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The distribution of long chain alkenones in modern lacustrine sediments in the Lake Qinghai and lakes from the Qaidam Basin

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This paper analysed the existence of long-chain alkenones from the surface sediments in the Lake Qinghai and lakes in Qaidam Basin. The ratios of C 37 to C 38 alkenone is observed larger than 1 in both freshwater and saline lakes, while less than 1 in salt lakes. The calculated temperatures based on 37 K U ′ equation reported in literatures can fall within the observed temperature ranges for the Lake Qinghai, but are lower than air temperatures observed for lakes in the Qaidam Basin. The abundances of the long-chain alkenones in the saline lakes are found higher than those in freshwater and salt lakes, with the highest abundance of 86.09g/L in Lake Gahai with salinity of 103.2g/L. Such characteristics suggest that the algal precursors might prefer to live in water bodies with intermediate salinity but do not grow well either in freshwater or salt lakes. Thus the fluctuation of long-chain alkenone abundance might indicate variations of freshwater or saline environments.
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. Lake Sci.(湖泊科学), 2008, 20(3): 285-290
http://www.jlakes.org. E-mail: jlakes@niglas.ac.cn
©2008 by Journal of Lake Sciences
青海湖及柴达木盆地地区现代湖泊沉积物中长链烯酮的分布特征*
付明义1,2, 刘卫国1,3, 李祥忠1,2, 徐黎明4, 1, 安芷生1
(1: 中国科学院地球环境研究所, 黄土与第四纪地质国家重点实验室, 西安 710075)
(2: 中国科学院研究生院, 北京 100049)
(3: 西安交通大学, 西安 710075)
(4: 中国科学院盐湖研究所, 西宁 810009)
: 研究了我国青海湖和柴达木盆地地区不同类型湖泊表层沉积物中的长链烯酮. 结果表明该地区湖泊中可能广泛存在
长链烯酮. 多数淡水湖、咸水湖现代沉积物中C37/C38>1, 而盐湖中C37/C38<1. 根据文献中报道的湖泊环境下长链烯酮不饱和度
37
K
U与温度的方程, 估计的温度在青海湖地区处于实际温度范围内, 而在柴达木盆地低于实际温度. 结果亦显示在青海湖和
柴达木盆地地区, 长链烯酮的含量在咸水湖中要明显的高于淡水湖和盐湖, 最高含量出现在咸水湖(盐度为103.2g/L)尕海中,
高达86.09µg/g; 这种含量和分布特征可能表明生产长链烯酮的藻类应该更喜欢生长于具有一定盐度的环境; 长链烯酮含量的
变化可能指示咸水或淡水环境.
关键词: 长链烯酮; 青海湖; 柴达木盆地; 盐度; 丰度
The distribution of long-chain alkenones in modern lacustrine sediments in the Lake
Qinghai and lakes from the Qaidam Basin
FU Mingyi1,2, LIU Weiguo1,3, LI Xiangzhong1,2, XU Liming4, WANG Zheng1& AN Zhisheng1
(1: State Key Laboratory of Loess and Quaternary Geology, IEE, CAS, Xi’an 710075, P.R . C h i n a )
(2: Graduate School of the Chinese Academy of Sciences, Beijing 100049, P. R . C h i n a )
(3: Xi’an Jiaotong University, Xi’an 710049, P.R . C h i n a )
(4: Qinghai Institute of Salt Lakes, CAS, Xining 810009, P.R . C h i n a )
Abstract: This paper analysed the existence of long-chain alkenones from the surface sediments in the Lake Qinghai and lakes in
Qaidam Basin. The ratios of C37 to C38 alkenone is observed larger than 1 in both freshwater and saline lakes, while less than 1 in salt
lakes. The calculated temperatures based on 37
K
Uequation reported in literatures can fall within the observed temperature ranges for
the Lake Qinghai, but are lower than air temperatures observed for lakes in the Qaidam Basin. The abundances of the long-chain
alkenones in the saline lakes are found higher than those in freshwater and salt lakes, with the highest abundance of 86.09g/L in Lake
Gahai with salinity of 103.2g/L. Such characteristics suggest that the algal precursors might prefer to live in water bodies with
intermediate salinity but do not grow well either in freshwater or salt lakes. Thus the fluctuation of long-chain alkenone abundance
might indicate variations of freshwater or saline environments.
