Exploring fault rocks at the nanoscale

This paper aims to demonstrate the potential role of micro/nanoscale investigations in the study of fault rocks, given that a multiscale and multidisciplinary approach linking structural geology, petrology and mineralogy from the outcrop to the unit-cell scale is essential to the comprehensive characterization of geological materials. To explore fault rocks at the sub-micrometer scale, a fundamental contribution is provided by the Transmission Electron Microscope (TEM), which offers a real-time combination of high-resolution images, diffraction patterns, and chemical data for extremely small volumes, providing accurate mineralogical and nanostructural determinations.This paper focuses on a few selected examples, that are particularly appropriate for TEM investigation, in particular: 1) grain-size determinations on ultrafine-grained fault rocks; 2) detection and characterization of poorly crystalline minerals (e.g., clays) and amorphous phases within fault rocks; 3) identification of deformation-induced mineral reactions occurring within fault zones (e.g., dolomite decarbonation and serpentine dehydration); and 4) observations of recurrent deformation nanotextures in phyllosilicates. TEM investigation can provide an unexpected amount of data, much of which cannot be obtained by conventional techniques, and it can therefore significantly contribute to an understanding of the physico-chemical conditions for faulting and fault mechanics.     

纳米探矿——用地气携带的纳米物质勘查隐伏矿

矿体周围广泛赋存着纳米物质,其可在地球排气的作用下从深部向地表迁移。在地表或地表附近可俘获这些纳米物质,这些纳米物质与矿体发出的直接信息密切相关。通过对其成分或聚集态等进行分析,可勘查隐伏矿。本文介绍了纳米探矿的应用现状和一些实例,探讨了该技术所存在的问题,并对今后的研究工作进行了展望。      

纳米零价铁地下水修复技术的最新研究进展

纳米零价铁（NZVI）是粒径在1～100nm之间的铁颗粒,它的比表面积和反应活性远远大于普通铁屑和铁粉,可以直接注入到含水层的重污染区,形成一个高效的原位反应带,灵活、高效、低成本地治理地下水污染。NZVI不仅可以降解各种卤代烃,还可以降解部分不含卤族元素的有机污染物,吸附或降解地下水中的重金属离子和多种无机阴离子。NZVI地下水修复技术在发达国家已经得到工程应用并正在迅速推广,原位场地因素对NZVI地下水修复效果的影响是今后该领域重要发展方向。NZVI在含水层中的有效分散和运移是今后NZVI用于地下水修复的主要突破点。     

地球化学探测:从纳米到全球

文中简要总结了勘查地球化学的发展历程,阐述了从纳米尺度到全球尺度地球化学探测的最新进展。勘查地球化学从诞生初期研究手标本化学成分,到研究矿床尺度原生晕,到20世纪70年代以后研究化学元素的区域分布,到90年代以后开始研究全球尺度化学元素分布。进入2000年以后,为了更深层次理解这些宏观地球化学模式是如何受元素的微观行为控制的,开始了纳米尺度地球化学探测。目前纳米尺度地球化学和全球尺度地球化学研究成为地球化学探测的两个前沿研究领域。笔者从微观、区域和全球不同尺度地球化学探测,各列举一个前缘领域进行了介绍。(1)在微观尺度上,从纳米水平研究化学元素的存在行为、分散和迁移机理,列举了有关纳米铜和纳米金晶体颗粒的发现及其对隐伏矿勘查的意义;(2)在区域尺度上,阐述了盆地砂岩型铀矿地球化学调查理论与技术进展;(3)在全球尺度上,列举了全球地球化学基准研究的最新进展,初步总结了全球尺度化学元素分布与地质背景、矿产资源、气候变化和人类活动的关系。     

Interpreting nanoscale size-effects in aggregated Fe-oxide suspensions: Reaction of Fe(II) with Goethite

