Natural peloids originating from subsea depths of 200 m in the hupo basin, South Korea: physicochemical properties for potential pelotherapy applications.

The present study firstly reports surface sediment from the subsea depth of 200 m as a potential natural peloid. The fine-silt sediment exhibited a consistent clay mineral composition dominated by illite, chlorite, kaolinite, and diatomite. The most abundant clay mineral was illite/mica, with other minerals loosely packed in a face-to-face orientation. The thermal conductivity, specific heat capacity, and cation-exchange capacity of the sediment were in the range 0.855-0.885 W/m K, 2.718-2.821 J/g °C, and 23.06-32.96 cmol/kg, respectively. The concentrations of most toxic elements in the sediment were considerably lower than the limits set by domestic cosmetic regulations and other international standards. The analyzed samples exhibited similar properties to those of previously reported peloids, thus making them suitable for use in the field of pelotherapy; furthermore, the consistency in data across a wide peloid-distribution area is expected to enable economically viable mining. Future investigations should aim to to evaluate the long-term effects on the skin, the bioavailability of potentially hazardous substances, and the therapeutic efficacy for various skin conditions.

Characterization and application of the nanocompiste packaging films containing clay and TiO2 on preservation of tomato fruit under cold storage.

BACKGROUND: Tomato (Lycopersicon esculentum), a valuable economic crop worldwide, often goes to waste due to improper packaging and handling. In the present study, three types of low-density polyethylene nanocomposite films containing 3% clay (Closite 20A), 3% TiO2 nanoparticles, and their combination were synthesized using melt blending method, and evaluated on the quality parameters of tomato fruit during 42 days of storage at 4 °C. RESULTS: Transmission electron microscopy confirmed the degree of dispersion and exfoliation of the nanoparticles. The TiO2/clay-nanocomposite films exhibited notable enhancements in Young's modulus and tensile strength compared to conventional films. The addition of clay and TiO2 nanoparticles resulted in reduced permeability to CO2, O2, and water vapor. Fruits packed with clay/TiO2 nanocomposite films showed decreased ethylene production, mitigated weight loss, and maintained pH, titratable acidity, total soluble solids, and firmness. Furthermore, clay/TiO2 nanocomposite films enhanced membrane stability, decreased membrane lipid peroxidation, and enhanced catalase and ascorbate peroxidase enzyme activity in fruits. CONCLUSIONS: The relatively good exfoliation of clay nanoparticles and the proper dispersion of TiO2 nanoparticles, which were confirmed by TEM, led to an increase in mechanical and physical properties in the Clay/TiO2 nanocomposite. This film displayed more potential in maintaining the quality properties of tomato fruit during cold storage. Therefore, this film can be considered a practical solution for minimizing pathogen risks and contamination, and enhancing the overall quality of tomato fruit.

Interface Binding Mechanism of Nanoclay Hybridized Coacervate Microdroplets for the Controllable Construction of Protocells.

Coacervate microdroplets, a protocell model in exploring the origin of life, have gained significant attention. Clay minerals, catalysts during the origin of life, are crucial in the chemical evolution of small molecules into biopolymers. However, our understanding of the relationship between clay minerals and the formation and evolution of protocells on early Earth remains limited. In this work, the nanoclay montmorillonite nanosheet (MMT-Na) was employed to investigate its interaction with coacervate microdroplets formed by oligolysine (K10) and adenine nucleoside triphosphate (ATP). As an anionic component, MMT-Na was noted to promote the formation of coacervate microdroplets. Furthermore, the efficiency of ssDNA enrichment and the degree of ssDNA hybridization within these microdroplets were significantly improved. By combining inorganic nanoclay with organic biopolymers, our work provides an efficient way to enrich genetic biomolecules in the primitive Earth environment and builds a nanoclay-based coacervate microdroplets, shedding new light on life's origin and protocell evolution.

Consolidation and seepage solutions in enclosure space based on non-zero-constant values boundary.

Research is ongoing to find solutions to the problem of Consolidation and seepage in saturated clay in enclosure space. Firstly, the boundary of non-zero-constant values is established, considering the seepage boundary of the clay is affected by pumping water or lowering boundary pressure on the site. Secondly, the differential equation is established to reflect the spatial and temporal variations of excess pore water pressure dissipation in the clay in enclosure space, and the solution is derived using variable separation methods. Finally, based on results of the solution derived, contour maps of the water pressure are drawn corresponding with the different inhomogeneous boundary conditions.

