不同净水工艺对含溴水体消毒副产物生成势的影响

以溴离子和有机物浓度不同的5个水厂原水和各工艺段出水为研究对象,考察了不同净水工艺对三卤甲烷(THMs)和卤乙酸(HAAs)这两类典型消毒副产物生成势和种类分布的影响。结果表明,仅采用常规处理工艺对THMs和HAAs生成势的控制效果不明显,而增设生物预处理和臭氧氧化预处理工艺能显著提高常规工艺对THMs和HAAs前体物的去除效果,臭氧/生物活性炭(O3/BAC)深度处理工艺能进一步去除THMs和HAAs的前体物。增设预处理和O3/BAC深度处理工艺,并采取砂滤池后置的净水工艺流程对THMs和HAAs生成势的控制效果最好。对于含溴水体,溴离子浓度越高,有机物中亲水性组分所占比例越高,经氯消毒后生成的溴代THMs和HAAs所占比例就越高。随着处理工艺流程的进行,THMs和HAAs的生成势逐渐降低,但是它们的溴结合因子逐渐增大,即毒性更大的溴代组分所占比例逐渐增大。     

臭氧催化氧化与BAC联用控制氯化消毒副产物

研究了臭氧催化氧化与生物活性炭联用技术对氯化消毒副产物（DBPs）的控制效能。结果表明：常规工艺出水中分子质量为2000u左右的疏水性有机物是氯化消毒副产物的主要前质，其占DOC与UV254的比例分别为70％和80％，并与UV254有良好的线性相关性，故可用UV254作为DBPs前质的替代指标。臭氧催化氧化与生物活性炭联用对DBPs前质的去除效果显著，其中臭氧催化氧化可有效去除三卤甲烷（THMs）前质中的疏水性有机物及部分亲水性有机物，并提高了DBPs前质的可生化性，是给水深度处理中控制THMs前质的主要工艺环节。臭氧催化氧化／生物活性炭对UV254的控制是减少DBPs生成的一条有效途径。     

Disinfection by-products and their precursors in a water treatment plant in North China: Seasonal changes and fraction analysis

A one-year-long monitoring project was conducted to assay the concentrations of THMs, HAAs and their formation potential along the conventional process in a water treatment plant in North China. Subsequent investigations of organic matter fractionation and the contribution of the algae to the precursor were also conducted to trace the source of the DBPs. The results showed that the concentration of DBPs and their formation potential varied with the seasons. The highest concentrations of THMs and the highest HAAs formation potential, each almost 500 microg/L, were detected in autumn and the lowest were in spring, no more than 100 microg/L. Both organic matter and algae were found to be important DBP precursors. The hydrophobic acid fraction in dissolved organic matter has the highest formation potential for both THM and HAA. Algae contribute about 20% to 50% of the total formation potential during an algal bloom. The efficiency of each unit process for DBPs and precursors was also assayed. Unfortunately, the conventional drinking water treatment process is limited in its efficiency for precursor removal. The pre-chlorination and filtration process had a negative effect on DBP or precursor removal.     

O3/BAC对氯化消毒副产物的控制作用

采用臭氧化—生物活性炭(O3／BAC)深度处理工艺去除水中消毒副产物前质的试验结果表明，该工艺能够有效去除水中消毒副产物前质，可控制氯化消毒副产物的生成，其中主臭氧化对三卤甲烷前质和卤乙酸前质均具有很好的去除效果，生物活性炭对卤乙酸前质表现出较好的去除效果，但对三卤甲烷前质的去除效果有限；藻类、有机物等在滤层的累积使得砂滤池在同一工作周期中的不同阶段对水中三卤甲烷前质的去除效果有所不同，因而需要合理设置砂滤池的反冲洗周期。臭氧化—生物活性炭工艺充分发挥了臭氧化和生物活性炭两种技术的优点，并相互促进和补充，能够充分保障饮用水的安全性。     

