Preparation and characterization of high-ash coal slime-based soil amendment as well as investigations of its adsorption performance and mechanisms towards heavy metals in soil.

In this study, high-ash coal slime-based mineral soil amendment (MSA) was prepared via the hydrothermal method using high-ash coal slime as raw material, supplemented with activator calcium oxide and additive KOH solution. After hydrothermal treatment at 230 °C for 5 h, the original crystalline phase (quartz and kaolinite) of the high-ash slime was completely transformed into hydrotalcite zeolite, tobermorite, and silicate of potassium aluminosilicate, which has the largest specific surface area. The adsorption of Pb2+ and Cd2+ was adherent to the kinetic equation of secondary adsorption and Freundlich models, and the removal of Pb2+ and Cd2+ reached up to 362.58 mg g-1 and 64.67 mg g-1. The successive releases of SiO2 and CaO from MSA conformed to the Elovich equation, whereas the releases of SiO2 in Cd-containing environments and CaO in Pb- and Cd-containing environments more closely conformed to the power function; the releases of K2O all conformed to the first-order kinetic equation. The presence of Pb2+ and Cd2+ in the environment promotes the release of potassium and calcium elements with MSA's ion-exchange ability, and attenuates the release of silicon elements. Combining Pb2+ and Cd2+ with silicon resulted in the intolerant precipitation of 3PbO·2SiO2 and Cd2SiO4. The mineral precipitation mechanism is the most important mechanism of MSA in immobilizing heavy metals, accounting for 72.7%-80.5% of the total adsorption. Further contaminated soil immobilization experiments also showed that the application of MSA significantly reduced the bioavailability of soil heavy metals. When the MSA addition amount was 1.6%, the residual state increased by 63.58%. In conclusion, preparing MSA may effectively utilize coal-based solid waste with high added value.

Hydrothermal alkaline synthesis and release properties of silicon compound fertiliser using high-ash coal slime.

High-ash coal slime is difficult to utilise as a boiler fuel, and its accumulation results in environmental pollution. In this study, we describe a new method for the preparation of high-ash coal slime silica compound fertiliser (HASF) using CaO-KOH mixed hydrothermal method to optimize the utilization of this industrial waste and relieve the pressure on the fertiliser industry. The coal slime (D0) used in this study and its dry basis ash content by 1 mol/L and 4 mol/L sulfuric acid pre-activation (D1, D4) were greater than 85%. The effective silicon content of D0, D1, and D4 silica compound fertilisers reached 30.24%, 31.24%, and 17.35%, respectively, and the sums of effective silica-calcium-potassium oxides were 57.28%, 58.87%, and 48.16%, respectively, under the optimal reaction conditions of 230 °C, 15 h, and 1 mol/L KOH, which met the market requirements, as determined using single-factor experiments. We used XRD, FTIR, and SEM-EDS analysis techniques to demonstrate that tobermorite and leucite were the main mineral phases of the compound fertiliser, and activated coal slime D4, which contains only quartz single crystals, required more demanding reaction conditions in the synthesis reaction. Subsequently, the cumulative release pattern of HASF silica was well described by the power function equation via repeated extraction and dissolution experiments, with the dissolution rate following D4 > D1 ≈ D0. Furthermore, 4 mol/L sulfuric acid pre-activation resulted in the enrichment of HASF combined with organic matter and increased the slow-release rate of HASF silica. Thus, the synthesized HASF could have potential application prospects in soil improvement and fertilisation.

Structural Characterization and Molecular Model Construction of High-Ash Coal from Northern China.

