海洋沉积物中色素生物标志物研究进展

海洋沉积物中的光合色素包含着水体、沉积物中浮游和底栖植物以及微生物群落的丰富信息,能表征特定生物来源,在埋藏到沉积物甚至发生某些改变之后仍然保留其源信息,是一类重要的化学生物标志物.结合总有机碳、总氮等其他海洋地球化学参数,沉积色素可用来研究海洋浮游植物和光合细菌的群落组成和丰度,反演海洋初级生产、水体富营养化水平及其历史趋势,指示水体和沉积物氧化还原条件,揭示海域气候条件等现状及其历史变化.沉积色素的研究,对于掌握海洋中碳的生物地球化学循环过程,回溯古环境、古海洋、古生态以及古气候记录,制定合理的海洋管理政策具有十分重要的意义.阐述了沉积物中色素的分类、来源、性质和分析方法,分析了色素在沉积物中的保存和变化规律,探讨总结了沉积色素作为化学生物标志物在海洋学研究中的应用.     

实验模拟氧化条件对微生物四醚脂的环境替代指标的影响

以古菌和细菌细胞膜脂甘油四烷基甘油四醚(GDGTs)为基础建立的古温度指标四醚指数(TEX86)与甲基化/环化指标(MBT/CBT),以及陆源输入指标(BIT)与干旱和盐碱化指标Ri/b,在海洋、湖泊、黄土-古土壤等沉积物的古环境重建中得到了广泛的应用.然而,利用这些微生物分子指标来重建古环境时,氧化等降解因素对GDGTs化合物,尤其是对细菌支链GDGTs的影响目前还不是很清楚.本研究通过过氧化氢模拟不同氧化程度对土壤中GDGTs化合物产生的影响,进而分析古菌和细菌GDGTs不同结构化合物抗氧化能力的差异,了解化学氧化降解对GDGTs各指标的影响.结果表明,古菌类异戊二烯GDGTs抗氧化能力低于细菌支链GDGTs,同时含环的古菌和细菌GDGTs抗化学氧化能力均要低于无环GDGTs.古菌GDGTs古温度指标TEX86在氧化过程中逐渐降低,在氧化条件下沉积的古菌GDGTs的TEX86指标用于古温度的重建存在低估的可能.在以无环细菌支链GDGTs为主的环境中,细菌MBT/CBT指标随氧化程度加深其重建温度基本不受影响.古菌与细菌GDGTs抗降解能力的差异导致陆源输入指标BIT指数随着氧化程度增加而升高,在地质体中应用此指标恢复古陆源输入存在高估的可能性.干旱化和盐碱化指标Ri/b随着氧化程度加深表现出逐渐降低的趋势,从而在应用上也可能存在低估.需要指出的是,实验室用的过氧化氢比自然条件下氧气的氧化作用强得多,本文的结论反映了一种比较极端的状况.     

氨氧化细菌和氨氧化古菌在百花湖沉积物中的垂直分布

采用定量氨单加氧酶基因(amoA)的荧光定量PCR(qPCR)方法,分析了氨氧化细菌(AOB)和氨氧化古菌(AOA)在百花湖沉积物中的垂直分布。以氨单加氧酶基因(amoA)数量来衡量氨氧化细菌(AOB)和氨氧化古菌(AOA),结果表明:百花湖沉积物中AOA的amoA基因数量在1.74×105~2.00×106拷贝/克沉积物(湿重)之间,且22~30cm的各层沉积物中,AOA的数量是1~21cm各层沉积物的2倍左右;AOB的amoA基因在百花湖沉积物中的数量随深度的增加变化不大,其拷贝数在6.10×106~3.88×107拷贝/g沉积物(湿重)之间;AOB与AOA的amoA基因的比例在浅层沉积物和深层沉积物中存在一定的差异。这些结果表明AOB和AOA都参与百花湖沉积物中的氨氧化作用,从两类微生物的数量来看,AOB是参与百花湖沉积物中氨氧化作用的主要微生物,而AOA对氨氧化作用的贡献则随着沉积物深度的增加而提高。     

