The effects of clay minerals and organic matter on nanoscale pores in Lower Paleozoic shale gas reservoirs,Guizhou, China

In organic-rich gas shales, clay minerals and organic matter (OM) have significant influences on the origin, preservation, and production of shale gas. Because of the substantial role of nanoscale pores in the generation, storage, and seepage of shale gas, we examined the effects of clay minerals and OM on nanoscale pore distribution characteristics in Lower Paleozoic shale gas reservoirs. Using the Niutitang and Longmaxi shales as examples, we determined the effects of clay minerals and OM on pores through sedimentation experiments. Field emission–scanning electron microscopy combined with low-pressure N₂ adsorption of the samples before and after sedimentation showed significant differences in pore location and pore size distribution between the Niutitang and Longmaxi shales. Nanoscale pores mostly existed in OM in the Longmaxi shale and in clay minerals or OM–clay composites in the Niutitang shale. The distribution differences were attributed largely to variability in thermal evolution and tectonic development and might account for the difference in gas-bearing capacity between the Niutitang and Longmaxi reservoirs. In the nanoscale range, mesopores accounted for 61–76% of total nanoscale pore volume. Considerably developed nanoscale pores in OM were distributed in a broad size range in the Longmaxi shale, which led to good pore connectivity and gas production. Numerous narrow pores (i.e., pores?<?20 nm) in OM–clay composites were found in the Niutitang shale, and might account for this shale’s poor pore connectivity and low gas production efficiency. Enhancing the connectivity of the mesopores (especially pores?<?20 nm and those developed in OM–clay composites) might be the key to improving development of the Niutitang shale. The findings provide new insight into the formation and evolutionary mechanism of nanoscale pores developed in OM and clay minerals.     

Variation in Pore Space and Structure of Organic-rich Oil-prone Shales from a Non-marine Basin: Constraints from Organic Matter and Minerals

Organic matter (OM) and minerals are major particle components of lacustrine shales. The influence of OM and minerals on pore space and structure in organic-rich oil-prone shales containing a large range of total organic carbon (TOC) contents is poorly understood. In this study, we investigated the variation in pore space and structure of low mature lacustrine shales in the Songliao Basin (NE China), based on a study of the mineralogy, petrography, geochemistry, and geophysical properties of shales. Different pore types make markedly different contributions to the mineral surface area (MSA) and pore volume (PV) of the shales. There exists a negative correlation between MSA/PV and TOC in mesopores (r2 = 0.75/0.65) and macropores (r2 = 0.74/0.68), and a positive correlation in micropores (r2 = 0.59/0.64), which are associated with the variation of mineral and TOC contents. A positive relationship between the throat/pore ratio and TOC (r2 = 0.82) shows an increase in throat radius and decrease in pore radius with increasing TOC content. This relationship is supported by the reduction in mean pore diameter (MPD) for large pores and increase in MPD for small pores. These variations are related to the decreased pores by quartz plus feldspar (Q + F) content, increased throats by clay minerals, and enhanced pore-fill by OM. We propose that the variation of OM and minerals is a key control on the pore space and structure of low mature organic-rich oil-prone shales.     

Mineralogical impact on organic nitrogen across a long-term soil chronosequence (0.3-4100 kyr)

