Pub Date : 2024-03-25DOI: 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。
{"title":"Pyrolysis of macroalgae: Insight into product yields and biochar morphology and stability","authors":"H.I. Petersen , H. Deskur , A. Rudra , S.B. Ørberg , D. Krause-Jensen , H. Sanei","doi":"10.1016/j.coal.2024.104498","DOIUrl":"https://doi.org/10.1016/j.coal.2024.104498","url":null,"abstract":"<div><p>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 + CO<sub>2</sub> 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 + CO<sub>2</sub> 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 (R<sub>o</sub>) 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 R<sub>o</sub> 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 R<sub>o</sub> distribution range above the inertinite benchmark (IBR<sub>o</sub>2%) of R<sub>o</sub> = 2% indicating high carbon stability. Conversely, the remaining four biochar samples exhibit R<sub>o</sub> distributions extending below IBR<sub>o</sub>2%, indicating the presence of a carbon fraction with lower long-term stability in soil. The statistically significant inverse relationship observed between the mean R<sub>o</sub> values and the peak hydrocarbon generation temperature (T<sub>max</sub>) 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 R<sub>o</sub> values. In conclusion, the findings from pyrolysis and organic petrography reveal: (1) Macr","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104498"},"PeriodicalIF":5.6,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0166516224000557/pdfft?md5=0d65373d62f36defcafced7d9787f013&pid=1-s2.0-S0166516224000557-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140321530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-21DOI: 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,
{"title":"High-cellulose content of in-situ Miocene fossil tree stumps and trunks from Lusatia lignite mining district, Federal Republic of Germany","authors":"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","doi":"10.1016/j.coal.2024.104494","DOIUrl":"10.1016/j.coal.2024.104494","url":null,"abstract":"<div><p>Second Miocene Seam Complex (2nd MFK; <em>germ.:</em> 2. Miozäner Flözkomplex) holds many <em>in-situ,</em> not permineralised fossil tree stumps and trunks with high-cellulose contents. The state of preservation of a set of <em>in-situ</em> fossil trees (<em>Taxodioxylon cryptomerioides</em>, <em>Sciadopityoxylon wettsteinii</em>, and <em>Quasisequoioxylon piskowitzense</em>) 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.</p><p>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.</p><p>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<sup>−1</sup>) and cellulose (bands at 1110 and 1040 cm<sup>−1</sup>). Micro-FTIR spectrometry indicated lack of preferential hydrolytic removal of polysaccharides in examined samples.</p><p>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.</p><p>Biomarker assemblages obtained from fossil wood show a distinct dominance of diterpenoids and δ<sup>13</sup>C 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.</p><p>While δ<sup>13</sup>C values of fossil wood are generally consistent with stratigraphic trends and chemotaxonomical classification, ","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104494"},"PeriodicalIF":5.6,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S016651622400051X/pdfft?md5=7962ebc6d65adfe24913c93fee7a4a1d&pid=1-s2.0-S016651622400051X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140270566","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-21DOI: 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。
{"title":"Origin and nature of pores in the Toolebuc Formation, a potential unconventional target in Australia","authors":"Xiaoxiao Mao , Grant K.W. Dawson , Victor Rudolph , Sandra Rodrigues , Suzanne D. Golding","doi":"10.1016/j.coal.2024.104497","DOIUrl":"10.1016/j.coal.2024.104497","url":null,"abstract":"<div><p>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 N<sub>2</sub> 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 cm<sup>3</sup>/100 g, and 1.26–9.65 m<sup>2</sup>/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 cm<sup>3</sup>/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 cm<sup>3</sup>/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 cm<sup>3</sup>/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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104497"},"PeriodicalIF":5.6,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0166516224000545/pdfft?md5=cf98cdb7f41de7d62bb00c9eb59b7312&pid=1-s2.0-S0166516224000545-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140272232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-20DOI: 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.
{"title":"From abandoned mines to carbon sinks: Assessing the CO2 storage capacity of Austrian low-rank coal deposits","authors":"Majid Safaei-Farouji , David Misch , Reinhard F. Sachsenhofer , Max Rauscher , Nikolaos Kostoglou","doi":"10.1016/j.coal.2024.104495","DOIUrl":"10.1016/j.coal.2024.104495","url":null,"abstract":"<div><p>This study represents the first assessment of CO<sub>2</sub> 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 N<sub>2</sub> and CO<sub>2</sub> 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 T<sub>max</sub> and vitrinite reflectance values agree with a low coal rank for both sites. According to the N<sub>2</sub> 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 N<sub>2</sub> adsorption volumes of pure coals from both locations (N<sub>2</sub> uptake up to 16 cm<sup>3</sup>/g; avg. for all samples 5.4 cm<sup>3</sup>/g). In contrast, the mean adsorbed CO<sub>2</sub> 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 CO<sub>2</sub> adsorption capacity trends in the investigated sample set. Furthermore, based on the existence of a hysteresis loop between CO<sub>2</sub> adsorption and desorption branches for all investigated samples, the occurrence of weak chemisorption phenomena during CO<sub>2</sub> adsorption is indicated. This effect helps to increase CO<sub>2</sub> uptake and storage safety since the chemisorption process is not fully reversible upon pressure decrease. Ultimately, the theoretical CO<sub>2</sub> 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 m<sup>3</sup> of CH<sub>4</sub> in place.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104495"},"PeriodicalIF":5.6,"publicationDate":"2024-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0166516224000521/pdfft?md5=5c56313ec144f9edbe6b12d09c45dc7d&pid=1-s2.0-S0166516224000521-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140278981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-19DOI: 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.
