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Pyrolysis of macroalgae: Insight into product yields and biochar morphology and stability 大型藻类的热解:对产品产量和生物炭形态及稳定性的深入研究
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-25 DOI: 10.1016/j.coal.2024.104498
H.I. Petersen , H. Deskur , A. Rudra , S.B. Ørberg , D. Krause-Jensen , H. Sanei

Pyrolysis of biomass residues into biochar is seen as a feasible way to mitigate climate change by biological carbon storage (carbon dioxide removal, CDR) and to substitute fossil fuel with sustainable biofuel. This study applies a combination of flash and ramp heating pyrolysis, and organic petrography to investigate the hydrocarbon (biofuel) potential and biochar stability and morphotypes of eight brown, red, and green macroalgal species of different tissue complexity. The carbon stability of biochar derived from macroalgae has not previously been assessed using organic petrography (reflectance measurements) and evaluated in the context of the geological carbon cycle. The biochar, hydrocarbon, and CO + CO2 yields vary due to different chemical composition of the macroalgal species, but the product yield variations are not related to the brown, red, or green macroalgal groups. The total biofuel yield shows an inverse trend with biochar yield. A slower heating rate produces more biochar and higher CO + CO2 and lower biofuel yields than the combined flash pyrolysis and faster heating rate. The morphotype composition of the biochar was qualitatively examined by reflected light microscopy while carbon stability was assessed by random reflectance (Ro) measurements. The diverse morphotype compositions observed in biochar formed under similar pyrolysis conditions likely stem from variations in the original algal composition. While some biochar samples show morphologies resembling the original macroalgal structure, porous morphotypes predominantly characterize the biochar samples overall. Despite a maximum pyrolysis production temperature (PT) of 650 °C, the highest mean Ro value among all biochar samples is 2.91%, corresponding to a carbonization temperature (CT) of 526 °C. This observation is tentatively related to the less lignocellulosic structure of the macroalgae compared to terrigenous biomass. Four biochar samples have their entire Ro distribution range above the inertinite benchmark (IBRo2%) of Ro = 2% indicating high carbon stability. Conversely, the remaining four biochar samples exhibit Ro distributions extending below IBRo2%, indicating the presence of a carbon fraction with lower long-term stability in soil. The statistically significant inverse relationship observed between the mean Ro values and the peak hydrocarbon generation temperature (Tmax) can be attributed to the behavior of residual macromolecules within the biochar. When these macromolecules reach peak biofuel generation at a lower temperature, they undergo carbonization over a more extended time interval during pyrolysis. Consequently, this prolonged exposure to the pyrolysis process leads to higher degrees of carbonization, as reflected by higher Ro values. In conclusion, the findings from pyrolysis and organic petrography reveal: (1) Macr

将生物质残渣热解成生物炭被认为是通过生物碳储存(二氧化碳去除,CDR)减缓气候变化以及用可持续生物燃料替代化石燃料的可行方法。本研究采用闪蒸和斜坡加热热解以及有机岩石学相结合的方法,研究了八种不同组织复杂性的棕色、红色和绿色大型藻类的碳氢化合物(生物燃料)潜力、生物炭稳定性和形态。从大型藻类中提取的生物炭的碳稳定性以前从未使用有机岩石学(反射率测量)进行过评估,也未在地质碳循环的背景下进行过评估。由于大型藻类的化学成分不同,生物炭、碳氢化合物和 CO + CO2 的产量也不同,但产品产量的变化与棕色、红色或绿色大型藻类无关。生物燃料总产量与生物炭产量呈反比趋势。与闪蒸热解和较快的加热速度相比,较慢的加热速度会产生更多的生物炭、更高的 CO + CO2 和更低的生物燃料产量。生物炭的形态组成是通过反射光显微镜进行定性检测的,而碳的稳定性则是通过随机反射率(Ro)测量进行评估的。在类似热解条件下形成的生物炭中观察到的不同形态组成可能源于原始藻类组成的变化。虽然一些生物炭样品显示出与原始大型藻类结构相似的形态,但多孔形态是生物炭样品的主要特征。尽管生物炭的最高热解生产温度(PT)为 650 °C,但所有生物炭样品的最高平均 Ro 值为 2.91%,对应的碳化温度(CT)为 526 °C。这一观察结果可能与大型藻类的木质纤维素结构少于陆生生物质有关。四个生物炭样品的整个 Ro 分布范围都高于 Ro = 2% 的惰性基(IBRo2%),这表明碳的稳定性很高。相反,其余四个生物炭样品的 Ro 分布范围则低于 IBRo2%,表明土壤中存在长期稳定性较低的碳部分。在平均 Ro 值和碳氢化合物生成峰值温度 (Tmax) 之间观察到的统计学意义上的显著反比关系可归因于生物炭中残留大分子的行为。当这些大分子在较低温度下达到生物燃料生成峰值时,它们在热解过程中会在更长的时间间隔内发生碳化。因此,在热解过程中暴露的时间越长,碳化程度越高,Ro 值越高。总之,热解和有机岩石学的研究结果表明:(1) 大型藻类具有生产生物燃料的潜力,但生物燃料的产量取决于大型藻类的种类和所采用的加热速率;(2) 本研究首次证明大型藻类的闪蒸+斜坡热解产生的生物炭适合长期碳储存。然而,从 Ro 频率分布推断出的碳稳定性和生物炭产量在不同的大型藻类和加热速率下都存在差异。
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引用次数: 0
High-cellulose content of in-situ Miocene fossil tree stumps and trunks from Lusatia lignite mining district, Federal Republic of Germany 德意志联邦共和国卢萨提亚褐煤矿区中新世原地化石树桩和树干中的高纤维素含量
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-21 DOI: 10.1016/j.coal.2024.104494
J. Kus , M. Dolezych , W. Schneider , J.C. Hower , T. Hofmann , E. Visiné Rajczi , A. Bidló , B. Bolodár-Varga , R.F. Sachsenhofer , A. Bechtel , K. Stojanović , D. Životić , I. Kojić , M. Mastalerz , T. Graupner , W.E. Lukens , L. Donaldson

Second Miocene Seam Complex (2nd MFK; germ.: 2. Miozäner Flözkomplex) holds many in-situ, not permineralised fossil tree stumps and trunks with high-cellulose contents. The state of preservation of a set of in-situ fossil trees (Taxodioxylon cryptomerioides, Sciadopityoxylon wettsteinii, and Quasisequoioxylon piskowitzense) collected from three open-cast mines (Welzow-Süd, Meuro, and Piskowitz) in Lusatia lignite mining district, Federal Republic of Germany was investigated using a multi-method research schema.

