Diagenesis of free and bound lipids in terrestrial detritus deposited in a lacustrine sediment

Recent sediments from an oligotrophic lake (Loch Clair) having uniform organic input for 2000 yr show changes in lipid abundance and composition, with increasing depth, attributed to diagenesis. Stability of free lipids decreases in the order n-alkanes, alkan-2-ones, sterols, n-alkanoic acids, n-alkanols, n-alkenoic acids. Diagenetic loss of shorter-chain homologues is complete within 400 yr. Stabilisation of bound relative to free lipids increases the proportion of the former with sediment age and reduces loss of shorter-chain bound homologues.In an eutrophic lake (Cross Mere), shorter-chain free and bound sedimentary lipids show increased abundance compared with Loch Clair. The relative importance of higher input of shorter-chain lipids derived from aquatic detritus, and slower initial diagenesis due to the anoxic hypolimnion, as causative factors for this difference between lake types cannot yet be assessed.     

Early diagenesis of fatty acids in lacustrine sediments—I. Identification and distribution of fatty acids in recent sediment from a freshwater lake

Fatty acids have been isolated and quantitatively determined from a 1.5 m sediment core of Lake Suwa, a eutrophic lake in the central districts of Japan.The fatty acids identified by combined gas chromatography-mass spectrometry were straight-chain saturated (C₁₂ to C₃₄), monounsaturated with even carbon number (C₁₆ to C₂₄) and branched-chain (iso, anteiso, 10-methyloctadecanoic) acids. The concentrations of the higher molecular weight (? C₂₀) saturated fatty acids remained nearly constant throughout the core, suggesting a high degree of preservation of those acids, whereas the monounsaturated and the lower molecular weight saturated fatty acids indicated a great decrease in concentration with depth to an approximately 20cm level. It is suggested that the microbial activity in sediments causes a significant reconstruction of the fatty acid distribution during early diagenesis.     

Fossilization and degradation of intact polar lipids in deep subsurface sediments: A theoretical approach

Intact polar membrane lipids (IPLs) are frequently used as markers for living microbial cells in sedimentary environments. The assumption with these studies is that IPLs are rapidly degraded upon cell lysis and therefore IPLs present in sediments are derived from in situ microbial production. We used a theoretical approach to assess whether IPLs in surface sediments can potentially represent fossilized IPLs derived from the upper part of the water column and whether IPLs can be preserved during sediment burial. Previous studies which examined the degradation kinetics of IPLs show that phospholipids, i.e. ester-linked lipids with a phosphor-containing head group, degrade more rapidly than glycosidic ether lipids, i.e. ether-linked lipids with a glycosidically bound sugar moiety. Based on these studies, we calculate that only a minor fraction of phospholipids but a major fraction of glycosidic ether lipids biosynthesized in the upper part of the water column can potentially reach deep-sea surface sediments. Using a simple model and power law kinetic degradation parameters reported in the literature, we also evaluated the degradation of IPLs during sediment burial. Our model predicts a log-log relationship between IPL concentrations and depth, consistent with what has been observed in studies of IPLs in subsurface sediments. Although our results do not exclude production of IPLs in subsurface sediment, they do suggest that IPLs present in the deep biosphere may contain a substantial fossil component potentially masking in situ IPL production.     

Evolution of organic matter in lignite-containing sediments revealed by analytical pyrolysis (Py–GC–MS)

Newly vegetated sites provide opportunities to enlighten organic matter (OM) transformation mechanisms in soils and sediments at very early stages of development which, in turn, is relevant to better understand general ecosystem functioning. Mine acid soils and sediments in the Lusatian open cast lignite mining district (Germany) contains a high concentration of fossil carbon (lignite) in ad mixture with recent OM from the local vegetation, both contributing to the humified OM pool. In this study, analytical pyrolysis (Py–GC–MS) was used to monitor the different C sources (lignite or plant derived) in developing mine tailing soils and sediments and their degree of degradation in contrasting environments. Representative vegetation and the organic carbon (OC) rich soil/sediment fraction (humus fraction) were sampled at two depths (0–5 and 5–10 cm) in three plots along a transect covering an upland forest soil, a partially submerged sediment at the land–water interface and a constantly submerged sediment. The analysis of plant (lipds, isoprenoids, methoxyphenols and carbohydrates) and possible lignite (alkyl napththalenes, alkyl benzenes and PAHs) biomarkers released after pyrolysis supports previous findings in the area using other proxies. It was possible to discern OM sources in soil/sediment humus fractions, both from the substrate (lignite) as well as from the prevailing vegetation of the area. Environmental conditions in the submerged sediment seem to favour OM protection and the accumulation of decomposing plant material, whereas more intense OM degradation seems to prevail in the land–water interface areas characterized by fluctuating water level. In addition, a well resolved series of organic sulfur compounds (OSCS) found in the submerged sediments of rehabilitated acid lakes, indicates the possible occurrence of particular mechanisms of C preservation in this extreme anoxic S rich environment, i.e. via sulphur “quenching” with plant derived lipids during early diagenesis.     

