Effects of a Curcumin/Silymarin/Yeast-Based Mycotoxin Detoxifier on Redox Status and Growth Performance of Weaned Piglets under Field Conditions.

The aim of this in vivo study was to investigate the effects of a novel mycotoxin detoxifier whose formulation includes clay (bentonite and sepiolite), phytogenic feed additives (curcumin and silymarin) and postbiotics (yeast products) on the health, performance and redox status of weaned piglets under the dietary challenge of fumonisins (FUMs). The study was conducted in duplicate in the course of two independent trials on two different farms. One hundred and fifty (150) weaned piglets per trial farm were allocated into two separate groups: (a) T1 (control group): 75 weaned piglets received FUM-contaminated feed and (b) T2 (experimental group): 75 weaned piglets received FUM-contaminated feed with the mycotoxin-detoxifying agent from the day of weaning (28 days) until 70 days of age. Thiobarbituric acid reactive substances (TBARSs), protein carbonyls (CARBs) and the overall antioxidant capacity (TAC) were assessed in plasma as indicators of redox status at 45 and 70 days of age. Furthermore, mortality and performance parameters were recorded at 28, 45 and 70 days of age, while histopathological examination was performed at the end of the trial period (day 70). The results of the present study reveal the beneficial effects of supplementing a novel mycotoxin detoxifier in the diets of weaners, including improved redox status, potential hepatoprotective properties and enhanced growth performance.

Recent advances in natural nanoclay for diagnosis and therapy of cancer: A review.

Cancer is still one of the deadliest diseases, and diagnosing and treating it effectively remains difficult. As a result, advancements in earlier detection and better therapies are urgently needed. Conventional chemotherapy induces chemoresistance, has non-specific toxicity, and has a meager efficacy. Natural materials like nanosized clay mineral formations of various shapes (platy, tubular, spherical, and fibrous) with tunable physicochemical, morphological, and structural features serve as potential templates for these. As multifunctional biocompatible nanocarriers with numerous applications in cancer research, diagnosis, and therapy, their submicron size, individual morphology, high specific surface area, enhanced adsorption ability, cation exchange capacity, and multilayered organization of 0.7-1 nm thick single sheets have attracted significant interest. Kaolinite, halloysite, montmorillonite, laponite, bentonite, sepiolite, palygorskite, and allophane are the most typical nanoclay minerals explored for cancer. These multilayered minerals can function as nanocarriers to effectively carry a variety of anticancer medications to the tumor site and improve their stability, dispersibility, sustained release, and transport. Proteins and DNA/RNA can be transported using nanoclays with positive and negative surfaces. The platform for phototherapeutic agents can be nanoclays. Clays with bio-functionality have been developed using various surface engineering techniques, which could help treat cancer. The promise of nanoclays as distinctive crystalline materials with applications in cancer research, diagnostics, and therapy are examined in this review.

The combined effects of lanthanum-modified bentonite and Vallisneria spiralis on phosphorus, dissolved organic matter, and heavy metal(loid)s.

The use of lanthanum-modified bentonite (LMB) combined with Vallisneria spiralis (V∙s) (LMB + V∙s) is a common method for controlling internal phosphorus (P) release from sediments. However, the behaviors of iron (Fe) and manganese (Mn) under LMB + V∙s treatments, as well as the associated coupling effect on P, dissolved organic matter (DOM), and heavy metal(loid)s (HMs), require further investigations. Therefore, we used in this study a microelectrode system and high-resolution dialysis technology (HR-Peeper) to study the combined effects of LMB and V∙s on P, DOM, and HMs through a 66-day incubation experiment. The LMB + V∙s treatment increased the sediment DO concentration, promoting in-situ formations of Fe (III)/Mn (IV) oxyhydroxides, which, in turn, adsorbed P, soluble tungsten (W), DOM, and HMs. The increase in the concentrations of HCl-P, amorphous and poorly crystalline (oxyhydr) oxides-bound W, and oxidizable HMs forms demonstrated the capacity of the LMB + V∙s treatment to transform mobile P, W, and other HMs forms into more stable forms. The significant positive correlations between SRP, soluble W, UV254, and soluble Fe (II)/Mn, and the increased concentrations of the oxidizable HMs forms suggested the crucial role of the Fe/Mn redox in controlling the release of SRP, DOM, and HMs from sediments. The LMB + V∙s treatment resulted in SRP, W, and DOM removal rates of 74.49, 78.58, and 54.78 %, which were higher than those observed in the control group (without LMB and V∙s applications). On the other hand, the single and combined uses of LMB and V·s influenced the relative abundances of the sediment microbial communities without exhibiting effects on microbial diversity. This study demonstrated the key role of combined LMB and V∙s applications in controlling the release of P, W, DOM, and HMs in eutrophic lakes.