Large portions of organic N (ON) in soil exist tightly associated with minerals. Mineral effects on the type of interactions, chemical composition, and stability of ON, however, are poorly understood. We investigated mineral-associated ON along a Hawaiian soil chronosequence (0.3-4100 kyr) formed in basaltic tephra under comparable climatic, topographic, and vegetation conditions. Mineral-organic associations were separated according to density (ρ > 1.6 g/cm³), characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge fine structure (NEXAFS) and analyzed for amino acid enantiomers and amino sugars. The ¹⁴C activity of mineral-bound OC was estimated by accelerator mass spectrometry. The close OC-ON relationship (r = 0.96) and XPS results suggest that ON exists incorporated in bulk mineral-bound OM and likely becomes associated with minerals as part of sorbing OM. The youngest site (0.3 kyr), with soils mainly composed of primary minerals (olivine, pyroxene, feldspar) and with little ON, contained the largest proportion of hydrolyzable amino sugars and amino acids but with a small share of acidic amino acids (aspartic acid, glutamic acid). In soils of the intermediate weathering stage (20-400 kyr), where poorly crystalline minerals and metal(hydroxide)-organic precipitates prevail, more mineral-associated ON was present, containing a smaller proportion of hydrolyzable amino sugars and amino acids due to the preferential accumulation of other OM components such as lignin-derived phenols. Acidic amino acids were more abundant, reflecting the strong association of acidic organic components with metal(hydroxide)-organic precipitates and variable-charge minerals. In the final weathering stage (1400-4100 kyr) with well-crystalline secondary Fe and Al (hydr)oxides and kaolin minerals, mineral-organic associations held less ON and were, relative to lignin phenols, depleted in hydrolyzable amino sugars and amino acids, particularly in acidic amino acids. XPS and NEXAFS analyses showed that the majority (59-78%) of the mineral-associated ON is peptide N while 18-34% was aromatic N. Amino sugar ratios and d-alanine suggest that mineral-associated ON comprises a significant portion of bacterial residues, particularly in the subsoil. With increasing ¹⁴C age, a larger portion of peptide N was non-hydrolyzable, suggesting the accumulation of refractory compounds with time. The constant d/l ratios of lysine in topsoils indicate fresh proteinous material, likely due to continuous sorption of or exchange with fresh N-containing compounds. The ¹⁴C and the d/l signature revealed a longer turnover of proteinous components strongly bound to minerals (not NaOH-NaF-extractable). This study provides evidence that interactions with minerals are important in the transformation and stabilization of soil ON. Mineral-associated ON in topsoils seems actively involved in the N cycling of the study ecosystems, accentuating N limitation at the 0.3-kyr site but increasing N availability at older sites.     

Association of specific organic matter compounds in size fractions of soils under different environmental controls

Inherent chemical recalcitrance and association of organic matter (OM) with minerals are mechanisms responsible for the long term preservation of OM in soils. The structural characteristics of OM are also believed to control specific interactions between OM and soil minerals. However, the extent of the relationship between recalcitrance and mineral protection and the specificity of these chemically driven interactions are not clearly understood at the molecular level. To measure chemical patterns of OM sequestration in sand-, silt-, clay-size and light fractions, we analyzed three soils, which mainly differed in carbon content and overlying vegetation, but have similar clay mineralogy, using biomarker analysis and nuclear magnetic resonance (NMR). Despite differences in environmental controls, long chain aliphatic compounds generally accumulated in the fine fractions of all soils. This accumulation is likely due to the strong interaction between recalcitrant forms of OM and soil minerals. For example, polymethylene and >C₂₀ organic acids accumulated in fine fractions, while lignin-derived phenols were protected from oxidation in silt-size fractions. Diffusion edited solution state ¹H NMR suggested that contributions from microbial-derived OM was greater in finer fractions, which is likely due to the accumulation of microbial-derived compounds or higher microbial activity in clay micro-sites. Our data suggest that, for these Prairie soils, the specific structure of OM and not environmental factors is responsible for long term preservation of OM in mineral fractions. Further research is necessary to understand the interplay between these preservation mechanisms such that the long term fate of OM can be further elucidated.     

Microstructure Evolution of Organic Matter and Clay Minerals in Shales with Increasing Thermal Maturity

