Haoran Dong

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.

Treatment of landfill leachate using immobilized Phanerochaete chrysosporium loaded with nitrogen-doped TiO2 nanoparticles

This study investigated the performance of immobilized Phanerochaete chrysosporium loaded with nitrogen-doped TiO2 nanoparticles in the treatment of raw landfill leachate with a very low biodegradability ratio (BOD5/COD) of 0.09. The effects of various operating parameters, such as initial chemical oxygen demand (COD) concentration, pH, temperature, and biosorbent dosage, were evaluated with respect to the removal efficiency of total organic carbon (TOC) and ammonia nitrogen (NH3-N). For the immobilized biosorbents, an optimum pH of 6.0 for TOC and 7.0 for NH3-N were found suitable for TOC and NH3-N removal at temperature of 37°C, respectively. The most superior removal efficiencies of TOC and NH3-N of landfill leachate were over 75% and 74% in 72 h at an initial COD concentration of 200 mg L(-1), respectively. In addition, heavy metals were partly removed by the immobilized biosorbents during the process of landfill leachate treatment. The species and mass percentage of organic compounds in landfill leachate after the treatment were found to have considerably declined according to the gas chromatography coupled with mass spectrometry (GC-MS) system. These results indicate that the immobilized P. chrysosporium loaded with nitrogen-doped TiO2 nanoparticles could be a convenient and efficient method for the treatment of landfill leachate.

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.

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.

Influence of Calcium Ions on the Colloidal Stability of Surface-Modified Nano Zero-Valent Iron in the Absence or Presence of Humic Acid

To decrease aggregation and enhance the mobility of nano zero-valent iron (NZVI) used for in-situ groundwater remediation, the surface of such NZVI must be modified using organic stabilizers, which can provide electrostatic repulsion, and steric or electrosteric stabilization. However, the stability of the nanoparticles can also be affected by groundwater components such as cations and humic acid (HA). In this study, the effect of Ca(2+) on the colloidal stability of NZVI coated with three types of stabilizers (i.e., polyacrylic acid (PAA), Tween-20 and starch) was evaluated in the absence or presence of HA. Differing stability behavior was observed for different surface-modified NZVIs. The presence of Ca(2+) exerted a slight influence on the settling of NZVI modified with PAA or Tween-20, in the absence or presence of HA. However, the presence of Ca(2+) caused significant aggregation and sedimentation for starch-modified NZVI in the absence of HA, and induced an even higher degree of aggregation and sedimentation in the presence of HA. It is presumed that, in the absence of HA, starch-modified NZVI particles undergo attachment with each other via Ca(2+) complexation with the coated starch molecules on the surface of the particles, thus enhancing the aggregation and the following sedimentation of starch-modified NZVI. However, in the presence of HA, spectroscopic analysis of the starch-modified NZVI aggregates indicated that the bridging interaction of HA with Ca(2+) was the predominant mechanism for the enhanced aggregation.

Catalytic reduction–adsorption for removal of p-nitrophenol and its conversion p-aminophenol from water by gold nanoparticles supported on oxidized mesoporous carbon

A highly efficient method for removal of p-nitrophenol and its conversion p-aminophenol from water was proposed using a novel catalyst-adsorbent composite of gold nanoparticles supported on functionalized mesoporous carbon (Au@CMK-3-O). The immobilized gold nanoparticles presented excellent catalytic ability to converse p-nitrophenol into p-aminophenol with the help of sodium borohydride, and the oxidized mesoporous carbon (CMK-3-O) serving as both carrier and adsorbent also exhibited high efficiency to remove p-aminophenol. The morphology and structure of the composite were characterized via SEM, TEM, FTIR and XPS analysis. Moreover, the mechanism of reaction process and the parameters of kinetics and thermodynamics were investigated. The activation energy was figured as 86.8 kJ mol(-1) for the adsorption and reduction of p-nitrophenol to p-aminophenol. The thermodynamic analysis based on the rate constants evaluated by pseudo-first-order model reveals that the adsorption-reduction process is an endothermic procedure with the rise of randomness. The anti-oxidation and regeneration study indicates that Au@CMK-3-O can be reused for 6 times with more than 90% conversion efficiency and keep high activity after exposing in air for 1 month, which possesses great prospects in application of nitroaromatic pollutant removal.

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.

Lab-scale simulation of the fate and transport of nano zero-valent iron in subsurface environments: aggregation, sedimentation, and contaminant desorption.

Heavy metal removal using nano zero-valent iron (NZVI) has drawn growing attention due to the ease of application and high removal efficiency. However, uncertainties regarding its fate and transport in subsurface environments have raised concerns that require further exploration. In this study, aggregation, sedimentation, and Cr/As desorption of three types of NZVIs were investigated under various conditions. It was found that the aggregation behavior of the NZVIs differed from one another in regard to reaction time and ionic strength, associated with the respective critical size for sedimentation. Sedimentation of NZVIs was positively related to the concentrations and average particle sizes. The sedimentation kinetics of NZVI followed two concomitant processes, i.e., (1) direct sedimentation of larger particles, and (2) initial aggregation and then sedimentation of smaller particles. When loaded with Cr/As, NZVIs tended to deposit faster, possibly due to the precipitation of Cr/As onto the nanoparticle surfaces resulting in larger particle sizes. Moreover, desorption of Cr/As from Cr/As loaded NZVIs was detected in the presence of typical groundwater ions, as well as natural organic matter, and poses a potential risk to the subsurface environment. The desorption of Cr was linearly related to the release of iron ions, while As desorption was mitigated when the immobilization of Cr increased.

pH-dependent degradation of p-nitrophenol by sulfidated nanoscale zerovalent iron under aerobic or anoxic conditions.

Sulfidated nanoscale zerovalent iron (S-NZVI) is attracting considerable attention due to its easy production and high reactivity to pollutants. We studied the reactivity of optimized S-NZVI (Fe/S molar ratio 6.9), comparing with pristine nanoscale zerovalent iron (NZVI), at various pH solutions (6.77-9.11) towards p-nitrophenol (PNP) under aerobic and anoxic conditions. Studies showed that the optimized extent of sulfidation could utterly enhance PNP degradation compared to NZVI. Batch experiments indicated that in anoxic S-NZVI systems the degradation rate constant increased with increasing pH up to 7.60, and then declined. However, in aerobic S-NZVI, and in anoxic or aerobic NZVI systems, it decreased as pH increased. It was manifested that anoxic S-NZVI systems preferred to weaker alkaline solutions, whereas aerobic S-NZVI systems performed better in acidic solutions. The highest TOC removal efficiency of PNP (17.59%) was achieved in the aerobic S-NZVI system at pH 6.77, revealing that oxygen improved the degradation of PNP by excessive amounts of hydroxyl radicals in slightly acidic conditions, and the TOC removal efficiency was supposed to be further improved in moderate acidic solutions. Acetic acid, a nontoxic ring opening by-product, confirms that the S-NZVI system could be a promising process for industrial wastewater containing sulfide ions.