High-ash coal, also known as low-grade coal, has becomes a viable alternative in recent years to high-quality coal because available resources have become increasingly scarce due to extensive mining activity. This work aims to provide a comprehensive understanding of the structural characteristics of high-ash coal and construct a plausible molecular structure to elucidate its chemical reactivity in future applications. Its properties were investigated using Solid-state 13C nuclear magnetic resonance (13C NMR), X-ray photoelectron spectroscopy analysis (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The molecular structure was constructed and validated using Material Studio, LAMMPS Software Package, and MATLAB program. The characterization results revealed that high-ash coal contains 72.15% aromatic carbon, significantly surpassing the percentage of aliphatic carbon (27.85%). The ratio of bridgehead carbon to peripheral aromatic carbon was calculated as 0.67, indicating that the pentacene is the main carbon skeleton form in the high-ash coal structure. Furthermore, oxygen-containing functional groups presented as C=O/O-C-O, C-O, and COO- within the structure along with pyridine and pyrrolic structures. Consequently, the molecular structure comprises pentacene with aliphatic carbon chains, such as methylene, that connect the benzene rings and form a three-dimensional network. The results of a simulated IR spectrum and contact angle simulation aligned with the experimental results, validating the molecular structure of high-ash coal. The chemical formula for the high-ash coal model was determined as C203H189N7O61S with a molecular weight of 3734.79.

Adsorption of Different Ionic Types of Polyacrylamide on Montmorillonite Surface: Insight from QCM-D and Molecular Dynamic Simulation.

This study investigates the interaction between montmorillonite and polyacrylamide (PAM) with different ionic types using quartz crystal microbalance with dissipation monitoring (QCM-D) and molecular dynamics (MD) simulations. The goal was to understand the effect of ionicity and ionic type on polymer deposition on montmorillonite surfaces. The results of the QCM-D analysis showed that a decrease in pH led to an increase in the adsorption of montmorillonite on the alumina surface. The ranking of adsorption mass on alumina and pre-adsorbed montmorillonite alumina surfaces was found to be cationic polyacrylamide (CPAM) > polyacrylamide (NPAM) > anionic polyacrylamide (APAM). The study also found that CPAM had the strongest bridging effect on montmorillonite nanoparticles, followed by NPAM, while APAM had a negligible bridging effect. The MD simulations showed that ionicity had a significant influence on the adsorption of polyacrylamides. The cationic functional group N(CH3)3+ had the strongest attraction interaction with the montmorillonite surface, followed by the hydrogen bonding interaction of the amide functional group CONH2, and the anionic functional group COO- had a repulsive interaction. The results suggest that at high ionicity levels, CPAM can be adsorbed on the montmorillonite surface, while at low ionicity levels, APAM may still be adsorbed with a strong coordination trend.

The Synergistic Effects of Al3+ and Chitosan on the Solid-Liquid Separation of Coal Wastewater and Their Mechanism of Action.

It is important to identify an environmentally friendly and efficient flocculant that can replace polyacrylamide for the solid-liquid separation of coal wastewater. In this study, to explore whether chitosan can be used as an environmentally friendly and efficient flocculant for the solid-liquid separation of coal wastewater, AlCl3-chitosan was used to conduct flocculation-sedimentation and dewatering tests under different chitosan dosages and shear-strength conditions for the prepared coal wastewater. Focused beam reflectance was measured to dynamically monitor the number of refractory fine particles, and the settled flocs were photographed and analyzed with microscopy to explore the effect of AlCl3-chitosan on the flocculation settlement effect and floc characteristics. The synergistic mechanisms of AlCl3 and chitosan were investigated using quartz crystal dissipative microbalance and zeta potential measurement. The results showed that the addition of chitosan can significantly improve the flocculation-sedimentation and dewatering effects of coal wastewater. A reasonable dosage under a certain shear strength is conducive to the reduction of fine slime particles, which results in a compact floc structure, increases the floc size, and improves the settling effect. The synergistic effect of AlCl3-chitosan improved the electric neutralization and adsorption bridging abilities of the chitosan, and the mixed solution of AlCl3 and chitosan had stronger adsorption on the carbon surface. This study provides a new approach to the selection of flocculants for coal wastewater treatment.

Removal of heavy metal ions and polybrominated biphenyl ethers by sulfurized nanoscale zerovalent iron: Compound effects and removal mechanism.

