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1.
Food Res Int ; 186: 114344, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38729696

ABSTRACT

The research aimed to evaluate the effect of ultrasonication and succinylation on the functional, iron binding, physiochemical, and cellular mineral uptake efficacy of chickpea protein concentrate. Succinylation resulted in significant improvements in the water-holding capacity (WHC) (25.47 %), oil-holding capacity (OHC) (31.38 %), and solubility (5.80 %) of the chickpea protein-iron complex. Mineral bioavailability significantly increased by 4.41 %, and there was a significant increase in cellular mineral uptake (64.64 %), retention (36.68 %), and transport (27.96 %). The ferritin content of the succinylated chickpea protein-iron complex showed a substantial increase of 66.31%. Furthermore, the dual modification approach combining ultrasonication and succinylation reduced the particle size of the protein-iron complex with a substantial reduction of 83.25 %. It also resulted in a significant enhancement of 51.5 % in the SH (sulfhydryl) content and 48.92 % in the surface hydrophobicity. Mineral bioavailability and cellular mineral uptake, retention, and transport were further enhanced through dual modification. In terms of application, the addition of single and dual-modified chickpea protein-iron complex to a fruit-based smoothie demonstrated positive acceptance in sensory attributes. Overall, the combined approach of succinylation and ultrasonication to the chickpea protein-iron complex shows a promising strategy for enhancing the physiochemical and techno-functional characteristics, cellular mineral uptake, and the development of vegan food products.


Subject(s)
Biological Availability , Cicer , Iron , Cicer/chemistry , Iron/chemistry , Iron/metabolism , Humans , Food, Fortified , Plant Proteins/chemistry , Digestion , Minerals/chemistry , Caco-2 Cells , Succinic Acid/chemistry , Particle Size , Food Handling/methods , Solubility , Ferritins/chemistry , Ferritins/metabolism
2.
Int J Mol Sci ; 25(9)2024 Apr 25.
Article in English | MEDLINE | ID: mdl-38731897

ABSTRACT

Inspired by nature's remarkable ability to form intricate minerals, researchers have unlocked transformative strategies for creating next-generation biosensors with exceptional sensitivity, selectivity, and biocompatibility. By mimicking how organisms orchestrate mineral growth, biomimetic and bioinspired materials are significantly impacting biosensor design. Engineered bioinspired materials offer distinct advantages over their natural counterparts, boasting superior tunability, precise controllability, and the ability to integrate specific functionalities for enhanced sensing capabilities. This remarkable versatility enables the construction of various biosensing platforms, including optical sensors, electrochemical sensors, magnetic biosensors, and nucleic acid detection platforms, for diverse applications. Additionally, bioinspired materials facilitate the development of smartphone-assisted biosensing platforms, offering user-friendly and portable diagnostic tools for point-of-care applications. This review comprehensively explores the utilization of naturally occurring and engineered biominerals and materials for diverse biosensing applications. We highlight the fabrication and design strategies that tailor their functionalities to address specific biosensing needs. This in-depth exploration underscores the transformative potential of biominerals and materials in revolutionizing biosensing, paving the way for advancements in healthcare, environmental monitoring, and other critical fields.


Subject(s)
Biomimetic Materials , Biosensing Techniques , Biosensing Techniques/methods , Biomimetic Materials/chemistry , Humans , Minerals/chemistry , Minerals/analysis , Animals , Biomimetics/methods
3.
Bioresour Technol ; 402: 130762, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38692371

ABSTRACT

Ionic cadmium (Cd (II)) in water is a significant threat to ecosystems, the environment, and human health. Research is currently focused on developing efficient adsorption materials to combat Cd (II) pollution in water. One promising solution involves co-pyrolyzing solid residue from anaerobic digestion of food waste with oil-based drill cuttings pyrolysis residue to create a biochar with high organic matter content. This biochar has a lower heavy metal content and leaching toxicity compared to China's national standards, making it both safe and resourceful. It exhibits a high adsorption capacity for Cd (II) in water, reaching up to 47.80 ± 0.37 mg/g. Raising the pyrolysis temperature above 600 °C and increasing the amount of pyrolysis residue beyond 30 % enhances the biochar's adsorption capacity. The adsorption process is primarily driven by mineral precipitation, offering a promising approach for dual waste resource management and reducing heavy metal pollution.


