Occurrence of long chain 1,14-diols in Apedinella radians

Long chain 1,14-diols have been reported in diatoms of the genus Proboscia and applied as specific biomarker lipids for such algae. We report here the presence of saturated C₂₈, C₃₀ and C₃₂ 1,14-diols in a culture of the marine heterokont alga Apedinella radians (Class Dictyochophyceae, order Pedinellales). Apedinella species occur globally, although predominantly in estuarine waters, so the finding has potential implications for the use of long chain 1,14-diols as biomarkers of Proboscia diatoms and as an indicator of upwelling.     

Quantitative measurement of the sea ice diatom biomarker IP25 and sterols in Arctic sea ice and underlying sediments: Further considerations for palaeo sea ice reconstruction

The lipid content of sea ice samples collected in 2011 and 2012 from Resolute Passage in the Canadian Arctic Archipelago was measured and compared with related samples obtained from the Amundsen Gulf in 2008. The highly branched isoprenoid (HBI) sea ice biomarker, IP₂₅, was found in sea ice samples from each study, consistent with its formation by diatoms during the spring bloom. Our analysis also revealed the occurrence of a number of sterols in Arctic sea ice and these were rigorously identified and quantified for the first time. Concentrations of IP₂₅ and sterols exhibited some variability between sampling studies, with somewhat higher values in samples from Resolute in 2012 than for the other two datasets, consistent with a general increase in biomass; however, major differences in biomarker concentration between sampling studies were not observed. An estimate of the proportion of Arctic sea ice diatoms that produce IP₂₅ (ca. 1–5%) was obtained by comparison of the concentration of IP₂₅ in the samples with those in laboratory cultures of known HBI-producing diatoms and cell enumeration in selected sea ice samples. The estimate is similar to the proportion of Haslea spp. in the same samples, providing further support to the suggestion that at least some species of the Haslea genus may be responsible for the biosynthesis of IP₂₅ and related HBI diatom lipids in Arctic sea ice and that IP₂₅ is made by a relatively small proportion of sea ice diatoms. In contrast, median sterol/IP₂₅ values were all substantially higher than those in cultures of HBI-producing diatoms, suggesting that sterols are made by the majority of sea ice diatoms. The sterol/IP₂₅ ratio was quite variable between locations and samples, likely as a result of differences in diatom assemblage; however, a comparison of individual and median sterol/IP₂₅ values in sea ice with those from surface sediments from different Arctic regions demonstrated that sterols from sea ice diatoms may, in some cases, have a significant impact on the sedimentary budget. This should be considered carefully for quantitative estimates of palaeo sea ice reconstruction using methods such as the PIP₂₅ index, which are based on the relative concentrations of IP₂₅ and sterols in Arctic marine sediment cores.     

Sources of neutral lipids in a temperate intertidal sediment

The compositions of sterol, alcohol and ketone fractions from an oxic intertidal surface sediment from Corner Inlet. Victoria, Australia, have been examined by capillary gas chromatographymass spectrometry and related to the lipids of diatoms cultured from the sediment and to lipids of the sea-grass Zostera muelleri. Of the more than thirty sterols in the sediment most appear to derive from diatoms, including the major sterol 24-methylcholesta-5.22E-dien-3β-ol. Small amounts of 24-ethylcholesterol probably derive from Zostera, with a minor diatom contribution. 5α-stanols, both fully saturated and with a side-chain double bond, represented ca. 14% of the total sterols: a significant proportion of these are probably derived from marine invertebrates. These organisms also contribute C₂₆ sterols. most of the cholesterol and possibly small amounts of Δ-sterols. The data suggest that in situ biohydrogenation of stenols was not a major process in sterol transformation in the surface oxic sediment. Alcohols ranged from C₁₂ to C₃₀ and showed an unusual abundance of unsaturated components with Δ⁹-16:1 being the major constituent. The long-chain alcohols probably originate largely from Zostera but the shorter-chain. C₁₂-C₂₀. alcohols are at least partly derived from wax esters of unknown origin. Diatoms do not contribute significant amounts of alcohols. Ketones were not major constituents of the sediment and consisted mainly of 6.10.14-trimethylpentadecan-2-one and a series of n-alkan-2-ones ranging from C₁₆ to C₃₃. The latter showed a similar distribution to that of the n-alkanes but the correspondence was not sufficient to substantiate a product-precursor relationship. Very long-chain C₃- C₃₉ unsaturated methyl and ethyl ketones, which may originate from the marine unicellular alga Emiliania huxleyi. were present in low concentration.     

