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Spatial distribution of remaining movable and non-movable oil fractions in a depleted Maastrichtian chalk reservoir, Danish North Sea: Implications for CO2 storage 丹麦北海枯竭马斯特里赫特白垩储层中剩余可移动和不可移动石油馏分的空间分布:对二氧化碳封存的影响
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-20 DOI: 10.1016/j.coal.2024.104624
Henrik I. Petersen , Kasper H. Blinkenberg , Kresten Anderskouv , Arka Rudra , Xiaowei Zheng , Hamed Sanei
Depleted oil and gas fields constitute potentially important storage sites for CO2 in the subsurface, but large-scale injection of supercritical (sc) CO2 in chalk has not yet been attempted. One of the risks is the adverse effect of the substantial amount of remaining oil in the chalk reservoirs on scCO2 injection. In order to counter an undesired effect on injectivity, a fundamental understanding of the spatial distribution and quantity of the movable, semi-movable, and non-movable oil, and solid bitumen/asphaltenes fractions of the remaining oil is critical. In this study a combination of organic geochemistry (gas chromatography of the saturated fraction and programmed pyrolysis), and reflected light microscopy was applied to evaluate and measure the spatial distribution, volume, and saturation of different oil fractions in a well-defined reservoir interval of a waterflooded Maastrichtian chalk reservoir in the Danish Central Graben, North Sea. A total of 127 samples from a slightly deviated vertical well and two ∼5 km-long horizontal wells from the Halfdan and Dan fields were analyzed. An original uneven distribution of oil saturation and composition or different production efficiency of different levels in the reservoir may account for variations in the total oil and oil fraction saturations. Gas chromatography shows that the solvent extractable oil is quite similar in composition, characterized by a dominance of polar compounds and a high content of asphaltenes. Extended slow heating (ESH) pyrolysis reveals that most of the remaining oil saturation consists of semi-movable oil and total non-movable oil (non-movable oil plus solid bitumen/asphaltenes). Reduced oil gravity values (API) are related to evaporation loss of the lightest hydrocarbon fraction during core storage and increase of the relative proportion of the heavier oil fractions by waterflooding during production. Microscopy disclosed three forms of oil: i) Patchy distributed lighter, movable oil showing a bluish fluorescence, ii) Brownish staining with a dark orange to brownish fluorescence, and iii) Dark brown non-fluorescing oil and black solid bitumen/asphaltenes occurring in microfossils and along deformation bands and stylolites, constituting the heavy non-movable oil fractions. There is a general correlation between bulk rock porosity and the total non-movable oil saturation. It thus appears that the heavy non-movable oil fractions preferentially occur in association with low-permeability heterogeneities within high-permeability stratigraphic intervals. These intervals appear to favor accumulation of non-movable oil and solid bitumen/asphaltenes and may carry a higher risk for impeding scCO2 flow.
枯竭油气田是地下二氧化碳的潜在重要封存地点,但在白垩中大规模注入超临界(sc)二氧化碳尚未尝试过。风险之一是白垩储层中大量剩余石油对 scCO2 注入的不利影响。为了消除对注入率的不利影响,必须从根本上了解剩余石油中可移动、半可移动和不可移动石油以及固体沥青/沥青质馏分的空间分布和数量。本研究将有机地球化学(饱和馏分的气相色谱法和程序热解)和反射光显微镜相结合,对北海丹麦中央海湾水淹马斯特里赫特白垩系储层中一个明确储层区间内不同油馏分的空间分布、体积和饱和度进行了评估和测量。共分析了来自哈夫丹和丹油田的一口略微偏离的垂直井和两口长达 5 千米的水平井的 127 个样本。油藏中原有的石油饱和度和成分分布不均或不同层位的生产效率不同,可能是总石油和石油馏分饱和度变化的原因。气相色谱法显示,溶剂萃取油的成分非常相似,以极性化合物为主,沥青质含量较高。延长缓慢加热(ESH)热解显示,剩余油饱和度大部分由半可移动油和总不可移动油(不可移动油加上固体沥青/沥青质)组成。石油重力值(API)的降低与岩心储存期间最轻碳氢化合物馏分的蒸发损失以及生产期间注水导致较重石油馏分相对比例的增加有关。显微镜检查发现了三种形式的石油:i) 斑状分布的较轻的可移动石油,呈现蓝色荧光;ii) 带有深橙色至褐色荧光的褐色染色;iii) 暗褐色无荧光石油和黑色固体沥青/沥青质,出现在微化石中,沿着变形带和花柱岩,构成了重的不可移动石油馏分。岩体孔隙度与不可移动石油总饱和度之间存在普遍的相关性。由此看来,重质不可移动石油馏分优先出现在高渗透性地层区间内的低渗透性异质中。这些区段似乎有利于不可移动石油和固体沥青/沥青质的积累,并可能具有较高的阻碍 scCO2 流动的风险。
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引用次数: 0
An improved convolutional architecture for quantitative characterization of pore networks in fine-grained rocks using FIB-SEM 利用 FIB-SEM 对细粒岩石孔隙网络进行定量表征的改进型卷积结构
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-19 DOI: 10.1016/j.coal.2024.104625
Bo Liu , Qamar Yasin , Mengdi Sun , Atif Ismail , David A. Wood , Xin Tian , Baiquan Yan , Li Fu
