Use of microbial enrichments for the study of the anaerobic degradation of cholesterol

To demonstrate the potential of model microbial assemblages in studies of the biogeochemistry of complex organic molecules, anaerobic microbial populations capable of degrading cholesterol (cholest-5-en-3β-ol) have been enriched from marine sediment sources. The bacterial enrichments actively mineralized the C-4 nucleus of the cholesterol ring system to carbon dioxide when nitrate was present as the terminal electron acceptor. Nitrite was found as an intermediate in the reduction of nitrate, indicating the presence of denitrifying bacteria in the enrichments. When sulfate was supplied as the sole electron acceptor, active dissimilation of cholesterol was not observed. In enrichments containing 5 mM nitrate, 95–98% of the added cholesterol was recovered as carbon dioxide (2–5%), transformation products (20–30%), or as the unmodified sterol (70–80%). Cholesterol transformation products thus far identified include 5α- and 5β-cholestan-3β-ol, cholest-4-en-3-one, 5α-androstan-3, 17-dione and androst-4-en-3, 17 dione.     

Occurrence of gorgosterol in diatoms of the genus Delphineis

The presence of the C₃₀ sterol gorgosterol (22,23-methylene-23,24-dimethylcholest-5-en-3ß-ol) and its analogues in some marine and freshwater environments is generally associated with invertebrate animals or dinoflagellates since there have been no reports of them in other microalgal classes. Here we show that two unialgal cultures of different species of the marine diatom Delphineis contain gorgosterol in addition to sterols more commonly found in diatoms. Our findings suggest that some reports of gorgosterol in seawater and marine sediments may well have an origin, at least in part, from diatoms.     

Sterols in the western North Atlantic Ocean

The sterol concentrations in fourteen surface and nine deep water samples collected from the continental shelf and slope waters of the western North Atlantic and Sargasso Sea ranged from 0.1 to 1.3μ/l seawater. Isolation and structural elucidation by gas chromatography and combined gas chromatography-mass spectrometry show that cholesterol and β-sitosterol (or clionasterol) are the major free sterols in both the surface and deep water. Fucosterol, brassicasterol, 22-dehydrocholesterol, campesterol (or 22,23-dihydrobrassicasterol), 22-methylenecholesterol, norcholestadienol, and stigmasterol (or poriferasterol) are found in lower concentrations at the surface and in the deep sea. Cholesterol is the major sterol ester in both the surface and deep water, while very low concentrations of other sterol esters were found. The ratio of total free sterols to total esterified sterols is approximately two in both the surface and deep water.Marine sources of sterols in seawater include phytoplankton, yeasts, and marine animals such as Crustacea and molluscs. Terrestrial plants also may contribute. Sterol transport to the deep sea may occur by convective overturn and vertical diffusion or from vertical fluxes of large particles from the surface.     

Scarcity of the C30 sterane biomarker, 24-n-propylcholestane,in Lower Paleozoic marine paleoenvironments

24-n-Propylcholestane (24-npc), a C₃₀ sterane compound derived from sterol precursors which are the major sterol constituents of modern pelagophyte microalgae, occurs in certain Neoproterozoic rocks and oils and throughout the Phanerozoic rock record. This broad distribution leads 24-npc to be widely considered a reliable indicator of open to partially restricted marine depositional conditions for source rocks and oils. Here we report two significant hiatuses in the occurrences of 24-npc in the Lower Paleozoic marine rock record: the first in the Middle–Late Cambrian and the second in the Late Ordovician–early Silurian transition for a range of lithofacies (carbonates and siliciclastic rocks), organic carbon contents (both organic-lean and organic-rich), and paleoceanographic environments (shelf and deeper water marine settings) and observed offshore of two paleocontinents, Laurentia and Baltica. The Ordovician–Silurian gap is at least 9 million years, and possibly up to 20 million years, in duration. Robust older occurrences of 24-npc steranes in some Neoproterozoic rocks and oils suggest that oceanographic conditions in our intervals of Lower Paleozoic time were unfavorable for the proliferation of pelagophyte algae as phytoplankton. Caution should therefore be applied when interpreting a lacustrine versus marine depositional environmental setting for source rocks and oils in these intervals of Early Paleozoic time using lipid biomarker assemblages.     

