Seasonal variations of lipid content and composition in perna viridis

The total lipid content, composition of main lipid classes, composition of sterols and composition of fatty acids in the main glycerolipids of Perna viridis were analyzed through four seasons using TLC-FID and GLC. Mussel samples were collected during different seasons between 2003 and 2004 from Shengsi Island, Zhejiang Province, China and stored frozen prior to freeze-drying and lipid extraction. Ten grams of dried mussel powder of each season were analyzed. Total lipid content ranged from 14.5 g/100 g in spring month to 7.8 g/100 g dried mussel powder in autumn month. The predominant lipid in spring month was triacylglycerol (TAG), however, in the other three seasons the phospholipids (PL) was the main lipid class. The most abundant fatty acid in TAG, PL and phosphatidylcholine (PC) was 16:0, with the summer samples having the highest proportion (24-30% of total fatty acid) and winter the lowest (14-22%). In phosphatidylethanolamine (PE), the spring samples had the highest proportions of 16:0. The predominant polyunsaturated fatty acids (PUFA) were 22:6n-3 and 20:5n-3 in TAG, PL, PE and PC (25-40%). The proportions of 22:6n-3 and 20:5n-3 were higher in spring than in other seasons in PL and PE. There were nine sterols identified, with cholesterol being the predominant sterol, and other main ones were desmostersol/brassicasterol and 24-methylenecholesterol. Proportions of other fatty acids in different lipid fractions and the sterol compositions as well also varied seasonally. There were subject to the seasonal variations. Differences in lipid content and composition, fatty acid composition in different lipid fractions may be caused by multiple factors such as lifecycle, sex, variation of plankton in different seasons and temperature, which could influence physiological activities and metabolism.

Lipid, FA, and sterol composition of New Zealand green lipped mussel (Perna canaliculus) and Tasmanian blue mussel (Mytilus edulis)

The lipid, FA, and sterol composition of the New Zealand green lipped mussel (NZGLM, Perna canaliculus) and of the Tasmanian blue mussel (TBM, Mytilus edulis) were compared using TLC-FID and GC-MS. The respective mussel species were obtained from three different sites in both New Zealand (NZ) and Tasmania. Lipid class distribution of both mussel species was characterized by a high proportion of phospholipid (PL, 57–79%) and TG (10–25%), FFA (7–12%), and sterols (ST, 12–18%). The NZGLM had higher proportions of TG, FFA, and ST (P<0.01), whereas the TBM had a higher proportion of PL (P<0.01). There were higher proportions of total PUFA, saturated FA, n−3 FA, and hydroxy and nonmethyleneinterrupted FA (P<0.05) in the TBM compared with the NZGLM. The major FA in the NZGLM were 16∶0 (15–17%), 20∶5n-3 (14–20%), and 22∶6n-3 (11–17%). The same FA dominated lipids in the TBM, although there were significantly higher proportions of 16∶0 (P=0.000) and 22∶6 n−3 (P=0.003) and lower proportions of 20∶5n-3 (P=0.0072) in the TBM. A novel PUFA, 28∶8n-3, was detected in both mussels with higher amounts in the TBM, which probably reflects a greater dietary contribution of dinoflagellates for this species. Cholesterol was the dominant sterol in both mussels. Other major sterols included brassicasterol, 22-methylcholesterol, trans-22-dehydrocholesterol, and desmosterol. There were significant differences (P<0.05) between the NZGLM and TBM for 12 of the 20 sterols measured. Six sterols showed significant site differences for the NZGLM, and 10 for the TBM. The differences in the FA and sterol composition between the two species may be due to the diet of the NZGLM being more diatom-derived and the diet of the TBM having a greater dinoflagellate component.

Fatty acid and sterol composition of frozen and freeze-dried New Zealand green lipped mussel (Perna canaliculus) from three sites in New Zealand