DBPs removal in GAC filter-adsorber

A rapid sand filter and granular activated carbon filter-adsorber (GAC FA) were compared in terms of dissolved organic carbon (DOC) and disinfection by-products (DBPs) removal. A water treatment plant (WTP) that had a high ammonia concentration and DOC in raw water, which, in turn, led to a high concentration of DBPs because of a high dose of pre-chlorination, was investigated. To remove DBPs and DOC simultaneously, a conventional rapid sand filter had been retrofitted to a GAC FA at the Buyeo WTP in Korea. The overall removal efficiency of DBPs and DOC was higher in the GAC FA than in the sand filter, as expected. Breakthrough of trihalomethanes (THMs) was noticed after 3 months of GAC FA operation, and then removal of THMs was minimal (<10%). On the other hand, the removal efficiency of five haloacetic acids (HAA(5)) in the GAC FA was better than that of THMs, though adsorption of HAA(5) decreased rapidly after 3.5 months of GAC FA operation. And then, gradual improvement (>90%) in HAA(5) removal efficiency was again observed, which could be attributed to biodegradation. At the early stage of GAC FA operation, HAA(5) removal was largely due to physical adsorption, but later on biodegradation appeared to prevail. Biodegradation of HAA(5) was significantly influenced by water temperature. Similar turbidity removal was noticed in both filters, while better manganese removal was confirmed in the sand filter rather than in the GAC FA.     

The influence of water treatment processes on the presence of organic surrogates and mutagenic compounds in water

The effects of granular activated carbon filtration and of the combination of ozonation and GAC filtration on the quality of Rhine water were studied in a pilot plant. The scope of the study was to compare both systems in relation to the removal of organic contaminants in water, and to the reduction of the side effects of chlorination. The water quality was measured with organic surrogate parameters (organohalogen, -nitrogen, -phosphorus and -sulphur) and in bacterial mutagenicity assays.In this particular setting, the combination of ozonation and GAC filtration was superior in all points to GAC filtration alone. The effects of ozonation are sometimes quite different, depending on the type of water treated. Its positive influence should be confirmed in a local situation.As GAC treatment causes a shift towards formation of more brominated THM after chlorination, special attention was given to this item. A higher inorganic bromide/DOC ratio resulted in higher brominated THM concentrations after chlorination. However, the mutagens formed during chlorination in presence of more inorganic bromide could be inactivated more easily by rat liver homogenate than in the normal setting. The results of this study confirmed earlier findings stating a negative influence of chlorination on water quality.     

Predicting disinfection by-product formation potential in water

Formation of regulated and non-regulated disinfection by-products (DBPs) is an issue at both potable water and wastewater treatment plants (W/WWTPs). Water samples from W/WWTPs across the USA were collected and DBP formation potentials (DBPFPs) in the presence of free chlorine and chloramine were obtained for trihalomethane (THM), haloacetic acid (HAA), haloacetonitrile (HAN), and N-nitrosodimethylamine (NDMA). With nearly 200 samples covering a range of dissolved organic carbon (0.6-23 mg/L), ultraviolet absorbance (0.01-0.48 cm⁻¹ at 254 nm wavelength), and bromide (0-1.0 mg/L) levels, power function models were developed to predict the carbonaceous DBP (C-DBP) and nitrogenous DBP (N-DBP) precursors spanning 3 orders of magnitudes. The predicted THM and HAA formation potentials fitted well with the measured data (analytical variance of less than 22%). Inclusion of dissolved organic nitrogen (DON) into the HANFP model improved the predictions. NDMAFP was the most difficult one to predict based upon the selected water quality parameters, perhaps suggesting that bulk measurements such as DOC or UVA₂₅₄ were not appropriate for tracking NDMAFP. These are the first such DBPFP models for wastewater systems, and among the few models that consider both C-DBPs and N-DBPs formation potentials from the same water sources.     

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.     

Removal of VUV pre-treated natural organic matter by biologically activated carbon columns

A potential alternative water treatment process using VUV (185 nm+254 nm) irradiation followed by a biological treatment is described. The system uses sufficient VUV radiation (16J cm(-2)) to significantly enhance the production of biologically degradable moieties prior to treatment with biologically activated carbon (BAC). Two similar activated carbons were used, one virgin and one taken from a water treatment plant with an established biofilm. The VUV-BAC process decreased the overall dissolved organic carbon (DOC) concentration of a natural water sample by 54% and 44% for the virgin carbon and previously used BAC, respectively. Furthermore, VUV-BAC treatment decreased the trihalomethane (THM) formation potential (THMFP) by 60-70% and the haloacetic acid (HAA) formation potential (HAAFP) by 74%. The BAC systems effectively removed the hydrogen peroxide residual produced by VUV irradiation. Although nitrite formation can result from VUV treatment of natural organic matter (NOM), none was detected before or after BAC treatment.     