Novel fibrous Ag(NP) decorated clay-polymer composite: Implications in water purification contaminated with predominant micro-pollutants and bacteria.

Due to the potential harm caused by emerging micro-pollutants to living organisms, contaminating water supplies by micro-pollutants like EDCs, pharmaceuticals, and microorganisms has become a concern in many countries. Considering both microbiological and micro-pollutant exposure risks associated with water use for agricultural/or household purposes, it is imperative to create a strategy for improving pollutant removal from treated wastewater that is both effective and affordable. Natural clay minerals efficiently remove contaminants from wastewater, though the pristine clay has less affinity to several organic pollutants. Hydrophilic polymers, viz., poly(ethylene glycol) (PEG), improve the dispersion of particles, flocculation processes, and surface properties. In this study, PEG grafted with attapulgite, thereby providing a high-specific surface-area, mesoporous materials for the adsorption of micro-pollutants like ciprofloxacin (CIP) and 17α-ethinylestradiol (EE2) at high rates. A gentle washing process regenerates the clay-polymer material several times with no performance loss, and the natural water implications show fair applicability of solid in decontaminating the CIP and EE2 in an aqueous medium. Further, greenly synthesized silver nanoparticles in situ disperse with the clay polymer efficiently remove the gram-positive and gram-negative bacterium viz., Bacillus subtilis, and Pseudomonas aeruginosa, which are commonly persistent in aquatic environments. The clay polymer outperformed a modified clay composite to eliminate microorganisms and organic micro-pollutants in significant quantities quickly. These results clearly show the importance of fibrous clay-polymer composite for water purification technologies.

Halloysite nanotubes-based hybrid silica monolithic spin tip for hydrophilic solid-phase extraction of sulbactam, cefoperazone, and cefuroxime in whole blood.

In this study, we proposed a novel method utilizing polyethyleneimine (PEI)-modified halloysite nanotubes (HNTs)-based hybrid silica monolithic spin tip to analyze hydrophilic ß-lactam antibiotics and ß-lactamases inhibitors in whole blood samples for the first time. HNTs were incorporated directly into the hybrid silica monolith via a sol-gel method, which improved the hydrophilicity of the matrix. The as-prepared monolith was further modified with PEI by glutaraldehyde coupling reaction. It was found that the PEI-modified HNTs-based hybrid silica monolith enabled a large adsorption capacity of cefoperazone at 35.7 mg g-1. The monolithic spin tip-based purification method greatly reduced the matrix effect of whole blood samples and had a detection limit as low as 0.1 - 0.2 ng mL-1. In addition, the spiked recoveries of sulbactam, cefuroxime, and cefoperazone in blank whole blood were in the range of 89.3-105.4 % for intra-day and 90.6-103.5 % for inter-day, with low relative standard deviations of 1.3-7.2 % and 4.9-10.5 %, respectively. This study introduces a new strategy for preparing nanoparticles incorporated in a hybrid silica monolith with a high adsorption capacity. Moreover, it offers a valuable tool to monitor sulbactam, cefoperazone, and cefuroxime in whole blood from pregnant women with the final aim of guiding their administration.

Mesocosm study of PAC-modified clay effects on Karenia brevis cells and toxins, chemical dynamics, and benthic invertebrate physiology.

Modified clay compounds are used globally as a method of controlling harmful algal blooms, and their use is currently under consideration to control Karenia brevis blooms in Florida, USA. In 1400 L mesocosm tanks, chemical dynamics and lethal and sublethal impacts of MC II, a polyaluminum chloride (PAC)-modified kaolinite clay, were evaluated over 72 h on a benthic community representative of Sarasota Bay, which included blue crab (Callinectes sapidus), sea urchin (Lytechinus variegatus), and hard clam (Mercenaria campechiensis). In this experiment, MC II was dosed at 0.2 g L-1 to treat bloom-level densities of K. brevis at 1 × 106 cells L-1. Cell removal in MC II-treated tanks was 57% after 8 h and 95% after 48 h. In the water column, brevetoxin analogs BTx-1 and BTx-2 were found to be significantly higher in untreated tanks at 24 and 48 h, while in MC II-treated tanks, BTx-3 was found to be higher at 48 h and BTx-B5 was found to be higher at 24 and 48 h. In MC II floc, we found no significant differences in BTx-1 or BTx-2 between treatments for any time point, while BTx-3 was found to be significantly higher in the MC II-treated tanks at 48 and 72 h, and BTx-B5 was higher in MC II-treated tanks at 24 and 72 h. Among various chemical dynamics observed, it was notable that dissolved phosphorus was consistently significantly lower in MC II tanks after 2 h, and that turbidity in MC II tanks returned to control levels 48 h after treatment. Dissolved inorganic carbon and total seawater alkalinity were significantly reduced in MC II tanks, and partial pressure of CO2 (pCO2) was significantly higher in the MC II-only treatment after 2 h. In MC II floc, particulate phosphorus was found to be significantly higher in MC II tanks after 24 h. In animals, lethal and sublethal responses to MC II-treated K. brevis did not differ from untreated K. brevis for either of our three species at any time point, suggesting MC II treatment at this dosage has negligible impacts to these species within 72 h of exposure. These results appear promising in terms of the environmental safety of MC II as a potential bloom control option, and we recommend scaling up MC II experiments to field trials in order to gain deeper understanding of MC II performance and dynamics in natural waters.

