Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.     

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.     

两种工艺对污水再生水中微量有机物的去除效果

以20种微量有机污染物为目标物,针对北京市2个再生水厂的不同工艺,系统地考察了污水再生水中目标化合物的去除效果,并采用重组酵母雌激素活性筛检法(YES法)对再生水中雌激素活性进行评价.结果表明,超滤(UF)+臭氧(O3)氧化处理工艺可有效地去除微量有机污染物,出水中雌二醇当量浓度(EEQ)低于YES法检出范围.A2/O+膜生物反应器(MBR)+反渗透(RO)处理工艺对微量有机污染物有很高的去除能力,出水中可检测出的目标化合物较少.2种工艺均可降低再生水的环境风险,保障其使用安全.     

油田采出水膜法处理技术应用研究进展

油田采出水的处理回用是一种必然的趋势.膜法处理技术可以解决传统水处理中存在的问题,有效地去除采出水中的油类、细菌、硬度,防止油层堵塞、结垢和外排水的环境污染,对于促进油气田可持续发展、水资源再利用和环境保护具有非常重要的意义.微滤、超滤和纳滤、反渗透膜技术在油田采出水处理中已有较多的应用研究.超滤在除油和除浊方面表现出...     

Pyrene partition behavior to the NOM: Effect of NOM characteristics and its modification by ozone preoxidation

Hydrophobic organic contaminants (HOCs)—pyrene, and natural organic matters (NOM) from different sources were taken as the test compounds to investigate the impact of physicochemical characteristics of NOM on HOCs’ partition to the NOM in this study. The effects of solution property, NOM characteristics, and modification by ozone preoxidation on pyrene partition to NOM were systematically evaluated. According to the fluorescence quenching method, the partition coefficient K _oc of pyrene to NOM was calculated, which was found to have a great relationship with the aromatic structures and hydrophobic functional groups of the NOM. The NOM characteristic modification corresponding to solution property could influence the interactions between the NOM and pyrene. Preozonation could destroy the aromatic or hydrophobic structures of the NOM and decrease K _oc of pyrene.     

QCM-D与AFM联用解析EfOM在SiO2改性PVDF超滤膜表面的吸附机制

为了进一步从微观角度上研究不同过滤阶段出水有机物(Ef OM)在纳米Si O2改性超滤膜表面的具体吸附机制,通过调节Si O2添加比例从而获得不同改性程度的实际膜.借用耗散型石英晶体微天平(QCM-D)与原子力显微镜(AFM)联用技术分别测定Ef OM在膜表面的吸附情况和Ef OM与膜之间的相互作用力.QCM-D实验结果与分析表明,膜表面的亲水性越好,膜表面Ef OM吸附量就越少,以及Ef OM在膜表面的吸附速率明显减缓.实验结果还发现,Ef OM的吸附经历了两个阶段:在初始阶段(15 min内),有机物快速吸附到膜表面并堆积;当Ef OM的吸附频率达到平衡时,耗散却处于非平衡状态,该现象说明虽然Ef OM在膜表面的吸附量达到稳定,但其吸附层的构象却仍在发生变化.AFM测定结果证明,随着亲水性的不断改善,Ef OM-膜、Ef OM-Ef OM之间的作用力均有所减小,该结果揭露了膜面Ef OM吸附量减少吸附速率下降的本质原因.QCM-D与AFM的联用有效地解释了膜改性对Ef OM吸附机制的影响.     

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.     