Carbon isotope fractionation of sapropelic organic matter during early diagenesis

Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of ¹³C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of ¹³C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4‰ in the δ ¹³C values of the organic matter is observed as a result of early diagenesis.     

Qualitative fatty acid and n-alkane stratigraphy of the Lake Turkana Basin,Kenya

In order to improve understanding of the stratigraphy of the Lake Turkana Basin, one of the important sites in the evolution of early man, this study evaluates the usefulness of organic biological marker compounds, n-alkanes and fatty acids, for correlation of isolated sedimentary strata.Eighty-five paleosol samples were collected from well-defined sedimentary horizons in two regions (Area 103 and Area 130) of the Koobi Fora area of Lake Turkana. Results indicate that most of the organic matter present was derived from terrestrial plant waxes. In sediments where extensive diagenesis has occurred, microbial input of organic matter may have been substantial. Algae were either not an important source of organic matter, or their marker compounds have been removed or altered by degradative processes.The fate of the original paleosol organic matter has been governed to some extent by weathering processes, especially in Area 130. Weathering decreased the amount of extractable lipids, particularly fatty acids and the low molecular weight alkanes (C₁₇C₂₀); produced or retained relatively large amounts of alkanes greater than C₂₁ within a unimodal distribution; and lowered CPI values. Consequently, stratigraphic correlation by unique alkane and fatty acid distributions has been confined to short distances (many meters).Both n-alkanes and fatty acids have been retained better by association with clay minerals than by sand matrices. The alkane distribution of sandstones differs from that of clay organics in having a narrower carbon chain length distribution and lower CPI values. In Area 103, where weathering was less severe, compositional variations with stratigraphic position indicate that lipid material has been retained within each of the facies examined.     

Laboratory thermal conversion of sedimentary lipids to kerogen-like matter

A laboratory heating experiment was conducted in an attempt to evaluate the possible role of lipids as precursors for petroleum hydrocarbons. Lipids were extracted from a Recent lake sediment (Lake Haruna, Japan), and heated under N₂ atmosphere, at 125–370°C, for 1–7 days. A significant amount of lipids was polymerized to kerogen-like matter (lipid-derived kerogen) at the low temperature of 175°C for 1 day. The polymerization follows first-order kinetics, and the half life of lipids is calculated to be 10⁴–10⁵ yr at 0–30°C. The lipid-derived kerogen generated a significant amount (62 mg/g) of n-alkanes (C₁₄–C₃₆) on heating at 350°C for 1 day.The results indicate a possible occurrence of lower temperature thermal polymerization of lipids in a relatively early stage of diagenesis as one of the formation pathways of kerogen with high hydrocarbon producing potential.     

铁元素对海相沉积物早期成岩作用的影响

铁元素是地壳中丰度最高的元素之一,在海相沉积物成岩过程中起着非常重要的作用.铁元素作为海洋初级生产力的微营养元素,影响海相沉积物中有机质的输入,其在早期成岩阶段与硫化物和磷元素的耦合关系,可以促进或者降低有机质的保存;铁元素在海相沉积物早期成岩过程中可以改变孔隙水的化学性质,影响亚稳定碳酸盐矿物的保存,导致碳酸盐沉积物...     

