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.     

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.     

Alkenones and coccoliths in ice‐rafted debris during the Last Glacial Maximum in the North Atlantic: implications for the use of UK37′ as a sea surface temperature proxy

The U^K₃₇′ index has proven to be a robust proxy to estimate past sea surface temperatures (SSTs) over a range of time scales, but like any other proxy, it has uncertainties. For instance, in reconstructions of the Last Glacial Maximum (LGM) in the northern North Atlantic, U^K₃₇′ indicates higher temperatures than those derived from foraminiferal proxies. Here we evaluate whether such warm glacial estimates are caused by the advection of reworked alkenones in ice‐rafted debris (IRD) to deep‐sea sediments. We have quantified both coccolith assemblages and alkenones in sediments from glaciogenic debris flows in the continental margins of the northern North Atlantic, and from a deep‐sea core from the Reykjanes Ridge. Certain debris flow deposits in the North Atlantic were generated by the presence of massive ice‐sheets in the past, and their associated ice streams. Such deposits are composed of the same materials that were present in the IRD at the time they were generated. We conclude that ice rafting from some locations was a transport pathway to the deep sea floor of reworked alkenones and pre‐Quaternary coccolith species during glacial stages, but that not all of the IRD contained alkenones, even when reworked coccoliths were present. We speculate that the ratio of reworked coccoliths to alkenone concentration might be useful to infer whether significant reworked alkenone inputs from IRD did occur at a particular site in the glacial North Atlantic. We also observe that alkenones in some of the debris flows contain a colder signal than estimated for LGM sediments in the northern North Atlantic. This is also clear in the deep‐sea core studied where the warmest intervals do not correspond to the intervals with large inputs of reworked coccoliths or IRD. We conclude that any possible bias to U^K₃₇′ estimates associated with reworked alkenones is not necessarily towards higher values, and that the high SST anomalies for the LGM are unlikely to be the result of a bias caused by IRD inputs. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

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.     

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.     

Distribution of the C37 tetra-unsaturated alkenone in Lake Qinghai, China: A potential lake salinity indicator

The alkenone unsaturation index U^K′₃₇ has been applied to reconstruct past temperature changes in both marine and lacustrine systems. However, few studies have addressed whether the relative abundance of the C_37:4 alkenone to the total C₃₇ production (%C_37:4) can reflect surface salinity changes in lacustrine systems. Here we present long-chain C₃₇ alkenone distribution patterns in surface sediments from Lake Qinghai, China. Surface sediments were sampled over a large range of surface salinity changes (1.7-25 g/l) within Lake Qinghai and its surrounding lakes, while temperature differences at these sampling locations should be relatively small. We have found that %C_37:4 varies from 15% to 49% as surface salinity decreases. We tentatively describe this %C_37:4-salinity link with a general linear regression: %C_37:4 = 53.4 (±7.8) − 1.73 (±0.45) × S (n = 28, r² = 0.62), although step-wise %C_37:4 changes in response to salinity variation may exist. U^K′₃₇ values vary between 0.10 and 0.16 at these sites and the inferred range of lake water temperature changes is ∼2-3 °C, suggesting that U^K′₃₇ largely reflects temperature signal across a large salinity range, consistent with previous findings that U^K′₃₇ can indicate temperature changes over a large diversity of environmental settings. We have also found that U^K′₃₇ values are correlated with salinity changes (r² = 0.4), and thus cannot exclude potential temperature effect on %C_37:4 and salinity effect on U^K′₃₇ in this study. However, even extreme estimates of temperature differences within the lake are still unable to explain the observed %C_37:4 changes. We therefore suggest that %C_37:4 could be used to infer past lake salinity changes at a regional scale.     

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.     

Climatic and environmental controls on the occurrence and distributions of long chain alkenones in lakes of the interior United States

Long chain alkenones (LCA) are temperature-sensitive lipids with great potential for quantitative reconstruction of past continental climate. We conducted the first survey for alkenone biomarkers from 55 different lakes in the Northern Great Plains and Nebraska Sand Hills of the United States. Among those surveyed, we found 13 lakes that contain LCAs in the surface sediments. The highest concentrations of alkenones in sediments are found in cold (mean annual air temperature ∼11 °C versus 17 °C in our warmest sites), brackish to mesosaline (salinity = 8.5-9.7 g/L), and alkaline (pH = 8.4-9.0) lakes with high concentrations of sodium and sulfate. The dynamics of stratification and nutrient availability also appear to play a role in LCA abundance, as early spring mixing promotes a bloom of alkenone-producing haptophytes. Four of the alkenone-containing sites contain the C_37:4 alkenone; however, we discovered an unprecedented lacustrine alkenone distribution in a cluster of lakes, with a total absence of C_37:4 alkenone. We attribute this unusual composition to a different haptophyte species and show that the sulfate:carbonate ratio may control the occurrence of these two distinct populations. We created a new in-situ temperature calibration for lacustrine sites that contain C_37:4 using a water-column calibration from Lake George, ND and show that is linearly correlated to lake water temperature (R² = 0.74), but is not. A number of lakes contain an unidentified compound series that elutes close to the LCAs, highlighting the importance of routine GC-MS examination prior to using lacustrine LCAs for paleotemperature reconstructions.     

