Sea ice dynamics across the Mid-Pleistocene transition in the Bering Sea.

Sea ice and associated feedback mechanisms play an important role for both long- and short-term climate change. Our ability to predict future sea ice extent, however, hinges on a greater understanding of past sea ice dynamics. Here we investigate sea ice changes in the eastern Bering Sea prior to, across, and after the Mid-Pleistocene transition (MPT). The sea ice record, based on the Arctic sea ice biomarker IP25 and related open water proxies from the International Ocean Discovery Program Site U1343, shows a substantial increase in sea ice extent across the MPT. The occurrence of late-glacial/deglacial sea ice maxima are consistent with sea ice/land ice hysteresis and land-glacier retreat via the temperature-precipitation feedback. We also identify interactions of sea ice with phytoplankton growth and ocean circulation patterns, which have important implications for glacial North Pacific Intermediate Water formation and potentially North Pacific abyssal carbon storage.

Source identification and distribution reveals the potential of the geochemical Antarctic sea ice proxy IPSO25.

The presence of a di-unsaturated highly branched isoprenoid (HBI) lipid biomarker (diene II) in Southern Ocean sediments has previously been proposed as a proxy measure of palaeo Antarctic sea ice. Here we show that a source of diene II is the sympagic diatom Berkeleya adeliensis Medlin. Furthermore, the propensity for B. adeliensis to flourish in platelet ice is reflected by an offshore downward gradient in diene II concentration in >100 surface sediments from Antarctic coastal and near-coastal environments. Since platelet ice formation is strongly associated with super-cooled freshwater inflow, we further hypothesize that sedimentary diene II provides a potentially sensitive proxy indicator of landfast sea ice influenced by meltwater discharge from nearby glaciers and ice shelves, and re-examination of some previous diene II downcore records supports this hypothesis. The term IPSO25-Ice Proxy for the Southern Ocean with 25 carbon atoms-is proposed as a proxy name for diene II.

Source identification of the Arctic sea ice proxy IP25.

Analysis of the organic geochemical biomarker IP25 in marine sediments is an established method for carrying out palaeo sea ice reconstructions for the Arctic. Such reconstructions cover timescales from decades back to the early Pleistocene, and are critical for understanding past climate conditions on Earth and for informing climate prediction models. Key attributes of IP25 include its strict association with Arctic sea ice together with its ubiquity and stability in underlying marine sediments; however, the sources of IP25 have remained undetermined. Here we report the identification of IP25 in three (or four) relatively minor (<5%) sea ice diatoms isolated from mixed assemblages collected from the Canadian Arctic. In contrast, IP25 was absent in the dominant taxa. Chemical and taxonomical investigations suggest that the IP25-containing taxa represent the majority of producers and are distributed pan-Arctic, thus establishing the widespread applicability of the IP25 proxy for palaeo Arctic sea ice reconstruction.

Autoxidative and photooxidative reactivity of highly branched isoprenoid (HBI) alkenes.

Autoxidation of several mono-, di-, tri- and tetra-unsaturated highly branched isoprenoid (HBI) alkenes was induced in organic solvents using a radical initiator and enhancer, and their degradation rates were compared to those of classical phytoplanktonic lipids (mono-unsaturated fatty acids, sterols and chlorophyll phytyl side-chain). Autoxidation of two HBI trienes was also investigated in senescent and highly photodegraded diatom cells, collected in the Antarctic, using Fe(2+) ions as radical inducers. Autoxidation rates of HBI alkenes were found to increase with the number of tri-substituted double bonds, as expected. Further, HBI trienes possessing one bis-allylic position (where hydrogen abstraction is highly favoured) were found to be particularly reactive towards autoxidation and degraded at similar rates compared to polyunsaturated fatty acids in diatom cells. By comparison of the autoxidation products of the most reactive tri-unsaturated HBI with the corresponding photooxidation products, some specific tracers of these two types of abiotic degradation processes were identified. The lack of reactivity of the mono-unsaturated HBI IP25 and a structurally similar di-unsaturated HBI towards autoxidative degradation supports the good preservation of these biomarkers in marine sediments.

Biosynthesis of unusual monocyclic alkenes by the diatom Rhizosolenia setigera (Brightwell).

Novel, polyunsaturated monocyclic sester- and triterpenes isolated from the diatom Rhizosolenia setigera (Brightwell), are biosynthesised mainly via the mevalonate pathway. The experiments involved incubation of the alga with [1-(13)C]acetate, isolation of the alkenes by extraction and silver ion HPLC, followed by determination of the labelling pattern of one of the monocyclic triterpenes by (13)C-NMR spectroscopy. In addition, the extent of (13)C incorporation was also measured by mass spectrometry which revealed that the involvement of the mevalonate route in the biosynthesis of these cyclic compounds was less than for the co-occurring acyclic highly branched isoprenoid alkenes.

A simple method for SEM examination of sectioned diatom frustules.

