the Eastern Tibet Plateau and Its Implication for Organic Matter Sources. Front. Earth Sci. 10:849041. doi: 10.3389/feart.2022.849041
Received
05 January 2022
Accepted
28 February 2022
Published
06 April 2022
Volume
10 - 2022
Edited by
Zhang Chengjun, Lanzhou University, China
Reviewed by
Yibo Yang, Institute of Tibetan Plateau Research (CAS), China
Amzad Hussain Laskar, Physical Research Laboratory, India
Huanye Wang, Institute of Earth Environment (CAS), China
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© 2022 Wei, Wang, Wang, Wei, He, Zhang, Ma, Zhang, Ma, Yu, Li and Li.
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*Correspondence: Yongli Wang, wyll6800@lzb.ac.cn; Gen Wang, gwang@lzb.ac.cn
This article was submitted to Quaternary Science, Geomorphology and Paleoenvironment, a section of the journal Frontiers in Earth Science
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