重金属-柠檬酸-针铁矿三元体系的表面络合模型研究

根际环境产生的柠檬酸等小分子有机酸可能影响重金属的溶出效应.本文研究了 4种重金属Cd、Pb、Cu、Ni及柠檬酸在针铁矿表面的三元体系吸附行为,结果发现柠檬酸促进了 4种重金属酸性条件下在针铁矿表面的吸附量,而Cu、Ni促进了柠檬酸碱性条件下的吸附.结合红外光谱图发现,重金属-柠檬酸-针铁矿主要存在以下2种三元体系形态...     

草甘膦在高指{201}二氧化钛表面的吸附去除

有机磷农药草甘膦(PMG)的广泛使用和环境残留严重威胁人体健康,其去除治理是环境领域面临的一大挑战.本文研究了草甘膦在高指{201}晶面二氧化钛(TiO_2)上的吸附行为,探讨了吸附时间、溶液pH和草甘膦浓度对吸附效率的影响,并通过Zeta电位表征和电荷分布多位点络合(CD-MUSIC)模型考察了草甘膦在二氧化钛上的络合结构.结果表明,{201}TiO_2对草甘膦的吸附在40 min内即可达到吸附平衡,吸附动力学符合准二级动力学方程.吸附等温线符合Langmuir方程,说明其吸附过程主要是近似单分子层的化学吸附.pH对吸附效率影响较大,酸性条件有利于草甘膦的吸附去除.Zeta电位的表征结果表明,草甘膦吸附后TiO_2表面等电点从5.6向左偏移至4.2,说明形成带负电的内层配合物,进一步的红外光谱结果表明草甘膦以P—O—Ti的络合形式与TiO_2表面结合.CD-MUSIC模型拟合结果表明草甘膦与TiO_2表面可能形成单齿单核或双齿双核的内层络合结构.本研究结果对深入理解草甘膦的微观界面行为及去除具有重要意义.     

Competitive sorption and diffusion of chromate and sulphate in a flow system with goethite in gel beads

Column experiments and model simulations were employed to evaluate the processes involved in multicomponent solute transport in a system with heterogeneous flow. Column experiments were performed with goethite embedded in polyacrylamide gel beads. The gel forms an immobile water region that can be accessed by diffusion. A two-region transport model with diffusion into spheres was combined with a surface complexation model to predict reactive transport in the goethite-gel bead system. Chromate and sulphate breakthrough curves were measured in a set of transport experiments, along with corresponding changes in the pH of the effluent. Sorption and transport of sulphate and chromate in separate columns were predicted from independently measured sorption parameters. The model overestimated the pH changes in the effluent, possibly because of proton buffering by the polyacrylamide gel. The effect of competitive sorption on transport was examined in experiments with both anions present. The model predicted the effect of competition very well in a system initially equilibrated with sulphate, followed by infiltration with chromate. However, when sulphate was infiltrated after equilibration with chromate, chromate desorption and sulphate adsorption were clearly overestimated by the transport model. The exchange between the more strongly bound chromate and the sulphate added subsequently may be too slow to cause a substantial chromate peak in the effluent. This suggests that the local equilibrium assumption was not applicable in this case.     

Recent progress of arsenic adsorption on TiO2 in the presence of coexisting ions: A review

Arsenic (As)-contaminated wastewater and groundwater pose a pressing environmental issue and worldwide concern. Adsorption of As using TiO₂ materials, in combination with filtration, introduces a promising technology for the treatment of As-contaminated water. This review presents an overview on the recent progress of the application of TiO₂ for removal of As from wastewater and groundwater. The main focus is on the following three pressing issues that limit the field applications of TiO₂ for As removal: coexisting ions, simulation of breakthrough curves, and regeneration and reuse of spent TiO₂ materials. We first examined how the coexisting ions in water, especially high concentrations of cations in industrial wastewater, affect the efficacy of As removal using the TiO₂ materials. We then discussed As breakthrough curves and the effect of compounded ions on the breakthrough curves. We successfully simulated the breakthrough curves by PHREEQC after integrating the CD-MUSIC model. We further discussed challenges facing the regeneration and reuse of TiO₂ media for practical applications. We offer our perspectives on remaining issues and future research needs.     

The interaction of boron with goethite: experiments and CD-MUSIC modeling

Boron (B) is an essential element for plants and animals growth that interacts with mineral surfaces regulating its bioavailability and mobility in soils, sediments, and natural ecosystems. The interaction with mineral surfaces is quite important because of a narrow range between boron deficiency and toxicity limits. In this study, the interaction of boric acid with goethite (α-FeOOH) was measured in NaNO₃ background solution as a function of pH, ionic strength, goethite and boron concentration representing as adsorption edges and isotherms. Boron adsorption edges showed a bell-shaped pattern with maximum adsorption around pH 8.50, whereas adsorption isotherms were rather linear. The adsorption data were successfully described with the CD-MUSIC model in combination with the Extended Stern (ES) model. The charge distribution (CD) of inner-sphere boron surface complexes was calculated from the geometry optimized with molecular orbital calculations applying density functional theory (MO/DFT). The CD modeling suggested dominant binding of boric acid as a trigonal inner-sphere complex with minor contributions of a tetrahedral inner-sphere complex (at high pH) and a trigonal outer-sphere complex (at low pH). The interpretation with the CD model is consistent with the spectroscopic observations.