Origin of hydroxyl GDGTs and regular isoprenoid GDGTs in suspended particulate matter of Yangtze River Estuary

Accepted Manuscript Origin of hydroxyl GDGTs and regular isoprenoid GDGTs in suspended particulate matter of Yangtze River Estuary Xiaoxia Lü, Jiali Chen, Tianwei Han, Huan Yang, Weichao Wu, Weihua Ding, Kai-Uwe Hinrichs PII: DOI: Reference:

S0146-6380(18)30277-8 https://doi.org/10.1016/j.orggeochem.2018.12.010 OG 3826

To appear in:

Organic Geochemistry

Received Date: Revised Date: Accepted Date:

12 September 2018 19 December 2018 24 December 2018

Please cite this article as: Lü, X., Chen, J., Han, T., Yang, H., Wu, W., Ding, W., Hinrichs, K-U., Origin of hydroxyl GDGTs and regular isoprenoid GDGTs in suspended particulate matter of Yangtze River Estuary, Organic Geochemistry (2018), doi: https://doi.org/10.1016/j.orggeochem.2018.12.010

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Origin of hydroxyl GDGTs and regular isoprenoid GDGTs in suspended particulate matter of

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Yangtze River Estuary

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Xiaoxia Lü1,2*, Jiali Chen1, Tianwei Han1, Huan Yang1, Weichao Wu3, Weihua Ding1,3, Kai-Uwe

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Hinrichs3

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1State

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Geosciences (Wuhan), 430074, Wuhan, China

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2College

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Wuhan, China

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3Organic

Key Laboratory of Biogeology and Environmental Geology, China University of

of Marine Science and Technology, China University of Geosciences (Wuhan), 430074,

Geochemistry Group, MARUM-Center for Marine Environmental Sciences, 28334,

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Bremen, Germany

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* Corresponding author. Tel: 86-27-67883063.

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Email address: [email protected] (X. Lü).

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Abstract

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Hydroxylated isoprenoid glycerol dialkyl glycerol tetraethers (OH-GDGTs) were found having the

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potential to track past sea surface temperatures (SST), in analogy to the TEX86 - a

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paleothermometer based on isoprenoid GDGTs (iGDGTs). Especially in estuarine regions with

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high terrestrial input, the ring index of OH-GDGTs (RI-OH) was more robust to trace the summer

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SST than TEX86. In order to clarify the potential sources of sedimentary GDGTs and to further

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elucidate the potential of OH-GDGTs as SST proxy, we investigated the seasonal distribution of

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core OH-GDGTs and iGDGTs in the suspended particulate matter in a transition section in

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Yangtze River Estuary. The concentrations of OH-GDGTs and iGDGTs were higher in the estuary

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than those in the lower Yangtze River, which suggested the OH-GDGTs and iGDGTs in estuarine

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sediment mainly came from marine autochthonous organisms, whereas the terrestrial contribution

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was relatively low. The higher content of OH-GDGTs and iGDGTs in summer than in winter

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indicated that sedimentary OH-GDGTs and iGDGTs mainly originated from the summer SPM

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deposition. In addition, the ratio of OH-GDGTs versus iGDGTs suggested that OH-GDGTs were

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relatively abundant in the upper water layer compared to iGDGTs, regardless of season.

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Furthermore, the distributions of iGDGTs and OH-GDGTs were found to be influenced by

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hydrodynamics. The increasing warm bias of iGDGT and OH-GDGT reconstructed temperatures

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with water depth suggested that either GDGTs in deeper waters derive mainly from surface water

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or GDGTs cyclization in deeper waters was influenced by reduced ammonium oxidation rates in

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response to the limited supply of ammonium and oxygen, especially in summer.

