Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange——Influence of material properties,sorption mechanism and modeling

Perfluorooctane sulfonate(PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N_2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force(LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient βs.The big difference in the initial mass transfer coefficient βs,0, when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate.But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range.     

Simultaneous removal of Cu(II) and Cr(VI) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20 mg/L) and Cr(VI) (40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200 mg/L) and Cr(VI) (400 mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg²⁺ and Al³⁺ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl⁻ in Cl-LDH interlayer, isomorphic substitution of Mg²⁺ with Cu²⁺, formation of Cu₂Cl(OH)₃ precipitation, and the adsorption of Cr(VI) by Cu₂Cl(OH)₃. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

地下水循环井技术处理土壤和地下水中甲基叔丁基醚研究

研究了MTBE在砂土中的静态吸附以及采用地下水循环井技术(GCW)去除砂土和地下水中MTBE的衰减规律。结果表明:MTBE在砂土中的吸附动力学符合准二级动力学方程,相关系数R2为0.99618,在砂土中的吸附平衡时间为24 h;吸附热力学符合Linear平衡吸附,吸附系数为0.00306 m3/kg。GCW运行30 h后,地下水饱和含水层中MTBE浓度由500 mg/L降至72.5 mg/L,去除率为85.5%;砂土中MTBE的吸附量由0.93 mg/g降至0.03 mg/g,去除率达96.4%。水平方向距GCW越近,MTBE的去除效率越快,垂直方向位于GCW上部的MTBE优先会被去除,最佳修复时间为运行15 h。GCW对砂土和地下水中高浓度MTBE具有良好的修复效果。     

Study of cyanide removal from contaminated water using zinc peroxide nanomaterial

The present study highlights the potential application of zinc peroxide(ZnO_2)nanomaterial as an efficient material for the decontamination of cyanide from contaminated water. A process patent for ZnO_2 synthesis has been granted in United States of America(US Patent number 8,715,612; May 2014),South Africa,Bangladesh,and India. The ZnO_2 nanomaterial was capped with polyvinylpyrrolidone(PVP)to control the particle size. The PVP capped ZnO_2nanomaterial(PVP-ZnO_2)before and after adsorption of cyanide was characterized by scanning electron microscope,transmission electron microscope,X-ray diffractometer,Fourier transform infrared spectroscopy and time of flight-secondary ion mass spectrometry. The remaining concentration of cyanide after adsorption by PVP-ZnO_2 was determined using ion chromatograph. The adsorption of cyanide over PVP-ZnO_2 was also studied as a function of p H,adsorbent dose,time and concentration of cyanide. The maximum removal of cyanide was observed in p H range 5.8–7.8 within 15 min. The adsorption data was fitted to Langmuir and Fruendlich isotherm and it has been observed that data follows both the isotherms and also follows second order kinetics.     

Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves

Bamboo charcoal(BC) was used as starting material to prepare iron-modified bamboo charcoal(Fe-MBC) by its impregnation in FeCl 3 and HNO 3 solutions simultaneously,followed by microwave heating.The material can be used as an adsorbent for Pb(Ⅱ) contaminants removal in water.The composites were prepared with Fe molar concentration of 0.5,1.0 and 2.0 mol/L and characterized by means of N 2 adsorption-desorption isotherms,X-ray diffraction spectroscopy(XRD),scanning electron microscopy coupled with energy dispersive X-ray spectrometry(SEM-EDS),Fourier transform infrared(FT-IR) and point of zero charge(pH pzc) measurements.Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation.The adsorbent with Fe molar concentration of 2 mol/L(2Fe-MBC) exhibited the highest surface area and produced the best pore structure.The Pb(Ⅱ) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(Ⅱ).The adsorption of Pb(Ⅱ) strongly depended on solution pH,with maximum values at pH 5.0.The ionic strength had a significant effect on the adsorption at pH < 6.0.The adsorption isotherms followed the Langmuir isotherm model well,and the maximum adsorption capacity for Pb(Ⅱ) was 200.38 mg/g for 2Fe-MBC.The adsorption processes were well fitted by a pseudo second-order kinetic model.Thermodynamic parameters showed that the adsorption of Pb(Ⅱ) onto Fe-MBC was feasible,spontaneous,and exothermic under the studied conditions,and the ion exchange mechanism played an significant role.These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(Ⅱ) from wastewater.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

低C/N条件下MUCT工艺数学模型的参数校正与验证

基于ASM2d模型建立了稳定运行的MUCT工艺营养物质去除过程的动力学反应模型,比较各种COD、TN、NH 4＋-N、TP的实测值和模拟值,以确定系统在低C/N条件下运行时的动力学和化学计量学参数.模拟结果表明,稳态模型中的动力学参数qPHA、KA、KPP、YPO3-4、μAUT和ηNO-3分别取值2.90 g.（g.d）-1、3.85 g.m-3、1.35 g.（g.d）-1、0.35、1.6和0.8.其他的动力学和化学计量学参数可采用IWA给出的默认值.     

硫酸羟胺的自加速分解温度和稳定性研究

通过快速筛选热分析试验对硫酸羟胺热危险性进行定性分析,对其热分解过程进行初步研究,获得温度、压力变化规律;再运用C80微量热仪对硫酸羟胺进行深入分析,得到硫酸羟胺的化学反应动力学参数,根据Semenov模型计算其自加速分解温度（SADT）。试验结果表明：由RSD初步筛选试验得到硫酸羟胺在164．2℃时即发生分解放热;用C80法得到硫酸羟胺的起始热分解温度为137．1℃,并计算了该物质在3种典型包装下的自加速分解温度。由SADT得到储存、运输过程中硫酸羟胺的控制温度,从而为减少硫酸羟胺事故的发生提供必要的参考数据。     

水体系中氧氟沙星的光化学降解研究

研究了高压汞灯和氙灯照射下氧氟沙星(OFLX)在蒸馏水、人工海水和天然海水中的光降解过程,探讨了光源、起始浓度、丙酮、表面活性剂等因素对OFLX光化学降解速率的影响.结果表明,OFLX在高压汞灯下的光反应速率比在氙灯下快得多,均符合一级反应动力学过程;在相同光源下,OFLX在海水中降解最快,其次是人工海水;当OFLX初始浓度为2、4、6mg.L-1时,其光解速率常数分别为0.163、0.140和0.132 min-1,随着OFLX初始浓度增大,其光解率降低;不同浓度的丙酮均能促进OFLX光降解的反应,其反应速率常数为0.084 2～0.102 min-1,且光敏效率与丙酮浓度呈正相关关系;然而当十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)、吐温-20(TW-20)等表面活性剂的浓度为5 mg.L-1,它们均抑制了水体中OFLX光降解反应的进程.另外,利用金藻8701单种培养进行了OFLX光化学降解前后的毒性试验,表明OFLX光解过程产生风险较高的中间产物,随着光解进行,产物毒性降低.     

微生物发酵米糠对Pb~(2+)的吸附研究

利用微生物对米糖进行发酵处理,制备出微生物发酵米糠重金属吸附剂,对微生物发酵米糠吸附Pb2+进行了研究,结果表明,微生物发酵米糠对Pb2+吸附效果好,吸附率可达96.5%。该吸附剂的最佳用量为20g/L。最优吸附条件为:pH4.5,温度30℃,Pb2+浓度不超过50mg/L,最佳吸附时间30min。