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7 pages, 179 KiB

Open AccessEditorial

Editorial for Special Issue “Nanomineralogy”

by Yiwen Ju, Quan Wan and Michael F. Hochella, Jr.

Minerals 2020, 10(6), 520; https://doi.org/10.3390/min10060520 - 5 Jun 2020

Cited by 3 | Viewed by 1951

Abstract

Nanoscience and nanotechnology study the properties of materials within the range 0 [...] Full article

(This article belongs to the Special Issue Nanomineralogy)

Research

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11 pages, 3135 KiB

Open AccessArticle

Structural Phase Transition and Metallization of Nanocrystalline Rutile Investigated by High-Pressure Raman Spectroscopy and Electrical Conductivity

by Meiling Hong, Lidong Dai, Heping Li, Haiying Hu, Kaixiang Liu, Linfei Yang and Chang Pu

Minerals 2019, 9(7), 441; https://doi.org/10.3390/min9070441 - 18 Jul 2019

Cited by 15 | Viewed by 3563

Abstract

We investigate the structural, vibrational, and electrical transport properties of nanocrystalline rutile and its high-pressure polymorphs by Raman spectroscopy, and AC complex impedance spectroscopy in conjunction with the high-resolution transmission electron microscopy (HRTEM) up to ~25.0 GPa using the diamond anvil cell (DAC). [...] Read more.

We investigate the structural, vibrational, and electrical transport properties of nanocrystalline rutile and its high-pressure polymorphs by Raman spectroscopy, and AC complex impedance spectroscopy in conjunction with the high-resolution transmission electron microscopy (HRTEM) up to ~25.0 GPa using the diamond anvil cell (DAC). Experimental results indicate that the structural phase transition and metallization for nanocrystalline rutile occurred with increasing pressure up to ~12.3 and ~14.5 GPa, respectively. The structural phase transition of sample at ~12.3 GPa is confirmed as a baddeleyite phase, which is verified by six new Raman characteristic peaks. The metallization of the baddeleyite phase is manifested by the temperature-dependent electrical conductivity measurements at ~14.5 GPa. However, upon decompression, the structural phase transition from the metallic baddeleyite to columbite phases at ~7.2 GPa is characterized by the inflexion point of the pressure coefficient and the pressure-dependent electrical conductivity. The recovered columbite phase is always retained to the atmospheric condition, which belongs to an irreversible phase transformation. Full article

(This article belongs to the Special Issue Nanomineralogy)

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18 pages, 6603 KiB

Open AccessArticle

Pyrite Morphology as an Indicator of Paleoredox Conditions and Shale Gas Content of the Longmaxi and Wufeng Shales in the Middle Yangtze Area, South China

by Ziyi Liu, Dongxia Chen, Jinchuan Zhang, Xiuxiang Lü, Ziyi Wang, Wenhao Liao, Xuebin Shi, Jin Tang and Guangjie Xie

Minerals 2019, 9(7), 428; https://doi.org/10.3390/min9070428 - 12 Jul 2019

Cited by 51 | Viewed by 5388

Abstract

Pyrite is the most common authigenic mineral preserved in many ancient sedimentary rocks. Pyrite also widely exists in the Longmaxi and Wufeng marine shales in the middle Yangtze area in South China. The Longmaxi and Wufeng shales were mainly discovered with 3 types [...] Read more.

Pyrite is the most common authigenic mineral preserved in many ancient sedimentary rocks. Pyrite also widely exists in the Longmaxi and Wufeng marine shales in the middle Yangtze area in South China. The Longmaxi and Wufeng shales were mainly discovered with 3 types of pyrites: pyrite framboids, euhedral pyrites and infilled framboids. Euhedral pyrites (Py4) and infilled framboids (Py5) belong to the diagenetic pyrites. Based on the formation mechanism of pyrites, the pyrites could be divided into syngenetic pyrites, early diagenetic pyrites, and late diagenetic pyrites. Under a scanning electron microscope (SEM), the syngenetic pyrites are mostly small framboids composed of small microcrystals, but the diagenetic pyrites are variable in shapes and the diagenetic framboids are variable in sizes with large microcrystals. Due to the deep burial stage, the pore space in the sediment was sharply reduced and the diameter of the late diagenetic framboids that formed in the pore space is similar to the diameter of the syngenetic framboids. However, the diameter of the syngenetic framboid microcrystals is suggested to range mainly from 0.3 µm to 0.4 µm, and that of the diagenetic framboid microcrystals is larger than 0.4 µm in the study area. According to the diameter of the pyrite framboids (D) and the diameter of the framboid microcrystals (d), the pyrite framboids could be divided into 3 sizes: syngenetic framboids (Py1, D < 5 µm, d ≤ 0.4 µm), early diagenetic framboids (Py2, D > 5 µm, d > 0.4 µm) and late diagenetic framboids (Py3, D < 5 µm, d > 0.4 µm). Additionally, the mean size and standard deviation/skewness values of the populations of pyrite framboids were used to distinguish the paleoredox conditions during the sedimentary stage. In the study area, most of the pyrite framboids are smaller than 5 µm, indicating the sedimentary water body was a euxinic environment. However, pyrite framboids larger than 5 µm in the shales indicated that the sedimentary water body transformed to an oxic-dysoxic environment with relatively low total organic carbon (TOC: 0.4–0.99%). Furthermore, the size of the framboid microcrystals could be used to estimate the gas content due to thermochemical sulfate reduction (TSR). The process of TSR occurs with oxidation of organic matter (OM) and depletes the H bond of the OM, which will influence the amount of alkane gas produced from the organic matter during the thermal evolution. Thus, syngenetic pyrites (d ranges from 0.35 µm to 0.37 µm) occupy the main proportion of pyrites in the Wufeng shales with high gas content (1.30–2.30 m³/t), but the Longmaxi shales (d ranges from 0.35 µm to 0.72 µm) with a relatively low gas content (0.07–0.93 m³/t) contain diagenetic pyrites. Because of TSR, the increasing size of the microcrystals may result in an increase in the value of δ¹³C₁ and a decrease in the value of δ¹³C₁-δ¹³C₂. Consequently, the size of pyrite framboids and microcrystals could be widely used for rapid evaluation of the paleoredox conditions and the gas content in shales. Full article

