强化混凝去除黄浦江水有机物的试验研究

强化混凝去除有机物的效果与水源的分子量分布特性有着密切的关系.由于黄浦江水中低分子量的溶解性有机物占多数,因此,强化混凝处理有机物效果有限.对于＜1k分子量区间的有机物.增加混凝剂投量可有效去除紫外吸光值(UV254),但去除溶解性有机碳(DOC)的效果很差.尽管增加混凝剂投量和降低pH都能有效地去除有机物,但决定强化混凝效果的主要因素是pH,去除黄浦江水有机物的最佳pH范围为6～5.     

pH modeling for maximum dissolved organic matter removal by enhanced coagulation

Correlations between raw water characteristics and pH after enhanced coagulation to maximize dissolved organic matter (DOM) removal using four typical coagulants (FeCl₃, Al₂(SO₄)₃, polyaluminum chloride (PACl) and high performance polyaluminum chloride (HPAC)) without pH control were investigated. These correlations were analyzed on the basis of the raw water quality and the chemical and physical fractionations of DOM of thirteen Chinese source waters over three seasons. It was found that the final pH after enhanced coagulation for each of the four coagulants was influenced by the content of removable DOM (i.e. hydrophobic and higher apparent molecular weight (AMW) DOM), the alkalinity and the initial pH of raw water. A set of feed-forward semi-empirical models relating the final pH after enhanced coagulation for each of the four coagulants with the raw water characteristics were developed and optimized based on correlation analysis. The established models were preliminarily validated for prediction purposes, and it was found that the deviation between the predicted data and actual data was low. This result demonstrated the potential for the application of these models in practical operation of drinking water treatment plants.     

混凝去除垃圾渗滤液中DOM的实验研究

选取氯化铁(FeCl3.6H2O)为混凝剂,以经0.45μm膜和1nm膜分子切割的垃圾渗滤液为研究对象,通过混凝剂投加量和混凝pH值实验,研究了垃圾渗滤液中DOM的去除情况,并比较了两种不同分子量水平的渗滤液中DOM的混凝去除特点。研究表明,pH值是影响渗滤液DOM去除的主要因素,氯化铁在pH=5、投加量为4g/L的条件下混凝效果最佳。混凝pH值对大分子量渗滤液中DOC去除的影响较大;而两种分子量水平的渗滤液UV254的去除差异不大。     

不同水体溶解性有机物的混凝去除特性

采用硫酸铝、工业氯化铁、无机高分子絮凝剂(PAC)3种无机混凝剂,对广州珠江、北京密云、天津滦河不同原水进行了混凝实验,分析了不同混凝剂去除水体有机物的特性以及不同水体溶解性有机物(DOM)的内在分级特征与其混凝去除率的关系.实验结果表明,①珠江水体由于碱度低,pH较易下降,高投药浓度下此水体DOM更易被氯化铁去除;中低投药下,在南方水体中,PAC与盐类絮凝剂对去除DOM的混凝性能差别不如在北方水体中明显,表明南北方水体DOM的内在特性存在一定差异,即北方水体DOM中可混凝去除部分的有机物易发生电中和作用,带有较多负电基团,南方珠江水体DOM含带电基团的有机物相对较少,而中性有机物含量相对较高,这与进一步分级结果一致.②所有水体从混凝收敛点看,总溶解性有机碳(DOC)去除率都是工业PAC最高,显示电中和(憎水化)-沉淀(吸附)可能为这些水体DOM的主要去除机理.③从不同水体的DOC平均去除率看,珠江水体高于密云水体,它们又明显高于滦河水体.对水体DOM进一步的化学分级研究结果表明,DOC去除率越高的水体,其中的憎水中性物质(HoN)含量也越高.这表明,除了碱度、总有机碳(TOC)外,原水DOM的内在化学分级特征也是影响水体DOC混凝去除率的重要因素.     

预压力混凝沉淀除藻工艺中DOC变化规律研究

为了探讨预压力混凝沉淀除藻工艺是否会使藻细胞破裂,导致水中溶解性有机物(DOC)增加,进而优化压力作用方式,得到安全、高效的预压力除藻工艺,实验研究了预压力、预氧化技术处理含藻水时DOC的变化,以及水中相对分子质量分布,并研究了混凝沉淀后藻类、浊度、DOC的去除效果.结果表明,在0.5~0.8 MPa压力作用后,水中DOC没有增加,反而减少,且有机物相对分子质量减小.而高锰酸钾与次氯酸钠预氧化均会导致DOC增加,相对分子质量分布没有明显变化.预压力混凝沉淀后藻类去除率96.23%;DOC去除率29.11%,高于预氧化混凝沉淀工艺10%~30%.     