As the two important components of shale, organic matter(OM) and clay minerals are usually thought to strongly influence the hydrocarbon generation, enrichment and exploitation. The evolution process of OM and clay minerals as well as their interrelationship over a wide range of thermal maturities are not completely clear. Taking Yanchang(T_3y), Longmaxi(S_1l) and Niutitang(?_1n) shales as examples, we have studied the microstructure characteristics of OM and clay minerals in shales with different thermal maturities. The effects of clay minerals and OM on pores were reinforced through sedimentation experiments. Using a combination of field emission scanning electron microscopy(FESEM) and low-pressure N_2 adsorption, we investigated the microstructure differences among the three shales. The results showed that both OM and clay minerals have strong effects on pores, and small mesopore(2–20 nm) is the dominant pore component for all three samples. However, the differences between the three samples are embodied in the distribution of pore size and the location. For the T_3y shale, clay minerals are loosely arranged and develop large amounts of pores, and fine OM grains often fill in intergranular minerals or fractures. Widespread OM pores distribute irregularly in S_1l shale, and most of the pores are elliptical and nondirectional. The ?_1n shale is characterized by the preferred orientational OM-clay aggregates, and lots of pores in the composites are in the mesopore range, suggesting that over maturity lead to the collapse and compaction of pores under huge pressure of strata. The results of the current research imply that with increasing thermal maturity, OM pores are absent at low maturity(T_3y), are maximized at high maturity(S_1l) and are destroyed or compacted at over-mature stage(?_1n). Meanwhile, clay minerals have gone through mineral transformation and orientational evolution. The interaction of the two processes makes a significant difference to the microstructure evolution of OM and clay minerals in shale, and the findings provide scientific foundation in better understanding diagenetic evolution and hydrocarbon generation of shale.     

Organic carbon distribution, speciation, and elemental correlations within soil microaggregates: Applications of STXM and NEXAFS spectroscopy

Soils contain the largest inventory of organic carbon on the Earth’s surface. Therefore, it is important to understand how soil organic carbon (SOC) is distributed in soils. This study directly measured SOC distributions within soil microaggregates and its associations with major soil elements from three soil groups (Phaeozem, Cambisol, and Ultisol), using scanning transmission X-ray microscopy (STXM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at a spatial resolution of 30 nm. Unlike previous studies, small intact soil microaggregates were examined directly in order to avoid preparatory procedures that might alter C speciation. We found that SOC exists as distinct particles (10s to 100s of nm) and as ubiquitous thin coatings on clay minerals and iron-oxides coatings. The distinct SOC particles have higher fractions of aromatic C than the coatings. NEXAFS spectra of the C coatings within individual microaggregates were relatively similar. In the Phaeozem soil, the pervasive spectral features were those of phenolic and carboxylic C, while in the Cambisol soil the most common spectral feature was the carboxyl peak. The Ultisol soil displayed a diffuse distribution of aromatic, phenolic, and carboxylic C peaks over all surfaces. In general, a wide range of C functional groups coexist within individual microaggregates. In this work we were able to, for the first time, directly quantify the major mineral elemental (Si, Al, Ca, Fe, K, Ti) compositions simultaneously with C distribution and speciation at the nm to μm scale. These direct microscale measurements will help improve understanding on SOC-mineral associations in soil environments.     

Physical protection of lignin by organic matter and clay minerals from chemical oxidation

The role of organic matter (OM) concentration, structure and composition and how these relate to mineral protection is important for the understanding of long term soil OM dynamics. Various OM–clay complexes were constructed by sequential sorption of lignin and dodecanoic acid to montmorillonite. Humic acid–montmorillonite complexes were prepared at pH 4 and 7 to vary OM conformation prior to sorption. Results obtained with constructed OM–clay complexes were tested with isolated mineral fractions from two soils. Oxidation with an acidic NaClO₂ solution was used to chemically oxidize lignin in the OM–clay complexes, sand-, silt- and clay-size soil fractions to test whether or not it can be protected from chemical attack. Gas chromatography–mass spectrometry was used to analyze lignin-derived phenols, cutin OH–acid (after CuO oxidation), fatty acid and n-alkanol concentrations and composition. We found that carbon content was not solely responsible for lignin stability against chemical oxidation. Lignin was protected from chemical oxidation through coating with dodecanoic acid and sorption of humic acid to clay minerals in a stretched conformation at pH 7. Therefore, interactions between OM constituents as well as OM conformation are important factors that protect lignin from chemical oxidation. Lignin-derived phenol dimers in the Grassland-Forest Transition soil fractions were protected from chemical oxidation to a greater extent compared to those in Grassland soil fractions. Therefore, although lignin was protected from degradation through mineral association, the extent of this protection was also related to OM content and the specific stability of lignin components.     

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N₂ at 77 K and CO₂ at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N₂ pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl₂-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r² > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.     

Biodegradation of forest floor organic matter bound to minerals via different binding mechanisms

Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca²⁺ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca²⁺ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca²⁺ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca²⁺ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.     

