An investigation into reservoir NOM reduction by UV photolysis and advanced oxidation processes

A comparison of four treatment technologies for reduction of natural organic matter (NOM) in a reservoir water was made. The work presented here is a laboratory based evaluation of NOM treatment by UV-C photolysis, UV/H(2)O(2), Fenton's reagent (FR) and photo-Fenton's reagent (PFR). The work investigated ways of reducing the organic load on water treatment works (WTWs) with a view to treating 'in-reservoir' or 'in-pipe' before the water reaches the WTW. The efficiency of each process in terms of NOM removal was determined by measuring UV absorbance at 254 nm (UV(254)) and dissolved organic carbon (DOC). In terms of DOC reduction PFR was the most effective (88% removal after 1 min) however there were interferences when measuring UV(254) which was reduced to a lesser extent (31% after 1 min). In the literature, pH 3 is reported to be the optimal pH for oxidation with FR but here the reduction of UV(254) and DOC was found to be insensitive to pH in the range 3-7. The treatment that was identified as the most effective in terms of NOM reduction and cost effectiveness was PFR.     

Minimization of the formation of disinfection by-products

The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA₂₅₄), specific UV absorbance at 254 nm (SUVA₂₅₄), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.     

Applicability of MIEX®DOC process for organics removal from NOM laden water

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题，分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究，同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示，水中的有机物为腐殖酸类物质，分子量分别为1600和3500，腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳，处理前后水样DOC浓度无明显变化，而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5，经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时，DOC降至7．6mg／L，然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外，当反应初始pH值为3，过氧化氢投加量为0．5％（v／v），亚铁和双氧水摩尔比为0．05时，出水DOC降至5．6mg／L，氧化后有小分子有机物生成。     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

土壤-纳滤系统处理再生水补充地下水的研究

为充分保障再生水回灌地下时的水质安全、提供高质量地下水资源,在土壤处理系统中嵌入纳滤技术强化对再生水的处理效果,并初步探讨土壤系统作为前处理对纳滤膜污染的控制机理.结果表明,未采用臭氧氧化预处理前,土壤处理对再生水DOC和UV254的平均去除率分别为22%和20%.臭氧氧化对UV254的平均去除率为51%,并将土壤对D...     

NOM characteristics and treatabilities of ozonation processes

The objectives of this study were intended to evaluate the effects of the characteristics of natural organic matter on the treatabilities of ozonation, coagulation, filtration, and granular activated carbon processes. The ultra-violet absorbance (UV254) was used as a surrogate parameter to assess each process in reducing the disinfection by-product formation potential (DBPFP). The results indicate that the DBPFP varies with the sources of water samples and treatment processes, but is closely related to the measurement of UV254/DOC. Coagulation/sedimentation can eliminate large molecular weight organic fractions. Both pre- and post-ozonation processes can reduce some of DBP precursors than the conventional treatment process, and are more reliable for reducing the overall DBPFP.     

土壤渗滤对有机微污染物去除性能研究

采用土壤柱试验研究了土壤渗滤对再生水中有机微污染物的去除性能。结果表明，土壤柱对再生水中的DOC、UV₂₅₄、总氮和总磷有较好的去除效果，并具有较高的抗冲击负荷的能力；土壤表层10 cm厚度对DOC的去除起主要作用；UV₂₅₄和AOX在土壤表层10 cm厚度降解效果不明显，随着深度增加去除率逐渐升高；液相色谱有机碳探测(LC-OCD)检测结果表明，土壤柱对溶解性有机物质的去除主要体现在对多糖物质的降解上，其次是有机酸类，对腐殖质也有一定的去除作用。     

Removal of NOM from drinking water: Fenton's and photo-Fenton's processes

The control of disinfection by-products during water treatment is primarily undertaken by reducing the levels of precursor species prior to chlorination. As many waters contain natural organic matter at levels of up to 15 mgl(-1) there is a need for a range of control methods to support conventional coagulation. Two such processes are the Fenton and photo-Fenton's processes and in this paper they are assessed for their potential to remove NOM from organic rich waters. The performance of both processes is shown to be depentent on pH, Fe: H2O2 ratio as well as Fe2+ dose. Under optimum conditions both processes achieved greater than 90% removal of DOC and UV254 absorbance. This removal lead to the trihalomethane formation potential of the water being reduced from 140 to below 10 microgl(-1), well below UK and US standards.     

