Measurement of dissolved organic nitrogen in a drinking water treatment plant: size fraction, fate, and relation to water quality parameters

This paper investigates the characteristics of dissolved organic nitrogen (DON) in raw water from the Huangpu River and also in water undergoing treatment in the full-scale Yangshupu drinking water treatment plant (YDWTP) in Shanghai, China. The average DON concentration of the raw water was 0.34 mg/L, which comprised a relatively small portion (~ 5%) of the mass of total dissolved nitrogen (TDN). The molecular weight (MW) distribution of dissolved organic matter (DOM) was divided into five groups: > 30, 10-30, 3-10, 1-3 and < 1 kDa using a series of ultrafiltration membranes. Dissolved organic carbon (DOC), UV absorbance at wavelength of 254 nm (UV254) and DON of each MW fraction were analyzed. DON showed a similar fraction distribution as DOC and UV254. The < 1 kDa fraction dominated the composition of DON, DOC and UV254 as well as the major N-nitrosodimethylamine formation potential (NDMAFP) in the raw water. However, this DON fraction cannot be effectively removed in the treatment line at the YDWTP including pre-ozonation, clarification and sand filtration processes. The results from linear regression analysis showed that DON is moderately correlated to DOC, UV254 and trihalomethane formation potential (FP), and strongly correlated to haloacetic acids FP and NDMAFP. Therefore, DON could serve as a surrogate parameter to evaluate the reactivity of DOM and disinfection by-products FP.     

Implications of organic carbon in the deterioration of water quality in reclaimed water distribution systems

Changes in water quality in reclaimed water distribution systems are a major concern especially when considering the potential for growth of pathogenic microbes. A survey of 21 wastewater process configurations confirmed the high quality effluent produced using membrane bioreactor (MBR) technology, but suggests that other technologies can be operated to produce similar quality. Data from an intensive twelve-month sampling campaign in four reclaimed water utilities revealed the important trends for various organic carbon parameters including total organic carbon (TOC), biodegradable dissolved organic carbon (BDOC), and assimilable organic carbon (AOC). Of the four utilities, two were conventional wastewater treatment with open reservoir storage and two employed MBR technology with additional treatment including UV, ozone, and/or chlorine disinfection. Very high BDOC concentrations occurred in conventional systems, accounting for up to 50% of the TOC loading into the system. BDOC concentrations in two conventional plants averaged 1.4 and 6.3 mg/L and MBR plants averaged less than 0.6 mg/L BDOC. Although AOC showed wide variations, ranging from 100 to 2000 μg/L, the AOC concentrations in the conventional plants were typically 3-10 times higher than in the MBR systems. Pipe-loop studies designed to understand the impact of disinfection on the microbiology of reclaimed water in the distribution system revealed that chlorination will increase the level of biodegradable organic matter, thereby increasing the potential for microbial growth in the pipe network. This study concludes that biodegradable organic carbon is an important factor in the microbial quality and stability of reclaimed water and could impact the public health risk of reclaimed water at the point of use.     

超滤膜处理净水厂沉淀池出水的中试研究

采用中试规模的内压式超滤膜系统处理水厂沉淀池出水,考察超滤膜系统长期运行的出水水质情况。结果表明,超滤膜系统在处理不同水质期沉淀池出水时具有较高的除浊率,平均除浊率达到93.4%,且99.4%的出水浊度<0.1 NTU,去除效果明显优于同期传统的滤池工艺。超滤膜系统对沉淀池出水中有机物的去除效果有限,对CODMn和UV254的平均去除率分别为17.2%和8.2%,出水CODMn≤2.0 mg/L的保证率在98%以上,膜出水CODMn浓度受进水水质和运行条件的影响不大。膜进水中以小分子质量有机物为主,在MW<1 ku区间内的DOC和UV254占到整体有机物含量的57.3%和53.5%。超滤膜系统对微生物的去除效果良好,膜出水水质大部分时间无需经过消毒就能保证卫生要求,可降低后续消毒的加氯量,从而减少消毒副产物的生成量。     

Probing reactivity of dissolved organic matter for disinfection by-product formation using XAD-8 resin adsorption and ultrafiltration fractionation