磁性离子交换树脂对原水中有机物去除效能的研究

采用磁性离子交换树脂(MIEX)预处理原水中有机物的中试试验结果表明,MIEX技术可有效地去除原水中的有机物,对UV254,DOC和CODMn的去除率分别稳定在82%、66%和50%,MIEX预处理可以有效强化混凝沉淀对有机物、藻细胞和浊度的去除.与常规工艺相比,在混凝剂聚合氯化铝投加量降低56%时,该工艺对UV254和CODMn的去除率分别为90%和71%,对藻细胞数和浊度的去除率分别为99%和95%.对溶解性有机物分级和分子量分布的测定表明,MIEX预处理主要去除混凝沉淀无法有效去除的小分子区间的亲水性和疏水性有机物,可以有效控制消毒副产物的产生,MIEX预处理与混凝沉淀联用工艺出水的三卤甲烷生成势(THMFP)和卤乙酸生成势(HAAFP)比原水降低了88%和87%.     

Selection of magnetic anion exchange resins for the removal of dissolved organic and inorganic matters

Four magnetic anion exchange resins (MAERs) were used as adsorbents to purify drinking water. The effect of water quality (pH, temperature, ionic strength, etc.) on the performance of MAER for the removal of dissolved organic matter (DOM) was also investigated. Among the four studied MAERs, the strong base resin named NDMP-1 with high water content and enhanced exchange capacity exhibited the highest removal rate of dissolved organic carbon (DOC) (48.9% removal rate) and UV-absorbing substances (82.4% removal rate) with a resin dose of 10 mL/L after 30 min of contact time. The MAERs could also effectively remove inorganic matter such as sulfate, nitrate and fluoride. Because of the higher specific UV absorbance (SUVA) value, the DOM in the raw water was found to be removed more effectively than that in the clarified water by NDMP resin. The temperature showed a weak influence on the removal of DOC from 6 to 26℃, while a relatively strong one at 36℃. The removal of DOM by NDMP was also affected to some extent by the pH value. Moreover, increasing the sulfate concentration in the raw water could decrease the removal rates of DOC and UV-absorbing substances.     

臭氧-生物活性炭对南方河网典型污染物的去除特性

以我国南方河网原水中有机物和季节性溴化物(Br^-)为对象,研究臭氧-生物活性炭(BAC)工艺净化过程中有机物相对分子质量(M_r)分布变化及溴酸盐(BrO^-₃)和消毒副产物(THMs)的形成规律.结果表明,原水中M_r在10³以下的有机物(DOC)约占总量的80%,常规工艺主要表现为对M_r >100×10³有机物的去除,出水DOC去除率为8%、 SUVA(UV₂₅₄/DOC)值下降14%;臭氧-活性炭工艺主要去除10³<M_r<5×10³的有机物,但亲水性小分子有机物抑制生物降解作用,出水DOC去除率仅提高至30%、SUVA值下降31%.当臭氧投加量高于2 mg/Ｌ时,臭氧氧化出水中BrO^-₃增加明显,氧化过程原水中Br^-浓度升高BrO^-₃生成量增大;生物活性炭对BrO^-₃的去除率平均仅为13%,且波动较大.与常规处理相比,臭氧-生物活性炭处理后各类THMs均有减少,总量减少40%;但氯量和Br^-对溴代副产物影响大,主要为CHBr₃生成量增加.     

MIEX预处理技术对长江原水中有机物的去除效能

利用烧杯试验研究了磁性离子交换树脂（magnetic ion exchange resin,MIEX）预处理对长江原水中有机物的去除效能,以总溶解有机碳(DOC)、254 nm紫外吸收值(UV254)、有机物相对分子质量分布、有机物分级、紫外扫描以及消毒副产物生成量等指标进行表征.结果表明,长江水源水中的有机物主要为小分子亲水性有机物,其含量占有机物总量的50%以上;MIEX预处理可以有效降低水中有机物的含量,投加量为10 mL/L、接触时间为15 min时,DOC的去除率超过35%,相对分子质量和分级的测定结果表明,小分子亲水性部分有机物的去除导致了DOC去除效果的改善;从紫外扫描结果可看出,MIEX预处理对在190～250 nm波长时有强吸收的有机物去除效果非常明显,但对在高于250 nm波长处有吸收的有机物去除效果与混凝阶段的效果相近.     