Examination of preservation state of thermally immature fossil woods revealed: (1) well-preserved (non-deformed, non-degraded, and non-flattened) textinite, (2) a retained structural integrity represented by multilayered (multi-zoned) cells with primary, secondary cell wall, and middle lamella, (3) microfracturing restricted to secondary walls only, (4) preservation of polyphenolic parenchyma cells (PP cells), (5) excellent preservation of pits in ray tracheids, (6) presence of amorphous silica (opal-A) coating, and (7) crystalline silica (opal-CT) fillings of small-bladed crystals.

Thermogravimetric analysis results showed dissimilar gelification status of fossil samples, supporting chlorite holocellulose assay results. The latter indicated anomalously high-cellulose values (15.6–37.6% holocellulose). The micro-FTIR data obtained revealed an excellent preservation of both hemicellulose (bands at 1740 and 1245 cm−1) and cellulose (bands at 1110 and 1040 cm−1). Micro-FTIR spectrometry indicated lack of preferential hydrolytic removal of polysaccharides in examined samples.

Biomarker patterns in lignite revealed forested and prevailing reed-mire vegetation. The results indicated lower contribution of Cupressaceae and emergent macrophyta to precursor organic matter of Welzow-Süd in comparison to Piskowitz lignite. Piskowitz lignite formed in permanent mire with stable water table under reducing, mesotrophic conditions. In contrast, more pronounced water level fluctuations (reducing to slightly oxic settings) and/or post-depositional events are postulated for Welzow-Süd samples.

Biomarker assemblages obtained from fossil wood show a distinct dominance of diterpenoids and δ13C values (−24.6 ‰ to −20.3 ‰) that clearly confirm gymnosperm sources. Distributions of diteprenoids and sesquiterpenoids, as well as fatty acids indicate the higher amount of saturated diterpenoids (pimarane, abietane) in fossil than in modern wood. This indicates reducing conditions promoting hydrogenation reactions. In addition to low Eh, preservation of cellulose in fossil wood was also favored by acidic conditions, very low degrees of aerobic fungal degradation, and protection of wood by Cupressaceae-derived resins.

While δ13C values of fossil wood are generally consistent with stratigraphic trends and chemotaxonomical classification,

第二中新世地层群(2nd MFK; germ.: 2. Miozäner Flözkomplex)拥有许多原生的、未经过永久矿化的、纤维素含量较高的树桩和树干化石。本研究采用多种研究方法,对从德意志联邦共和国卢萨提亚褐煤矿区的三个露天矿(Welzow-Süd、Meuro 和 Piskowitz)采集的一组原地树化石(Taxodioxylon cryptomerioides、Sciadopityoxylon wettsteinii 和 Quasisequoioxylon piskowitzense)的保存状况进行了调查。对热不成熟木材化石的保存状态进行了研究,结果表明(1) 保存完好(未变形、未退化、未扁平化)的纹理,(2) 保留了结构的完整性,表现为多层(多分区)细胞,包括主细胞壁、次细胞壁和中间薄片,(3) 微裂纹仅限于次细胞壁、(4) 保留了多酚实质细胞(PP 细胞);(5) 射线气管中的凹坑保存完好;(6) 存在无定形二氧化硅(蛋白石-A)涂层;(7) 晶体二氧化硅(蛋白石-CT)填充小叶片晶体。热重分析结果表明化石样本的凝胶化状态各不相同,支持绿泥石全纤维素检测结果。后者显示出异常高的纤维素值(全纤维素含量为 15.6-37.6%)。获得的显微傅立叶变换红外光谱数据显示,半纤维素(1740 和 1245 厘米-1 处的条带)和纤维素(1110 和 1040 厘米-1 处的条带)均保存完好。显微傅立叶变换红外光谱分析表明,所检测样品中的多糖没有被优先水解去除。结果表明,与皮斯科维兹褐煤相比,Welzow-Süd 的冲天香柏科和浮游大型植物对前体有机物的贡献较低。皮斯科维兹褐煤形成于地下水位稳定的永久性沼泽地,处于还原性中营养条件下。从化石木材中获得的生物标志物组合显示,二萜类化合物和δ13C值(-24.6 ‰至-20.3 ‰)明显占优势,这清楚地证实了裸子植物的来源。二萜和倍半萜以及脂肪酸的分布表明,化石木材中饱和二萜(pimarane、abietane)的含量高于现代木材。这表明还原条件促进了氢化反应。除了低 Eh 值之外,酸性条件、极低的需氧真菌降解程度以及源自濯缨草的树脂对木材的保护也有利于化石木材中纤维素的保存。虽然化石木材的δ13C值与地层趋势和化学分类学分类基本一致,但与已发表的裸子植物化石木材δ13C数据相比,Welzow-Süd和Meuro露天矿中分别记录的T. cryptomerioides和S. wettsteinii的δ13C值略有升高,这也表明纤维素保存良好。中新世化石树桩和树干在原地的保存以及高纤维素含量的保留,都被认为与反复的、由风化控制的干湿循环引起的高振幅时间波动有关:(1) 以凝灰岩和流纹岩为主的酸性火山岩和劳西茨花岗闪长岩的风化,(2) 与此相关的有蚀岩的侵蚀,以及 (3) 泥炭来源的富含腐殖酸和富立酸的水循环。后者导致了中新世高岭石沉积的形成,以及硅酸的释放和随后以蛋白石-A 的形式沉淀。后者影响了化石木材中高纤维素含量的保存。
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引用次数: 0
Origin and nature of pores in the Toolebuc Formation, a potential unconventional target in Australia 澳大利亚潜在的非常规目标--托勒布克地层孔隙的起源和性质
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-21 DOI: 10.1016/j.coal.2024.104497
Xiaoxiao Mao , Grant K.W. Dawson , Victor Rudolph , Sandra Rodrigues , Suzanne D. Golding

