Reply to D. F. Lascelles. Discussion on ‘Microplaty hematite—its varied nature and genesis’ by R. C. Morris and ‘Genesis modelling for the Hamersley BIF-hosted iron ores of Western Australia: a critical review’ by R. C. Morris and M. Kneeshaw

Abstract

The third (Es₃) member of the Eocene Shahejie Formation is the main hydrocarbon source rock interval in the Raoyang Sag of the Bohai Bay Basin. The lower Es₃ (Es₃^L) and upper Es₃ (Es₃^U) submembers display clear differences in source rock quality. The formation mechanisms of the source rocks are investigated via geochemical methods using 60 samples from three wells to reconstruct the paleo-environment during deposition. The major element parameters exhibit changes in paleoclimate from humid to arid. Indicators such as Sr/Ba, B/Ga, the gammacerane index and isotopic data suggest fresh–brackish and hydrological open lakes with unstable water column stratification likely occurred during deposition of the Es₃^L submember and saline and hydrologically closed lakes with stable water column stratification likely during deposition of the Es₃^U submember. Carbon isotope values of organic matter, trace elements and biomarker parameters suggest that the Es₃^L submember had moderate productivity, with a significant contribution from terrigenous organic matter whereas the Es₃^U submember had slightly enhanced productivity, with no or minor contributions from terrigenous organic matter. Furthermore, the pristane/phytane ratio and the enrichment of Mo and U indicate that the euxinic bottom-water conditions (sulfidic) of the lakes during deposition of the Es₃^U submember were best for preserving organic matter. Comparison of the models of source rock deposition of the Es₃^L and Es₃^U submembers indicates that the redox conditions play an important role in the formation of organic-rich source rocks in the Raoyang Sag.     

南黄海北部海底沉积物饱和烃地球化学特征及物源判识

对南黄海北部48个海底表层沉积物样品进行了常规的有机地球化学分析测试,对沉积有机质中的饱和烃组分进行了色谱定量、色谱—质谱分析。测试结果显示沉积有机质受微生物的降解作用在饱和烃色谱图中出现不同程度的UCM鼓包,峰型为双峰型,奇偶碳优势明显,且长链烃奇数碳优势更加显著;石油烃参数Pr/nC17和Ph/nC18比值较高;甾、萜烷成熟度生物标志物参数均显示了有机质进入生烃的热成熟阶段。综合分析认为,南黄海北部海底沉积物受双源控制,以陆源输入为主,有机质保存条件好,成熟度较高,推测可能有外源烃的污染。     

小麦和苜蓿根系分泌物中饱和烃馏分

为深入研究根系分泌物对根际土中有机物贡献的特点,用柱色层族组成分离方法, 对小麦和苜蓿根际土及二者交界地中提出的可溶有机物采用了GC/MS分析测定。从样品的非极性馏分中分析检测出正构烷烃、类异戊二烯烷烃及酯类3个系列的生物标志化合物,并对小麦地、苜蓿地及二者的交界地中的正构烷烃的奇偶优势比（OEP）、∑C₂₂^-/∑C₂₃⁺比值和姥植比（Pr/Ph）进行了分析比较。小麦和苜蓿的GC/MS的主峰均为nC₃₁,正构烷烃奇偶优势比OEP值大小顺序为苜蓿地>交界地>小麦地,且三者数值均>1.4。正构烷烃∑C₂₂^-/∑C₂₃⁺比值大小顺序为小麦地>交界地>苜蓿地。姥植比（Pr/Ph）的比较结果为苜蓿地>交界地>小麦地。这表明小麦和苜蓿根系分泌物进入土壤后演化程度不一样,小麦地有机质演化程度高于苜蓿地。     

Origin of light volatile hydrocarbon gases in mud volcano fluids, Gulf of Cadiz — Evidence for multiple sources and transport mechanisms in active sedimentary wedges

Widespread mud volcanism across the thick (≤ 14 km) seismically active sedimentary prism of the Gulf of Cadiz is driven by tectonic activity along extensive strike–slip faults and thrusts associated with the accommodation of the Africa–Eurasia convergence and building of the Arc of Gibraltar, respectively. An investigation of eleven active sites located on the Moroccan Margin and in deeper waters across the wedge showed that light volatile hydrocarbon gases vented at the mud volcanoes (MVs) have distinct, mainly thermogenic, origins. Gases of higher and lower thermal maturities are mixed at Ginsburg and Mercator MVs on the Moroccan Margin, probably because high maturity gases that are trapped beneath evaporite deposits are transported upwards at the MVs and mixed with shallower, less mature, thermogenic gases during migration. At all other sites except for the westernmost Porto MV, δ¹³C–CH₄ and δ²H–CH₄ values of ~ − 50‰ and − 200‰, respectively, suggest a common origin for methane; however, the ratio of CH₄/(C₂H₆ + C₃H₈) varies from ~ 10 to > 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C₂₊ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C₂₊-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH₄ having δ¹³C–CH₄ ~ − 50‰, as at most sites, but markedly lower δ²H–CH₄ values < − 250‰, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH₄ is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments ~ 2–4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH₄.     

