Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride(FeCl3), aluminum sulfate(Al2(SO4)3),polyaluminum chloride(PACl) and composite polyaluminum(HPAC), in order to remove dissolved organic matter(DOM). Considering the disinfection byproduct(DBP) precursor treatability, DOM was divided into five chemical fractions based on resin adsorption.Trihalomethane formation potential(THMFP) and haloacetic acid formation potential(HAAFP) were measured for each fraction. The results showed that hydrophobic acids(HoA), hydrophilic matter(HiM) and hydrophobic neutral(HoN) were the dominant fractions.Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally,HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation.HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions.DOC removal was highest for enhanced coagulation using FeCl3 while DBPFP was lowest using PACl. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PACl under enhanced coagulation could reach51% and 59% respectively.     

Effects of pre-ozonation on organic matter removal by coagulation with IPF-PACI

Ozone plays an important role as a disinfectant and oxidant in potable water treatment practice and is increasingly being used as a pre-oxidant before coagulation. The purpose of this study is to obtain insight into the mechanisms that are operative in pre-ozonized coagulation. Effects ofpre-ozonation on organic matter removal during coagulation with IPF-PAC1 were investigated by using PDA （photometric disperse analysis）, apparent molecular weight distribution and chemical fractionation. The dynamic formation of flocs during coagulation process was detected. Changes of aquatic organic matter （AOM） structure resulted from the influence of pre-ozonation were evaluated. Results show that dosage of O3 and characteristics of AOM are two of the major factors influencing the performance of O3 on coagulation. No significant coagulation-aid effect of O3 was observed for all experiments using either A1C13 or PAC1. On the contrary, with the application of pre-ozonation, the coagulation efficiency of A1C13 was significantly deteriorated, reflected by the retardation of floc formation, and the removal decreases of turbidity, DOC, and UV254. However, if PACl was used instead of AlCl3, the adverse effects of pre-ozonation were mitigated obviously, particularly when the O3 dosage was less than 0.69 （mg O3/mg TOC）. The difference between removals of UV254, and DOC indicated that pre-ozonation greatly changed the molecular structure of AOM, but its capability of mineralization was not remarkable. Only 5% or so DOC was removed by pre-ozonation at 0.6--0.8 mg/L alone. Fractionation results showed that the organic products of pre-ozonation exhibited lower molecular weight and more hydrophilicity, which impaired the removal of DOC in the following coagulation process.     

Preferential binding between intracellular organic matters and Al13 polymer to enhance coagulation performance

Coagulation is the best available method for removing intracellular organic matter (IOM), which is released from algae cells and is an important precursor to disinfection by-products in drinking water treatment. To gain insight into the best strategy to optimize IOM removal, the coagulation performance of two Al salts, i.e., aluminum chloride (AlCl₃) and polyaluminum chloride (PACl, containing 81.2% Al₁₃), was investigated to illuminate the effect of Al species distribution on IOM removal. PACl showed better removal efficiency than AlCl₃ with regard to the removal of turbidity and dissolved organic carbon (DOC), owing to the higher charge neutralization effect and greater stability of pre-formed Al₁₃ species. High pressure size exclusion chromatography analysis indicated that the superiority of PACl in DOC removal could be ascribed to the higher binding affinity between Al₁₃ polymer and the low and medium molecular weight (MW) fractions of IOM. The results of differential log-transformed absorbance at 254 and 350?nm indicated more significant formation of complexes between AlCl₃ and IOM, which benefits the removal of tryptophan-like proteins thereafter. Additionally, PACl showed more significant superiority compared to AlCl₃ in the removal of < 5?kDa and hydrophilic fractions, which are widely viewed as the most difficult to remove by coagulation. This study provides insight into the interactions between Al species and IOM, and advances the optimization of coagulation for the removal of IOM in eutrophic water.     

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.     

