基于Zeta电位法研究腐殖酸对超滤膜的污染

基于Zeta电位法表征膜表面的荷电性能,分析单一腐殖酸或与Ca~(2+)共存下的吸附行为对超滤膜表面Zeta电位的影响及膜通量的变化,深入了解膜与腐殖酸的作用机制,阐释超滤膜污染的作用机理,为表征超滤膜的耐污染性能提供一种新颖的有效手段。结果表明,在中性溶液中,PVDF超滤膜表面ζ0,电性为负;腐殖酸的吸附导致膜通量大幅衰减,同时Zeta电位变化明显,随着腐殖酸浓度的增加,Zeta负电位变大; Ca~(2+)加速了对腐殖酸的吸附,同时中和膜表面所吸附的负电荷,削弱膜与腐殖酸分子之间的静电排斥作用,导致吸附增加,膜通量下降,加重膜污染。     

反洗水组分对超滤膜污染的影响

超滤反洗如同短时间的"死端过滤",反洗水组分对超滤膜污染进程有重要影响,以腐殖酸(HA)、Na~+和Ca~(2+)模拟反洗水中的小分子有机物、一价和二价金属阳离子,将海藻酸钠(SA)作为典型污染物,通过死端过滤的方式分析了反洗水中的不同组分对PVDF超滤膜污染的影响。同时借助质量守恒定律对膜的反洗效率和反洗后污染物的去除情况进行了定量分析。结果表明,反洗水中单独存在的小分子有机物对膜污染的影响并不显著,但小分子有机物协同金属阳离子对膜污染产生了较为明显的不利影响;一方面Ca~(2+)、Na~+等阳离子能够与带负电的HA小分子吸附结合,形成尺寸较大的聚集体,导致膜内壁污染以及反洗膜孔的堵塞,从而降低反洗效率,加剧膜面污染物的积累;另一方面,通过Ca~(2+)、Na~+等阳离子的"架桥作用"与电荷屏蔽效应,强化了膜表面污染物与膜壁之间的静电吸附作用,导致了更为严重的不可逆污染。     

不同离子对纳滤去除水中腐殖酸的影响研究

腐殖酸（HA）作为天然有机物（NOM）的主要成分之一，广泛存在与水体之中，对纳滤处理过程影响较大。本文以三种模拟配水作为研究对象，通过分析纳滤对水中腐殖酸去除率和膜通量的变化，得出了不同离子对纳滤去除水中腐殖酸的影响的变化规律，并进行了膜污染程度的比较及分析。结果表明：在纳滤处理三种模拟配水过程中，HA 配水的截留率下降54.0%；Na++HA 配水的截留率下降26.2%；HA+Ca2+配水的截留率下降30.8%。整体而言，不同价态离子对三种模拟配水通量变化影响很小。     

聚电解质强化超滤处理低浓度含Cd~(2+)废水效能

分别采用聚丙烯酸(PAA)和壳聚糖(CTS)作为聚电解质,研究了聚电解质强化超滤法处理含Cd~(2+)重金属废水,并考察了聚电解质浓度、pH值、共存离子对截留率、渗透性能和膜污染的影响。结果表明,对于20 mg/L的含Cd~(2+)废水,当PAA、CTS浓度为100 mg/L时去除效果最好,对Cd~(2+)的去除率分别为90.1%和91.6%,对PAA和CTS的去除率分别为71.5%和69.4%。pH值对Cd~(2+)的去除影响较大,Cd~(2+)去除率随着pH值的上升而明显增加,PAA和CTS的去除率则无明显变化。在PAA溶液中,4种共存离子对Cd~(2+)的去除影响程度排序为Na~+Cu~(2+)Mg~(2+)Ca~(2+);在CTS溶液中,对Cd~(2+)的去除影响程度排序则为Cu~(2+)Na~+≈Mg~(2+)Ca~(2+)。聚电解质浓度越高,产生的膜污染越严重,而且投加CTS的膜污染更严重。     