Kinetics of glyphosate and aminomethylphosphonic acid sorption onto montmorillonite clays in soil and their translocation to genetically modified corn.

The co-occurrence 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. A major route of exposure is through contact with contaminated soil and consumption of crops containing GLP and AMPA residues. However, clay-based sorption strategies for mixtures of GLP and AMPA in soil, plants and garden produce have been very limited. In this study, in vitro soil and in vivo genetically modified corn models were used to establish the proof of concept that the inclusion of clay sorbents in contaminated soils will reduce the bioavailability of GLP and AMPA in soils and their adverse effects on plant growth. Effects of chemical concentration (1-10 mg/kg), sorbent dose (0.5%-3% in soil and 0.5%-1% in plants) and duration (up to 28 days) on sorption kinetics were studied. The time course results showed a continuous GLP degradation to AMPA. The inclusion of calcium montmorillonite (CM) and acid processed montmorillonite (APM) clays at all doses significantly and consistently reduced the bioavailability of both chemicals from soils to plant roots and leaves in a dose- and time-dependent manner without detectable dissociation. Plants treated with 0.5% and 1% APM inclusion showed the highest growth rate (p ≤ 0.05) and lowest chemical bioavailability with up to 76% reduction in roots and 57% reduction in leaves. Results indicated that montmorillonite clays could be added as soil supplements to reduce hazardous mixtures of GLP and AMPA in soils and plants.

Functionality and mechanistic parametric study of the potential of waste plantain peels and commercial bentonite for soybean oil refining.

The consumption of unrefined vegetable oil poses acute and chronic health issues, yet improper disposal of waste plantain peels is not environmentally sustainable. This research investigates the feasibility, mechanism and thermodynamics of waste plantain peels, and commercial bentonite clay for soybean oil refining. Experiment was carried out using masses (1-4 g) of commercial bentonite clay, and unripe plantain peel ash (UPPA) to degummed and neutralized free fatty acid (FFA) contents in crude soybean oil at varying temperatures (50-120 °C), and time (15-35 min) for treatment of soybean oil. FTIR spectroscopy, SEM, and XRF techniques were applied to characterize the sample. The results established that at optimum 4.0 g dosage, the UPPA (97.73%) was more effective in the removal of FFA from oil at 50 °C and 20 min, while the clay (90%) was more effective in the removal of colour pigment from the vegetable oil 100 °C, and 25 min. The optimum efficiency of Clay-Ash-composite (70:30) in adsorbing pigment from soybean oil corresponds to 80%. The impact of changing viscosities, densities, and acid values on the performance of UPPA, clay, and clay-UPPA composite was investigated. Mechanistic studies confirmed the pseudo-second-order kinetics at 5 × 10-2 g/mg min-1 and 1.87 × 10-1 g/mg min-1, with corresponding adsorption capacity of 30.40 mg/g and 4.91 mg/g, at R2 ≤ 0.9982. The UPPA-driven sorption of FFA occurred as a physisorption and exothermic process (- 620.60 kJ/mol), while colour pigment removal occurred by chemisorption and endothermic process (22.40 kJ/mol). The finding recommends UPPA and composite as economically feasible for refining soybean oil.

