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A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Environmental Mineralogy and Biogeochemistry".

Deadline for manuscript submissions: closed (31 December 2019) | Viewed by 39923

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Prof. Dr. Jinwook Kim

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Guest Editor

Department of Earth System Sciences, Yonsei University, Seoul 03722, Republic of Korea
Interests: microbe-mineral interaction; extreme einvrionments; Fe-liberation, smectite-to-illite reaction; diagenesis; petrophysical properties
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Special Issue Information

Dear Colleagues,

Clays and clay materials are important components in natural environments, as well as in industrial applications. Clays and clay minerals are important components in soils, sediments, and sedimentary rocks, and they undergo biotic and abiotic reactions in natural environments, including extreme environments. These mineral reactions impact a number of geological and environmental processes, such as sediment diagenesis, colloid transport, the mobility and the ultimate fate of organic and inorganic contaminants, integrity of waste repositories, and stability of the ocean floor. Furthermore, the science and technologies of industrial clays, including exploration and clay resource development, particle engineering from macro to nano, chemical and physical modification of industrial application and sustainable resource development are currently being investigated. We invite contributions on, but not limited to, microscopic/spectroscopic/geochemistry studies of clay mineral reactions at both laboratory and field scales. We especially encourage papers on the development of novel methods and/or novel applications of existing techniques with an interdisciplinary perspective.

The first round of submission deadline was 15 January 2019.

Prof. Dr. Jinwook Kim
Guest Editor

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Keywords

Clays
Biotic clay reaction
Abiotic clay reaction
Diagenesis
Microbial interaction
Extreme environments
Geological process
Environmental process
Industrial clay
Physical modification of clays

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Published Papers (8 papers)

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18 pages, 5670 KiB

Open AccessFeature PaperArticle

Microbial Diversity Responding to Changes in Depositional Conditions during the Last Glacial and Interglacial Period: NE Ulleung Basin, East Sea (Sea of Japan)

by Kee Hwan Lee, Chang Hwan Kim, Chan Hong Park, Kiho Yang, Sang Hoon Lee, In Soo Lee, You Jin Kwack, Jae Woo Kwak, Jaewoo Jung and Jinwook Kim

Minerals 2020, 10(3), 208; https://doi.org/10.3390/min10030208 - 26 Feb 2020

Cited by 2 | Viewed by 3142

Abstract

Microbial interaction with minerals are significantly linked with depositional conditions during glacial and interglacial periods, providing a unique redox condition in the sedimentary process. Abiotic geophysical and geochemical properties, including sedimentary facies, magnetic susceptibility, grain size, clay mineralogy, and distribution of elemental compositions in the sediments, have been widely used to understand paleo-depositional environments. In this study, microbial abundance and diversity in the core sediments (6.7 m long) from the northeastern slope of Dokdo Island were adapted to characterize the conventionally defined sedimentary depositional units and conditions in light of microbial habitats. The units of interglacial (Unit 1, <11.5 ka) and late glacial (Unit 2, 11.5–14.5 ka) periods in contrast to the glacial period (Unit 3, >14.5 ka) were distinctively identified in the core, showing a sharp boundary marked by the laminated Mn-carbonate (CaM) mud between bioturbated (Unit 1 and 2) and laminated mud (Unit 3). Based on the marker beds and the occurrence of sedimentary facies, core sediments were divided into three units, Unit 1 (<11.5 ka, interglacial), Unit 2 (11.5–14.5 ka, late glacial), and Unit 3 (>14.5 ka, glacial), in descending order. The sedimentation rate (0.073 cm/year), which was three times higher than the average value for the East Sea (Sea of Japan) was measured in the late glacial period (Unit 2), indicating the settlement of suspended sediments from volcanic clay in the East Sea (Sea of Japan), including Doldo Island. The Fe and Mg-rich smectite groups in Unit 2 can be transported from volcanic sediments, such as from the volcanic island in the East Sea or the east side of Korea, while the significant appearance of the Al-rich smectite group in Unit 1 was likely transported from East China by the Tsushima Warm Current (TWC). The appearance of CaM indicates a redox condition in the sedimentary process because the formation of CaM is associated with an oxidation of Mn²⁺ forming Mn-oxide in the ocean, and a subsequent reduction of Mn-oxide occurred, likely due to Mn-reducing bacteria resulting in the local supersaturation of Mn²⁺ and the precipitation of CaM. The low sea level (−120 m) in the glacial period (Unit 3) may restrict water circulation, causing anoxic conditions compared to the late glacial period (Unit 2), inducing favorable redox conditions for the formation of CaM in the boundary of the two units. Indeed, Planctomycetaceae, including anaerobic ammonium oxidation (ANAMMOX) bacteria capable of oxidizing ammonium coupled with Mn-reduction, was identified in the CaM layer by Next Generation Sequencing (NGS). Furthermore, the appearance of aerobic bacteria, such as Alphaproteobacteria, Gammaproteobacteria, and Methylophaga, tightly coupled with the abundance of phytoplankton was significantly identified in Unit 1, suggesting open marine condition in the interglacial period. Bacterial species for each unit displayed a unique grouping in the phylogenetic tree, indicating the different paleo-depositional environments favorable for the microbial habitats during the glacial and interglacial periods. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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11 pages, 2483 KiB

