Characteristics and distribution of clay minerals and their effects on reservoir quality: Huagang Formation in the Xihu Sag,East China Sea Basin

Abstract

The characteristics and distribution of clay minerals and their effects on reservoir quality in the Huagang sandstones in the Xihu Sag, East China Sea Basin were studied by using X-ray diffraction, casting thin-sections, scanning electron microscopy, electron microprobe analysis, fluid inclusion analysis, constant-rate mercury injection and nuclear magnetic resonance. Clay minerals consist of kaolinite, chlorite, illite and illite–smectite mixed layer (I/S); kaolinite forms from dissolved feldspars, chlorite occurs as clay coatings that are transformed from clay precursors owing to the flocculation of suspended detrital clays or the crystallisation of pore fluids, and illite forms from the illitisation of detrital smectite, authigenic kaolinite and K-feldspars. Clay distribution is controlled by sedimentary environments, burial history and lithologies. Typical reservoirs in the western sub-sag are thin and developed in braided river facies at relatively shallow burial depths with clays dominated by kaolinite. However, typical reservoirs in the central inversion tectonic zone are thicker and developed in a braided delta front facies at deeper burial depths with clays mainly consisting of chlorite, illite and I/S. High-quality reservoirs are characterised by coarse granularity, high quartz content and low clay content with widespread development of chlorite coatings that inhibit quartz cements at low temperatures. At higher temperatures, the high-quality reservoirs develop more pores providing growth space for quartz cements and result in the coexistence of chlorite coatings and quartz cements. The high-quality reservoirs are controlled by their lithological characteristics rather than chlorite coatings. Illite and I/S clays create severe damage to reservoirs by reducing the size and connectivity of pore-throats.     

鄂尔多斯盆地东部太原组碎屑岩中自生伊利石形成机制及其对储层形成的影响

鄂尔多斯盆地东部太原组砂岩骨架颗粒中几乎没有碎屑长石,残余的微量长石(在岩石中的平均含量为0.4%.低于X射线衍射检测限)主要为钾长石,同时具有较低的自生高岭石含量(1.02%)、很低的自生石英含量和同期火山物质含量,以及较高的自生伊利石含量(1.22%),这表明太原组的自生伊利石主要是在相对高温的深埋藏封闭条件下,通过钾长石溶解反应:钾长石+H~++H_2O→高岭石+硅质+K~+和高岭石伊利石化反应:高岭石+K~+→伊利石+H~++H_2O或其加和反应:钾长石+高岭石→硅质+伊利石+H_2O形成,后者通过消耗钾离子而克服钾长石溶解的动力学屏障,是前者的重要驱动反应,并向流体输出氢离子,因此对次生孔隙的形成、尤其是在相对深埋藏的成岩过程中与钾长石溶解有关的次生孔隙的形成具有显著的积极作用.     

Microstructures and compositional variation in the intravolcanic bole clays from the eastern Deccan volcanic province: Palaeoenvironmental implications and duration of volcanism

Clay minerals associated with intra-volcanic bole horizons of varied colours and thicknesses contain montmorillonite, halloysite and kaolinite, show distinct microstructures and microaggregates. In kaolinite, Fe³⁺ ions substitute for Al³⁺ at octahedral sites. Most of these clays are dioctahedral type, show balance between net layer and interlayer charges. The interstratified illite — smectite (I/S) mixed layers containing variable proportions of montmorillonite. Illite contains sheet-like, well oriented microaggregates. The parallel stacks of chlorite sheets show chlorite/smectite (C/S) mixed layers. Progressive enrichment of Fe and depletion of Al ions with the advancement of kaolinization process is observed. High order of structural and compositional maturity observed in these bole clays, indicate long hiatus between the two volcanic episodes.     

