Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

藻类有机物的特性以及对超滤膜的污染

采用凝胶色谱、亲疏水性、荧光色谱等方法研究铜绿微囊藻类有机物的特性.结果表明,铜绿微囊藻类有机物(AOM)主要由亲水性组分构成,占78%,比紫外吸光度仅为1.1 L/(mg.m).超滤膜法测定结果表明,藻类有机物中相对分子质量30 000的有机物占40%以上,并且主要由中性亲水性组分构成.荧光色谱分析表明,AOM中含有蛋白质类和腐殖质类物质.膜过滤试验表明,藻类有机物对超滤膜造成严重的通量下降,这可归结为大分子的中性亲水性组分堵塞膜孔的缘故.     

藻源型溶解性有机氮的产生及不同时期藻类有机物的特性

研究了铜绿微囊藻藻细胞全生命周期中氮的转化过程以及藻类有机物的性质,结果表明:溶解性有机氮(DON)在藻类生长周期中总体呈现上升趋势,藻细胞在其生长初期释放量小于0.05mgDON/107cells,衰亡期释放能力约为0.40mgDON/107cells;胞外有机物(EOM)中分子量分布在对数期和衰亡期以100kDa为主,稳定期以100kDa范围内.三维荧光光谱分析表明,EOM中荧光物质主要为类腐植酸和溶解性微生物代谢产物;而IOM主要由类芳香蛋白和溶解性微生物代谢产物组成.     

FeOOH催化臭氧氧化滤后水中NOM的小分子副产物的生成

以滤后水中富集、分离出的6种不同特性的天然有机物(NOM)组分为对象,考察了羟基氧化铁（FeOOH）催化臭氧氧化NOM各组分后小分子醛、酮及酮酸副产物的生成情况.发现FeOOH催化氧化比臭氧氧化提高了对NOM 各组分DOC和SUVA的去除率.FeOOH催化氧化并不能有效地降低NOM各组分小分子副产物的产量.催化氧化和臭氧氧化后,憎水中性物质(HON)的醛、酮、酮酸的总产量都最高,NOM碱性组分的小分子副产物产量都相对最低.NOM各组分催化氧化后甲醛和丙酮酸的产量最大,这和单独臭氧氧化的结论一致.特别是HON的甲醛产率占其醛、酮总产量的71.6%,单位DOC丙酮酸的产量达78.6 μg/mg.用NOM组分的小分子副产物折算DOC占各组分氧化后DOC的质量分数来间接显示氧化后剩余DOC的可生物降解性,发现催化氧化比单独臭氧氧化进一步提高了滤后水中NOM各组分的可生化性.     

蓝藻AOM特征与DBPs生成关系的研究进展

蓝藻水华期间,藻细胞因自然生长或受水处理工艺影响(如预氧化和混凝),会向水中释放大量藻源有机物(AOM),能够与氯消毒剂反应生成大量消毒副产物(DBPs),增加了饮用水安全风险.了解AOM的特征及其对DBPs生成的影响对于AOM的控制和饮用水安全保障至关重要.本文综述了蓝藻AOM的主要理化特征(溶解性有机碳、溶解性有机氮、亲疏水性、光学特性、分子量、化学结构)及其对饮用水处理过程中AOM的削减转化规律和DBPs生成的影响,并讨论了AOM前体表征技术在蓝藻水处理过程中追踪AOM变化和预测DBPs的应用前景,最后展望了未来的研究方向.     