膜蒸馏法浓缩反渗透浓水的试验研究

采用直接接触式膜蒸馏法浓缩处理反渗透浓水,系统研究了未经预处理、酸化预处理和阻垢预处理后的反渗透浓水在膜蒸馏浓缩过程中产水电导率、产水通量和膜污染的变化规律.试验结果表明,在三种膜蒸馏试验中,膜蒸馏的脱盐率均稳定.未经预处理的反渗透浓水在膜蒸馏过程中产水通量下降迅速,膜表面CaCO3污染是其主要原因.酸化预处理在一定程度上延缓了膜蒸馏浓缩过程产水通量的衰减,但随着浓缩过程的进行,仍然有沉积物在膜表面形成,导致通量下降.经阻垢预处理后膜蒸馏浓缩过程的膜通量比较稳定.这是因为阻垢预处理在一定程度上预防了难溶盐在膜表面的沉积,减缓了膜污染.对经阻垢预处理后的反渗透浓水保持浓缩倍数为3,在112 h的长周期运行中产水电导率稳定在5μS/em以下,且产水通量下降缓慢,至试验结束时产水通量为13.9 kg/( m2·h),较初始通量只下降了10.9％.     

有机物分子尺度对纳滤膜污染的影响研究

以市政污水处理厂的MBR出水作为纳滤进水,从有机物分子尺度分布的微观角度分析进水中有机物分布特征与纳滤膜污染的相关性,研究含不同分子质量的有机物水样对纳滤膜通量衰减、脱盐率以及膜表面污染的影响规律.结果表明,随着进水中溶解性有机物分子质量的减小,膜比通量衰减幅度不断增加,特别是分子质量＜1 ku的溶解性有机物引起膜通量衰减幅度最大,连续运行28 h后膜比通量下降了85.2％.电镜扫描分析进一步表明,进水中分子质量＜1 ku的有机物是造成膜有机污染的主要成分.此外,水中有机物在纳滤膜表面的累积会使纳滤膜的脱盐率有所增加.当进水中有机物分子质量在1 ku以下时,纳滤膜的初始脱盐率在94％左右,经28h连续运行后脱盐率上升了3.5％ ～4％;进水中有机物分子质量在100 ku以下时,纳滤膜的初始脱盐率为91％ ～92％,经28 h连续运行后脱盐率上升4％ ～4.5％.     

PAC-UF组合工艺去除水中腐殖质类有机物效能及膜污染研究

研究了采用PAC-UF组合工艺处理含有腐殖酸的水时,PAC投加量对膜通量、有机物去除率和膜污染阻力的影响。结果表明,有机物去除率随PAC投加量的增加而提高;膜通量在低PAC投加量下得到提高,在高PAC投加量下降低;水中腐殖质类有机物主要造成不可逆膜污染;PAC投加量为20 mg/L时,能有效降低不可逆污染阻力,缓解膜污染。     

Ca~(2+)浓度对膨润土掺砂混合土渗透性能的影响

垃圾填埋场底部铺设含黏土或膨润土掺砂混合土的防渗系统,防止渗滤液流入地下污染周边环境。采用模型试验研究Ca~(2+)离子浓度和基础局部沉降对膨润土掺砂混合土渗透特性的影响。试验结果表明Ca~(2+)浓度对膨润土掺砂混合土的渗透性能有较大影响,渗透液中Ca~(2+)浓度超过一定值后混合土渗漏;Ca~(2+)离子浓度与发生渗透时间之间有很大关系,浓度越高发生渗透的时间越短;同样沉降量条件下,含Ca~(2+)离子溶液渗透的混合土均发生渗漏,而用蒸馏水作渗透液的没有出现渗漏;钠基膨润土遇Ca~(2+)离子溶液后,当Ca~(2+)离子浓度大于两倍Na+就会发生离子交换,钠基膨润土转化为钙基膨润土,混合土的防渗性能下降。因此开展Ca~(2+)离子浓度对膨润土掺砂混合土渗透特性的研究具有较好的理论和实际意义。     

减压膜蒸馏浓缩脱硫液试验研究

采用减压膜蒸馏(VMD)技术浓缩脱硫液,研究了减压膜蒸馏过程中脱硫液浓度、流速、热侧料液温度、冷侧真空度及膜组件装实密度对膜通量和截留率的影响。试验结果表明:当脱硫液浓度较低时,膜通量随脱硫液浓度的升高而下降缓慢,当脱硫液浓度较高时,膜通量随脱硫液浓度的升高呈抛物线式下降;随着热侧料液流速的增加,膜通量略有增加;热侧料液温度升高,膜通量线性增加;随着冷侧真空度的增加,膜通量先略有增加,当冷侧真空度超过一临界值时,膜通量显著增加;膜通量随着组件内膜丝数目的增加而线性减少;试验过程中截留率保持在99.0%以上,表明聚偏氟乙烯(PVDF)中空纤维膜具有良好的疏水性。     

