Xiaohong Guan

The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures: the development in zero-valent iron technology in the last two decades (1994-2014).

Over the past 20 years, zero-valent iron (ZVI) has been extensively applied for the remediation/treatment of groundwater and wastewater contaminated with various organic and inorganic pollutants. Based on the intrinsic properties of ZVI and the reactions that occur in the process of contaminants sequestration by ZVI, this review summarizes the limitations of ZVI technology and the countermeasures developed in the past two decades (1994-2014). The major limitations of ZVI include low reactivity due to its intrinsic passive layer, narrow working pH, reactivity loss with time due to the precipitation of metal hydroxides and metal carbonates, low selectivity for the target contaminant especially under oxic conditions, limited efficacy for treatment of some refractory contaminants and passivity of ZVI arising from certain contaminants. The countermeasures can be divided into seven categories: pretreatment of pristine ZVI to remove passive layer, fabrication of nano-sized ZVI to increase the surface area, synthesis of ZVI-based bimetals taking advantage of the catalytic ability of the noble metal, employing physical methods to enhance the performance of ZVI, coupling ZVI with other adsorptive materials and chemically enhanced ZVI technology, as well as methods to recover the reactivity of aged ZVI. The key to improving the rate of contaminants removal by ZVI and broadening the applicable pH range is to enhance ZVI corrosion and to enhance the mass transfer of the reactants including oxygen and H(+) to the ZVI surface. The characteristics of the ideal technology are proposed and the future research needs for ZVI technology are suggested accordingly.

Application of titanium dioxide in arsenic removal from water: A review

Natural arsenic pollution is a global phenomenon and various technologies have been developed to remove arsenic from drinking water. The application of TiO(2) and TiO(2)-based materials in removing inorganic and organic arsenic was summarized. TiO(2)-based arsenic removal methods developed to date have been focused on the photocatalytic oxidation (PCO) of arsenite/organic arsenic to arsenate and adsorption of inorganic and organic arsenic. Many efforts have been taken to improve the performance of TiO(2) by either combing TiO(2) with adsorbents with good adsorption property in one system or developing bifunctional adsorbents with both great photocatalytic ability and high adsorption capacity. Attempts have also been made to immobilize fine TiO(2) particles on supporting materials like chitosan beads or granulate it to facilitate its separation from water. Among the anions commonly exist in groundwater, humic acid and bicarbonate have significant influence on TiO(2) photocatalyzed oxidation of As(III)/organic arsenic while phosphate, silicate, fluoride, and humic acid affect arsenic adsorption by TiO(2)-based materials. There has been a controversy over the TiO(2) PCO mechanisms of arsenite for the past 10 years but the adsorption mechanisms of inorganic and organic arsenic onto TiO(2)-based materials are relatively well established. Future needs in TiO(2)-based arsenic removal technology are proposed.

Removal of arsenic from water: Effects of competing anions on As(III) removal in KMnO4–Fe(II) process

Effects of sulfate, phosphate, silicate and humic acid (HA) on the removal of As(III) in the KMnO(4)-Fe(II) process were investigated in the pH range of 4-9 with permanganate and ferrous sulfate applied at selected dosage. Sulfate decreased the removal of arsenic by 6.5-36.0% at pH 6-9 and the decrease in adsorption did not increase with increasing concentration of sulfate from 50 to 100mg/L. In the presence of 1mg/L phosphate, arsenic removal decreased gradually as pH increased from 4 to 6, and a sharp drop occurred at pH 7-9. The presence of 10mg/L silicate had negligible effect on arsenic removal at pH 4-5 whereas decreased the arsenic removal at pH 6-9 and the decrease was more significant at higher pH. The presence of HA dramatically decreased the arsenic removal over the pH range of 6-9 and HA of higher concentration resulted in greater drop in arsenic removal. The effects of the competing anions on arsenic removal in the KMnO(4)-Fe(II) process were highly dependent on pH and the degree of these four anions influencing As(III) removal decreased in the following order, phosphate>humic acid>silicate>sulfate. Sulfate differed from the other three anions because sulfate decreased the removal of arsenic mainly by competitive adsorption while phosphate, silicate and HA decreased the removal of As(III) by competitive adsorption and sequestering the formation of ferric hydroxide derived from Fe(II).

Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron.