Long chain glycolipids with pentose head groups as biomarkers for marine endosymbiotic heterocystous cyanobacteria

Marine endosymbiotic heterocystous cyanobacteria make unique heterocyst glycolipids (HGs) containing pentose (C₅) moieties. Functionally similar HGs with hexose (C₆) moieties found in free-living cyanobacteria occur in the sedimentary record, but C₅ HGs have not been documented in the natural environment. Here we developed a high performance liquid chromatography multiple reaction monitoring (MRM) mass spectrometry (HPLC–MS²) method specific for trace analysis of long chain C₅ HGs and applied it to cultures of Rhizosolenia clevei Ostenfeld and its symbiont Richelia intracellularis which were found to contain C₅ HGs and no C₆ HGs. The method was then applied to suspended particulate matter (SPM) and surface sediment from the Amazon plume region known to harbor marine diatoms carrying heterocystous cyanobacteria as endosymbionts. C₅ HGs were detected in both marine SPM and surface sediments, but not in SPM or surface sediment from freshwater settings in the Amazon basin. Rather, the latter contained C₆ HGs, established biomarkers for free-living heterocystous cyanobacteria. Our results indicate that the C₅ HGs may be potential biomarkers for marine endosymbiotic heterocystous cyanobacteria.     

A diatomaceous origin for long-chain diols and mid-chain hydroxy methyl alkanoates widely occurring in quaternary marine sediments: indicators for high-nutrient conditions

For the first time a biological source for the long-chain alkyl 1,14-diols and 12-hydroxy methyl alkanoates, lipids widely occurring in the marine water column and sediments, has been identified. Cultures of Proboscia indica and Proboscia alata, rhizosolenoid diatoms belonging to the widespread diatom genus Proboscia, contain C₂₈, C_28:1, C₃₀, and C_30:1 alkyl 1,14-diols, and C₂₇ and C₂₉ 12-hydroxy methyl alkanoates as major neutral lipids. These components form a substantial fraction of lipid fractions from sediment traps or sediments, especially in areas with an elevated primary production such as upwelling regions. Examination of literature data reveals that as much as 20 to 35% of the total lipid flux in the Arabian Sea is derived from Proboscia diatoms during the start of the upwelling season. Their rapid transfer to the water-sediment interface may explain why corresponding 1,14-keto-ols, inferred oxidation products of diols, are hardly formed. These interpretations are supported by compound-specific carbon isotopic analysis of long-chain keto-ols and diols in surface sediments of the Arabian Sea. The data indicate that long-chain alkyl 1,14-diols and 12-hydroxy methyl alkanoates can be applied as indicators for high-nutrient conditions in the photic zone.     

Possible clay structures in frustules of living diatoms

Comparison of X-ray diffraction spectra of marine diatom frustules and suspended clay minerals suggests the presence of a distinctive smectite in diatoms. The frustules contained 1.5% Al₂O₃ and were partly covered with particles of 0.02 μm in diameter. The source of Al and the fate of diatoms in the sediment are briefly discussed.     

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.     

Identification and characterisation of a novel mono-unsaturated highly branched isoprenoid (HBI) alkene in ancient Arctic sediments

The occurrence of a novel C₂₅ highly branched isoprenoid (HBI) mono-unsaturated hydrocarbon in Arctic marine sediments from the Fram Strait is described. The structure was determined following synthesis from a closely related diene and NMR spectroscopic analysis. The position of the double bond was confirmed by oxidation (RuO₄) and comparison of the mass spectrum of the resulting C₁₉ ketone with that of an authentic sample synthesised previously. The same C₁₉ ketone was also present following oxidation of the Fram Strait sediment extracts. The source of the novel HBI monoene biomarker is not known, but is believed to be certain marine diatoms on the basis of structural similarities with other HBIs from such sources. It does not, however, appear to be biosynthesised by Arctic sea ice diatoms, unlike its regio isomer, IP₂₅, an established proxy for Arctic sea ice. Alternatively, it may represent a diagenetic product of the sea ice diatom biomarker IP₂₅; this seems unlikely, however, on the basis of their respective structures. Since the new HBI monoene and IP₂₅ possess similar gas chromatographic and mass spectral properties, but probably have contrasting sources, we suggest that future paleo sea ice reconstruction studies based on the occurrence of IP₂₅ should pay further attention to the rigorous assignment of this biomarker in marine sediment extracts. Some suggestions for achieving this, based on analytical purification and mass spectrometric measurements, are provided.     