Impact of polychaetes (Nereis spp. and Arenicola marina) on carbon biogeochemistry in coastal marine sediments

Known effects of bioturbation by common polychaetes (Nereis spp. and Arenicola marina) in Northern European coastal waters on sediment carbon diagenesis is summarized and assessed. The physical impact of irrigation and reworking activity of the involved polychaete species is evaluated and related to their basic biology. Based on past and present experimental work, it is concluded that effects of bioturbation on carbon diagenesis from manipulated laboratory experiments cannot be directly extrapolated to in situ conditions. The 45–260% flux (e.g., CO₂ release) enhancement found in the laboratory is much higher than usually observed in the field (10–25%). Thus, the faunal induced enhancement of microbial carbon oxidation in natural sediments instead causes a reduction of the organic matter inventory rather than an increased release of CO₂ across the sediment/water interface. The relative decrease in organic inventory (G _b /G _u) is inversely related to the relative increase in microbial capacity for organic matter decay (k _b /k _u). The equilibrium is controlled by the balance between organic input (deposition of organic matter at the sediment surface) and the intensity of bioturbation. Introduction of oxygen to subsurface sediment and removal of metabolites are considered the two most important underlying mechanisms for the stimulation of carbon oxidation by burrowing fauna. Introduction of oxygen to deep sediment layers of low microbial activity, either by downward irrigation transport of overlying oxic water or by upward reworking transport of sediment to the oxic water column will increase carbon oxidation of anaerobically refractory organic matter. It appears that the irrigation effect is larger than and to a higher degree dependent on animal density than the reworking effect. Enhancement of anaerobic carbon oxidation by removal of metabolites (reduced diffusion scale) may cause a significant increase in total sediment metabolism. This is caused by three possible mechanisms: (i) combined mineralization and biological uptake; (ii) combined mineralization and abiogenic precipitation; and (iii) alleviation of metabolite inhibition. Finally, some suggestions for future work on bioturbation effects are presented, including: (i) experimental verification of metabolite inhibition in bioturbated sediments; (ii) mapping and quantification of the role of metals as electron acceptors in bioturbated sediments; and (iii) identification of microbial community composition by the use of new molecular biological techniques. These three topics are not intended to cover all unresolved aspects of bioturbation, but should rather be considered a list of obvious gaps in our knowledge and present new and appealing approaches.     

Composition and sources of extractable organic matter from a sediment core in Lake Kivu,East African rift valley

Lake Kivu is a gas-charged East African rift lake with currently anoxic bottom water. The extractable compounds and residual organic matter of a short sediment core have δ¹³C values typical of lacustrine microbial detritus. The total extracts consist primarily of polar compounds such as n-alkanoic acids, hydroxyalkanoic acids, triterpenoids, steroids and monosaccharides, with minor amounts of n-alkanes and n-alkanols. These tracer compounds and δ¹³C values indicate that the organic matter in the surficial and deeper sedimentary record was dominated by bacterial sources. The sapropelic sediment between these horizons contains organic matter from primarily algal with lesser bacterial input. Terrestrial organic markers are minor in all samples. The major fractions of the compounds in the total extracts were oxidized in the upper water column prior to transit through the anoxic bottom water to sedimentary deposition. The sapropelic horizon may reflect lake water turnover with ventilation or hydrothermal activity and consequently increased algal blooms.     

Relationships between microbial communities and environmental parameters at sites impacted by mining of volcanogenic massive sulfide deposits,Prince William Sound,Alaska

The relations among geochemical parameters and sediment microbial communities were examined at three shoreline sites in the Prince William Sound, Alaska, which display varying degrees of impact by acid-rock drainage (ARD) associated with historic mining of volcanogenic massive sulfide deposits. Microbial communities were examined using total fatty acid methyl esters (FAMEs), a class of compounds derived from lipids produced by eukaryotes and prokaryotes (bacteria and Archaea); standard extraction techniques detect FAMEs from both living (viable) and dead (non-viable) biomass, but do not detect Archaeal FAMEs. Biomass and diversity (as estimated by FAMEs) varied strongly as a function of position in the tidal zone, not by study site; subtidal muds, Fe oxyhydroxide undergoing biogenic reductive dissolution, and peat-rich intertidal sediment had the highest values. These estimates were lowest in acid-generating, intertidal zone sediment; if valid, the estimates suggest that only one or two bacterial species predominate in these communities, and/or that Archeal species are important members of the microbial community in this sediment.     