Formation and sedimentation of oil-mineral aggregates in the presence of chemical dispersant.

The formation and sedimentation of oil-mineral aggregates (OMAs) is the major method to transport spilled oil to the seafloor. In this study, the formation and sedimentation experiments of OMA using montmorillonite and four crude oils were performed in a wave tank in the presence of chemical dispersant. Most of the formed OMAs were droplet OMAs, and single droplet OMA would aggregate into multiple ones under the action of the dispersant. The size of the oil droplets trapped in the OMA increased with time and was larger for the oil with higher viscosity. The sinking velocities of OMAs formed in this study were between 100-1200 µm s-1 and they were positively correlated with their diameter. The density of OMA was of the same order as that of the crude oil that formed them. An increase in the dispersant dosage could promote the formation of OMAs. The oil content in OMAs was higher for the denser oil in the presence of a dispersant. The maximum oil trapping efficiency of OMAs was 48.05%. This study provides fundamental data on the formation kinetics of OMAs.

Immobilization of phosphorus in water-sediment system by iron-modified attapulgite, calcite, bentonite and dolomite under feed input condition: Efficiency, mechanism, application mode effect and response of microbial communities and iron mobilization.

Four kinds of iron-based materials, i.e., iron-modified attapulgite, calcite, bentonite and dolomite (abbreviated as Fe-ATP, Fe-CA, Fe-BT and Fe-DOL, respectively) were prepared and used to immobilize the phosphorus in the system of overlying water (O-water) and sediment under the feed input condition, and their immobilization efficiencies and mechanisms were investigated. The influence of application mode on the immobilization of phosphorus in the water-sediment system by Fe-ATP, Fe-CA, Fe-BT and Fe-DOL was researched. The effects of Fe-ATP, Fe-CA, Fe-BT and Fe-DOL on the concentration of labile iron in the water-sediment system and the microbial communities in sediment were also studied. The results showed that the Fe-ATP, Fe-CA, Fe-BT and Fe-DOL addition all can effectively immobilize the soluble reactive phosphorus (SRP), dissolved total phosphorus (DTP) and diffusive gradients in thin-films (DGT)-labile phosphorus in O-water under the feed input condition, and also had the ability to inactivate the DGT-labile phosphorus in the top sediment. Although the change in the application mode from the one-time addition to the multiple addition reduced the inactivation efficiencies of SRP and DTP in O-water in the early period of application, it increased the immobilization efficiencies in the later period of application. Although Fe-ATP, Fe-CA, Fe-BT and Fe-DOL had a certain releasing risk of iron into the pore water, they had negligible risk of iron release into O-water. The addition of Fe-ATP, Fe-CA, Fe-BT or Fe-DOL reshaped the sediment bacterial community structure and can affect the microorganism-driven phosphorus cycle in the sediment. Results of this work suggest that Fe-ATP, Fe-CA, Fe-BT and Fe-DOL are promising phosphorus-inactivation materials to immobilize the phosphorus in the water-sediment system under the feed input condition.

Stable microbial community in compacted bentonite after 5 years of exposure to natural granitic groundwater.