硫酸钠溶液pH值对硅酸盐水泥砂浆析钙及侵蚀产物的影响

将水泥砂浆浸泡在pH值为5,9,13的Na_2SO_4溶液中至330d,采用化学滴定法测定砂浆中Ca~(2+),OH~-的析出量,采用X射线衍射(XRD)仪和差示扫描量热法(DSC)对不同侵蚀龄期下侵蚀产物进行半定量分析,并通过扫描电子显微镜(SEM)对钙硅比和微结构进行了分析.结果表明:溶液pH值越低,Ca~(2+)析出速率越快、析出量越大,且低pH值条件下Ca~(2+)的大量析出有助于其与侵入的SO_4~(-2)结合,形成更多低溶解度的CaSO_4·2H_2O,从而加速Ca~(2+)析出和SO_4~(-2)扩散渗入;低pH值环境下大量石膏的形成伴随着Ca(OH)_2的大量消耗,且会引起C-S-H凝胶的脱钙,导致水泥砂浆的胶凝性降低,引起试件的软化和剥落.     

Membrane and solution effects on solute rejection and productivity

Limited understanding of the physical and chemical processes involved in membrane processes affects their widespread application in drinking water treatment. Insight into these processes was attained through a systematic manipulation of solution chemistry in membrane filtration with three ‘loose’ nanofiltration membranes. Eighteen known solutions were created varying pH, ionic strength, and major cation valence in the presence of a commercial humic acid. The membrances varied as well, including a non-ionic hydrophobic, a non-ionic hydrophilic, and an anionic hydrophilic membrane surface. Specific membrane productivity and TOC and conductivity rejection were monitored.

In all cases, the presence of divalent cations decreased the rejection of both conductivity and organic matter. Divalent cations also greatly increased the rate of productivity decline over equivalent tests in solutions with monovalent cations. The most hydrophobic membrane had the greatest productivity decline rate under all solution conditions. The lowest ionic strength solutions showed the greatest TOC and conductivity rejection and the greatest rate of productivity decline for each of the membranes.     

Comparison of humic acid rejection and flux decline during filtration with negatively charged and uncharged ultrafiltration membranes

Increasingly stringent regulations for drinking water quality have stimulated the ultrafiltration (UF) to become one of the best alternatives replacing conventional drinking water treatment technologies. However, UF is not very effectively to remove humic acid due to the comparatively larger pore size compared to the size of humic acid. Fouling issue is another factor that restricts its widespread application. In this study, rejection of humic acid and flux decline were compared with essentially neutral, negatively charged version of a regenerated cellulose membrane, in which electrostatic interaction was explored for a better humic acid removal and less fouling. Solution environment, including ionic strength, pH and calcium ion concentration, affecting humic acid removal and flux decline on negatively charged and neutral membranes was also compared. Results indicated that the appropriate charge modification on the neutral UF membrane could be an effective way for better removal of NOM and reduction of the membrane fouling due to the electrostatic interactions with the combination effect of membrane pore size. Electrostatic interactions are significant important to achieve high humic acid removal and less fouling, and to improve the water quality and protect people’s health.     

