Yankai Xie

Stabilization of nanoscale zero-valent iron (nZVI) with modified biochar for Cr(VI) removal from aqueous solution

Three types of modified biochar (BC) were produced respectively with acid (HCl) treatment (HCl-BC), base (KOH) treatment (KOH-BC) and oxidation (H2O2) treatment (H2O2-BC) of raw biochar. Both the raw biochar and modified biochars supported zero valent iron nanopartilces (nZVI) (i.e. nZVI@BC, nZVI@HCl-BC, nZVI@KOH-BC and nZVI@H2O2-BC) were synthesized and their capacities for Cr(VI) removal were compared. The results showed that the nZVI@HCl-BC exhibited the best performance and the underlying mechanisms were discussed. The surface elemental distribution maps of the nZVI@HCl-BC after reaction with Cr(VI) showed that Fe, Cr and O elements were deposited on the surface of HCl-BC evenly, indicating that the formed Cr(III)/Fe(III) could settle on the surface of HCl-BC uniformly rather than coated only on the nZVI surface. This reveals that the supporter HCl-BC could also play a role in alleviating the passivation of nZVI. Besides, the effects of mass ratio (nZVI/HCl-BC), pH, and initial Cr(VI) concentration on Cr(VI) removal were examined. At lower mass of HCl-BC, nZVI aggregation cannot be fully inhibited on the surface of HCl-BC, whereas excessive biochar can block the active sites of nZVI. Additionally, it was found that Cr(VI) removal by nZVI@HCl-BC was dependent on both pH and initial Cr(VI) concentration.

The interactions between nanoscale zero-valent iron and microbes in the subsurface environment: A review.

Nanoscale zero-valent iron (NZVI) particles, applied for in-situ subsurface remediation, are inevitable to interact with various microbes in the remediation sites directly or indirectly. This review summarizes their interactions, including the effects of NZVI on microbial activity and growth, the synergistic effect of NZVI and microbes on the contaminant removal, and the effects of microbes on the aging of NZVI. NZVI could exert either inhibitive or stimulative effects on the growth of microbes. The mechanisms of NZVI cytotoxicity (i.e., the inhibitive effect) include physical damage and biochemical destruction. The stimulative effects of NZVI on certain bacteria are associated with the creation of appropriate living environment, either through providing electron donor (e.g., H2) or carbon sources (e.g., the engineered organic surface modifiers), or through eliminating the noxious substances that can cause bactericidal consequence. As a result of the positive interaction, the combination of NZVI and some microbes shows synergistic effect on contaminant removal. Additionally, the aged NZVI can be utilized by some iron-reducing bacteria, resulting in the transformation of Fe(III) to Fe(II), which can further contribute to the contaminant reduction. However, the Fe(III)-reduction process can probably induce environmental risks, such as environmental methylation and remobilization of the previously entrapped heavy metals.

The dual effects of carboxymethyl cellulose on the colloidal stability and toxicity of nanoscale zero-valent iron.

Nanoscale zero-valent iron (NZVI) particles are usually modified with surface coating to mitigate the particle stability in water during the environmental application. However, the surface coating may not only influence the particle stabilization but also the particle cytotoxicity. In this study, we investigated the dual effects of carboxymethyl cellulose (CMC) on the colloidal stability and cytotoxicity of NZVI towards gram-negative Escherichia coli (E. coli) and discussed the interrelation between particle stability and cytotoxicity. The effect of CMC concentration, ionic strength (Ca(2+)) and aging treatment on the particle cytotoxicity were also examined. Specifically, the aqueous stability of NZVI suspensions with CMC ratio dose-dependently strengthened within 1 h. The inactivation of E. coli by bare NZVI was significant and concentration- and time-dependent. On the contrary, an increasing reduction in cytotoxicity of NZVI with CMC ratio increasing was observed, even though the particles became more dispersed. TEM analysis demonstrates the membrane disruption and the cellular internalization of nanoparticles after exposure of E. coli to NZVI. However, in the case of CMC-modified NZVI (CNZVI), the bacterial cell wall displays an outer shell of a layer of nanoparticles attached around the outer membrane, but the cell membrane was kept intact. The presence of Ca(2+) can either increase or decrease the cytotoxicity of NZVI and CNZVI, depending on the concentration. The aged NZVI and CNZVI particles did not seem to present obvious bactericidal effect due to the transformation of Fe(0) to the less toxic or non-toxic iron oxides, as indicated by the XRD analysis.

