Zhanqiang Fang

Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: Influencing factors, kinetics, and mechanism

Polybrominated diphenyl ethers have been identified as a new class of organic pollutants with ecological risk due to their toxicity, bioaccumulation, and global distribution. Proper remediation technologies are needed to remove them from the environment. In this paper, Ni/Fe bimetallic nanoparticles were synthesized by chemical deposition and used to degrade decabromodiphenyl ether (BDE209). The characteristics of Ni/Fe nanoparticles were analyzed by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and Brunnaer-Emmett-Teller surface area analysis. Ni/Fe bimetallic nanoparticles with diameters in the order of 20-50 nm could effectively degrade BDE209 in the solvent (tetrahydrofuran/water). Influence factors, such as Ni/Fe nanoparticle dosage, initial BDE209 concentration, and Ni loading, on the removal of BDE209 were studied. The results indicated that the degradation of BDE209 followed pseudo-first-order kinetics, and the degradation rate of BDE209 increased with increasing the amount of nano Ni/Fe particles, Ni/Fe ratio, and decreasing the initial concentration of BDE209. Through analyzed the mass balance of the BDE209 removal, degradation was the main process of BDE209 removal. The mechanism of debromination was deduced by analyzing the reaction products using gas chromatography-mass spectrometry, the bromide ion in the solution and varying the solvent conditions. Stepwise hydrogen reduction is the main process of debromination, and the hydrion play an important role in the reaction. Moreover, the experiment of long term performance and leaching of Ni were also carried out to test the stability and durability of Ni/Fe nanoparticles in BDE209 degradation.

Degradation of decabromodiphenyl ether by nano zero-valent iron immobilized in mesoporous silica microspheres

The agglomeration of nanoparticles reduces the surface area and reactivity of nano zero-valent iron (NZVI). In this paper, highly dispersive and reactive NZVI immobilized in mesoporous silica microspheres covered with FeOOH was synthesized to form reactive mesoporous silica microspheres (SiO(2)@FeOOH@Fe). The characteristics of SiO(2)@FeOOH@Fe were analyzed by transmission electron microscopy, Fourier transform infrared spectroscopy simultaneous thermal analysis, X-ray photoelectron spectroscopy, and Brunnaer-Emmett-Teller surface area analysis. The mean particle size of the reactive mesoporous silica microspheres was 450 nm, and its specific surface area was 383.477 m(2) g(-1). The degradation of dcabromodiphenyl ether (BDE209) was followed pseudo-first-order kinetics, and the observed reaction rate constant could be improved by increasing the SiO(2)@FeOOH@Fe dosage and by decreasing the initial BDE209 concentration. The stability and longevity of the immobilized Fe nanoparticles were evaluated by repeatedly renewing the BDE209 solution in the reactor. The stable degradation of BDE209 by SiO(2)@FeOOH@Fe was observed within 10 cycles. Agglomeration-resistance and magnetic separation of SiO(2)@FeOOH@Fe were also performed. The improved dispersion of SiO(2)@FeOOH@Fe in solution after one-month storage and its good performance in magnetic separation indicated that SiO(2)@FeOOH@Fe has the potential to be efficiently applied to environmental remediation.

Characterization of endophytic Rahnella sp. JN6 from Polygonum pubescens and its potential in promoting growth and Cd, Pb, Zn uptake by Brassica napus.

Microbe-assisted phytoremediation has been considered as a promising measure for the remediation of heavy metal-polluted soils. In this study, a metal-tolerance and plant growth-promoting endophytic bacterium JN6 was firstly isolated from roots of Mn-hyperaccumulator Polygonum pubescens grown in metal-contaminated soil and identified as Rahnella sp. based on 16S rDNA gene sequence analysis. Strain JN6 showed very high Cd, Pb and Zn tolerance and effectively solubilized CdCO(3), PbCO(3) and Zn(3)(PO(4))(2) in culture solution. The isolate produced plant growth-promoting substances such as indole-3-acetic acid, siderophore, 1-aminocyclopropane-1-carboxylic deaminase, and also solubilized inorganic phosphate. Based upon its ability in metal tolerance and solubilization, the isolate JN6 was further studied for its effects on the growth and accumulation of Cd, Pb and Zn in Brassica napus (rape) by pot experiments. Rape plants inoculated with the isolate JN6 had significantly higher dry weights, concentrations and uptake of Cd, Pb and Zn in both above-ground and root tissues than those without inoculation grown in soils amended with Cd (25 mg kg(-1)), Pb (200 mg kg(-1)) or Zn (200 mg kg(-1)). The isolate also showed a high level of colonization in tissue interior of rapes. The present results demonstrated that Rahnella sp. JN6 is a valuable microorganism, which can cost-effectively improve the efficiency of phytoremediation in soils contaminated by Cd, Pb and Zn.