光催化/活性炭/纳滤组合工艺处理二级出水及对膜污染的控制

污水的资源化与回用可作为城市和各类建筑的非传统水源,必须满足相关水质标准,其中有机物一直是广泛关注的重要指标.本文采用华北某市大型污水厂的二级出水,研究了二氧化钛光催化氧化(UV-TiO_2)和颗粒活性炭(GAC)技术对溶解性有机物的去除特性以及对纳滤(NF)的膜污染控制特性,构建了UV-TiO_2/GAC/NF组合工艺,评价了组合工艺的有机物去除效能和膜污染控制作用,解析了影响NF膜污染程度的有机物种类和相对分子质量分布特征.结果表明,UV-TiO_2和GAC技术均可不同程度地缓解NF膜的不可逆污染、降低膜通量衰减速率; UV-TiO_2/GAC联用的不可逆膜污染程度比单独UV-TiO_2或GAC技术分别降低了48. 7%或61. 4%.类蛋白质和类腐殖质等有机污染物是不可逆膜污染的主要组分;相对分子质量为小于3×10~3和30×10~3～100×10~3的有机物是造成纳滤膜通量下降的主要因素. UV-TiO_2/GAC/NF组合工艺的COD、DOC和UV_(254)去除率为45. 7%、74. 5%和89. 2%,出水中COD、DOC和UV_(254)等有机物指标均得到有效去除.研究成果为城市和各类建筑非传统水源的深度净化与多途径回用提供了技术支持.     

Removal of polycyclic aromatic hydrocarbons and phenols from coking wastewater by simultaneously synthesized organobentonite in a one-step process

The optimal condition for a one-step process removing organic compounds from coking wastewater by simultaneously synthesized organobentonite as a pretreatment was investigated. Results showed that sorption of organic compounds by organobentonite was positively correlated to the cation surfactant exchange on the bentonite and the octanol-water partition coefficient (K_ow) of the solutes. With 0.75 g/L bentonite and 180 mg/L (60% of bentonite cation exchange capacity) cetyltrimethylammonium bromide, the removal efficiencies of the 16 polycyclic aromatic hydrocarbon (PAHs) specified by the US Environmental Protection Agency in coking wastewater except naphthalene were more than 90%, and that of benzo(a)pyrene was 99.5%. At the same time, the removal efficiencies of COD_Cr, NH₃-N, volatile phenols, colour and turbidity were 28.6%, 13.2%, 8.9%, 55% and 84.3%, respectively, and the ratio of BOD₅/COD_Cr increased from 0.31 to 0.41. These results indicated that the one-step process had high removal efficiency for toxic and refractory hydrophobic organic compounds, and could improve the biodegradability of the coking wastewater. Therefore it could be a promising technology for the pretreatment of toxic and refractory organic wastewater.     

DOM对纳滤膜去除磺胺甲恶唑效果影响研究

试验研究几种不同可溶性有机物(DOM)对纳滤膜(NF)去除抗生素磺胺甲恶唑(SMZ)的影响效果.试验所用DOM选定腐殖酸(HA)、单宁酸(TA)和海藻酸钠(SA).结果显示3种DOM对SMZ去除率和通量影响迥异,并与DOM的亲疏水性有密切的关系.为更好了解DOM对NF去除SMZ的影响机理,试验对臭氧化HA也进行了研究.臭氧化HA相对于臭氧前HA亲水性显著提高,对SMZ去除率的影响相应提高.结果表明在有多种DOM共同存在的天然原水中,SMZ的去除机理十分复杂,DOM的本身物理化学性质对于目标物的去除效果十分重要.     

Degradation of dissolved organic matter in effluent of municipal wastewater plant by a combined tidal and subsurface flow constructed wetland

Dissolved organic matter (DOM) is an important constituent of wastewater treatment plant (WWTP) effluent. A novel combined tidal and subsurface flow constructed wetland (TF-SSF-CW) of 90 L was constructed for a ten-month trial of advanced treatment of the WWTP effluent. Excitation emission matrix (EEM) fluorescence spectroscopy, parallel factor (PARAFAC) analysis and a two end-member mixing model were employed to characterize the composition and removal process of the effluent DOM (EfOM) from the WWTP. The results showed that the TF-SSF-CW performed an efficient EfOM removal with dissolved organic carbon (DOC) removal rate of 88% and dissolved organic nitrogen (DON) removal rate of 91%. Further analysis demonstrated that the EfOM consisted mainly of two protein moieties and two humic-like groups; protein moieties (76%) constituted the main content of EfOM in raw water and humic-like groups (57%) became the dominating contributor after treatment. The EfOM from the WWTP was mainly of aquatic bacterial origin and evolved to a higher proportion of terrigenous origin with higher humification in the TF-SSF-CW effluent. A common controlling treatment-related factor for determining the concentrations of the same kind of substances (protein groups or humic-like groups) was revealed to exist, and the ratio of removal rates between the same substances in treatment was calculated. Our study demonstrates that the TF-SSF-CW can be a novel and effective treatment method for the EfOM from WWTPs, and is helpful for understanding of the character of EfOM in wetland treatment.     

