Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance

This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.     

The exploration of potassium ferrate(VI) as a disinfectant/coagulant in water and wastewater treatment

This paper aims to explore potassium ferrate(VI) (K2FeO4) as an alternative water treatment chemical for both drinking water and wastewater treatment. The performance of potassium ferrate(VI) was evaluated in comparison with that of sodium hypochlorite (NaOCl) and that of NaOCl plus ferric sulphate (FS) or alum (AS). The dosages of ferrate(VI), NaOCl and FS/AS and sample pH values were varied in order to investigate the effects of these factors on the treatment performance. The study demonstrates that in drinking water treatment, ferrate(VI) can remove 10-20% more UV(254)-abs and DOC than FS for the same dose compared for natural pH range (6 and 8). The THMFP was reduced to less than 100 microg l(-1) by ferrate(VI) at a low dose. In addition to this, ferrate(VI) can achieve the disinfection targets (>6 log10 inactivation of Escherichia coliform (E. coli)) at a very low dose (6 mg l(-1) as Fe) and over wide working pH in comparison with chlorination (10 mg l(-1) as Cl2) plus coagulation (FS, 4 mg l(-1) as Fe). In wastewater treatment, ferrate(VI) can reduce 30% more COD, and kill 3log10 more bacteria compared to AS and FS at a similar or even smaller dose. Also, potassium ferrate(VI) can produce less sludge volume and remove more pollutants, which could make sludge treatment easier.     

Comparison of modified montmorillonite adsorbents. Part I: Preparation,characterization and phenol adsorption

This study concerns with the development of modified montmorillonites as adsorbents for water treatment. Polymeric aluminium and iron intercalated forms of montmorillonites have been prepared in the absence and presence of an alkylammonium cationic surfactant (Hexdecyl-trimethyl-ammonium bromide, HDTMA). Montmorillonites intercalated with polymeric Al, Fe, Fe/Al (2:1 Fe to Al ratio in solution), possess large N2 Brunauer-Emmett-Teller (BET) surface areas. XRD data also shows trace amounts of illite and plagioclase within the clay materials. Montmorillonites intercalated with HDTMA, polymeric Fe/HDTMA, polymeric Al/HDTMA and polymeric Fe/Al/HDTMA (1:1 metal to surfactant molar ratio in solution) undergo some losses of N2 BET surface areas. Preliminary adsorption studies on phenol have shown that polymeric Al/HDTMA- and HDTMA-only-modified montmorillonites possess a good affinity for phenol, whereas the polymeric Al/Fe modified- and starting montmorillonites have little affinity for phenol adsorption.     

Removal of cyanobacterial blooms in Taihu Lake using local soils. II. Effective removal of Microcystis aeruginosa using local soils and sediments modified by chitosan

After sepiolite was modified with Fe3+ to increase its surface charge, the initial algal removal rate increased significantly, but its Q8h was not improved substantially at clay loadings below 0.1 g/L. Modification on netting and bridging properties of clays by either chitosan or polyacrylamide (PAM) dramatically increased flocculation (Q8h) of MA cells in freshwaters. Algal removal efficiencies of different solids, including Type III clays, local soils and sediments, were all improved to a similar level of >90% at a total loading of 0.011 g/L (contained 0.001 g/L chitosan) after they were modified with chitosan, making the idea of clearing up algal blooms using local soils/sediments possible. The mechanism of netting and bridging was confirmed to be the most important factor in improving the removal efficiency of cells, whereas clays also played important roles in the sedimentation of the floc.     

