渝东南地区黑色页岩中粘土矿物特征兼论其对储层物性的影响——以彭水县鹿角剖面为例

为探索渝东南地区下志留统龙马溪组黑色页岩中粘土矿物特征及其与储层物性的关系,在综合前人对含油气盆地粘土矿物分析的基础上,以重庆市彭水县鹿角剖面为例,深入分析了鹿角剖面黑色页岩粘土矿物组合与分布特征、粘土矿物的形成机理及其控制因素以及粘土矿物对孔隙度和渗透率的影响。结果表明,一方面根据古盐度的计算,龙马溪组上部古水介质含盐度较低,下部较高,具有上淡下咸的特点;另一方面该套黑色页岩属于晚成岩阶段B期。储层中粘土矿物的类型、数量及其分布特征等对储层孔渗条件具有一定的控制作用。伊利石(含伊/蒙有序混层矿物)含量与孔隙度有弱正相关关系,与渗透率呈负相关关系,原因可能是成岩伊利石不断生长,一方面由于其体积减小使得显微孔隙体积有所增加,但另一方面,由于自生伊利石晶体细小,使得页岩粒间孔隙遭到不同程度的破坏,致使平均孔隙半径变小,渗透率变差。绿泥石含量与孔隙度呈现微弱的正相关关系,而与渗透率呈现较好的正相关关系。这是由于成岩绿泥石主要来源于长石溶解或蚀变形成的高岭石的转化,因此,绿泥石与孔隙度和渗透率的关系可能反映其与页岩中长石矿物的含量有关。     

Strontium distribution and origins in a natural clayey formation (Callovian-Oxfordian, Paris Basin, France): A new sequential extraction procedure

Strontium is a good monitor of geochemical processes in natural clayey formations. In the Callovian-Oxfordian formation of Bure in France, strontium is sorbed on clay minerals and carried by carbonates, detrital minerals and accessory celestite. In order to determine the strontium distribution among these different phases, four-step sequential extractions (1. cobalt hexamine trichloride, 2. acetic acid, 3. EDTA and 4. tri-acid) were performed on samples from different levels of the clayey formation. The leachates were also analyzed for strontium isotopes, in order to determine the strontium origins. This sequential procedure is well suited to determining strontium distribution in claystones, although it is less efficient in clay-rich limestones and in celestite-rich samples. The carbonates (38-47% of the total strontium) show ⁸⁷Sr/⁸⁶Sr ratios (0.7070-0.7071) that have recorded the isotopic composition of the Callovian-Oxfordian seawater. Diagenetic carbonates (dolomite, ankerite and siderite) have almost not incorporated any strontium, which has been trapped by celestite during the late diagenesis. The major part of the celestite shows ⁸⁷Sr/⁸⁶Sr ratios (0.7069-0.7070) quite close to the primary carbonates. However, a second generation of celestite (0.7074) shows a slight ⁸⁷Sr-enrichment and is isotopically in equilibrium with the exchangeable strontium (27-48% of the total strontium with a mean ⁸⁷Sr/⁸⁶Sr value of 0.70745) and the present-day porewater (0.7074). This very low ⁸⁷Sr-enrichment could be explained by the partial destabilisation of detrital minerals (feldspars, micas, clays) which exhibit ⁸⁷Sr/⁸⁶Sr ratios consistent with their pristine Hercynian origin (0.7229-0.7350). Diffusion of strontium from the subjacent Dogger aquifers (0.7076-0.7082) could also be invoked to explain the slight ⁸⁷Sr-enrichment.     

Contact and fracture ultramafic assemblages from Norway: Rb-Sr evidence for crustal contamination

