Sand veins and MISS from the Mesoproterozoic black shale (ca. 1.7 Ga) in North China: Implication for methane degassing from microbial mats

The Mesoproterozoic Chuanlinggou Formation (ca. 1.7 Ga) consists mainly of dark-gray to black shales that are widespread in the North China Platform. Abundant centimeter-scale sand veins are present within the shale layers of this unit, particularly in the middle part. Sand veins display ptygmatic shapes, perpendicular or with a high angle to bedding planes. They penetrate the black shale layers but are often terminated by thin, lenticular sandstone beds, forming small-scale ‘tepee-like’ structures. On bedding planes, sand veins are expressed as small ridges with 1–3 mm positive relief. Lack of polygonal shapes and their occurrence in thinly laminated, relatively deep-water shales preclude an origin from sand-filled desiccation cracks. Instead, their close association with microbially induced sedimentary structures (MISS) such as micro-wrinkles and gas blisters, putative bacterial fossils (possibly coccoidal cyanobacteria) and framboidal pyrites, suggests that they were formed by degassing of methane from microbial mat decay. Methane gas disrupted overlying sedimentary layers, creating fractures open to seawater. Fine-grained quartz sands, which were transported into the depositional environment by strong winds, filled the fractures. Sand-filled fractures were shortened and folded during burial compaction, forming ptygmatic shapes. The presence of dispersed dolomite and siderite in these sand veins suggests authigenic carbonate precipitation from anaerobic oxidation of methane (AOM). Sand veins are intensely distributed within the Chuanlinggou Formation and are spatially widespread in the North China Platform. If their methane origin is confirmed, they may have important implications for the Mesoproterozoic paleoclimate. With anoxic oceans and low seawater sulfate concentration during the Mesoproterozoic, methane release from microbial mat decay and/or microbial methanogenesis during shallow burial may have been proportionally higher than that of the modern marine environments, with resultant increase in the relative importance of methane in maintaining the Mesoproterozoic greenhouse climate.     

Methane-derived authigenic carbonates from the Ulleung basin sediments,East Sea of Korea

Authigenic carbonates were sampled in methane-enriched piston core sediments collected from gas venting sites on the western continental slope of the Ulleung Basin, East Sea of Korea. Multidisciplinary investigations on these carbonates, including the scanning electronic microscope (SEM) observations and mineralogical-geochemical compositions, were carried out to identify the carbon and oxygen sources and the forming mechanism of these carbonates. The authigenic carbonates from the study area correspond to semi-consolidated, compact concretions or nodules ranging from 2 to 9 cm in size. X-ray diffraction and electron microprobe analyses showed that most of the sampled carbonate concretions were composed of almost purely authigenic high-Mg calcite (10.7–14.3 mol% MgCO₃). Characteristically, microbial structures such as filaments and rods, which were probably associated with the authigenic minerals, were abundantly observed within the carbonate matrix. The carbonates were strongly depleted in δ¹³C (−33.85‰ to −39.53‰ Peedee Belemnite (PDB)) and were enriched in δ¹⁸O (5.16–5.60‰ PDB), indicating that the primary source of carbon is mainly derived from the anaerobic oxidation of methane. Such methane probably originated from the destabilization of the underlying gas hydrates as strongly supporting from the enriched ¹⁸O levels. Furthermore, the strongly depleted δ¹³C values (−60.7‰ to −61.6‰ PDB) of the sediment void gases demonstrate that the majority of the gas venting at the Ulleung Basin is microbial methane by CO₂ reduction. This study provides another example for the formation mechanism of methane-derived authigenic carbonates associated with gas-hydrate decomposition in gas-seeping pockmark environments.     

CH4-consuming microorganisms and the formation of carbonate crusts at cold seeps

To understand the role played by microorganisms in the formation of cold seep carbonates, we conducted an integrated microbial, mineralogical and organic geochemical study of methane-related authigenic carbonate crusts formed on eastern Mediterranean mud volcanoes. We show that supersaturation with respect to carbonate minerals is induced by microbial anaerobic oxidation of methane. Combined lipid biomarker analysis and 16S rRNA gene surveys identified a highly diversified methane-consuming archaeal community possibly comprising novel species, implying that the anaerobic oxidation of methane is phylogenetically widespread and directly implicating these organisms in the process of crust precipitation. Moreover, pore-water sulphate gradients produced by co-occurring methane-based sulphate reduction exert the main control on aragonite versus magnesian calcite precipitation. We propose that this may be the dominant mode of carbonate crust formation at cold seeps world-wide, in agreement with aquatic chemistry predictions and explaining carbonate mineralogy.     