Occurrence and biomarker potential of 23-methyl steroids in diatoms and sediments

23-Methyl sterols have been reported to be synthesized by a few marine algae, but unambiguous identification of 23-methyl steroids in sediments and petroleum is lacking. We report the presence of 23-methylcholesta-5,22E-dien-3β-ol in 14 out of 106 diatom cultures, thereby showing that diatoms, together with dinoflagellates, may be an important environmental source for such steroids. Synthesis of authentic 23-methylcholestanes showed that their mass spectra are identical to those of 24-methylcholestanes, but that they elute earlier on apolar stationary phases during gas chromatography (GC) analysis. Co-injection of the authentic standards with sediment extracts revealed the presence of these compounds in the Skole unit of the Oligocene Menelite Formation, the Miocene Monterey Formation and the Messinian Vena del Gesso Formation. In addition, we tentatively identified 23,24-dimethyl-27-norcholestanes in some of these sediments. Molecular clock calculations suggest that diatoms are a possible source for 23-methyl steroids in sediments and petroleum from the late Jurassic onwards.     

Climate-induced changes in sedimentary regimes for organic matter supply on the continental shelf off northern Norway

With this study, I suggest that changes in biogeochemical processes in northern Norwegian fjords during the last glacial/interglacial transition (14.3 to 6.3 ka B.P.) are predominantly climate induced. Variable strength in Atlantic water inflow, intrusion of Arctic waters and sea-ice coverage, various nutrient supply, as well as several re-advances of continental ice-sheets are recorded by both bulk organic and selected biomarkers in sediments of the Andfjord. Stable isotope (δ¹³C_org, δ¹⁵N) and Rock-Eval pyrolysis data indicate a strong supply of terrestrial organic matter during stadials (e.g., Younger Dryas, Older Dryas) whereas enhanced input of marine organic matter prevailed during the interstadials (Bølling/Allerød). Profiles of selected biomarkers of marine origin show a characteristic climate-induced variation during the whole time interval, where relatively low concentrations of dinosterols and C₃₇ alkenones may indicate—similar to today—a minor contribution of their respective plankton groups (coccolithophorids, dinoflagellates). The prevalence of Arctic waters and seasonal sea-ice coverage during the Younger Dryas is indicated by a single maximum of 24-methylenecholesterol probably indicating the dominance of sea-ice diatoms and/or the prevalence of diatoms of Thalassiosiraceae in surface waters. The sediments of the Allerød, in contrast, show a pronounced maximum in dinosterols, indicating a better adaptation of dinoflagellates to an oceanic regime that is characterized by incipient intrusion of Atlantic water, highly variable sea surface temperatures, and well stratified water masses. The concentration of higher-molecular-weight n-alkanes, however, follows the deglacial-early Holocene trend of climate amelioration from the last deglaciation to the middle Holocene, with maxima during ice advances (stadials) and minima during the middle Holocene warm period.These new results significantly improve the understanding of climate-induced response on organic matter supply in fjords and provide a better knowledge of past variations of biogeochemical processes in high-latitude coastal environments.     

The relative utility of foraminifera and diatoms for reconstructing late Holocene sea-level change in North Carolina, USA

Foraminifera and diatoms preserved in salt-marsh sediments have been used to produce high-resolution records of Holocene relative sea-level (RSL) change. To determine which of these microfossil groups is most appropriate for this purpose we investigated their relative utility from salt marshes in North Carolina, USA. Regional-scale transfer functions were developed using foraminifera, diatoms and a combination of both (multi-proxy) from three salt marshes (Oregon Inlet, Currituck Barrier Island and Pea Island). We evaluated each approach on the basis of transfer-function performance. Foraminifera, diatoms and multi-proxy-based transfer functions all demonstrated a strong relationship between observed and predicted elevations (r²_jack > 0.74 and RMSEP < 0.05 m), suggesting that they have equal utility. Application of the transfer functions to a fossil core from Salvo to reconstruct former sea levels enabled us to consider relative utility in light of ‘paleo-performance’. Fossil foraminifera had strong modern analogues, whilst diatoms had poor modern analogues making them unreliable. This result reflects the high diversity and site-specific distribution of modern diatoms. Consequently, we used foraminifera to reconstruct RSL change for the period since ∼ AD 1800 using a ²¹⁰Pb- and ¹⁴C-based chronology, and we were able to reconcile this with tide-gauge records.     