Tephrostratigraphy study for the last 18,000 14C years in a deep-sea sediment sequence for the South Adriatic

A detailed tephrostratigraphy supported by accelerator mass spectrometry (AMS) ¹⁴C dating and isotopic and geochemical analyses has been carried out for a deep-sea core collected from the Southern Adriatic Sea, which spans the last 18 ¹⁴C kyr. Fourteen ash layers have been recognized in the marine core and the origin was determined by comparing their age and geochemistry with tephra detected in terrestrial deposits. The geochemical signatures of marine ash layers indicate a prevailing Campanian and subordinate Etnean and Eolian provenances. Collectively, they are attributed to sources in the Phlegraean Fields (LAM-Lagno Amendolare; LN1/LN2-GM1; C-2/NYT-Neapolitan Yellow Tuff; C-1-Agnano Pomici Principali; AMS/PF-Agnano Monte Spina; AST-Astroni), Somma-Vesuvius (L9-Pomici di Base; L8-Greenish), Mount Etna (Et1-Y1-Biancavilla Ignimbrite), Lipari (E-1-Gabellotto-Fiumebianco) and Palinuro seamount (Pal 1). Some of these eruptions have been detected for the first time in marine cores (Astroni, LAM, L9, L8), and three were detected and dated by marine tephra (LN1, LN2, and Pal 1) providing new more precise stratigraphic markers for the last 18  kyr in the South Adriatic marine record.     

Age and extent of the Barents and Kara ice sheets in Northern Russia

The youngest ice marginal zone between the White Sea and the Ural mountains is the W-E trending belt of moraines called the Varsh-Indiga-Markhida-Harbei-Halmer-Sopkay, here called the Markhida line. Glacial elements show that it was deposited by the Kara Ice Sheet, and in the west, by the Barents Ice Sheet. The Markhida moraine overlies Eemian marine sediments, and is therefore of Weichselian age. Distal to the moraine are Eemian marine sediments and three Palaeolithic sites with many C-14 dates in the range 16-37 ka not covered by till, proving that it represents the maximum ice sheet extension during the Weichselian. The Late Weichselian ice limit of M. G. Grosswald is about 400 km (near the Urals more than 700 km) too far south. Shorelines of ice dammed Lake Komi, probably dammed by the ice sheet ending at the Markhida line, predate 37 ka. We conclude that the Markhida line is of Middle/Early Weichselian age, implying that no ice sheet reached this part of Northern Russia during the Late Weichselian. This age is supported by a series of C-14 and OSL dates inside the Markhida line all of >45 ka. Two moraine loops protrude south of the Markhida line; the Laya-Adzva and Rogavaya moraines. These moraines are covered by Lake Komi sediments, and many C-14 dates on mammoth bones inside the moraines are 26-37 ka. The morphology indicates that the moraines are of Weichselian age, but a Saalian age cannot be excluded. No post-glacial emerged marine shorelines are found along the Barents Sea coast north of the Markhida line.     

A study of oxic/anoxic effects on degradation of sterols at the simulated sediment–water interface of coastal sediments

Laboratory incubation experiments were conducted to determine the behavior of sterols at the sediment–water interface in oxic and anoxic sediments. Both plankton and 4- -cholesterol were used as tracers. Cholesterol was rapidly degraded at the sediment–water interface: 55% of -cholesterol was lost from sediments under anoxic conditions and 78% under oxic conditions over three and one-half months. About 3% of initially-added free radiolabel was incorporated into a bound pool that was released only by saponification of solvent-extracted sediment. Less than 1% of initially-added radiolabel remained in pore waters after three and one-half months. Rate constants for degradation of cholesterol in oxic and anoxic surficial sediments were estimated by tracking variations in radioactivity and sterol concentration as a function of time. We discuss our results in terms of factors affecting sterol degradation in coastal marine sediments, including molecular structure, sediment matrix effect, and redox conditions.     

