Characteristics and comparison of algal biomarkers in seawater and sediments of the East China Sea shelf
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摘要:
对东海内陆架杭州湾附近的季节性水体悬浮颗粒物和表层沉积物中的主要藻类生物标志物进行分析，如菜籽甾醇、甲藻甾醇和长链烯酮，分别对应于硅藻、甲藻和定鞭藻，分析探讨水体颗粒物和沉积物中藻类生物标志物的分布特征及控制因素。研究结果显示，东海内陆架表层沉积物中藻类生物标志物空间分布特征明显，由杭州湾近岸向海，含量随水深增加而增加；颗粒物中生物标志物含量的季节变化突出，夏季样品的含量最高。生物标志物的时空变化主要受控于藻类生产力的变化。由于营养盐丰富，高初级生产力主要分布在远离河口的冲淡水和外海海流交汇的水域；夏季由于长江冲淡水携带营养盐影响扩大，近岸浮游植物生产力最高。此外，结果还显示表层沉积物与颗粒物中优势甾醇有显著差异，颗粒物中菜籽甾醇占优势，而表层沉积物中甲藻甾醇占比更大。除了通常解释的颗粒物中有机质主要反映局部地点的瞬时性，而表层沉积物中有机质反映更广区域的多年平均性，我们认为沉积物中可能发生的菜籽甾醇后期氢化作用改造有巨大影响，导致沉积物中菜籽甾醇含量相对甲藻甾醇大量降低。本研究结果强调沉积物中生物标志物沉积历史的复杂性，理解表层沉积物中生物标志物的相对变化对于沉积记录中生物标志物的准确解读具有重要意义。
Abstract:Major algal biomarkers brassicasterol, dinosterol, and long-chain alkenones, representing diatoms, dinoflagellates, and haptophytes, respectively, were analyzed in seasonal suspended particles and surface sediments near Hangzhou Bay in the inland shelf of the East China Sea. The distribution characteristics and controlling factors of algal biomarkers in particles and sediments were studied. Results show that the spatial distribution characteristics of algal biomarkers in the surface sediments of the East China Sea inland shelf are obvious, and the abundances of algal biomarkers increase with the increase of water depth. The seasonal variation of algal biomarkers in particles is prominent, and the highest abundance in summer samples. Consistent with the results of previous studies, the temporal and spatial changes of biomarkers are mainly controlled by the changes of algae productivity. Due to the abundance of nutrients, high primary productivity is mainly distributed in the waters where the dilute water away from estuaries meets offshore currents. In summer, the coastal phytoplankton productivity is the highest due to the increased influence of nutrients carried by the diluted water of the Yangtze River. In addition, our results show a significant difference between the dominant sterols in surface sediments and particles. Brassicasterols dominate in particles, while dinosterols dominate in surface sediments. In addition to the common knowledge that the organic matter in particles mainly reflects the transient nature of local sites and in the surface sediment reflects the multi-year average of a wider area, we believed that the possible late hydrogenation of brassicasterol in sediments has a significant effect, leading to a significant decrease in brassicasterol abundances relative to dinosterol in the sediments. This study emphasized the complexity of sedimentary history of biomarkers in sediments. It is important to understand the relative changes of biomarkers in surface sediments for accurate interpretation of biomarkers in sedimentary records.
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Keywords:
- water suspended particles /
- surface sediments /
- brassicasterol /
- dinosterol /
- brassicastanol /
- East China Sea shelf
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图 1 研究区域(a)和取样站位图(b)
黑点为取样站位，棕色轮廓区域为报道的长江口外缺氧区（据Zhang等[40]）。实心蓝色箭头指示区域海流，包括黄海沿岸流（the Yellow Sea Coastal Current, YSCC）、长江冲淡水（Changjiang Diluted Water, CDW）、浙闽沿岸流（Zhe-Min Coastal Current, ZFCC）、黑潮（Kuroshio Current, KC）、台湾暖流（Taiwan Warm Current, TWC）和近岸黑潮支流（Nearshore Kuroshio Branch Current, NKBC）。
Figure 1. Study area (a) and sampling station (b)
The black spots are sampling stations, and the brown line confines the reported bottom hypoxia area near the Changjiang River estuary (according to Zhang et al [40]). Solid blue arrows indicate regional currents, including: the Yellow Sea Coastal Current (YSCC), Changjiang Diluted Water (CDW), Zhe-Min Coastal Current (ZFCC), Kuroshio Current (KC), Taiwan Warm Current (TWC), and the Nearshore Kuroshio Branch Current (NKBC).