The Toolebuc Formation of Australia, a potential unconventional hydrocarbon resource, has limited studies on its pore structure and sorption characteristics. In this study, shale samples covering the lower mixed argillaceous mudstone (MAM) lithofacies, the middle interbedded calcareous mudstone and shelly thin beds (CM-STB) lithofacies, and the upper interbedded calcareous mudstone and shelly horizons (CM-SH) lithofacies of the Toolebuc Formation were collected. These samples were analysed for pore structure using a combination of scanning electron microscopy, X-ray diffraction, helium pycnometry, mercury intrusion porosimetry, and N2 physisorption techniques. Additionally, methane sorption isotherms were measured under in-situ conditions. The results reveal that most pores are mineral-related intraparticle (intraP) and interparticle pores, with slit, equant and elongated shapes. Organic matter (OM) pores are rare. Porosity, total pore volume and BET specific surface area (SSA) are 3.25–8.26%, 1.32–3.55 cm3/100 g, and 1.26–9.65 m2/g, respectively. Pore volume is dominated by mesopores and macropores while specific surface area is dominated by fine mesopores and micropores. The porosity of the organic matter is significantly low due to the rarity of OM pores in the stage of early oil-window thermal maturity; organic matter consequently occludes pore space and also negatively impacts the average porosity. Clay by contrast is positively correlated to the average porosity. Carbonate provides intraP pores in fecal pellets, but also fills in other pore spaces as occlusion. Methane isotherms exhibit linear shapes, suggesting that a portion of the gas is stored in solution. The lower MAM lithofacies, characterised by rich clay, high porosity and BET SSA, was measured to have an in-situ methane sorption capacity of 4.32 cm3/g; the middle CM-STB lithofacies has intermediate porosity, but exhibits excellent gas generation potential and high in-situ methane sorption capacity (4.12–5.5 cm3/g). Within the CM-STB lithofacies, porosity declines with depth. The upper CM-SH lithofacies is carbonate-rich, exhibiting the lowest porosity and in-situ methane sorption capacity (2.56 cm3/g), but may act as an intraformational seal. The combination and vertical stacking pattern of the three lithofacies provided a favourable setting for gas storage.

澳大利亚图勒布克地层是一种潜在的非常规碳氢化合物资源,但对其孔隙结构和吸附特征的研究却很有限。在这项研究中,采集了页岩样本,涵盖了 Toolebuc Formation 的下部混合砾质泥岩(MAM)岩性、中部互层钙质泥岩和薄层钙质泥岩(CM-STB)岩性以及上部互层钙质泥岩和钙质地层(CM-SH)岩性。采用扫描电子显微镜、X 射线衍射、氦气比重测定法、汞侵入孔隙测定法和 N2 物理吸附技术对这些样本的孔隙结构进行了分析。此外,还在原位条件下测量了甲烷吸附等温线。结果表明,大多数孔隙是与矿物有关的颗粒内(intraP)和颗粒间孔隙,形状有狭缝形、等长形和拉长形。有机物(OM)孔隙很少见。孔隙率、总孔隙体积和 BET 比表面积(SSA)分别为 3.25%-8.26%、1.32-3.55 立方厘米/100 克和 1.26-9.65 平方米/克。孔隙体积主要是中孔和大孔,而比表面积主要是细中孔和微孔。在早期油窗热成熟阶段,由于有机质孔隙稀少,有机质的孔隙率明显偏低;有机质因此堵塞了孔隙空间,也对平均孔隙率产生了负面影响。相比之下,粘土与平均孔隙度呈正相关。碳酸盐在粪便颗粒中提供了 P 内孔隙,但也作为闭塞物填充了其他孔隙空间。甲烷等温线呈现线性形状,表明部分气体储存在溶液中。下层 MAM 岩性的特点是富粘土、高孔隙度和 BET SSA,经测量,其甲烷原位吸附能力为 4.32 立方厘米/克;中层 CM-STB 岩性的孔隙度居中,但表现出良好的气体生成潜力和较高的甲烷原位吸附能力(4.12-5.5 立方厘米/克)。在 CM-STB 岩性中,孔隙度随深度下降。上部的 CM-SH 岩性富含碳酸盐,孔隙度和原位甲烷吸附能力最低(2.56 立方厘米/克),但可能起到地层内部封闭的作用。三种岩性的组合和垂直堆积模式为天然气储存提供了有利条件。
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引用次数: 0
From abandoned mines to carbon sinks: Assessing the CO2 storage capacity of Austrian low-rank coal deposits 从废弃矿井到碳汇:评估奥地利低阶煤层的二氧化碳储存能力
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-20 DOI: 10.1016/j.coal.2024.104495
Majid Safaei-Farouji , David Misch , Reinhard F. Sachsenhofer , Max Rauscher , Nikolaos Kostoglou