Subject(s)
Cadmium , Charcoal , Solid Waste , Cadmium/chemistry , Charcoal/chemistry , Adsorption , Pyrolysis , Water Pollutants, Chemical/chemistry , Minerals/chemistry , Chemical Precipitation , Water Purification/methods
4.
J Colloid Interface Sci ; 669: 64-74, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38705113

ABSTRACT

The intricate organization of goethite nanorods within a silica-rich matrix makes limpet teeth the strongest known natural material. However, the mineralization pathway of goethite in organisms under ambient conditions remains elusive. Here, by investigating the multi-level structure of limpet teeth at different growth stages, it is revealed that the growth of goethite crystals proceeds by the attachment of amorphous nanoparticles, a nonclassical crystallization pathway widely observed during the formation of calcium-based biominerals. Importantly, these nanoparticles contain a high amount of silica, which is gradually expelled during the growth of goethite. Moreover, in mature teeth of limpet, the content of silica correlates with the size of goethite crystals, where smaller goethite crystals are densely packed in the leading part with higher content of silica. Correspondingly, the leading part exhibits higher hardness and elastic modulus. Thus, this study not only reveals the nonclassical crystallization pathway of goethite nanorods in limpet teeth, but also highlights the critical roles of silica in controlling the hierarchical structure and the mechanical properties of limpet teeth, thus providing inspirations for fabricating biomimetic materials with excellent properties.


Subject(s)
Crystallization , Iron Compounds , Minerals , Nanoparticles , Nanotubes , Silicon Dioxide , Silicon Dioxide/chemistry , Minerals/chemistry , Nanotubes/chemistry , Iron Compounds/chemistry , Nanoparticles/chemistry , Animals , Tooth/chemistry , Gastropoda/chemistry , Particle Size
5.
Waste Manag ; 182: 259-270, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38677143

ABSTRACT

Phosphogypsum (PG) presents considerable potential for agricultural applications as a secondary primary resource. However, it currently lacks environmentally friendly, economically viable, efficient, and sustainable reuse protocols. This study firstly developed a PG-based mineral slow-release fertilizer (MSRFs) by internalization and fixation of urea within the PG lattice via facet-engineering strategy. The molecular dynamics simulations demonstrated that the binding energy of urea to the (041) facet of PG surpassed that of the (021) and (020) facets, with urea's desorption energy on the (041) facet notably higher than on the (021) and (020) facets. Guided by these calculations, we selectively exposed the (041) dominant facet of PG, and then achieving complete urea fixation within the PG lattice to form urea-PG (UPG). UPG exhibited a remarkable 48-fold extension in N release longevity in solution and a 45.77% increase in N use efficiency by plants compared to conventional urea. The facet-engineering of PG enhances the internalization and fixation efficiency of urea for slow N delivery, thereby promoting nutrient uptake for plant growth. Furthermore, we elucidated the intricate interplay between urea and PG at the molecular level, revealing the involvement of hydrogen and ionic bonding. This specific bonding structure imparts exceptional thermal stability and water resistance to the urea within UPG under environmental conditions. This study has the potential to provide insights into the high-value utilization of PG and present innovative ideas for designing efficient MSRFs.


Subject(s)
Calcium Sulfate , Fertilizers , Phosphorus , Calcium Sulfate/chemistry , Phosphorus/chemistry , Urea/chemistry , Minerals/chemistry , Nitrogen/chemistry , Molecular Dynamics Simulation , Agriculture/methods , Nutrients
6.
Waste Manag ; 182: 271-283, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38688046

