纳滤去除水中的内分泌干扰物

采用陶氏DOW FILMTEC NF270芳香聚酰胺类复合纳滤膜处理水中内分泌干扰物——17α-乙炔雌二醇（EE2），实验中分别考察了原液浓度、操作压力、pH值、Ca²⁺浓度及腐殖酸共存等不同条件下对EE2截留效果的影响。结果表明，NF270对于去除水中的EE2具有很好的效果，截留率可达到97.6%，而且，实验发现，原液浓度对EE2的截留效果影响较小；当操作压力为0.6 MPa时，膜对EE2的截留效果最好；而随着pH值和Ca²⁺浓度的增加，膜对EE2的截留率均呈上升趋势；而当腐殖酸存在时膜对EE2的截留率有明显提高，但同时也造成膜污染加剧和膜通量下降，特别是在EE2、腐殖酸和Ca²⁺共存时，膜污染更加严重。     

荷负电超滤膜同时去除水中天然有机物和铅离子

通过特定的化学反应对截留分子量为30 k D的再生纤维素(RC)超滤膜进行改性,得到荷负电超滤膜,并研究了其表面荷电性能。选用腐殖酸作为天然有机物的代表物质,研究荷负电改性膜同时去除溶液中腐殖酸和铅离子,主要考察了p H值和腐殖酸铅离子络合作用对两者截留率的影响,并对比了荷负电膜和未改性膜去除天然有机物和铅离子的研究结果。得到如下结论:(1)在酸性及中性溶液环境下,随着p H值的升高,荷负电超滤膜对腐殖酸和铅离子的截留率都提高。(2)铅离子与腐殖酸共存时,腐殖酸铅离子络合体的荷负电性相比于原腐殖酸分子降低,荷负电超滤膜对混合溶液中腐殖酸的截留率有一定程度降低,络合在腐殖酸表面的铅离子随着腐殖酸的截留而被截留,铅离子截留率得到一定程度提升。(3)由于腐殖酸与铅离子络合体带负电,其与荷负电膜之间存在静电作用,所以荷负电改性膜对腐殖酸和铅离子的截留率比未改性中性膜高。     

用微观作用力解析无机离子对腐殖酸的膜污染行为影响

基于Na+、Ca2+离子在天然水体中的普遍存在及对超滤膜有机污染行为的影响,本研究主要考察了不同离子条件下腐殖酸(HA)对PVDF超滤膜污染行为的影响机理。使用原子力显微镜结合自制的膜材料及污染物探针定量测定了不同离子条件下PVDF-HA及HA-HA之间的相互作用力,同时进行了相应的膜污染实验及定量研究腐殖酸的去除效果。结果表明,PVDF-HA及HA-HA之间的相互作用力大小与膜污染速率及污染幅度呈正相关关系。一价Na+离子通过电荷屏蔽可降低HA表面的带电量,对HA膜污染行为及PVDF-HA及HA-HA之间作用力的影响并不明显。二价Ca2+离子通过电荷中和作用大幅度降低了HA表面的有效带电量,使得PVDF-HA及HA-HA之间的粘附力增大,加剧了膜污染速率。而过多的Ca2+离子会加剧HA之间的聚合,降低了HA进入膜孔内的机率,虽然会短暂的增加腐殖酸的去除效率但无法从根本减轻膜污染。     

有机物性质对混凝-微滤-纳滤去除水中重金属的影响

为了探明有机物性质对混凝-微滤-纳滤去除水中重金属的影响,将腐殖酸和乙酸分别作为背景有机物,系统考察了组合工艺对镉(Cd)、铜(Cu)、镍(Ni)和锌(Zn)的去除效能及其膜通量变化过程,并通过物料衡算对4种重金属的去除行为进行了比较分析。结果表明,当原水中不含有机物时,Cu的截留率最高,达到97%以上,纳滤膜是去除其他3种重金属的主要步骤。随着原水中腐殖酸含量的增大,混凝-微滤阶段对重金属的截留能力显著增强,膜通量衰减速度加快。相反地,乙酸的存在对于组合工艺处理效能具有明显的负面效应。此时,重金属既不能被铝盐絮体有效吸附,也不能通过静电作用截留在NF膜表面。4种重金属在滤液和浓水中的回收率R_(rec)都超过了80%,膜通量的变化与处理无机重金属溶液时相近。     