The Materials Corrosion Test (MaCoTe) at the Underground Research Laboratory in Grimsel, Switzerland, assesses the microbiology and corrosion behavior of engineered barrier components of a deep geological repository (DGR) for long-term disposal of high-level nuclear waste. Diversity and temporal changes of bentonite-associated microbial community profiles were assessed under DGR-like conditions for compacted Wyoming MX-80 bentonite (1.25 g/cm3 and 1.50 g/cm3 targeted dry densities) exposed to natural groundwater. Using culture-dependent and molecular techniques, samples taken from the outside layer of 5-year borehole modules revealed up to 66% and 23% of 16S rRNA gene sequences affiliated with Desulfosporosinus and Desulfovibrio, respectively. Putatively involved in sulfate reduction, these taxa were almost undetectable within the bentonite core. Instead, microbial profiles of the inner bentonite core were similar to uncompacted bentonite used to pack modules years earlier, and were consistent with a previously published 1-year time point, revealing no detectable microbial growth. Abundances of culturable aerobic and anaerobic heterotrophic bacteria in the uncompacted bentonite were relatively low, with less than 1,000 and 100 colony-forming units (CFUs) per gram dry weight, respectively. Nearly 5 years after emplacement, culturable heterotrophic bacterial CFUs and sulfate-reducing bacteria did not change significantly inside the bentonite core. Phospholipid fatty acid data indicated similar lipid abundance, and corresponding cell abundance estimates, for inner 5-year MaCoTe bentonite samples compared to those previously obtained for 1-year incubations. Collectively, our results provide complementary evidence for microbial stability inside highly compacted bentonite exposed to conditions that mimic engineered barrier components of a deep geological repository. IMPORTANCE The long-term safety of a deep geological repository for used nuclear fuel is dependent on the performance of the engineered and natural barriers. Microbial activity can produce chemical species that can influence the corrosion of the disposal containers for used nuclear fuel. Although previous studies have evaluated the microbiology of compacted bentonite clay within subsurface environments, these have been limited to relatively short incubations (i.e., 1 year). The current study provides a unique 5-year perspective that reinforces previous findings of growth inhibition for bentonite clay exposed to in situ subsurface conditions.

Effects of different chemical agents on changes in sediment phosphorus composition and the response of sediment microbial community.

Controlling the release of sediment phosphorus (P) using chemical agents is a promising method for controlling internal P in eutrophic lakes. However, mineral P formation and changes in the organic P composition after sediment amendment with P-inactivation agents remain poorly understood. Furthermore, little is known about the changes in the sediment microbial community composition after remediation. Here, various ratios of poly aluminum chloride (PAC) and lanthanum-modified bentonite (LMB) were added to nutrient-rich sediments and incubated. Sequential P extraction, solution/solid-state 31P nuclear magnetic resonance (NMR), and microbial analyses were periodically performed on the inactivated sediments. The results indicate that PAC and LMB effectively reduced sediment iron-bound P and organic P, respectively, markedly increasing the content of aluminum- and calcium-bound P in the sediment, respectively. Solid-state 31P NMR results confirmed the formation of rhabdophane (LaPO4. nH2O) in the LMB-amended sediment. Solution 31P NMR results showed that PAC preferentially reduced the organic P fractions of pyrophosphate, whereas LMB efficiently reduced the organic P fractions of orthophosphate, monoesters, and diesters in the sediment. Compared with the control sediment, PAC addition can cause short-term negative effects on sediment microbes at high doses, whereas LMB addition can increase bacterial diversity or richness in the sediment. These results provide a deeper understanding of the differences between PAC and LMB in internal sediment P control.

Layered Clay Minerals in Cancer Therapy: Recent Progress and Prospects.

Cancer is one of the deadliest diseases, and current treatment regimens suffer from limited efficacy, nonspecific toxicity, and chemoresistance. With the advantages of good biocompatibility, large specific surface area, excellent cation exchange capacity, and easy availability, clay minerals have been receiving ever-increasing interests in cancer treatment. They can act as carriers to reduce the toxic side effects of chemotherapeutic drugs, and some of their own properties can kill cancer cells, etc. Compared with other morphologies clays, layered clay minerals (LCM) have attracted more and more attention due to adjustable interlayer spacing, easier ion exchange, and stronger adsorption capacity. In this review, the structure, classification, physicochemical properties, and functionalization methods of LCM are summarized. The state-of-the-art progress of LCM in antitumor therapy is systematically described, with emphasis on the application of montmorillonite, kaolinite, and vermiculite. Furthermore, the property-function relationships of LCM are comprehensively illustrated to reveal the design principles of clay-based antitumor systems. Finally, foreseeable challenges and outlook in this field are discussed.