Characterization of dissolved organic matter as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluorescence

It is very important to identify the dominant precursors for N-nitrosamine formation from bulk organic matter, to enhance the understanding of N-nitrosamine formation pathways in water treatment plants and allow the development of practical treatment technologies. In this study, dissolved organic matter (DOM) from two source waters was fractionated with XAD resins and ultra- filtration membranes. The N-nitrosamine formation potential (FP) (ng of N-nitrosamines formed per mg of dissolved organic carbon (DOC)) from raw water and each fraction were measured and correlated with the fluorescence excitation-emission matrix (EEM), molecular weight (MW) and other assays. The results showed that the hydrophilic fraction had N-nitrosamine FP 1.3 to 3.5 times higher than the hydrophobic fraction from both source waters. The DOM fraction with low MW was the dominant fraction in these two source waters and contributed more precursors for N-nitrosamine formation than the larger MW fraction. The EEM spectra indicated there were notable amounts of soluble microbial products (SMPs) and aromatic proteins in the two studied rivers, which probably originated from wastewater discharge. The SMPs tended to be more closely correlated with N-nitrosodimethylamine formation potential than the other DOM components. Higher N-nitrosamine FP were also related to fractions with lower DOC/DON ratios and lower SUVA 254 values.     

融雪期城市河流中溶解性有机物的时空分布特征

以沈阳市新开河为研究对象,考察了河水中溶解性有机物(DOM)含量的月份变化,以及融雪期河水中DOM含量和特性的时空变化规律.利用XAD树脂将DOM分为5个部分:疏水性有机酸(HPO-A),疏水性中性有机物(HPO-N),过渡亲水性有机酸(TPI-A),过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明,融雪期河水中的溶解性有机碳(DOC)浓度较高,HPO-N和TPI-N是融雪期河水中的主要DOM组分,并且DOM中的荧光物质主要为类芳香族蛋白质荧光物质和类腐植酸荧光物质.融雪期水体中的DOC、波长254nm处的紫外吸光度(UV-254)和三卤甲烷生成势(THMFP)呈先降低然后波动最后升高的变化趋势.特征紫外吸光度(SUVA)和三卤甲烷生成活性(STHMFP)与以上三者的变化规律相反.融雪期河水中的DOC受污水排放影响大,有排污口处的DOC含量明显大于其他区域.污水排放也使受纳水体中UV-254对THMFP的指示作用减弱.     

Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products

Anion exchange resins （AERs） with different properties were evaluated for their ability to remove dissolved organic matter （DOM） and bromide, and to reduce disinfection by-product （DBP） formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin （MIEX） showed faster dissolved organic carbon （DOC） removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency, MIEX showed significant chlorinated DBP removal because it had the highest DOC removal within 30 rain, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.     

混凝和活性炭吸附去除微污染水源水中DON的研究

溶解性有机氮(dissolved organic nitrogen,DON)作为饮用水中新兴氮消毒副产物(nitrogenous disinfection by-products,N-DBPs)的前体物逐渐受到国内外学者的关注.为探讨混凝和活性炭吸附对微污染水源水中DON的去除机制,首先测定原水中DON、溶解性有机炭(dissolved organic carbon,DOC)、NH4+-N、UV254、pH和溶解氧(dissolved oxygen,DO)等指标和DON、DOC分子量分布;接着通过混凝和活性炭吸附试验来考察原水中DON、DOC和UV254变化,并应用三维荧光光谱对原水中DON变化进行表征.结果表明,微污染水源水中DON、DOC和UV254分别为1.28 mg.L-1、8.56 mg.L-1和0.16 cm-1,DOC与DON比值(DOC/DON)为6.69 mg.mg-1,SUVA为1.87 m-1.(mg.L-1)-1;小分子量(<6 000)DON占较高比例约为68%,大分子量(>20 000)DON占的比例为22%;当混凝剂投加量为10 mg.L-1,DON的去除率大约为20%,DOC和UV254去除率约26%、70%;当活性炭投加量为1.0 g,DON、DOC和UV254的去除率大约为60%、35%、100%;混凝和活性炭吸附组合试验时,对DON、DOC的去除率大约为82%和64%;三维荧光光谱证实,原水中DON变化与3个主要峰有关,分别代表物质为色氨酸类蛋白质、芳香族类蛋白质和富里酸类物质.     