Immobilization and phytotoxicity of chromium in contaminated soil remediated by CMC-stabilized nZVI.

The toxic effect of Cr(VI)-contaminated soil remediated by sodium carboxymethyl cellulose stabilized nanoscale zero-valent iron (CMC-stabilized nZVI) was assessed through in vitro toxicity and phytotoxicity tests. In vitro tests showed that 0.09 g L(-1) of Fe(0) nanoparticles (soil-to-solution ratio was 1 g:5 mL) significantly reduced the toxicity characteristic leaching procedure (TCLP) leachability and physiological based extraction test (PBET) bioaccessibility of Cr by 82% and 58%, respectively. Sequential extraction procedures (SEP) revealed that exchangeable (EX) Cr was completely converted to Fe-Mn oxides (OX) and organic matter (OM). Accordingly, phytotoxicity tests indicated that after 72-h remediation, Cr uptakes by edible rape and Chinese cabbage were suppressed by 61% and 36%, respectively. Moreover, no significant increase in Cr uptake was observed for either species after a 1-month static period for the amended soil. Regarding Fe absorption, germination and seedling growth, both plant species were significantly affected by CMC-nZVI-exposed soils. However, similar phytotoxicity tests conducted after 1 month showed an improvement in cultivation for both plants. Overall, this study demonstrated that CMC-nZVI could significantly enhance Cr immobilization, which reduced its leachability, bioavailability and bioaccumulation by plants. From a detoxification perspective, such remediation is technologically feasible and shows great potential in field applications.

Remediation of polybrominated diphenyl ethers in soil using Ni/Fe bimetallic nanoparticles: influencing factors, kinetics and mechanism.

Polybrominated diphenyl ethers (PBDEs) are commonly used as additive flame retardants in all kinds of electronic products. PBDEs are now ubiquitous in the environment, with soil as a major sink, especially in e-waste recycling sites. This study investigated the degradation of decabromodiphenyl ether (BDE209) in a spiked soil using Ni/Fe bimetallic nanoparticles. The results indicated that Ni/Fe bimetallic nanoparticles are able to degrade BDE209 in soil at ambient temperature and the removal efficiency can reach 72% when an initial pH of 5.6 and at a Ni/Fe dosage of 0.03 g/g. A declining trend in degradation was noticed with decreasing Ni loading and increasing of initial BDE209 concentration. The degradation products of BDE209 were analyzed by GC-MS, which showed that the degradation of BDE209 was a process of stepwise debromination from nBr to (n-1)Br. And a possible debromination pathway was proposed. At last, the degradation process was analyzed as two-step mechanism, mass transfer and reaction. This current study shows the potential ability of Ni/Fe nanoparticles to be used for removal of PBDEs in contaminated soil.

Remediation of hexavalent chromium contaminated soil by biochar-supported zero-valent iron nanoparticles.

In this study, a kind of high-efficiency and low-cost biochar-supported zero-valent iron nanoparticles (nZVI@BC) was synthesised and used in the remediation of Cr(VI)-contaminated soil. The remediation tests indicated that the immobilisation efficiency of Cr(VI) and Crtotal was 100% and 91.94%, respectively, by 8g nZVI@BC per kg soil for 15 d of remediation. Further investigations showed that exchangeable Cr was almost completely converted to Fe-Mn oxides and organic matter. Moreover, nZVI@BC could effectively improve soil fertility and reduce the leachability of Fe caused by nZVI. At the same time, the cabbage mustard growth experiments indicated that the phytotoxicity of Cr(VI) and Fe in the seedlings was effectively decreased by nZVI@BC treatment, and that the cabbage mustard growth was enhanced.