Strontium isotopes are used as tracers of crustal contamination of alpine-type ultramafic rocks from the Basal Gneiss Complex of the Caledonides of southern Norway. Minerals from anhydrous assemblages that occur in the cores of these ultramafic lenses give Sr⁸⁷/Sr⁸⁶ ratios (0.7011 to 0.7047) that reflect the expected ambient Sr⁸⁷/Sr⁸⁶ conditions of the ancient upper mantle. Rb-Sr evidence for crustal contamination is found in hydrous assemblages that occur within fractures and around the margins of the ultramafio bodies. Olivine, enstatite, amphibole, and magnesite from these assemblages have present-day Sr⁸⁷/Sr⁸⁶ ratios (0.7049 to 0.7085) that are significantly higher than those of compositionally equivalent minerals from the interiors of the ultramafic bodies. The high Sr⁸⁷/Sr⁸⁶ values were acquired as a result of the reaction between the ultramafic rock and ion-charged hydrous solutions carrying strontium with the ambient Sr⁸⁷/Sr⁸⁶ ratio (around 0.713) of the enclosing country rook during the waning phases of the Caledonian Orogeny. Mineral separates from the interiors of these ultramafic bodies can yield useful information on the ancient upper mantle. Wholerock samples, however, will show some evidence of contamination from the crust as a result of the formation of at least trace amounts of secondary hydrous minerals. Most whole-rook Sr⁸⁷/Sr⁸⁶ ratios from alpine-type ultramafic rocks from other orogenic belts show evidence of this contamination.     

Diagenesis of diatomite from the Kolubara Coal Basin,Baroševac,Serbia

Diatomite associated with the Kolubara Coal Basin was studied to better understand early stage silica diagenesis of shallow water deposits. The Kolubara Basin consists of Neogene siliciclastic rocks, diatomite, marlstone and rare carbonates. Palaeozoic metamorphic and Mesozoic sedimentary and igneous basement rocks are transgressively overlain by Upper Miocene sandstone, siltstone, shale and mudstone. This Upper Miocene section is transgressively overlain by the Pontian section, which contains diatomite and coal beds. White and grey diatomite forms beds 0.7-2.2 m thick that are continuous over an area of about 2 km². Siliceous rocks vary in composition from diatomite (81-89 per cent SiO₂) to diatom-bearing shale (58-60 per cent SiO₂). Siliceous deposits are laminated in places, with the laminae defined by variations in clay minerals, organic matter and diatoms. Diatomite shows only incipient diagenesis characterized by the fragmentation of diatom frustules, the minor to moderate corrosion of frustules and the formation of minor amounts of opal-A' (X-ray amorphous inorganic opal) cement. The low degree of diagenesis results from the young age of the deposits, low burial temperatures and possibly also from the presence of abundant organic matter and the dissolution of kaolinite. The presence of only weak diagenesis is also reflected by the characteristically poor consolidation of the rocks and low rank of the associated coal.     

A Rubidium--Strontium Geochronological Study of the Willyama Complex, Broken Hill, Australia

Rubidium-strontium isotopic measurements are reported for total-rockand minerals from igneous and high-grade metamorphic rocks fromthe Willyama Complex, Broken Hill, Australia. The results ofmeasurements on total-rocks and some minerals from the high-gradegneisses indicate that nearly complete strontium isotopic redistributionoccurred within individual rock units 164040 m. y. ago. Thisage is interpreted as that of the high-grade regional metamorphismwhich recrystallized the Willyama rocks to gneisses in the BrokenHill area. Analyses of total-rocks and some minerals from intrusivemuscovite granites and pegmatites give consistent ages of 154O5Om. y. indicating that these rocks were emplaced soon after thehigh-grade regional metamorphism. Rubidium-strontium isotopic analyses of all biotites, and ofmuscovites from pegmatites concordant in schists at Thackaringareveal a 500 m. y. metamorphic episode of lesser intensity accompaniedby pegmatite emplacement. This metamorphism was not of sufficientstrength to open the total-rock systems significantly to rubidiumand strontium isotopes. Biotites, however, appear to have losttheir radiogenic strontium almost completely at this time andit is probable that this event accounts for the observed disturbanceof the potash-feldspar rubidium-strontium systems in most gneissand muscovite granite samples investigated. There is a close similarity between the rubidium-strontium ageresults and the Broken Hill model lead ages. This supports thehypothesis of two-stage lead development and, with the strontiumisotope evidence, suggests that the region has evolved largelyas a closed chemical system since at least the high-grade metamorphism.     

