Ozonation effect on natural organic matter adsorption and biodegradation - Application to a membrane bioreactor containing activated carbon for drinking water production

More stringent legislation on dissolved organic matter (DOM) urges the drinking water industry to improve in DOM removal, especially when applied to water with high dissolved organic carbon (DOC) contents and low turbidity. To improve conventional processes currently used in drinking water treatment plants (DWTPs), the performances of a hybrid membrane bioreactor containing fluidised activated carbon were investigated at the DWTP of Rennes. Preliminary results showed that the residual DOC was the major part of the non-biodegradable fraction. In order to increase the global efficiency, an upstream oxidation step was added to the process. Ozone was chosen to break large molecules and increase their biodegradability. The first step consisted of carrying out lab-scale experiments in order to optimise the necessary ozone dose by measuring the process yield, in terms of biodegradable dissolved organic carbon (BDOC). Secondly, activated carbon adsorption of the DOC present in ozonated water was quantified. The whole process was tested in a pilot unit under field conditions at the DWTP of Rennes (France). Lab-scale experiments confirmed that ozonation increases the BDOC fraction, reduces the aromaticity of the DOC and produces small size organic compounds. Adsorption tests led to the conclusion that activated carbon unexpectedly removes BDOC first. Finally, the pilot unit results revealed an additional BDOC removal (from 0.10 to 0.15 mg L⁻¹) of dissolved organic carbon from the raw water considered.     

Measurements of dissolved organic nitrogen (DON) in water samples with nanofiltration pretreatment

Dissolved organic nitrogen (DON) measurements for water samples with a high dissolved inorganic nitrogen (DIN, including nitrite, nitrate and ammonia) to total dissolved nitrogen (TDN) ratio using traditional methods are inaccurate due to the cumulative analytical errors of independently measured nitrogen species (TDN and DIN). In this study, we present a nanofiltration (NF) pretreatment to increase the accuracy and precision of DON measurements by selectively concentrating DON while passing through DIN species in water samples to reduce the DIN/TDN ratio. Three commercial NF membranes (NF90, NF270 and HL) were tested. The rejection efficiency of finished water from the Yangshupu drinking water treatment plant (YDWTP) is 12%, 31%, 8% of nitrate, 26%, 28%, 23% of ammonia, 77%, 78%, 82% of DOC (dissolved organic carbon), and 83%, 87% 88% of UV₂₅₄ for HL, NF90 and NF270, respectively. NF270 showed the best performance due to its high DIN permeability and DON retention (∼80%). NF270 can lower the DIN/TDN ratio from around 1 to less than 0.6 mg N/mg N, and satisfactory DOC recoveries as well as DON measurements in synthetic water samples were obtained using optimized operating parameters. Compared to the available dialysis pretreatment method, the NF pretreatment method shows a similar improved performance for DON measurement for aqueous samples and can save at least 20 h of operating time and a large volume of deionized water, which is beneficial for laboratories involved in DON analysis. DON concentration in the effluent of different treatment processes at the YDWTP and the SDWTP (Shijiuyang DWTP) in China were investigated with and without NF pretreatment; the results showed that DON with NF pretreatment and DOC both gradually decreased after each water treatment process at both treatment plants. The advanced water treatment line, including biological pretreatment, clarification, sand filtration, ozone-BAC processes at the SDWTP showed greater efficiency of DON removal from 0.37 to 0.11 mg N L⁻¹ than that at the YDWTP, including pre-ozonation, clarification and sand filtration processes from 0.18 to 0.11 mg N L⁻¹.     

Membrane bioreactor for the drinking water treatment of polluted surface water supplies

A laboratory membrane bioreactor (MBR) using a submerged polyethylene hollow-fibre membrane module with a pore size of 0.4 microm and a total surface area of 0.2 m2 was used for treating a raw water supply slightly polluted by domestic sewage. The feeding influent had a total organic carbon (TOC) level of 3-5 mg/L and an ammonia nitrogen (NH(3)-N) concentration of 3-4 mg/L. The MBR ran continuously for more than 500 days, with a hydraulic retention time (HRT) as short as 1h or less. Sufficient organic degradation and complete nitrification were achieved in the MBR effluent, which normally had a TOC of less than 2 mg/L and a NH(3)-N of lower than 0.2 mg/L. The process was also highly effective for eliminating conventional water impurities, as demonstrated by decreases in turbidity from 4.50+/-1.11 to 0.08+/-0.03 NTU, in total coliforms from 10(5)/mL to less than 5/mL and in UV(254) absorbance from 0.098+/-0.019 to 0.036+/-0.007 cm(-1). With the MBR treatment, the 3-day trihalomethane formation potential (THMFP) was significantly reduced from 239.5+/-43.8 to 60.4+/-23.1 microg/L. The initial chlorine demand for disinfection decreased from 22.3+/-5.1 to 0.5+/-0. 1mg/L. The biostability of the effluent improved considerably as the assimilable organic carbon (AOC) decreased from 134.5+/-52.7 to 25.3+/-19.9 microg/L. All of these water quality parameters show the superior quality of the MBR-treated water, which was comparable to or even better than the local tap water. Molecular size distribution analysis and the hydrophobic characterisation of the MBR effluent, in comparison to the filtered liquor from the bioreactor, suggest that the MBR had an enhanced filtration mechanism. A sludge layer on the membrane surface could have functioned as an additional barrier to the passage of typical THM precursors, such as large organic molecules and hydrophobic compounds. These results indicate that the MBR with a short HRT could be developed as an effective biological water treatment process to address the urgent need of many developing countries that are plagued by the serious contamination of surface water resources.     