This study represents the first assessment of CO2 storage potential in Austrian coal seams. Coal samples were taken from Fohnsdorf and Leoben abandoned coal mines, with particular emphasis on the Fohnsdorf coal since Leoben coal reserves were largely mined during previous coal production. Several methods were used to compare coal characteristics, including Rock-Eval pyrolysis (RE), organic petrography, and low-pressure N2 and CO2 sorption measurements. Both Fohnsdorf and Leoben coal samples show low sulfur and ash yields, as well as correspondingly high total organic carbon (TOC) contents. The pyrolysis Tmax and vitrinite reflectance values agree with a low coal rank for both sites. According to the N2 adsorption measurements at 77 K, low-lying mire coals from Fohnsdorf show a higher BET-specific surface area (BET-SSA) and BJH pore volume compared to raised-mire coals from Leoben. However, sapropelic shales and high-ash coals from Leoben show the highest BET-SSA and BJH pore volumes of all investigated samples and considerably exceed the N2 adsorption volumes of pure coals from both locations (N2 uptake up to 16 cm3/g; avg. for all samples 5.4 cm3/g). In contrast, the mean adsorbed CO2 uptake measured at 273 K and ∼ 1 bar followed the order of Fohnsdorf low-lying mire coals > Leoben raised-mire coals > Leoben sapropelic coals and shales, ranging at ∼0.8 mmol/g, ∼0.7 mmol/g, and ∼ 0.2 mmol/g, respectively. This shows that BET-SSA and BJH equations did not allow for adequate estimation of CO2 adsorption capacity trends in the investigated sample set. Furthermore, based on the existence of a hysteresis loop between CO2 adsorption and desorption branches for all investigated samples, the occurrence of weak chemisorption phenomena during CO2 adsorption is indicated. This effect helps to increase CO2 uptake and storage safety since the chemisorption process is not fully reversible upon pressure decrease. Ultimately, the theoretical CO2 sequestration potential of the remaining unmined Fohnsdorf coal reserves was estimated at 4.65 million tons, with an additional potential for enhanced coal bed methane production due to the gas-rich nature of Fohnsdorf coals with an estimated 1.2 billion m3 of CH4 in place.

这项研究首次对奥地利煤层的二氧化碳封存潜力进行了评估。煤炭样本取自 Fohnsdorf 和 Leoben 废弃煤矿,重点是 Fohnsdorf 煤炭,因为 Leoben 煤炭储量大部分在以前的煤炭生产过程中被开采。比较煤炭特征的方法有多种,包括岩石热解(RE)、有机岩石学以及低压 N2 和 CO2 吸附测量。福恩斯多夫和莱奥本煤炭样本的硫含量和灰分含量都很低,总有机碳 (TOC) 含量也相应较高。热解 Tmax 和玻璃光泽反射率值与这两个地点的煤炭等级较低相吻合。根据 77 K 下的 N2 吸附测量结果,与莱奥本的高地煤相比,福恩斯多夫的低洼泥沼煤显示出更高的 BET 比表面积(BET-SSA)和 BJH 孔隙体积。不过,在所有调查样本中,莱奥本的皂质页岩和高灰分煤炭的 BET-SSA 和 BJH 孔隙度最高,大大超过了这两个地方的纯煤炭的 N2 吸附量(N2 吸收量高达 16 cm3/g;所有样本的平均值为 5.4 cm3/g)。相反,在 273 K 和 ∼ 1 bar 条件下测量的平均二氧化碳吸附量依次为 Fohnsdorf 低洼泥沼煤和 gt、Leoben 高洼泥沼煤和 gt、Leoben 皂质煤和页岩,分别为 ∼ 0.8 mmol/g、∼ 0.7 mmol/g 和 ∼ 0.2 mmol/g。这表明,BET-SSA 和 BJH 方程无法充分估计所研究样品集的二氧化碳吸附容量趋势。此外,基于所有调查样品的二氧化碳吸附和解吸分支之间存在滞后环,表明在二氧化碳吸附过程中存在微弱的化学吸附现象。由于化学吸附过程在压力降低时并不完全可逆,因此这种效应有助于提高二氧化碳吸收和封存的安全性。最终,剩余未开采的福恩斯多夫煤炭储量的二氧化碳理论封存潜力估计为 465 万吨,由于福恩斯多夫煤炭富含气体(估计有 12 亿立方米的甲烷),因此还具有提高煤层甲烷产量的潜力。
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引用次数: 0
A complex case of thermal maturity assessment in a terrigenous sedimentary system: The Northwestern Black Sea basin 陆相沉积系统热成熟度评估的复杂案例:黑海西北盆地
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-19 DOI: 10.1016/j.coal.2024.104496
Hamed Sanei , Oskar Hagelskjær , Henrik I. Petersen , Arka Rudra , Søren B. Nielsen , François Lorant , François Gelin

An integrated approach combining fluorescence spectrometry, pyrolysis geochemistry, and dispersed organic matter (DOM) maceral analysis has been used to determine the thermal maturity of Oligocene source rocks in two neighboring offshore wells within the complex deep-sea system of the Northwestern Black Sea. The samples contain predominantly immature Type II kerogen, including a mixture of marine liptinite (alginite, liptodetrinite), degraded liptinite, primary vitrinite, and reworked vitrinitic macerals. The occurrence of several vitrinite reflectance (VRo) populations in the samples is attributed to a high influx of reworked vitrinite transported to the marine basin from multiple terrestrial sources with diverse degrees of degradation. The presence of multiple VRo populations complicates the application of VRo for determining the thermal maturity of the organic matter. Further, the VRo measurements on the primary vitrinite population show only a subtle increasing trend with depth. A significantly improved thermal maturity resolution was obtained using the red to green quotient (R/G). R/G was measured on the autochthonous unicellular Tasmanites-type alginite under UV-excitation. In contrast to VRo the results show a significant correlation between increasing R/G values with increasing depth. This indicates that the R/G quotient is a better maturity proxy for the studied low maturity marine system with a large influx of sediments. The beginning of the downward declining trend in the temporal variation of liptinite is regarded as the onset of catagenesis. This occurs at a burial depth of 2.5 km and a R/G value of 0.50, corresponding to a VRo equivalent (VRo Eq) of 0.44%. At a burial depth of 3.2 km and a R/G value of 0.57 (VRo Eq = 0.57%), the onset of the oil window is marked by an increase in the amount of solid bitumen (initial oil solid bitumen). The observed alterations in maceral composition with burial depth align with the thermal maturity of the wells. However, the data suggest that the thermal evolution of the organic matter is out of sync with the surrounding formation temperature, possibly due to rapid burial induced by a high sedimentation rate.