The effect of weathering on the distribution of strontium isotopes in weathering profiles

The strontium isotope ratio in sea water has varied through geologic time owing to the input of strontium from rock weathering. To evaluate the possibility that $\text{Sr}{}^{87}\text{Sr}{}^{86}$ ratios might be altered during weathering, seven weathering profiles developed on Mesozoic arkoses located along the length of New Zealand were investigated. The rubidium-strontium-strontium isotope relations in these profiles give ‘isochron’ ages less than the ages of deposition of the arkoses. These ages appear to result from the weathering of a homogeneous source rock. The age calculated from the rubidium-strontium system (t′) is related to the original age (t) by the equation t′/t = (n ? 1)/n, where n is the ratio of the amounts of common and radiogenic strontium leached from the rock. Shales formed by the accumulation of these residual solids may inherit misleading isochron relationships which may not be erased during deposition or early diagenesis. The strontium which goes into solution and is transported to the sea is slightly less radiogenic than the strontium in the unweathered rock, while the residual clays may be much more radiogenic.     

湖南省寒武系黑色岩系页岩型钒矿概论

湖南省寒武系黑色岩系蕴藏着丰富的钒矿资源,钒矿床产于寒武系底部富含有机质的碳、磷、硅质黑色岩系中;矿体呈层状、似层状,形态简单,产状稳定。多项测试结果表明,钒的载体岩石为黑色页岩(碳质页岩、硅质碳质页岩);钒主要呈类质同象形式赋存于伊利石晶格中;矿石类型主要为钒矿石,少数矿床中石煤钒矿石也是重要的矿石类型;钒的价态以V3+为主。钒的富集主要发生在沉积阶段,与黑色岩系的沉积过程一致;矿床形成于缺氧环境中,大部分钒被黏土质吸附,随有机质、黏土质和硅质呈胶态腐泥沉入海底;在成岩过程中,云母类黏土矿物结构发生再结晶,将原有表面吸附的钒(V3+)转化为类质同象形式进入云母晶格中取代部分铝(Al3+),形成含钒伊利石并聚集成为钒矿床。研究表明,本区黑色岩系及其有关的钒矿在沉积成岩成矿过程中都离不开生物地球化学作用,矿床成因属于在热水作用参与下沉积形成的海相化学和生物地球化学沉积矿床,矿床类型为黑色页岩型钒矿。     

临兴地区海陆过渡相页岩及页岩气地球化学特征

为揭示鄂尔多斯盆地东缘上古生界海陆过渡相页岩及页岩气地球化学特征,选取临兴地区页岩样,开展薄片鉴定、全岩和黏土含量、扫描电镜、有机碳、岩石热解、干酪根显微组分和干酪根碳同位素测试,分析页岩解吸气的气体组分和碳同位素组成。结果表明:临兴地区过渡相页岩矿物组分主要是石英和黏土矿物,含少量方解石、斜长石、钾长石、白云石和黄铁矿等。受矿物成因、沉积环境等多方面的影响,不同矿物组分与有机质赋存方式各异。石英与有机质存在2种赋存方式,黏土矿物存在3种赋存方式,黄铁矿存在4种赋存方式。有机质类型为Ⅱ₂–Ⅲ型,有机碳含量平均值大于2.0%,干酪根碳同位素介于–24.5‰~–23.2‰。镜质体反射率介于0.92%~1.30%,t_max值介于427~494℃,有机质热演化达到成熟阶段。页岩气中烃类气以甲烷为主,含有少量乙烷、丙烷,总体属于干气。甲烷碳同位素均值为–40.0‰,介于海相页岩气和陆相页岩气甲烷碳同位素之间;乙烷碳同位素值介于–26.8‰~–22.56‰,均大于–29‰,整体呈现出δ13C₁＜δ13C₂＜δ13C₃正碳序列。研究认为,该区页岩具备大量生成页岩气的潜力,页岩气主要来源于上古生界偏腐殖型页岩,属于由干酪根裂解而生成的有机热成因煤成气。      

Application of the trace element and isotope geochemistry of strontium to studies of carbonate diagenesis