海洋极端环境微生物活动与油气资源关系

为了弄清海洋极端环境下微生物参与油气资源形成和演化的潜在机制, 进行了现代海洋热泉和冷泉等环境中微生物类型分析和生物量估算, 探讨了极端微生物活动和油气资源的潜在关系.认为海洋极端环境下微生物类型主要为细菌和古细菌, 热泉微生物群落主要为异养发酵菌、硫酸盐还原菌、产甲烷菌等; 冷泉微生物群落主要为ANME-2族的厌氧甲烷氧化古细菌、硫酸盐还原细菌和ANME-1族厌氧甲烷氧化古菌.这些极端微生物利用CH₄和H₂S等气体进行能量固定, 有较高的生物丰度和较低的分异度, 具有垂向和水平分带性, 并能营生一套独特的宏体生物.极端微生物活动直接和间接地参与了油气资源的形成和改造, 示踪海底油气资源的变迁.对于探索地球早期海洋微生物活动与油气资源形成, 寻找地史时期或华南地史早期烃源岩具有重要理论和实践指导意义.      

硝酸盐氮氧稳定同位素分馏过程记录的海洋氮循环研究进展

海洋生态系统中的氮素生物地球化学循环主要是由微生物的代谢过程来驱动的,包括氮固定、氮同化、硝化以及反硝化和厌氧氨氧化过程,这些过程都伴随着不同程度的氮氧同位素的分馏,直接影响着海洋硝酸盐中的氮氧稳定同位素组成.因此,通过检测海洋硝酸盐中的氮氧稳定同位素信号,就可以捕捉到海洋中发生的具体氮素循环过程.细菌反硝化法是这一研究最有力的手段,通过细菌的作用把硝酸盐中记录的氮氧稳定同位素信号转化到N2O中,再通过痕量N2O的同位素质谱测定和分析,准确地反映海洋中发生的氮素转化过程.硝酸盐氮氧稳定同位素分馏过程为深入理解海洋氮循环提供了一个重要的工具,有力推动了海洋氮素生物地球化学的研究,在近10年来取得了重要进展.     

完整极性脂质化合物对海洋微生物活动的指示及应用局限性

回顾了近10年来完整极性脂质化合物(IPLs)在海洋微生物研究中的应用及存在的问题,并展望了IPLs应用的发展前景。作为新的热点之一,对海洋水体悬浮颗粒物中IPLs的研究,不仅推进了人们对水柱中IPLs分布和转化的了解,同时也深化了对古环境指标TEX86适用性的认识,有助于更好地开展古环境重建研究。色谱和质谱技术的发展,新型化合物的发现以及IPLs单体碳同位素分析的应用,使得IPLs在示踪海洋环境中真核生物与微生物共生作用、微生物介导的好氧和厌氧氨氧化以及甲烷厌氧氧化作用、微生物的代谢状态等方面也取得了重要研究进展。需要注意的是,由于不同的IPLs降解速率并不一致,其中部分古菌糖脂的降解周期可能远大于微生物群落的更新周期,因此可能并不适于表征活体生物量;同时,环境中氧气含量及有机质浓度也会对IPLs的降解速率造成影响;另外,在微生物不同的生长阶段,或者微生物由于生长环境条件变化产生生理响应时,IPLs组成也可能会发生变化。因此,应用IPLs指示微生物活动和反演古环境时应注意指标的适用性。     

海洋沉积物的锌同位素地球化学及其应用

锌同位素体系是海洋地球化学研究的新示踪剂,应用于示踪海水中锌元素的来源及其运移过程.海洋沉积物作为锌元素重要的"源"与/或"汇",其锌同位素组成的研究有助于理解海洋锌元素的地球化学循环.海洋沉积物记录了海水组成的信息,可以反演古海水锌同位素组成的变化,前提是理解沉积物与海水之间的分馏.对海水及海洋不同储库锌同位素研究进行系统总结,包括河流输入、热液体系、不同类型海洋沉积物(如富碳酸盐的沉积物、陆源硅酸盐碎屑、硅质沉积物、铁锰结核、贫氧-缺氧沉积物)的锌同位素组成,阐述了海洋沉积物锌同位素组成变化在古气候、古环境重建以及古海洋学等领域的应用以及重要性.      