Focused ion beam scanning electron microscope (FIB-SEM) is one of the most advanced imaging techniques for analyzing and understanding complex pore networks in shale and other fine-grained formations. However, FIB-SEM imaging tends to be time-consuming and labor-intensive and can result in biased interpretations associated with pore analysis. Recently, U-Net or its variants for image segmentation have been applied to capture microscopic pores at higher resolutions. The ‘traditional’ encoder-decoder-based approaches tend to detect very fine-scale microscopic pores poorly. This study presents an improved convolutional architecture for automatically analyzing pore structures in shale reservoirs using FIB-SEM. It does so by applying an overcomplete convolutional architecture, KiU-Net, to capture very fine-scale microscopic pores by accurately defining their edges in the input FIB-SEM images. The KiU-Net learns low and high-level features by making the model more sensitive to fine-scale microscopic pores in the input images. The purpose of this study is to demonstrate KiU-Net's capabilities by analyzing different shale formations with varying characteristics. The results indicate that KiU-Net is more accurate and efficient than other methods in predicting nanopores in the Longmaxi, Niutitang, Qingshankou, Qianjiang, and Yanchang Formations (China), Bakken shale (Canada), and coal reservoirs (China). Furthermore, KiU-Net demonstrated the advantage of requiring fewer parameters and achieving super convergence compared to the Attention U-Net technique. KiU-Net addresses the challenges of the Edge-Threshold Automatic Processing (ETAP) methods by capturing very fine-scale microscopic pores with accurate edges. This study further enhances the accuracy and efficiency of pore analysis in shales, thereby offering an improved method for understanding shale reservoir quality with the potential to improve petroleum recovery from such formations.
聚焦离子束扫描电子显微镜(FIB-SEM)是分析和了解页岩和其他细粒地层中复杂孔隙网络的最先进成像技术之一。然而,FIB-SEM 成像往往耗时耗力,并可能导致与孔隙分析相关的解释出现偏差。最近,用于图像分割的 U-Net 或其变体已被用于以更高分辨率捕捉微观孔隙。基于 "传统 "编码器-解码器的方法往往不能很好地检测到非常精细的微观孔隙。本研究提出了一种改进的卷积结构,用于利用 FIB-SEM 自动分析页岩储层中的孔隙结构。它通过应用超完全卷积结构 KiU-Net,在输入的 FIB-SEM 图像中精确定义孔隙边缘,从而捕捉极细微尺度的微观孔隙。KiU-Net 通过提高模型对输入图像中细微孔隙的敏感度来学习低级和高级特征。本研究的目的是通过分析不同特征的页岩层来展示 KiU-Net 的能力。结果表明,KiU-Net 在预测龙马溪地层、牛池塘地层、青山口地层、黔江地层、延长地层(中国)、巴肯页岩(加拿大)和煤储层(中国)中的纳米孔隙时,比其他方法更准确、更高效。此外,与注意力 U-Net 技术相比,KiU-Net 还具有所需参数更少、收敛性更强的优势。KiU-Net 通过捕捉具有精确边缘的极细尺度微观孔隙,解决了边缘阈值自动处理(ETAP)方法所面临的挑战。这项研究进一步提高了页岩中孔隙分析的准确性和效率,从而为了解页岩储层质量提供了一种更好的方法,有望提高此类地层的石油采收率。
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引用次数: 0
Organic petrographic and geochemical insights into organic matter derived from land plants and marine algae in the Lark Formation, Danish North Sea 丹麦北海云雀地层陆生植物和海洋藻类有机物质的有机岩石学和地球化学见解
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-19 DOI: 10.1016/j.coal.2024.104627
Zhiheng Zhou , Qingyong Luo , Arka Rudra , Henrik Ingermann Petersen , Niels Hemmingsen Schovsbo , Hamed Sanei
Climatic fluctuations from the Eocene to the Miocene highlight the importance of investigating the paleoenvironment of the latest Eocene to the Middle Miocene Lark Formation in the Danish North Sea. This study investigates immature sedimentary organic matter in the Lark Formation using 54 cuttings samples and one core sample collected from seven wells in the eastern North Sea Basin. Organic petrography and molecular geochemistry analyses were performed to determine the variations in the quantity and origin of allochthonous and autochthonous organic matter. Additionally, the study assesses the impact of climate fluctuations on marine productivity in the eastern North Sea Basin and land plant vegetation at the basin margins during the latest Eocene to the Middle Miocene.
The organic matter in the Lark Formation originated from mixed sources, primarily land plants, with a secondary contribution from marine algae. This is indicated by the maceral composition and the types and abundance of aliphatic and aromatic hydrocarbon biomarker compounds. Moreover, the presence of diterpenoids (gymnosperm biomarkers) and non-hopanoid triterpenoids (angiosperm biomarkers) reveals that the allochthonous organic matter originated from conifers and angiosperms.