Aldehyde-containing clays: a sustainable approach against the olive tree pest, Bactrocera oleae.

A set of organic/inorganic layered materials was obtained by functionalizing a montmorillonite-containing bentonite natural clay with linear aliphatic C6 or C7 aldehydes through a cost-effective and technologically simple incipient-wetness deposition method. The solids were investigated by means of a multi-technique approach (X-ray powder diffraction, XRPD, scanning electron microscopy, SEM, Fourier-transform infrared spectroscopy, FT-IR, thermogravimetric analysis, TGA, elemental analysis and solid-state nuclear magnetic resonance, ssNMR) to clarify the nature of the deposited organic species and the mode of interaction between the aldehyde and the clay. Since both natural clays and short-chain linear aldehydes find application as alternative strategies in the control of the olive fruit fly, Bactrocera oleae, the hybrid layered materials were tested under real-life conditions and their insect-inhibiting capability was evaluated in open-field trials on olive tree orchards in Tuscany, Central Italy. Specific tests were conducted to evaluate the resistance of the solids to weathering and their capability to provide a constant and long-lasting release of the bioactive ingredient. Aldehyde-containing bentonite clays have shown promising performance in controlling B. oleae infestation (with up to 86-95% reduction of affected olive fruits) in open-field trials across two years in two locations with different pedological and meteo-climatic characteristics.

Comparison of Synthetic Pathways for Obtaining Fluorescent Nanomaterials Based on Halloysite and Carbon Dots for Potential Biological Sensing.

Recently, fluorescent sensors have gained considerable attention due to their high sensitivity, low cost and noninvasiveness. Among the different materials that can be used for this purpose, carbon dots (CDs) represent valuable candidates for applications in sensing. These, indeed, are easily synthesized, show high quantum yield and are highly biocompatible. However, it was pointed out that the photoluminescence properties of these nanomaterials are strictly dependent on the synthetic and purification methods adopted. The presence of halloysite nanotubes (HNTs), a natural, low cost and biocompatible clay mineral, has been found to be efficient in obtaining small and highly monodispersed CDs without long and tedious purification techniques. Herein, we report the comparison of synthetic pathways for obtaining halloysite-N-doped CDs (HNTs-NCDs) that could be used in biological sensing. One was based on the synthesis of N-doped CDs by a bottom-up approach on HNTs' surface by a MW pyrolysis process; the other one was based on the post-modification of pristine N-doped CDs with halloysite derivatives. The evaluation of the best synthetic route was performed by different physico-chemical techniques. It was found that the bottom-up approach led to the formation of N-doped CDs with different functional groups onto the HNTs' surface. This evidence was also translated in the different fluorescence quantum yields and the existence of several functional groups in the obtained materials was investigated by potentiometric titrations. Furthermore, the ability of the synthesized nanomaterials as sensors for Fe3+ ions detection was assessed by spectroscopic measurements, and the cellular uptake was verified by confocal/fluorescence microscopies as well.

Influence of Different Rates of Plant-Based Compost on Clay Soil Metal Behavior and Human Health Risk Assessment in Moringa oleifera Leaf Biomass.