Volcanic Activity, Hydrothermal Alteration and Epithermal Gold-Silver Mineralization in the Ryuo Mine Area in the Kitami Metallogenic Province, Hokkaido, Japan

Abstract: Characterization of Neogene magmatism in the Ryuo mine area in the Kitami metallogenic province was carried out on the basis of K-Ar data for felsic–to–mafic terrestrial extrusive and intrusive volcanism from Late Miocene to Early Pliocene. The Ryuo epithermal gold-silver deposit occurs primarily in the felsic volcaniclastic rocks of the Ikutahara Formation and in Ryuo Rhyolite. The Ryuo mineralization age of 7. 7 – 8. 1 Ma coincides well with the hydrothermal alteration age (7. 7 Ma) of Ryuo Rhyolite hosting ore veins. It is concluded that the Ryuo mineralization was essentially accompanied by felsic volcanic activity during the sedimentation of the Ikutahara Formation, and was closely related both temporally and spatially to the intrusive activity of Ryuo Rhyolite. Hydrothermal alteration related to the epithermal gold-silver mineralization of the Ryuo deposit is primarily characterized by early regional and vein-related alterations, and late steam-heated alteration. Early regional alteration consists of a smectite halo (smectite+pyrite±quartz±opal–CT±mordenite°Clinoptilolite–heulandite series mineral). Early vein-related alteration is primarily marked by potassic alteration. This alteration halo can be subdivided into a K-feldspar halo (quartz+adular–ia+pyrite±illite±interstratified illite/smectite±smectite), an illite halo (quartz+illite + chlorite + pyrite ± interstratified illite/smec–tite±smectite) and an interstratified illite/smectite halo (quartz + interstratified illite/smectite+pyrite±smectite). Late steam-heated alteration characterized by kaolinite or alunite locally overprints the early K-feldspar halo. The style of the Ryuo gold-silver deposit is a low-sulfidation epithermal type. The gold–silver–bearing quartz vein precipitates during boiling of ore fluid. The origin of the ore fluid might be meteoric water. The temperature and sulfur fugacity conditions during precipitation of electrum and acanthite are estimated to be 206°– 238°C and 10^-13.5 – 10^-11.6 atm, respectively.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.     

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks,Bowen Basin,Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite–smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R≥3) illite–smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)_sn ratios show negative correlations with the illite content in illite–smectite and positive correlations with the δ¹⁸O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)_sn ratios and illite content in illite–smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/rock ratio conditions. Increasing HREE enrichment with δ¹⁸O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin.Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins.     

Clay mineralogy and geochemistry and their palaeoclimatic interpretation of the Pleistocene deposits in the Xuancheng section,southern China

A red soil profile in Xuancheng, Anhui province, southern China, in the middle to lower reaches of the Yangtze River, was investigated using X‐ray diffraction, X‐ray fluorescence spectrometer, and scanning electron microscopy. The mobile components K₂O and Na₂O and trace elements Ba and Sr of the Xuancheng section exhibit a general trend of decrease downward along the red soil profile, together with an increase downward of chemical index of alteration (CIA) values, suggesting more intense depletion in the lower portion than in the upper portion. The major components SiO₂, Al₂O₃ and Fe₂O₃, as well as SiO₂/Al₂O₃, SiO₂/Fe₂O₃ and Al₂O₃/Fe₂O₃ ratios, show notable fluctuations along the soil profile, indicating intense climatic oscillations in the area during the Pleistocene age. The clay mineral assemblage of the Xuancheng section can be generally subdivided into three groups, suggesting a general trend of three stages of climate changes. The lower portion of ～10.4–6.3 m depth has a lower illite content and higher abundance of kaolinite and illite–smectite (I/S) clays, indicating that a warm and wet climate prevailed over the episode of ca. 600–350 ka BP. A decrease in abundance of kaolinite and I/S clays and increase in illite content at a depth of ～6.3–2.2 m probably indicate a transition stage of climate change from warm/humid to cool/dry in the period ca. 350–80 ka BP. The higher illite content and lower abundance of kaolinite and I/S clays in the upper portion of ～2.2–0 m depth suggest that a relatively cool and dry climate dominated since ca. 80 ka BP. Based on changes in clay mineralogy and chemical indices of the sediments, seven warm/cold fluctuations were determined in the area since the Middle Pleistocene. Climate changes documented in the Xuancheng section are in agreement with the δ¹⁸O records of sediments from the equatorial Pacific Core V28‐238 and the loess–palaeosol sequences in the Loess Plateau of northwestern China. Correlated to the episode of S4 and S5 soil units in the Loess Plateau, the period of ca. 600–350 ka BP in the Xuancheng area was dominated by the particularly strong East Asia summer monsoon, as indicated by its most abundant kaolinite and I/S clays. Fluctuations in clay mineralogy along the Xuancheng soil profile were mainly controlled by both the East Asia summer and winter monsoons in response to the global changes in the Middle–Late Pleistocene. Copyright © 2009 John Wiley & Sons, Ltd.     