小球藻来源溶解有机质的光化学降解特性

利用三维荧光光谱-平行因子分析(EEM-PARAFAC)手段结合吸收光谱分析,研究了小球藻指数期和稳定期培养液中溶解有机物(DOM)在秋季天然太阳辐射作用下的光降解动力学特征.结果表明,小球藻生长过程中除能产生短波激发类腐殖质组分C1(其荧光峰的激发/发射波长位置为240,335 nm /406 nm)及类蛋白质组分C3(225,275 nm/334 nm)外,还会形成长波激发类腐殖质组分C2(260,395 nm /502 nm),表明C2组分并非仅有传统认为的陆源属性,同时也具有自生源属性.稳定期培养液的吸收光谱在250~300 nm范围内出现的肩峰,可用于指示水环境中现场自生源的贡献.不同生长时期培养液中DOM的吸收系数和荧光组分的降解动力学都符合一级反应方程.稳定期类腐殖质荧光组分(C1和C2)的光降解程度略高于指数期,但指数期类色氨酸组分(C3)的光降解程度略高于稳定期.经太阳辐照6 d后,小球藻培养液的吸收系数a₃₅₀及各荧光组分的平均损失率分别达到83.0%、84.0%、64.8%和80.0%,对应的半衰期只有1.6~5.0 d,揭示出藻类自生来源的DOM具有很强的光化学降解活性.     

两种海洋硅藻透明胞外聚合颗粒物的产生及其生态学意义

透明胞外聚合颗粒物（transparent exopolymer particles,TEP）是一类由胞外多糖组成的透明胶状颗粒物质,对海洋生态系统碳循环具有重要意义。本研究以两种海洋硅藻布氏双尾藻（Ditylume brightwelii）和窄隙角毛藻（Chaetoceros affinis）为研究对象,研究了其在不同生长时期的TEP含量、TEP与叶绿素a（Chlorophyll a,Chl a）的关系及TEP的C:N。结果表明:两种硅藻在整个生长时期均产生TEP,且在不同生长时期的TEP含量不同。布氏双尾藻和窄隙角毛藻最大TEP产量分别在指数期、衰亡期。窄隙角毛藻单位细胞体积和单位Chl a所产最大TEP含量分别是184.91±14.03 fg Xeq./μm3、38.06±4.96 μg Xeq./μg Chl a,高出布氏双尾藻相应单位TEP含量的16倍和5倍。对两种硅藻的Chl a与TEP关系分析表明,在指数期会呈现TEP=α（Chl a）β的函数关系（布氏双尾藻:R2=0.98;窄隙角毛藻:R2=0.80）。两种硅藻TEP的C:N均高于Redfield比值（C:N=106:16）。说明TEP的产生具有种间差异性,且生长时期显著影响TEP产生效率。TEP的高含碳量对海洋碳循环有直接贡献。     

不同相对分子质量的有机物对膜通量的影响

采用截留分子量分别为10、30kDa的聚醚砜膜和100kDa的聚偏氟乙烯膜对原水进行分级处理,并采用截留分子量分别为150kDa的聚偏氟乙烯膜和0.1μm的醋酸纤维素膜对出水进行膜过滤试验,研究不同相对分子质量的有机物对膜通量的影响.结果表明,虽然相对分子质量>30kDa的大分子有机物仅为总有机物的15%,但它分别引起微滤膜的通量下降86%和超滤膜通量下降54%.混凝处理可以去除相对分子质量>100kDa的有机物,这部分有机物导致通量下降40%以上.因此,尽管混凝处理仅去除10%的有机物,但改善通量的效果显著.粉末活性炭可以去除相对分子量<30kDa的小分子有机物,这部分有机物对通量下降的贡献程度甚低.因此,尽管粉末活性炭去除76%的有机物,但改善通量的效果甚微.预处理改善通量的效果并不取决于去除有机物的多少,而是取决于所去除的有机物对通量的影响大小.     