Tracking the reactivity of ozonation towards effluent organic matters from WWTP using two-dimensional correlation spectra

The characteristics of effluent organic matter (EfOM) from a wastewater treatment plant (WWTP) during ozonation were investigated using excitation and emission matrix (EEM) spectra, Fourier transform infrared spectroscopy (FT-IR) and high-performance size exclusion chromatography (HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra (2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC. The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution (MWD). According to 2D-COS analysis, microbial humic-like substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence: phenolic and alcoholic CO groups?>?aromatic structures containing CC double bonds?>?aliphatic CH. X-ray photoelectron spectroscopy (XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.     

荷电超滤膜去除水中天然有机物的研究进展

较传统的超滤过程,使用荷电膜的超滤技术能实现对水中天然有机物(NOM)更高的去除率,并同时减少膜污染。文章从膜材料性质、溶液环境和NOM性质这几方面来综述荷电超滤膜去除水中天然有机物的研究进展。最后对荷电超滤膜去除NOM方面的进一步研究工作提出了建议。     

DPR-SNED系统处理低C/N城市污水与硝酸盐废水的运行特性

为实现低C/N城市污水与含硝酸盐废水的同步处理,采用SBR接种活性污泥,通过合理控制厌氧/缺氧/低氧时间和溶解氧(DO)浓度,实现了反硝化除磷耦合同步硝化内源反硝化(DPR-SNED)系统的启动,并对启动过程中系统的脱氮除磷特性进行了研究.结果表明采用厌氧/低氧的运行方式,控制厌氧时间为3 h,好氧段DO浓度为0. 5～1. 0 mg·L-1,60 d可实现同步硝化内源反硝化除磷(SNEDPR)系统的启动,出水PO_4~(3-)-P浓度0. 5 mg·L-1,系统氮磷去除率维持在90%以上,COD的去除率维持在80%以上,系统SNED率和CODins率分别维持在70%和95%左右;随后改变运行方式,采用厌氧/缺氧/低氧的方式运行,缺氧段前进含硝酸盐废水,45 d可实现DPR-SNED系统的启动,缺氧末PO_4~(3-)-P浓度1. 1 mg·L-1,出水PO_4~(3-)-P浓度0. 5 mg·L-1,系统磷、COD去除率均维持在90%以上,氮去除率维持在88%以上,系统SNED率和CODins率分别维持在62%和90%左右. DPR-SNED系统的成功启动后,厌氧段聚糖菌和聚磷菌对城市污水有限碳源的充分利用和强化储存,可为后续缺氧段及好氧段的脱氮除磷提供充足的内碳源.此外,DPR-SNED系统缺氧段内源短程反硝化的进行保障了系统在低C/N(4)条件下的高效脱氮.     

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.     

Selective elimination of chromophoric and fluorescent dissolved organic matter in a full-scale municipal wastewater treatment plant

Effluent organic matter (EfOM) from municipal wastewater treatment plants potentially has a detrimental effect on both aquatic organisms and humans. This study evaluated the removal and transformation of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) in a full-scale wastewater treatment plant under different seasons. The results showed that bio-treatment was found to be more efficient in removing bulk DOM (in terms of dissolved organic carbon, DOC) than CDOM and FDOM, which was contrary to the disinfection process. CDOM and FDOM were selectively removed at various stages during the treatment. Typically, the low molecular weight (MW) fractions of CDOM and protein-like FDOM were more efficiently removed during bio-treatment process, whereas the humic-like FDOM exhibited comparable decreases in both bio-treatment and disinfection processes. Overall, the performance of the WWTP was weak in terms of CDOM and FDOM removal, resulting in enrichment of CDOM and FDOM in effluent. Moreover, the total removal of the bulk DOM (P < 0.05) and the protein-like FDOM (P < 0.05) displayed a significant seasonal variation, with higher removal efficiencies in summer, whereas removal of CDOM and the humic-like FDOM showed little differences between summer and winter. In all, the results provide useful information for understanding the fate and transformation of DOM, illustrating that sub-fractions of DOM could be selectively removed depending on treatment processes and seasonality.     

