Methane adsorption in the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou,Hebei

The adsorption capacity of high–over-matured shale has been widely investigated, but the adsorption capacity and the main factors influencing low–middle-matured, type II kerogen-containing, and organic-rich marine shale have been rarely explored. This research conducts organic geochemistry, mineralogical composition, adsorption isotherm tests to reveal the adsorption and main influencing factors of the different geochemistry characteristics, mineralogical compositions, temperature and pressure conditions of the low–middle-matured Neoproterozoic Xiamaling marine shale in Zhangjiakou, Hebei. The investigated shale is in a low–middle maturity stage, contains type II kerogen and is rich in organic matter. The results show that the total organic carbon (TOC) content of the Xiamaling shale is positively correlated with the methane adsorption capacity, which is the most important influencing factor on the adsorptive property of shale. The methane adsorption capacity first decreases to the minimum value as the temperature reaches 360°C equivalent Ro (EqRo = 1.0%), then increases and reaches the maximum value at 620°C (EqRo = 3.28%) and finally decreases again as the temperature rises at the last simulation stage. The mineral components exhibit an insignificant influence on the methane absorbability because of organic-matter coatings. The TOC-normalised methane adsorption capacity is positively correlated with the illite–smectite and clay-mineral contents but shows no significant correlation with brittle minerals, such as quartz. Soluble organic matter and kerogen caused the methane dissolution and adsorbtion, respectively. The strong dissolution property of the soluble organic matter is the most important cause of the larger adsorption capacity of the original shale compared with that of the residual samples. Moreover, the methane adsorption capacity of the Xiamaling shale decreases with increasing temperature, and increases with pressure below the critical pressure but decreases exceeding the critical pressure.     

冀西北下马岭组沉积层序分析及生油层

冀西北下马岭组构成了一个完整的沉积旋回,在这个陆棚沉积层序中,可划分为海侵体系域与高水位体系域,两者之间的黑色页岩、硅质泥岩及油页岩是本区油苗的生油层。     

燕山地区冀北坳陷元古界下马岭组沥青砂岩岩石学特征和沉积环境

通过对冀北坳陷中新元古界下马岭组进行剖面实测,对下马岭组底部的沥青砂岩进行室内薄片鉴定和扫描电镜分析,观察与分析了下马岭组沥青砂岩的出露分布特征,镜下研究了此砂岩的碎屑颗粒和填隙物的组分特征和磨圆、分选、粒度等结构特征,依据岩石学特征、粒度分析系列参数等研究了沥青砂岩的沉积环境。结果表明此砂岩为成分与结构成熟度均高的纯石英砂岩和石英砂岩,硅质与沥青质填隙、沥青含量达5%~15%,细粒为主,分选好到极好。粒度分析是本段松散状沥青砂有效环境判别标志。综合分析认为下马岭沥青砂岩形成于无障壁海岸体系的滨浅海环境,形成于前滨到临滨的海相高能环境,可能的沉积位置是前滨下部到中上临滨;此砂岩主要来自临滨潮下高能带的沉积物、含部分前滨下部沉积物、也夹少量潮汐水道沉积物。不同剖面位置所处的沉积环境不同,凌源地区和平泉地区为临滨带的中上部的水下高能带沉积为主,宽城地区为临滨带上部沉积和前滨下部沉积,凌源地区和宽城地区也包含少量的潮汐水道沉积。     

华北青白口系下马岭组凝灰岩锆石SHRIMP U-Pb定年

华北中、新元古代地层一直是建立中国晚前寒武纪地层标准剖面的主要目标,其年代地层位置一直是地学界关注的基础地质问题。然而,许多关键层位仍缺乏高质量同位素年龄的约束。首次在华北青白口系下马岭组凝灰岩中获得大量岩浆型锆石,利用SHRIMPII技术进行了高精度定年,测得凝灰岩层锆石206Pb/238U加权平均年龄为1368Ma±12Ma。进而结合区域资料讨论了锆石年龄的地质意义。该同位素年代学资料为华北青白口系下马岭组最新的资料,不仅准确地确定了地层的形成时代,而且对整个华北地台中、新元古代地层地质演化史的认识有着重要的意义。     