细菌藿多醇的环境指示作用及其在海洋生态环境重建中的应用

细菌藿多醇（Bacteriohopanepolyols,BHPs）是细菌细胞膜中高度结构变异的五环三萜类化合物,易保存且受成岩作用影响较小,广泛分布于陆地和海洋环境中。BHPs作为一种新型微生物标志物,由于其细菌来源专属性和环境专属性,近年来已在示踪有机质来源、环境演变过程以及反演古环境方面表现出巨大的应用潜力。本文系统分析了近年来全球土壤、沉积物和海水中BHPs的组成、分布和来源,发现热带和温带区域中BHPs的多样性和含量通常高于寒带区域,且由土壤、河流、近海到外海海域逐渐降低。探讨了土壤标志物BHPs、细菌霍四醇同分异构体（BHT- Ⅱ）和35- 氨基霍多醇在有机质来源、缺氧环境、厌氧氨氧化和甲烷氧化活动方面的环境指示作用及在海洋生态环境重建中的应用,以期为示踪海洋生态环境变化提供新指标和新途径。     

蓝细菌和浮游古菌在南海第四纪氮循环中的作用初探

南海晚第四纪沉积物中的氮同位素在冰期-间冰期气候旋回中只有微弱的变化,与东太平洋的反硝化记录截然不同,可能反应了局地的氮生物地球化学过程.文章对位于南海南部钻取的一根柱状样MD05-2897的海洋氧同位素阶段(MIS)3～5期的有机氮同位素、反映蓝细菌贡献的2-甲基藿烷指数和反映氨氧化古菌Thaumarchaea的泉古菌醇进行了分析.结果显示,有机氮同位素在MIS 5期有明显降低,对应于这一降低,2-甲基藿烷指数和泉古菌醇都显示了升高的特点,暗示蓝细菌固氮作用和古菌氨氧化作用可能是导致OIS 5期的氮同位素降低的重要过程.     

病毒对海洋细菌代谢的影响及其生物地球化学效应

病毒是海洋生态系统中丰度最高的生命形式,其中超过90%属于浮游细菌(细菌和古菌)病毒,是海洋生态系统的重要参与者和海洋生物地球化学循环的重要驱动力。作为海洋浮游细菌主要的致死因子之一,病毒通过裂解宿主释放出大量的有机物和营养盐,调控宿主群落的代谢行为,进而影响生物地球化学循环。同时,伴随侵染的发生,病毒挟持宿主细胞的代谢系统完成自身的生命周期,从而改变宿主胞内的代谢途径和代谢产物。概述了病毒在个体层面和群落层面对海洋浮游细菌代谢的影响,及其对海洋元素循环的作用,评估了气候变化、环境因子对病毒调控细菌代谢的潜在影响,有助于人们对微生物参与的海洋生物地球化学循环的全面认识。     

Stable carbon isotopic compositions of intact polar lipids reveal complex carbon flow patterns among hydrocarbon degrading microbial communities at the Chapopote asphalt volcano

