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.     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Formation of nitrogenous disinfection by-products from pre-chloramination

A sampling survey investigated the formation of nitrogenous disinfection by-products (N-DBPs) and carbonaceous DBPs (C-DBPs) from pre-chloramination, an increasingly common treatment strategy in China for regulated C-DBP control, followed by subsequent conventional water treatment processes, i.e., coagulation, sedimentation, and filtration. Dihalogenated N-DBPs typically peaked in the summer and early autumn with a relatively higher temperature, with the maximum levels of dichloroacetamide (DCAcAm), dichloroacetonitrile (DCAN), bromochloroacetonitrile, dibromoacetonitrile and dichloroacetone at 1.8, 6.3, 6.0, 2.6 and 1.8 μg L⁻¹ in the finished water, respectively. Also, the levels of all the dichlorinated N-DBPs were correlated with the ratio of dissolved organic nitrogen (DON) to dissolved organic carbon, implying autochthonous DON played an essential role in the formation of these DBPs. In contrast, the yields of trihalogenated DBPs [chloroform (CF), trichloronitromethane (TCNM) and trichloroacetone (TCAce)] appeared not to be significantly affected by seasons. CF and DCAN were the dominant species in trihalomethanes (THMs) and dihaloacetonitriles (DHANs), respectively. Bromine was more readily incorporated into DHANs to form brominated DBPs than THMs during pre-chloramination. Although pre-chloramination can ensure the finished water to meet with the current Chinese THM regulatory limits, the increased levels of TCNM and TCAce may be a new water quality concern.     

Comparison of inclined plate sedimentation and dissolved air flotation for the minimisation of subsequent nitrogenous disinfection by-product formation

The formation of disinfection by-products (DBPs), including both nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products (C-DBPs), was investigated upon chlorination of water samples following two treatment processes: (i) coagulation-inclined plate sedimentation (IPS)-filtration and (ii) coagulation-dissolved air flotation (DAF)-filtration. The removal of algae, dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV₂₅₄ by coagulation-DAF-filtration was superior to coagulation-IPS-filtration. On average, 53%, 53% and 31% of DOC, DON and UV₂₅₄ were removed by coagulation-DAF-filtration process, which were higher than 47%, 31% and 27% of that by coagulation-IPS-filtration process. Additionally, coagulation-IPS-filtration performed less well at removing the low molecular weight organics than coagulation-DAF-filtration process. The concentrations of chloroform, dichloroacetamide (DCAcAm) and dichloroacetonitrile (DCAN) formed during chlorination after coagulation-DAF-filtration reached their maximum values of 13, 1.5 and 4.7 μg L⁻¹, respectively, and were lower than those after coagulation-IPS-filtration with the maximum detected levels of 17, 2.9 and 6.3 μg L⁻¹. However, the trichloronitromethane (TCNM) concentration after the two processes was similar, suggesting that DON may have less of a contribution to TCNM formation than DCAcAm and DCAN.     

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.     

Formation of Disinfection Byproducts (DBPs) in Surface Water Sources: Differential Ultraviolet (UV) Absorbance Approach

Chlorination for drinking water forms various disinfection byproducts (DBPs) of trihalomethanes (THMs) and haloacetic acids (HAAs). Chlorination has been attributed to the destruction of activated aromatic sites of the natural organic matter (NOM) predominantly at electron rich sites. Experiments with Istanbul surface waters showed that the magnitude of the decrease in the ultraviolet (UV) absorbance at 272 nm (UV₂₇₂) was an excellent indicator of destruction of these sites by chlorine. The main objective of the present study is to develop the differential UV₂₇₂ absorbance (ΔUV₂₇₂) related models for the prediction of the formation of THM, HAA, and their species in raw water samples from Terkos, Buyukcekmece, and Omerli lakes under different chlorination conditions. Significant factors affecting DBP formation in the raw waters were identified through numerical and graphical techniques. The R² values of the models varied between 0.94 and 0.97, indicating excellent predictive ability for THM₄ and HAA₉ in the raw waters. The models were validated using additional data. The results of this study concluded that addition of ΔUV₂₇₂ parameter into THM₄ and HAA₉ models make the prediction of these DBP compounds more precisely than those of DBP models developed in the past. A better understanding of these modeling systems will help the water treatment plant operators to minimize the DBP formation, providing a healthier and better drinking water quality as well as identifying strategies to improve water treatment and disinfection processes.     