The disinfection by-product (DBP) reactivity (yield and speciation upon reaction with chlorine) of dissolved organic matter (DOM) isolated from two surface waters was investigated. The source waters, each having significantly different specific ultraviolet absorbance (SUVA254), molecular weight (MW) distribution and polarity, were fractionated using XAD-8 resin adsorption and ultrafiltration (UF), with good DOM mass balance closures (based on dissolved organic carbon). It was found that such fractionation preserved both the SUVA and the reactivity of the source waters, as demonstrated by statistically similar DBP formation and speciation from chlorinated source water and source waters reconstituted from XAD-8 or UF fractions. In addition, there was no evidence of synergistic effects among DOM components when reacting with chlorine. Consistent trends between DBP yields and MW were not found. Hydrophobic fractions of DOM (isolated by XAD-8) were the most reactive DOM components; however, hydrophilic components also showed appreciable DBP yields, contributing up to 50% of total DBP formation. In contrast, strong and unique correlations were observed between the SUVA of individual fractions and their trihalomethane (THM) and haloacetic acid (HAA9) yields, confirming that the aromaticity of DOM components is more directly related to reactivity than other physicochemical properties. The finding of a single correlation independent of the fractionation process employed is notable because XAD-8 adsorption and UF fractionate DOM by significantly different mechanisms. These results confirm that SUVA is a distributed parameter that reflects DOM heterogeneity. Therefore, the SUVA distribution within natural water represents an important property that can be used as a reliable predictor of DBP formation. Finally, bromine appears to be more effectively incorporated into low UV-absorbing (i.e., low SUVA), low MW and hydrophilic DOM fractions.     

供水管网中AOC、消毒副产物的变化规律

以西南L市的供水管网为研究对象,以可同化有机碳（AOC）、三卤甲烷（THMs)、卤乙酸（HAAs)为评价指标,研究了不同季节给水管网中水质的变化情况,结果表明：三卤甲烷在管网中只受余氯的影响,其含量一般随管道长度的增加而增加;卤乙酸和AOC在管网中的变化受余氯和微生物活性的影响,其含量一般随管网延伸而先增加后减少,温度越高则下降越快,温度和余氯是管网中控制消毒副产物和AOC浓度的重要因素。     

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools.Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV₂₅₄ irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV₂₅₄ irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl₃) from solution. Dichloromethylamine (CH₃NCl₂) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH₃NCl₂ photodecay was observed. Dichoroacetonitrile (CNCHCl₂) formation (from L-histidine and L-arginine) was promoted by UV₂₅₄ irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study.The results indicate that UV₂₅₄ irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates.     

Comparison of advanced oxidation processes for the removal of natural organic matter

This study examined the impact of UV, ozone (O₃), advanced oxidation processes (AOPs) including O₃/UV, H₂O₂/UV H₂O₂/O₃ in the change of molecular weight distribution (MWD) and disinfection by-product formation potential (DBPFP). Bench-scale experiments were conducted with surface river water and changes in the UV absorbance at 254 nm (UV₂₅₄), total organic carbon (TOC), trihalomethane and haloacetic acid formation potential (THMFP, HAAFP) and MWD of the raw and oxidized water were analyzed to evaluate treatment performance. Combination of O₃ and UV with H₂O₂ was found to result in more TOC and UV₂₅₄ reduction than the individual processes. The O₃/UV process was found to be the most effective AOP for NOM reduction, with TOC and UV₂₅₄ reduced by 31 and 88%, respectively. Application of O₃/UV and H₂O₂/UV treatments to the source waters organics with 190-1500 Da molecular weight resulted in the near complete alteration of the molecular weight of NOM from >900 Da to <300 Da H₂O₂/UV was found to be the most effective treatment for the reduction of THM and HAA formation under uniform formation conditions. These results could hold particular significance for drinking water utilities with low alkalinity source waters that are investigating AOPs, as there are limited published studies that have evaluated the treatment efficacy of five different oxidation processes in parallel.     

Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH₄ against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water.     

Effect of alum treatment on the trihalomethane formation and bacterial regrowth potential of natural and synthetic waters

Waters from five reservoirs and "synthetic waters", prepared using terrestrially derived dissolved organic matter (DOM) extracted from vegetation and reservoir catchment soils, were studied for their treatability with alum using a jar test procedure. DOM in drinking water is a precursor for the formation of trihalomethanes (THM) following chlorine disinfection and can also be a substrate for microbial growth in the drinking water distribution system. The trihalomethane formation potential (THMFP) represents an upper concentration limit on THMs formed by chlorination, while bacterial regrowth potential (BRP) is an indicator of the bioavailability of DOM. BRP and THMFP were measured before and after alum treatment and the results were related to the source of the DOM. It was found that freshly derived terrestrial DOM in synthetic water resulted in higher THMFP and BRP than DOM in reservoir waters. For the samples investigated, conventional alum treatment did not always reduce the THM precursor levels formed in laboratory tests below the NH&MRC (1996) guideline level of 250 microg/L nor produce microbially stable waters.     

