Controls on alkenone unsaturation ratios along the salinity gradient between the open ocean and the Baltic Sea

Alkenone unsaturation ratios of sedimentary lipids are used as a geochemical proxy for sea surface temperatures, and interest is growing in their potential as indicators of different water masses and possibly of salinity. We analyzed the abundance of unsaturated C₃₇ to C₃₈ ketones in lipid extracts of 57 surface sediment (0-1 cm) samples along a salinity gradient from 8 to 33 psu in the transition from the Skagerrak to the Baltic Sea (NW Europe). In addition to surface sediments, we analyzed alkenones in suspended particulate matter at 13 stations—over a gradient in salinity from 25 to 33 psu—during a bloom of the coccolithophore Emiliania huxleyi. Alkenones were detected in all samples (suspended matter and sediment) with variable contributions of the tetra-unsaturated C₃₇ alkenone compound (%C_37:4; range from 2 to 10% of total C₃₇ alkenone content). Comparing the alkenone unsaturation index (U₃₇^K′) and %C_37:4 data to climatological sea surface temperature and sea surface salinity data sets revealed that SST estimated from U₃₇^K′ of saline end members (samples from the Skagerrak) is in the general range of modern SST during bloom periods of haptophytes. At salinities below ∼30 psu %C_37:4 increases to above 5% and the unsaturation ratios cease to be related to climatological annual or seasonal sea surface temperatures. On the other hand, the %C_37:4 appears to be inversely and significantly correlated to salinity: Highest C_37:4 proportions in the inner Baltic Sea are caused by an unidentified organism, but in the transition area at salinities down to 10 psu, the producer apparently is E. huxleyi. The suspended matter data together with those from the water column support the hypothesis of changing biosynthesis of alkenones under salt stress by the coccolithophore E. huxleyi, but constrain the maximum of %C_37:4 attributable to salt stress to 10% of all C₃₇ alkenones.     

Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ∼25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C₂₁-C₃₁) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C₂₁n-alkane, and the C₂₅ and C₂₇ alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C₃₀ 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U₃₇^K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U₃₇^K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.     

Dinosterol δD values in stratified tropical lakes (Cameroon) are affected by eutrophication

In freshwater settings, dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) is produced primarily by dinoflagellates, which encompass various species including autotrophs, mixotrophs and heterotrophs. Due to its source specificity and occurrence in lake and marine sediments, its presence and hydrogen isotopic composition (δD) should be valuable proxies for paleohydrological reconstruction. However, because the purity required for hydrogen isotope measurements is difficult to achieve using standard wet chemical purification methods, their potential as a paleohydrological proxy is rarely exploited. In this study, we tested δD values of dinosterol in both particulate organic matter (POM) and sediments of stratified tropical freshwater lakes (from Cameroon) as a paleohydrological proxy, the lakes being characterized by variable degrees of eutrophication. In POM and sediment samples, the δD values of dinosterol correlated with lake water δD values, confirming a first order influence of source water δD values. However, we observed that sedimentary dinosterol was D enriched from ca. 19 to 54‰ compared with POM dinosterol. The enrichment correlated with lake water column conditions, mainly the redox potential at the oxic–anoxic interface (E_h OAI). The observations suggest that paleohydrologic reconstruction from δD values of dinosterol in the sediments of stratified tropical lakes ought to be sensitive to the depositional environment, in addition to lake water δD values, with more positive dinosterol δD values potentially reflecting increasing lake eutrophication. Furthermore, in lake sediments, the concentration of partially reduced vs. non-reduced C₃₄ botryococcenes, stanols vs. stenols, and bacterial (diploptene, diplopterol and ββ-bishomohopanol) vs. planktonic/terrestrial lipids (cholesterol, campesterol and dinosterol) correlated with E_h OAI. We suggest using such molecular proxies for lake redox conditions in combination with dinosterol δD values to evaluate the effect of lake trophic status on sedimentary dinosterol δD values, as a basis for accurately reconstructing tropical lake water δD values.     