Carbonate rocks and natural waters exhibit a wide range in the concentration and isotopic composition of strontium. This wide range and the quantifiable covariation of these parameters can provide diagnostic tools for understanding processes of fluid-rock interaction. Careful consideration of the uncertainties associated with trace element partitioning, sample heterogeneity and fluid-rock interaction mechanisms is required to advance the application of the trace element and isotope geochemistry of strontium to studies of diagenesis, goundwater evolution, ancient seawater chemistry and isotope stratigraphy. A principal uncertainty involved in the application of Sr concentration variations to carbonate systems is the large range of experimental and empirical results for trace element partitioning of Sr between mineral and solution. This variation may be a function of precipitation rate, mineral stoichiometry, crystal growth mechanism, fluid composition and temperature. Calcite and dolomite in ancient limestones commonly have significantly lower Sr concentrations (20–70 p.p.m.) than would be expected from published trace element distribution coefficient values and Sr/Ca ratios of most modern sedimentary pore waters. This discrepancy probably reflects the uncertainties associated with determining distribution coefficient values. As techniques improve for the analytical measurement and theoretical modelling of Sr concentration and isotopic variations, the petrological analysis of carbonate samples becomes increasingly important. The presence of even small percentages of non-carbonate phases with high Rb concentrations and high ⁸⁷ Sr⁸⁶ Sr values, such as clay minerals, can have significant effects on the measured ⁸⁷ Sr/⁸⁶ Sr values of carbonate rocks, due to the decay of ⁸⁷Rb to ⁸⁷ Sr. For example, a Permian marine limestone with 50 p.p.m. Sr and 1 p.p.m. Rb will have a present-day ⁸⁷ Sr/⁸⁶ Sr value that is >2 × 10^?4 higher than its original value. This difference is an order of magnitude greater than the analytical uncertainty, and illustrates the importance of assessing the need for and accuracy of such corrections. A quantitative evaluation of the effects of water-rock interaction on Sr concentrations and isotope compositions in carbonates strengthens the application of these geochemical tracers. Geochemical modelling that combines the use of trace elements and isotopes can be used to distinguish between different mechanisms of water-rock interaction, including diffusive and advective transport of diagenetic constituents in meteoric pore fluids during the recrystallization of carbonate minerals. Quantitative modelling may also be used to construct diagnostic fluid-rock interaction trends that are independent of distribution coefficient values, and to distinguish between mixing of mineral end-members and fluid-rock interaction.     

Isotopic constraints on the genesis and age of autochthonous glaucony in the Oligo-Miocene Torquay Group, south-eastern Australia

The Oligo‐Miocene Torquay Group at Bird Rock in south‐eastern Australia comprises a sequence of fine‐grained skeletal carbonates and argillaceous and glauconitic sandstones, deposited in a cool‐water, mid‐shelf environment. The Bird Rock glaucony is autochthonous and consists predominantly of randomly interstratified glauconitic smectite, which constitutes bioclast infills and faecal pellet replacements. The results of Rb–Sr and oxygen isotopic analysis of samples taken from a single glauconitic horizon (the BW horizon) indicate that the glaucony developed through a series of simultaneous dissolution–crystallization reactions, which occurred during very early diagenesis in a closed or isochemical system, isolated from the ambient marine environment. The constituent ions of the glaucony were derived primarily from terrigenous clay minerals, but considerable potassium may have been sourced indirectly from sea water, through potassium enrichment of clay precursors. The pore fluids associated with glauconitization were marine derived, but progressively modified by the dissolution–crystallization of detrital clay minerals and autochthonous glaucony. Rb–Sr data for the BW horizon indicate that dating glauconies may be somewhat problematic, as co‐genetic glauconitic minerals can show a range of initial strontium compositions, which reflect the incorporation of strontium derived from mineralogical precursors and/or contemporaneous sea water. Rb–Sr isochrons indicate that the glaucony of the BW horizon formed at 23 ± 3 Ma. This age is in good agreement with both the established biostratigraphy and a ⁸⁷Sr/⁸⁶Sr age for the horizon (23 ± 1 Ma), but could only be determined using the independent age constraint and the estimate of the ⁸⁷Sr/⁸⁶Sr ratio of contemporaneous sea water provided by analysis of associated biogenic carbonate.     

