DOC removal by multi-stage ozonation-biological treatment

Multi-stage ozonation-biological treatment process for dissolved organic carbon (DOC) removal was evaluated to apply for drinking water treatment. Waters with different types of DOC were used, i.e. a reservoir water for drinking water supply, a secondary effluent from a municipal wastewater treatment plant and a solution of humic substances extracted from leaf mold. The multi-stage ozonation-biological treatment process was compared with conventional single-stage ozonation-biological treatment process. Amount of DOC removed in biological treatment was defined as amount of biodegradable dissolved organic carbon (BDOC) in influent of biological treatment. DOC removal in the multi-stage ozonation-biological treatment was higher than that in the conventional single-stage ozonation-biological treatment with the same total ozonation time for the reservoir water and humic substances solution. Moreover, three- or four-stage ozonation for 5 min followed by biological treatment (total ozonation time 15 or 20 min) showed higher removal of DOC than the single-stage ozonation (60 min) and biological treatment. The higher DOC removal in the multi-stage treatment was due to the production of BDOC by ozonation. The long-term ozonation was not effective to produce BDOC because most of ozone was utilized to oxidize BDOC produced in the early stage of ozonation. In the multi-stage treatment, ozonation was effective to decompose refractory DOC and to produce BDOC because BDOC was removed by biological treatment. However, multi-stage ozonation-biological treatment was not effective for the secondary effluent. The reason seems to be high concentration of ozone scavengers in that water and low reactivity of DOC for ozone.     

Determination of the biodegradable fraction of dissolved organic matter in waters

Two bioassay procedures are proposed for determining biodegradable dissolved organic carbon (BDOC) in waters. Both involves sterile filtration of the sample, reinoculation with a natural assemblage of bacteria from the same origin as the sample, and incubation for at least 10 days in the dark at 20°C. In the first procedure, dissolved organic carbon (DOC) is followed, until a plateau is reached and the difference between initial and final DOC is taken as a measure of BDOC. In the second procedure, bacterial biomass and mortality rate are followed and the integrated flux of mortality during the incubation period is calculated and divided by the growth yield to give an estimate of BDOC. Both procedures provide closely concordant results.An example of application to the study of ozonation and biological activated carbon filtration in drinking water treatment is presented.     

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.     

颗粒活性炭吸附对预臭氧后微污染原水水质影响研究

在不同的预臭氧浓度条件下处理微污染原水,考察了颗粒活性灰（GAC）吸附对处理后水样水质的影响.选择化学需氧量（CODMn）、溶解性有机碳（DOC）、生物可降解溶解性有机碳（BDOC）、UV254和氨氮（NH;-N）含量及有机物分子量分布作为考察吸附效果的检测指标.结果表明,在静态吸附时间达到5天时,颗粒活性炭吸附曲线开始趋于平缓,吸附时间超过5天之后吸附趋于饱和;预臭氧含量为2.5 mg/L时,颗粒活性炭对有机物的吸附效果最佳,对CODMn、DOC、BDOC的去除率分别为53.2％,63.2％和36.2％;在不同预臭氧处理条件下,颗粒活性炭对NH;-N的吸附效果并未表现出较大的差异,吸附去除率约为5％;颗粒活性炭优先吸附水中分子量＞ 10kDa的有机物,其次为分子量＜1 kDa的有机物.     

动态循环法测定可生物降解溶解性有机碳

试验以葡萄糖和邻苯二甲酸作为易生物降解和难生物降解的代表有机物，研究了一种动态循环测定ＢＤＯＣ的方法，将待测水样不断循环通过生物载体反应器，使其中可生物降解有机碳充分降解，测定ＤＯＣ的变化以确定ＢＤＯＣ值。结果表明：（１）以动态循环法 ２流程和管 ＢＤＯＣ的变化显示，水源水预氯化后ＢＤＯＣ增辑３１．５８％，出厂水加氯同样使ＢＤＯＣ增加；（２）动态循环测定ＢＤＯＣ的方法有测定时间短，能评价不同水源不     

Adsorption of dissolved organic matter onto activated carbon--the influence of temperature, absorption wavelength, and molecular size