In view of previously reported anti-inflammatory bioactivity of the New Zealand Green Lipped Mussel (NZGLM), the overall lipid profile and fatty acid and sterol composition of the NZGLM from various sites in New Zealand (Hallam Cove, Port Ligar, Little Nikau) were investigated using thin layer  chromatography (TLC) and gas liquid chromatography (GLC). Samples were either frozen (F) or freeze-dried (FD) soon after collection. It was also thought prior to the study, there may be differences in the dietary sources of phytoplankton between the sites, responsible for the bioactivity, however data collected in New Zealand reported no difference in the type of phytoplankton, but a difference in the quantity. There were no major significant differences in the major components of the lipid, fatty acid and sterol composition between FD or frozen samples, nor were there any significant differences in the major composition between sites. The only major difference was between total lipid composition of the freeze-dried and frozen samples due to the removal of water during freeze-drying. Total lipid content on a dry weight basis in FD samples was 8.4 g/100g tissue and was significantly higher than frozen samples (P < 0.05) and there was no significant site variation. The lipid class content between sites was also not significantly different as judged by TLC. Triglyceride (TG) lipid fraction appeared to be the most prominent in the frozen and FD samples. The free fatty acid (FFA) band was the next most prominent band and was visually more prominent in the frozen samples. Sterol esters (SE) were detected in higher amounts in the frozen samples compared with the FD samples. Phospholipid (PL) and sterols (ST) were distributed throughout all samples. Polyunsaturated fatty acids (PUFA) were the main group of fatty acids in both FD and frozen samples (45-46%), most of which were omega-3 (n-3) fatty acids (40-41%). Saturated fatty acids (SFA) accounted for approximately one quarter of total fatty acids, with little variation between FD and frozen samples. The major fatty acids of the NZGLM were docosahexaenoic acid (DHA; 22:6n-3) (19% in both FD and frozen samples), eicosapentaenoic acid (EPA; 20:5n-3) and palmitic acid (16:0) (15% in both FD and frozen samples). Cholesterol was the most prominent sterol (31% of total sterols). Other major sterols included desmosterol/ brassicasterol (co-eluting), 24-methylenecholesterol, trans-22-dehydrocholesterol, 24- nordehydrocholesterol and occelasterol. This study is unique as it compares the lipid composition of the NZGLM from three sites in New Zealand with the additional effect of processing. This is the second comparative study investigating the lipid, fatty acid and sterol composition of the NZGLM with added interest in the effect of freeze drying on the lipid content of the mussel. This study showed that there were no major significant differences in lipid, sterol and fatty acid composition between the FD and frozen samples of the NZGLM for three sites in New Zealand. Food chain studies and further research is warranted to investigate the presence and role of major and minor lipid.
components of the NZGLM.

Extratos de sementes de gergelim preto (Sesamum indicum L) obtidos via CO2 supercrítico: isotermas de rendimento global, dados cinéticos e ajustes, ácidos graxos totais, fitosteróis e efeitos neuroprotetores

Na medicina popular brasileira, sementes de gergelim preto (Sesamum indicum L) é um dos mais importantes ingrediente presentes em um chá usado para tratar vítimas de acidente vascular encefálico (AVE). Porém, o isolamento de extratos de gergelim preto para fins medicinais usando a tecnologia do fluido supercrítico não foi realizado. O objetivo deste trabalho foi investigar algumas variáveis de processo da extração com fluido supercrítico em sementes de gergelim preto para gerar extratos aplicáveis a pesquisa do AVE isquêmico focal. Duas isotermas (40 e 60 ºC) foram exploradas, combinadas com pressões de 200-400 bar, em vazão mássica de CO₂ constante de 5,9 x 10^-5 kg/s. Os rendimentos globais foram de 37-53% em base seca. O maior rendimento foi obtido em 60 ºC e 400 bar. A composição de ácidos graxos mostrou uma elevada razão de insaturados/ saturados. A análise de conteúdo de fitosteróis no extrato de maior rendimento revelou maiores quantidades de β-sitosterol + sitostanol, colesterol, campesterol + campestanol + 24-metileno colesterol, Δ-5 avenasterol and estigmasterol, enquanto que menores níveis de Δ-5,24 estigmastadienol, brassicasterol, clerosterol + Δ-5-23 estigmastadienol, Δ-7 avenasterol, eritrodiol and Δ-7 estigmastenol foram observados. As curvas de extração das extrações com fluido supercrítico no menor e maior rendimento mássico (200 e 400 bar a 60 ºC) foram ajustadas pelos modelos de Tan e Liou (1989), Martinez et al. (2003), Esquível et al. (1999), Goto et al. (1993) e Sovová (1994 e 2012). Os modelos de Tan e Liou (1989), Goto et al. (1993) e Sovová (1994 e 2012) apresentaram as melhores valores nominais de somas residuais dos quadrados. Experimentos pilotos sugerem que o extrato obtido via fluido supercrítico de gergelim preto é neuroprotetor em relação a isquemia focal por endotelina-1 no córtex motor de ratos machos adultos, observada a redução da área de infarto isquêmico.

