A review of functions and mechanisms of clay soil conditioners and catalysts in thermal remediation compared to emerging photo-thermal catalysis.

High temperatures and providing sufficient time for the thermal desorption of persistent organic pollutants (POPs) from contaminated clay soils can lead to intensive energy consumption. Therefore, this article provides a critical review of the potential additives which can improve soil texture and increase the volatility of POPs, and then discusses their enhanced mechanisms for contributing to a green economy. Ca-based additives have been used to reduce plasticity of bentonite clay, absorb water and replenish system heat. In contrast, non-Ca-based additives have been used to decrease the plasticity of kaolin clay. The soil structure and soil plasticity can be changed through cation exchange and flocculation processes. The transition metal oxides and alkali metal oxides can be applied to catalyze and oxidize polycyclic aromatic hydrocarbons, petroleum and emerging contaminants. In this system, reactive oxygen species (•O2- and •OH) are generated from thermal excitation without strong chemical oxidants. Moreover, multiple active ingredients in recycled solid wastes can be controlled to reduce soil plasticity and enhance thermal catalysis. Alternatively, the alkali, nano zero-valent iron and nano-TiN can catalyze hydrodechlorination of POPs under reductive conditions. Especially, photo and photo-thermal catalysis are discussed to accelerate replacement of fossil fuels by renewable energy in thermal remediation.

Modification of polymethylmethacrylate bone cement with halloysite clay nanotubes.

BACKGROUND: Polymethylmethacrylate (PMMA) bone cement is used in orthopedics and dentistry to get primary fixation to bone but doesn't provide a mechanically and biologically stable bone interface. Therefore, there was a great demand to improve the properties of the PMMA bone cement to reduce its clinical usage limitations and enhance its success rate. Recent studies demonstrated that the addition of halloysite nanotubes (HNTs) to a polymeric-based material can improve its mechanical and thermal characteristics. OBJECTIVES: The purpose of the study is to assess the compressive strength, flexural strength, maximum temperature, and setting time of traditional PMMA bone cements that have been manually blended with 7 wt% HNT fillers. METHODS: PMMA powder and monomer liquid were combined to create the control group, the reinforced group was made by mixing the PMMA powder with 7 wt% HNT fillers before liquid mixing. Chemical characterization of the HNT fillers was employed by X-ray fluorescence (XRF). The morphological examination of the cements was done using a scanning electron microscope (SEM). Analytical measurements were made for the compressive strength, flexural strength, maximum temperature, and setting time. Utilizing independent sample t-tests, the data was statistically assessed to compare mean values (p < 0.05). RESULTS: The findings demonstrated that the novel reinforced PMMA-based bone cement with 7 wt% HNT fillers showed higher mean compressive strength values (93 MPa) and higher flexural strength (72 MPa). and lower maximum temperature values (34.8 °C) than the conventional PMMA bone cement control group, which was (76 MPa), (51 MPa), and (40 °C), respectively (P < 0.05). While there was no significant difference in the setting time between the control and the modified groups. CONCLUSION: The novel PMMA-based bone cement with the addition of 7 wt% HNTs can effectively be used in orthopedic and dental applications, as they have the potential to enhance the compressive and flexural strength and reduce the maximum temperatures.

Resourceful exploitation of sedimentary clay: Designing a dual-chambered borosilicate glass reactor system for the efficient treatment of malachite green and phenol through SCRT adsorption and 5%Fe@SRCT catalysis via CWPO, with evaluation of seed germination and fish survival.

