Modification of ultrasound-pretreated montmorillonite using poly(diallyldimethylammonium chloride) for W and Mo separation and the sequential application in removal of heavy metals.

The use of a resin to selectively separate thiomolybdate from a tungsten (W) feed solution is a well-known protocol for achieve high-purity W products; however, the regeneration of saturated resin is laborious. In this study, poly(diallyl dimethyl ammonium chloride) (PDADMA) was used to modify ultrasound-pretreated montmorillonite (Mt) for W and molybdenum (Mo) separation for the first time, and the resultant tetrathiomolybdate (MoS42-)-loaded composite was further tested to remove heavy metals instead of regeneration. Among the three variables of ultrasound pretreatment, that is, Mt concentration, ultrasound power, and treatment time, the Mt concentration exhibited the most significant influence followed by ultrasound power on the separation performance of W and Mo. Compared to the distance of the interlayer space and the surface charge of the modified Mt, the PDADMA content showed a closer correlation with the W/Mo separation coefficient. Assisted by Box-Behnken design, with Mt concentration of 6.9 g/L, ultrasound power of 593.8 W, and treatment time of 13.8 min, the composite with the greatest separation coefficient was obtained. The adsorption of Cu(II) on the optimal W/Mo separation-derived composite was ascribed to the formation of Cu-S complexes, while that of Pb(II) was attributed to complexation and surface precipitation. In contrast, ion exchange with the initially loaded anions, reduction by sulfide to Cr(III), and formation of Cr(III)-S complexes accounted for Cr(VI) removal. The adsorption of Cu(II) and Pb(II) equilibrated faster and showed higher acid-resistance than that of Cr(VI). The adsorption capacities for Cu(II), Pb(II), and Cr(VI) were 0.535, 1.398, and 0.882 mmol/g, respectively. Applying PDADMA to modify Mt as a reagent for W/Mo separation was feasible, and the derived composite was capable of removing cationic and anionic heavy metals.

Grafting of R4N+-Bearing Organosilane on Kaolinite, Montmorillonite, and Zeolite for Simultaneous Adsorption of Ammonium and Nitrate.

Modification of aluminosilicate minerals using a R4N+-bearing organic modifier, through the formation of covalent bonds, is an applicable way to eliminate the modifier release and to maintain the ability to remove cationic pollutants. In this study, trimethyl [3-(trimethoxysilyl) propyl] ammonium chloride (TM) and/or dimethyl octadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DMO) were used to graft three aluminosilicate minerals, including calcined kaolinite (Kaol), montmorillonite (Mt), and zeolite (Zeol), and the obtained composites were deployed to assess their performance in regard to ammonium (NH4+) and nitrate (NO3-) adsorption. Grafting of TM and/or DMO had little influence on the crystal structures of Kaol and Zeol, but it increased the interlayer distance of Mt due to the intercalation. Compared to Kaol and Zeol, Mt had a substantially greater grafting concentration of organosilane. For Mt, the highest amount of loaded organosilane was observed when TM and DMO were used simultaneously, whereas for Kaol and Zeol, this occurred when only DMO was employed. 29Si-NMR spectra revealed that TM and/or DMO were covalently bonded on Mt. As opposed to NO3-, the amount of adsorbed NH4+ was reduced after TM and/or DMO grafting while having little effect on the adsorption rate. For the grafted Kaol and Zeol, the adsorption of NH4+ and NO3- was non-interfering. This is different from the grafted Mt where NH4+ uptake was aided by the presence of NO3-. The higher concentration of DMO accounted for the larger NO3- uptake, which was accompanied by improved affinity. The results provide a reference for grafting aluminosilicate minerals and designing efficient adsorbents for the co-adsorption of NH4+ and NO3-.

Synthesis of Fe3O4@Phoslock® composites and the application in adsorption of phosphate from aqueous solution.