Identifying “free” and “bound” lipid fractions in stalagmite samples: An example from Heshang Cave,Southern China

Stalagmites are good archives for paleoecological change, as they are easy to date, and contain multiple environmental proxy records, including climatic records from oxygen isotopes. Lipid biomarkers preserved within stalagmites have recently been used to investigate changes in the overlying soil and vegetation. However, the understanding of lipid records from stalagmites is still at an early stage, and is hindered by the low abundances of lipids preserved and the complexity of the organic matter signal. Here the first results of a sequential extraction procedure are presented, that enables examination of the distribution patterns of “free” (solvent extraction) and “bound” (including physically bound within the calcite matrix and chemically bound to macromolecules) lipids in a stalagmite from southern China. In both groups the dominant compounds are saturated fatty acids, which are an order of magnitude more abundant in the “bound” phase. n-alkanes and n-alcohols chiefly appear in the “free” lipids. In contrast, 3-hydroxy acids are predominantly released under strong acid reflux conditions, suggesting a principal input from bacterial membrane compounds. A direct comparison between the present results and the published data from an Ethiopian stalagmite shows significant differences in the lipid signals from separate sites, with a stronger microbial signal in the Chinese sample. This preliminary investigation of lipid distributions in different modes highlights the importance of microbial geochemical processes in karst systems and supports the use of stalagmites in paleoecological reconstruction.     

Organic geochemistry of Walvis Bay diatomaceous ooze—I. Occurrence and significance of the fatty acids

Diatomaceous ooze of the shelf off Walvis Bay (S.W. Africa) was analysed for lipid material. The lipids from the sediment consist of a mixture of hydrocarbons, alcohols, ketones, fatty acids, sterols, carotenoid pigments and chlorophylls. The total fatty acid mixture has been analysed by capillary gas chromatography mass spectrometry and shown to consist of straight chain, iso-, anteiso- and isoprenoid acids. The environmental setting of the S.W. African shelf (Walvis Bay) makes it possible to discuss these fatty acids as markers for the fate of organic matter. The acids in the sediment point to a generation during passage of algal lipids through levels of microbial activity either on or slightly above the burial surface.     

Very early diagenesis in a calcareous,organic-rich mudrock from Jordan

The diagenesis in the organic-rich Cretaceous to Eocene Al Hisa Phosphorite Formation (AHP), Muwaqqar Chalk Marl Formation (MCM) and Umm Rijam Chert-Limestone Formation (URC) formations of Jordan can be linked directly to the fluctuating sedimentary environment of this shelf depositional system in the Middle to Late Eocene, and its influence on the composition of the deposited sediment and the early burial diagenetic environment. Most cementation was early, mostly within the first 10 m of burial, perhaps entirely within the first 100 m of burial. We propose that the siliceous cements are derived from biogenic silica, probably of diatoms, deposited in a shelf of enhanced productivity. Volumetrically, the most important processes were the redistribution of biogenic opal-A (diatoms) and calcite to form pervasive, layered and nodular cements. The formation of the silica and carbonate cements is closely linked through the effects their dissolution and precipitation have on pore fluid chemistry and pH. The chert beds have a biogenic silica origin, formed through replacement of diatoms and radiolaria by opal-CT, and subsequently by quartz. Calcite cement has carbonate derived from microbial diagenesis of organic matter and calcium derived from seawater. The Mg for early dolomite may have been generated by replacement of opal-CT by quartz, ore dissolution of unstable high Mg calcite bioclasts. The silica and carbonate diagenetic processes are both linked to microbial diagenesis of organic matter, and are intimately linked in both time and space, with pH possibly influencing whether a silica or a carbonate mineral precipitates. The paucity of metal cations capable of precipitating as sulphides is crucial to the creation of acidic pore water favourable to silica precipitation, either as opal-CT, chalcedony or quartz. The lack of clay minerals as a sink for the Mg required for opal-CT polymerisation is the principal factor responsible for the remarkably early silica cementation. All the diagenetic processes, with the probable exception of the opal-CT to quartz transition are early, almost certainly within the first 10 m of burial, possibly much less. A paragenetic sequence is presented here based on these two cores that should be tested against a wider core distribution to see whether this diagenetic history can be generalised throughout the basin. Warm bottom water temperatures probably led to silica diagenesis at much shallower burial depths than occurs in many other sedimentary basins. Silicified layers, in turn, commonly host fractures, suggesting that mechanical properties of the strata began to differentiate at a very early stage in the burial cycle. This has wide implications for processes linking diagenesis to deformation.     

Structural diversity and fate of intact polar lipids in marine sediments

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.     