Open AccessArticle

Chemical Weathering of Granite in Ice and Its Implication for Weathering in Polar Regions

by Hyun Young Chung, Jaewoo Jung, Du Hyeong Lee, Sunghan Kim, Min Kyung Lee, Jae Il Lee, Kyu-Cheul Yoo, Yong Il Lee and Kitae Kim

Minerals 2020, 10(2), 185; https://doi.org/10.3390/min10020185 - 19 Feb 2020

Cited by 6 | Viewed by 4806

Abstract

Recently, it has been reported that some chemical reactions are enhanced in below-freezing conditions. Despite the high denudation typical of polar regions, chemical weathering that occurs under ice has not been investigated. In this study, we investigated the dissolution of granite in ice. The mixture of granite and deionized water (DW) or solution adjusted to pH 2 or 3 was split into two groups: the test group was frozen at −20 °C, while the control was maintained at room temperature. After 29 days of batch experiments, the filtrate was analyzed to measure the concentrations of cations and silica. The filtered powder was analyzed to investigate the mineral compositions and crystallinities of the granite before and after the experiments. Despite the low temperature, a significant quantity of cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) were dissolved out, even from the ice samples. During X-ray diffraction (XRD) analysis, the decreased crystallinities of granite in ice samples were identified regardless of the pH condition. To verify the observed freeze concentration effect, the concentration of granite in the ice grain boundaries was observed using optical microscopy with a cold chamber. The low concentration of silica in the ice samples could explain the silica anomaly in polar regions. This study also provides a new perspective for the dissolution mechanism in polar regions. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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14 pages, 2812 KiB

Open AccessArticle

Controls on the Formation and Stability of Siderite (FeCO₃) and Chukanovite (Fe₂(CO₃)(OH)₂) in Reducing Environment

by Tae-hee Koo and Jinwook Kim

Minerals 2020, 10(2), 156; https://doi.org/10.3390/min10020156 - 11 Feb 2020

Cited by 14 | Viewed by 6397

Abstract

The formation of ferrous carbonate mineral is a significant geochemical reaction linked to iron and carbon cycling in the sedimentary environment. However, knowledge of the controlling factors and conditions for the mineral formation is limited. Two types of ferrous carbonate mineral, siderite (FeCO₃) and chukanovite (Fe₂(CO₃)(OH)₂) were synthesized under a FeCl₂–NaHCO₃ system with various concentration ranges (10–100 mmolal) and ratios (Fe:Dissolved inorganic carbon (DIC) = 1:1, X:50, and 50:X) to verify the concentration limit and control species for the formation of those minerals. The mineralogy of filtered precipitates at the reaction time of 1 week and 1 month were identified by X-ray diffraction (XRD), and scanning/transmission electron microscopic (S/TEM) analyses were applied for direct identification of the synthesized siderite and chukanovite at various conditions. A semi-quantitative calculation to estimate siderite proportion (siderite/[siderite + chukanovite]) in the precipitates was carried out using peak intensity ratios of siderite (d₁₀₄ [2θ = 32.02°]) and chukanovite (d₂₁₁ [2θ = 33.98°]) from XRD profiles. The framboids or trigonal-rhombohedron crystals and flaky rosette-shaped minerals were identified in SEM analysis. In addition, the chemical compositions of Fe and C of framboid (Fe:C = 1:1.01) and flaky mineral (1:2.04) were identified as siderite and chukanovite, respectively. The formation of siderite was predominated over chukanovite in 50 mmolal (both Fe and DIC) or higher conditions (siderite proportion = 49–100%). The estimated siderite proportion increased (27–100%) as DIC concentration increased (15–100 mmolal) in conditions of varying ratios of iron and DIC (50:X), indicating that DIC is a decisive factor in siderite formation. The increase in the reaction time promotes the siderite proportion increase, so that chukanovite may be dissolved and re-precipitated as siderite for the long-term reaction, except in the enriched DIC condition (Fe:DIC = 15:50). This study demonstrates that various conditions, not limited to the concentrations or reaction time, may affect the geochemical pathways of carbonate mineral formations. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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12 pages, 3509 KiB

