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Vulcanodinium is an ecologically relevant dinoflagellate genus due to its production of neurotoxins known as pinnatoxins. We present here the first examination of the sterols of a Vulcanodinium rugosum isolate. Sterols are ringed lipids that assist in maintaining rigidity of cellular membranes, and the Dinophyceae are well-studied for their ability to produce a diverse array of sterols, many of which have chemotaxonomic utility. We have determined that V. rugosum produces a set of major sterols, namely cholesterol, dinosterol, 4α,24-dimethyl-5α-cholest-22E-en-3β-ol, and 4α,24-dimethyl-5α-cholestan-3β-ol, common to the Dinophyceae. However, this displayed marked differences from those studied members of the genera Scrippsiella and Peridinium, the closest phylogenetic relatives. Included in these differences is production by V. rugosum of a much lower percentage of dinostanol, a saturated form of dinosterol.

Phytoplankton productivity and community structure in the East China Sea (ECS) play an important role in marine ecology and carbon cycle, but both have been changing rapidly in response to recent oceanic and atmospheric circulation changes. However, the lack of long-term records of phytoplankton productivity and community structure variability in the region hinders our understanding of natural forcing mechanisms. Here, we use the phytoplankton biomarker (brassicasterol, dinosterol and alkenones) contents as well as the ratios between these biomarkers in three sediment cores from the ECS shelf to reconstruct the spatiotemporal variations of productivity and community of diatoms, dinoflagellates and coccolithophores during the Holocene, respectively. During 9–7 ka, the ECS shelf was characterized by low phytoplankton productivity with low coccolithophore contribution, caused by the oligotrophic condition mainly owing to the restricted Kuroshio Current (KC) intrusion under low sea-level conditions, thus the lack of nutrient input. Phytoplankton productivity generally increased during 7–4.6 ka, in response to the initial intrusion of the Yellow Sea Warm Current (YSWC, a branch of the KC), bringing nutrient from the subsurface KC to the upper layer of the ECS for phytoplankton growth. Phytoplankton productivity continuously increased during 4.6–1 ka, due to an enhanced circulation system (YSWC and Yellow Sea Coastal Current (YSCC)) driven by strong East Asia Winter Monsoon (EAWM). Significantly, high alkenone contents and coccolithophore contribution in the eastern core F11A was associated with its location closer to the warm and saline YSWC, which was suitable for coccolithophore growth. Beyond diagenetic processes which could partly account for higher biomarker contents near core tops, elevated phytoplankton productivity during the last 1 ka might be induced by more nutrient supply from the intensified circulation system driven by enhanced KC and anthropogenic activities. The latter also resulted in high dinoflagellate proportions in all three cores. These temporal and spatial changes of phytoplankton productivity and community structure in the ECS during the Holocene corresponded to different mechanisms by the air-sea interaction, providing insights into distinguishing natural forcing and anthropogenic influences on marine ecology.

The ocean’s biological pump strongly influences atmospheric CO2 and regulates Earth’s climate. Determining the contribution of different phytoplankton groups to the biological pump over geological timescales remains an important, yet elusive, goal in biogeochemistry and organic geochemistry. Towards that end, source-specific lipid biomarkers can be used, but this approach requires the quantification of the biomarker-to-carbon ratio in different phytoplankton species, and under differing environmental conditions. We investigated responses of brassicasterol, dinosterol and C37 alkenones to three temperatures (15, 20 and 25 °C) and three N:P supply ratios (10:1, 24:1 and 63:1 mol mol−1) in three diatoms, three dinoflagellates and one coccolithophore, in laboratory experiments. Brassicasterol was produced by one diatom species, three dinoflagellates and the coccolithophore Emiliania huxleyi, while dinosterol and C37 alkenones were produced by dinoflagellates and E. huxleyi, respectively. Overall, carbon-normalized contents of lipid biomarkers varied by about a factor of three over the wide ranges of temperature and N:P supply ratios, in all species. Within the factor of three, brassicasterol was highest under the balanced N:P condition in diatoms, but under N and P deficiency in dinoflagellates. Brassicasterol in E. huxleyi was highest at lower temperatures. Dinosterol in dinoflagellates and C37 alkenones in E. huxleyi varied with temperature and N:P supply ratios, but not systematically. Compared to those in our experiments, smaller ranges are expected of N:P ratios and temperature and hence carbon-normalized biomarker contents at individual locations over time. Thus, our results imply that lipid biomarkers can be used to estimate taxon-specific carbon fluxes through time.

During the past hundred years, the majority of lakes along the middle and lower reaches of the Yangtze River (MLRYZ) have been greatly impacted by human intervention, resulting in a significant spatial heterogeneity in water and ecosystem quality. We quantified the fatty acid (FA), n-alkanol, sterol and long-chain alkyl diol content of surface sediments of MLRYZ lakes in order to determine how ecological differences (algae versus macrophyte-dominated state) and trophic status influence the composition, origin and abundance of lipid biomarkers in the sediments. Based on the results, variation in FAs appears to be mainly controlled by the type of organisms within the lakes. Short-chain n-alkanoic acids, monounsaturated FAs (MUFAs) and polyunsaturated FAs (PUFAs) were generally more abundant in sediments of algal lakes (lacking macrophyte growth) than in lakes with macrophyte growth. The opposite trend was apparent for long-chain n-alkanoic acids. Ratios of (C26 + C28)/(C22 + C24) n-alkanoic acids differed significantly between macrophyte and algal lakes. In the alcohol fraction, lipid biomarker abundance appeared to be controlled by trophic status of the lake, with the exception of cholesterol and long-chain n-alkanols whose abundances were closely related to the present organisms and exhibiting greater abundances in algal lakes. Enhanced levels of total phosphorus (TP) and total nitrogen (TN) in a lake create greater concentrations of C32 1,15 alkyl diol and brassicasterol respectively, while the abundance of dinosterol and the ratio of dinosterol/brassicasterol decline in line with increase in TP and TN, respectively. Ratios of (C26 + C28)/(C22 + C24) n-alkanol were also greatly influenced by the type of organisms present, exhibiting higher values in algal lakes. The sensitivity of these sediment lipid biomarker responses points to a potentially useful role as proxies for biological community types and trophic status in paleolimnology studies.