This study presents an innovative double-walled borosilicate glass reactor system for the efficient treatment of liquid and gaseous wastewater. This reactor system allows precise temperature control, continuous pH monitoring, and controlled dosing of reagents to optimize reaction conditions. Detailed characterization was carried out by X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR), BET (specific surface area) analysis, point of zero charge (PZC), and scanning electron microscopy (SEM) for the SCR, SCRT, and 5%Fe@SCRT materials. For Malachite Green adsorption, SRCT demonstrated a maximum adsorption capacity of 39.78 ± 0.5 mg/g using the Langmuir isotherm model and followed pseudo-second-order kinetics. Optimum conditions for adsorption were found to be: an initial concentration of 50 ppm, an adsorbent dosage of 1 g/l, a pH of 8.5, and a temperature of 50°C. For the catalytic oxidation of phenol, 5%Fe@SRCT achieved a remarkable removal rate of 99.9 ± 0.1% under optimum conditions (50 ppm phenol, 1 g/l catalyst dosage, pH 3.5, H2O2 concentration 8.7 mM, and temperature 70°C). Intermediates identified during the reaction included hydroquinone, benzoquinone, catechol, and resorcinol, with degradation occurring over a 60-minute reaction period. The 5%Fe@SCRT material showed excellent reusability in the removal of phenol by catalytic oxidation, with no significant loss of efficiency over three cycles, while the SRCT underwent three cycles of regeneration for the adsorption of Malachite Green. Scavenger tests confirmed the involvement of hydroxyl radicals in the catalytic oxidation process. In addition, fish survival tests after catalytic oxidation of phenol by 5%Fe@SRCT showed no impact on fish, underlining the environmental safety of this process. In addition, germination tests after decolorization of MG by SRCT demonstrated a good effect with no negative impact, reinforcing the ecological value of this innovative technology. These results highlight the innovative use of SCRT and 5%Fe@SCRT as versatile materials for environmental remediation, exploiting their effective adsorption capacities and efficient catalytic oxidation performance within the proposed double-walled borosilicate glass reactor system. PRACTITIONER POINTS: The study demonstrates the effectiveness of an innovative reactor system employing SRCT adsorbent and Fe@SRCT catalyst for efficient removal of malachite green and phenol from wastewater. Environmental impact assessment, including seed germination and fish survival evaluation, validates the method's eco-friendly potential. Implementation of this approach could significantly contribute to sustainable water treatment practices.

Research on the expansion, shrinkage properties and fracture evolution of red clay stabilised with phosphogypsum under dry-wet cycles.

In view of the special engineering properties of red clay and the waste of phosphogypsum resources, the expansion and contraction deformation and fissure evolution of phosphogypsum stabilized red clay under different conditions were investigated by laboratory tests and image processing system. The research results show that: (1) the absolute expansion and absolute shrinkage of phosphogypsum stabilized red clay are positively correlated with the compaction degree, the number of dry and wet cycles and the cement dosage, and negatively correlated with the initial water content and the phosphogypsum dosage; (2) the fissure rate increases with the increase of the number of dry and wet cycles, and decreases with the increase of the initial water content, the compaction degree, the cement, and the phosphogypsum dosage; (3) The relationship among absolute expansion rate (absolute shrinkage), degree of compaction and fracture rate can be fitted by the equation f(x,y) = ax+by+cx2+dy2+e; (4) Phosphogypsum has an obvious inhibiting effect on the expansion, shrinkage and cracking of the mix. It is recommended that the cement mixing amount of 6% and phosphogypsum: red clay = 1:1~1:2 as roadbed filler.

Study on the dry shrinkage characteristics and size effect of swell-shrink characteristic soil.