Plant-based green fabrication of CuO-CdO-bentonite S-scheme heterojunction with enhanced photocatalytic performance for the degradation of levofloxacin.

In this research, for the first time, CuO and CdO nanoparticles (NPs) were synthesized using Ferula persica and anchored on layered bentonite as a novel S-scheme nano-heterojunction (denoted as CuO-CdO-BT). Ferula persica acted as a naturally-sourced reducing agent and stabilizer for the synthesis of NPs. The performance of CuO-CdO-BT was evaluated for the degradation of levofloxacin from an aqueous solution under sunlight. The characterization results clarified that the bentonite as a support not only reduced the agglomeration of CuO and CdO NPs but also decreased the size of biosynthesized NPs, which increased the active surface of NPs and the photodegardation efficiency. The effect of operational reaction system variables was examined to optimize the photocatalytic capability of CuO-CdO-BT. Under optimum conditions (catalyst dosage = 0.4 g/L, LVF concentration = 10 mg/L and pH = 8), 96.11% of levofloxacin was degraded using CuO-CdO-BT after 30 min with degradation kinetic of 0.108 min-1, which was about 2.4 and 4.2 times higher than those of bare CuO and CdO NPs, respectively. The improvement of the photocatalytic degradation efficiency of CuO-CdO-BT compared to CuO and CdO NPs was due to preventing the recombination of charge carriers in the S-scheme system. The radical quenching experiments ascertained the generation of [Formula: see text]·OH, and [Formula: see text] species in the CuO-CdO-BT system, indicating that ·OH radicals have a more prominent role than [Formula: see text] and [Formula: see text] in the photocatalytic reaction. The six possible levofloxacin pathways of LVF degradation were suggested based on HPLC-MS analysis. Over 88.5% LVF was removed using CuO-CdO-BT after three catalyst reuse cycles, indicating a cost-effectiveness potential of the biosynthesized photocatalyst reusability. Almost complete mineralization of LVF was obtained by the CuO-CdO-BT photocatalyst after 180 min of reaction. Based on findings, the S-scheme mechanism of photo-generated electron-hole pairs transfer in the CuO-CdO-BT system was found. The unique structural features of the new generation of S-scheme heterojunction and green synthesis of NPs using plants provide promising photocatalysts to improve wastewater treatment.

Development and characterization of a novel active and intelligent film based on pectin and betacyanins from peel waste of pitaya (Hylocereus undatus).

In the present study, peel waste of pitaya (Hylocereus spp.) was used to develop a novel active and functional film. The film was developed with a combination of the white-fleshed pitaya peel pectin (WPPP) as a biopolymer and white-fleshed pitaya peel betacyanins (WPPB) as an active constituent, respectively. Furthermore, montmorillonite (MMT), a cheap and environmental-friendly silicate material, was introduced into film matrix as a filler to reduce the moisture sensitivity of the film. The effect of the incorporation of WPPB on the properties of WPPP/MMT films was investigated. The colorimetric response of WPPP/MMT/WPPB to pH and ammonia was examined, respectively. Moreover, WPPP/MMT/WPPB-2 was employed to monitor the freshness of shrimp. The color of the film changed from redness to reddish-brown, and further to brownness, echoing the shrimp turned from fresh to spoiled. Therefore, WPPP/MMT/WPPB-2 composite films showed promise for the applications in monitoring the freshness of shrimp.

A combined study on Vallisneria spiralis and lanthanum modified bentonite to immobilize arsenic in sediments.