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Keywords: OH-GDGTs; iGDGTs; suspended particle matter; Yangtze River Estuary

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1. Introduction

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Marginal seas, representing a link between continent and ocean, are strongly influenced by

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terrestrial input and characterized by high primary production and shallow water depth (Rosenberg

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et al., 1990; Antony et al., 2002). Organic matter (OM) from autochthonous marine and

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allochthonous terrestrial origins are mostly deposited in continental margin sediments, with their

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production and deposition being sensitive to environment and climate change (e.g. Huguet et al.,

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2006; Shintani et al., 2011; Chen et al., 2017).

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Isoprenoidal glycerol dialkyl glycerol tetraethers (iGDGTs) are mainly produced by marine

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planktonic Thaumarchaeota, which are among the most abundant organisms in the ocean (DeLong

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et al., 1994; Karner et al., 2001). Thaumarchaeota are observed to adjust the number of

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cyclopentane rings in their membrane lipids to adapt to the growth temperature (Uda et al., 2001,

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Schouten et al., 2002, Elling et al., 2015). TEX86 is a robust paleotemperature proxy and can be

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applied in most marine and some lacustrine environments, especially in warm paleo-oceans (e.g.

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Schouten et al., 2002; Sluijs et al., 2006; Forster et al., 2007; Sinninghe Damsté et al., 2010;

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Schouten et al., 2013). However, its application is not feasible in some environments with high

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salinity, low nutrient, current disturbance, or high terrestrial input (Menzel et al., 2006; Weijers et

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al., 2006; Turich et al., 2007; Trommer et al., 2009).

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GDGTs with one or two hydroxylations in the isoprenoidal alkyl chain (OH-GDGTs) are

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widespread in marine sediments and thought to be derived mainly from planktonic

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Thaumarchaeota (Liu et al., 2012; Elling et al., 2014, 2015). The relative abundance of OH-

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GDGTs vs. iGDGTs in marine surface sediments has been shown to be well correlated with sea

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surface temperature (SST; Huguet et al., 2013). In polar and subpolar regions, the relative

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abundance of cyclopentane rings in OH-GDGTs increased with SST (Fietz et al., 2013). Lü et al.

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(2015) observed that the weighted average number of cyclopentane moieties in OH-GDGT-1 and -

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2 (RI-OH) could serve as a proxy for seasonal SST in Chinese coastal seas, and even in estuarine

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regions with high terrestrial input (BIT~0.8). Currently, it appears that OH-GDGTs in marine

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sediments have the potential to trace SST more accurately than TEX86, especially in estuaries and

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polar and subpolar regions. The hypothesis that the source organisms of OH-GDGTs mainly

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inhabit the uppermost water layer compared to the vertically more widely distributed sources of

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iGDGTs still requires further validation. Therefore, we studied suspended particulate matter

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(SPM) to further constrain the sources of iGDGTs and OH-GDGTs and build a mechanistic

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understanding why RI-OH may be a more reliable SST proxy than TEX86 in estuarine and coastal

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regions.

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The East China Sea (ECS) is a typical shallow marginal sea in the western North Pacific Ocean,

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and the sediments in ECS are mainly supplied by Yangtze River and Yellow River (Liu et al.,

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2006; Xu et al., 2009). Sedimentary OM is not only from autochthonous production but also from

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terrestrial input (Lü et al., 2006; Hu et al., 2012). Both proxies TEX86H and RI-OH were correlated

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well with summer SST, and the high terrestrial input did not have significant influence on the

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application as would be expected (Sluijs et al., 2006; Lü et al., 2014; 2015). However, little is

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known about the underlying mechanisms that would explain the lack of significant bias in

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reconstructed SST based on TEX86 and RI-OH under conditions of high terrestrial input. Here, we

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compared the distribution of OH-GDGTs and iGDGTs in suspended particulate matter (SPM)

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collected from a transect from the lower reaches of Yangtze River to estuary in summer and

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winter. The study aims to disentangle the origins of OH-GDGTs and iGDGTs in this setting, and

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further to understand the influence of terrestrial OM input on the validity of RI-OH and TEX86H

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for SST reconstruction.