The hydrogen isotope ratio (2H/1H) of microalgal lipids has become a useful tool for reconstructing hydrologic conditions in the geologic past from marine and lacustrine sediments. Culture studies have shown that, in addition to the 2H/1H ratio of growth water, parameters such as salinity, growth rate, and irradiance, can have a large effect on lipid 2H/1H ratios. But aside from salinity, these effects have not been well studied in the field. In this work, hydrogen isotope fractionation relative to growth water was measured in four algal lipids - C37:3 and C37:2 methyl alkenones, (3β,4α,5α,22E)-4,23-Dimethylergost-22-en-3-ol (dinosterol), and 24-methylcholesta-5,22E-dien-3β-ol (brassicasterol) – in the upper water column of two North Pacific Ocean locations. By comparing lipid 2H/1H variations as a function of depth at tropical Station ALOHA (22°45′N, 158°00′W) and mid-latitude Gyre (41°30′N, 132°00′W in the Transition Zone) it was possible to evaluate the H isotope effects of nutrient limitation and irradiance on natural phytoplankton populations by comparing measured fractionation factors (αlipid) with those derived from laboratory-based empirical relationships. Significant distinctions were observed between the inferred causes of H isotope fractionation in different algal lipids at the two locations. At Station Aloha, 2H/1H fractionation in coccolithophorid-derived alkenones was primarily caused by nutrient-limited growth, while at Gyre it was caused by light limitation. Distinctions were less clear for the two sterols. 2H/1H fractionation in dinosterol was possibly influenced by nutrient-limited growth or light limitation at greater depths at both stations, while 2H/1H fractionation in brassicasterol matched values expected for nutrient-limited growth at both locations. Although systematic trends with depth in αlipid on the order of 10–30‰ were observed for each lipid, inter-day variability was some 3–7‰ depending on the lipid and site, and the magnitude of αlipid changes observed in the field were much less than those expected based on culture studies. This implies that the effects of nutrient and light limitation on natural phytoplankton populations in the ocean may not have a large influence on hydroclimate reconstructions based on 2H/1H ratios of microalgal lipids in marine sediments.

The South Pacific Convergence Zone (SPCZ) is the largest precipitation feature in the Southern Hemisphere supplying freshwater to 11 million people. Despite its significance, little is known about the location and intensity of SPCZ precipitation prior to instrumental records, hindering attempts to predict precipitation changes in a warming world. Here we use sedimentary molecular fossils to establish a tool for extending the historical record of precipitation. Freshwater lake sediments and water samples were collected from 30 lakes that span a 4.6 mm d−1 range in precipitation rates from the Global Precipitation Climatology Project (GPCP). 2Hlakewater values from 29 lakes ranged from –29 to +23‰ and were inversely correlated (r= −0.51, R2=0.26, p

The sedimentary environment and ecological system in the South Yellow Sea (SYS) changed dramatically due to sea level change caused by glacial-interglacial cycles. The authors report the use of marine biomarkers (brassicasterol, dinosterol and C37 alkenones) and terrigenous biomarkers (C28+C30+C32 n-alkanols) in core DLC70-3 from the SYS to reconstruct the variation in the phytoplankton productivity and community structure and possible mechanisms during the middle Pleistocene. The results show that the primary productivity and that of single algae presented a consistent trend for the whole core during the middle Pleistocene, which was high during interglacial periods and low during glacial periods, with the highest being in marine isotope stage (MIS) 5–9 and MIS 19–21. The main reason is that the Yellow Sea Warm Current (YSWC) carried much of high temperature, high salinity water into the SYS, causing upwelling and vertical mixing and stirring, which increased the nutrient supply in the photosynthetic layer. The phytoplankton community structure mainly showed an increase in the relative content of haptophytes in MIS 5–9 and MIS 19–21, while the relative content of diatoms and dinoflagellates decreased; there was no evidence for a haptophyte content in other stages. The results reveal a shift from a coccolitho-phorid-dominated community during MIS 5 –9 and MIS 19 –21 to a diatom-dominated community during the other stages, mainly as a result of surface salinity variation, attributed to the invasion of the YSWC during high sea level periods.

Some dinoflagellates, such as Symbiodinium, are able to form symbiotic relationships with larger marine organisms. An important aspect of dinoflagellate symbiosis involves the exchange of lipids, namely sterols, from the symbiont to the host. Much research has explored the lipid biochemistry of the symbiotic relationship between cnidarians and Symbiodinium dinoflagellates. However, no research has addressed the sterol biochemistry of the symbiosis between radiolarians and dinoflagellates such as Zooxanthella nutricula. To this end, we have provided the first sterol characterization of Z. nutricula isolated from a spumellarian polycystine radiolarian. Fifteen sterols and one steroidal ketone were observed where the major sterol identified was C27 22-dehydrocholesterol, which does not tend to be a dominant sterol among dinoflagellates, including closely related peridinioid species in the genus Heterocapsa. However, C30 dinosterol and dinostanol were major sterols in both Z. nutricula and Heterocapsa spp., thus indicating common sterols between closely related taxa. Major sterols of the distantly related genus Symbiodinium, a symbiont of foraminifera and cnidarians, have included C27 cholesterol and C30 gorgosterol, whereas in Z. nutricula these sterols were minor and absent, respectively. Our results indicate potentially different sterol pools available to cnidarian and radiolarian symbiont hosts during their respective relationships with symbiotic dinoflagellates.

Pyrodinium bahamense is a dinoflagellate of concern in subtropical and tropical coastal environments. To date, there is only a single published study on its fatty acids, but no published data on its sterol composition. Sterols, which are membrane-reinforcing lipids in eukaryotes, display a great diversity of structures in dinoflagellates, with some serving as chemotaxonomic markers. We have examined the sterol compositions of two isolates of P. bahamense from Indian River Lagoon and Tampa Bay, Florida, and have found both to produce three sterols: cholesterol, dinosterol, and 4α-methylgorgostanol. All three sterols are found in closely related, armored taxa.

Long chain alkyl diols have shown important potential for the reconstruction of sea surface temperature, productivities and upwelling conditions in marine or lacustrine environments. However, little is known about the distribution and sources of the diols in eastern China marginal seas (CMS), which are areas of important organic carbon sink. Here the contents of C30 and C32 1,15-diols were analyzed in 181 surface sediments from eastern CMS. The similar distribution pattern and strong linear correlation between C30 and C32 diols indicated that they had similar biological source, with a dominance of C30 diol. Their contents ranged from 7–2726 ng g−1 for C30 diol and 5–669 ng g−1 for C32 diol, and both showed higher values mainly in the mud area of the Yellow Sea, while the TOC normalized contents showed a more obvious seaward increasing trend. The similar distribution pattern and significant positive correlation between diols and the other marine biomarkers (brassicasterol, dinosterol, C37 alkenones) indicated C30 and C32 diols in eastern CMS were mainly from marine algae. This conclusion was also supported by principal component analysis (PCA). Our results also showed that sediment diol contents were generally related to marine productivity, suggesting that diols could be applied for marine productivity reconstruction in eastern CMS.