Applications of Light Stable Isotopes(C,O, H) in the Study of Sandstone Diagenesis: A Review

This article reviews the applications of light stable isotope, including carbon, oxygen and hydrogen, in thestudies on origin and formation temperature of authigenic carbonate, quartz and clay minerals. Theoretical knowledge andanalytical methods for major light stable isotopes are introduced in detail. Negative and positive δ¹³C values indicatesignificant differences on the origin of carbonate cements. The δ¹⁸O value is an effective palaeotemperature scale forauthigenic minerals formation. Various fractionation equations between δ¹⁸O and temperature are proposed for carbonatecements, quartz cements and clay minerals, whose merit and demerit, applicable conditions are clarified clearly. Clumpedisotope analysis can reconstruct the temperature of carbonate precipitation with no requirement on the δ¹⁸O of initial waters,which makes temperature calculation of carbonate cements formation more convenient and accurate. Hydrogen and oxygenisotopes mainly reflect the origin of diagenetic fluid for clay mineral formation, providing reliable evidence for diageneticenvironment analysis. This work aims at helping researchers for better understanding the applications of light stable isotopein sandstone diagenesis.     

The significance of rubidium-strontium age of sedimentary rock

The isotopic composition of strontium and the rubidium and strontium contents were measured for samples of the Lower Permian Havensville Shale collected at four different localities across a distance of approximately 200 miles in Kansas and northern Oklahoma. The Rb-Sr dates ranged from 320 m.y. to 395 m.y. The initial Sr⁸⁷/Sr⁸⁶ ratios were between 0.709 and 0.717. The ages are interpreted to be intermediate between the age of the source material and the time of sedimentation and, therefore, are not indicative of any geologic event. A model has been proposed to explain the colinearity of the Rb-Sr data and the evolution of different Rb-Sr dates for the same stratigraphic unit at different localities.     

川东北普光气田下三叠统飞仙关组白云岩成因——来自岩石结构与Sr同位素和Sr含量的证据

研究了川东北普光气田下三叠统飞仙关组白云岩储层的岩石结构Sr的含量和Sr同位素组成,讨论了它的成因,飞仙关组优质储层为成岩期埋藏交代白云化作用的产物,来自岩石结构和Sr同位素和Sr含量的证据包括如下几个方面:(1)与准同生白云岩比较,埋藏白云岩的岩石结构和Sr同位素和Sr含量地球化学特征与前者有显著差别;(2)飞仙关组所有各类碳酸盐岩(或矿物)具有早三叠世海水Sr同位素组成特征,~(87)Sr/~(86)Sr比值变化范围为0.706588～0.708187,覆盖了全球早三叠世海水Sr同位素的变化范围(0.7076～0.7078),平均值0.707656与全球早三叠世平均值(0.707743)基本一致;(3)埋藏白云岩~(87)Sr/86Sr比值变化范围为0.707122～0.707419,平均值0.707421,都略低于全球早三叠世海水Sr同位素变化范围和平均值,但与已报道的川东北早三叠世飞仙关期海水Sr同位素变化范围(0.707330～0.707383)和平均值(0.707350)都非常接近,说明白云石化流体具有强烈的川东北地区早三叠世飞仙关期海水Sr同位素组成特征;(4)综合岩石结构、Sr同位素和Sr含量地球化学特征,证明飞仙关组白云岩储层为成岩期埋藏交代作用产物,白云石化流体来自地层中高Sr和高盐度的海源地层水.     

石英矿物类型及其对页岩气富集开采的控制:以四川盆地及其周缘五峰组-龙马溪组为例

页岩矿物组成控制着页岩的储层类型和岩石力学性质,并影响着页岩气的富集和开发.为了分析不同类型石英矿物的纵向变化特征及其对页岩气富集开采的控制作用,以四川盆地及其周缘五峰组-龙马溪组WF2-LM4和LM5-LM8两个笔石带页岩为主要研究对象,利用普通薄片观察、扫描电镜、矿物成岩世代关系、能谱分析等手段,识别出陆源碎屑石英、生物成因石英和黏土矿物转化过程中形成的3种石英类型.结果表明不同的页岩层段,3种成因的石英含量不同.生物成因石英在WF2-LM4笔石带页岩最为富集,向上到LM5-LM8笔石带页岩逐渐减少.在WF2-LM4笔石带页岩,生物成因石英与有机碳含量呈明显的正相关性,有利于页岩优质储层的形成,对页岩储层的压裂改造具有积极作用,实现了页岩赋气和改造的有机统一.研究认为四川盆地及其周缘地区五峰组-龙马溪组一段下部黑色页岩（WF2-LM4笔石带页岩）具有生物成因石英含量高,页岩生烃、储集能力和可压裂性最优的特点,是页岩气富集开采的有利层段.      