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2. Material and Methods

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2.1 Study area

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The Yangtze River is the fourth and fifth largest river in the world in terms of mean sediment and

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water discharge, respectively. Every year, it transports about 928 km3 of water and 4.68×108 tons

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of sediment into ECS, and about 50% of sediment is deposited in its estuary (Milliman et al.,

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1985; Zhang et al., 1990; Huang et al., 2001). The ECS is influenced by the wet/warm southeast

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monsoon in summer and dry/cold northwest monsoon in winter, which results in a large seasonal

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variation in SST, pH, salinity and nutrients (Yao et al., 2007). The flux of SPM in the study area is

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highest in summer (Wang et al., 2003; He et al., 2013; Wu et al., 2013).

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2.2 Sample collection

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Thirty-six SPM samples were collected from seven sites in Yangtze River Estuary by the Chinese

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National Fund-Sharing cruise in 2014 (Fig. 1). We filtered 4-6 L water to collect the SPM onto

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pre-combusted and weighed 0.7-µm GF/F filters (Whatman GF/F) by vacuum filtration. Sixteen

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SPM samples were collected from different depths at six sites in winter (February, 2014) and 20

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were collected from different depths at six identical or nearby sites in summer (July, 2014; Table

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1). All the samples were immediately stored at -20 ºC until further treatment. The in situ

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temperature and O2 content were recorded by CTD during the two cruises. The ammonium was

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detected using Skalar Sanplus segmented flow nutrient autoanalyzer and standard colorimetric

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techniques (Sanders & Jickells, 2000).

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2.3 Lipid analysis

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The SPM-loaded filters were freeze-dried and then weighed in the lab. The SPM weight was

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obtained by the difference of the dry weight of filters before and after sample collection. The

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freeze-dried particulate matter samples were weighed after drying to determine the SPM

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concentration (0.004 g/L ~ 0.72 g/L). Then SPM was extracted using a modified Bligh and Dyer

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protocol as described by Sturt et al. (2004) at the State Key Laboratory of Biogeology and

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Environmental Geology, China University of Geosciences, Wuhan, China. Total lipid extracts

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(TLEs) were stored at -20 ºC until further treatment.

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Due to the limited filtered water volume, only the core lipids were analyzed. High performance

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liquid chromatography-mass spectrometry (HPLC-MS) analysis was performed at the MARUM,

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University of Bremen, as described by Lü et al. (2015). An aliquot of each TLE was dissolved in

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100 µl n-hexane/propan-2-ol (99.5:0.5, v:v) and analyzed on an Bruker maXis quadrupole time-

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of-flight mass spectrometer (qTOF-MS) operated in atmospheric pressure chemical ionization

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(APCI) mode and coupled to an Dionex Ultimate 3000RS HPLC system. Compound separation

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was achieved using two coupled Acquity BEH HILIC amide columns (2.1 × 150 mm, 1.7µm;

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Waters, Eschborn, Germany) maintained at 50 °C. GDGTs were eluted using the following

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gradient with eluent A [n-hexane] and eluent B [n-hexane: isopropanol (90:10, v:v)] at 0.5 ml

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min-1: the initial gradient was 3% B to 5% B in 2 min, followed by increasing B to 10% in 8 min,

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to 20% in 10 min, to 50% in 15 min and 100% in 10 min. The column was washed with 100% B

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for 6 min at 0.6 ml min-1. Finally, the column was equilibrated with 3% B for 9 min. Detection of

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GDGTs was achieved using positive ion APCI, while scanning a m/z range from 150 to 2000;

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source parameters were optimized during infusion of a mixture of GDGTs and were as follows:

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corona current 3500 nA, nebulizer gas 5 bar, drying gas 8 l min-1, drying gas 160 °C, and

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vaporizer 400 °C. Relative abundances of iGDGTs (m/z 1302, 1300, 1298, 1296, 1292) was

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determined by peak area integration of [M+H]+ in the extracted ion chromatogram. For OH-

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GDGTs (m/z 1318, 1316, 1314) the dehydrated ions (m/z 1300, 1298, 1296) were used for

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quantification as described by Liu et al. (2012).

