Solid bitumens: an assessment of their characteristics, genesis, and role in geological processes

Familiar since antiquity, and subject in contemporary times to various characterization schemes, the exact nature of solid bitumen is not yet fully known. Bitumens have ‘random polymer-like’ molecular structures, are mobile as highly viscous fluids or were once fluids but have since turned into solids. Solid bitumens consist mainly of large moieties, of polyclyclic aromatic hydrocarbons, occasionally with finely admixed, fine-grained cryptocrystalline graphite. Solid bitumens are distinguished from kerogen, which is the syngenetic and generally finely dispersed particulate organic matter in sedimentary rock that virtually does not migrate following its deposition. Occurrences of solid bitumens are relevant to petroleum exploration as well as the search for, and evaluation of, a variety of metallic mineral deposits. Genesis of bitumen is in many cases linked to the thermal and hydrothermal history of organic matter in sedimentary rock. Apparently bitumen, or more specifically organic acids generated along with bitumen during diagenesis, may alter porosity of reservoir rocks or otherwise prepare the ground for ore deposition. Bitumen is also relatively sensitive to alteration processes, some of which, such as oxidative weathering, water leaching, biodegradation (contact) metamorphism and ionizing radiation may likewise affect its nature. Elemental composition of bitumen commonly reflects the nature of mineral deposits. Is is possible that in petroleum exploration, trace metal abundances of bitumen may eventually allow prediction of crude oil types and volumes anticipated from a given source rock? Beside transition elements, notably Ni and V, highly anomalous concentrations of U, Pt and Au occur in some solid bitumens. During the generation of petroleum from kerogen, the trend in δ¹³C is toward lighter values. The opposite seems to occur when liquid petroleum is subjected to thermal cracking (and /or related processes) yielding solid bitumen enriched in ¹³C, and isotopically light methane. In fact, except for deasphalting and possibly some irradiation processes, the result of thermal cracking, oxidation, water leaching, inspissation (drying) and bacterial degradation of crude oil is that lower molecular weight hydrocarbons are removed leaving bitumen residues enriched in aromatic hydrocarbons, heteroatomic compounds (NSO) and ¹³C. Such phenomena are relevant to bitumen paragenesis in petroleum reservoir rocks, to certain Phanerozoic occurrences of multiple generations of bitumens, and to bitumens in mineral deposits.     

Anomalous Enrichment of Silver in Organic Matter of the Songxi Shale-hosted Ag-Sb Deposit in Northeastern Guangdong

The silver contents of organic matter in the host rocks of the Songxi shale-hosted Ag-Sb deposit of northeastern Guangdong, South China, have been directly determined using the electron microprobe technique. The silver contents in two types of organic matter, marine vitrinite and solid bitumen, vary in the range from 100×10-6to 350×10-6, which are from tens of times to thousands of times higher than those of the host rocks in the ore deposit. The average silver content of the organic matter is also several times higher than the pay grade of silver for commercial mining of the ore deposit. It is quite obvious that the organic matter of the host rocks in the ore district is characterized by an anomalous enrichment of silver. The results of this study indicate that the silver anomalies in the organic matter have been derived from both the host rocks and the silver-bearing fluids of the Songxi black shale ore source. In the course of sedimentation and later hydrothermal reworking, organic matter was able     

Characterization of solid bitumens originating from thermal chemical alteration and thermochemical sulfate reduction

Solid bitumen can arise from several reservoir processes acting on migrated petroleum. Insoluble solid organic residues can form by oxidative processes associated with thermochemical sulfate reduction (TSR) as well as by thermal chemical alteration (TCA) of petroleum. TCA may follow non-thermal processes, such as biodegradation and asphaltene precipitation, that produce viscous fluids enriched in polar compounds that are then altered into solid bitumens. It is difficult to distinguish solid bitumen formed by TCA from TSR since both processes occur under relatively high temperatures. The focus of the present work is to characterize solid bitumen samples associated with TSR- or TCA-processes using a combination of solid-state X-ray Photoelectron Spectroscopy (XPS), Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES), and ¹³C NMR. Naturally occurring solid bitumens from three locations, Nisku Formation, Brazeau River area (TSR-related); La Barge Field, Madison Formation (TSR-related); and, the Alaskan North Slope, Brooks Range (TCA-related), are compared to solid bitumens generated in laboratory simulations of TSR and TCA.The chemical nature of solid bitumens with respect to organic nitrogen and sulfur can be understood in terms of (1) the nature of hydrocarbon precursor molecules, (2) the mode of sulfur incorporation, and (3) their concentration during thermal stress. TSR-solid bitumen is highly aromatic, sulfur-rich, and nitrogen-poor. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (S/C atomic ratio >0.035) into aromatic structures and to initial low levels of nitrogen in the unaltered petroleum. In contrast, TCA-solid bitumen is derived from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. TCA-bitumens from the Brooks Range have <75% aromatic carbon. TCA-bitumens exposed to greater thermal stress can have a higher aromaticity, like that observed in TSR-bitumens. Organic sulfur in TCA-organic solids remains relatively constant with increasing maturation (S/C atomic ratio <0.035) due to offsetting preservation and H₂S elimination reactions. Although S-XANES and ¹³C NMR provide information needed to understand changes in structure and reactivity that occur in the formation of petroleum solids, in some cases XPS analysis is sufficient to determine whether a solid bitumen is formed by TCA or TSR.     