Pyrolysis-GC-MS and NMR studies of dissolved seawater humic substances and isolates of a marine diatom

¹³C- and ¹H-NMR spectra were obtained for humic substances isolated from a coastal marine environment and also for the intracellular and extracellular extracts of a marine diatom. Phaeodactylum tricornutum Bohlin. Highly branched alkyl chains constitute a large proportion of the structure of the marine humic material, whereas aromatic components are less important. Carbohydrate-type materials, possibly uronic acids, are also present in appreciable amounts. Furans (derived from carbohydrates). pyrroles and nitriles (derived from proteins, nucleic acids and/or tetrapyrroles) and phenols and methylphenols (non-lignin derived) are pyrolysis products derived from pyrolysis-gas chromatography-mass spectrometry of the extracts. The results indicate the similarities in chemical structure of P. tricornutum exudate and dissolved marine humic material.     

Architecture and development of the alluvial sediments of the Upper Jurassic Tordillo Formation in the Cañada Ancha Valley, northern Neuquén Basin, Argentina

The Upper Jurassic Tordillo Formation at Cañada Ancha area, northern Neuquén Basin, Argentina, comprises a multi-stage suit of predominantly alluvial sediments that is heterolithic in nature. In that suit, several lithofacies, architectural elements, and bounding surfaces of different order have been identified and their lateral and vertical distribution characterized. This analysis allowed the differentiation of 3 main units (lower, middle and upper), 20 subunits (C-1 to C-20), and the characterization of their alluvial styles.The lower unit (which comprises subunits C-1 to C-4) is mainly formed by fine- to medium-grained sandstones, which become medium- to coarse-grained towards the top. These sandstones characterize settings ranging from floodplains with isolated, unconfined flows, to more complex, vertically stacked, multi-storey sheet sandstones of braided fluvial systems. The middle unit (C-5 to C-10) is dominated by pale brown-grey fine-to coarse-grained sands and medium size subangular to angular conglomerates, which reflect amalgamated complexes of sandstone sheets and downstream accretion macroforms. Remarkably, this alluvial sedimentation was episodically punctuated by volcaniclastic flows. The upper unit (C-11 to C-20) consists of finer sediments, mainly pink to white fine-to medium grained sandstones and red to green siltstones. Towards the top, bioturbation becomes important, and also the presence of volcanosedimentary flows is noticeable. Fluvial settings include braided sheet sandstones with waning flood deposits evolving to isolated high-sinuosity fluvial systems, with flash flood deposits. At the top of this unit, facies may suggest marine influence.Vertical changes in the fluvial style result from both climatic and tectonic controls. A semiarid to arid climate and the active tectonism linked to the eastward migration of the Andean volcanic arc determined major bounding surfaces, fluvial style evolution and the presence of the volcano-sedimentary deposits. Different stages of high and low subsidence rates has been deduced from the vertical stacking of sediments.     

石油碳、氢同位素组成的研究

通过对我国18个含油气区、385个石油样品进行碳、氢同位素和部分馏份碳同位素分析,将所获数据对两种不同性质的石油如正常原油和轻质（凝析）油分别研究其碳、氢同位素地球化学特征,提出轻质（凝析）油的碳同位素值（δ13C为-32.5‰～ -24.3‰）比正常原油δ13C为-34.4‰～ -24.6 ‰．6‰）相对偏高;石油馏份中芳烃碳同位素组成的变化受母质继承效应更为明显。因此,用芳烃碳同位值可以判识不同母质来源的石油。与海相有关的轻质（凝析）油的氢同位素值大于-15.0‰,而非海相轻质（凝析）油的δD值( δD为-21.0‰～-1.05‰）基本覆盖了海相轻质油的分布范围,从淡水－微咸水－半咸水和海水环境其氢同位素有明显变重趋势,表明氢同位素主要与沉积环境密切相关。     

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.     