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3. Results and Discussion

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In estuarine and coastal environments, the validity of the TEX86 proxy was thought to be mainly

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limited by the input of terrigenous isoprenoidal GDGTs (e.g. Weijers et al., 2006; Sinninghe

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Damsté et al., 2010; Zhu et al., 2011). Some studies suggest that the TEX86 can be applicable in

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the regions where the BIT values are < 0.4 (Weijers et al., 2006; Zhu et al., 2011, Lü et al., 2014;

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Wu et al., 2014). However, the BIT values in ECS decreased rapidly from 0.8 to 0.2 at the mouth

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of estuary (Zhu et al., 2011; Lü et al., 2014), which suggests that the TEX86 could be applicable in

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ECS, even in the estuary where the sediment is mainly derived from terrestrial input.

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The concentrations of iGDGTs and OH-GDGTs in the summer SPM were in the range of 27.6-

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6230 ng/L and 1.0-137 ng/L, respectively, and those in winter SPM in the range of 17.6-3010 ng/L

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and 0.9-64.7 ng/L, respectively (Table 1, Fig. 2a-d). We note that only core lipids were analyzed

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due to sample limitation. The inclusion of intact polar lipids would have provided a more

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comprehensive and selective view of signals from the live archaeal community, although we

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consider it unlikely that a substantial fossil component accumulates in SPM at these shallow sites.

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Obviously, no matter whether in winter or summer, the concentrations of iGDGTs and OH-

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GDGTs in SPM in the lower Yangtze River were significantly lower than those in the estuary

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(Fig.2a-d). This suggests that the iGDGTs and OH-GDGTs in the estuary area mainly originate

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from marine planktonic archaea, while terrestrial contributions are low. The result is also

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supported by the BIT values, which decrease rapidly from river to sea, except at site A6-6,

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especially in winter (Fig. 2e, f), and further verify the BIT distribution in the estuarine sediment

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(Zhu et al., 2011; Lü et al., 2014). The high BIT at Site A6-6 in winter may be due to the

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following two facts: 1) This site is located at the front of several currents such as Yangtze River

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diluting water (CDW), Taiwan warm current (TWC), Zhejiang-Fujian coastal current (ZMCC)

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and Yellow Sea warm current (YSWC) (e.g. Chang and Isobe, 2003; Liu et al., 2007; Yuan and

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Hsueh, 2010). Therefore, most of the SPM is concentrated here (Li et al., 2016; Pang et al., 2016).

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2) In winter, the water undergoes strong vertical mixing due to the strengthening winter monsoon

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and the weakening solar radiation (Shi and Wang, 2010), so that significantly more SPM is

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brought to the surface creating high turbidity water (Milliman et al., 1985).

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The abundance of Thaumarchaeota is seasonally variable; they are dominant in the season when

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the overall phytoplankton productivity is low (Galand et al., 2010; Pitcher et al., 2011). However,

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we observed that the TEX86 and RI-OH obtained from surface sediments were more strongly

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correlated with summer SST than winter SST (Lü et al., 2014; 2015). In this study, the

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concentrations of iGDGTs and OH-GDGTs of SPM in summer were similar to those in winter

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except in bottom SPM of site A6-8 in summer (Table 1; Fig. 2a-d). Obviously, in the estuary, the

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concentration of iGDGTs in the summer SPM from the surface layer was lower than at the bottom

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layer (Fig. 2a, c). However, in the winter this trend was reversed, which may be attributed to the

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low in situ production of Thaumarchaeota in the surface layer due to the nutrient competition with

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phytoplankton in summer and elevated Thaumarchaeota production in winter surface water due to

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the water current convergence here. The concentrations of OH-GDGTs in the surface layer in

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summer were similar to those at bottom, while those in winter were higher in the surface layer.

