Aerobic methanotrophy at ancient marine methane seeps: A synthesis

The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of ¹³C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, ¹³C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ¹³C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ¹³C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ¹³C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs.     

Biomarkers for aerobic methanotrophy in the water column of the stratified Gotland Deep (Baltic Sea)

Filter samples from the oxic zone and suboxic zone of the physically stratified water column and sediment samples of the Gotland Deep, Baltic Sea, were analyzed for bacteriohopanepolyol (BHP) and phospholipid fatty acid (PLFA) concentrations. In total, eight BHPs were identified, with the greatest diversity in the suboxic zone. There, 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), whose concentrations decreased concurrently from the lower to the upper suboxic zone, indicated type I methanotrophic bacteria and thus aerobic oxidation of methane. The presence and activity of type I aerobic methanotrophic bacteria was further supported by the presence of ¹³C-depleted PLFAs, specifically 16:1ω8c and 16:1ω5c (δ¹³C as low as −41.2‰). However, the relative amount of methanotroph-specific compounds was low (aminopentol, <0.2% of total BHPs; 16:1ω8c, ca. 0.5% of total PLFAs), suggesting a minor contribution of aerobic methanotrophic bacteria to the particulate organic matter. The distinctive BHP pattern in the suboxic zone, including aerobic methanotroph biomarkers and a tentative marker for a pelagic redoxcline [putative 22S isomer of the ubiquitous 22R-bacteriohopanetetrol (BHT)], was mirrored in the sediment samples. Our data indicate that a major portion of the sedimentary hopanoids of the Gotland Deep is sourced from the suboxic part of the water column via an effective but unknown transport mechanism.     

Highly isotopically depleted isoprenoids: molecular markers for ancient methane venting

We propose that organic compounds found in a Miocene limestone from Marmorito (Northern Italy) are source markers for organic matter present in ancient methane vent systems (cold seeps). The limestone contains high concentrations of the tail-to-tail linked, acyclic C₂₀ isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), a C₂₅ homolog 2,6,10,15,19-pentamethylicosane (PME), and a distinctive glycerol ether lipid containing 3,7,11,15-tetramethylhexadecyl (phytanyl-) moieties. The chemical structures of these biomarkers indicate a common origin from archaea. Their extremely ¹³C-depleted isotope compositions (δ¹³C ≈ −108 to −115.6‰ PDB) suggest that the respective archaea have directly or indirectly introduced isotopically depleted, methane-derived carbon into their biomass. We postulate that a second major cluster of biomarkers showing heavier isotope values (δ¹³C ≈ −88‰) is derived from sulfate-reducing bacteria (SRB). The observed biomarkers sustain the idea that methanogenic bacteria, in a syntrophic community with SRB, are responsible for the anaerobic oxidation of methane in marine sediments. Marmorito may thus represent a conceivable ancient scenario for methane consumption performed by a defined, two-membered bacterial consortium: (1) archaea that perform reversed methanogenesis by oxidizing methane and producing CO₂ and H₂; and (2) SRB that consume the resulting H₂. Furthermore, the respective organic molecules are, unlike other compounds, tightly bound to the crystalline carbonate phase. The Marmorito carbonates can thus be regarded as “cold seep microbialites” rather than mere “authigenic” carbonates.     

Stromatolitic fabric of authigenic carbonate crusts: result of anaerobic methane oxidation at cold seeps in 4,850 m water depth

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low '¹³C values. This indicates the presence of methane-consuming archaea, and '¹³C values of -42 to -51‰ PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as ¹⁴C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.     

