地下水中天然有机物对生物除铁滤柱的影响研究

采用生物滤柱对地下水进行试验研究,用膜过滤法对其出水进行了分子量分析,考察了生物除铁滤柱对不同分子量区间天然有机物的去除效果。结果表明:有机物分子量大小对出水水质有较大的影响,有机物分子量越大,铁去除率越低,DOC和UV254去除率也越低。生物滤柱对原水中分子量1 kDa的有机物的去除率为82.4%,而对分子量30 kDa的有机物的去除率只有28.5%。     

三种饮用水消毒副产物形成模型对比研究

选取反应时间(t)、水温(T)、pH、总有碳(TOC)、特别紫外吸光度(UV254)、溴离子浓度(Br-)及反应的氯剂量(Cl2)等相关的水质参数,构建了三卤甲烷及卤乙酸两大类消毒副产物的多元线性回归、非线性回归及神经网络预测模型。结果表明,消毒副产物的多元线性回归模型能逐步筛选回归因子,得出影响消毒副产物形成的主要因素及影响程度,各消毒副产物的多元线性回归方程的线性非常显著(p≤0.05);消毒副产物的非线性回归模型能分析预测各种对消毒副产物的影响不呈线性关系的因素;各消毒副产物神经网络预测的判定参数均大于0.83,表明采用神经网络预测消毒副产物的形成可以获得较精确的预测值。     

饮用水中氯化消毒副产物的控制研究进展

探讨了DBPs的形成机理及其种类,然后介绍了DBPs对人体的健康风险,并总结了目前国内外控制DBPs的方法,为饮用水高效安全消毒技术的进一步研究提出了意见和建议。     

Effects of ozonation and ultraviolet irradiation on biodegradability of oil shale wastewater organic solutes

Ozonation and u.v. irradiation were evaluated for their abilities to (1) mineralize organic solutes that remained in a biooxidized oil shale process wastewater and (2) effect sufficient structural modification of the remaining biorefractory organic solutes to promote secondary biooxidation. Full-spectrum u.v. radiation (5 h, total dose of 10.2 × 10⁶ J l⁻¹) failed to mineralize or effect the biooxidation of any of the biorefractory carbon. Although ozonation (5 h, total dose of 1.6 g O₃ l⁻¹) directly mineralized only 8% of the biorefractory carbon, it enhanced secondary biooxidation; 26% of the refractory carbon was mineralized by an acclimated microbial inoculum. When u.v. irradiation and ozonation were combined simultaneously, a synergistic effect was observed; 3 h of combined treatment (5.9 × 10⁶ J l⁻¹ and 0.83 g O₃ l⁻¹) was as effective a pretreatment for secondary biooxidation as was 5 h of ozonation. Sequential application of primary biooxidation, 6 h of combined u.v./ozonation, and secondary biooxidation removed only 59% of the dissolved organic carbon; total reduction of 87% was achieved by using a culture in the secondary biooxidation step that was specifically adapted to this oxidized water. Each time-course sample was analyzed for the distribution of polar and nonpolar organic solutes. In general, ozonation and combined u.v./ozonation mineralized carbon from the nonpolar fraction; biooxidation of formerly refractory carbon was promoted by oxidation of nonpolar carbon to yield more polar or lower-molecular-weight species.     

The ozonation of organic halide precursors: effect of bicarbonate

A laboratory study of the effect of bicarbonate on the ozonation of organic halide precursors in fulvic acid solutions and in a raw drinking water was conducted. The experimental variables were bicarbonate concentration, ozone dose and pH of chlorination. Results are expressed in terms of trihalomethane (THM), total organic halide (TOX), trichloracetic acid, dichloroacetic acid, trichloroacetone and dichloroacetonitrile precursor concentrations. Kinetic studies showed that bicarbonate slowed the decomposition of ozone in the presence of fulvic acid, and thereby, led to a greater degree of destruction of u.v.-absorbing substances. Similarly, precursor destruction increased with increasing bicarbonate concentrations in the range of 10⁻⁴spd 10⁻² M. Precursor destruction was greatest when chlorination was performed at low pH. At high pH's of chlorination, some precursor enhancement was noted, especially in the absence of bicarbonate. Results are interpreted both from a mechanistic standpoint and with respect to their applicability to water treatment practice.     