Nano-silver in drinking water and drinking water sources: stability and influences on disinfection by-product formation

Nano-silver is increasingly used in consumer products from washing machines and refrigerators to devices marketed for the disinfection of drinking water or recreational water. The nano-silver in these products may be released, ending up in surface water bodies which may be used as drinking water sources. Little information is available about the stability of the nano-silver in sources of drinking water, its fate during drinking water disinfection processes, and its interaction with disinfection agents and disinfection by-products (DBPs). This study aims to investigate the stability of nano-silver in drinking water sources and in the finished drinking water when chlorine and chloramines are used for disinfection and to observe changes in the composition of DBPs formed when nano-silver is present in the source water. A dispersion of nano-silver particles (10 nm; PVP-coated) was used to spike untreated Ottawa River water, treated Ottawa River water, organic-free water, and a groundwater at concentrations of 5 mg/L. The diluted dispersions were kept under stirred and non-stirred conditions for up to 9 months and analyzed weekly using UV absorption to assess the stability of the nano-silver particles. In a separate experiment, Ottawa River water containing nano-silver particles (at 0.1 and 1 mg/L concentration, respectively) was disinfected by adding sodium hypochlorite (a chlorinating agent) in sufficient amounts to maintain a free chlorine residual of approximately 0.4 mg/L after 24 h. The disinfected drinking water was then quenched with ascorbic acid and analyzed for 34 neutral DBPs (trihalomethanes, haloacetonitriles, haloacetaldehydes, 1,1 dichloro-2-propanone, 1,1,1 trichloro-2-propanone, chloropicrin, and cyanogen chloride). The results were compared to the profile of DBPs obtained under the same conditions in the absence of nano-silver and in the presence of an equivalent concentration of Ag⁺ ions (as AgNO₃). The stability of the nano-silver dispersions in untreated Ottawa River water, with a dissolved organic carbon concentration of 6 mg/L, was significantly higher than the stability of the nano-silver dispersions in distilled, organic-free water. Nano-silver particles suspended in the groundwater agglomerated and were quickly and quantitatively removed from the solution. Our data confirm previous observations that natural dissolved organic matter stabilizes nano-silver particles, while the high-ionic strength of groundwater appears to favor their agglomeration and precipitation. As expected, nano-silver was not stable in Ottawa River water through the chlorination process, but survived for many days when added to the Ottawa River water after treatment with chlorine or chloramines. Stirring appeared to have minimal effect on nano-silver stability in untreated and treated Ottawa River water. The profile of DBPs formed in the presence of nAg differed significantly from the profile of DBPs formed in the absence of nAg only at the 1 mg/L nAg concentration. The differences observed consisted mainly in reduced formation of some brominated DBPs and a small increase in the formation of cyanogen chloride. The reduced formation of brominated congeners may be explained by the decrease in available bromide due to the presence of Ag⁺ ions. It should be noted that a concentration of 1 mg/L is significantly higher than nAg concentrations that would be expected to be present in surface waters, but these results could be significant for the disinfection of some wastewaters with comparably high nano-silver concentrations.     

Reducing the formation of disinfection by-products by pre-ozonation.

The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.     