Sterols are widely distributed in nature from lipids in organisms to sediments. As a conventional method, extraction and derivatization with TMS have been applied for sterol analysis, requiring a long preparation time for gas chromatography&ndash, mass spectrometry analysis. In this study, for sterol analysis, thermochemolysis using tetramethylammonium hydroxide (TMAH) was applied. This method performs hydrolysis and methylation simultaneously, thus, free and ether-bonding sterols can be analyzed as sterol methyl ethers in a relatively short time period. A sediment sample from a tideland (the Yatsu tideland, Japan) was analyzed using the TMAH method, and we detected more than 10 sterols, which include cholest-5-en-3&beta, ol (cholesterol), 24-ethylcholest-5-en-3&beta, ol (sitosterol), 24-methylcholesta-5,22E-3&beta, ol (brassicasterol), 24-ethylcholesta-5,24(28)Z-dien-3&beta, ol (isofucosterol), 4&alpha, 23,24-trimethyl-5&alpha, (H)-cholest-22E-en-3&beta, ol (dinosterol), and 5&beta, (H)-cholestan-3&beta, ol (coprostanol). The detection of the various sterols can be attributed to multiple natural and artificial sources around the Yatsu tideland. In this paper, the mass spectra of these sterols are provided together with an interpretation of their fragmentation patterns. Additionally, the fecal pollution in the Yatsu tideland is discussed in the context of the detection of coprostanol.

Past sea ice conditions and open water phytoplankton production were reconstructed from a sediment core taken in Disko Bugt, West Greenland, using the sea ice biomarker IP25 and other specific phytoplankton biomarker (i.e., brassicasterol, dinosterol, HBI III) records. Our biomarker record indicates that Disko Bugt experienced a gradual expansion of seasonal sea ice during the last 2.2 kyr. Maximum sea ice extent was reached during the Little Ice Age around 0.2 kyr BP. Superimposed on this longer term trend, we find short-term oscillations in open water primary production and terrigenous input, which may be related to the Atlantic Multidecadal Oscillation and solar activity changes as potential climatic trigger mechanisms. A direct sample-to-sample multiproxy comparison of our new biomarker record with microfossil (i.e., benthic foraminifera, dinocysts, and diatoms) and other geochemical records (i.e., alkenone biomarkers) indicates that different proxies are influenced by the complex environmental system with pronounced seasonal changes and strong oceanographic gradients, e.g., freshwater inflow from the Greenland Ice Sheet. Differences in sea ice reconstructions may indicate that the IP25 record reflects only the relatively short sea ice season (spring), whereas other microfossil reconstructions may reflect a longer (spring–autumn) interval.

The extractable lipids and bulk organic geochemical parameters in three sediment cores (M-1, M-3 and M-7) from southern, central and northern Bohai Sea were analyzed in order to reconstruct environmental changes since 1900. The C/N ratio and multiple biomarkers (e.g., C27 + C29 + C31 n-alkanes, C24 + C26 + C28 n-alkanols, branched versus isoprenoid tetraether index) suggest more terrigenous organic carbon (OC) inputs in southern Bohai Sea. The abrupt changes of biomarker indicators in core M-1 are generally synchronous with the Yellow River mouth relocation events (e.g., 1964, 1976 and 1996), suggesting the distance to the river mouth being an important factor for sedimentary OC dispersal in the southern Bohai Sea. However, in cores M-3 and M-7, terrigenous biomarkers (i.e., BIT) show a long-term declining trend, consistent with a continuous reduction of the Yellow River sediment load, whereas marine biomarkers such as cholesterol, brassicasterol and dinosterol dramatically increased post-1980, apparently related to human-induced eutrophication in the Bohai Sea. Our study suggests different controlling factors on sedimentary OC distribution in the southern (high turbidity) and other parts (less turbidity) of the Bohai Sea, which should be considered for interpretation of paleoenvironments and biogeochemical processes in the river dominated margins that are hotspots of the global carbon cycling.

Little is known about temporal changes in sedimentary organic matter (OM) in the East China Sea (ECS) due to the lack of continuous high-resolution records. In this study, we used a multi-proxy approach to reconstruct sedimentary OM variations over the past 100years from three sediment cores collected from the coastal areas of the ECS. For the three cores, total organic carbon (TOC) normalized concentrations of phytoplankton biomarkers (brassicasterol+dinosterol+alkenones) and a marine archaea biomarker (crenarchaeol) showed gradual increases over the past 100years with a greater increase after the 1980s. These increases are attributed to eutrophic conditions caused by monsoonal variation and intensified human activities in the Yangtze River Basin (YRB) over the past century. Conversely, TOC-normalized concentrations of higher plant biomarker long-chain n-alkanes (∑(C27+C29+C31n-alkanes)) showed no obvious trend over the past 100years. The δ13C values of TOC (δ13CTOC), the terrestrial and marine biomarker ratio (TMBR) index, and the branched and isoprenoid tetraether (BIT) index for the three cores record a gradual decrease in the contribution of terrestrial organic matter (TOM) since the 1960s. This decrease is likely linked to enhanced dam construction in the YRB from the 1960s onwards, leading to a reduction in TOM input to the ECS. A three end-member mixing model based on δ13CTOC values and the TMBR index was used to further divide sedimentary OM into three factions: marine organic matter (MOM), plant OM, and soil OM. The MOM contribution gradually increased over the past 100years, while the contribution of soil OM gradually decreased over the past 100years with a significant decline during the past 50years. This trend can also be related to intensify dam construction in the middle and upper reaches of the YR since the 1960s.

The Southern Yellow Sea (SYS) is an important reservoir of anthropogenic organic contaminants, such as polybrominated diphenyl ethers (PBDEs). To reconstruct the historical records of PBDEs and examine their relationships with the human activities and organic matters, a210Pb-dated sediment core was collected from the central mud area in the SYS. The concentrations of tri-to hepta-BDEs (∑7PBDEs) and BDE-209 ranged from 9.8 to 99.8 pg g-1 d.w. and from 12.1 to 855.4 pg g-1 d.w., respectively, both displaying the increasing trends from the bottom to the surface. More importantly, there was a faster increase for PBDEs since the 1990s, especially for BDE-209, which responded well with the rapid economic growth, and the increases of urbanization and industrialization in the local areas of the SYS. The analogously vertical patterns and significant relationships between PBDEs and total organic carbon (TOC) implied the TOC-dependent deposition of PBDEs in the core. Furthermore, multiple biomarker-based proxies of terrestrial organic matter (TOM) and marine organic matter (MOM) were introduced to systematically investigate the different effects of TOM and MOM on PBDE deposition in the SYS. The similarly down-core profiles and significant correlations were found between PBDEs and the MOM proxies (sum of rassicasterol, dinosterol and C37 alkenones (∑A + B + D) and marine TOC) as well as the branched and isoprenoid tetraether (BIT), but not for TOM proxies (∑C27+C29+C31n-alkanes, terrestrial and marine biomarker ratio (TMBR) and terrestrial TOC), indicating that MOM was an important factor driving PBDE deposition in the sediment core from the SYS.

