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.     

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。     

水环境中典型纳米颗粒对菲的吸附特征

以典型三环多环芳烃菲为代表,选取11种典型纳米颗粒对水中不同浓度的菲进行吸附实验,探究水体中的纳米颗粒对菲的吸附特征.结果表明,Freundlich模型对所有样品的拟合结果最好.logKFr值显示,有机膨润土及3种炭黑对菲的吸附作用最强,且远远大于其他纳米颗粒.有机膨润土对菲的吸附表现为线性吸附(n=1.08),而3种炭黑均表现出显著的非线性特征(n＜0.5),且非线性特征随吸附能力的增强而增强,其他几种纳米颗粒均表现出非线性吸附特征(n＜0.9).水中所有的纳米颗粒在与菲作用的过程中,吸附的强弱与颗粒表面电位、粒径及比表面积均无显著相关性,即对于所有纳米颗粒来说,这几种性质并不是决定吸附作用的最主要因素,而吸附剂的化学组成及结构特性可能是引起吸附作用差异的主要原因.     

Utilizing surfactants to control the sorption, desorption, and biodegradation of phenanthrene in soil-water system

An integrative technology including the surfactant enhanced sorption and subsequentdesorption and biodegradation of phenanthrene in the soil-water system was introduced and tested. For slightly contaminated agricultural soils, cationic-nonionic mixed surfactant- enhanced sorption of organic contaminants onto soils could reduce their transfer to plants, therefore safe-guarding agricultural production. After planting, residual surfactants combined with added nonionic surfactant could also promote thedesorption and biodegradation of residual phenanthrene, thus providing a cost-effective pollution remediation technology.0ur results showed that the cationic-nonionic mixed surfactantsdodecylpyridinium bromide (DDPB) and Triton X-100 (TX100) significantly enhanced soil retention of phenanthrene. The maximum sorption coefficient Kd* of phenanthrene for contaminated soils treated by mixed surfactants was about24.5 times that of soils without surfactant (Kd ) and higher than the combined effects of DDPB and TX100 individually, which was about 16.7 and 1.5 times Kd , respectively.0n the other hand, TX100 could effectively remove phenanthrene from contaminated soils treated by mixed surfactants, improving the bioavailability of organic pollutants. Thedesorption rates of phenanthrene from these treated soils were greater than 85% with TX100 concentration above2000 mg/L and approached 100% with increasing TX100 concentration. The biodegradation rates of phenanthrene in the presence of surfactants reached over 95% in30days. The mixed surfactants promoted the biodegradation of phenanthrene to some extent in 10-22days, and had no obvious impact on phenanthrene biodegradation at the end of the experiment. Results obtained from this study provide some insight for the production of safe agricultural products and a remediation scheme for soils slightly contaminated with organic pollutants.     

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.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.     

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.