An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

炼化企业中水紫外线消毒及其影响因素简

研究水质对254 nm紫外线透射率的影响，通过动态实验考察了照射时间、254 nm紫外线透射率以及紫外线剂量对炼化企业中水消毒效果的影响并同时考察异养菌、硫酸盐还原菌和铁细菌的光复活及暗修复现象。结果表明，有机物是影响炼化企业中水紫外线消毒的重要因素；紫外线对炼化企业中水中的异养菌具有良好的灭活作用；增加照射时间对消毒效果的提升作用受254 nm紫外线透射率的影响；紫外线透射率在较低的范围内时对消毒效果的影响相对较大，在较高的范围内时影响较小；紫外线剂量-响应曲线受254 nm紫外线透射率的影响；剂量的“成分”，即照射时间和透射率的不同组合，也会对消毒效果产生影响；在80 mJ/cm²的剂量下，20 h内异养菌出现了较强烈的光复活和暗修复现象，铁细菌仅出现了明显的光复活现象，硫酸盐还原菌没有表现出明显的复活。     

Disinfection by-products in Finnish drinking waters

Disinfection by-products (DBPs) were measured in plant effluents of 35 Finnish waterworks, which utilized different treatment processes and raw water sources. DBPs were measured also from the distribution systems of three waterworks. Di- and trichloroacetic acids, and chloroform were the major DBPs found in treated water samples. The concentration of six haloacetic acids (HAA6) exceeded the concentrations of trihalomethanes (THMs). Chlorinated drinking waters (DWs) originating from surface waters contained the highest concentration of HAA6 and THMs: 108 and 26 microg/l, respectively. The lowest concentrations of DBPs were measured from ozonated and/or activated carbon filtrated and chloraminated DWs. Higher concentrations of HAA6, THMs, and adsorbable organic halogens were measured in summer compared to winter. The levels of chlorinated acetic acids, chloroform, and bromodichloromethane correlated positively with mutagenicity. Past mutagenicity levels of DWs were examined. A major reduction in the use of prechlorination, increased use of chloramine disinfection, and better removal of organic carbon were the most important reasons for the 69% decrease in mutagenicity from 1985 to 1994.     

The occurrence of disinfection by-products in the drinking water of Athens,Greece

Application of chlorination for the disinfection of drinking water results in the formation of a wide range of organic compounds, called disinfection by-products (DBPs), which occur due to the reaction of chlorine with natural organic materials. The occurrence of DBPs was studied in samples from four drinking-water treatment plants (WTPs) and from the distribution network of Athens, Greece. Twenty-four compounds, which belong to different categories of DBPs, were monitored, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HAKs), chloral hydrate (CH) and chloropicrin (CP). Sampling was performed monthly for a period of two years, from three different points at each WTP and from eight points atthe distribution network. Samples were analyzed by GC-ECD methods, which included pretreatment with liquid-liquid extraction for volatile DBPs and acidic methanol esterification for HAAs. The results of the analyses have shown the presence of disinfection by-products belonging to all categories studied in all water samples collected after prechlorination. The major categories of DBPs detected were THMs and HAAs, while the other volatile DBPs occurred at lower concentrations. The concentrations of DBPs did not in any case exceed the maximum contaminant levels (MCL) set by USEPA and WHO. However, monitoring these compounds needs to be continued, because their levels could increase due to changes in the quality of water entering the water treatment plants. Reduction of the concentrations of DBPs could be achieved by optimization of the chlorination conditions, taking into account the effect of time. Moreover, research on alternative disinfection methods (e.g. ozone, chlorine dioxide, chloramines) and their by-products should be conducted to evaluate their applicability in the case of the drinking water of Greece.     