Swell-shrink characteristic soils exhibit a high susceptibility to cracking during the drying process, which poses a significant risk of various geological disasters. Among these, the occurrence of drying shrinkage acts as a prerequisite for the cracking phenomenon. Therefore, it is of utmost importance to comprehend the specific characteristics associated with the drying shrinkage mechanism. To investigate the drying shrinkage behavior of swell-shrink characteristic soils, a series of drying shrinkage experiments were conducted on long strip samples of red clay and expansive soil. Utilizing three-dimensional digital image correlation (DIC) technology, the surface displacement, strain, and anisotropic shrinkage rates of the soil samples during the drying process were obtained, and the size effect on the drying shrinkage of swell-shrink characteristic soil were analyzed. The research findings are as follows: The displacement development of the soil samples in the X and Y directions can be divided into two stages: a linear growth stage and a stable displacement stage. In the Z direction, the soil surface deformation can be divided into three stages: soil surface arching, vertical shrinkage, and shrinkage stabilization. The drying shrinkage of swell-shrink characteristic soil exhibits anisotropy, with the vertical shrinkage rate being the largest, followed by the longitudinal and then the transverse directions. Additionally, the soil sample shrinkage exhibits a size effect, whereby the shrinkage rates in all directions increase with increasing sample width and thickness. During the drying shrinkage process, the stress state on the soil surface evolves from initial tensile strain to subsequent compressive strain. The strain at different positions and times within the soil sample is not uniform, resulting in the non-uniformity and anisotropy of the sample shrinkage. This study provides important insights into the cracking mechanism of swell-shrink characteristic soils and serves as a valuable reference for related laboratory experiments, which will contribute to better prediction and control the geological hazards caused by the drying shrinkage of swell-shrink characteristic soils.

Improving landfill liner performance with bentonite-slag blend permeated with ammonia for a Municipal solid waste landfill.

Leachate emanating from landfills contains ammonia which may cause serious health effects on living things. An effectively designed clay barrier should not allow the contaminant to infiltrate the soil and groundwater systems. The utilization of certain industrial by-products in engineered landfill barriers, not only reduces the need for conventional liner materials but also helps in sustainable waste management. This study investigated the hydraulic conductivity, unconfined compressive strength, compaction, and adsorption characteristics of lithomargic clay blended with an optimum percentage of bentonite (10%) and granulated blast furnace slag (15%) permeated with ammonia. The results revealed that increasing the content of granulated blast furnace slag decreased the maximum dry density while increasing the optimum moisture content. In comparison to lithomargic clay, the hydraulic conductivity of the amended soil liner permeated with ammonia decreased from a value of 3 × 10-8 m/s to 5 × 10-10 m/s. The unconfined compressive strength of the amended soil specimens showed an increasing trend with curing times (i.e., 0, 14, 28, and 56 days). The batch adsorption results revealed that Freundlich and Langmuir's isotherm fits the equilibrium adsorption data and the adsorption of ammonia on clay liner follows non-linear behaviour. Overall, the experimental results implied that lithomargic clay blended with 10% bentonite and 15% granulated blast furnace slag can be used as an impermeable soil reactive barrier in engineered landfills.

Microbial life in preferential flow paths in subsurface clayey till revealed by metataxonomy and metagenomics.

BACKGROUND: Subsurface microorganisms contribute to important ecosystem services, yet little is known about how the composition of these communities is affected by small scale heterogeneity such as in preferential flow paths including biopores and fractures. This study aimed to provide a more complete characterization of microbial communities from preferential flow paths and matrix sediments of a clayey till to a depth of 400 cm by using 16S rRNA gene and fungal ITS2 amplicon sequencing of environmental DNA. Moreover, shotgun metagenomics was applied to samples from fractures located 150 cm below ground surface (bgs) to investigate the bacterial genomic adaptations resulting from fluctuating exposure to nutrients, oxygen and water. RESULTS: The microbial communities changed significantly with depth. In addition, the bacterial/archaeal communities in preferential flow paths were significantly different from those in the adjacent matrix sediments, which was not the case for fungal communities. Preferential flow paths contained higher abundances of 16S rRNA and ITS gene copies than the corresponding matrix sediments and more aerobic bacterial taxa than adjacent matrix sediments at 75 and 150 cm bgs. These findings were linked to higher organic carbon and the connectivity of the flow paths to the topsoil as demonstrated by previous dye tracer experiments. Moreover, bacteria, which were differentially more abundant in the fractures than in the matrix sediment at 150 cm bgs, had higher abundances of carbohydrate active enzymes, and a greater potential for mixotrophic growth. CONCLUSIONS: Our results demonstrate that the preferential flow paths in the subsurface are unique niches that are closely connected to water flow and the fluctuating ground water table. Although no difference in fungal communities were observed between these two niches, hydraulically active flow paths contained a significantly higher abundance in fungal, archaeal and bacterial taxa. Metagenomic analysis suggests that bacteria in tectonic fractures have the genetic potential to respond to fluctuating oxygen levels and can degrade organic carbon, which should result in their increased participation in subsurface carbon cycling. This increased microbial abundance and activity needs to be considered in future research and modelling efforts of the soil subsurface.