纳滤工艺去除水中微量内分泌干扰物

主要研究了DL1210型纳滤膜去除水中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、乐果和莠去津的影响因素,考察了温度、pH值、初始浓度、跨膜压力(TMP)和运行时间对膜通量和截留率的影响。结果表明,纳滤工艺是去除水中微量DBP、DEHP、乐果和莠去津的有效方法,初始pH值和温度的升高会导致纳滤膜对DBP、DEHP、乐果和莠去津的截留率的降低,膜对DBP和DEHP的截留率随初始浓度的升高而降低,TMP和运行时间不会对膜通量和目标污染物的截留率造成显著影响。当初始pH为5、初始浓度为5μg/L、温度为5℃、TMP为0.4 MPa时,纳滤工艺对DBP、DEHP、乐果和莠去津的截留率达到最佳,分别为91.8%、89.8%、98.02%和77.6%,出水中DBP、DEHP、乐果和莠去津浓度分别为0.41、0.49、0.099和1.12μg/L。     

SPEEK涂层纳滤膜处理草甘膦废水

以聚醚砜(PES)超滤膜为基膜,采用涂层法制备磺化聚醚醚酮(SPEEK)中空纤维复合纳滤膜,研究其对草甘膦的浓缩和去除。考察了该膜在浓缩草甘膦模拟废水中的操作条件,如跨膜压力、进料浓度、进料pH和离子强度等对通量和截留率的影响。结果表明,随跨膜压力的增加,草甘膦的截留率和水通量均增加,当跨膜压力由0.3 MPa增加到0.8 MPa时,水通量由34.0 L/(m2.h)增加至98.0 L/(m2·h),截留率高于98%;增加进料浓度和离子强度,截留率和通量均减小,当进料浓度由100 mg/L增至1 000 mg/L,水通量降低12.4%,截留率降低8.4%;而pH由3.0升至11.0时,截留率增加,但通量几乎不变。当把该膜材料用于浓缩含高浓度NaCl的草甘膦母液时,发现在0.5 MPa压力和pH=11.0下,复合纳滤膜对NaCl的截留率低于20%,对草甘膦的截留率可达90%。这说明该复合纳滤膜可以把草甘膦与NaCl有效分离开来,为草甘膦的回收利用提供了基础。     

正渗透膜过滤特性及污染物截留性能

采用Na Cl为汲取液溶质,研究正渗透膜分离过程中膜朝向、汲取液溶质浓度和错流速率对膜过滤性能的影响,以及正渗透膜对Na Cl、生活污水和垃圾渗滤液的污染物截留性能。结果表明,活性层朝向汲取液(AL-DS)时水通量(Jw)明显大于活性层朝向原料液(AL-FS)时,但随时间下降较快;Jw和溶质反向扩散通量(Js)均与汲取液溶质浓度正相关,但非线性增加,原因与内浓差极化有关;Jw同样与错流速率正相关,但随错流速率增加不明显。以葡萄糖为汲取液溶质时,正渗透膜对Na Cl的截留率能够达到90%以上。相同汲取液浓度下,处理生活污水时的Jw略大于垃圾渗滤液。正渗透膜对2种废水的污染物截留效果均较好。处理生活污水时,总有机碳和总氮的平均截留率分别为82%和90%以上;处理垃圾渗滤液时则分别能达到77%和95%以上。正渗透膜对渗滤液中的二价离子(钙、镁)的截留率达到98%以上。     

3种正渗透膜对水中卡马西平的截留

采用3种商业正渗透膜对污水中的卡马西平进行截留,研究了膜活性层朝向、汲取液浓度、流速和汲取液溶质对卡马西平截留效果的影响。结果表明,活性层朝原料液的正渗透(FO)模式对卡马西平的截留效果要优于活性层朝向汲取液的模式。3种膜对卡马西平的截留率随着汲取液浓度的升高有所提高,但高浓度的汲取液时增幅并不显著且会引起严重的盐返混。NaCl是截留卡马西平最适合的汲取液溶质,对卡马西平的截留率随着水通量增加而增加,但是过高的盐返混可能导致卡马西平截留率的下降。醋酸纤维素聚酯网膜是所选3种膜中对卡马西平的截留率较高的膜。这些实验结果可为FO应用于卡马西平废水的处理提供参数。     

pH对沟渠沉积物截留农田排水沟渠中氮、磷的影响研究

通过摇瓶动态实验和箱体静止实验,研究了不同pH条件下沟渠沉积物对农田流失氮、磷的截留效应,分析了pH对氮、磷截留效应及其界面交换作用的影响.结果表明:在实验pH变化范围内,沟渠沉积物对NH 4-N的吸附量和NO-2-N的硝化量以及对TN的截留率都是随着pH的增加而增加;沟渠沉积物对总溶解性磷(TDP)的吸附量随着pH的增加而增加,TP的截留率在5 d前随pH的增加而增加,但在此后基本不发生变化;在不同的pH下,通过影响微生物的活动直接或间接影响氮的界面交换行为,同时pH通过影响沉积物的吸附作用和离子交换作用来影响磷在沉积物-水界面的交换行为.阐明pH对沟渠沉积物氮、磷截留效应的影响有助于掌握氮、磷在农田排水沟渠中的迁移转化机理,从而对控制农业面源污染具有重要的意义.     