The kinetics of Se(IV) removal by zero valent iron (ZVI) open to the air as a function of pH and the involved mechanisms were investigated in this study. The specific rate constants of Se(IV) removal by ZVI decreased from 92.87 to 6.87 L h(-1) m(-2) as pH increased from 4.0 to 7.0. The positive correlation between the removal rate of Se(IV) and the generation rate of Fe(II) and the depression of Se(IV) removal in the presence of 1,10-phenanthroline indicated that both ZVI and adsorbed Fe(II) on ZVI surface contributed to the reductive removal of Se(IV). The soft X-ray STXM measurement confirmed the adsorption of Fe(II) on the surface of ZVI and freshly formed ferric (hydr)oxides. Se(IV) was removed by adsorption followed by reduction to Se(0) on ZVI surface at pH 4.0-7.0, as revealed by XANES spectra. A core-shell structure was observed when ZVI reacted with Se(IV)-containing solution for 3 h at pH 6.0. Se(IV) was reduced to Se(0) and co-precipitated with the freshly formed Fe(III), forming the shell surrounding the iron core. After reaction for 24 h, the generated Se(0) was surrounded by multiple layers of Fe(III) oxides/hydroxides. SEM images and XRD patterns revealed that the corrosion products of ZVI at pH 6.0 transformed from amorphous iron hydroxides to lepidocrocite (γ-FeOOH) as reaction proceeded. The final corrosion products of ZVI contained both lepidocrocite and goethite at pH 5.0 while they were X-ray amorphous at pH 4.0 and 7.0.

Magnetic Metal–Organic Frameworks: γ‐Fe2O3@MOFs via Confined In Situ Pyrolysis Method for Drug Delivery

A general one-step in situ pyrolysis route for the construction of metal-organic frameworks encapsulating superparamagnetic γ-Fe2O3NPs dispersed in the confined cavities of MOFs homogeneously is described. The integration of γ-Fe2O3 NPs or clusters into MOFs can endow these porous materials with superparamagnetic element. By the combination of the thermal stability of MOFs and pyrolysis of metal triacetylacetonate complex at matched conditions, the porous structure of MOFs are well maintained while the size-induced superparamagnetic property of nano γ-Fe2O3 is obtained. As a proof of concept, both the γ- Fe2O3@ZIF-8 and γ-Fe2O3@MIL-53(Al) were successfully prepared, and the latter was chosen to demonstrate its potential drug delivery as a magnetic MOF.

Activating persulfate by Fe0 coupling with weak magnetic field: Performance and mechanism

Weak magnetic field (WMF) and Fe(0) were proposed to activate PS synergistically (WMF-Fe(0)/PS) to degrade dyes and aromatic contaminants. The removal rates of orange G (OG) by WMF-Fe(0)/PS generally decreased with increasing initial pH (3.0-10.0) and increased with increasing Fe(0) (0.5-3.0 mM) or PS dosages (0.5-3.0 mM). Compared to its counterpart without WMF, the WMF-Fe(0)/PS process could induce a 5.4-28.2 fold enhancement in the removal rate of OG under different conditions. Moreover, the application of WMF significantly enhanced the decolorization rate and the mineralization of OG. The degradation rates of caffeine, 4-nitrophenol, benzotriazole and diuron by Fe(0)/PS were improved by 2.1-11.1 fold due to the superimposed WMF. Compared to many other sulfate radical-based advanced oxidation technologies under similar reaction conditions, WMF-Fe(0)/PS technology could degrade selected organic contaminants with much greater rates. Sulfate radical was identified to be the primary radical species responsible for the OG degradation at pH 7.0 in WMF-Fe(0)/PS process. This study unraveled that the presence of WMF accelerated the corrosion rate of Fe(0) and thus promoted the release of Fe(2+), which induced the increased production of sulfate radicals from PS and promoted the degradation of organic contaminants. Employing WMF to enhance oxidation capacity of Fe(0)/PS is a novel, efficient, promising and environmental-friendly method since it does not need extra energy and costly reagents.

Coupled Effects of Aging and Weak Magnetic Fields on Sequestration of Selenite by Zero-Valent Iron

The sequestration of Se(IV) by zero-valent iron (ZVI) is strongly influenced by the coupled effects of aging ZVI and the presence of a weak magnetic field (WMF). ZVI aged at pH 6.0 with MES as buffer between 6 and 60 h gave nearly constant rates of Se(IV) removal with WMF but with rate constants that are 10- to 100-fold greater than without. XANES analysis showed that applying WMF changes the mechanism of Se(IV) removal by ZVI aged for 6-60 h from adsorption followed by reduction to direct reduction. The strong correlation between Se(IV) removal and Fe2+ release suggests direct reduction of Se(IV) to Se(0) by Fe0, in agreement with the XANES analysis. The numerical simulation of ZVI magnetization revealed that the WMF influence on Se(IV) sequestration is associated mainly with the ferromagnetism of ZVI and the paramagnetism of Fe2+. In the presence of the WMF, the Lorentz force gives rise to convection in the solution, which narrows the diffusion layer, and the field gradient force, which tends to move paramagnetic ions (esp. Fe2+) along the higher field gradient at the ZVI particle surface, thereby inducing nonuniform depassivation and eventually localized corrosion of the ZVI surface.