荷电超滤膜对天然有机物去除及膜污染行为的影响

以Aldrich 腐殖酸溶液为水样,研究比较了溶液环境(pH值、离子强度和钙离子)对荷电改性再生纤维素超滤膜和传统中性未改性再生纤维素超滤膜过滤过程的影响.结果表明, ①pH值主要通过质子化作用影响荷电膜以及腐殖酸分子的荷电量,进而影响荷电超滤过程.溶液pH值从7.5下降到3.5时,荷电超滤膜对腐殖酸的截留率从92%减少到79%,超滤4 h时,膜通量下降从26%增加到36%.②离子强度的改变是通过影响腐殖酸分子的物化性质和静电屏蔽作用来影响超滤过程的.当溶液离子强度为0、 3和100 mmol/L时,初始截留率依次降低,分别为92%、 87%和48%,超滤4 h时,荷电超滤膜的通量下降依次增加,分别为26%、 35%和63%.③Ca2+浓度的影响,需要综合考虑静电屏蔽作用、Ca2+的架桥作用以及滤饼层的压实性等各方面的影响.④pH值、离子强度和钙离子对中性超滤膜过滤行为的影响趋势与荷电超滤膜相似,但其影响程度有着较大的差别.研究结果对荷电超滤膜技术在实际应用中选择合适环境条件提供了参考.     

The role of extracellular organic matter on the cyanobacteria ultrafiltration process

The membrane fouling caused by extracellular organic matter (EOM) and algal cells and organic matter removal of two typical cyanobacteria (M. aeruginosa and Pseudoanabaena sp.) during ultrafiltration (UF) process were studied in this work. The results showed that EOM had a broad molecular weight (Mw) distribution and the irreversible membrane fouling was basically caused by EOM. Moreover, humic acid and microbial metabolites were major components of EOM of two typical cyanobacteria. Since EOM could fill the voids of cake layers formed by the algal cells, EOM and algal cells played synergistic roles in membrane fouling. Fourier transform infrared spectroscopy analysis indicated that the CH₂ and CH₃ chemical bonds may play an important role in membrane fouling caused by EOM. Interestingly, the cake layer formed by the algal cells could trap the organic matter produced by algae and alleviate some irreversible membrane fouling. The results also showed that although the cake layer formed by the algal cells cause severe permeate flux decline, it could play a double interception role with UF membrane and increase organic matter removal efficiency. Therefore, when using UF to treat algae-laden water, the balance of membrane fouling and organic matter removal should be considered to meet the needs of practical applications.     

高锰酸钾对水中天然有机物氯化活性的影响

利用树脂分离技术将水中天然有机物分为腐殖酸(HA)、富里酸(FA)、亲水酸(HPIA)和其它亲水物质(HPI-NA)等4部分,研究了高锰酸钾对不同有机组分卤代活性的影响.结果表明,高锰酸钾增加了腐殖酸和其它亲水物质加氯的卤代活性,降低了富里酸和亲水酸的卤代活性,如投加0.75 mg/L高锰酸钾时,腐殖酸和其它亲水物质的卤代活性增加了39.3%和13.8%,而富里酸和亲水酸卤代活性降低了33.6%和46.9%;通过对SUVA的考察可知,高锰酸钾增加了腐殖酸和其它亲水物质的碳碳不饱和双键的含量,使其卤代活性增     

臭氧氧化对天然有机物在氧化铝表面吸附行为的影响

为进一步明确臭氧预氧化对颗粒的脱稳作用,选用氧化铝（α-Al₂O₃）作为悬浮颗粒,考察了臭氧氧化后天然有机物（natural organic matters,NOM）特性及吸附行为的变化.结果表明,臭氧氧化能够破坏NOM的芳香结构,SUVA值降低25%～35%,氧化后酸性官能团含量增多,总酸度增加0.3～1.4 mmol·g^-1,分子量和极性的变化与NOM的性质有关;有机物初始浓度相对于臭氧投量较低时,NOM的溶解性增强,与其酸性官能团增加产生的吸附促进作用相抵消,因而吸附性能出现不变甚至降低的现象;有机物初始浓度较高时,臭氧能够起到强化NOM吸附的作用.采用2.5　mg·L^-1臭氧进行氧化后,以商用腐殖酸为代表的NOM的吸附形貌,由密集分布的球形对称聚集结构向网状结构过渡,分子之间的交联作用十分明显,吸附高度低于其氧化处理前,云母的表面覆盖率较氧化前略有提高.     