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图 2 样品中甾醇（a）和烯酮（b）的色谱图
Figure 2. Chromatogram of sterols (a) and alkenones (b) in the samples
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图 3 表层沉积物中生物标志物的平面分布
分别为2019年3月、7月和10月，2020年7月和10月5个时间的4种生物标志物含量。A-E：菜籽甾醇，F-J：甲藻甾醇，K-O：烯酮，P-T：胆甾醇。
Figure 3. Distribution of biomarkers in the surface sediments
Abundances of four biomarkers in March, July, and October in 2019, and July and October in 2020, separately. A-E:brassicasterol, F-J:dinosterol, K-O: alkenone, and P-T:cholesterol.
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图 4 表层颗粒物中生物标志物的平面分布
分别为2019年3月、7月和10月，2020年7月和10月5个时间的3种生物标志物含量。A-E：菜籽甾醇，F-J：甲藻甾醇，K-O：胆甾醇。
Figure 4. Distribution of biomarkers in surface particles
Abundances of three biomarkers in March, July and October in 2019, and July and October in 2020, separately. A-E: brassicasterol, F-J: dinosterol, and K-O: cholesterol.
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图 5 表层沉积物和悬浮颗粒物中菜籽甾醇和甲藻甾醇的含量
Figure 5. Abundances of brassicasterol and dinosterol in surface sediments and suspended particles
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图 6 表层沉积物和悬浮颗粒物中菜籽甾醇和菜籽甾烷醇的含量
Figure 6. Abundances of brassicasterol and brassicastanol in surface sediments and suspended particles
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表 1 采样站位信息
Table 1 Information of the sampling stations
年 断面 时间 3月 7月 10月 站位 经纬度 水深/m 经纬度 水深/m 经纬度 水深/m 2019 A9 A9-1 30°00.039'N、122°29.632'E 23 30°00.863'N、122°19.320'E 19 29°59.941'N、122°29.959'E 21 A9-2 29°58.988'N、122°34.376'E 27 29°58.652'N、122°34.180'E 24 29°58.813'N、122°34.169'E 27 A9-3 29°57.339'N、122°38.746'E 34 29°57.436'N、122°37.838'E 30 29°57.418'N、122°38.852'E 35 A9-4 29°54.600'N、122°47.032'E 43 29°54.711'N、122°46.441'E 42 29°54.607'N、122°47.570'E 43 A9-5 29°51.876'N、122°55.945'E 52 29°21.510'N、122°38.149'E 52 29°52.450'N、122°55.699'E 53 A11 A11-1 29°31.197'N、122°23.903'E 21 29°38.651'N、122°24.338'E 20 29°30.644'N、122°24.402'E 22 A11-2 29°28.644'N、122°29.658'E 31 29°28.527'N、122°29.774'E 31 29°28.603'N、122°29.576'E 30 A11-3 29°25.042'N、122°33.742'E 43 29°24.792'N、122°33.791'E 42 29°25.010'N、122°33.792'E 41 A11-4 29°21.510'N、122°38.149'E 49 29°21.458'N、122°38.093'E 50 29°21.614'N、122°37.628'E 46 A12 A12-1 29°16.393'N、122°19.320'E 16 