Geochemical and mineralogical impacts of H2SO4 on clays between pH 5.0 and −3.0

Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H₂SO₄ leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H₂SO₄ on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H₂SO₄ solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H₂SO₄ on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed.     

The Effects of Diagenesis on the Reservoir Characters in Ridge sandstone of Jurassic Jumara dome,Kachchh, Western India

Ridge sandstone of Jurassic Jumara dome of Kachchh was studied in an attempt to quantify the effects of diagenetic process such as compaction, cementation and dissolution on reservoir properties. The average framework composition of Ridge sandstone is Q₈₀F₁₇L₃, medium-to coarse grained and subarkose to arkose. Syndepositional silty to clayey matrix (3% average) is also observed that occurs as pore filling. The diagenetic processes include compaction, cementation and precipitation of authigenic cements, dissolution of unstable grains and grain replacement and development of secondary porosity. The major cause of intense reduction in primary porosity of Ridge sandstone is early cementation which include silica, carbonate, iron, kaolinite, illite, smectite, mixed layer illite-smectite and chlorite, which prevents mechanical compaction. The plots of COPL versus CEPL and IGV versus total cement suggest the loss of primary porosity in Ridge sandstone is due to cementation. Cements mainly iron and carbonate occurs in intergranular pores of detrital grains and destroys porosity. The clay mineral occurs as pore filling and pore lining and deteriorates the porosity and permeability of the Ridge sandstone. The reservoir quality of the studied sandstone is reduced by clay minerals (kaolinite, illite, smectite, mixed layer illitesmectite, chlorite), carbonate, iron and silica cementation but on the other hand, it is increased by alteration and dissolution of the unstable grain, in addition to partial dissolution of carbonate cements. The potential of the studied sandstone to serve as a reservoir is strongly related to sandstone diagenesis.     

Kaolin deposits in the lower cretaceous Baqueró formation (Santa Cruz Province, Patagonia, Argentina)

Sedimentary kaolin deposits in the Lote 18 area (Santa Cruz Province, Patagonia, Argentina) have been mined since 1951. They constitute 30% of the country's production and are mainly used in the ceramic whiteware industry. The deposits belong to the Baqueró Formation (Lower Cretaceous) and unconfomably overlie either the ash-flow tuffs of the Chon-Aike Formation (Middle Jurassic), which are altered to kaolinite and minor illite, or the ash-fall tuffs of Bajo Grande Formation (Upper Jurassic-Lower Cretaceous), which are altered mainly to smectites. The presence of illite or smectite, as well as the kaolinite crystallinity, depends on the stratigraphic position of the kaolin horizons within the Lower Member of the Baqueró Formation and on the lithology of the underlying rocks. Kaolin beds composed of well-crystallized kaolinite at the base of the sequence overlaying Chon-Aike rocks are the purest. Kaolinite becomes less well cystallized with transport. Edge-to-face and swirl SEM textural patterns indicate the compaction of flocculated clays and clay movement during drainage and compaction. Mineralogical, petrological, and physico-structural evidence (i.e., form, extent, thickness) indicates that the kaolin deposits are sedimentary, formed by the transportation and deposition of previously formed kaolinite. Kaolin beds are ovoidal in plan and lenticular in profile, with thickness ranging from centimeters to 11 meters, and the culmination of fining-upward clastic sequences. Sedimentary facies analysis indicates that the kaolin deposits were formed in a fluvial environment from currents with a high suspended-load/bed-load ratio, as would result from deposition in ox-bow lakes.     