Sulfurized nanoscale zerovalent iron (S-nZVI) has been widely reported to be able to quickly remove heavy metals/persistent organic pollutants, but the limited understanding of the complicated removal process of heavy metals-organic combined pollutants restricts the application of S-nZVI. Here, we demonstrate that there is significant difference in the effectiveness of S-nZVI for removing single pollutant and complex pollutants. The removal kinetic constant (kobs) of heavy metals by S-nZVI followed a sequence of Cr(VI)>Pb(II)>Ni(II)>Cd(II) with or without polybrominated diphenyl ethers (PBDEs). While the capacity of co-existing cations increasing the kobs of PBDEs followed the order: Ni(II)>Pb(II)>Cd(II), and the co-existence of Cr(VI) anion inhibited the reduction of PBDE by S-nZVI because the generated Cr-Fe precipitate hindered the electron transfer. The de-passivation process on S-nZVI surface by Cd(II) ions slightly accelerated the transformation rate of electron. Nevertheless, the co-existing Pb(II) significantly accelerated the transformation of BDE-209 via the galvanic effect from the generated Pb0/Fe0 bimetal. Interestingly, the kobs of BDE-47 in Ni(II)/S-nZVI system was 5.51 times higher than that of Pb(II)/S-nZVI system, implying that an atomic hydrogen mechanism dominated the reduction of BDE-47 by Ni(II)/S-nZVI. In conclusion, the results provided a deep comprehending of removal mechanism of heavy metal-organic complex pollutants by S-nZVI.

Removal of triphenyl phosphate by nanoscale zerovalent iron (nZVI) activated bisulfite: Performance, surface reaction mechanism and sulfate radical-mediated degradation pathway.

Recently, sulfate radical-based advanced oxidation processes (SR-AOPs) have been studied extensively for the removal of pollutants, however, few researches focused on the activation of bisulfite by nanoscale zerovalent iron (nZVI), especially, surface reaction mechanism and sulfate radical-mediated degradation pathway have not been elucidated in detail. In this study, influencing factors, the kinetics, transformation pathway and mechanism of triphenyl phosphate (TPHP) degradation in the nZVI/bisulfite system were systematically discussed. Compared with Fe2+, nZVI was found to be a more efficient and long-lasting activator of bisulfite via gradual generation of iron ions. The optimal degradation efficiency of TPHP (98.2%) and pseudo-first-order kinetics rate constant (kobs = 0.2784 min-1) were obtained by using 0.5 mM nZVI and 2.0 mM bisulfite at the initial pH 3.0. Both Cl- and NO3- inhibited the degradation of TPHP and the inhibitory effect of Cl- was stronger than that of NO3- due to the higher reaction rate of Cl- with •SO4-. Furthermore, SEM, XRD and XPS characterization revealed that a thin passivation layer (Fe2O3, Fe3O4, FeOOH) deposited on the surface of fresh nZVI and a few iron corrosion products generated and assembled on the surface of reacted nZVI. Radical quenching tests identified that •SO4- was the dominant reactive oxidative species (ROS) for TPHP removal. Based on HRMS analysis, six degradation products were determined and a sulfate radical-mediated degradation pathway was proposed. In a word, this study revealed that the nZVI/bisulfite system had a great potential for the TPHP elimination in waterbody.

Reductive debromination of decabromodiphenyl ether by iron sulfide-coated nanoscale zerovalent iron: mechanistic insights from Fe(II) dissolution and solvent kinetic isotope effects.

The mechanism that iron sulfide-coated nanoscale zero valent iron (S-nZVI) has better reduction activity towards organic pollutants than nanoscale zero-valent iron (nZVI) has long been debated. In this work, a systematic study was investigated to compare differences of main influences, BDE-209 degradation pathway, degradation kinetics and reduction mechanism of BDE-209 between nZVI and S-nZVI systems. The observed transformation rate of BDE-209 (kobs) by S-nZVI was 58.3 and 7.1 times greater than that by S2- and nZVI, respectively. The valence change of Fe and S on S-nZVI surface before and after BDE-209 degradation process based on XPS characterization confirmed that both Fe0 and iron sulfide were the reduction entity of the surface-mediated reaction. The presence of tetrahydrofuran (THF) promoted the surface contact of BDE-209 with S-nZVI, thus accelerating the BDE-209 degradation process. Compared with nZVI, the iron sulfide coated on the Fe0 core surface could not only greatly reduce unnecessary electron loss via Fe0 corrosion with water, but also accelerate the transmission of electrons from Fe0 core to organic pollutants according to Fe(II) dissolution and solvent kinetic isotope effects investigations. These findings help to clarify the synergistic degradation mechanism between Fe0 core and iron sulfide shell layer.