An investigation of the impact of adding plant-based organic compost to clay soil from a Moringa oleifera farm focusing on the metal content, bioavailability, and accumulation of nutrients in M. oleifera leaves was conducted. Clay soil was mixed with 15%, 30%, 45% and 60% plant-based organic compost (by volume) in 20 cm wide, 2 L pots. Moringa oleifera plants were planted in four replicates of each treatment and control group. Results revealed that the addition of compost significantly (P < 0.05) altered the concentration of metals in the soil. Correspondingly, accumulation of nutrients in M. oleifera leaves increased with the addition of compost to the soil, except for cobalt and chromium. Trace elements had minimal bioavailability in the amended soils, and their presence in the leaves was lower than the permissible trace metal levels in food. The 30% combination had the highest concentration of calcium (45 042.5 mg/kg), magnesium (17430.0 mg/kg) and phosphorous (8802. 5 mg/kg) in M. oleifera leaves. The study concluded the addition of compost improved bioavailability of nutrients in the soil and their concentration in M. oleifera leaves. The target hazard quotients for heavy metals was less than one, indicating that M. oleifera leaf biomass harvested from soil amended with plant-based compost is safe for human consumption. These results serve as guidelines for recommended organic certification requiremets where plant-based compost is often used in the fast-growing herbal industry.

High levels of soil calcium and clay facilitate the recovery and stability of organic carbon: Insights from different land uses in the karst of China.

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.

Critical Role of Mineral Fe(IV) Formation in Low Hydroxyl Radical Yields during Fe(II)-Bearing Clay Mineral Oxygenation.

In subsurface environments, Fe(II)-bearing clay minerals can serve as crucial electron sources for O2 activation, leading to the sequential production of O2•-, H2O2, and •OH. However, the observed •OH yields are notably low, and the underlying mechanism remains unclear. In this study, we investigated the production of oxidants from oxygenation of reduced Fe-rich nontronite NAu-2 and Fe-poor montmorillonite SWy-3. Our results indicated that the •OH yields are dependent on mineral Fe(II) species, with edge-surface Fe(II) exhibiting significantly lower •OH yields compared to those of interior Fe(II). Evidence from in situ Raman and Mössbauer spectra and chemical probe experiments substantiated the formation of structural Fe(IV). Modeling results elucidate that the pathways of Fe(IV) and •OH formation respectively consume 85.9-97.0 and 14.1-3.0% of electrons for H2O2 decomposition during oxygenation, with the Fe(II)edge/Fe(II)total ratio varying from 10 to 90%. Consequently, these findings provide novel insights into the low •OH yields of different Fe(II)-bearing clay minerals. Since Fe(IV) can selectively degrade contaminants (e.g., phenol), the generation of mineral Fe(IV) and •OH should be taken into consideration carefully when assessing the natural attenuation of contaminants in redox-fluctuating environments.

Influence of clay minerals on pH and major cation concentrations in acid-leached sands: Column experiments and reactive-transport modeling.

A series of laboratory experiments are conducted to simulate the acidification and subsequent recovery of a sand aquifer exploited by in situ recovery (ISR) mining. A sulfuric acid solution (pH 2) is first injected into a column packed with sand from the Zoovch Ovoo uranium roll front deposit (Mongolia). Solutions representative of local groundwater or enriched in cations (Na+, Mg2+) are then circulated through the column to simulate the inflow of aquifer water. pH and major ion concentrations (Na+, Cl-, SO42-, Ca2+, Mg2+, K+) measured at the column outlet reproduce the overall evolution of porewater chemistry observed in the field. The presence of minor quantities of swelling clay minerals (≈6 wt% smectite) is shown to exert an important influence on the behavior of inorganic cations, particularly H+, via ion-exchange reactions. Numerical models that consider ion-exchange on smectite as the sole solid-solution interaction are able to reproduce variations in pH and cation concentrations in the column experiments. This highlights the importance of clay minerals in controlling H+ mobility and demonstrates that sand from the studied aquifer can be described to a first order as an ion-exchanger. The present study confirms the key role of clay minerals in controlling water chemistry in acidic environments through ion-exchange processes. In a context of managing the long-term environmental footprint of industrial and mining activities (ISR, acid mine drainage…), this work will bring insights for modeling choices and identification of key parameters to help operators to define their production and/or remediation strategies.

Mechanism of clay mineral modified biochar simultaneously immobilizes heavy metals and reduces soil carbon emissions.