A comprehensive approach to the study of methane-seep deposits from the Lincoln Creek Formation, western Washington State, USA

ABSTRACT A comprehensive approach using palaeontology, petrography, stable isotope geochemistry and biomarker analyses was applied to the study of seven small methane‐seep carbonate deposits. These deposits are in the Oligocene part of the Lincoln Creek Formation, exposed along the Canyon and Satsop Rivers in western Washington. Each deposit preserves invertebrate fossils, many representing typical seep biota. Authigenic carbonates with δ¹³C values as low as ?51‰ PDB reveal that the carbon is predominately methane derived. Carbonates contain the irregular isoprenoid hydrocarbons 2,6,11,15‐tetramethylhexadecane (crocetane) and 2,6,10,15,19‐pentamethylicosane (PMI), lipid biomarkers diagnostic for archaea. These lipids are strongly depleted in ¹³C (δ¹³C values as low as ?120‰ PDB), indicating that archaea were involved in the anaerobic oxidation of methane. Small filaments preserved in the carbonate may represent methanotrophic archaea. Archaeal methanogenesis induced the formation of a late diagenetic phase, brownish calcite, consisting of dumbbell‐shaped crystal aggregates that exhibit δ¹³C values as high as +7‰ PDB. Clotted microfabrics of primary origin point to microbial mediation of carbonate precipitation. Downward‐directed carbonate aggregation in the seeps produced inverted stromatactoid cavities. Large filaments, interpreted as green algae based on their size, shape, arrangement and biomarkers, imply that deposition occurred, in places, in water no deeper than 210 m.     

Microbial ecology of the stratified water column of the Black Sea as revealed by a comprehensive biomarker study

The stratified water column of the Black Sea is partitioned into oxic, suboxic, and euxinic zones, each characterized by different biogeochemical processes and by distinct microbial communities. In 2003, we collected particulate matter by large volume in situ filtration at the highest resolution to date for lipid biomarker analysis and bacterioplankton for enumeration of major prokaryotic groups. Abundances of several prokaryotic groups were estimated using CARD-FISH probes specific for Bacteria, Archaea (Crenarchaeota and Euryarchaeota), epsilonproteobacteria (mainly sulfide oxidizers) and sulfate reducing bacteria. We also measured a wide range of bacterial and archaeal lipid biomarkers. Depth distributions of diagnostic biomarkers are matched with zonation of microbial processes, including aerobic bacterial oxidation of methane, oxidation of ammonium by bacteria and archaea, metal reduction, and sulfide oxidation at the chemocline, and bacterial sulfate reduction and anaerobic oxidation of methane by archaea in the anoxic zone. Cell densities for archaea and sulfate reducing bacteria are estimated based on water column biomarker concentrations and compared with CARD-FISH results.     

Stable carbon isotopic compositions of intact polar lipids reveal complex carbon flow patterns among hydrocarbon degrading microbial communities at the Chapopote asphalt volcano

Seepage of asphalt forms the basis of a cold seep system at 3000 m water depth at the Chapopote Knoll in the southern Gulf of Mexico. Anaerobic microbial communities are stimulated in the oil-impregnated sediments as evidenced by the presence of intact polar membrane lipids (IPLs) derived from archaea and Bacteria at depths up to 7 m below the seafloor. Detailed investigation of stable carbon isotope composition (δ¹³C) of alkyl and acyl moieties derived from a range of IPL precursors with distinct polar head groups resolved the complexity of carbon metabolisms and utilization of diverse carbon sources by uncultured microbial communities. In surface sediments most of the polar lipid-derived fatty acids with phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and diphosphatidylglycerol (DPG) head groups could be tentatively assigned to autotrophic sulfate-reducing bacteria, with a relatively small proportion involved in the anaerobic oxidation of methane. Derivatives of phosphatidyl-(N)-methylethanolamine (PME) were abundant and could be predominantly assigned to heterotrophic oil-degrading bacteria. Archaeal IPLs with phosphate-based hydroxyarchaeols and diglycosidic glyceroldibiphytanylglyceroltetraethers (GDGTs) were assigned to methanotrophic archaea of the ANME-2 and ANME-1 cluster, respectively, whereas δ¹³C values of phosphate-based archaeols and mixed phosphate-based and diglycosidic GDGTs point to methanogenic archaea. At a 7 m deep sulfate-methane transition zone that is linked to the upward movement of gas-laden petroleum, a distinct increase in abundance of archaeal IPLs such as phosphate-based hydroxyarchaeols and diglycosidic archaeol and GDGTs is observed; their δ¹³C values are consistent with their origin from both methanotrophic and methanogenic archaea. This study reveals previously hidden, highly complex patterns in the carbon-flow of versatile microbial communities involved in the degradation of heavy oil including hydrocarbon gases that would not have been evident from classical compound-specific isotope analyses of either bulk IPL or apolar lipid derivatives.     