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface.With the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon burial.As compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon cycle.Soil carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric CO2drawdown.Thus,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively differentiated.In this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North China.Based on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite veins.The modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric CO2.The low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric CO2sink.Nevertheless,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million years.Finally,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.     

The formation mechanism of high-quality dolomite reservoir in the deep of Puguang Gas Field

The discovery of Puguang Gas Field provides the exploration of China deep marine carbonate rock with important references. In Puguang Gas Field, the dolomite reservoirs discovered in the deep are the best in the present of China, which present big thickness and wide-range distribution, and develop abundant secondary porosity. The researches show that Puguang Gas Field bears the characteristics of early gas-filling time, deep burial, high matured organic matter and long-term interaction of hydrocarbon (oil and gas)-water-rock (carbonate reservoir). The developments of secondary pores in this area are affected by multiple diagenesis and their formation mechanisms are complicated. Through the research on depositional environment, sedimentary facies and reservoir porosity characters of Changxing and Feixianguan Formations, it is thought that high-quality dolomite reservoirs of Puguang Gas Field form on the favorable sedimentary facies belts, which are the integrate result affected by several factors including superficial corrosion, burial corrosion, overpressure and tectonic movement, among which burial corrosion of TSR to reservoir and overpressure formed by thermal evolution of organic matter have great effect on the formation of secondary porosity of Changxing and Feixianguan Formations.     

The formation mechanism of high-quality dolomite reservoir in the deep of Puguang Gas Field

The discovery of Puguang Gas Field provides the exploration of China deep marine carbonate rock with important references.In Puguang Gas Field,the dolomite reservoirs discovered in the deep are the best in the present of China,which present big thickness and wide-range distribution,and develop abundant secondary porosity.The researches show that Puguang Gas Field bears the characteristics of early gas-filling time,deep burial,high matured organic matter and long-term interaction of hydrocarbon(oil and gas)-water-rock(carbonate reservoir).The developments of secondary pores in this area are affected by multiple diagenesis and their formation mechanisms are complicated.Through the research on depositional environment,sedimentary facies and reservoir porosity characters of Changxing and Feixianguan Formations,it is thought that high-quality dolomite reservoirs of Puguang Gas Field form on the favorable sedimentary facies belts,which are the integrate result affected by several factors including superficial corrosion,burial corrosion,overpressure and tectonic movement,among which burial corrosion of TSR to reservoir and overpressure formed by thermal evolution of organic matter have great effect on the formation of secondary porosity of Changxing and Feixianguan Formations.     

Biogeochemical conditions in sediments enriched by organic matter from net-pen fish farms in the Bolinao area, Philippines

Sedimentation and sediment metabolism was measured at eight active milkfish fish pens and at one abandoned site in the Bolinao area, Philippines in order to examine the interactions between sediment and water in this shallow coastal zone. The rates of sedimentation were high in the area due to siltation, but the activities in the fish pens also contributed to enhanced sedimentation as indicated by the difference between the abandoned and active sites. The sediment metabolism appeared to decrease with increasing rates of sedimentation indicating that the microbial activity reached a saturation level in the fish pen sediments. Anaerobic processes dominated the organic matter decomposition, and sulfate reduction rates are among the highest measured in fish farm sediments. The rates decreased with increasing organic loading despite high concentrations of sulfate (>10 mM) at all sites. Presence of methane bubbles in the sediments suggests that sulfate reduction and methanogenesis were coexisting. The sediment metabolism was significantly reduced at the abandoned site indicating that the stimulation of microbial activities is due to active fish production. The anaerobic activity remained high at the abandoned site indicating that the sediment biogeochemical conditions remain affected long time after fish production has ceased.     

