多胺功能化介孔炭对Pb（Ⅱ）的吸附动力学与机制

采用硝酸氧化和乙二胺聚合在微波辅助磷酸活化中孔蔗渣基介孔炭孔道内修饰了含氮多胺基团,制备了多胺功能化生物质炭材料AC-EDA,分析了溶液pH、初始浓度和吸附时间等参数对材料吸附Pb(Ⅱ)影响,探讨了其动力学吸附行为与吸附机制.结果表明,多胺功能化炭材料AC-EDA对Pb(Ⅱ)有较好的吸附效率,5 min内可达饱和吸附量的70%;酸性条件下,增大溶液pH有利于Pb(Ⅱ)吸附;材料AC-EDA对Pb(Ⅱ)的吸附位能量存在差异化,在吸附初始阶段,吸附速率由颗粒内扩散控制,中后期主要由膜扩散控制;准二级方程能很好地描述多胺功能化炭材料对Pb(Ⅱ)的吸附动力学行为.AC-EDA对Pb(Ⅱ)的吸附是自发的吸热反应过程,提高温度对铅(Ⅱ)离子吸附有促进作用;D-K-R吸附能>11 kJ·mol-1,表明化学反应在Pb(Ⅱ)吸附过程中起主导作用;吸附Pb(Ⅱ)前后的AC-EDA材料XPS图谱表明,多胺基团参与了吸附反应,是材料高效吸附Pb(Ⅱ)的重要因素.     

黄原酸化废弃污泥吸附Cu2+研究

将污水处理厂废弃污泥在碱性环境中用CS2处理,制备黄原酸酯类重金属吸附剂,探究一种有效的废弃污泥资源化途径.用傅里叶转换红外光谱(fourier transform infrared spectroscopy,FTIR)对污泥进行了表征,并通过批量实验研究了污泥对Cu2+的吸附性能以及pH和初始Cu2+浓度的影响.结果表明,黄原酸化成功引入了含硫基团,使黄原酸化污泥的吸附量相对于原始废弃污泥提高了20.6%~46.9%.当Cu2+初始浓度为25 mg·L-1时,黄原酸化污泥对Cu2+的去除率可达96.7%.吸附动力学遵循准二级动力学模型(Pseudo-second-order equation),平衡时间为3 h,吸附速率同时受膜扩散和颗粒内扩散两过程控制;吸附过程符合Langmuir等温模型和Freundlich等温模型,25℃下,由Langmuir模型得到的最大吸附量达142.92 mg·g-1(pH=5),且吸附容量随pH(1~5)及初始Cu2+浓度升高而升高.黄原酸化废弃污泥可作为高效重金属离子吸附剂,实现废弃资源的回收利用.     

改性粘土矿物的制备及其对水体中二氯喹啉酸的吸附研究

采用固-液吸附法,以天然钙基蒙脱石为原料,硫酸和十六烷基三甲基溴化铵(HDTMAB)为改性剂,制备了3种改性蒙脱石,并借助X-射线衍射、比表面积全分析及有机碳含量测定对所得的改性蒙脱石进行表征.结果表明,先酸化后再进行有机改性所得的改性蒙脱石(AHM)不仅具有较大的比表面积、层间距,而且有机碳含量是最高的.同时,采用批量平衡实验比较了这3种改性蒙脱石和天然蒙脱石对二氯喹啉酸的吸附能力.结果表明,天然蒙脱石对二氯喹啉酸的吸附率最小,不足5%,而先酸化再进行HDTMAB改性所得的改性蒙脱石对二氯喹啉酸的吸附率最高,其对二氯喹啉酸的吸附容量约为天然蒙脱石的20倍.二氯喹啉酸在这种改性蒙脱石上吸附速率很快,吸附平衡时间为2 h,吸附动力学满足准二级动力学方程,吸附等温线可用Linear和Freundlich模型较好地拟合.     

