Jinxiang Li

Improving the Reactivity of Zerovalent Iron by Taking Advantage of Its Magnetic Memory: Implications for Arsenite Removal

Premagnetization was employed to enhance the reactivity of zerovalent iron (ZVI) toward As(III) sequestration for the first time. Compared to the pristine ZVI (Pri-ZVI), the rate of As(III) elimination by the premagnetized ZVI (Mag-ZVI) was greater over the pHini range of 4.0-9.0 and increased progressively with increasing intensity of the magnetic field for premagnetization. Mag-ZVI could keep its reactivity for a long time and showed better performance than Pri-ZVI for As(III) removal from synthetic groundwater in column tests. The Fe K-edge XAFS analysis for As(III)-treated ZVI samples unraveled that premagnetization promoted the transformation of ZVI to iron (hydr)oxides and shifted the corrosion products from maghemite and magnetite to lepidocrocite, which favored the arsenic sequestration. The arsenic species analysis revealed that premagnetization facilitated the oxidation of As(III) to As(V). ZVI pretreated with grinding was very different from Mag-ZVI with regard to As(III) removal, indicating that the improved reactivity of Mag-ZVI should not be associated with the physical squeezing effect of the ZVI grains during magnetization. The positive correlation between the remanence of Mag-ZVI and the rate constants of total arsenic removal indicated that the enhanced reactivity of Mag-ZVI was mainly ascribed to its magnetic memory, i.e., the remanence kept by Mag-ZVI.

Premagnetization for Enhancing the Reactivity of Multiple Zerovalent Iron Samples toward Various Contaminants

Premagnetization was applied to enhance the removal of various oxidative contaminants (including amaranth (AR27), lead ion (Pb(2+)), cupric ion (Cu(2+)), selenite (Se(4+)), silver ion (Ag(+)), and chromate (Cr(6+))) by zerovalent iron (ZVI) from different origins under well-controlled experimental conditions. The rate constants of contaminants by premagnetized ZVI (Mag-ZVI) samples were 1.2-12.2-fold greater than those by pristine ZVI (Pri-ZVI) samples. Generally, there was a linear correlation between the specific reaction rate constants (kSA) of one particular contaminant removal by various Pri-ZVI or Mag-ZVI samples and those of the other contaminant, which could be successfully employed to predict the kSA of one contaminant by one ZVI sample if kSA of the other contaminant by this ZVI sample was available. The specific rate constant of Fe(II) release at pH 4.0 was proposed in this study to stand for the intrinsic reactivity of a ZVI sample. All Mag-ZVI samples had higher intrinsic reactivity than their counterparts without premagnetization. There were strong correlations between the intrinsic reactivity of various Pri-ZVI/Mag-ZVI samples and the removal rate constants of a specific contaminant by these ZVI samples not only at pH 4.0 when the intrinsic reactivity was determined but also at other pH levels. This correlation could be employed to predict the removal rate constant of this contaminant by a ZVI sample that was not included in the original data set once the intrinsic reactivity of the ZVI sample was known.

Aging of Zerovalent Iron in Synthetic Groundwater: X-ray Photoelectron Spectroscopy Depth Profiling Characterization and Depassivation with Uniform Magnetic Field

Scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) depth profiling were employed to characterize the aged zerovalent iron (AZVI) samples incubated in synthetic groundwater. The AZVI samples prepared under different conditions exhibited the passive layers of different morphologies, amounts, and constituents. Owing to the accumulation of iron oxides on their surface, all the prepared AZVI samples were much less reactive than the pristine ZVI for Se(IV) removal. However, the reactivity of all AZVI samples toward Se(IV) sequestration could be significantly enhanced by applying a uniform magnetic field (UMF). Moreover, the flux intensity of UMF necessary to depassivate an AZVI sample was strongly dependent on the properties of its passive layer. The UMF of 1 mT was strong enough to restore the reactivity of the AZVI samples with Fe3O4 as the major constituent of the passive film or with a thin layer of α-Fe2O3 and γ-FeOOH in the external passive film. The flux intensity of UMF necessary to depassivate the AZVI samples would increase to 2 mT or even 5 mT if the AZVI samples were covered with passive films being thicker, denser, and contained more γ-FeOOH and α-Fe2O3. Furthermore, increasing the flux intensity of UMF facilitated the reduction of Se(IV) to Se(0) by AZVI samples.

