壳聚糖改性粘土去除城市湖泊中藻类的研究

对壳聚糖改性粘土用于城市湖泊中藻类的絮凝去除进行了研究。实验表明,粘土经过壳聚糖改性后,对高藻水中藻细胞的去除效能得到很大的提高。相比单独投加壳聚糖,粘土的加入增加了絮体密实度,减少了絮体体积,并使絮体分布更均匀。在壳聚糖与粘土配比为1∶20时,叶绿素的去除率和浊度的去除率均为最佳。粘土的种类对除藻效果有一定影响,其中以高粘凹凸棒石为最佳,在最佳投加量28 mg.L-1时,对叶绿素的去除率达到96.2%;粘土的粒径对絮凝效果基本没有影响,在粒径为60μm与300μm之间改性粘土对藻细胞的凝聚效果是一致的。经壳聚糖改性的粘土在酸性条件下絮凝效果较好,当pH值大于7时,其絮凝能力迅速下降。     

Effect of algal flocculation on dissolved organic matters using cationic starch modified soils

Modified soils(MSs) are being increasingly used as geo-engineering materials for the sedimentation removal of cyanobacterial blooms. Cationic starch(CS) has been tested as an effective soil modifier, but little is known about its potential impacts on the treated water.This study investigated dissolved organic matters in the bloom water after algal removal using cationic starch modified soils(CS-MSs). Results showed that the dissolved organic carbon(DOC) could be decreased by CS-MS flocculation and the use of higher charge density CS yielded a greater DOC reduction. When CS with the charge density of 0.052, 0.102 and0.293 meq/g were used, DOC was decreased from 3.4 to 3.0, 2.3 and 1.7 mg/L, respectively.The excitation–emission matrix fluorescence spectroscopy and UV254 analysis indicated that CS-MS exhibits an ability to remove some soluble organics, which contributed to the DOC reduction. However, the use of low charge density CS posed a potential risk of DOC increase due to the high CS loading for effective algal removal. When CS with the charge density of 0.044 meq/g was used, DOC was increased from 3.4 to 3.9 mg/L. This study suggested, when CS-MS is used for cyanobacterial bloom removal, the content of dissolved organic matters in the treated water can be controlled by optimizing the charge density of CS. For the settled organic matters, other measures(e.g., capping treatments using oxygen loaded materials) should be jointly applied after algal flocculation.     

离子强度对粘土和改性粘土絮凝去除水华铜绿微囊藻的影响

研究了水体的离子强度对粘土和壳聚糖改性粘土絮凝去除铜绿微囊藻的影响 .离子强度的增加有利于粘土对藻类的絮凝去除 .与一般粘土除藻相反 ,壳聚糖改性粘土却在离子强度低的条件下具有更好的除藻效果 ,是适合在湖泊 ,水库和江河等淡水 (低含盐量 )水体中应用的应急除藻技术 .当离子强度从 0.17mol/L降到 0mol/L时 ,海泡石除藻率从 90 %以上降为 70 %以下(投加量700mg/L) ,而壳聚糖改性海泡石的除藻率却从 70%左右升至 95% (投加量仅为 11mg/L) .用粘度法研究了壳聚糖改性海泡石的絮凝机理 ,发现相对低的离子强度更有利于壳聚糖分子链上阳电荷的相互排斥作用 ,有利于壳聚糖分子链的舒展 ,从而可以充分发挥架桥网捕作用 ,利于絮凝除藻 .     

壳聚糖改性粘土对水华优势藻铜绿微囊藻的絮凝去除

研究了壳聚糖改性对粘土絮凝去除铜绿微囊藻的影响.经壳聚糖包覆改性后的海泡石在投加总量仅为11 mg/L时,0.5h即可去除80%的藻细胞,2h去除率达到90%.不同粘土改性后絮凝除藻能力均有大幅度提高,原来除藻能力相去甚远的不同粘土,包括一般的黄土,改性后除藻能力被提升到相近的水平,投加量11 mg/L,可去除铜绿微囊藻90%以上.改性粘土和一般絮凝剂一样有一最佳投加量(本研究为11 mg/L),低于或超过此最佳值,絮凝除藻效果均下降.     