还原共沉淀法制备Fe-Ti复合氧化物及其吸附水中As(Ⅴ)的研究

采用还原-共沉淀法制备了无定型纳米复合Fe-Ti氧化物(FFT)吸附剂,并研究其对水中低浓度As(Ⅴ)的去除性能.XRD表征结果表明,制备的纳米FFT物相为无定型,BET比表面积达325.3 m2·g-1,计算得到的BJH吸附平均孔径为2.46 nm(4V/A),颗粒分布均匀.同时,考察了纳米FFT吸附As(Ⅴ)的动力学、热力学、吸附等温线,以及温度、水中共存离子对其去除As(Ⅴ)的影响.结果发现,纳米FFT对As(Ⅴ)的吸附符合拟二级动力学模型,计算出的孔道扩散系数DP在10-11~10-13cm2·s-1之间,显示孔扩散是速率限速步骤.Langmuir、Freundlich和DubininRadushkevich(D-R)吸附等温式均可较好地拟合吸附行为,低浓度下Langmuir吸附模型计算出的Qm达到26.46 mg·g-1.最后,研究了地下水中常见的共存离子对吸附的影响,发现Ca2+、Mg2+能够促进吸附,H2PO-4和HCO-3则明显抑制吸附过程.     

不同氧化锰矿物与砷的交互作用

利用从土壤铁锰结核中分离筛选得到的1株锰氧化细菌(芽孢杆菌,Bacillus sp.)GY16合成生物氧化锰,与化学合成的水钠锰矿进行比较,研究了不同氧化锰对As的氧化吸附特征.结果表明,生物氧化锰和化学氧化锰对As(Ⅲ)均有强烈的氧化作用,化学氧化锰对As(Ⅲ)的氧化速率要高于生物氧化锰,而单位物质的量的生物氧化锰对As(Ⅲ)的氧化量可达化学氧化锰的5倍,并且对As(Ⅴ)有非常明显的吸附作用,而化学氧化锰对As(Ⅴ)的吸附量则非常少.此外,随着生物氧化锰与As(Ⅲ)/As(Ⅴ)反应的进行,生物氧化锰对As(Ⅲ)/As(Ⅴ)的氧化吸附速率均逐渐降低.随着pH的增加,生物氧化锰对As(Ⅲ)的氧化量及As(Ⅴ)的吸附量均呈现出明显的下降趋势,但是化学氧化锰对As(Ⅴ)的吸附量却有微弱的增加.研究结果可为生物氧化锰应用于环境修复提供可靠的技术支撑.     

滇池表层沉积物对磷的吸附特征

在室内模拟条件下,从滇池表层沉积物对磷的吸附动力学与热力学两个角度出发,研究了滇池沉积物对磷的吸附特征,同时探讨了不同磷形态对磷吸附特性的影响,结果表明:1滇池不同形态磷含量顺序为:有机磷钙(O-P)钙结合态磷(Ca-P)金属氧化物结合态磷(Al-P)残渣态磷(Res-P)可还原态磷(Fe-P)弱吸附态磷(NH4Cl-P);2沉积物对磷的吸附动力学过程分为2个阶段,即快吸附和慢吸附阶段.快吸附阶段主要发生在0~0.5 h内,而慢吸附阶段主要发生在0.5~4 h.滇池沉积物对磷的吸附过程主要在4 h内完成.3外海北部上覆水磷酸盐(SRP)浓度低于沉积物中磷的吸附/解吸平衡浓度(EPC0),可初步判断该区域沉积物有向上覆水体释放磷的风险.4不同区域沉积物磷的最大吸附量(Qmax)和总最大吸附量(TQmax)均以外海南部最大.5沉积物本底吸附态磷含量(NAP)与钙结合态磷(Ca-P)呈显著正相关关系(R2=0.5139,p0.05),而其他吸附特征参数与磷形态之间相关性均不显著.6与洱海、太湖等湖泊相比,滇池沉积物磷的本底吸附态磷(NAP)和最大吸附量(Qmax)均处于较高水平,磷污染较为严重.     