We describe an innovative yet straightforward method to obtain high quality thin sections of diatom exoskeletons for observation by scanning electron microscopy (SEM). The use of this new technique allows for clear observations of some ultrastructural valve features, including the raphe, which are generally difficult to observe and describe accurately using transmission electron microscopy analysis of thin sections or SEM of randomly fractured diatom valves. In addition, because this method involves the complete removal of the organic content of the diatom cells, resulting in clean and mostly undisturbed skeletal thin cross-sections, even the intact valvar structures of weak girdle bands can be studied.

Factors influencing the distributions of polyunsaturated terpenoids in the diatom, Rhizosolenia setigera.

Polyunsaturated highly branched isoprenoid (HBI) hydrocarbon distributions of laboratory cultures of five strains of the planktonic diatom Rhizosolenia setigera (Brightwell) are shown herein to be highly variable. Some strains produced both haslenes with from three to five double bonds and rhizenes. The haslenes comprised not only Delta5 alkenes but also those with C7(20) unsaturation, including hasla-7(20),9E,Z, 23-trienes and hasla-7(20),9E,Z-13, 23-tetraenes. The rhizenes contained C7(25) unsaturation and the vinyl moiety common to all algal haslenes so far characterised. The effects of temperature and salinity on HBI composition, along with isotopic content, were determined in strain CS 389/A. Increase in growth temperature from 18 to 25 degrees C increased the degree of unsaturation in the haslenes and E to Z isomerisation in the triene. There was also an increase in unsaturation in the rhizenes at the highest growth temperature, with hexaenes dominant over the pentaenes but in the rhizenes, Z to E isomerisation increased. Increased salinity from 15 to 35 psu increased cell growth and rhizene production but decreased haslene production. Unsaturation in haslenes was not changed by increased salinity but unsaturation in the rhizenes decreased. These may reflect growth rate differences. The carbon isotopic compositions of the haslenes and rhizenes were similar to that of the major sterol at 18 degrees C, but the major HBI isomers were 3-4 per mil depleted relative to phytol released by saponification from chlorophyll a. This suggests biosynthesis of HBIs from a different isotopic pool of isopentenyl biphosphate to that from which phytol is biosynthesised. At 25 degrees C, further isotopic differences were observed. The variables controlling HBI distributions in R. setigera are still not fully understood and rationalisation of the environmental controls on the sedimentary distributions of the HBIs from R. setigera may only be possible once such factors are established.

Haslea salstonica sp. nov. and Haslea pseudostrearia sp. nov. (Bacillariophyta), two new epibenthic diatoms from the Kingsbridge estuary, United Kingdom.

Two new diatom species, Haslea salstonica and Haslea pseudostrearia are described in light and electron microscopy and compared with two well-known members of Haslea. Scanning electron microscope observations confirm that the new species belong to the genus Haslea. This study extends previous observations on the genus, particularly with respect to the development of a pseudostauros. The characteristic features of the genus are discussed briefly.

Variable stereochemistry in highly branched isoprenoids from diatoms.

C(25) highly branched isoprenoid (HBI) alkenes are ubiquitous lipids found in geochemical samples around the globe. The origins of these widespread geochemicals are believed to be restricted to a limited number of diatoms, including Haslea ostrearia (and related species), Rhizosolenia setigera, and Pleurosigma intermedium. The unsaturation of the HBI alkenes ranges from 2-6 in different species and cultures. The number of stereogenic centres is usually limited to two in the HBI alkenes due to double bond positions. The relative and/or absolute configurations for these have been determined for a range of HBI alkenes produced from different diatoms cultured under a number of growth conditions. These determinations have involved a combined spectroscopic and chromatographic analysis using NMR spectroscopy and chiral gas chromatography, respectively. HBIs isolated from Haslea spp. belong to a specific structural type which exhibit configurational diastereoisomerism, while those isolated from P. intermedium and R. setigera represent a different structural type and usually exist as mixtures of geometric isomers only. HBIs are reported from a new species of diatom whose stereochemical properties lie between those found for Haslea spp. and P. intermedium.

Effects of temperature on polyunsaturation in cytostatic lipids of Haslea ostrearia.

Unusual chemicals produced by the-'blue oyster' diatom, Haslea ostrearia, include the water-soluble blue pigment marennine and numerous polyunsaturated sesterterpene oils or haslenes. Aqueous extracts of the alga exhibit in vitro and in vivo activities against human lung cancer cells and anti-HIV effects. Here we report that three haslenes also demonstrate in vitro cytostatic action against a human lung cancer cell line. The most active haslene is the most unsaturated and unsaturation in the haslenes increases with increasing algal growth temperature.

Tetra-unsaturated sesterterpenoids (Haslenes) from Haslea ostrearia and related species.

The structures and distributions of C25 highly branched isoprenoid (HBI) alkenes (Haslenes) have been determined following isolation from cultures of the diatoms Haslea ostrearia, Haslea crucigera, Haslea pseudostrearia and Haslea saltstonica. The distributions of the HBIs change between Haslea species and also between different cultures of the same species. Large scale culturing of H. ostrearia and H. pseudostrearia has enabled the structures of three new tetra-unsaturated alkenes to be determined by NMR spectroscopy. The structural relationships between different Haslenes together with the potential significance of the biosynthesis of HBIs by the Haslea genus is discussed.