Lipid geochemistry of Lake Kinneret

Lake Kinneret, a relict lake from the Neogene, is characterised by the dominance among its phytoplankton of the dinoflagellate Peridinium cinctum. The lipid geochemistry of Lake Kinneret is discussed herein in terms of the biology, chemistry and hydrology of the lake. Lipids isolated from two sediment sections (surface and 15 cm deep), obtained from the deepest point of Lake Kinneret, include: (1) 4α-methyl-5α (H)-stanols and related derivatives characteristic of P. cinctum, the novel sterol 4a-methylgorgosterol, and peridinosterol and 4α-methylgorgostanol, not previously reported to occur in lacustrine sediments; (2) C₃₀ and C₃₂ alkane-1,15-diols, not previously reported to occur in contemporary lacustrine deposits, and (3) products of early diagenesis. Many similarities were observed with the more widely studied marine dinoflagellates and marine sediments with dinoflagellate input.     

Comparison of lipid character of sediments from the Great Lakes and the Northwestern Atlantic

Geolipid compositions of surficial sediments from Lake Michigan, Lake Huron, and from three locations in the Northwestern Atlantic were determined to compare source inputs and alteration processes in different sedimentary environments. Fatty acids, sterols, fatty alcohols, and alkanes were examined in both unbound and bound extracts of these samples. Significant amounts of long chain fatty acids, alcohols, and hydrocarbons are present in the deep ocean station, yet this location contains a proportionally larger amount of short chain geolipids than do marine stations closer to shore. Larger proportions of long chain lipids present in the Lake Michigan, Lake Huron, and Gulf of Maine samples relative to the open ocean samples reflect larger inputs of land-derived lipids to sediments closer to terrigenous sources. Marine samples contain a more complex mixture of sterols than is found in lake sediments, suggesting that sterol inputs and alteration processes in the marine environment are more complex than in lacustrine settings. Ratios of 16:1/16:0 and 18:1/18:0 fatty acids decrease with increasing distance from land, which suggests that fatty acid degradation before and during deposition becomes more extensive in the open deeper ocean stations.     

Sterols in interstitial waters of marine sediments

In order to attempt to elucidate the nature of biogeochemical processes occurring at the water-sediment interface, sterols have been analysed in near bottom sea and interstitial waters collected in the eastern and western intertropical Atlantic ocean. Free and esterified sterol concentrations range from 0.2 to 82 μg l^?1 and are much higher than those found in overlying sea water, which range from 0.2 to 1.7 μg l^?1 for the dissolved fraction and from 0.01 to 0.07 μg l^?1 for the particulate fraction. Cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol are the dominant sterols in sea and interstitial waters. The variability encountered for the relative importance of minor sterols such as 24-methylcholesta-5,24(28)-dien-3β-ol and stanols, 5α-cholest-22(E)-en-3β-ol, 5α-cholestan-3β-ol and 24-ethyl-5α-cholestan-3β-ol in interstitial water and their variation with depth is discussed in terms of diversity of inputs and bacterial activity. For sediments cored off the Mauritanian coast, a productive area characterized by an intense upwelling, the chemical signatures observed in interstitial water through stanol/stenol ratios occur at levels of very high heterotrophic aerobic bacterial biomass estimations. The study of the sterol composition of interstitial water could constitute a valuable tool in appreciating the intensity of chemical and biological processes occurring in the first few metres of recent marine sediments.     

Sedimentary pigments as markers for environmental change in an Antarctic lake

Fossil pigments were identified in a sediment core from Kirisjes Pond, a small lake in the Larsemann Hills, east Antarctica, using reversed-phase HPLC and LC–MS/MS. Chlorophyll a- and b-derived components indicate the presence of oxygenic primary producers; steryl chlorin esters provide evidence of grazing, while shifts in their esterifying sterol composition record changes in the primary producer community. Bacteriochlorophyll c- and d-derived components, indicative of photic zone anoxia, were identified with structural variations including extensive alkylation in the macrocycle up to C₆. The pigment distribution reveals a change from oxygenated freshwater to a stratified water body with development of photic zone anoxia. This coincides with a marine incursion identified from diatom records and is followed by re-isolation and reversion to oxygenated freshwater conditions.     