29°16.367'N、122°20.070'E 20 29°16.088'N、122°20.302'E 19 A12-2 29°13.817'N、122°24.249'E 28 29°28.644'N、122°29.658'E 29 29°13.772'N、122°24.599'E 29 A12-3 29°10.717'N、122°28.987'E 41 29°10.563'N、122°29.100'E 42 29°10.744'N、122°29.240'E 41 A12-4 29°05.060'N、122°33.270'E 50 29°05.174'N、122°32.810'E 49 29°05.136'N、122°32.887'E 50 A13 A13-1 29°04.268'N、122°15.399'E 24 29°04.823'N、122°16.119'E 22 29°04.746'N、122°15.036'E 23 A13-2 29°03.758'N、122°20.100'E 32 29°03.238'N、122°21.191'E 32 29°03.584'N、122°21.192'E 33 A13-3 29°00.193'N、122°25.169'E 42 29°00.254'N、122°25.440'E 43 29°01.223'N、122°24.913'E 42 A13-4 28°59.351'N、122°29.906'E 49 28°59.661'N、122°30.100'E 50 28°59.497'N、122°29.689'E 50 2020 A9 A9-1 30°00.079'N、122°30.342'E 19.3 30°00.32'N、122°29.66'E 20 A9-2 29°58.482'N、122°33.619'E 24.4 29°58.75'N、122°33.55'E 24 A9-3 29°57.564'N、122°38.048'E 32.2 29°57.53'N、122°37.85'E 37 A9-4 29°54.795'N、122°46.660'E 43.3 29°54.59'N、122°46.24'E 42 A9-5 29°51.900'N、122°53.992'E 52.4 29°51.66'N、122°55.70'E 52 A11 A11-1 29°29.474'N、122°23.860'E 17.5 29°31.19'N、122°24.26'E 21 A11-2 29°27.339'N、122°29.468'E 28.5 29°28.93'N、122°29.19'E 29 A11-3 29°25.140'N、122°33.531'E 39.2 29°25.07'N、122°33.50'E 41 A11-4 29°24.109'N、122°38.866'E 48.1 29°22.88'N、122°38.59'E 49 A12 A12-1 29°16.710'N、122°19.897'E 17.1 29°16.79'N、122°20.05'E 21 A12-2 29°14.123'N、122°23.968'E 26.4 29°13.53'N、122°24.35'E 30 A12-3 29°10.760'N、122°29.152'E 40.0 29°10.67'N、122°28.21'E 41 A12-4 29°05.210'N、122°32.744'E 49.4 29°04.92'N、122°34.34'E 50 A13 A13-1 29°04.731'N、122°15.401'E 23.9 29°04.71'N、122°16.05'E 23 A13-2 29°03.600'N、122°20.770'E 33.2 29°03.35'N、122°21.22'E 32 A13-3 29°00.604'N、122°24.737'E 41.7 29°01.13'N、122°25.21'E 41 A13-4 29°00.850'N、122°29.793'E 48.6 28°59.82'N、122°30.33'E 49 
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表 2 表层沉积物和悬浮颗粒物中不同季节主要生物标志化合物的含量变化范围及平均值
Table 2 Range and average abundances of biomarkers in surface sediments and suspended particles of different seasons
