The long-term use of animal manure in agriculture has resulted in estrogen pollution, which poses risks to facility vegetable soils. Owing to the complex soil composition, estrogen may exhibit a variety of behaviors at the water/soil interface. This study demonstrated the role of humic acid (HA) on the 17β-estradiol (E2) adsorption by clay minerals (montmorillonite, kaolinite, and hematite). The interfacial behaviors were investigated using adsorption kinetics and isotherms data. Then, the effects of temperature, pH, and bisphenol A (BPA) on the interactions between humic-mineral complexes and E2 were explored. The adsorption of E2 is an exothermic and spontaneous process, and the addition of HA to minerals significantly promoted their E2 adsorption capacities. Higher pH levels (>10) and the presence of BPA decreased the adsorption capacities of minerals and mineral complexes for E2. Moreover, intercalation, hydrophobic partitioning, π-π interactions and hydrogen bonding could dominate the E2 adsorption onto complexes. These results provided insight into the interfacial behaviors of E2 on the surfaces of humic-mineral complexes and promoted the understanding of the migration and transport of estrogens in soils.

Iron-bearing clays are ubiquitously distributed as mineral dusts in the atmosphere. Bromophenols were reported as the major products from thermal decomposition of the widely used brominated flame retardants (BFRs). However, little information is available for the reactivity of iron associated with mineral dusts to interact with the atmospheric bromophenols and the subsequent toxic effects. Herein, three common clay minerals (montmorillonite, illite and kaolinite) were used to simulate mineral dusts, and the reactions with gaseous 2-bromophenol were systematically investigated under environmentally relevant atmospheric conditions. Our results demonstrate that structural Fe(III) in montmorillonite and Fe(III) from iron oxide in illite mediated the dimerization of 2-bromophenol to form hydroxylated polybrominated biphenyl and hydroxylated polybrominated diphenyl ether. The surface reaction is favored to occur at moisture environment, since water molecules formed complex with 2-bromophenol and the reaction intermediates via hydrogen bond to significantly lower the reaction energy and promote the dimerization reaction. More importantly, the formed dioxin-like products on clay mineral dust increased the toxicity of the particles to A549 lung cell by decreasing cell survival and damaging cellular membrane and proteins. The results of this study indicate that not only mineral dust itself but also the associated surface reaction should be fully considered to accurately evaluate the toxic effect of mineral dust on human health.

The increased applications and production of graphene oxide (GO) make the necessity to study information on the interaction of GO with minerals. In this work, adsorption and desorption were used to study the reversibility of interaction between GO and goethite/kaolinite. Result showed that the pH value, ionic strength, and temperature had significant effects on the adsorption and desorption behavior of GO. Interaction force was stronger between GO and goethite than that of kaolinite. The interaction may be attributed to the electrostatic, hydrogen-bonding, and Lewis acid base interactions. The irreversible interaction between GO and minerals may be a main mechanism for the observed desorption hysteresis. These results are important for evaluating the fate and health risk of GO in the environment.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

Residues from mining, as metabasalt powder from amethyst exploration, can be used to improve soil properties. Although there is a high-load content of clay minerals in metabasalt, the effects of this residue on cooper (Cu²⁺) and zinc (Zn²⁺) sorption and desorption have not been studied. The aim of this work was to evaluate Cu²⁺ and Zn²⁺ sorption capacity of metabasalt powder and to discuss the mineralogical behavior facing this phenomenon. This residue sorption capacity was compared to reference clay minerals under two Cu²⁺ and Zn²⁺ concentrations (8 and 16 cmolc/kg) in a competitive system (Cu²⁺ + Zn²⁺). The sorption capacity was estimated by sequential desorption using cation exchange resin. A survey of mineralogical and Cu²⁺ and Zn²⁺ concentrations was performed on metabasalt before and after sorption, and after desorption tests. All materials sorbed higher amounts of Cu²⁺ than Zn²⁺. The sorption magnitude decreased in the following order: metabasalt > montmorillonite > illite > kaolinite. Cu²⁺ and Zn²⁺ desorption from metabasalt is lower than the standard clay minerals, since the metabasalt sorption sites are expandable interlayers of clay minerals. The relevance and application of our findings are critical in providing information for the management of metabasalt residue, suggesting potential use as a remediation agent in contaminated water, especially those with high Cu²⁺ and Zn²⁺ loading. It also suggests that the Cu²⁺ and Zn²⁺ enrichment of this residue could potentially be used for converting the metabasalt into a useful source of slow nutrient supply for agricultural soils.