In this study, batch and column adsorption experiments with granular activated carbon (GAC) were carried out for removing dissolved organic matter (DOM) of a pond water at different water temperatures (5, 20, and 35 °C). The water was characterized before and after the adsorption step using UV/VIS spectroscopy and size-exclusion chromatography (SEC) combined with diode array detection (DAD). DOM breakthrough of GAC filters has been found to be slower at higher water temperatures, the DOM removal being most effective at 35 °C. UV/VIS spectra and SEC chromatograms of water samples treated at different water temperatures indicate that an increase in temperature especially supports the adsorption of small DOM molecules as well as molecules absorbing at higher wavelengths, specifying aromatic structures of DOM. SEC-DAD has been demonstrated to be an efficient method for characterizing DOM of natural waters and for detecting relative changes of DOM during the water treatment process.     

Ozone enhanced removal of natural organic matter from drinking water sources

The use of ozone as a pre-oxidant or intermediate oxidant in drinking-water treatment is becoming increasingly common. The ozonation of natural source waters containing natural organic matter produces biodegradable by-products such as organic acids, aldehydes, and ketoacids. These organic by-products serve as carbon source for bacteria, potentially causing regrowth problems in distribution systems. The measurement of biodegradable dissolved organic carbon (BDOC) provides quantitative insight into the amount of BDOC that is present. In drinking-water treatment, removal of BDOC can also reduce the formation potential of chlorination disinfection by-products such as trihalomethanes and haloacetic acids. Removal of BDOC was optimal at an applied ozone:DOC ratio of 2:1 (mg/mg) for source waters containing DOC levels ranging from 3 to 6 mg/liter. The use of biotreatment resulted in a 40–50% decrease in DOC, a 90–100% reduction in aldehydes, and a 40–60% reduction in trihalomethane formation potential. No removal of bromate ion and dibromoacetic acid was observed. A positive correlation was obtained between BDOC and assimilable organic carbon; both parameters indicate a tendency to plateau at an applied ozone/DOC weight ratio of 2:1.     

Fractionation of dissolved organic matter from surface waters using macroporous resins

To obtain fractions enriched with biodegradable dissolved organic carbon (BDOC) or with organic compounds responsible for the chlorine demand (CID) and for trihalomethane formation potential (THMFP), Seine river water samples were percolated on various macroporous resins (anionic, cationic and non-ionic) and compared with granulated activated carbon (GAC). In addition, measurement of UV absorbance at 254 nm and the fluorescence index (λ_excitation 320 nm) had allowed to follow up the retention of dissolved organic matter by the different adsorbants. In contrast to cationic and non-ionic resins, anionic resins confirm their excellent retention capacity of organic compounds responsible for UV 254 absorbance and fluorescence index. The relative values of BDOC/DOC ratio (mg-C/mg-C) are slightly increased in the effluents of anionic resins, indicating that they retain a little preferentially the refractory fraction instead of the biodegradable fraction. There is no significant difference between the ratio of CID/DOC (mg-Cl₂/mg-C) in influent and effluent of anionic resins. Cationic resin has a low capacity for retention of DOC, but they seem to retain significantly the organic compounds responsible for CID. The capability of anionic resins to retain THMFP is similar to that of GAC.     

Characteristics of dissolved organic matter following 20 years of peatland restoration

The changes in the amounts and composition of dissolved organic matter (DOM) following long-term peat restoration are unknown, although this fraction of soil organic matter affects many processes in such ecosystems. We addressed this lack of knowledge by investigating a peatland in south-west Germany that was partly rewetted 20 years ago. A successfully restored site and a moderately drained site were compared, where the mean groundwater levels were close to the soil surface and around 30 cm below surface, respectively. The concentrations of dissolved organic carbon (DOC) at 4 depths were measured over one year. The specific absorbance was measured at 280 nm and the fluorescence spectra were used to describe the aromaticity and complexity of DOM.The investigations showed that 20 years of peatland restoration was able to create typical peatland conditions. The rewetted site had significantly lower DOC concentrations at different depths compared to the drained site. The specific UV absorbance showed that the rewetted site had a lower level of aromatic DOM structures. The decreasing specific UV absorbance might indicate an increasing contribution of small organic molecules to DOM. It was hypothesized that the decreasing DOC concentrations and the relative enrichment of small, readily degradable organic molecules, reflect the slower decomposition of organic matter after the re-establishment of the water table. Seasonal trends provided substantial evidence for our hypothesis that reduced DOC concentrations were caused by reduced peat decomposition. During summer, the elevated DOC values were accompanied by an increase in DOM aromaticity and complexity. Our results demonstrated a close link between C mineralization and DOC production. We concluded that long-term peatland restoration in the form of the successful re-establishment of the water table might result in reduced peat decomposition and lower DOC concentrations. The restoration of peatlands seems to have a positive impact on C sequestration.     