Low-pressure membrane integrity tests for drinking water treatment: A review

Low-pressure membrane systems, including microfiltration (MF) and ultrafiltration (UF) membranes, are being increasingly used in drinking water treatments due to their high level of pathogen removal. However, the pathogen will pass through the membrane and contaminate the product if the membrane integrity is compromised. Therefore, an effective on-line integrity monitoring method for MF and UF membrane systems is essential to guarantee the regulatory requirements for pathogen removal. A lot of works on low-pressure membrane integrity tests have been conducted by many researchers. This paper provides a literature review about different low-pressure membrane integrity monitoring methods for the drinking water treatment, including direct methods (pressure-based tests, acoustic sensor test, liquid porosimetry, etc.) and indirect methods (particle counting, particle monitoring, turbidity monitoring, surrogate challenge tests). Additionally, some information about the operation of membrane integrity tests is presented here. It can be realized from this review that it remains urgent to develop an alternative on-line detection technique for a quick, accurate, simple, continuous and relatively inexpensive evaluation of low-pressure membrane integrity. To better satisfy regulatory requirements for drinking water treatments, the characteristic of this ideal membrane integrity test is proposed at the end of this paper.     

Characteristics of microfiltration membranes in a membrane coupled sequencing batch reactor system

Factors affecting filtration performance were investigated in a sequencing batch reactor (SBR) coupled with a submerged microfiltration module. Special bioreactors for aerobic and anoxic phases were specifically designed in order to differentiate the effect of dissolved oxygen (DO) from that of mixing intensity, on membrane filterability. When the filterability of a submerged microfilter was examined at each SBR phase, DO concentration, as well as mixing intensity proved to have a major influence on the membrane performance regardless of the SBR phase. A higher DO concentration resulted in a slower rise in TMP, corresponding to less membrane fouling, which was investigated in depth through a series of analyses including resistance measurements and compressibility of the cake layer as well as particle sizes as a functions of DO for both aerobic and anoxic phases in SBR.     

纳滤用于饮用水深度处理的研究

采用纳滤膜对某市自来水进行深度处理试验,研究了纳滤对自来水中有机物及离子等的去除效果.结果表明,采用一级纳滤工艺,在回收率为70%的情况下,能有效去除自来水中的有机物、离子、内分泌干扰物和细菌等.对CODMn浊度、Cr6+和阿特拉津的平均去除率分别为81.06%,85.47%,77.20%和83.90%;对总硬度和阴离子的去除率保持在一个适中的水平;出水中未检测出细菌.     

反应器理论在水处理中的应用

针对如何应用HSY算法识别水质模型CSTR的参数进行了探讨,并介绍了反应器理论在中药废水处理工程中的应用,通过分析反应器原理,得出反应器参数与实际处理效率的关系,对改进反应器的运行状态,提高处理效率具有重要意义。     

Rejection of pharmaceuticals in nanofiltration and reverse osmosis membrane drinking water treatment

This paper investigates the removal of a broad range of pharmaceuticals during nanofiltration (NF) and reverse osmosis (RO) applied in a full-scale drinking water treatment plant (DWTP) using groundwater. Pharmaceutical residues detected in groundwater used as feed water in all five sampling campaigns were analgesics and anti-inflammatory drugs such as ketoprofen, diclofenac, acetaminophen and propyphenazone, beta-blockers sotalol and metoprolol, an antiepileptic drug carbamazepine, the antibiotic sulfamethoxazole, a lipid regulator gemfibrozil and a diuretic hydrochlorothiazide. The highest concentrations in groundwater were recorded for hydrochlorothiazide (58.6-2548ngL(-1)), ketoprofen (85%). Deteriorations in retentions on NF and RO membranes were observed for acetaminophen (44.8-73 %), gemfibrozil (50-70 %) and mefenamic acid (30-50%). Furthermore, since several pharmaceutical residues were detected in the brine stream of NF and RO processes at concentrations of several hundreds nanogram per litre, its disposal to a near-by river can represent a possible risk implication of this type of treatment.     