ABSTRACT

High water and pharmaceutical and care products (PPCPs) bounded in sludge flocs limit its utilization and disposal. The advanced oxidation process of perxymonosulfate (PMS) catalyzed by iron salts has been widely used in sludge conditioning. In this study, two iron-rich minerals pyrite and siderite were proposed to enhance sludge dewatering performance and remove the target contaminant of triclosan (TCS). The permanent release of Fe2+ in the activation of PMS made siderite more effective in enhancing sludge dewater with capillary suction time (CST) diminishing by 60.5 %, specific resistance to filtration (SRF) decreasing by 79.2 %, and bound water content (BWC) dropping from 37.1 % to 2.6 % at siderite/PMS dosages of 0.36/0.20 mmol/g-TSS after 20 min of pretreatment. Pyrite/PMS performed slightly inferior under the same conditions and the corresponding CST and SRF decreased by 51.5 % and 71.8 % while the BWC only declined to 17.8 %. Rheological characterization was employed to elucidate the changes in sludge dewatering performance, with siderite/PMS treated sludge showing a 48.3 % reduction in thixotropy, higher than 28.4 % of pyrite/PMS. Oscillation and creep tests further demonstrated the significantly weakened viscoelastic behavior of the sludge by siderite/PMS pretreatment. For TCS mineralization removal, siderite/PMS achieved a high removal efficiency of 43.9 %, in comparison with 39.9 % for pyrite/PMS. The reduction in the sludge solids phase contributed the most to the TCS removal. Free radical quenching assays and EPR spectroscopy showed that both siderite/PMS and pyrite/PMS produced SO4-·  and ·OH, with the latter acting as the major radicals. Besides, the dosage of free radicals generated from siderite/PMS exhibited a lower time-dependence, which also allowed it to outperform in destroying EPS matrix, neutralizing the negative Zeta potential of sludge flocs, and mineralizing macromolecular organic matter.


Subject(s)
Iron , Peroxides , Sewage , Triclosan , Waste Disposal, Fluid , Sewage/chemistry , Triclosan/chemistry , Iron/chemistry , Waste Disposal, Fluid/methods , Peroxides/chemistry , Water Pollutants, Chemical/chemistry , Minerals/chemistry , Oxidation-Reduction
7.
Water Res ; 256: 121582, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38608621

ABSTRACT

Ion-adsorption rare earth element (REE) deposits distributed in the subtropics provide a rich global source of REEs, but in situ injection of REEs extractant into the mine can result in leachate being leaked into the surrounding groundwater systems. Due to the lack of understanding of REE speciation distribution, particularly colloidal characteristics in a mining area, the risks of REEs migration caused by in situ leaching of ion-adsorption REE deposits has not been concerned. Here, ultrafiltration and asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (AF4-ICP-MS) were integrated to characterize the size and composition of REEs in leachate and groundwater from mining catchments in South China. Results show that REEs were associated with four fractions: 1) the <1 kDa fraction including dissolved REEs; 2) the 1 - 100 kDa nano-colloidal fraction containing organic compounds; 3) the 100 kDa - 220 nm fine colloids including organic-mineral (Fe, Mn and Al (oxy)hydroxides and clay minerals); 4) the >220 nm coarse colloids and acid soluble particles (ASPs) comprising minerals. Influenced by the ion exchange effect of in situ leaching, REEs in leachate were mostly dissolved (79 %). The pH of the groundwater far from the mine site was increased (5.8 - 7.3), the fine organic-mineral colloids (46 % - 80 %) were the main vectors of transport for REEs. Further analysis by AF4 revealed that the fine colloids can be divided into mineral-rich (F1, 100 kDa - 120 nm) and organic matter-rich (F2, 120 - 220 nm) populations. The main colloids associated with REEs shifted from F1 (64 % ∼ 76 %) to F2 (50 % ∼ 52 %) away from the mining area. For F1 and F2, the metal/C molar ratio decreased away from the mining area and middle to heavy REE enrichment was presented. According to the REE fractionation, organic matter was the predominant component capable of binding REEs in fine colloids. Overall, our results indicate that REEs in the groundwater system shifted from the dissolved to the colloidal phase in a catchment affected by in situ leaching, and organic-mineral colloids play an important role in facilitating the migration of REEs.