中国南方海相生烃成藏研究的若干新进展(一) 南方四套区域性海相烃源岩的分布

通过对上、中、下扬子区121个地表及钻井剖面烃源岩的密集扫描取样和地化分析,系统研究了下寒武统、上奥陶统—下志留统、上二叠统、下二叠统四套区域性海相烃源岩的厚度及有机质丰度的纵横向分布,明确了海相烃源岩在纵向上以下寒武统和上二叠统为最好,横向上以上扬子区为最好,其次为下扬子区;确定了五个烃源岩发育区。明确了海相烃源岩以泥岩为主,碳酸盐岩烃源岩只出现在下二叠统栖霞组—茅口组,实测最大厚度为150m,从而表明中国南方不存在上千米厚的碳酸盐岩烃源岩。对四套海相烃源岩的厚度问题、层位问题、原始生烃潜量和碳酸盐岩烃源岩的鉴别问题等提出了认识。     

Organic contamination identification in sediments from a Mediterranean coastal ecosystem: The case of the Nador lagoon (Eastern Morocco)

The Nador lagoon ecosystem (North-East of Morocco) displays a major socioeconomic interest. In fact, it is essential to evaluate consequences of anthropogenic activities in the lagoon especially by organic matter studies (nature and distribution) in the sedimentary compartment. Surface sediments show variable rates in total organic carbon and in sulfur, high in some cases (7.5 and 1.8% respectively). These high contents are recorded in the center of the lagoon. Their distributions are controlled by the hydrodynamism and the anthropogenic degree. The molecular biomarkers analyses and especially n-alkanes distribution reveal: a zone of marine influence; and a zone of continental influence. The occurrence of pentacyclic triterpanes with a typical distribution of a thermally mature organic matter reveals a contamination due to petroleum products in the entire lagoon except for the center. Coprostanol occurrence near cities indicates wastewater effluents inputs and reducing conditions underlined by high values of stanols/sterol ratios. Thus, the organic contamination (petroleum by-products and wastewater effluents) occurs in the vicinity of the cities whereas the littoral edge and center remain weakly affected by these contaminations.     

新疆且末县迪木那里克一带1∶5万航磁异常查证新进展

新疆若羌县祁漫塔格—且末县迪木那里克一带1∶5万航磁异常查证工作重点是对阿尔金南缘深大断裂带之南侧迪木那里克铁矿东西两侧的航磁异常进行查证。通过查证工作证实,新C-2008-2200、C-2008-2201、C-2008-2202、C-2008-2220、C-2008-2221与迪木那里克铁矿所在的新C-2206、C-2207、C-2008异常均在阿尔金深大断裂带南侧的"长沙沟构造蛇绿混杂岩带"之中的复理石岩片千枚岩中,可确定迪木那里克铁矿带已控制长度达50 km。其中,在新C-2200、C-2201、C-2202异常区,新发现且末县玉岭铁矿;在新C-2008-2220、C-2008-2221异常区,新发现若羌县河肃铁矿。并确定新C-2008-C-2196、C-2008-C-2198、C-2008-C-2199、C-2008-C-2230、C-2008-C-2280航磁异常有进一步工作价值。     

Diatoms as a source for 4-desmethyl-23,24-dimethyl steroids in sediments and petroleum

Analysis of the sterol composition of more than 100 diatom cultures, representing all major marine diatom orders, indicates that this group of algae may be an important source for 4-desmethyl-23,24-dimethyl steroids in sediments and petroleum, as their precursors, i.e. 4-desmethyl-23,24-dimethyl sterols, were present in 22 of the cultures. The phylogenetic positions of diatom species that produce 4-desmethyl-23,24-dimethyl sterols show that, within the centric diatoms, only a specific group of diatoms is able to produce these sterols, while within the pennate diatoms, a phylogenetic relationship between 4-desmethyl-23,24-dimethyl sterol-producing diatoms is less apparent. Based on the phylogenetic relationship, it is suggested that diatoms inherited the ability of producing these sterols from a single common ancestor, which originated between 150 and 100 Ma ago. Co-injection of an authentic 23R,24R-dimethyl-5α-cholestane standard with extracts confirmed its presence in sediments. We also tentatively identified three other 4-desmethyl-23,24-dimethyl sterane isomers having different side-chain stereo-configurations and observed that some of the isomers co-elute with other steranes including 24-ethyl-5α-cholestane.     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.