Special Issue "Organo-Mineral Interactions"

A special issue of Minerals (ISSN 2075-163X).

Deadline for manuscript submissions: closed (30 June 2017)

Special Issue Editor

Guest Editor
Dr. Pablo Cubillas

Department of Earth Sciences, Durham University, Durham DH1 3LE, UK
Website | E-Mail
Interests: scanning probe microscopy; mineral-water interface geochemistry; organo-mineral interactions; environmental geochemistry

Special Issue Information

Dear Colleagues,

Mineral-organic interactions play a crucial role in a wide range of natural systems and processes, including weathering, dissolution and precipitation (including biomineralization), element cycling, sorption and mobility of pollutants, hydrocarbon formation, migration and retention, soil formation and maturity, origin of life, among many others. In addition, mineral-organic interactions are vital in a wide range of industrial processes, such as oil recovery operations (scale formation, drilling muds), paper coatings, ceramics, waste water treatment, desalination, etc.

For the aforementioned reasons, the study of mineral-organic interactions has received great consideration by the scientific community, as well as industry. Recent advancements on characterization techniques (AFM, cryo-TEM, cryo-XPS), as well as computational methods/simulation (from quantum ab-initio to molecular dynamics) have led to a greater understanding of the fundamental reactions that govern these interactions across many different systems. However, many questions remain regarding these fundamental reactions, as well as their scaling into large scale processes/systems.

In this Special Issue of Minerals we would like to invite authors to contribute original research papers that will contribute to further our understanding of these important processes. We would like to produce a well balanced issue, and therefore are open to both experimental and theoretical/computational studies dealing with fundamental and/or applied aspects of mineral-organic interactions on any of the aforementioned fields.

Dr. Pablo Cubillas
Guest Editor

Manuscript Submission Information

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Keywords

  • biomineralization
  • clay-organic interactions
  • origin of life
  • organic geochemistry
  • soil science
  • diagenesis
  • environmental geochemistry
  • enhanced oil recovery
  • weathering
  • waste water treatment
  • petroleum geology

Published Papers (7 papers)