Drinking water treatment using a submerged internal-circulation membrane coagulation reactor coupled with permanganate oxidation

A submerged internal circulating membrane coagulation reactor(MCR) was used to treat surface water to produce drinking water. Polyaluminum chloride(PACl) was used as coagulant,and a hydrophilic polyvinylidene fluoride(PVDF) submerged hollow fiber microfiltration membrane was employed. The influences of trans-membrane pressure(TMP), zeta potential(ZP) of the suspended particles in raw water, and KMnO_4 dosing on water flux and the removal of turbidity and organic matter were systematically investigated. Continuous bench-scale experiments showed that the permeate quality of the MCR satisfied the requirement for a centralized water supply, according to the Standards for Drinking Water Quality of China(GB 5749-2006), as evaluated by turbidity(1 NTU) and total organic carbon(TOC)(5 mg/L)measurements. Besides water flux, the removal of turbidity, TOC and dissolved organic carbon(DOC) in the raw water also increased with increasing TMP in the range of 0.01–0.05 MPa. High ZP induced by PACl, such as 5–9 mV, led to an increase in the number of fine and total particles in the MCR, and consequently caused serious membrane fouling and high permeate turbidity.However, the removal of TOC and DOC increased with increasing ZP. A slightly positive ZP, such as 1–2 mV, corresponding to charge neutralization coagulation, was favorable for membrane fouling control. Moreover, dosing with KMnO_4 could further improve the removal of turbidity and DOC, thereby mitigating membrane fouling. The results are helpful for the application of the MCR in producing drinking water and also beneficial to the research and application of other coagulation and membrane separation hybrid processes.     

壳聚糖改性粘土絮凝除藻的机理探讨

粘土除藻是一种有前景和环境友好的应急除藻技术。对粘土进行改性以提高其除藻效果是该技术的发展方向之一。文章探讨了壳聚糖改性粘土絮凝除藻的机理。壳聚糖改性修饰后的粘土既能通过壳聚糖的粘结架桥作用絮凝藻细胞,又能通过粘土表面电性的改变凝聚带负电的藻细胞,使改性粘土的絮凝除藻能力大幅度提高。     

壳聚糖改性铝污泥对铜绿微囊藻的絮凝去除

采用给水厂副产物铝污泥代替黏土作为下沉载体,利用壳聚糖改性,将其用于铜绿微囊藻的絮凝去除.结果表明,壳聚糖与铝污泥以1：50的质量比复合改性后除藻效果明显提高：对于藻密度约为4.88×10⁶cells/mL的含藻水,当改性铝污泥最佳投加量为0.25g/L,30min后藻密度和浊度去除率分别达到100%和98.92%,形成的絮体完整紧实,分形维数值为1.719.通过Zeta电位、SEM等表征分析,此过程主要依靠壳聚糖、铝污泥及藻类之间的"电性中和"与"吸附架桥"等的作用,混凝絮凝过程快速高效且投加量小,最佳环境pH值介于7~9.5,外加NaCl、CaCl₂在离子强度较低情况下基本不影响絮凝沉淀过程.加之铝污泥对水体中的磷具有良好的吸附作用,因此壳聚糖改性铝污泥对淡水水体中铜绿微囊藻的去除及生长抑制具有良好的效果,实现了"以废治污".     

铜绿微囊藻对混凝除氟的促进作用及机理分析

以铜绿微囊藻、氯化铝（AlCl₃·6H₂O）为研究对象,通过三维荧光、场发射扫描电镜等表征,探究了藻类对氟化物混凝去除机制的影响.结果表明,在pH值为7.0,8.0,9.0,Al投加量在20.0~80.0mg/L的条件下,铜绿微囊藻对混凝除氟有明显的促进作用,其促进作用主要在于藻絮体对氟的表面吸附.铜绿微囊藻与氯化铝水解产物通过吸附架桥和网捕卷扫作用,聚集成较大较多的絮体.絮体粒径越大,除氟率越高.pH值为7.0,Al投加量为40.0mg/L时,絮体粒径达到最大值500μm,此时氟去除率最高,为77.37%;当Al投加量为80.0mg/L时,藻细胞破损严重,有机物过多释放,对混凝除氟起阻碍作用.絮体破碎吸附实验结果表明,对絮体进行一定强度破碎可以增加吸附位点,从而提高氟的去除率;但破碎强度过大,絮体粒径过小,对氟的吸附效率亦会降低.     