Climatic impacts on land plants and marine algae during the latest Eocene to the Middle Miocene are revealed by several parameters: the Averaged Chain Length (ACL) of land plant waxes, the proportion of coniferous contribution (C/(C + A)), and the whole rock volume percentages of huminite, inertinite (H + I, vol%) and liptinite (L, vol%). The shifts to cooler and drier climates highlighted the cold adaptation of onshore conifers and resulted in the input of higher molecular weight waxy components into the sediments. However, under these conditions, reduced precipitation and runoff resulted in lower amounts of terrigenous organic matter supplied to the basin. Additionally, the drop in water temperature and the warm-affinity of local algae assemblage led to reduced marine productivity. Together, these factors contributed to an overall decrease in organic richness. In contrast, during shifts to warmer and more humid climates, the trend reversed. The contribution of conifers to the floral assemblage diminished, but higher amounts of terrigenous organic matter were transported to the basin due to increased precipitation and runoff. This was accompanied by warmer water temperatures, boosting the productivity of organic-walled microplankton in the marine environment and contributing to greater organic richness.
从始新世到中新世的气候波动凸显了调查丹麦北海最新始新世到中新世云雀地层古环境的重要性。本研究利用从北海盆地东部七口井中采集的 54 份切屑样本和一份岩心样本,对云雀地层中的未成熟沉积有机物进行了调查。通过有机岩石学和分子地球化学分析,确定了同生和自生有机物的数量和来源变化。此外,该研究还评估了气候波动对北海盆地东部海洋生产力以及最近始新世至中新世期间盆地边缘陆地植物植被的影响。云雀地层中的有机质来源于混合来源,主要是陆地植物,其次是海洋藻类。这一点可以从大分子成分以及脂肪族和芳香族烃类生物标记化合物的类型和丰度中看出。此外,二萜类化合物(裸子植物生物标志物)和非跳类三萜类化合物(被子植物生物标志物)的存在表明,异源有机物来自针叶树和被子植物。陆地植物蜡质的平均链长(ACL)、针叶树的贡献比例(C/(C + A))以及腐植质、惰性石灰质(H + I,体积百分比)和石灰质(L,体积百分比)的整个岩石体积百分比等几个参数揭示了最近始新世到中新世期间气候对陆地植物和海洋藻类的影响。向更凉爽、更干燥气候的转变凸显了陆生针叶树对寒冷的适应性,并导致较高分子量的蜡质成分进入沉积物。然而,在这些条件下,降水和径流的减少导致向盆地提供的陆生有机物数量减少。此外,水温下降和当地藻类的暖亲和性也导致海洋生产力下降。这些因素共同导致有机物丰富度总体下降。与此相反,在向更温暖、更潮湿的气候转变期间,这一趋势发生了逆转。针叶树对花卉组合的贡献减少,但由于降水和径流的增加,更多的陆生有机物被输送到盆地。随之而来的是水温升高,提高了海洋环境中有机壁微型浮游生物的生产率,增加了有机物的丰富度。
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引用次数: 0
Geological and hydrological controls on the pressure regime of coalbed methane reservoir in the Yanchuannan field: Implications for deep coalbed methane exploitation in the eastern Ordos Basin, China 对延川南煤田煤层气储层压力机制的地质和水文控制:对中国鄂尔多斯盆地东部深层煤层气开发的影响
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-18 DOI: 10.1016/j.coal.2024.104619
Xiaoming Wang , Shihui Hou , Xingjin Wang , Yudong Yuan , Zheng Dang , Mingkai Tu
The pressure regimes of the No. 2 coalbed methane (CBM) reservoir in the Yanchuannan field located in the southeastern Ordos Basin are highly variable and divided into overpressured (pressure gradient >9.80 kPa/m), slightly underpressured (pressure gradient of 8–9.80 kPa/m), and moderately underpressured (pressure gradient of 5–8 kPa/m). The controlling factors for the variable pressure regimes were investigated through the analysis of geological and hydrological characteristics. The pressure regimes are controlled by different mechanisms in different hydrodynamic environments. In the closed hydrodynamic environment characterized by TDS > 10,000 mg/L and NaCl type of groundwater, the pressure regime is dominated by overpressured to slightly underpressured and is controlled by CBM migration. Overpressure was developed by thermogenic CBM generation during the coalification process and is maintained by thermogenic CBM migration from the extended northwestward and deeply buried CBM reservoir during tectonic uplift. The transition from overpressure to slight underpressure and then to moderate underpressure towards the southeast is the result of the progressively weakened migrated thermogenic CBM with increasing migration distance. In the open hydrodynamic environment characterized by TDS < 10,000 mg/L and NaHCO3 type of groundwater, the pressure regime is dominated by slightly to moderately underpressured and is governed by hydrodynamics. Groundwater is fed by meteoric recharge along the structurally upturned basin margin and creates the hydrodynamic framework during tectonic uplift. The transition from moderate to slight underpressure towards the southwest is associated with the minor decrease range in ground elevation from basin margin to basin interior and the gradually weakened runoff intensity of groundwater with increasing distance to meteoric recharge. The idealized models for the pressure regimes are established, which can provide guidance to deep CBM sweet spot identification in CBM fields in the eastern Ordos Basin and elsewhere.