The Fe(II)/Fe(III) redox couple plays an important role in both the subsurface fate and transport of groundwater pollutants and the global cycling of carbon and nitrogen in iron-limited marine environments. Iron oxide particles involved in these redox processes exhibit broad size distributions, and the recent demonstrations of dramatic nanoscale size-effects with various metal oxides has compelled us, as well as many others, to consider whether the rate and extent of Fe(II)/Fe(III) cycling depends upon oxide particle size in natural systems. Here, we investigated the reaction of Fe(II) with three different goethite particle sizes in pH 7.5 suspensions. Acicular goethite rods with primary particle dimensions ranging from 7 by 80 nm to 25 by 670 nm were studied. Similar behavior with respect to Fe(II) sorption, electron transfer and nitrobenzene reduction was observed on a mass-normalized basis despite almost a threefold difference in goethite specific surface areas. Scanning electron microscopy (SEM) images, dynamic light scattering (DLS) and sedimentation measurements all indicated that, at pH 7.5, significant aggregation occurred with all three sizes of goethite particles. SEM images further revealed that nanoscale particles formed dense aggregates on the order of several microns in diameter. The clear formation of particle aggregates in solution raises questions regarding the use of primary particle surface area as a basis for assessing nanoscale size-effects in iron oxide suspensions at circum-neutral pH values. In our case, normalizing the Fe(II) sorption densities and rate constants for nitrobenzene reduction by BET surface area implies that goethite nanoparticles are less reactive than larger particles. We suspect, however, that aggregation is responsible for this observed size-dependence, and argue that BET values should not be used to assess differences in surface site density or intrinsic surface reactivity in aggregated particle suspensions. In order to realistically assess nanoscale size-effects in environmentally relevant systems that are likely to aggregate, new methods are needed to quantify the amount of surface area accessible for sorption and reaction in wet nanoparticle suspensions, rather than assuming that this value is equivalent to the surface area determined from the characterization of dry nanoparticles.     

Comparison of 1,2,3-Trichloropropane reduction and oxidation by nanoscale zero-valent iron,zinc and activated persulfate

Trichloropropane(TCP) is a chlorinated solvent which derives from chemical manufacturing as a precursor, and it is also an important constituent of solvent formulations in cleaning/degreasing operations. The control and remediation of TCP in polluted sites is a challenge for many conventional remediation techniques due to its refractory behaviour. This challenge in mind, some nano-materials and oxidants were tested to evaluate their effectiveness as in TCP degradation in a laboratory setting. Experimental results indicate that the use of nanoscale zero-valent iron prepared by green tea(GT) as a reductant has negligible degradation effect on TCP under normal temperature and pressure conditions. However, zinc powders of similar size but higher surface reactivity, demonstrated stronger dechlorination capacity in the breakdown of TCP, as almost all of TCP was degraded by carboxymethocel(CMC) stabilized nanoscale zinc within 24 h. Activated persulfate by citric acid(CA) and chelated Fe(Ⅱ) was also used for TCP treatment with a TCP removal efficiency rate of nearly 50% within a 24 h reaction period, and a molar ratio of S_2O_8~(2-), Fe~(2+) and CA is 20:5:1. Both the reduction and oxidation reactions are in accordance with the pseudo-first order kinetic equation. These results are promising for future use of TCP for the remediation of polluted sites.     

Changes in size distribution of fresh water nanoscale colloidal matter and associated elements on mixing with seawater