(This article belongs to the Special Issue Nanomineralogy)

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21 pages, 8867 KiB

Open AccessArticle

Metal-Bearing Nanoparticles Observed in Soils and Fault Gouges over the Shenjiayao Gold Deposit and Their Significance

by Bimin Zhang, Zhixuan Han, Xueqiu Wang, Hanliang Liu, Hui Wu and Hui Feng

Minerals 2019, 9(7), 414; https://doi.org/10.3390/min9070414 - 5 Jul 2019

Cited by 21 | Viewed by 3587

Abstract

Mineral deposits concealed by thick cover sequences present special problems for geochemical exploration. A variety of penetrating geochemical methods have been developed in the last few decades to explore for buried deposits. The theoretical basis of the mechanism by which metals migrate upward [...] Read more.

Mineral deposits concealed by thick cover sequences present special problems for geochemical exploration. A variety of penetrating geochemical methods have been developed in the last few decades to explore for buried deposits. The theoretical basis of the mechanism by which metals migrate upward from buried deposits through the cover to the surface is still not fully understood. One hypothesis is that metal particles or metal elements could be carried onto bubbles or micro-flow of geogas and migrate upward to the surface. After years of study, nano-scale metal-bearing particles have been widely observed in geogas samples from different kinds of concealed deposits. However, the occurrence of these metal-bearing particles carried by geogases in near-surface media, such as soil, has not been studied in detail. In this study, metal-bearing nanoparticles were observed in samples from soils and fault gouges over the Shenjiayao gold deposit. The results indicate that (1) the ore-forming elements in soils can only come from deep-seated ore bodies and they occur in nanoparticles in the study area; (2) there is an obvious relationship between metal nanoparticles in fault gouges and soils; (3) the metallic nanoparticles in fault gouges represent a transitional phase along the whole vertical migration process. In addition, the observation results show that the metal-bearing nanoparticles tend to be adsorbed on the surface of clay minerals, which provide theoretical support for using fine fraction soils as sampling media to carry out geochemical exploration in sediment-covered terrains. Based on the results and discussion, a simple migration model was built in this paper. Full article

(This article belongs to the Special Issue Nanomineralogy)

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25 pages, 17211 KiB

Open AccessArticle

Geochemical Alteration and Mineralogy of Coals under the Influence of Fault Motion: A Case Study of Qi’nan Colliery, China

by Hewu Liu and Bo Jiang

Minerals 2019, 9(7), 389; https://doi.org/10.3390/min9070389 - 27 Jun 2019

Cited by 5 | Viewed by 3492

Abstract

Geochemical characteristics of rocks in fault zones have been extensively studied, while there are limited studies on coal occurring in fault zones of underground coal mine. In this study, five coal samples were carefully collected from a reverse fault zone in Qi’nan colliery. [...] Read more.

Geochemical characteristics of rocks in fault zones have been extensively studied, while there are limited studies on coal occurring in fault zones of underground coal mine. In this study, five coal samples were carefully collected from a reverse fault zone in Qi’nan colliery. Systematical detection methods were employed to analyze the different chemical and physical characteristics of fault-related coal samples. Through comparative analysis, the following insights are obtained. Three subdivided fault zones were classified according to the deformation characteristics of coal samples. Frictional heat and strong ductile deformation generated by fault motion led to the dissociation of phenol and carboxyl groups in coal molecules, which sharply decreased the concentrations of elements Co and Mo bound to these functional groups in zone I. The modified pore-cleat system in zone I with higher pore volume and lower permeability allowed solutions containing enriched trace elements to migrate through zone I locally. Concentrations of HREE, MREE and related elements associated with the invasive solutions showed significant positive anomalies in zone I. Precipitation and smearing of clay minerals in zone I led to poorer connectivity. Disruption and delamination of laminar clay minerals by strong compression-shear stress significantly increased the adsorption sites for related elements, especially the HREE and MREE. Nano-scale clay minerals resulting from stress-induced scaly exfoliation also enhanced the retention capability of REE in zone I. Full article

(This article belongs to the Special Issue Nanomineralogy)

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19 pages, 5928 KiB

Open AccessArticle

Nano-Scale Pore Structure and Fractal Dimension of Longmaxi Shale in the Upper Yangtze Region, South China: A Case Study of the Laifeng–Xianfeng Block Using HIM and N₂ Adsorption

by Cheng Huang, Yiwen Ju, Hongjian Zhu, Yu Qi, Kun Yu, Ying Sun and Liting Ju

Minerals 2019, 9(6), 356; https://doi.org/10.3390/min9060356 - 12 Jun 2019

Cited by 21 | Viewed by 3598

Abstract

This paper tries to determine the key evaluation parameters of shale reservoirs in the complex tectonic provinces outside the Sichuan Basin in South China, and also to target the sweet spots of shale reservoirs accurately. The pore-structure characteristics of the Lower Silurian Longmaxi [...] Read more.