Enhancing aerobic digestion potential of municipal waste-activated sludge through removal of extracellular polymeric substance

A protease-secreting bacteria was used to pretreat municipal sewage sludge to enhance aerobic digestion. To enhance the accessibility of the sludge to the enzyme, extracellular polymeric substances were removed using citric acid thereby removing the flocs in the sludge. The conditions for the bacterial pretreatment were optimized using response surface methodology. The results of the bacterial pretreatment indicated that the suspended solids reduction was 18 % in sludge treated with citric acid and 10 % in sludge not treated with citric acid whereas in raw sludge, suspended solids reduction was 5.3 %. Solubilization was 10.9 % in the sludge with extracellular polymeric substances removed in contrast to that of the sludge with extracellular polymeric substances, which was 7.2 %, and that of the raw sludge, which was just 4.8 %. The suspended solids reduction in the aerobic reactor containing pretreated sludge was 52.4 % whereas that in the control reactor was 15.3 %. Thus, pretreatment with the protease-secreting bacteria after the removal of extracellular polymeric substances is a cost-effective and environmentally friendly method.     

Specific resistance to filtration of biomass from membrane bioreactor reactor and activated sludge: effects of exocellular polymeric substances and dispersed microorganisms.

This study investigates the effect of dispersed microorganisms and exocellular polymeric substances on biomass dewaterability. Specific resistance to filtration (SRF) was measured for biomass from a membrane bioreactor and a completely mixed activated sludge system. Both laboratory-scale reactors were fed with synthetic wastewater and operated at a high food-to-microorganism ratio (F/M) (1 to 11 kilograms chemical oxygen demand per kilogram mixed liquor volatile suspended solids per day [kgCOD/(kg MLVSS.d)]) and short solids retention times (0.25 to 5 d). The SRF values were affected by strong interactions of three parameters: (1) the mixed liquor suspended solids concentration, (2) the amount of dispersed microorganisms, and (3) the exocellular polymeric substances (EPS) concentration. At F/M smaller than 2 kg COD/(kg MLSS.d) and mixed liquor suspended solids (MLSS) concentration higher than 2000 mg/L, increasing amount of dispersed microorganisms in the biomass yielded higher SRF values. However, at high F/M (> 5 kg COD/kg MLSS.d) and low MLSS concentrations (< 600 mg/L), lower EPS concentrations resulted in slightly smaller SRF values, even though the amount of dispersed microorganisms in the biomass was much higher. Thus, at low MLSS concentrations, EPS concentrations rather than the amount of dispersed microorganisms tend to control SRF.     

Effect of solids concentration on bacterial leaching of heavy metals from sewage sludge

Microbial metal leaching from sewage sludge (2-9% w/v) was carried out with the iron-oxidizing bacterium Thiobacillus ferrooxidans. Measurements of pH, oxidation-reduction potential, and concentration of Fe2+ indicated that T. ferrooxidans was effective in removing metals from an incubation bath containing less than 5% sludge solids concentration. Specifically, Cu leaching was completely suppressed at a high solids concentration of 9% (w/v). Results indicated that the deactivation of T. ferrooxidans at a high sludge content was mainly due to the presence of inhibiting materials such as organic matter. A mixed culture of sulfur-oxidizing bacteria was obtained by enrichment from anaerobically digested sewage sludge to enhance the efficiency of the microbial leaching process. These bacteria were much more effective in metal leaching than was iron-oxidizing T. ferrooxidans. At 9% (w/v) solids concentration, the leaching efficiencies of Zn and Cu were 78% (2.66 g/kg dry sludge) and 59% (1.36 g/kg dry sludge), respectively. Therefore, when removing heavy metals from the anaerobically digested sewage sludge, the indigenous sulfur-oxidizing bacteria isolated in the current study were more efficient than T. ferrooxidans, especially at high sludge solids concentrations.     

Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece

The occurrence and fate of endocrine disrupting compounds (EDCs) in a sewage treatment plant and two industrial wastewater treatment plants from textile and tannery factories were investigated. EDCs of interest are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, triclosan and steroid estrogens. Target compounds were determined in dissolved fraction, total suspended solids and sludge by employing solid phase extraction and ultrasonication followed by gas chromatography–mass spectrometry.Nonylphenols and oligomers with one or two ethoxy groups were the most abundant compounds in raw wastewater as well as in effluents from all the treatment stages of sewage treatment plant, followed by triclosan and bisphenol A. Steroids were found at very low concentrations. Almost all phenolic EDCs compounds were predominantly associated to suspended solids in influents whereas the dissolved fraction dominated the treated effluents. High removal rates, ranging from 86% to 99%, were observed throughout the whole treatment process. Biodegradation was the main removal pathway of EDCs. Tannery wastewaters exhibited high concentrations of nonylphenolic compounds. This type of wastewaters could pose a significant risk to the aquatic and terrestrial environment.     