Analysis of natural diatom communities reveals novel insights into the diversity of long chain polyamine (LCPA) structures involved in silica precipitation

The intricately nanopatterned siliceous frustules of diatoms are formed under the control of template organic molecules, some of which are tightly incorporated into the frustule during formation. Long chain polyamines (LCPAs) attract dissolved silicic acid species, enhance silica precipitation and play a role in frustule nanopattern formation. LCPAs thus play a central biogeochemical role, linking the cycling of organic matter with the cycling of silicic acid in the photic zone of the upper ocean. Their distribution and molecular diversity in the environment are as yet unknown. We used high performance liquid chromatography electrospray ionization–mass spectrometry (HPLC–ESI–MSⁿ) to investigate the distribution and molecular diversity of aliphatic LCPAs extracted from the frustules of diatoms in mixed marine plankton communities collected within the euphotic zone of the northeastern Pacific coast, Bering Sea, and Puget Sound estuary. An astonishing variety of over 100 natural LCPAS with complex distribution patterns was found in each sample. Structural variation included degree of methylation, overall chain length, presence of secondary amine functionalities, incorporation of quaternary ammonium and occurrence of sulfonated derivatives. Putrescine-based LCPAs with various degrees of methylation and N-methyl propylamine repeat units were ubiquitous. Although some LCPA species overlapped between samples, there were regional differences in composition and structural characteristics. The structural variety of LCPAs employed by diatoms to produce their nanopatterned silicified exoskeleton could inform biomimetic studies of silica precipitation.     

Silicon Deficiency Induces Alkaline Phosphatase Enzyme Activity in Cultures of Four Marine Diatoms

Alkaline phosphatase (AP) was detected using ELF-97® in silicon-starved Pseudo-nitzschia multiseries cells; thus, we tested two, alternative hypotheses: Pseudo-nitzschia multiseries has a high phosphate demand, showing signs of phosphate deficiency even when concentrations of orthophosphate are high, or silicate deficiency can stimulate the AP enzyme in this species. We also studied the effect of silicon deficiency on AP in three other common marine diatoms: Thalassiosira pseudonana, Nitzschia pusilla, and Nitschia closterium. Each of the species tested showed a different pattern of AP regulation. AP levels, however, increased in the four diatoms as a result of silicon deficiency, suggesting that AP may be involved in a variety of intracellular processes related to silicon deficiency. Additionally, the results of this study indicate that AP could be stimulated by stressors other than phosphate deficiency, such as silicon deficiency; therefore, it should be used cautiously as an indicator of phosphate limitation.     

Sources and occurrence of C12C22n-alkane distributions with even carbon-number preference in sedimentary environments

The occurrence of C₁₂C₂₂n-alkanes with a strong even carbon-number preference is reported in recent and Miocene sediments, encompassing marine and freshwater systems, deposited under oxic and anoxic conditions. It is therefore shown that these n-alkanes can be found in a wider type of sedimentary environment than those previously described. The occurrence in some cases of a parallel distribution of C₁₄C₂₀n-alk-1-enes is also illustrated. A variety of biological sources, including both marine and freshwater bacteria as well as fungi and yeast species is suggested to account for such distributions.     

New data on diatoms from the marine Paleogene of Western Kamchatka

Diatom assemblages from the marine Paleogene of Western Kamchatka (the Kovachina, Viventek, and Kuluven formations) are studied. The shallow-water neritic assemblage from the Kovachina Formation of the Pyatibratskii Cape section is tentatively attributed to the middle Eocene, as it is lacking zonal index species. A high abundance and great taxonomic diversity are characteristic of diatoms from the upper part of the Viventek Formation in the Kovran River section. The zonal index species Cavitatus rectus identified here among the diatoms suggests that the respective assemblage is macerated from the synonymous diatom zone of the middle Oligocene (29.6?28.2 Ma). According to its taxonomic composition and structure, this assemblage is indicative of transgression environments and the presumable influence of the middle Oligocene climatic optimum. The Rocella gelida (upper part) and Thalassiosira praefraga diatom zones of the Oligocene-Miocene transition are established in the Kuluven Formation sediments of the Mt. Uvuch section in Kovachina Bay.     