Archaea mediate anaerobic oxidation of methane in deep euxinic waters of the Black Sea

We evaluate anaerobic oxidation of methane (AOM) in the Black Sea water column by determining distributions of archaea-specific glyceryl dialkyl glyceryl tetraethers (GDGTs) and ¹³C isotopic compositions of their constituent biphytanes in suspended particulate matter (SPM), sinking particulate matter collected in sediment traps, and surface sediments. We also determined isotopic compositions of fatty acids specific to sulfate-reducing bacteria to test for biomarker and isotopic evidence of a syntrophic relationship between archaea and sulfate-reducing bacteria in carrying out AOM. Bicyclic and tricyclic GDGTs and their constituent ¹³C-depleted monocyclic and bicyclic biphytanes (down to −67‰) indicative of archaea involved in AOM were present in SPM in the anoxic zone below 700 m depth. In contrast, GDGT-0 and crenarchaeol derived from planktonic crenarchaeota dominated the GDGT distributions in the oxic surface and shallow anoxic waters. Fatty acids indicative of sulfate-reducing bacteria (i.e., iso- and anteiso-C₁₅) were not strongly isotopically depleted (e.g., −32 to −25‰), although anteiso-C₁₅ was 5‰ more depleted in ¹³C than iso-C₁₅. Our results suggest that either AOM is carried out by archaea independent of sulfate-reducing bacteria or those sulfate-reducing bacteria involved in a syntrophy with methane-oxidizing archaea constitute a small enough fraction of the total sulfate-reducing bacterial community that an isotope depletion in their fatty acids is not readily detected. Sinking particulate material collected in sediment traps and the underlying sediments in the anoxic zone contained the biomarker and isotope signature of upper-water column archaea. AOM-specific GDGTs and ¹³C-depleted biphytanes characteristic of the SPM in the deep anoxic zone are not incorporated into sinking particles and are not efficiently transported to the sediments. This observation suggests that sediments may not always record AOM in overlying euxinic water columns and helps explain the absence of AOM-derived biomarkers in sediments deposited during past periods of elevated levels of methane in the ocean.     

Lipid Biomarkers and Their Stable Carbon Isotopes inAncient Seep Carbonates from SW Taiwan,China

Four massive brecciated, chimney-like, and slender pipe network carbonate samples(JA-4, JA-5, JX-8 and BG-12) were collected from southwestern Taiwan, which were suggested to have formed as a result of anaerobic oxidization of methane(AOM). Considering that the environmental conditions of the carbonates precipitation and the sources of carbon and organic matter need to be further declared, molecular fossils and compound-specific carbon isotopic investigations of the carbonates were conducted in this study. According to lipid biomarkers of 2,6,10,15,19-pentamethyleicosane(PMI) and squalane diagnostic to methanotrophic archaea, as well as the extremely low δ¹³C values(as low as -1¹³.4‰) detected in samples JA-4, JA-5 and JX-8, these carbonates were revealed to be a result of AOM. Based on the varied δ¹³C values of characteristic archaea biomarkers in specific samples, biogenic methane was proposed to be responsible for the formation of samples JA-4 and JA-5, whereas a mixed carbon source of ¹³C-depleted methane and ¹³C-enriched residual CO_2 from methanogenesis was suggested for the carbonate of JX-8 due to the co-occurrence of a highly positive δ¹³ C_carb value(+8‰) and a moderate ¹³C depletion of PMI. The low content of AOM-related biomarkers and the absence of indicators for ANME-2 suggested that these carbonates were formed in weak seep settings. By comparison, no typical lipid biomarkers for methanotrophic archaea was detected in carbonate BG-12. The short-chain and long-chain n-alkanes accounted for 30% and 45% of all hydrocarbons, respectively, with a CPI value of 1.2, suggesting that the n-alkanes were derived from both marine organisms and terrestrial inputs. A low thermal maturity could be revealed by the incomplete equilibrium value of the C³¹αβ 22S/(22S+22R) ratio(0.5), and the carbonate BG-12 was probably deposited in a suboxic condition indicated by a value of Pr/Ph ratio(2.5).     