Coupled Effect of Ferrous Ion and Oxygen on the Electron Selectivity of Zerovalent Iron for Selenate Sequestration

Although the electron selectivity (ES) of zerovalent iron (ZVI) for target contaminant and its utilization ratio (UR) decide the removal capacity of ZVI, little effort has been made to improve them. Taking selenate [Se(VI)] as a target contaminant, this study investigated the coupled influence of aeration gas and Fe(II) on the ES and UR of ZVI. Oxygen was necessary for effective removal of Se(VI) by ZVI without Fe(II) addition. Due to the application of 1.0 mM Fe(II), the ES of ZVI was increased from 3.2-3.6% to 6.2-6.8% and the UR of ZVI was improved by 5.0-19.4% under aerobic conditions, which resulted in a 100-180% increase in the Se(VI) removal capacity by ZVI. Se(VI) reduction by Fe0 was a heterogeneous redox reaction, and the enrichment of Se(VI) on ZVI surface was the first step of electron transfer from Fe0 core to Se(VI). Oxygen promoted the generation of iron (hydr)oxides, which facilitated the enrichment of Se(VI) on the ZVI particle surface. Therefore, the high oxygen fraction (25-50%) in the purging gas resulted in only a slight decrease in the ES of ZVI. Fe(II) addition resulted in a pH drop and promoted the generation of lepidocrocite and magnetite, which benefited Se(VI) adsorption and the following electron transfer from underlying Fe0 to surface-located Se(VI).

Combined Effect of Weak Magnetic Fields and Anions on Arsenite Sequestration by Zerovalent Iron: Kinetics and Mechanisms

In this study, the effects of major anions (e.g., ClO4-, NO3-, Cl-, and SO42-) in water on the reactivity of zerovalent iron (ZVI) toward As(III) sequestration were evaluated with and without a weak magnetic field (WMF). Without WMF, ClO4- and NO3- had negligible influence on As(III) removal by ZVI, but Cl- and SO42- could improve As(III) sequestration by ZVI. Moreover, the WMF-enhancing effect on As(III) removal by ZVI was minor in ultrapure water. A synergetic effect of WMF and individual anion on improving As(III) removal by ZVI was observed for each of the investigated anion, which became more pronounced as the concentration of anion increased. Based on the extent of enhancing effects, these anions were ranked in the order of SO42- > Cl- > NO3- ≈ ClO4- (from most- to least-enhanced). Furthermore, the inhibitory effect of HSiO3-, HCO3-, and H2PO4- on ZVI corrosion could be alleviated taking advantage of the combined effect of WMF and SO42-. The coupled influence of anions and WMF was associated with the simultaneous movement of anions with paramagnetic Fe2+ to keep local electroneutrality in solution. Our findings suggest that the presence of anions is quite essential to maintaining or stimulating the WMF effect.

Advances in Sulfidation of Zerovalent Iron for Water Decontamination

Sulfidation has gained increasing interest in recent years for improving the sequestration of contaminants by zerovalent iron (ZVI). In view of the bright prospects of the sulfidated ZVI (S-ZVI), this review comprehensively summarized the latest developments in sulfidation of ZVI, particularly that of nanoscale ZVI (S-nZVI). The milestones in development of S-ZVI technology including its background, enlightenment, synthesis, characterization, water remediation and treatment, etc., are summarized. Under most circumstances, sulfidation can enhance the sequestration of various organic compounds and metal(loid)s by ZVI to various extents. In particular, the reactivity of S-ZVI toward contaminants is strongly dependent on S/Fe molar ratio, sulfidation method, and solution chemistry. Additionally, sulfidation can improve the selectivity of ZVI toward targeted contaminant over water under anaerobic conditions. The mechanisms of sulfidation-induced improvement in contaminants sequestration by ZVI are also summarized. Finally, this review identifies the current knowledge gaps and future research needs of S-ZVI for environmental application.

Enhanced Reactivity and Electron Selectivity of Sulfidated Zerovalent Iron toward Chromate under Aerobic Conditions

When zerovalent iron (ZVI) is used in reductive removal of contaminants from industrial wastewater, where dissolved oxygen (DO) competes with target contaminant for the electrons donated by ZVI, both the reactivity and the electron selectivity (ES) of ZVI toward target contaminant are critical. Thus, the reactivity and ES of two sulfidated ZVI (S-ZVI) samples, synthesized by ball-milling with elemental sulfur (S-ZVIbm) and reacting with Na2S (S-ZVINa2S), toward Cr(VI) under aerobic conditions were investigated. Sulfidation appreciably increased the reactivity of ZVI and the ratio of the rate constants for Cr(VI) removal by S-ZVIbm or S-ZVINa2S to their counterparts without sulfur fell in the range of 1.4-29.9. ES of S-ZVIbm and S-ZVINa2S toward Cr(VI) were determined to be 14.6% and 13.3%, which were 10.7- and 7.5-fold greater than that without sulfidation, respectively. This was mainly ascribed to the greater improving effect of sulfidation on the reduction rate of Cr(VI) than that of DO by ZVI. The improving effects of sulfidation on the performance of ZVI were mainly due to the following mechanisms: sulfidation increased the specific surface area of ZVI, the FeS x layer facilitated the enrichment of Cr(VI) anions on S-ZVI surface because of its anions selective property and favored the electron transfer from Fe0 core to Cr(VI) at the surface because of its role as efficient electron conductor.