利用纳米压痕实验研究层理性页岩岩石力学性质——以渝东南酉阳地区下志留统龙马溪组为例

采用点矩阵纳米压痕技术对渝东南酉阳地区下志留统龙马溪组页岩进行弹性模量、硬度、断裂韧性等力学参数测量,借助场发射扫描电镜和能量色散X射线荧光光谱对压痕形貌及压痕区域矿物组成进行定量分析,提出基于矿物强度分类的三组分页岩微观力学模型,采用Mori-Tanaka方法实现力学参数从纳米向厘米尺度升级,并利用页岩单轴压缩实验结果进行对比分析。实验结果表明,纳米尺度下的页岩弹性模量与硬度、弹性模量与断裂韧性之间具有良好的线性关系,垂直层理方向的页岩弹性模量、硬度、断裂韧性等略小于平行层理方向;力学参数具有Weibull分布特点,硬度结果离散性最强,分析主要为页岩本身非均质性和压痕投影不确定性所导致。对比纳米压痕均值统计、尺度升级模型与宏观单轴压缩实验结果发现,纳米尺度下力学参数结果要高于尺度升级模型和单轴力学实验参数结果,证实不同尺度下的力学参数存在差异性,岩心尺寸越大,包含颗粒间孔隙和内部缺陷越多,则会导致岩石力学参数值减小。

上扬子区奥陶系五峰组—志留系龙马溪组沉积期火山活动对页岩有机质富集程度的影响

利用等时地层格架内建立的火山活动事件与海洋古生产力及氧化还原环境的对应关系,对上扬子区奥陶系五峰组—志留系龙马溪组沉积期火山活动及其对页岩有机质富集程度的影响进行研究。结果表明,研究区斑脱岩主要发育在五峰组沉积期海侵体系域(TST1)与龙马溪组沉积期海侵体系域(TST2)中,这两个体系域均对应高硅高炭的优质页岩相。根据斑脱岩发育的分段性特征,将TST1划为斑脱岩密集段,TST2划为斑脱岩稀疏段,前者斑脱岩发育频次大于1.5层/Ma且斑脱岩累计厚度比(斑脱岩厚度/页岩厚度)大于1%,后者斑脱岩发育频次小于1.5层/Ma且累计厚度比小于1%。TST1(密集段)较TST2(稀疏段)火山活动强度大且频次高,造成TST1有机质含量普遍较TST2高。剧烈且频繁的火山活动对页岩有机质富集具有双重促进作用,一方面火山灰提供营养物质促进海洋生物生产力,另一方面火山作用产生极度缺氧的环境提高有机质的埋藏量和保存率。

Impact of residual zircon on Nd-Hf isotope decoupling during sediment recycling in subduction zone

The subduction factories in convergent plate margins exert crucial control on recycling terrestrial components and returning to the overlying crust. The Nd and Hf isotopic systems provide potential tracers to evaluate these processes. Here we present a case where these isotopic systems are decoupled in a suite of granites from the Chinese Altai, showing a wide range of εHf(t) values(from -4.7 to +10.8) in contrast to a limited range of εNd(t) values(from -5.8 to -1.9). The zircon xenocrysts occurring frequently in these rocks show markedly negative εHf(t) values(from -34.3 to -6.5) and positive d7 Li values(from +12.5 to +18.2). We propose a model to explain the observed relationship between residual zircon and Nde Hf isotope decoupling. We suggest that the Altai granites originated from partial melting of subducted slab components under relatively low temperature conditions which aided the residual zircon from oceanic sediments to inherit and retain a significant amount of177 Hf in the source, thereby elevating the^(176) Hf/^(177) Hf ratio of the melt, and decoupling from the^(143) Nd/^(144) Nd ratio during the subsequent magmatic processes. Our study illustrates a case where sediment recycling in subduction zone contributes to decoupling of Nd and Hf isotopic systems, with former providing a more reliable estimate of the source characteristics of granitic magmas.

Investigation of mechanical properties of bedded shale by nanoindentation tests: A case study on Lower Silurian Longmaxi Formation of Youyang area in southeast Chongqing, China