Optimization of Coagulation and Ozonation Processes for Disinfection by–Products Formation Potential Reduction

Optimization of coagulation and ozonation processes for removal of disinfection by–products (DBP) formation potential in raw water was conducted by a pilot scale system. Proper poly–aluminum–chloride–sulfates (PACS), pre–ozone and post–ozone dosages are required for improving the removal performance of DBP formation potential to guarantee the safety of drinking water. Considering the treatment performances and economic costs, the optimum PACS, pre–ozone and post–ozone dosages for treating raw water with high organic concentration should be around 8.9 mg/L Al₂O₃, 0.5 and 2.5 mg/L, respectively. The combined drinking water treatment system of pre–ozonation, coagulation/sedimentation, sand filtration, post–ozonation, granular activated carbon filtration and disinfection is a promising process to reduce DBP formation potential from raw water in southern China. Under the optimum conditions, this combined system removed total trihalomethanes and haloacetic acids formation potential 50.16 and 69.10%, respectively.     

Biofiltration of wastewater treatment plant effluent: effective removal of pharmaceuticals and personal care products and reduction of toxicity

This study investigates biofiltration for the removal of dissolved organic carbon (DOC), pharmaceuticals and personal care products (PPCPs), and for the reduction of non-specific toxicity expressed as baseline toxicity equivalent concentration (baseline-TEQ). Two filtering media, sand and granular activated carbon, were tested. The influence of pre-ozonation and empty-bed contact time (EBCT, from 30 to 120 min) was determined. The experiments were performed at a pilot-scale with real WWTP effluent. A previous study showed that biological activity had developed on the filtering media and dissolved organic removal had reached a steady state before sampling commenced. The results show that biological activated carbon (BAC) has a good potential for the removal of DOC (35-60%), PPCPs (>90%) and baseline-TEQ (28-68%) even without pre-ozonation. On the contrary, the sand shows limited improvement of effluent quality. Varying the EBCT does not influence the performance of the BAC filters; however, dissolved oxygen concentration could be a limiting factor. The performances of the BAC filters were stable for over two years suggesting that the main mechanism of organic matter and PPCPs removal is biodegradation. It is concluded that BAC filtration without pre-ozonation could be implemented as a low cost advanced treatment option to improve WWTP effluent chemical quality.     

强化常规工艺对三卤甲烷前体物的去除效果研究

分别通过小试和生产性试验研究了强化混凝和强化过滤对三卤甲烷前体物的去除效果。结果表明,强化混凝能有效提高三卤甲烷前体物的去除效果,两组试验去除率最高分别可提高至50.62%和44.75%;相对石英砂滤池,采用炭砂滤池和活性无烟煤滤池进行强化过滤可将三卤甲烷前体物的去除率提高10%~20%,强化过滤出水加氯消毒后三卤甲烷生成总量比石英砂滤池出水低30%~40%,强化过滤后三卤甲烷生成风险显著降低。     

Formation and fate of haloacetic acids (HAAs) within the water treatment plant

Most research on the occurrence of chlorinated disinfection by-products (DBPs) in drinking water has focused on trihalomethane (THM) formation and evolution, in particular within distribution systems. In this research, we investigated the variability of the occurrence of haloacetic acids (HAAs) during the treatment process in two facilities where surface water is pre-chlorinated before being treated by conventional physico-chemical processes. The investigation focused on both seasonal and point-to-point fluctuations of HAAs. In both facilities, samples were collected weekly during 1 complete year at four points in order to generate robust data on HAAs and on complementary parameters. The results showed that the initial formation of HAAs was the highest and the most variable in the plant where levels of DBP precursor indicators and the pre-chlorination dose were both higher and more variable. Subsequent formation of HAAs from the pre-chlorination point until the settled water occurred due to remaining levels of residual chlorine and DBP precursors. However, HAA levels and in particular dichloroacetic acid (DCAA) (the preponderant HAA species in the waters under study) decreased dramatically during filtration, very probably because of biodegradation within the filter. The effect of filtration on DCAA fate was season-dependant, with the highest degradation in warm water periods and practically no variation during winter. Statistical modeling was applied to empirically identify the operational factors responsible for HAA formation and fate. Model performance to identify HAA variability in waters following pre-chlorination was much better than for water following filtration, which is due to the lack of information on mechanisms and conditions favoring DCAA degradation.     