Distributions and origins of lipid biomarkers in surface sediments from the southern Yellow Sea

This paper reports on the spatial distribution patterns and investigates the controlling mechanisms of phytoplankton biomarkers (brassicasterol for diatoms, alkenones for haptophytes, dinosterol for dinoflagellates) and terrestrial biomarkers (odd C number long-chain (C₂₇ + C₂₉ + C₃₁) n-alkanes) in surface sediments from the southern Yellow Sea (SYS). The contents of the phytoplankton biomarkers in the SYS surface sediments reveals a clear spatial pattern, with low values near the coasts and increased values seaward, caused by higher phytoplankton primary productivity and low sedimentation rates in the basin. The contents of terrestrial biomarkers show high values in the northern part of the study areas off the Shandong Peninsula and Jiangsu coast, caused by inputs of materials from the modern Huanghe River and the old Huanghe delta, respectively. The results also indicate that biomarker ratios offer the best approach for reconstructing marginal sea C cycles, as these proxies can be used to estimate the contributions of both terrestrial and marine organic matter and to reconstruct paleoproductivity and paleoecological changes in the SYS.     

Reconstruction of phytoplankton productivity and community structure in the South Yellow Sea

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.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Biomarker seasonality study in Lake Van, Turkey

The endorheic Lake Van in eastern Anatolia (Turkey) is the world’s largest soda lake and it is an important site in paleoclimate studies to understand past continental conditions in western Asia. In order to gain further insights into the biomarker signatures in Lake Van’s sediments we have analyzed particulate material in sediment traps deployed between August 2006 and July 2007. The biomarkers used were long chain alkenones (LCAs C₃₇-C₃₉, haptophyte lipids), isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs, Archaea membrane lipids) and pigments (chlorins and fucoxanthin). The biomarker fluxes indicate a strong seasonality in export primary productivity and the phytoplankton community structure. The highest total mass and organic carbon fluxes were found in summer, coupled to strong stratification while the lowest mass fluxes occurred in winter at the time of water column mixing. With increasing temperatures in early spring, phytoplankton export productivity grew, coupled with an increase of total mass flux and organic carbon, which might be associated to enhanced nutrient input from snowmelt runoff. The percentage of C_37:4 shows some correspondence with observed seasonal changes in Lake Van’s stratification structure. We also evaluated the potential applicability of molecular temperature proxies derived from Archaea and haptophyte lipids. The use of the TEX₈₆ proxy was precluded by low GDGT abundances. Estimated LCA temperatures were consistent with temperatures in the photic zone but no seasonality changes were observed despite the wide annual temperature range measured at Lake Van.     

Salinity control on long-chain alkenone distributions in lake surface waters and sediments of the northern Qinghai-Tibetan Plateau, China

Long-chain alkenones in lacustrine settings are potentially excellent biomarkers for the reconstruction of past terrestrial environmental conditions, and have been found in many different types of lakes around the globe. A wider range of factors influence the occurrence and distribution of alkenones in lake sediments and waters when compared to marine systems. Lake environmental conditions, such as temperature (in particular) and salinity, are among the key factors controlling alkenone distributions in lacustrine settings. Here we investigated alkenone distribution patterns in lakes of the northern Qinghai-Tibetan Plateau, China, and their possible relationship with environmental conditions, by analyzing paired samples of suspended particulate matter in surface waters and surface sediments. Salinity of investigated lake waters ranges from almost 0 to ∼100 g/L, while temperature variation among the lakes is minimal, effectively eliminating temperature effects on the alkenone distribution patterns observed here. We show that (1) alkenone concentrations vary substantially between the lakes, yet controlling mechanisms remain elusive; (2) C₃₇/C₃₈ ratios are substantially lower in the lakes of the Qaidam Basin than in the Lake Qinghai region, probably indicating different alkenone producers in the two regions; and (3) large variations in %C_37:4 (the percentage of the C_37:4 alkenone), determined from both surface waters and sediments, are negatively correlated with salinity. We suggest that the %C_37:4 index could be used as a salinity indicator at least on a regional scale, with careful considerations of other potentially complicating factors. However, potential reasons for why salinity could significantly affect %C_37:4 values need further investigation.     