Comparison of inclined plate sedimentation and dissolved air flotation for the minimisation of subsequent nitrogenous disinfection by-product formation

The formation of disinfection by-products (DBPs), including both nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products (C-DBPs), was investigated upon chlorination of water samples following two treatment processes: (i) coagulation-inclined plate sedimentation (IPS)-filtration and (ii) coagulation-dissolved air flotation (DAF)-filtration. The removal of algae, dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV₂₅₄ by coagulation-DAF-filtration was superior to coagulation-IPS-filtration. On average, 53%, 53% and 31% of DOC, DON and UV₂₅₄ were removed by coagulation-DAF-filtration process, which were higher than 47%, 31% and 27% of that by coagulation-IPS-filtration process. Additionally, coagulation-IPS-filtration performed less well at removing the low molecular weight organics than coagulation-DAF-filtration process. The concentrations of chloroform, dichloroacetamide (DCAcAm) and dichloroacetonitrile (DCAN) formed during chlorination after coagulation-DAF-filtration reached their maximum values of 13, 1.5 and 4.7 μg L⁻¹, respectively, and were lower than those after coagulation-IPS-filtration with the maximum detected levels of 17, 2.9 and 6.3 μg L⁻¹. However, the trichloronitromethane (TCNM) concentration after the two processes was similar, suggesting that DON may have less of a contribution to TCNM formation than DCAcAm and DCAN.     

Improvement of DOC removal by multi-stage AOP-biological treatment

The single and multi-stages advanced oxidation process (AOP)-biological treatments were evaluated to apply for drinking water treatment, especially for the water containing less susceptible dissolved organic carbon (DOC) to ozone, comparing with the ozonation-biological treatment. Minaga reservoir water and the secondary effluent from a Municipal wastewater treatment plant were used as dissolved organic matter (DOM) solutions. DOC removals after 60 min AOP-biological treatment were 62% and 41% in the Minaga reservoir water and the secondary effluent, respectively, whereas those in the ozonation-biological treatment only 40% and 15% of DOC were removed, respectively. The result indicated that the single-stage AOP-biological treatment could improve DOC removal in comparison with the single-stage ozonation-biological treatment. This is because the AOP mineralized both biodegradable dissolved organic carbon (BDOC) produced in the early stage of oxidation and non-biodegradable dissolved organic carbon (NBDOC), whereas only BDOC was mineralized by further ozonation and NBDOC was not oxidized in the ozonation-biological treatment. The multi-stage treatment could not improve DOC removal in comparison with the single-stage treatment in the ozonation-biological treatment for the secondary effluent containing less susceptible DOC to ozone. However, the multi-stage AOP-biological treatment significantly reduced DOC and achieved 71% of DOC removal by 4 times repetition of 15 min oxidation, whereas DOC removal was 41% in the single-stage AOP-biological treatment for the same oxidation time. The improvement of DOC removal by the multi-stage AOP-biological treatment was due to BDOC removal as a radical scavenger by subsequent biological treatment in the early stage of oxidation and direct mineralization in the latter stage of oxidation.     

改性TiO2/浮石光催化去除二级出水中有机物

为了实现城市污水厂二级出水的回用,将La3+、Fe3+共掺杂TiO2/浮石光催化用于二级出水中有机物的去除。在优化工艺条件下,该方法对TOC的去除率为49.0%,对UV254的去除率为76.5%;出水BDOC/DOC值大幅度提高,由最初的0.21提高到0.56,增加了出水的可生化性;二级出水中存在着影响光催化去除有机物的因素,其中阴离子对有机物的去除有一定的抑制作用;光催化反应在通过O3强化后对有机物的去除率得到提高,TOC的去除率达到75.0%,光催化和O3氧化对有机物的去除具有协同效应;随着光催化反应次数的增加,催化剂活性有下降趋势,使用10次后TOC去除率下降到第一次使用时的16.7%,再生能够使催化活性恢复到使用前的95%,催化剂在使用15次以内稳定性较好。     

Reducing the formation of disinfection by-products by pre-ozonation.

The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.     

臭氧光催化降解地下水中天然有机物的研究

在现场开展了中试规模的臭氧光催化降解天然有机物的研究.研究表明,对大分子天然有机物占很大比例且重碳酸盐含量较高的地下水,臭氧投加量10 mg/L和反应时间10 min条件下,TOC的去除率不到20%,但UV254和三卤甲烷生成潜力(THMFP)去除率分别达到近60%和33.5%.臭氧光催化与活性炭吸附相连,能显著提高UV254的THMFP的去除率,但TOC去除率并不明显高于单独活性炭吸附.臭氧光催化使大分子有机物转化为小分子有机物,后者在活性炭上的吸附性提高且生化性改善,可望在生物活性炭上更有效地去除.     

