Removal and recovery of toxic nanosized Cerium Oxide using eco-friendly Iron Oxide Nanoparticles

• Eco-friendly IONPs were synthesized through solvothermal method. • IONPs show very high removal efficiency for CeO₂ NPs i.e. 688 mg/g. • Removal was >90% in all synthetic and real water samples. • >80% recovery of CeO₂ NPs through sonication confirms reusability of IONPs. Increasing applications of metal oxide nanoparticles and their release in the natural environment is a serious concern due to their toxic nature. Therefore, it is essential to have eco-friendly solutions for the remediation of toxic metal oxides in an aqueous environment. In the present study, eco-friendly Iron Oxide Nanoparticles (IONPs) are synthesized using solvothermal technique and successfully characterized using scanning and transmission electron microscopy (SEM and TEM respectively) and powder X-Ray diffraction (PXRD). These IONPs were further utilized for the remediation of toxic metal oxide nanoparticle, i.e., CeO₂. Sorption experiments were also performed in complex aqueous solutions and real water samples to check its applicability in the natural environment. Reusability study was performed to show cost-effectiveness. Results show that these 200 nm-sized spherical IONPs, as revealed by SEM and TEM analysis, were magnetite (Fe₃O₄) and contained short-range crystallinity as confirmed from XRD spectra. Sorption experiments show that the composite follows the pseudo-second-order kinetic model. Further R²>0.99 for Langmuir sorption isotherm suggests chemisorption as probable removal mechanism with monolayer sorption of CeO₂ NPs on IONP. More than 80% recovery of adsorbed CeO₂ NPs through ultrasonication and magnetic separation of reaction precipitate confirms reusability of IONPs. Obtained removal % of CeO₂ in various synthetic and real water samples was>90% signifying that IONPs are candidate adsorbent for the removal and recovery of toxic metal oxide nanoparticles from contaminated environmental water samples.     

Utilizing transparent and conductive SnO2 as electron mediator to enhance the photocatalytic performance of Z-scheme Si-SnO2-TiOx

• A novel Z-scheme Si-SnO₂-TiO_x with SnO₂ as electron mediator is first constructed. • Transparent and conductive SnO₂ can pass light through and promote charge transport. • V_O from SnO₂ and TiO_x improve photoelectrochemical performances. • Efficient photocatalytic degradations originate from the Z scheme construction. Z-scheme photocatalysts, with strong redox ability, have a great potential for pollutants degradation. However, it is challenging to construct efficient Z-scheme photocatalysts because of their poor interfacial charge separation. Herein, by employing transparent and conductive SnO₂ as electron mediator to pass light through and promote interfacial charge transportation, a novel Z-scheme photocatalyst Si-SnO₂-TiO_{x (1<x<2)} was constructed. The Z-scheme photocatalyst displayed an order of magnitude higher photocurrent density and a 4-fold increase in open-circuit potential compared to those of Si. Moreover, the onset potential shifted negatively for approximately 2.2 V. Benefiting from these advantages, this Z-scheme Si-SnO₂-TiO_x exhibited efficient photocatalytic performance toward phenol degradation and mineralization. 75% of the phenol was degraded without bias potential and 70% of the TOC was removed during phenol degradation. Other typical pollutants such as bisphenol A and atrazine could also be degraded without bias potential. Introducing a transparent and conductive electron mediator to construct Z-scheme photocatalyst gives a new sight to the improvement of photocatalytic performance in Z scheme.     

(Super)paramagnetic nanoparticles as platform materials for environmental applications: From synthesis to demonstration

• The fabrication of monodisperse, (super)paramagnetic nanoparticles is summarized. • Monolayer and bilayer surface coating structures are described. • Mono/bilayer coated nanoparticles showed high sorption capacities for U, As, and Cr. Over the past few decades, engineered, (super)paramagnetic nanoparticles have drawn extensive research attention for a broad range of applications based on their tunable size and shape, surface chemistries, and magnetic properties. This review summaries our recent work on the synthesis, surface modification, and environmental application of (super)paramagnetic nanoparticles. By utilizing high-temperature thermo-decomposition methods, first, we have broadly demonstrated the synthesis of highly monodispersed, (super)paramagnetic nanoparticles, via the pyrolysis of metal carboxylate salts in an organic phase. Highly uniform magnetic nanoparticles with various size, composition, and shape can be precisely tuned by controlled reaction parameters, such as the initial precursors, heating rate, final reaction temperature, reaction time, and the additives. These materials can be further rendered water stable via functionalization with surface mono/bi-layer coating structure using a series of tunable ionic/non-ionic surfactants. Finally, we have demonstrated platform potential of these materials for heavy metal ions sensing, sorption, and separation from the aqueous phase.     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

Synthesis of core-shell magnetic molecular imprinted polymer by the surface RAFT polymerization for the fast and selective removal of endocrine disrupting chemicals from aqueous solutions

In this study, we present a general protocol for the making of surface-imprinted core-shell magnetic beads via reversible addition-fragmentation chain transfer (RAFT) polymerization using RAFT agent functionalized iron oxide nanoparticles as the chain transfer agent. The resulting composites were characterized by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface-imprinted magnetic beads were demonstrated with a homogeneous polymer films (thickness of about 22 nm), spherical shape, and exhibited magnetic property (Ms = 0.41 mA m² g⁻¹) and thermal stability. Rebinding experiments were carried out to determine the specific binding capacity and selective recognition. The as-synthesized surface-imprinted core-shell magnetic beads showed outstanding affinity and selectivity towards bisphenol A over structurally related compounds, and easily reach the magnetic separation under an external magnetic field. In addition, the resulting composites reusability without obviously deterioration in performance was demonstrated at least five repeated cycles.     

