A Comparison Study of Synkinematic Illite Isolation,Quantitative X-ray Powder Diffraction,and K-Ar Dating for Direct Fault Gouge Analyses

K-Ar dating of synkinematic illite is increasingly recognized as a central method to constrain the timing of shallow crustal faulting.Methods of efficient sample preparation and quantitative identification of illite polytypes are critical to acquiring K-Ar isotope data for authigenic clays.In this respect,we compared the commonly used clay size separation method through centrifugation with vacuum filtration technology,showing that the former is prone to extract fractions with finer particle sizes under similar conditions,thus improving the error in the authigenic end-member age.Additionally,we demonstrated that the side-packed mounting method for X-ray diffraction analysis can significantly enhance the randomness in powder samples,thus improving the quantification accuracy compared with the front-packed and back-packed methods.The validity of our quantification method was confirmed by comparing Profex■modeling patterns with a suite of synthetic mixtures of known compositions,yielding an average analytical error of 3%.Dating results of these artificial mixtures and the reference materials indicated that a large range in percentages of detrital illite and a sufficient amount of age data will produce reliable results for ages of both extrapolated end-members.However,if the range is limited,the extrapolated age close to those of datasets is still reliable.

Illite Crystallinity Mapping of Very Low Grade Metamorphism of Triassic Metapelites in the Zoigê Area,Western China

X-ray diffraction methods for estimating the metamorphic grade of diagenetic, anchizone and epizone in metapelites are reviewed and applied to samples from a 7000 m＋ borehole in western China and surface samples from the surrounding Zoige area. Kiibler＇s illite crystallinity （IC） measurements provide more consistent results than calculated values of percentage of illite in the I/S mixed layers and percentage of I/S mixed layers. Down-borehole IC values display a typical burial metamorphic relationship between stratigraphic level and IC. A method for preparing very low grade metamorphic maps is described, and isograds plotted on a regional geological map at selected values of IC, delineating a high temperature diagenetic zone, an anchizone, and an epizone. The map shows that IC values are controlled by stratigraphic level in the north of the study area （i.e. burial metamorphism）, and proximity to an igneous intrusive body in the south （i.e. contact metamorphism）.

Silurian-Devonian and Jurassic Thermal Events in the Ordos Basin, China: Indications from K-Ar Dating on Illites

In the Ordos basin, two distinct thermal events of different ages have been identified for the first time by means of K-Ar dating combined with illite crystallinity analysis. For the Late Triassic and Late Permian samples, the K-Ar ages of the < 0.2μm fractions (159-173 Ma) reflect an illitization age related to the Yanshanian movement and indicate a short thermal event in the Middle Jurassic; the K-Ar ages of the <2 μm fractions (210-308 Ma) are interpreted as mixed ages of detrital material and authigenic illites. The K-Ar ages of both < 0.2μm and < 2μm fractions of a Middle Cambrian sample (368 Ma and 419 Ma) correspond to the ages of the metamorphism and earliest granite intrusion in the northern Caledonian Qinling fold zone (380-420 Ma) and show a thermal event during Silurian-Devonian time.

K-Ar Dating of Authigenic Illites and Its Applications to the Study of Hydrocarbon Charging Histories of Typical Sandstone Reservoirs in Tarim Basin, China

The Tarim Basin in China comprises eight sets of sandstone reservoirs, five of which are investigated in detail in this study. The main purpose of this study is to investigate the hydrocarbon charging histories of reservoirs by applying K-Ar dating of authigenic illites. The ages of authigenic illites from the Lower Silurian bituminous sandstones in the Central Uplift area range from 383.5 to 235.2 Ma, suggesting that the Silurian oil accumulations were formed from the late Caledonian till the late Hercynian. The ages of authigenic illites from the Upper Devonian Donghe Sandstone reservoirs range from 263.8 to 231.3 Ma, indicating that hydrocarbon accumulations within the Donghe sandstone were formed mainly in the late Hercynian. The authigenic illites ages from the Lower Jurassic Yangxia Group sandstones in the Yinan-2 gas reservoir (Yinan-2, Kuqa Depression) range from 28.1 to 23.9 Ma, suggesting that the initial hydrocarbon charging occurred in the Miocene. The ages of the authigenic illites from the Lower Cretaceous sandstones in the Akemomu gas field (Ake-1, Kashi Sag, Southwest Depression) range from 22.6 to 18.8 Ma, indicating a probable early oil accumulation or early migration of hydrocarbon within this area. The illites from the Paleogene sandstones in the Dina-2 gas reservoir (Dina-201, Kuqa Depression) have a detrital origin; they cannot be used to study the hydrocarbon charging histories. The ages of authigenic illites in the underlying Cretaceous sandstones in the same well (Dina-201) range from 25.5 to 15.5 Ma, indicating that hydrocarbon charging in this reservoir probably occurred within the Miocene. This study highlights the potential of applying K-Ar dating of authigenic illites to investigate the timing of hydrocarbon charging histories of the Tarim Basin reservoir sandstones.