Investigation of colloidal biogenic sulfur flocculation: Optimization using response surface analysis

The colloidal properties of biogenic elemental sulfur(S~0)cause solid–liquid separation problems,such as poor settling and membrane fouling.In this study,the separation of S~0 from bulk liquids was performed using flocculation.Polyaluminum chloride(PAC),polyacrylamide(PAM)and microbial flocculant(MBF)were compared to investigate their abilities to flocculate S~0 produced during the treatment of sulfate-containing wastewater.A novel approach with response surface methodology(RSM)was employed to evaluate the effects and interactions of flocculant dose,pH and stirring intensity,on the treatment efficiency in terms of the S~0 flocculation and the supernatant turbidity removal.The dose optimization results indicated that the S~0 flocculation efficiency decreased in the following order PACMBFPAM.Optimum S~0 flocculation conditions were observed at pH 4.73,a stirring speed of 129 r/min and a flocculant dose of 2.42 mg PAC/mg S.During optimum flocculation conditions,the S~0f locculation rate reached 97.53%.Confirmation experiments demonstrated that employing PAC for S~0 flocculation is feasible and RSM is an efficient approach for optimizing the process of S~0 flocculation.The results provide basic parameters and conditions for recovering sulfur during the treatment of sulfate-laden wastewaters.     

Coagulation behavior and floc properties of compound bioflocculant-polyaluminum chloride dual-coagulants and polymeric aluminum in low temperature surface water treatment

This study was intended to compare coagulation behavior and floc properties of two dualcoagulants polyaluminum chloride–compound bioflocculant(PAC–CBF)(PAC dose first) and compound bioflocculant–polyaluminum chloride(CBF–PAC)(CBF dose first) with those of PAC alone in low temperature drinking water treatment. Results showed that dualcoagulants could improve DOC removal efficiency from 30% up to 34%. Moreover, CBF contributed to the increase of floc size and growth rate, especially those of PAC–CBF were almost twice bigger than those of PAC. However, dual-coagulants formed looser and weaker flocs with lower breakage factors in which fractal dimension of PAC–CBF flocs was low which indicates a looser floc structure. The floc recovery ability was in the following order:PAC–CBF PAC alone CBF–PAC. The flocculation mechanism of PAC was charge neutralization and enmeshment, meanwhile the negatively charged CBF added absorption and bridging effect.     

Purification, characterization and application of dual coagulants containing chitosan and different Al species in coagulation and ultrafiltration process

The objective of this study was to investigate the effect of different Al species and chitosan (CS) dosages on coagulation performance, floc characteristics (floc sizes, strength and regrowth ability and fractal dimension) and membrane resistance in a coagulation–ultrafiltration hybrid process. Results showed that different Al species combined with humic acid in diverse ways. Al_a had better removal efficiency, as determined by UV₂₅₄ and dissolved organic carbon, which could be further improved by the addition of CS. In addition, the optimal dosage of different Al species was determined to be 4.0 mg/L with the CS concentration of 1.0 mg/L, by orthogonal coagulation experiments. Combining Al_a/Al_b/Al_c with CS resulted in larger flocs, higher recovery, and higher fractal dimension values corresponding to denser flocs; in particular, the floc size at the steady state stage was four times larger than that obtained with Al species coagulants alone. The results of ultrafiltration experiments indicated that the external fouling percentage was significantly higher than that of internal fouling, at around 85% and 15%, respectively. In addition, the total membrane resistance was significantly decreased due to CS addition.     

改性壳聚糖混凝去除太湖藻研究

对太湖不同区域的水使用改性壳聚糖做混凝除藻实验。对于泵取水,投加量0.7 mg/L时,藻去除率可达89.6%,对于岸边高浓藻水,投加量4 mg/L,0.5 h内藻去除率即可达为85.77%。改性壳聚糖复配黏土可解决岸边高浓藻絮体的上浮问题,黏土投加0.8 g/L絮体可完全下沉,除藻率fe从85.77%提升到94.35%。但复配黏土造成UV254去除率下降。改性壳聚糖复配0.3 g/L PDMDAAC改性粉煤灰投加或复配0.4 g/L改性沸石时,絮体也可完全下沉,除藻率都可提升到98%以上。同时,两种药剂都加强了系统对有机物的去除,UV254去除率从56.94%提升到72%以上。     