Effects of long term oxic degradation on the U37K′, TEX86 and BIT organic proxies

One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the $U_{37}^{K^{\prime }}$ and TEX₈₆ palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the $U_{37}^{K^{\prime }}$ index of long chain alkenones increased only slightly (0.01, corresponding to <0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C_37:3 alkenone, in agreement with previous studies. TEX₈₆ values showed a small increase (0.02, corresponding to ～2 °C) in the F-turbidite, like $U_{37}^{K^{\prime }}$, while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ～6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX₈₆, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.     

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments

Degradation patterns of sedimentary algal lipids were tracked with time under variable redox treatments designed to mimic conditions in organic-rich, bioturbated deposits. Uniformly ¹³C-labeled algae were mixed with Long Island Sound surface muddy sediments and exposed to different redox regimes, including continuously oxic and anoxic, and oscillated oxic: anoxic conditions. Concentrations of several ¹³C-labeled algal fatty acids (16:1, 16:0 and 18:1), phytol and an alkene were measured serially. Results showed a large difference (∼10×) in first-order degradation rate constants of cell-associated lipids between continuously oxic and anoxic conditions. Exposure to oxic conditions increased the degradation of cell-associated lipids, and degradation rate constants were positive functions (linear or nonlinear) of the fraction of time sediments were oxic. Production of two new ¹³C-labeled compounds (iso-15:0 fatty acid and hexadecanol) further indicated that redox conditions and oxic: anoxic oscillations strongly affect microbial degradation of algal lipids and net synthesis of bacterial biomass. Production of ¹³C-labeled iso-15:0 fatty acid (a bacterial biomarker) was inversely proportional to the fraction of time sediments were oxic, rapidly decreasing after 10 days of incubation under oxic and frequently oscillated conditions. Turnover of bacterial biomass was faster under continuously or occasionally oxic conditions than under continuously anoxic conditions. ¹³C-labeled hexadecanol, an intermediate degradation product, accumulated under anoxic conditions but not under oxic or periodically oxic conditions. The frequency of oxic: anoxic oscillation clearly alters both the rate and pathways of lipid degradation in surficial sediments. Terminal degradation efficiency and lipid products from degradation of algal material depend on specific patterns of redox fluctuations.     

Composition of organic matter in subducted and unsubducted sediments off the Nicoya peninsula, Costa Rica (ODP Leg 170, Sites 1039 and 1040)

Investigation of sediment samples from Sites 1039 and 1040 (ODP Leg 170) drilled off the Nicoya peninsula (Costa Rica) by organic geochemical and organic petrological methods has revealed that subduction has only little influence on the composition of the sedimentary organic matter. Organic carbon contents reached 1.5% in the Pleistocene samples but Miocene and Pliocene sediments had an average organic carbon content of less than 0.5%. Organic carbon/sulfur ratios are generally below 2.8, reflecting an intense sulfate reduction in the uppermost sediments which was enhanced by sulfate supply both from sea water and deeper strata. Microscopical examinations indicate that the organic matter is mainly derived from marine sources. A small amount of terrigenous organic matter is, however, present as well according to n-alkane and fatty acid distributions. The alkenone unsaturation index U₃₇^k′ shows only a slight decrease during the Miocene and Pliocene, and stronger variations in the Pleistocene, probably indicating more stable sea surface temperatures during the Miocene and Pliocene. Variations in the Pleistocene can possibly be related to glacial/interglacial changes.     

Unusual C35 and C36 alkenones in a paleoceanographic benchmark strain of Emiliania huxleyi

Our specimen of the cultured Emiliania huxleyi strain (CCMP1742, also known as NEPCC55a) that provides the benchmark for -based paleothermometry has started producing, for reasons yet unclear, major amounts of three new alkenones identified as ω15,22-C₃₅ methyl ketone, ω15,22-C₃₆ ethyl ketone and ω16,23-C₃₆ methyl ketone. Comparison of these structures with those established now by the same OsO₄ derivatization method applied to the di-unsaturated C₃₇, C₃₈ and C₃₉ alkenones typically found in this organism provides insight into the possible pathway for their biosynthesis. Isothermal batch culture experiments also show the content and composition of these new compounds change systematically and quite significantly in cells when subjected to environmental conditions such as nutrient depletion, variation in light availability and prolonged darkness. Alkenones of similarly unusual short-chain length are evident in suspended particulate materials from present day surface waters in the Ligurian Sea (Mediterranean) and in two different Holocene time horizons (Unit I and Unit II deposits) in Black Sea sediments. However, the positions of the double bonds are different from those that we now report in our culture, implying a different biosynthetic sequence. These alkenones are most likely derived from another, as yet unknown, haptophyte species. If this other organism accounts for all documented occurrences of these compounds in natural samples, then either it has a capacity for growth over a remarkably wide salinity range or surface water salinity in the early Holocene Black Sea may not have been as low as is currently believed.     