The effect of pH on the sorption of gold nanoparticles on illite

Sorption between nanoparticles(NPs)and minerals may critically affect the migration of associated elements as well as the environmental impact of NPs.Since illite is widely present in soil,sediment,and water,we have experimentally investigated the sorption behavior of citrate-coated gold nanoparticles(AuNPs)as model NPs on illite under different pH and mineral mass conditions.We demonstrated that sorption of these negatively charged AuNPs strongly depended on the suspension pH.At pH above 8,which coincided with the apparent point of zero charge(pH 7.9)of our illite sample,only marginal sorption of AuNPs was observed.At pH 3-8,significant sorption of AuNPs on illite was found,with almost complete sorption occurring at more acidic conditions(pH 3-4).TEM observations revealed that sorption took place through the attachment AuNPs on illite edges.At pH 2,AuNPs mostly formed chain-like fused structures and precipitated out of the suspension.Based upon the above pH dependence,residual organic ligand content after sorption,and complementary sorption results with positively charged AuNPs,we conclude that the sorption process is mainly driven by the electrostatic attraction between negatively charged AuNPs and positively charged illite edges,with possible competitive involvement of citrate molecules.We expect that our findings will improve our understanding of NP-mineral interaction and the environmental fate of NPs.

Evaluation of 40^Ar/39^Ar Geochronology of Authigenic Illites in Determining Hydrocarbon Charge Timing： A Case Study from the Silurian Bituminous Sandstone Reservoirs, Tarim Basin, China

The Silurian bituminous sandstones（SBS） in the Tarim Basin, China are important basinwide reservoirs with an estimated area of approximately 249000 km^2. We investigated the ages of authigenic illites in the SBS reservoirs and constrained their formation timing by using the 40^Ar/39^Ar step wise heating method. The age spectra, 39^Ar recoil loss and their controlling factors were investigated systematically. The 40^Ar/39^Ar ages were compared with the conventional K/Ar ages of identical clay fractions. The clay in the SBS reservoirs is dominated by orderly mixed-layer illite/smectite（I/S） with 5%–30% smectite layers. The I/S minerals morphology comprises primarily honeycomb, short filamentous and curved-lath particles, characteristic of authigenic illites. The unencapsulated 40^Ar/39^Ar total gas ages（UTGA） of the authigenic illites range from 188.56 ± 6.20 Ma to 491.86 ± 27.68 Ma, which are 7% to 103% older than the corresponding K/Ar ages of 124.87 ± 1.11 Ma to 383.45 ± 2.80 Ma, respectively. The K-Ar ages indicate multistage accumulations with distinct distribution patterns in the Tarim Basin： older（late Caledonian-early Hercynian） around the basin margin, younger（late Hercynian） in the basin centre, and the youngest（middle to late Yanshanian） in the Ha-6 well-block, central area of the North Uplift. The age difference is believed to have been caused by the 39^Ar recoil loss during the irradiation process. Compared with the K/Ar ages, the estimated 39^Ar recoil losses in this study are in the range from 7% to 51%. The 39^Ar recoil loss appears to increase not only with the decreasing particle sizes of the I/S, but also with increasing percentage of smectite layers（IR） of the I/S, and smectite layer content（SLC） of the samples. We conclude that due to significant 39^Ar recoil losses, UTGA may not offer any meaningful geological ages of the authigenic illite formation in the SBS and thus can not be used to represent the hydrocarbon charge timing. 39^Ar recoil losses during 40^Ar/39^Ar dating can not be neglected when dating fine authigenic illite, especially when the ordered mixed-layer I/S containing small amount of smectite layers（IR30%） in the reservoir formations. Compared with the unencapsulated Ar-Ar method, the conventional K-Ar method is less complicated, more accurate and reliable in dating authigenic illites in petroleum reservoirs.