Comparative toxicity assessment of ozone and activated carbon treated sewage effluents using an in vivo test battery

Wastewater treatment plants do not eliminate micropollutants completely and are thus important point sources for these substances. Ozonation and activated carbon treatment might be beneficial for ecosystem health as these techniques provide effective barriers to organic contaminants. However, a toxicity evaluation is required to investigate toxicity reduction and to assess the potential formation of toxic oxidation byproducts during ozonation.Therefore a comparative toxicity evaluation of different treated wastewater effluents was performed on site at a half scale treatment plant equipped with an ozonation step and an activated carbon treatment step in parallel subsequent to conventional activated sludge treatment. For this purpose four invertebrate and one higher plant toxicity test were selected to assess potential biological effects on whole organisms.The reproduction test with the mudsnail Potamopyrgus antipodarum exhibited a decreased reproductive output after advanced treatment compared to conventional treatment. This indicates an effective estrogenicity removal by ozonation and activated carbon treatment and is confirmed by results of the yeast estrogen screen with a reduction of in vitro estrogenic activity by >75%. The Lumbriculus variegatus test revealed a significantly enhanced toxicity after ozonation compared to conventional treatment whereas this effect was reduced following subsequent sand filtration. When ozonation was applied, a significantly increased genotoxicity was observed, detected with the comet assay using haemolymph of the zebra mussel. Again, this effect was removed by subsequent sand filtration to the level of conventional treatment. Activated carbon treatment even resulted in a significant reduction of genotoxicity.Adverse effects after the ozone reactor are possibly a result of the formation of toxic oxidation byproducts. Biologically active sand filtration obviously is an effective barrier to such compounds.     

Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation

Disinfection with chloramines is often used to reduce the production of regulated disinfection by-products (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs). However, chloramination can lead to the formation of N-nitrosamines, including N-nitrosodimethylamine (NDMA), a probable human carcinogen. Previous research used dimethylamine (DMA) as a model precursor of NDMA, but certain widely used tertiary dimethylamines (e.g. the pharmaceutical ranitidine) show much higher conversion rates to NDMA than DMA. This study investigates the NDMA formation potential of several tertiary amines including pharmaceuticals and herbicides. The reactivity of these molecules with monochloramine (NH₂Cl) is studied through the formation of NDMA, and other halogenated DBPs such as haloacetonitriles (HANs) and AOX (Adsorbable Organic Halides). Several compounds investigated formed NDMA in greater amounts than DMA, revealing the importance of structural characteristics of tertiary amines for NDMA formation. Among these compounds, the pharmaceutical ranitidine showed the highest molar conversion to NDMA. The pH and dissolved oxygen content of the solution were found to play a major role for the formation of NDMA from ranitidine. NDMA was formed in higher amounts at pH around pH 8 and a lower concentration of dissolved oxygen dramatically decreased NDMA yields. These findings seem to indicate that dichloramine (NHCl₂) is not the major oxidant involved in the formation of NDMA from ranitidine, results in contradiction with the reaction mechanisms proposed in the literature. Dissolved oxygen was also found to influence the formation of other oxygen-containing DBPs (i.e. trichloronitromethane and haloketones). The results of this study identify several anthropogenic precursors of NDMA, indicating that chloramination of waters impacted by these tertiary amines could lead to the formation of significant amounts of NDMA and other non-regulated DBPs of potential health concern (e.g. dichloroacetonitrile or trichloronitromethane). This could be of particular importance for the chloramination of wastewater effluents, especially during water reuse processes.     

Enhanced coagulation using a magnetic ion exchange resin

The objective of this investigation was to examine the effectiveness of a magnetic ion exchange resin (MIEX) to enhance the coagulation of disinfection by-product precursors in nine surface waters, each representing a different element of the USEPA's 3 x 3 enhanced coagulation matrix. The effect of MIEX-pretreatment on the requisite alum dose needed for subsequent coagulation of turbidity was also evaluated. Enhanced coagulation with MIEX was found to be very effective for removing trihalomethane (THM) and haloacetic acid (HAA) precursors from the nine waters examined. THM and HAA formation potential was reduced by more than 60% in all of the waters studied; reductions approaching 90% were seen in the waters with the highest specific ultraviolet absorbance values. The residual total organic carbon concentration, ultraviolet absorbance, and THM and HAA formation potential were all substantially lower as a result of MIEX and alum treatment compared to alum coagulation alone. MIEX pre-treatment also lowered the coagulant demand of each of the waters substantially.     