The Xiamaling oil shale generated through Rhodophyta over 800 Ma ago

A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations (350 m in thickness) in the third member of Xiamaling Formation of the Upper Proterozoic Qingbaikou Series (900―873 MaBP), Xiahuayuan, Hebei Province, China. The oil shale, combustible with strong bitumen odour, has su- per-high TOC contents ranging from 21.4% to 22.9%, bitumen “A” contents from 0.58% to 0.88% and oil length from 5.29% to 10.57%. The ultrathin section observation of the shale and the identification of its kerogen demonstrate that its hydrocarbon-generative parent material is mainly benthonic Rhodophyta whose specific tetrasporangia are legible and abundant. It is rarely reported in the literature that such a hydrocarbon-generative parent material, composed mainly of Rhodophyta and with extraordinarily high contents of TOC and bitumen “A”, developed into a set of high-quality source rocks. The extracts of the oil shale are characteristic of richness in 17α(H)-diahopanes and n-alkyl tricyclic terpenoids but low in steranes. Such a biomarker feature is obviously different from that of the extracts from other Proterozoic marine carbonate source rocks of the studied area. Since the biological constitution of this oil shale is rather simple, it is clear that these biomarkers most likely represent to certain extent the specific mo- lecular constitutions of the benthonic Rhodophyta identified in the ultrathin sections of the samples. Studies on its lithologic association and depositional sequences suggest that this suit of the carbona- ceous-siliceous mudstone formation, which contains oil shales, was probably developed in an under- compensation deep-bay environment when a maximum transgression occurred during the formation of the third member of Xiamaling Formation. The high concentration of SiO2 in this organic-rich rock and the positive correlation between TOC and some trace elements such as P, Cu, Ni, W and Mo indicate that this suit of rocks was affected by activities of bottom thermal currents as deposited.     

蓟县下马岭组地层中菱铁矿成因及古海洋意义

蓟县铁岭子村附近新出露的下马岭组下部黑色岩系中富含菱铁矿,对这些菱铁矿形成机制的认识直接关系到对下马岭期乃至中元古代古海洋氧化还原状态和地球化学性质的判断。文中利用碳同位素对其成因加以制约,进而反演该时期的古海洋环境。结果显示,这些菱铁矿的碳同位素组成变化范围为-19.2‰~-7.8‰,平均约-15.0‰,明显偏离正常海相沉积碳酸盐岩,而更接近有机质来源的碳酸盐或重碳酸根的δ13C值,说明菱铁矿碳酸根的碳主要源自于有机质。这意味着这些菱铁矿是在早期成岩过程中由三价铁的氧化物或氢氧化物转化而来,而不是直接从海水中沉淀形成。海洋中的铁首先以氧化铁或氢氧化铁的形式发生沉淀,并与有机质一起埋藏于海底缺氧带中。后在成岩过程中发生氧化还原反应,三价铁作为氧化剂氧化有机质使之生成CO2,有机质则作为还原剂将三价铁还原为二价铁,二者结合即构成菱铁矿。同时,有机质热脱羧反应提供的CO2保证了更多的二价铁以菱铁矿的形式保存在地层中。据此可推断,至少在燕辽盆地,下马岭期古海洋已呈现广泛氧化状态,其氧化程度足以将海洋中的铁氧化为三价铁。同时,地层中硫含量极低,说明该时期古海洋贫硫。下马岭期燕辽盆地这种氧化、贫硫的古海洋特征不同于传统的分层海洋模式,因此有必要进行更深入系统的研究。     

蓟县下马岭组菱铁矿的成因及古海洋意义

蓟县铁岭子村附近新出露的下马岭组下部黑色岩系中富含菱铁矿,对这些菱铁矿形成机制的认识直接关系到对下马岭期乃至中元古代古海洋氧化还原状态和地球化学性质的判断.文中利用碳同位素对其成因加以制约,进而反演该时期的古海洋环境.结果显示,研究区菱铁矿的δ13C的变化范围为-19.2‰～-7.8‰,平均约-15.0‰,明显富集碳的轻同位素.根据自然界中不同碳库的碳同位素组成特征,判定这些菱铁矿中的碳主要来源于有机碳.虽然海洋中大量有机质被氧化释放出富12C的CO2溶解于海水后可直接沉淀出轻同位素富集的碳酸盐岩,但这往往要求极端氧化的水体环境,而这种情况下并不能形成菱铁矿沉淀,因此认为研究区菱铁矿应是成岩过程中由有机质降解产生的CO2与孔隙水中的Fe2结合的产物.海洋中的铁首先以氧化铁或氢氧化铁的形式沉淀下来,并与有机质一起埋藏于海底缺氧带中,后在成岩过程中发生氧化还原反应,三价铁作为氧化剂氧化有机质使之生成CO2,有机质则作为还原剂将三价铁还原为二价铁,二者结合即构成菱铁矿.同时,有机质热脱羧反应提供的CO2保证了更多的二价铁以菱铁矿的形式保存在地层中.海洋中铁的沉淀形式表明,至少在燕辽海盆,下马岭期古海洋已呈现广泛氧化状态,其氧化程度足以将海洋中的铁氧化为三价铁.同时,地层中的硫含量极低,说明该时期古海洋贫硫.然而下马岭期燕辽海盆广泛氧化、贫硫的古海洋特征不同于传统的分层海洋模式,对此有必要进行更深入系统的研究.     