超滤工艺净化微污染原水的试验研究

采用混凝沉淀-超滤工艺对微污染原水进行试验,对组合工艺的除污染特性进行了研究。结果表明,组合工艺对浊度、颗粒物和藻类的去除效果非常好。出水浊度稳定在0.1NTU以下,水中粒径>2μm的颗粒数约19个/mL,藻类平均数量约为2.2×104个/L。在去除有机物方面,组合工艺对高锰酸盐指数、UV254和DOC的去除率分别为38.0%、15.2%和32.6%,其中对高锰酸盐指数的去除效果较为突出,出水高锰酸盐指数浓度为2.69~2.87mg/L。组合工艺去除的有机物是分子量大于3KD的大分子有机物,对小分子有机物去除效果不明显。其中,混凝沉淀主要去除了水中的疏水性有机物和亲水荷电有机物,超滤膜去除的有机物则以亲水中性有机物为主。在工艺运行期间,超滤膜的跨膜压差增加了约12.3%,跨膜压差的升高主要由被超滤膜吸附的小分子有机物产生。     

Changes in the quality of river water before, during and after a major flood event associated with a La Niña cycle and treatment for drinking purposes

The treatment of organics present in the lower reaches of a major river system（the Murray–Darling Basin, Australia） before（March–July 2010）, during（December 2010–May 2011） and after（April–December 2012） a major flood period was investigated. The flood period（over 6 months）occurred during an intense La Nia cycle, leading to rapid and high increases in river flows and organic loads in the river water. Dissolved organic carbon（DOC） increased（2–3 times） to high concentrations（up to 16 mg/L） and was found to correlate with river flow rates. The treatability of organics was studied using conventional jar tests with alum and an enhanced coagulation model（mEnCo）. Predicted mean alum dose rates（per mg DOC） were higher before（9.1 mg alum/mg DOC） and after（8.5 mg alum/mg DOC） than during the flood event（8.0 mg alum/mg DOC）,indicating differences in the character of the organics in raw waters. To assess the character of natural organic matter present in raw and treated waters, high performance size exclusion chromatography with UV and fluorescence detectors were used. During the flood period, high molecular weight UV absorbing compounds（〉2 kDa） were mostly detected in waters collected,but were not evident in waters collected before and afterwards. The relative abundances of humic-like and protein-like compounds during and following the flood period were also investigated and found to be of a higher molecular weight during the flood period. The treatability of the organics was found to vary over the three climate conditions investigated.     

贵州百花湖水中溶解有机质的分子量分布随深度的变化规律

利用高效体积排阻色谱法测量了百花湖水中溶解有机质的分子量及其分布。结果表明百花湖水中溶解有机质（DOM）主要以分子量小于3500道尔顿（Da）的组分为主,其中重均（Mw）和数均（Mn）分子量分别界于2300～2500 Da和1900～2150 Da之间,说明其主要来源于降水对土壤有机物的淋滤和径流作用。根据色谱分析的结果,可以把溶解有机质的分子量分布分为四个组分：大分子量组分（MW〉3500 Da）;中等偏大分子量组分（3500～2000 Da）;中等分子量组分（2000～1000 Da）和小分子量组分（MW〈1000 Da）。由于生物活动和光降解作用以及有机物的分解作用,导致各分子量组分随深度的变化规律不同,其中分子量在3500～2000 Da之间的有机物的含量随深度的增大而增大,其余组分的含量随深度的增大而减少。计算所得的溶解有机质的Mw和Mn在表层较小,在中部随深度基本保持不变,到底部又变大。这种变化趋势与分子量组分的变化结果一致。     

Dissolved organic matter removal using magnetic anion exchange resin treatment on biological effluent of textile dyeing wastewater

This study investigated the removal of dissolved organic matter（DOM） from real dyeing bio-treatment effluents（DBEs） with the use of a novel magnetic anion exchange resin（NDMP）.DOMs in two typical DBEs were fractionized using DAX-8/XAD-4 resin and ultrafiltration membranes. The hydrophilic fractions and the low molecular weight（MW）（〈3 kDa） DOM fractions constituted a major portion（〉50%） of DOMs for the two effluents. The hydrophilic and low MW fractions of both effluents were the greatest contributors of specific UV254absorbance（SUVA254）,and the SUVA254 of DOM fractions decreased with hydrophobicity and MW. Two DBEs exhibited acute and chronic biotoxicities. Both acute and chronic toxicities of DOM fractions increased linearly with the increase of SUVA254 value. Kinetics of dissolved organic carbon（DOC） removal via NDMP treatment was performed by comparing it with that of particle active carbon（PAC）. Results indicated that the removal of DOC from DBEs via NDMP was 60%,whereas DOC removals by PAC were lower than 15%. Acidic organics could be significantly removed with the use of NDMP. DOM with large MW in DBE could be removed significantly by using the same means. Removal efficiency of NDMP for DOM decreased with the decrease of MW. Compared with PAC,NDMP could significantly reduce the acute and chronic bio-toxicities of DBEs. NaCl/NaOH mixture regenerants,with selected concentrations of 10% NaCl（m/m）/1%NaOH（m/m）,could improve desorption efficiency.     

