The effect of pretreatment to ultrafiltration of biologically treated sewage effluent: a detailed effluent organic matter (EfOM) characterization

Ultrafiltration alone can remove only a portion of the effluent organic matter (EfOM) from biologically treated sewage effluent (BTSE). Use of pretreatment not only improves the EfOM removal but also reduces the membrane fouling. In this research, NTR 7410 ultrafiltration membrane was employed to remove EfOM from BTSE. Different pretreatments namely FeCl(3) flocculation and powder activated carbon adsorption were evaluated. The highest removal of organic matter was observed when flocculation followed by adsorption was used as pretreatment. The flocculation and adsorption removed 68.5% and 71.4% of hydrophobic organics, respectively. The molecular weight (MW) of the EfOM in BTSE ranged from 300 to about 400000 Da. After the flocculation pretreatment, the majority of large MW organic matter was removed. The pretreatment of the flocculation followed by adsorption led to very high removal of both small and large organic matter. Further, this pretreatment led to practically no filtration flux decline.     

Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters

Since the mid-1990s, numerous studies on the treatment of drinking water by photocatalysis have been reported. Once optimised, the photocatalytic process can completely degrade numerous natural and artificial organic compounds. In this study, a hybrid photocatalysis/membrane process was used as a polishing treatment of surface water containing a small concentration of natural organic matters (i.e. total organic carbon (TOC) concentration of around 3mg/L) which may be difficult to remove using conventional filtration or coagulation. An optimum pH of 4.5 and a TiO(2) concentration of 0.1g/L were found to lead to the highest removal efficiencies. The relative effect of the individual processes featuring in the hybrid system (UV radiation, TiO(2) adsorption and membrane filtration) was also assessed for different pH values. The membrane separation process was accounted to remove around 18% of the initial TOC concentration, while TiO(2) adsorption alone was generally responsible for less than 5% of TOC removal during the 120 min of the experiments. However, when the natural water was only radiated by UV light, up to 70% of TOC was removed. A synergetic effect was observed when the three processes (TiO(2), UV and membrane) were used together. Comparison of removal efficiencies obtained during real and model (International Humic Substance Society) waters treatment by photocatalysis is also presented, revealing the importance of the nature of the feed in this type of treatment.     

Advanced treatment of the reverse osmosis concentrate produced during reclamation of municipal wastewater

The work investigated the treatment of the concentrate produced from the reverse osmosis treatment of an MBR effluent. Two conventional chemical processes, coagulation and activated carbon adsorption, and three advanced oxidation processes (electrochemical treatment, photocatalysis and sonolysis) were applied. Coagulation with alum gave dissolved organic carbon (DOC) removals up to 42%, while FeCl(3) achieved higher removals (52%) at lower molar doses. Adsorption with granular activated carbon showed the highest DOC removals up to 91.3% for 5 g/L. The adsorption isotherm was linear with a non-adsorbable organic fraction of around 1.2 mg/L DOC. The three oxidation methods employed, electrolytic oxidation over a boron-doped diamond electrode, UVA/TiO2 photocatalysis and sonolysis at 80 kHz, showed similar behavior: during the first few minutes of treatment there was a moderate removal of DOC followed by further oxidation at a very slow rate. Electrolytic oxidation was capable of removing up to 36% at 17.8A after 30 min of treatment, sonolysis removed up to 34% at 135W after 60 min, while photocatalysis was capable of removing up to 50% at 60 min.     

Is semi-flocculation effective as pretreatment to ultrafiltration in wastewater treatment?

In this study, ferric chloride (FeCl(3)) flocculation was used as a pretreatment to ultrafiltration (UF) in treating synthetic wastewater containing synthetic organic matter (SOM). The effect of flocculant dose was studied in terms of organic removal and membrane flux decline. The UF with optimum dose of FeCl(3) (68 mg L(-1)) did not experience any flux decline during the whole operation of 6 h. The preflocculation with a smaller dose of 20 mg L(-1) of FeCl(3) led to a severe flux decline in the UF (more than 65% in 6 h). To understand the phenomenon of the flux decline of UF, the MW ranges of SOM removed by different doses of FeCl(3) and by the post treatment of UF were studied. Flocculation with at least 50 mg L(-1) of FeCl(3) dose was found to be necessary to avoid any significant flux decline and to obtain superior DOC removal.     