Effects of a dynamic membrane formed with polyethylene glycol on the ultrafiltration of natural organic matter

The formation of a dynamic membrane (DM) was investigated using polyethylene glycol (PEG) (molecular weight of 35000 g/mol, concentration of 1 g/L). Two natural organic matters (NOM), Dongbok Lake NOM (DLNOM) and Suwannee River NOM (SRNOM) were used in the ultrafiltration experiments along with PEG. To evaluate the effects of the DM with PEG on ultrafiltration, various transport experiments were conducted, and the analyses of the NOM in the membrane feed and permeate were performed using high performance size exclusion chromatography, and the effective pore size distribution (effective PSD) and effective molecular weight cut off (effective MWCO) were determined. The advantages of DM formed with PEG can be summarized as follows: (1) PEG interferes with NOM transmission through the ultrafiltration membrane pores by increasing the retention coefficient of NOM in UF membranes, and (2) low removal of NOM by the DM is affected by external factors, such as pressure increases during UF membrane filtration, which decreases the effective PSD and effective MWCO of UF membranes. However, a disadvantage of the DM with PEG was severe flux decline; thus, one must be mindful of both the positive and negative influences of the DM when optimizing the UF performance of the membrane.     

臭氧氧化饮用水过程中可同化有机碳生成的影响因素

研究臭氧化过程中,臭氧投加量、p H值和离子强度对可同化有机碳(assimilable organic carbon,AOC)生成量的影响.结果表明,臭氧投加量在1~5 mg·L~(-1)范围,AOC的生成量随着投加量的增加而增加,但过高的臭氧投加量(9 mg·L~(-1))反而导致AOC生成量下降.p H越高(6~9),AOC的生成量也越高.AOC的生成量随着离子强度的升高而下降.臭氧氧化强疏组分AOC的生成量最高,其次为弱疏,而极亲和中亲最低.研究发现,AOC的生成量与小分子有机物的SUVA有密切的关系,较低的SUVA产生较多的AOC.     

磷对四尾栅藻代谢有机物生成规律的影响

通过改变培养基中ρ(TP),并结合TOC(总有机碳)分析、考马斯亮蓝法、蒽酮硫酸法和茚三酮法研究不同ρ(TP)对水华中常见绿藻——四尾栅藻的生长规律及其IOMs(胞内有机物)和EOMs(胞外有机物)中TOC、蛋白质、碳水化合物和氨基酸代谢规律的影响. 结果表明,随着ρ(TP)的增加,四尾栅藻生长的指数期变长. ρ(TP)为0.01 mg/L时有利于四尾栅藻EOMs中碳水化合物的形成与积累,ρ(碳水化合物)在指数期达到最大,为89.25 mg/L;ρ(TP)为0.20 mg/L时则有利于四尾栅藻EOMs中氨基酸的形成,并且ρ(氨基酸)在稳定期达到最大,为13.72 mg/L. ρ(TP)为0.01 mg/L时有利于四尾栅藻IOMs中氨基酸的形成,ρ(氨基酸)在指数期达到最大值(21.85 mg/L). 利用EEM(三维荧光)对四尾栅藻的EOMs和IOMs进行表征发现,ρ(TP)的改变会对四尾栅藻IOMs和EOMs中不同物质的峰强产生影响;同时,随着藻细胞的生长,ρ(TP)也会影响四尾栅藻EOMs中的物质组成.      