微团聚体分析在工程地质研究中的应用

微团聚体是天然粘性土的基本结构单元, 微团聚体的组成、水稳性和强度是粘性土工程性质形成的重要原因。本文通过对黄土与海相软土这两种典型的粘性土颗粒分析与微团聚体分析结果的对比, 研究了水稳性与非水稳性微团聚体的形成原因, 并在此基础上探讨它们的工程特性的形成。     

Linking lithology and land use to sources of dissolved and particulate organic matter in headwaters of a temperate, passive-margin river system

A number of rivers have been found to transport highly aged organic matter [OM]; however, the sources of this aged material remain a matter of debate. One potential source may be erosion and weathering of headwater lithologies rich in ancient sedimentary OM. In this study, waters, suspended particulates, streambed sediments, rocks and soils from fourteen small headwater watersheds of a mid-size, temperate, passive margin river were sampled and characterized by Δ¹⁴C, δ¹³C, and POC/TPN ratios to identify sources of particulate and dissolved OM delivered to the river mainstem. These headwater sites encompass a range in lithology (OM-rich shales, OM-lean carbonate/mudstone facies, and OM-free crystalline rocks) and land use types (forested and agricultural), and allow investigation of the influence of agriculture and bedrock types on stream OM characteristics. Streams draining large areas of both agricultural land use and OM-rich lithology contain particulate OM [POM] that is more ¹⁴C-depleted than streams draining forested, shale-free watersheds. However, this is not sufficient to account for the significantly lower Δ¹⁴C-POC measured in the river mainstem. Dissolved OM [DOM] Δ¹⁴C are in all cases enriched compared to POM from the same stream, but are otherwise highly variable and unrelated to either land use or lithology. POC/TPN ratios were likewise highly variable. POC and DOC δ¹³C signatures were similar across all watersheds. Based on isotope mass balance, ¹⁴C-free fossil OM sources contribute 0-12% of total stream POM. Although these results do not unequivocally separate the influences of land use and lithology, watershed coverage by shale and agriculture are both important controls on stream Δ¹⁴C-POC. Thus export of aged, particle-associated OM may be a feature of river systems along both passive and active continental margins.     

Pore structure and heterogeneity of shale gas reservoirs and its effect on gas storage capacity in the Qiongzhusi Formation

Fine characterization of pore systems and heterogeneity of shale reservoirs are significant contents of shale gas reservoir physical property research.The research on micro-control factors of low productivity in the Qiongzhusi Formation(Fm.)is still controversial.The lower Cambrian Qiongzhusi Fm.in the Qujing,Yunnan was taken as the object to investigate the influence of mineral compositions on the phys-ical properties of the reservoir and the heterogeneity of shale,using the algorithm to improve the char-acterization ability of Atomic Force Microscopy(AFM).The results showed that:(1)The pores are mainly wedge-shaped pores and V-shaped pores.The pore diameter of the main pore segment ranges from 5 to 10 nm.Mesopores are mainly developed in the Qiongzhusi Fm.shale in Well QD1,with the average pore diameter of 6.08 nm.(2)Microscopic pore structure and shale surface properties show strong hetero-geneity,which complicates the micro-migration of shale gas and increases the difficulty of identifying high-quality reservoirs.(3)The increase of clay mineral content intensifies the compaction and then destroys the pores.Conversely,brittle minerals can protect pores.The support and protection of brittle minerals to pores space depend on their content,mechanical properties and diagenesis.(4)Compression damage to pores,large microscopic roughness and surface fluctuations and strong pore structure heterogeneity are the reasons for the poor gas storage capacity of the Qiongzhusi Fm.,which will lead to poor productivity in the Qiongzhusi Fm.     

