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.

Risk assessment of heavy metals in agricultural soil based on the coupling model of Monte Carlo simulation-triangular fuzzy number.

Soils in areas wherein agriculture and mining coexist are experiencing serious heavy metal contamination, posing a great threat to the ecological environment and human health. In this study, heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) in agricultural soil samples from mining areas were analyzed to explore pollution status, bioavailability, potential sources, and ecological/health risks. Particularly, the coupling model of Monte Carlo simulation-triangular fuzzy number (MCS-TFN) was established to quantify ecological/health risks accurately. Results showed that Cd was heavily enriched in soil and had the highest bioavailability based on both geo-accumulation index (Igeo) and chemical speciation analysis. Pollution sources apportioned with the absolute principal component score-multiple linear regression (APCS-MLR) model demonstrated that heavy metals were mainly derived from agricultural activities, followed by mining activities and natural sources. The MCS-TFN ecological risk assessment classified Cd into the high-risk category with a probability of 40.96%, whereas other heavy metals were categorized as the low risk. Cd was regarded as the major pollutant for the ecosystem. Moreover, the MCS-TFN health risk assessment indicated that As showed high noncarcinogenic risk (0.07% probability) and moderate carcinogenic risk (1.87% probability), and Cd presented low carcinogenic risk (80.19% probability). As and Cd were identified as the main heavy metals that pose a threat to human health. The MCS-TFN risk assessment is superior to the traditional deterministic risk assessment since it can obtain the risk level and the corresponding probability, and significantly reduce the uncertainty in risk assessment.

Degradation of malachite green by g-C3N4-modified magnetic attapulgite composites under visible-light conditions.

Water resources are seriously threatened by dye wastewater, and the removal of the dye molecules from the wastewater has garnered considerable interest. People have favored photocatalytic technology in recent years for the treatment of dye wastewater. In this work, attapulgite (ATP) was used as a carrier, Fe3O4 and g-C3N4 were grafted onto ATP, and the surface was then modified with polyethyleneimine (PEI) to produce photocatalyst ATP-Fe3O4-g-C3N4-PEI, which was used in Malachite green (MG) dye wastewater. The structure and surface properties of the composites were analyzed and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray spectrum (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Uv-vis spectrum analysis, zeta potential measurement, and vibrating-sample magnetometry (VSM) analysis. The removal performance of ATP-Fe3O4-gC3N4-PEI for MG was studied, and the removal mechanism was explored and revealed. It has been shown that the heterojunction formed by Fe3O4 and g-C3N4 can inhibit the compounding of photogenerated electrons and holes, effectively improving the performance of the ATP-Fe3O4-g-C3N4-PEI. Electron paramagnetic resonance (EPR) analysis confirmed that ATP-Fe3O4-g-C3N4-PEI could generate hydroxyl radicals (·OH) and superoxide radicals (·O2-) to degrade the MG. It was believed that ATP-Fe3O4-g-C3N4-PEI could generate hydroxyl radicals (·OH) through the photocatalysis and the Fenton reaction of the composite materials. Under the action of H+, ·O2-, and ·OH, the removal rate of MG by ATP-Fe3O4-g-C3N4-PEI exceeded 98 % at an optimal condition. The intermediate products and degradation pathways of MG degradation were also inferred by LC-MS analysis. These results showed that the prepared photocatalyst has excellent degradation performance for MG and could be used in dye wastewater treatment.

Contamination, Source Apportionment, and Health Risk Assessment of Heavy Metals in Farmland Soils Surrounding a Typical Copper Tailings Pond.

Tailings resulting from mining and smelting activities may cause soil heavy-metal pollution and harm human health. To evaluate the environmental impact of heavy metals from tailings on farmland soils in the surrounding area, heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) in tailings and farmland soils in the vicinity of a typical copper tailings pond were analyzed. Contamination status, potential sources, and health risks for farmland soils were investigated. The results showed that the tailings contained a high concentration of Cu (1136.23 mg/kg). The concentrations of Cd and Cu in the farmland soils exceeded the soil quality standard. The geoaccumulation index (Igeo) indicated that the soils were moderately polluted by Cu and Cd, and slightly polluted by Ni, Cr, and Zn. The absolute principal component scores-multiple linear regression (APCS-MLR) model was applied for source apportionment. The results showed that tailings release is the main source of soil heavy-metals contamination, accounting for 35.81%, followed by agricultural activities (19.41%) and traffic emission (16.31%). The health risk assessment suggested that the children in the study region were exposed to non-carcinogenic risks caused by As, while the non-carcinogenic risk to adults and the carcinogenic risk to both adults and children were at acceptable levels. It is necessary to take effective measures to control heavy-metal contamination from tailings releases to protect humans, especially children, from adverse health risks.