{"title":"A complex case of thermal maturity assessment in a terrigenous sedimentary system: The Northwestern Black Sea basin","authors":"Hamed Sanei , Oskar Hagelskjær , Henrik I. Petersen , Arka Rudra , Søren B. Nielsen , François Lorant , François Gelin","doi":"10.1016/j.coal.2024.104496","DOIUrl":"10.1016/j.coal.2024.104496","url":null,"abstract":"<div><p>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 (VR<sub>o</sub>) 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 VR<sub>o</sub> populations complicates the application of VR<sub>o</sub> 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 <em>Tasmanites</em>-type alginite under UV-excitation. In contrast to VR<sub>o</sub> 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 VR<sub>o</sub> equivalent (VR<sub>o Eq</sub>) of 0.44%. At a burial depth of 3.2 km and a R/G value of 0.57 (VR<sub>o Eq</sub> = 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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104496"},"PeriodicalIF":5.6,"publicationDate":"2024-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0166516224000533/pdfft?md5=c25dfaa5878aa022d98e07e9e6b20c57&pid=1-s2.0-S0166516224000533-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140205789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-19DOI: 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。
{"title":"Solid bitumen as an indicator of petroleum migration, thermal maturity, and contact metamorphism: A case study in the Barrandian Basin (Silurian - Devonian), Czech Republic","authors":"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","doi":"10.1016/j.coal.2024.104493","DOIUrl":"10.1016/j.coal.2024.104493","url":null,"abstract":"<div><p>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% R<sub>r</sub>, 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% R<sub>r</sub>) 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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"286 ","pages":"Article 104493"},"PeriodicalIF":5.6,"publicationDate":"2024-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140205786","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}
Pub Date : 2024-03-17DOI: 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
{"title":"Novel insights about petroleum systems from source and reservoir rock characterization, Cretaceous Deposits, Babouri-Figuil Basin, Northern Cameroon","authors":"W. Gaspard Owona Manga , Javin J. Hatcherian , Paul C. Hackley , Moise Bessong , Carole L. Bapowa , Henri E. Pougue , Arsène Meying","doi":"10.1016/j.coal.2024.104491","DOIUrl":"10.1016/j.coal.2024.104491","url":null,"abstract":"<div><p>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 ","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"285 ","pages":"Article 104491"},"PeriodicalIF":5.6,"publicationDate":"2024-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140142226","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}
Pub Date : 2024-03-15DOI: 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.
{"title":"Evaluating the impact of artificial maturation on the petrophysical and geochemical properties of unconventional shale formations by integrating dielectric and NMR measurements","authors":"Amjed Hassan , Mahmoud Elsayed , Ali Oshaish , Salah Al-Ofi , Ammar El-Husseiny , Israa S. Abu-Mahfouz , Mohamed Mahmoud , Mohamed Abouelresh , Hussein Attia","doi":"10.1016/j.coal.2024.104492","DOIUrl":"10.1016/j.coal.2024.104492","url":null,"abstract":"<div><p>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 <em>T</em><sub><em>2</em></sub> 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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"285 ","pages":"Article 104492"},"PeriodicalIF":5.6,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140142230","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}
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.
{"title":"Depositional conditions, wildfires, maturity, and hydrocarbon potential evaluation of Central Carpathian Paleogene Basin based on integrative approach from Orava Basin","authors":"Dorota Staneczek , Dariusz Więcław , Leszek Marynowski","doi":"10.1016/j.coal.2024.104490","DOIUrl":"10.1016/j.coal.2024.104490","url":null,"abstract":"<div><p>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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"285 ","pages":"Article 104490"},"PeriodicalIF":5.6,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140142222","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}
Pub Date : 2024-03-12DOI: 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.
{"title":"Burial and thermal history modeling of basins in convergent oblique-slip mobile zones: A case study of the Ardmore Basin, southern Oklahoma","authors":"Ian A. Cox, Jack C. Pashin","doi":"10.1016/j.coal.2024.104486","DOIUrl":"10.1016/j.coal.2024.104486","url":null,"abstract":"<div><p>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% R<sub>o</sub>), 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.</p></div>","PeriodicalId":13864,"journal":{"name":"International Journal of Coal Geology","volume":"285 ","pages":"Article 104486"},"PeriodicalIF":5.6,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140142208","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}