位于鄂尔多斯盆地东南部的延川南煤田 2 号煤层气储层压力变化很大,分为超压(压力梯度为 9.80 kPa/m)、轻度欠压(压力梯度为 8-9.80 kPa/m)和中度欠压(压力梯度为 5-8 kPa/m)。通过对地质和水文特征的分析,对不同压力状态的控制因素进行了研究。在不同的水动力环境中,压力状态受不同机制的控制。在以 TDS > 10,000 mg/L 和 NaCl 型地下水为特征的封闭水动力环境中,压力状态以超压到轻微欠压为主,并受煤层气迁移控制。超压是由煤化过程中产生的热成煤层气形成的,并由构造隆升过程中向西北延伸并深埋的煤层气储层中的热成煤层气迁移来维持。从超压到轻微欠压,再到向东南方向的中度欠压,是随着迁移距离的增加,迁移的热成煤层气逐渐减弱的结果。在以 TDS < 10,000 mg/L 和 NaHCO3 型地下水为特征的开放水动力环境中,压力制度以轻微至中度欠压为主,并受水动力支配。地下水由构造隆升的盆地边缘的流星补给,并在构造隆升过程中形成了水动力框架。从中度欠压向西南方向过渡到轻度欠压,与盆地边缘到盆地内部的地面高程略有下降有关,也与地下水的径流强度随着与流星补给距离的增加而逐渐减弱有关。所建立的理想化压力机制模型可为鄂尔多斯盆地东部及其他地区煤层气田的深层煤层气甜点识别提供指导。
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引用次数: 0
Calcite UPb dating and geochemical constraints on fracture opening in organic-rich shales 富含有机质的页岩中方解石 UPb 定年和断裂开放的地球化学制约因素
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-17 DOI: 10.1016/j.coal.2024.104621
Dadong Liu , Hui Tian , Chengzao Jia , Qingqing Fan , Xuesong Lu , Mingyang Xu , Yan Song , Chen Zhang
Gas-bearing, organic-rich shales commonly host numerous opening-mode fractures; however, their formation mechanism remains controversial, with competing arguments of tectonic-origin and/or hydrocarbon generation pressurization-origin. Here, we studied fracture fillings in shale reservoirs of the lower Silurian Longmaxi Formation in the Luzhou area, southern Sichuan Basin, SW China. Using in-situ UPb geochronology, rare earth elements (REEs) and C-O-Sr isotope geochemistry, and fluid inclusion analyses, we investigated the timing and geochemical attributions of fracture fills and identify the mechanism of fracture formation. The results show that, the cements that occupy fractures in the Longmaxi Formation shales contain mainly calcite and quartz. The calcite cements show crack-seal and fibrous textures, indicating that they are syn-kinematic mineral deposits. The 87Sr/86Sr values of the calcite cements essentially overlap with those of their proximal host shales. This result, combined with slight depletions in δ13CPDB and relatively uniform fluid δ18OSMOW isotopic features, indicate that the fluids from which the calcite precipitated were largely derived from their surrounding host shales. Abundant methane inclusions are present in fracture cements, with trapping pressures of 104.5–157.5 MPa and pressure coefficients of 1.92–2.43, suggesting they were trapped in an overpressurized fluid system. In-situ UPb dating of calcite cements yielded ages of ca. 160 Ma and ca. 110 Ma, which coincide with the timing of thermal cracking of oil to gas during burial. In combination with the overpressurized, geochemically closed fluid system, the fractures were most likely triggered by gas generation. Our study emphasizes that natural fracturing induced by hydrocarbon generation overpressurization is an essential mode of brittle failure in tectonically quiescent basins worldwide.
富含有机质的含气页岩通常具有大量的开裂模式裂缝;然而,这些裂缝的形成机理仍存在争议,有构造成因和/或碳氢化合物生成加压成因之争。在此,我们研究了中国西南部四川盆地南部泸州地区志留系下统龙马溪地层页岩储层中的裂缝充填。利用原位UPb地质年代、稀土元素(REEs)和C-O-Sr同位素地球化学以及流体包裹体分析,我们研究了裂缝填充的时间和地球化学属性,并确定了裂缝形成的机制。结果表明,龙马溪地层页岩中占据裂缝的胶结物主要含有方解石和石英。方解石胶结物呈现裂缝密封和纤维状纹理,表明它们是同步共生矿床。方解石胶结物的 87Sr/86Sr 值与其近主页岩的 87Sr/86Sr 值基本重叠。这一结果,再加上δ13CPDB的轻微损耗和相对均匀的流体δ18OSMOW同位素特征,表明沉淀方解石的流体主要来自周围的寄主页岩。断裂胶结物中存在大量甲烷包裹体,其捕获压力为 104.5-157.5 兆帕,压力系数为 1.92-2.43,表明它们被困在超压流体系统中。方解石胶结物的原位 UPb 测定年龄分别为约 160 Ma 和约 110 Ma,与埋藏过程中油到气的热裂解时间相吻合。结合超压、地球化学封闭的流体系统,断裂很可能是由气体生成引发的。我们的研究强调,烃生成超压诱发的天然断裂是全球构造静止盆地脆性破坏的一种基本模式。
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引用次数: 0
Petroleum evolution and its genetic relationship with the associated Jinding PbZn deposit in Lanping Basin, Southwest China 石油演化及其与中国西南兰坪盆地金鼎铅锌矿床的成因关系
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-16 DOI: 10.1016/j.coal.2024.104620
Xiang Ge , Jiajia Xiang , Yulin Jin , Wenpan Cen , Guangyou Zhu , Chuanbo Shen
The spatial association of hydrocarbons with metalliferous ore deposits is found worldwide and is particularly common to MVT PbZn deposits. Heavy oil and bitumen are found in the Jinding PbZn deposit within the Lanping Basin, South China. However, the temporal and genetic associations between hydrocarbons and the deposit are still controversial. To this end, integrating Raman analysis, ReOs geochronology and transmission electron microscopy analysis of the bitumen and in situ S isotope analyses of the sulfide, the petroleum evolution of the Jinding reservoir and its genetic relationship with the PbZn deposits were discussed. Bitumen ReOs data from this study and published works indicate that the late Triassic shales underwent two distinct oil-generation events before mineralisation (∼25 Ma), with initial oil generation occurring during the early Cretaceous (∼116 Ma) and the second during the early Paleogene (ca. 68–59 Ma). These two ages agree with the modelled thermal history of the Jinding reservoir. Combining the oil-before-ore timing sequence, high metal abundance of the bitumen, two negative sulfur isotope peaks of the sulfide and high S/C atomic ratio of the bitumen from the Jinding deposit, the oil-containing aqueous solutions were considered as one metal carrier during the hydrocarbon migration and accumulation; further, bacterial sulfate reduction and thermo-chemically induced sulfate reduction processes could have participated in the supply of reduced sulfur for the PbZn deposit precipitation.