超滤膜/混凝生物反应器去除饮用水中有机物的效能

采用超滤膜/混凝生物反应器(UF-MCBR)处理模拟微污染源水,考察了对有机污染物的去除效能与机理.结果表明,当聚合氯化铝投加量为10mg/L时,UF-MCBR对DOC、UV254、TOC、CODMn、BDOC和AOC的去除率分别为44.0%、54.5%、49.0%、58.5%、72.8%和58.3%.UF-MCBR通过超滤、生物降解以及混凝三者之间的协同作用去除溶解性有机物,就DOC的去除而言,三种作用的贡献率分别为11.1%、6.2%和26.7%.UF-MCBR系统中的UF膜表面为污泥层所覆盖,该污泥层能有效强化UF膜对分子质量为300-6000u 有机物的截留,UF膜(连同污泥层)对僧水碱、憎水中性物、憎水酸、弱憎水酸和亲水性物质的截留率分别达到了37.0%、42.8%、52.7%、39.8%和19.0%.     

A method for the measurement of biodegradable organic carbon in waters

In the last few years several methods have been proposed for determining biodegradable dissolved organic carbon (BDOC) in waters. A modification of an original method for measuring BDOC is proposed. This method is suitable for discrete samples and for measuring the biodegradability of organic compounds dissolved in water. It consists of a dynamic procedure that measures the decrease in the dissolved organic carbon (DOC) in the sample of water. The sample is recirculated through a glass column containing a biofilm attached to a novel support medium. The method has been used to study waters at different steps in a water-treatment process and to measure the biodegradability of different dissolved organic substances in water.     

Determination of biodegradable dissolved organic carbon in waters: comparison of batch methods

An effect of different types of bacterial inocula upon the final biodegradable dissolved organic carbon (BDOC) result was investigated in samples of both low and high BDOC concentrations. Stream water and leaf leachate samples were incubated either with free, suspended bacteria or with bacteria attached to the stream sediment particles or attached to artificial substrata. The time course of dissolved organic carbon (DOC) decomposition was observed using absorbance analysis of DOC. BDOC determination by means of commonly used suspended bacteria as the inoculum made for an underestimation of BDOC between 5% and 25%, compared with attached bacterial community (biofilm). The reason for these findings could be the higher microbial diversity, higher metabolic activity of attached bacteria and abiotic adsorption of organic molecules to inorganic support and biofilm matrix surfaces. Adsorbed DOC is easily hydrolyzed and utilized by biofilm bacteria.     

Long term case study of MIEX pre-treatment in drinking water; understanding NOM removal

Removal of natural organic matter (NOM) is a key requirement to improve drinking water quality. This study compared the removal of NOM with, and without, the patented magnetic ion exchange process for removal of dissolved organic carbon (MIEX DOC) as a pre-treatment to microfiltration or conventional coagulation treatment over a 2 year period. A range of techniques were used to characterise the NOM of the raw and treated waters. MIEX pre-treatment produced water with lower concentration of dissolved organic carbon (DOC) and lower specific UV absorbance (SUVA). The processes incorporating MIEX also produced more consistent water quality and were less affected by changes in the concentration and character of the raw water DOC. The very hydrophobic acid fraction (VHA) was the dominant NOM component in the raw water and was best removed by MIEX pre-treatment, regardless of the raw water VHA concentration. MIEX pre-treatment also produced water with lower weight average apparent molecular weight (AMW) and with the greatest reduction in complexity and range of NOM. A strong correlation was found between the VHA content and weight average AMW confirming that the VHA fraction was a major component of the NOM for both the raw water and treated waters.     