在黑海西北部复杂的深海系统中,采用荧光光谱仪、热解地球化学和分散有机物(DOM)宏观分析相结合的综合方法,确定了两口相邻海上油井中新世源岩的热成熟度。这些样本主要含有不成熟的第二类角质,包括海洋褐铁矿(藻褐铁矿、褐铁矿)、降解褐铁矿、原生褐铁矿和再造褐铁矿大分子的混合物。样本中出现多个玻璃光泽反射率(VR)种群的原因是,从多个陆地来源运输到海洋盆地的再造玻璃光泽大量涌入,而这些玻璃光泽的降解程度各不相同。由于存在多个椭偏荧光团,应用椭偏荧光团来确定有机物的热成熟度变得更加复杂。此外,对原生钙钛矿群的 VRo 测量结果仅显示出随着深度的增加而微妙增加的趋势。利用红绿商(R/G)可以大大提高热成熟度的分辨率。R/G 是在紫外线激发下对自生单细胞海藻进行测量的。与 VR 不同的是,结果显示 R/G 值的增加与深度的增加之间存在显著的相关性。这表明,对于所研究的大量沉积物涌入的低成熟度海洋系统来说,R/G 商数是一个更好的成熟度代表。锂辉石的时间变化开始呈下降趋势,这被认为是催化作用的开始。这发生在埋藏深度为 2.5 千米、R/G 值为 0.50、VR 当量为 0.44% 时。在埋藏深度为 3.2 千米、R/G 值为 0.57(VR = 0.57%)时,石油窗口的出现标志着固体沥青量(初始石油固体沥青)的增加。随着埋藏深度的增加,观察到的宏观组成变化与油井的热成熟度相一致。然而,数据表明,有机质的热演化与周围地层温度不同步,这可能是由于高沉积率引起的快速埋藏造成的。
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引用次数: 0
Solid bitumen as an indicator of petroleum migration, thermal maturity, and contact metamorphism: A case study in the Barrandian Basin (Silurian - Devonian), Czech Republic 固体沥青作为石油迁移、热成熟度和接触变质作用的指标:捷克共和国巴兰盆地(志留纪-泥盆纪)案例研究
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-19 DOI: 10.1016/j.coal.2024.104493
Václav Suchý , Ivana Sýkorová , Jiří Zachariáš , Kateřina Pachnerová Brabcová , Petr Dobeš , Martina Havelcová , Ivan Rozkošný , Qingyong Luo , Weixun Cao , Jin Wu , Petra Mácová , Alberto Viani , Ivo Svetlik , Daniel Maxa

Silurian and Devonian marine shales and limestones of the Barrandian Basin host abundant black solid, non-fluorescing bitumens that fill tectonic fractures and veins, and occlude fossil moulds and diagenetic concretions. Solid bitumen, interpreted as thermally degraded petroleum, entered the rocks during several successive episodes of fracture-bound petroleum migration that occurred during deeper burial of the strata. Regional distribution of bitumen reflectance values that range between ∼0.9–2.3% Rr, correlate with variations of its FT-IR and Raman spectroscopic characteristics and aromatic hydrocarbon composition, and collectively evidence the maturity trend increasing across the basin from the southwest to the northeast. The reflectance of chitinozoans and graptolites (∼0.8–1.9% Rr) in the country rocks and homogenization temperatures of hydrocarbon fluid inclusions document palaeotemperatures ranging between ∼90–150 °C, characteristic of the oil window zone grading into the gas/condensate zone. Although in a basin-wide perspective the averaged values of solid bitumen and zooclast optical reflectance converge and indicate the same northeastern-increasing regional diagenetic trend, solid bitumen reflectance values vary considerably at individual localities and even within some bitumen samples. The wide scatter of optical reflectance values and the heterogeneity of optical properties, which were attributed to the presence of multiple source rocks in the basin, the variable lithology of bitumen host rocks, or other variables, hamper the use of solid bitumen as a simple alternative to zooclast/vitrinite reflectance palaeothermometers in a given basin. On the other hand, the highly anisotropic domain and the mesophase “coking” textures of the solid bitumen that were recognized in the NE part of the basin provide unique evidence on an anomalous, hitherto unrecognized, geologically short-lasting thermal event that affected the Palaeozoic rocks. A line of indirect evidence suggests that the coking of the bitumen was caused by a cryptic intrusion, possibly a concealed branch of the Central Bohemian Pluton, which intruded into the strata during the Variscan orogeny. More rarely occurring semi-solid, vividly yellow fluorescing waxy bitumen, that postdates solid bitumen in some fractures and voids, does not reveal a regional thermal maturation trend. It precipitated from relict waxy oils that migrated through the strata during a post-Neogene uplift of the Barrandian region.

巴兰盆地的志留纪和泥盆纪海相页岩和灰岩中蕴藏着大量黑色固态非荧光沥青,这些沥青填充了构造裂缝和岩脉,并遮蔽了化石模和成岩凝块。固态沥青被解释为热降解石油,是在地层深埋过程中发生的几次连续的裂缝石油迁移过程中进入岩石的。沥青反射率的区域分布在 ~0.9-2.3% R 之间,与沥青的傅立叶变换红外光谱和拉曼光谱特征以及芳香烃成分的变化相关,共同证明了成熟度在盆地内从西南向东北递增的趋势。乡土岩中壳虫和爬行岩的反射率(~ 0.8-1.9% R)以及烃类流体包裹体的均质化温度记录了~90-150 °C之间的古温度,这是石油窗口区向天然气/凝析气区分级的特征。虽然从整个盆地的角度来看,固体沥青和动物沉积物光学反射率的平均值趋于一致,并显示出相同的东北向区域成岩趋势,但固体沥青的反射率值在个别地方甚至在某些沥青样本中存在很大差异。由于盆地中存在多种源岩、沥青主岩的岩性多变或其他变量,光学反射率值的巨大差异和光学性质的异质性阻碍了在特定盆地中使用固体沥青作为动物群/岩性反射率古温度计的简单替代方法。另一方面,在盆地东北部发现的固体沥青的高度各向异性域和介相 "焦化 "纹理,为影响古生代岩石的异常的、迄今未被发现的、地质学上持续时间短的热事件提供了独特的证据。一系列间接证据表明,沥青焦化是由一个隐秘的侵入体造成的,该侵入体可能是中波西米亚岩块的一个隐蔽分支,在瓦里斯坎造山运动期间侵入地层。在一些断裂和空隙中,半固态、鲜黄色荧光蜡状沥青的出现时间晚于固态沥青,但这种沥青很少出现,并没有显示出区域性的热成熟趋势。它析出自巴兰迪地区新近纪后隆起过程中通过地层迁移的残余蜡油。
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引用次数: 0
Novel insights about petroleum systems from source and reservoir rock characterization, Cretaceous Deposits, Babouri-Figuil Basin, Northern Cameroon 喀麦隆北部巴布里-菲吉尔盆地白垩纪矿床,从源岩和储层岩石特征中获得有关石油系统的新见解
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-17 DOI: 10.1016/j.coal.2024.104491
W. Gaspard Owona Manga , Javin J. Hatcherian , Paul C. Hackley , Moise Bessong , Carole L. Bapowa , Henri E. Pougue , Arsène Meying