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Pang et al. (2016) found that the net deposition of suspended sediment in Yangtze River Estuary

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was almost 5 times larger in summer than in winter due to the riverine suspended sediment input.

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Therefore, sedimentary iGDGTs and OH-GDGTs, especially OH-GDGTs, are mainly derived

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from the high flux of SPM in summer. The result can explain why the TEX86 and RI-OH in the

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surface sediment had the most significant correlation with summer SST. Furthermore, the ratio of

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OH-GDGTs versus iGDGTs was higher in the upper layer than in bottom water of the estuary

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independent of season (Fig. 2g, h), which further indicates that the producers of OH-GDGTs

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predominantly inhabited the upper layer, while the sources of iGDGTs are more diverse and likely

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include planktonic archaea occupying deeper water layers.

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The vertical distribution of TEX86H and RI-OH in summer differed from that in winter (Fig. 3a-d).

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We calculated the summer and winter temperature at different water layers using the models of

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marginal seas calibrated by Lü et al. (2014, 2015). Obviously, the reconstructed temperature in

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different layers showed significant deviations from in situ temperature both in summer and winter

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(Fig.4a, b). Interestingly, the difference between both proxy-reconstructed SST and in situ

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temperature (ΔT) was generally positive, i.e., proxy-based temperature estimates were generally

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higher than in situ temperature. Furthermore, ΔT showed a significant negative linear correlation

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with in situ temperature in summer (Fig. 4a. i.e., ΔT decreased with increasing in situ

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temperature). Moreover, in summer the ΔT also showed a positive correlation with water depth

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(Fig. 4c). The phenomenon of increasing ΔT with water depth has been previously observed in

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several studies (Schouten et al., 2012; Basse et al., 2014; Xie et al., 2014; Kim et al., 2016; Zhu et

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al., 2016; Hurley et al., 2018). Hurley et al. (2016) demonstrated in chemostat experiments of N.

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maritimus that TEX86 is inversely correlated with ammonium oxidation rate, providing a potential

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explanation according to which limited ammonium supply in deeper water layers influences

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GDGT cyclization, resulting in elevated ΔT. Accordingly, the increasing ΔT with water depth

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could result from lowered oxygen concentrations in deeper waters (Table 1, Fig. 4e), i.e., one of

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the reactants required for thaumarchaeal nitrification and thus limiting ammonium oxidation rates.

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Alternatively, the higher ΔT in deeper waters could have resulted from efficient downward

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transport of surface-derived GDGTs. However, we found that the ΔT - water depth relationship

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found in summer did not occur during winter (Fig. 4d). This difference between summer and

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winter may be due to a combination of the following two factors 1) the lower zooplankton activity

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during winter and consequently reduced downward flux of fecal matter carrying microbial

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biomass from surface waters; 2) the vertically uniform and relatively high O2 and NH4+

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concentration caused by strong vertical water mixing in winter (cf. Table 1), which eliminates the

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depth dependent limitation of archaeal productivity in winter. Interestingly, ΔT and O2/NH4+

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concentration are positively correlated in winter, in contrast to the negative correlation observed in

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summer (Fig. 4e-h). However, the mechanisms underlying this reversal cannot be elucidated with

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the available data.

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4. Conclusions

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In this study, we investigated the distribution of iGDGTs and OH-GDGTs in SPM at different

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depth along a transect from the lower reaches of Yangtze River to estuary. The concentrations of

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iGDGTs and OH-GDGTs were much higher in estuary than in the lower reaches of the Yangtze

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River, suggesting that the GDGTs are predominantly sourced from in situ production of marine

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archaea. The higher concentration of OH-GDGTs and iGDGTs in summer than in winter indicated

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that archaea were more abundant during the warmer season. The distributions of iGDGTs and

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OH-GDGTs were influenced by hydrodynamics. Furthermore, the ratio of OH-GDGTs versus

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iGDGTs indicated that OH-GDGTs were concentrated in the upper layer, both in summer and in

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winter. The increase of the difference between proxy and in-situ temperature with water depth

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during summer suggested that GDGT cyclization in deeper water layers was influenced by lower

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ammonium oxidation rates.