Spectroscopic study on variations in illite surface properties after acid-base titration

FT IR, Raman microscopy, XRD, 29 Si and 27 Al MAS NMR, were used to investigate changes in surface properties of a natural illite sample after acid base potentiometric titration. The characteristic XRD lines indicated the presence of surface Al Si complexes, preferable to Al(OH) 3 precipitates. In the microscopic Raman spectra, the vibration peaks of Si O and Al O bonds diminished as a result of treatment with acid, then increased after hydroxide back titration. The varied ratio of signal intensity between IV Al and VI Al species in 27 Al MAS NMR spectra, together with the stable BET surface area after acidimetric titration, suggested that edge faces and basal planes in the layer structure of illite participated in dissolution of structural components. The combined spectroscopic evidence demonstrated that the reactions between illite surfaces and acid leaching silicic acid and aluminum ions should be considered in the model description of surface acid base properties of the aqueous illite.

Displacement of shale gas confined in illite shale by flue gas: A molecular simulation study

The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefore,using CO_(2) gas to displace shale gas has become an important topic.In this work,we use molecular simulations to study the displacement of shale gas by flue gas rather than CO_(2),in which flue gas is modeled as a binary mixture of CO_(2) and N_(2) and the shale model is represented by inorganic Illite and organic methylnaphthalene.CH_(4) is used as a shale gas model.Compared to the pure CO_(2),flue gas is easily available and the cost of displacement by flue gas would become lower.Results indicate that the pore size of shale is an important factor in the process of displacing shale gas and simultaneously sequestrating flue gas,while the flue gas N_(2)-CO_(2) ratio shows a small effect on the process of CH_(4) displacement,because the high partial pressure of flue gas is the main driving force for displacement of shale gas.Moreover,the geological condition also has a significant effect on the process of CH_(4) displacement by flue gas.Therefore,we suggest that the burial depth of 1 km is suitable operation condition for shale gas displacement.It is expected that this work provides a useful guidance for exploitation of shale gas and sequestration of greenhouse gas.

Study of the Stacking Sequences of an Irregular Mixed-Layer Illite/Smectite (I/S) Clay Mineral—with a Discussion on the Existence of Minerals with Two-Dimentional Lattice and One-Dimentional Quasi-Lattice

There are two aspects in the study of irregular mixed-layer clay minerals: one is the kinds and ratios of their basic structural unit layers and the other is the junction probabilities of the unit layers. Irregular mixed-layer illite/smectite clay minerals (I/S) are widespread in nature. While studying the clay minerals from the Permian-Triassic (P/T) boundary bed, the authors found that I/S clay minerals are developed in all P/T boundary clay layers in areas from the northwest to southeast of China. Systematic mineralogical studies of the I/S clay minerals from Hunan, Hubei, Sichuan and Zhejiang were made by means of X-ray, infrared spectroscopic, electron microscopic and chemical analyses and a deepened study of the stacking sequences of their structural unit layers was conducted by the MacEwan one—dimentional direct Fourier transform. It was found that the stacking of the illite and smectite crystal layers along the c axis can be derived from Fibonacci sequences. Hence, the authors propose that such I/S clay minerals are possessed of two—dimentional crystal lattice and one—dimentional quasicrystal lattice.

Dating Model of Illite Grain Rb-Sr Isochron and Its Application to Precambrian Stratigraphy

This paper discusses the Rb-Sr geochemical behaviour of illites in the sedimentary process, and points out that illites of the lmd and lm types could reach Sr-isotopic equilibrium with its environmental medium during the sedimentary process and initial stage of diagenesis, and illite grains of different sizes have various Rb contents. A new dating method for sedimentary rocks----a dating model of illite grain Rb-Sr isochron----is established, in consideration of the geochemical process of Sr-isotopic homogenization and differentiation in the course of their formation and evolution. In addition, the paper concerns the application of the dating model to the Precambrian unmetamorphosed sedimentary rocks in western Henan Province, which gives satisfactory results coincident with the geological facts.

Surface charge property governing co-transport of illite colloids and Eu(Ⅲ) in saturated porous media

The transport of colloids and radionuclides is sophisticated because of the variety of charge properties between colloidal particles and host subsurface media, which causes great difficulty in establishing a reliable model of radionuclides migration by taking the colloid phase into consideration. In this work,the co-transport of illite colloids(IC) and Eu(Ⅲ) in the quartz sand and iron-coated sand porous media was investigated by column experiments to address the predominant mechanism of charge properties on co-transport. Results showed that Eu(Ⅲ) transport was driven by the illite colloids and electrostatic interaction was critical in governing the co-transport patterns. The promotion of Eu(Ⅲ) transport by IC was attenuated in the iron-coated sand systems;more IC-Eu(Ⅲ) complexes were retained uniformly in the column. The pore throat shrinkage caused by electrostatic attachment between aggregated IC and iron oxides exacerbated the physical straining and size exclusion effect of IC-Eu(Ⅲ) complexes. An aggravated irreversible retention of IC-Eu(Ⅲ) was detected in iron-coated sand column due to the electrostatic attraction of IC-Eu(Ⅲ) to host media. The findings are essential for improving the understanding on the potential transport, retention and release risk of colloids associated radionuclides, and imply that the positively charged permeable reactive barrier is an effective strategy to reduce the transport risk of colloid associated radionuclides.