高锰酸盐复合药剂强化混凝改善再生水景观湖水质研究

实验通过投加助凝剂以强化混凝沉淀过程,从而达到去除再生水景观水中的藻类。以PAC为混凝剂,高锰酸盐复合药剂(PPC)为预氧化助凝剂,通过烧杯实验确定PPC、PAC同时投加,最佳投量分别为1 mg/L、60 mg/L。生产性实验中,机械加速澄清池强化混凝对TP、叶绿素、藻密度的去除率分别为54%、32.3%和35.4%,湖水中TP、TN逐渐降低分别由4.9 mg/L、23 mg/L降至0.72 mg/L、10.3 mg/L。PPC提高了混凝沉淀对藻类的去除效果,改善了再生水景观湖水质,降低水中氮磷营养盐的含量。     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.     

The degradation of dissolved organic nitrogen associated with melanoidin using a UV/H2O2 AOP

The aim of this study was to examine the simultaneous degradation of dissolved organic nitrogen (DON) and associated colour from wastewater containing melanoidins by an advanced oxidation process (AOP). UV irradiation of H2O2 was used as the mechanism to create the hydroxyl radical for oxidation. Melanoidins are large nitrogenous organic compounds that are refractory during biological wastewater treatment processes. The simultaneous degradation of DON and colour, present as a result of these compounds, was investigated using an AOP. The oxidation process was much more capable of removing colour (99% degradation), dissolved organic carbon (DOC) (50% degradation) and DON (25% degradation) at the optimal applied dose of hydrogen peroxide for the system (3300 mg l(-1)). This indicated that colour and DON removal were decoupled problems for the purpose of treating melanoidin by an AOP and thus colour removal can not be used as an indication of DON removal Colour was caused by organic molecules with molecular weight greater than 10 kDa. Oxidation caused a partial reduction of the DON (41-15% of the total dissolved nitrogen) and DOC (29-14% of the DOC) associated with the large molecular weight fraction (>10 kDa) and almost complete colour removal (87-3% of the total colour). The degraded DON was mostly accounted for by the formation of ammonia (31% of the nitrogen removed from the large fraction) and small molecular weight compounds (66% of the nitrogen removed from the large fraction). The degraded DOC appeared to be mostly mineralised (to CO2) with only 20% of the degraded compounds appearing as small molecular weight DOC.     

聚合氯化铝与粉末活性炭联合强化混凝处理垃圾渗滤液

研究了联合粉末活性炭与聚合氯化铝(PAC)强化混凝对垃圾渗滤液原水的处理效果。结果表明,在原水COD为4 100 mg/L、浊度为147 NTU、UV254为20的条件下,粉末活性炭的加入可以有效增加垃圾渗滤液中有机物的去除率,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,COD的去除率由21.6%提高到29.1%,UV254去除率由29.8%提高到39.9%,剩余浊度由138 NTU降到133 NTU。该强化混凝过程使原水中溶解性小分子有机物的去除率提高显著,PAC投加量为0.6 g/L时,投加0.6 g/L粉末活性炭,在分子量小于1 kDa的范围内,UV254去除率由2.9%上升为10%。     

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.     

臭氧/高锰酸盐预氧化对生物过滤净水效能的影响

比较了臭氧(O3)和高锰酸盐复合药剂(PPC)对水源水预氧化的助凝效果及其对后续陶粒生物过滤净水效能的影响.结果表明,两种预氧化剂投加量均为2 mg/L时,PPC的助凝效果较为明显,浊度和溶解性有机碳(DOC)的去除率分别由未投加氧化剂时的85.7%和24.2%提高到88.3Z和35.2%;O3能够增加沉淀后水的可生化性,使特征紫外吸光度(SUVA)由0.97L/(m·mg)降至0.89 L/(m·mg).PPC预氧化有助于生物过滤对浊度的稳定去除,而O3预氧化则有助于生物过滤对DOC的去除.与O3预氧化相比,PPC预氧化有利于后续生物过滤运行初期对NH4 -N的去除,二者后续生物过滤在前3个月对NH4 -N的平均去除率分别为26.6%和73.1%,运行后期二者NH4 -N去除率接近.当进水NH4 -N大于2.0 mg/L时,DO是其去除的主要限制因素.