Seepage of asphalt forms the basis of a cold seep system at 3000 m water depth at the Chapopote Knoll in the southern Gulf of Mexico. Anaerobic microbial communities are stimulated in the oil-impregnated sediments as evidenced by the presence of intact polar membrane lipids (IPLs) derived from archaea and Bacteria at depths up to 7 m below the seafloor. Detailed investigation of stable carbon isotope composition (δ¹³C) of alkyl and acyl moieties derived from a range of IPL precursors with distinct polar head groups resolved the complexity of carbon metabolisms and utilization of diverse carbon sources by uncultured microbial communities. In surface sediments most of the polar lipid-derived fatty acids with phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and diphosphatidylglycerol (DPG) head groups could be tentatively assigned to autotrophic sulfate-reducing bacteria, with a relatively small proportion involved in the anaerobic oxidation of methane. Derivatives of phosphatidyl-(N)-methylethanolamine (PME) were abundant and could be predominantly assigned to heterotrophic oil-degrading bacteria. Archaeal IPLs with phosphate-based hydroxyarchaeols and diglycosidic glyceroldibiphytanylglyceroltetraethers (GDGTs) were assigned to methanotrophic archaea of the ANME-2 and ANME-1 cluster, respectively, whereas δ¹³C values of phosphate-based archaeols and mixed phosphate-based and diglycosidic GDGTs point to methanogenic archaea. At a 7 m deep sulfate-methane transition zone that is linked to the upward movement of gas-laden petroleum, a distinct increase in abundance of archaeal IPLs such as phosphate-based hydroxyarchaeols and diglycosidic archaeol and GDGTs is observed; their δ¹³C values are consistent with their origin from both methanotrophic and methanogenic archaea. This study reveals previously hidden, highly complex patterns in the carbon-flow of versatile microbial communities involved in the degradation of heavy oil including hydrocarbon gases that would not have been evident from classical compound-specific isotope analyses of either bulk IPL or apolar lipid derivatives.     

Fossilization and degradation of intact polar lipids in deep subsurface sediments: A theoretical approach

Intact polar membrane lipids (IPLs) are frequently used as markers for living microbial cells in sedimentary environments. The assumption with these studies is that IPLs are rapidly degraded upon cell lysis and therefore IPLs present in sediments are derived from in situ microbial production. We used a theoretical approach to assess whether IPLs in surface sediments can potentially represent fossilized IPLs derived from the upper part of the water column and whether IPLs can be preserved during sediment burial. Previous studies which examined the degradation kinetics of IPLs show that phospholipids, i.e. ester-linked lipids with a phosphor-containing head group, degrade more rapidly than glycosidic ether lipids, i.e. ether-linked lipids with a glycosidically bound sugar moiety. Based on these studies, we calculate that only a minor fraction of phospholipids but a major fraction of glycosidic ether lipids biosynthesized in the upper part of the water column can potentially reach deep-sea surface sediments. Using a simple model and power law kinetic degradation parameters reported in the literature, we also evaluated the degradation of IPLs during sediment burial. Our model predicts a log-log relationship between IPL concentrations and depth, consistent with what has been observed in studies of IPLs in subsurface sediments. Although our results do not exclude production of IPLs in subsurface sediment, they do suggest that IPLs present in the deep biosphere may contain a substantial fossil component potentially masking in situ IPL production.     

Applications of Intact Polar Lipids for Tracing the Marine Microbial Activity and Their Limitations

Intact Polar Lipids (IPLs) are synthesized predominately or uniquely by specific organisms and would degrade rapidly after cell death. Such biomarker IPLs can be used to indicate the microbial distribution and activity in marine environment. Here the progress of the aforementioned studies made over the last decade was reviewed. With the development of chromatography and mass spectrometry, the discovery of new IPLs compounds and the application of stable carbon isotope composition (δ¹³C) of IPLs, our understanding of the composition and transformation of IPLs in suspended particulate matter in the water column and of the applicability of the TEX₈₆ proxy are greatly improved. Besides, IPLs are widely applied in the study of marine eukaryotes-bacteria symbiosis, aerobic and anaerobic ammonia oxidation, anaerobic methane oxidation and microbial metabolic states. Meanwhile, it is suggested by recent studies that different IPLs often exhibit differential degradation. Some IPLs, especially glycolipids, have the potential to be preserved as fossil molecules for very long time upon dead cells, and therefore, they can not specifically indicate living biomass. Furthermore, the IPLs degradation rate and completeness would be affected by such factors as oxygen concentration and organic matter content. It is also suggested that the composition of IPLs might be affected by microbial metabolism. Therefore, it is essential to take these factors into account when IPLs are used as proxies to trace marine microbial activities and reconstruct the palaeoenvironment.     