普光气田及邻区碳酸盐储层沥青的分子地球化学研究

从普光气田及邻近地区二叠系和下三叠统15个含沥青碳酸盐储集岩样品分步提取了自由态油气组分和油气包裹体组分,并且应用限定体系(金管)热解实验获取了固体沥青热解组分.各组分进一步做色谱和色谱-质谱分析获取了生物标志物组成.分析结果表明,从油气包裹体组分、自由态油气组分至固体沥青热解组分,伽马蜡烷/C31升藿烷比值依次增高.同时油气包裹体组分 C23三环萜烷/(C23三环萜烷+C30藿烷)、C21/(C21+ΣC29)甾烷、C27重排甾烷/(C27重排甾烷+C27规则甾烷)、20S/(20R+20S) C29甾烷和αββ/(ααα+αββ) C29甾烷等成熟度指标与自由态组分相近,而明显高于固体沥青热解组分.根据分子指标,可以推断古油藏的原油来源于不同的烃源岩,早期充注的原油来源于下志留统烃源岩,具有较低的伽马蜡烷含量和较高的成熟度;晚期充注的原油来源于上二叠统烃源岩,具有较高的伽马蜡烷含量和较低的成熟度.固体沥青主要为晚期充注、来源于上二叠统烃源岩的原油裂解生气的产物     

长坑矿田金,银矿床地球化学特征及形成差异分析

长坑矿田金、银矿体主要产于下石炭统与上三叠统不整合面之下的硅质岩中,金、银矿体分离。金矿体主要为浸染状,富集As、Sb、Hg;银矿体主要为脉状,富集Cu、Pb、Zn。金矿体铅同位素组成与寒武纪—石炭纪地层及硅质岩的相同,银矿体铅同位素组成与金矿体的不同。金、银矿体的氢、氧、碳同位素组成也明显不同。银矿体Rb-Sr等时线年龄为70.4Ma。据上述特征,笔者认为长坑金、银矿床是不同成矿作用形成的,金矿主要是热水沉积形成,银矿主要是燕山期晚期改造形成。     

盆地形成及成矿与地幔流体间的成因联系

文中共讨论以下5个问题:(1)盆地起源于幔壳溃变和膨隆,后者是地幔流体(超临界态(>375℃)HACONS流体,简称幔汁)上涌、渗入、交代、富化、致熔的产物。地幔流体造成油气盆地深部的高热流、异常超高压、伊利水云母化、硅化和地层有机碳的加氢成油作用。(2)盆地成矿可分两大阶段,先是沉积时的同生成矿;地层沉积后还有众多的后生成矿。两者组成“盆地矿套”(杜乐天,2002)。成矿无论同生还是后生,其分布均受断裂控制,都和地幔流体活动有关。(3)黑色页岩的实质是碳-硅-泥三元岩系,和热液成矿中的碳酸盐-硅质-泥质蚀变三元完全相当。此类岩系中总是有几十种亲壳亲幔亲气元素的特殊富集。奇异的是,石油、油页岩、沥青及砂岩型铀矿彼此有完全类似的继承性元素特殊富集。此等元素群不可能都是来自盆地之外蚀源区岩体的风化。研究证明,相当多的元素是地幔流体携带上来的。(4)盆地地层中广泛发育由地幔流体衍生的热液作用。(5)盆地实质上是气盆,全盆地排气。许多气田是地幔流体排气形成的。沙漠(原地型)和天然气田的共生很值得注意,两者皆源于地球强烈排气,导致地下和大气增温,过度蒸发,不易降雨,长期干旱而形成沙漠。     

