Zhenqing Shi

A novel multi-reaction model for kinetics of Zn release from soils: Roles of soil binding sites

The kinetics of Zn release from soil is a key process affecting the fate and bioavailability of Zn in soil, which may be complicated by multiple soil binding sites and reactions during the Zn release process. In this study, we developed a novel quantitative model for the dynamic Zn speciation in soil during the Zn release process, by integrating the mechanistic equilibrium model WHAM 7 and molecular level investigation of Zn speciation with X-ray absorption spectroscopy (XAS). The kinetics model specifically considered Zn reactions with soil organic matter (SOM), iron (hydr)oxides, and clay minerals, and dissolution of Zn precipitates. Batch and replenishment experiments were conducted to study kinetics of Zn release from laboratory-spiked soils and XAS was employed to identify soil Zn speciation. Overall, the model described the experimental data reasonably well with minimal model fitting parameters. We quantitatively assessed the dynamic changes of Zn speciation in different soil components and SOM binding sites at various time scales and reaction conditions. Our kinetics model provides a quantitative framework for predicting the dynamic behavior of Zn in soil environments.

Effective Extraction of Cr(VI) from Hazardous Gypsum Sludge via Controlling the Phase Transformation and Chromium Species

Through controlling the phase transformation and chromium species under hydrothermal condition, the Cr(VI) was extracted fully from hazardous Cr(VI)-containing gypsum sludge, with a very high efficiency of more than 99.5%. Scanning transmission electron microscopy, X-ray absorption fine structure, and density functional theory calculation results revealed that the dissolution-recrystallization of CaSO4·2H2O into CaSO4 was the key factor to fully release the encapsulated Cr(VI). Moreover, the mineralizer (persulfate salt) provided H+ and SO42- ions, the former made an acidic condition to transform the released CrO42- into the specie (Cr2O72-) with less similarity to SO42-, which further prevented the recombination of the released Cr(VI) with gypsum; and the latter was essential to accelerate crystal growth of calcium sulfate so as to enhance Cr(VI) extraction. This work would provide an instructive guidance to fully extract heavy metals from hazardous solid wastes via the control of crystal transformation and the pollutant species.

Coupled Kinetics of Ferrihydrite Transformation and As(V) Sequestration under the Effect of Humic Acids: A Mechanistic and Quantitative Study

In natural environments, kinetics of As(V) sequestration/release is usually coupled with dynamic Fe mineral transformation, which is further influenced by the presence of natural organic matter (NOM). Previous work mainly focused on the interactions between As(V) and Fe minerals. However, there is a lack of both mechanistic and quantitative understanding on the coupled kinetic processes in the As(V)-Fe mineral-NOM system. In this study, we investigated the effect of humic acids (HA) on the coupled kinetics of ferrihydrite transformation into hematite/goethite and sequestration of As(V) on Fe minerals. Time-resolved As(V) and HA interactions with Fe minerals during the kinetic processes were studied using aberration-corrected scanning transmission electron microscopy, chemical extractions, stirred-flow kinetic experiments, and X-ray absorption spectroscopy. Based on the experimental results, we developed a mechanistic kinetics model for As(V) fate during Fe mineral transformation. Our results demonstrated that the rates of As(V) speciation changes within Fe minerals were coupled with ferrihydrite transformation rates, and the overall reactions were slowed down by the presence of HA that sorbed on Fe minerals. Our kinetics model is able to account for variations of Fe mineral compositions, solution chemistry, and As(V) speciation, which has significant environmental implications for predicting As(V) behavior in the environment.

Immobilization of Sphingomonas sp. GY2B in polyvinyl alcohol–alginate–kaolin beads for efficient degradation of phenol against unfavorable environmental factors

In this study, batch experiments were carried out to evaluate the biodegradation of phenol by Sphingomonas sp. GY2B, which were immobilized in polyvinyl alcohol (PVA)-sodium alginate-kaolin beads under different conditions. The optimal degradation performance was achieved by GY2B immobilized in beads containing 1.0% (w/v) of kaolin, 10% (w/v) of PVA, 0.3% (w/v) of sodium alginate, 10% (v/v) of biomass dosage, and exposed to an initial phenol concentration of 100 mg/L. The experimental results indicated that PVA-sodium alginate-kaolin beads can accelerate the degradation rate of phenol by reducing the degradation time and also improve degradation rate. The biodegradation rate of phenol by immobilized cells (16.79 ± 0.81 mg/(L·h)) was significantly higher than that of free cells (11.49 ± 1.29 mg/(L·h)) under the above optimal conditions. GY2B immobilized on beads was more competent than free GY2B in degradation under conditions with high phenol concentrations (up to 300 mg/L) and in strong acidic (pH = 1) and alkaline (pH = 12) environments. Higher phenol concentrations inhibit the biomass and reduce the biodegradation rate, while the lower biodegradation rate at low initial phenol concentrations is attributed to mass transfer limitations. The Haldane inhibitory model was in agreement with the experimental data well, revealing that phenol showed a considerable inhibitory effect on the biodegradation by Sphingomonas sp. GY2B, especially at concentrations higher than 90 mg/L. Intra-particle diffusion model analysis suggests that adsorption of phenol by immobilized beads was controlled by both rapid surface adsorption as well as pore diffusion mechanism. Its worth noting that the presence of 1 mg/L Cr(VI) enhanced the biodegradation of phenol by free cells, while Cr(VI) showed no obvious impact on the removal of phenol by immobilized cells. In addition, immobilized cells were reused 16 times and removed 99.5% phenol, and when stored at 4 °C for 90 days, more than 99% phenol was removed. These results showed that immobilized cells can significantly improve the microbial degradation performance, and protect microorganisms against unfavorable environment. It is implied that PVA -sodium alginate-kaolin beads have great potential to be applied in a practical and economical phenolic wastewater treatment system.