Open AccessArticle

Physico–Chemical Interaction between Clay Minerals and Albumin Protein according to the Type of Clay

by Hyoung-Mi Kim and Jae-Min Oh

Minerals 2019, 9(7), 396; https://doi.org/10.3390/min9070396 - 28 Jun 2019

Cited by 7 | Viewed by 5154

Abstract

Clay minerals are widely utilized in pharmaceutical and dermatological sciences as a gastrointestinal medicine or skin remediation agent. In order to verify the feasibility of clays as an injection, pill, or topical agent, it is important to study their interactions with biological components, such as proteins. In this study, we utilized a protein fluorescence quenching assay and circular dichroism spectroscopy to evaluate general aspects of protein denaturation and conformational change, respectively. Three different clays; layered double oxide (LDO), montmorilonite (MMT) and halloysite nanotube (HNT), were treated with albumin and the physico-chemical effect on the protein’s conformation was investigated. MMT was shown to influence the conformational change the most, owing to the large accessible adsorption site. HNT showed meaningful circular dichroism (CD) band collapse as well as fluorescence quenching in the protein, suggesting a potential harmful effect of HNT toward the protein. Among the three tested clays, LDO was determined to affect protein structure the least in terms of three-dimensional conformation and helical structure. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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14 pages, 3668 KiB

Open AccessEditor’s ChoiceArticle

Elemental Compositions of Smectites Reveal Detailed Sediment Provenance Changes during Glacial and Interglacial Periods: The Southern Drake Passage and Bellingshausen Sea, Antarctica

by Young Kyu Park, Jae Il Lee, Jaewoo Jung, Claus-Dieter Hillenbrand, Kyu-Cheul Yoo and Jinwook Kim

Minerals 2019, 9(5), 322; https://doi.org/10.3390/min9050322 - 26 May 2019

Cited by 11 | Viewed by 5308

Abstract

Variations in clay mineral assemblages have been widely used to understand changes in sediment provenance during glacial and interglacial periods. Smectite clay minerals, however, have a range of various elemental compositions that possibly originated from multiple different sources. Therefore, it might be crucial to distinguish the various types of smectites by analyzing their elemental composition in order to verify the sediment provenances with certainty. This hypothesis was tested for the clay mineral characteristics in a marine sediment core from the southern Drake Passage (GC05-DP02). Rare earth elements and

ε_{N d}

data had previously indicated that fine grained detritus was supplied from the Weddell Sea to the core site during interglacial periods, when the sediments contained more Al-rich smectite (montmorillonite). Indeed, marine sediments collected close to the Larsen Ice Shelf on the eastern Antarctic Peninsula continental shelf, western Weddell Sea embayment, show more Al-rich smectite components as compared with other possible West Antarctic sources, such as the Ross Sea embayment or King George Island, South Shetland Islands. Furthermore, two types of smectite (Al-rich and Al-poor) were identified in core GC360 from the Bellingshausen Sea shelf, suggesting that during glacial periods some sediment is derived from subglacial erosion of underlying pre-Oligocene sedimentary strata containing predominantly Al-rich montmorillonite. This finding reveals different sources for smectites in sediments deposited at site GC360 during the last glacial period and during the present interglacial that show only minor differences in smectite contents. For the interglacial period, two groups of smectite with a wide range of Al-rich and Mg–Fe-rich were identified, which indicate delivery from two different sources: (1) the detritus with high contents of Mg–Fe-rich smectite supplied from Beethoven Peninsula, southwestern Alexander island and (2) the detritus with higher contents of Al-rich smectite (montmorillonite) possibly derived from the subglacial reworking of pre-Oligocene sedimentary strata. These results demonstrate that the elemental compositions of smectites can be used to differentiate the sources of smectites in marine sediments, which is an important tool to define sediment provenance in detail, when down-core changes observed in clay mineral assemblages are interpreted. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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17 pages, 3731 KiB

Open AccessArticle

Characterization of Microbial Communities Associated with Ceramic Raw Materials as Potential Contributors for the Improvement of Ceramic Rheological Properties

by Angela M. Garcia-Sanchez, Bernardino Machado-Moreira, Mário Freire, Ricardo Santos, Sílvia Monteiro, Diamantino Dias, Orquídia Neves, Amélia Dionísio and Ana Z. Miller