Effects of pelagic food web structure and nutrient concentration on anaerobic methane metabolism in lake sediments

Although anaerobic metabolism in lake sediments is strongly related to organic material from the trophogenic layer, little is known about the role of food web structure in this respect. We tested the influence of planktivorous fish (treatments with or without fish, ±F) and nutrients (treatments with or without fertilization, ±N) on chlorophyll a, zooplankton, sedimentation of particulate organic carbon (POC), and methane accumulation in large enclosures with anoxic hypolimnia (10 m diameter, 8 m deep, 2 × 2 factorial design). Additionally, methane production potential from settled material was estimated in laboratory experiments. In the enclosures, methane accumulation rate increased in the order +F/−N, −F/+N, −F/−N, and +F/+N, while POC sedimentation was similar in all treatments. Settled POC was more efficiently transformed into methane in −F/−N than in +F/−N treatments. However, an opposite effect was observed between −F/+N and +F/+N treatments. In the laboratory, methane production potential was higher when (1) POC content in settled matter increased, and (2) no fish were present. This corresponded well only to field results obtained in −F/−N and +F/−N treatments. The unexpectedly high methane accumulation in the +F/+N treatment was very likely related to abrupt depletion of other electron acceptors in the hypolimnion, which attenuated effects of food web structure. In conclusion, our results indicate that food web structure indirectly affects anaerobic microbial activity primarily due to changes in the decomposition potential of settled organic matter.     

Geobiological processes of the formation of lacustrine source rock in Paleogene

Gypsum-salt rocks and coccolith calcareous shale are widely deposited in the lower part of the Paleogene Shahejie Formation in the Dongying Sag,Shandong Province.The gypsum-salt rock is believed to be formed during the earlier deposition in salt lake,while the overlying coccolith shale in saline lake with relatively low salinity.By comparing the lake environment and lacustrine microbial communities between ancient and recent lakes,cyanobacteria are regarded as the main representative of productivity during the formation of gypsum-salt strata series,with the annual productivity of 1500-2000 gC m-2 yr-1.Based on the research of ultramicrofossils in the calcareous shale,coccolith is considered as the main contributor to the productivity during the formation of calcareous shale.On the basis of statistic data of sedimentary rates,shale laminations,and coccolith fossils in each lamination,the quantitative value of productivity is calculated,with the annual productivity of 2250-3810gC m-2 yr-1(averagely 3120 gC m-2 yr-1).Statistic data of large amount of pyrite framboids indicate that the lower water column was persistently in sulfidic or anoxic conditions during the deposition of gypsum-salt strata series,but it changed to be dysoxic when the coccolith calcareous shale was deposited.Both of these water conditions are favorable for the preservation of organic matter.It is estimated that the organic carbon burial efficiency of the Lower Paleogene salt lakes and saline lakes of Dongying Depression is about 10%-15%,which is calculated and analyzed using the multi-parameter geobiological model.     

Late Cretaceous paleoenvironment and lake level fluctuation in the Songliao Basin,northeastern China

Study of Late Cretaceous lacustrine sedimentary strata in the eastern Songliao Basin, China revealed that the paleoclimate was relatively arid and hot during sedimentation of the upper Santonian of the Yaojia Formation, but became relatively humid and warm during deposition of the lower Campanian Nenjiang Formation. The upper Yaojia Formation was deposited in a freshwater lake environment, while the lower Nenjiang Formation was deposited in a slightly brackish to brackish environment. The average total organic carbon content in the upper Yaojia Formation is 0.15%, while the hydrogen index is 36 mg_HC/g_TOC, implying poor source rock for oil generation and the organic matter comprised of a mixture of woody and herbaceous organic matter. In contrast, the hydrogen index of oil shale and black shale of the lower Nenjiang Formation is 619 mg_HC/g_TOC, and total organic carbon content on average is 3.37%, indicating a mixed algae and herbaceous source of kerogen and an increase in aquatic bioproductivity. The black shale and oil shale have low Pristane/Phytane and C₂₉ 5α,14α,17α(H) ? stigmastane 20R/(20R + 20S) ratios, with maximum concentration of n‐alkanes at n‐C₂₃, implying an anoxic depositional environment with algae, bacteria and higher plants providing most of the organic matter. Relatively abundant gammacerane and a higher Sr/Ba ratio in the oil shales suggest the presence of brackish water and development of salinity stratification in the lake. During sedimentation of the upper Yaojia through the lower Nenjiang Formations, the level of Songliao lake increased and a deep‐lake environment was formed with bottom waters being oxygen depleted. Concomitantly, as the lake deepened bottom conditions were changing from oxic to anoxic, and the input of organic matter changed from predominantly higher plants to a mixture of bacteria, algae and higher plants providing favorable conditions for oil source rock accumulation.     