氯化消毒副产物的控制研究进展

探讨了CDBPs的形成机理,总结了目前国内外控制CDBPs的方法,并为饮用水高效安全消毒技术的进一步研究提出了意见和建议,以确保饮用水的安全性。     

The effect of ozonation on natural organic matter removal by alum coagulation

Natural organic matter (NOM) was extracted from a moderately colored, eutrophic surface water source (Forge Pond, Granby, MA), and fractionated into quasi-homogeneous fractions. Fulvic acid (FA) and hydrophilic neutrals (HN) were the two most abundant NOM fractions that were isolated. Adsorption affinity of the isolated NOM fractions on preformed aluminum hydroxide flocs increased with increase in specific organic charge of the fractions, except for the two most highly charged fractions, FA and hydrophilic acids (HAA), which showed less adsorption affinity than expected based on their specific organic charge. Prior ozonation of FA and HN fractions resulted in a decline and an increase, respectively, in their adsorption affinity on aluminum hydroxide surface. Prior ozonation of Forge Pond raw water resulted in a progressive decline in dissolved organic carbon (DOC) removal by alum coagulation with increase in ozone dose. It appeared that ozone applied to raw water reacted preferentially with the humic fraction of NOM, resulting in the detrimental effects of ozonation on subsequent NOM removal by alum coagulation being magnified. Forge Pond raw water was pre-coagulated to remove humic substances. Ozonation of the pre-coagulated water demonstrated the beneficial effects of ozonation on the removal of non-humic NOM through alum coagulation. A strategy for staged coagulation with intermediate ozonation was proposed for waters containing both humic and non-humic NOM for maximum DOC and specific UV absorbance at 254nm (SUVA) removal.     

The removal of estrogenic activity and control of brominated by-products during ozonation of secondary effluents

The purposes of this study were to investigate the behavior of brominated by-products, such as bromate ion and total organic bromide, formed during ozonation for the removal of estrogenic activity in sewage effluents and to propose operation parameters for the ozonation process. It is necessary to reduce the E(2) equivalent concentration of estrogenic activity in secondary effluent treated by 90% of the initial one. To do so, ozonation until dissolved ozone concentration increased to 0.1mg/L (which corresponds to approximately 1mg O(3)/mg DOC(0) [consumed ozone per initial DOC] of consumed ozone for the effluent in this study) is proposed as an operation parameter for ozonation without the formation of brominated by-products.     

Identification of ozonation by-products of 4- and 5-methyl-1H-benzotriazole during the treatment of surface water to drinking water

During the treatment of surface water to drinking water, ozonation is often used for disinfection and to remove organic trace substances, whereby oxidation by-products can be formed. Here we use the example of tolyltriazole to describe an approach for identifying relevant oxidation by-products in the laboratory and subsequently detecting them in an industrial-scale process. The identification process involves ozonation experiments with pure substances at laboratory level (concentration range mg L⁻¹). The reaction solutions from different ozone contact times were analyzed by high performance liquid chromatography - quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS) in full scan mode. Various approaches were used to detect the oxidation by-products: (i) target searches of postulated oxidation by-products, (ii) comparisons of chromatograms (e.g., UV/VIS) of the different samples, and (iii) color-coded abundance time courses (kinetic) of all detected compounds were illustrated in a kind of a heat map. MS/MS, H/D exchange, and derivatization experiments were used for structure elucidation for the detected by-product. Due to the low contaminant concentrations (ng L⁻¹-range) of contaminants in the untreated water, the conversion of results from laboratory experiments to an industrial-scale required the use of HPLC-MS/MS with sample enrichment (e.g., solid phase extraction.) In cases where reference substances were not available or oxidation by-products without clear structures were detected, reaction solutions from laboratory experiments were used to optimize the analytical method to detect ng L⁻¹ in the samples of the industrial processes. We exemplarily demonstrated the effectiveness of the methodology with the industrial chemicals 4- and 5-methyl-1H-benzotriazole (4- and 5-MBT) as an example. Moreover, not only did we identify several oxidation by-products in the laboratory experiments tentatively, but also detected three of the eleven reaction products in the outlet of the full-scale ozonation unit.     

