A new series of steryl chlorin esters: pheophorbide a steryl esters in an oxic surface sediment

Investigation of chlorins in the oxic surface sediment of a small eutrophic alpine lake (Motte lake) revealed the presence of a new series of steryl chlorin esters containing the pheophorbide a nucleus, together with their pyropheophorbide a steryl ester counterparts previously observed in the anoxic surface sediment of the same lake. Identification of the pheophorbide a steryl esters was based on comparison of spectroscopic, chromatographic and mass spectrometric characteristics of the compounds with those of a synthetic standard and of pyropheophorbide a steryl esters. Combined liquid chromatography-mass spectrometry analysis confirmed the absence of pheophorbide a steryl esters in the anoxic sediment but allowed their detection in traces in the water column, indicating that pheophorbide a steryl esters are, like their pyropheophorbide a analogs, formed in the water column. The distribution of sterols released by hydrolysis of the pheophorbide a steryl esters shows close similarities to that of the free sterols in the water column and of the sterols of the pyropheophorbide a steryl esters. It appears that, like their pyropheophorbide a counterparts, pheophorbide a steryl esters incorporate mainly sterols of phytoplanktonic origin. Their formation probably involves the same mechanism as for pyropheophorbide a steryl ester formation, i.e. metabolism by zooplankton grazing on phytoplankton. The presence of pheophorbide a steryl esters in the oxic sediment and their absence from the anoxic sediment is probably due to a lower stability of compounds containing a carbomethoxy substituent in the anoxic environment.     

长江口外赤潮多发区近几十年来的古生产力记录及环境意义

选取长江口外赤潮多发区沉积物柱状样,在高分辨率测年基础上,通过有机碳、有机碳同位素(δ13C)、生物硅、绿素等多项指标的分析获得了调查海区古生产力的变化信息。并结合近几十年来营养盐浓度及组成结构的变化探讨了海洋浮游藻类组成结构的变化在海洋古环境中的记录。柱状样年代可追溯到20世纪40年代初。δ13C值在柱中的分布为-26.15×10-3~-19.5×10-3,表明有机碳为陆源与海生的混合。生物标志物在柱状样中的分布可大致分为三个阶段,50年代以前含量均较低;50年代至80年代含量均增加,表明海洋浮游藻类活动强烈且以硅藻为主,与此阶段长江口营养盐浓度迅速增加相对应;80年代以后,生物硅的含量下降至整个柱中最低水平,绿素有所降低,但高于50年代前的水平,而有机碳含量增加,表明在该时段硅藻生物量降低,其他藻类生物量有所增加,这与长江口营养盐氮盐持续增加而硅酸盐逐年降低、氮与磷的含量比值、磷与硅的含量比值迅速增大有关。沉积记录还表明此阶段陆源有机碳的贡献增强。     

Sedimentary Steryl Chlorin Esters (SCEs) and Other Photosynthetic Pigments as Indicators of Paleolimnological Change Over the Last 28,000 Years from the Buguldeika Saddle of Lake Baikal

Detailed depth profiles of photosynthetic pigments in a sediment core (G-12) collected at the BDP93 site, the Buguldeika saddle, of south Lake Baikal, along with depth profiles of total organic carbon (TOC) and biogenic silica, were studied to elucidate the temporal changes of phytoplankton assemblages in the lake during the past 28 kyr. In addition to the quantification of carotenoids by high-performance liquid chromatography with photodiode-array detection (HPLC-PDA), steryl chlorin esters (SCEs) were analyzed by HPLC-PDA, HPLC-mass spectrometry (LC-MS) and sterols in SCEs by gas chromatography–mass spectrometry (GC–MS) to enrich the taxonomical information on the phytoplankton composition. Allochthonous input of organic matter from the Selenga River resulted in the higher TOC contents in core G-12 than in a previously reported core (G-6) collected at another site from the southern basin. The poorer correlation in core G-12 than in G-6 between TOC and chlorophyll-a-originating pigments, which are indicative of autochthonous production, also indicated a significant allochthonous input at the site. The abundance of lutein among the carotenoids detected, and the good correlation of total chlorophyll a and b shows that green algae represented a significant portion of the phytoplankton, accompanying the diatoms at the G-12 site, after the last glacial period. The presence of cryptomonads and cyanobacteria were confirmed from marker carotenoids in the sediment core. GC–MS analysis of sterols in SCEs detected marker sterols of diatoms, green algae, chrysophytes and dinoflagellates. The depth profiles of the measured indicators gave consistent features for temporal changes in phytoplankton assemblage at the G-12 site of Lake Baikal after the last glacial maximum. Notably, the profile of a chrysophyte-specific sterol in SCEs was consistent with the reported distribution of chrysophyte cysts during the Holocene. The presence of phytoplankton, such as green algae, diatoms and chrysophytes, in Lake Baikal during the late last glacial period was indicated by the analysis of sterols in SCEs. Sedimentary carotenoids and sterols in SCEs were found to give complementary information about phytoplankton composition. These molecular indicators allow us to reconstruct past lake phytoplankton assemblages responding to environmental changes with a time resolution as high as age–depth relationship in sediments attainable at present.     

Variations in paleoproductivity and the environmental implications over the past six decades in the Changjiang Estuary

Total organic carbon and organic carbon stable isotope, biogenic silica, chlorin were measured from a high resolution sediment core to indicate the variation in paleoproductivity and the environmental implications over the past decades (1942 to 1997) in the Changjiang Estuary. Based on these biomarkers, the shift in the phytoplankton community structure in the past decades was discussed in response to the long-term variations in nutrient concentrations and nutrient ratios. The results showed that the δ 13 C values varied from –26.15‰ to –19.5‰, suggesting the combined organic carbon sources of riverine and marine organisms. Based on the biogenic proxies, paleoproductivity changes were categorized into three stages: low production before 1950; an increase in production with the dominance of diatoms during 1950 to 1980, consistent with increasing of nutrient concentrations; a decrease in production after 1980 when the diatom production decreased while the production of non-silicious phytoplankton increased due to high nutrient inputs, and high N/P and P/Si ratios in the Changjiang Estuary. The sedimentation records also indicated that the riverine organic carbon increased since 1980.