This paper tries to determine the key evaluation parameters of shale reservoirs in the complex tectonic provinces outside the Sichuan Basin in South China, and also to target the sweet spots of shale reservoirs accurately. The pore-structure characteristics of the Lower Silurian Longmaxi shale gas reservoirs in Well LD1 of the Laifeng–Xianfeng Block, Upper Yangtze region, were evaluated. N₂ adsorption and helium ion microscope (HIM) were used to investigate the pore features including pore volume, pore surface area, and pore size distribution. The calculated results show good hydrocarbon storage capacity and development potential of the shale samples. Meanwhile, the reservoir space and migration pathways may be affected by the small pore size. As the main carrier of pores in shale, organic matter contributes significantly to the pore volume and surface area. Samples with higher total organic carbon (TOC) content generally have higher porosity. Based on the Frenkel–Halsey–Hill equation (FHH model), two different fractal dimensions, D₁ and D₂, were observed through the N₂ adsorption experiment. By analyzing the data, we found that large pores usually have large values of fractal dimension, owing to their complex pore structure and rough surface. In addition, there exists a good positive correlation between fractal dimension and pore volume as well as pore surface area. The fractal dimension can be taken as a visual indicator that represents the degree of development of the pore structure in shale. Full article

(This article belongs to the Special Issue Nanomineralogy)

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20 pages, 8865 KiB

Open AccessArticle

Tectonic and Thermal Controls on the Nano-Micro Structural Characteristic in a Cambrian Organic-Rich Shale

by Hongjian Zhu, Yiwen Ju, Cheng Huang, Yu Qi, Liting Ju, Kun Yu, Wuyang Li, Xin Su, Hongye Feng and Peng Qiao

Minerals 2019, 9(6), 354; https://doi.org/10.3390/min9060354 - 10 Jun 2019

Cited by 16 | Viewed by 3498

Abstract

Until recently, the characteristics of nano-microscale structures in the naturally deformed, overmature, marine shales were poorly known. Thermally overmature Lujiaping shales in the complex tectonic area of the northeast part of the upper Yangtze area, China have experienced strong tectonic deformation and are [...] Read more.

Until recently, the characteristics of nano-microscale structures in the naturally deformed, overmature, marine shales were poorly known. Thermally overmature Lujiaping shales in the complex tectonic area of the northeast part of the upper Yangtze area, China have experienced strong tectonic deformation and are considered as potentially important strata for shale gas exploration. Naturally deformed samples from the main source rocks are selected from the Lower Cambrian Lujiaping Formation in the Dabashan Thrust-fold Belt to investigate nanometer- to micrometer-sized structures. A combination of scanning electron microscope (SEM), low-pressure nitrogen adsorption (LPNA), and low-field nuclear magnetic resonance (NMR) suggests that the pore types are dominantly fracture-related pores with a lesser abundance of mineral-hosted pores. These two pore types account for the 90% of total pore space. Organic matter (OM)-hosted pores are rare and make up a small part of the pore systems (less than 10%) due to high thermal maturity and intensive tectonic compression. Overall, the Lujiaping deformed, overmature samples have abundant nanometer- to micrometer-sized inorganic pores. High-resolution SEM images provide direct evidence of the formation of nano- and microsized structures such as OM–clay aggregates and silica nanograins. OM–clay aggregates are commonly observed in samples, which also exhibit abundant open microfractures and interparticle pores. Quartz can occur as silica nanograins and botryoids typically 20–100 nm in size, which may influence porosity through the creation or occupying interparticle pore space. Full article

(This article belongs to the Special Issue Nanomineralogy)

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14 pages, 3134 KiB

Open AccessArticle

Predominantly Ferruginous Conditions in South China during the Marinoan Glaciation: Insight from REE Geochemistry of the Syn-glacial Dolostone from the Nantuo Formation in Guizhou Province, China

by Shangyi Gu, Yong Fu and Jianxi Long

Minerals 2019, 9(6), 348; https://doi.org/10.3390/min9060348 - 5 Jun 2019

Cited by 16 | Viewed by 3469

Abstract

The Neoproterozoic Era witnessed two low-latitude glaciations, which exerted a fundamental influence on ocean–atmosphere redox conditions and biogeochemical cycling. Climate models and palaeobiological evidence support the belief that open waters provided oases for life that survived snowball Earth glaciations, yet independent geochemical evidence [...] Read more.