Analytical and Antimicrobial Characterization of Zn-Modified Clays Embedding Thymol or Carvacrol.

Carvacrol and thymol are broad-spectrum natural antimicrobial agents. To reduce their volatility and improve their antimicrobial performance, synergistic systems were prepared loading the active molecules in zinc-modified clays. Montmorillonite (MMT) and zeolite (ZEO) were modified with zinc ions (ZnMMT and ZnZEO), with well-known antimicrobial properties, and then with carvacrol or thymol, reaching the 26 ± 3% and 33 ± 2% w/w of loading, respectively. The resulting hybrid materials were characterized by FT-IR, XPS, XRD, TGA, and GC-MS to evaluate carvacrol/thymol release in simulating food matrices. Antimicrobial assays carried out using spoiler and pathogenic bacterial strains showed that the antimicrobial activity of both thymol and carvacrol was largely preserved once they were loaded into Zn-modified clays. However, MMT hybrids showed an antibacterial activity significantly higher than ZEO hybrids at 50 mg/mL of thymol and carvacrol. For this reason, deeper antimicrobial evaluations were carried out only for ZnMMT composites. ZnMMT loaded with thymol or carvacrol produced inhibition zones against most of the target strains, also at 3.12 mg/mL, while the positive controls represented by the single molecule thymol or carvacrol were not active. The hybrid materials can be useful for applications in which the antimicrobial activity of natural molecules need to be displayed over time as requested for the control of microbial pathogens and spoilage bacteria in different applications, such as active packaging, biomaterials, and medical devices.

Development of alginate film filled with halloysite-carbon dots for active food packaging.

The development of functional bionanocomposites for active food packaging is of current interest to replace non-biodegradable plastic coatings. In the present work, we report the synthesis of an alginate-based nanocomposite filled with modified halloysite nanotubes (HNTs) to develop coatings with improved barrier properties for food packaging. Firstly, HNTs were chemically modified by the introduction of carbon dots units (CDs) onto their external surface (HNTs-CDs) obtaining a nanomaterial where CDs are uniformly present onto the tubes as verified by morphological investigations, with good UV absorption and antioxidant properties. Afterwards, these were dispersed in the alginate matrix to obtain the alginate/HNTs-CDs nanocomposite (Alg/HNTs-CDs) whose morphology was imaged by AFM measurements. The UV and water barrier properties (in terms of moisture content and water vapor permeability) were investigated, and the antioxidant properties were evaluated as well. To confer some antimicrobial properties to the final nanocomposite, the synthetized filler was loaded with a natural extract (E) from M. cisplatensis. Finally, the extract kinetic release both from the filler and from the nanocomposite was studied in a medium mimicking a food simulant and preliminary studies on the effect of Alg/HNTs-CDs/E on coated and uncoated fruits, specifically apples and bananas were also carried out.

Bed bug control with various dusts: Efficacy comparison between silicon dioxide, diatomaceous earth, and Sommières earth.

Bed bugs are considered a major public health problem in industrialized countries. Usually, bed bug infestations are managed using a combination of physical and chemical methods. In recent years, new strategies for bed bug control have emerged, particularly the use of dusts like diatomaceous earth and silicon dioxide. However, in Europe, the use of silicon dioxide is restricted to professional, while diatomaceous earth can be harmful to the lungs. This study aimed to assess bed bug mortality rates associated with Sommières earth, green clay, talc, and sodium bicarbonate compared to silicon dioxide and diatomaceous earth from a pest management company, diatomaceous earth for litter conditioner, and diatomaceous earth from a supermarket. We tested permanent exposure, short exposure, horizontal transfer and repellent effect on two bed bug colonies. Sommières earth demonstrated efficacy ranging from 75% to 100% in permanent and short exposures, similar to the efficacy of diatomaceous earth from the pest management company. On the contrary, diatomaceous earth for litter conditioner and diatomaceous earth from a supermarket, green clay, talc, and sodium bicarbonate were found to be ineffective. This study demonstrates, for the first time, the efficacy of Sommières earth against bed bugs, but also highlights the variability in efficacy of diatomaceous earths on bed bugs depending on their quality.