几种典型红壤模拟降雨条件下的泥沙特征研究

泥沙是土壤侵蚀过程的产物,直接反映了土壤的侵蚀特征。本文利用人工模拟降雨,研究了南方几种典型母质发育红壤侵蚀泥沙的颗粒分布特征、不同粒级中胶结物质的种类和含量。研究结果表明,径流优先选择携带0.002~0.02 mm颗粒,该级别颗粒占泥沙总量的26.68%~60.33%。粘粒含量高的第四纪粘土红壤,泥沙中粗颗粒含量较高,且多为较稳定的团聚体;沙粒和粉粒含量较高的页岩红壤和花岗岩红壤侵蚀泥沙中单粒含量较高,且泥沙分散后粉粒和粘粒的含量高于原土壤。花岗岩红壤侵蚀泥沙中Fe_d,Al_d,Al_o和Si_o含量随泥沙粒径的增大而降低,而泥质页岩红壤和第四纪粘土红壤中,Fe_d,Al_d,Al_o含量随粒径增大而增加,因此其粗粒径泥沙具有较强的稳定性。侵蚀泥沙对有机质有富集作用,泥质页岩红壤和第四纪粘土红壤的粗颗粒对有机质的富集作用强于细颗粒。     

Silica nanoparticles and silver-doped silica nanoparticles induce endoplasmatic reticulum stress response and alter cytochrome P4501A activity

Engineered silica nanoparticles (SiO₂-NPs) find widespread application and may lead to exposure of humans and the environment. Here we compare the effects of SiO₂-NPs and SiO₂-NPs doped with silver (SiO₂-Ag-NPs) on survival and cellular function of human liver cells (Huh7) and Pimephales promelas (fathead minnow) fibroblast cells (FMH). In Huh7 cells we investigate effects on the endoplasmatic reticulum (ER), including ER stress, and interactions of nanoparticles (NPs) with metabolizing enzymes and efflux transporters. The NPs formed agglomerates/aggregates in cell culture media as revealed by SEM and TEM. SiO₂ and SiO₂-1% Ag-NPs were taken up into cells as demonstrated by agglomerates occurring in vesicular-like structures or freely dispersed in the cytosol. Cytotoxicity was more pronounced in Huh7 than in FMH cells, and increased with silver content in silver-doped NPs. Dissolved silver was the most significant factor for cytotoxicity. At toxic and non-cytotoxic concentrations SiO₂-NPs and SiO₂-1% Ag-NPs induced perturbations in the function of ER. In Huh7 cells NPs induced the unfolded protein response (UPR), or ER stress response, as demonstrated in induced expression of BiP and splicing of XBP1 mRNA, two selective markers of ER stress. Additionally, SiO₂-1% Ag-NPs and AgNO₃ induced reactive oxygen species. Pre-treatment of Huh7 cells with SiO₂-1% Ag-NPs followed by exposure to the inducer benzo(a)pyrene caused a significant reduced induction of CYP1A activity. NPs did not alter the activity of ABC transporters. These data demonstrate for the first time that SiO₂-NPs and SiO₂-1% Ag-NPs result in perturbations of the ER leading to the ER stress response. This represents a novel and significant cellular signalling pathway contributing to the cytotoxicity of NPs.     

Formation of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) from a refinery process for zinc oxide used in feed additives: a source of dioxin contamination in Chilean pork

The Republic of Korea found dioxin at concentrations exceeding the Korean maximum residue limit (MRL) in pork (2 pg TEQ g⁻¹ fat) imported from Chile in June 2008. Korea and Chile collaborated and investigated to find out the sources of contamination. An isotope dilution method and high resolution gas chromatography/mass spectrometry (HR-GC/MS) were used for the analysis of PCDD/Fs. PCDD/Fs were found from 2.17 to 36.7 pg TEQ g⁻¹ fat from Chilean pork. 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF were found as the major congeners in pork samples. 2,3,4,7,8-PeCDF showed the highest concentration and contributed about 30% among the congeners in most of the samples. 2,3,7,8-TCDD, 1,2,3,7,8,9-HxCDD, OCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 1,2,3,7,8,9-HxCDF, and OCDF were not detected or exist at background levels in the less contaminated samples. Remarkably high concentrations of PCDD/Fs were found in samples of zinc oxide (17 147 pg TEQ g⁻¹), zinc oxide based premix (6673 pg TEQ g⁻¹), and the residue crust (800 pg TEQ g⁻¹) in a mixing chamber in the feed mill. From the results of various investigations, this case concluded that zinc oxide in the feed was the major source of the dioxin contamination in pork. The dioxins were formed from a metal refinery process to collect zinc oxide.     

Ozone-enhanced catalytic oxidation of monochlorobenzene over iron oxide catalysts

In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O₃ over Fe₂O₃ in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O₃ concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe₂O₃ in the absence of O₃ was only 3%; it increased to 91% over Fe₂O₃ in the presence of 1200 ppm of O₃ at a high SV of 83 s⁻¹. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol⁻¹ for MCBz oxidation over Fe₂O₃ in the presence of O₃.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.