Assisted with an organosilane, Fe3O4@Phoslock® composites with different constituents were synthesized to separate phosphate from aqueous solution. The experimental adsorption data of kinetics and isothermal studies by the composites were well fitted by pseudo-second order and Freundlich models, respectively, suggesting the chemical and heterogeneous adsorption process, i.e., ligand exchange and precipitation. After loading of Fe3O4, Phoslock® became magnetic at the expense of the certain decrease of phosphate uptake from 10.4 to 8.1 mg P/g when [P]0 = 1.0 mmol/L and the solid/liquid ratio of 1.0 g/L were applied. However, compared with the original Fe3O4 nanoparticles, Fe3O4@Phoslock® showed more favorable phosphate uptake and stability against pH variation. The inhibitory influence of anionic ions on phosphate adsorption by three composites followed the order: HCO3- > humate > SiO32- > NO3- ≈ Cl- ≈ SO42-, while the facilitating effect of cations followed the order: Ca2+ > Mg2+ > NH4+. The regeneration rate was higher than 50% for all composites after recycled for 5 times by NaOH, and two of the composites successfully removed 75% phosphate from the landfill leachate treated by the Anammox process with the solid/liquid ratio of 5.0 g/L. This suggests that Fe3O4@Phoslock® composites would be a competitive adsorbent for phosphate removal from real wastewater.

Immobilization of W(VI) and/or Cr(VI) in soil treated with montmorillonite modified by a gemini surfactant and tetrachloroferrate (FeCl4-).

The coexistence of highly toxic chromium (Cr) and the emerging contaminant tungsten (W) in the soil adjacent to W mining areas is identified. Immobilization of W and/or Cr is vital for the safe utilization of contaminated soil. In this study, the cationic gemini surfactant (butane-1,4-bis(dodecyl dimethyl ammonium bromide)) and tetrachloroferrate (FeCl4-)-modified montmorillonite (FeOMt) was applied to investigate the retention performance of W and/or Cr in the soil. Regardless of the initially spiked amount of WO42- and/or CrO42-, the W and/or Cr leached in soil solution was rapidly immobilized within 5 min. The immobilization rates of W and/or Cr in the single and binary soil systems were stably maintained against the variations in pH and coexisting anion. FeOMt showed more favorable performance in the retention of W and/or Cr with respect to the precursors (i.e., the original Mt and surfactant-modified Mt) and efficiently inhibited the phytotoxicity and bioaccumulation of W and/or Cr in mung beans. Due to the ion exchange, complexation, reduction, and flocculation, the addition of FeOMt transformed W and/or Cr from exchangeable/carbonate species to reducible/oxidizable fractions, reducing the environmental risk. FeCl4- complex, as a byproduct of the steel pickling process in industry, plays the pivotal role in the efficient retention of W and Cr. Based on the facile synthesis procedure and the efficient performance, the use of FeOMt for the amendment of W- and/or Cr-contaminated soil is feasible and promising.

Gemini surfactant-modified montmorillonite with tetrachloroferrate (FeCl4-) as a counterion simultaneously sequesters nitrate and phosphate from aqueous solution.

Alkyl quaternary ammonium-modified clay minerals, which are common environmentally friendly materials, have been widely studied and applied for the removal of pollutants. However, there are few reports on functionalizing the counterions to expand the application. In this study, the cationic gemini surfactant butane-1,4-bis(dodecyl dimethyl ammonium bromide) (gBDDA) and tetrachloroferrate (FeCl4-) are designed to modify montmorillonite (Mt), and the obtained FeCl4-/Gemini-Mt composite (FeOMt) is used for the removal of nitrate and/or phosphate from aqueous solution. The successful intercalation of gBDDA and favorable loading of FeCl4- into FeOMt are suggested by the characterization results of X-ray diffraction and Raman spectroscopy. Nitrate and/or phosphate are rapidly sequestered, and the respective maximum uptakes of 8.77 (N) and 28.1 (P) mg/g in the binary system are obtained. The phosphate uptake is stably maintained against many coexisting ions, but the nitrate uptake decreases with the increase in ionic strength. FeOMt is reusable and shows comparable uptake for nitrate and phosphate with respect to gBDDA-modified Mt and polymerized ferric chloride. Considering the multi-functionality and facile synthesis, FeOMt shows promising potential in the purification of wastewater contaminated simultaneously by poorly hydrated anions (e.g., ClO4-, TcO4-, etc.) and iron-selective anions (e.g., H2AsO4-, etc.).

Synergistic effect of ClO4- and Sr2+ adsorption on alginate-encapsulated organo-montmorillonite beads: Implication for radionuclide immobilization.