Archaeal polar lipids in subseafloor sediments from the Nankai Trough: Implications for the distribution of methanogens in the deep marine subsurface

Although the methane in marine methane hydrates is mainly of microbial origin, information about the distribution of methanogens in subseafloor sediments is limited. To address this issue, we analyzed sediment core samples from two sites in the Nankai Trough, off the Pacific coast of central Japan, including those bearing methane hydrates from depths > 100 m below the seafloor (mbsf), for isopranyl ether-linked polar lipids (i.e. with polar head groups of phosphate, sugar, or both) as biomarkers of archaea, including methanogens. In most samples, including the deepest (381 mbsf), archaeol, and sn-2- and sn-3-hydroxyarchaeols were detected as their hydrolyzed derivatives. Concentrations of these three archaeal lipids correlated strongly with each other, suggesting a common biological source. The δ¹³C values of phytane derived from the phytanyl groups in the archaeal lipids were distinctly higher than those of methane, indicating that methanogens rather than anaerobic methanotrophic archaea were the major biological source. Depth profiles of polar sn-2-hydroxyarchaeol concentration were consistent with those of the potential methane production activity previously estimated from incubation of core sediments from the same sites. This observation, together with results of previous studies showing the presence of sn-2-hydroxyarchaeol mainly in shallow young sediments, strongly suggests that this polar lipid is a valid biomarker for in situ methanogens in sediments. There was a strong correlation between the concentration of polar sn-2-hydroxyarchaeol and that of total organic carbon, suggesting that bulk organic matter concentration is a primary control on the distribution of methanogens in sediments.     

Methylhopanoids: Molecular indicators of ancient bacteria and a petroleum correlation tool

Methylhopanoids are organic compounds synthesized by certain bacteria, that when preserved in sediments act as molecular fossils or biomarkers for organic matter inputs from specific bacterial sources. Two series of methylhopanoids occur, each mainly deriving from a distinct bacterial source: cyanobacteria (2-methyl) and methanotrophic bacteria (3-methyl). The abundance and composition of methylhopanoids within sediments of modern depositional environments varies widely, apparently due to different bacterial communities contributing to the sedimentary organic matter. Comparable molecular characteristics are found in oils and their source rocks. Consequently, methylhopanoids are valuable in oil-oil and oil-source rock correlations, distinguishing between samples related to different depositional environments. In particular, abundant 3β-methylhopanoids (from methanotrophic bacteria or an additional unknown bacterial source) are characteristic of some modern alkaline saline lake environments. Comparable compositional features in the methylhopanes of oils allow the assignment of lacustrine oils offshore West Africa to two distinct lacustrine source rock facies, and to distinguish between different marine source facies, thus refining oil-source rock correlation.     

