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The removal of dyes from effluents of textile industries represents a technological challenge, due to their significant environmental impact. The application of halloysite (Hal) and palygorskite (Pal) clay minerals as adsorbents for the removal of Congo red (CR) and methylene blue (MB) was evaluated in this work. The materials were applied both in natural and acid-treated forms, and characterized by XRD, XPS, SEM-EDS, FTIR, and N 2 adsorption-desorption isotherm techniques to identify their properties and main active sites. The adsorbents showed potential to remove CR (> 98%) and MB (> 85%) within 180 min, using 0.3 g adsorbent and initial dye concentration of 250 mg L -1 . Semi-empirical quantum mechanical calculations (SQM) confirmed the interaction mechanism between dyes and the adsorbents via chemisorption (- 69.0 kcal mol -1  < E ads  <  - 28.8 kcal mol -1 ), which was further observed experimentally due to the high fit of adsorption data to pseudo-second order kinetic model (R 2  > 0.99) and Langmuir isotherm (R 2  > 0.98). The use of Pal and Hal to remove dyes was proven to be economically and environmentally viable for industrial application., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Globodera pallida, an obligate sedentary endoparasite, is a major economic pest that causes substantial potato yield losses. This research aimed to study the effects of gene silencing of three FMRFamide-like peptides (FLPs) genes to reduce G. pallida infestation on potato plants by using kaolinite nanoclay as a carrier to deliver dsRNAs via drenching. A dsRNA dosage of 2.0 mg/ml silenced flp-32c by 89.5%, flp-32p by 94.6%, and flp-2 by 94.3%. J2s incubated for 5 and 10 h showed no phenotypic changes. However, J2s of G. pallida efficiently uptake dsRNA of all targeted genes after 15 h of incubation. On the other hand, J2s that had been kept for 24 h had a rigid and straight appearance. Under fluorescence microscopy, all dsRNA-treated nematodes showed fluorescein isothiocyanate (FITC) signals in the mouth, nervous system, and digestive system. The untreated population of J2s did not show any FITC signals and was mobile as usual. The drenching of potato cultivar Kufri Jyoti with the dsRNA-kaolinite formulations induced deformation and premature death of J2s, compared with untreated J2s that entered J3 or J4 stages. This study validates that the nanocarrier-delivered RNAi system could be employed effectively to manage G. pallida infestations., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

In this study, four Brazilian clays (Bofe, Verde-lodo, commercial Fluidgel, and expanded commercial vermiculite) were evaluated for their adsorptive capacity and removal percentage in relation to different toxic metals (Ni 2+ , Cd 2+ , Zn 2+ , and Cu 2+ ). The best results were obtained by expanded vermiculite, with cadmium removal reaching values of 95%. The most promising clay was modified by the sodification process, and the metal cadmium was used to evaluate the ion exchange process. The clays expanded vermiculite (EV) and VNa-sodified vermiculite were evaluated by equilibrium study at 25, 35, and 45 °C. At 25 °C, EV obtained a maximum adsorption capacity of 0.368 mmol/g and sodified vermiculite 0.480 mmol/g, which represents an improvement of 30.4% in modified clay capacity. At 45 °C, the sodified vermiculite reached 0.970 mmol/g adsorption capacity. The Langmuir, Redlich-Peterson Freundlich, and Dubinin-Raduskevich models were adjusted to the results. Langmuir provided the best fit among the models. The thermodynamic quantities (ΔS, ΔH, and ΔG) demonstrated that the process is spontaneous and endothermic and the metal is captured by physisorption and chemisorption in the studied temperature range. For the ion exchange equilibrium, the binary Langmuir and binary Langmuir-Freundlich models were adjusted to the expanded vermiculite and sodified vermiculite isotherms, respectively. Both models were predictive. Thermal analysis indicated good heat resistance even after material modification. The apparent and real densities demonstrated that after each treatment or contamination, the clayey material undergoes contraction in its structure. An improved efficiency of the adsorbent was found after sodification., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Soil-bentonite (S-B) barriers have been widely used for heavy metal pollution containment. This study conducted batch adsorption tests and diffusion-through tests to evaluate how ionic strength and bentonite ratio influence the migration of Cr(VI) in natural clay-bentonite mixtures. The test results indicated that the adsorption of Cr(VI) exhibited an obvious anion adsorption effect, the pH of the soil mixture increased with the addition of bentonite, resulting in a decrease in the positive surface charge. This change led to a decrease in Cr(VI) adsorption capacity, from 775.19 mg/kg for pure clay to 378 mg/kg for mixture samples with excessive bentonite. Furthermore, as the ionic strength increases from 0 to 0.1 M, the Cr(VI) adsorption capacity increases slightly due to the weakening of electrostatic repulsion on the clay particle surface, but the effective diffusion coefficient (D e ) increases by 21.97%. The compression of the diffusion double layer (DDL) under high ionic strength conditions enlarges the diffusion path and enhances the migration of Cr(VI) through the pore flow paths. Moreover, hydrated bentonite effectively fills the interaggregate pores of natural clay, thus creating narrower and more tortuous flow paths. However, excessive bentonite increases the pH value and pore volume, resulting in changes to the soil microstructure and disrupting the continuous skeleton of natural clay, which is unfavorable for Cr(VI) containment. Based on the study of the Cr(VI) contaminated site, a bentonite ratio of 2:10 is recommended for optimal natural performance of the natural clay-bentonite barrier., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The metal intoxication and its associated adverse effects to humans have led to the research for development of water treatment technologies from pollution hazards. Therefore, development of cheaper water remediation technologies is more urgent than ever. Clays and clay minerals are naturally occurring, inexpensive, non-toxic materials possessing interesting chemical and physical properties. As a result of interesting surface properties, these have been developed as efficient absorbent in water remediation. Recently, clay-polymer nanocomposites have provided a cost-effective technological platform for removing contaminants from water. Covering research advancements from past 25 years, this review highlights the developments in clay-polymer nanocomposites and their advanced technical applications are evaluated with respect to the background and issues in remediation of toxic metals and organic compounds from water. The extensive analysis of literature survey of more than two decades suggests that future work need to highlight on advancement of green and cost-effective technologies. The development of understanding of the interaction and exchange between toxin and clay-polymer composites would provide new assembly methods of nanocomposites with functional molecules or nanomaterials need to be extended to increase the detection and extraction limit to parts per trillion., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Pyrophyllite is the least studied natural clay in terms of its potential in biomedical applications, although there are many deposits of this aluminosilicate around the world. Genotoxicity study was performed in vitro for this mineral. Subsequently, Wister rats were exposed to the pyrophyllite micronized to below 100 µm. After the exposure period, histology of the lung, liver, kidney and gastric tissues were performed, followed by the stereological and hematological analysis. The physicochemical analyses revealed typical XRD characteristics of pyrophyllite clay with particle-size distribution ranging 50 nm-100 μm with stable mineral composition and unique buffering property to pH around 8. The results showed that there were no cytotoxic effects on to THP-1 cells, or genotoxicity of pyrophyllite measured by the Comet assay. In vivo studies are accompanied by the thorough physicochemical characterization of the micronized pyrophyllite. Histology of the lung tissue proved presence of an inflammatory reaction. On the other hand, gastric tissue has shown the selective accumulation of nanoparticles in enterocytes of the stomach only, as supported by ultrastructural analysis. Liver and kidney tissues have shown tolerability for pyrophyllite particles. The results give directions for further comprehensive studies of potential biomedical applications of the pyrophyllite., (© 2024. The Author(s).)