To identify the sedimentary organic matter (OM) sources and reconstruct primary productivity evolution process in the coastal areas of the East China Sea (ECS), carbon, nitrogen and carbon stable isotope (δ13C) combined with sterols were studied in the surface and core sediments. The quantitative calculations of δ13C model and characteristic sterols suggested that the OM is derived from mixed marine and terrestrial inputs. Sinking marine phytoplankton was the dominant marine OM (MOM) source, with the average MOM proportion calculated by two end-member model of δ13C and characteristic sterol analysis of 73% and 62%, respectively. Terrestrial organic matter (TOM) displayed a decreasing trend seaward, attributed to the Changjiang River input as the dominant terrestrial source pathway. The decreased proportion of TOM with age in the core sediment was mainly controlled by the fluctuating changes of freshwater and sediment influxes of the Changjiang River. The sum content of epi-brassicasterol and dinosterol increased with age in recent 30 years, suggesting the increasing phytoplankton productivity. Enhanced anthropogenic nutrient inputs from the Changjiang River as well as the incremental nutrient supplement from the deep waters of the coastal upwelling area aggravated the phytoplankton blooms. Besides, the increasing ratio of epi-brassicasterol to dinosterol contents (B/D ratio) with age revealed the increasing diatom productivity relative to dinoflagellate productivity. This variation was mostly attributed to the natural forcing of the increased nutrient supplement from intensified coastal upwelling in the Zhejiang coastal mud area.

Hydrogen isotope ratios (2H/1H or δ2H) were measured in lipid biomarkers from algal, plant and microbial sources in sediment cores from a lake and a peat bog on the small, sparsely-inhabited Washington Island (4°43′N, 160°25′W) to assess central equatorial Pacific hydroclimate conditions during the last millennium. High δ2H values in lipids from a variety of biological sources indicate that the driest period of the last millennium occurred ∼1450–1600 CE, during the first half of the Little Ice Age (LIA; 1450–1850 CE). An Intertropical Convergence Zone (ITCZ) located south of its modern position, less frequent and/or weaker El Nino events, and/or a La Nina-like mean state in the tropical Pacific are potential causes for this drying at Washington Island. From ∼1600 to 1650 CE, an abrupt transition to modern-like low δ2H values in phytoplankton, plant, and microbial lipids occurred, signaling the establishment of a high-rainfall regime similar to that observed today. This transition coincided with increased ENSO variability, an excess of central-Pacific relative to eastern-Pacific El Ninos, and a decline in the zonal SST gradient across the tropical Pacific, reflecting an El Nino-like mean state. The Medieval Warm Period (MWP; 900–1250 CE) was characterized by high δ2H values in lipids from phytoplankton (dinosterol, dinostanol), bacteria (hop-21-ene), and vascular plants (sitostanol), and by extension a drier climate relative to the modern lake. An increasing δ2H trend through the MWP in lipids from all sources implies drying as Northern Hemisphere temperatures declined from the early to the late MWP. This drying is hypothesized to have been driven by extensive volcanism in northern, southern, and tropical latitudes, all of which tend to cause zonal mean drying at the latitude of WI (5°N). Finally, the transition period between the LIA and MWP ∼1250–1450 CE was characterized by declining δ2H values of plant and microbial lipids in peat sediments, indicating a trend toward wetter conditions; in the absence of known internal or external climate forcings, this may have been a regional or local event. This study demonstrates that the application of compound-specific δ2H measurements of lipids from multiple biological sources and in multiple sedimentary archives from a single location can yield hydroclimate reconstructions with higher confidence than those based on single lipids. Such reconstructions are particularly important in the vast tropical Pacific, where few hydroclimate records exist.

Multi-biomarker indexes were analyzed for two piston cores from potential cold seep areas of the South China Sea off southwestern Taiwan. Total organic carbon (TOC) normalized terrestrial (n-alkanes) and marine (brassicasterol, dinosterol, alkenones and iso-GDGTs) biomarker contents and ratios (TMBR, 1/P mar-aq, BIT) were used to evaluate the contributions of terrestrial and marine organic matter (TOM and MOM respectively) to the sedimentary organic matter, indicating that MOM dominated the organic sources in Core MD052911 and the sedimentary organic matter in Core ORI-860-22 was mainly derived from terrestrial inputs, and different morphologies were the likely reason for TOM percentage differences. BIT results suggested that river-transported terrestrial soil organic matter was not a major source of TOM of sedimentary organic matter around these settings. Diagnostic biomarkers for methane-oxidizing archaea (MOA) were only detected in one sample at 172 cm depth of Core ORI-860-22, with abnormally high iso-GDGTs content and Methane Index (MI) value (0.94). These results indicated high anaerobic oxidation of methane (AOM) activities at or around 172 cm in Core ORI-860-22. However in Core MD052911, MOA biomarkers were not detected and MI values were lower (0.19–0.38), indicated insignificant contributions of iso-GDGTs from methanotrophic archaea and the absence of significant AOM activities. Biomarker results thus indicated that the discontinuous upward methane seepage and insufficient methane flux could not induce high AOM activities in our sampling sites. In addition, the different patterns of TEX86 and Uk′ 37 temperature in two cores suggested that AOM activities affected TEX86 temperature estimates with lower values in Core ORI-860-22, but not significantly on TEX86 temperature estimates in Core MD052911.

The effect of iron (Fe) fertilization on biological productivity and community structure in the equatorial Pacific, a region with high nutrient and low chlorophyll concentrations, has been debated for many years. Here we present lipid biomarker and geochemical proxy records in a sediment core from the central equatorial Pacific spanning from 1100 to 600 ka to investigate the response of marine phytoplankton communities to eolian Fe supply and to assess links to environmental fluctuations during the Pleistocene. We found a strong link between change in eolian Fe input and phytoplankton community structure. Our data demonstrate that an increase in eolian Fe supply across the 800 ka boundary resulted in a shift in the major primary producer from coccolithophores (alkenones) to diatoms (epi-brassicasterol) and dinoflagellates (dinosterol) at the study site. This strong link between changes in eolian Fe supply and the community structure of plankton during 800–600 ka may have been associated with a change in atmospheric and ocean conditions due to southward migration of the Intertropical Convergence Zone (ITCZ). The lipid biomarker results show that such a high supply of eolian Fe might have led to a change in the dominant phytoplankton group. However, the opal record, which is often used as a primary productivity indicator, was not consistent with the biomarker results. Therefore, the results indicate that multi-proxy approaches should be used in paleoenvironmental studies because different proxies can reveal different aspects of environmental conditions, thus contributing to a better understanding of paleoceanographic conditions.

The burial of sedimentary organic matter (SOM) in large river-influenced estuarine-coastal regions is affected by hydrodynamic sorting, diagenesis and human activities. Typically, the inner shelf region of the East China Sea is a major carbon sink for the Yangtze River-derived fine-grained sediments. Most of the previous work concentrated on studies of surface sediments or used a single-proxy in this region. In this study, two cores from the Zhejiang-Fujian Coast were analyzed using bulk (TOC, TN and δ 13 C TOC ) and molecular biomarker ( n -alkane, brassicasterol, dinosterol and glycerol dialkyl glycerol tetraether lipids) techniques to clarify the sources, spatiotemporal distribution and fate of SOM in the Yangtze River Estuary and adjacent shelf. Results indicated that the effects of diagenesis and diffusion on different sedimentary biomarkers resulted in overestimation of the relative contribution of terrestrial organic matter (%OM terr ), compared with those based on δ 13 C TOC . The amount of terrestrial plant organic matter (OM plant ) and %OM terr in sediments decreased offshore. In contrast, the amount of marine organic matter (OM marine ) increased offshore, but closer to the Yangtze River mouth, the amount of soil organic matter (OM soil ) increased. Moreover, the amounts of TOC, OM plant and OM marine biomarkers increased, but OM soil and %OM terr decreased over time in recent decades. Our study suggests that spatial OM distribution patterns in marine shelf sediments were controlled primarily by hydrodynamic sorting and nutrient concentration, and temporally diverse patterns were controlled predominantly by anthropogenic influence (e.g. dam construction and soil conservation, reclamation and agricultural plantations, anthropogenic nutrient input, dust storms, eutrophication, etc.) and climate events (e.g. interdecadal climatic jump and heavy rain events) in the geological period.