Light carbon isotope events of foraminifera attributed to methane release from gas hydrates on the continental slope,northeastern South China Sea

In 2013, the China Geological Survey and Guangzhou Marine Geological Survey conducted the second Chinese gas hydrate expedition in the northern South China Sea(SCS) and successfully obtained visible gas hydrate samples. Five of the thirteen drilling sites were cored for further research. In this work, Site GMGS2-08 is selected for the stable isotopic analysis of foraminifera present in the boreholes in order to reveal the carbon isotopic characteristics of the foraminifera and their response to methane release in the gas hydrate geological system. Our results show that the methane content at Site GMGS2-08 is extremely high, with headspace methane concentrations up to 39300 μmol L~(-1). The hydrocarbon δ~(13)C values, ranging from-69.4‰ to-72.3‰ PDB, distinctly indicate biogenic generation. Based on the δD analytical results(~(-1)83‰ to~(-1)85‰ SMOW), headspace methane is further discriminated to be microbial gas, derived from CO_2 reduction. By isotopic measurement, five light δ~(13)C events are found in the boreholes from Site GMGS2-08, with foraminiferal δ~(13)C values being apparently lower than the normal variation range found in the glacial-interglacial cycles of the SCS. The δ~(13)C values of benthic Uvigerina peregrina are extremely depleted(as low as~(-1)5.85‰ PDB), while those of planktonic Globigerinoides ruber reach-5.68‰ PDB. Scanning electron micrograph(SEM) studies show that foraminiferal tests have experienced post-depositional alteration, infilled with authigenic carbonate, and the diagenetic mineralization is unlikely to be related to the burial depths. The correlation calculation suggests that the anaerobic oxidation of organic matter has only weak influences on the δ~(13)C composition of benthic foraminifera. This means that the anomalous δ~(13)C depletions are predominantly attributed to the overprinting of secondary carbonates derived from the anaerobic oxidation of methane(AOM). Furthermore, the negative δ~(13)C anomalies, coupled with the positive δ18O anomalies observed at Site GMGS2-08, are most likely the critical pieces of evidence for gas hydrate dissociation in the geological history of the study area.     

Methanogenesis and organic matter destruction in bottom sediments of technogenic water bodies

Traits have been revealed in the microbial processes of methane formation and organic matter destruction in bottom sediments of technogenic water bodies, in which at the abundance of C_org compounds, including toxic, dissolved oxygen deficiency, and low redox potential, organic matter decay in sediments is mostly anaerobic with the predominance of methanogenesis and sulfate reduction. Data on major microbial processes are used to calculate the total sludge destruction; it is maximal in the sediments of low-toxicity technogenic water bodies; organic matter destruction in them is mostly due to methanogenesis; it is minimal in high-toxicity water bodies, the share of sulfate reduction in them increases, and that of methanogenesis decreases.     

Treatment of Groundwater Containing Methane – Combination of the Processing Stages Desorption and Filtration

Methane is produced under anaerobic conditions by metabolic processes in microbes and can occur in waters of the types anoxic‐anaerobic (RG 1/2) and anaerobic‐reduced (RG 2). If the concentration of methane lies below 0.2 mg/L, then no special treatment processes are required apart from dosing of oxygen and rapid sand filtration, which are performed to remove iron, manganese, and ammonium. The research results show that a higher concentration of methane must be specially treated. From the point of view of stable deferrisation, oxidation of up to 2 mg/L is tolerable in rapid sand filtration. However, an unusual increase in regrowth potential was observed. For this reason, the oxidation of methane should be reduced to 0.5 mg/L until further experiments yield results on the microbiological stability of treated water. Rapid sand filters for nitrification and demanganisation should have a maximum methane loading of 0.2 mg/L. The experiments show that nitrification first occurs at a methane concentration below 0.1 mg/L. During the working in of demanganisation, the inlet water should be free of methane. Therefore desorption is often required. If there is less than 1 mg/L to be degassed, then desorption can be achieved with overpressure in the oxidiser without any change in the carbonate‐bicarbonate equilibrium. With other systems, such as packed columns, wetted‐wall columns, or percolators, carbon dioxide is removed simultaneously. By means of the coefficients of similarity found, it was shown that methane and carbon dioxide desorb in different proportions depending on the system, and that the discharge of carbon dioxide can be reduced through a decrease in the air/water ratio.     