The objective of this study is to assess the effectiveness of a novel structure comprising a geocomposite drainage layer and a thin sand layer (GDL + sand) in mitigating the rapid dumping of excavated clay and its associated issues, such as landslides. Two sets of direct shear tests were conducted to investigate the influence of sand layer thickness and compaction degree on the interface shear behavior of the GDL + sand structure. As the sand layer thickness increased, both the interface shear strength and friction angle gradually increased, first more sharply and then at a slower rate toward stability, while the interface cohesion decreased gradually. The optimal sand layer thickness for achieving the most effective reinforcement in stabilizing the clay was identified as 10 mm. A higher sand layer compaction degree was found to result in increased interface shear strength, interface friction angle, and interface cohesion. Building on these findings, the reinforcing efficiency of the GDL + sand structure was investigated through mechanism analysis in comparison to that of a geogrid + sand structure and GDL structure as per the interface friction coefficient. The ranking of interface friction coefficients among the three structures emerged as: geogrid + sand > GDL + sand > GDL. These results suggests that the GDL + sand structure exhibits superior reinforcement efficiency compared to the GDL structure and offers better drainage efficiency than the geogrid + sand structure., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The development of bifunctional hybrid materials based on natural clays and layered double hydroxide (LDH) and their application on the simultaneous adsorption of Cd(II) and As(V) was investigated in this work. Two different synthesis routes, in situ and assembly, were employed to obtain the hybrid materials. Three types of natural clays, namely bentonite (B), halloysite (H), and sepiolite (S), were used in the study. These clays are characterized by a laminar, tubular, and fibrous structural arrangement, respectively. The physicochemical characterization results indicate that the hybrid materials were formed through interactions between the Al-OH and Si-OH groups present in the natural clays, and the Mg-OH and Al-OH groups present in the LDH for both synthesis routes. However, the "in situ" route yields a more homogenous material because the LDH formation is performed on the natural clay surface. The hybrid materials showed an anion and cation exchange capacity up to 200.7 meq/100 g and an isoelectric point near 7. The arrangement of natural clay has no impact on the properties of hybrid material but influences the adsorption capacity. The adsorption of Cd(II) onto hybrid materials was enhanced in comparison with natural clays, obtaining adsorption capacities of 80, 74, 65, and 30 mg/g for 15:1 (LDH:H) INSITU , 1:1 (LDH:S) INSITU , 1:1 (LDH:B) INSITU , and 1:1 (LDH:H) INSITU , respectively. The adsorption capacities of hybrid materials to adsorb As(V) were between 20 and 60 μg/g. The 15:1 (LDH:H) INSITU sample showed the best adsorption capacity being ten folds greater than halloysite and LDH. In all cases, the hybrid materials showed a synergistic effect for Cd(II) and As(V) adsorption. The adsorption study of Cd(II) onto hybrid materials showed that the primary adsorption mechanism is cation exchange between the interlayer cations in natural clay and Cd(II) in the aqueous solution. The adsorption of As(V) showed that the adsorption mechanism is attributed to anion exchange between CO 2 3- in the interlayer space of LDH and H 2 ASO 4 - in the solution. The simultaneous adsorption of As (V) and Cd (II) shows that, during the As(V) adsorption, there is no competition by the adsorption sites. Still, the adsorption capacity towards Cd(II) was enhanced 1.2-folds. This study ultimately revealed that the arrangement of clay has a significant influence on the adsorption capacity of the hybrid material. This can be attributed to the similar morphology between the hybrid material and natural clays, as well as the important diffusion effects observed in the system., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Soil organic carbon (SOC) is a crucial medium of the global carbon cycle and is profoundly affected by multiple factors, such as climate and management practices. However, interactions between different SOC fractions and land-use change have remained largely unexplored in karst ecosystems with widespread rock outcrops. Owing to the inherent heterogeneity and divergent response of SOC to land-use change, soil samples with close depth were collected from four typical land-use types (cropland, grassland, shrubland, and forestland) in the karst rocky desertification area of China. The aim of this study was to explore the responses of SOC dynamics to land-use types and underlying mechanism. The results showed that land-use type significantly affected SOC contents and its fractions. Compared with cropland, the other three land uses increased the total organic carbon (TOC), microbial biomass carbon (MBC), and non-labile organic carbon (NLOC) contents by 6.11-129.44%, 32.58-173.73%, and 90.98-347.00%, respectively; this demonstrated that a decrease in both labile and recalcitrant carbon resulted in SOC depletion under agricultural land use. Readily oxidized organic carbon (ROC) ranged from 42 to 69%, accounting for almost half of the TOC in the 0-40-cm soil layer. Cropland soil showed significantly higher ROC:TOC ratios than other land-use types. These results indicated that long-term vegetation restoration decreased SOC activity and improved SOC stability. Greater levels of soil exchangeable calcium (ECa) and clay contents were likely responsible for higher stabilization and then accumulation of SOC after vegetation restoration. The carbon pool index (CPI) rather than the carbon pool management index (CPMI) exhibited consistent variation trend with soil TOC contents among land-use types. Thus, further study is needed to validate the CPMI in evaluating land use effects on soil quality in karst ecosystems. Our findings suggest that land-use patterns characterized by grass or forest could be an effective approach for SOC-sequestration potential and ensure the sustainable use of soil resources in the karst area., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

This study focused on the efficacy of a calcined layered double hydroxide (CLDH) clay in adsorbing two antiretroviral drugs (ARVDs), namely efavirenz (EFV) and nevirapine (NVP), from wastewater. The clay was synthesized using the co-precipitation method, followed by subsequent calcination in a muffle furnace at 500 °C for 4 h. The neat and calcined clay samples were subjected to various characterization techniques to elucidate their physical and chemical properties. Response surface modelling (RSM) was used to evaluate the interactions between the solution's initial pH, adsorbent loading, reaction temperature, and initial pollutant concentration. Additionally, the adsorption kinetics, thermodynamics, and reusability of the adsorbent were evaluated. The results demonstrated that NVP exhibited a faster adsorption rate than EFV, with both reaching equilibrium within 20-24 h. The pseudo-second order (PSO) model provided a good fit for the kinetics data. Thermodynamics analysis revealed that the adsorption process was spontaneous and exothermic, predominantly governed by physisorption interactions. The adsorption isotherms followed the Freundlich model, and the maximum adsorption capacities for EFV and NVP were established to be 2.73 mg/g and 2.93 mg/g, respectively. Evaluation of the adsorption mechanism through computational analysis demonstrated that both NVP and EFV formed stable complexes with CLDH, with NVP exhibiting a higher affinity. The associated adsorption energies were established to be -731.78 kcal/mol for NVP and -512.6 kcal/mol for EFV. Visualized non-covalent interaction (NCI) graphs indicated that hydrogen bonding played a significant role in ARVDs-CLDH interactions, further emphasizing physisorption as the dominant adsorption mechanism., (© 2024. The Author(s).)