Metal enrichments in solid bitumens: A review

The association of oils and solid bitumens with ore deposits is widely recorded. The oils and bitumens may actually be enriched with metals. Unlike oils, metal enrichments within bitumens do not reflect the role of petroleum as a transporting agent for metals. By contrast, they may be a result of the reduction of metal ions on contact with bitumen, and may reach levels so high that ore mineral inclusions are precipitated. Metal determinations of British bitumens suggest that new metal anomalies can be detected by this approach, that some metal anomalies within bitumens may be related to ore mineralization, and that bitumens from different sources may be distinguished by their metal contents. The potential use of bitumen distribution and/or metal enrichment within bitumen for ore exploration is dependent on the metal concerned, and in particular whether the metal is transported by association with organic materials or reduced in the presence of organic materials.     

Hydrocarbon migration in the Solway Basin

Carboniferous rocks in the north Solway onshore outcrop show evidence of hydrocarbon migration. Oil residues occur as intergranular bitumen in sandstones, thoriferous bitumen nodules in sandstones and uraniferous bitumens in fractures associated with the North Solway Fault at the northern margin of the Solway Basin. Oil was emplaced in sandstones after the dissolution of dolomite, calcite and clay cements. The radioelement-rich bitumens represent deposition following interactions between migrating hydrocarbons and metalliferous fluids. The close proximity of the Caledonian Criffel granodiorite, unroofed by Carboniferous times, suggests that the pluton was the source of uranium and thorium. Hydrocarbon source rocks are identified further east in the more complete succession exposed in the Esk Valley region, along with further oil residues. Time-temperature modelling suggests that oil was generated from Lower Carboniferous source rocks during the Permo-Triassic. Chemical age dating of uraninite in bitumen yields early Jurassic ages, which may reflect the time of hydrocarbon migration along the North Solway Fault system, and may be related to a mid-Jurassic episode of regional uplift. Analyses of thorite in bitumen nodules give a wider spread of data, probably due to the migration of daughter lead.     

华南某大型铀矿床成因新识

华南某大型铀矿床具典型的岩溶特征。研究发现矿石中铀主要以微脉浸染状沥青铀矿形式存在，沥青铀矿的晶胞参数ａ０＝５．４１６～５．４２８，含氧系数为２．３１～２．３４，属低、中温热液成因。矿床中出现一套低、中温热液矿物组合。测得成矿温度为１５０～１８１℃（均一法）。矿床中热水叠加改造特征明显，故建议称之为岩溶热造铀矿床，是一种特殊的新成矿类型。     

陕西镇安丘岭卡林型金矿金的赋存状态和富集机理

丘岭金矿床是西秦岭地区重要的卡林型金矿之一, 金矿化赋存于上泥盆统南阳山组和下石炭统袁家沟组地层中, 容矿岩石的岩性为钙质粉砂岩、粉砂质页岩和泥质灰岩.金矿石中主要金属矿物为黄铁矿和毒砂, 非金属矿物则以石英、方解石和绢云母为主.通过对矿石矿物黄铁矿和毒砂的扫描电镜-能谱分析、电子探针分析和激光剥蚀电感耦合等离子体质谱分析, 对丘岭金矿床金的赋存形式和富集机理进行了较为详细的研究.结果表明, 丘岭金矿床中金主要以次显微不可见金的形式存在, 其次为显微可见金.次显微金包括: (1)固溶体金(Au+), 主要存在于环带状细粒黄铁矿的含砷增生边区域和毒砂中, 少量存在于环带状黄铁矿的核部不含砷区域; (2)纳米级自然金颗粒(Au0), 存在于粗晶黄铁矿中.环带状细粒黄铁矿核部的次显微金可能主要以胶体吸附的形式存在, 暗示容矿岩石在沉积成岩过程中有金的初步富集, 而环带状黄铁矿幔部和毒砂中的Au则主要来源于成矿流体, 以S和As的络合物形式搬运.显微可见金主要分布在细粒黄铁矿的晶体边缘和热液蚀变绢云母、石英及方解石中, 粒径通常小于3~5 μm, 其形成可能与成矿流体中金的局部过饱和及成矿流体对细粒黄铁矿和毒砂中次显微金的活化和再次富集有关.      