Synergetic effect between photocatalytic degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater

The photocatalytic degradation of two phenolic compounds, p-coumaric acid and caffeic acid, was performed with a suspended mixture of TiO₂ and powdered activated carbon (PAC) (at pH = 3.4 and 8). Adsorption, direct photolysis and photocatalytic degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV lamps). The potential for reusing this catalyst mixture in sequential photocatalytic runs was examined as well. Quantum yields for the direct photolysis of caffeic acid under solar and artificial 365 nm light were calculated (for the first time) as 0.005 and 0.011, respectively.A higher removal rate of contaminants by either adsorption or photocatalysis was obtained at a low pH (pH 4). Furthermore, the addition of PAC increased the removal efficiency of the phenolic compounds. Fast removal of the pollutants from the solution over three sequential runs was achieved only when both TiO₂ and PAC were present. This suggests that at medium phenolic concentrations, the presence of PAC as a co-sorbent reduces surface poisoning of the TiO₂ catalyst and hence improves photocatalysis degradation of phenolic pollutants.The adsorption equilibrium of caffeic acid or p-coumaric acid on TiO₂, PAC and the combined mixture of TiO₂ and PAC follows the Langmuir isotherm model. Experiments with PAC TiO₂ mixture and olive mill wastewater (anaerobically treated and diluted by a factor of 10) showed higher removal of polyphenols than of chemical oxygen demand (COD). 87% removal of total polyphenols, compared to 58% of COD, was achieved after 24 h of exposure to 365 nm irradiation (7.6 W/m²) in the presence of a suspended mixture of TiO₂ and PAC, indicating “self-selectivity” of polyphenols.     

Degradation of natural organic matter by TiO2 photocatalytic oxidation and its effect on fouling of low-pressure membranes

Natural organic matter (NOM) fouling continues to be the major barrier to efficient application of microfiltration (MF) and ultrafiltration (UF) in drinking water treatment. In this study, the potential of TiO2/UV photocatalytic oxidation to control fouling of membranes by NOM was evaluated. Decomposition kinetics of NOM was investigated using a commercial TiO2 catalyst, and the effect of various experimental parameters including TiO2 dosage and initial total organic carbon (TOC) concentration were also determined. The reaction kinetics was found to increase with increasing TiO2 dosage, but decrease with increasing initial TOC concentration. Even though the rate of TOC removal was relatively low, the TiO2/UV process was very effective in controlling membrane fouling by NOM. At a TiO2 concentration of 0.5 g/L, fouling of both an MF and a UF membrane was completely eliminated after 20 min of treatment. Careful analyses of specific UV absorbance (SUVA) and molecular weight (MW) distribution of NOM revealed that the effectiveness in membrane fouling control is the result of the changes in NOM molecular characteristics, namely MW and SUVA due to the preferential removal and transformation of large, hydrophobic NOM compounds. Results from this study show that TiO2/UV photocatalytic oxidation is a promising pretreatment method for MF and UF systems.     

粉末活性炭吸附对超滤膜污染的影响研究

进行了粉末活性炭(PAC)吸附缓解浸没式和内压式超滤膜污染试验研究,并探讨了PAC吸附缓解膜污染的机理。浸没式超滤膜试验结果表明:PAC通过吸附溶解小分子有机物,减少了膜孔堵塞和膜孔内吸附污染,缓解了运行初期通量的快速下降;但PAC在膜表面的累积会降低浸没式超滤膜的起始通量。内压式超滤膜试验结果表明:膜前PAC吸附预处理能提高对有机物的去除效能,降低膜表面的污染负荷,从而降低TMP及其增长速度。     

Solar photocatalytic treatment of synthetic municipal wastewater

The photocatalytic organic content reduction of a selected synthetic municipal wastewater by the use of heterogeneous and homogeneous photocatalytic methods under solar irradiation has been studied at a pilot-plant scale at the Plataforma Solar de Almeria. In the case of heterogeneous photocatalysis the effect of catalysts and oxidants concentration on the decomposition degree of the wastewater was examined. By an accumulation energy of 50 kJL(-1) the synergetic effect of 0.2 gL(-1)TiO(2) P-25 with hydrogen peroxide (H(2)O(2)) and Na(2)S(2)O(8) leads to a 55% and 73% reduction of the initial organic carbon content, respectively. The photo-fenton process appears to be more efficient for this type of wastewater in comparison to the TiO(2)/oxidant system. An accumulation energy of 20 kJL(-1) leads to 80% reduction of the organic content. The presence of oxalate in the Fe(3+)/H(2)O(2) system leads to an additional improvement of the photocatalytic efficiency.     