The application of bentonite (Bt) as an adsorbent for heavy metals has been limited due to its hydrophobicity and insufficient surface area. Herein, we present cellulose nanocrystal (CNC) modified Bt composite (CNC@Bt) with enhanced efficiency for Cr(VI) removal. CNC@Bt exhibited an increased specific surface area and a porous structure, while maintaining the original crystal structure of Bt. This was achieved through a synergistic function of ion exchange, hydrogen bonding, electrostatic interactions, and steric hindrance. The adsorption of Cr(VI) by CNC@Bt followed the pseudo-second-order kinetic and Langmuir isotherm adsorption model. Moreover, the process was endothermic and spontaneous. At an initial Cr(VI) concentration of 20 mg/L and pH = 4.0, 10 g/L CNC@Bt achieved a removal rate of 92.7%, and the adsorption capacity was 1.85 mg/g, significantly higher than bare Bt (37.9% and 0.76 mg/g). The removal efficiency remained consistently above 80% over a wide pH range, indicating the potential practical applicability of CNC@Bt. With its fast adsorption rate, pH adaptability, and stable performance, CNC@Bt presents promising prospects for the rapid treatment of Cr-contaminated wastewater., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Iron-based catalysts are environmentally friendly, and iron minerals are abundant in the earth's crust, with great potential advantages for PMS-based advanced oxidation process applications. However, homogeneous Fe 2+ /PMS systems suffer from side reactions and are challenging to reuse. Therefore, developing catalysts with improved stability and activity is a long-term goal for practical Fe-based catalyst applications. In this study, we prepared Fe-HNTs nanoreactors by encapsulating a nitrogen-doped carbon layer with one-dimensional halloysite nanotubes (HNTs) using the molten salt-assisted method. Subsequently, Fe (Co, Ni) nanoclusters were anchored onto the nitrogen-doped carbon layer at a relatively low temperature (550℃), resulting in stable and uniform distribution of metal nanoclusters on the surface of HNTs carriers in the form of Fe-N x coordination. The results showed that the dissolution of the molten salt and leaching of post-treated metal oxides generated numerous mesopores within the Fe-HNTs nanoreactor, leading to a specific surface area more than 10 times that of HNTs. This enhanced mass transfer capability facilitates rapid pollutant removal while exposing more active sites. Remarkably, Fe-HNTs adsorbed up to 97% of tetracycline within 60 min. In the Fe-HNTs/PMS system, the predominant reactive oxygen species has been shown to be 1 O 2 , and the added tetracycline was degraded by more than 98% within 5 min. The removal of tetracycline was maintained above 96% in the presence of interfering factors such as wide pH (3-11) and inorganic anions (5 mM Cl - , HCO 3 - , NO 3 - , and SO 4 2- ). The investigated mechanism suggests that efficient degradation and interference resistance of the Fe-HNTs/PMS system is attributed to the synergistic effect between the rapid adsorption of porous structure and the non-radical ( 1 O 2 )-dominated degradation pathway., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Clay minerals are abundant on Earth and have been crucial to the advancement of human civilization. The ability of clay minerals to absorb chemicals is frequently utilized to remove hazardous compounds from aquatic environments. Moreover, clay-based adsorbent products are both environmentally acceptable and affordable. This study provides an overview of advances in clay minerals in the field of groundwater remediation and related predictions. The existing literature was examined using data and information aggregation approaches. Keyword clustering analysis of the relevant literature revealed that clay minerals are associated with groundwater utilization and soil pollution remediation. Principal component analysis was used to assess the relationships among clay mineral modification methods, pollutant properties, and the Langmuir adsorption capacity (Q max ). The results demonstrated that pollutant properties affect the Q max of pollutants adsorbed by clay minerals. Systematic cluster analysis was utilized to classify the collected data and investigate the relationships. The pollution adsorption mechanism of the unique structure of clay minerals was investigated based on the characterization results. Modified clay minerals exhibited changes in surface functional groups, internal structure, and pH pzc . This review provides a summary of recent clay-based materials and their applications in groundwater remediation, as well as discussions of their challenges and future prospects., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this study, Tunisian raw clay (RC) was utilized as a cheap source of silicium and aluminum for the preparation of faujasite zeolite (FAU syn ) using the alkaline fusion technique. The zeolite's structural analysis was carried out using the XRD, nitrogen adsorption-desorption, and SEM-EDX techniques. The data collected demonstrate that the produced zeolite only included one homogeneous faujasite phase. Textural analysis shows that the FAU syn prepared from RC has a hierarchical porosity (micro-, meso-, and macropores). The total porosity was found to be 0.33 cm 3 /g as well as the BET area was equal to 360 m 2 /g. Adsorption experiments for propene capture were performed using the FAU syn as adsorbent material. The performance of the column was examined in relation to various parameter impacts, including flow rate (50, 100, and 150 mL/min), input concentration (4, 8, and 12 mg/L), and bed depth (10, 14, and 18 cm). Finally, experimental and theoretical studies were investigated to predict adsorption capacities and kinetics parameters. To clarify and estimate column inputs, a model that incorporates axial dispersion, Langmuir equation, and migration within the adsorbent's pore was improved. COMSOL Multiphysics software was used to execute the model and resolve it computationally. The results of the experiments and the expected breakthrough curves were very well agreed. Modeling obtained results can be extrapolated to industrial level., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Clay liners have been widely used in landfill engineering. However, large-scale clay excavation causes secondary environmental damage. This study investigates the feasibility of replacing clay liners with high-density polyethylene (HDPE) geomembranes with different specifications and parameters. Laboratory interface shear tests between municipal solid waste (MSW) samples of different ages and geomembranes were conducted to study the influence of landfill age on interface shear strength. Finite element method was adopted to compare the long-term stability of landfills with HDPE geomembrane versus clay as intermediate liner. The interfacial shear test results show that the cohesion of MSW increases in a short term and then decreases with landfill age. The internal friction angle exhibits an increasing trend with advancing age, however, the rate of its increment declines with age. The rough accuracy of the film surface can increase the interfacial shear strength between MSW. The simulation results show that, unlike clay-lined landfills, the sliding surface of geomembrane-lined landfills is discontinuous at the lining interface, which can delay the penetration of slip surfaces and block the formation of slip zone in the landfill. In addition, the maximum displacement of landfills with geomembrane is 10% lower than that with clay, and the absolute displacement of slope toe decreases with the increase of roughness at the interface of geomembrane. Compared with clay-lined landfills, the overall stability safety factor increased by 18.5-30%. This study provides references for landfill design and on-site stability evaluation, contributing to enhanced long-term stability., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

When soils available for the construction of liners do not display the characteristics necessary for a good performance, mixtures with other materials can be employed for achieving the desired quality. Several researchers have addressed those mixtures from either a geotechnical or a gas diffusion perspective, emphasizing low hydraulic conductivity. However, in recent years, growing attention has been drawn to the ability of liners to mitigate contamination. The literature lacks studies on the use of amendments for soil liners or cover systems to retain potentially toxic metals, which are important inorganic contaminants. This paper provides a systematic review of the literature considering publications available on Web of Science and SpringerLink databases between January 1st, 2012, and December 5th, 2022. The aim of the review was to identify the types of soils and amendments studied as liners or cover systems for such retention of potentially toxic metals, the methodologies of application of the alternative materials in the soils, and the research gaps and perspectives in the field. Seventeen papers that addressed 31 materials as amendments were retrieved. The most studied amendment was coal fly ash, and 17 amendments were residues or by-products, which indicates concerns over waste destination and sustainability. Among the potentially toxic metals analyzed are Pb, Cu, and Cd. Gaps such as lack of pilot, field-scale, and long-term studies, as well as perspectives for future research (e.g., different liner configurations, concomitant mixtures of two or more materials in the soil, and focus on the sustainability of amendments), were identified., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