塔里木盆地YN2井储层沥青的地球化学特征及成因分析

塔里木盆地东北部英吉苏凹陷YN 2井侏罗系、志留系储层分布有固体沥青,通过对此固体沥青的地球化学特征进行分析,并根据生物标志物组合特征,进行储层固体沥青-烃源岩中抽提物组成特征的地球化学对比研究,结果表明:YN 2井侏罗系、志留系储层沥青属于混合成因的固体沥青,主要由古油藏石油热蚀变作用造成的,并遭受了一定程度的生物降解;其正构烷烃呈双峰型前峰态或前峰型分布,主峰碳主要为nC16,饱和烃色谱基线下存在未分辨的复杂混合物。伽马蜡烷含量较高,ααα20R甾烷C27,C28,C29呈V型分布,ααα20R甾烷C27含量大于ααα20R甾烷C29为主。在m/z177色质谱图存在25-降藿烷。表明YN 2井的储层沥青遭受了生物降解。     

SOVESTKAYA GEOLOGIYA (SOVIET GEOLOGY) IN COVER-TO-COVER TRANSLATION, 1961 NO. 1

Parts of certain alkalic intrusive massifs contain up to 63 cc methane per kilogram of rock, with smaller amounts of heavier hydrocarbon gases, bitumen, hydrogen, carbon monoxide and carbon dioxide. The authors argue that the hydrocarbons cannot have come from assimilated limestone, because the igneous rocks contain much more of these gases than do the enclosing limestones. Likewise, the hydrocarbons cannot have been introduced by late solutions because they are much lower in hydrothermal and metasomatic fades than in primary minerals of the high temperature intrusive facies. Hydrocarbons are not stable at magmatic temperatures; the authors conclude that these must have formed in the presence of natural catalysts during slow cooling below 500°C, in accordance with industrial synthesis of hydrocarbons. The C¹²/C¹³ ratio of the bitumens is in the range for ordinary petroleum, suggesting that they formed at relatively low temperature, but the carbon of the gaseous hydrocarbons is lighter, which may indicate that they formed at somewhat higher temperatures. -- E. Ingerson.     

Sterane distribution of solid bitumen pyrolyzates. Changes with biodegradation of crude oil in the Ouachita Mountains,Oklahoma

Solid bitumens (grahamite and impsonite) of southeastern Oklahoma have been shown to originate from near-surface alteration of crude oil (Curiale, 1981; Curiale and Harrison, 1981). Pyrolysis of these solids has been employed to compare the sterane distribution of geographically proximate oils to that of the bitumens. The ratio of rearranged to regular steranes is higher in the pyrolyzates than in the oils, a finding consistent with a bitumen origin due to biodegradation of oil. The remaining presence of steranes, particularly regular steranes, in the bitumens suggests that sterane occlusion may have occurred prior to or during the alteration process, thus removing tetracyclic compounds from the influence of microbial attack. These data suggest that pyrolysis-$\text{GC}\text{MS}$ offers a viable approach to correlation problems involving solid bitumens.     

Organic-Inorganic Interaction Recorded by Polycyclic Aromatic Steranes in Continental Epithermal Ore Deposits

Continental epithermal ore deposits are commonly associated with sedimentary organic matter, oils or solid bitumen. These organics embedded in mineral deposits can convey valuable information of the ore genesis. However, the extent to which the formation of ore minerals was recorded by organic compounds remains largely unknown, as also is how metal-rich ores interfere with the molecular proxies in the temperature regime envisaged for hydrothermal activity. The molecular compositional changes of ...     

贵州务川瓦厂坪铝土矿床地质特征

研究表明[2~5],铝土矿产于中下志留统韩家店组(S1-2hj)页岩或上石炭统黄龙组(C2h)灰岩侵蚀面上,含矿层位为中二叠统梁山组(P2l),赋矿围岩主要为炭质页岩和铝土质页岩,分布受向斜构造控制,含矿岩系厚度与铝土矿层厚度、铝土矿石质量关系密切;矿床成因属古风化壳沉积型。     

福建省永定县樟坑-张岩下铜多金属矿化异常区的地质与矿化特征

闽西南坳陷带矿产资源丰富,是福建省铁、铜、金、煤、石灰岩等金属、非金属矿产的重要产地.永定樟坑-张岩下位于该带的西南部,通过对该区的地质、地球物理等方面的工作,对已发现的主要矿体进行系统的研究,发现了新的矿产地.文章论述了樟坑-张岩下铜多金属矿床的地质与地球物理特征,初步认为是复成因层控型矿床,是由于石炭系与早二叠系碳酸盐岩地层受到中、中酸性岩浆侵入而发生较大规模的夕卡岩化,成矿热液沿断裂面和层间滑脱构造面进一步对碳酸盐岩进行改造、交代而成.     