Origins of archaeal tetraether lipids in sediments: Insights from radiocarbon analysis

Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect paleotemperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX₈₆ paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The ¹⁴C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX₈₆-derived temperatures agree more closely with foraminiferal temperatures than do temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in ¹⁴C relative to both alkenones and foraminifera, and TEX₈₆ temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute ¹⁴C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX₈₆ temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in ¹⁴C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX₈₆ index shows that it is a significant influence on the sensitivity of temperature reconstructions.     

Concurrent purification of sterols,triterpenols and alkenones from sediments for hydrogen isotope analysis using high performance liquid chromatography

Three methods are presented on how to purify acetylated sterols, acetylated triterpenols and individual alkenones for hydrogen isotope analysis from marine and lacustrine sediments using reverse-phase high performance liquid chromatography (RP-HPLC). The main advantages over previous HPLC methods are reduced operator time, increased automation and the ability to simultaneously purify multiple target compounds from a sample. These gains are achieved primarily by acetylating compounds prior to purification rather than after, and also by using a fraction collector with semi-preparatory rather than analytic configuration. The effectiveness of the method is demonstrated for (i) dinosterol and taraxerol in sediment from the brackish pond Poza del Diablo, Galápagos, (ii) for di- and tri-unsaturated C₃₇ and C₃₈ alkenones in cultured Emiliania huxleyi, (iii) for brassicasterol, and di-, tri- and tetra-unsaturated C₃₇ alkenones in sediment from Manito Lake, Saskatchewan, Canada, and (iv) for brassicasterol, dinosterol and di-, tri- and tetra-unsaturated C₃₇ alkenones in sediment from the Great Salt Lake, Utah. The purification process yields 80–90% recoveries and results in no measurable hydrogen isotope alteration.     

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.     

Amino acid and amino sugar transformation during sedimentation in lacustrine systems

We compared the degradation behaviour of amino sugars (ASs) and amino acids (AAs) during sedimentation in two lakes. Concentrations of individual ASs and AAs were measured in plankton, sediment trap and sediment samples from Lake Zug (LZ; eutrophic, stratified, permanently anoxic below 170 m) and Lake Brienz (LB; oligotrophic, oxic throughout the water column). In the plankton samples AAs comprised 37–50% of the organic carbon (C_org) and 41–65% of the N. With increasing water depth the fraction of C_org and N as AAs almost halved in both lakes. At the sediment surface the contribution of AAs to the C_org pool was slightly greater, but in the sediments the proportion further decreased downwards to values of 1% of the C_org pool in LB and 8% in LZ, and 3% and 17% of the N pool, respectively. ASs contributed to a smaller extent to the planktonic organic matter (OM). Within the water column, the contribution decreased in both lakes. In contrast, in the sediments the contribution of ASs to the C_org and N pools increased slightly with depth, indicating AS accumulation. We applied degradation indices based on ASs, AAs and chlorins, which all revealed transformation with OM sedimentation. However, some indices were more sensitive to early degradation (e.g. reactivity index) and others to an intermediate level of degradation (e.g. chlorin index and non-protein AAs). Despite the different trophic status and redox conditions, the general pattern of degradation was similar in both lakes, but was more pronounced in the sediments of the eutrophic LZ.     

Recycling of Organic Matter in the Sediments of Santa Monica Basin,California Borderland

Geochemical and isotopic data for the uppermost 1.2 m of the sediments of the central Santa Monica Basin plain were examined to better understand organic matter deposition and recycling at this site. Isotopic signatures (Δ¹⁴C and δ¹³C) of methane (CH₄) and dissolved inorganic carbon (DIC) indicate the occurrence of anaerobic oxidation of CH₄ that is fueled by CH₄ supplied from a relict reservoir that is decoupled from local organic carbon (C_org) degradation and methanogenesis. This finding was corroborated by a flux budget of pore-water solutes across the basal horizon of the profile. Together these results provide a plausible explanation for the anomalously low ratio between alkalinity production and sulfate consumption reported for these sediments over two decades ago. Shifts in Δ¹⁴C and δ¹³C signatures of C_org have previously been reported across the 20-cm depth horizon for this site and attributed to a transition from oxic to anoxic bottom water that occurred ~350 years BP. However, we show that this horizon also coincides with a boundary between the base of a hemipelagic mud section and the top of a turbidite interval, complicating the interpretation of organic geochemical data across this boundary. Radiocarbon signatures of DIC diffusing upward into surface sediments indicate that remineralization at depth is supported by relatively ¹⁴C-enriched C_org within the sedimentary matrix. While the exact nature of this C_org is unclear, possible sources are hemipelagic mud sections that were buried rapidly under thick turbidites, and ¹⁴C-rich moieties dispersed within C_org-poor turbidite sections.