Title: Lutte contre les punaises de lit avec des poudres : comparaison de l'efficacité du dioxyde de silicium, de la terre de diatomée et de la terre de Sommières. Abstract: Les punaises de lit sont considérées comme un problème de santé publique majeur dans les pays industrialisés. Habituellement, les infestations de punaises de lit sont gérées en utilisant une combinaison de méthodes physiques et chimiques. Ces dernières années, de nouvelles stratégies de lutte contre les punaises de lit ont vu le jour, notamment l'utilisation de poudres comme la terre de diatomées et le dioxyde de silicium. Cependant, en Europe, l'usage du dioxyde de silicium est réservé aux professionnels tandis que la terre de diatomées peut être nocive pour les poumons. Cette étude visait à évaluer les taux de mortalité des punaises de lit associés à la terre de Sommières, à l'argile verte, au talc et au bicarbonate de sodium par rapport au dioxyde de silicium, à la terre de diatomées d'une entreprise de lutte antiparasitaire, à la terre de diatomées pour conditionneur de litière et à la terre de diatomées d'un supermarché. Nous avons testé l'exposition permanente, l'exposition courte, le transfert horizontal et l'effet répulsif sur deux colonies de punaises de lit. La terre de Sommières a démontré une efficacité allant de 75% à 100% en exposition permanente et courte, similaire à l'efficacité de la terre de diatomées d'une entreprise de lutte antiparasitaire. Au contraire, la terre de diatomées pour conditionneur de litière et la terre de diatomées d'un supermarché, l'argile verte, le talc et le bicarbonate de sodium se sont révélés inefficaces. Cette étude démontre, pour la première fois, l'efficacité de la terre de Sommières contre les punaises de lit mais met également en évidence la variabilité de l'efficacité des terres de diatomées sur les punaises de lit en fonction de leur qualité.

Anti-tumor therapy through high ROS performance induced by Ag nanoenzyme from boron cluster with halloysite clay nanotubes.

The conventional silver nanoparticles (Ag NPs) are characterized with high loading rate and stacking phenomenon, leading to shedding caused biotoxicity and low catalytic efficiency. This seriously hinders their application in biomedicine. Here, we modified the highly dispersible Ag NPs and Ag single-atoms (SAs) synthesis by combining the halloysite clay nanotubes (HNTs) and dodecahydro-dodecaborate (closo-[B12H12]2-) to increase the biocompatible properties and decrease the loading rate. This novel Ag single-atom nanoenzyme alongside Ag NPs nanoenzyme avoid the elevated-temperature calcination while maintaining the exceptionally high-level efficiency of Ag utilization via the reducibility and coordination stabilization of closo-[B12H12]2- and HNTs. With theoretical calculation and electron paramagnetic resonance, we confirmed that both Ag SAzymes and Ag NPs in HNT@B12H12@Ag nanoenzyme are capable decompose the H2O2 into hydroxyl radical (·OH). For the application, we investigated the catalytic activity in the tumor cells and antitumor effects of HNT@B12H12@Ag nanoenzyme both in vitro and in vivo, and confirmed that it effectively suppressed melanoma growth through ·OH generation, with limited biotoxicity. This study provides a novel Ag nanoenzyme synthesis approach to increase the possibility of its clinical application.

A synthetic and transparent clay removes Microcystis aeruginosa efficiently.