Subject(s)
Colloids , Groundwater , Metals, Rare Earth , Minerals , Mining , Water Pollutants, Chemical , Groundwater/chemistry , Colloids/chemistry , China , Minerals/chemistry , Adsorption
8.
Water Res ; 256: 121580, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38614029

ABSTRACT

This study aimed to develop surface complexation modeling-machine learning (SCM-ML) hybrid model for chromate and arsenate adsorption on goethite. The feasibility of two SCM-ML hybrid modeling approaches was investigated. Firstly, we attempted to utilize ML algorithms and establish the parameter model, to link factors influencing the adsorption amount of oxyanions with optimized surface complexation constants. However, the results revealed the optimized chromate or arsenate surface complexation constants might fall into local extrema, making it unable to establish a reasonable mapping relationship between adsorption conditions and surface complexation constants by ML algorithms. In contrast, species-informed models were successfully obtained, by incorporating the surface species information calculated from the unoptimized SCM with the adsorption condition as input features. Compared with the optimized SCM, the species-informed model could make more accurate predictions on pH edges, isotherms, and kinetic data for various input conditions (for chromate: root mean square error (RMSE) on test set = 5.90 %; for arsenate: RMSE on test set = 4.84 %). Furthermore, the utilization of the interpretable formula based on Local Interpretable Model-Agnostic Explanations (LIME) enabled the species-informed model to provide surface species information like SCM. The species-informed SCM-ML hybrid modeling method proposed in this study has great practicality and application potential, and is expected to become a new paradigm in surface adsorption model.


Subject(s)
Chromium , Iron Compounds , Machine Learning , Adsorption , Chromium/chemistry , Iron Compounds/chemistry , Arsenic/chemistry , Minerals/chemistry , Arsenates/chemistry , Water Pollutants, Chemical/chemistry , Kinetics
9.
Environ Pollut ; 350: 124004, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38641039

ABSTRACT

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).


Subject(s)
Ferric Compounds , Metals, Heavy , Minerals , Ferric Compounds/chemistry , Minerals/chemistry , Metals, Heavy/chemistry , Cations, Divalent , Sulfates/chemistry , Ferrous Compounds/chemistry , Manganese/chemistry , Iron/chemistry , Soil Pollutants/chemistry
10.
Environ Pollut ; 350: 124014, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38642792

ABSTRACT

Biochar has been used for soil Cr(VI) remediation in the last decade due to its enriched redox functional groups and good electrochemical properties. However, the role of soil inherent Fe-bearing minerals during the reduction of Cr(VI) has been largely overlooked. In this study, biochar with different electron-donating capacities (EDCs) was produced at 400 °C (BC400) and 700 °C (BC700), and their performance for Cr(VI) reduction in soils with varied properties (e.g., Fe content) was investigated. The addition of BC400 caused around 14.2-36.0 mg g-1 Cr(VI) reduction after two weeks of incubation in red soil, paddy soil, loess soil, and fluvo-aquic soil, while a less Cr(VI) was reduced by BC700 (2.57-16.7 mg g-1) with smaller EDCs. The Cr(VI) reduction by both biochars in different soils was closely related to Fe content (R2 = 0.93-0.98), so red soil with the richest Fe (14.8% > 1.79-3.49%) showed the best reduction capability, and the removal of soil free Fe oxides (e.g., hematite) resulted in 71.9% decrease of Cr(VI) reduction by BC400. On one hand, Fe-bearing minerals could increase the soil acidity, neutralize the surface negative charge of biochar, enhance the contact between Cr(VI) and biochar, and thus facilitate the direct Cr(VI) reduction by biochar in soils. On the other hand, Fe-bearing minerals could also facilitate the indirect Cr(VI) reduction by mediating the electron from biochar to Cr(VI) with the cyclic transformation of Fe(II)/Fe(III). This study demonstrates the key role of soil Fe-bearing minerals in Cr(VI) reduction by biochar, which advances our understanding on the biochar-based remediation mechanism of Cr(VI)-contaminated soils.


Subject(s)
Charcoal , Chromium , Environmental Restoration and Remediation , Iron , Minerals , Oxidation-Reduction , Soil Pollutants , Soil , Charcoal/chemistry , Chromium/chemistry , Soil Pollutants/chemistry , Soil/chemistry , Minerals/chemistry , Iron/chemistry , Environmental Restoration and Remediation/methods , Electrons
11.
Chemosphere ; 356: 141878, 2024 May.
Article in English | MEDLINE | ID: mdl-38582172