碳氢化合物与金属矿床的空间关联在世界各地都有发现,尤其常见于中低压铅锌矿床。在中国南方兰坪盆地的金鼎铅锌矿床中发现了重油和沥青。然而,碳氢化合物与该矿床之间的时间和遗传关联仍存在争议。为此,结合沥青的拉曼分析、ReOs地质年代学和透射电子显微镜分析以及硫化物的原位S同位素分析,讨论了金鼎储层的石油演化及其与铅锌矿床的成因关系。本研究和已发表的沥青ReOs数据表明,晚三叠世页岩在成矿之前(25Ma)经历了两次不同的石油生成过程,第一次石油生成发生在早白垩世(116Ma),第二次发生在早古近纪(约68-59Ma)。这两个年代与金鼎油藏的模拟热历史相吻合。结合金鼎矿床先油后矿时间序列、沥青的高金属丰度、硫化物的两个负硫同位素峰和沥青的高S/C原子比,可以认为含油水溶液是碳氢化合物迁移和聚集过程中的一个金属载体;此外,细菌的硫酸盐还原和热化学诱导的硫酸盐还原过程可能参与了铅锌矿床沉淀的还原硫供应。
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引用次数: 0
Pyrite trace metal and sulfur isotopic compositions track metalliferous fluid circulation within the Ordovician/Silurian organic-rich black shales in the eastern Sichuan Basin, southwestern China 黄铁矿痕量金属和硫同位素组成追踪中国西南部四川盆地东部奥陶纪/志留纪富含有机质黑色页岩中的冶金流体循环
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-14 DOI: 10.1016/j.coal.2024.104617
Shaojie Li , Qilin Xiao , Suyang Cai
Depicting metalliferous fluid flows in sedimentary basins has a remarkable implication for understanding the formation and evolution of organic-rich sediments. The Middle-Upper Yangtze region in South China hosts voluminous gaseous hydrocarbons and MVT-type ZnPb deposits. Natural gases are mainly distributed in the Sichuan Basin, yet ZnPb deposits are found in surrounding regions of the basin. Such a unique distribution pattern implies that the interplay between metalliferous fluids and organic-rich sediments may be extensive in the boundary of these two types of deposits. A typical Ordovician/Silurian (Wufeng/Longmaxi formations) organic-rich black shale outcrop occurs in the eastern boundary of the Sichuan Basin. Pyrites are frequently distributed across this section, providing an ideal opportunity to investigate features of metalliferous fluids and their potential impacts on organic-rich sediments. Pyrites associated with high-angle carbonate veinlets are recognized in the studied area, and this group of pyrites (“Group 2”) commonly display planar-laminated morphologies, moderate δ34S values (0.78 ‰–8.86 ‰), and elevated trace metal contents (Ni, Pb, Mn, Mo, Tl, and REE) than those not associated with carbonate veinlets. These features suggest that this group of pyrites may be precipitated via local metalliferous fluid flows. Besides, pyrites with relatively lower trace metal contents can be further divided into two groups, including a group of euhedral/subhedral pyrites with more depleted δ34S values (−18.06 ‰ – -1.15 ‰; “Group 1”) and a group of planar-laminated/cubic pyrites with enriched δ34S values (10.55 ‰–37.62 ‰; “Group 3”). Pyrites of Group 1 and Group 3 may be formed via bacterial sulfate reduction (BSR) and thermochemical sulfate reduction (TSR), respectively. The discovery of fluid-related, trace-metal-enriched pyrites implies that fluid circulation within organic-rich black shales has the potential to remobilize, transport, and re-deposit trace metals. Besides, metalliferous fluid may also promote organic matter maturation within the Sichuan Basin. The outcomes of this study, combined with previous findings of metalliferous fluid flows in the center of the basin and ZnPb mineralization belts surrounding the basin, imply that a widespread Ediacaran-Palaeozoic fluid circulation system may exist in the Middle-Upper Yangtze region.