A comparison between multi-proxy and historical data of drift-ice conditions on the East Greenland shelf

The reduction in sea ice along the SE Greenland coast during the last century has severely impacted ice-rafting to this area. In order to reconstruct ice-rafting and oceanographic conditions in the area of Denmark Strait during the last ~150 years, we conducted a multiproxy study on three short (20 cm) sediment cores from outer Kangerdlugssuaq Trough (~300 m water depth). The proxy-based data obtained have been compared with historical and instrumental data to gain a better understanding of the ice sheet-ocean interactions in the area. A robust chronology has been developed based on 210Pb and 137Cs measurements on core PO175GKC#9 (~66.2°N, 32°W) and expanded to the two adjacent cores based on correlations between calcite weight percent records. Our proxy records include sea-ice and phytoplankton biomarkers, and a variety of mineralogical determinations based on the <2 mm sediment fraction, including identification with quantitative x-ray diffraction, ice-rafted debris counts on the 63-150 µm sand fraction, and source identifications based on the composition of Fe oxides in the 45-250 µm fraction. A multivariate statistical analysis indicated significant correlations between our proxy records and historical data, especially with the mean annual temperature data from Stykkishólmur (Iceland) and the storis index (historical observations of sea-ice export via the East Greenland Current). In particular, the biological proxies (calcite weight percent, IP25, and total organic carbon %) showed significant linkage with the storis index. Our records show two distinct intervals in the recent history of the SE Greenland coast. The first of these (ad 1850-1910) shows predominantly perennial sea-ice conditions in the area, while the second (ad 1910-1990) shows more seasonally open water conditions.

Age determination of sediment cores off western Spitsbergen

The Late Weichselian glacial history of the continental shelf off western Spitsbergen is discussed, based on acoustic sub-bottom records and sediment cores. The outer part of Isfjorden and the inner shelf to the west of this fjord are characterized by a thin veneer (10-20 m) of glacigenic sediments and absence of ice-marginal features. Towards the outer shelf the sediment thickness increases significantly, and exceeds 500 m at the shelf edge. Possible moraine complexes were identified in this outer part. Sediment cores from the inner shelf sampled a firm diamicton, interpreted as till, beneath soft glaciomarine sediments. Radiocarbon dates on shells from the clay resting directly on the till, suggest an age of around 12,500 yrs B.P. for the base of the marine sequence. We argue that grounded ice covered the sites shortly before. In contrast to suggestions that the fjords and coast were partly ice free during the Late Weischselian, we conclude that the ice must have reached out onto the continental shelf.

Age determination of sediment cores from the western Svalbard margin

The deglaciation of the continental shelf to the west of Spitsbergen and the main fjord, Isfjorden, is discussed based on sub-bottom seismic records and sediment cores. The sea floor on the shelf to the west of Isfjorden is underlain by less than 2 m of glaciomarine sediments over a firm diamicton interpreted as till. In central Isfjorden up to 10 m of deglaciation sediments were recorded, whereas in cores from the innermost tributary, Billefjorden, less than a meter of ice proximal sediments was recognized between the till and the 'normal' Holocene marine sediments. We conclude that the Barents Sea Ice Sheet terminated along the shelf break during the Late Weichselian glacial maximum. Radiocarbon dates from the glaciomarine sediments above the till indicate a stepwise deglaciation. Apparently the ice front retreated from the outermost shelf around 14.8 ka. A dramatic increase in the flux of line-grained glaciomarine sediments around 13 ka is assumed to reflect increased melting and/or current activity due to a climatic warming. This second stage of deglaciation was interrupted by a glacial readvance culminating on the mid-shelf area shortly after 12.4 ka. The glacial readvance, which is correlated with a simultaneous readvance of the Fennoscandian ice sheet along the western coast of Norway, is attributed to the so-called 'Older Dryas' cooling event in the North Atlantic region. Following this glacial readvance the outer part of Isfjorden became rapidly deglaciated around 12.3 ka. During the Younger Dryas the inner fjord branches were occupied by large outlet glaciers and possibly the ice front terminated far out in the main fjord. The remnants of the Barents Sea Ice Sheet melted quickly away as a response to the Holocene warming around 10 ka.

Organic geochemistry of sediment cores from the Arbian Sea

Two deep-sea sediment cores from the northeastern and the southeastern Arabian Sea were studied in order to reconstruct the palaeoenvironments of the past glacial cycles. Core 136KL was recovered from the high-productivity area off Pakistan within the modern oxygen-minimum zone (OMZ). By contrast, modern primary productivity at the site of MD900963 close to Maldives is moderate and bottom waters are today well oxygenated. For both cores, we reconstructed the changes in palaeoproductivity using a set of biomarkers (alkenones, dinosterol and brassicasterol); the main result is that primary productivity is enhanced during glacial stages and lowered during interstadials. The proxies associated with productivity show a 23 kyr cyclicity corresponding to the precession-related insolation cycle. Palaeoredox conditions were studied in both cores using a new organic geochemical parameter (C35/C31-n-alkane ratio) developed by analysing surface sediments from a transect across the OMZ off Pakistan. The value of this ratio in core 136KL shows many variations during the last 65 kyr, indicating that the OMZ was not stable during this time: it disappeared completely during Heinrich- and the Younger Dryas events, pointing to a connection between global oceanic circulation and the stability of the OMZ. The C35/C31 ratio determined in sediments of core MD900963 shows that bottom waters remained rather well oxygenated over the last 330 kyr, which is confirmed by comparison with authigenic metal concentrations in the same sediments. A zonally averaged, circulation-biogeochemical ocean model was used to explore how the intermediate Indian Ocean responds to a freshwater flux anomaly at the surface of the North Atlantic. As suggested by the geochemical time series, both the abundance of Southern Ocean Water and the oxygen concentration are significantly increased in response to this freshwater perturbation.