Occurrence and removal of pharmaceuticals and hormones through drinking water treatment

The occurrence of fifty-five pharmaceuticals, hormones and metabolites in raw waters used for drinking water production and their removal through a drinking water treatment were studied. Thirty-five out of fifty-five drugs were detected in the raw water at the facility intake with concentrations up to 1200 ng/L. The behavior of the compounds was studied at each step: prechlorination, coagulation, sand filtration, ozonation, granular activated carbon filtration and post-chlorination; showing that the complete treatment accounted for the complete removal of all the compounds detected in raw waters except for five of them. Phenytoin, atenolol and hydrochlorothiazide were the three pharmaceuticals most frequently found in finished waters at concentrations about 10 ng/L. Sotalol and carbamazepine epoxide were found in less than a half of the samples at lower concentrations, above 2 ng/L. However despite their persistence, the removals of these five pharmaceuticals were higher than 95%.     

Chemical and biological oxidation of NOM surrogates and effect on HAA formation

Formation of disinfection by-products (DBPs) can be controlled by removal of disinfection by-product precursors before disinfection. Variable success has been reported, depending on the treatment used and water tested. Chemical and biological oxidations are candidate technologies to control DBP formation. Given the uncertainty over the identity of DBP precursors, the use of surrogates of natural organic matter (NOM) allows fundamental probing of the links between compound character, removal and DBP formation. Nine compounds were chosen to represent NOM and their removal by two advanced oxidation processes (AOPs), UV-C irradiation and biological treatment compared while haloacetic acid (HAA) formation before and after treatment was measured. Although AOPs were able to fully remove all compounds, incomplete mineralisation led to increased HAA levels, dramatically in the case of two amino acids. Biological treatment was effective in removing amino acids but also moderately increased the HAA formation potential (HAAFP) of hydrophilic compounds. These findings indicate waters with high amino acid concentrations will be susceptible to raised HAA levels following AOP treatment and careful process selection for HAA control is required in such cases.     

Occurrence and control of nitrogenous disinfection by-products in drinking water--a review

The presence of nitrogenous disinfection by-products (N-DBPs), including nitrosamines, cyanogen halides, haloacetonitriles, haloacetamides and halonitromethanes, in drinking water is of concern due to their high genotoxicity and cytotoxicity compared with regulated DBPs. Occurrence of N-DBPs is likely to increase if water sources become impacted by wastewater and algae. Moreover, a shift from chlorination to chloramination, an option for water providers wanting to reduce regulated DBPs such as trihalomethanes (THMs) and haloacetic acids (HAAs), can also increase certain N-DBPs. This paper provides a critical review of the occurrence and control of N-DBPs. Data collated from surveys undertaken in the United States and Scotland were used to calculate that the sum of analysed halonitromethanes represented 3-4% of the mass of THMs on a median basis; with Pearson product moment correlation coefficients of 0.78 and 0.83 between formation of dihaloacetonitriles and that of THMs and HAAs respectively. The impact of water treatment processes on N-DBP formation is complex and variable. While coagulation and filtration are of moderate efficacy for the removal of N-DBP precursors, such as amino acids and amines, biofiltration, if used prior to disinfection, is particularly successful at removing cyanogen halide precursors. Oxidation before final disinfection can increase halonitromethane formation and decrease N-nitrosodimethylamine, and chloramination is likely to increase cyanogen halides and NDMA relative to chlorination.     

Demonstration of 20 pharmaceuticals and personal care products (PPCPs) as nitrosamine precursors during chloramine disinfection

The worldwide detection of pharmaceuticals and personal care products (PPCPs) in the aquatic environment and drinking water has been a cause for concern in recent years. The possibility for concurrent formation of nitrosamine DBPs (disinfection by-products) during chloramine disinfection has become another significant concern for delivered drinking water quality because of their potent carcinogenicity. This study demonstrates that a group of PPCPs containing amine groups can serve as nitrosamine precursors during chloramine disinfection. Molar yields higher than 1% are observed for eight pharmaceuticals, with ranitidine showing the strongest potential to form N-nitrosodimethylamine (NDMA). The molar conversion increases with the Cl₂:N mass ratio, suggesting that dichloramine is relevant to the formation of NDMA from these precursors. Although the trace level of PPCPs in the environment suggests that they may not account for the majority of nitrosamine precursors during the disinfection process, this study demonstrates a connection between the transformation of PPCPs and the formation of nitrosamines during chloramine disinfection. This both expands the pool of potential nitrosamine precursors, and provides a possible link between the presence of trace levels of certain PPCPs in drinking water sources and potential adverse health effects.