Aging study on carboxymethyl cellulose-coated zero-valent iron nanoparticles in water: Chemical transformation and structural evolution.

To assess the long-term fate and the associated risks of nanoscale zero-valent iron (nZVI) used in the water remediation, it is essential to understand the chemical transformations during aging of nZVI in water. This study investigated the compositional and structural evolution of bare nZVI and carboxymethyl cellulose (CMC) coated nZVI in static water over a period of 90 days. Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the corrosion products of nZVI and CMC-nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging, but the coating of CMC could slow down the aging rate of nZVI (as indicated by the slower drop in Fe(0) intensity in XRD pattern). For the bare nZVI, magnetite (Fe3O4) and/or maghemite (γ-Fe2O3) are the dominant corrosion products after 90 days of aging. However, for the CMC-nZVI, the core-shell spheres collapses to acicular-shaped structures after aging with crystalline lepidocrocite (γ-FeOOH) as the primary end product. Moreover, more lepidocrocite present in the corrosion products of CMC-nZVI with higher loading of CMC, which reveals that the CMC coating could influence the transformation of iron oxides.

Chromate removal by surface-modified nanoscale zero-valent iron: Effect of different surface coatings and water chemistry.

This study investigated the correlation between the colloidal stability and reactivity of surface-modified nano zero-valent iron (SM-nZVI) as affected by the surface coating (i.e., polyacrylic acid [PAA] and starch) under various geochemical conditions. Generally, the colloidal stability of nZVI was enhanced with increasing loading of surface coating, while there is an optimum loading for the most efficient Cr(VI) removal by SM-nZVI. At lower loadings than the optimum loading, the surface coating could enhance the particle stabilization, facilitating the Cr(VI) reduction by providing more available surface sites. However, the over-loaded surface coating on the surface of nZVI particles decreased the Cr(VI) reduction due to the occupation of the reactive sites and the inhibition of the mass transfer of Cr(VI) ions from water to the particle surface by providing the electrostatic or steric repulsion. The effects of Ca(2+) ions or humic acid (HA) on the colloidal stability and reactivity of PAA-modified nZVI (P-nZVI) and starch-modified nZVI (S-nZVI) were examined. Differing stability behavior and reactivity were observed for different SM-nZVI. It was found that the presence of Ca(2+) or HA altered surface chemistry of SM-nZVI, the particle-particle interaction and the particle-contaminant interaction, and hence influencing the stability behavior and reactivity of the particles.

The impact of silver nanoparticles on the co-composting of sewage sludge and agricultural waste: Evolutions of organic matter and nitrogen

This study evaluated the influence of silver nanoparticles (AgNPs) on evolutions of organic matter and nitrogen during co-composting of sewage sludge and agricultural waste. Two co-composting piles were conducted, one was treated without AgNPs (pile 1) and the other with AgNPs (pile 2). Results showed that the AgNPs affected the quality of final composts. Less organic matter (OM) losses were determined in pile 2 (57.96%) than pile 1 (61.66%). 27.22% and 30.1% of the initial total organic matter (TOC) was decomposed in pile 1 and pile 2, respectively. The final water soluble carbon (WSC) concentration in pile 2 was 23559.27mg/kg DW compost which was significantly lower than pile 1 (25642.75mg/kg DW compost). Changes of different forms of nitrogen in the two piles showed that AgNPs could reduce the losses of TN but increase the losses of mineral N.

Influence of fulvic acid on the colloidal stability and reactivity of nanoscale zero-valent iron.

This study investigated the effect of fulvic acid (FA) on the colloidal stability and reactivity of nano zero-valent iron (nZVI) at pH 5, 7 and 9. The sedimentation behavior of nZVI differed at different pH. A biphasic model was used to describe the two time-dependent settling processes (i.e., a rapid settling followed by a slower settling) and the settling rates were calculated. Generally, the settling of nZVI was more significant at the point of zero charge (pHpzc), which could be varied in the presence of FA due to the adsorption of FA on the nZVI surface. More FA was adsorbed on the nZVI surface at pH 5-7 than pH 9, resulting in the varying sedimentation behavior of nZVI via influencing the electrostatic repulsion among particles. Moreover, it was found that there was a tradeoff between the stabilization and the reactivity of nZVI as affected by the presence of FA. When FA concentration was at a low level, the adsorption of FA on the nZVI surface could enhance the particle stabilization, and thus facilitating the Cr(VI) reduction by providing more available surface sites. However, when the FA concentrations were too high to occupy the active surface sites of nZVI, the Cr(VI) reduction could be decreased even though the FA enhanced the dispersion of nZVI particles. At pH 9, the FA improved the Cr(VI) reduction by nZVI. Given the adsorption of FA on the nZVI surface was insignificant and its effect on the settling behavior of nZVI particles was minimal, it was proposed that the FA formed soluble complexes with the produced Fe(III)/Cr(III) ions, and thus reducing the degree of passivation on the nZVI surface and facilitating the Cr(VI) reduction.