ABSTRACT

In this study, a sulfur-modified magnetic hydrochar was synthesized by grafting thiol-containing groups onto the sludge-derived hydrochar. The modified hydrochar exhibited effective adsorption of Cu2+, Pb2+, Zn2+, and Cd2+ over a wide pH range and in the presence of coexisting ions, and showed almost no secondary leaching in three acidic solutions. In the mult-metal ion system, the modified hydrochar exhibited maximum adsorption capacities were 39.38, 105.74, 26.53, and 38.11 mg g-1 for Cu2+, Pb2+, Zn2+, and Cd2+, respectively. However, the binding capacity and adsorption amount of modified hydrochar for metal ions were lower in the mult-metal ion system compared to the unit-metal ion system. Notably, Pb2+ showed a strong inhibitory effect on the adsorption of other heavy metal ions by modified hydrochar due to strong competition for xanthate functional groups. The Pb2+ occupied the xanthate and native functional groups (-OH, -NH2, and Fe-O etc.), leaving only a small amount of adsorption sites for Cu2+, Zn2+ and Cd2+. Simulation results further supported these findings, indicating that Pb2+ had the highest density profiles near the four functional groups, and the density profiles of the four heavy metals near the xanthate functional groups were greater compared to the other three functional groups. Furthermore, the SEM-EDS, TOF-SIMI, and XPS results indicated that modified hydrochar achieved excellent mineral binding mainly through electrostatic interaction, ion exchange, and chelation. Overall, these results highlight the sulfur-modified magnetic hydrochar as a highly efficient adsorbent for heavy metals in environmental applications.


Subject(s)
Metals, Heavy , Sewage , Water Pollutants, Chemical , Adsorption , Metals, Heavy/chemistry , Sewage/chemistry , Water Pollutants, Chemical/chemistry , Minerals/chemistry
12.
Water Res ; 257: 121656, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38677110

ABSTRACT

Schwertmannite (Sch) is considered as an effective remover of Chromium (Cr) due to its strong affinity for toxic Cr species. Since the instability of Sch, the environmental fate of Cr deserves attention during the transformation of Sch into a more stable crystalline phase. The ubiquitous manganese(II) (Mn(II)) probably affects the transformation of Sch and thus the environmental fate of Cr. Therefore, this study investigated the impact of Mn(II) on the transformation of Cr-absorbed Sch (Cr-Sch) and the associated behavior of SO42- and Cr. We revealed that the transformation products of Cr-Sch at pH 3.0 and 7.0 were goethite and Sch, respectively. The presence of Mn(II) weakened the crystallinity of the transformation products, and the trend was positively correlated with the concentration of Mn(II). However, Mn(II) changed the transformation products of Cr-Sch from hematite to goethite at pH 10.0. Mn(II) replaced Fe(III) in the mineral structures or formed Mn-O complexes with surface hydroxyl groups (-OH), thereby affecting the transformation pathways of Sch. The presence of Mn(II) enhanced the immobilization of Cr on minerals at pH 3.0 and 7.0. Sch is likely to provide an channel for electron transfer between Mn(II) and Cr(VI), which promotes the reduction of Cr(VI). Meanwhile, Mn(Ⅱ) induced more -OH production on the surface of secondary minerals, which played an important role in increasing the Cr fixation. In addition, part of the Mn(Ⅱ) was oxidized to Mn(Ⅲ)/Mn(Ⅳ) at pH 3.0 and pH 7.0. This study helps to predict the role of Mn(II) in the transformations of Cr-Sch in environments and design remediation strategies for Cr contamination.


Subject(s)
Chromium , Iron Compounds , Manganese , Minerals , Chromium/chemistry , Manganese/chemistry , Minerals/chemistry , Iron Compounds/chemistry , Phase Transition , Hydrogen-Ion Concentration , Ferric Compounds/chemistry
13.
Protein Expr Purif ; 220: 106489, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38685535