华北古陆中、新元古代年代地层框架SHRIMP锆石年龄新依据

建立中国晚前寒武纪地层的标准剖而,并使其成为国际地层对比的参考标准,一直是中国地质学家的追求.华北蓟县中、新元古代地层一直作为这一标准地层的主要研究剖面,已进行了岩石地层、生物地层、化学地层、磁性地层和层序地层等多学科研究.但是,高质量的同位素年代学研究和以此为基础的年代地层框架的优化一直是华北古陆中、新元古界研究的薄弱环节.长期以来,由于关键层位和关键界而缺乏高质量的同位素年龄标定,致使蓟县剖面争取成为国际层面标准剖面的竞争力受到影响.近期,随着锆石SHRIMP年龄测定技术在华北古陆前寒武纪地层学研究中的成功应用,在几个关键层位定年研究中取得实质性进展.北京西山下马岭组中部班脱凝灰岩中获得锆石SHRIMP加权平均年龄为(1370±11)Ma,使得下马岭组这个青白口群的关键地层单位划归为中元古界.天津蓟县大红峪组碱性火山岩中获得锆石SHRIMP加权平均年龄为(1625.9±8.9)Ma.可用于标定华北古陆中元古代裂解时间得北京密云环斑花岗岩获得锆石SHRIMP加权平均年龄为(1685±15)Ma.这些SHRIMP测年结果使华北古陆中、新元古界年代地层划分与全球对比有了年龄"锚点",必定有利于准确厘定华北地区中、新元古界的内涵.由于华北蓟县中、新元占界剖面是我国晚前寒武纪地层的标准剖面,因此上述年代地层框架的优化对于我国地质填图的修正和精确地层对比有着重要的促进作用.同时,对于我国前寒武纪生物演化,特别是宏观藻类发育的时间研究具有重要意义.这必定有助于提升华北中、新元古界剖面的国际地位.     

蓟县下马岭组富菱铁矿地层的基本地质特征

天津蓟县铁岭子村附近新出露的下马岭组下部黑色岩系中富含菱铁矿,本文从野外产出特征、岩石学特征及常量元素特征等3个方面对这一富菱铁矿地层的基本地质特征进行了报道.该剖面地层主要以黑色页岩、粉砂质富铁层/菱铁矿结核层互层产出为特征,夹有少量粉砂岩.部分富铁层由于风化严重,野外露头以褐铁矿层出现.菱铁矿为地层中主要的铁矿物相,可以形成菱铁矿结核,显微镜下具泥晶或微晶结构;也可以与含量相当的石英粉砂一起,构成致密粉砂质富铁层;亦或呈颗粒状零星分布于黑色页岩、粉砂岩中;另外褐铁矿层中亦存在极少量的菱铁矿残余.地层的常量元素特征整体表现为富含SiO2、TFe及有机质,而贫MnO、CaO、MgO、P2O5及S元素,且除风化层位中的铁多呈三价外,其余多呈二价.总有机碳(TOC)含量由高到低依次为菱铁矿结核、粉砂质富铁层、黑色页岩、粉砂岩.TFe与Al2O3含量的相关性图解显示,在富铁地层中,二者呈现出很好的负相关关系,而在正常的黑色页岩和粉砂岩中,二者则呈现一定的正相关关系,表明富铁地层中的铁主要为海洋自身铁的化学沉积,而正常的黑色页岩和粉砂岩中的铁主要源自陆源碎屑.同时新鲜样品中FeO与TOC含量呈现出很好的正相关关系,表明菱铁矿的形成可能与有机质有关.     

华北中元古代下马岭组旋回地层与前寒武纪轨道天文周期律

轨道驱动的气候变化在显生宙已被广泛证实。对于更早的前寒武纪,米兰科维奇周期性是否存在未有定论。本文选择华北中元古代下马岭组赵家山剖面,结合同位素年代学数据,对其三段中、上部开展旋回地层学研究。在对研究层段十分发育的岩性旋回进行高分辨率测量与分析的基础上,提出基于岩相认识的编码规则,建立时间序列,并对其展开定量分析。频谱分析结果与天文学理论计算吻合较好,这意味着前寒武纪也应该存在米兰科维奇天文周期律。此项研究为认识更早地质时期地球的轨道参数及天文状态提供了思路,对旋回地层学研究在前寒武纪的拓展有一定启示意义。