Screening of 47 organic microcontaminants in agricultural irrigation waters and their soil loading

Reclaimed water usage for crop irrigation is viewed both as an excellent sustainable water source and as a potential entrance for emerging organics into the food chain. This concern is backed by the already documented pollutant crop uptake potential. In the present study, irrigation waters used in agricultural fields (Torroella de Montgri, NE Spain) were screened for 47 analytes in a two year study (2007-2008). A total of 26 contaminants belonging to different chemical classes namely, pesticides, pharmaceuticals, personal care products, phenolic estrogens, antioxidants and disinfection by-products, were detected. Marked differences in concentration trends for the different chemical classes were evidenced from 2007 to 2008, and attributed to a persistent drought endured by the region in 2008. Also, loading mass rates of chemical classes were estimated based on crop irrigation regimes and they ranged from 0.8 to 121.3 g ha⁻¹ per crop cycle. These values were contrasted with those obtained for other water sources from countries where crop irrigation is commonly practiced. Finally, crops grown under these irrigation regimes, namely alfalfa and apple, were analyzed and 5 anthropogenic compounds were identified and quantitated, whose concentrations ranged from 13.9 to 532 ng g⁻¹ (fresh weight).     

The effect of nitrate on VOC removal in trickle-bed biofilters

In response to the growing concern over volatile organic compounds (VOCs), biofiltration is becoming an established economical air pollution control technology for removing VOCs from waste air streams. Current research efforts are concentrating on improving control over key parameters that affect the performance of gas phase biofilters. This study utilized diethyl ether as a substrate, nitrate as the sole nutrient nitrogen source within two co-currently operated trickle-bed biofilters, for over 200 days. The two pelletized medium biofilters were operated at a low empty bed contact time of 25 s, inlet gas flow rates of 8.64 m³/day, nutrient liquid flow rates of 1 liter/day, and COD loading rates of 1.8 and 3.6 kg/m³ per day, respectively. Operational parameters including contaminant concentration in the gas phase, nutrient nitrate concentration in the aqueous phase, and the frequency of biomass removal were considered. Special attention was given to the effect and the role of nitrate on VOC removal. Throughout the experiment, nitrate persisted in the liquid effluent and the ether removal efficiencies improved with increasing influent nitrate concentration, which suggest that the nitrate diffusion into the biofilms is rate determining. By increasing the concentration of oxygen in the feed to this biofilter from 21% (ambient air) to 50 and 100%, while maintaining an influent ether concentration of 133 ppmv and a feed nitrate concentration of 67 mg-N/liter, the performance of the biofilter was not significantly affected. These results suggest that nitrogen was rate limiting as a growth nutrient rather than as an electron acceptor for the respiration of ether. The results also indicated that removal of excess biomass is necessary to maintain long-term performance. However, the required frequency of biomass removal depends on operating parameters such as loading.     

Effect of chlorination on the formation of odorous disinfection by-products

In order to explain some of the possible origins of an odor episode, which took place in a drinking water supply in the region of Paris (France), the chlorination reaction of some simple amino acids (valine, leucine and phenylalanine) was investigated. In addition to the commonly admitted intermediates and products of this reaction (monochloramines, aldehydes and nitriles), the formation of far less documented products was observed: N-chloroaldimines which proved to present particular properties. These products appeared to remain relatively stable in water, especially at low temperatures, and can be formed under disinfection conditions relevant to those of drinking water treatment (i.e. at high chlorination rates). N-chloroaldimines also present strong swimming pool odors with a floral background, with odor detection thresholds close to 1microgL(-1) and even less. These values were established with a laboratory-made protocol. These products appeared more odorous than the corresponding aldehydes, known for a long time as potent odor causing chemicals and which have previously been involved in some odor problems in the field of drinking water treatment. N-chloroaldimines are consequently products of interest for water treaters and are now suspected to be a source of off-flavor concerns among consumers. We have therefore developed an analytical method (gas chromatography coupled with mass spectrometry) to demonstrate the presence of some of these compounds in water at concentrations close to their odor detection thresholds. Considering the levels of amino acids that can be reached in water, this level of chloroaldimines concentration could be obtained under certain pollution conditions.     