描绘沉积盆地中的金属流体流对于了解富含有机质沉积物的形成和演化具有重要意义。中国南方的长江中上游地区蕴藏着大量的气态碳氢化合物和 MVT 型锌铅矿床。天然气主要分布在四川盆地,而锌铅矿床则分布在盆地周边地区。这种独特的分布模式意味着,在这两类矿床的边界地区,冶金流体与富含有机质的沉积物之间可能存在着广泛的相互作用。四川盆地东部边界有一个典型的奥陶系/志留系(五峰/龙马溪地层)富含有机质的黑色页岩露头。黄铁矿经常分布在这一地段,为研究金属流体的特征及其对富有机沉积物的潜在影响提供了理想的机会。与高角度碳酸盐细脉相关的黄铁矿在所研究的地区得到了确认,与不与碳酸盐细脉相关的黄铁矿相比,这组黄铁矿("第 2 组")通常显示出平面层状形态、中等的 δ34S 值(0.78 ‰-8.86 ‰)和较高的微量金属含量(镍、铅、锰、钼、钛和稀土元素)。这些特征表明,这类黄铁矿可能是通过当地的金属流体流沉淀而成的。此外,微量金属含量相对较低的黄铁矿可进一步分为两组,包括一组δ34S值较低的八面体/亚面体黄铁矿(-18.06‰--1.15‰;"第1组")和一组δ34S值较高的平面层状/立方体黄铁矿(10.55‰-37.62‰;"第3组")。第 1 组和第 3 组黄铁矿可能分别是通过细菌硫酸盐还原(BSR)和热化学硫酸盐还原(TSR)形成的。与流体有关的痕量金属富集黄铁矿的发现,意味着富含有机质的黑色页岩内部的流体循环有可能使痕量金属再移动、迁移和再沉积。此外,含金属流体还可能促进四川盆地内有机质的成熟。本研究的结果,结合之前在盆地中心金属流体流和盆地周围锌铋成矿带的发现,意味着在长江中上游地区可能存在一个广泛的埃迪卡拉-古生代流体循环系统。
{"title":"Pyrite trace metal and sulfur isotopic compositions track metalliferous fluid circulation within the Ordovician/Silurian organic-rich black shales in the eastern Sichuan Basin, southwestern China","authors":"Shaojie Li ,&nbsp;Qilin Xiao ,&nbsp;Suyang Cai","doi":"10.1016/j.coal.2024.104617","DOIUrl":"10.1016/j.coal.2024.104617","url":null,"abstract":"<div><div>Depicting metalliferous fluid flows in sedimentary basins has a remarkable implication for understanding the formation and evolution of organic-rich sediments. The Middle-Upper Yangtze region in South China hosts voluminous gaseous hydrocarbons and MVT-type Zn<img>Pb deposits. Natural gases are mainly distributed in the Sichuan Basin, yet Zn<img>Pb deposits are found in surrounding regions of the basin. Such a unique distribution pattern implies that the interplay between metalliferous fluids and organic-rich sediments may be extensive in the boundary of these two types of deposits. A typical Ordovician/Silurian (Wufeng/Longmaxi formations) organic-rich black shale outcrop occurs in the eastern boundary of the Sichuan Basin. Pyrites are frequently distributed across this section, providing an ideal opportunity to investigate features of metalliferous fluids and their potential impacts on organic-rich sediments. Pyrites associated with high-angle carbonate veinlets are recognized in the studied area, and this group of pyrites (“Group 2”) commonly display planar-laminated morphologies, moderate δ<sup>34</sup>S values (0.78 ‰–8.86 ‰), and elevated trace metal contents (Ni, Pb, Mn, Mo, Tl, and REE) than those not associated with carbonate veinlets. These features suggest that this group of pyrites may be precipitated via local metalliferous fluid flows. Besides, pyrites with relatively lower trace metal contents can be further divided into two groups, including a group of euhedral/subhedral pyrites with more depleted δ<sup>34</sup>S values (−18.06 ‰ – -1.15 ‰; “Group 1”) and a group of planar-laminated/cubic pyrites with enriched δ<sup>34</sup>S values (10.55 ‰–37.62 ‰; “Group 3”). Pyrites of Group 1 and Group 3 may be formed via bacterial sulfate reduction (BSR) and thermochemical sulfate reduction (TSR), respectively. The discovery of fluid-related, trace-metal-enriched pyrites implies that fluid circulation within organic-rich black shales has the potential to remobilize, transport, and re-deposit trace metals. Besides, metalliferous fluid may also promote organic matter maturation within the Sichuan Basin. The outcomes of this study, combined with previous findings of metalliferous fluid flows in the center of the basin and Zn<img>Pb mineralization belts surrounding the basin, imply that a widespread Ediacaran-Palaeozoic fluid circulation system may exist in the Middle-Upper Yangtze region.</div></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"294 ","pages":"Article 104617"},"PeriodicalIF":5.6,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Experimental investigation on the oil occurrence and mobility of lacustrine shales in offshore area of China using 1D/2D nuclear magnetic resonance and centrifugal techniques 利用一维/二维核磁共振和离心技术对中国近海地区湖相页岩的石油成因和流动性进行实验研究
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-13 DOI: 10.1016/j.coal.2024.104618
Sijia Nie , Feng Yang , Long Luo , Kong Deng , Luyu Du
Shale oil occurrence mechanism and mobility have significant influences on hydrocarbons extraction from shale systems. However, the effects of petrophysical and petroleum geochemical properties on oil mobility are not understood. In this study, shales with different lithofacies were investigated using thin sections, scanning electron microscopy, nuclear magnetic resonance (NMR), and organic geochemical analysis. Shales at original, extracted, oil-saturated, and centrifugal states were systematically scanned using 1D and 2D NMR technologies. The multi-scaled pores were obtained by comparing the T2 spectra of samples at different states. The 2D NMR identification spectra for hydrocarbon-bearing components were established. The free oil, adsorbed oil, mobile oil contents were quantitatively evaluated and the geological controls on oil mobility were discussed.