Drinking water treatment using a submerged internal-circulation membrane coagulation reactor coupled with permanganate oxidation

A submerged internal circulating membrane coagulation reactor(MCR) was used to treat surface water to produce drinking water. Polyaluminum chloride(PACl) was used as coagulant,and a hydrophilic polyvinylidene fluoride(PVDF) submerged hollow fiber microfiltration membrane was employed. The influences of trans-membrane pressure(TMP), zeta potential(ZP) of the suspended particles in raw water, and KMnO_4 dosing on water flux and the removal of turbidity and organic matter were systematically investigated. Continuous bench-scale experiments showed that the permeate quality of the MCR satisfied the requirement for a centralized water supply, according to the Standards for Drinking Water Quality of China(GB 5749-2006), as evaluated by turbidity(1 NTU) and total organic carbon(TOC)(5 mg/L)measurements. Besides water flux, the removal of turbidity, TOC and dissolved organic carbon(DOC) in the raw water also increased with increasing TMP in the range of 0.01–0.05 MPa. High ZP induced by PACl, such as 5–9 mV, led to an increase in the number of fine and total particles in the MCR, and consequently caused serious membrane fouling and high permeate turbidity.However, the removal of TOC and DOC increased with increasing ZP. A slightly positive ZP, such as 1–2 mV, corresponding to charge neutralization coagulation, was favorable for membrane fouling control. Moreover, dosing with KMnO_4 could further improve the removal of turbidity and DOC, thereby mitigating membrane fouling. The results are helpful for the application of the MCR in producing drinking water and also beneficial to the research and application of other coagulation and membrane separation hybrid processes.     

南水北调丹江口水库原水有机物分子组成规律及其强化混凝处理的效能对比

以取自南水北调中线工程的丹江口水库原水作为研究对象,考察了丹江口水库原水中有机物的分子量大小和亲疏水性分子组成规律,并确定了其所适用的强化混凝工艺条件.分离试验表明,丹江口原水中有机物主要以小分子量形式存在.其中,1 000组分的溶解性有机碳(DOC)和UV254所占比例最大,分别为39.98%和39.10%,且此区间还具有最高的三卤甲烷生成潜能(THMFP)和含氮消毒副产物生成潜能(N-DBPFP).亲疏水性方面,原水中弱疏水性组分含量最高,疏水性有机物的比例用DOC表征时超过80%.强疏水性组分含量最低但是强疏水性组分的THMFP最大,占总量的57.31%,而各组分的NDBPFP则相差不大.混凝试验表明,当采用聚合硫酸铁(PFS,4 mg·L-1)和聚丙烯酰胺(PAM,0.4 mg·L-1)处理丹江口原水时,强化混凝效果最好,可实现较为有效的去除浊度(76.33%)、DOC(25.57%)、UV254(37.78%)及THMFP(23.16%).本研究成果可为南水北调河南受水区既有水厂升级改造与工艺的优化运行提供有效的理论和技术支持.     

强化混凝对二级处理出水中溶解性有机物特性的影响

以沈阳市B污水处理厂二级处理出水为研究对象,采用FeCl3.6H2O作为混凝剂,研究了强化混凝对二级处理出水中溶解性有机物(DOM)的卤代活性和荧光特性的影响.按照DOM在XAD树脂上的吸附特性将其分为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,强化混凝(混凝剂投加量为80mg.L-1,pH=5.00)对DOC的去除率为55.3%.强化混凝对HPO-A的去除率最高,而对HPI的去除率最低.强化混凝后,HPO-N的三卤甲烷生成活性(STHMFP)上升,而其他4种DOM组分的STHMFP下降.强化混凝能够有效去除类富里酸荧光物质和具有高环数和高聚合度的稠环类芳香性荧光物质.强化混凝对DOM组分的去除率和DOM组分的荧光强度下降率的相关性不显著.     

强化絮凝法去除水中DBP先质研究

采用强化絮凝的方法，实验研究和探明了混合反应强度，浊度，ＰＨ值等因素对去除水中ＤＢＰ先质的影响规律，进一步揭示了强化絮凝条件下除浊与除ＤＢＰ先质的相互关系，求得了不同水质条件下的最佳ＰＨ值和最佳投药量。     

臭氧对有机物混凝的影响

采用PDA(Photometric Disperse Analysis)和有机物表观分子量分级、有机物化学极性分级技术从絮体形成过程、絮体表现、有机物分子水平变化等方面研究了臭氧预氧化对混凝过程的影响;并对比了不同混凝剂在预臭氧条件下的混凝过程和效率.结果表明:臭氧预氧化对混凝过程有复杂的影响,其剂量和水体有机物特征决定了其对混凝的整体影响效果.有机物分级显示,臭氧化对有机物结构有重要影响,导致有机物极性、亲水性组分含量大幅提高(36.7%),小分子量组分(<10×10³)大幅增高(100%左右);但总的DOC去除率不高(3.28%).对PACl而言,在中、低剂量(O₃/TOC<0.7)下,臭氧对絮体形成过程影响较小,但对絮体沉降性和浊度去除已经有阻碍作用.在中、高剂量下(O₃/TOC>0.7),对絮体形成有显著滞后,浊度、有机物去除效率下降.AlCl₃对臭氧化作用反应敏感,臭氧化在试验剂量条件下,对絮体形成和浊度、有机物去除都有明显的阻碍作用.     