酒石酸钾钠（PST）对纳滤处理重金属废水的强化效果

以酒石酸钾钠（PsT）为络合剂，分别选取cd、zn、As和Ph4种金属废水，探索络合纳滤工艺对金属离子去除率和膜通量的强化效果，测定纳滤膜表面接触角以表征膜通量变化规律，并研究了压力、金属浓度和溶液pH参数对络合纳滤过程的影响。结果表明，PsT对4种金属去除的强化效果存在相似规律，分别有一个最佳PsT添加浓度。随PsT浓度的增加，金属离子去除率先增大后减小，而膜通量一直增大。研究发现，纳滤膜表面接触角与膜通量呈稳定的反比例关系，与金属离子种类和PsT添加量无关。随着操作压力的增大，膜通量线性增加，去除率基本不变；金属离子浓度的增加对膜通量影响不大，金属去除率略有上升；pH在4～5之间变化时，As去除中膜通量和去除率均有所升高，而cd、zn和Ph3种溶液处理效果基本不受pH影响。     

Removal of humic substances from water by means of calcium-ion-enriched natural zeolites.

The ability of the natural zeolited Neapolitan Yellow Tuff (NYT) enriched with calcium ions to remove humic acids from water was evaluated by batch adsorption equilibrium tests and dynamic experiments carried out by percolating humic acid solutions through a small NYT column (breakthrough curves). Under the experimental condition explored, the sorption capacity increases with the ionic strength and has the highest value at pH 7.4. The partition coefficient for a low concentration of humic acid ([humic acid] --> 0), at pH 7.4 in 0.01 M sodium chloride, was approximately 1000 L/kg, versus the value of approximately 100 L/kg in the absence of the alkaline metal salt. Therefore, after humic acids have been adsorbed in a column filled with the calcium-ion-enriched tuff, a reduction of the salt concentration in the ongoing solution enhances the release of the adsorbed material. These findings show that NYT can be used for the removal of humic acids from water.     

Surface charge and adsorption from water onto quartz sand of humic acid

The surface charge of humic acid under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)) was determined by a titration method using a cationic polyelectrolyte as titrant. Adsorption isotherms in batch experiments of the polymer from water onto quartz sand were determined at 20 degrees C, 40 degrees C, and 60 degrees C and under different conditions of ionic strength, pH, and the presence of various cationic ions (Cu(2+), Zn(2+), Ba(2+), and Ca(2+)). The data indicate significant decrease of humic acid surface charge by decreasing the pH value from 10.0 to 4.1. Similar decrease of humic acid surface charge was observed by increasing either the ionic strength or the affinity of the divalent cation toward the humic acid. At ambient temperature the adsorption of humic acid on the quartz sand seems to be controlled mainly by electrical interaction between the organic particle and the solid substrate. A correlation is found between the surface charge and the adsorbed amount of the polymer, the adsorbed amount increases when the surface charge of humic acid decreases. The increase of the adsorbed amount with the temperature suggests that adsorption process is endothermic.     

Effects of aquatic humic substances on a hydrophobic ultrafiltration membrane

Natural humic surface water (pH 5.9), ion exchanged samples of the same water (pH 5.5), and aqueous solutions of isolated humic substances at pH 4.5, 5.5 and 6.5, respectively, were ultrafiltered (15°C, 0.5 bar) using hydrophobic polysulfone membranes (GR51) in a cross-flow flat sheet module. The used membrane did not completely retain natural organic matter from the surface water and the addition of complexing metals did not affect the retention any further. The changes which were induced in the membranes during each filtration run were studied by simultaneous streaming potential and flux measurements in 0.01 M KCl solutions. Zeta potentials were calculated based on the streaming potentials and the results showed changes towards more negative values for all the samples due to adsorption of organic matter onto the surface of the membrane pores. Humic acid affected the membrane charges more than fulvic acid. High ionic strength and low pH enhanced flux reduction and fouling. Filtration of natural waters caused more pore plugging and flux reduction than filtration of solutions of the isolated humic substances.     

Kinetics of disaggregation of humic acid in water

The extent of disaggregation of humic acid particles in water was measured as a function of time, initial concentration, pH of the suspension and the temperature. In all experiments the amount of humic acid particles disaggregated was characterized by the corresponding fraction of the suspension, which was able to pass a 0.01 μm membrane filter.It was found that the amount disaggregated after 1000 hours was proportional to the initial concentration of the humic acid particles in the aqueous suspension and increased considerably with the temperature. Decreasing the pH of the suspension from about 6 to zero caused the extent of disaggregation also to decrease continuously.The kinetic measurements revealed that about 3% of the humic acid are disaggregated within 25 hours, 4% within 200 hours and 5% within 1500 hours at a pH around 4. The rates of disaggregation were found to be proportional to the initial concentration of the particles and increased considerably with the temperature.     