Biosorption of humic and fulvic acids to live activated sludge biomass

Biosorption of high molecular weight humic substances (HS) to activated sludge (AS) biomass may be considered as a preliminary step previous to enzymatic hydrolysis breakdown and biological uptake. Two standard HS, Suwannee River humic and fulvic acids, were biosorbed onto live AS biomass collected from full-scale wastewater treatment plants. Biosorption isotherms were corrected for interference from organic matter desorbed from AS biomass. The effect of pH, calcium and ionic strength on biosorption was tested. HS biosorption to live AS biomass obeyed the Freundlich isotherm equation. Biosorption increased with decreasing pH, increasing calcium and ionic strength concentration. Higher biosorption at low pH may be attributed to hydrophobic interactions between HS and AS biomass extracellular polymers (EPS). Hydrophobic and cationic bridging effects between HS and AS EPS were the mechanisms responsible for biosorption under the presence of divalent cations; however, the former was most significant at low pH, whereas the latter was predominant near neutral pH. The effect of ionic strength on HS biosorption followed the colloidal chemistry theory as the electric double layer became compressed when the ionic strength increased, resulting in closer approach of HS and AS biomass. The humic acid fraction of Suwannee River was removed more efficiently than its fulvic acid fraction because the humic acid was more hydrophobic. These results showed that pH, divalent cation concentration and ionic strength play an important role in the fate and removal of influent wastewater HS in full-scale treatment plants.     

混凝-超滤去除腐殖酸的试验研究

进行了直接超滤和混凝－超滤组合工艺对腐殖酸的去除效果和膜污染状况的试验。结果表明，超滤前另混凝土预处理对腐殖酸的DOC和UV254的去除率分别从28％、40％提高到53％、78％。同时高效液相色普（HPLC）分析表明，混凝－超滤组合工艺对分子质量＜6000u的有机物的去除率提高幅度更为显著。混凝－超滤组合工艺的最佳pH值条件pH=7,通过卷扫混凝使小分子有机物结合成微絮体，降低了膜孔污染，使超滤保持了较同的渗透通量。     

Trichloroethylene adsorption by activated carbon preloaded with humic substances: effects of solution chemistry

Trichloroethylene (TCE) adsorption by activated carbon previously loaded ("preloaded") with humic substances was found to decrease with increasing concentrations of monovalent ions (NaCl), calcium (until solubility was exceeded), or dissolved oxygen in the preloading solution. For a given percentage of organic carbon removal during humic acid loading, greater reductions in TCE adsorption occurred with increasing monovalent ion concentration and calcium concentration at constant ionic strength. However, this effect was related primarily to the amount of humic material adsorbed--the reduction in TCE adsorption was independent of the ionic composition of the preloading solution when compared at similar humic acid loading. Experiments were performed which showed that calcium ions can associate with humic material after the humic has been adsorbed, which subsequently reduces TCE uptake, but this effect does not dominate when calcium is present during humic loading. At sufficiently high calcium concentrations (approaching solubility), aggregation or co-precipitation of humic acid mitigated the effects of preloading. In contrast to the effects of ionic composition, the presence of dissolved oxygen did fundamentally change the mechanism by which organic macromolecules compete with TCE. TCE uptake was lower when preloading by poly(maleic acid) (PMA) occurred in the presence of dissolved oxygen, even when the amount loaded was the same. One explanation invokes a coupling mechanism promoted by the carbon surface, which results in either additional blockage of TCE sorption sites, additional site competition, or both. In all experiments, the effects of preloading were consistent with those reported previously, which have been interpreted as a loss of high-energy sites available to TCE, causing a significant reduction in the site-energy heterogeneity, and reduced uptake in the low concentration region.     

Impact of humic acid fouling on membrane performance and transport of pharmaceutically active compounds in forward osmosis

The impact of humic acid fouling on the membrane transport of two pharmaceutically active compounds (PhACs) – namely carbamazepine and sulfamethoxazole – in forward osmosis (FO) was investigated. Deposition of humic acid onto the membrane surface was promoted by the complexation with calcium ions in the feed solution and the increase in ionic strength at the membrane surface due to the reverse transport of NaCl draw solute. The increase in the humic acid deposition on the membrane surface led to a substantial decrease in the membrane salt (NaCl) permeability coefficient but did not result in a significant decrease in the membrane pure water permeability coefficient. As the deposition of humic acid increased, the permeation of carbamazepine and sulfamethoxazole decreased, which correlated well with the decrease in the membrane salt (NaCl) permeability coefficient. It is hypothesized that the hydrated humic acid fouling layer hindered solute diffusion through the membrane pore and enhanced solute rejection by steric hindrance, but not the permeation of water molecules. The membrane water and salt (NaCl) permeability coefficients were fully restored by physical cleaning of the membrane, suggesting that humic acid did not penetrate into the membrane pores.     