粉末活性炭/污泥回流工艺强化膜前预处理的研究

采用粉末活性炭(PAC)吸附/混凝沉淀/浸没式超滤膜组合工艺处理苏州市某河水,考察了PAC/污泥回流工艺对膜前预处理的强化效果及对膜污染的影响,并与常规混凝沉淀、污泥回流强化混凝沉淀、PAC吸附/混凝沉淀等3种预处理工艺进行了对比。结果表明,PAC/污泥回流强化预处理工艺对浊度、DOC、UV254和THMFP的去除率分别为80.2%、47.5%、42.3%和52.3%,均比其他预处理工艺的高,对MW30 ku和MW1 ku有机物的去除效果明显。PAC/污泥回流强化预处理和超滤膜组合工艺对浊度、DOC、UV254和THMFP的去除率分别可达到99.2%、54.1%、47.2%和60.2%;经过15 d的运行,超滤膜的跨膜压差基本保持稳定,而其他预处理工艺虽能在一定程度上减轻膜污染,但无法避免不可逆膜污染的发生。     

Adsorption combined with ultrafiltration to remove organic matter from seawater

Organic fouling and biofouling are the major severe types of fouling of reverse osmosis (RO) membranes in seawater (SW) desalination. Low pressure membrane filtration such as ultrafiltration (UF) has been developed as a pre-treatment before reverse osmosis. However, UF alone may not be an effective enough pre-treatment because of the existence of low-molecular weight dissolved organic matter in seawater. Therefore, the objective of the present work is to study a hybrid process, powdered activated carbon (PAC) adsorption/UF, with real seawater and to evaluate its performance in terms of organic matter removal and membrane fouling. The effect of different PAC types and concentrations is evaluated. Stream-activated wood-based PAC addition increased marine organic matter removal by up to 70% in some conditions. Moreover, coupling PAC adsorption with UF decreased UF membrane fouling and the fouling occurring during short-term UF was totally reversible. It can be concluded that the hybrid PAC adsorption/UF process performed in crossflow filtration mode is a relevant pre-treatment process before RO desalination, allowing organic matter removal of 75% and showing no flux decline for short-term experiments.     

Adsorption of As(V) and As(III) by nanocrystalline titanium dioxide

This study evaluated the effectiveness of nanocrystalline titanium dioxide (TiO(2)) in removing arsenate [As(V)] and arsenite [As(III)] and in photocatalytic oxidation of As(III). Batch adsorption and oxidation experiments were conducted with TiO(2) suspensions prepared in a 0.04 M NaCl solution and in a challenge water containing the competing anions phosphate, silicate, and carbonate. The removal of As(V) and As(III) reached equilibrium within 4h and the adsorption kinetics were described by a pseudo-second-order equation. The TiO(2) was effective for As(V) removal at pH<8 and showed a maximum removal for As(III) at pH of about 7.5 in the challenge water. The adsorption capacity of the TiO(2) for As(V) and As(III) was much higher than fumed TiO(2) (Degussa P25) and granular ferric oxide. More than 0.5 mmol/g of As(V) and As(III) was adsorbed by the TiO(2) at an equilibrium arsenic concentration of 0.6mM. The presence of the competing anions had a moderate effect on the adsorption capacities of the TiO(2) for As(III) and As(V) in a neutral pH range. In the presence of sunlight and dissolved oxygen, As(III) (26.7 microM or 2mg/L) was completely converted to As(V) in a 0.2g/L TiO(2) suspension through photocatalytic oxidation within 25 min. The nanocrystalline TiO(2) is an effective adsorbent for As(V) and As(III) and an efficient photocatalyst.     

TiO2/AC光催化剂对卡马西平的降解特性

以椰壳粉末活性炭(PAC)为载体,钛酸丁酯和乙醇为原料,采用溶胶凝胶-浸渍法制备负载型光催化剂(TiO2/AC),并研究其降解模拟废水中微量污染物卡马西平的效果.结果表明:TiO2/AC对卡马西平的处理效果明显优于粉末二氧化钛(TiO2)和活性炭,TiO2/AC对卡马西平的去除率是TiO2的1.7倍.当卡马西平初始浓度为10 mg/L时,TiO2/AC的投加量为500 mg/L、TiO2的负载量为11.2％、反应pH值为7时,卡马西平去除率达到90.6％.TiO2/AC对不同初始浓度卡马西平溶液的降解过程符合准二级反应动力学,二级反应常数与浓度成反比.利用Langmuir-Hinshelwood(L-H)模型可得出表观吸附平衡常数Ka=9.215×103 L/mol,表面反应速率常数Kr=3.678×10-6 mol/(L·min),微波辐照是实现催化剂再生的最佳方法.     

