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.

The environmental behavior of antibiotics is not well known and the precise environmental risk assessment is not practical. This study investigated the sorption kinetics of ofloxacin, a widely used antibiotics, on soil particles with different organic carbon contents as well as soil components (a humic acid, ferric oxide and kaolinite). Two-compartment sorption kinetics were mathematically recognized (except ferric oxide because of its very fast sorption). The apparent sorption rate and the contribution of fast sorption compartment decreased with the increased organic carbon content with the exception of humic acid, suggesting that the slow sorption sites were partially located in organo-mineral complex. The OFL concentration-dependent sorption kinetics suggested that the slow sorption compartment was not controlled by diffusion process as indicated by slower sorption at higher OFL loading. The difference between OFL sorption kinetics and those of hydrophobic organic contaminants was discussed and possible mechanism of OFL two-compartment sorption was proposed.

The removal of pesticide residues in soil is a research hotspot. The metolachlor (MET) adsorption by walnut shell biochar (BC) modified with montmorillonite (MBC), illite (IBC), and kaolinite (KBC), as well as the original BC (OBC) was investigated. The characteristics of samples were studied by scanning electron microscopy and mapping analysis, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetry, and chemical stability analysis. The effects of the dosage, ionic strength, and pH, and determined the adsorption kinetics and isotherms for MET with the BCs were analyzed. In addition, response surface methodology regression model analysis was conducted and the adsorption mechanisms were investigated. The results showed that the thermal stability and chemical stability of MBC, IBC, and KBC were higher than those of OBC, and MBC had the greatest stability. The MET adsorption rates of OBC, MBC, IBC, and KBC were 62.15%, 92.47%, 87.97%, and 83.31%, respectively. The kinetic fitting results and adsorption mechanisms showed that the modification of BC with minerals enhanced the physical adsorption of MET. The maximum MET adsorption capacities by OBC, MBC, IBC, and KBC were 39.68 mg g⁻¹, 68.49 mg g⁻¹, 65.79 mg g⁻¹, and 65.36 mg g⁻¹, respectively. Hydrogen bonds, π–π bonds, coordination bonds, and hydrophobic interactions were the key adsorption mechanisms. Therefore, the mineral-modified BCs were characterized by high adsorption rates and stability. This approach can make BC more efficient, with higher performance as a low cost soil amendment.

The wide utilization of plastic related products leads to the ubiquitous presence of plastic particles in natural environments. Plastic particles could interact with kaolinite (one type of typical clay particles abundant in environments) and form plastic-kaolinite heteroaggregates. The fate and transport of both plastic particles and kaolinite particles thus might be altered. The cotransport and deposition behaviors of micron-sized plastic particles (MPs) with different surface charge (both negative and positive surface charge) with kaolinite in porous media in both 5 and 25 mM NaCl solutions were investigated in present study. Both types of MPs (negatively charged carboxylate-modified MPs (CMPs) and positively charged amine-modified MPs (AMPs)) formed heteroaggregates with kaolinite particles under both solution conditions examined, however, CMPs and AMPs exhibited different cotransport behaviors with kaolinite. Specifically, the transport of both CMPs and kaolinite was increased under both ionic strength conditions when kaolinite and CMPs were copresent in suspensions. While, when kaolinite and positively charged AMPs were copresent in suspensions, negligible transport of both kaolinite and AMPs were observed under examined salt solution conditions. The competition deposition sites by kaolinite (the portion suspending in solution) with CMPs-kaolinite heteroaggregates led to the increased transport both CMPs and kaolinite when both types of colloids were copresent. In contrast, the formation of larger sized AMPs-kaolinite heteroaggregates with surface charge heterogeneity led to the negligible transport of both kaolinite and AMPs when they were copresent in suspensions. The results of this study show that when plastic particles and kaolinite particles are copresent in natural environments, their interaction with each other will affect their transport behaviors in porous media. The alteration in the transport of MPs or kaolinite (either increased or decreased transport) is highly correlated with the surface charge of MPs.

Environmental colloids play crucial roles in the transport of environmental pollutants in porous media by acting as pollutant carriers. In this work, the dispersion stability and correlated transport of kaolinite colloid were investigated as a function of solution pH, solution ionic strength, and concentration of humic acid (HA), the roles of kaolinite colloid in driving Eu(III) transport were discussed. The results showed that the dispersion of kaolinite colloid was favorable at alkaline and extremely acidic pH values, the trend of aggregation with varying pH was critically reversed at pH ∼3.2 due to the transformation of surface electrical properties. Cations with higher valence and mineral affinity showed a more significant contribution in inducing colloid aggregation, which was generally in accordance with the Schulze-Hardy rule and Hofmeister series. HA greatly increased the colloid stability by altering the surface electrostatic potential and steric effect. The Derjguin-Landau-Verwey-Overbeek (DLVO) model suggested that the electrostatic force between colloidal particles controlled the aggregation and destabilizing trend of colloid, and the theoretically calculated critical coagulation concentration was consistent with that determined from kinetic aggregation experiments. The roles of kaolinite colloid in driving Eu(III) transport varied under different conditions, and the transport behavior was highly correlated with the dispersion stability trend of colloid. These results can provide an enhanced understanding of the environmental fate of kaolinite colloid as well as commensal pollutants.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

Natural aquifers typically exhibit a variety of structural heterogeneities. However, the effect of mineral colloids and natural organic matter on the transport behavior of uranium (U) in saturated heterogeneous media are not totally understood. In this study, heterogeneous column experiments were conducted, and the constructed columns contained a fast-flow domain (FFD) and a slow-flow domain (SFD). The effect of kaolinite, humic acid (HA), and kaolinite/HA mixture on U(VI) retention and release in saturated heterogeneous media was examined. Media heterogeneity significantly influenced U fate and transport behavior in saturated subsurface environment. The presence of kaolinite, HA, and kaolinite/HA enhanced the mobility of U in heterogeneous media, and the mobility of U was the highest in the presence of kaolinite/HA and the lowest in the presence of kaolinite. In the presence of kaolinite, there was no difference in the amount of U released from the FFD and SFD. However, in the presence of HA and kaolinite/HA, a higher amount of U was released from the FFD. The findings in this study showed that medium structure and mineral colloids, as well as natural organic matter in the aqueous phase had significant effects on U transport and fate in subsurface environment.

Natural soil montmorillonite and kaolinite nanoparticles (NPs) were tested as efficient sorbents for organic contaminant (OC) removal through mimicking their natural environmental dispersive states. Sorption of both mineral NPs decreased with increasing pH with ionizable pentachlorophenol (PCP), but increased with pH with non-ionizable phenanthrene (PHE), within the pH range of 4–10. In contrast, sorption decreased consistently for both PCP and PHE, as a function of increasing ion concentration (0.001–0.1 mol L−1). Sorption differences were likely caused by the electrolytic conditions dependent upon surface chemistry of OCs and mineral NPs. The results confirmed that the highly dispersive soil mineral NPs would prevail over both engineered NPs and their regular μm-sized colloids for OC removal, due to their ecological advantages and higher sorption properties. This finding provided a realistic assessment of the environmental function of soil natural minerals in water once they are released from soil into OC polluted aqueous systems.