Results show that the siliceous shales have the highest total oil and movable oil contents, while the argillaceous shales have the lowest values due to the limited pore space and poor connectivity. Mobile oil mainly stores in interparticle pores, dissolution-related pores and bedding fractures. Its content increases with the increasing felsic minerals. Oil in siliceous shales are rich in low carbon-chain hydrocarbons and has high mobility. Based on oil distribution in multi-scaled pores, a strategy about the mobile oil distribution were proposed: Ultramicropores region is the immobile oil zone; Micropores region is the oil difficult-to-flow zone; Transition pores region is the oil easy-to-flow zone; Macropores region is the completely mobile oil zone. The mobile oil mainly accommodates in transition pores and macropores (pore size >20 nm and mobile oil saturation exceeds 60 %).
页岩油的发生机理和流动性对从页岩系统中提取碳氢化合物有重大影响。然而,岩石物理和石油地球化学性质对石油流动性的影响尚不清楚。本研究使用薄片、扫描电子显微镜、核磁共振(NMR)和有机地球化学分析对不同岩性的页岩进行了研究。利用一维和二维核磁共振技术对原始状态、提取状态、石油饱和状态和离心状态的页岩进行了系统扫描。通过比较不同状态下样本的 T2 光谱,获得了多尺度孔隙。建立了含碳氢化合物成分的二维核磁共振识别光谱。结果表明,硅质页岩的总油含量和可移动油含量最高,而由于孔隙空间有限且连通性较差,霰质页岩的总油含量和可移动油含量最低。可移动油主要储存在颗粒间孔隙、溶解相关孔隙和层理裂缝中。其含量随着长石矿物的增加而增加。硅质页岩中的油富含低碳链碳氢化合物,具有很高的流动性。根据石油在多尺度孔隙中的分布,提出了石油流动分布的策略:超微孔区为不流动油区;微孔区为难流动油区;过渡孔区为易流动油区;大孔区为完全流动油区。流动油主要容纳在过渡孔隙和大孔隙中(孔径为 20 nm,流动油饱和度超过 60%)。
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引用次数: 0
Occurrences of paleo-wildfires in the early Albian, Erlian Basin, NE China: Evidence from coal petrography and geochemistry 中国东北二连盆地早白垩世古野火的发生:来自煤岩相学和地球化学的证据
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-10-10 DOI: 10.1016/j.coal.2024.104616
Shuang Gao , Yong Li , Longyi Shao , Cai Tie , Junhui Li , Yuping Zhou
The Albian in the early Cretaceous was a period with extensive and frequent wildfires, yet the wildfire types, intensity, and implications are not well understood due to the lack of continuous wildfire records. In this study, a total of 79 coal samples were collected from a 13 m thick coal seam in the early Cretaceous in the Erlian Basin, Inner Mongolia, China, which were analyzed using Zircon UPb dating, coal petrography analysis, scanning electron microscopy, and gas chromatography–mass spectrometry techniques. Zircon dating of an interbedded volcanic ash layer shows the coal was deposited in the early Albian, at 111.14 ± 1.14 Ma. Petrographic and proximate analysis show that the coals are characterized by mainly huminite (18.7–84.2 vol%, average 52.7 vol%, mmf—mineral matter free) and inertinite (15.1–80.7 vol%, average 46.2 vol%, mmf), with high volatile matter yields (average 39.7 %, dry and ash-free basis) and low ash yields (average 7.45 %, air dry basis). The frequent wildfire events are recognized by: (1) the inertinite content, mostly composed of fusinite, semifusinite, and inertodetrinite, and higher than most of the reported inertinite contents in the other Cretaceous coals around the world; (2) inertinite, representative of fossil charcoal is typified by homogenized cell walls and vesicles generated under high temperature; and (3) the polycyclic aromatic hydrocarbons (PAHs) are composed of 16 types of 2–6 ring aromatic hydrocarbon compounds, with the average pyrogenic PAHs accounting for 73.9 % of the total PAHs and the medium and high-molecular-weight PAHs accounting for 70.6 % of total molecular-weight PAHs. The average inertinite reflectance values range between 0.86 % and 1.60 %, with an average of 1.21 %, reflecting the fire temperature values ranging from 230 to 436 °C, with an average of 327 °C. The main wildfire types were ground and surface fires under low to moderate temperatures, and wildfire intensity variation was shown by the total content of fusinite and semifusinite, pyrogenic PAHs concentrations, and inertinite reflectance of the coals. Maceral and mineral matter composition indicated that the coals were formed under wet moor with intermittent moderate to high flooding. The peat in topogenous and ombrotrophic raised mires is evidenced by the presence of tonstein and a low ash yield. Changes in fire types and intensity in the Erlian Basin provide new evidence that the Albian is a unique “high fire” period within the Cretaceous.