Treatment of chemical mechanical polishing wastewater by electrocoagulation: system performances and sludge settling characteristics

Treatment of copper chemical mechanical polishing (CMP) wastewater from a semiconductor plant by electrocoagulation is investigated. The CMP wastewater was characterized by high suspended solids (SS) content, high turbidity (NTU), chemical oxygen demand (COD) concentration up to 500 mgl(-1) and copper concentration up to 100 mgl(-1). In the present study, electrocoagulation was employed to treat the CMP wastewater with an attempt to simultaneously lower its turbidity, copper and COD concentrations. The test results indicated that electrocoagulation with Al/Fe electrode pair was very efficient and able to achieve 99% copper ion and 96.5% turbidity removal in less than 30 min. The COD removal obtained in the treatment was better than 85%, with an effluent COD below 100 mgl(-1). The effluent wastewater was very clear and its quality exceeded the direct discharge standard. In addition, sludge settling velocities after electrocoagulation were measured and the data were employed to verify the empirical sludge settling velocity models. Finally, the sludge settling characteristic data were also utilized to establish the relation between the solids flux (G) and the initial solids concentration.     

A/O-MBR中MLSS浓度对污泥性能及膜通量的影响

采用国产聚丙烯中空纤维帘式膜组件,进行了A/O-MBR系统处理生活污水的实验研究,主要探讨了系统中污泥浓度(MLSS)与膜通量变化过程的关系。实验结果表明,MLSS由3 805 mg/L升高到6 912 mg/L时,污泥混合液胞外聚合物(EPS)由43 mg/g VSS增加到81 mg/g VSS,EPS中多糖与蛋白质的比例从0.87增加到1.08。同时,污泥相对疏水性(RH)的降低与Zeta电位的升高也在一定程度上共同促进了膜污染速率的上升。实验条件下,当运行时间为60 d左右,MLSS升高至6 200 mg/L时,跨膜压差上升迅速,膜组件清洗周期由初始的22 d缩短为11 d。A/O-MBR中由于MLSS浓度变化而导致的活性污泥混合液特性的变化,是影响膜通量变化的重要原因。     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Mercury in contaminated sediments and pore waters enriched in sulphate (Tagus Estuary,Portugal)

Three sediment cores, collected nearby the effluent of a chlor-alkali industry, were sliced in 0.5-cm layers and centrifuged for pore water extraction. Mercury, Fe and Mn were determined in the solids as total concentration, hydroxylamine extractable fraction and HCl extractable fraction. Sulphur was determined in the HCl extraction. Total and reactive mercury, chlorinity, S(2-), SO(4)(2-), total Fe, and total Mn were measured in pore waters. The solids contained 3.0-60 nmol g(-1) of total Hg and pore waters 70-5800 pM of total Hg and 1.8-76 pM of reactive mercury. Pore waters presented 2.3-94 times more sulphate than the overlying estuarine waters due to the input from the industry. In layers where hydroxylamine extractable Fe exhibited a broad maximum (precipitation of Fe-oxides) sulphate was reduced to S(2-). The competition between the high content of SO(4)(2-) and Fe(III) as electron acceptors, in chemical reactions occurring in the upper sediments, may explain the co-existence of S(2-) and Fe-oxides in the same layers. Mercury was detected in the hydroxylamine extracts (20-29 nmolg(-1)) in the layers where Fe-oxides were formed, and reactive dissolved Hg showed minimum concentrations. The excess of sulphate in pore waters favoured the abundant Fe-oxides in the upper solid sediments, which appear to work as a barrier limiting the escape of mercury to the water column.     