Keywords: Long-chain alkenone; Lake Qinghai; Qaidam Basin; salinity; abundance
长链烯酮系指一类含有 2-4个双键的直链不饱和甲基和乙基酮, C原子数在 37-39 之间, 广泛分
布于海洋沉积物中[1-2]; 主要是由定鞭金藻纲, 特别是该纲中的颗石藻 Emiliania huxleyi 及其它少数种属
Gephyrocapsa oceanica 合成的一种特征性生物标记化合物[2-5]; C37 烯酮的不饱和度值(37
K
U)已经被成
功地用来重建古海洋水表温[6-9]. 近年来, 一些研究者把目光对准了湖泊环境中的长链烯酮, 期望通过
* 国家自然科学基金项目(40599422, 40523002, 40121303)和国家重点基础研究发展规划项目(2004CB720200)联合资助.
2007-06-08 收稿; 2007-07-27 收修改稿. 付明义, , 1982 年生; E-mail: 2005f868@sina.com.
J. Lake Sci.(湖泊科学), 2008, 20(3)
286
C37烯酮的不饱和度值重建湖泊区域气候的变化. 研究者们已在全球范围内的湖泊中发现了长链烯酮的
存在. Zink[10]研究了俄罗斯、澳大利亚、德国及美国古代和现代湖泊中的长链烯酮, 并建立了德国湖泊
37
K
U与湖泊表层水温的线性相关关系. 在我国, Li[11]发现了青海湖中存在长链烯酮; Wang[12]和盛国
英等[13]研究了碱性碳酸盐型咸水湖和盐湖沉积物中的长链烯酮; 孙青等[14]研究硫酸盐型盐湖中的长链
烯酮, 发现咸水湖和盐湖沉积物中 37
K
U与年平均气温存在良好线性关系; Chu[15]研究了中国38个不同类
型湖泊中长链烯酮的分布、组成, 建立了长链烯酮不饱和度(37
K
U
)与年平均气温的线性关系. 在南美洲的
Titicaca, Theissen[16]认为: 只要能够确定其母源, 长链烯酮不饱和度可以作为湖泊环境下温度的替代
指标. D’Andra[17]Liu[18]依据已有的 37
K
U
与温度的关系方程分别重建了格陵兰湖和青海湖地区的温
度变化.
然而, 已有的研究对柴达木盆地地区现代湖泊中长链烯酮在不同类型水体中的组成、分布及丰度特
征尚缺乏较系统的认识. 本文从青海湖和柴达木盆地部分现代湖泊中采集了表层沉积物, 分析不同类型
湖泊中长链烯酮的分布、丰度及不饱和趋势, 为长链烯酮不饱和度在湖泊环境下的应用提供依据.
1 样品和实验
1.1 研究区概况和样品
青海湖(99°36´-100°47´E, 36º32´-37°15´N)是我国最大的内陆高原微咸水湖泊, 湖面海拔1981
年为3193.92m, 湖水矿化度1986年为13.84g/L[21]. 湖区年均气温1.2 , 多年平均降水量336.6mm,
属高寒半干旱气候. 湖区为大通山、日月山和青海湖南山所环绕, 有大小河流40, 都属内陆封闭
水系. 此外, 在蒸发最强、补给最弱的东部湖滨, 出现三个子湖尕海(100°34´E, 37°00´N)耳海和海
晏湾[21].
柴达木盆地(90º00´-98º20´E, 35º55´-39º10´N)居于青藏高原的东北侧, 是我国第三大内陆盆地. 四周
为阿尔金山、祁连山南麓和昆仑山北麓所环绕, 东西长约850km, 南北宽逾300 km, 面积达25×104km2.
拔分布在2675-3171m. 盆地内气候干旱, 多风少雨, 具有高原荒漠的气候特征. 年均气温为2-4. 盆地
内现有湖泊33. 其中淡水湖1个、半咸水-咸水湖7, 盐湖15. 此外, 还有一些无表面湖水的“干盐
”, 如大浪滩、一里平、察尔汗等. 盐湖的平均含盐量高达332.4g/L; 湖水一般都较浅, 面积多变[22].
样品采自青海湖及柴达木盆地的尕海、克鲁克湖、大苏干湖、小苏干湖、托素湖、大柴旦湖、小柴
旦湖及冷湖等湖泊表层0-2cm的现代沉积物(1).