Palaeoenvironmental conditions during deposition of the Upper Cretaceous oil shale sequences in the Songliao Basin (NE China): Implications from geochemical analysis

Excellent hydrocarbon source rocks (oil shales), containing Type I organic matter (OM), were deposited in the continental Songliao rift basin during the Late Cretaceous. A major contribution of aquatic organisms (dinoflagellates, green algae, botryococcus) and minor input from macrophytes and land plants to OM accumulation is indicated by n-alkane distribution, steroid composition and δ¹³C values of individual biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria and chemoautotrophic bacteria, as well as purple and green sulfur bacteria. The presence of methanotrophic bacteria is indicated by ¹³C-depleted methyl hopane. The sediments were deposited in a eutrophic, alkaline palaeolake. Highly reducing (saline) bottom water conditions and a stratified water column existed during OM accumulation of the Qingshankou Formation and Member 1 of the Nenjiang Formation. This is indicated by low pristane/phytane, gammacerane index and MTTC ratios, and the presence of β-carotane and aryl isoprenoids. However, an abrupt change in environmental conditions during deposition of Member 2 of the Nenjiang Formation is indicated by significant changes in salinity and redox-sensitive biomarker ratios. A freshwater environment and suboxic conditions in the deep water prevailed during this period. Higher input of terrigenous OM occurred during deposition of the upper Nenjiang Formation.Good oil-to-source rock correlation was obtained using biomarker fingerprints of oil-stained sandstone from the Quantou Formation and oil shales from the Qingshankou Formation. Based on the extent of isomerisation of C₃₁ hopanes, the oil was most probably derived from oil shales of the Qingshankou Formation in deeper parts of the basin.     

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.     

南海北部海马冷泉区表层沉积物的AOM生物标志化合物特征及意义

选取采自南海天然气水合物赋存区海马冷泉,管状蠕虫区（ROV06站位）和贻贝区（HM101站位）的2个表层沉积物柱状样品,提取其中的生物标志化合物,对其种类和稳定碳同位素进行了测定,用以探讨海底表层沉积物中的有机质来源、微生物种群分布及其对冷泉渗漏活动的响应特征. 两个站位的沉积物中均发现了大量与甲烷厌氧氧化古菌（ANME）有关的生物标志物,如2,6,11,15?四甲基十六烷（crocetane）、2,6,10,15,19?五甲基二十烷（PMI）等类异戊二烯烃,古醇（archaeol）、sn2?羟基古醇（sn2?OH?Ar）等,以及来源于硫酸盐还原菌（SRB）的异构/反异构脂肪酸iso?C₁₅和ai?C₁₅等. 这些生物标志物均具有极低的碳同位素特征（古菌生标δ13C值低至-126‰,硫酸盐还原菌生标δ13C值低至?89‰）,表明沉积物中发生了甲烷厌氧氧化作用（AOM）. ROV06和HM101站位沉积物中均检测到了crocetane,大多数sn2?羟基古醇/古醇大于1,同时ai?C₁₅/iso?C₁₅脂肪酸比值小于2,这说明两个站位沉积物中的甲烷厌氧氧化古菌主要以ANME?2/DSS为主,指示甲烷渗漏强度较强. ROV06站位的表层沉积物含有crocetane,但sn2?羟基古醇/古醇小于1,且ai?C_15/iso?C₁₅脂肪酸比值大于2.1,指示了ANME?1/DSS和ANME?2/DSS混合存在的种群特征,说明ROV06站位顶部甲烷渗漏强度有减小的趋势. 根据古菌种群ANME?2化合物对甲烷的碳同位素分馏（Δ:-50‰）及古菌生物标志物（PMI、古醇、sn2?羟基古醇）的平均δ13C值,计算得到甲烷δ13C值（-58‰~-53‰）,显示甲烷为热成因和生物成因混合气. 虽然ROV06和HM101站位的甲烷具有相近的δ13C值,但ROV06站位的SRB生物标志物比HM101站位要更加亏损13C（Δδ13C:18‰）,这可能与管状蠕虫的共生菌（硫氧化菌）吸收硫化物并释放出硫酸盐有关,因为其不断释放出的硫酸盐很可能极大地增强了甲烷厌氧氧化作用,使沉积物中含有更多13C亏损的无机碳.      