滤后水中NOM经臭氧氧化产生的小分子醛、酮和酮酸

以富集、分离得到的滤后水中6种不同特性的天然有机物(NOM)为对象,测定了臭氧氧化NOM各组分后小分子醛、酮及酮酸的生成情况.NOM各组分臭氧氧化后甲醛和丙酮酸产量最大,特别是憎水中性物质(HON)的甲醛产率是其醛、酮总产率的70.58%,单位DOC丙酮酸的产率达103.2 μg/mg;憎水性NOM组分的小分子醛、酮、酮酸产率比亲水性组分的高,特别是憎水中性物质(HON)和憎水酸(HOA)的小分子醛、酮及酮酸类总产率最高,二者之和分别占NOM各组分的醛酮总产率及酮酸总产率的55.56%和60%; NOM碱性组分的醛、酮、酮酸产量最低.用小分子醛、酮、酮酸总量折算DOC占氧化后NOM的DOC的百分比作为衡量氧化后各组分可生物降解性的参考,则臭氧氧化后HON和HOA的可生物降解性比其他组分高得多.     

强化混凝-光电氧化组合技术深度处理垃圾渗滤液

采用铁锰氧化物+聚合氯化铝(PACI)混凝和光电氧化技术处理已生化处理过的垃圾渗滤液,研究了组合工艺对渗滤液化学需氧量(COD)、总有机碳(TOC)、氨氮和色度的去除效果.结果表明,在一定铁锰复合氧化物投量下,加入PACI共同混凝可以取得较好的有机物去除效果,当铁锰氧化物投舒为600 mg·L-1,PACI投量为100...     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter(NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon(DOC) in the source water. KMn O4pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O3+ activated carbon treatment are another available technology for eliminating the color and UV254 in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organic matter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2%of color, 96.0% of UV254 and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

城市景观水体混凝除藻过程对氮元素协同去除特性初探

以城市景观水体净化为目标,考察混凝除藻同时去除氮元素的特性和影响因素. 结果发现,水体内较高的DOC(溶解性有机质)含量会阻碍藻浊度的去除. 聚合氯化铝(PACl)以及PACl与硫酸铝(Alum)的复合剂(PACl+Alum)对藻浊度的去除效果均相对单独使用PACl或Alum较好,其中PACl+Alum对其他物质(如氮、DOC等)的去除效果也相对单独使用PACl或Alum更佳;在同样的最佳投药量时,低pH条件能获得更好的藻浊度去除率;对氮元素去除的进一步研究发现,DON(溶解性有机氮)的去除特征和过程与TN(总氮)非常一致,表明该水体TN的去除主体上是通过DON的去除实现的;低pH条件同样有利于氮和DOC的去除;但DOC与DON去除的不同步性,说明DOC中的DON成分和性质是非均一性的,是未来可进一步深入研究的重要方向.      

炼油厂达标废水中溶解性有机物的表征

采用超滤和凝胶色谱法调查了炼油厂达标废水中溶解性有机物 (DOM)的分子量分布 ,并用树脂吸附和离子交换技术研究了该废水DOM中疏水性酸 (HoA)、碱 (HoB)及中性物 (HoN)和亲水性酸 (HiA)、碱 (HiB)及中性物 (HiN)的比例 ,用气相色谱 质谱法 (GC MS)定性分析了疏水性有机物的组成 .结果表明 ,某炼油厂达标废水的TOC为 12 0 6～ 16 80mg·L-1,其中溶解性有机碳 (DOC)为 10 15～ 14 4 4mg·L-1;分子量 <1k的DOM约为 80 % (以TOC计 ) ;DOM中HiN、HoN、HoA、HiB、HoB及HiA的含量分别为 2 9 7% ,2 6 5 % ,2 1 1% ,13 4 % ,5 1%及 4 2 % .鉴定出的HoN包括脂肪烃、苯系物、含硫化合物及邻苯二甲酸酯类化合物等 ,其中C10和C11脂肪烃、甲基亚硫酰苯及邻苯二甲酸二丁脂化合物的含量相对较高 .根据表征结果提出了回用处理建议.     