Determination of sediment provenance at drift sites using hydrogen isotopes and unsaturation ratios in alkenones

The large (∼20‰) hydrogen isotopic gradient in surface waters of the northwest Atlantic Ocean is exploited to track changes in the source of alkenones to the Bermuda Rise sediment drift. Cultures of the predominant alkenone-producing coccolithophorid, E. huxleyi, were grown in deuterium-enriched seawater and shown to possess alkenones with a D/H ratio that closely tracked the water D/H ratio (r² = 0.999, n = 5 isotopic enrichments) with a fractionation factor (α) between 0.732 and 0.775. A hydrogen isotopic depletion of -193 ± 3‰ (n = 9) was measured in alkenones from suspended particles relative to seawater in the subpolar and subtropical northwest Atlantic Ocean. This value was used to calculate the water δD values in which alkenones from Bermuda Rise sediment were synthesized, and by extension, the water mass in which they were produced. Applying this technique we find that 60% to 100% of the alkenones in late Holocene Bermuda Rise sediment were produced in deuterium-depleted subpolar water to the northwest of the drift. To reconcile values of the alkenone unsaturation ratio (U^k′₃₇), a widely used proxy for sea surface temperature, with the δD values of alkenones in late Holocene sediments from the Bermuda Rise at least three sources of sediment must be invoked: a cold, very isotopically depleted source, almost certain to be the Scotian Margin; a warm, moderately isotopically-depleted source, likely to be the northwestern edge of the subtropical gyre; and a cold, isotopically enriched source, which we hypothesize to be the subpolar waters overlying the main branch of North Atlantic Deep Water flowing southwest from the Nordic Seas.     

A biogeochemical study of sediments from the eutrophic Lake Lugano and the oligotrophic Lake Brienz,Switzerland

The biomarker composition and stable isotope (C, O) ratio values of organic matter (OM) and carbonate from sediment cores from the oligotrophic Lake Brienz and the eutrophic Lake Lugano (both in Switzerland) are compared, in order to obtain information about OM sources and transformation processes. Eutrophic conditions at Lake Lugano are reflected in elevated total organic carbon (TOC) content and hydrogen index (HI) values, as well as higher lipid concentrations. Parallel down core trends in δ¹³C values of TOC and calcite in the Lake Lugano sediments reflect bioproductivity cycles. Variations in δ¹⁸O values of calcite are consistent with changes in mean summer temperature over the time interval covered by the core. In contrast, such a correlation does not exist for Lake Brienz and there the stable isotope composition of calcite reflects its allochthonous origin. In the sediments of both lakes, fatty acid (FA) distributions and the composition of n-alkanols and n-alkanes indicate highly variable proportions of autochthonous OM sources (algae, zooplankton, bacteria) and OM from land plants. Enhanced in situ microbial synthesis during sediment deposition in Lake Lugano is suggested by the higher TOC-normalised concentrations of branched chain FAs (C₁₅–C₁₇), hopanoic acids and triterpenoid alcohols (i.e. tetrahymanol, diplopterol). Variations in the concentrations of cholesterol are related to contributions from zooplankton and/or green algae, while sitosterol concentrations reflect the input of vascular plants. Periods of increased input of OM from diatoms are evidenced by high 24-methylcholesta-5,22-dien-3β-ol (either epibrassicasterol or brassicasterol) and/or highly branched isoprenoid (HBI) alkenes concentrations. High relative concentrations of diplopterol in Lake Lugano sediments are consistent with the predominance of cyanobacteria commonly observed in eutrophic lakes. The presence of archeol and hydroxyarcheol in very low concentrations in the Lugano sediments argues for the activity of methanogens and/or anaerobic methanotrophs.Differences in OM degradation processes are reflected in higher chlorin index values in the Brienz sediments but higher saturated vs. unsaturated n-FAs in the core from Lugano. Higher concentrations of branched chain FAs and 16:1ω7 n-FA, as well as enhanced 18:1ω7/18:1ω9 n-FA, are consistent with enhanced bacterial biomass in the Lugano water column or sediments. The preservation of phytol seems to be enhanced in sediments with a high relative contribution of land plant OM. Major factors affecting OM accumulation in the lakes are differences in OM sources (i.e. terrestrial OM vs. autochthonous production), extent of bacterial activity and most likely oxygen availability in the water column.     

Evidence for differential degradation of alkenones under contrasting bottom water oxygen conditions: implication for paleotemperature reconstruction

The successful reconstruction of sea surface temperatures using alkenone paleothermometry (U₃₇^k′) has relied on the premise that there is no significant differential degradation of alkenones with different states of unsaturation during diagenetic processes. To test this assumption, we conducted a comparative study of contemporary sediments in oxic and anoxic bottom waters from the Santa Monica Basin, offshore California. Long-chain alkenones were quantified and sea surface temperature were calculated using the calibrated U₃₇^k′–T relationship of Prahl et al. (1988). Our results show that temperature record from the oxic sediments is higher by as much as 4°C compared to those from time-equivalent anoxic sediments as a result of differential degradation of long-chain unsaturated alkenones and bioturbation mixing in the oxic sediments. The differential degradation of C_37:3 vs. C_37:2 alone could account for up to 2.5°C difference between these two records. This finding has significant implication in the interpretation of paleo–sea surface temperature data using alkenone paleothermometry.     