Polar and neutral isopranyl glycerol ether lipids as biomarkers of archaea in near-surface sediments from the Nankai Trough

The molecular and carbon isotopic compositions of polar isopranyl glycerol ether lipids, which are direct indicators of viable archaea, and neutral isopranyl glycerol ether lipids, which are derived from polar lipids via hydrolysis, in near-surface sediments from a methane seep in the Nankai Trough (off central Japan) were investigated. Procedures for extracting, separating and derivatizing polar and neutral ether lipids for detection using gas chromatography were first examined with one sediment sample and a cultivated methanogen. For all sediment samples, archaeol and hydroxyarchaeol were detected in both the polar and neutral ether lipid fractions. Acyclic and cyclic biphytanes were also detected in both types of lipid fractions after treatment with HI/LiAlH₄ for ether cleavage and alkylation. The δ¹³C values of archaeol, sn-2-hydroxyarchaeol, and sn-3-hydroxyarchaeol in the sample from 0.82 m below the seafloor were lower than −100‰ relative to PDB, indicating that diverse living methanotrophic archaea are present in the seep sediments. Biphytanes released from polar ether lipids in the same sample were less depleted in δ¹³C (−71‰ to −36‰). The wide range of δ¹³C values suggests that the biphytanes were derived not only from methanotrophic but also from non-methanotrophic archaea, and that the relative contributions of the methanotrophic and non-methanotrophic archaea differed, depending on the biphytane compound. The vertical profiles and δ¹³C values of the neutral ether lipids were similar to those of the intact polar ether lipids, suggesting that neutral ether lipids derived from fossil archaea in the samples had mainly been lost by the time of sampling.     

Coupled uranium mineralisation and bacterial sulphate reduction for the genesis of the Baxingtu sandstone-hosted U deposit,SW Songliao Basin,NE China

The Baxingtu deposit is a typical redox front tabular-shaped uranium deposit hosted in sandstones of the Late Cretaceous Yaojia Formation deposited within a braided river environment during the post-rift stage of the Songliao Basin, in northeast China. This study proposes the first metallogenic model for the Baxingtu deposit and provides new data on genetic processes involved in the uranium mineralisation of sandstone-type deposits that were characterised through petrographic observations, whole-rock geochemistry, and geochemical and/or mineralogical study of iron disulphide, uranium minerals, Fe-Ti oxides (EPMA, LA-ICP-MS), and organic matter (REP). The δ³⁴S value has been measured in situ by SIMS on the different generations of iron disulphide.Within regional primary reduced sandstones, pre-ore uranium enrichment (U_mean = 7.6 ppm in whole rock) was identified on altered Fe-Ti oxides along with minor concentrations on organic matter (respectively 26.3% and 1.3% of the whole-rock U content), which together represent a significant source of uranium for the mineralisation. Additional pre-ore uranium concentrations may also be associated with clay minerals. Petrographic observations and REP data indicate that organic matter occurring in the host-sandstone is mainly inherited from land plants and corresponds to type III or type IV kerogens. Ore-stage iron disulphides largely occur as framboids and in replacement of organic matter or also as sub-idiomorphic to idiomorphic cement and crystal. Trace element signatures detected within framboids are likely indicative of formation mainly from a single event. Framboids and iron disulphide in replacement of organic matter have a light sulphur isotope signature characterised by δ³⁴S values from −72.0 to −6.2‰, suggesting that sulphur originated from bacterial sulphate reduction, which was mainly responsible for (1) the liberation of U from Fe-Ti oxides and organic matter, (2) the generation of ore-stage iron disulphides, (3) the bioreduction of uranium and (4) the production of a secondary H₂S-rich reducing barrier also involved in uranium reduction. Uranyl and sulphate ions were transported through the host sandstone by low-temperature oxygenated groundwater and U(IV) was precipitated at the redox interface as nano to microcrystals of pitchblende and coffinite, dominantly associated with bacterial substrate and as intergrowth with biogenic iron disulphide or directly associated with organic matter and residual Ti-Fe oxides. The uranium mineralisation does not replace ore-stage iron disulphides. Therefore, the combined mineralogical, geochemical, and isotopic characteristics of the Baxingtu tabular uranium deposit characterise dominantly biogenic processes for the genesis of the uranium mineralisation.     