Geochemistry of the Hepworth Carboniferous sediment sequence and origin of the diagenetic iron minerals and concretions

The major element geochemistry of a mudstone sequence of Westphalian age has been studied in detail and mineralogical distributions calculated. Quartz and zircon trends indicate the energy of the depositional environment and this is closely reflected in the clay mineralogical composition. Of the detrital clays kaolinite is concentrated in the finer-grained sediments relative to illite. Chlorite and interstratified illite-smectite probably underwent diagenetic modification and small amounts of authigenic clays may have formed.Siderite, which occurs in both concretionary and disseminated form, and pyrite developed during diagenesis under reducing conditions and account for most of the iron present. Pyrite grew first deriving its iron partly from detrital clays. Carbon isotopic evidence suggests that early siderite precipitated in pore space as nodules and later in dispersed form. A second concretionary phase, pistomesite, grew during late dewatering. Siderite iron was derived mainly from Mn-rich oxidate phases.Titanium occurs as anatase uniformly distributed through the sequence. Phosphorus is mainly in diagenetic apatite and the $\text{sodium}\text{potassium}$ ratio is controlled by the micas. Adsorbed water is closely related to grain size and clay content.     

Relationships between Volcanism, Hydrothermal Alteration and Epithermal Gold-Silver Mineralization in the Muka Mine Area in the Kitami Metallogenic Province, Hokkaido, Japan

Abstract: Neogene magmatism in the Muka mine area in the Kitami metallogenic province was characterized on the basis of K-Ar age data by felsic–to–mafic terrestrial extrusive and intrusive volcanism from Late Miocene to Early Pliocene. The geology of the Muka mine area comprises the Upper Cretaceous-Paleocene Yubetsu Group, consisting primarily of sandstone and shale; Upper Miocene Ikutahara Formation, consisting of clastic and felsic volcaniclastic rocks and Kane-hana Lava (rhyolite) of 7. 5 Ma; Upper Miocene Yahagi Formation, consisting of clastics, felsic volcaniclastics and rhyolite lavas; Late Miocene andesite and rhyolite dikes (Chidanosawa Rhyolite of 7. 2 Ma and Hon-Mukagawa Andesite of 6. 6 Ma); Lower Pliocene Hakugindai Lava (basalt: 4. 0 Ma); and Quaternary System. The volcanism consists of earlier Late Miocene felsic extrusive activity during the sedimentation of the Ikutahara Formation, later Late Miocene felsic extrusive and intrusive activities during the sedimentation of the Yahagi Formation and intermediate intrusive activity after the sedimentation of the Yahagi Formation and Early Pliocene mafic extrusive activity. The Muka gold-silver ore deposit occurs primarily in the felsic volcaniclastic rocks and Kanehana Lava of the Ikutahara Formation and in Hon-Mukagawa Andesite. These wall–rocks, the clastic rocks of the Ikutahara Formation and the clastic and felsic volcaniclastic rocks of the Yahagi Formation were affected to various extents by hydrothermal alteration. The hydrother-mal alteration can be divided into two stages (early and late) based on the modes of occurrence and mineral assemblages. Early hydrothermal alteration is characterized by regional and vein-related alterations associated with epithermal gold-silver mineralization in a near-neutral hydrothermal system. Regional alteration can be subdivided into a zeolite zone (mordenite+adularia±heulandite–clinoptilolite series mineral±smectite±quartz°Cristobalite±opal–CT) and a smectite zone (smec–tite±quartz±opal–CT). Vein-related alteration can be subdivided into a K-feldspar zone (quartz+adularia±illite±interstratified illite/smectite±pyrite), an illite zone (quartz+illite°Chlorite±interstratified illite/smectite±smectite±pyrite) and an interstratified illite/smectite zone (quartz+interstratified illite/smectite±smectite±pyrite). The adularization age of 6. 8 Ma in the K-feldspar zone that developed in Kanehana Lava hosting ore veins coincides well with the epithermal gold-silver mineralization age of 6. 6 Ma. Late hydrothermal alteration is characterized by a kaolinite zone (kaolinite±dickite±alunite±quartz°Cristobalite± tridymite±pyrite) in an acid hydrothermal system, and cuts early alteration zones such as the K-feldspar zone. Other modes of occurrence of acid alteration are a 7Å halloysite-kaolinite vein in the hydrothermal explosion breccia dike and smectite–kaoli–nite veins along joint planes of Kanehana Lava. The style of the gold-silver deposit associated with early near-neutral hydrothermal alteration is a low-sulfidation epithermal type. The low-sulfidation epithermal gold-silver mineralization of 6. 6 Ma in the vicinity of the Muka ore deposit was essentially accompanied by felsic volcanic activity during the sedimentation of the Yahagi Formation, and was closely related both temporally and spatially to the felsic intrusive activity of Chidanosawa Rhyolite of 7. 2 Ma. The related hydrother-mal activity of the gold-silver mineralization took place at intervals of approximately 0. 4–0. 6 Ma after the volcanic activity related to the mineralization.     