Temperature and Salinity Effects on Alkenone Ratios Measured in Surface Sediments from the Indian Ocean

We compare alkenone unsaturation ratios measured on recent sediments from the Indian Ocean (20°N–45°S) with modern sea oceanographic parameters. For each of the core sites we estimated average seasonal cycles of sea surface temperature (SST) and salinity, which we then weighted with the seasonal productivity cycle derived from chlorophyll satellite imagery. The unsaturation index (U₃₇^K′) ranges from 0.2 to 1 and correlates with water temperature but not with salinity. TheU₃₇^K′versus SST relationship for Indian Ocean sediments (U₃₇^K′= 0.033 SST + 0.05) is similar to what has been observed for core tops from the Pacific and Atlantic oceans and the Black Sea. A global compilation for core tops givesU₃₇^K′= 0.031 T + 0.084 (R= 0.98), which is close to a previously reported calibration based on particulate organic matter from the water column. For temperatures between 24° and 29°C, however, the slope seems to decrease to about 0.02U₃₇^K′unit/°C. For Indian Ocean core tops, the ratios of total C₃₇alkenones/total C₃₈alkenones and the slope of theU₃₇^K′-SST relationship are similar to those previously observed for cultures ofEmiliania huxleyibut different from those previously published forGephyrocapsa oceanica.EitherE. huxleyiis a major producer of alkenones in the Indian Ocean or strains ofG. oceanicaliving in the northern Indian Ocean behave differently from the one cultured. In contrast with coccolithophorid assemblages, the ratios of C₃₇alkenones to total C₃₈alkenones lack clear geographic pattern in the Indian Ocean.     

The lipid chemistry of an interfacial sediment from the Peru Continental Shelf: Fatty acids,alcohols, aliphatic ketones and hydrocarbons

A sample of the sediment-water column interface which lies on the continental shelf under the Peru upwelling regime, has been examined for fatty acids, fatty alcohols, ketones and hydrocarbons. Fatty acids were the most abundant compound class, ranging from C₁₂-C₂₄, with 16:0 as the major component (765.5 μg/g dry sediment). The alcohols were dominated by 3,7,11,15-tetramethylhexadeca-2-en-ol (phytol), with even-chain n-alcohols in the range C₁₄-C₂₀. The ketones consisted of C₃₇-C₃₉ di- and tri-unsaturated alken-2-ones and alken-3-ones. Both alkanes and alkenes were present in the hydrocarbon fraction; the alkanes ranging from C₁₃ — C₂₀ and comprising both straight chain and isoprenoid compounds; the alkenes consisting of isomeric pairs of C₂₅ branched trienes and tetraenes. The data indicate that the organic content has been contributed very largely from marine sources (probably mainly from phytoplankton and bacteria), showing little terrigenous influence. The presence of labile compounds such as polyunsaturated fatty acids (with two to six double bonds), implies that the sediment has undergone very little diagenetic alteration, and the lipids are probably largely unchanged from the state in which they actually reached the sediment. They may therefore serve as a useful baseline in assessing diagenesis in older sediments, where diagenetic transformations are more advanced.     

Hydrogen isotopes in individual alkenones from the Chesapeake Bay estuary

Hydrogen isotope ratios of individual alkenones from haptophyte algae were measured in suspended particles and surface sediment from the Chesapeake Bay (CB) estuary, eastern USA, in order to determine their relationship to water δD values and salinity. δD values of four alkenones (MeC_37:2, MeC_37:3, EtC_38:2, EtC_38:3) from particles and sediments were between −165‰ and −221‰ and increased linearly (R² = 0.7-0.9) with water δD values from the head to the mouth of the Bay. Individual alkenones were depleted in deuterium by 156-188‰ relative to water. The MeC₃₇ alkenones were consistently enriched by ∼12‰ relative to the EtC₃₈ alkenones, and the di-unsaturated alkenones of both varieties were consistently enriched by ∼20‰ relative to the tri-unsaturated alkenones. All of the increase in alkenone δD values could be accounted for by the water δD increase. Consequently, no net change in alkenone-water D/H fractionation occurred as a result of the salinity increase from 10 to 29. This observation is at odds with results from culture studies with alkenone-producing marine coccolithophorids, and from two field studies, one with a dinoflagellate sterol in the CB, and one with a wide variety of lipids in saline ponds on Christmas Island, that indicate a decline in D/H fractionation with increasing salinity. Why D/H fractionation in alkenones in the CB showed no dependence on salinity, while D/H fractionation in CB dinsoterol decreased by 1‰ per unit increase in salinity remains to be determined. Two hypotheses we consider to be valid are that (i) the assemblage of alkenone-producing haptophytes changes along the Bay and each species has a different sensitivity to salinity, such that no apparent trend in α_{alkenone-water} occurs along the salinity gradient, and (ii) greater osmoregulation capacity in coastal haptophytes may result in a diminished sensitivity of alkenone-water D/H fractionation to salinity changes.     