The Babouri-Figuil Basin (BFB) is a frontier basin for petroleum in Cameroon. It belongs to the series of Cretaceous rift basins of the West and Central Rift System (WCARS), the origin of which is related to the opening of the South Atlantic. Within the same rift system, commercial hydrocarbon accumulations have been discovered in Chad, Sudan, Niger and, more recently, in Nigeria (Gongola Basin). The study of the geology of the BFB just recently received considerable attention, mainly because of its presumed hydrocarbon potential. In the pursuit of researching possible petroleum systems in the BFB, the current study provides a first look into the characterization of source and reservoir rock and its integration into a 2D lithostratigraphic model. The study was solely based on outcrop samples. Black shale and massive claystone are good to excellent hydrocarbon source rocks [e.g., up to 38 wt% total organic carbon (TOC), up to 943 mg/g hydrogen index, up to 85 m thickness, up to 20–30 km lateral extension], with moderate to high values of extractable organic matter (e.g., >10,000 ppm). Calcareous claystone, on the other hand, are poor source rocks [e.g., <0.20 wt% TOC]. The samples are thermally immature, except for those located close to volcanic intrusion at Golombe that have reached the threshold for oil generation (Tmax >435 °C, production index >0.1). The petrographic analysis of sandstone revealed that they are fine-grained to coarse-grained, poorly to moderately sorted, texturally and compositionally immature to submature, subarkosic to arkosic arenites. The main diagenetic processes that affected sandstones are as follows: moderate to intense compaction characterized by the development of long, concavo-convex, and sutured contacts between grains; cementation through calcite, iron oxide, and quartz cements; alteration of mica and feldspar grains; partial to complete dissolution of feldspar, mica, amphibole grains, and calcite cement; and the replacement of feldspar and mica grains by clay minerals. Alteration and dissolution increase the porosity of sandstone through the creation of secondary pores. However, mechanical compaction through the development of a pseudomatrix and cementation as pore-filling materials have significantly reduced the quality of sandstone beds as conventional petroleum reservoirs. Hence, the best reservoir-quality sandstones in the basin are generally located in the upper portion of the basin in terms of its lithostratigraphic model. They are the cleanest sandstones with the smallest amount of cement and the lowest ductile grain content (pseudomatrix), with a thickness that varies from 3 m to 120 m and a lateral extension of 20 km. The lithostratigraphic model of the basin is characterized by an extensive lacustrine environment that provided a thick sequence of organic-rich formations; sand deposited as extensive reservoirs sandwiched between shale/claystone beds; the development of stratigraphic

巴布里-菲吉尔盆地(BFB)是喀麦隆的一个石油前沿盆地。它属于中西部裂谷系统(WCARS)的白垩纪裂谷盆地系列,其起源与南大西洋的开辟有关。在同一裂谷系统中,乍得和苏丹以及最近在尼日利亚(Gongola 盆地)发现了商业油气储藏。对 BFB 地质的研究最近刚刚受到相当大的关注,这主要是因为它被认为具有油气潜力。为了研究 BFB 可能的石油系统,本研究首次对源岩和储层岩的特征进行了分析,并将其纳入二维岩石地层模型。这项研究完全基于露头样本。黑页岩和块状粘土岩是良好至极佳的碳氢化合物源岩[例如,总有机碳(TOC)高达 38 wt%,氢指数高达 943 mg/g,厚度达 85 米,横向延伸达 20-30 千米],可提取有机物的数值为中等至高等(例如,>10,000 ppm)。另一方面,钙质粘土岩属于贫源岩[例如,435 °C,生产指数大于 0.1]。砂岩的岩相分析表明,它们属于细粒至粗粒、分选差至中等、质地和成分不成熟至亚稳态、亚赤铁矿至赤铁矿。影响砂岩的主要成岩过程如下:中等到强烈的压实,特点是岩粒之间形成长而凹凸的缝合接触;方解石、氧化铁和石英胶结物的胶结;云母和长石岩粒的蚀变;长石、云母、闪石岩粒和方解石胶结物的部分到完全溶解;以及粘土矿物对长石和云母岩粒的取代。蚀变和溶解会产生次生孔隙,从而增加砂岩的孔隙率。然而,通过形成假基质和胶结物作为孔隙填充材料进行机械压实,大大降低了砂岩床作为常规石油储层的质量。因此,从岩石地层模型来看,盆地中储层质量最好的砂岩一般位于盆地上部。它们是最洁净的砂岩,胶结物含量最少,韧性颗粒含量(假矩阵)最低,厚度从 3 米到 120 米不等,横向延伸 20 千米。该盆地岩石地层模型的特点是:广泛的湖沼环境提供了厚厚的富含有机质的地层序列;砂沉积为广泛的储层,夹在页岩/粘土岩床之间;通过横向面层变化形成地层陷阱;湖沼和洪积平原粘土岩广泛沉积,提供了区域封印。巴布里-菲吉尔盆地与其他世界卡斯特罗裂谷盆地已探明的石油系统之间的相似性表明,该盆地可能存在至少一个石油系统,其中有活跃的生成源岩。
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引用次数: 0
Evaluating the impact of artificial maturation on the petrophysical and geochemical properties of unconventional shale formations by integrating dielectric and NMR measurements 通过整合介电测量和核磁共振测量评估人工成熟对非常规页岩层岩石物理和地球化学性质的影响
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-15 DOI: 10.1016/j.coal.2024.104492
Amjed Hassan , Mahmoud Elsayed , Ali Oshaish , Salah Al-Ofi , Ammar El-Husseiny , Israa S. Abu-Mahfouz , Mohamed Mahmoud , Mohamed Abouelresh , Hussein Attia