夏季巢湖入湖河流溶解性有机质来源及其空间变化

使用紫外-可见光吸收光谱（UV-vis）和三维荧光光谱-平行因子分析法（EEM-PARAFAC）,分析了2019年夏季巢湖流域丰乐河、杭埠河、岐阳河、兆河和南淝河水体溶解性有机质（dissolved organic matter,DOM）的来源及其空间变化.结果表明,南淝河DOM吸收特征参数SUVA₂₅₄显著低于其它河流,而光谱斜率比S_R显著高于杭埠河,表明城市污染物径流排入降低了南淝河水体DOM的芳香性,但对其分子量影响较低.南淝河DOM荧光指数（FI）和生物源指数（BIX）大于其它河流,而腐殖化指数（HIX）低于其它河流,指示其DOM自生源高于其它河流.使用EEM-PARAFAC从河流DOM中提取出4种类腐殖质组分（C1~C4）和2种内源类蛋白荧光组分（C5、C6）,其中,类腐殖质组分包括陆源有机质（C1、C3和C4）和微生物降解产物（C2）.沿河流方向,5条河流河水溶解性有机碳（dissolved organic carbon,DOC）、 a（355）和DOM荧光组分呈不同的空间变化特征,其中丰乐河、杭埠河、岐阳河和兆河DOM受农田土壤径流输入影响明显,而南淝河DOM主要受城市污染物径流和污水处理厂出水影响.     

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.     

固定床生物活性炭吸附天然有机物及其模型化研究

以日本长良川原水为研究对象,提高水处理出水水质为目标,研究了生物活性炭(BAC)小柱对原水中天然有机物(NOM)的去除效果。比较了不同NOM进水浓度时BAC小柱对其的去除率,研究了小柱层内及出水中NOM的相对分子量分布随着通水时间增加的变化情况,并利用结合了理想吸附溶液理论(IAST)的平推流表面扩散模型对出水中NOM的浓度进行模拟。结果表明,BAC小柱对不同浓度原水中NOM的去除率均高于相同试验条件下的粒状活性炭(GAC)小柱;BAC小柱对相对分子量分布为1000~5200g/mol内各分子量区间的有机物均可去除;平推流表面扩散模型对试验数据拟合结果较好。     

Effect of water matrices on removal of veterinary pharmaceuticals by nanofiltration and reverse osmosis membranes

This study explored the removal of five veterinary pharmaceuticals (VPs) (sulfamethoxazole (SMETOX), trimethoprim (TMP), ciprofloxacin (CIPRO), dexamethasone (DEXA) and febantel (FEBA)) from different water matrices (Milli-Q water, model water, tap water and real pharmaceutical wastewater using four types of nanofiltration (NF) membranes (NF90, NF270, NF and HL) and two reverse osmosis (RO) membranes (LFC-1 and XLE). All VPs were added to different water matrices at a concentration of 10 mg/L. Rejections of VPs and water flux were measured. The rejection increased with increase of molecular weight. The highest rejections were obtained with RO membranes (LFC-1, XLE) and tight NF (NF90) membrane. In general, the rejection of VPs was higher in model water and tap water than in Milli-Q water, but the water flux was lower. This was mainly explained by ion adsorption inside the membranes pores. Narrower pore size counteracted the effect of presence of low concentration of natural organic matter (NOM) in tap water. The NOM was assumed to enhance the adsorption of VPs onto membrane surface, increased the size exclusion and electrostatic repulsion also appeared during the transport. Investigated water matrices had influence on water flux decline due to their complexity.