Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0?mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85?±?0.18?mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65?% fulvic and 14?% humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309?±?15?μg/L). Ozonation at pH?6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90?% achieved using 3.0?mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH?10 (up to 68?% HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1?±?6.0?μg/mg DOC in raw water to 152?±?8?μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH?10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.     

Removal of NOM from drinking water: Fenton's and photo-Fenton's processes

The control of disinfection by-products during water treatment is primarily undertaken by reducing the levels of precursor species prior to chlorination. As many waters contain natural organic matter at levels of up to 15 mgl(-1) there is a need for a range of control methods to support conventional coagulation. Two such processes are the Fenton and photo-Fenton's processes and in this paper they are assessed for their potential to remove NOM from organic rich waters. The performance of both processes is shown to be depentent on pH, Fe: H2O2 ratio as well as Fe2+ dose. Under optimum conditions both processes achieved greater than 90% removal of DOC and UV254 absorbance. This removal lead to the trihalomethane formation potential of the water being reduced from 140 to below 10 microgl(-1), well below UK and US standards.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

土壤渗滤对有机微污染物去除性能研究

采用土壤柱试验研究了土壤渗滤对再生水中有机微污染物的去除性能。结果表明，土壤柱对再生水中的DOC、UV₂₅₄、总氮和总磷有较好的去除效果，并具有较高的抗冲击负荷的能力；土壤表层10 cm厚度对DOC的去除起主要作用；UV₂₅₄和AOX在土壤表层10 cm厚度降解效果不明显，随着深度增加去除率逐渐升高；液相色谱有机碳探测(LC-OCD)检测结果表明，土壤柱对溶解性有机物质的去除主要体现在对多糖物质的降解上，其次是有机酸类，对腐殖质也有一定的去除作用。     

Minimization of the formation of disinfection by-products

The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA₂₅₄), specific UV absorbance at 254 nm (SUVA₂₅₄), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.     

Advanced oxidation of natural organic matter using hydrogen peroxide and iron-coated pumice particles

The oxidative removal of natural organic matter (NOM) from waters using hydrogen peroxide and iron-coated pumice particles as heterogeneous catalysts was investigated. Two NOM sources were tested: humic acid solution and a natural source water. Iron coated pumice removed about half of the dissolved organic carbon (DOC) concentration at a dose of 3000 mg l(-1) in 24 h by adsorption only. Original pumice and peroxide dosed together provided UV absorbance reductions as high as 49%, mainly due to the presence of metal oxides including Al(2)O(3), Fe(2)O(3) and TiO(2) in the natural pumice, which are known to catalyze the decomposition of peroxide forming strong oxidants. Coating the original pumice particles with iron oxides significantly enhanced the removal of NOM with peroxide. A strong linear correlation was found between iron contents of coated pumices and UV absorbance reductions. Peroxide consumption also correlated with UV absorbance reduction. Control experiments proved the effective coating and the stability of iron oxide species bound on pumice surfaces. Results overall indicated that in addition to adsorptive removal of NOM by metal oxides on pumice surfaces, surface reactions between iron oxides and peroxide result in the formation of strong oxidants, probably like hydroxyl radicals, which further oxidize both adsorbed NOM and remaining NOM in solution, similar to those in Fenton-like reactions.     

Influence of eutrophication on the coagulation efficiency in reservoir water

Water from the three reservoirs, Min-ter, Li-yu-ten and Yun-ho-shen, was examined for concentration of chlorophyll a, ultraviolet absorption (UV(254)), fluorescence intensity (FI), concentration of dissolved organic carbon (DOC), and fractionation of dissolved molecules by molecular weight. The water samples were collected over the change from spring to summer (May to July but before the typhoon season) when the water temperature and extent of eutrophication increase. Analytical results indicate that the concentration of DOC is proportional to the concentration of chlorophyll a, but not to the values of UV(254) and FI. Therefore, eutrophication, extraneous contaminants of small molecules, and the extracellular products of algae cause an increase in DOC, but a decrease in the proportion of large organic molecules such as of humic substances. The fraction of DOC with a molecular weight of less than 5000 Da increases with the concentration of chlorophyll a. All these data suggest that changes in the quality of water after eutrophication make the treatment of drinking water more difficult. The method of enhanced coagulation was recently developed for removing DOC. However, the results of this paper demonstrate that the efficiency of DOC removal falls as the degree of eutrophication increases. When the percentage of DOC with small molecules excreted by algae increased by 1%, the efficiency of DOC removal decreased by approximately 1%, implying that enhanced coagulation are not able to remove the DOC excreted by the algae during eutrophication, and resulting an increased concentration of trihalomethanes formation in water disinfections process.     