Biomarker proxies on sediment cores in the central Arctic Ocean

Although the permanently to seasonally ice-covered Arctic Ocean is a unique and sensitive component in the Earth's climate system, the knowledge of its long-term climate history remains very limited due to the restricted number of pre-Quaternary sedimentary records. During Polarstern Expedition PS87/2014, we discovered multiple submarine landslides over a distance of >350 km along Lomonosov Ridge. Removal of younger sediments from steep headwalls has led to exhumation of Miocene to early Quaternary sediments close to the seafloor, allowing the retrieval of such old sediments with gravity cores. Multi-proxy biomarker analyses of these gravity cores reveal for the first time that the late Miocene central Arctic Ocean was relatively warm (4-7°C) and ice-free during summer, whereas sea ice occurred during spring and autumn/winter. A comparison of our proxy data with Miocene climate simulations seems to favour relatively high late Miocene atmospheric CO2 concentrations. These new findings from the Arctic region provide new benchmarks for groundtruthing global climate reconstructions and modeling.

Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Particle analysis in the Kara Sea

In September 1999 two short-term moorings with cylindrical sediment traps were deployed to collect sinking particles in bottom waters off the Ob and Yenisei river mouths. Samples were studied for their bulk composition, pigments, phytoplankton, microzooplankton, fecal material, amino acids, hexosamines, fatty acids and sterols and compared to suspended matter and surface sediments in order to collect information about the nature and cycling of particulate matter in the water column. Results of all measured components in sinking particles point to an ongoing seasonality in the pelagic system from blooming diatoms in the first phase to a more retention system in the second half of trap deployment. Due to a phytoplankton bloom observed north of the Ob estuary, flux rates were generally higher in the trap deployed off the Ob than off the Yenisei. The Ob trap collected fresh surface-derived particulate matter. Particles from the Yenisei trap were more degraded and resembled deep water suspension. This material may partly have been derived from resuspended sediments.

Biomarker distributions and calculated sea surface temperatures from the North Pacific Ocean

In order to study the modern sea surface characteristics of the sub-polar North Pacific and the Bering Sea, i.e. sea surface temperature (SST) and sea ice cover, surface sediments recovered during the RV Sonne Expedition 202 in 2009 were analysed. To distinguish between marine and terrestrial organic carbon, hydrogen index values, long chain n-alkanes and specific sterols have been determined. The results show that in the Bering Sea, especially on the sea slope, the organic carbon source is mainly caused by high primary production. In the North Pacific, on the other hand, the organic material originates predominantly from terrestrial higher plants, probably related to dust input from Asia. SST has been reconstructed using the modified alkenone unsaturation index. Calibration from Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) offers the most reliable estimate of mean annual temperature in the central North Pacific but does not correlate with mean annual temperature throughout the study area. In the eastern North Pacific and the Bering Sea, the Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) calibration seems to be more accurate and matches summer SST. The distribution of the novel sea ice proxy IP25 (highly branched C25 isoprenoid alkene) in surface sediments is in accord with the modern spring sea ice edge and shows the potential of this proxy to track past variation in sea ice cover in the study area.

Temporal and spatial LGM variability of biomarker records in the Arctic Ocean

Using the sea ice proxy IP25 and phytoplankton-derived biomarkers (brassicasterol and dinosterol) Arctic sea-ice conditions were reconstructed for Marine Isotope Stage (MIS) 3 to 1 in sediment cores from the north of Barents Sea continental margin across the Central Arctic to the Southern Mendeleev Ridge. Our results suggest more extensive sea-ice cover than present-day during MIS 3, increasing sea-ice growth during MIS 2 and decreased sea-ice cover during the last deglacial. The summer ice edge sustained north of the Barents Sea even during extremely cold (i.e., Last Glacial Maximum (LGM)) as well as warm periods (i.e., Bølling-Allerød). During the LGM, the western Svalbard margin and the northern Barents Sea margin areas were characterized by high concentrations of both IP25 and phytoplankton biomarkers, interpreted as a productive ice-edge situation, caused by the inflow of warm Atlantic Water. In contrast, the LGM high Arctic proper (north of 84°N) was covered by thick permanent sea ice throughout the year with rare break up, indicated by zero or near-zero biomarker concentrations. The spring/summer sea-ice margin significantly extended southwards to the southern Lomonosov Ridge and Mendeleev Ridge during the LGM. Our proxy reconstructions are very consistent with published model results based on the North Atlantic/Arctic Ocean Sea Ice Model (NAOSIM).