Decreasing DOC trends in soil solution along the hillslopes at two IM sites in southern Sweden--geochemical modeling of organic matter solubility during acidification recovery

Numerous studies report increased concentrations of dissolved organic carbon (DOC) during the last two decades in boreal lakes and streams in Europe and North America. Recently, a hypothesis was presented on how various spatial and temporal factors affect the DOC dynamics. It was concluded that declining sulphur deposition and thereby increased DOC solubility, is the most important driver for the long-term DOC concentration trends in surface waters. If this recovery hypothesis is correct, the DOC levels should increase both in the soil solution as well as in the surrounding surface waters as soil pH rises and the ionic strength declines due to the reduced input of SO₄²⁻ ions. In this project a geochemical model was set up to calculate the net humic charge and DOC solubility trends in soils during the period 1996-2007 at two integrated monitoring sites in southern Sweden, showing clear signs of acidification recovery. The Stockholm Humic Model was used to investigate whether the observed DOC solubility is related to the humic charge and to examine how pH and ionic strength influence it. Soil water data from recharge and discharge areas, covering both podzols and riparian soils, were used. The model exercise showed that the increased net charge following the pH increase was in many cases counteracted by a decreased ionic strength, which acted to decrease the net charge and hence the DOC solubility. Thus, the recovery from acidification does not necessarily have to generate increasing DOC trends in soil solution. Depending on changes in pH, ionic strength and soil Al pools, the trends might be positive, negative or indifferent. Due to the high hydraulic connectivity with the streams, the explanations to the DOC trends in surface waters should be searched for in discharge areas and peat lands.     

混凝剂中的铝形态对藻类混凝过程的影响

为了考察混凝剂中的铝形态对藻类混凝过程的影响,使用3种具有不同铝形态分布的混凝剂对含藻水进行了混凝试验。结果表明,硫酸铝由于具有较低含量的Alb,电中和能力较差,故需要较大的投量才能去除藻类,形成絮体;含藻水体系中的有机物主要是腐殖酸及富里酸类物质,微生物代谢产物(SMP)在硫酸铝作混凝剂时得到较好的去除,而腐殖酸及富里酸的去除率较低可能是造成硫酸铝混凝效果较差的原因;Alc(Al(30))在混凝中的作用机理主要是吸附架桥作用,可有效去除水体中的有机物,Al₁₃的主要作用机理是电中和作用,可以有效去除水体中的颗粒物;Al₁₃与Al₃₀由于具有形态的稳定性,其混凝过程受pH值的影响较小。絮体强度因子随着pH值的升高先增大后减小,Al₁₃作混凝剂时絮体恢复因子随pH值的升高先增大后减小,而其他两种混凝剂所形成絮体的恢复因子随pH值的升高而增大。     

Adsorption of synthetic organic chemicals by carbon nanotubes: Effects of background solution chemistry

With the significant increase in the production and use of carbon nanotubes (CNTs), they will be inevitably released into aquatic environments. Therefore, the fate and transport of CNTs in aqueous solutions have attracted extensive attention. In the present work, the effects of natural organic matter (NOM), solution pH and ionic strength on adsorption of three synthetic organic chemicals (SOCs) by both pristine and surface functionalized single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) were investigated. The three SOCs (phenanthrene, biphenyl, and 2-phenylphenol) with different planarity, polarity, and hydrogen/electron-donor/acceptor ability, representing typical scenarios for the SOC-CNT interactions, were employed as probe molecules. Among the three background solution characteristics examined, NOM showed the most significant effect on SOC adsorption, while solution pH and ionic strength exhibited minimal or negligible impacts. The presence of NOM greatly suppressed the SOC adsorption by CNTs, and the impact on the SWNTs was higher than that on the MWNTs. The planarity and hydrophobicity of SOCs were two important factors determining the effects of NOM, solution pH and ionic strength on their adsorption by CNTs.     

Characteristics of humic acid and organic compounds concentrated from tapwater using the aquella virus concentrator

Humic acid and other organic compounds present in eluates from filters used to process large volumes of treated tapwater using the Aquella virus concentrator were found to share certain properties. Both humic acid and the other organic compounds in the filter eluates adsorbed to membrane filters at low pH, were eluted from membrane filters at high pH, interfered with virus adsorption to membrane filters, formed flocs at low pH, and were removed by anion-exchange resins.