Submerged plants and lanthanum-modified bentonite (LMB) have important applications for the remediation of contaminated sediments; however, their combined effect on arsenic (As) removal has not been comprehensively evaluated. In this study, the physicochemical properties and changes in soluble As in sediments treated with LMB, Vallisneria spiralis (V. spiralis), and LMB + V. spiralis were observed at three time points (days 15, 35, and 66), and the changes in microbial and As species in sediments on day 66 were analyzed. LMB + V. spiralis treatment was the most effective for As removal. On day 66, the average concentrations of soluble As at a depth of 0-100 mm decreased by 12.71%, 48.81%, and 59.73% following treatment with LMB, V. spiralis, and LMB + V. spiralis, respectively. Further analysis showed that LMB is more effective at removing As(V) than V. spiralis, while V. spiralis is more effective at removing As(III), and the combination of LMB + V. spiralis is more effective for removing both As(III) and As(V) than individual LMB and V. spiralis treatments. LMB + V. spiralis enhanced the transformation of mobile As to Fe2O3/oxyhydroxide-bound As in sediments and the activity of As-oxidizing microorganisms. LMB promoted the growth of V. spiralis and enhanced the removal of As. This study indicates that this combination is an effective method for removing mobile As from sediments, and could effectively inhibit the release of As from sediments to overlying water.

Unlocking the bentonite microbial diversity and its implications in selenium bioreduction and biotransformation: Advances in deep geological repositories.

Selenium, 79Se, is one of the most critical radionuclides in radioactive waste disposed in future deep geological repositories (DGRs). Here, we investigate the impact of bentonite microbial communities on the allotropic transformation of Se(IV) bioreduction products under DGR relevant conditions. In addition, Se amendment-dependent shifts in the bentonite microbial populations are assessed. Microcosms of water-saturated bentonites were spiked with a bacterial consortium, treated with selenite and incubated anaerobically for six months. A combination of X-Ray Absorption Spectroscopy, Electron Microscopy, and Raman Spectroscopy was used to track the allotropic changes of the Se bioreduction products. Interestingly, the color of bentonite shifted from orange to black in the selenite-treated microcosms. In the orange layers, amorphous or monoclinic Se(0) were identified, whilst black precipitates consisted of stable trigonal Se(0) form. Illumina DNA sequencing indicated the distribution of strains with Se(IV) reducing and Se(0) allotropic biotransformation potential, like Pseudomonas, Stenotrophomonas, Desulfosporosinus, and unclassified-Desulfuromonadaceae. The archaea Methanosarcina decreased its abundance in the presence of Se(IV), probably caused by this oxyanion toxicity. These findings provide an understanding of the bentonite microbial strategies involved in the immobilization of Se(IV) by reduction processes, and prove their implication in the allotropic biotransformation from amorphous to trigonal Se(0) under DGR relevant conditions.

The Effect of Montmorillonites on the Physicochemical Properties of Potato Starch Films Plasticized with Deep Eutectic Solvent.

In the paper, the method of obtaining the potato starch nanocomposites plasticized with a deep eutectic solvent is described. The deep eutectic solvent based on choline chloride and malic acid (CM, molar ratio 1:1) was used as the plasticizer. The effect of the sodium and calcium montmorillonite (MMTNa, MMTCa respectively) addition on the properties of potato starch films was investigated. The thermal, mechanical, and barrier properties were determined. Moreover, a moisture absorption test was performed. The starch gelatinization temperature increased in the presence of montmorillonite. The values of glass transition determined by DMTA depended on the nanofiller type. For the systems containing MMTCa, they generally decreased with its content (although still lower than reference samples). The obtained nanocomposites showed improved mechanical and barrier properties. The highest values of tensile strength and Young's modulus were noted for the system containing 1% MMTNa. The XRD revealed that only the films with MMTNa exhibited intercalation. The homogeneity of the samples decreased with increasing nanofiller concentration. This was probably due to the occurrence of choline chloride-montmorillonite interactions, which were more favored than clay-starch interactions.

Comparative study for removal of phosphorus from aqueous solution by natural and activated bentonite.