In the present work, halloysite nanotubes modified with gold nanoparticles (AuNPs-HNT) are successfully prepared by wet chemical method for the catalytic degradation of phenothiazine dyes (azure B (AZB) and toluidine blue O (TBO)) and also cleaner reduction of 4-(4-nitrophenyl)morpholine (4NM) in the sodium borohydride (NaBH 4 ) media. The catalyst is formulated by modifying the HNT support with a 0.964% metal loading using the HNT supports modified with 3-aminopropyl-trimethoxysilane (APTMS) coupling agent to facilitate the anchoring sites to trap the AuNPs and to prevent their agglomeration/aggregation. The AuNPs-HNT catalyst is investigated for structural and morphological characterization to get insights about the formation of the catalyst for the effective catalytic reduction of dyes and 4NM. The microscopic studies demonstrate that AuNPs (2.75 nm) are decorated on the outer surface of HNT. The as-prepared AuNPs-HNT catalyst demonstrates AZB and TBO dye degradation efficiency up to 96% in 10 and 11 min, respectively, and catalytic reduction of 4NM to 4-morpholinoaniline (MAN) is achieved up to 97% in 11 min, in the presence of NaBH 4 without the formation of any by-products. The pseudo-first-order rate constant (K 1 ) value of the AuNPs-HNT catalyst for AZB, TBO, and 4NM were calculated to be 0.0078, 0.0055, and 0.0066 s -1 , respectively. Moreover, the synthesized catalyst shows an excellent reusability with stable catalytic reduction for 7 successive cycles for both the dyes and 4NM. A plausible mechanism for the catalytic dye degradation and reduction of 4NM by AuNPs-HNT catalyst is proposed as well. The obtained results clearly indicate the potential of AuNPs-HNT as an efficient catalyst for the removal of dye contaminants from the aquatic environments and cleaner reduction of 4NM to MAN, insinuating future pharmaceutical applications., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A novel SnO 2 -Sb/AP (attapulgite) particle electrode was prepared for three-dimensional electrocatalytic oxidation (3D/EO) of organic pollutants using a co-sintering method. The electrochemical properties and micromorphology were determined using polarization, cyclic voltammetry (CV), and field emission scanning electron microscope (FE-SEM), and compared with activated carbon (AC), AP, and TiO 2 /AP particle electrodes. Besides, their potential application in the electrochemical degradation of phenol was investigated. The SnO 2 -Sb/AP particle electrode exhibited higher electrochemical activity than other particle electrodes due to its large number of active sites, low transfer coefficient (α, 0.12), and high-volt ampere charge (q * , 1.18 C·cm -2 ). The electrochemical COD Cr degradation efficiency (100%) of phenol on SnO 2 -Sb/AP particle electrodes is much higher than for other particle electrodes. Moreover, an excellent stability of the SnO 2 -Sb/AP particle electrode is also verified by repeated experiments. These results indicate that the SnO 2 -Sb/AP particle electrodes broaden the application area of clays and are expected to be a promising method for 3D/EO., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this paper, the performance of ladle furnace slag (LFS), a by-product of secondary steel refining, is evaluated as a binder to stabilize clayey soils of low bearing capacity. The aim is to define whether additions of this by-product to clayey soil can stabilize the soil in accordance with the technical specifications of Spanish standards. To do so, three different soils stabilized with 5% LFS were compared with the same soils stabilized with 2% lime and with no stabilization, in order to investigate their different behaviors. The chemical and mineralogical characterizations of all the soil mixes were conducted using X-ray fluorescence, X-ray diffraction, and scanning electron microscopy. The Atterberg limit test was used to study the plastic behavior of the soils, and the results of compaction, bearing capacity, unconfined compressive strength, and direct shear strength (cohesion and friction angle) tests defined their strength characteristics. The analysis was completed with the pH monitoring of the mixes along the curing time in order to relate the pH changes with the strength evolution. The addition of LFS to the soils has resulted in an increase in the liquid limit and plastic limit, causing therefore a slight decrease in the plasticity index. All the soils showed increases between 30% and 70% in their California Bearing Ratios immediately after mixing with 5% LFS, and after 90 days of curing, improvements of 30-188% in their unconfined compressive strength were noted in comparison with untreated soil, which were higher than the lime-stabilized soils. The cohesion of soils stabilized with LFS at 28 days of curing obtained improvements ranging from 40 to 300% depending on the type of soil. However, the friction angle showed a slight increase of 10% in two of the soils and zero in another. The high initial pH in LFS-stabilized soils was maintained during the curing time, which favored the development of pozzolanic reactions that improve the soil strength. These results confirmed that the substitution of lime with LFS is a feasible option for soil stabilization., (© 2023. The Author(s).)