Clay-algae flocculation is a promising method to remove harmful algal blooms (HABs) in aquatic ecosystems. Many HAB-generating species, such as Microcystis aeruginosa (M. aeruginosa), a common species in lakes, produce toxins and harm the environment, human health, and the economy. Natural clays, such as bentonite and kaolinite, and modification of these clays have been applied to mitigate HABs by forming large aggregates and settling down. In this study, we aim to examine the impact of laponite, a commercially available smectite clay that is synthetic, transparent, compatible with human tissues, and degradable, on removing HABs. We compare the cell removal efficiencies (RE) of laponite, two natural clays, and their polyaluminum chloride (PAC)-modified versions through clay-algae flocculation experiments. Our results show that the optimum concentrations of laponite, bentonite, kaolinite, PAC-modified bentonite, and PAC-modified kaolinite to remove 80 % of the M. aeruginosa cells from the water column are 0.05 g/L, 2 g/L, 4 g/L, 2 g/L and 0.3 g/L respectively. Therefore, to achieve the same cell removal efficiency, the amount of laponite needed is 40 to 80 times less than bentonite and kaolinite, and 6 times less than PAC-modified kaolinite. We demonstrate that the superior performance of laponite clay is because of its smaller particle size, which increases the encounter rate between cells and clay particles. Furthermore, experiments using water samples from Powderhorn Lake confirmed laponite's effectiveness in mitigating HABs. Our price analysis also suggests that this commercially-available clay, laponite, can be used in the field at a relatively low cost.

Effects of ionic strength and bentonite ratio on the migration of Cr(VI) in clayey soil-bentonite engineered barrier.

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 (De) 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.

Variable and Large Losses of Diagnostic Biomarkers After Simulated Cosmic Radiation Exposure in Clay- and Carbonate-Rich Mars Analog Samples.

Mars has been exposed to ionizing radiation for several billion years, and as part of the search for life on the Red Planet, it is crucial to understand the impact of radiation on biosignature preservation. Several NASA and ESA missions are looking for evidence of ancient life in samples collected at depths shallow enough that they have been impacted by galactic cosmic rays (GCRs). In this study, we exposed a diverse set of Mars analog samples to 0.9 Megagray (MGy) of gamma radiation to mimic 15 million years of exposure on the Martian surface. We measured no significant impact of GCRs on the total organic carbon (TOC) and bulk stable C isotopes in samples with initial TOC concentration > 0.1 wt. %; however, diagnostic molecular biosignatures presented a wide range of degradation that didn't correlate to factors like mineralogy, TOC, water content, and surface area. Exposure dating suggests that the surface of Gale crater has been irradiated at more than five times our dose, yet using this relatively low dose and "best-case scenario" geologically recalcitrant biomarkers, large and variable losses were nevertheless evident. Our results empasize the importance of selecting sampling sites at depth or recently exposed at the Martian surface.

Products from Photolysis Reactions of Tetracycline Mediated by Clay and Humic Substance Induce Contrasting Expressions of Target Resistance Genes.

Phototransformation is a key process affecting the fate of many antibiotics in the environment, but little is known about whether their photoproducts exert selective pressure on bacteria by inducing antibiotic resistance genes (ARGs). Here, we examined the expression of tetracycline resistance gene tet(M) of a fluorescent Escherichia coli whole-cell bioreporter influenced by the phototransformation of tetracycline. The presence of suspended smectite clay (montmorillonite or hectorite, 1.75 g/L) or dissolved humic substance (Pahokee Peat humic acid or Pahokee peat fulvic acid, 10 mg C/L) in aqueous solutions markedly facilitated the transformation of tetracycline (initially at 400 µg/L) with half-life shortened by 1.4-2.6 times. Despite the similar phototransformation ratios (80-90%) of the total loaded tetracycline after 60 min irradiation, the decreased ratios of cell fluorescence intensity (which was proportional to the expression amount of ARG tet(M)) were much higher with the two clays (94 and 93%) than with the two humic substances (44 and 69%) when compared to the respective dark controls. As illustrated by mass spectroscopic and chemical analyses, tetracycline was proposed to be mainly transformed to amide (ineffective in inducing ARGs) with the presence of clays by reaction with self-photosensitized singlet oxygen (1O2), while the humic substances might catalyze the production of another two demethylated and/or deaminated compounds (still effective in inducing ARGs) in addition to the amide compound via reaction with triplet excited state dissolved organic matter (3DOM*). As clay minerals and humic substances are important soil constituents and ubiquitously present in surface environments, the observed clay and humic-dependent photooxidation pathways of tetracycline and the differing selective pressures of the associated products highlight the need for monitoring the transformation compounds of antibiotics and provide critical insight into the development of antibiotic treatment protocols.