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Acknowledgements

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This research was funded by the National Natural Science Foundation of China (41376090), the

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Strategic Priority Research Program of the Chinese Academy of Sciences (XDA11020102) and

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the Marine Safeguard Project (GZH201200503). We thank all members of the Organic

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Geochemistry Group from the State Key Laboratory of Biogeology and Environmental Geology

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(SKLBEG) at the China University of Geosciences (CUG) and the Hinrichs Lab at the Center for

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Marine Environmental Sciences (MARUM) in Bremen University for supporting the lab work.

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We also thank two anonymous reviewers, the associate editor and the major editor - Dr. Erdem

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Idiz for their constructive comments.

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386

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387

2920.13289.

388 389 390 391 392

393 394

Figure legends

395

Fig. 1. Sampling sites in Yangtze River Estuary. The red diamonds and blue circles refer to

396

summer and winter SPM sites, respectively.

397

Fig. 2. Vertical distribution of concentrations of iGDGTs and OH-GDGTs (a-d), BIT indices (e-f)

398

and the ratio of OH-GDGTs versus iGDGTs (g-h) in SPM from Yangtze River Estuary in summer

399

and winter. The blue crosses represent SPM locations.

400

Fig.3 Vertical distribution of TEX86H and RI-OH in summer and winter

401

Fig.4 The correlation of the difference between proxy-reconstructed and in situ temperature with

402

in situ temperature (a: summer; b: winter), depth (c: summer; d: winter); dissolved O2 (e: summer;

403

f: Winter) and NH4+ (g: summer; h: winter). The in situ temperature was recorded by CTD during

404

the two cruises.

405

406

407

408 409 410

Table 1 The concentrations of iGDGTs and OH-GDGTs of SPM from Yangtze River Estuary and the temperature, oxygen and ammonium contents at different water depth

Se as on

S

W

L

D

on g.

it

D L

e

at.

pt h

e s

( m )

(º E)

(º

(

N

m

)

)

G

G

G

G

G

D

D

D

D

D

G

G

G

G

G

T-

T-

T-

T-

T-

0

1

2

3

5

G

iG

O

O

O

D

D

H

H

H

GT

G

-

-

-

-5'

Ts

0

1

2

(ng/L)

T

RI

T

O

E

-

e

H

X8

O

m

s

H

H

p.

6

O 2

N H4 +

(º

(

(µ

C

m

mo

)

g/

l/L

L)

)

C

1

1

7

C

1

7

2

A 6 -

7

1

12

31

1.

.7

1

49

12

31

1.

.2

8

34

12

31

2.

.0

06

54

0

0

0

6

1

-

8

4

12

30

2.

.8

5

69

Su

A 6

2

-

9

6

12

30

2.

.7

83

71

6

6

-

1

8

12

30

3.

.6

25

38

62.

11.

0

8

2.9

6.8

1.3

2.6

3

45. 3

80. 9

1.0

2.0

0.

1.

6

5

2

3

0

91.

1.

0.

1.

2.

4

0

7

0

7

16

2.

2.

2.

7.

-

6.0

2

3

4

0

0.

1.

31

50

61.

12.

7

0

1

60.

11.

8

0

6

14

21.

11.

2.3

0

9

1

23

34.

14.

0

3.9

1

3

2

48

95.

41.

15.

70

11.

0

7.4

4

8

9

4.2

8

3

22

40.

23.

10.

46

0

9.2

2

9

7

3.7

18

67.

41.

25.

36

43.

73

9.4

1

6

9

2.8

9

0.7

1

58

13

11

61.

0

3.5

9.0

5.5

8

9

8.5

7.2

8.7

3.6

4.2

4.8

6.6

7.7

15

0.5

0.

