The synthesis of clay-biochar composite has been recognized as an effective way to enhance the removal of pollutants. The interaction between clay mineral and biomass during thermal pyrolysis and the sorption capacity for ionic/nonionic organic containments have not been elaborated. In this study, two types of biochar were obtained from pyrolytic carbonization of the cellulosic-rich corn straw (C) and lignin-rich pine wood (P) at 500 or 700 °C. Typical clay minerals kaolinite and montmorillonite were selected to prepare clay-biochar composite. The results showed that the addition of clay mineral could strengthen dehydration reaction of corn straw biomass and reinforce its carbon structure. Montmorillonite-biochar composite owned more CC functional groups and porous structure than kaolinite-biochar composite. The addition of clay minerals could promote electrostatic attraction of ionic formed norfloxacin (NOR) on clay-pine wood biochar. However, the sorption capacity of nonionic diethyl phthalate (DEP) adsorption on clay-corn straw biochar decreased, owing to that clay increased the compactness of the biochar carbon structure, thus inhabited hydrophobic partition of nonionic organic compounds on disordered carbon fraction. The results from this study provide insights into the suitable contaminated site remediation by clay-biochar composite.

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.

Bacteria–phyllosilicate complexes are commonly found in natural environments and are capable of immobilizing trace metals. However, the molecular binding mechanisms of heavy metals to these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive Bacillus subtilis, Gram-negative Pseudomonas putida and their binary mixtures with montmorillonite using surface complexation model, Cd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and isothermal titration calorimetry (ITC). We have shown that larger amounts of Cd are adsorbed by B. subtilis than by P. putida at pH<∼6, and Cd sorption that binding to phosphate groups plays a more important role in P. putida than in B. subtilis. This remind us that we should consider the microbe species when predict the biochemical behavior of trace metals in microbe-bearing environments. The observed Cd adsorption on the binary bacteria–clay composites was more than that predicted based on the component additivity approach. When taking bacteria–clay (1:1 mass ratio) as a representative example, an approximately 68%:32% metal distribution between the bacterial and mineral fraction was found. Both the EXAFS and ITC fits showed that the binding stoichiometry for Cd-carboxyl/phosphate was smaller in the binary mixtures than that in pure bacteria. We proposed that the significant deviations were possibly due to the physical-chemical interaction between the composite fractions that might reduce the agglomeration of the clay grains, increase the negative surface charges, and provide additional bridging of metals ions between bacterial cells and clays.

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.

This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg-1 and Sector 3: pH 4.2, total Cu = 112 mg Cu kg-1) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg-1 (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils. In situ remediation of Cu-contaminated soils with a synthetic mica (Na-2-mica) will aid in re-vegetative efforts.

High-performance two-dimensional montmorillonite supported-poly (acrylamide-co-acrylic acid) hydrogel for dye removal was investigated. Montmorillonite cooperated with acrylamide and acrylic acid via polymerization, hydrogen-bond, amidation and electrostatic interactions to form the three-dimensional reticular-structured hydrogel with the free entrance for macromolecules. Adsorption tests revealed that the efficient removal (97%) for methylene blue at high concentration (200 mg/L) could be achieved via a small dose of hydrogel (0.5 g/L) within a short time (20 min). The excellent adsorption performance was profited from the electronegative surface and fully exposed reaction sites of two-dimensional montmorillonite, which could save the treatment cost and promote the removal effect compared with the conventional adsorbents. The adsorption process of methylene blue onto hydrogel could be fitted by both the pseudo-first-order and pseudo-second-order kinetics models, and the adsorption isotherm corresponded to the Sips model. The mechanism analysis based on Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy measurements illustrated that the reaction between carboxyl groups and methylene blue molecules as well as the cation-exchange enabled the hydrogel performing extraordinary adsorption efficiency.

Increasing interests in carbon dots (CDs) research resulted in the increased production of CDs and the risk to be released into the environment, including surface water and groundwater. To assess the environmental behavior of CDs, the stability of CDs in aqueous solutions were first examined by different environmental conditions, followed by the systematic investigation of the adsorption behaviors of CDs onto Al2O3 surface. Electrostatic interactions were considered as the dominant forces in CDs adsorption onto Al2O3 process, which were further confirmed by controlling experiments as compared with other minerals or oxides, such as montmorillonite, kaolinite and SiO2. Theoretical calculations and characterization of Al2O3/CDs revealed chemisorptions exist in the adsorption process. Our investigation results provided fundamental understanding towards the interaction of CDs with Al2O3 surface, and potential fate of CDs under natural conditions in aquatic environment, as well as in soils and sediments.

Serious pollution is caused by heavy metals (HMs) emission during sludge combustion treatment, but the addition of minerals has the ability to alleviate the migration of HMs to the gaseous state. In this study, HMs (As, Cr, Zn and Cu) behavior, speciation, and environmental risk during sludge combustion with CaO and montmorillonite (MMT) additive was investigated in the lab-scale tube furnace. The results showed that the sludge combustion was mainly determined by volatile matter. In general, CaO inhibited the volatilization of Cr, Zn, and Cu, but promoted As volatilization. MMT inhibited the volatilization of HMs, but the effect was not obvious at high temperatures. Besides, the improvement of retention effect was not found for Cr and Cu with the increase of CaO at 1000 °C, there might exist threshold value for CaO on HMs retention process. Meanwhile, CaO increased acid-soluble fraction of As significantly at high temperatures, decreased residual fraction of Cr by oxidation, converted Zn and Cu to residual fraction. MMT increased the acid-soluble fraction of As and residual fraction of Cr. In view of the HMs environmental risk in ash, the combustion temperature of sludge was necessary to control under 1000 °C and minerals additive amount was needed to manage above 1000 °C.

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.

Heavy metal pollution is very common in soils. Soils are complex systems including minerals, bacteria, and various other substances. In Cd(II) contaminated soil, the combined effects of clay minerals and heavy metals on bacterial biofilm and Cd(II) adsorption are unappreciated. Our study showed that the combination of clay minerals (goethite, kaolinite, and montmorillonite) and heavy metals promoted Serratia marcescens S14 biofilm development significantly more than clay minerals or Cd(II) alone. The amount of biofilm after binary treatment with clay minerals and Cd(II) was 2.3–7.3 times than that in control. Mineral-induced cell death and the expression of the fimA, bsmA, and eps were key players in biofilm formation. Binary treatment with montmorillonite and Cd(II) significantly enhanced biofilm development and consequently increased the adsorption of Cd(II). Cd(II) removal is the result of co-adsorption of bacteria and minerals. Bacterial biofilm played an important role in Cd(II) adsorption. FTIR spectroscopy showed the components of biofilm were not affected by minerals and revealed the functional groups –OH, –NH, –CH₂, –SH, –COO participated in Cd(II) immobilization. Our findings are of fundamental significance for understanding how minerals and Cd(II) affect biofilms and thereby enhance Cd(II) adsorption and predicting the mobility and fate of heavy metals in heavy metal-contaminated soil.