时间 表层沉积物/(ng/g) 悬浮颗粒物/(ng/L) 菜籽甾醇 甲藻甾醇 烯酮 胆甾醇 菜籽甾醇 甲藻甾醇 烯酮 胆甾醇 2019-03 范围 124.5～854.0 163.0～1378.4 0～60.9 297.6～1244.4 0.7～34.2 0.2～2.5 ND 2.4～95.8 均值 429.1 707.7 22.2 580.8 11.8 0.9 24.4 2019-07 范围 155.8～873.8 240.0～1653.5 0～82.8 286.9～1448.3 25.5～271.4 3.7～84.9 ND 35.1～334.5 均值 574.7 827.8 13.0 942.1 133.8 40.8 155.6 2019-10 范围 142.8～623.2 138.0～914.2 5.6～34.1 178.1～816.3 13.8～103.1 1.8～30.8 ND 24.7～167.1 均值 278.3 322.4 14.1 362.6 47.1 8.6 64.3 2020-07 范围 252.9～1007.7 324.7～2290.7 0～23.2 374.3～1508.2 73.5～557.0 3.4～18.5 ND 45.2～623.5 均值 487.6 1016.2 12.7 819.4 247.0 9.6 180.9 2020-10 范围 55.3～803.1 179.8～1805.6 10.3～32.2 116.1～1263.5 78.7～510.4 3.8～13.2 ND 52.7～703.4 均值 420.3 980.3 18.7 703.5 228.2 7.1 179.6 注：ND为低于检测限。
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表 3 表层沉积物和颗粒物中生物标志物的相对含量和比值
Table 3 Percentages and ratios of biomarker abundances in surface sediments and particles
时间 表层沉积物 悬浮颗粒物 菜籽甾醇/% 甲藻甾醇/% 烯酮/% 菜籽甾醇/甲藻甾醇 菜籽甾醇/% 甲藻甾醇/% 菜籽甾醇/甲藻甾醇 2019-03 范围 29.6～43.3 55.5～67.1 0～3.5 0.44～0.76 39.2～97.3 2.7～60.8 0.65～36.35 均值 37.1 61.2 1.7 0.61 80.6 19.4 11.93 2019-07 范围 34.6～48.2 51.8～65.4 0～4.5 0.53～0.93 59.8～93.0 7.0～40.2 1.49～13.38 均值 40.9 58.3 0.8 0.71 76.7 23.3 4.02 2019-10 范围 39.4～51.2 47.0～58.2 1.5～3.6 0.68～1.09 71.4～91.3 8.7～28.6 2.50～10.44 均值 46.3 51.5 2.2 0.91 84.8 15.2 6.46 2020-07 范围 24.1～50.5 48.3～75.2 0～2.8 0.32～1.05 92.2～98.7 1.3～7.8 11.83～75.92 均值 34.5 64.4 1.0 0.56 95.6 4.4 27.73 2020-10 范围 21.9～38.5 59.6～74.5 0.5～6.8 0.30～0.65 93.2～98.8 1.2～6.8 13.60～79.88 均值 29.0 69.0 2.0 0.43 96.4 3.6 34.64 相对百分含量：菜籽甾醇%=菜籽甾醇/（菜籽甾醇+甲藻甾醇+烯酮），甲藻甾醇%=甲藻甾醇/（菜籽甾醇+甲藻甾醇+烯酮），烯酮%=烯酮/（菜籽甾醇+甲藻甾醇+烯酮）。
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表 4 表层沉积物与颗粒物中主要的甾烷醇、甾醇含量及它们的比值变化
Table 4 Ranges and average of stanol and stenol, and their ratios in surface sediments and particles
时间 颗粒物 沉积物 菜籽甾烷醇/
(ng/L)胆甾烷醇/
(ng/L)菜籽甾烷醇/
菜籽甾醇胆甾烷醇/
胆甾醇菜籽甾烷醇/
(ng/g)胆甾烷醇/
(ng/g)菜籽甾烷醇/
菜籽甾醇胆甾烷醇/
胆甾醇2019-03 范围 0.8～4.7 1.3～8.2 0～0.20 0.07～0.53 77.5～509.5 110.2～771.6 0.42～0.70 0.37～0.72 均值 2.0 3.5 0.05 0.22 257.9 358.4 0.60 0.61 2019-07 范围 3.2～26.2 9.7～91.8 0～0.29 0.16～0.56 119.6～454.3 210.4～772.9 0.36～0.77 0.39～0.73 均值 15.4 46.5 0.11 0.31 279.2 481.8 0.49 0.52 2019-10 范围 1.9～10.2 2.8～16.4 0.05～0.16 0.07～0.17 80.6～365.5 118.1～543.8 0.51～0.76 0.54～0.80 均值 3.6 6.5 0.08 0.10 168.6 233.6 0.60 0.65 2020-07 范围 1.9～13.9 5.4～20.7 0.02～0.06 0.03～0.18 101.2～445.1 NS 0.28～0.60 — 均值 6.5 10.6 0.03 0.08 201.6 NS 0.41 — 2020-10 范围 1.3～17.8 2.1～38.9 0.01～0.08 0.01～0.23 34.2～391.9 NS 0.39～0.70 — 均值 6.4 10.9 0.03 0.08 216.6 NS 0.53 — 注：NS为未分离，其中2020年表层沉积物样品的图谱中胆甾烷醇与C28直链醇未分离。
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