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of p CO 2 based on studies indicating a CO 2 -dependence of photosynthetic carbon isotope fractionation (e P ). It recently was proposed that the δ 13 C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for p CO 2 . However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate e P as a function of CO 2 concentration and growth rate in the dinoflagellate Alexandrium tamarense . Experiments were conducted in nitrate-limited chemostat cultures. Values of e P were measured on cells having growth rates (μ) of 0.14–0.35 d −1 and aqueous carbon dioxide concentrations of 10.2–63 μmol kg −1 and were found to correlate linearly with μ/[CO 2(aq) ] ( r 2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (e f ) value of 27‰ was characterized from the intercept of the experiments, representing the first value of e f determined for an algal species employing Form II RubisCO—a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ e f values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO 2 -dependence of e P values in our experiments strengthens the proposal to use dinocyst δ 13 C values as a p CO 2 proxy. Moreover, the similarity between the e f value for A. tamarense and the consensus value of ∼25‰ indicates that the CO 2 -sensitivity of carbon isotope fractionation saturates at similar CO 2 levels across all three ecologically prominent clades of eukaryotic phytoplankton. This continuity of e f across taxa may help to explain why there is no coherent signature of phytoplankton evolutionary succession in Phanerozoic carbon isotope records.

A variety of biomarkers were examined from Ocean Drilling Program Core 1202B to reconstruct temperature and phytoplankton community structures in the southern Okinawa Trough since 20 ka. Two molecular temperature proxies ( $${\rm U}_{{37}}^{{{\rm K}\prime}} $$ and TEX86) show 5°C to ~6°C warming during the glacial-interglacial transition. Prior to the Holocene, the $${\rm U}_{{37}}^{{{\rm K}\prime}} $$ -derived temperature was generally 1°C to 4°C higher than TEX86-derived temperature. This difference, however, was reduced to °C in the Holocene. Correspondingly, the phytoplankton biomarkers (e.g., C37:2 alkenone, brassicasterol, C30 1,15 diol, and dinosterol) indicate a shift of planktonic community structures, with coccolithophorids becoming more abundant in the Holocene at the expense of diatoms/dinoflagellates. This shift is related to the variability of nutrients, temperature, and salinity in the Okinawa Trough, likely controlled by the sea level and the intensity of the Kuroshio Current. The phytoplankton community change may have had profound implications for atmospheric CO2 fluctuations during glacial-interglacial cycles since diatoms and dinoflagellates have a higher efficiency of the biological pump than coccolithophorids.

Understanding early organic matter alteration and preservation in marine carbonate-evaporite systems could improve understanding of carbon cycling and hydrocarbon source rock prediction in such environments. It is possible that organic-rich microbial mats are important contributors to preserved hydrocarbons, and to explore this we examined changes in lipid composition in such a mat from a mesohaline intertidal lagoon, eastern Qatar. The mat reaches > 5 cm thickness over a carbonate mud substrate, rich in seagrass, gastropods and other small bioclasts. Clear lamination, with distinct downward colour changes from green to pink to brown, reflects different microbial mat communities. The layers contain spheroids of probable dolomite, the precipitation of which was plausibly bacterially-mediated. Lipids [n-alkanes, fatty acids (FAs), hopanoids, isoprenoid hydrocarbons, dialkyl glycerol diethers (DAGEs), and isoprenoid (0 to 4) and branched (Ia to IIIa) GDGTs] reflect the diverse mat-building phototrophic, heterotrophic and chemoorganotrophic microorganisms, as well as some likely allochthonous material (i.e. steroids, n-alkanols, high molecular weight n-alkanes). The lipids clearly document the change in microbial community, with phytene being the predominant hydrocarbon in the phototrophic surface layer. Oxygen and pH drop significantly 0.2 cm below the mat surface, coincident with the predominance of Deltaproteobacteria and increased concentrations of archaeal and bacterial glycerol dialkyl glycerol tetraether lipids andC15/C16 and C16/C17 dialkyl glycerol ether lipids in the deeper layers. Archaeol, likely of methanogen origin, is most abundant in the deepest layer. Allochthonous inputs occur throughout the mat, including abundant steroids, especially dinosterol and dinostanol, that are possibly related to periodic algal (dinoflagellate) blooms in the Arabian Gulf. Both n-alkanes and n-alkanols appear to be derived from seagrass. Organic matter contents decrease in the deepest mat; this suggests an overall low preservation potential of OM in intertidal mesohaline-hypersaline mats of the Arabian Gulf, which in turn suggests that these are not the major source of hydrocarbons in microbially-dominated carbonate-evaporite systems.

A variety of biomarkers of sediment core KET-1 were studied to reconstruct both paleoproductivity and phytoplankton community structure variations and to reflect the local climate change of Kuroshio mainstream of east Taiwan over the past millennium. The results showed that sterols in sediments derived from the mixed terrestrial and marine inputs, with the riverine input from eastern Taiwan as the main terrestrial sterol source. The upward increase of terrestrial organic matter over the past millennium suggested the increasing riverine input of eastern Taiwan. The variation of the marine primary productivity was mainly influenced by the nutrient supplements from the riverine input. The changes of brassicasterol to dinosterol ratio indicated a phytoplankton community shift from dinoflagellate-dominated to diatom-dominated since 1500 CE. The increasing terrestrial inputs and the change of phytoplankton community change over time were related to “dry-humid” climate change.

In this study, organic geochemical analyses of two sediment cores (BL16 and LV63–23) recovered from the western Bering Sea were carried out to examine the sea-ice variability and its relationship to phytoplankton community evolution over the past century. Bulk stable organic carbon isotopic composition (δ13CTOC) showed pronounced depletion on the northern shelf since the late 1970s, indicating greater terrigenous organic matter (OM) under warming during recent decades. Variation in sedimentary OM in the southward core was closely associated with marine primary productivity and regional deposition processes. Arctic sea-ice proxy IP25 throughout the two cores with different temporal profile patterns demonstrated sea-ice presence with the spatio-temporal variability across the study area over the past century. The phytoplankton marker-IP25 index (PIP25), a proxy for estimating semi-quantitatively sea-ice concentrations, reflected a decreased sea-ice cover with more distinct interannual fluctuations between 0.7 and 0.2 (especially in core BL16) after the late 1970s, coinciding with the recent warming scenario. Increased concentrations of phytoplankton biomarkers (brassicasterol and dinosterol) and their ratios as well as the PIP25 record in core BL16 indicated a synchronous variability of reduced sea-ice cover with the enhancement of phytoplankton productivity since the late 1970s. These results suggested a coupled interaction of the sea-ice condition and planktonic ecosystem in the north Bering shelf. Our results also revealed recent (since the 2000s) spatial heterogeneity in sea-ice coverage between the northern and southern parts of the Bering Sea.