Direct visualization of clay microfabric signatures driving organic matter preservation in fine-grained sediment

We employed direct visualization of organic matter (OM) sequestered by microfabric signatures in organo-clay systems to study mechanisms of OM protection. We studied polysaccharides, an abundant class of OM in marine sediments, associated with the nano- and microfabric of clay sediment using a novel application of transmission electron microscopy, histochemical staining (periodic acid-thiosemicarbazide-silver proteinate), and enzymatic digestion techniques. We used two experimental organo-clay sediment environments. First, laboratory-consolidated sediment with 10% chitin (w/w) added was probed for chitin before and after digestion with chitinase. Second, fecal pellets from the polychaete Heteromastus filiformis were used as a natural environment rich in clay and polysaccharides. Sections of this material were probed with silver proteinate for polysaccharides before and after digestion with a mixture of enzymes (amylase, cellulase, chitinase, dextranase, and pectinase). In both environments, chitin or other polysaccharides were found within pores, bridging clay domains, and attached to clay surfaces in undigested samples. Digested samples showed chitin or polysaccharides more closely associated with clay surfaces and in small pores. Our results imply protective roles for both sorption to clay surfaces and encapsulation within clay microfabric signatures.     

应用氩离子抛光-扫描电镜方法研究四川九老洞组页岩微观孔隙特征

微观孔隙结构是页岩储层研究的重点,而扫描电镜方法无法识别机械抛光中由于页岩硬度差异所造成的不规则形貌。本文利用氩离子抛光-扫描电镜方法对四川威远区块九老洞组页岩进行研究,发现了三种孔隙类型:1无机孔以粒间孔和黏土矿物层间孔为主,同时发育晶间孔和生物孔,孔径主体100~500 nm;2有机孔受控于热成熟度或有机黏土复合体,孔径范围数十纳米至数微米;3微裂缝包括成岩收缩裂缝、高压碎裂缝、构造裂缝和人为裂缝,缝宽数微米,缝长数微米至数十微米。研究表明无机孔和微裂缝是九老洞组页岩气的主要储集空间。     

Pore structure and adsorption behavior of shale gas reservoir with influence of maturity: a case study of Lower Silurian Longmaxi formation in China

Knowledge of pore structure and adsorption capacity provides guidance for better studying the origin, hydrocarbon distribution, and productivity of shale gas reservoir. In this study, pore structure characteristics of six shale core plugs with different maturity from the Lower Silurian Longmaxi formation in south China were investigated using the Rock-eval analysis, X-ray diffraction, total organic carbon (TOC) content test, and scanning electron microscope (SEM) observation. To further investigate the influence of maturity, the adsorption behavior of gas shale was experimentally measured, with the maximal pressure being 20 MPa. Rock-eval analysis indicates that Ro is 0.67~1.34%. SEM results show that organic matter (OM) pores are abundant in high-maturity shale sample. The OM pores are mainly irregular to elliptical in shape, the size is 8~100 nm. The TOC content is 0.16~4.21% and shows a positive correlation with the BET surface area. A negative relationship exists between TOC content and average pore diameter, which indicates that abundant nanometer pores are related to the OM. A noticeable characteristic in the pore size distribution curve is that the content of micropores (pore width <?2 nm) increases with the increasing TOC content. Additionally, the thermal maturity results in significant difference in methane adsorption capacity. Maximal adsorption capacity of shale samples is also lineally correlated with TOC content, which increases with maturity. This study provides a quantitative understanding of how maturity affects pore structure and adsorption behavior of shale gas reservoir.     

基于压汞法的冻融循环对土体孔隙特征影响的试验研究

冻融循环会改变土的微观结构, 孔隙特征的变化是其结构性发生改变的重要体现. 以青藏铁路沿线粉质黏土为研究对象, 借助压汞技术对不同冻融次数下重塑土样的孔隙特征进行了研究. 结果表明:土体孔隙特征分布曲线表现出明显的双峰特征, 据此可将土样的孔隙分为大孔和小孔两大类; 冻融循环次数对小孔隙的影响较小, 小孔隙直径和体积基本保持不变; 冻融循环次数对大孔隙的影响较大, 特别是孔径为20～40 μm的孔隙, 其直径和体积均随冻融次数的增加而增大. 试样的孔隙率随冻融次数的增加并无明显规律, 但总体的变化趋势是先增大后减小. 由孔隙分形维数计算结果可知, 冻融循环在改变土体孔隙结构的同时, 使孔隙内壁的粗糙程度及孔隙结构的复杂程度降低.     