ZnO/O3工艺降解水中微量有机物的研究

以实验室制备的粉末氧化锌(ZnO)为催化剂,考察了ZnO/O3工艺去除水中有机物的效能.采用总有机碳(TOC)指标反映水中有机污染物的含量.结果表明:臭氧投量为1 mg/L、ZnO投量为300 mg/L时,反应60 min后ZnO-O3工艺对TOC的去除率为46%,比单独臭氧化提高了1倍;反应温度明显影响该工艺对有机物的降解效果,在水温为5,10,20和25 ℃时,TOC的去除率分别为17.5%,31.5%,45.9%和51.3%.臭氧浓度和催化剂投量的增加,可以提高TOC的氧化降解效率.     

Evaluation of the prediction of trace organic compound removal during ozonation of secondary effluents using tracer substances and second order rate kinetics

The application of the R_CT-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k_O3 = 10⁴ M⁻¹ s⁻¹ to k_O3 = 10⁶ M⁻¹ s⁻¹ were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry.     

The effect of boiling water on disinfection by-product exposure

Chloraminated and chlorinated waters containing bromide were used to determine the impact of boiling on disinfection by-product (DBP) concentrations. No significant changes were detected in the concentrations of the dihalogenated haloacetic acids (DXAAs) (i.e., dichloro-, bromochloro-, dibromoacetic acid) upon boiling of chloraminated water, whereas the levels of the trihalogenated haloacetic acids (TXAAs) (i.e., trichloro- (TCAA), bromodichloro- (BDCAA), dibromochloroacetic acid (DBCAA)) decreased over time (e.g., 9-37% for TCAA). Increased DXAA concentrations (58-68%) were detected in the boiled chlorinated sample, which likely resulted from residual chlorine reacting with DXAA precursors. TCAA concentration was unchanged after boiling chlorinated water for 1 min, but a 30% reduction was observed after 5 min of boiling. BDCAA concentrations decreased 57% upon boiling for 1 min and were completely removed after 2 min of boiling, whereas DBCAA was removed after boiling chlorinated water for 1 min. Trihalomethane concentrations were reduced in both chloraminated (74-98%) and chlorinated (64-98%) water upon boiling. Boiling chloraminated water for 1 min reduced chloroform concentration by 75%. Chloroform was reduced by only 34% in chlorinated water after a 1 min boil, which indicates that simultaneous formation and volatilization of chloroform was occurring. Most of the remaining DBPs (e.g. haloketones, chloral hydrate, haloacetonitriles) were removed by at least 90% after 1 min of boiling in both samples. These data suggest that other mechanisms (e.g., hydrolysis) may have been responsible for removal of the non-volatile DBPs and further highlight the importance of examining individual species when estimating thermal effects on DBP concentrations.     

Evaluating dissolved organic carbon-water partitioning using polyparameter linear free energy relationships: Implications for the fate of disinfection by-products

The partitioning of micropollutants to dissolved organic carbon (DOC) can influence their toxicity, degradation, and transport in aquatic systems. In this study carbon-normalized DOC-water partition coefficients (K_DOC-w) were measured for a range of non-polar and polar compounds with Suwannee River fulvic acid (FA) using headspace and solid-phase microextraction (SPME) methods. The studied chemicals were selected to represent a range of properties including van der Waal forces, cavity formation and hydrogen bonding interactions. The K_DOC-w values were used to calibrate a polyparameter linear free energy relationship (pp-LFER). The difference between experimental and pp-LFER calculated K_DOC-w values was generally less than 0.3 log units, indicating that the calibrated pp-LFER could provide a good indication of micropollutant interaction with FA, though statistical analysis suggested that more data would improve the predictive capacity of the model. A pp-LFER was also calibrated for Aldrich humic acid (HA) using K_DOC-w values collected from the literature. Both experimental and pp-LFER calculated K_DOC-w values for Aldrich HA were around one order of magnitude greater than Suwannee River FA. This difference can be explained by the higher cavity formation energy in Suwannee River FA. Experimental and pp-LFER calculated K_DOC-w values were compared for halogenated alkanes and alkenes, including trihalomethane disinfection by-products, with good agreement between the two approaches. Experimental and calculated values show that DOC-water partitioning is generally low; indicating that sorption to DOC is not an important fate process for these chemicals in the environment.     