1 青海湖及柴达木盆地采样湖泊分布( 淡水湖、 咸水湖、 盐湖)
Fig.1 Map of sampled lakes in Lake Qinghai and Qaidam Basin
付明义等: 青海湖及柴达木盆地地区现代湖泊沉积物中长链烯酮的分布特征
287
1.2 实验方法
样品采集后, 冷冻保存. 实验时, 样品在 40下烘干, 于玛瑙研钵中磨至 100 , 称取 2g 左右,
ASE(Accelerated Solvent Extraction)200 (温度 100, 压力 1500psi)加速抽提, 提取液为 9:1 CH2Cl2
MeOH 的混合液, 重复抽提 4; 提取液在柔和的氮气下吹干, 加入 6%的氢氧化钾甲醇溶液 3ml, 超生震
10min, 室温放置过夜, 次日再超声震荡一次, 用正己烷萃取其中的非极性成分 4; 在硅胶柱上分别利
用正己烷和二氯甲烷提取烷烃和酮类组分的溶液[24]; 含烯酮的馏分加入 C36 正构烷烃内标(即采用外标法),
在氮气下吹干, 溶于 20L 甲苯中, 超声震荡 1min 后进行 GC 分析.
气相色谱分析(GC)Agilient 6890 气相色谱仪上进行, 柱头进样温度 310. 色谱柱为 HP-1MS 型毛
细管柱(60m×0.32mm×0.25m), 氦气作为载气, FID 检测. 升温程序为:初始温度 60下保留 1min, 然后以
15.00/min 升温至 200, 再以 5.00/min 升温至 270, 再以 2.00/min 升温至 300, 恒温 40.00min,
再以 5.00/min 升温至 310, 恒温 10.00min. 化合物的鉴定主要依据 GC 保留时间及与标准色谱图的对
比来确定[11,18]. 按长链烯酮各异构体与 C36 正构烷烃的响应因子为 1计算长链烯酮各异构体的浓度, 计算
公式为: 长链烯酮各异构体的浓度=C36 正构烷烃含量×长链烯酮各异构体的峰面积×1/C36 正构烷烃的峰
面积.
2 结果与讨论
2.1 长链烯酮的分布特征
青海湖和柴达木盆地的尕海、克鲁克湖、大苏干湖、小苏干湖、大柴旦湖、小柴旦湖、托素湖及冷
湖等湖泊的表层沉积物中均检测到了 C37-C39 长链烯酮.
不同盐度环境下, C37-C38 长链烯酮各异构体的组成和丰度呈现出相似的分布特征. C37 不饱和酮是由
C37:4C37:3 C37:2 3个异构体组成的; C38 不饱和酮一般是由 C38:4C38:3 C38:2 3个异构体组成. 具有相
同碳数的长链烯酮中, 3C=C 的长链烯酮(C37:3 C38:3)在其各同系物中通常是丰度最高的. 研究湖
泊中, 多数的淡水和咸水湖(包括青海湖)沉积物中长链烯酮丰度随碳链的增长丰度逐渐变小(一般是
C37>C38>C39), 与开阔海洋[9,25]、临海[26-27]以及部分湖泊环境[10-15,28] 下长链烯酮的丰度变化顺序相同;
数盐湖沉积物中长链烯酮的丰度变化一般是 C38>C37>C39. C39 长链烯酮的丰度很低.
C37 C38 不饱合酮的比值(C37/C38)在自然环境中, 特别是在开放海洋环境下一般都比较低; 而湖泊
环境下的 C37/C38 比值似乎变化范围较大[11,14,25]. C37/C38 比值可能受到环境状况、营养水平、藻类细胞的
生理状态和生长温度的影响[29]; Chu [15]认为: C37/C38 比值较大的变化还可能指示了生产烯酮的不同藻
类物种的输入. 在我们研究的青海湖和柴达木盆地地区, 多数淡水和咸水湖的沉积物中 C37/C38>1, 而大
柴旦湖、小柴旦湖等盐湖的沉积物中 C38 长链烯酮的含量较高, C37/C38<1, 普遍存在着两种模式(C37/C38>1
C37/C38<1); C37/C38 比值变化很大(0.40<C37/C38<7.66), 可能暗示了青海湖与柴达木盆地湖泊中的长链
烯酮来源于不同的生产藻类.