Changes in size distribution and elemental composition of 0.5-50 nm fresh water colloids during estuarine mixing have been studied by in-laboratory mixing of natural creek water and synthetic seawater, followed by size fractionation with Asymmetrical Flow Field-Flow Fractionation, and online elemental quantification by High-Resolution ICPMS. At least two types of colloids were present in the studied size region; 0.5-3 nm fluorescent dissolved organic matter (FDOM), and >3 nm colloids that were rich in Fe and colored dissolved organic matter (CDOM). Most trace elements were associated in different proportions to these two populations of colloids. Following mixing with synthetic seawater, the >3 nm Fe-rich colloids and CDOM were extensively removed from the studied size region by salt induced aggregation. The degree of removal with increasing salinity was greatest below 2.5‰ salinity, continued to a lesser degree between 2.5‰ and 15‰ salinity, above which only very small additional removal could be distinguished. At 25‰ salinity, the Fe concentration in the 0.5-50 size region had been reduced down to 15% of its original value in freshwater, while the amount of CDOM had been reduced to 55%. On the contrary, the concentration of the 0.5-3 nm FDOM was unchanged by the increased concentration of sea salt. Therefore, colloidally associated Al, P, Co, Cu, Zn, Ce, Lu and Pb were removed from the 0.5-50 nm size region according to their relative distributions between the FDOM and the Fe-rich colloids. Consequently, at 25‰ salinity, the 0.5-50 nm concentrations of Al, Mn, P and Pb, (mainly associated with the Fe-rich colloids) had been reduced down to 13-26 % of their values in freshwater, while the concentrations of Co and Cu (with higher preferences for FDOM) were less reduced, down to 46% and 57%, respectively. Changes in the elemental composition of the remaining colloidal matter were observed, the most pronounced were increased contents of P, Al and Pb in Fe-rich colloidal matter of medium size (∼3-15 nm) and increased Pb content in Fe-rich colloidal matter of larger size (∼5-50 nm).     

Characterization of preferential flow paths between boreholes in fractured rock using a nanoscale zero-valent iron tracer test

Recent advances in borehole geophysical techniques have improved characterization of cross-hole fracture flow. The direct detection of preferential flow paths in fractured rock, however, remains to be resolved. In this study, a novel approach using nanoscale zero-valent iron (nZVI or ‘nano-iron’) as a tracer was developed for detecting fracture flow paths directly. Generally, only a few rock fractures are permeable while most are much less permeable. A heat-pulse flowmeter can be used to detect changes in flow velocity for delineating permeable fracture zones in the borehole and providing the design basis for the tracer test. When nano-iron particles are released in an injection well, they can migrate through the connecting permeable fracture and be attracted to a magnet array when arriving in an observation well. Such an attraction of incoming iron nanoparticles by the magnet can provide quantitative information for locating the position of the tracer inlet. A series of field experiments were conducted in two wells in fractured rock at a hydrogeological research station in Taiwan, to test the cross-hole migration of the nano-iron tracer through permeable connected fractures. The fluid conductivity recorded in the observation well confirmed the arrival of the injected nano-iron slurry. All of the iron nanoparticles attracted to the magnet array in the observation well were found at the depth of a permeable fracture zone delineated by the flowmeter. This study has demonstrated that integrating the nano-iron tracer test with flowmeter measurement has the potential to characterize preferential flow paths in fractured rock.     

Focussed ion beam–transmission electron microscopy applications in ore mineralogy: Bridging micro- and nanoscale observations

Focussed ion beam–scanning electron microscopy (FIB–SEM) is a relatively new analytical tool that has been little applied to problems of ore genesis. The technique enables high-resolution (cross-section) imaging and can be used to prepare thinned foils for study by transmission electron microscopy (TEM). FIB–SEM methods applied to sulphides and related compounds represent an in-situ approach for sample characterisation and thus provides for crystal–chemical data that can be placed into the geological context of a given ore deposit.We present four study cases: these deal with minor element incorporation and release in ZnS; intergrowths and replacement among Cu–(Fe)-sulphides; fabrics in Au-bearing, As-free pyrite; and symplectites of Bi-sulphosalts within galena. The data is discussed in the context of polytypism and planar defects for minor element incorporation and release, superstructure ordering and formation of fine particles (100–2500 nm) or nanoparticles (< 100 nm) during replacement processes. Several analytical difficulties encountered when preparing FIB–TEM samples from sulphides are discussed, in particular mechanical and chemical damage to the surface. The FIB–TEM foils are difficult to thin for direct high-resolution TEM imaging but are usable for Scanning Transmission Electron Microscopy (STEM) and High-Angle Annular Dark Field (HAADF)-STEM imaging.     