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.

[Preparation of Functional Attapulgite Composite and Its Adsorption Behaviors for Congo Red].

Heavy metal ion wastewater poses a serious threat to human health and the environment. The adsorption method is an important method to remove heavy metal ions from heavy metal wastewater. Magnetic attapulgite (ATP) composite nanomaterials with excellent adsorption properties were prepared by grafting the Fe3O4 nanoparticles and using 3-aminopropyl triethoxy silane (APTES) modification. The prepared ATP-Fe3O4-APTES materials were used as adsorbents and applied to the treatment of heavy metal ion wastewater. The structure and surface properties of the materials were characterized by FT-IR, XRD, SEM, TEM, and BET characterization, Zeta potential, and VSM. The effects of pH, adsorption time, adsorption temperature, and initial concentration of Pb2+ on the adsorption properties of the ATP-Fe3O4-PEI materials were investigated. The results show that the maximum adsorption capacity of the materials for Pb2+ was 129.32 mg·g-1 under optimum conditions. The adsorption process conformed to the pseudo second order kinetic model and Langmuir adsorption isotherm, which indicates that the adsorption of Pb2+ is a monolayer chemical adsorption and a spontaneous endothermic process. The driving force of adsorption mainly comes from the coordination between the amino group (-NH2) on the ATP-Fe3O4-APTES surface and Pb2+. These results indicate that the functionalized magnetic attapulgite adsorbent has good adsorption properties for heavy metal ions and is expected to be used in the treatment of heavy metal ion 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.

Highly Efficient and Thermally Stable Eu2+-Doped Ca9Nd(PO4)7 Phosphor for Near-Ultraviolet White-Emission LED Applications.

Various Eu2+-based Ca9Nd(PO4)7 (CNP:xEu2+, with different x values) materials are prepared via facile solid-state reaction. Their crystal structures are investigated in detail by means of the Rietveld refinement. The structure of CNP:Eu2+ with a trigonal lattice is analogous to that of ß-Ca3(PO4)2. Therefore, Eu2+ ions tend to incorporate calcium sites in the host. All the obtained samples can be excited using near ultraviolet (nUV) light to present blue-green emission. An optimal dopant concentration is verified at x = 0.8 with a large critical interaction radius (11.21 Å). The mechanism of the concentration quenching effect is assigned to the multipole-multipole interaction. CNP:xEu2+ possesses a short decay lifetime of ∼60 µs and can endure severe working conditions thanks to its great thermal stability. The relative photoluminescence (PL) intensity of CNP:0.8Eu2+ can retain 84.75% of the pristine intensity measured at room temperature, and the relative intensity remains as high as 69.97% at 423 K. The CNP:Eu2+ phosphors also show great performance in the WLED demonstration. The correlated color temperature (CCT) of the prototype device is 3404 K, with an extremely high Ra (97.6). Therefore, CNP:xEu2+ could be regarded as a promising alternative to blue green phosphors in nUV chip-based WLED applications.

Compatibility of Photoluminescence Properties in ScPO4:Eu3+, Tb3+ Phosphor for White Light Emitting Diodes.

ScPO4:Eu3+, Tb3+ phosphors with tuned emission color were prepared through high temperature solid-state reaction. The structure, morphology and photoluminescence properties of the title samples were collected by XRD, SEM and fluorescence spectrophotometer, respectively. Co-doping Eu3+ and Tb3+ in ScPO4 does not change the body-centered tetragonal structure of the host. And the morphology remains essentially unchanged except for slight agglomeration. Changing the ratio of Tb3+/Eu3+, the tuned emission can be achieved, the color could be adjusted from green through yellow to orange-red. The ScPO4:0.03Tb3+, 0.03Eu3+ phosphor with high thermal stability as the single matrix phosphor can be suitable for the NUV-pumped white LED. The white LED with a color rendering index of 86.5 and a correlated color temperature of 3470 K has been generated by packaging BAM:Eu2+ with ScPO4:0.03Tb3+, 0.03Eu3+ on an NUV-InGaN chip.