鄂尔多斯盆地东部上古生界黏土矿物主控因素分析及研究意义

利用铸体薄片、扫描电镜及X射线衍射等分析资料对鄂尔多斯盆地东部主要含气层系黏土矿物的特征进行分析,盆地东部黏土矿物主要受物源区母岩、沉积相和成岩作用特征等方面影响,不同层系黏土矿物受影响程度不同,其中二叠系石千峰组千五段和石盒子组盒八段受物源区母岩和沉积相影响较大,山西组二段和太原组受成岩作用和沉积相影响作用明显;加强对不同层系黏土矿物的特征研究,可明确主要含气层系储层的潜在敏感性,这个初步结论对有针对性地保护储层和储层改造具有一定的借鉴意义。     

中亚盆地钾盐矿床盐类矿物Rb-Sr同位素体系研究及其意义

中亚盆地钾盐矿床的形成时代目前被限定为晚侏罗世至早白垩世,较为宽泛.盐类矿物沉积之后若未被改造,可测定其形成时代;若被改造则可利用同位素测年研究其沉积后作用.为了得到中亚盆地钾盐矿床的形成时代和/或了解盐类矿物受到的后期改造过程,利用Rb-Sr同位素定年对矿床中的盐类矿物进行了测定.结果表明,无法形成可靠的Rb-Sr等...     

基于热模拟实验的富有机质泥页岩成岩作用及演化特征

富有机质泥页岩蕴含丰富的油气资源,但成岩研究基础薄弱,已成为制约页岩油气勘探开发进程的重要因素。通过开展成岩热模拟实验,结合扫描电镜观察、流体成分测试及有机酸测试等实验测试手段,全面描述实验过程中所发生的水-岩化学反应,试图揭示泥页岩成岩过程及成岩演化规律。研究结果显示,有机质热演化过程中存在一个较宽的有机酸生成窗口,对孔隙流体性质具有重要影响;长石和方解石存在接力溶蚀现象,长石溶蚀高峰过后紧接着出现方解石溶蚀高峰,但方解石溶蚀窗较窄,此后出现方解石重新沉淀结晶;黏土矿物转化及长石的溶蚀过程中会产生大量自生微晶石英,成链状或簇状胶结泥页岩骨架。泥页岩地层作为一个相对封闭体系,各类成岩作用之间相互关联,相互影响,构成错综复杂的成岩体系,进一步增加其成岩作用研究难度。     

青藏高原北部东昆仑地区三叠系页岩成岩作用及其对储层的影响

青藏高原北部东昆仑地区八宝山盆地作为高原页岩气成藏特征探索的典型区域之一,对影响储层储集性能的关键因素——成岩作用的研究程度很低,不足以更大限度地发挥其勘探价值。基于岩性观察及薄片、铸体薄片、扫描电镜、X-射线衍射等实验分析资料,对该区三叠系页岩成岩作用及对储层的影响开展研究,结果显示,三叠系八宝山组页岩成岩作用共有6类：压实、胶结、黏土矿物转化、交代、溶蚀及有机质热成熟作用。综合有机质成熟度、岩石热解最高峰温、伊蒙混层比中蒙皂石占比、黏土矿物组合、孔隙类型等指标得出：研究区页岩处于中成岩B期-晚成岩阶段。结合各成岩作用对储层孔隙度的影响,研究区压实作用、胶结作用、黏土矿物转化作用易于造成孔隙度的减小,溶蚀作用、有机质热成熟作用易于孔隙度的增大,而交代作用对孔隙影响小。     

The geochemistry of iron in Recent tidal-flat sediments of the Wash area,England: a mineralogical,Mössbauer,and magnetic study