四种净水工艺对水源水微量有机物去除的研究

以UV254和CODMn代表饮用水源水中有机物替代指标.对常规处理、生物陶粒预处理、生物滤池、生物活性炭(BAC)、颗粒活性炭(GAC)、纳滤和光催化氧化进行组合,形成不同的处理流程,研究各流程对UV254和CODMn的去除效果.结果表明,各工艺流程都有一定的处理效率,其中以生物滤池和纳滤为主的组合流程处理效果最佳.此流程对UV254的去除率接近100%,CODMn的去除率达到78.6%,大大提高了饮用水的安全性.     

Effect of pre-ozonation on optimized coagulation of a typical North-China source water

Although ozone is widely used as a pre-oxidant before coagulation in water treatment, the effect of pre-ozonation on optimized coagulation for removal of particle and natural organic matter (NOM) is still not fully understood. In this paper, pilot-scale investigation was conducted to examine the impact of pre-ozonation on coagulation for particle and NOM removal. Changes in the particle and NOM distributions were characterized by various methods, including laser light granularity system, particle counter, ultrafiltration, and resin absorbent fractionation. A novel composite flocculant–HPAC was compared with the traditional ferric chloride coagulant in terms of coagulation efficiency under the influence of pre-ozonation. Typical micro-polluted North China surface water was used for pilot coagulation tests. The results show that the effect of pre-ozonation on coagulation is associated with the dosage of ozone, coagulant type, and water contamination characteristics. For FeCl₃, pre-ozonation acts as a coagulation aid at low dosage (1.0 mg L⁻¹ O₃) for turbidity and UV₂₅₄ removal; while at higher dosage (2.0 mg L⁻¹ O₃), pre-ozonation is detrimental to UV₂₅₄ removal although it is still beneficial for turbidity removal. In the case of composite flocculant–HPAC, pre-ozonation demonstrates negligible influence on both turbidity and UV₂₅₄ removal. Ozone can simultaneously aggregate fine particles and break down large ones, making them more mineralized and easier to remove. NOM with intermediate molecular weight and hydrophobic neutral property increases at lower ozone dosage, favoring removal by coagulation. At higher ozone dosages, NOM becomes more hydrophilic and its molecular weight becomes smaller, decreasing NOM removal.     

Effect of Pre-ozonation on Optimized Coagulation of a Typical North-China Source Water

Although ozone is widely used as a pre-oxidant before coagulation in water treatment, the effect of pre-ozonation on optimized coagulation for removal of particle and natural organic matter (NOM) is still not fully understood. In this paper, pilot-scale investigation was conducted to examine the impact of pre-ozonation on coagulation for particle and NOM removal. Changes in the particle and NOM distributions were characterized by various methods, including laser light granularity system, particle counter, ultrafiltration, and resin absorbent fractionation. A novel composite flocculant–HPAC was compared with the traditional ferric chloride coagulant in terms of coagulation efficiency under the influence of pre-ozonation. Typical micro-polluted North China surface water was used for pilot coagulation tests. The results show that the effect of pre-ozonation on coagulation is associated with the dosage of ozone, coagulant type, and water contamination characteristics. For FeCl₃, pre-ozonation acts as a coagulation aid at low dosage (1.0 mg L⁻¹ O₃) for turbidity and UV₂₅₄ removal; while at higher dosage (2.0 mg L⁻¹ O₃), pre-ozonation is detrimental to UV₂₅₄ removal although it is still beneficial for turbidity removal. In the case of composite flocculant–HPAC, pre-ozonation demonstrates negligible influence on both turbidity and UV₂₅₄ removal. Ozone can simultaneously aggregate fine particles and break down large ones, making them more mineralized and easier to remove. NOM with intermediate molecular weight and hydrophobic neutral property increases at lower ozone dosage, favoring removal by coagulation. At higher ozone dosages, NOM becomes more hydrophilic and its molecular weight becomes smaller, decreasing NOM removal.     