河流型水源地源水典型氯化消毒副产物及其前体物的强化去除工艺

以长三角某典型河流型水源地源水为研究对象,设计了传统工艺及基于凹凸棒土处理单元的6种强化工艺,对各工艺及其处理单元应用于典型氯化消毒副产物(三卤甲烷和卤乙酸)及其前体物控制的技术和经济可行性进行了系统分析。结果表明,预O3+凹土强化混凝+O3-GAC强化的工艺对上述2种消毒副产物及其前体物的控制效果最佳;在传统工艺中单纯增加O3处理也能在一定程度上提高其对消毒副产物前体物的去除效果;KMnO4控制消毒副产物的效果一般,但KMnO4处理可强化后续单元对消毒副产物前体物的去除效果。各工艺处理出水中三卤甲烷和卤乙酸单项指标均能达标,但传统工艺和经凹土强化混凝+GAC强化的工艺出水三卤甲烷4种化合物的实测浓度与其各自限值的比值之和均大于1.0,不能满足水质要求,必须进行强化处理。凹土强化混凝单元在6种强化工艺条件下对三卤甲烷生成潜能(THMFP)和卤乙酸生成潜能(HAAFP)的去除率较传统混凝单元平均提高15.99%和4.92%;各强化工艺对THMFP和HAAFP的去除率较传统工艺均提高20%以上(除凹土强化混凝+GAC强化的工艺外),消毒副产物产生量降低40%以上,工艺成本降低20%以上。     

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.     

Characteristics of organic precursors and their relationship with disinfection by-products

The molecular weight distribution and chemical composition of precursors and their relationship with disinfection by-products (DBPs) were investigated. Most of the organic matter responsible for the major DBP precursors in the Pan-Hsin water are small compounds with a molecular weight less than 1 kDa. The hydrophobic acids display the greatest ability to produce DBP. Therefore, effective removal of small molecules or hydrophobic acidic organics prior to disinfection process will significantly reduce the DBP concentration in the finished water. Although the coagulation process is effective in removing large organic precursors and the removal efficiencies of CHCl3 formation potential and organic carbon increase proportionally to the molecular weight of the precursors, the conventional treatment methods have limited efficiency in eliminating small precursors, which have high DBP formation potential.     

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.     

聚合氯化铝与粉末活性炭联合强化混凝处理垃圾渗滤液

研究了联合粉末活性炭与聚合氯化铝(PAC)强化混凝对垃圾渗滤液原水的处理效果。结果表明,在原水COD为4 100 mg/L、浊度为147 NTU、UV254为20的条件下,粉末活性炭的加入可以有效增加垃圾渗滤液中有机物的去除率,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,COD的去除率由21.6%提高到29.1%,UV254去除率由29.8%提高到39.9%,剩余浊度由138 NTU降到133 NTU。该强化混凝过程使原水中溶解性小分子有机物的去除率提高显著,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,在分子量小于1 kDa的范围内,UV254去除率由2.9%上升为10%。     

Photodecomposition of humic acid and natural organic matter in swamp water using a TiO2-coated ceramic foam filter: Potential for the formation of disinfection byproducts

This paper reports on the photodecomposition of aqueous humic acid (HA) by a TiO₂-coated ceramic foam filter (TCF) reactor and on the potential for the formation of disinfection byproducts (DBPs) upon chlorination of the photocatalytically treated solutions. This photocatalytic reactor can also be applied to the removal of natural organic matter (NOM) in swamp waters. The proposed photocatalytic reaction system was operated as per standardized methodologies. First, the ability of the TCF to decompose HA (a representative compound of NOM) was evaluated from the changes in the total organic carbon (TOC) and UV₂₅₄ with the reaction time. Remarkably, TOC removal and UV₂₅₄ values ranging from 44% to 61% and from 60% to 83%, respectively, were achieved. The potential for the formation of DBPs (total trihalomethane and total haloacetic acid) by chlorination of the phototreated solution was strongly dependent on the TOC removal and UV₂₅₄ values in the solution. The degree of photodecomposition of NOMs in the swamp water samples and the DBP formation potential showed similar trends as in the case of the standard solutions containing HA. The method used in this study could be effectively used to evaluate the efficiency of TCF for reducing HA and NOM, while suppressing the formation of DBP products.