松辽盆地东南部油气、煤层气后生蚀变硫同位素特征

对松辽盆地东南部上白垩统泉头组、姚家组和嫩江组岩石中黄铁矿及硫同位素特征研究表明,泉头组、姚家组中后生还原褪色作用形成的灰色、灰绿色砂岩中的黄铁矿及硫同位素均显示出了深部来源的油气、煤层气有机流体作用成分特征。该区原生沉积成岩岩石及黄铁矿中硫同位素的δ^34SV-CDT为正值,油气、煤层气有机流体还原作用岩石及黄铁矿中δ^34SV-CDT为负值。油气、煤层气还原作用不仅使杂色、紫红色原生氧化砂岩还原为灰色、灰绿色还原性砂岩,还使岩石还原容量大大增强,而且油气、煤层气在有机流体与岩石的相互作用过程中有铀的叠加富集,岩石铀含量普遍增加,局部可形成铀异常、铀矿化。首次在门达地区姚家组含矿砂岩中发现网脉状水云母化,显示铀成矿具有低温热液蚀变特征,铀矿化与低温热流体作用有关。     

吐哈盆地十红滩铀矿床铀成矿过程中微生物—有机质相互作用研究

生物、有机质成矿作用是目前国际成矿作用研究前沿领域。本文以我国典型层间氧化带砂岩型铀矿床——吐哈盆地十红滩铀矿床为研究对象,分析了矿床的有机质、微生物地球化学特征,探讨了有机质和微生物的相互作用。认为好氧微生物积极地参与了矿床层间氧化带的形成。氧化带铁的生物氧化作用催化了铀的氧化、溶解以及迁移,为铀成矿提供了重要的铀源条件。在氧化还原过渡带,硫酸盐还原菌利用有机质生物化学作用的产物——轻烃和可溶有机物作为碳源,使容矿层地下水中硫酸盐发生还原作用形成硫化氢,地下水Eh降低和pH向弱酸性转化,导致铀的还原成矿和吸附成矿作用,有机质和微生物的相互作用对矿床的形成具有重要的控制作用。     

Biogeochemical processes of carbon and sulfur cycles in sediments of the outer shelf of the Black Sea (Russian Sector)

Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using ³⁵S and ¹⁴C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.     

Algal-bacterial fabrics of ores and their genetic implications in the longtang lead-zinc deposit at Yanbian,Sichuan

The Longtang Pb-Zn deposit occurs in the Upper Sinian Guanyinyan Formation. The host rocks include sandy shale, cherty limestone and dolomitic limestone. The deposit is a typical one of thallogen origin. The mineral assemblage in the ore is made up of sphalerite, galena, pyrite, enargite, tennantite, seligmannite, asphalt, etc. The ore-forming process is possessed of multiepisode and multi-stage characters. Generally, sphalerites exhibit algal stromatolitic, bacterial and algal colloidal textures, providing evidence for the direct involvement of algae and bacteria in mineralization of ore-forming elements during sedimentary diagenesis. This is the first transmigration of ore-forming elements. However, pyrite embracing bacteria and galena replacing/filling trichomes are typical organic textures, which are related to organic carbon and bitumen that can adsorb or reduce ore-forming elements. This is an indirect process of organic mineralization, i.e., the second transmigration of ore-forming elements. δ³⁴S values are all greater than 5%., indicating the dominance of the heavy sulfur isotopes. The ore-forming temperature deduced from fluid inclusions ranges from 100°C to 150°C±. All this goes to show that the Longtang Pb-Zn deposit is of thallogen origin. This project was granted by the National Natural Science Foundation of China.