早白垩世的白垩纪是一个野火广泛而频繁的时期,但由于缺乏连续的野火记录,人们对野火的类型、强度和影响还不甚了解。本研究从中国内蒙古二连盆地早白垩世13米厚的煤层中采集了79个煤样,采用锆石UPb测年、煤岩相分析、扫描电子显微镜和气相色谱-质谱联用技术进行了分析。对夹层火山灰层进行的锆石定年显示,煤炭沉积于早阿尔卑斯时期,时间为 111.14 ± 1.14 Ma。岩相和近物性分析表明,煤炭的主要特征是腐植质(18.7-84.2 vol%,平均 52.7 vol%,mmf-不含矿物物质)和惰性质(15.1-80.7 vol%,平均 46.2 vol%,mmf),挥发物含量高(平均 39.7%,干燥和无灰分),灰分含量低(平均 7.45%,气干)。频繁的野火事件可通过以下方面识别(1)惰性石英含量,主要由富石英、半富石英和惰性铁石英组成,高于世界上其他白垩纪煤炭中的惰性石英含量;(3) 多环芳烃(PAHs)由 16 种 2-6 环芳烃化合物组成,其中热成多环芳烃平均占 PAHs 总量的 73.9 %,中高分子量多环芳烃占总分子量多环芳烃的 70.6 %。惰性系数的平均反射率在 0.86 % 到 1.60 % 之间,平均为 1.21 %,反映出火灾温度值在 230 ℃ 到 436 ℃ 之间,平均为 327 ℃。主要的野火类型是中低温下的地面火和地表火,野火强度的变化表现在煤炭中的燧石和半燧石总含量、热成多环芳烃浓度和惰性反射率上。宏观矿物和矿物物质组成表明,煤炭是在间歇性中度至高度洪水的湿润荒原下形成的。表生和外生凸起沼泽中的泥炭由碳酸盐和低灰分产率证明。二连盆地火灾类型和强度的变化提供了新的证据,证明阿尔卑斯时期是白垩纪中一个独特的 "高火 "时期。
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引用次数: 0
Paleoredox and lithofacies assessments in Deepwater intervals of the Monterey Formation, Santa Maria Basin, California: Insights from organic sulfur geochemistry 加利福尼亚州圣玛丽亚盆地蒙特雷地层深水区段的古氧化还原和岩性评估:有机硫地球化学的启示
IF 5.6 2区 工程技术 Q2 ENERGY & FUELS Pub Date : 2024-09-06 DOI: 10.1016/j.coal.2024.104606
Ana Vielma , Joseph A. Curiale , Humberto Carvajal-Ortiz , Jagoš R. Radović , Qi Fu , Thomas B. Malloy , K.K. (Adry) Bissada

Although the Monterey Formation has been studied extensively for its petroleum system and Miocene climate insights, debates persist regarding its paleo-redox conditions. Furthermore, its characteristic lithofacies offer a natural laboratory for developing tools to differentiate siliceous and calcareous rocks in deepwater environments. This study evaluated the potential of the Sulfur Index (SI = mg Sorg/g TOC), measured by Rock-Eval 7S, as a proxy for assessing paleoredox conditions by comparing the SI with iron speciation data. Additionally, high-resolution molecular analyses were performed to investigate possible relationships between sulfur compounds and rocks with different carbonate content. The findings indicate higher SI values and higher concentrations of benzothiophenes over dibenzothiophenes in the siliceous lithofacies compared to the calcareous lithofacies. This suggests that the mineral matrix plays a crucial role in influencing the process by which sulfur-rich kerogen undergoes cracking when placed under thermal stress. The SI may support a paleoredox interpretation for the Monterey Formation, differing from previous interpretations based only on iron speciation. This alternative interpretation involves a more extensive water-column euxinia, distinct from the seasonal euxinia suggested in previous work. This study represents a practical and pioneering workflow based on sulfur data derived from Rock-Eval 7S for paleoredox and lithofacies assessments, opening avenues for further research.

尽管人们对蒙特雷地层的石油系统和中新世气候进行了广泛研究,但关于其古氧化还原条件的争论依然存在。此外,其特征岩相为开发区分深水环境中硅质岩和钙质岩的工具提供了一个天然实验室。本研究通过比较硫指数(SI = mg Sorg/g TOC)与铁标本数据,评估了用 Rock-Eval 7S 测量的硫指数(SI = mg Sorg/g TOC)作为评估古氧化还原条件的替代物的潜力。此外,还进行了高分辨率分子分析,以研究硫化合物与不同碳酸盐含量的岩石之间可能存在的关系。研究结果表明,与钙质岩层相比,硅质岩层的 SI 值更高,苯并噻吩的浓度高于二苯并噻吩。这表明,矿物基质在影响富硫角质在热应力作用下发生裂解的过程中起着至关重要的作用。SI可能支持对蒙特雷地层进行古氧化还原解释,有别于以往仅根据铁的种类进行的解释。这种替代解释涉及到更广泛的水柱氧化作用,有别于之前研究中提出的季节性氧化作用。这项研究代表了一种基于 Rock-Eval 7S 得出的硫数据进行古氧化还原和岩性评估的实用和开创性的工作流程,为进一步的研究开辟了道路。
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International Journal of Coal Geology
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