ABSTRACT

Phytate (inositol hexaphosphate) is the major storage form of phosphorus (P) in nature, and phytases catalyze the hydrolysis of P from phytate and the formation of inositol phosphate isomers. In this study, a bacterium that produces phytase was isolated in a phytase screening medium. The bacterium was identified as Klebsiella sp. using phenotypic and molecular techniques. The PhyK phytase gene was successfully amplified from the genome, inserted into the pET-21a (+) vector, and expressed as a recombinant protein in E. Coli BL21. The efficiency of a laboratory phytase (Lab-Ph, PhyK phytase) was determined and compared with a commercial phytase (Com-Ph, Quantum Blue 40P phytase, AB Vista) under an in vitro digestion assay. The native signal peptide effectively facilitated the translocation of the protein to the periplasmic space of E. Coli BL21, resulting in the proper folding of the protein and the manifestation of desirable enzyme activity. The Lab-Ph displayed the temperature and pH optima at 50 °C and 5 respectively. In addition, the Lab-Ph was inactivated at 80 °C. Under an in vitro digestion assay condition, Lab-Ph improved the P solubility coefficient in broiler diets. In comparison, the Com-Ph significantly increased the P solubility coefficient even when compared with the Lab-Ph. In summary, this study has shown that Lab-Ph possesses the necessary biochemical properties to be used in various industrial applications. However, Lab-Ph is extremely sensitive to heat treatment. The Lab-Ph and Com-Ph under an in vitro digestion assay improved the solubility coefficient of P in the broiler diet.


Subject(s)
6-Phytase , Chickens , Escherichia coli , Klebsiella , Recombinant Proteins , Solubility , Animals , Recombinant Proteins/genetics , Recombinant Proteins/chemistry , Recombinant Proteins/metabolism , 6-Phytase/genetics , 6-Phytase/chemistry , 6-Phytase/metabolism , Klebsiella/genetics , Klebsiella/enzymology , Escherichia coli/genetics , Escherichia coli/metabolism , Animal Feed , Bacterial Proteins/genetics , Bacterial Proteins/chemistry , Bacterial Proteins/metabolism , Hydrogen-Ion Concentration , Minerals/metabolism , Minerals/chemistry , Phytic Acid/metabolism , Phytic Acid/chemistry
14.
Environ Sci Technol ; 58(16): 7217-7227, 2024 Apr 23.
Article in English | MEDLINE | ID: mdl-38588505

ABSTRACT

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.


Subject(s)
Clay , Metals, Rare Earth , Minerals , Adsorption , Metals, Rare Earth/chemistry , Clay/chemistry , Minerals/chemistry , Hydrogen-Ion Concentration , Aluminum Silicates/chemistry
15.
Water Res ; 256: 121645, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38653093

ABSTRACT

Mercury contamination is a global concern, and the degradation and detoxification of methylmercury have gained significant attention due to its neurotoxicity and biomagnification within the food chain. However, the currently known pathways of abiotic demethylation are limited to light-induced photodegradation process and little is known about light-independent abiotic demethylation of methylmercury. In this study, we reported a novel abiotic pathway for the degradation of methylmercury through the oxidation of both mineral structural iron(II) and surface-adsorbed iron(II) in the absence of light. Our findings reveal that methylmercury can be oxidatively degraded by reactive oxygen species, specifically hydroxyl and superoxide radicals, which are generated from the oxidation of iron(II) minerals under dark conditions. Surprisingly, Hg(0) trapping experiments demonstrated that inorganic Hg(II) resulting from the oxidative degradation of methylmercury was rapidly reduced to gaseous Hg(0) by iron(II) minerals. The demethylation of methylmercury, coupled with the generation of Hg(0), suggests a potential natural attenuation process for methylmercury. Our results highlight the underappreciated roles of iron(II) minerals in the abiotic degradation of methylmercury and the release of gaseous Hg(0) into the atmosphere.


Subject(s)
Mercury , Methylmercury Compounds , Minerals , Oxidation-Reduction , Methylmercury Compounds/chemistry , Mercury/chemistry , Minerals/chemistry , Iron/chemistry , Ferrous Compounds/chemistry , Ferrous Compounds/metabolism
16.
Chemosphere ; 358: 142076, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38670506