The Neoproterozoic Era witnessed two low-latitude glaciations, which exerted a fundamental influence on ocean–atmosphere redox conditions and biogeochemical cycling. Climate models and palaeobiological evidence support the belief that open waters provided oases for life that survived snowball Earth glaciations, yet independent geochemical evidence for marine redox conditions during the Marinoan glaciation remains scarce owing to the apparent lack of primary marine precipitates. In this study, we explore variability in rare earth elements (REEs) and trace metal concentrations in dolostone samples of the Cryogenian Nantuo Formation taken from a drill core in South China. Petrological evidence suggests that the dolostone in the Nantuo Formation was formed in near-shore waters. All the examined dolostone samples featured significant enrichment of manganese (345–10,890 ppm, average 3488 ppm) and middle rare earth elements (MREEs) (Bell Shape Index: 1.43–2.16, average 1.76) after being normalized to Post-Archean Australian Shale (PAAS). Most dolostone samples showed slight to no negative Ce anomalies (Ce*/Ce 0.53–1.30, average 0.95), as well as positive Eu anomalies (Eu*/Eu 1.77–3.28, average 1.95). This finding suggests that the dolostone samples were deposited from suboxic to iron-enriched and anoxic waters. Although total REE concentrations correlated positively with Th concentrations in dolostone samples, MREE-enriched PAAS-normalized patterns preclude the conclusion that REEs were largely introduced by terrestrial contamination. Rather, we interpret the correlation between REEs and Th as an indication that the former were transported by colloids and nanoparticles in meltwaters. Taken together, we propose that anoxic and ferruginous water columns dominated in South China during the Marinoan glaciation with a thin oxic/suboxic layer restricted to coastal waters. The extreme anoxic and ferruginous conditions prevailing in the Cryogenian would have provided a baseline for subsequent transient Ediacaran ocean oxygenation and life evolution. Full article

(This article belongs to the Special Issue Nanomineralogy)

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14 pages, 4100 KiB

Open AccessArticle

Enhanced Potential Toxic Metal Removal Using a Novel Hierarchical SiO₂–Mg(OH)₂ Nanocomposite Derived from Sepiolite

by Qi-Zhi Yao, Sheng-Hui Yu, Tian-Lei Zhao, Fei-Jin Qian, Han Li, Gen-Tao Zhou and Sheng-Quan Fu

Minerals 2019, 9(5), 298; https://doi.org/10.3390/min9050298 - 15 May 2019

Cited by 15 | Viewed by 4025

Abstract

Clays are widely used as sorbents for heavy metals due to their high specific surface areas, low cost, and ubiquitous occurrence in most soil and sediment environments. However, the low loading capacity for heavy metals is one of their inherent limitations. In this [...] Read more.

Clays are widely used as sorbents for heavy metals due to their high specific surface areas, low cost, and ubiquitous occurrence in most soil and sediment environments. However, the low loading capacity for heavy metals is one of their inherent limitations. In this work, a novel SiO₂–Mg(OH)₂ nanocomposite was successfully prepared via sequential acid–base modification of raw sepiolite. The structural characteristics of the resulting modified samples were characterized by a wide range of techniques including field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and nitrogen physisorption analysis. The results show that a hierarchical nanocomposite constructed by loading the Mg(OH)₂ nanosheets onto amorphous SiO₂ nanotubes can be successfully prepared, and the nanocomposite has a high surface area (377.3 m²/g) and pore volume (0.96 cm³/g). Batch removal experiments indicate that the nanocomposite exhibits high removal efficiency toward Gd(III), Pb(II), and Cd(II), and their removal capacities were greatly enhanced in comparison with raw sepiolite, due to the synergistic effect of the different components in the hierarchical nanocomposite. This work can provide a novel route toward a hierarchical nanocomposite by using clay minerals as raw material. Taking into account the simplicity of the fabrication route and the high loading capacities for heavy metals, the developed nanocomposite also has great potential applications in water treatment. Full article

(This article belongs to the Special Issue Nanomineralogy)

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13 pages, 2237 KiB

Open AccessFeature PaperArticle

Iron-Rich Nanoparticles in Natural Aquatic Environments

by Bjorn von der Heyden, Alakendra Roychoudhury and Satish Myneni

Minerals 2019, 9(5), 287; https://doi.org/10.3390/min9050287 - 11 May 2019

Cited by 10 | Viewed by 4212

Abstract

Naturally-occurring iron nanoparticles constitute a quantitatively-important and biogeochemically-active component of the broader Earth ecosystem. Yet detailed insights into their chemical speciation is sparse compared to the body of work conducted on engineered Fe nanoparticles. The present contribution briefly reviews the analytical approaches that [...] Read more.

Naturally-occurring iron nanoparticles constitute a quantitatively-important and biogeochemically-active component of the broader Earth ecosystem. Yet detailed insights into their chemical speciation is sparse compared to the body of work conducted on engineered Fe nanoparticles. The present contribution briefly reviews the analytical approaches that can be used to characterize natural Fe nanoparticles, before detailing a dedicated synchrotron-based X-ray spectro-microscopic investigation into the speciation of suspended Fe nanoparticles collected from fluvial, marine, and lacustrine surface waters. Ferrous, ferric and magnetite classes of Fe nanoparticles (10–100 nm) were identified, and all three classes exhibited a high degree of heterogeneity in the local bonding environment around the Fe center. The heterogeneity is attributed to the possible presence of nanoparticle aggregates, and to the low degrees of crystallinity and ubiquitous presence of impurities (Al and organic moieties) in natural samples. This heterogeneity further precludes a spectroscopic distinction between the Fe nanoparticles and the larger sized Fe-rich particles that were evaluated. The presented results provide an important baseline for natural nanoparticle speciation in pristine aquatic systems, highlight the degree of inter-particle variability, which should be parameterized in future accurate biogeochemical models, and may inform predictions of the fate of released engineered Fe nanoparticles as they evolve and transform in natural systems. Full article

(This article belongs to the Special Issue Nanomineralogy)

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13 pages, 6510 KiB

Open AccessArticle

Facile Hydrothermal Synthesis of Nanocubic Pyrite Crystals Using Greigite Fe₃S₄ and Thiourea as Precursors

by Xin Nie, Suxing Luo, Meizhi Yang, Ping Zeng, Zonghua Qin, Wenbin Yu and Quan Wan

Minerals 2019, 9(5), 273; https://doi.org/10.3390/min9050273 - 1 May 2019

Cited by 16 | Viewed by 4715

Abstract

Nanocubic pyrite (FeS₂) crystals with exposed (100) crystal faces and sizes of 100–200 nm were successfully synthesized via a facile hydrothermal method using greigite (Fe₃S₄) as the iron precursor and thiourea (NH₂CSNH₂) as [...] Read more.