Heavy metal pollution in farmland soil has become increasingly severe, and multi-element composite pollution has brought enormous harm to human production and life. Environmental changes in cold regions (such as freeze-thaw cycles and dry-wet alternations) may increase the potential physiological toxicity of heavy metals and exacerbate pollution risks. In order to reveal the effectiveness of sepiolite modified biochar in the remediation of the soil contaminated with lead (Pb), cadmium (Cd), and chromium (Cr), the rice husk biochar pyrolyzed at 500 and 800 °C were selected for remediation treatment (denoted as BC500 and BC800). Meanwhile, different proportions of sepiolite were used for modification (biochar: sepiolite = 1: 0.5 and 1: 1), denoted as MBC500/MBC800 and HBC500/HBC800, respectively. The results showed that modified biochar with sepiolite can effectively improve the immobilization of heavy metals. Under natural conservation condition, the amount of diethylenetriaminepentaacetic acid (DTPA) extractable Pb in BC500, MBC500, and HBC500 decreased by 5.95, 12.39, and 13.55%, respectively, compared to CK. Freeze-thaw cycles and dry-wet alternations activated soil heavy metals, while modified biochar increased adsorption sites and oxygen-containing functional groups under aging conditions, inhibiting the fractions transformation of heavy metals. Furthermore, freeze-thaw cycles promoted the decomposition and mineralization of soil organic carbon (SOC), while sepiolite hindered the release of active carbon through ion exchange and adsorption complexation. Among them, and the soil dissolved organic carbon (DOC) content in HBC800 decreased by 49.39% compared to BC800. Additionally, the high-temperature pyrolyzed biochar (BC800) enhanced the porosity richness and alkalinity of material, which effectively inhibited the migration and transformation of heavy metals compared to BC500, and reduced the decomposition of soil DOC.

Influence of salinity gradients on the diffusion of water and ionic species in dual porosity clay samples.

Most of the available data on diffusion in natural clayey rocks consider tracer diffusion in the absence of a salinity gradient despite the fact that such gradients are frequently found in natural and engineered subsurface environments. To assess the role of such gradients on the diffusion properties of clayey materials, through-diffusion experiments were carried out in the presence and absence of a salinity gradient using salt-diffusion and radioisotope tracer techniques. The experiments were carried out with vermiculite samples that contained equal proportions of interparticle and interlayer porosities so as to assess also the role played by the two types of porosities on the diffusion of water and ions. Data were interpreted using both a classical Fickian diffusion model and with a reactive transport code, CrunchClay that can handle multi-porosity diffusion processes in the presence of charged surfaces. By combining experimental and simulated data, we demonstrated that (i) the flux of water diffusing through vermiculite interlayer porosity was minor compared to that diffusing through the interparticle porosity, and (ii) a model considering at least three types of porous volumes (interlayer, interparticle diffuse layer, and bulk interparticle) was necessary to reproduce consistently the variations of neutral and charged species diffusion as a function of salinity gradient conditions.

Insights into how characteristics of dissolved algal organic matter affect the efficiency of modified clay in controlling harmful algal blooms.

Dissolved algal organic matter (dAOM) originating from harmful algal blooms (HABs) can deteriorate the quality of municipal water supplies, threaten the health of aquatic environments, and interfere with modified clay (MC)-based HABs control measures. In this study, we explored the composition of dAOM from Prorocentrum donghaiense, a typical HAB organism, and assessed the influence of dAOM on MC flocculation. Our results suggested that dAOM composition was complex and had a wide molecular weight (MW) distribution. MW and electrical properties were important dAOM characteristics affecting flocculation and algal removal efficiency of MC. Negatively charged high-MW components (>50 kDa) critically affected algal removal efficiency, reducing the zeta potential of MC particles and leading to small and weak flocs. However, the effect of dAOM depended on its concentration. When the cell density of P. donghaiense reached HAB levels, the high-MW dAOM strongly decreased the algal removal efficiency of MC.

Simple and scalable preparation of lignin based porous carbon coated nano-clay composites and their efficient removal for the diversified iodine.

Here, lignin and nano-clay were used to prepare novel composite adsorbents by one-step carbonization without adding activators for radioactive iodine capture. Specially, 1D nano-clay such as halloysite (Hal), palygorskite (Pal) and sepiolite (Sep) were selected as skeleton components, respectively, enzymatic hydrolysis lignin (EHL) as carbon source, lignin based porous carbon/nano-clay composites (ELC-X) were prepared through ultrasonic impregnation, freeze drying, and carbonization. Characterization results indicated lignin based porous carbon (ELC) well coated on the surface of nano-clay, and made its surface areas increase to 252 m2/g. These composites appeared the micro-mesoporous hierarchical structure, considerable N doping and good chemical stability. Results of adsorption experiments showed that the introduction of ELC could well promote iodine vapor uptake of nano-clay, and up to 435.0 mg/g. Meanwhile, the synergistic effect between lignin based carbon and nano-clay was very significant for the adsorption of iodine/n-hexane and iodine ions, their capacity were far exceed those of a single material, respectively. The relevant adsorption kinetic and thermodynamics, and mechanism of ELC-X composites were clarified. This work provided a class of low-cost and environmentally friendly adsorbents for radioactive iodine capture, and opened up ideas for the comprehensive utilization of waste lignin and natural clay minerals.