Adsorption behavior and mechanism of Serratia marcescens for Eu(III) in rare earth wastewater.

Directly discharging low-concentration rare-earth wastewater not only wastes rare-earth resources but also pollutes the environment. In this study, the biosorption behavior of Serratia marcescens for Eu(III) was studied with emphasis on the optimization of adsorption conditions, adsorption kinetics, and adsorption isotherm. It was shown that the maximum adsorption capacity of Serratia marcescens reached 115.36 mg·g-1 under an optimal condition, indicating the good adsorption capability of Serratia marcescens for Eu(III). The adsorption kinetics and adsorption isotherm analysis showed that the adsorption process conforms to the pseudo-second-order kinetic model and Langmuir adsorption isotherm, indicating that the adsorption of Eu(III) by Serratia marcescens is a monolayer chemical adsorption process. In addition, the adsorption mechanism was investigated by using characterizations of zeta potential, scanning electron microscope-energy dispersive spectrometer (SEM-EDS), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses. It was revealed that the adsorption of Eu(III) by S. marcescens is a combination of electrostatic attraction, ions exchange and coordination. These findings indicate that S. marcescens can be used as a potential biosorbent to recover rare earth elements from rare earth wastewater.

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.).

Facile preparation of chitosan modified magnetic kaolin by one-pot coprecipitation method for efficient removal of methyl orange.

Chitosan modified magnetic kaolin (CS/kaolin/Fe3O4) composite was prepared by a facile one-pot coprecipitation method and used for the removal of methyl orange (MO) from aqueous medium. Under alkaline condition, Fe3O4 nanoparticles were deposited on the kaolin layer by in-situ growth method and chitosan was deposited on the kaolin layer by pH-precipitation method. With the modification of CS, adsorption sites for anionic species were introduced onto the adsorbent. The prepared CS/kaolin/Fe3O4 could remove more than 94 % of MO and showed a high saturated adsorption capacity of 349.7 mg/g. The adsorption process was controlled by film diffusion and well described by Langmuir model. The thermodynamic studies indicated that the adsorption process was exothermic in nature. Furthermore, the adsorbent exhibited satisfactory recycle ability. The results suggested that the modification with CS broadened the application scope of kaolin in anionic species removal and the CS/kaolin/Fe3O4 composite could be a promising adsorbent for wastewater treatment.

Preparation and tribological study of a peptide-containing alkylsiloxane monolayer on silicon.

A peptide-containing alkylsilane self-assembled monolayer on silicon surface has been prepared successfully by a simple one-step strategy. The formation and structure of the peptide-containing SAMs were characterized by means of contact angle measurement, ellipsometry, FT-IR, and AFM morphology observation. It was found that the water content in the hydrolysis solution plays a key role in determining the quality of the monolayers. The micro-tribological properties of various films were evaluated by using AFM, while the macro-tribological study was performed on a ball-on-plate tribometer. It was found that the peptide-containing monolayers possess excellent friction-reduction and antiwear ability, which was attributed to its amide-containing structure. In other words, the interchain hydrogen bonds among the molecules enhance the stability of the monolayers against rubbing the counterpart ball and thus endow it an outstanding antiwear ability.

Preparation and tribological studies of C60 thin film chemisorbed on a functional polymer surface.

A novel self-assembled C60 film was prepared by chemical adsorption of C60 molecules onto an amino-group-containing polyethyleneimine-coated silicon substrate surface. The contact angle of distilled water on the C60 film was measured, the thickness was determined by means of ellipsometric analysis, and the morphology was observed with an atomic force microscope. The tribological properties of the films were investigated as well. It was found that the C60 thin film had a contact angle of about 72 degrees and thickness of 1.8 nm and exhibited a surface domain microstructure composed of fullerene clusters. Due to the hydrophobicity and low surface energy, the C60 film possessed good adhesive resistance and had an adhesive force of about 7.1 nN, which was about an order of magnitude lower than that of the silicon substrate surface. Moreover, the C60 film showed good friction reduction, load-carrying capacity, and antiwear ability, which were attributed to the higher mechanical stiffness and elastic modulus of C60 molecules. Besides, the friction coefficient decreased with increasing sliding velocity and normal loads, due to the rolling effect of the physisorbed C60 molecules.