The novelty of the current article is to investigate the adsorption potential of the Egyptian natural and activated bentonite (Na-bentonite) to inorganic and organic phosphorus (IP, OP) in aqueous media. The natural bentonite (NB) was activated to Na-bentonite (Na-B) by a new facile method within 2 h. NB and Na-B were also characterized using XRD, XRF, BET ESM, and FT-IR. The batch experiment has been employed to select the ideal conditions for the removal of inorganic and organic phosphorus (IP, OP) from aqueous solutions. The findings clearly showed that the Na-bentonite is enriched with sodium in the form of Na-montmorillonite with a higher specific area 138.51 m2/g than the value for the natural bentonite 74.21 m2/g. The batch experiment showed maximum absorption for both IP and OP adsorbents occurred at an equilibrium pH = 6, contact time of 40 to 50 min, 40 °C temperature, and a dose rate of 2 mg/L and 1 mg/L, respectively. The equilibrium data displayed better adjustment to Langmuir than the Freundlich, Temkin, and Dubinin-Radushkevich isotherms and adsorption kinetics followed the pseudo-second-order-type kinetic, and the parameters of thermodynamics reveal that adsorption occurs spontaneously and exothermic nature. Na-bentonite proved to be more efficient in removing target material than natural bentonite. The spent bentonites were easily regenerated by chemical methods.

Effect of Ca(II) on U(VI) and Np(VI) retention on Ca-bentonite and clay minerals at hyperalkaline conditions - New insights from batch sorption experiments and luminescence spectroscopy.

In deep geological repositories for radioactive waste, interactions of radionuclides with mineral surfaces occur under complex geochemical conditions involving complex solution compositions and high pH resulting from degradation of cementitious geo-engineered barriers. Ca2+ cations have been hypothesized to play an important role as mediators for the retention of U(VI) on Ca-bentonite at (hyper)alkaline conditions, despite the anionic character of both the mineral surface and the aqueous uranyl species. To gain deeper insight into this sorption process, the effect of Ca2+ on U(VI) and Np(VI) retention on alumosilicate minerals has been comprehensively evaluated, using batch sorption experiments and time-resolved laser-induced luminescence spectroscopy (TRLFS). Sorption experiments with Ca2+ or Sr2+ and zeta potential measurements showed that the alkaline earth metals sorb strongly onto Ca-bentonite at pH 8-13, leading to a partial compensation of the negative surface charge, thereby generating potential sorption sites for anionic actinyl species. U(VI) and Np(VI) sorption experiments in the absence and presence of Ca2+ or Sr2+ confirmed that these cations strongly enhance radionuclide retention on kaolinite and muscovite at pH ≥ 10. Concerning the underlying retention mechanisms, site-selective TRLFS provided spectroscopic proof for two dominating U(VI) species at the alumosilicate surfaces: (i) A ternary U(VI) complex, where U(VI) is bound to the surface via bridging Ca cations with the configuration surface ≡ Ca - OH - U(VI) and, (ii) U(VI) sorption into the interlayer space of calcium (aluminum) silicate hydrates (C-(A-)S-H), which form as secondary phases in the presence of Ca due to partial dissolution of alumosilicates under hyperalkaline conditions. Consequently, the present study confirms that alkaline earth elements, which are ubiquitous in geologic systems, enable strong retention of hexavalent actinides on clay minerals under hyperalkaline repository conditions.

Response of sediment phosphorus partitioning to lanthanum-modified clay amendment and porewater chemistry in a small eutrophic lake.