A clay-based adsorbent (CBA) was purified from a sustainable precursor (raw clay, RC), which was obtained from the Amazon region in Brazil. The CBA was characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Brunauer-Emmet-Teller surface area (S BET , RC = 23.386 m 2 .g -1 , CBA = 33.020 m 2 .g -1 ), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), thermogravimetric analysis (TGA), cation exchange capacity (CEC, CBA = 44.75 cmol/kg), and point of zero charge analyses (pH PZC , CBA = 2.20). Subsequently, CBA was used to adsorb basic yellow 2 (BY2) dye from aqueous solutions. A CBA dosage (1 g/L), initial concentration of dye (C 0  = 15 mg/L), and pH (5.6) were ideal conditions for the BY2 dye removal of ~ 98%. The BY2 kinetics was better represented by the pseudo-first-order (PFO) model while the BY2 equilibrium was well represented by the Sips model, with a maximum adsorption capacity of q ms  = 18.04 mg/g at 28 °C. The negative values of ΔG° and ΔH° showed that the studied process is spontaneous and exothermic, while the values of isosteric heat (∆H st , -16 to -20 kJ/mol) suggest a predominance of physical interactions. The molecular chemical reactivity of BY2 was investigated using quantum chemical descriptors calculated based on Density Functional Theory (DFT) optimization of the dye molecule, and the results revealed a large energy gap value (4.3900 eV) and considerable chemical hardness (η = 2.1950 eV). Therefore, the correlation between DFT and experimental results consistently sustains that BY2 dye tends to be adsorbed on the CBA surface by electrostatic interactions, thus, this is the possible adsorption mechanism of this process., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The present study demonstrates the synthesis of eco-friendly metal oxide-clay composites (MgO-clay and CaO-clay) with phytochemical functionalization. The physical and chemical properties of prepared composites were characterized using standard techniques viz. scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The effect of pH on the dye adsorption capability of the synthesized composites was studied. The adsorption of an anionic dye methyl orange (MO) and a cationic due methylene blue (MB) was favored in the acidic and basic regions, respectively. The Taguchi design approach was adopted for the removal of MO and MB from wastewater using the synthesized composites. The obtained results suggest that initial dye concentration and composite dosage were the most influential parameters in dye removal among all the studied parameters. The adsorption experiments were carried out using MgO-clay and CaO-clay composites with the optimum conditions obtained from Taguchi optimization to validate the predicted response. The experimental parameters viz. the effect of contact time, initial dye concentration, and solution temperature were studied for screened composite (CaO-clay) with optimized conditions. The obtained results were interpreted using standard isotherms and kinetic models. A maximum adsorption capacity of 571 ± 10 and 859 ± 14 mg g -1 was obtained from the Langmuir adsorption isotherm for MO and MB, respectively. Regeneration studies suggested that the CaO-clay composite can be utilized up to 3 cycles with reduced adsorption capacity of the dyes over cycles due to the solid binding nature of dyes on the CaO-clay composite. The fresh and utilized CaO-clay composite were tested for their environmental toxicity analysis using ecologically important soil microorganisms. The obtained results suggested no detrimental effects on soil microbe's functionality, indicating their threat-free disposal in the soil environment., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Removal of emerging contaminants, such as antibiotics, from wastewater by adsorption is a simple, low-cost, and high-performance process; however, regeneration and reuse of the exhausted adsorbent are necessary to make the process economically viable. This study aimed to investigate the possibility of electrochemical-based regeneration of clay-type materials. For this, the calcined Verde-lodo (CVL) clay was saturated with the antibiotics ofloxacin (OFL) and ciprofloxacin (CIP) in one-component systems by an adsorption process and then subjected to photo-assisted electrochemical oxidation (0.45 A, 0.05 mol/L NaCl, UV-254 nm, and 60 min), which promotes both pollutant degradation and adsorbent regeneration. The external surface of the CVL clay was investigated by X-ray photoelectron spectroscopy before and after the adsorption process. The influence of regeneration time was evaluated for the CVL clay/OFL and CVL clay/CIP systems, and the results demonstrate high regeneration efficiencies after 1 h of photo-assisted electrochemical oxidation. Clay stability during regeneration was investigated by four successive cycles in different aqueous matrices (ultrapure water, synthetic urine, and river water). The results indicated that the CVL clay is relatively stable under the photo-assisted electrochemical regeneration process. Furthermore, CVL clay was able to remove antibiotics even in the presence of natural interfering agents. The hybrid adsorption/oxidation process applied here demonstrated the electrochemical-based regeneration potential of CVL clay for the treatment of emerging contaminants, since it can be operated quickly (1h of treatment) and with lower consumption of energy (3.93 kWh kg -1 ) than the traditional method of thermal regeneration (10 kWh kg -1 )., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The co-occurrence of mixtures of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment, and plants is a cause for concern due to potential threats to the ecosystem and human health. Major routes of exposure include contact with contaminated water and soil and through consumption of crops containing GLP and AMPA residues. Calcium montmorillonite (CM) and acid-processed montmorillonite (APM) clays were investigated for their ability to tightly sorb and detoxify GLP and AMPA mixtures. In vitro adsorption and desorption isotherms and thermodynamic analysis indicated saturable Langmuir binding of both chemicals with high capacities, affinities, enthalpies, and free energies of sorption and low desorption rates. In silico computational modeling indicated that both GLP and AMPA can be readily absorbed onto clay surfaces through electrostatic interactions and hydrogen bonding. The safety and efficacy of the clays were confirmed using well-established living organisms, including an aquatic cnidarian (Hydra vulgaris), a soil nematode (Caenorhabditis elegans), and a floating plant (Lemna minor). Low levels of clay inclusion (0.05% and 0.2%) in the culture medium resulted in increased growth and protection against chemical mixtures based on multiple endpoints. Results indicated that montmorillonite clays may be used to bind mixtures of GLP and AMPA in water, soil, and plants., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Clays are often envisaged as an alternative to activated carbon for wastewater pollutant adsorption. However, conclusive results have only been obtained for clays heavily chemically modified. In this study, a greener approach is proposed to improve the retention capacity of clays. It consists in mixing clay (C) with eggshell (ES) and calcine, and then exposing to gliding arc plasma (ESC-800/PL). The resulting materials were characterized by nitrogen physisorption, FTIR, XRD, TGA/DTG, and point of zero charge analyses. The preparation gives porous platelet agglomerates resulting from the kaolinite-metakaolinite transition, thereby increasing their internal specific surface area and capacity to retain pollutants. This granular distribution is kept stable by partial pozzolanic reactions avoiding deagglomeration. The specific surface area and total pore volume increased respectively from 14 m 2  g -1 and 0.049 cm 3  g -1 to 89 m 2  g -1 and 0.061 cm 3  g -1 leading to an enhanced removal efficiency of Fast Green and Orange G dyes from polluted water. The maximum adsorption capacity occurred at 298 K attaining values of 32.34 and 14.78 mg g -1 for OG and FG, respectively. The pH plays a crucial role in the maximum sorption of dyes, and the experimental data were successfully adjusted to pseudo-first-order kinetic and Liu isotherm model., (© 2022. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

One of the newest advances in 3D printing is the printing process of bio-scaffolds. The 3D printing of true materials for cartilage repairs accelerates cell growth and proliferation. In this study, a novel biomaterial was developed for the 3D printing of cartilage scaffolds composed of alginate, thymoquinone and halloysite nanotube. Calcium chloride was used as a cross-linker to form hydrogels. Experimental and numerical studies such as scanning electron microscopy, experimental tensile tests, and compression tests, chondrocyte cell seed, and MTT assay were also done. According to the results, alginate and halloysite nanotube increased the printing quality and mechanical performance of biomaterials. Tensile strength in bio-ink with the 30 mg/ml of alginate, 40 mg/ml of halloysite nanotube with 5% of thymoquinone increased up to 372 ± 42 kPa, while compressive stress reached 894 ± 39 kPa. Numerical results indicated that tensile and compressive properties of the scaffold structure depend on the space between printed rows. The best structure was obtained when the distance of rows was chosen at 0.4 mm, and the nozzle diameter was 0.3 mm. Finally, the biomaterial with the 30 mg/ml of alginate, 40 mg/ml of halloysite nanotube with 5% of thymoquinone showed a high mechanical and biological performance, compared to pure alginate bio-scaffolds. Biomaterials included alginic acid sodium salt/thymoquinone/halloysite nanotube mixed and 3D printed in high technology bioprinter, then mechanical and biological properties of printed bio-scaffolds obtained by different experimental tests., (© 2022. International Federation for Medical and Biological Engineering.)

Entrapment of halloysite nanotubes (HNTs) loaded with enzyme, into a polymer matrix (PVA/Alg), is a way to produce an environment surrounding the adsorbed enzyme molecules which improves the enzyme properties such as storage and operational stability. Hence, in this study, we optimised the factors affecting lipase adsorption onto halloysite nanotubes including halloysite amounts (5, 42.5 and 80 mg), lipase concentrations (30, 90 and 150 µg/ml), temperatures (5, 20 and 35 °C) and adsorption times (30, 165 and 300 min). The optimal conditions were determined as an halloysite amount of 50 to 80 mg, a lipase concentration of 30 to 57 μg/ml, an adsorption temperature of 20 °C and an adsorption time of 165 min, which resulted in a specific activity and adsorption efficiency of 15,000 (U/g protein) and 70%, respectively. Then, lipase adsorbed under optimal conditions was entrapped in a PVA/Alg hydrogel. The formation mechanism of immobilized lipase was investigated by FESEM and FTIR. Subsequent entrapment of adsorbed lipase improved the lipase storage and operational stability. K m , V max , K cat and K cat /K m values showed an increase in the entrapped HNT-lipase performance in comparison with the free and adsorbed lipase.

Short-chain halogenated aliphatic hydrocarbons (e.g. perchloroethene, trichloroethene) are among the most toxic environmental pollutants. Perchloroethene and trichloroethene can be dechlorinated to non-toxic ethene through reductive dechlorination by Dehalococcoides sp. Bioaugmentation, applying cultures containing organohalide-respiring microorganisms, is a possible technique to remediate sites contaminated with chlorinated ethenes. Application of site specific inocula is an efficient alternative solution. Our aim was to develop site specific dechlorinating microbial inocula by enriching microbial consortia from groundwater contaminated with trichloroethene using microcosm experiments containing clay mineral as solid phase. Our main goal was to develop fast and reliable method to produce large amount (100 L) of bioactive agent with anaerobic fermentation technology. Polyphasic approach has been applied to monitor the effectiveness of dechlorination during the transfer process from bench-scale (500 mL) to industrial-scale (100 L). Gas chromatography measurement and T-RFLP (Terminal Restriction Fragment Length Polymorphism) revealed that the serial subculture of the enrichments shortened the time-course of the complete dechlorination of trichloroethene to ethene and altered the composition of bacterial communities. Complete dechlorination was observed in enrichments with significant abundance of Dehalococcoides sp. cultivated at 8 °C. Consortia incubated in fermenters at 18 °C accelerated the conversion of TCE to ethene by 7-14 days. Members of the enrichments belong to the phyla Bacteroidetes, Chloroflexi, Proteobacteria and Firmicutes. According to the operational taxonomic units, main differences between the composition of the enrichment incubated at 8 °C and 18 °C occurred with relative abundance of acetogenic and fermentative species. In addition to the temperature, the site-specific origin of the microbial communities and the solid phase applied during the fermentation technique contributed to the development of a unique microbial composition.