Measuring the concentrations of drinking water disinfection by-products using capillary membrane sampling-flow injection analysis

A capillary membrane sampling-flow injection analysis method is presented for selectively measuring the concentrations of total trihalomethanes (THMs) and total haloacetic acids (HAAs) in drinking water. The method is based on the reaction between nicotinamide and THM or HAA species to yield a fluorescent product. Two configurations are presented, one selective for total THMs and another selective for total HAAs. The construction of a capillary membrane sampler is described, and the results of method detection limit, accuracy and precision studies are reported for each method. Interference, selectivity and linearity studies are reported as well as the effect of temperature and ionic strength changes. Drinking water samples were analyzed by each proposed method and the results were compared to USEPA methods 502.2 and 552.3.     

The effects of combined ozonation and filtration on disinfection by-product formation

The effects of combined ozonation and membrane filtration on the removal of the natural organic matter (NOM) and the formation of disinfection by-products (DBPs) were investigated. Ozonation/filtration resulted in a reduction of up to 50% in the dissolved organic carbon (DOC) concentration. Furthermore, humic substances were converted to non-humic substances, with changes in the humic and non-humic substance concentrations of up to −50% and +20%, respectively. Ozonation/filtration resulted in the formation of partially oxidized compounds from NOM that were less reactive with chlorine, decreasing the concentration of simulated distribution system total trihalomethanes (SDS TTHMs) and simulated distribution system halo acetic acids (SDS HAAs) by up to 80% and 65%, respectively. Reducing the molecular weight cut-off (MWCO) of the membranes resulted in reductions in the concentrations of SDS TTHMs and SDS HAAs. Using a membrane with a 5 kD MWCO, the minimum gaseous ozone concentration required to bring about effective NOM degradation and meet regulatory requirements for chlorinated DBPs was 2.5 g/m³.     

Influence of the characteristics of natural organic matter on the fouling of microfiltration membranes

Natural organic matter (NOM) plays a significant role in fouling microfiltration membranes in drinking water treatment processes even though the NOM is retained only to a small extent. The aim of this study was to obtain a better understanding of the interactions between the fractional components of NOM and microfiltration membranes. Filtration experiments were performed using 0.22 μm hydrophobic and hydrophilic polyvinylidene fluoride (PVDF) membranes in a stirred-cell system on the NOM isolated from three Australian surface waters. As expected, the fouling rate for the hydrophobic membrane was considerably greater than for the hydrophilic membrane. Focusing on the hydrophobic membrane, it was shown that the high molecular weight fraction of NOM (>30 kDa) was responsible for the major flux decline. Filtration tests on the four fractions of NOM isolated on the basis of hydrophobicity and charge using non-functionalised and anionic resins revealed that the fouling potential for the three waters was hydrophilic neutral>hydrophobic acids>transphilic acids>hydrophilic charged. The low-aromatic hydrophilic neutral compounds were the main determinant of the rate and extent of flux decline. This was linked to the colloidal size fraction (>30 kDa) and to the selective concentration of calcium in the fraction leading to organics-Ca²⁺ bridging. It was also shown that the higher the aromaticity of the NOM the greater the flux decline, and the aromatics mainly resided in the hydrophobic acids fraction. Overall, the fouling mechanism controlling the flux decline involved the combined effects of adsorptive and colloidal fouling by the hydrophilic neutral fraction in the internal pore structure of the membrane.     

The effect of operational parameters of the process of sludge ozonation on the solubilisation of organic and nitrogenous compounds

An evaluation of various operational parameters on the process of sludge ozonation was carried out based on semi-batch experiments. Particular reference has been given to examine the main parameters affecting the solubilisation of organic matter and nitrogenous compounds. Various sets of experiments were undertaken using real sewage sludge to feed a semi-industrial ozonation plant. Applying ozone dosages between 25 and 35 mg O(3)/gTSS, the organic matter solubilisation obtained through ozonation increases proportionally to ozone dosage until a maximum value of 430 mg COD/L. Concerning the nitrogenous compounds, no variation in nitrite concentration and a low increase in nitrate concentration were attained, regardless of the applied ozone dosage. Little increase in ammonia concentration was achieved for low ozone dosages, whilst applying dosages higher than 20 mg O(3)/gTSS, the variation of ammonia increased proportionally with ozone dosage. Experiments using hydraulic retention time (HRT) between 10 and 60 min resulted in a similar COD solubilisation, confirming a rapid rate of cell lysis during ozonation of sludge.