The effects of low-molecular-weight organic acids (LMWOAs) on the transport of graphene oxide nanoparticles in saturated kaolinite- and goethite-coated sand columns were studied. Acetic acid, glycolic acid, malonic acid, and tartaric acid were chosen in the experiments. LMWOAs enhanced the mobility of GO by electrostatic/steric repulsion. In addition, they competed with GO for limited deposition sites on grain surfaces. The effects of organic acids on the transport of GO strongly depended on organic acid species. In general, the transport enhancement effects followed the order of tartaric acid > malonic acid > glycolic acid > acetic acid; this difference may be related to the number and type of functional groups of organic acids. Different LMWOAs enhanced the transport of GO in goethite-coated sand to a larger extent than did in kaolinite-coated sand under the test conditions; this was likely related to the differences of physicochemical characteristics between goethite and kaolinite. Organic acids significantly inhibited the deposition of GO at 0.5 mM Ca²⁺; this was possible that Ca²⁺ enhanced adsorption of organic acids by complexing with the surface O-functionalities of both LMWOAs and sand grain. Consequently, more organic acid molecules competed with GO for deposition sites on grain surfaces. Additionally, a two-site transport model was used to fit the transport data. Our findings have important implications for the understanding of the deposition and fate of GO in soil especially in rhizosphere environments where various low-molecular-weight organic acids are active.

This paper determines the impact of two clay minerals (kaolinite and montmorillonite) and three oxides (goethite, δ-MnO₂, and bayerite) on the elemental composition and FTIR spectra of humic-like acid (HLA) extracted from microbial-mineral residue formed from the microbial utilization of lignin in liquid shake flask cultivation. Goethite, bayerite, and δ-MnO₂ showed higher enrichment capabilities of C and O + S in the HLA than kaolinite and montmorillonite. Goethite showed the highest retention of organic C, followed by bayerite, but kaolinite exhibited the least exchangeability. Kaolinite and montmorillonite enhanced microbial consumption of N, resulting in the absence of N in HLA. A few aliphatic fractions were preferentially gathered on the surfaces of kaolinite and montmorillonite, making the H/C ratios of HLA from the clay mineral treatments higher than those of HLA from the oxide treatments. δ-MnO₂ was considered the most effective catalyst for abiotic humification, and goethite and bayerite ranked second and third in this regard. This trend was proportional to their specific surface areas (SSAs). However, comparing the effects of different treatments on the promotion of HLA condensation by relying solely on the SSA of minerals was not sufficient, and other influencing mechanisms had to be considered as well. Additionally, Si–O–Al and Si–O of kaolinite participated in HLA formation, and Si–OH, Si–O, and Si–O–Al of montmorillonite also contributed to this biological process. Fe–O and phenolic –OH of goethite, Mn–O of δ-MnO₂, and Al–O of bayerite were all involved in HLA formation through ligand exchange and cation bridges. Lignin was better protected from microbial decomposition by the kaolinite, bayerite, and δ-MnO₂ treatments, which caused lignin-like humus (HS) formation. Under the treatments of δ-MnO₂, goethite, and bayerite, HLA showed a greater degree of condensation compared to HLA precipitated by kaolinite and montmorillonite. Contributions from Si–O, and Si–O–Al of clay minerals, and Fe–O, Mn–O, and Al–O of oxides were the mechanisms by which minerals catalyzed the formation of HS from lignin.

Numerous studies have shown that the invasion of the chemicals plays an important role on the geomechanical properties of the soil. This article aims to investigate the shear behavior of contaminated soil by laboratory tests and develop an extended shear strength model on the basis of the experimental results. In order to explicitly evaluate the effect of solution concentration on the shear strength behavior of soil, the remolded samples of kaolinite mixed with different concentrations of CuCl₂ solutions were prepared to carry out a series of consolidated-undrained triaxial shear strength tests. The results indicate that different CuCl₂ solution concentrations have significant influence on the shear strength property of kaolinite. With the increase of CuCl₂ solution concentration, the shear strength of soil displays a declining tendency, and the strength properties including cohesion and internal friction angle are also reduced, which indicates the Cu (II) that existed in the soil samples has deteriorated the soil strength strongly. Based on the experimental results, an extended Mohr–Coulomb strength model for contaminated soils has been proposed by introducing osmotic suction as a macro variable parameter. The conclusions in this study can provide reference for pollution prevention of existing and future foundations.