Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

Cadmium (Cd) pollution in alkaline soil in some areas of northern China has seriously threatened wheat production and human health. However, there are still few effective amendments for alkaline soil, and the mechanism of amendments with a good immobilization effect remains unclear. In this study, soil sterilization experiments were conducted to investigate the effects of soil microorganisms on the immobilization of a novel amendment—mercapto palygorskite (MPAL) in Cd-contaminated alkaline soils. The results showed that the mercapto on the MPAL surface was not affected by autoclaving. Compared with the control, the available Cd concentration in 0.025% MPAL treatments decreased by 18.80-29.23% after 1 d of aging and stabled after 10 d of aging. Importantly, the immobilization of MPAL on Cd in sterilized soil was significantly better than that in natural soil due to the changes in Cd fractions. Compared with MPAL-treated natural soil, exchangeable Cd fraction and carbonate-bound Cd fraction in MPAL-treated sterilized soil decreased by 20.79–27.09% and 20.05–26.45%, while Fe/Mn oxide-bound Cd fraction and organic matter-bound Cd fraction increased by 17.77–22.68% and 18.85–27.32%. Phylogenetic investigation of communities by reconstruction of unobserved states (PICRUSt) analysis found that the potential functions of the microbial community in normal and sterilized soil were different significantly. Soil sterilization increased the soil pH and decreased the arylsulfatase activity, but did not change the soil zeta potential and available sulfur. The changes in Cd fractions in MPAL-treated sterilized soil may be related to the reduction in the bacterial community and the changes in function microbial, but not to the soil properties. In addition, MPAL application had little effects on the bacterial community, soil pH value, zeta potential, available sulfur, and arylsulfatase. These results showed that the immobilization of MPAL on Cd in alkaline soil was stable and effective, and was not affected by soil sterilization and soil microorganism reduction.

Palygorskite (PAL) is a good heavy metal adsorbent due to its high surface area, low cost, and environmentally compatibility. But the natural PAL has limited its adsorption capacity and selectivity. In this study, a cost-effective and readily-generated absorbent, l-threonine-modified palygorskite (L-PAL), was used and its performance for Cu(II) removal in simulated aquaculture wastewater was evaluated. After preparation, L-PAL was characterized by using Fourier transform infrared spectroscopy, scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The impacts of pH, adsorbent dosage, contact time, and initial Cu(II) concentration on the adsorption capacity of L-PAL were examined. The Cu(II) adsorption capacity on L-PAL was enhanced almost 10 times than that of raw PAL. The adsorption isotherms of Cu(II) fit the Langmuir isotherms, and the adsorption kinetics was dominated by the pseudo-second-order model. The thermodynamic parameters at four temperatures were calculated, which indicated that the adsorption was spontaneous and endothermic. The adsorption mechanism involves complexation, chelation, electrostatic attraction, and micro-precipitation. Furthermore, L-PAL is shown to have a high regeneration capacity. These results indicate that L-PAL is a cheap and promising absorbent for Cu(II) removal and hold potential to be used for aquaculture wastewater treatment.

The photocatalytic discoloration of industrial dyes, Novacron blue (NB) and Novacron yellow (NY), was investigated using composites based on TiO₂ and natural palygorskite (Pal-Ti10 and Pal-Ti30). The method consisted of synthesizing the composites starting from a physical mixture of TiO₂ and natural palygorskite in the presence of alcohol, for impregnation through calcination under conditions of temperature equal to 450 °C and atmospheric air. The characterization techniques used in this work were FTIR, XRD, XRF, SEM, particle size analysis and zeta potential. The photocatalysis for the NB dye was investigated through the application of a factorial 2⁴ experimental design, aiming at the best experimental conditions and finally applying them in another NY industrial dye. The investigated concentrations of NB were 10 ppm and 30 ppm, the composites were synthesized using 10 and 30% (p/p) of titanium dioxide in palygorskite, the two pH values were 2.0 and 6.0 and the light intensities 9 and 18 W were used. Tests performed at pH 2.0, Pal-Ti30 composite, power 18 W and 10 ppm of dye showed 100% color removal of both dyes in 90 min. The bleaching process followed the pseudo-first order kinetic model, and the apparent constants (Kₐₚₚ) were 0.0216 min⁻¹ and 0.0193 min⁻¹ for NB and NY dyes, respectively. The results of total organic carbon (TOC) showed mineralization of 61.70% and 58.06% for NB and NY, respectively, in 90 min of treatment, and the by-products were detected by GC-MS.

The effectiveness of gemini-modified palygorskite (PGS) as the novel remediation material in polycyclic aromatic hydrocarbons (PAHs)-contaminated water remediation was revealed and examined. The sorption behavior of gemini surfactants at the PGS/aqueous interface was addressed using a developed two-step adsorption and partition model (TAPM). The characterizations of gemini-modified PGS were investigated using infrared spectroscopy, cationic exchange capacity, and surface area analysis. The effects of pH, ionic strength, humic acid, and temperature on sorption of phenanthrene (PHE) to untreated and modified PGS were systematically studied. Analysis of the equilibrium data indicated that the sorption isotherms of gemini fitted TAPM well. The modification of PGS with gemini surfactants provided a favorable partition medium for PHE and enhanced PHE retention in solid particles. The solution parameters played significant effects on PHE sorption to the modified PGS. The sorption isotherms of PHE on PGS at different temperatures well fitted the Freundlich equation. Thermodynamic calculations confirmed that the sorption process of PHE on modified PGS was spontaneous and exothermic from 293 to 303 K. It is revealed that the modification with gemini surfactants probably offered some unique surface characteristics to the clay mineral as a new type of remediation material. This can provide a reference to the potential application of PGS in PAH-contaminated water remediation process.