Transformation of dissolved organic matter during ozonation: effects on trihalomethane formation potential

Transformation of dissolved organic matter (DOM) during ozonation results in a higher reduction in trihalomethane formation potential (THMFP) relative to dissolved organic carbon (DOC). This study was conducted to determine the effect of DOM transformation after ozonation on THM formation and to elucidate the difference in THMFP and DOC removal. Changes in DOC, THMFP, reactivities of the hydrophilic and hydrophobic DOC, and phenolic-OH were determined to explain the difference in THMFP and DOC removal after ozonation. Higher reduction in THMFP (24-46%) relative to DOC (10-16%) was obtained and was attributed to the following: transformation of DOM from a more reactive hydrophobic DOC (microg THM produced per mg organic carbon) to a less reactive hydrophilic DOC and to the decrease in the reactivities of both the hydrophobic and hydrophilic DOC after ozonation. The results also showed decrease in phenolic-OH indicating the oxidation of some reactive sites like resorcinol or meta-dihydroxy benzene ring structures, which are prone to chlorine substitution, consequently decreasing the reactivity of the organic carbon to form THM. These changes in DOM led to a significant decrease in THMFP with no remarkable removal in DOC.     

Determination of biodegradable dissolved organic carbon using entrapped mixed microbial cells

Several methods for determining biodegradable dissolved organic carbon (BDOC) in water have been developed within the last two decades. However, the problem with most of these methods is the length of time required for the start-up (colonization) and/or determination from days to weeks. In this study, a simple and rapid continuous bioreactor procedure using immobilized cells was developed for BDOC determination. In the first stage of the development, the bioreactors were aerated to ensure that dissolved oxygen was not rate limiting. However, BDOC results obtained from the aerated bioreactors suffered from a large error caused by the release of background dissolved organic carbon (DOC). As a consequence, a different bioreactor scheme, in which the feed (sample) instead of the bioreactor was aerated, was tested. Results show that the feed aerated (FA) bioreactor is a better tool for BDOC determination especially for waters with low initial organic concentrations because of less background DOC released by the immobilized cell systems. Using the FA bioreactor, the accurate and reproducible measurement of BDOC can be achieved within a hydraulic retention time of 3 h, and no start-up period is required.     

Characterization of dissolved organic matter in effluents from wastewater treatment plants

Dissolved organic matter (DOM) in effluents from sewage and human-wastes treatment plants (STPEs and HWTPEs) was fractionated using resin adsorbents into six classes: aquatic humic substances (AHS), hydrophobic bases (HoB), hydrophobic neutrals (HoN), hydrophilic acids (HiA), hydrophilic bases (HiB), and hydrophilic neutrals (HiN). DOM-fraction distribution varied substantially depending on the kind of wastewater and the type of treatment process. AHS and HiA dominated in all effluents, collectively accounting for more than 55% of the DOM measured as dissolved organic carbon (DOC). In particular, HiA were the most abundant fraction in the effluents, constituting 32-74% of the DOM. AHS appeared to be the second most dominant fraction and varied considerably, accounting for 3-28% of the DOM. The HoN fraction also varied from 0-21%. AHS, HoN, and HiA were the fractions that changed substantially and differed characteristically among the samples studied. The ratios of ultraviolet absorbance to DOC (UV: DOC ratio) in all effluents exhibited a common relationship: AHS> total DOM > HiA. Nevertheless, the ratios were substantially different between STPEs and HWTPEs and among HWTPEs. For HWTPEs, the effluent from the chemical coagulation process had the highest UV: DOC ratios. On the other hand, the effluent from the ultrafiltration and activated carbon adsorption processes had the lowest ratios. Molecular size distribution of the effluents was determined by size exclusion chromatography and found to exhibit a relatively narrow size range and low weight-averaged molecular weights ranging from 380 to 830 g mol(-1). The weight-averaged molecular weight of DOM increased as the UV: DOC ratio of total DOM increased.     