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.     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter (NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon (DOC) in the source water. KMnO₄ pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O₃ + activated carbon treatment are another available technology for eliminating the color and UV₂₅₄ in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organicmatter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2% of color, 96.0% of UV₂₅₄ and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

典型南方水强化混凝有机物分级处理研究

采用强化常规工艺,对有效去除水体有机物,降低DBP前驱物进行了系统研究.通过烧杯试验和现场试验(中试和生产性试验)对强化混凝和使用PAM作助凝剂进行了对比;着重利用吸附树脂DAX-8的选择性吸附作用,测定了原水、沉后水的有机物分离分级组成状况.发现强化混凝和助凝强化对亲水性致UV₂₅₄物质有较好地处理效果,去除率可达90%以上;现场条件下强化混凝对疏水碱性物和疏水酸性物有较好的处理能力,相应去除率分别为66%和35%;助凝强化对亲水性有机物效果较好,相应去除率为45%左右;但二者总体去除TOC效果相当.     

Changes in different organic matter fractions during conventional treatment and advanced treatment

XAD-8 resin isolation of organic matter in water was used to divide organic matter into the hydrophobic and hydrophilic fractions. A pilot plant was used to investigate the change in both fractions during conventional and advanced treatment processes. The treatment of hydrophobic organics (HPO), rather than hydrophilic organicas (HPI), should carry greater emphasis due to HPO’s higher trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP). The removal of hydrophobic matter and its transmission into hydrophilic matter reduced ultimate DBP yield during the disinfection process. The results showed that sand filtration, ozonation, and biological activated carbon (BAC) filtration had distinct influences on the removal of both organic fractions. Additionally, the combination of processes changed the organic fraction proportions present during treatment. The use of ozonation and BAC maximized organic matter removal e ciency, especially for the hydrophobic fraction. In sum, the combination of pre-ozonation, conventional treatment, and O3-BAC removed 48% of dissolved organic carbon (DOC), 60% of HPO, 30% of HPI, 63% of THMFP, and 85% of HAAFP. The use of conventional treatment and O3-BAC without pre-ozonation had a comparable performance, removing 51% of DOC, 56% of HPO, 45% of HPI, 61% of THMFP, and 72% of HAAFP. The e ectiveness of this analysis method indicated that resin isolation and fractionation should be standardized as an applicable test to help assess water treatment process e ciency.     

污水厂出水DOM的分级及三卤甲烷生成势研究

研究目的在于调查寒冷季节城市污水处理厂出水中天然有机物化学组分分级,探讨各分级组分与消毒副产物生成潜能间之关系。采集污水厂二级出水,以三种不同树脂把污水厂出水中有机物分离成六类不同组分,其中A水厂含量最高的物质为亲水酸性物质(33%)而B水厂的疏水性中性物质含量最多约占总有机物的64%。从总体来看两水厂的疏水性物质含量大于亲水性物质含量,疏水性物质的三卤甲烷生成势也较大,是水体中消毒副产物的主要前驱物质。疏水性有机物质较多,代表受生活污水污染严重,得知该城市污水主要受民生污染较多。     

混凝沉淀-UF工艺去除二级出水中ARGs效能研究

为了研究混凝沉淀-UF工艺对城市污水处理厂二级出水中ARGs（抗生素抗性基因）去除的影响,以PACl（聚合氯化铝）和PFS（聚合硫酸铁）作为混凝剂,采用qPCR（实时荧光定量聚合酶链式反应）和EEM（三维荧光光谱）等分析混凝沉淀-UF工艺对ARGs的削减及其影响因素.结果表明:① PACl、PFS投加量（分别以Al、Fe计,下同）分别为0.85、0.50 mmol/L时,与直接UF工艺相比,混凝沉淀-UF工艺对水中各类ARGs的去除量高2~3个数量级,其中PACl-UF工艺的效果更好,去除量为2.51~3.52个数量级;对水中DOC（溶解性有机碳）、富里酸类及溶解性微生物代谢产物的去除效果更好,DOC去除率由18%升至36%.②直接UF、PACl-UF、PFS-UF 3种工艺膜进、出水的线性拟合结果显示,ARGs浓度与ρ（DOC）、16S rDNA浓度均呈显著正相关.研究显示,混凝沉淀-UF工艺可以有效去除二级出水中的ARGs,且有机物、16S rDNA的去除有助于ARGs的削减.