Nanocubic pyrite (FeS₂) crystals with exposed (100) crystal faces and sizes of 100–200 nm were successfully synthesized via a facile hydrothermal method using greigite (Fe₃S₄) as the iron precursor and thiourea (NH₂CSNH₂) as the sulfur source. When the concentration of thiourea was 40 mmol/L, both pyrite and hematite were observed in the as-prepared sample, indicating incomplete conversion of greigite into pyrite. With an increased thiourea concentration to 80 mmol/L, pyrite was found to be the only crystalline phase in the synthesized samples. All greigite could be transformed to pyrite within 24 h via the hydrothermal method, while further prolonging the hydrothermal time had insignificant effect on the crystal phase composition, crystallinity, and morphologies of the prepared nanocubic pyrite crystals. In contrast, when a mixture of Na₂S and S powder was used to replace the thiourea as the sulfur source, tetragonal, orthorhombic, cubic, and irregular pyrite crystal particles with sizes of 100 nm–1 μm were found to co-exist in the prepared samples. These results demonstrate the critical influence of sulfur source on pyrite morphology. Furthermore, our hydrothermal process, using a combination of greigite and thiourea, is proved to be effective in preparing nanocubic pyrite crystals. Our findings can also provide new insight into the formation environments and pathways of nanocubic pyrite under hydrothermal conditions. Full article

(This article belongs to the Special Issue Nanomineralogy)

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11 pages, 3048 KiB

Open AccessArticle

The Characterization and Amoxicillin Adsorption Activity of Mesopore CaCO₃ Microparticles Prepared Using Rape Flower Pollen

by Lvshan Zhou, Tongjiang Peng, Hongjuan Sun, Xiaogang Guo and Dong Fu

Minerals 2019, 9(4), 254; https://doi.org/10.3390/min9040254 - 25 Apr 2019

Cited by 16 | Viewed by 3844

Abstract

A precipitation reaction method was employed to prepare mesopore calcium carbonate (CaCO₃) using rape flower pollen as the template. CaCO₃ adsorbent was characterized using X-ray diffraction (XRD), scanning electronic microscopy (SEM), and Brunner−Emmet−Teller measurements (BET). The equilibrium adsorption data on [...] Read more.

A precipitation reaction method was employed to prepare mesopore calcium carbonate (CaCO₃) using rape flower pollen as the template. CaCO₃ adsorbent was characterized using X-ray diffraction (XRD), scanning electronic microscopy (SEM), and Brunner−Emmet−Teller measurements (BET). The equilibrium adsorption data on amoxicillin were explained using Langmuir, Freundlich, and Temkin adsorption isotherm models. The pseudo-first order, second order, pseudo-second order, and intra-particle diffusion kinetic models were used to explore adsorption kinetics. Equilibrium adsorption of as-prepared CaCO₃ was better depicted using the Langmuir adsorption model with an R² of 0.9948. The separation factor (R_L) was found to be in the range of 0 < R_L < 1, indicating the favorable adsorption of amoxicillin. The adsorption capacity of mesopore CaCO₃ reached 13.49 mg·g⁻¹ in 0.2 g∙L⁻¹ amoxicillin solution. The values of adsorption thermodynamic parameters (ΔH^θ, ΔS^θ, ΔG^θ) were obtained. In addition, the adsorption process turned out to be endothermic and spontaneous for the CaCO₃ product at 298 K, 308 K, and 318 K. Full article

(This article belongs to the Special Issue Nanomineralogy)

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17 pages, 6603 KiB

Open AccessArticle

Fractal Characteristics and Heterogeneity of the Nanopore Structure of Marine Shale in Southern North China

by Kun Yu, Yiwen Ju, Yu Qi, Peng Qiao, Cheng Huang, Hongjian Zhu and Hongye Feng

Minerals 2019, 9(4), 242; https://doi.org/10.3390/min9040242 - 19 Apr 2019

Cited by 23 | Viewed by 3815

Abstract

The characteristics of the nanopore structure in shale play a crucial role in methane adsorption and in determining the occurrence and migration of shale gas. In this study, using an integrated approach of X-ray diffraction (XRD), N₂ adsorption, and field emission scanning [...] Read more.