This paper addresses challenges in characterizing unconventional shale reservoirs. For the first time, the nuclear magnetic resonance (NMR) and dielectric responses are integrated to characterize intact, saturated, and kerogen-rich subsurface shale samples at various maturation stages. The NMR and dielectric were measured separately using independent pieces of equipment, and all NMR and dielectric measurements were carried out at surface conditions. A comprehensive assessment is provided to address the changes induced by maturation through combined geochemical and petrophysical analyses. Shale samples from the Upper Cretaceous sequence of Jordan were characterized using Rock-Eval analysis, before and after maturation treatments. The total organic carbon (TOC) was decreased from 17.4 to 13.8 and 11.3 wt% and the pyrolyzed sulfur content was decreased from 3.32 to 0.25 and 0.15 3.18%, after maturing the samples at 250 °C for 1 and 5 days, respectively. The study employed NMR to track changes in pore structure via T2 relaxation time and measured dielectric properties and conductivity dispersion across frequencies from 10 MHz to 1 GHz using a wideband open-ended coaxial probe. After the maturation treatments, the dielectric constant of saturated shale samples doubled, and the conductivity increased by over three times. These changes in dielectric properties can be attributed to increased fluid-rock interfacial polarization and the formation of new pore spaces during maturation. NMR findings also indicated the emergence of a new pore system within the organic matter and the development of new fractures, resulting in a 6 to 12% increase in total porosity. The results obtained indicate that maturation-induced microstructural changes have a more significant influence on the dielectric responses than alterations on total organic carbon.

本文探讨了非常规页岩储层的表征难题。本文首次将核磁共振(NMR)和介电反应结合起来,对处于不同成熟阶段的完整、饱和和富含角质的地下页岩样本进行了表征。核磁共振和介电分别使用独立的设备进行测量,所有核磁共振和介电测量都是在地表条件下进行的。通过综合地球化学和岩石物理分析,对成熟引起的变化进行了全面评估。使用 Rock-Eval 分析方法对约旦上白垩统序列的页岩样本在熟化处理前后的特征进行了分析。样品在 250 °C 下熟化 1 天和 5 天后,总有机碳 (TOC) 分别从 17.4% 降至 13.8% 和 11.3%,热解硫含量分别从 3.32% 降至 0.25% 和 0.15 3.18%。研究采用核磁共振技术通过弛豫时间跟踪孔隙结构的变化,并使用宽带开口同轴探针测量了介电性能和电导率色散,频率范围从 10 MHz 到 1 GHz。经过熟化处理后,饱和页岩样品的介电常数增加了一倍,电导率增加了三倍多。介电性质的这些变化可归因于成熟过程中流体-岩石界面极化的增加和新孔隙的形成。核磁共振研究结果还表明,有机质中出现了新的孔隙系统,并形成了新的裂缝,从而使总孔隙度增加了 6% 至 12%。研究结果表明,与有机碳总量的变化相比,成熟引起的微观结构变化对介电响应的影响更为显著。
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引用次数: 0
Depositional conditions, wildfires, maturity, and hydrocarbon potential evaluation of Central Carpathian Paleogene Basin based on integrative approach from Orava Basin 基于奥拉瓦盆地的综合方法评估喀尔巴阡山中古近纪盆地的沉积条件、野火、成熟度和碳氢化合物潜力
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-13 DOI: 10.1016/j.coal.2024.104490
Dorota Staneczek , Dariusz Więcław , Leszek Marynowski

Central Carpathian Paleogene Basin (CCPB, Central Western Carpathians) comprises mainly Oligocene clastic autochthonous age-equivalents of the widely known Menilite shale formation from the Outer Carpathians. However, little is known about the paleoenvironment and its subsequent changes during the basin's evolution. Furthermore, the available hydrocarbon potential data are based on anachronous methods and are not investigated on the sub-basin level. Gas chromatography-mass spectrometry (GC–MS) analyses supported by Rock-Eval data along with petrographic measurements enabled us to identify and document the paleoenvironmental evolution of the Orava sub-basin (NW remnant of CCPB). Thermal maturity based on vitrinite reflectance, 22S/(22S + 22R) homohopane ratio and 20S/(20S + 20R) sterane ratio increases from N to S and from Upper to Lower Oligocene. In the least mature samples ββ-hopanes, hopenes, and oleanenes are present, whereas in the most mature deposits less thermally stable compounds dissapeared. This maturation trend is shown also by the Rock-Eval data. Terrestrial organic matter input is documented by the predominance of III- and II/III-type of kerogen and the occurrence of several biomarkers, such as 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, cadalene, retene, and perylene. The significant contribution of polycyclic aromatic hydrocarbons (PAHs) may be linked with wildfire-related land degradation and following runoff to the basin. Based on the measured fusinite reflectance values the wildfire types could range from hotter crown fires to colder surface fires. Depositional conditions in Lower Oligocene units are characterized by intermittent euxinia, as derived from small (<5 μm) pyrite framboid diameters and the presence of isorenieratane. Subsequently, a change of conditions to oxic/dysoxic in younger units is observed, and the input of terrestrial organic matter increased.