Possibility of brewery wastes application to soil as an organic improver of biological and chemical properties.

Soil degradation, marked by declining organic matter, threatens global food security. The impact of brewer's spent yeast (BSY) on clay and sand was analysed at varying application rates to assess its effectiveness in improving soil quality. A randomized complete block design with three replicates was employed. One kilogram of soil were mixed with BSY at application rates of 2 t/ha and 5 t/ha. The samples were incubated at 26 °C for 5 months with daily watering. We analysed pH, total nitrogen, organic carbon, total phosphorus, and electrical conductivity (EC); microbial activity (total heterotrophic bacteria, actinobacteria, and fungi) and soil enzyme activity (dehydrogenase, catalase, protease). BSY application improved soil quality, particularly in clay. Clay showed increased in pH, EC, N and C. BSY significantly boosted microbial populations (bacteria, fungi) in clay with a lesser effect in sand. Enzyme activity and a fertility index also improved in BSY-treated clay, while sand displayed increased activity of a different enzyme. Results suggest BSY holds promise as an organic fertilizer, especially for clay soils. Further research is needed to optimize application, understand long-term effects, and evaluate economic feasibility and social acceptance. This study contributes to the search for sustainable, local solutions to improve soil health and agricultural practices.

Use of rice straw nano-biochar to slow down water infiltration and reduce nitrogen leaching in a clayey soil.

Biochar exhibits numerous advantages in enhancing the soil environment despite a few limitations due to its lower surface energy. Nanomodified biochar combines the advantages of biochar and nanoscale materials. However, its effects on water infiltration and N leaching in a clayey soil remain unclear. Therefore, this study prepared rice straw nano-biochar by a ball milling method, and investigated its physicochemical properties and effects of bulk biochar and nano-biochar at various addition rates (0 %, 0.5 %, 1 %, 2 %, 3 %, and 5 %) on wetting peak migration, cumulative infiltration, water absorption and retention, and N leaching. The results showed that, compared with bulk biochar, nano-biochar presented a more abundant pore structure with an increase in specific surface area of approximately 1.5 times, accompanied by a 20 % increase in acid functional groups. Compared with those for clayey soil without biochar addition, the wetting front migration time was increased by 10.2 %-123.9 % and 17.0 %-257.9 %, and the cumulative infiltration volume at 60 min was decreased by 26.0 %-48.4 % and 14.1 %-62.4 % for bulk biochar and nano-biochar, respectively. The parameter S of Philip model and the parameter a of Kostiakov model for nano-biochar were lower than those for bulk biochar, whereas the parameter b of Kostiakov model was greater, indicating that nano-biochar decreased initial soil infiltration rate and increased attenuation degree of the infiltration rate. Nano-biochar increased water absorption by 8.03 % and subsequently enhanced water retention capacity relative to bulk biochar. In addition, bulk biochar and nano-biochar reduced NH4+-N leaching by 3.0 %-13.1 % and 5.7 %-39.2 %, respectively, and NO3--N leaching by 2.7 %-3.6 % and 9.0 %-43.3 %, respectively, by decreasing N concentration and leachate volume relative to those with no biochar addition. This study provides new knowledge for nano-biochar application in a clayey soil.

Mechanisms of enhancing MgO for stabilization/solidification of Pb-contaminated red clay through CO2 sequestration.