Geochemical constraints on the methane seep activity in western slope of the middle Okinawa Trough,the East China Sea

Anaerobic oxidation of methane and sulfate reduction was studied in the pore waters of four cores at two stations of the middle Okinawa Trough. Pore water vertical distributions of sulfate, methane, sulfide, total alkalinity, ammonium, and phosphate were determined in this study. Our results show strong linear sulfate concentration gradients of 6.83 mmol/L m?1 in Core A and 5.96 mmol/L m?1 in Core C, which were collected from two stations. Concurrent variations of methane, total alkalinity and hydrogen sulfide all exhibit steep increases with depth at both cores, which indicate active methane seep activities around two stations. Pore water ammonium and phosphate concentrations reveal minor influences of organic matter degradation on sulfate reduction at two stations. Sulfate methane interface(SMI) was extrapolated from linear sulfate profiles in methane seep cores. Shallower SMI depths(A: 4.9 mbsf; C: 5.4 mbsf) indicate strong methane fluxes and active anaerobic oxidation of methane in the underlying sediments.     

湖泊生态系统产甲烷与甲烷氧化微生物研究进展

湖泊生态系统是重要的大气甲烷来源,其甲烷释放量占全球自然生态系统的40%.产甲烷和甲烷氧化微生物在湖泊甲烷生产和消耗过程中发挥关键作用.本文综述了近期有关湖泊生态系统甲烷产生与氧化过程的研究进展,重点介绍产甲烷与甲烷氧化微生物在湖泊中的分布特征、代谢途径以及调控机制.现有研究表明,湖泊中甲烷的生成不仅仅依靠赋存于沉积物和水体厌氧层的产甲烷古菌,还可能来自有氧环境中其他产甲烷微生物的代谢作用.湖泊中的甲烷在脱离水体逸散至大气之前,被甲烷氧化微生物利用,转化成二氧化碳和小分子有机化合物(如甲醇、甲醛和甲酸等).除了传统依赖氧气作为电子受体的好氧氧化过程外,新近研究还揭示了多种厌氧甲烷氧化过程,包括依赖还原硫酸盐、硝酸盐和亚硝酸盐以及Fe~(3+)/Mn~(4+)等金属离子的甲烷氧化过程.文献综合分析表明,反硝化型厌氧甲烷氧化过程主要发生在淡水湖泊中,而硫酸盐还原型主要发生在高盐度或者高碱度湖泊中.水体温度、溶解氧浓度可以显著影响产甲烷与甲烷氧化微生物的丰度与群落结构,其他湖泊环境条件,如盐度、pH和有机质类型等都可能改变产甲烷与甲烷氧化微生物的分布和代谢活性.不同湖泊类型的比较研究,有助于全面掌握影响湖泊产甲烷与甲烷氧化微生物的时空分布与代谢特征的主导因素.     

Methane biotransformation in the ocean and its effects on climate change: A review

Methane is a potent greenhouse gas. Continental margins contain large reservoirs of methane as solid gas hydrate and the dissolved and gaseous forms of methane. Submarine methane seeps along the global continental margins, including the coastal seas, have been estimated to contribute 0.01 to 0.05 Gt of carbon to the atmosphere annually, accounting for between 1% and 5% of the global methane emissions to the atmosphere. Much of this methane is exhausted via microbial anaerobic methane oxidation. Methane biotransformation in the ocean has effects on global climate change. This review mainly introduces the mechanisms of methanogenesis and methane oxidation and describes new findings that will provide information that will improve the understanding of the balance in terms of the generation, migration and consumption of methane in marine environments. Moreover, this review provides new insights into methane biogeochemical cycles and the effects of marine methane budgets on global climate.     