Minerals 2019, 9(5), 316; https://doi.org/10.3390/min9050316 - 23 May 2019

Cited by 4 | Viewed by 4098

Abstract

Technical ceramics are being widely employed in the electric power, medical and engineering industries because of their thermal and mechanical properties, as well as their high resistance qualities. The manufacture of technical ceramic components involves complex processes, including milling and stirring of raw materials in aqueous solutions, spray drying and dry pressing. In general, the spray-dried powders exhibit an important degree of variability in their performance when subjected to dry-pressing, which affects the efficiency of the manufacturing process. Commercial additives, such as deflocculants, biocides, antifoam agents, binders, lubricants and plasticizers are thus applied to ceramic slips. Several bacterial and fungal species naturally occurring in ceramic raw materials, such as Sphingomonas, Aspergillus and Aureobasidium, are known to produce exopolysaccharides. These extracellular polymeric substances (EPS) may confer unique and potentially interesting properties on ceramic slips, including viscosity control, gelation, and flocculation. In this study, the microbial communities present in clay raw materials were identified by both culture methods and DNA-based analyses to select potential EPS producers based on the scientific literature for further assays based on the use of EPS for enhancing the performance of technical ceramics. Potential exopolysaccharide producers were identified in all samples, such as Sphingomonas sp., Pseudomonas xanthomarina, P. stutzeri, P. koreensis, Acinetobacter lwoffi, Bacillus altitudinis and Micrococcus luteus, among bacteria. Five fungi (Penicillium citrinum, Aspergillus niger, Fusarium oxysporum, Acremonium persicinum and Rhodotorula mucilaginosa) were also identified as potential EPS producers. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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12 pages, 2110 KiB

Open AccessArticle

Clay Mineralogical Characteristics of Sediments Deposited during the Late Quaternary in the Larsen Ice Shelf B Embayment, Antarctica

by Jaewoo Jung, Kyu-Cheul Yoo, Kee-Hwan Lee, Young Kyu Park, Jae Il Lee and Jinwook Kim

Minerals 2019, 9(3), 153; https://doi.org/10.3390/min9030153 - 3 Mar 2019

Cited by 12 | Viewed by 4505

Abstract

Variations in grain size, clay mineral composition, and stable isotopes (δ¹³C and δ¹⁵N) are closely linked to the sedimentary facies that reflect mineralogical and geochemical modification during the retreat and advance of the Larsen ice shelf. A whole round core of marine sediment (EAP13-GC17, 236 cm below the sea floor) was collected on the northwestern Larsen B embayment of the Antarctic Peninsula during a marine geological expedition (the ARA13 Cruise Expedition by the Korea Polar Research Institute, 2013). Four sedimentary facies (U1–U4) were clearly distinguishable: bioturbated sandy mud (open marine, U1), laminated sandy mud (sub–floating ice shelf, U2), sandy clay aggregates (deglacial, U3), and muddy diamictons (sub-glacial, U4), as well as interbedded silty. Clay minerals, including smectite, chlorite, illite, and kaolinite, were detected throughout the core. An increase in the clay mineral ratio of smectite/(illite + chlorite) was clearly observed in the open marine condition, which was strongly indicated by both a heavier isotopic composition of δ¹³C and δ¹⁵N (−24.4‰ and 4.3‰, respectively), and an abrupt increase in ¹⁰Be concentration (~30 times). An increase in the average values of the crystal packet thickness of illite (~1.5 times) in U1 also indicated sediments transported in open marine conditions. Based on the clay mineral composition in U1, the sediments are likely to have been transported from the Weddell Sea. The clay mineralogical assessments conducted in this region have significant implications for our understanding of paleodepositional environments. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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15 pages, 2974 KiB

Open AccessReview

Biocompatible Hydrotalcite Nanohybrids for Medical Functions

by Wenji Jin, Dongki Lee, Yukwon Jeon and Dae-Hwan Park

Minerals 2020, 10(2), 172; https://doi.org/10.3390/min10020172 - 14 Feb 2020

Cited by 35 | Viewed by 5904

Abstract

Biocompatible hydrotalcite nanohybrids, i.e., layered double hydroxide (LDH) based nanohybrids have attracted significant attention for biomedical functions. Benefiting from good biocompatibility, tailored drug incorporation, high drug loading capacity, targeted cellular delivery and natural pH-responsive biodegradability, hydrotalcite nanohybrids have shown great potential in drug/gene delivery, cancer therapy and bio-imaging. This review aims to summarize recent progress of hydrotalcite nanohybrids, including the history of the hydrotalcite-like compounds for application in the medical field, synthesis, functionalization, physicochemical properties, cytotoxicity, cellular uptake mechanism, as well as their related applications in biomedicine. The potential and challenges will also be discussed for further development of LDHs both as drug delivery carriers and diagnostic agents. Full article

(This article belongs to the Special Issue Clays and Micro-Organisms: From Nature to Industry)

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