Aliphatic hydrocarbons in the bitumens of the Puertollano oil shales

The aliphatic fraction of the bitumens from 3 bands of the Puertollano oil shale field have been studied by gas chromatography and gas chromatography/mass spectrometry. Previous work published over the last years reached different conclusions about the origin of the organic matter in the Puertollano oil shales. A reappraisal of some of the biomarkers was then needed for a better understanding of the aliphatic hydrocarbons assemblage. The identified compounds, mainly n-alkanes in the medium to high boiling point region, acyclic isoprenoids and hopane-related compounds point towards a predominant algal/bacterial input. No unequivocally higher plant derived biomarkers have been detected in significant amounts, suggesting that the bulk of the organic matter derive from authocthonous organisms living in the basin. The biomarker maturity ratios indicate that the 3 Puertollano oil shales have similar maturities and are close to the onset of oil generation, assessing a slightly higher maturity than that determined by petrographic techniques.     

四川天宝山矿床闪锌矿Rb-Sr年代学、稳定同位素及地质意义

四川天宝山铅锌矿床是赋存于震旦系灯影组白云岩中的大型铅锌矿床,一直以来缺乏精确的成矿年龄数据,致使其成矿构造环境存在争议.获取了闪锌矿Rb-Sr年龄,联合H-O、C-O同位素数据,以确定其成矿年代、成矿物质来源及成矿构造环境.闪锌矿Rb-Sr年龄为348.5±7.2 Ma(MSWD=1.10),表明矿床形成于早石炭世.热液矿物δD_H2O、δ18O值分别为-19.3‰~-58.1‰、-1.4‰~0.6‰,沿海水与地层有机质反应线分布,并有向雨水线漂移的趋势,说明成矿流体中水是海水与地层有机质反应并加入雨水的混合体.热液方解石δ13C、δ18O值明显分为两群,分别为-1.7‰~-1.6‰、12.9‰~15.2‰和-6.5‰~-4.9‰、19.3‰~20.2‰,暗示成矿流体中C、O可能来源于赋矿围岩溶解作用和有机质脱羧基作用.闪锌矿(87Sr/86Sr)_i值为0.710 42 ±0.000 13,高于赋矿围岩Sr同位素值而明显低于基底Sr同位素值,指示成矿物质主要来源于赋矿围岩与基底.结果表明川滇黔地区存在两期铅锌成矿作用,分别形成于晚泥盆世-早石炭世与古特提斯洋张开有关的伸展构造环境和晚三叠世-早侏罗世与古特提斯洋闭合有关的收缩构造环境.      

The characteristics of the biomarkers and δ13C of n-alkanes released from thermally altered solid bitumens at various maturities by catalytic hydropyrolysis

Solid bitumen occurs extensively in the paleo-reservoirs of marine sequences in southern China. The fluids in these paleo-reservoirs have usually experienced severe secondary alteration such as biodegradation and/or thermal maturation. The concentrations of extractable organic matter (EOM) in the resulting solid bitumens are too low to satisfy the amount required for instrumental analysis such as GC–MS and GC–IRMS. It is also difficult to get enough biomarkers and n-alkanes by dry pyrolysis or hydrous pyrolysis directly because such solid bitumens are hydrogen poor due to high maturities. Catalytic hydropyrolysis (HyPy) can release much more EOM from solid bitumen at mature to highly over-mature stages than Soxhlet extraction, dry pyrolysis and hydrous pyrolysis. However, whether the biomarkers in hydropyrolysates can be used for bitumen-source or bitumen–bitumen correlations has been questionable. In this study, a soft biodegraded solid bitumen sample of low maturity was thermally altered to various maturities in a closed system. HyPy was then employed to release bound biomarkers and n-alkanes. Our results show that the geochemical parameters for source and maturity based on biomarkers released from these thermally altered bitumen residues by HyPy are insensitive to the degree of thermal alteration. Furthermore, the maturity parameters are indicative of lower maturity than bitumen maturation products at a corresponding temperature. This suggests that biomarker source and maturity parameters, based on the products of HyPy, remain valid for bitumens which have suffered both biodegradation and severe thermal maturation. The distributions of δ¹³C of n-alkanes in hydropyrolysates are also insensitive to the temperature used for bitumen artificial maturation. Hence, the δ¹³C values of n-alkanes in hydropyrolysates may also provide useful information in bitumen–bitumen correlation for paleo-reservoir solid bitumens.