Undisturbed core samples of Recent sediments from the Wash tidal flats, East Anglia, England, obtained using a Delft corer, were studied with special reference to the diagenesis and geochemical behaviour of iron. The Mössbauer effect in ⁵⁷Fe was used to monitor the distribution of Fe between different phases as a function of depth, together with the magnetic mineralogy and palaeomagnetic properties.The cores consist of, successively downwards: 0.36 m brown clay; 1.5 m finely laminated silts and fine sands, and 7.14 m homogeneous fine sands. The dominant minerals are quartz, feldspar, calcite and clay minerals, and chemical analysis for Al, Si, Mg, Mn, Ca, Fe, Na, K showed variations closely linked to lithological changes. Illite is the most abundant clay mineral (mean 48%), followed by mixed layer illite-montmorillonite and montmorillonite, kaolinite and chlorite. Chlorite is the major iron-bearing clay mineral and represents 4 to 10% of the <2 μm fraction throughout the core. Sulphide minerals are present throughout the core, including framboidal pyrite.Computer fit analysis of the Mössbauer spectra of best quality showed contributions from Fe²⁺ and Fe³⁺ in clay minerals (essentially chlorite), low-spin Fe²⁺ in pyrite, and magnetically ordered iron in greigite (Fe₃S₄). Systematic variations, as a function of sample depth, indicate a relative increase in the amount of Fe in pyrite at the expense of the clay minerals.Magnetite and titanium-bearing magnetite are the carriers of natural magnetic remanence in these sediments.The direction and intensity of natural remanence in the samples compare well with the known secular variation of the Earth's magnetic field derived from the historic-archaeomagnetic record and this enables the samples to be dated and sedimentation rates to be determined (1.5 mm yr^?1 for the upper 2 m and ~7.7 mm yr^?1 for the lower 7 m).     

Behaviour of lithium and its isotopes during weathering in the Mackenzie Basin, Canada

We report Li isotopic compositions, for river waters and suspended sediments, of about 40 rivers sampled within the Mackenzie River Basin in northwestern Canada. The aim of this study is to characterize the behaviour of Li and its isotopes during weathering at the scale of a large mixed lithology basin. The Mackenzie River waters display systematically heavier Li isotopic compositions relative to source rocks and suspended sediments. The range in δ⁷Li is larger in dissolved load (from +9.3‰ to +29.0‰) compared to suspended sediments (from −1.7‰ to +3.2‰), which are not significantly different from δ⁷Li values in bedrocks. Our study shows that dissolved Li is essentially derived from the weathering of silicates and that its isotopic composition in the dissolved load is inversely correlated with its relative mobility when compared to Na. The highest enrichment of ⁷Li in the dissolved load is reported when Li is not or poorly incorporated in secondary phases after its release into solution by mineral dissolution. This counterintuitive observation is interpreted by the mixing of water types derived from two different weathering regimes producing different Li isotopic compositions within the Mackenzie River Basin. The incipient weathering regime characterizing the Rocky Mountains and the Shield areas produces ⁷Li enrichment in the fluid phase that is most simply explained by the precipitation of oxyhydroxide phases fractionating Li isotopes. The second weathering regime is found in the lowland area and produces the lower δ⁷Li waters (but still enriched in ⁷Li compared to bedrocks) and the most Li-depleted waters (compared to Na). Fractionation factors suggest that the incorporation of Li in clay minerals is the mechanism that explains the isotopic composition of the lowland rivers. The correlation of boron and lithium concentrations found in the dissolved load of the Mackenzie Rivers suggests that precipitation of clay minerals is favoured by the relatively high residence time of water in groundwater. In the Shield and Rocky Mountains, Li isotopes suggest that clay minerals are not forming and that secondary minerals with stronger affinity for ⁷Li appear.Although the weathering mechanisms operating in the Mackenzie Basin need to be characterized more precisely, the Li isotope data reported here clearly show the control of Li isotopes by the weathering intensity. The spatial diversity of weathering regimes, resulting from a complex combination of factors such as topography, geology, climate and hydrology explains, in fine, the spatial distribution of Li isotopic ratios in the large drainage basin of the Mackenzie River. There is no simple relationship between Li isotopic composition and chemical denudation fluxes in the Mackenzie River Basin.