Diagenesis of clay minerals and K-bentonites in Late Permian/Early Triassic sediments of the Sichuan Basin (Chaotian section,Central China)

Detailed clay mineralogical analyses were carried out on Late Permian/Early Triassic carbonate sediments exposed on the Chaotian section (Sichuan Basin, Central China). The clay assemblages are dominantly composed of illite in platform carbonates and clay seams, and illite–smectite mixed-layers (I/S) in tuff layers (K-bentonites) intercalated in the carbonate succession. Detrital and authigenic volcanogenic clay minerals have been partially replaced through illitisation processes during burial, raising questions about diagenetic effects. The precise determination of I/S occurring in K-bentonites shows that the sediments reached a temperature of about 180 °C, which is consistent with (1) previous estimates based on fluid-inclusion homogenisation temperature analysis, (2) the burial depth of the sedimentary series deduced from the post-Palaeozoic geological history of the Sichuan Basin and (3) the new data (T_max) obtained on organic matter indicating the transition between oil and gas windows. The Wangpo Bed, located close to the Guadalupian–Lopingian Boundary, is interpreted either as a volcanic acidic tuff or as a clastic horizon. This controversial origin probably results from mixed volcanogenic and detrital influences. The Wangpo Bed is therefore interpreted as a reworked bentonite as revealed by the occurrence of I/S similar to those found in tuff layers, together with preserved detrital kaolinite.     

Clay record of climate change since the mid‐Pleistocene in Jiujiang,south China

To obtain a better understanding of climate change in south China in the Quaternary, a clay mineralogical study was undertaken on the red earth profile at Jiujiang, using X‐ray diffraction (XRD) and particle‐size distribution analysis methods. The XRD results showed that the clay minerals of the Jiujiang red earth were mainly mixed‐layer illite–smectite (I/S), illite, kaolinite and vermiculite, with trace amounts of mixed‐layer kaolinite–smectite (K/S). Changes in clay mineral composition displayed a trend of three‐stage evolution. The higher mixed‐layer I/S clays and kaolinite contents in the lower portion suggest extremely warm and humid climates over the period c. 700 to c. 350 ka ago. A gradual decrease in I/S clays and kaolinite reveals a gradual climate change from warm/humid to cool/dry during the period c. 350 to c. 130 ka ago. The higher illite and vermiculite contents indicate a relatively cool and dry climate during the period since c. 130 ka ago. The particle‐size distribution pattern of the upper section was similar to that of the Xiashu loess, while that of the middle to lower section was similar to those of fluvially reworked red earth. A rapid increase in the abundance of large grain‐size components at 2.6 m depth indicates an intensification of the winter monsoon and a cool and dry climate during the period, in good agreement with results from the clay mineral composition and homogeneous structure. The red earth sequences in south China could probably be used to test the response of tropical to subtropical regions to global climate changes.     

Influence of tectonics and palaeoenvironment on late cretaceous clay sedimentation in the upper benue trough,Nigeria

The Late Cretaceous sedimentary sequence in the Upper Benue Trough consists of seven formations. Outcrop samples from the type localities of these units were analysed by X-ray diffraction for their day mineral content. The composition and distribution of the clay minerals are influenced by tectonics, relief and water depth. Three main depositional phases are recognizable on the basis of clay mineral assemblages, two of which are associated with tectonic movements. The first phase, characterized by the presence of chlorite, illite, kaolinite and mixed-layer clays is common to Albian-Cenomanian sediments. This phase is succeeded by mixed-layer clays and smectite-rich, Turonian-Early Santonian sediments. The re-occurrence of chlorite and illite in association with kaolinite and mixed-layer clays in the Post-Santonian sediments constitutes the third depositional phase. These clay mineral assemblages are indicative of two periods of tectonism (Albian and Late Santonian) and an intervening Turonian-Early Santonian period of quiescence in the Upper Benue Trough.     