UV-induced effects on chlorination of creatinine

Ultraviolet (UV) irradiation is commonly employed for water treatment in swimming pools to complement conventional chlorination, and to reduce the concentration of inorganic chloramine compounds. The approach of combining UV irradiation and chlorination has the potential to improve water quality, as defined by microbial composition. However, relatively little is known about the effects of this process on water chemistry. To address this issue, experiments were conducted to examine the effects of sequential UV₂₅₄ irradiation/chlorination, as will occur in recirculating system of swimming pools, on disinfection byproduct (DBP) formation. Creatinine, which is present in human sweat and urine, was selected as the target precursor for these experiments.     

强化混凝去除黄浦江原水中有机物研究

就氯化铁和硫酸铝两种混凝剂对黄浦江原水中有机物的去除效果进行对比，确定了针对黄浦江原水的最佳混凝条件：混凝剂为氯化铁，投加量为30mg／L，混凝pH值为5．5，此时对DOC、AOC和UV254的去除率分别为42％、60％和56％，SUVA值也从2．3降为1．7，降低了26．1％。紫外扫描结果显示，强化混凝主要去除对波长〉250nm的紫外光有吸收的有机物，同时可降低60％以上的需氯量，这是因为它去除了在波长为272nm附近对紫外光有强烈吸收的有机物，而这部分物质被认为是最易生成消毒副产物的部分；此外，强化混凝还可有效去除原水中的细菌，对其灭活率可达2．09-lg，明显高于常规混凝的1．0-lg。     

再生水用于地下回灌的加氯消毒研究

针对城市污水厂二级出水用于地下回灌的两种深度处理工艺,确定了达到消毒要求的加氯量,并且研究了加氯消毒对有关水质参数DOC、AOX、CHCl3、CCl4、UV254等的影响。研究发现,有效氯投加量在8mg/L左右时,水中细菌总数与总大肠菌群数均能达到我国饮用水卫生标准。加氯后水的DOC值变化不大,AOX值则有较明显的增大,CHCl3浓度略有增加,CCl4基本维持在加氯前的水平,UV254值也较加氯前有所增大。研究结果还表明,粒状活性炭处理工艺在污水深度处理流程中对去除消毒副产物（AOX）及其前驱物发挥着重要的作用。     

Reducing the concentration of assimilable organic carbon (AOC) in treated drinking water

This study focuses on reducing the concentration of assimilable organic carbon (AOC) in treated drinking water. Experiments were conducted to evaluate the efficiency of AOC removal by biological activated carbon filters (BACF) in a pilot-scale system. The measured values of AOC in treated drinking water were approximately 59.0 ± 8.6 μg acetate-C/L. The results show that BACFs reduce the total concentration of AOC. The concentration of AOC primarily indicates microbial growth in a water supply network, and the amount of AOC in the water is significantly reduced after BACF treatment. After BACF treatment, the removal of AOC was approximately 58% after 40 min of empty-bed contact time. An AOC empirical equation was established by determining the relationship between water quality parameters, such as total organic carbon, dissolved organic carbon, UV₂₅₄, ammonia nitrogen, and total phosphorous.     

Impact of UV/H(2)O(2) advanced oxidation treatment on molecular weight distribution of NOM and biostability of water

The presence of natural organic matter (NOM) poses several challenges to the commercial practice of UV/H₂O₂ process for micropollutant removal. During the commercial application of UV/H₂O₂ advanced oxidation treatment, NOM is broken down into smaller species potentially affecting biostability by increasing Assimilable Organic Carbon (AOC) and Biodegradable Organic Carbon (BDOC) of water. This work investigated the potential impact of UV/H₂O₂ treatment on the molecular weight distribution of NOM and biostability of different water sources. A recently developed flow cytometric method for enumeration of bacteria was utilized to assess biological stability of the treated water at various stages through measurement of AOC. BDOC was also assessed for comparison and to better study the biostability of water. Both AOC and BDOC increased by about 3-4 times over the course of treatment, indicating the reduction of biological stability. Initial TOC and the source of NOM were found to be influencing the biostability profile of the treated water. Using high performance size exclusion chromatography, a wide range of organic molecule weights were found responsible for AOC increase; however, low molecular weight organics seemed to contribute more. Positive and meaningful correlations were observed between BDOC and AOC of different waters that underwent different treatments.     

Comparative effect of simulated solar light,UV, UV/H2O2 and photo-Fenton treatment (UV–Vis/H2O2/Fe) in the Escherichia coli inactivation in artificial seawater

Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H₂O₂/UV₂₅₄ and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L⁻¹ Fe²⁺ and 10 mg L⁻¹ of H₂O₂, led to the fastest bacterial inactivation kinetics. Using H₂O₂/UV₂₅₄ high disinfection rates were obtained similar to those obtained with photo-Fenton under UV₂₅₄ light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH^• radicals generated in the treatment of photo-Fenton and H₂O₂/UV₂₅₄. Despite the negative effect of inorganic ions, especially HCO₃^-, the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV₂₅₄). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe³⁺-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV₂₅₄. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV₂₅₄ and H₂O₂/UV₂₅₄ treatments.     