The measurement of D/H ratio in alkenones and their isotopic heterogeneity

Previous paleoenvironmental studies reported the δD values of a mixture of coeluting alkenones. Here, we present a semi-preparative normal-phase high-performance liquid chromatography–mass spectrometry (NP-HPLC–MS) method for purifying long chain (C₃₇ and C₃₈) unsaturated methyl and ethyl ketones (alkenones) on the basis of chain length and degree of unsaturation.The method was applied to purify alkenones in suspended particles and surface sediments from a site in Chesapeake Bay, eastern USA. The hydrogen isotopic composition of di- and triunsaturated C₃₇ and C₃₈ alkenones differed significantly on the basis of chain length and the degree of unsaturation, demonstrating the importance of gas chromatography–isotope ratio-mass spectrometry (GC–irMS) analysis of individual alkenones for accurate paleoenvironmental reconstruction. Constant fractionation factors between alkenones with different chain length but the same degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{38:2}}\text{and}{\alpha }_{{\text{C}}_{37:3}''–''{\text{C}}_{38:3}}=1.01$) and those with the same chain length but different degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{37:3}}\text{and}{\alpha }_{{\text{C}}_{38:2}''–''{\text{C}}_{38:3}}=0.97$) in all samples suggest that the values may represent hydrogen isotope fractionation associated with elongation and desaturation during alkenone biosynthesis.     

Long-chain alkenone distributions and temperature dependence in lacustrine surface sediments from China

Long-chain alkenones (LCK) of lacustrine surface sediments were analyzed in 37 lakes from China. The results obtained were complemented by published data from 13 other Chinese lakes. These lakes are located across large temperature and precipitation gradients, therefore allowing for an assessment of the distribution pattern of LCK and their temperature dependency. Different distribution patterns of LCK (C₃₇ predominant pattern and C₃₈ predominant pattern) were detected in the surface sediment samples. The ratio of C_37:4 methyl ketone to the sum of C₃₇ alkenones observed in the different lakes is highly variable (5%-96%, with mean value of 55%), and more than that seen in marine systems. The finding that some of the ocean LCK precursor algae (Gephyrocapsa oceanica, Coccolithus pelagicus) were also present in the limnic systems suggested that both systems might have similar biosynthetic sources. Empirical relationships between the alkenone unsaturation index U₃₇^k′ and different temperature sets (mean annual air temperature, mean annual air temperature in different seasons, and lake surface water temperature of July) were tested. The best correlation between U₃₇^k′ and temperature was obtained using mean annual air temperature. A general linear regression of U₃₇^k′ and MAAT can be expressed as U₃₇^k′ = 0.0328 × T + 0.126 (n = 38, r² = 0.83). Although questions such as species-uncertainty and other unknown factors for U₃₇^k′ temperature dependence still remain, the equation might be representative of the average contribution of LCK to sediments for these data over a wide range of surface temperatures, water chemistry and different alkenones-producer algal populations. The general relationship of U₃₇^k′ and mean annual air temperature is consistent with that in marine systems. It supports the suggestion that the biosynthetic pathway of alkenones and the mechanism of their temperature signal may be similar in both marine and limnic systems. LCK might be used as an important paleotemperature proxy in limnic environment.     