The adhesive systems have the function to establish the connection between the restorative material and dental tissue, therefore it is of fundamental importance, because failures in the adhesive interface can reduce the life of a dental restoration. This study investigated the possibility of using the adhesive layer as a chlorhexidine modified release system evaluating their impact on the properties of these systems as well as evaluating the impact of these systems on immediate and post-aging dentin adhesion. Were used a matrix with BisGMA, UDMA, HEMA and TEGDMA copolymer and clay particles (Dellite 67G); associated with a chlorhexidine and a camphorquinone photoinitiator system. The properties of these systems were evaluated by the XRD, FTIR spectrophotometer, flexural strength, elasticity modulus, drug release, enzymatic inhibition and dentin adhesion resistance. The presence of the clay can raise the mechanical properties of the adhesive systems engendering a more resistant hybrid layer and led to a more sustained release of chlorhexidine in the systems, allowing a longer effective period of MMP-2 inhibition. The hypothesis that the addition of clays as release modulators could increase the effectiveness of these drugs in inhibiting the dentin's MPPs and consequently enhancing the adhesive durability was confirmed. These results indicate that the controlled release of chlorhexidine is able to reduce the process of loss of adhesion presenting itself as a promising system to increase the longevity of dental restorations.

The natural clay is an abundant, accessible, and low-cost material that has the potential for use in the water and wastewater industry. In this paper, Iranian natural clay and clay/Fe-Mn composite were used to remove toxic arsenic from the liquid environment. The natural clay and clay/Fe-Mn composite were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), energy-dispersive X-ray (EDX), X-ray diffractometry (XRD), thermo-gravimetric analysis (TGA), and atomic force microscopy (AFM) techniques. The effects of parameters (initial pH, temperature, sorption dose, and contact time) on the efficiency and behavior of the arsenic(V) adsorption process were studied. Freundlich (R 2 = 0.945 and 0.989), Langmuir (R 2 = 0.922 and 0.931), modified Langmuir (R 2 = 0.921 and 0.929), and Dubinin-Radushkevich (R 2 = 0.706 and 0.723) models were fitted to evaluate the equilibrium data of arsenic(V) adsorption process by natural clay and clay/Fe-Mn composite, respectively. The Langmuir adsorption capacity of arsenic(V) by the natural clay and clay/Fe-Mn composite was determined to be 86.86 mg/g and 120.70 mg/g, respectively. The arsenic(V) adsorption process followed the pseudo-second-order model. Negative values of ΔG° and ΔH° showed that the arsenic(V) sorption by the studied materials is thermodynamically spontaneous and exothermic. According to the findings, the natural clay and clay/Fe-Mn are suitable and recyclable sorbents for arsenic(V) adsorption from aqueous solutions. Also, the composite of clay with iron and manganese can improve the efficiency of clay in the removal of arsenic.

A synthetic, dispersible magnesium aminoclay (MgAC) was synthesized in the present study. Besides, structural and spectroscopic detections were conducted to investigate the MgAC nanoclay. With a poor aqueous solubility, methotrexate (MTX) has been applied as a valid antitumor agent in recent years. In our research, an unobtrusive sol-gel process was carried out to manufacture the MgAC-MTX nanohybrids through entrapment of MTX over MgAC in situ. The final product was capable of desquamating and thus dispersed in water, equably. In comparison with rough MTX, the MgAC-MTX nanocomposite with a preferable treatment efficacy against MCF-7 cells was mainly attributed to the preeminent enhanced aqueous solubility, controlled release and the increased cellular uptake capacity. Moreover, with excellent anticancer function and hypotoxicity as vindicated in vivo, the MgAC-MTX nanohybrid was supposed to own the potency in the application of malignant tumors cure as a valid nanomedicine. It turned out that, by virtue of its high bioavailability, the MgAC-MTX nanohybrids with high bioavailability is deserving of further study for the treatment of cancers.

The objective of this research was to evaluate the interaction of landfill leachate of urban solid waste in clayey (CL) and sandy soils (SL) in order to determine physical and chemical parameters that can be used as indicators of soil contamination when there are faults in the landfill waterproofing. In the diffusion tests, compacted soil samples were placed in contact with leachate (methanogenic phase). The temporal analysis (200 days) considered the parameters pH, electrical conductivity (EC), alkalinity, nitrogen series, chemical oxygen demand (COD), solids and color for the leachate and pH, ΔpH, EC, total nitrogen (TN), chemical elements, and cation exchange capacity (CEC) for the soils. Correlation analysis and principal component analysis (PCA) were performed to results. It was observed that the studied soils have potential to attenuate chemicals present in the leachate; this indicates the possibility of using them as base in landfills. Correlation analysis and PCA carried out to CL showed that in a process of CL monitoring the pH would be the key parameter to indicate contamination of this soil, due to the high correlation of this parameter with the others analyzed. For the SL, the parameters pH, alkalinity, apparent color, and COD (total and filtered) could be used as indicators of contamination. In both soils, monitoring of concentrations of Ca, Mg, K, SB, V, and CTC can be used to indicate possible faults in the waterproofing system of the landfill.

Incorporation of organic amendments is one of the most eco-friendly and economic strategies for the restoration of contaminated soils through diminishing mobility and bioavailability of heavy metals in these soils. This study was carried out under field conditions during the summer season of 2017 on a clay loam soil naturally polluted with Cd (7.61 mg kg -1 ) due to successive irrigations with wastewater. The main goal of this study was to evaluate the influence of sugarcane bagasse-derived biochar (SBDB) at different rates on fractionation of Cd in soil and its implications on the growth of soybean and concentrations of Cd within the different plant parts. Incorporation of SBDB into the chosen contaminated soil caused noticeable changes in soil pH, electrical conductivity and organic matter, especially with increasing the rate of application. Immobilization of Cd in the used soil was highly influenced by soil properties. According to the sequential extraction procedure, application of SBDB had an efficient role in reducing the soluble/exchangeable fraction. Moreover, it declined both the reducible and oxidizable forms of Cd. The dry weight of soybean organs (roots, seeds, and straw) improved significantly with SBDB additions. The highest dry weight values of straw and seeds for soybean plants were recorded when the soil was treated with SBDB at rates of 15 and 30 t ha -1 . Concentrations of Cd in straw and seeds of soybean were markedly affected by its availability in the soil. They decreased from 2.77, 0.96, and 0.62 mg kg -1 at the control treatment (CK) to 1.75, 0.47, and 0.20 mg kg -1 at B4 treatment (30 t SBDB) ha -1 in roots, straw, and seeds of soybean, respectively. In conclusion, the use of SBDB showed high efficiency in the amelioration of Cd-polluted soils and in decreasing Cd toxicity on soybean plants.