冻融作用对土壤中溶解性有机物的光谱学特性的影响

以受季节性冻融过程影响显著的辽宁省棕壤和暗棕壤为研究对象,考察了冻结温度、融化温度、冻结时间和冻融次数对土壤中溶解性有机物(DOM)的光谱学特性的影响.结果表明:冻融处理条件下土壤中的溶解性有机碳(DOC)含量、波长254 nm处的紫外吸光度(UV-254)和单位浓度DOC的紫外吸收值(SUVA)的变化规律相似,均随冷冻和融化温度的升高而增大,随冷冻时间的延长先减小后增大,随冻融次数的增多而减小.冻融作用使DOM的腐殖化程度提高,分子量减小.随着冷冻时间的延长,DOM中类富里酸荧光物质和类腐殖酸荧光物质的含量先减少后增多;随着冻融次数的增多,DOM中荧光物质的含量逐渐减少.研究成果对于准确掌握冻融条件下土壤中DOM的变化规律,以及实施有效的土壤生态环境和地表水流域环境管理具有重要的理论意义和实用价值.     

Improving biodegradation potential of domestic wastewater by manipulating the size distribution of organic matter

Carbon source is a critical constraint on nutrient removal in domestic wastewater treatment. However, the functions of particulate organic matter (POM) and some organics with high molecular weight (HMW) are overlooked in the conventional process, as they cannot be directly assimilated into cells during microbial metabolism. This further aggravates the problem of carbon source shortage and thus affects the effluent quality. Therefore, to better characterize organic matter (OM) based MW distribution, microfiltration/ultrafiltration/nanofiltration (MF/UF/NF) membranes were used in parallel to fractionate OM, which obtained seven fractions. Hydrolysis acidification (HA) was adopted to manipulate the MW distribution of dissolved organic matter (DOM) and further explore the correlation between molecular size and biodegradability. Results showed that HA pretreatment of wastewater not only promoted transformation from POM to DOM, but also boosted biodegradability. After 8 hr of HA, the concentration of dissolved organic carbon (DOC) increased by 65%, from the initial value of 20.25 to 33.48 mg/L, and the biodegradability index (BOD5 (biochemical oxygen demand)/SCOD (soluble chemical oxygen demand)) increased from 0.52 to 0.74. Using MW distribution analysis and composition optimization, a new understanding on the characteristics of organics in wastewater was obtained, which is of importance to solving low C/N wastewater treatment in engineering practice.     

High-performance size exclusion chromatography with a multi-wavelength absorbance detector study on dissolved organic matter characterisation along a water distribution system

This study examined the associations between dissolved organic matter(DOM) characteristics and potential nitrification occurrence in the presence of chloramine along a drinking water distribution system. High-performance size exclusion chromatography(HPSEC) coupled with a multiple wavelength detector(200–280 nm) was employed to characterise DOM by molecular weight distribution, bacterial activity was analysed using flow cytometry, and a package of simple analytical tools, such as dissolved organic carbon, absorbance at 254 nm, nitrate,nitrite, ammonia and total disinfectant residual were also applied and their applicability to indicate water quality changes in distribution systems were also evaluated. Results showed that multi-wavelength HPSEC analysis was useful to provide information about DOM character while changes in molecule weight profiles at wavelengths less than 230 nm were also able to be related to other water quality parameters. Correct selection of the UV wavelengths can be an important factor for providing appropriate indicators associated with different DOM compositions. DOM molecular weight in the range of 0.2–0.5 k Da measured at210 nm correlated positively with oxidised nitrogen concentration(r = 0.99), and the concentrations of active bacterial cells in the distribution system(r = 0.85). Our study also showed that the changes of DOM character and bacterial cells were significant in those sampling points that had decreases in total disinfectant residual. HPSEC-UV measured at210 nm and flow cytometry can detect the changes of low molecular weight of DOM and bacterial levels, respectively, when nitrification occurred within the chloraminated distribution system.