Perchlorate (ClO4-) and pertechnetate (TcO4-) exhibit similar adsorption characteristics on alkyl quaternary ammonium-modified montmorillonite (Mt), and 99mTcO4- normally coexists with 90Sr2+ in radionuclide-contaminated water. In this study, hexadecyl pyridinium (HDPy)-modified Mt (OMt) was encapsulated in alginate beads to inhibit HDPy release and simultaneously immobilize ClO4- and Sr2+ ions. The release of HDPy was remarkably reduced (78 times) from OMt after alginate encapsulation. Adsorption of ClO4- and Sr2+ on the obtained composite demonstrated synergistic effects, with adsorption capacities reaching 0.542 and 0.484 mmol/g, respectively. Compared to the single-adsorbate system, adsorption capacities of ClO4- and Sr2+ increased significantly. The characterization of solids using X-ray diffraction, Fourier transform infrared spectroscopy, 13C nuclear magnetic resonance, and X-ray photoelectron spectroscopy, as well as the chemical analysis of the aqueous solution, demonstrated that HDPy+-COO- disintegration accounted for the adsorption synergy. HDPy was extracted from the Mt interlayer space during the synthesis of OMt/alginate and then partially re-intercalated back after interacting with ClO4- during the adsorption of ClO4- and/or Sr2+. In the binary-adsorbate system, the synergy-induced adsorption capacity was superior to many previously reported adsorbents, implying that OMt/alginate beads can be a promising adsorbent for the remediation of aqueous solutions contaminated with multiple radionuclides.

Modeling the performance of Single-stage Nitrogen removal using Anammox and Partial nitritation (SNAP) process with backpropagation neural network and response surface methodology.

Two novel feedforward backpropagation Artificial Neural Networks (ANN)-based-models (8:NH:1 and 7:NH:1) combined with Box-Behnken design of experiments methodology was proposed and developed to model NH4+ and Total Nitrogen (TN) removal within an upflow-sludge-bed (USB) reactor treating nitrogen-rich wastewater via Single-stage Nitrogen removal using Anammox and Partial nitritation (SNAP) process. ANN were developed by optimizing network architecture parameters via response surface methodology. Based on the goodness-of-fit standards, the proposed three-layered NH4+ and TN removal ANN-based-models trained with Levenberg-Marquardt-algorithm demonstrated high-performance as computations exhibited smaller deviations-(±2.1%) as well as satisfactory coefficient of determination (R2), fractional variance-(FV), and index of agreement-(IA) ranging 0.989-0.997, 0.003-0.031 and 0.993-0.998, respectively. The computational results affirmed that the ANN architecture which was optimized with response surface methodology enhanced the efficiency of the ANN-based-models. Furthermore, the overall performance of the developed ANN-based models revealed that modeling intricate biological systems (such as SNAP) using ANN-based models with the view to improve removal efficiencies, establish process control strategies and optimize performance is highly feasible. Microbial community analysis conducted with 16S rRNA high-throughput approach revealed that Candidatus Kuenenia was the most pronounced genera which accounted for 13.11% followed by Nitrosomonas-(6.23%) and Proteocatella-(3.1%), an indication that nitrogen removal pathway within the USB was mainly via partial-nitritation/anammox process.

Performance, microbial community evolution and neural network modeling of single-stage nitrogen removal by partial-nitritation/anammox process.

Single-stage nitrogen removal by anammox/partial-nitritation (SNAP) process was proposed and explored in a packed-bed-EGSB reactor to treat nitrogen-rich wastewater. With dissolved oxygen (DO) maintained within 0.2-0.5 mg/L, reactor performance and microbial community dynamics were evaluated and reported. To ascertain whether control/prediction of the SNAP process was feasible with mathematical modeling, a novel 3-layered backpropagation-artificial-neural-network-(BANN) was also developed to model nitrogen removal efficiencies. When NLR of 300 gN/m3·d and DO of <0.3 mg/L was employed, the SNAP-process demonstrated autotrophic nitrogen removal pathways with NH4+-N and TN removal of 91.1% and 81.9%, respectively. Microbial community succession revealed by 16S rRNA high-throughput gene-sequencing indicated that Candidatus-Kuenenia-(33.83%), Nitrosomonas-(3.4%) Armatimonadetes_gp5-(1.39%), Ignavibacterium-(1.80%), Thiobacillus-(1.33%), and Nitrospira-(1.17%) were the most pronounced genera at steady-state. The proposed BANN-model demonstrated high-performance as computational results revealed smaller deviations (±3%) and satisfactory coefficient of determination-(R2 = 0.989), fractional variance-(FV = 0.0107), and index of agreement-(IA = 0.997). Thus, forecasting the efficiency of a SNAP-process with neural-network modeling was highly feasible.

Gemini surfactant: A novel flotation collector for harvesting of microalgae by froth flotation.