Modern seasonal and inter-annual precipitation variability in Palau is linked to both meridional movement of the Intertropical Convergence Zone (ITCZ) and changes in the Pacific Walker Circulation (PWC) associated with the El Nino–Southern Oscillation. Thus, Palau’s hydroclimate should be sensitive to mean shifts in the ITCZ and PWC on decadal to centennial time scales. Using compound-specific hydrogen isotope ratios (δ2H) of dinosterol in lake sediments, we generated a decadal-resolution proxy record of hydroclimatic variability in Palau spanning the past 800 yr. Results indicate a drying trend during the Little Ice Age in Palau, consistent with a southward displacement of the ITCZ. In addition to the secular drying trend, there are persistent large (∼20‰) multi-decadal to centennial oscillations in the δ2H record, the most recent of which indicates an abrupt shift to drier conditions in the mid-1970s that coincides with a decadal-scale negative shift in the Southern Oscillation Index.

Human activity-induced eutrophication and harmful algal blooms are main causes of the expansion of the hypoxic zone in the Changjiang Estuary. Among the many changes in biogeochemical processes, anaerobic ammonium oxidation (anammox) is proposed to play an important role in the nitrogen cycle in hypoxic areas. Ladderane lipids have been used as biomarkers to indicate anammox activity in ecosystems, but the origins of anammox bacteria and ladderanes in suspended particulates are still unclear. In this study, we report the results of a suite of biomarker analyses of suspended particulates across a salinity gradient of the Changjiang Estuary in both the spring and summer to evaluate the origins of the ladderanes and their potential as proxies for anammox activity and hypoxia. The spatio-temporal variations in terrestrial biomarkers ( n -alkanes and n -alkanols), marine biomarkers (brassicasterol and dinosterol), and the Terrestrial and Marine Biomarker Ratio and Branched and Isoprenoid Tetraether indices reveal that marine organic matter was dominant in the particulates in both the spring (55%) and summer (86%) seasons. Correlations with both marine and terrestrial biomarkers suggest that ladderanes were mainly produced in the water column, and therefore that ladderane concentrations in suspended particulates in the Changjiang Estuary mainly reflect anammox activity in the water column, although changes in anammox bacterial assemblages may also have played a role in ladderane concentrations. Overall, ladderane results suggest that anammox activity was widespread in the Changjiang Estuary; but higher ladderane concentrations in the summer (especially in the upwelling zone) were correlated with lower dissolved oxygen concentrations, which suggest that they are useful proxies for hypoxia.

We present lipid biomarker records of two cores (ZY1 and ZY3) from the central South Yellow Sea mud area to investigate the changes in sources and transport processes of the sedimentary organic matter (OM) throughout the Holocene. Based on the analysis of marine biomarker content ( S PB (Phytoplankton Biomarker, total content of brassicasterol, dinosterol and C37-alkenones) and crenarchaeol), and terrestrial biomarkers ( S n -alkanols and brGDGTs) as well as TMBR′ and BIT index values, the marine organic matter (MOM) and terrestrial organic matter (TOM) deposition history was reconstructed. Changes in TOM and MOM were related to variations in land vegetation density and marine productivity, as well as transport processes dominated by the oceanic circulation system. The marine biomarker contents from the South Yellow Sea have generally increased throughout the Holocene, indicating that the increased MOM contents were mainly controlled by the strengthening of the circulation system. The terrestrial biomarkers, on the other hand, were more variable, indicating more complex influence of TOM burial in the Yellow Sea. During the Early Holocene (7200–6000 cal yr BP), the moderate TOM input revealed by the terrestrial proxy records may result from abundant land source supply by strong river transport despite the lack of transport via circulation system. The Mid-Holocene (6000–3000 cal yr BP) was characterized by decreased terrestrial biomarker contents. The balance between the decrease in land source supply and increase of transportation by the current system of the TOM resulted in the lower but stable contents of TOM. During the Late Holocene (3000 cal yr BP to present), the TOM deposition in the South Yellow Sea increased as the current system was further enhanced and thus transported more TOM to the central South Yellow Sea, although the land supply of TOM was further reduced.

The East China Sea (ECS) and the Southern Yellow Sea (SYS) ecosystem is undergoing dramatic changes, but the spatiotemporal patterns and forcing mechanisms of phytoplankton variations remain understudied. Phytoplankton lipid biomarkers are useful proxies for productivity and community structure changes, and they were measured in suspended particles of more than 81 sites from spring and summer of 2011 in the ECS and SYS. In spring, the concentrations of brassicasterol (4.7–127 ng L−1) and dinosterol (0.7–37 ng L−1) were markedly higher in the northern and central SYS, while C37 alkenones (0–15 ng L−1) were detected at only seven sites in the ECS. In summer, brassicasterol (25.3–1178 ng L−1) and dinosterol (0–125 ng L−1) showed high values off the Changjiang River Estuary (CRE), while C37 alkenones (0–410 ng L−1) had high values in the northwest and central SYS. The mean concentrations of the three lipid biomarkers in summer were 3 to 61 times higher than those in spring. Spatiotemporal patterns of biomarkers reveal higher ratios of diatom/dinoflagellate and diatom/haptophyte in higher productivity areas, off the CRE in summer and the northern and central SYS in spring. This study validates the applicability of brassicasterol, dinosterol, and alkenones as proxies of productivity and community structure of the three phytoplankton taxa: diatoms, dinoflagellates, and haptophytes. The results indicate that nutrients (in summer) and turbidity-induced photosynthetic available radiation (in spring) play important roles in regulating spatiotemporal variations of phytoplankton in the ECS and SYS.