The characteristics of the nanopore structure in shale play a crucial role in methane adsorption and in determining the occurrence and migration of shale gas. In this study, using an integrated approach of X-ray diffraction (XRD), N₂ adsorption, and field emission scanning electron microscopy (FE-SEM), we systematically focused on eight drilling samples of marine Taiyuan shale from well ZK1 in southern North China to study the characteristics and heterogeneity of their nanopore structure. The results indicated that different sedimentary environments may control the precipitation of clay and quartz between transitional shale and marine shale, leading to different organic matter (OM)–clay relationships and different correlations between total organic carbon (TOC) and mineral content. The shale with high TOC content tended to have more heterogeneous micropores, leading to a higher fractal dimension and a more complex nanopore structure. With the increase of TOC content and thermal evolution of OM, the heterogeneity of the pore structure became more significant. Quartz from marine shale possessed abundant macropores, resulting in a decrease of the Brunauere–Emmette–Teller (BET) surface area (SA) and an increase of the average pore size (APS), while clay minerals developed a large number of micropores which worked together with OM to influence the nanopore structure of shale, leading to the increase of the SA and the decrease of the APS. The spatial order of interlayer pores increased with the increase of mixed-layer illite–smectite (MLIS) content, which naturally reduced the fractal dimensions. In contrast, kaolinite, chlorite, and illite have a small number of nanopores, which might enhance the complexity and reduce the connectivity of the nanopore system by mean of pore-blocking. Taiyuan shale with higher heterogeneity is highly fractal, and its fractal dimensions are principally related to the micropores. The fractal dimensions correlate positively with the SA and total pore volume, suggesting that marine shale with higher heterogeneity may possess a larger SA and a higher total pore volume. Full article

(This article belongs to the Special Issue Nanomineralogy)

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12 pages, 3680 KiB

Open AccessArticle

Two Hydrothermal Events at the Shuiyindong Carlin-Type Gold Deposit in Southwestern China: Insight from Sm–Nd Dating of Fluorite and Calcite

by Qinping Tan, Yong Xia, Zhuojun Xie, Zepeng Wang, Dongtian Wei, Yimeng Zhao, Jun Yan and Songtao Li

Minerals 2019, 9(4), 230; https://doi.org/10.3390/min9040230 - 12 Apr 2019

Cited by 26 | Viewed by 4547

Abstract

The Shuiyindong Gold Mine hosts one of the largest and highest-grade, strata-bound Carlin-type gold deposits discovered to date in Southwestern China. The outcrop stratigraphy and drill core data of the deposit reveal Middle–Upper Permian and Lower Triassic formations. The ore is mainly hosted [...] Read more.

The Shuiyindong Gold Mine hosts one of the largest and highest-grade, strata-bound Carlin-type gold deposits discovered to date in Southwestern China. The outcrop stratigraphy and drill core data of the deposit reveal Middle–Upper Permian and Lower Triassic formations. The ore is mainly hosted in Upper Permian bioclastic limestone near the axis of an anticline. The gold is mainly hosted in arsenian pyrite and arsenopyrite, mainly existing in the form of crystal lattice gold, submicroscopic particles and nanoparticles. Fluorite commonly occurs at the vicinity of an unconformity between the Middle–Upper Permian formations, which is proposed to be the structural conduit that fed the ore fluids. Calcite commonly fills fractures at the periphery of decarbonated rocks, which contain high grade orebodies. This study aimed to verify the occurrence of two distinct hydrothermal events at the Shuiyindong, based on Sm–Nd isotope dating of the fluorite and calcite. For this purpose, rare-earth element (REE) concentrations, Sm/Nd isotope ratios, and Sm–Nd isochron ages of the fluorite and calcite were determined. The fluorite and calcite contain relatively high total concentrations of REE (12.3–25.6 μg/g and 5.71–31.7 μg/g, respectively), exhibit variable Sm/Nd ratios (0.52–1.03 and 0.57–1.71, respectively), and yield Sm–Nd isochron ages of 200.1 ± 8.6 Ma and 150.2 ± 2.2 Ma, with slightly different initial

ε_{Nd} (t)

values of −4.4 and −1.1, respectively. These two groups of Sm–Nd isochron ages suggest two episodes of hydrothermal events at the Shuiyindong gold deposit. The age of the calcite probably represents the late stage of the gold mineralization period. The initial

ε_{Nd} (t)

values of the fluorite and calcite indicate that the Nd was probably derived from mixtures of basaltic volcanic tuff and bioclastic limestone from the Permian formations. Full article

(This article belongs to the Special Issue Nanomineralogy)

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20 pages, 3807 KiB

Open AccessArticle

Pore Connectivity Characterization of Lacustrine Shales in Changling Fault Depression, Songliao Basin, China: Insights into the Effects of Mineral Compositions on Connected Pores

by Zhuo Li, Zhikai Liang, Zhenxue Jiang, Hailong Yu, Youdong Yang and Lei Xiao

Minerals 2019, 9(3), 198; https://doi.org/10.3390/min9030198 - 26 Mar 2019

Cited by 14 | Viewed by 3562

Abstract

Pore connectivity of lacustrine shales was inadequately documented in previous papers. In this work, lacustrine shales from the lower Cretaceous Shahezi Formation in the Changling Fault Depression (CFD) were investigated using field emission scanning electron microscopy (FE-SEM), mercury intrusion capillary pressure (MICP), low [...] Read more.