珠江水中有机物分子量分布及其去除研究

采用超滤膜分级方法考察了常规混凝、高锰酸钾和粉末活性炭预处理等工艺对珠江水中各级分子量有机物的去除效果。结果表明,珠江水中有机物以分子量小于1kDa的小分子有机物为主,各级分子量有机物TOC和UV254具有良好的相关性。常规混凝工艺主要去除大分子有机物,且去除率随分子量的减小而降低。高锰酸钾预处理能够全面提高各级分子量有机物的去除效果;粉末活性炭主要吸附中小分子有机物,对各级分子量有机物的去除效果与常规混凝成互补。     

HPLC-fluorescence detection and adsorption of bisphenol A, 17beta-estradiol,and 17alpha-ethynyl estradiol on powdered activated carbon

The adsorption of three estrogenic compounds (bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynyl estradiol (EE2)) on several powdered activated carbons (PAC) was investigated. Without preconcentration, method detection limits (MDL) using high-performance liquid chromatography (HPLC) with fluorescence detection at an excitation wavelength of 280 nm and an emission wavelength of 310 nm were 0.88, 1.15, and 0.96 nM for BPA, E2, and EE2, respectively. Compound recoveries were >90% in raw drinking water matrices. PAC screening studies (six PAC brands) indicated all three compounds were removed by PAC, but the percentage removal ranged from 31% to >99% based upon PAC type/dosage and presence/absence of natural organic matter. The order of removal (E2>EE2>BPA) corresponded with logK(ow) values for the compounds (3.1-4.0, 3.7-3.9, 3.3, respectively). Kinetic and PAC dose-response experiments were conducted with the two best performing PACs. Increasing contact time and PAC dose improved compound removal. Freundlich isotherm parameters were fit to the experimental data. This study confirms that PAC treatment is feasible for >99% removal of three estrogenic compounds from raw drinking waters that may be at risk for containing such compounds, at least at initial concentration of 500 ng/l and higher.     

粉末活性炭强化处理京杭运河常州段微污染原水

以京杭运河常州段微污染原水为研究对象,对其进行常规处理的同时增投粉末活性炭(PAC),通过静态吸附试验考察了最佳的投炭点和投加量.结果表明,投炭点在净水工艺流程中越靠前,则PAC对污染物的吸附效果越好;增投粉末活性炭可大幅度提高对有机污染物的去除效果;粉末活性炭的最佳投加点为吸水井,最佳投量为30 mg/L.     

Photocatalytic oxidation and ozonation of catechol over carbon-black-modified nano-TiO2 thin films supported on Al sheet

The photocatalytic activity of the carbon-black-modified nano-TiO2) (CB-TiO2) thin films was 1.5 times higher than that of TiO2 thin films in degrading Reactive Brilliant Red X-3B. Photocatalytic oxidation and ozonation of catechol over CB-TiO2 thin films supported on Al sheet was investigated. The experiments showed that ozone concentrations had an important effect on TOC removal. The combined photocatalysis with UV irradiation and ozonation (TiO2/UV/O3) process considerably increased TOC removal rate compared to combined photocatalysis with UV irradiation and oxygen oxidation (TiO2/UV/O2) process, ozonation alone (O3) process, combined ozonation and UV irradiation (UV/O3) process. The complete mineralization of catechol followed pseudo-zero-order kinetics dependent upon ozone (oxygen) concentration and indicated catechol concentration did not affect the kinetics during UV/O3 and TiO2/UV/O3 (O2) processes. The kinetic study showed that the rate constants in the complete mineralization of catechol with TiO2/UV/O3 are 1.32-1.80 times higher than that of UV/O3 with the same concentration of ozone. The rate constants are 2.56-5.36 times higher than the maximal rate constants of TiO2/UV/O2 and 4.68-9.8 times higher than the maximal rate constants of TiO2/UV.     