Development of chlorine dioxide-related by-product models for drinking water treatment.

Factorial experiments were conducted using source waters from seven drinking water treatment plants in Ontario, Canada to develop statistically based model equations capable of predicting chlorine dioxide consumption and chlorite and chlorate formation upon chlorine dioxide application. The equations address raw water quality and operational parameters including pH, temperature, chlorine dioxide concentration, reaction time and water organic content (as described by non-purgeable organic carbon x ultraviolet absorbance measured at 254 nm, NPOC x UV254). Terms describing two-factor interaction effects were also included, improving the accuracy of the predictive equations in fitting measured response concentrations as evaluated through internal and external validations. Nearly 80% of the predictions for chlorine dioxide consumption and chlorite formation were observed to be within 20% of the measured levels. Over 90% of the predicted chlorate levels were within +/- 0.1 mg/L of the measured levels. Chlorine dioxide concentration and NPOC x UV254 were key parameters when developing the predictive models.     

UV/H2O2 treatment of drinking water increases post-chlorination DBP formation

Ultraviolet (UV) irradiation has become popular as a primary disinfectant because it is very effective against Cryptosporidium and does not directly form regulated disinfection by-products. Higher UV doses and UV advanced oxidation (UV/H₂O₂) processes are under consideration for the treatment of trace organic pollutants (e.g. pharmaceuticals, personal care products). Despite the disinfection effectiveness of UV light, a secondary disinfectant capable of maintaining a distribution system residual is required to meet current U.S. regulation. This study investigated changes in disinfection by-product (DBP) formation attributed to UV or UV/H₂O₂ followed by application of free chlorine to quench hydrogen peroxide and provide residual disinfectant. At a UV dose of 1000 mJ/cm², trihalomethane (THM) yield increased by up to 4 μg/mg-C and 13 μg/mg-C when treated with low and medium pressure UV, respectively. With the addition of hydrogen peroxide, THM yield increased by up to 25 μg/mg-C (5 mg-H₂O₂/L) and 37 μg/mg-C (10 mg-H₂O₂/L). Although no changes in DBPs are expected during UV disinfection, application of UV advanced oxidation followed by chlorine addition was assessed with regard to impacts on DBP formation.     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

Preliminary laboratory investigation of disinfection by-product precursor removal using an advanced oxidation process

Natural organic matter (NOM) is ubiquitous in surface and ground waters throughout the world. During drinking water treatment, the NOM that remains in treated water can react with chlorine to form disinfection by‐products. It has been shown that titanium dioxide photocatalysis can achieve over 96% reduction in ultraviolet (UV)₂₅₄ absorbing species such as hydrophobic NOM and over 81% reduction in dissolved organic carbon (DOC). However, an additional filtration stage is required to recover the suspended catalyst before it is suitable for municipal drinking water application. To overcome this problem, we have used immobilised catalysts prepared using chemical sol–gels, and their performance has been assessed during bench‐scale experiments. An immobilised catalyst enables in situ regeneration using UV light and subsequent reuse of the catalyst. In this research, titanium dioxide sol–gels have been used to coat substrates at a laboratory scale. Results showed that the various coatings prepared had different removal efficiencies for both DOC and UV₂₅₄ absorbance. Maximum removals were 1.336 g/m² and 89%, respectively.     

Improving on SUVA 254 using fluorescence-PARAFAC analysis and asymmetric flow-field flow fractionation for assessing disinfection byproduct formation and control

Several challenges with disinfection byproduct (DBP) control stem from the complexity and diversity of dissolved organic matter (DOM), which is ubiquitous in natural waters and reacts with disinfectants to form DBPs. Fluorescence parallel factor (PARAFAC) analysis and asymmetric flow-field flow fractionation (AF4) were used in combination with free chlorine DBP formation potential (DBPFP) tests to study the physicochemical DOM properties and DBP formation in raw- and alum-coagulated waters. Enhanced coagulation with alum became more effective at removing DBP-precursors as the pH decreased from 8 to 6. AF4-UV₂₅₄ fractograms indicated enhanced coagulation at pH 6 preferentially removed larger DOM, whereas no preferential size removal occurred at pH 8. Fluorescence-PARAFAC analysis revealed the presence of one protein-like and three humic-like fluorophore groups; stronger linear correlations were found between chloroform and the maximum intensity (F_MAX) of a humic-like fluorophore (r² = 0.84) than with SUVA₂₅₄ (r² = 0.51). This result indicated that the fluorescence-PARAFAC approach used here was an improvement on SUVA₂₅₄, i.e., fluorescence-based measurements were stronger predictors of chloroform formation.