Fenton组合工艺处理焦化厂生化出水的应用研究

比较了Fenton氧化、Fenton氧化+活性炭及Fenton氧化+生物活性炭工艺对焦化厂生化出水的处理效果.结果表明,Fe2+、H2O2的投加量分别为56、27.2 mg/L时,Fenton氧化工艺对水样的UV254、颜色度(VIS380)、COD和总氰均有较好的去除效果;Fenton氧化+活性炭工艺在有效去除UV254、VIS380、COD和总氰的同时,能强化活性炭的吸附效果,并能显著提高水样的生化性能;Fenton氧化+生物活性炭工艺能有效去除UVM254,VIS380、COD与总氰,使出水达到<污水综合排放标准>(GB 8978-1996)一级标准.     

MFC-MBR耦合系统运行效果

膜生物反应器(MBR)是一种高效的污水处理工艺,而微生物燃料电池(MFC)能有效降解污泥中的胞外生物有机质(EBOM)并回收电能.将MFC与MBR联用,建立了一套能够有效抑制膜污染同时回收电能的新系统——MFC-MBR耦合系统,MBR的剩余污泥经MFC处理后回流.以传统MBR为对照,对耦合系统中污水处理效果、膜污染情况和污泥混合液的性质进行研究.研究表明,耦合系统的污水处理效果没有明显恶化,COD去除率为94％,NH4+-N的去除率为92％.耦合系统能够有效减缓膜污染的发生,清洗周期延长了28％.污泥混合液的MLVSS/MLSS稳定在80％ ～ 88％,系统内几乎没有无机颗粒积累.松散结合态胞外聚合物(LB-EPS)降低了48％,使污泥混合液性质得到改善.较低的污泥比阻(2.69×1012m/kg)和标准化毛细吸水时间(1.67 s·L/g MLSS),证明耦合系统污泥混合液脱水性能提高了.     

Ultraviolet disinfection of fecal coliform in municipal wastewater: effects of particle size.

Suspended solids interfere with the efficiency of disinfection using UV radiation by decreasing the rate of disinfection and inducing tailing. However, conventional measures of solids (total suspended solids, turbidity, and UV transmittance) do not adequately predict the presence or degree of these effects. Bacteria and viruses can become associated with particles in wastewater. A fractionation technique was developed to separate particle-associated bacteria into three fractions, based on particle size. The results show that the degree to which particles interfere with UV disinfection efficiency is dependent on particle size. The small size fraction (< 5 microm) consistently produced a statistically significant faster disinfection rate than the large fraction (> 20 microm), with the unfiltered sample and the medium fraction (particles > 5 microm, but < 20 microm) between the two extremes. Tailing also was observed only in the large fraction. Correlations between the disinfection rate constant and the percentage of large fraction bacteria of a sample were good.     

铝铁电极联用电絮凝法处理Cu-EDTA络合废水

采用电絮凝法处理Cu-EDTA模拟废水,研究电极组合方式、初始pH值和氯化钠浓度3个因素对化学需氧量(COD)和Cu去除效果的影响。实验研究发现,当电极组合方式为2个铝阳极和2个铁阴极,起始pH值为3,氯化钠浓度为0.5 g/L,换极周期为40 min,反应时间为80 min时,COD去除率达到78.7%,Cu离子去除率达到99.9%。通过实验研究确定EDTA的去除机制主要是:酸性条件下的次氯酸氧化作用,碱性条件下的氢氧化物絮凝沉淀作用及单核态铝/铁与多核态铝/铁电荷中和作用,Cu的去除机制主要是氢氧化物的絮凝沉淀作用和铁电极的电沉积作用。     