Marine algal-derived lipid biomarkers (alkenones, brassicasterol, dinosterol, and long-chain diol/keto-ol representing haptophytes, diatoms, dinoflagellates, and eustigmatophytes, respectively) were used to evaluate the phytoplankton productivity and community structure changes in core MD05-2901 from the western South China Sea, which features distinct summer upwelling induced by southwest Asian monsoon. The results revealed substantial differences in the distribution patterns between the four major marine primary producers. Diatom and dinoflagellate biomarkers displayed slightly higher abundances, mostly in interglacials especially after MIS 8, while alkenones exhibited lower values in MIS 12 and MIS 1, with higher values in between especially in the middle of MIS 7, but eustigmatophytes increased in most glaciations, indicating complex responses of different phytoplanktons to paleoclimatic and paleoenvironmental changes over the past 450 ka. The sum of the four phytoplanktons shows subtle glacial–interglacial patterns, probably reflecting the combined hydrological dynamics driven by enhanced summer monsoon during summer/interglacials and enhanced winter monsoon during winter/glacials in the region. The biomarker-based community structure showed relative high contribution from diatoms and dinoflagellates during interglacials, high contribution in the middle part of the section centered at ~210 ka from the coccolithophorids, but varying levels from the eustigmatophytes with high percentages in most glacials. Diatoms show strong nutrient sensitivity and positive relation with other paleo-proxies, and their enrichments during interglacials can be attributed to enhanced nutrient level induced by the East Asian summer monsoon, which could have been coupled with the influence of the global ice volume, the summer insolation and the Southern Hemisphere latent heat.

Four algal biomarkers, brassicasterol, C30-diol/keto-ol, dinosterol and C37-alkenone, representing diatoms, estigmatophytes, dinoflagellates and coccolithophorids, respectively, were detected in samples collected during two South China Sea cruises to study the modern phytoplankton community structure in the region. For the first time, the basin-wide distribution of these phytoplankton algal biomarkers in the sea surface water during two intermonsoon seasons (spring 2010 and autumn 2011) is documented and charted. Generally, the abundance of the biomass is higher in spring than autumn, with high productivity mostly in the regions of Pearl River estuary, off Palawan and around the Luzon Strait, showing the abundance order: diatoms>estigmatophytes>dinoflagellates>coccolithophorids. We run both redundancy analysis (RDA) and SPSS correlation analysis to interpret the relationship between individual groups and environmental variables. The results indicate that temperature and salinity play a dominant role in controlling the distribution of phytoplankton in these intermonsoon seasons, followed by nitrate playing a secondary role. Our biomarker survey provides important reference data for interpreting paleo-productivity in the geological records in the SCS.

Drifting sediment trap measurements were carried out at high temporal frequency in the northwestern Mediterranean Sea in the course of the DYNAPROC 2 campaign, during the transition between late summer to autumn conditions. Molecular biomarkers were analyzed in selected subsets of consecutive samples collected for 6 h at 200 m depth. Fluxes of n-alkanes, long-chain alkenones, sterols and steroid ketones show high variability between consecutive 6-h samples, comparable in range to seasonal variability. n-Alkane export ranges from 1.4 to 29.7μg m−2 d−1, fluxes of C37 alkenones varies from 0 to 14.2 μg m−2 d−1. Fluxes of sterols, steroid ketones and C30 alkane diol respectively range from 31 to 377, 2.2 to 46 and 0.3 to 9.3 μg m−2 d−1. Biomarker flux ranges are coherent with the relatively low primary production and the low export ratio encountered during the study. Molecular characteristics of biomarker composition is consistent with reworked algal and zooplanktonic organic matter. Lipid biomarker composition points to the dominance of haptophytes over dinoflagellates in the exported material, and to a minor contribution of diatoms and eustigmatophytes. The intrusion of coastal water at the study site was recorded by an enhanced imprint of higher plant n-alkanes. Two processes can be responsible for the pulses in biomarker flux: changes in the magnitude of particle flux (dry weight mass flux) and changes in the concentration of biomarkers in the particles. Concurrent variability in fluxes, significant Pearson correlations between fluxes of biomarkers of haptophytes, dinoflagellates, eustigmatophytes, zooplankton activity and higher plants (alkenones, dinosterol, alkyl diols, dehydrocholesterol, steroid ketones, pn=31, suggest that the short term temporal variability of biomarker export fluxes depends primarily on the intensity of particle dry weight flux. Biomarker concentrations vary on a relatively narrower range than biomarker fluxes, indicating that changes in particle composition (due to degradation or change in source apportionment) has a weaker influence on flux variability. Thus, particle aggregation and sinking are key processes to explain the dynamic of biomarker export at a temporal scale of 6 h. None the less, abrupt changes of OC-normalized concentrations of biomarkers, in the time scale of 6 h, indicate that the exported particles composition also show short-time variability. Highest biomarker flux values recorded by the trap samples from 27 to 29 September correspond to highest values of zooplankton biomass integrated between the surface and 200 m. The decrease in primary production after the October wind events is echoed by minima in biomarker flux values. Despite these correspondences, the coupling between primary production and biomarker export is complex.

Paleoclimatic changes during MIS7 and MIS6 remain poorly described in the Near East. We quantified source-specific biomarkers in Lake Van sediments during the interglacial/glacial cycle MIS7/MIS6. Long-chain n-alkanes produced by land-derived vegetation, as well as long-chain alkenones and sterols (namely brassicasterol and dinosterol) produced by aquatic algae were investigated. Stable hydrogen isotopic measurements (delta H-2) on n-C-29 alkanes were used as a proxy for aridity and revealed three wetter periods interrupted by two drier intervals during MIS7. In contrast, during the MIS6 glaciation, a generally drier climate was predominant. During the warmer and wetter periods of MIS7, a higher input of aquatic organic matter to Lake Van sediments was recorded by higher concentrations of long-chain alkenones, dinosterol and brassicasterol. Long-chain alkane abundances do not show a pattern related to aridity and were observed in higher concentrations in wetter as well as drier periods. Generally, in the Eastern Mediterranean, a wetter interglacial interrupted by drier episodes followed by a dry glacial period was the common feature observed during the MIS7/MIS6 interglacial/glacial cycle. However, in comparison to the last interglacial/glacial cycle the extreme dry glacial period registered around Lake Van from MIS5d to MIS2 was apparently unique and not equaled by a similar event within the last 250 ka. (C) 2019 Elsevier Ltd. All rights reserved.

In this study, we aimed to reconstruct spring (April–June) sea ice changes in the western Arctic Ocean over recent centuries (ca. the last 250 years) by measuring biomarker distributions in a multicore (ARA01B-03MUC) retrieved from the Chukchi Shelf region and to evaluate outcomes against known or modelled estimates of sea ice conditions. Specifically, we analyzed for the Arctic sea ice proxy IP25 and assessed the suitability of a further highly branched isoprenoid (HBI) lipid (HBI III), epi-brassicasterol, and dinosterol as complementary biomarkers for use with the so-called phytoplankton marker-IP25 index (PIP25; PIIIIP25, PBIP25, and PDIP25, respectively). The presence of IP25 throughout core ARA01B-03MUC confirms the occurrence of seasonal sea ice at the study site over recent centuries. From a semi-quantitative perspective, all three PIP25 indices gave different trends, with some dependence on the balance factor c, a term used in the calculation of the PIP25 index. PIIIIP25-derived spring sea ice concentration (SpSIC) estimates using a c value of 0.63, determined previously from analysis of Barents Sea surface sediments, were likely most reliable, since SpSIC values were high throughout the record (SpSIC > 78%), consistent with the modern context for the Chukchi Sea and the mean SpSIC record of the 41 CMIP5 climate models over recent centuries. PBIP25-based SpSIC estimates were also high (SpSIC 108%−127%), albeit somewhat over-estimated, when using a c value of 0.023 obtained from a pan-Arctic distribution of surface sediments. In contrast, PDIP25 values using a pan-Arctic c value of 0.11, and PIP25 data based on the mean biomarker concentrations from ARA01B-03MUC, largely underestimated sea ice conditions (SpSIC as low as 13%), and exhibited poor agreement with instrumental records or model outputs. On the other hand, PBIP25 values using a c factor based on mean IP25 and epi-brassicasterol concentrations exhibited a decline towards the core top, which resembled recent decreasing changes in summer sea ice conditions for the Chukchi Sea; however, further work is needed to test the broader spatial generality of this observation.