黏土絮凝沉降铜绿微囊藻的动力学及其作用机理

研究了26种天然黏土矿物凝聚沉降铜绿微囊藻的动力学过程在投加量为0.7 g·L^-1时按平衡除藻率和除藻速率将26种黏土分成3类.第1类矿物(滑石、三氧化二铁、海泡石、四氧化三铁、高岭土等)的8 h平衡除藻率大于90%,去除50%藻细胞所需时间t₅₀＜30 min,去除80%藻细胞所需时间t₈₀＜2.5 h第2类黏土(轻质页岩、陶土、凹凸棒、累托土、伊利土等7种)的8 h平衡除藻率为50%～80%,t₅₀＜2.5 h,t80＞5 h.第3类黏土(铁矾土,云母,沸石、浮石、硅藻土、高钾长石和石英等14种)的8 h平衡除藻率低于50%,t₅₀>>8 h.当投加量逐步降低到0.2～0.1 g·L^-1时,25种黏土矿物的8 h平衡除藻率均降到60%以下,只有第1类黏土中的海泡石仍接近90%.与黏土相比,在0.02～0.2 g·L^-1投加量下单独使用聚合氯化铝(PAC)时的8 h平衡除藻率均低于40%.进一步对海泡石进行电性改性后发现,虽然黏土颗粒表面电位的提高(pH 7.4时,Zeta电位由-24.0 mV提高到+0.43 mV)可以显著加快海泡石的除藻速率,但其平衡除藻率并没有显著提高.在分析了本研究中的凝聚机理后提出:架桥网捕作用可能在黏土-藻凝聚过程中发挥了十分关键的作用,增强黏土对藻细胞的架桥网捕作用可能是今后进一步提高除藻效率、大幅度降低投加量的一个重要方向.     

基于Zeta电位的硅藻土复配剂强化混凝研究

采用硅藻土与传统无机絮凝剂复配处理模拟生活污水,考察硅藻土复配剂强化混凝过程中絮体Zeta电位的变化,以及浊度和COD的去除情况,研究絮体Zeta电位与强化混凝效果的关系。实验结果表明,絮体的Zeta电位与复配剂的强化混凝效果密切相关,可用于反映硅藻土复配剂的混凝处理效果。研究发现,氯化铝复配剂强化混凝时絮体Zeta电位在加药后迅速上升,25min后趋于稳定;絮体Zeta电位在pH值等于7时接近等电点,此时浊度与COD去除率最高,分别达到99.05%和45.77%;用硅藻土复配剂强化混凝时Zeta电位的控制值为-9.0～0mV之间,不同无机絮凝剂与硅藻土复配混凝时获得较好混凝效果的Zeta电位控制值略有差异。     

新型两性壳聚糖絮凝剂的合成及其絮凝效果的研究

该研究旨在通过化学修饰壳聚糖提高其污水处理的絮凝效果。通过壳聚糖的氨基与甲醛和酚类物质的曼尼希反应引入硫酸根基团,制备了3种具有不同取代度的两性壳聚糖衍生物。红外及核磁谱图分析结果证实,合成产物中具有苯并噁嗪环结构。经处理高岭土的水悬浮液进行模拟絮凝实验发现,这3种苯并噁嗪壳聚糖衍生物的絮凝效果随絮凝剂用量、污水pH和离子强度等条件变化而有较大变化,并均可在适当絮凝条件下获得最佳值。它们的絮凝效果全面优于未经处理的壳聚糖对比样品。取代度为80%左右的硫酸化壳聚糖絮凝剂处理污水可达近100%的浊度净化率。     

壳聚糖接枝三元共聚阳离子絮凝剂对高岭土悬浊液的絮凝特性

采用烧杯混凝实验研究了壳聚糖(CTS)、CTS与丙烯酰胺和丙烯酸乙酯季铵盐三元接枝共聚阳离子絮凝剂(CAS)对高岭土悬浊液的絮凝特性.结果表明,CAS具有比CTS絮凝效果好、用量少、pH值适用范围广等优点.CAS絮凝效能受胶体颗粒性质的影响小,对自来水和蒸馏水配置的高岭土悬浊液均具有较好的絮凝效能.中性条件下,CAS的最佳投加量仅为CTS的1/10.在pH值2.0-11.0范围内,CAA对浊度的去除率在95%左右.CAS投加量与原水浊度的关系为:投加量低于0.5nag·L-1时,絮凝效果随原水浊度的升高降低;投加量大于0.5 mg·L-1,浊度去除率随原水浊度的增大而提高;投加量超过1.0 mg·L-1后,对浊度(10～160 NTU)的悬浊;液浊度去除率均在85%以上.悬浮颗粒聚集状态的变化分析、颗粒ξ电位测定、絮体粒径分布测定及其形态结构的观察结果表明,电性中和、吸附架桥是CAS的主要絮凝作用机理,絮凝过程是多种机制共同起作用的动态变化过程.     