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Research

Open AccessArticle
Relationship between Mineral and Organic Matter in Shales: The Case of Shahejie Formation, Dongying Sag, China
Minerals 2018, 8(6), 222; https://doi.org/10.3390/min8060222
Received: 27 April 2018 / Revised: 18 May 2018 / Accepted: 21 May 2018 / Published: 23 May 2018
Cited by 3 | PDF Full-text (9663 KB) | HTML Full-text | XML Full-text
Abstract
Types of organic matter and mineral associations and microstructures of shales can reflect the depositional mechanism and sedimentary environment. Therefore, analysis of organic matter and mineral associations is a prerequisite for research on fine-grained sedimentary rocks. Shales from the Eocene Shahejie Formation in [...] Read more.
Types of organic matter and mineral associations and microstructures of shales can reflect the depositional mechanism and sedimentary environment. Therefore, analysis of organic matter and mineral associations is a prerequisite for research on fine-grained sedimentary rocks. Shales from the Eocene Shahejie Formation in the Dongying Sag of China were selected to classify their lithofacies and to investigate the characteristics of their organic matter and mineral associations. This analysis identified six lithofacies (e.g., laminated shales and massive mudstones); in all the lithofacies, clay minerals exhibit a positive correlation with detrital minerals, thus indicating that they were derived from the same source. The comprehensive analysis of mineral and organic matter associations reveals that detrital minerals were deposited with low-hydrogen index (HI) OM. The deposition of detrital minerals was mainly a physical process. Clay minerals can undergo deposition in one of two ways due to their surface charge: they can either aggregate with high-HI OM via chemical deposition, thus forming organic-rich laminae, or they can be deposited together with low-HI OM via physical deposition, thus forming clay-rich laminae or a massive matrix. Carbonate minerals, which often coexist with high-HI OM, are biological sediments. The analysis of the sedimentary characteristics of these organic matter and mineral associations indicates that the sedimentary processes differ between various lithofacies: e.g., the discontinuous laminated shale represents the product of biophysical processes. Differences in depositional mechanisms are also present in each sub-member. Therefore, it is important to analyze the properties of minerals and organic matter, as well as their associations, to more deeply understand the classification of lithofacies and the depositional processes of shales and mudstones. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
Understanding Cationic Polymer Adsorption on Mineral Surfaces: Kaolinite in Cement Aggregates
Minerals 2018, 8(4), 130; https://doi.org/10.3390/min8040130
Received: 15 February 2018 / Revised: 6 March 2018 / Accepted: 16 March 2018 / Published: 23 March 2018
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Abstract
We present a joint experimental and theoretical investigation into the adsorption of polycationic quaternary ammonium polymers on the clay mineral kaolinite. Within the cement and concrete manufacturing industries such polymers are used to improve the final product by inerting the adsorption capacity of [...] Read more.
We present a joint experimental and theoretical investigation into the adsorption of polycationic quaternary ammonium polymers on the clay mineral kaolinite. Within the cement and concrete manufacturing industries such polymers are used to improve the final product by inerting the adsorption capacity of the clay minerals for more expensive additives. The adsorption of the presently used polymer (FL22) was compared with both a similar variant, but without a hydroxyl group (Fl22mod) and uncharged polyvinyl alcohol (PVA). Experimental results show that adsorption of FL22 is higher than that of FL22mod at both pH 6 and at pH > 10 and that the adsorption of PVA is the highest. Theoretical density functional theory (DFT) results and simplified models consisting of the basal surfaces of kaolinite, with monomers of FL22, FL22mod and PVA gave monomer coverage per unit surface area of kaolinite, a comparison of the configurations of the relaxed models, formation energies and Mulliken charges. These results show that the polycationic polymers interact with the basal surfaces of kaolinite electrostatically, explaining the high affinity of these polymers for kaolinite surfaces in the experimental results. The hydroxyl groups of FL22 and PVA form hydrogen bonds with the basal surfaces of kaolinite in conditions of pH 6. The joint experimental and theoretical results suggest that, due to the presence of the hydroxyl group, the conformation of FL22 changes under pH, where at neutral pH it lies relatively flat to the kaolinite surfaces, but at higher pH, conformational changes of the polymer occur, thereby increasing the adsorbed quantity of FL22. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
Chemical Force Microscopy Study on the Interactions of COOH Functional Groups with Kaolinite Surfaces: Implications for Enhanced Oil Recovery
Minerals 2017, 7(12), 250; https://doi.org/10.3390/min7120250
Received: 10 November 2017 / Revised: 5 December 2017 / Accepted: 12 December 2017 / Published: 19 December 2017
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Abstract