Dissolved Al in sediments and waters of the East China Sea: Implications for authigenic mineral formation

Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H⁺ relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX_0.91Mg_0.77Al_5.0Si_2.7O₁₀(OH)₈ (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution—reprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H⁺ activity in the surrounding environment.     

Clay mineralogy, organic carbon burial, and redox evolution in Proterozoic oceans

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1M_d illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M₁ illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian-Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.     

安徽庐枞盆地酸性蚀变岩帽地质地球化学特征研究

酸性蚀变岩帽是浅成低温热液系统演化的产物,形成于酸性高氧化性流体的化学条件下;在高硫化型浅成低温热液金矿床中广泛发育,是该类矿床的显著识别特征。通过对酸性蚀变岩帽的野外地质特征、矿物共生组合和地球化学特征研究,能较好阐明浅成低温成矿热液系统的特征、性质、发生和发展演化及成矿作用过程。庐枞矿集区是长江中下游成矿带重要的矿集区之一,盆地内广泛发育以明矾石为特征蚀变矿物的酸性蚀变岩帽,面积超过30km~2,指示盆地内高硫化浅成低温热液系统的存在。目前为止,前期工作主要针对明矾石矿床地质特征和明矾石资源储量进行,该酸性蚀变岩帽的地质地球化学特征研究尚未开展。本次工作通过对酸性蚀变岩帽系统的野外采样、全岩地球化学分析和短波红外光谱测试分析技术(PNIRS测试)分析,确定其主要赋存在砖桥组火山岩中,组成矿物为石英、明矾石、高岭石、地开石,此外有少量绢云母、伊利石、珍珠陶土、叶蜡石、褐铁矿,极少数的叶腊石和黄钾铁矾等,在钻孔深部存在浸染状和半自形粒状黄铁矿。由于受到地表风化剥蚀和不同热热中心的影响,水平方向从矾山明矾石矿床向外围发育石英+明矾石带、石英+高岭石/地开石+明矾石带、石英+高岭石/地开石带、硅化带以及最外围的泥质带即高岭石±绢云母±伊利石带。根据酸性蚀变岩帽的矿物组合和主量元素特征,可将其分为三类:硅质蚀变岩、明矾石蚀变岩和粘土蚀变岩。硅质蚀变岩中SiO_2含量发生明显的富集作用,其余主量元素(K_2O、Na_2O、Al_2O_3、Fe_2O_3、P_2O5)含量显著降低;明矾石蚀变岩和粘土蚀变岩具有相似的地球化学特征,SiO_2、Al_2O_3、Fe_2O_3、P_2O_5元素含量范围变大,K_2O和Na_2O含量降低,且Na_2O降低更加明显;而钛为不活泼元素,在岩石发生蚀变过程中TiO_2含量变化很小。矾山地区的酸性蚀变岩帽的产状、蚀变类型、地球化学特征受构造和地层的双重控制。     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

太平洋中部沉积物中粘土矿物的初步研究

笔者对采自太平洋中部170°E至178°W,6°到17°S,即新赫布里底群岛至乌佛阿岛,斐济群岛到埃利斯群岛间海区(见图1)的10个站位,20个海底沉积物样品,进行了分析和研究。 该区的地质构造受西太平洋岛孤活动带的控制,海底地形复杂,水深变化大。火山活动频繁,区内散布许多白垩纪至老第三纪形成的火山岛和水下火山体。第四纪以来,火山活动依然十分频繁[1]。根据海底地形，水深和沉积物的差异，将该区分为三个小区。(1)斐济群岛和霍恩群岛以北海区，水深一般小于2500米，但深度变化大，地形复杂，水下火山体和珊瑚礁星罗棋布，沉积物以钙质生物沉积为主。( 2)北斐济海盆，水深多为3000-400。米，海盆边缘散布着许多水下火山体，沉积物以钙质生物沉积一火山碎屑沉积为主。(3)美拉尼西亚海盆南部，水深5000米左右，海域开阔，水下火山体较少，沉积物以多源性红粘土沉积为主。