Toxic cyanobacterial breakthrough and accumulation in a drinking water plant: a monitoring and treatment challenge

The detection of cyanobacteria and their associated toxins has intensified in recent years in both drinking water sources and the raw water of drinking water treatment plants (DWTPs). The objectives of this study were to: 1) estimate the breakthrough and accumulation of toxic cyanobacteria in water, scums and sludge inside a DWTP, and 2) to determine whether chlorination can be an efficient barrier to the prevention of cyanotoxin breakthrough in drinking water. In a full scale DWTP, the fate of cyanobacteria and their associated toxins was studied after the addition of coagulant and powdered activated carbon, post clarification, within the clarifier sludge bed, after filtration and final chlorination. Elevated cyanobacterial cell numbers (4.7 × 10⁶ cells/mL) and total microcystins concentrations (up to 10 mg/L) accumulated in the clarifiers of the treatment plant. Breakthrough of cells and toxins in filtered water was observed. Also, a total microcystins concentration of 2.47 μg/L was measured in chlorinated drinking water. Cyanobacterial cells and toxins from environmental bloom samples were more resistant to chlorination than results obtained using laboratory cultured cells and dissolved standard toxins.     

Analytical fractionation of dissolved organic matter in water using on-line carbon detection

A routine method is described for the analytical fractionation of dissolved organic matter (DOM) in natural freshwater and in used waters. The fractionation is based on the different adsorption behaviours of various constituents of the DOM on octadecyl-silica as a function of pH. The DOM is separated into a hydrophilic, an acid and a hydrophobic fraction. The detection is carried out by an on-line carbon detector. The method requires only small water samples (20 ml) with low dissolved organic carbon (DOC) concentrations (1–5 mg Cl⁻¹). The samples can be analysed rapidly with no preconcentration. Fractionation of model compounds and mixtures demonstrates the performance of the method. The application of the method is illustrated by an investigation of the changes of the DOC composition occurring in a longitudinal transect of a river and during the infiltration of river water to groundwater.     

Comparison of methods for the measurement of biodegradable organic carbon and assimilable organic carbon in water

In the last few years different methods for determining assimilable organic carbon (AOC) and biodegradable dissolved organic carbon (BDOC) in drinking water have been proposed. However, there is no agreement on the most suitable methods for the assessment of treatment processes. A comparison of six methods, one for AOC(P17) determination and five for BDOC determination, using water samples taken at different steps in a water-treatment process in Sant Joan Despí (Barcelona, Spain) is reported. Results show that the biodegradable matter values given by AOC measurements are substantially lower than those obtained using BDOC methods. The various BDOC methods do not differ significantly in their results.     

Membrane coagulation bioreactor (MCBR) for drinking water treatment

In this paper, a novel submerged ultrafiltration (UF) membrane coagulation bioreactor (MCBR) process was evaluated for drinking water treatment at a hydraulic retention time (HRT) as short as 0.5h. The MCBR performed well not only in the elimination of particulates and microorganisms, but also in almost complete nitrification and phosphate removal. As compared to membrane bioreactor (MBR), MCBR achieved much higher removal efficiencies of organic matter in terms of total organic carbon (TOC), permanganate index (COD(Mn)), dissolved organic carbon (DOC) and UV absorbance at 254nm (UV(254)), as well as corresponding trihalomethanes formation potential (THMFP) and haloacetic acids formation potential (HAAFP), due to polyaluminium chloride (PACl) coagulation in the bioreactor. However, the reduction of biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) by MCBR was only 8.2% and 10.1% higher than that by MBR, indicating that biodegradable organic matter (BOM) was mainly removed through biodegradation. On the other hand, the trans-membrane pressure (TMP) of MCBR developed much lower than that of MBR, which implies that coagulation in the bioreactor could mitigate membrane fouling. It was also identified that the removal of organic matter was accomplished through the combination of three unit effects: rejection by UF, biodegradation by microorganism and coagulation by PACl. During filtration operation, a fouling layer was formed on the membranes surface of both MCBR and MBR, which functioned as a second membrane for further separating organic matter.