2.2 长链烯酮不饱和度与温度的关系
青海湖及柴达木地区湖泊表层沉积物中长链烯酮的 37
K
U
值如表 1. 利用 Chu [15]的方程(37
K
U
=
0.0328T+0.126, R2=0.83), 得到的年平均气温在青海湖地区为 0.5, 而在柴达木盆地处于了冰点
以下, 为-0.7. 利用Zink [10]的方程(37
K
U
=0.02T-0.121, R2=0.89), 我们得到青海湖和柴达木盆地
地区湖泊的夏季年平均表层水温分别为 13.211.2 . 与现代气象资料比较(近几十年来, 青海
湖地区年均气温在 1.2左右, 夏季年均气温在 13.2左右 [21,23]; 柴达木盆地年均气温大约为 2-5,
夏季年均气温在 15.0左右[22,30-31]), 青海湖地区的温度重现很好, 而柴达木盆地地区的恢复温度
偏低; 这可能是受到生产长链烯酮藻类的物种差异、繁殖期不同及其它环境因素(盐度、营养水平等)
的影响[16]; 同时, 也应该考虑到不同湖泊沉积速率的差异, 表层沉积物代表了不同的沉积时间,
能降低了 37
K
U值与湖区气温的相关性及柴达木盆地特殊气候环境, 降水主要集中在夏季, 湖水面积
变化较大等因素. 这些都需要我们做进一步的工作来确定柴达木盆地地区长链烯酮不饱和度与温度
的关系.
J. Lake Sci.(湖泊科学), 2008, 20(3)
288
1 湖泊特征及长链烯酮丰度
Tab.1 Characteristics of the lakes investigated and alkenone abundance
类型 湖泊名称 水化学类型[21] pH 水深(m) 盐度(g/L) C37(µg/g) C38(µg/g) C37+C38(µg/g) C37/C38 37
K
U2)
淡水湖 克鲁克湖 硫酸钠亚型 8.0[21] 2.94[21] 1.0 0.17 0.15 0.32 1.10 0.05
咸水湖 托素湖 硫酸镁亚型 8.9 [21] 3-4[22] 15.9[21] 0.07 0.06 0.13 1.30 0.17
托素湖 氯化钠亚型 8.9 [21] 3-4[22] 15.9[21] 0.11 0.11 0.22 1.04 0.20
托素湖 硫酸钠亚型 8.9 [21] 3-4[22] 15.9[21] 0.09 0.15 0.24 0.62 0.12
青海湖 氯化钠亚型 9.3[15] 17.9[21] 13.9[15] 0.03[15] 0.02[15] 0.05[15] 1.33[15] 0.14[15]
青海湖 氯化钠亚型 9.23[21] 17.9[21] 16 13.99 2.0 16.02 6.87 0.15
青海湖 氯化钠亚型 9.23[21] 17.9[21] 16 13.44 2.0 15.46 7.66 0.14
青海湖 氯化钠亚型 9.23[21] 17.9[21] 16.2 4.67 0.6 5.29 6.71 0.14
小苏干湖 硫酸钠亚型 7.4[21] 1) 3.5 0.15 0.12 0.27 1.22 0.18
小苏干湖 硫酸钠亚型 7.4[21] 1) 3.5 0.09 0.08 0.17 1.12 0.11
大苏干湖 硫酸钠亚型 8.9[21] 2.00[22] 37.3 19.38 25.05 44.42 0.77 0.10
冷湖 硫酸钠亚型 8.2[21] 1) 48.3 0.07 0.17 0.24 0.44 0.08
尕海 硫酸镁亚型 8.28[21] 8.00[22] 103.2 44.99 41.09 86.09 1.09 0.08
盐湖 大柴达木湖 硫酸镁亚型 157.95[21] 0.34[22] 280.6 0.13 0.16 0.29 0.84 0.06
大柴达木湖 硫酸镁亚型 7.95[21] 0.34[22] 280.6 0.15 0.18 0.33 0.81 0.08
小柴旦湖 钠、镁硫酸亚型 7.8[21] 0.26[22] 192.8 0.06 0.13 0.18 0.46 0.09
小柴旦湖 钠、镁硫酸亚型 7.8[21] 0.26[22] 192.8 0.05 0.08 0.12 0.66 0.08
小柴旦湖 钠、镁硫酸亚型 7.8[21] 0.26[22] 192.8 0.13 0.33 0.47 0.40 0.04
1)无数据; 2) 37
K
U=[C37:2]/[C37:3+C37:2].