Effect of weak magnetic field on arsenate and arsenite removal from water by zerovalent iron: an XAFS investigation.

In this study, a weak magnetic field (WMF), superimposed with a permanent magnet, was utilized to improve ZVI corrosion and thereby enhance As(V)/As(III) removal by ZVI at pHini 3.0-9.0. The experiment with real arsenic-bearing groundwater revealed that WMF could greatly improve arsenic removal by ZVI even in the presence of various cations and anions. The WMF-induced improvement in As(V)/As(III) removal by ZVI should be primarily associated with accelerated ZVI corrosion, as evidenced by the pH variation, Fe(2+) release, and the formation of corrosion products as characterized with X-ray absorption fine structure spectroscopy. The arsenic species analysis in solution/solid phases at pHini 3.0 revealed that As(III) oxidation to As(V) in aqueous phase preceded its subsequent sequestration by the newly formed iron (hydr)oxides. However, both As(V) adsorption following As(III) oxidation to As(V) in solution and As(III) adsorption preceding its conversion to As(V) in solid phase were observed at pHini 5.0-9.0. The application of WMF accelerated the transformation of As(III) to As(V) in both aqueous and solid phases at pHini 5.0-9.0 and enhanced the oxidation of As(III) to As(V) in solution at pHini 3.0.

Fate of As(V)-treated nano zero-valent iron: Determination of arsenic desorption potential under varying environmental conditions by phosphate extraction

Nano zero-valent iron (NZVI) offers a promising approach for arsenic remediation, but the spent NZVI with elevated arsenic content could arouse safety concerns. This study investigated the fate of As(V)-treated NZVI (As-NZVI), by examining the desorption potential of As under varying conditions. The desorption kinetics of As from As-NZVI as induced by phosphate was well described by a biphasic rate model. The effects of As(V)/NZVI mass ratio, pH, and aging time on arsenic desorption from As-NZVI by phosphate were investigated. Less arsenic desorption was observed at lower pH or higher As(V)/NZVI mass ratio, where stronger complexes (bidentate) formed between As(V) and NZVI corrosion products as indicated by FTIR analysis. Compared with the fresh As-NZVI, the amount of phosphate-extractable As significantly decreased in As-NZVI aged for 30 or 60 days. The results of the sequential extraction experiments demonstrated that a larger fraction of As was sorbed in the crystalline phases after aging, making it less susceptible to phosphate displacement. However, at pH 9, a slightly higher proportion of phosphate-extractable As was observed in the 60-day sample than in the 30-day sample. XPS results revealed the transformation of As(V) to more easily desorbed As(III) during aging and a higher As(III)/As(V) ratio in the 60-day sample at pH 9, which might have resulted in the higher desorption.

Enhanced paramagnetic Cu2+ ions removal by coupling a weak magnetic field with zero valent iron

A weak magnetic field (WMF) was proposed to enhance paramagnetic Cu(2+) ions removal by zero valent iron (ZVI). The rate constants of Cu(2+) removal by ZVI with WMF at pH 3.0-6.0 were -10.8 to -383.7 fold greater than those without WMF. XRD and XPS analyses revealed that applying a WMF enhanced both the Cu(2+) adsorption to the ZVI surface and the transformation of Cu(2+) to Cu(0) by ZVI. The enhanced Cu(2+) sequestration by ZVI with WMF was accompanied with expedited ZVI corrosion and solution ORP drop. The uneven distribution of paramagnetic Cu(2+) along an iron wire in an inhomogeneous MF verified that the magnetic field gradient force would accelerate the paramagnetic Cu(2+) transportation toward the ZVI surface due to the WMF-induced sharp decay of magnetic flux intensity from ZVI surface to bulk Cu(2+) solution. The paramagnetic Fe(2+) ions generated by ZVI corrosion would also accumulate at the position with the highest magnetic flux intensity on the ZVI surface, causing uneven distribution of Fe(2+), and facilitate the local galvanic corrosion of ZVI, and thus, Cu(2+) reduction by ZVI. The electrochemical analysis verified that the accelerated ZVI corrosion in the presence of WMF partly arose from the Lorentz force-enhanced mass transfer.