Experiment of the ^(40)Ar/^(39)Ar dating of diagenetic illite in gas reservoirs

40Ar/39Ar dating of diagenetic illite has been performed to investigate gas reservoirs in the Sulige Gas Field of the northern Ordos Basin. A series of technical challenges were confronted, including illite purification, Ar recoil loss, and separation of diagenetic illite from detrital illite. Mineral growth ages for diagenetic illite were obtained by this experiment, from which the age of gas emplacement was deduced to be later than 169 Ma.

Ore-forming fluid constraints on illite crystallinity(IC)at Dexing porphyry copper deposit,Jiangxi Province

Illite, a distinctive kind of clay minerals of potassiumalteration within the hydrothermal alteration zone, frequently occurs at the Tongchang porphyry copper deposit ore field. The illite crystallinity (IC) value and expandability are mainly affected by water/rock ratio or fluid flux. It was formed by illitization of plagioclase and micas during hydrothermal fluid-rock interaction within the porphyry body and near the contact zone with wall rocks. Moreover, the negative correlation between illite index (IC) and copper grade indicates that within the alteration zone, the smaller the illite crystallinity value, the higher the alteration degree, and the higher the copper grade due to higher water/rock ratio. At lower levels of the porphyry body, however, the illite crystallinity (IC) values are mainly controlled by temperature and time duration.

Microstructure characteristics of illite from Chuanlinggou Formation of Changcheng System in Jixian County, Tianjin City

The microstructure charateristics of illite from the Chuanlinggou Formation of Changcheng System (Chch) in Jixian County, Tianjin City has been studied by means of high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), X-ray energy dispersive spectrum (EDS) and X-ray powder diffraction (XRD). The Kübler index of "illite crystallinity" is 0.505°△2θ, which indicates that the host rock is in a middle diagenetic stage. The chemical analyses of EDS for illite studied indicate a heavily absent in interlayer cation and an average chemical formula of K0.57(Al1.80Mg0.42Fe2+0.12)Σ=2.34 (Si2.92Al1.08)Σ=4O10(OH)2. It is found, from one-dimensional lattice images, that the layers of illite not only stack in a flat way but also in a curving way. A "matting fabric" illite structure results from stacking faults. Combined with SAED analysis the illite studied can be affirmed as 1M illite. The two-dimensional lattice images are obtained from [100] and [110] incidences, whose lattice images have the same d-values but different intersecting angles. The two-dimensional lattice image with [100] incidence is orthogonal to each other, whilst that with [110] incidence is oblique. This paper provides some important structure information of authigenic clay minerals for the well-known mesoproterozoic section of Jixian County.

Origin of illites in the Luochuan loess section——Evidence from TEM study

Morphology and composition of illite from the Luochuan loess section were investigated by TEM. The results show that most of the illite grains are characterized by rounded shapes and chemical compositions are closely similar to those of anchizonal illites. The enrichment of illites in paleosol over loess was mainly caused by the weak winter monsoon during the interglacial periods, and was not related to the in situ pedogenesis. Illite can serve as an indicator for tracing eolian dust from Loess Plateau in pelagic and lacustrine sediments.

Synthesis of a novel illite@carbon nanocomposite adsorbent for removal of Cr(Ⅵ)from wastewater

A novel illite@carbon（I@C） nanocomposite adsorbent has been synthesized via a facile hydrothermal carbonization process（HTC） using glucose as carbonaceous source and illite as the carrier.The morphology,microstructure and surface properties of the prepared nanocomposite adsorbent were analyzed by FESEM,TGA,XRD,FT-IR and Zeta potential measurements.Batch experiments were carried out on the adsorption of Cr（Ⅵ） to determine the adsorption properties of the composite.The adsorption of Cr（Ⅵ） onto the I@C nanocomposite was well described by the pseudo-second-order kinetic model and Langmuir isotherm.Compared with the illite and carbon material（SC） separately,the prepared I@C nanocomposite adsorbent exhibited enhanced adsorption performance for Cr（Ⅵ） with a maximum adsorption capacity of 149.25 mg/g,which was higher than that of most reported adsorbents.In addition,the adsorption process was spontaneous and endothermic based on the adsorption thermodynamics study.The adsorption of Cr（Ⅵ） by I@C was highly p H-dependent and the optimum adsorption occurred at p H 2.0.The Zeta potential analysis results indicated that the electrostatic interactions between anionic Cr（Ⅵ） and the positively charged surface of the adsorbent might be critical to the adsorption mechanism.This study demonstrated that the I@C nanocomposite should be a promising candidate for a low-cost,environmental friendly and highly efficient adsorbent for the removal of toxic Cr（Ⅵ） from wastewater.