Assessing the effectiveness of nanoscale zero-valent iron particles produced by green tea for Cr(VI)-contaminated groundwater remediation

Nanoscale zero-valent iron particles (NZVI) produced by using green tea (GT) extract as a reductant can remove Cr(VI) from water effectively, which can be utilized in groundwater remediation. In order to define the reaction mechanism and removal effect in the aquifer, in this study, GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance, and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(VI) in groundwater. The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10–20 nm, which could disperse in water stably. The main component of GT-NZVI was α-Fe with superficial polyphenols as a stabilizer. GT-NZVI suspension had good ability to reduce the Cr(VI) to Cr(III) in water. When the concentration of GT-NZVI was 1 g/L, the removal efficiency of Cr(VI) with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction. In column tests, GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%. The simulated in-situ reaction zone (IRZ) with GT-NZVI was used to remediate Cr(VI) contaminated groundwater. The outflow concentration of Cr(VI) kept in 0.14–0.32 mg/L corresponding to the outflow rate below 0.32% within 15 days, and the removal efficiency of Cr(VI) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size, groundwater flow rate and ionic strength. Most of Cr(III) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI, which indicated effective immobilization for chromium.     

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.     

Immobilization of Cr(VI) by sulphate green rust and sulphidized nanoscale zerovalent iron in sand media: batch and column studies

The study presented in this work emerged as a result of a multiyear regional geochemical survey based on low-density topsoil sampling and the ensuing geochemical atlas of Croatia. This study focuses on the Dinaric part of Croatia to expound the underlying mechanisms controlling the mobilities and variations in distribution of potentially harmful elements as observed from different environmental angles. Although serious environmental degradation of the vulnerable karst soil landscapes was expected to occur chiefly through the accumulation of various heavy metals, the most acute threat materialized through the soil acidification (Al-toxicity) affecting the entire Dinaric karst area. This picture surfaced from the analysis of all three investigated discriminant function models employing the abovementioned environmental criteria selected autonomously with respect to the evaluated soil geochemistry, namely, geologic setting, regional placement and land use. These models are presented by not only the characteristic discriminant-function diagrams but also a set of appropriate mathematically derived geochemical maps disclosing the allocations of potential threats to the karst soil landscapes posed by soil acidity.     

Ore minerals down to the nanoscale: Cu-(Fe)-sulphides from the iron oxide copper gold deposit at Olympic Dam,South Australia

Cu-Fe-sulphide mineral assemblages from the Olympic Dam (OD) Fe-oxide Cu-U-Au-Ag deposit, South Australia, are studied down to the nanoscale to explore the potential these minerals have for understanding genetic processes such as primary deposit zonation. Cu-Fe-sulphide pairs: ‘brown’ bornite associated with chalcopyrite (bornite-chalcopyrite zone); and symplectites of ‘purple’ bornite with species from the chalcocite group, Cu_2 − xS (bornite-chalcocite zone), co-define an upwards and inwards deposit-scale zonation at OD. In the bornite-chalcocite zone, there is also an increase in the proportion of chalcocite relative to bornite within the symplectites towards upper levels. In this case, two-phase Cu_2 − xS assemblages are also present, as anisotropic, hexagonal chalcocite (CcH) with lamellar exsolutions of digenite, distinguishable at the μm-scale. Using compositional data (electron microprobe) combined with Transmission Electron Microscopy (TEM) study of foils prepared in–situ via Focused Ion Beam (FIB)-SEM, we show that Cu-Fe-sulphides from different ore zones feature nanoscale intergrowths, lattice defects, superstructure domains (na) and antiphase boundary domains (APBs) that can be interpreted as due to exsolution, coarsening and phase transformation during cooling from high-T solid solutions in the system Cu-Fe-S and sub-systems according to published phase diagrams. ‘Brown’ bornite [(Cu + Fe)/S > 5] contains pervasive lamellae of chalcopyrite which extend down to the nanoscale; such specimens appear homogeneous at the μm-scale. ‘Purple bornite’ [(Cu + Fe)/S < 5] in high-bornite symplectites is associated with chalcocite that shows APBs with 6a digenite and low-T chalcocite. Comparable APBs are also found in the ‘chalcocite’ zone with apparent homogeneity at the μm-scale. Both bornites contain exsolutions of djurleite. Systematic variation of Me/S and Cu/Fe in the two types of bornite points, however, to distinct origins from different bornite solid-solutions in the system Cu-Fe-S. Both show 2a and 4a intermediate superstructures. High-order superstructures (6a and incommensurate na) are restricted to the ‘purple’ bornite whereas the 2a4a low-T superstructure is found in both cases. Me/S ratios in the chalcocite group are variable; lower ratios (down to 1.8; digenite) are more common in chalcocite from symplectites with ‘purple’ bornite. Me/S can be as low as 1.4 where associated with ‘blue’ varieties (‘blaubleibender covellin’) of replacement origin. The two-phase Cu_2 − xS associations contain hexagonal chalcocite (Me/S = 1.95), lamellae of Cu-rich digenite (Me/S = 1.92), and anilite (Cu₇S₄) as nm-scale lamellae. Digenite shows 3a and 6a superstructures and CcH shows transition to pseudo-orthorhombic chalcocite. The presence of superstructures, high-T species and APBs is evidence for Cu-(Fe)-sulphide formation from high-T solid solutions at T > 300 °C (high-T phases, Cu-poor digenite), followed by cooling along distinct paths down to < 120 °C (APBs). The scenario of ‘exsolution from primary solid-solution’, corroborated by the consistency in phase relations within each zone across different scales of observation from deposit scale to nanoscale, backs up a model of primary hypogene ore precipitation rather than replacement, and accounts for the observed vertical zoning at OD. The FIB-TEM approach here is readily applicable to other deposits and shows that nanoscale observations are a valuable, although often overlooked, source of information to constrain ore genesis.     