2.3 长链烯酮含量与盐度的关系
D’Andrea [17]发现在格陵兰湖泊中长链烯酮的分布似乎依赖于盐度, 长链烯酮在淡水湖中普遍没有
检出, 而出现在具有较高盐度的湖泊中. 然而, 通过对中国 50 个湖泊较系统的研究, Chu [15]发现: 长链
烯酮的含量在淡水湖、咸水湖和盐湖中并没有表现出明显差别; 但是, 长链烯酮在高盐度的硫酸盐型湖
泊中含量很低, 可能这类环境并不利于长链烯酮生产藻类的生长. 我们研究地区的湖泊包括了淡水湖、
水湖和盐湖三种类型, 盐度变化范围为 1.0-280.6g/L. 2a 是沉积物中长链烯酮(C37+C38)含量与盐度的相
关关系(R2=0.0035), 可能指示了青海湖和柴达木地区湖泊中长链烯酮的含量似乎并不受控于盐度的变化.
经对比, 可看出: 咸水湖中长链烯酮的含量普遍比淡水湖和盐湖中的高1-2个数量级, 最高含量出现在咸
水湖(盐度为 103.2g/L)尕海中, 高达 86.09g/L; 低盐度环境下, 长链烯酮的含量与盐度(盐度≤103.2g/L)
在一定的关系(R2=0.75)(2b). 同时, 自从 Cranwell [19]在英国的淡水湖泊中发现了长链烯酮后, 报道
的湖泊环境中长链烯酮的分布也多在高蒸发量、无外流的封闭湖泊环境, 而这类环境通常是具有一定盐
度的. 结果显示: 长链烯酮生产藻类应该更喜欢生长于具有一定盐度的咸水或微咸水环境, 过高或过低
的盐度可能都不适合产生长链烯酮的藻类生长; 而合适的盐度环境下(如托素湖和冷湖)出现了低含量的
长链烯酮, 这可能是由于自然环境下别的因素限制了生产长链烯酮的藻类的生长.
3 结论
分析了我国青海湖和柴达木盆地地区不同类型湖泊表层沉积物中的长链烯酮. 结果表明我国青海湖
和柴达木地区湖泊中可能广泛存在长链烯酮. 多数淡水湖、咸水湖现代沉积物中C37/C38>1, 而盐湖中
C37/C38<1. 利用湖泊环境下长链烯酮不饱和度 37
K
U
与温度的相关方程, 估计的温度在青海湖地区处于实
际温度范围内, 而在柴达木盆地低于了实际温度. 青海湖和柴达木盆地地区, 咸水湖中长链烯酮的含量普
付明义等: 青海湖及柴达木盆地地区现代湖泊沉积物中长链烯酮的分布特征
289
2 青海湖及柴达木盆地湖泊中(C37+C38 )长链烯酮丰度与盐度关系
(a: 所有研究湖泊; b: 低盐度湖泊)
Fig.2 Correlation between alkenone abundance (C37+C38) and salinity in Lake Qinghai and lakes from the Qaidam Basin
(a)all lakes investigated and (b)lower salinity lakes
遍比淡水湖和盐湖高, 而最高含量出现在咸水湖(盐度为 103.2g/L)尕海中, 高达 86.09g/g; 这种含量和分
布特征可能表明生产长链烯酮的藻类应该更喜欢生长于具有一定盐度的环境. 长链烯酮丰度的变化可能
指示咸水或淡水环境. 未来对更多青藏高原不同类型湖泊的研究将有助于深入的认识高原湖泊长链烯酮
地球化学意义.
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Long-chain alkenones in microbial mats from Mediterranean solar salterns and coastal areas from the Mediterranean Sea and North Sea have been studied. These ecosystems exhibit a distinct C37–C40 alkenone composition characterized by a predominance of triunsaturated compounds in all C37–C40 homologues and by a specific correspondence between carbonyl position and chain length. Thus, C37 and C39 homologues are methyl ketones and C38 and C40 homologues are ethyl ketones. The distribution also contains tetraunsaturated alkenones in significant proportion, particularly among the C37 homologues. The double bonds are located at Δ8,15,22,29 and Δ9,16,23,30 in the methyl and ethyl ketones, respectively, indicating that the number of carbon atoms between the carbonyl group and the first double bond remains constant.This distribution is different from C37–C40 alkenone mixtures previously found in open sea waters or freshwater environments. It suggests a biological origin distinct from that previously described for marine algal cultures or recent or ancient open sea sediments. The uniformity of the distributions, despite the strong salinity differences considered in the present study (salinity of 35–200) is remarkable. Depth analysis of the microbial mats from hypersaline environments shows fluctuations in total alkenone concentration, but no defined trends involving selective changes in compounds with a specific degree of unsaturation or chain length.