Clay–oil interactions play a critical role in determining the wettability of sandstone oil reservoirs, which, in turn, governs the effectiveness of enhanced oil recovery methods. In this study, we have measured the adhesion between –COOH functional groups and the siloxane and aluminol faces [...] Read more.
Clay–oil interactions play a critical role in determining the wettability of sandstone oil reservoirs, which, in turn, governs the effectiveness of enhanced oil recovery methods. In this study, we have measured the adhesion between –COOH functional groups and the siloxane and aluminol faces of kaolinite clay minerals by means of chemical force microscopy as a function of pH, salinity (from 0.001 M to 1 M) and cation identity (Na+ vs. Ca2+). Results from measurements on the siloxane face show that Ca2+ displays a reverse low-salinity effect (adhesion decreasing at higher concentrations) at pH 5.5, and a low salinity effect at pH 8. At a constant Ca2+ concentration of 0.001 M, however, an increase in pH leads to larger adhesion. In contrast, a variation in the Na+ concentration showed less effect in varying the adhesion of –COOH groups to the siloxane face. Measurements on the aluminol face showed a reverse low-salinity effect at pH 5.5 in the presence of Ca2+, whereas an increase in pH with constant ion concentration resulted in a decrease in adhesion for both Ca2+ and Na+. Results are explained by looking at the kaolinite’s surface complexation and the protonation state of the functional group, and highlight a more important role of the multicomponent ion exchange mechanism in controlling adhesion than the double layer expansion mechanism. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
Optical Observations and Geochemical Data in Deep-Sea Hexa- and Octo-Coralla Specimens
Minerals 2017, 7(9), 154; https://doi.org/10.3390/min7090154
Received: 13 July 2017 / Revised: 17 August 2017 / Accepted: 23 August 2017 / Published: 25 August 2017
Cited by 2 | PDF Full-text (8780 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Coral skeletons are built by Ca-carbonate (calcite or aragonite) crystals that exhibit distinct morphological patterns and specific spatial arrangements that constitute skeletal microstructures. Additionally, the long-standing recognition that distinct coral species growing in similar conditions are able to record environmental changes with species-specific [...] Read more.
Coral skeletons are built by Ca-carbonate (calcite or aragonite) crystals that exhibit distinct morphological patterns and specific spatial arrangements that constitute skeletal microstructures. Additionally, the long-standing recognition that distinct coral species growing in similar conditions are able to record environmental changes with species-specific responses provides convincing evidence that, beyond the thermodynamic rules for chemical precipitation, a biological influence is at work during the crystallization process. Through several series of comparative structural and geochemical (elemental and isotopic) data, this paper aims to firmly establish the specific properties of the distinct major taxonomic units that are commonly gathered as deep-water “corals” in current literature. Moreover, taking advantage of recent micrometric and infra-micrometric observations, attention is drawn to the remarkable similarity of the calcareous material observed at the nanoscale. These observations suggest a common biomineralization model in which mineralogical criteria are not the leading factors for the interpretation of the geochemical measurements. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
The Role of Seawater on the Trace Element Geochemistry of Some UK Coals and a Tribute to Goldschmidt
Minerals 2017, 7(8), 148; https://doi.org/10.3390/min7080148
Received: 27 June 2017 / Revised: 8 August 2017 / Accepted: 11 August 2017 / Published: 17 August 2017
Cited by 5 | PDF Full-text (1054 KB) | HTML Full-text | XML Full-text
Abstract
The Pennsylvanian coals in the UK were deposited in a low-lying delta plain which was periodically inundated by the sea. This resulted in high S contents, mainly due to early diagenetic pyrite. Based on a statistical analysis of the geochemical data, pyrite is [...] Read more.
The Pennsylvanian coals in the UK were deposited in a low-lying delta plain which was periodically inundated by the sea. This resulted in high S contents, mainly due to early diagenetic pyrite. Based on a statistical analysis of the geochemical data, pyrite is the major host for As, Se, Hg, Tl and Pb and an important host for Mo, Cd, Ni, Sb and Cu. All of these elements are enriched in the coals compared with non-marine mudrocks in the sequence, as is Ge and Be, although theirs is an organic association. The pattern of enrichment in the coals is similar to that in marine shales and coals overlain by marine shales, demonstrating the seawater influence. Goldschmidt was a pioneer in the geochemical study of coals and this paper will demonstrate that many of his ideas have stood the test of time. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
Electron Microscopy Observation of Biomineralization within Wood Tissues of Kurogaki
Minerals 2017, 7(7), 123; https://doi.org/10.3390/min7070123
Received: 9 May 2017 / Revised: 14 July 2017 / Accepted: 15 July 2017 / Published: 19 July 2017
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Abstract