Factors controlling the distribution of anaerobic methanotrophic communities in marine environments: Evidence from intact polar membrane lipids

Three distinct types of microbial consortia appear to mediate the anaerobic oxidation of methane with sulfate as electron acceptor in marine sediments and are distributed ubiquitously. These consortia consist of ANerobic MEthanotrophic (ANME) archaea of the ANME-1, ANME-2 and ANME-3 clades and their sulfate-reducing bacterial partners either of the Desulfosarcina-Desulfococcus (ANME-1/DSS and ANME-2/DSS) or Desulfobulbus spp. (ANME-3/DBB) branches. Frequently one consortium type dominates the community, but the selective factors are not well constrained. Here we analyzed patterns in the composition of intact polar lipids extracted from bacterial and archaeal communities of different marine seep environments. Further, we investigated if different environmental and geographical factors were responsible for the observed patterns, and hence could be important in the selection of seep communities. Intact polar lipids (IPLs) provide a more robust distinction of the composition of extant communities than their less polar derivatives. In ANME-1/DSS-dominated communities, glycosidic- and phospho-glyceroldialkylglyceroltetraethers were abundant, while ANME-2/DSS and ANME-3/DBB-dominated communities showed abundant archaeol-based IPLs, either with glycosidic and phospho-headgroups or only phospho-headgroups, respectively. The relative proportion of bacterial IPLs varied widely from 0% to 93% and was generally lower in samples of the ANME-1 type, suggesting lower bacterial biomasses in the respective communities. In addition to these lipid signatures, distinctive features were related to the habitat characteristics of these communities: lower amounts of phosphate-based IPLs were generally observed in communities from calcified microbial mats compared to sediments, which may reflect phosphate limitation. Based on statistical analyses of IPLs and environmental data this study constrained for the first time the occurrence of three environmental factors controlling the distribution of different ANME-associated communities in a wide range of hydrocarbon seep systems. Habitats dominated by ANME-1/DSS communities were characterized by high temperature and low oxygen content in bottom waters (or even anoxia), while ANME-2/DSS and ANME-3/DBB-dominated sediments were located in settings with lower temperatures and higher oxygen content in bottom waters. Furthermore, ANME-2/DSS communities were particularly prominent in environments in which a relatively high supply of sulfate was sustained.     

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ¹³C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in ¹³C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate-methane transition zone 6-7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.     

Separation of core and intact polar archaeal tetraether lipids using silica columns: Insights into living and fossil biomass contributions

Intact polar lipids (IPLs) are frequently used as biomarkers for living microbial cells and can be separated from core lipids (i.e. lipids without polar headgroups), which are mainly derived from fossil (i.e. dead) cell material, using column chromatography. We have compared the effect of various silica column conditions on the separation and recovery of archaeal glycerol dialkyl glycerol tetraether (GDGT) core lipids, glycolipids and phosphoglycolipids using authentic standards and direct analysis with various high performance liquid chromatography-mass spectrometry (HPLC-MS) techniques. The commonly used procedure to separate these compound classes using dichloromethane, acetone and methanol as eluents, respectively, did not separate core GDGTs from glyco- and phosphoglyco-GDGTs. In contrast, a recently described procedure using hexane:ethyl acetate (3:1, v:v), ethyl acetate and methanol achieved both high recovery and successful separation of core GDGTs from the other IPLs. Application of the method to a geothermally heated soil and suspended particulate matter from the North Sea showed that it separates most of the core GDGTs from the other IPLS and that considerable qualitative and quantitative differences can occur between core and IPL-GDGTs. We conclude that the method is therefore appropriate for the separation of intact archaeal IPLs and their fossil analogues.     

Structural diversity and fate of intact polar lipids in marine sediments

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.     