Natural organic matter (NOM) and pesticides removal using a combination of ion exchange resin and powdered activated carbon (PAC)

The combination of anion exchange resins (AERs) and powdered activated carbon (PAC) was studied to remove both natural organic matter (NOM) and pesticides. Experiments were conducted with high dissolved organic carbon (DOC) surface water (about 6.0mg DOC/L) spiked with both atrazine and isoproturon. AERs, like MIEX and IRA938, showed up to 75% removal of DOC after 30min contact time. The addition of PAC after treatment with these AERs only slightly decreased the residual DOC from 1.4 to 1.2mg/L. Experiments conducted with high (200microg/L) and low (1microg/L) initial pesticide concentrations showed that simultaneous and successive combinations of AER and PAC significantly improve the removal of both pesticides compared with PAC treatment on raw water. The improvement of short-term adsorption kinetics was explained by the adsorption of pesticides on AERs (about 5%) and the removal of high molecular weight (MW) NOM structures by AERs that reduce pore blockage phenomena. For 24h contact time with PAC (adsorption isotherms), the benefit of AER treatment was lower, which indicates that the refractory DOC to AER treatment still competes through direct site competition mechanism. MIEX resin had a distinct behavior since the simultaneous treatment with PAC showed no benefit on pesticide adsorption. The presence of fine residues of MIEX was shown to interfere with PAC adsorption.     

混凝法去除水中TiO_2纳米颗粒

为了探讨混凝法去除水中纳米颗粒的可行性及最佳条件,研究了无机混凝剂(PAC、PFS、PAFC)和有机絮凝剂(CPAM、APAM、NPAM)对TiO_2纳米颗粒的去除效果,并考察了投加量、pH、沉淀时间、水力条件及有机无机复配对TiO_2纳米颗粒去除效率的影响。单独投加PAC、PFS和PAFC时,三者对应的最高去除率分别为92.51%、84.43%、95.66%。单独投加CPAM、APAM、NPAM时三者对应的去除率仅为61.72%、29.06%、55.37%。复配最佳混凝条件为:投加40mg/LPAC和3mg/LCPAM,pH值为9,G值143.5/s,沉淀时间15min,此时,TiO_2纳米颗粒去除率为99.6%。     

Photodecomposition of bisphenol A on nanometer-sized TiO2 thin film and the associated biological toxicity to zebrafish (Danio rerio) during and after photocatalysis

We investigated the relationship between the TiO2 photocatalytic decomposition of bisphenol A and biological toxicity to zebrafish (Danio rerio). TiO2 particles, which prepared using a solvothermal method, were applied to produce a nanometer-sized TiO2 thin film. An alcoholic solution containing the TiO2 particles and an inorganic binder was directly coated on the UV-lamp substrate. It was equipped in a photoreactor that was manufactured in our laboratory. The attachment of the thin TiO2 film to the UV-lamp substrate resulted in a stable and transparent coating. The TiO2 particles on the thin film were approximately 20-30 nm in size, and the resulting film thickness was approximately 200 nm after a single coat. The bisphenol A, which was eluted from epoxy resin in a drinking water tank, was completely degraded by the TiO2 photocatalysis. We initially detected approximately 7.8 ng/ml of bisphenol A in the epoxy-resin tank, but its concentration was undetectable after a 48-h photocatalytic reaction over TiO2. We observed a decreased survival rate in zebrafish that were reared in water exposed to the leaching process of the epoxy resin. After the photocatalysis, however, no toxic effects on the hatching rates or morphogenesis of the zebrafish were observed. In summary, toxicity during the TiO2 photocatalysis was observed; however, toxicity was no longer observed once the bisphenol A was completely decomposed by the TiO2 photocatalysis. On the basis of these experimental observations, we suggest that TiO2 photocatalysis can be adopted as a treatment method to purify an epoxy-resin tank.     

Reverse osmosis concentrate treatment via a PAC-MF accumulative countercurrent adsorption process

Organic pollutants in reverse osmosis (RO) concentrates from wastewater reclamation are mainly comprised of low molecular weight biorefractory compounds. Generally, advanced oxidation methods for oxidizing these organics require a relatively high level of energy consumption. In addition, conventional adsorption removal methods require a large dose of activated carbon. However, the dose can be reduced if its full adsorption capacity can be used. Therefore, the combined technology of powdered activated carbon (PAC) adsorption and microfiltration (MF) membrane filtration was studied to develop a countercurrent two-stage adsorption process. A PAC accumulative adsorption prediction method was proposed based on the verification of a PAC multi-stage adsorption capacity equation. Moreover, the prediction method was amended for a more accurate prediction of the effluent quality because adsorption isotherm constants were affected by the initial adsorbate concentration. The required PAC dose for the accumulative countercurrent two-stage adsorption system was 0.6 g/L, whereas that of the conventional adsorption process was 1.05 g/L when the dilution factor(F) was 0.1 and the COD and DOC removal rates were set to 70% and 68.1%, respectively. Organic pollutants were satisfactorily removed with less consumption of PAC. Effluent from this combined technology can be further reclaimed by an RO process to improve the overall recovery rate to between 91.0% and 93.8% with both economic and environmental benefits.