The present research highlights the use of a montmorillonite clay to remove p-nitrophenol (PNP) from aqueous solution. The montmorillonite clay was characterized using powder X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, X-ray fluorescence, Brunauer-Emmett-Teller analyses, and zero point charge in order to establish the adsorption behavior-properties relationship. The physiochemical parameters like pH, initial PNP concentration, and adsorbent dose as well as their binary interaction effects on the PNP adsorption yield were statistically optimized using response surface methodology. As a result, 99.5% removal of PNP was obtained under the optimal conditions of pH 2, adsorbent dose of 2 g/l, and PNP concentration of 20 mg/l. The interaction between adsorbent dose and initial concentration was the most influencing interaction on the PNP removal efficiency. The mass transfer of PNP at the solution/adsorbent interface was described using pseudo-first-order and intraparticle diffusion. Langmuir isotherm well fitted the experimental equilibrium data with a satisfactory maximum adsorption capacity of 122.09 mg/g. The PNP adsorption process was thermodynamically spontaneous and endothermic. The regeneration study showed that the montmorillonite clay exhibited an excellent recycling capability. Overall, the montmorillonite clay is very attractive as an efficient, low-cost, eco-friendly, and recyclable adsorbent for the remediation of hazardous phenolic compounds in industrial effluents.

This study analyzed the performance of organophilic clays obtained from the chemical modification of sodium bentonite clay when applied to the adsorption of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Kinetic curves and equilibrium isotherms were obtained in order to determine time and adsorption capacity of the material, as well as understand the mechanisms involved in this phenomenon. The results showed that the most predictive kinetic model for experimental data was of pseudo-second order (R 2  > 0.98), and that external mass transfer is the dominant factor in the time of operation. Isotherms were obtained at temperatures of 298, 308, and 318 K, under which the Dubinin-Radushkevich model was shown to have a good fit to data (R 2  > 0.96), according to mathematical adjustments. The maximum adsorption capacity obtained experimentally was 50.36 mg g -1 , found at a temperature of 298 K, being higher or compatible with other materials reported in the literature. With help of the thermodynamic studies on the process, it was observed that the adsorption of 2,4-D in organophilic clays refers to a spontaneous (ΔG° ads  < 0), exothermal (ΔH° ads  = - 9.99 kJ mol -1 ) process of physical nature. Lastly, it was observed that the adsorbent can be easily regenerated when subjected to eluents such as mixtures containing fractions of ethanol/water (desorption = 95%).

Sodium alginate (SA) is a linear biopolymer, which is the nontoxic, biodegradable, and rich in carboxyl and hydroxyl groups. In the paper, the SA-based hydrogel bead was prepared by the cationic hectorite clay and anionic sodium alginate with a simple ionic gelation method under freeze-drying, and the adsorption properties were evaluated by the removal of copper ions from aqueous solutions. The composites were characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption isotherm (BET), thermal analysis (TG), and Fourier transform infrared spectroscopy (FT-IR). The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data and the Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin models were applied to describe the adsorption isotherms. The results showed that the adsorption process was found to follow the Freundlich isotherm model and the maximum sorption capacity was observed to be 160.28 mg/g under the initial concentration from 10 to 700 mg/L at 45 °C. Adsorption kinetics data fitted well with pseudo-second-order rate model. The porous structure of the composite was responsible for the adsorption of Cu 2+ ions. But the adsorption ability could be improved by pH. Finally, the adsorption mechanism was suggested. Graphical abstract.

The purpose of this study was to determine the remediation effect of various substances (manure, clay, charcoal, zeolite and calcium oxide) on limiting the influence of high cobalt doses (0, 20, 40, 80, 160 and 320 mg/kg of soil) on the content of macroelements in grain, straw and roots of oat. The doses of cobalt applied in this experiment as well as soil amendments such as manure, clay, charcoal, zeolite and calcium oxide had a significant effect on the content of the analysed macronutrients in grain, straw and roots of oat. In the series without any neutralising substances, the soil contamination with cobalt caused an increase in the content of nitrogen, phosphorus, sodium, calcium and, partly, potassium, in grain, straw and roots of oat. Among the neutralising substances tested, the most unambiguous effect was produced by manure, which raised the content of all macronutrients (except calcium and magnesium) in oat grain, straw and roots. The influence of the other substances on the content of macronutrients in oat plants was less equivocal. However, all of them, especially calcium oxide, tended to induce a decrease in the content of most macronutrients in grain, straw and roots of oat.

A regional raw clay was used as the starting material to prepare iron-pillared clays with different iron contents. The catalytic activity of these materials was tested in the heterogeneous photo-Fenton process, applied to the degradation of 2-chlorophenol chosen as the model pollutant. Different catalyst loads between 0.2 and 1.0 g L -1 and pH values between 3.0 and 7.0 were studied. The local volumetric rate of photon absorption (LVRPA) in the reactor was evaluated solving the radiative transfer equation applying the discrete ordinate method and using the optical properties of the catalyst suspensions. The photonic and quantum efficiencies of the 2-chlorophenol degradation depend on both the catalyst load and the iron content of the catalyst. The higher values for these parameters, 0.080 mol Einstein -1 and 0.152 mol Einstein -1 , respectively, were obtained with 1.0 g L -1 of the catalyst with the higher iron content (17.6%). For the mineralization process, photonic and quantum efficiencies depend mainly on the catalyst load. Therefore, it was possible to employ a natural and cheap resource from the region to obtain pillared clay-based catalysts to degrade organic pollutants in water.

The study was conducted in dune restoration sites introduced with maritime pine (MP, Pinus pinaster Aiton) and stone pine (SP, Pinus pinea L.) at different development stages (diameters at breast height (DBH) in which small-diameter forests (SDF) = 0-8 cm, medium-diameter forests (MDF) = 8-20 cm, large-diameter forests (LDF) = 20-36 cm, and upper large-diameter forests (UDF) = > 36 cm). There were 15 replicated plots in each stage of both species and 25 dune sites; thus, a total of 145 sample plots were selected. Soil samples were taken from six different depth layers (0-5, 5-15, 15-30, 30-50, 50-70, and 70-100 cm). Forest floors were sampled with five replicates in each plot, and they were separated into leaf + fermentation and humus layers to determine unit mass and carbon concentration. Forest floor mass is significantly increased (17-34 t/ha in MP and 28-57 t/ha in SP) with the development stage. Low organic carbon (0.09-0.36% in MP and 0.13-0.84% in SP) was found in the top soil layer despite a significant accumulation of forest floor. The soil organic carbon density varies between 3 and 34 t C/ha. As the stand development stage increases, clay concentrations in every depth layer increased and soil pH and calcium carbonate values tend to decrease. Results indicated that both species have capability to grow on sandy material within poor nutrient and water capacities in a 50-year restoration process. However, the accumulation of forest floor increased and organic matter storage in the topsoil (0-5 cm) remained quite low due to the slow decomposition process.

A raw illite-smectite mixed-layered clay (RI/S) was ground for preparing nano-sized I/S clay (NI/S) and subsequently amino-functionalized via grafting of 3-aminopropyltrithoxysilane (APTES) (NH 2 -RI/S and NH 2 -NI/S, respectively). The samples were characterized by particle size analysis, specific surface area measurement, X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and 29 Si nuclear magnetic resonance ( 29 Si NMR). Compared to RI/S, NI/S has a narrow particle size distribution and appears in a platelet-like morphology due to the disintegration/exfoliation of RI/S after grinding. Based on the 29 Si NMR spectra, the appearances of tri-silicate units indicate the chemically grafting of APTES molecules on NH 2 -RI/S and NH 2 -NI/S, respectively. NH 2 -NI/S can adsorb greater amounts of Pb(II) cations and Cr(VI) anions rather than NH 2 -RI/S since NH 2 -NI/S grafts more amounts of amine groups (-NH 2 ). The isotherm data for adsorption of Pb(II) cations and Cr(VI) anions can be described by the Langmuir model at different temperatures (i.e., 10 °C, 30 °C, and 50 °C), respectively. The maximum adsorption amounts of Pb(II) cations and Cr(VI) anions onto NH 2 -NI/S calculated by the Langmuir isotherm model are 131.23 mg/g and 36.91 mg/g at 50 °C, respectively. The adsorptions of Pb(II) cations and Cr(VI) anions onto NH 2 -NI/S involve in the surface complexation of NI/S and amine groups.