溶解氧对底泥扰动状态下水体中磷去除和固定的影响

以太湖梅梁湾底泥和上覆水为研究对象,通过实验室实验研究了底泥扰动状态下溶解氧水平（2～4mg／L、5～6mg／L、7～8mg／L）对上覆水中磷去除和固定的影响。结果表明,底泥扰动和溶解氧水平对上覆水中磷迁移有明显影响。扰动时间延长,溶解性磷酸盐（DIP）和溶解性总磷（DTP）均呈降低的趋势;但溶解氧水平提高,上覆水中DIP和DTP浓度有所增加。底泥扰动和溶解氧水平改变了悬浮物上不同形态磷的数量分布。随着溶解氧水平提高,NH4Cl-P（1～5d平均值）和Fe／Al—P（1～5d平均值）含量及其占总磷（Tot—P）的百分比均呈逐渐降低的趋势。另外,闭蓄态铁铝结合态磷（Fe／Al—P）占Fe／Al—P的比值从51．2％（2～4mg／L）增加至54．1％（7～8mg／L）。     

Comparison of hematite/Fe(II) systems with cement/Fe(II) systems in reductively dechlorinating trichloroethylene

Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons are unknown. This study initially evaluated reactivities of potential reactive agents of cement/Fe(II) systems such as hematite (alpha-Fe(2)O(3)), goethite (alpha-FeOOH), lepidocrocite (gamma-FeOOH), akaganeite (beta-FeOOH), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)), Friedel's salt (Ca(4)Al(2)Cl(2)(OH)(12)), and hydrocalumite (Ca(2)Al(OH)(6)(OH).3H(2)O) in reductively dechlorinating trichloroethylene (TCE) in the presence of Fe(II). It was found that a hematite/Fe(II) system shows TCE degradation characteristics similar to those of cement/Fe(II) systems in terms of degradation kinetics, Fe(II) dose dependence, and final products distribution. It was therefore suspected that Fe(III)-containing phases of cement hydrates in cement/Fe(II) systems behaved similarly to the hematite. CaO, which was initially introduced as a pH buffer, was observed to participate in or catalyze the formation of reactive reductants in the hematite/Fe(II) system, because its addition enhanced the reactivities of hematite/Fe(II) systems. From the SEM (scanning electron microscope) and XRD (X-ray diffraction) analyses that were carried out on the solids from hematite/Fe(II) suspensions, it was discovered that a sulfate green rust with a hexagonal-plate structure was probably a reactive reductant for TCE. However, SEM analyses conducted on a cement/Fe(II) system showed that hexagonal-plate crystals, which were presumed to be sulfate green rusts, were much less abundant in the cement/Fe(II) than in the hematite/Fe(II) systems. It was not possible to identify any crystalline minerals in the cement/Fe(II) system by using XRD analysis, probably because of the complexity of the cement hydrates. These observations suggest that major reactive reductants of cement/Fe(II) systems may differ from those of hematite/Fe(II) systems.     

Improvement of coagulation-flocculation process using anionic polyacrylamide as coagulant aid

A physicochemical treatment (coagulation-flocculation) was applied to a slaughterhouse wastewater, using anionic polyacrylamide as coagulant aid to improve the settling velocity of the flocs formed with the coagulants used: ferric sulphate, aluminium sulphate and polyaluminium chloride. The optimum speed and stirring time for the flocculation stage were ascertained along with the optimum pH and coagulant and coagulant aid doses. The speed and coagulation time were initially set according to recommendations in the literature concerning the treatment of this type of water. Chemical oxygen demand (COD), biochemical oxygen demand at 5 days (BOD5) and total suspended solids (TSS) were recorded at the beginning and end of each experiment in order to monitor the process. Once the optimal conditions had been established, several parameters were measured in order to assess the coagulation-flocculation process: particle number and size, sludge volume, nutrients (ammonia nitrogen, total Kjeldahl nitrogen, albuminoid nitrogen, orthophosphate, total phosphorus) and the residual concentration of iron and aluminium in clarified water. Anionic polyacrylamide, when added with ferric sulphate or polyaluminium chloride led to a significant increase in the settling speed.