土压缩模量预测回归分析方法

在土压缩模量Es的分析计算中,常用的分析方法是根据土的e-p曲线试验资料建立公式求解,本文引入了数学上的回归分析方法来探讨Es与其它各项物理力学指标参数之间的相关关系,旨在找出对Es影响最显著的指标参数,并建立最优回归方程式,以此来预测Es。研究结果表明:该方法通用性强,应用范围广,亦可推广应用于其它相关领域。     

Geochemistry of Thermal Waters of Continental Margin of Far East of Russia

Studied waters belong to warm(T=30-50℃),alkaline(pH=8.9-9.3),low mineralized(TDS235 mg/1)Na-HCO_3 or Na-SO_4-HCO_3 thermal waters with high content of SiO_2(up to 81 mg/l)and F(up to 3.9 mg/1),occur on modern volcano-tectonic rejuvenated areas of Eastern Sikhote-Alin orogenic belt.Low~3He concentration as well as N_2/O_2 and N_2/Ar ratios exclude influence of deep mantle fluid.New rare earth element data constrain our understandmg of water-rock interaction occurring in the water source region.Meteoric origin of waters is proved by stable isotope values varying from-71‰to-136.1‰and from-10.8‰to-18.8‰forδ~2U andδ~(18)O respectively.REE patterns reflect high pH,resultfing from water-rock interaction and oxidative conditions.Calculations of deep aquifer temperature using Na-K and quartz geothermometers show 116.8-131.1°C and 82.2-125.8℃respectively.Presence of deep faults both with abnormal thermal gradient(~45-50 K/km)define unique geochemical shape of thermal waters of Sikhote-Alin,area,where no present volcanic activity is registered.     

岩石坚硬程度对核电厂地基-基础地震响应特征的影响分析

考虑核电厂地基-基础的动力相互作用,应用显式动力有限差分法分析了地震作用下极软岩、较软岩、坚硬岩上核电厂建筑结构基础的地震响应特征,比较了岩石坚硬程度对基础加速度反应谱的影响。研究表明：随着岩石坚硬程度的提高,核电厂建筑物结构基础的地震响应有增加的趋势;在周期轴上,基础处的加速度反应谱曲线会随着岩石坚硬程度的提高逐渐向短周期（高频段）方向移动。在高频段,建造于较坚硬岩石上基础结构的加速度反应谱值偏大;在中等频段,建造于较软岩石上基础结构的加速度反应谱值偏大;在低频段,岩石坚硬程度对加速度反应谱的影响不显著。