Ultrasonic Fenton-like catalytic degradation of bisphenol A by ferroferric oxide (Fe3O4) nanoparticles prepared from steel pickling waste liquor

In this study, Fe3O4 NPs (named as Fe3O4 NPs-PO) were prepared by steel pickling waste liquor to reduce the cost of preparation, and were compared with those obtained by the common co-precipitation method (named as Fe3O4 NPs-CP) which prepared from chemical reagent using BET, XRD, XPS, TEM and SEM techniques. The results indicated that Fe3O4 NPs-PO nanoparticles mainly existed in the form of Fe3O4 and appeared to be roughly spherical in shape with a size range of 20-50 nm. The heterogeneous Fenton-like catalytic capacity of Fe3O4 NPs-PO in US+Fe3O4+H2O2 system was comprehensively investigated. BPA could be degraded within a wide pH range of 7-10. The removal efficiencies of BPA were close to 100% and about 45% total organic carbon (TOC) in solution was eliminated at the optimized conditions. It was found that ·OH radicals which mainly caused the degradation of BPA were promptly generated due to the catalysis of the Fe3O4 NPs-PO. Furthermore, the comparative study of catalytic activity, stability and reusability between Fe3O4 NPs-PO and Fe3O4 NPs-CP showed that the two catalysts both remained good activity after several reaction cycles and no significant change in composition and structure was observed, the loss of catalyst was negligible, which demonstrated that Fe3O4 NPs-PO were promising in ultrasonic Fenton-like process to treat refractory organics.

Excellently reactive Ni/Fe bimetallic catalyst supported by biochar for the remediation of decabromodiphenyl contaminated soil: Reactivity, mechanism, pathways and reducing secondary risks

Ni/Fe bimetallic nanoparticles were synthesized using biochar as a support (BC@Ni/Fe) and their effectiveness in removing BDE209 from soil was investigated. BET, SEM, TEM, XPS and FTIR were used to characterize the catalyst, and the efficiencies of biochar, Ni/Fe nanoparticles and BC@Ni/Fe for removing BDE209 from soil were compared. The results showed that Ni/Fe bimetallic nanoparticles highly dispersed in the biochar, reducing its agglomeration. Thus, the reaction activity of BC@Ni/Fe was increased. The removal efficiency of BDE209 by BC@Ni/Fe was 30.2% and 69% higher than that by neat Ni/Fe and biochar, respectively. Meanwhile, an enhanced degradation efficiency of PBDEs in soil was realized by monitoring the formation of Br- ions with time in the system. In addition, the degradation products identified by GC-MS showed that the reductive degradation of BDE209 proceeded through stepwise or multistage debromination, for which the degradation pathways and removal mechanisms were speculated. Furthermore, BC@Ni/Fe reduced the bioavailability of metals in soil and adsorbed the degradation products of BDE209, representing an improvement over neat Ni/Fe nanoparticles for the remediation of PBDEs-contaminated soil.

Comparisons of the reactivity, reusability and stability of four different zero-valent iron-based nanoparticles

Our previous reports showed that nano zero-valent iron (nZVI), steel pickle liquor for the synthesis of nZVI (S-nZVI), nZVI immobilised in mesoporous silica microspheres (SiO2@FeOOH@Fe) and nano Ni/Fe bimetallic particles (Ni/Fe) have been proved to show good property for elimination of polybrominated diphenyl ethers (PBDEs). However, it is necessary to compare their reactivity, reusability and stability when applied to in situ remediation. In this study, the performances of different iron-based nanoparticles were compared through reusability, sedimentation and iron dissolution experiments. The SiO2@FeOOH@Fe and Ni/Fe nanoparticles were shown to have higher reusability and stability, as they could be reused more than seven times, and that the SiO2@FeOOH@Fe can effectively avoid leaching iron ions into the solution and causing secondary pollution in the reaction. This study may serve as a reference for PBDE remediation in the future.

Remediation of lead contaminated soil by biochar-supported nano-hydroxyapatite

In this study, a high efficiency and low cost biochar-supported nano-hydroxyapatite (nHAP@BC) material was used in the remediation of lead (Pb)-contaminated soil. The remediation effect of nHAP@BC on Pb-contaminated soil was evaluated through batch experiments. The stability, bioaccessibility of Pb in the soil and the change in soil characteristics are discussed. Furthermore, the effects of the amendments on the growth of cabbage mustard seedlings and the accumulation of Pb were studied. The results showed that the immobilization rates of Pb in the soil were 71.9% and 56.8%, respectively, after a 28 day remediation using 8% nHAP and nHAP@BC materials, and the unit immobilization amount of nHAP@BC was 5.6 times that of nHAP, indicating that nHAP@BC can greatly reduce the cost of remediation of Pb in soil. After the nHAP@BC remediation, the residual fraction Pb increased by 61.4%, which greatly reduced the bioaccessibility of Pb in the soil. Moreover, nHAP@BC could effectively reduce the accumulation of Pb in plants by 31.4%. Overall, nHAP@BC can effectively remediate Pb-contaminated soil and accelerate the recovery of soil fertility.