4

0

A

1

3.7

0.3

7.8

13 4.0

13 0.8

20 1.4

32 9.7

10 29. 8

3.8

2.8

3.4

4.3

5.7

9.5

66. 4

2

30

12

10

35.

56

12

0

0.3

5.6

5.7

9

5.7

1.0

3

59

17

13

60.

0

2.2

5.0

4.1

5

12 90. 5

81. 3

2

0.

0

m

r

37.

0.6

-

27.

12.

0

me

1

0.9

10.

75.

0 A

15.

26

2.

3.

3.

9.

1.0

8

6

1

5

22

4.

4.

2.

1.8

2

2

9

21

1.

2.

2.

5.

9.3

2

2

3

7

38

7.

7.4

7

62

8.

9.

7.

5.5

2

3

3

13

1

1

56.

3.

5

1 0. 3

6. 9

0.

1.

6.

22

57

7

-

2

0.

1.

7.

23

59

2

-

-

2

0.

1.

3.

25

47

6

1

-

2

1.

0.

1.

2.

3

27

41

8

-

2

0.

1.

2.

23

51

2

2

-

2

4.

0.

1.

4.

9

28

40

5

2

-

4.

0.

1.

1.

8

35

44

3

1

4

-

8.

4.

6.

0.

1.

0.

0

4

9

3

37

45

1

1

1

3

-

1.

3.

4.

0.

1.

0.

3

3

4

28

43

0

1

2

2

5

-

4.

1.

0.

6.

0.

1.

4.

0

6

7

2

20

49

0

19

4

4

4

95.

4.

5.

6.

9

9

3

9

77 7.1

9. 9

-

-

-

2

2

2

1

2

3

-

7.

0.

1.

1

20

51

12 54.

2

-

2

3. 9

-

2

0.

2.

17

-

1

23

3

3

3

1

-

1

33.

4.

7.

1.

0

0.

1.

9.

6

1

5

8

3.

21

46

1

-

u.d .

0.

u.d

41

.

-

0. 39

0. 29

0. 27

0. 37

0. 26

0. 18

0. 17

0. 43

0. 38

0. 29

0. 21

u.d .

2.8

2.7

2.8

4.0

-

3.9

4.2

3.7

-.

-.

4.1

4 4

50

12

95.

39.

0

2.2

0.1

1

0

5 9

0

C

1

1

7

12

31

1.

.7

1

49

8

1

7

2

12

31

1.

.2

8

34

Wi

73. 9

43. 4

25

95.

7.1

8.3

2

6.9

5.2

17.

10.

8.9

7

8

35.

7

8

6

38

10

1

0

C

17

27. 0

5.9

1

19.

2

3

7.2

4.3

0.9

3.1

5.2

2.8

0.5

2.0

1.9

3.6

3.3

1.1

0.3

0.8

10 59. 4 35 99. 6

63. 5

17 6.9

50. 1

46. 2

9.7

38. 7

54. 4

11 8.3

1.9

3.2

3.8

0.6

0.2

0.7

18 70.

-

-

-

2

0 A 6 -

7

1

12

31

2.

.0

06

54

3

7

0 A 6

1

-

4

3

12

30

2.

.9

38

03

7

95.

12.

7

3

56. 8

12. 0

7.3

1.7

8.4

4.7

0.9

10

13.

11.

2.3

6

9

67. 6

7.9

6.0

1

20

23.

11.

4

2.8

5

3

3.6

1.4

0.4

6.4

2.1

5.0

16 7.4

10 0.9

18. 6

16 9.5

11 6.6

36 5.3

2.9

2.0

0.8

5.2

2.7

6.8

4

3

4

32.

8.

9.

4.

5

1

6

1

12

2.

2.

1.

5.

2.7

1

0

7

8

32

4.

4.

3.

1.1

6

0

8

10

3.

2.

2.

7.

5.6

1

0

1

2

81.

1.

1.

1.

3.

9

4

2

3

9

17.

0.

0.

0.

0.

6

3

3

2

9

64.