臭氧光催化降解地下水中天然有机物的研究

在现场开展了中试规模的臭氧光催化降解天然有机物的研究.研究表明,对大分子天然有机物占很大比例且重碳酸盐含量较高的地下水,臭氧投加量10 mg/L和反应时间10 min条件下,TOC的去除率不到20%,但UV254和三卤甲烷生成潜力(THMFP)去除率分别达到近60%和33.5%.臭氧光催化与活性炭吸附相连,能显著提高UV254的THMFP的去除率,但TOC去除率并不明显高于单独活性炭吸附.臭氧光催化使大分子有机物转化为小分子有机物,后者在活性炭上的吸附性提高且生化性改善,可望在生物活性炭上更有效地去除.     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

Applicability of MIEX®DOC process for organics removal from NOM laden water

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.     

改性TiO2/浮石光催化去除二级出水中有机物

为了实现城市污水厂二级出水的回用,将La3+、Fe3+共掺杂TiO2/浮石光催化用于二级出水中有机物的去除。在优化工艺条件下,该方法对TOC的去除率为49.0%,对UV254的去除率为76.5%;出水BDOC/DOC值大幅度提高,由最初的0.21提高到0.56,增加了出水的可生化性;二级出水中存在着影响光催化去除有机物的因素,其中阴离子对有机物的去除有一定的抑制作用;光催化反应在通过O3强化后对有机物的去除率得到提高,TOC的去除率达到75.0%,光催化和O3氧化对有机物的去除具有协同效应;随着光催化反应次数的增加,催化剂活性有下降趋势,使用10次后TOC去除率下降到第一次使用时的16.7%,再生能够使催化活性恢复到使用前的95%,催化剂在使用15次以内稳定性较好。     

Photodegradation of an azo dye of the textile industry

An advanced oxidation treatment, UV/H2O2, was applied to an azo dye, Hispamin Black CA, widely used in the Peruvian textile industry. Rates of color removal and degradation of the dye have been evaluated. A strongly absorbing solution was completely decolorized after 35 min of treatment, and after 60 min an 82% reduction of the total organic carbon (TOC) was obtained. It has been found that the degradation rate increased until an optimum value, beyond which the reagent exerted an inhibitory effect. The degradation rate was also function of pH.     

NOM characteristics and treatabilities of ozonation processes

The objectives of this study were intended to evaluate the effects of the characteristics of natural organic matter on the treatabilities of ozonation, coagulation, filtration, and granular activated carbon processes. The ultra-violet absorbance (UV254) was used as a surrogate parameter to assess each process in reducing the disinfection by-product formation potential (DBPFP). The results indicate that the DBPFP varies with the sources of water samples and treatment processes, but is closely related to the measurement of UV254/DOC. Coagulation/sedimentation can eliminate large molecular weight organic fractions. Both pre- and post-ozonation processes can reduce some of DBP precursors than the conventional treatment process, and are more reliable for reducing the overall DBPFP.     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

Formation of hazardous by-products resulting from the irradiation of natural organic matter: comparison between UV and VUV irradiation

The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.     

Enhanced coagulation with polyaluminum chlorides: role of pH/alkalinity and speciation

Enhanced coagulation is considered to be among the best available techniques (BAT) for disinfection by-product (DBP) precursor removal in water treatment. Improving existing understanding requires further consideration of nuances of chemical speciation relative to source water chemistry. In this paper, the effect of alkalinity/pH and speciation on inorganic polymer flocculants, polyaluminum chlorides (PACls) for enhanced particle and natural organic matter (NOM) removal was investigated. Three kinds of well-characterized typical source waters in China with low, moderate, and high alkalinity were selected. Performance of coagulants is controlled not only by preformed species but also by those formed in situ. At neutral and basic pH values, PACls with higher basicity (ratio of OH(-)/Al), which have more stable preformed Alb (the rapid reacted species as in ferron assay), are more efficient for turbidity and NOM removal. At slightly acidic pH, PACls with lower basicity are more efficient since more Alb can be formed in situ. Optimal NOM removal was achieved at pH 5.5-6.5 for all PACls. Basicity, speciation, and dosage of coagulant should be optimized based on raw water alkalinity to enhance the removal efficiency of NOM.