基于随机森林算法的陆相沉积烃源岩定量地震刻画:以东海盆地长江坳陷为例

烃源岩的定量地震刻画对于勘探开发区块的优选、盆地油气资源量的估算都具有重要意义.陆相沉积环境下的浅湖或半深湖相的烃源岩横向变化快,其空间展布需要依靠钻井约束下的反射地震进行刻画,但是其地震弹性特征与岩性和有机质含量的映射关系呈现高度非线性化,因而很难利用传统基于地震岩石物理模型驱动的烃源岩地震预测方法进行有效刻画.本文以低勘探区的东海盆地长江坳陷为例,提出了一种在数据驱动的机器学习框架下,综合利用地质约束、钻井录井、测井、地球化学和叠前地震数据进行烃源岩的定量地震刻画的工作流程.其核心思想是利用随机森林集成学习算法对小样本数据表现优异的特征,以井位处的测井弹性数据(纵波速度和密度)、岩性、地球化学标定的总有机碳含量(TOC)为样本标签数据,在地质导向约束下通过随机森林算法生成学习网络,并将该网络与叠前地震反演结果相结合,采取先预测泥岩再预测总有机碳含量的“两步走”策略,完成对烃源岩空间分布及其非均质性的定量地震刻画,并对预测结果的不确定性进行评价.测试结果显示,随机森林算法相较于其他的机器学习算法能够更准确的识别陆相沉积地层的泥岩,并比传统的利用阻抗转化方法获得更可靠的总有机碳含量预测结果.     

Two Experimental Methods to Determine the Speciation of Cadmium in Sediment from the River Neckar

The binding forms of Cd to an anaerobic sediment of low sulfide content from Lauffen reservoir (River Neckar, Germany) were studied using two different approaches, i. e. sequential extraction (modified from published protocols) and titrimetric study of the pH-dependent Cd release. Thermodynamic equilibrium calculations were applied to calculate both the release pattern of Cd during the titrations and the speciation of Cd within the single fractions of the extraction protocol. The calculations were based on measured sediment parameters such as hydrous ferric oxide (HFO), acid volatile sulfide, carbonate content and total Cd content, and the extractants (oxalate, acid etc.) used. The results of the two independent approaches coincided well in that they both assigned more than two thirds of the total Cd content to be adsorbed to organic matter. Cd bound as CdS is of little importance. Sequential extraction after a 3-month oxidation period at pH 7 revealed a shift of Cd from being mainly bound in stronger surface complexes with organic matter to being mainly bound in weaker surface complexes with organic matter and HFO, and thus becoming more bioavailable. This study suggests that the use of sequential extraction although being frequently criticized due to its operational character can be used to determine binding forms of metal ions if they are accompanied by 1) careful supporting experiments, 2) analysis of important sediment parameters, and 3) the use of thermodynamic equlibrium models which can help to understand Cd speciation within the extraction fractions.     

Anaerobic methane oxidation: Rate depth distributions in Skan Bay sediments

A radiotracer method that measures rates of oxidation of methane to carbon dioxide has been applied to anoxic marine sediments. The results confirm the occurrence of anaerobic methane oxidation and agree with model predictions of a zone of intense anaerobic methane oxidation at the base of the sulfate-reducing zone.     

Methylhopane biomarker hydrocarbons in Hamersley Province sediments provide evidence for Neoarchean aerobiosis

Bacteriohopanepolyols with A-ring methyl substituents are bacterial lipid biomarkers that are presently known to originate from just a few specific taxa. When preserved in ancient rocks, the fossilized hydrocarbon skeletons of these molecules have the potential to provide biogeochemical records of those taxa and their respective physiologies. Considering both their occurrences in modern organisms, and their Proterozoic and Phanerozoic sedimentary distributions, hopanes carrying 2-methyl or 3-methyl substituents are proposed to be derived from cyanobacteria and oxygen-respiring methanotrophs, respectively. Here we report the distribution of methylhopanes in 2.72–2.56 billion-year-old, Neoarchean rocks from the Hamersley Province on the Pilbara Craton. The relative abundance of C₃₁-3β-methylhopane, but not that of C₃₁-2α-methylhopane, shows a strong correlation to the carbon isotopic composition of co-occurring kerogen (insoluble particulate organic matter). The unanticipated nature of this relationship provides evidence for a shallow-water locus of carbon cycling through aerobic oxidation of CH₄ and, coincidentally, a means to demonstrate biomarker syngenicity. 2α-Methylhopanes are most abundant in both shale and carbonate from shallow-water sediments, and a positive correlation to carbonate abundance, contrasts to variable, but generally lower, 2α-methylhopane abundances of deeper water facies. These observations are consistent with their origin from cyanobacteria which were likely the cornerstone of microbial communities in shallow-water ecosystems providing molecular oxygen, fixed carbon, and possibly fixed nitrogen.