Interactions between minerals and microorganisms play a crucial role in living wood tissues. However, living wood tissues have never been studied in the field. Fortunately, we found several kurogaki (black persimmon; Diospyros kaki) trees at Tawara in Kanazawa, Ishikawa, Japan. Here, we [...] Read more.
Interactions between minerals and microorganisms play a crucial role in living wood tissues. However, living wood tissues have never been studied in the field. Fortunately, we found several kurogaki (black persimmon; Diospyros kaki) trees at Tawara in Kanazawa, Ishikawa, Japan. Here, we report the characterization of kurogaki based on scanning electron microscopy equipped with energy-dispersive spectroscopy (SEM-EDS) and transmission electron microscopy (TEM), associated with inductively coupled plasma-mass spectrometry (ICP-MS) analyses, X-ray fluorescence analyses (XRF) and X-ray powder diffraction (XRD) analyses. This study aims to illustrate the ability of various microorganisms associated with biominerals within wood tissues of kurogaki, as shown by SEM-EDS elemental content maps and TEM images. Kurogaki grows very slowly and has extremely hard wood, known for its striking black and beige coloration, referred to as a “peacock pattern”. However, the scientific data for kurogaki are very limited. The black “peacock pattern” of the wood mainly comprises cellulose and high levels of crystal cristobalite. As per the XRD results, the black taproot contains mineralized 7 Å clays (kaolinite), cellulose, apatite and cristobalite associated with many microorganisms. The chemical compositions of the black and beige portions of the black persimmon tree were obtained by ICP-MS analyses. Particular elements such as abundant Ca, Mg, K, P, Mn, Ba, S, Cl, Fe, Na, and Al were concentrated in the black region, associated with Pb and Sr elements. SEM-EDS semi-qualitative analyses of kurogaki indicated an abundance of P and Ca in microorganisms in the black region, associated with Pb, Sr, S, Mn, and Mg elements. On the other hand, XRF and XRD mineralogical data showed that fresh andesite, weathered andesite, and the soils around the roots of kurogaki correlate with biomineralization of the black region in kurogaki roots, showing clay minerals (kaolinite) and cristobalite formation. In conclusion, we describe how the biominerals in the black region in the cellulose within wood tissues grow chemically and biologically in the sap under the conditions associated with the beige portions of the taproot. This can explain why the crystals produce the “peacock pattern” in the kurogaki formed during the year. We conclude that kurogaki microbiota are from bacteria in the andesitic weathered soil environment, which produce silicification. In other words, the patterned portions of kurogaki consist of silicified wood. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Open AccessArticle
The Role of Organic Matter in the Formation of High-Grade Al Deposits of the Dopolan Karst Type Bauxite, Iran: Mineralogy, Geochemistry, and Sulfur Isotope Data
Minerals 2017, 7(6), 97; https://doi.org/10.3390/min7060097
Received: 23 March 2017 / Revised: 20 May 2017 / Accepted: 31 May 2017 / Published: 12 June 2017
Cited by 2 | PDF Full-text (6559 KB) | HTML Full-text | XML Full-text
Abstract
Mineralogical and geochemical analyses of the Dopolan karstic bauxite ore were performed to identify the characteristics of four bauxite horizons, which comprise from top to bottom, bauxitic kaolinite, diaspore-rich bauxite, clay-rich bauxite, and pyrite-rich bauxite. Diaspore, kaolinite, and pyrite are the main minerals; [...] Read more.
Mineralogical and geochemical analyses of the Dopolan karstic bauxite ore were performed to identify the characteristics of four bauxite horizons, which comprise from top to bottom, bauxitic kaolinite, diaspore-rich bauxite, clay-rich bauxite, and pyrite-rich bauxite. Diaspore, kaolinite, and pyrite are the main minerals; böhmite, muscovite, rutile, and anatase are the accessory minerals. The main minerals of the Dopolan bauxite deposit indicate slightly acidic to alkaline reducing conditions during bauxitization. Immobile elements (Nb, Ta, Zr, Hf, and rare earth elements) are enriched in the diaspore-rich horizon, which also has the highest alumina content, whereas redox sensitive elements (e.g., Cr, Cu, Ni, Pb, Zn, Ag, U, and V) are enriched in the lowest horizon of pyrite-rich bauxite. The presence of a high content of organic matter was identified in different horizons of bauxitic ore from wet chemistry. The presence of organic matter favored Fe bioleaching, which resulted in Al enrichment and the formation of diaspore-rich bauxite. The leached Fe2+ reacted with the hydrogen sulfur that was produced due to bacterial metabolism, resulting in the formation of the pyrite-rich horizon towards the bottom of the Dopolan bauxite horizons. Biogeochemical activity in the Dopolan bauxitic ore was deduced from the reducing environment of bauxitization, and the deposition of framboidal and cubic or cubic/octahedral pyrite crystals, with large negative values of δ34S of pyrite (−10‰ to −34‰) and preserved fossil cells of microorganisms. Full article
(This article belongs to the Special Issue Organo-Mineral Interactions)
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Graphical abstract

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