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Distribution patterns of C37 and C38 polyunsaturated long-chain alkenones (LCAs) serve as proxies for the determination of paleotemperatures for marine surface waters. We studied Recent/Subrecent and Late Glacial/Holocene sediments from Germany, Austria, Russia, and the U.S. to test for a correspondence between LCA distribution and surface water temperature in limnic systems. Previously, reports of LCA occurrence were restricted to sediments of 6 wide distributed freshwater and alkaline lakes. In this study 13 of 27 investigated lakes contained LCAs in surface sediments with concentrations varying between 12 to 205 μg/g TOC. Late Glacial to Holocene sediment sequences from Lake Steisslingen and Lake Wummsee, (Germany), Lake Pichozero (Russia), and Brush Lake (U.S.A.) contained abundant LCAs with averaged concentrations of 33 to 7536 μg/g TOC. For the first time we observed the occurrence of LCAs within in the water column of oligotrophic Lake Stechlin (NE-Germany). Alkenones were restricted to the zone of maximum chlorophyll concentration within the water column indicating that LCAs have a biosynthetic origin and can be attributed to phototrophic (micro)algae. Attempts to identify the producing organism, however, were not successful. Culture experiments allow various phytoplankton to be excluded as producers. Alkenone-producing algae are evidently of small size, hindering microscopical identification. LCAs commonly occur in high concentrations in Late Glacial sediments, mainly during the cold period of the Younger Dryas, whereas the Holocene usually is devoid of polyunsaturated alkenones. The episodic occurrence of LCAs restricts their utility as proxies for continuous geological records. Furthermore, lack of microscopical verification and the episodic distribution allow for different producers of unsaturated alkenones in Recent and Late Glacial sediments. An empirical relationship between LCA distribution and temperature was observed. In fossil sediments from Lake Steisslingen, there is a good correspondence between Uk37 and the temperature-controlled δ18O isotope ratio of lake chalk. Comparison of LCA patterns obtained from the uppermost centimetres of lake sediments with averaged summer surface water temperatures of the lakes studied, demonstrates a trend of covariance (r2: Uk′37 = 0.90, Uk37 = 0.67; n = 9). Hence, the same mechanism that causes temperature-dependence of LCA patterns in marine systems might be effective in limnic settings. Identification of alkenone producers and their culture under controlled temperature are still mandatory before LCAs can be routinely applied as paleotemperature proxy in limnic systems.
Article
Long-chain C37 to C40 alkenones with di-, tri-, and tetra-unsaturation are very abundant in sediment trap material and Holocene to Late Pleistocene core samples from the Earth's largest soda lake, Lake Van (Turkey). Thus, the known distribution range of these typical biomarkers for haptophyte microalgae is extended to highly alkaline environments. The observed unsaturation patterns differ strikingly from those found in open marine haptophytes and sediments by an enhanced relative abundance of the tetra-unsaturated compounds, especially the C37:4 methyl ketone. Their preponderance is suggested to be a facies marker pattern for lacustrine and marginal marine areas of sedimentation. Using published U37K calibrations, no reliable absolute temperatures were obtained for the Lake Van samples. Accordingly, marine sea surface temperature determinations based on long-chain alkenones should be applied with caution when a contribution of these compounds from coastal or nonmarine sources can not be excluded. The presence of tetrahymanol and gammacer-3-one in the Lake Van materials is attributed to organic matter contributions of ciliates. The relative abundance of long-chain alkenones and of tetrahymanol/gammacer-3-one is considered to reflect changes in the environmental conditions, in particular in the hydrological setting. We suggest that times of pronounced stagnation are recognised by very high tetrahymanol/gammacer-3-one concentrations together with drastically increased stanol/stenol ratios, and intervals of enhanced convection or of high freshwater input are characterised by high alkenone contributions.