Asynchronous alkenone and foraminifera records from the Benguela Upwelling System

Radiocarbon stratigraphy is an essential tool for high resolution paleoceanographic studies. Age models based on radiocarbon ages of foraminifera are commonly applied to a wide range of geochemical studies, including the investigation of temporal leads and lags. The critical assumption is that temporal coupling between foraminifera and other sediment constituents, including specific molecular organic compounds (biomarkers) of marine phytoplankton, e.g. alkenones, is maintained in the sediments.To test this critical assumption in the Benguela upwelling area, we have determined radiocarbon ages of total C₃₇-C₃₉ alkenones in 20 samples from two gravity cores and three multicorer cores. The cores were retrieved from the continental shelf and slope off Namibia, and samples were taken from Holocene, deglacial and Last Glacial Maximum core sections. The alkenone radiocarbon ages were compared to those of planktic foraminifera, total organic carbon, fatty acids and fine grained carbonates from the same samples. Interestingly, the ages of alkenones were 1000 to 4500 yr older than those of foraminifera in all samples.Such age differences may be the result of different processes: Bioturbation associated with grain size effects, lateral advection of (recycled) material and redeposition of sediment on upper continental slopes due to currents or tidal movement are examples for such processes.Based on the results of this study, the age offsets between foraminifera and alkenones in sediments from the upper continental slope off Namibia most probably do not result from particle-selective bioturbation processes. Resuspension of organic particles in response to tidal movement of bottom waters with velocities up to 25 cm/s recorded near the core sites is the more likely explanation.Our results imply that age control established using radiocarbon measurements of foraminifera may be inadequate for the interpretation of alkenone-based proxy data. Observed temporal leads and lags between foraminifera based data and data derived from alkenone measurements may therefore be secondary signals, i.e. the result of processes associated with particle settling and biological activity.     

Characteristics of alkenones synthesized by a bloom of emiliania huxleyi in the Bering Sea

We investigated the characteristics of the alkenones produced by a bloom of Emiliania huxleyi in the eastern Bering Sea in 2000. Alkenones were detected in surface waters between 57°N and 63°N, where phosphate concentrations were low and the ammonium/nitrate ratio was high. The total alkenone content (C_37:2, C_37:3, and C_37:4) ranged from 22.0 to 349 μg g⁻¹ in suspended particles and from 0.109 to 1.42 μg g⁻¹ in surface sediments. This suggests that a large proportion of the particulate alkenones synthesized in the surface water rapidly degraded within the water column and/or at the water-sediment interface of the Bering Shelf. The change in the stable carbon isotopic composition (δ¹³C) of C_37:3 alkenone could not be explained only by variation in [CO₂(aq)] in the surface water but also depended on the growth rate of E. huxleyi. The alkenone unsaturation index (U^K′₃₇) was converted into an alkenone “temperature” with three equations [Prahl et al 1988], [Sikes et al 1997] and [Müller et al 1998]; Sikes et al.’s (1997) equation gave the best correlation with the observed sea surface temperature (SST) in the eastern Bering Sea. However, some temperatures estimated by Sikes et al.’s (1997) equation from the U^K′₃₇ varied from the observed SST, possibly because of the rapidly changing rate of alkenone synthesis in the logarithmic growth stage or the low rate of alkenone synthesis when nutrients were limiting. Temperatures estimated from U^K′₃₇ in the surface sediments (6.8-8.2°C) matched the observed SST in September (7-8°C) but differed from the annual average SST of 4 to 5°C, suggesting that most of the alkenone in the eastern Bering Sea was synthesized during limited periods, for instance, in September. The relative amounts of C_37:4 alkenone as proportions of the total alkenones (referred to as C_37:4%) were high, ranging from 18.3 to 41.4%. Low-salinity water (<32 psu) within the study area would have contributed to the high C_37:4% because a negative linear relationship between C_37:4% and salinity was found in this study.     

Hydrogen isotopes in dinosterol from the Chesapeake Bay estuary

The hydrogen isotope ratio of the dinoflagellate sterol dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) was measured in suspended particles and surface sediments from the Chesapeake Bay estuary in order to evaluate the influence of salinity on hydrogen isotope fractionation. D/H fractionation was found to decrease by 0.99 ± 0.23‰ per unit increase in salinity over the salinity range 10-29 PSU, a similar decrease to that observed in a variety of lipids from hypersaline ponds on Christmas Island (Kiribati). We hypothesize that the hydrogen isotopic response to salinity may result from diminished exchange of water between algal cells and their environment, lower growth rates and/or increased production of osmolytes at high salinities. Regardless of the mechanism, the consistent sign and magnitude of dinosterol δD response to changing salinity should permit qualitative to semi-quantitative reconstructions of past salinities from sedimentary dinosterol δD values.