The mechanical properties such as Young's modulus, hardness and fracture toughness of Lower Silurian Longmaxi shale samples from Youyang area in southeast Chongqing, China were investigated using dot matrix nanoindentation measurements. With the help of field emission scanning electron microscope(FESEM) and energy dispersive X-ray fluorescence spectroscopy(EDS), the indentation morphology and mineral composition in indentation area were quantitatively analyzed. According to mechanical strength classification, a micromechanical model with three components was introduced and the Mori-Tanaka model was used to upscale mechanical parameters from nano-scale to centimeter-size scale, which were further compared with uniaxial compression results. The experimental results show that there is a positive linear correlation between Young's modulus and hardness and between the Young's modulus and the fracture toughness under nano-scale; the Young's modulus, hardness and fracture toughness perpendicular to the bedding are slightly lower than those parallel with the bedding. According to data statistics, the mechanical properties at the nano-scale follow Weibull distribution feature and the dispersion degree of hardness results is the highest, which is mainly due to shale anisotropy and nanoindentation projection uncertainty. Comparing the results from nanoindentation test, with those from upscaling model and uniaxial compression test shows that the mechanical parameters at the nano-scale are higher than those from upscaling model and uniaxial compression test, which proves mechanical parameters at different scales have differences. It's because the larger the core, the more pores and internal weakness it contains, the less accurate the interpreted results of mechanical parameters will be.

Chlorinated Dioxin and Furan Congener Profiles from Pentachlorophenol Sources

Pentachlorphenol (PCP) was widely used as a biocide and insecticide for wood preservation. Chlorinated dioxins and furans (2,3,7,8-substituted PCDD and PCDF congeners) were inadvertent byproducts of PCP production. As such, it is an important source of PCDD/F contamination in treated wood and in soil/ sediment near sites that produced or used PCP. It has been noted in the literature, that PCP congener profiles are similar to some combustion profiles, as well as sewage sludge and particulate deposition. In a very broad sense, this is true. OCDD and 1,2,3,4,6,7,8-HpCDD are typically the dominant constituents in these source categories. There is however, a distinct, consistent and repeatable feature in the lower chlorinated tetra, penta and hexa PCDD/F range of PCP related samples: an order of magnitude increase in concentration as a function of degree of chlorination. Because lower chlorinated furans concentrations make up less than 1% of the total PCDD/F in PCP, it is difficult to differentiate PCP from other OCDD dominated source profiles on bargraphs that use a linear-scale y axis. Using a log-scale y axis, however, PCP impacted profiles are obvious, and are not easily confused with congener profiles from other sources.

Polychlorinated Dibenzofurans and Dibenzo-p-Dioxin in Tree Bark from an Industrialized Area: What the 2,3,7,8-Cl Substituted Congeners Tell Us, and What Is Missing

We analyzed polychlorinated dibenzofurans (PCDF) and dibenzo-p-dioxins (PCDD) in 27 tree bark samples from the industrialized area near Sauget, Illinois, USA. The trees were located within 4 km of the W. G. Krummrich (WGK) plant, the oldest and largest chemical plant in Sauget, with 24 of 27 samples collected from residential areas. The percent of total PCDF or PCDD profiles of ten 2,3,7,8- Cl substituted PCDF and seven PCDD congeners is homogeneous: 90% of the variance among the samples is explained by 3 eigenvalues in a principal components analysis. The homogeneity of the data suggests that samples were affected by similar types of sources which may have been influenced by electric power generation, chemical waste incineration, and large-scale thermal production of chlorinated chemicals. Quantitatively, the 2,3,7,8-Cl substituted congener analysis does not account for 90% of the concentration of tetra- and penta-Cl homologues and 80% of hexa-Cl and 50% of hepta-Cl homologues. The World Health Organization stated during establishment of toxic equivalence factors (TEF, 2005 version) that calculation of toxic equivalents (TEQs) is not suitable for abiotic matrices, such as tree bark, which are not involved in human exposures. Our results show that the non-2,3,7,8-Cl substituted congeners have high concentrations and should be included in analysis.

Lacustrine Shale Deposition and Variable Tectonic Accommodation in the Rift Basins of the Bohai Bay Basin in Eastern China

Organic-rich lacustrine shales are widely distributed in China and have significant potential for unconventional shale gas and oil production although the primary factors controlling the deposition of lacustrine shale are disputed. This work clarifies the different characteristics of tectonic evolution and shale among sub-basins in the Bohai Bay Basin in eastern China as a case study by studying basal subsidence, tectonic subsidence rate, basin extensional proportions and shale chemical characteristics. The paper summarizes the correlation between structure and shale deposition, and concludes that tectonic activity is the primary controlling factor for shale development. Episodic tectonic activity controls not only the timing of shale deposition（with the greatest shale deposition occurring primarily during the peak period of basin tectonic activity） but also the spatial distribution of shale（located mainly in areas of maximum subsidence）, the migration pattern of shale（conforming to that of the basin subsidence center）, and shale strata thickness. Tectonic activity also affects the total organic carbon content and organic matter type in shale. When the tectonic activity was the most active and basal subsidence was the maximum, the total organic carbon content of the shale reached its highest value with organic matter type mainly Type I. As tectonic activity weakened, the total organic carbon content decreased, and the organic matter type changed from Type I to Type I-III.