Froth flotation has been proved to be a promising approach for commercial scale harvesting of microalgae. However, all the surfactants used in the microalgae flotation harvesting process are conventional monomeric surfactants contain a single similar hydrophobic group in the molecule, which results in a low harvesting efficiency. In this work, a novel Gemini surfactant, N,N'-bis(cetyldimethyl)-1,4-butane diammonium dibromide (BCBD) was prepared, and originally recommended as a collector for froth flotation harvesting of Chlorella vulgaris from culture medium. The performance of BCBD was compared with the results acquired using its conventional monomeric surfactant cetyl trimethyl ammonium bromide (CTAB). The bench-scale flotation results showed that BCBD had excellent collecting power for Chlorella vulgaris. Achieving the obviously superior flotation harvesting performance (flotation recovery increased by 21.4% and enrichment ratio increased by 22.9), the dosage of Gemini type BCBD collector is five times less than that of monomeric CTAB collector.

Accelerated start-up, long-term performance and microbial community shifts within a novel upflow porous-plated anaerobic reactor treating nitrogen-rich wastewater via ANAMMOX process.

The anaerobic ammonium oxidation (anammox) process has gained much popularity in recent years following its success in nitrogen removal. However, not much has been reported on techniques to promote anammox bacteria immobilization and associated microbial community evolution. In this study, a novel upflow porous-plate anaerobic reactor (UPPAR) was developed and explored to promote biomass (anammox) retention and growth. To comprehend the performance of the UPPAR, its nitrogen removal efficiencies, as well as the microbial community dynamics involved in the nitrogen removal process, was evaluated and reported. When NLR ranging 0.98-1.08 kg m-3 d-1 was introduced at various stages of the UPPAR operation, a rapid start-up was achieved in 63 d, and the overall nitrogen removal rate could reach 90-95%. By the end of the start-up period, it was revealed that Proteobacteria abundance had reduced by 43.92% as opposed Planctomycetes which increased from 2.95% to 43.52%. Conversely, after the UPPAR had been operated for 124 d, thus at steady-state, the most pronounced phylum observed was Planctomycetes (43.52%) followed by Proteobacteria (26.63%), Chloroflexi (5.87%), Ignavibacteriae (5.55%), and Bacteroidetes (4.9%). Predominant genera observed included Candidatus Kuenenia - (25.46%) and Candidatus Brocadia - (3.15%), an indication that nitrogen removal mechanism within the UPPAR was mainly conducted via autotrophic anammox process. Scanning electron microscopy (SEM) revealed that sludge samples obtained at steady-state were predominantly in granular form with sizes ranging between 2 mm to 5 mm. Granules surfaces were dominated with normal to coccoid-shaped cells as revealed by the SEM.

Microwave/ultrasound-assisted modification of montmorillonite by conventional and gemini alkyl quaternary ammonium salts for adsorption of chromate and phenol: Structure-function relationship.

Butane-1,4-bis(dodecyl dimethyl ammonium bromide) (gBDDA) and dodecyl trimethyl ammonium bromide (DTMA) in same stoichiometric amounts were applied to modify montmorillonite (Mt) under microwave and ultrasound conditions. The composition and structure of products were obtained through multiple characterizations including XRD, FTIR, TG/DTG, SEM, TEM, and N2 adsorption/desorption measurements, and the adsorption performance of chromate and phenol on these products were also investigated. Intercalations of gBDDA and DTMA into interlayer space of Mt were observed, but the amount of anchored modifier on the external surface was larger for gBDDA compared with DTMA when the stoichiometric amount of modifier larger than 1.0 times cation exchange capacity of Mt was added. Although there was no significant difference in morphology among products, the interlayer space distance, specific surface area, and pore size distribution were closely associated with the species and amount of applied modifier. Adsorption of phenol on products through partition mechanism relied on not only organic content, but also the configuration of modifier. Meanwhile, adsorption of chromate mainly depended on the presence of counter ion (bromide), which accounted for the high adsorption capacity and initial adsorption rate on gOMt-0.75. The fitting parameters of adsorption results using pseudo-second order model and Freundlich model suggested that gBDDA-modified Mt could sequester phenol or chromate in the faster manner with higher affinity. Compared with the conventional surfactant such as DTMA, the study revealed that, using gemini surfactant such as gBDDA to modify Mt would significantly reduce or even has the potential to eradicate the secondary pollution by modifier release during adsorption process. This study provides a new direction for Mt modification intended to be used as adsorbents to treat polluted water with high standards such as drinking water.