Identification and distribution of intact polar branched tetraether lipids in peat and soil

Branched glycerol dialkyl glycerol tetraether lipids (GDGTs) are membrane lipids of soil bacteria that occur ubiquitously in soil, but their occurrence as intact polar lipids (IPLs) has not been well studied. Here, we report the identification and distribution of IPL-branched GDGTs throughout a depth profile of a Swedish peat bog. In addition to two reported glycosidic IPL branched GDGTs, we identified IPL branched GDGTs with a hexose-glycuronic acid, phospho-hexose, or hexose-phosphoglycerol head group, based on mass spectrometry. A selected reaction monitoring (SRM) assay was developed to monitor changes in head group distribution with depth. The abundance of the IPL branched GDGTs increased below the water table, suggesting that they were primarily produced in this part of the peat. This was supported by the concentrations of core lipid and IPL-derived branched GDGTs, which also substantially increased below the water table. However, individual IPL trends differed, which may be due to changes in the microbial community composition with depth or to different degradation rates for the different IPL branched GDGTs. The SRM method was also applied to two different soil types, which showed that similar IPL branched GDGTs as those in peat were present, albeit with different distributions.     

Differential degradation of intact polar and core glycerol dialkyl glycerol tetraether lipids upon post-depositional oxidation

Archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) are used in various proxies, such as TEX₈₆ and the BIT index. In living organism, they contain polar head groups (intact polar lipids – IPLs). IPL GDGTs have also been detected in ancient marine sediments and it is unclear whether or not they are fossil entities or are part of living cells. In order to determine the extent of degradation of IPL GDGTs over geological timescales, we analyzed turbidite deposits, which had been partly reoxidized for several kyr after deposition on the Madeira Abyssal Plain. Analysis of core lipid (CL) and IPL-derived GDGTs showed a reduction in concentration by two orders of magnitude upon post-depositional oxidation, while IPL GDGTs with a mono- or dihexose head group decreased by 2–3 orders of magnitude. The BIT index for CL- and IPL-derived GDGTs increased substantially upon oxidation from 0.1 to up to 0.5. Together with changing MBT/CBT values, this indicates preferential preservation of soil-derived branched GDGTs over marine isoprenoid GDGTs, combined with in situ production of branched GDGTs in the sediment. The TEX₈₆ value for IPL-derived GDGTs decreased by 0.07 upon oxidation, while that of CL GDGTs showed no significant change. Isolation of IPLs revealed that the TEX₈₆ value for monohexose GDGTs was 0.55, while the that for dihexose GDGTs was substantially higher, 0.70. Thus, the decrease in TEX₈₆ for IPL-derived GDGTs was in agreement with the dominance of monohexose GDGTs in the oxidized turbidite, probably caused by a combination of in situ production as well as selective preservation of terrestrial isoprenoid GDGTs. Due to the low amount of IPL GDGTs vs. CL GDGTs, the impact of IPL degradation on CL-based TEX₈₆ paleotemperature estimates was negligible.     

Short chain ladderanes: Oxic biodegradation products of anammox lipids

Anammox, the microbial anaerobic oxidation of ammonium by nitrite to produce dinitrogen gas, has been recognized as a key process in both the marine and freshwater nitrogen cycles, and found to be a major sink for fixed inorganic nitrogen in the oceans. Ladderane lipids are unique anammox bacterial membrane lipids that have been used as biomarkers for anammox bacteria in recent and past environmental settings. However, the fate of ladderane lipids during diagenesis is as of yet unknown. In this study, we performed oxic degradation experiments (at 20-100 °C) with anammox bacterial biomass to simulate early diagenetic processes occurring in the water column and at the sediment-water interface. Abundances of C₁₈ and C₂₀ ladderane lipids decreased with increasing temperatures, testifying to their labile nature. The most abundant products formed were ladderane lipids with a shorter alkyl side chain (C₁₄ and C₁₆ ladderane fatty acids), which was unambiguously established using two-dimensional NMR techniques on an isolated C₁₄-[3]-ladderane fatty acid. The most pronounced production of these short-chain lipids was at 40 °C, suggesting that degradation of ladderane lipids was microbially mediated, likely through a β-oxidation pathway. An HPLC-MS/MS method was developed for the detection of these ladderane alteration products in environmental samples and positively tested on various sediments. This showed that the ladderanes formed during degradation experiments also naturally occur in the marine environment. Thus, short-chain ladderane lipids may complement the original longer-chain ladderane lipids as suitable biomarkers for the detection of anammox processes in past depositional environments.