ABSTRACT

Much of the toxicity in oil sands process-affected water in Athabasca oil sands tailings has been attributed to naphthenic acids (NAs) and associated naphthenic acid fraction compounds (NAFCs). Previous work has characterized the environmental behaviour and fate of these compounds, particularly in the context of constructed treatment wetlands. There is evidence that wetlands can attenuate NAFCs in natural and engineered contexts, but relative contributions of chemical, biotic, and physical adsorption with sequestration require deconvolution. In this work, the objective was to evaluate the extent to which prospective wetland substrate material may adsorb NAFCs using a peat-mineral mix (PMM) sourced from the Athabasca Oil Sands Region (AOSR). The PMM and NAFCs were first mixed and then equilibrated across a range of NAFC concentrations (5-500 mg/L) with moderate ionic strength and hardness (∼200 ppm combined Ca2+ and Mg2+) that approximate wetland water chemistry. Under these experimental conditions, low sorption of NAFCs to PMM was observed, where sorbed concentrations of NAFCs were approximately zero mg/kg at equilibrium. When NAFCs and PMM were mixed and equilibrated together at environmentally relevant concentrations, formula diversity increased more than could be explained by combining constituent spectra. The TOC present in this PMM was largely cellulose-derived, with low levels of thermally recalcitrant carbon (e.g., lignin, black carbon). The apparent enhancement of the concentration and diversity of components in PMM/NAFCs mixtures are likely related to aqueous solubility of some PMM-derived organic materials, as post-hoc combination of dissolved components from PMM and NAFCs cannot replicate enhanced complexity observed when the two components are agitated and equilibrated together.


Subject(s)
Carboxylic Acids , Oil and Gas Fields , Soil , Wetlands , Adsorption , Carboxylic Acids/chemistry , Soil/chemistry , Minerals/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Sand/chemistry
17.
J Hazard Mater ; 470: 134193, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38569341

ABSTRACT

Arsenopyrite and pyrite often coexist in metal deposits and tailings, thus simultaneous bioleaching of both sulfides has economic (as well as environmental) significance. Important targets in bio-oxidation operations are high solubilization rates and minimized accumulation of Fe(III)/As-bearing secondary products. This study investigated the role of pyrite bioleaching in the enhancement of arsenopyrite dissolution. At a pyrite to arsenopyrite mass ratio of 1:1, 93.6% of As and 93.0% of Fe were solubilized. The results show that pyrite bio-oxidation can promote arsenopyrite dissolution, enhance S0 bio-oxidation, and inhibit the formation of jarosites, tooeleite, and amorphous ferric arsenate. The dry weight of the pyrite & arsenopyrite residue was reduced by 95.1% after bioleaching, compared to the initial load, while only 5% weight loss was observed when pyrite was absent. A biofilm was formed on the arsenopyrite surface in the presence of pyrite, while a dense passivation layer was observed in the absence of pyrite. As(III) (as As2O3) was a dominant As species in the pyrite & arsenopyrite residue. Novel and detailed findings are presented on arsenopyrite bio-dissolution in the presence of pyrite, and the presented approach could contribute to the development of novel cost-effective extractive bioprocesses. ENVIRONMENTAL IMPLICATION: The oxidation of arsenopyrite presents significant environmental hazards, as it can contribute to acid mine drainage generation and arsenic mobilization from sulfidic mine wastes. Bioleaching is a proven cost-effective and environmentally friendly extractive technology, which has been applied for decades in metal recovery from minerals or tailings. In this work, efficient extraction of arsenic from arsenopyrite bioleaching was presented through coupling the process with bio-oxidation of pyrite, resulting in lowered accumulation of hazardous and metastable Fe(III)/As-bearing secondary phases. The results could help improve current biomining operations and/or contribute to the development of novel cost-effective bioprocesses for metal extraction.


Subject(s)
Arsenicals , Iron Compounds , Iron , Minerals , Sulfides , Sulfides/chemistry , Iron/chemistry , Arsenicals/chemistry , Kinetics , Minerals/chemistry , Iron Compounds/chemistry , Oxidation-Reduction , Solubility , Arsenic/chemistry , Biofilms , Acidithiobacillus/metabolism
18.
Environ Sci Pollut Res Int ; 31(19): 28443-28453, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38546920