1.

1.

1.

3.

6

4

2

2

8

29

5.

4.

4.

0.2

1

1

0

17

3.

2.

2.

8.

3.2

6

8

4

7

34.

0.

0.

0.

1.

5

5

4

4

3

30

8.

6.

3.

9.0

9

5

7

20

5.

4.

2.

2.9

9

1

8

8.

5.

2

5

4.6

0.

9.

1 1. 4

-

1

62

61

1

21

nte r

-

-

1 1

3

-

1.

0.

1.

8

26

53

9. 0

0. 20

0. 19

0.

1.

25

47

1

-

2.

0.

1.

4

30

49

-

-

-

-

-

-

-

-

-

-

-

-

0.

1.

20

52

0.

1.

29

52

0.

1.

27

44

0.

1.

27

50

1

-

3.

0.

1.

1

26

49

0.

1.

28

46

0.

1.

25

47

1

-

9.

0.

1.

1

20

36

1

-

2.

0.

1.

8

24

40

2

-

5.

0.

1.

1

30

40

6. 1

11 .5 9

-

3.3

19. 4

19. 4

19. 4

25. 4

25. 1

25. 1

17. 0

6.

9.

16.

1

49

9

6. 1

10 .3 8

6.

8.

7

81

6.

8.

7

17

6.

8.

7

19

16. 9

8.1

7.7

7.8

35

34.

28.

19.

35

1.2

2

6

8

2.2

1

13

21.

12.

5

2.2

7

8

2

60

89.

44.

9

1.6

0

0

08.

0 A 6

2

-

9

6

12

30

2.

.7

83

71

11

5

A 6

6

-

1

8

411 412

12

30

3.

.6

25

38

9.9

79 5.9

20

10.

39

6.3

6

3.1

17.

90

19.

5

3

7.6

6

19

10

41.

5.3

0.6

5

9.4

15 31. 7

34. 7

2

1

1

5

-

7.

3.

0.

1.

0.

1.

4

3

5

2

20

44

5.

5.

2

-

8

4

2.

0.

1.

8

22

48

1 1. 6

8.

8.

6

60

9.

7.

3

67

16

2

1

1

6

-

1

79.

9.

5.

9.

4.

0.

1.

0.

5

2

8

7

7

32

55

2

30

2

2

1

6

-

12.

2.

0.

7.

0.

0.

1.

1.

1

2

9

1

8

7

32

47

6

2

-

6.

0.

1.

1.

6

35

53

6

1

1

36

63.

29.

10.

49

11.

97

9.

7.

9.

0

8.5

2

5

3

5.1

7

8.4

7

9

0

3

68

12

62.

25.

19

1

1

1

4

-

0

0.6

0.3

0

5

15.

4.

4.

2.

1.

0.

1.

1.

3

5

5

7

7

33

47

6

4

81

17

76.

28.

22

1

1

1

4

-

0

4.9

2.8

1

6

31.

6.

6.

5.

8.

0.

1.

1.

9

4

2

6

2

36

49

7

6

24

51.

36.

20.

45

25.

82

1

3

-

0

0.5

7

8

2

5.0

2

9.4

2.

8.

0.

1.

1.

5

0

21

56

7

10 08. 9 11 10. 8

17. 9

28. 7

1 5. 5

9. 9

1

1

1

8. 02

7. 81

7. 18

7. 81

8. 12

8. 29

5.8

5.9

5.7

6.0

-

5.9

-

6.1

Note: ‘WD’ means water depth of each site. ‘–’ means means not analyzed. ‘u.d.’ means the concentration was lower than the detection limit of instrument.

413

Highlights:

414 415 416

1. Pools of OH-GDGTs and iGDGTs in the estuary are not strongly impacted by

417

riverine input.

418

2. The hydrodynamics influence the distribution of thaumarchaeal lipids.

419

3. GDGTs cyclization may be influenced by ammonium oxidation rates, especially in

420

summer.

421 422