Removal of arsenate with hydrous ferric oxide coprecipitation：Effect of humic acid

Insights from the adverse effect of humic acid(HA) on arsenate removal with hydrous ferric oxide(HFO) coprecipitation can further our understanding of the fate of As(V) in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As(V) on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering(SERS), extended X-ray absorption fine structure(EXAFS) spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared(ATR-FTIR) measurement, and charge distribution multisite complexation(CDMUSIC) modeling. The As(V) removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As(V) mass concentration. The SERS analysis excluded the HA-As(V) complex formation. The EXAFS results indicate that As(V) formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26–3.31 ?. The in situ ATR-FTIR measurements show that As(V) replaces surface hydroxyl groups and forms innersphere complex. High concentrations of HA may physically block the surface sites and inhibit the As(V) access. The adsorption of As(V) and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As(V) and HA reasonably well.     

Metal composition of layered double hydroxides (LDHs) regulating ClO4- adsorption to calcined LDHs via the memory effect and hydrogen bonding

A series of calcined carbonate layered double hydroxides （CLDHs） with various metal compositions and different M^2＋/M^3＋ ratios were prepared as adsorbents for perchlorate. Adsorption isotherms fit Langmuir model well, and the adsorption amount followed the order of MgA1-CLDHs 1〉 MgFeCLDHs 〉〉 ZnA1-CLDHs. The isotherms of MgA1-CLDHs and MgFe-CLDHs displayed a two-step shape at low and high concentration ranges and increased with an increase in the M^2＋/M^3＋ ratio from 2 to 4. The two-step isotherm was not observed for ZnA1-CLDHs, and the adsorption was minimally affected by the M^2＋/M^3＋ ratio. The LDHs, CLDHs and the reconstructed samples were characterized by X-ray diffraction, SEM, FT-IR and Raman spectra to delineate the analysis of perchlorate adsorption mechanisms. The perchlorate adsorption of MgA1-CLDHs and MgFe-CLDHs was dominated by the structural memory effect and the hydrogen bonds between the free hydroxyl groups on the reconstructed-LDHs and the oxygen atoms of the perchlorates. For ZnAI-CLDHs, the perchlorate adsorption was controlled by the structural memory effect only, as the hydroxyl groups on the hydroxide layers preferred to form strong hydrogen bonds with carbonate over perchlorate, which locked the intercalated perchlorate into a more confined nano-interlayer. Several distinct binding mechanisms of perchlorate by CLDHs with unique M^2＋ ions were proposed.     

Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products

Anion exchange resins （AERs） with different properties were evaluated for their ability to remove dissolved organic matter （DOM） and bromide, and to reduce disinfection by-product （DBP） formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin （MIEX） showed faster dissolved organic carbon （DOC） removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency, MIEX showed significant chlorinated DBP removal because it had the highest DOC removal within 30 rain, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.     

水介质中C60纳米晶体颗粒与Cu2+对小鼠腹腔巨噬细胞的复合毒性研究

为考察C60纳米晶体颗粒和Cu2+复合体系的生物毒性,本文以小鼠腹腔巨噬细胞RAW264.7作为受试对象,研究了C60纳米晶体颗粒物(n C60)和Cu2+对RAW 264.7的复合毒性影响.结果表明,当单独暴露n C6024 h,n C60浓度为6.6 mg·L-1时,细胞活性降低了45%,n C60浓度为9.9 mg·L-1时,细胞活性降低了70%,表现出剂量-毒性效应和时间-毒性效应.水中出现Cu2+可以降低n C60的细胞毒性,当Cu2+浓度为2 mg·L-1,n C60浓度为6.6 mg·L-1时,细胞的活性降低至25%,当Cu2+浓度为5 mg·L-1,n C60浓度为9.9 mg·L-1时,细胞的活性下降至15%.研究表明,n C60表面能够吸附Cu2+,并且吸附符合Langmuir吸附等温模型.n C60纳米晶体颗粒表面对Cu2+的吸附,可能是n C60对细胞毒性降低的重要原因.