页岩组分对五峰-龙马溪组与牛蹄塘组页岩孔隙发育差异的影响——以渝东南焦页1井与湘西北慈页1井为例

根据页岩样品不同孔径范围的累计孔体积与累计比表面积,结合焦页1井五峰-龙马溪组与慈页1井牛蹄塘组页岩样品的地球化学参数与岩样各矿物组分百分含量,分析页岩组分对两套地层孔隙发育差异的影响.结果显示,TOC与微孔呈正相关关系,表明有机质微孔对页岩孔隙发育提供了一定的贡献,五峰-龙马溪组页岩较牛蹄塘组更为发育有机质微孔.石英...     

泥页岩有机质孔隙差异特征及影响因素分析 ——以我国典型海相、陆相、过渡相储层为例

泥页岩中有机质孔隙是有机质向烃类转化的产物,也是烃类重要的纳米级赋存空间。以我国不同沉积相泥页岩（鄂尔多斯盆地延长组、四川盆地东南缘龙马溪组和牛蹄塘组、南华北盆地山西组）为研究对象,通过有机地球化学和微区分析等手段对有机质孔隙发育特征及影响因素进行了精细表征和深入探讨。结果表明:TOC与孔隙参数的相关性随热成熟度的增加展现出规律性变化,表明热演化是有机质孔隙发育的主要驱动因素。除热成熟度外,四组样品中有机质孔隙的发育特征受多种因素影响:延长组有机质孔隙处于形成阶段,多数有机质不发育孔隙,孔隙的形成主要受有机质类型和显微组分的影响。龙马溪组有机质孔隙普遍发育,为孔隙发育的高峰阶段,有机—无机相互作用制约着孔隙的结构和形貌特征。牛蹄塘组因排烃作用较为完全而处于孔隙收缩阶段,已有较多有机质孔隙被压实而消失,孔隙形态主要受控于微裂隙和有机质—黏土复合体的发育情况。山西组因过高的热演化程度引起有机质结构塌陷,且保存条件极差,处于孔隙的转化和消失阶段;有机质孔隙的发育情况与有机质类型和内部结构直接相关,并受保存条件的严重影响。相关结论有助于深刻理解页岩油气资源赋存富集机理,促进页岩油气资源的勘探开发。     

基于聚焦离子束-扫描电镜方法研究页岩有机孔三维结构

页岩中纳米级有机孔的大小直接影响页岩气含气量,其连通性亦对气体运移和开采至关重要。本文选择漆辽地区龙马溪组富有机质页岩,利用聚焦离子束-扫描电镜(FIB-SEM)在纳米尺度上(10 nm)进行有机孔结构的三维重构。研究结果表明:(1)FIB-SEM方法适用于微米级页岩的纳米(3 nm)孔隙结构特征研究。(2)蜂窝状有机孔发育均匀,孔径集中于10~200 nm,连通性较差;界面有机孔孔径集中于200~300 nm,局部连通性较好。(3)页岩总孔隙度与有机质含量成正比。研究认为,对于以有机孔为重要储集空间的页岩,有机质分布越集中,连续性越好,研究孔隙度的表征单元体尺度越小。     

阿尔及利亚X区块泥盆系Siegenian组储层微观特征及成岩作用对其影响

通过岩石薄片、铸体薄片、扫描电镜、压汞分析及粘土矿物X衍射分析等资料,从储层的岩性、成岩作用、孔隙类型及影响孔隙结构的因素方面,对阿尔及利亚三叠盆地泥盆系Siegenian组储层的微观特征及成岩作用对其影响进行了研究。研究结果表明,该储层以石英细砂岩、粉砂岩为主,成分成熟度高。储集空间主要有原生粒间孔、粒内溶孔、粒间溶孔、铸模孔、胶结物内溶孔及构造裂缝6种,主要以次生溶蚀孔隙为主,且首次在研究区发现了石英溶蚀孔,并研究了碱性流体的来源。孔隙结构以细孔、细喉-微喉型为主,少量中孔细喉型和微孔微喉型。成岩作用类型多样,在区内发现了碱性溶蚀作用。成岩作用对储层发育具有重要的影响,压实、胶结作用是导致孔隙度和渗透率降低的主要因素,溶蚀作用是区内储层改善的最重要的成岩作用类型。X区块勘探程度低,明确其储层微观特征有利于X区块的进一步勘探开发。