Sustained eutrophication of the aquatic environment by the remobilization of legacy phosphorus (P) stored in soils and sediments is a prevailing issue worldwide. Fluxes of P from the sediments to the water column, referred to as internal P loading, often delays the recovery of water quality following a reduction in external P loads. Here, we report on the vertical distribution and geochemistry of P, lanthanum (La), iron (Fe) and carbon (C) in the culturally eutrophied Lake Bromont. This lake underwent remediation treatment using La modified bentonite (LMB) commercially available as Phoslock™. We investigated the effectiveness of LMB in decreasing soluble reactive phosphorus (SRP) availability in sediments and in reducing dissolved fluxes of P across the sediment-water interface. Sediment cores were retrieved before and after LMB treatment at three sites representing bottom sediment, sediment influenced by lakeside housing and finally littoral sediment influenced by the lake inflow. Sequential extractions were used to assess changes in P speciation. Depth profiles of dissolved porewater concentrations were obtained after LMB treatment at each site. Results indicate that SRP extracted from the sediments decreased at all sites, while total extracted P (PTOT) bound to redox-sensitive metal oxides increased. 31P NMR data on P extract reveals that 20-43% of total solid-phase P is in the form of organic P (Porg) susceptible to be released via microbial degradation. Geochemical modelling of porewater data provides evidence that LaPO4(s) mineral phases, such as rhabdophane and/or monazite, are likely forming. However, results also suggest that La3+ binding by dissolved organic carbon (DOC) hinders La-phosphate precipitation. We rely on thermodynamic modelling to suggest that high Fe2+ would bind to DOC instead of La3+, therefore promoting P sequestrations by LMB under anoxic conditions.

Combined remediation mechanism of bentonite and submerged plants on lake sediments by DGT technique.

The diffusive gradients in thin films (DGT) technique was applied to determine the mechanism by which bentonite improves the eutrophic lake sediment microenvironment and enhances submerged plant growth. The migration dynamics of N, P, S, and other nutrient elements were established for each sediment layer and the remediation effects of bentonite and submerged plants on sediments were evaluated. Submerged plant growth in the bentonite group was superior to that of the Control. At harvest time, the growth of Vallisneria spiralis and Hydrilla verticillata was optimal on a substrate consisting of five parts eutrophic lake sediment to one part modified bentonite (MB5/1). Bentonite addition to the sediment was conducive to rhizosphere microorganism proliferation. Microbial abundance was highest under the MB5/1 treatment whilst microbial diversity was highest under the RB1/1 (equal parts raw bentonite and eutrophic lake sediment) treatment. Bentonite addition to the sediment may facilitate the transformation of nutrients to bioavailable states. The TP content of the bentonite treatment was 22.47%-46.70% lower than that of the Control. Nevertheless, the bentonite treatment had higher bioavailable phosphorus (BIP) content than the control. The results of this study provide theoretical and empirical references for the use of a combination of modified bentonite and submerged plants to remediate eutrophic lake sediment microenvironments.

Reduction of U(VI) on Chemically Reduced Montmorillonite and Surface Complexation Modeling of Adsorbed U(IV).

Adsorption and subsequent reduction of U(VI) on Fe(II)-bearing clay minerals can control the mobility of uranium in subsurface environments. Clays such as montmorillonite provide substantial amounts of the reactive surface area in many subsurface environments, and montmorillonite-containing materials are used in the storage of spent nuclear fuel. We investigated the extent of reduction of U(VI) by Fe(II)-bearing montmorillonite at different pH values and sodium concentrations using X-ray absorption spectroscopy and chemical extractions. Nearly complete reduction of U(VI) to U(IV) occurred at a low sodium concentration at both pH 3 and 6. At pH 6 and a high sodium concentration, which inhibits U(VI) binding at cation-exchange sites, the extent of U(VI) reduction was only 70%. Surface-bound U(VI) on unreduced montmorillonite was more easily extracted into solution with bicarbonate than surface-bound U(IV) generated by reduction of U(VI) on Fe(II)-bearing montmorillonite. We developed a nonelectrostatic surface complexation model to interpret the equilibrium adsorption of U(IV) on Fe(II)-bearing montmorillonite as a function of pH and sodium concentration. These findings establish the potential importance of structural Fe(II) in low iron content smectites in controlling uranium mobility in subsurface environments.