江汉盐湖盆地中高成熟原油的地球化学特征及油源探讨

江汉盐湖盆地中钟76井潜江组潜四段3300m以下发现的高成熟轻质原油,其基本特征是：饱和烃含量特高,非烃和沥青质含量很低;富含植烷、伽马蜡烷、C35升藿烷、孕甾烷和C27胆甾烷等指示高盐度、强还原环境的生物标志物。尤其明显的是C27-C29甾烷异构化程度高,αββ20R和20S峰十分突出,C29甾烷的两个参数值均大于等于0．5,指示了原油的成熟度已处于高成熟阶段。根据油源条件分析,认为该地区潜江组潜一段至潜四上段烃源岩埋深浅于3000m,P值小于1％,处于未成熟-成熟阶段,不具有形成高成熟原油的可能性,只有潜四下段烃源岩已进入生烃高峰高成熟早期阶段,能够提供轻质原油的油源。生物标志物多项地球化学资料及参数综合对比表明,本区两种成因类型的高成熟原油,其油源确系来自潜四下段两种不同沉积环境形成的泥质灰岩和灰质泥岩,明显具有近源运移聚集、自生、自储的特征,这展示了该地区潜四下段及其下覆的古潜山深层油气勘探有着良好的前景。     

长直链烷基苯及其异构体母质来源研究及地球化学意义

烷基苯系列化合物广泛分布在岩石圈中,但其母质来源和指示意义仍存在一定争议。对四川盆地晚三叠世须家河组和鄂尔多斯盆地晚三叠世延长组烃源岩样品进行了岩石热解及GC-MS（GC-MS-MS）分析,检测出一系列的长直链烷基苯及其异构体。烃源岩基本地球化学参数表明四川盆地和鄂尔多斯盆地样品均遭受过较强程度的微生物降解作用,有机质类型以腐殖腐泥型为主,埋藏期间经历过一定程度的黏土矿物催化作用,以弱氧化的淡水沉积为主。此外,两个研究区样品中长直链烷基苯及其异构体的相对含量呈现出相反的分布模式,在前人研究基础上并结合研究区烃源岩沉积环境和热演化背景,认为烷基苯系列化合物可能来自于类脂化合物（如脂肪酸和脂肪醇）或简单芳烃化合物与类脂化合物的反应,且热作用会导致长直链烷基苯向其异构体转化。综合以上研究表明长直链烷基苯及其异构体可以作为一种指示有机质热演化程度和母质来源的有效参数。     

Composition and origin of lipid biomarkers in the surface sediments from the southern Challenger Deep,Mariana Trench

The surface sediments collected from the southern Mariana Trench at water depths between ca. 4900 m and 7068 m were studied using lipid biomarker analyses to reveal the origin and distribution of organic matters. For all samples, an unresolved complex mixture (UCM) was present in the hydrocarbon fractions, wherein resistant component tricyclic terpanes were detected but C₂₇–C₂₉ regular steranes and hopanes indicative of a higher molecular weight range of petroleum were almost absent. This biomarker distribution patterns suggested that the UCM and tricyclic terpanes may be introduced by contamination of diesel fuels or shipping activities and oil seepage elsewhere. The well-developed faults and strike-slip faults in the Mariana subduction zone may serve as passages for the petroleum hydrocarbons. In addition, the relative high contents of even n-alkanes and low Carbon Preference Indices indicated that the n-alkanes were mainly derived from bacteria or algae. For GDGTs, the predominance of GDGT-0 and crenarchaeol, together with low GDGT-0/Crenarchaeol ratios (ranging from 0.86 to 1.64), suggests that the GDGTs in samples from the southern Mariana Trench were mainly derived from planktic Thaumarchaeota. However, the high GDGT-0/crenarchaeol ratio (10.5) in sample BC07 suggests that the GDGTs probably were introduced by methanogens in a more anoxic environment. Furthermore, the n-alkanes C₁₉–C₂₂ and the n-fatty acids C_20:0–C_22:0 were depleted in ¹³C by 3‰ compared to n-alkanes C₁₆–C₁₈ and the n-fatty acids C_14:0–C_18:0, respectively, which was interpreted to result from the preferential reaction of fatty acid fragments with carbon “lighter” terminal carboxyl groups during carbon chain elongation from the precursors to products. The abundance of total alkanes, carboxylic acids, alcohols and total lipids were generally increased along the down-going seaward plate, suggesting the lateral organic matter inputs play an important role in organic matter accumulation in hadal trenches. The extremely high contents of biomarkers in sample BC11 were most likely related to trench topography and current dynamics, since the lower steepness caused by graben texture and proximity to the trench axis may result in higher sedimentation rate. This paper, for the first time, showed the biomarker patterns in surface sediments of the Mariana Trench and shed light on biogeochemistry of the hardly reached trench environment.     

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.