The comparison of Se(IV) and Se(VI) sequestration by nanoscale zero-valent iron in aqueous solutions: The roles of solution chemistry

The sequestration of Se(IV) and Se(VI) by nanoscale zero-valent iron (NZVI) particles were compared under different solution conditions. Firstly, the comparison was conducted at three pH values (4.0, 6.0 and 8.0) in deionized water. Generally, the removal of Se(IV)/Se(VI) by NZVI was more rapid under acidic conditions and the removal efficiency of Se(IV) was much higher than that of Se(VI). Moreover, the pH variation exhibited much larger influence on the sequestration of Se(VI) than that of Se(IV) by NZVI. The spectroscopic analysis showed that both the Se(IV) and Se(VI) were reduced to Se0 and Se2-, while NZVI was transformed into iron (hydr)oxides. When the selenium-NZVI reactions occurred in synthetic groundwater, all the reaction systems were inhibited in varying degrees. The individual effects of humic acid (HA) and typical inorganic ions were also examined. It seems that HA could substantially hinder the sequestration of Se(IV) compared with that in deionized water, while sulfate (SO42-) and bicarbonate (HCO3-) inhibited the Se(VI) removal significantly. Notably, the presence of cations (i.e., Na+ or Ca2+) ions did not cause obvious interference to the Se(IV)/Se(VI) removal by NZVI, while the presence of Ca2+ could alleviate the adverse effect of HA on Se(IV) removal to some degree.

Pathway and mechanism of nitrogen transformation during composting: Functional enzymes and genes under different concentrations of PVP-AgNPs

Polyvinylpyrrolidone coated silver nanoparticles (PVP-AgNPs) were applied at different concentrations to reduce total nitrogen (TN) losses and the mechanisms of nitrogen bio-transformation were investigated in terms of the nitrogen functional enzymes and genes. Results showed that mineral N in pile 3 which was treated with AgNPs at a concentration of 10 mg/kg compost was the highest (6.58 g/kg dry weight (DW) compost) and the TN loss (47.07%) was the lowest at the end of composting. Correlation analysis indicated that TN loss was significantly correlated with amoA abundance. High throughput sequencing showed that the dominant family of ammonia-oxidizing bacteria (AOB) was Nitrosomonadaceae, and the number of Operational Taxonomic Units (OTUs) reduced after the beginning of composting when compared with day 1. In summary, treatment with AgNPs at a concentration of 10 mg/kg compost was considerable to reduce TN losses and reserve more mineral N during composting.

Single and combined removal of Cr(VI) and Cd(II) by nanoscale zero-valent iron in the absence and presence of EDDS

This study examined the feasibility of nanoscale zero-valent iron (nZVI) for the single and combined removal of Cr(VI) and Cd(II) with or without ethylene diamine disuccinic acid (EDDS). The effects of pH and dissolved oxygen (DO) on the removal process were investigated. Results show that the single removal of either Cr(VI) or Cd(II) by nZVI was pH dependent, where the higher Cr(VI) removal was achieved under acidic conditions, whereas the higher Cd(II) removal was achieved under alkaline conditions. The presence of DO enhanced Cd(II) removal but inhibited Cr(VI) removal under alkaline conditions. In the co-existence of Cr(VI) and Cd(II), it was found that Cd(II) exerted insignificant effect on Cr(VI) removal, while the presence of Cr(VI) remarkably enhanced the Cd(II) removal. The addition of EDDS exhibited different influences on Cr(VI) and Cd(II) removal, which were associated with pH and DO. The EDDS enhanced Cr(VI) removal at pH 5.6-9.0 in the absence of DO, but decreased Cr(VI) removal at pH 9.0 in the presence of DO. For the removal of Cd(II) at pH 5.6-7.0, either facilitation or inhibition effect of EDDS was observed, depending on EDDS concentration and the co-existence of Cr(VI). However, Cd(II) removal was always significantly inhibited by EDDS at pH 9.0.