Various geochemical studies have yielded conflicting data on whether humic coatings decrease or increase adsorption of heavy metals by soil minerals. The objective of the present study is to determine how humate pre-adsorption affects subsequent retention of Cd and Pb by palygorskite and sepiolite, as special silicate clay minerals of soil in many arid regions. For this purpose, a series of equilibrium batch experiments were conducted on the interactions of Pb and Cd with Ca–palygorskite and Ca–sepiolite before and after humate adsorption. The results showed that the Langmuir (L), Freundlich (F), Langmuir–Freundlich (LF), and Toth (T) equations satisfactorily described metal sorption data on the minerals. In the presence of humate as the pre-adsorbate, the values for sorption capacities of palygorskite and sepiolite for Cd and Pb slightly decreased. This can be attributed to the competition between humates and metal ions for mineral active sites and steric hindrance of the adsorbed humates, which reduces the access of metal ions to the mineral surface and internal channels. Humate coatings decreased the adsorption equilibrium constants of Cd, suggesting that the affinity of the organo-clays for Cd sorption is lower than those of Ca–clays. The values for the heterogeneity factor (β) generally showed an increasing trend with increasing humate coverage on palygorskite and sepiolite, which can be explained by the increased diversity of adsorption centers on humate–clay complexes. It may be concluded that the presence of humate bound on fibrous clay surfaces can influence the sorption, and hence the bioavailability and mobility of heavy metals in fibrous clay-containing arid and semiarid soils.

Herbicides are hazardous organic pollutants that contribute to the risk of environmental contamination. The aim of this work was to investigate the synergistic effect of silver (Ag) and gold (Au) bimetallic nanoparticles deposited on palygorskite (PAL) in the presence of TiO₂ for photodegradation of bentazone (BTZ) herbicide under UV light. Ag and Au@Ag nanoparticles exhibited an average size below 75 nm and surface charge values less than − 30 mV. UV-Vis spectroscopy indicates the formation of core@shell bimetallic nanoparticles. XRD results showed the interactions between the NPs and the palygorskite structure. SEM images clearly illustrate the presence of small spherical particles distributed in the clay fibers. The control of the size and distribution of the nanoparticles played an important role in the properties of the composites. The degradation of the herbicide BTZ showed that nanoparticles, clay, and only TiO₂ did not produce satisfactory results; however, when Ag-Pal and Au@Ag-Pal were in the presence of the TiO₂, the degradation was efficient. The best photodegradative system was Au@Ag-Pal+TiO₂, which was maintained after the third cycle. The bentazone photodegradation using Au@Ag-PAL+TiO₂ exhibited toxicity against Artemia salina. Therefore, Au@Ag-PAL+TiO₂ photocatalyst showed that the synergy of bimetallic nanoparticles deposited on clay for enhanced photodegradation activity of bentazone herbicide.

Silicate clay materials are promising natural adsorbents with abundant, low cost, stable, and eco-friendly advantages, but the limited adsorption capacity restricts their applications in many fields. Herein, palygorskite (PAL) was facilely activated with alkali to enhance its adsorptive removal capability for methylene blue (MB). The effects of alkali activation on the microstructure, physicochemical, and adsorption properties of PAL for MB were intensively investigated. It was found that the moderate alkali activation can partially remove the metal cations (i.e., Al³⁺, Mg²⁺) and Si in the crystal backbone of PAL by which new “adsorption sites” were created and the surface negative charges increased. The adsorption capacity and rate of PAL for MB were evidently enhanced due to the effective activation. The adsorption isotherms were described by Freundlich isotherm model very well, and the adsorption kinetics can be accurately presented by a pseudo-second-order model. It can be inferred from the fitting results that the overall adsorption process was controlled by external mass transfer and intra-particle diffusion (the dominant role). The multiple adsorption interactions (hydrogen bonding, electrostatic interactions, mesopore filling, and complexing) were turned out to be the dominant factors to improve the adsorption properties. It was revealed that the activated PAL could be used as a potential adsorption candidate for environmental applications.

Clay minerals have been utilized for the remediation of heavy metal-polluted soil. However, information on the remediation stability of various clay minerals with different performances is limited. In this study, a kind of palygorskite (PAL) with a sorption amount for Cd²⁺about 40 mg/g, which is much larger than common minerals, was selected as amendment for in situ immobilization field demonstration. Besides, sorption stability which is essential for remediation was investigated in an ideal solid solution system by sorption and desorption behaviors of Cd²⁺on PAL, including isotherms, kinetics, and various stimulated environmental factors such as pH, temperature, and background electrolytes. The calculated thermodynamic parameters confirmed the sorption process was endothermic and driven by entropy changes. Only minimal desorption was caused by stimulated irrigation or runoff and acid rain. The temperature, pH, and background electrolyte dependence confirmed that the sorption of Cd²⁺on PAL was stable. Various characterization results including X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) mapping, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) confirmed the sorption mechanisms were surface precipitation of CdCO₃and surface complexation with hydroxyl groups.

Natural palygorskite was used as an adsorbent for the removal of copper, cobalt and nickel from an aqueous solution. All assays were performed under controlled conditions to establish the adsorption capacity of the solid. Initially, the clay was characterized by chemical analysis, XRD, infrared spectroscopy and thermogravimetry. Adsorption experiments for the ions in aqueous solution were carried out by a batch method through which the reaction time, initial concentration of cations, temperature and pH of the aqueous solution were systematically varied. First-order, pseudo-second-order and intraparticle diffusion models were used to describe the kinetic data. The results show that the processes were fitted well by the pseudo-second-order model. Moreover, the equilibrium solid–cation systems followed the Langmuir isotherm model. The results indicate that raw palygorskite could be employed as a low-cost material for the removal of heavy metals from aqueous solution.