Pore connectivity of lacustrine shales was inadequately documented in previous papers. In this work, lacustrine shales from the lower Cretaceous Shahezi Formation in the Changling Fault Depression (CFD) were investigated using field emission scanning electron microscopy (FE-SEM), mercury intrusion capillary pressure (MICP), low pressure gas (CO₂ and N₂) sorption (LPGA) and spontaneous fluid imbibition (SFI) experiments. The results show that pores observed from FE-SEM images are primarily interparticle (interP) pores in clay minerals and organic matter (OM) pores. The dominant pore width obtained from LPGA and MICP data is in the range of 0.3–0.7 nm and 3–20 nm. The slopes of n-decane and deionized (DI) water SFI are in the range of 0.34–0.55 and 0.22–0.38, respectively, suggesting a mixed wetting nature and better-connected hydrophobic pores than hydrophilic pores in the Shahezi shales. Low pore connectivity is identified by the dominant nano-size pore widths (0.3–20 nm), low DI water SFI slopes (around 0.25), high geometric tortuosity (4.75–8.89) and effective tortuosity (1212–6122). Pore connectivity follows the order of calcareous shale > argillaceous shale > siliceous shale. The connected pores of Shahezi shales is mainly affected by the high abundance and coexistence of OM pores and clay, carbonate minerals host pores. Full article

(This article belongs to the Special Issue Nanomineralogy)

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21 pages, 4415 KiB

Open AccessArticle

The Impacts of Matrix Compositions on Nanopore Structure and Fractal Characteristics of Lacustrine Shales from the Changling Fault Depression, Songliao Basin, China

by Zhuo Li, Zhikai Liang, Zhenxue Jiang, Fenglin Gao, Yinghan Zhang, Hailong Yu, Lei Xiao and Youdong Yang

Minerals 2019, 9(2), 127; https://doi.org/10.3390/min9020127 - 22 Feb 2019

Cited by 23 | Viewed by 3415

Abstract

The Lower Cretaceous Shahezi shales are the targets for lacustrine shale gas exploration in Changling Fault Depression (CFD), Southern Songliao Basin. In this study, the Shahezi shales were investigated to further understand the impacts of rock compositions, including organic matters and minerals on [...] Read more.

The Lower Cretaceous Shahezi shales are the targets for lacustrine shale gas exploration in Changling Fault Depression (CFD), Southern Songliao Basin. In this study, the Shahezi shales were investigated to further understand the impacts of rock compositions, including organic matters and minerals on pore structure and fractal characteristics. An integrated experiment procedure, including total organic carbon (TOC) content, X-ray diffraction (XRD), field emission-scanning electron microscope (FE-SEM), low pressure nitrogen physisorption (LPNP), and mercury intrusion capillary pressure (MICP), was conducted. Seven lithofacies can be identified according to on a mineralogy-based classification scheme for shales. Inorganic mineral hosted pores are the most abundant pore type, while relatively few organic matter (OM) pores are observed in FE-SEM images of the Shahezi shales. Multimodal pore size distribution characteristics were shown in pore width ranges of 0.5–0.9 nm, 3–6 nm, and 10–40 nm. The primary controlling factors for pore structure in Shahezi shales are clay minerals rather than OM. Organic-medium mixed shale (OMMS) has the highest total pore volumes (0.0353 mL/g), followed by organic-rich mixed shale (ORMS) (0.02369 mL/g), while the organic-poor shale (OPS) has the lowest pore volumes of 0.0122 mL/g. Fractal dimensions D₁ and D₂ (at relative pressures of 0–0.5 and 0.5–1 of LPNP isotherms) were obtained using the Frenkel–Halsey–Hill (FHH) method, with D₁ ranging from 2.0336 to 2.5957, and D₂ between 2.5779 and 2.8821. Fractal dimensions are associated with specific lithofacies, because each lithofacies has a distinctive composition. Organic-medium argillaceous shale (OMAS), rich in clay, have comparatively high fractal dimension D₁. In addition, organic-medium argillaceous shale (ORAS), rich in TOC, have comparatively high fractal dimension D₂. OPS shale contains more siliceous and less TOC, with the lowest D₁ and D₂. Factor analysis indicates that clay contents is the most significant factor controlling the fractal dimensions of the lacustrine Shahezi shale. Full article

(This article belongs to the Special Issue Nanomineralogy)

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17 pages, 4566 KiB

Open AccessArticle

Green Preparation of Nanoporous Pyrrhotite by Thermal Treatment of Pyrite as an Effective Hg(Ⅱ) Adsorbent: Performance and Mechanism

by Ping Lu, Tianhu Chen, Haibo Liu, Ping Li, Shuchuan Peng and Yan Yang

Minerals 2019, 9(2), 74; https://doi.org/10.3390/min9020074 - 27 Jan 2019

Cited by 23 | Viewed by 3842

Abstract

The removal of Hg(II) from aqueous solutions by pyrrhotite derived from the thermal activation of natural pyrite was explored by batch experiments. The adsorption isotherms demonstrated that the sorption of Hg(II) by modified pyrite (MPy) can be fitted well by the Langmuir model. [...] Read more.