Pb-contaminated soil poses significant environmental and health risks as well as soil stability issues. Research on sandy soils highlights CO2-enhanced reactive MgO as a promising solution for improving the solidification of Pb-contaminated soils. However, carbonation effects can differ markedly between soil types owing to varying soil properties. In this study, we evaluated the effects of CO2-enhanced reactive MgO on the engineering and environmental characteristics of Pb-contaminated red clay and explored its mechanism of carbonation solidification. The results showed that CO2-enhanced reactive MgO increased the strength of Pb-contaminated red clay to over 3 MPa within 1 h, which was approximately 25 times the strength of untreated soil (0.2 MPa) and significantly higher than that of reactive MgO-treated, uncarbonated soil (0.8 MPa). The pH of the carbonated soil (9-10) facilitated Pb2+ immobilization, and the increase over the initial parameter elevated the electrical conductivity value. Moreover, CO2-enhanced reactive MgO reduced the Pb2+ leaching concentration to below 0.1 mg/L, even at high Pb concentrations (10,000 mg/kg). Pb2+ transformed into lead carbonates during the carbonation process, with the hydrated magnesium carbonates forming a dense internal structure. This solidification mechanism included chemical precipitation, physical adsorption, and encapsulation. Notably, the carbonation time should be controlled within 1 h to prevent soil expansion. Together, these findings support the potential of CO2-enhanced reactive MgO for efficient and low-carbon application in the solidification of Pb-contaminated red clay.

In Situ Evolution of Ionic Sites at Clay Mineral Interfaces Facilitates Fluoride and Phosphorus Mineralization.

Soil minerals influence the biogeochemical cycles of fluoride (F) and phosphorus (P), impacting soil quality and bioavailability to plants. However, the cooperative mechanisms of soil minerals in governing F and P in the soil environment remain a grand challenge. Here, we reveal the essential role of a typical soil mineral, montmorillonite (Mt), in the cycling and fate of F and P. The results show that the enrichment of metal sites on the Mt surface promotes the mineralization of F to the fluorapatite (FAP) phase, thereby remaining stable in the environment, simultaneously promoting P release. This differential behavior leads to a reduction in the level of F pollution and an enhancement of P availability. Moreover, solid-state NMR and HRTEM observations confirm the existence of metastable F-Ca-F intermediates, emphasizing the pivotal role of Mt surface sites in regulating crystallization pathways and crystal growth of FAP. Furthermore, the in situ atomic force microscopy and theoretical calculations reveal molecular fractionation mechanisms and adsorption processes. It is observed that a competitive relationship exists between F and P at the Mt interface, highlighting the thermodynamically advantageous pathway of forming metastable intermediates, thereby governing the activity of F and P in the soil environment at a molecular level. This work paves the way to reveal the important role of clay minerals as a mineralization matrix for soil quality management and offers new strategies for modulating F and P dynamics in soil ecosystems.

Bromelain Immobilized onto Clay-Carboxymethylcellulose Composites for Improving Nutritive Value of Soybean Meal.

Improvement of nutritional value and reduction of antinutritional factors (ANFs) of soybean meal (SBM) for animal feed applications could be achieved by using bromelain immobilized onto bentonite (Bt)-carboxymethylcellulose (CMC) composites. The composite with mass ratio between CMC to calcium ion (Ca2+) at 1:20 provided the highest enzyme activity, immobilization yield higher than 95%, with superior thermal and storage stabilities. Performance of the immobilized bromelain for soybean protein hydrolysis was further studied. The results showed that at 60 °C, the immobilized bromelain exhibited the highest efficiency in enzymatic hydrolysis to release free alpha amino nitrogen (FAN) as a product with high selectivity and to effectively reduce SBM allergenic proteins within 30 min. In conclusion, immobilization of bromelain onto Bt-CMC composites leads to stability enhancement of the enzyme, enabling effective improvement in SBM quality in a short treatment time and showing great potential for application in animal feed industries.