中喀尔巴阡山古近纪盆地(CCPB,中西喀尔巴阡山脉)主要由外喀尔巴阡山脉广为人知的梅尼利特页岩层的渐新世碎屑岩自生时代等同物组成。然而,人们对该盆地演化过程中的古环境及其随后的变化知之甚少。此外,现有的碳氢化合物潜力数据是基于过时的方法得出的,并没有在次盆地层面进行调查。气相色谱-质谱法(GC-MS)分析得到了岩石评价数据和岩相测量数据的支持,使我们能够确定并记录奥拉瓦子盆地(中央盆地西北部残余)的古环境演变。根据玻璃光泽反射率、22S/(22S + 22R)均质烷比率和 20S/(20S + 20R)立体烷比率得出的热成熟度从北到南,从上新世到下新世逐渐升高。在最不成熟的样本中存在ββ-蒎烷、蒎烯和齐墩果烯,而在最成熟的矿藏中,热稳定性较低的化合物消失了。岩石评价数据也显示了这种成熟趋势。陆地有机物的输入主要体现在 III 型和 II/III 型角质层以及一些生物标志物,如 3,3,7-三甲基-1,2,3,4-四氢菊烯、蒈烯、芸苔烯和苝。多环芳烃(PAHs)的大量存在可能与野火导致的土地退化以及随后流入盆地的径流有关。根据测得的燧石反射率值,野火类型可能包括较热的树冠火和较冷的地表火。下渐新世单元的沉积条件以间歇性蚀变为特征,这可以从黄铁矿框胞直径较小(<5 μm)和异菱锰矿的存在中推测出来。随后,在较年轻的单元中观察到条件变为缺氧/缺氧,陆地有机物的输入增加。
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引用次数: 0
Burial and thermal history modeling of basins in convergent oblique-slip mobile zones: A case study of the Ardmore Basin, southern Oklahoma 收敛斜滑移动带盆地的埋藏和热历史建模:俄克拉荷马州南部阿德莫尔盆地案例研究
IF 5.6 2区 工程技术 Q1 Earth and Planetary Sciences Pub Date : 2024-03-12 DOI: 10.1016/j.coal.2024.104486
Ian A. Cox, Jack C. Pashin

The burial and thermal history of sedimentary basins within oblique-slip mobile zones are unique and multifaceted, with irregular periods of subsidence that are closely related to compressional and shear stress. Modern basin modeling techniques can constrain the timing of tectonic events and thermal history as well as determine rates and magnitudes of basin subsidence, which in turn, helps guide exploration for hydrocarbons. The work presented here is the first modern basin modeling effort in the Ardmore Basin in southern Oklahoma. The study uses 12 one-dimensional burial history models to evaluate the thermal maturity of the Late Devonian (Famennian)–Early Mississippian (Tournaisian) Woodford Shale and the Early–Late Mississippian (Tournaisian–Serpukhovian) Caney Shale hydrocarbon source rocks. All models display a similar tectonic evolution with subsidence during and following Cambrian Iapetan rifting, tectonic stability during a Silurian–Late Mississippian passive margin phase, Pennsylvanian synorogenic subsidence, Permian post-orogenic subsidence, Late Permian–Early Cretaceous regional uplift and unroofing, and Early Cretaceous–Paleogene subsidence of the Gulf of Mexico Basin. Episodic Pennsylvanian subsidence appears to have been synchronous with sequential uplift of the Wichita Uplift and the Arbuckle Uplift in response to major left-lateral transpression. Rapid and high magnitude Late Mississippian–Permian subsidence (>250 m/m.y.; 820 ft/m.y. in basin synclines) suggests the Ardmore Basin functioned episodically as an elevator basin, which is typical of sedimentary basins in oblique-slip mobile zones. The Devonian–Mississippian shale section has a broad range of thermal maturity (vitrinite reflectance, 0.40–2.00% Ro), which is strongly dependent on structural position. Isoreflectance lines are subhorizontal and cross-cut structure, indicating post-kinematic thermal maturation in which strata are thermally immature in uplifts and thermally overmature in the deepest synclines. The post-kinematic pattern is a product of a rapid, early phase of synkinematic thermal maturation that has been obscured by a prolonged period of post-kinematic thermal maturation. Variations in basal heat flow, structural history, and general variability of hydrocarbon source rock organic composition, particularly at low thermal maturity levels, have resulted in a modest degree of scatter in the vitrinite reflectance-depth data.

斜滑动带内沉积盆地的埋藏和热历史是独特和多方面的,其不规则的沉降期与压应力和剪应力密切相关。现代盆地建模技术可以制约构造事件和热历史的时间,并确定盆地沉降的速率和幅度,这反过来又有助于指导碳氢化合物的勘探。本文介绍的工作是俄克拉荷马州南部阿德摩尔盆地的首次现代盆地建模工作。该研究使用了 12 个一维埋藏史模型来评估晚泥盆世(法门期)-早密西西比世(图尔奈斯期)伍德福德页岩和早-晚密西西比世(图尔奈斯期-塞普霍维亚期)卡尼页岩碳氢化合物源岩的热成熟度。所有模型都显示了类似的构造演化过程,包括寒武纪伊阿佩坦断裂期间和之后的沉降、志留纪-晚密西西比被动边缘阶段的构造稳定、宾夕法尼亚同源沉降、二叠纪后同源沉降、二叠纪晚期-白垩纪早期的区域隆升和解顶,以及白垩纪早期-古近纪墨西哥湾盆地的沉降。宾夕法尼亚沉降似乎与威奇托隆起和阿巴克尔隆起的相继隆升同步,是对左侧大移位的反应。密西西比-二叠纪晚期的快速、高幅度下沉(>250 米/米年;盆地向斜中的 820 英尺/米年)表明,阿德摩尔盆地曾偶尔作为一个升降盆地,这是斜滑移动带沉积盆地的典型特征。泥盆纪-密西西比页岩段的热成熟度(玻璃光泽反射率,0.4-2.0% R)范围很广,与构造位置密切相关。等反射率线是近水平的,并与构造交叉,这表明了运动后的热成熟,其中隆起地层的热成熟度较低,而最深的切向地层的热成熟度较高。后构造模式是同步热成熟早期快速阶段的产物,被后构造热成熟的长期阶段所掩盖。基底热流的变化、构造历史以及烃源岩有机成分的普遍变化,尤其是在热成熟度较低的情况下,导致了玻璃光泽反射深度数据的适度分散。
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引用次数: 0
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International Journal of Coal Geology
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