Early diagenesis of organic matter in the water column and sediments: Microbial degradation and resynthesis of lipids in Lake Haruna

Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C₁₂–C₁₉ fatty acids and polyunsaturated C₁₈ acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C₂₀–C₃₀ acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.     

Impact de la vie benthique sur la genèse de nodules calcaires dans les black shales

The study of calcareous nodules from four organic-rich black shale series allows us to suggest a prominent part for benthic organisms in creating heterogeneities in the sediment, thus favouring microbially mediated early diagenesis based on organic matter consumption. To cite this article: J.-G. Bréhéret et al., C. R. Geoscience 336 (2004).     

Diterpenoid compounds and other lipids in deep-sea sediments and their geochemical significance

Cyclic diterpenoid compounds have been found by various investigators in the geosphere (e.g. fossil resins, coals, soil, shale and deep-sea sediments). These compounds occur in significant amounts only in higher plants and are therefore potential markers of terrigenous plant lipids.Diterpenoids with the abietane skeleton (mainly dehydroabietic acid) have been identified in the lipids of sediment samples from the northeast Pacific Ocean, Black Sea and North Atlantic Ocean. The presence of these resin-derived compounds correlated with the terrigenous clay components and with the presence of pollen. The presence of polycyclic diterpenoids was also correlated with the distribution patterns and inferred sources of other sediment lipid constituents (e.g. n-alkanes, n-fatty acids, etc.).Potamic transport, followed by turbidite redistribution are the probable input mechanisms of these resin-derived compounds to the deep-sea sediments. These diterpenoids appear to be excellent biological markers of resinous higher plants.     

Microbial mat structures in profile: The Neoproterozoic Sonia Sandstone,Rajasthan, India

Ubiquitous microorganisms, especially cyanobacteria preferably grow on the sediment surface thereby producing microbial mats. In the absence of grazers and bioturbators, microbial mat is a unique feature of the Proterozoic. Most of the papers so far published described a wide variety of bed surface microbial mat structures with rare illustrations from sections perpendicular to bedding. Nonetheless, bed surface exposures are relatively rare in rock records. This limitation of bed surface exposures in rock records suggest that a study of microbial mats in bed-across sections is needed. The 60 m thick coastal marine interval of the Sonia Sandstone Formation is bounded between two terrestrial intervals, a transgressive lag at the base and an unconformity at the top, and has been chosen for exploration of microbial mat structures in bed-across sections. A wide variety of microbial mat-induced structures in bed-across sections are preserved within the coastal interval of the Sonia Sandstone. Though many of these structures are similar in some aspects with bed surface structures, some of those presented here are new. The palaeogeographic range of these microbial structures extends from supralittoral to neritic. Diagenetic alterations of microbial mats produce pyrite and those zones are suitable for the preservation of microbial remains. SEM and EDAX analyses show fossil preservation of filamentous microbial remains that confirm the presence of microbial mats within the coastal interval of the Sonia Sandstone. Effects of proliferation of microbial mats in the siliciclastic depositional setting are numerous. The mat-cover on sediment surfaces hinders reworking and/or erosion of the sediments thereby increases the net sedimentation rate. Successive deposition and preservation of thick microbial mat layer under reducing environments should have a great potential for hydrocarbon production and preservation and therefore these Proterozoic formations could be a target for exploration.     

Deposition and early diagenesis of microbial mud in the Florida Everglades

Microbial carbonate mud in the modern (<4 kyr) palustrine environment of the Florida Everglades is surprisingly susceptible to early diagenetic alteration. The low‐Mg calcite crystals show an open, trellis‐like crystal structure that yields a high surface area to volume ratio. This textural complexity, likely to be a result of organic influence, leads to abundant reaction sites vulnerable to both dissolution and subsequent precipitation. Rapid degradation of organics is attributed to both aerobic and anaerobic metabolisms. Geochemical signatures suggest increased denitrification within the freshwater environment and increased sulphate reduction at the (slightly) brackish mangrove transition zone. A transition from a freshwater to brackish depositional environment is likely to follow the Holocene sea‐level transgression. The textural complexity in these microbial carbonates causes an unexpectedly low preservation potential of original textural and geochemical signatures, even in low‐Mg calcite. Given the potential for early diagenesis of palustrine and perhaps other microbial carbonates, they should be used cautiously as archives for palaeoenvironmental proxies.