溶解性有机物对冰相中蒽和芘光降解的影响

以Suwannee River Fulvic Acid Standard II(SRFA)、Upper Mississippi River NOM(UMRN)、Elliott Soil Humic Acid Standard IV(ESHA)和Leonardite Humic Acid Standard(LHA) 4种溶解性有机物(Dissolved Organic Matter, DOM)为研究对象,利用125 W高压汞灯作为模拟光源进行室内模拟光解实验,考察了DOM对冰相中蒽和芘光降解的影响.其中,SRFA和UMRN是水源DOM,ESHA和LHA是陆源DOM.结果表明,蒽和芘在冰相中均可以发生直接光降解.4种DOM对冰相中蒽和芘光降解的影响行为并不相同,水源DOM对冰相中蒽和芘光降解的影响程度小于陆源DOM.DOM对冰相中蒽和芘光降解的抑制以光屏蔽效应为主.4种DOM对冰相中蒽和芘光降解均产生淬灭效应,但淬灭程度相异,DOM对蒽激发态的淬灭程度高于其对芘激发态的淬灭程度.与DOM共存条件下,冰相中芘的表观光解速率常数与DOM的SUVA值具有显著正相关性(p0.01).     

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.     

光照、温度和氮磷限制对6种典型鱼毒性藻类生长及产毒的影响

为了探究温度、光照、和营养盐对鱼毒性藻类产毒的影响,本文分析了6种我国沿海典型具溶血活性的鱼毒性藻类在不同温度(15℃,25℃,30℃)、光照强度(20 mol/m2/s,60 mol/m2/s,100 mol/m2/s)、氮磷限制(1:1;1:16;1:128)条件下的生长和溶血活性的变化。结果表明,鱼毒性藻类的溶血活性在不同生长期差异明显。海洋卡盾藻(香港株)(Chattonella marina)、卵圆卡盾藻(C.ovata)、米氏凯伦藻(Karenia mikimotoi)、赤潮异弯藻(Heterosigma akashiwo)在对数期溶血活性较高,衰亡期溶血活性较低,而球形棕囊藻(Phaeocystis globosa)与小定鞭藻(Prymnesium parvum)在稳定期溶血活性最高,对数期溶血活性最低。藻类的培养环境和营养条件对鱼毒性藻类溶血毒素的合成有明显的影响,在光照强度、温度和氮磷限制条件下,藻类单个细胞的溶血活性会发生明显变化,6种藻类的溶血活性均随光照强度的升高而增强,在培养温度15~30℃范围内,除球形棕囊藻外,其他5种藻类的单个藻细胞溶血活性随温度的上升而增加,氮磷限制可促进溶血毒素的合成。     

东江水源水中有机物分子量分布特征研究

采用超滤膜法考察了东江水源水中有机物分子量分布特点,研究了东江泄洪和不泄洪水源水中有机物分子量分布的变化特征。结果表明,东江水源水在不泄洪期间水源水中的溶解性有机物主要为小分子量的有机物。而在泄洪期间,东江水源水中溶解性有机物主要为大分子量的有机物。UV254的分布和有机物分子量分布一致,DOC与UV254具有良好的相关性。泄洪期间水源水中SUVA值小于3,水体中有机物很难通过常规混凝工艺去除,此结果与水厂的实际运行情况相吻合。     

Comparison of zinc complexation properties of dissolved organic matter from surface waters and wastewater treatment plant effluents

Abstract: Unlike natural organic matter(NOM), wastewater organic matter(WWOM) from wastewater treatment plant effluents has notbeen extensively studied with respect to complexation reactions with heavy metals such as copper or zinc. In this study, organic matter trom sunface waters and a wastewater treatment plant effluent were concentrated by reverse osmosis(FIC)) method. The samples were treated in the laboratory to remove trace metals and major cations. The zinc complexing properties of both NOM and the WVVOM were studied by square wave anodic stripping voltammetry(SWASV). Experimental data were compared to predictions using the Windermere Humic Aqueous Model(WHAM) Version Ⅵ. We found that the zinc binding of WVVOM was much stronger than that of NOM and not well predicted by WHAM.This suggests that in natural water boodies that receive wastewater teatment plant effluents the ratio of WWOM to NOM must be taken into account in order to accurately predict ferr zinc activities.