全氟辛烷磺酸盐(PFOS)在藻渣/小球藻上的吸附行为及机理

为了开发新型廉价生物吸附剂,以高效吸附去除水体中全氟辛烷磺酸盐(PFOS),对小球藻提取生物柴油后的藻渣吸附酸性水体中的PFOS进行了吸附行为及机理的研究。小球藻提取生物质柴油后,比表面积、孔容、孔径几乎没有变化;等电点由3.3降低至2.7;蛋白质含量由51.45%提高到57.35%。在酸性条件下(pH≤3),小球藻和藻渣对PFOS的吸附率均达到99%以上;随着pH值增加至7,二者的吸附去除率迅速降低,但仍保持在22%~26%。小球藻和藻渣对PFOS的最大吸附容量分别为353.69 mg/g和444.83 mg/g。Freundlich模型能较好地拟合二者对PFOS的吸附数据,表明为多层吸附,即小球藻以静电吸引的形式吸附PFOS阴离子,并疏水分配至所含蛋白质中;而藻渣中含量较高的蛋白质对PFOS的疏水性分配作用是导致藻渣吸附量增高的主要原因。     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

混凝絮凝法去除腐质酸的研究

进行了混凝絮凝法去除水中腐殖酸的研究，结果表明，同传统的絮凝剂相比，微生物絮凝剂不仅用量少，去除效果好(去除率可达60％)，而且不产生二次污染，可应用于废水特别是给水中腐殖酸的去除工艺中，对絮凝剂的絮凝机理进行了初步研究，研究表明，微生物絮凝剂去除腐殖酸主要是通过架桥完成的，不同于A12(SO4)3的电中和机理。     

The reactions of paraquat and divalent metal ions with humic acid: Factors influencing stoichiometry 2

Abstract

Laurentide humic acid has been titrated with paraquat and with selected divalent metal ions. In some cases, the humic acid was spiked with one cation before titration with another one. Several equivalence points were determined for the binding of the divalent cations, including paraquat. Three equivalence points agreed well with values predicted from the acidic properties of the humic acid. Eight independent experiments gave nine replicate values for an equivalence point that corresponds to 79.2 mole % of the total pairs of carboxyl groups. It is postulated that this represents a large molecular weight or structural fraction of the humic acid. The remaining 20.8 mole % can either bind one divalent cation to two carboxylate anions or bind one divalent cation to one carboxylate anion, with another anion providing for charge balance. Aggregation ‐ disaggregation and dissolution ‐precipitation phenomena may determine which case prevails, and they in turn are sensitive to the chemical compositions of samples. It should be possible to develop analytical chemical methods for characterizing the stoichiometric properties of humic acid samples.     

凹凸棒土对腐殖酸的低温吸附性能研究

首次研究凹凸棒土对饮用水中腐殖酸的低温吸附性能,考察5℃条件下,吸附时间与腐殖酸初始浓度、吸附剂投加量、pH对凹凸棒土吸附腐殖酸的影响,确定吸附剂的吸附等温线、吸附动力学和热力学等相关理论参数,研究凹凸棒土对腐殖酸的吸附性能与机理。结果表明,江苏盱眙凹凸棒土在温度5℃、pH=4、水中腐殖酸初始浓度为5 mg/L,投加量为15 g/L的条件下,吸附180 min后对腐殖酸的去除率可达97.26%。凹凸棒土对腐殖酸的吸附符合二级吸附动力学方程与Freundlich吸附等温式,吸附过程由孔隙内扩散过程控制,吸附为自发的吸热过程,包括物理吸附与化学吸附。根据Fre-undlich吸附等温式拟合计算,5℃、pH=7时理论最大吸附量为9 mg/g,说明凹凸棒土对于低温饮用水中腐殖酸具有良好的吸附效果。     

Influence of suspended clay minerals and humic matter on the solid phase extraction efficiency of selected pesticides from water

The purpose of this investigation was to determine the influence of humic acids (HA) and Ca-montmorillonite (CaM) on the solid-phase extraction (SPE) efficiency of atrazine, alachlor and alpha-cypermethrin from water samples at various pH-values. The nature and intensity of binding of the studied pesticides to CaM were determined by X-ray diffraction analysis and termogravimetric analysis (TGA) test. The studied pesticides eluted from discs were analysed by thin-layer chromatography (TLC). The effects of CaM and humic acid were generally pH-dependent and acted independently in extraction efficiency influence. Lower recovery of pesticides was observed at higher pH values when CaM was > or =0.1 g and was attributed to greater dispersion of clay, increased surface area and subsequent adsorption. Concentrations of dissolved organic carbon (DOC) in humic acid had less effect on the extraction efficiency when water was at pH 8 compared to water at pH 2, which was probably due to greater nonpolar interactions of the pesticides to the charge-neutralized humic acid molecule.