Identification of sources and distribution of terrigenous organic matter (TOM) are significant to understand the carbon transport in East China Sea (ECS). However, sources of TOM buried in the ECS are diverse and complex, which are likely derived from the Changjiang River, Yellow River and/or small rivers from China mainland and Taiwan. In order to evaluate the fate of TOM offshore in the ECS, the study sampled 80 surface sediments from outer shelf-slope-Okinawa Trough (OT) region in the ECS. Both terrigenous and marine organic biomarkers were detected. The concentration (ng/g dry weight sediment) of terrigenous biomarkers including ƩC27 + C29 + C31 n-alkanes ranged from 12.2 to 990.9; while the content of marine biomarkers varied from 1.3 to 3891.2 for C37 alkenones, 2.6 to 922.6 for brassicasterol and 7.1 to 1535.8 for dinosterol. Bulk organic carbon and TOM distributions were controlled by the hydrodynamic conditions. The terrigenous and marine biomarker ratio (TMBR) (ƩC27 + C29 + C31 n-alkanes)/(ƩC27 + C29 + C31 n-alkanes + (brassicasterol + dinosterol +alkenones)) increased first and decreased from the outer shelf to OT spatially, showing the distribution pattern of relative proportion of TOM. Hotspots of significant deposition of TOM were observed in the ECS by δ13C and TMBR proxies that the mechanism was unclear yet. Binary model revealed higher percentage of TOM based on TMBR than δ13C for both slope (32.1% vs. 20.0%) and trough (23.1% vs. 15.2%) region. An underestimation of C4 vegetation contribution likely biased the bulk carbon model. Carbon preference index suggested a zonation distribution of TOM that outer shelf had different sources from the slope and OT attributed to cross shelf transport of terrigenous organic matter.

Anaerobic ammonium oxidation (anammox), an important process for converting fixed nitrogen to N2, plays an important role in the present-day marine nitrogen cycle. However, little is known about anammox activities in the past, especially in regions that were strongly affected by human activities, evidenced by eutrophication and hypoxia, which promote anammox bacteria growth. In this study, ladderanes have been measured in a sediment core and suspended particulate matter (SPM) in the East China Sea (ECS), to reconstruct the anammox record and to evaluate its responses to eutrophication and hypoxia. The detection and distribution of different ladderane lipids in SPM provide additional evidence that ladderanes were mostly produced in the water column and could reflect anammox activities. Summed ladderane content from the core varied between 11 and 300 ng/g dry weight (dw) sediment, with C20-[5]-ladderane fatty acid methyl esters (FAME) as the predominant compound (5–150 ng/g dw), followed by C20-[3]-ladderane FAME (1–110 ng/g dw), C18-[3]-ladderane FAME (1–32 ng/g dw) and C18 -[5]-ladderane FAME (3–11 ng/g dw). The detection of ladderanes over the last century indicate the existence of anammox in the past. The rapidly increasing trend of ladderanes since the 1960s correlates with an increase in phytoplankton biomarkers (Σ(B + D + A), brassicasterol (B), dinosterol (D) and C37 alkenones (A)), indicating that eutrophication exacerbated anammox growth. The co-variation between our ladderane record and published records of low-oxygen tolerant foraminiferal microfossils and hypoxia events over the past 60 years suggested that sediment ladderanes are a useful indicator for past changes of oxygen depletion or hypoxia in the ECS.

In this study we have applied different indices based on long-chain diols, i.e., the long-chain diol index (LDI) as a proxy for past SST, the diol index as an indicator of past upwelling conditions, and the nutrient diol index (NDI) as a proxy for nitrate and phosphate concentrations in seawater. The proxies were analyzed in marine sediments recovered at ODP Site 1234, located within the Peru–Chile upwelling system, with a ∼2 kyr resolution covering the last 150 kyr. We also generated TEX86H and U37K′ temperature and planktonic δ18O records, as well as total organic carbon (TOC) and accumulation rates (ARs) of TOC and lipid biomarkers (i.e., C37 alkenones, GDGTs, dinosterol, and loliolide) to reconstruct past phytoplankton production. The LDI-derived SST record covaries with TEX86H- and U37K′-derived SST records as well as with the planktonic δ18O record, implying that the LDI reflects past SST variations at this site. TOC and phytoplankton AR records indicate increased export production during the last interglacial (MIS 5), simultaneous with a peak in the abundance of preserved Chaetoceros diatoms, suggesting intensified upwelling during this period. The diol index is relatively low during the upwelling period, but peaks before and after this period, suggesting that Proboscia diatoms were more abundant before and after the period of upwelling. The NDI reveals the same trends as the diol index, suggesting that the input of nitrate and phosphate was minimal during upwelling, which is unrealistic. We suggest that the diol index and NDI should perhaps be considered as indicators for Proboscia productivity instead of upwelling conditions or nutrient concentrations.

The Kara Sea is an important area for paleo-climatic research since sea ice and brine formation take place on its shelf—two processes inducing supra-regional climatic implications and thereby connecting regional environmental variability with global climatic conditions. To gain information about past sea ice coverage and variations, three sediment cores distributed in the southern and central parts of the marginal Sea were investigated. By applying the sea ice biomarker IP25 and the PIP25 index [phytoplankton biomarker (dinosterol)-IP25 index] post-glacial sea ice variability could be detected in the central Kara Sea (Core BP00-36/4), with most intense sea ice cover between 12.4 and 11.8 ka coinciding with the Younger Dryas (12.9–11.6 ka), and reduced sea ice cover between 10 and 8 ka during the Holocene Thermal Maximum. During the last ~ 7 ka, increasing sea ice indicators might indicate a Holocene cooling trend, probably induced by declining summer insolation. Furthermore, temporal changes in the fast ice—polynya distribution in the southern Kara Sea were detected: expanding fast ice during the late Holocene and a cyclic short-term Holocene climate variability documented by abrupt changes in the sea ice coverage at the BP00-07/7 core site. Core BP99-04/7 from the Yenisei estuary recorded consistently seasonal sea ice cover since ~ 9.3 ka, apart from five short phases of fast ice expansion to the core site. The strong influence of river run-off as well as estuary processes might prevent the detection of (short-term) climatic signals at this study site.