壳聚糖助凝对三氯化铁絮体形态和强度的影响

采用三氯化铁(FeCl3)为混凝剂、壳聚糖(CTS)为助凝剂进行给水混凝处理,研究了CTS助凝对FeCl3絮体形态和强度的影响.结果表明,在FeCl3投加量为29mg/L(以Fe计)、CTS投加量为0.1mg/L条件下,CTS助凝对絮体形态和强度有明显影响,分形维数由单独投加FeCl3时的1.1855增加到CTS助凝后的1.3028,絮体强度因子(SF)由50~60变为60~70,CTS助凝后形成的絮体密实、易沉降,絮体强度大且不易破碎.另外,添加CTS助凝后,TOC、色度、UV254、浊度的去除均明显提高.     

The role of extracellular organic matter on the cyanobacteria ultrafiltration process

The membrane fouling caused by extracellular organic matter (EOM) and algal cells and organic matter removal of two typical cyanobacteria (M. aeruginosa and Pseudoanabaena sp.) during ultrafiltration (UF) process were studied in this work. The results showed that EOM had a broad molecular weight (Mw) distribution and the irreversible membrane fouling was basically caused by EOM. Moreover, humic acid and microbial metabolites were major components of EOM of two typical cyanobacteria. Since EOM could fill the voids of cake layers formed by the algal cells, EOM and algal cells played synergistic roles in membrane fouling. Fourier transform infrared spectroscopy analysis indicated that the CH₂ and CH₃ chemical bonds may play an important role in membrane fouling caused by EOM. Interestingly, the cake layer formed by the algal cells could trap the organic matter produced by algae and alleviate some irreversible membrane fouling. The results also showed that although the cake layer formed by the algal cells cause severe permeate flux decline, it could play a double interception role with UF membrane and increase organic matter removal efficiency. Therefore, when using UF to treat algae-laden water, the balance of membrane fouling and organic matter removal should be considered to meet the needs of practical applications.     

Urease inhibitor reduces N losses and improves plant-bioavailability of urea applied in fine particle and granular forms under field conditions

A field lysimeter/mini plot experiment was established in a silt loam soil near Lincoln, New Zealand, to investigate the effectiveness of urea fertilizer in fine particle application (FPA), with or without the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT - “Agrotain”), in decreasing nitrogen (N) losses and improving N uptake efficiency. The five treatments were: control (no N) and ¹⁵N-labelled urea, with or without NBPT, applied to lysimeters or mini plots (unlabelled urea), either in granular form to the soil surface or in FPA form (through a spray) at a rate equivalent to 100 kg N ha⁻¹. Gaseous emissions of ammonia (NH₃) and nitrous oxide (N₂O), nitrate (NO₃⁻) leaching, herbage dry-matter (DM) production, N-response efficiency, total N uptake and total recovery of applied ¹⁵N in the plant and soil varied with urea application method and with addition of NBPT. Urea with NBPT, applied in granular or FPA form, was more effective than in application without NBPT: N₂O emissions were reduced by 7-12%, NH₃ emissions by 65-69% and NO₃⁻ leaching losses by 36-55% compared with granular urea. Urea alone and with NBPT, applied in FPA form increased herbage DM production by 27% and 38%, respectively. The N response efficiency increased from 10 kg DM kg⁻¹ of applied N with granular urea to 19 kg DM kg⁻¹ with FPA urea and to 23 kg DM kg⁻¹ with FPA urea plus NBPT. Urea applied in FPA form resulted in significantly (P < 0.05) higher ¹⁵N recovery in the shoots compared with granular treatments and this was improved further when urea in FPA form was applied with NBPT. These results suggest that applying urea with NBPT in FPA form has potential as a management tool in mitigating N losses, improving N-response efficiency and increasing herbage DM production in intensive grassland systems.     

胞外物质影响铁盐混凝除铜绿微囊藻的效能与机制

藻及其代谢产物严重威胁着饮用水质的安全.混凝是饮用水处理工艺中去除藻细胞最为重要的单元,而藻细胞的胞外有机物(EOM)是影响藻细胞脱稳和去除的重要因素.本文以铜绿微囊藻为研究对象,对比混凝对原始藻细胞和经离心去除EOM的藻细胞(裸藻)的去除效果.结果发现,在pH为6.0、7.0和8.0的条件下,铁盐混凝对裸藻细胞(去除EOM的藻细胞)的去除率比原始藻细胞分别提高了5.01%、29.24%和27.45%,证实EOM对铁盐混凝除藻具有抑制作用.此外,絮体粒径动态分析表明,在pH分别为6.0、7.0和8.0下,裸藻细胞对应的最大絮体粒径均比原始藻细胞要高.Zeta电位分析表明,裸藻比原始藻的Zeta电位更高,因此,更容易通过压缩双电层脱稳.三维荧光分析结果表明,EOM易与金属发生络合反应,生成螯合物,从而抑制混凝除藻.