ABSTRACT

This study investigated the applicability of industrial waste. The high affinity of Fe-based products is widely used for industrial effluents because of their capability to oxidize contaminants. Waste foundry dust (WFD) is an Fe oxide that has been investigated as a potential reactive material that causes the generation of reactive oxidants. We aimed to investigate the physicochemical properties of WFD and the feasibility in the Fenton oxidation process. The WFD was used as a catalyst for removing Congo red (CR), to evaluate the generation of •OH and dissolution of Fe during the oxidation process. The linkage of •OH generation by WFD with eluted Fe(II) through the Fe dissolution was found. The Fenton oxidation reaction, CR degradation was affected by H2O2 concentration, initial pH, WFD dosage, initial CR concentration, and coexisting anions. The CR degradation efficiency increased with an increase in H2O2 concentration and WFD dosage. In addition, chloride and sulfate in solution promoted CR degradation, whereas carbonate had a negative effect on the Fenton oxidation process. The elution of Fe promotes CR degradation, over three reuse cycles, the degradation performance of the CR decreased from 100 to 81.1%. For the Fenton oxidation process, •OH generation is linked to Fe redox cycling, the surface passivation and Fe complexes interrupted the release of reactive oxidants, which resulted in the degradation of the CR decreased. This study proposed that WFD can serve as catalysts for the removal of CR.


Subject(s)
Congo Red , Dust , Hydrogen Peroxide , Iron , Minerals , Oxidation-Reduction , Congo Red/chemistry , Iron/chemistry , Minerals/chemistry , Hydrogen Peroxide/chemistry , Industrial Waste , Coloring Agents/chemistry , Water Pollutants, Chemical/chemistry
19.
Environ Sci Pollut Res Int ; 31(19): 28007-28024, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38526715

ABSTRACT

The coal's mechanical properties have a significant influence on mining safety and the mine environment. Preparing a standard sample and conducting repeat mechanical testing are challenging because the coal is primarily soft, fragmented, and rich in developed fractures. This study used nanoindentation technology, combined with X-ray diffraction, small-angle X-ray, a high magnification microscope, and mechanical parameter scale-up analysis, to study the micromechanical of three coals being dominated by heterogeneous components and pores. The results show that load-displacement curves with different maximum loads (50 mN, 100 mN, and 200 mN) all appear the pop-in events, and coal heterogeneity affects the frequency of their occurrence. As the maximum load is increased, pop-in event of DSC appears once each, YW increases from zero to three times and HM decreases from four to two times. The heterogeneity of pore structure has little effect on residual displacement, which is mainly affected by hard minerals, and hard minerals reduce the law that residual displacement increases with the increase in maximum load. The micromechanical parameters of soft coals are mainly affected by large pores, while hard coals are mainly affected by hard minerals. The coal's heterogeneity does not affect the linear relationship between hardness and elastic modulus, but stronger heterogeneity will weaken the linear relationship between fracture toughness and elastic modulus. Compared to the mechanical parameters after scale-up, the values obtained based on nanoindentation are less than 15.588% larger, and the increase in the heterogeneity and hard minerals can make the predicted parameters more accurate. The nanoindentation technique can not only provide an efficient and accurate method for studying the mechanical properties of heterogeneous coal at the nanoscale, an important guide for large-scale coal.


Subject(s)
Coal , Minerals , Minerals/chemistry , X-Ray Diffraction
20.
Environ Sci Pollut Res Int ; 31(17): 24724-24744, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38503955

ABSTRACT

Clay minerals are abundant on Earth and have been crucial to the advancement of human civilization. The ability of clay minerals to absorb chemicals is frequently utilized to remove hazardous compounds from aquatic environments. Moreover, clay-based adsorbent products are both environmentally acceptable and affordable. This study provides an overview of advances in clay minerals in the field of groundwater remediation and related predictions. The existing literature was examined using data and information aggregation approaches. Keyword clustering analysis of the relevant literature revealed that clay minerals are associated with groundwater utilization and soil pollution remediation. Principal component analysis was used to assess the relationships among clay mineral modification methods, pollutant properties, and the Langmuir adsorption capacity (Qmax). The results demonstrated that pollutant properties affect the Qmax of pollutants adsorbed by clay minerals. Systematic cluster analysis was utilized to classify the collected data and investigate the relationships. The pollution adsorption mechanism of the unique structure of clay minerals was investigated based on the characterization results. Modified clay minerals exhibited changes in surface functional groups, internal structure, and pHpzc. This review provides a summary of recent clay-based materials and their applications in groundwater remediation, as well as discussions of their challenges and future prospects.


Subject(s)
Environmental Pollutants , Groundwater , Humans , Clay/chemistry , Minerals/chemistry , Soil/chemistry , Adsorption
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