A novel magnetic attapulgite-biochar composite (MABC) derived from natural attapulgite, cauliflower leaves, and FeCl 3 was successfully prepared as a low-cost adsorbent for oxytetracycline (OTC) removal from aqueous solution. Characterization experiments by different techniques suggested that attapulgite clay particles and Fe 3 O 4 nanoparticles were successfully covered on the MABC surface. Compared with the pristine biochar (CLB) and attapulgite-biochar composite (ABC), MABC had the largest surface area, well-developed pore structure, and more surface oxygen-containing functional groups which could interact with organic pollutant via hydrogen bonding, π-π electron coupling, complexation, and ion exchange. The maximum adsorption capacity of MABC by the Langmuir model was 33.31 mg/g, which was dramatically higher than that of CLB and ABC. The effects of solution initial pH had little difference on the adsorption of OTC because of the buffering effect. Adsorbent-regeneration studies of MABC exhibited good reusability and separation property. All the results indicated that MABC could be used as a potential adsorbent because of its easy preparation and separation, high efficiency, wide pH range application, and abundant and cheap raw materials in the global ecosystem. Graphical abstract.

Castilla-La Mancha (central Spain) is a region characterized by significant agricultural production aimed at high-quality food products such as wine and olive oil. The quality of agricultural products depends directly on the soil quality. Soil geochemistry, including dispersion maps and the recognition of baselines and anomalies of various origins, is the most important tool to assess soil quality. With this objective, 200 soil samples were taken from agricultural areas distributed among the different geological domains present in the region. Analysis of these samples included evaluation of edaphological parameters (reactivity, electrical conductivity, organic matter content) and the geochemistry of major and trace elements by X-ray fluorescence. The dataset obtained was statistically analyzed for major elements and, in the case of trace elements, was normalized with respect to Al and analyzed using the relative cumulative frequency (RCF) distribution method. Furthermore, the geographic distribution of analytical data was characterized and analyzed using the kriging technique, with a correspondence found between major and trace elements in the different geologic domains of the region as well as with the most important mining areas. The results show an influence of the clay fraction present in the soil, which acts as a repository for trace elements. On the basis of the results, of the possible elements related with clay that could be used for normalization, Al was selected as the most suitable, followed by Fe, Mn, and Ti. Reference values estimated using this methodology were lower than those estimated in previous studies.

In the vulnerable Arctic environment, the impact of especially hazardous wastes can have severe consequences and the reduction and safe handling of these waste types are therefore an important issue. In this study, two groups of heavy metal containing particulate waste materials, municipal solid waste incineration (MSWI) fly and bottom ashes and mine tailings (i.e., residues from the mineral resource industry) from Greenland were screened in order to determine their suitability as secondary resources in clay-based brick production. Small clay discs, containing 20 or 40% of the different particulate waste materials, were fired and material properties and heavy metal leaching tests were conducted before and after firing. Remediation techniques (washing in distilled water and electrodialytical treatment) applied to the fly ash reduced leaching before firing. The mine tailings and bottom ash brick discs obtained satisfactory densities (1669-2007 kg/m 3 ) and open porosities (27.9-39.9%). In contrast, the fly ash brick discs had low densities (1313-1578 kg/m 3 ) and high open porosities (42.1-51. %). However, leaching tests on crushed brick discs revealed that heavy metals generally became more available after firing for all the investigated materials and that further optimisation is therefore necessary prior to incorporation in bricks.

Soil specific surface area (SSA) is an important property of soil. Depending on the measurement techniques, determination of the SSA is costly and time consuming. Hence, a limited number of studies have been conducted to predict the SSA from the soil variables. In this study, the soil samples were taken from the literature. Fractal parameters (FP) were calculated by the model of Bird et al. (European Journal of Soil Science 51, 55-63, 2000) used as the input variables to predict the SSA. Some studies have been carried out on the prediction capability of the different parameters using the artificial neural networks (ANNs). The ANNs were further used and 20 models were developed to investigate the value of input variables to predict the SSA. The results showed that the PTF13 (RMSE = 0.13) and PTF18 (RMSE = 0.13) with the input variables of particle-size distribution and Atterberg limits revealed better performance than the other PTFs (in the training step). It is because of the fact that free swelling index (FSI) and Atterberg limits were closely correlated to the soil clay mineralogy as one of the important factors controlling the SSA. In general, this results demonstrated that the PTF9 with the variables of sand, clay, plastic limit (PL), liquid limit (LL), and FSI showed the best (RMSE = 0.37) results in the estimation of the SSA. In conclusion, there was not a strong correlation between the soil mechanical properties and SSA but also ANNs were a suitable method to predict the SSA from the soil variables.

Some volcanic soils like andosols contain short-range order nanoclays (allophane) which build aggregates with a tortuous and fractal microstructure. The aim of the work was to study the influence of the microstructure and mesoporosity of the allophane aggregates on the pesticide chlordecone retention in soils. Our study shows that the allophane microstructure favors pollutants accumulation and sequestration in soils. We put forth the importance of the mesoporous microstructure of the allophane aggregates for pollutant trapping in andosols. We show that the soil contamination increases with the allophane content but also with the mesopore volume, the tortuosity, and the size of the fractal aggregate. Moreover, the pore structure of the allophane aggregates at nanoscale favors the pesticide retention. The fractal and tortuous aggregates of nanoparticles play the role of nanolabyrinths. It is suggested that chlordecone storage in allophanic soils could be the result of the low transport properties (permeability and diffusion) in the allophane aggregates. The poor accessibility to the pesticide trapped in the mesopore of allophane aggregates could explain the lower pollutant release in the environment.

The widespread use of cadmium (Cd)-containing organic fertilizers is a source of heavy metal inputs to agricultural soils in suburban areas. Therefore, the research and development of new materials and technologies for the remediation of Cd-contaminated soil is of great significance and has the potential to guarantee the safety of agricultural products and the protection of human health. We performed pot experiments to determine the potential of combined amendments of illite/smectite (I/S) clay with bone chars for the remediation of Cd-contaminated agricultural soils in a suburban area of Beijing, China. The results showed that both diethylene triamine pentaacetic acid (DTPA)-extractable Cd in soil and the Cd in Brassica chinensis were significantly decreased by the application of 1, 2, or 5% combined amendments with various I/S and bone char (BC) ratios. The higher proportions of BC used in the combined amendments resulted in a better immobilization of soil Cd. The application of the 5% amendment that combined I/S with either pig or cattle BC resulted in the best immobilization. All of the combined amendments, regardless of the composition and ratio of the components, had no negative effects on the growth of B. chinensis. Therefore, it was concluded that combined amendments of I/S and BC have a good potential for remediating Cd-contaminated soils.

The adsorption of o-xylene onto raw clay material in a fixed bed using a thermal conductivity detector gas chromatography was investigated. Experimental and theoretical studies were established to evaluate the removal efficiency of o-xylene by adsorption on clay materials and to predict kinetic parameters. Column data were describing at different conditions using Bohart-Adams, Wolborska, Thomas, Yoon and Nelson, dose-response, and bed depth service time models. All used models were satisfactory to predict the breakthrough curves. A suitable advection-dispersion-sorption (ADS) model has been also developed to simulate the measured data, based on the nature of the various equilibrium relationships of solid-gas and diverse descriptions of the mass transfer processes within of the adsorbent particle. The experiments can be fitted with high correlated coefficient R 2  = 0.996.