The removal of Hg(II) from aqueous solutions by pyrrhotite derived from the thermal activation of natural pyrite was explored by batch experiments. The adsorption isotherms demonstrated that the sorption of Hg(II) by modified pyrite (MPy) can be fitted well by the Langmuir model. The removal capacity of Hg(II) on MPy derived from the Langmuir model was determined to 166.67 mg/g. The adsorption process of Hg(II) on MPy was well fitted by a pseudo-second-order model. The sorption of Hg(II) on MPy was a spontaneous and endothermic process. The removal of Hg(II) by MPy was mainly attributed to a chemical reaction resulting in cinnabar formation and the electrostatic attraction between the negative charges in MPy and positive charges of Hg(II). The results of our work suggest that the thermal activation of natural pyrite is greatly important for the effective utilization of ore resources for the removal of Hg(II). Full article

(This article belongs to the Special Issue Nanomineralogy)

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12 pages, 3848 KiB

Open AccessArticle

Total Porosity Measured for Shale Gas Reservoir Samples: A Case from the Lower Silurian Longmaxi Formation in Southeast Chongqing, China

by Fangwen Chen, Shuangfang Lu, Xue Ding, Hongqin Zhao and Yiwen Ju

Minerals 2019, 9(1), 5; https://doi.org/10.3390/min9010005 - 22 Dec 2018

Cited by 20 | Viewed by 5253

Abstract

Measuring total porosity in shale gas reservoir samples remains a challenge because of the fine-grained texture, low porosity, ultra-low permeability, and high content of organic matter (OM) and clay mineral. The composition content porosimetry method, which is a new method for the evaluation [...] Read more.

Measuring total porosity in shale gas reservoir samples remains a challenge because of the fine-grained texture, low porosity, ultra-low permeability, and high content of organic matter (OM) and clay mineral. The composition content porosimetry method, which is a new method for the evaluation of the porosity of shale samples, was used in this study to measure the total porosity of shale gas reservoir samples from the Lower Silurian Longmaxi Formation in Southeast Chongqing, China, based on the bulk and grain density values. The results from the composition content porosimetry method were compared with those of the Gas Research Institute method. The results showed that the composition content porosimetry porosity values of shale gas reservoir samples range between 2.05% and 5.87% with an average value of 4.04%. The composition content porosimetry porosity generally increases with increasing OM and clay content, and decreases with increasing quartz and feldspar content. The composition content porosimetry results are similar to the gas research institute results, and the differences between the two methods range from 0.05% to 1.52% with an average value of 0.85%. Full article

(This article belongs to the Special Issue Nanomineralogy)

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14 pages, 6402 KiB

Open AccessArticle

One-Step Synthesis of Hydroxysodalite Using Natural Bentonite at Moderate Temperatures

by Bo Liu, Hongjuan Sun, Tongjiang Peng and Qian He

Minerals 2018, 8(11), 521; https://doi.org/10.3390/min8110521 - 9 Nov 2018

Cited by 12 | Viewed by 4996

Abstract

Ca-bentonite was used as the feedstock material for the synthesis of hydroxysodalite due to its high Al, Si content, good chemical reactivity, and natural abundance. A one-step method is proposed here to fabricate hydroxysodalite in a water bath at moderate temperature. The effects [...] Read more.

Ca-bentonite was used as the feedstock material for the synthesis of hydroxysodalite due to its high Al, Si content, good chemical reactivity, and natural abundance. A one-step method is proposed here to fabricate hydroxysodalite in a water bath at moderate temperature. The effects of the Na/Si molar ratio, Si/Al molar ratio, reaction time, and reaction temperature on the synthesis of hydroxysodalite have been systematically investigated here. The crystallizing phases and morphology of the synthetic products were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results showed that the Na/Si molar ratio and reaction temperature both played important roles in controlling the degree of crystallinity of the synthetic hydroxysodalite. The Si/Al molar ratio and reaction time both affect the purity of the synthetic hydroxysodalite. Optimum conditions for synthesizing hydroxysodalite using a one-step water-bath method at moderate temperature are as follows: a Na/Si molar ratio of 12, a Si/Al molar ratio of 1.0, a reaction temperature of 90 °C, and a reaction time of 12 h. Full article

(This article belongs to the Special Issue Nanomineralogy)

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Review

Jump to: Editorial, Research

25 pages, 3962 KiB

Open AccessReview

Nanocrystalline Principal Slip Zones and Their Role in Controlling Crustal Fault Rheology

by Berend A. Verberne, Oliver Plümper and Christopher J. Spiers

Minerals 2019, 9(6), 328; https://doi.org/10.3390/min9060328 - 28 May 2019

Cited by 16 | Viewed by 5729

Abstract

Principal slip zones (PSZs) are narrow (<10 cm) bands of localized shear deformation that occur in the cores of upper-crustal fault zones where they accommodate the bulk of fault displacement. Natural and experimentally-formed PSZs consistently show the presence of nanocrystallites in the <100 [...] Read more.

Principal slip zones (PSZs) are narrow (<10 cm) bands of localized shear deformation that occur in the cores of upper-crustal fault zones where they accommodate the bulk of fault displacement. Natural and experimentally-formed PSZs consistently show the presence of nanocrystallites in the <100 nm size range. Despite the presumed importance of such nanocrystalline (NC) fault rock in controlling fault mechanical behavior, their prevalence and potential role in controlling natural earthquake cycles remains insufficiently investigated. In this contribution, we summarize the physical properties of NC materials that may have a profound effect on fault rheology, and we review the structural characteristics of NC PSZs observed in natural faults and in experiments. Numerous literature reports show that such zones form in a wide range of faulted rock types, under a wide range of conditions pertaining to seismic and a-seismic upper-crustal fault slip, and frequently show an internal crystallographic preferred orientation (CPO) and partial amorphization, as well as forming glossy or “mirror-like” slip surfaces. Given the widespread occurrence of NC PSZs in upper-crustal faults, we suggest that they are of general significance. Specifically, the generally high rates of (diffusion) creep in NC fault rock may play a key role in controlling the depth limits to the seismogenic zone. Full article

(This article belongs to the Special Issue Nanomineralogy)

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