Isotopic compositions of tropical East African flora and their potential as source indicators of organic matter in coastal marine sediments

The C and N stable isotope compositions of some flora of East Africa from coastal Tanzania and Amboseli National Park (Kenya) are used to assess if they can be used as a terrestrial end member during the estimation of terrestrial fraction in coastal marine sediments. The results of C isotope composition of various tree leaves, which average −29.3 ± 1.4%, indicate that these tropical higher land plant species follow a Calvin-Benson or non-Kranz (C₃) type of metabolism. The results for grass species, which average −13.2 ± 2.4%, indicate that most of them follow a Hatch-Slack or Kranz (C₄) type of metabolism. However, some of the succulent plants from the Amboseli National Park have δ¹³C values that average −14.7%, an indication that they follow a CAM (Crassulacean Acid Metabolism) type of metabolism. The N isotope values are relatively higher than expected for the terrestrial organic material. The average δ¹⁵N values for both tree and grass samples are higher than 5% and fall within the range normally considered to be marine. The high enrichment in ¹⁵N may be related to the environmental conditions in which plants thrive. Plants growing in sandy, dry and overgrazed environments are expected to be enriched in ¹⁵N owing to full utilisation of all available N species, regardless of their isotopic compositions. Other processes which may cause an enrichment in ¹⁵N include adsorption by various types of clay minerals, supply of ¹⁵N-enriched nitrate through sea-spray, and local denitrification, especially in swampy and lake margins where the input of organic matter may be higher than the rate of decomposition.The stable isotopic composition of organic C and N for surficial organic matter for the coastal marine sediments averages −17.0 ± 0.9% and 5.4 ± 1.1%, respectively. These values indicate a substantial contribution of C₄ plants and sea grasses. However, contribution of C₄ relative to that of sea grasses can not be evaluated owing to the fact that there is no significant difference in the isotopic compositions between the two groups.In the savannah environment, where a contribution from the C₄ types of plants might be substantial, the δ¹³C value for a terrestrial end member needs to be established prior to evaluation of the terrestrially derived organic matter in the marine environment. Owing to a significant contribution of sea grasses to the total organic matter preserved in coastal marine sediments, the stable isotopes of organic C seem to have a limited applicability as source indicators in the East African coastal waters. Furthermore, the results indicate that N stable isotopes seem to have a limited applicability as source indicators in coastal waters of East Africa. However, more work needs to be conducted to determine the terrestrial and sea grass end member values for the coastal areas.     

Geochemistry of C25 and C30 biogenic alkenes in sediments of the narragansett bay estuary

The distributions of a series of structurally related C₂₅ and C₃₀ biogenic alkenes in sediments of the Narragansett Bay estuary have been determined. The suite of alkenes detected differs both quantitatively and qualitatively from those previously reported in other estuanne and coastal regions. Four C₂₅ mono- and dienes and one C₃₀ diene comprise 73–91% of the total alkenes in all surface (upper 2.5–5 cm) sediments analyzed. However, significant geographic variations exist in the relative abundance of these five compounds throughout the estuary. A comparison of alkene concentrations with δ¹³C of the bulk sedimentary organic matter has shown that the geographic variations of some alkenes reflect the distribution of marine organic matter, suggesting a marine source for these compounds. The distributions of other alkenes are not similarly correlated. In particular, concentrations of the C₃₀ diene are relatively constant and exhibit no dependence on the origin of organic matter in these sediments. This distribution implies an in situ production of this alkene throughout the estuary. Analysis of several sediment cores reveals that alkene concentrations are generally highest at the surface and decrease to low, constant values within the upper 25 cm. An exception is the subsurface concentration of one C₂₅ diene, which exhibits an increase at the same depth in two separate upper bay cores.     

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.     

Linking phytoplankton community composition with juvenile-phase growth in the Northern QuahogMercenaria mercenaria (L.)

This study examined whetherMercenaria mercenaria (L.) (quahog) growth is influenced by variability in phytoplantkon community composition in the waters of Long Island, New York. Field studies conducted during 1999 and 2000 compared juvenile quahog growth and phytoplankton assemblages between West Sayville (WS), an embayment in Great South Bay along Long Island’s south shore where quahog landings have recently declined, and Oyster Bay (OB), an embayment on Long Island’s north shore where quahog landings are still high. Quahogs grew better at OB than WS during both study years. Centric diatoms were typically the dominant phytoplankton species at OB, and pennate diatoms and dinoflagellates characterized WS. At WS, the phytoplankton community consisted of heterotrophic dinoflagellates during a brown tide in 2000 and pennate diatoms afterward. Nanoflagellates were abundant (10⁵–10⁶ cells ml^?1) at WS throughout the summer of 2000. Multiple regression analysis revealed a significant effect of site and temperature on individual clam biomass during both years, but brown tide was only significant during 2000. Biomass comparisons of dominant phytoplantkon taxa with laboratory physiology studies showed that 0B, with its abundance of centric diatoms, likely represented a more nutritional diet for quahogs than pennate diatoms, which were abundant at WS. Small flagellates, which were common at WS, may also have been important for sustaining growth during some months. Variability in plankton assemblages between OB and WS likely represented two distinct, diets that were critical influences on clam growth.