Evaluating the agronomic efficiency of alternative phosphorus sources applied in Brazilian tropical soils.

Understanding the efficacy of alternative phosphorus (P) sources in tropical soils is crucial for sustainable farming, addressing resource constraints, mitigating environmental impact, improving crop productivity, and optimizing soil-specific solutions. While the topic holds great importance, current literature falls short in providing thorough, region-specific studies on the effectiveness of alternative P sources in Brazilian tropical soils for maize cultivation. Our aim was to assess the agronomic efficiency of alternative P sources concerning maize crop (Zea mays L.) attributes, including height, shoot dry weight, stem diameter, and nutrient accumulation, across five Brazilian tropical soils. In greenhouse conditions, we carried out a randomized complete block design, investigating two factors (soil type and P sources), evaluating five tropical soils with varying clay contents and three alternative sources of P, as well as a commercial source and a control group. We evaluated maize crop attributes such as height, dry weight biomass, and nutrient accumulation, P availability and agronomic efficiency. Our results showed that, although triple superphosphate (TSP) exhibited greater values than alternative P sources (precipitated phosphorus 1, precipitated phosphorus 2 and reactive phosphate) for maize crop attributes (e.g., height, stem diameter, shoot dry weight and phosphorus, nitrogen, sulfur, calcium and magnesium accumulation). For instance, PP1 source increased nutrient accumulation for phosphorus (P), nitrogen (N), and sulfur (S) by 37.05% and 75.98% (P), 34.39% and 72.07% (N), and 41.94% and 72.69% (S) in comparison to PP2 and RP, respectively. Additionally, PP1 substantially increased P availability in soils with high clay contents 15 days after planting (DAP), showing increases of 61.90%, 99.04%, and 38.09% greater than PP2, RP, and TSP. For Ca and Mg accumulation, the highest values were found in the COxisol2 soil when PP2 was applied, Ca = 44.31% and 69.48%; and Mg = 46.23 and 75.79%, greater than PP1 and RP, respectively. Finally, the highest values for relative agronomic efficiency were observed in COxisol2 when PP1 was applied. The precipitated phosphate sources (PP1 and PP2) exhibited a similar behavior to that of the commercial source (TSP), suggesting their potential use to reduce reliance on TSP fertilization, especially in soils with low clay contents. This study emphasized strategies for soil P management, aimed at assisting farmers in enhancing maize crop productivity while simultaneously addressing the effectiveness of alternative P sources of reduced costs.

Influence of kaolin and red clay on ceramic specimen properties when galvanic sludge is incorporated to encapsulate heavy metals.

This study presented the influence of two types of clay: kaolin (Kao) and red clay (RC) on the chemical and physical properties of ceramic specimens when galvanic sludge (GS) is incorporated to encapsulate heavy metals. Samples were obtained of GS from the industrial district of Manaus - Amazonas State, Brazil, and kaolin (Kao), and red clay (RC) from the Central Amazon. A fourth sample was prepared by mixing GS, Kao, and RC in the ratio 1:1:8 (GS + Kao + RC). This mixture was ground, and ceramic specimens were prepared, and heat treated at 950 °C and 1200 °C for three hours for phase detection, compressive strength, leaching of Fe, Ni and Cr metals and life cycle assessment. Galvanic sludge, Kao, and RC were also, and heat treated to at 950 °C and 1200 °C for three hours, obtaining GS950, GS1200, Kao950, Kao1200, RC950, and RC1200. The samples were submitted to XRF, XRD, Rietveld refinement, Mössbauer spectroscopy, TG/DTG/DSC, and SEM. The results show that the formation of nickel oxide and a spinel solid solution of the type Fe3+{Fe1-y3+,Fe1-x2+,Nix2+,Cry3+}O4 (in which [] = tetrahedral site, {} octahedral site) occurs in GS1200, which is caused by sulfate decomposition to SO2. At 1200 °C, heavy metals are encapsulated, forming other phases such as nickel silicate and hematite. Life cycle assessment was used to verify the sustainability and value of GS in clay for making bricks, and it indicated that the production of ceramics is feasible, reduces the use of clays, and is sustainable.

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.