Alkylammonium cations treating and K-Ar dating of illite from mudstones

Two kinds of mudstones from the Tarim Basin and the Tuna Basin were treated with C8 and C18 alkylammonium cations. Both of them were dated by the K-Ar method. One kind of rock contains mainly diagenetic illite, and the other contains mixed layer illite/smectite (I/S). Sample separation and alkylamnionium cations treatment were performed first, and K-Ar dating followed. The result shows that fine-grained minerals have younger K-Ar ages and coarse-grained components have older ages. Plots of K-Ar age versus K2O (%) are linear, the range of diagenetic age can be estimated by extrapolation. The reaction results of the above samples are different after alkylamnionium cations treatments. The samples containing mainly illite show a decrease in K2O and an increase in age by 1-25 Ma, suggesting that preferential exchange of young diagenetic clay rather than detrital clay by alkylamnionium cations, therefore the age of diagenetic illite can be calculated directly by the % K2O and radiogenic 40Ar removed. For the

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline（CTC） were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite（IS） clay,sodium silicate and magnesium sulfate as the starting materials.In this process,IS clay was ＂teared up＂ and then ＂rebuilt＂ as new porous silicate adsorbent with high specific surface area of 363.52 m^2/g（about 8.7 folds higher than that of IS clay） and very negative Zeta potential（- 34.5 mV）.The inert Si- O- Si（Mg,Al） bonds in crystal framework of IS were broken to form Si（Al）- O^- groups with good adsorption activity,which greatly increased the adsorption sites served for holding much CTC molecules.Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81 mg/g of CTC（only 159.7 mg/g for raw IS clay） and remove 99.3%（only 46.5%for raw IS clay） of CTC from 100 mg/L initial solution（pH 3.51;adsorption temperature 30℃;adsorbent dosage,3 g/L）.The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model,Temkin equation and pseudo second-order kinetic model.The mesopore adsorption,electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties.As a whole,the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC.

THE ELECTRON MICROSCOPY STUDY ON THE MIXED LAYER OF ILLITE AND CHLORITE

Clay minerals having the same type of octahedral layer commonly occur as mixed layers. With the application of electron microscopy in day mineralogy, it is recognized that clay minerals which have different octahedral sheets can also form mixed layers, such as the mixed layer of illite and chlorite which has been well studied. However, there are different opinions on its origin. Based on the study of transmission electron microscopy (TEM)

A comparative study on the illite crystallinity and the clay mineral reflectance spectral index for subdividing the very low-grade metamorphic belt along the Lizhou-Hekou geological section in the Youjiang sedimentary basin, Guangxi, China

To examine the application potential of hyperspectral remote sensing techniques in classifying very low-grade metamorphic belts, the composition of clay minerals and the cyrstallinity of illite from mudstones were measured using XRD and VIS-SWIR (400—2500 nm) reflectance spectroscopy. Based on the illite cyrstallinity, Kbler Index (KI), the Early Triassic LuoLou Group and the Middle Triassic lower Baifeng Formation were classified as the lower Epizone with KID2q° ranging from 0.22 to 0.25, the upper Baifeng Formation as upper anchizone with KID2q° ranging from 0.26 to 0.33, and the Hekou Formation as lower anchizone with KID2q° ranging from 0.38 to 0.40. According to a KID2q° value of 0.43, it is possible that there may exist a local diagenetic zone in the upper strata. The illite cyrstallinity Kbler index and the metamorphic grade increase from the bottom to the top of the stratigraphic sequence. The metamorphic grade boundaries nearly match the stratigraphic boundaries, indicating a burial metamorphism nature for the stratigraphic sequence. From the bottom to the top of the sequence, the spectral absorption band center of clay minerals from fresh rocks is around 2200 nm. The absorption band centers change towards shorter wavelengths: the Luolou Group being at 2220 nm, the Baifeng Formation at 2217—2213 nm, the lower member of the Hekou Formation at 2214—2206 nm, and the upper member of the Hekou Formation at 2205—2197 nm. The spectral absorption band center of illite shows the same change pattern. These results indicate that very low-grade metamorphic belts can be subdivided using spectral indices of clay minerals, which are measured by using field portable spectroradiometers. However, it may not work well with satellite and airborne sensors.