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.     

A permeability-controlled microfiltration membrane for reduced fouling in drinking water treatment

A novel surface-modified polypropylene microfiltration membrane is investigated for its potential use in drinking water treatment. The flux decline rate of the modified membrane is substantially lower than the original polypropylene membrane for filtration of a soft, high-natural organic matter (NOM) surface water because a progressive adjustment in membrane permeability counteracts the flux decline due to fouling. In general, the prospects for reduced flux decline by membrane modification depend upon the characteristics of raw water such as hardness, particulate and NOM properties and concentration, and pretreatment strategies.     

微污染水源水传统处理工艺的强化措施

分析了我国目前水资源污染现状、主要危害及微污染水源水水质特点,结合我国国情及常规处理工艺的特点,探讨了强化混凝、强化沉淀和强化过滤、强化消毒去除水中有机物的净化机理。     

Reduced membrane fouling in a novel bio-entrapped membrane reactor for treatment of food and beverage processing wastewater

A novel Bio-Entrapped Membrane Reactor (BEMR) packed with bio-ball carriers was constructed and investigated for organics removal and membrane fouling by soluble microbial products (SMP). An objective was to evaluate the stability of the filtration process in membrane bioreactors through backwashing and chemical cleaning. The novel BEMR was compared to a conventional membrane bioreactor (CMBR) on performance, with both treating identical wastewater from a food and beverage processing plant. The new reactor has a longer sludge retention time (SRT) and lower mixed liquor suspended solids (MLSS) content than does the conventional. Three different hydraulic retention times (HRTs) of 6, 9, and 12 h were studied. The results show faster rise of the transmembrane pressure (TMP) with decreasing hydraulic retention time (HRT) in both reactors, where most significant membrane fouling was associated with high SMP (consisting of carbohydrate and protein) contents that were prevalent at the shortest HRT of 6 h. Membrane fouling was improved in the new reactor, which led to a longer membrane service period with the new reactor. Rapid membrane fouling was attributed to increased production of biomass and SMP, as in the conventional reactor. SMP of 10-100 kDa from both MBRs were predominant with more than 70% of the SMP <100 kDa. Protein was the major component of SMP rather than carbohydrate in both reactors. The new reactor sustained operation at constant permeate flux that required seven times less frequent chemical cleaning than did the conventional reactor. The new BEMR offers effective organics removal while reducing membrane fouling.     

Behavior and characteristics of dissolved organic matter during column studies of soil aquifer treatment

Soil column experiments were performed to investigate the behavior and characteristics of dissolved organic matter (DOM) during soil aquifer treatment (SAT), and to differentiate among the mechanisms responsible for the changes in the structural and functional properties of DOM during SAT. To determine the biological transformation of DOM, biodegradability tests using a biodegradation-column system were conducted. DOM was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). Dissolved organic carbon (DOC) was removed by 70% during SAT, and the sorption and anaerobic biodegradation in SAT led to a DOC reduction of 27.4%. The significant changes in fluorescence properties of DOM were observed during SAT. However, the sorption and anaerobic biodegradation in SAT seemed to have no significant effect on the chemical structure of fluorescing constituents in DOM. The DOM fractions exhibited different changes in Fourier-transform infrared (FT-IR) spectra characteristics during SAT. Biodegradation resulted in the enrichment of aromatic structures and the decreased content of the oxygen-containing functional groups, such as CO and C-O, in DOM. On the other hand, the production of C-O and amide-2 functional groups occurred as a result of the sorption combined with anaerobic biodegradation in SAT.     

MBR技术处理高氨生活污水的研究

根据MBR技术的优点,采用连续式MBR反应器处理高氨生活污水,介绍了MBR反应器装置及试验用水水质,并对MBR去除COD,NH4^＋-N效果进行了分析,实验结果表明,系统处理效果稳定且没有每天在线清洗的必要性。     

Impact of polymer flocculants on coagulation-microfiltration of surface water

Organic polymers are widely used as flocculants in pretreatment for microfiltration. However, their impact on microfiltration system performance was not well understood. In this study, the effects of three types of polymer flocculants on microfiltration permeate water quality and membrane fouling were evaluated using a hollow fiber membrane under two different operation modes, coagulation/flocculation-sedimentation-microfiltration (CFSM) and coagulation/flocculation-microfiltration (CFM). Interestingly, the effect of polymers on membrane fouling did not appear to reflect their impact on dissolved organic matter content or floc particle properties in the membrane feed water. The addition of polymer flocculants resulted in floc particles of larger size and smaller fractal dimension and slightly enhanced the removal of dissolved organic matter, both of which were expected to reduce membrane fouling. However, it significantly aggravated membrane fouling in all cases except when the positively charged poly(diallyldimethylammonium) chloride was used in the CFSM process. In particular, all polymers greatly increased hydraulically irreversible fouling in the CFM mode. The increased fouling in the CFSM mode is attributed to the residual polymer, while that in the CFM mode is attributed to the enhanced irreversible floc particle attachment on the membrane surface. Considering the potential severe membrane fouling and the small improvement in treated water quality when polymers are used, the application of polymers in microfiltration pretreatment needs to be carefully evaluated.     

Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment

The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ·mol⁻¹. At pH 7.0 and 25 °C, the rate constant was 25.2 ± 0.4 M⁻¹ s⁻¹. Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for <5% and ≥95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 μg L⁻¹), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 μg L⁻¹). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.     

Optimization of a gravity‐driven membrane (GDM) system operated with simple manual cleanings for household drinking water treatment

Manual cleaning protocols were developed for a gravity‐driven membrane (GDM) module. Such a module is a promising solution for household water treatment in low‐ and middle‐income countries. A filtration system equipped with the GDM module was tested in a batchwise manner using three different feed water solutions. Two types of manual cleaning protocols were performed to delay the permeability decrease, namely cleaning between batches and long‐term cleaning (every 15 batches). The optimized protocol for cleaning between batches consisted of 3 twisting and 10 vertical shaking movements; the optimized long‐term cleaning protocol consisted of 70 vertical shaking movements for both the middle region of the module and the module header. These cleaning protocols allowed the filtration system to produce sufficient water to meet the minimum requirements for a five person family using all three kinds of feed water solutions. The module produced water without Escherichia coli, even for the wastewater influent.     

Anaerobic biodegradability and treatment of grey water in upflow anaerobic sludge blanket (UASB) reactor

Feasibility of grey water treatment in an upflow anaerobic sludge blanket (UASB) reactor operated at different hydraulic retention time (HRT) of 16, 10 and 6h and controlled temperature of 30 degrees C was investigated. Moreover, the maximum anaerobic biodegradability without inoculum addition and maximum removal of chemical oxygen demand (COD) fractions in grey water were determined in batch experiments. High values of maximum anaerobic biodegradability (76%) and maximum COD removal in the UASB reactor (84%) were achieved. The results showed that the colloidal COD had the highest maximum anaerobic biodegradability (86%) and the suspended and dissolved COD had similar maximum anaerobic biodegradability of 70%. Furthermore, the results of the UASB reactor demonstrated that a total COD removal of 52-64% was obtained at HRT between 6 and 16 h. The UASB reactor removed 22-30% and 15-21% of total nitrogen and total phosphorous in the grey water, respectively, mainly due to the removal of particulate nutrients. The characteristics of the sludge in the UASB reactor confirmed that the reactor had a stable performance. The minimum sludge residence time and the maximum specific methanogenic activity of the sludge ranged between 27 and 93 days and 0.18 and 0.28 kg COD/(kg VS d).     

Comparing microfiltration-reverse osmosis and soil-aquifer treatment for indirect potable reuse of water

Microfiltration (MF) followed by reverse osmosis (RO) and soil-aquifer treatment (SAT) are the two principal technologies considered for indirect potable reuse of wastewater. This study, conducted at the Northwest Water Reclamation Plant, Mesa (Arizona), evaluated MF/RO and SAT (>6 months residence time) treated tertiary effluent with respect to organics removal. Effluent organic matter was characterized as total organic carbon (TOC), by UV absorbance (UVA), solid-state carbon-13 nuclear magnetic resonance spectroscopy, and size exclusion chromatography. Several trace organic micropollutants, including EDTA, NTA, and alkylphenolethoxylate residues, were analyzed by GC/MS. The study revealed that final TOC concentrations of MF/RO and SAT are 0.3 and 1.0 mgl(-1), respectively. Based on the characterization techniques used, the character of bulk organics present in final SAT water resembles the character of natural organic matter present in drinking water. Depending on the molecular weight cut-off, RO membranes can efficiently reject high molecular weight organic matter (characterized as humic and fulvic acids). However, approximately 40-50 percent of the remaining TOC in permeates consists of low molecular weight acids and neutrals representing a molecular weight range of approximately 500Da and less. In the SAT treated effluent, EDTA and APECs were removed to approximately 4.3 and 0.54 microg/l, respectively, but were below the detection limit in the MF/RO treated effluent.     

浸没式膜混凝吸附反应器处理北江水的试验研究

采用浸没式膜混凝反应器(MCR)和浸没式膜混凝吸附反应器(MCAR)处理北江流域地表水,考察了两种工艺对污染物的去除效果及膜污染情况。结果表明,MCR与MCAR的出水浊度均低于0.100 NTU;随着混凝剂投加量的增加,MCR对有机物的去除效果逐渐提高,跨膜压差(TMP)的增加速率逐渐降低;在相同混凝剂投加量条件下,MCAR对有机物的去除效果优于MCR,且膜污染程度会进一步减缓。