基于2D-COS分析的难凝聚有机物臭氧化特性研究

基于二维相关光谱分析,对污水厂二级出水难凝聚有机物的臭氧化特性进行了研究.结果表明,混凝很难去除污水厂二级出水中的溶解性有机物,污水厂二级出水溶解性有机物大部分属于难凝聚有机物,以腐殖酸类物质为主.臭氧氧化可以降低二级出水混凝后上清液的色度及UV₂₅₄,去除率分别可达到70%和40%以上,但是对难凝聚有机物的去除率较低,去除率在10%以下,只是与难凝聚有机物进行了反应,改变其性质.同时,臭氧可以降低二级出水中难凝聚有机物的荧光强度,其中腐殖酸类物质的荧光强度降低较为明显.基于不同臭氧投加量下难凝聚有机物的同步荧光分析,可以得到二级出水难凝聚有机物的二维相关光谱,结果表明,腐殖酸类物质对臭氧氧化最为敏感,腐殖酸类物质与富里酸类物质相比会优先和臭氧反应.     

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.     

SBR生物反应器出水溶解态有机物性质特点研究

研究中考察了SBR生物反应器处理实际生活污水过程中,反应器内部溶解性有机物的变化情况,重点分析了污泥龄对于SBR反应器出水溶解态有机物性质特点的影响.研究结果表明,生物降解过程中,以分子量650Da、1700Da和2000Da为代表的腐殖质类有机物逐渐积累,小分子量有机物(<200Da)逐渐转化为具有中间分子量(500...     

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.     

HRT对城市污水厂尾水反硝化深度脱氮的影响

污水厂尾水回用作为水源时,其ρ(TN)较高是亟待解决的问题. 在调研污水厂尾水水质的基础上,利用MBBR(移动床生物膜反应器)对其进行深度脱氮,并考察HRT(水力停留时间)对不同填料(聚乙烯和陶粒)的MBBR运行效果的影响. 结果表明,NO₃--N是尾水中氮的主要形态,其质量浓度约占ρ(TN)的80.8%±8.4%. HRT分别为12、8和4 h时,对NO₃--N去除率影响不大,均能达到90%以上,但反硝化能力随着HRT的缩短而成倍增加;HRT为4 h时各反应器的反硝化能力最大,聚乙烯和陶粒MBBR中分别为(28.4±14.5)和(27.4±14.3)mg/(L·d)(以NO₃--N计). 随着HRT的减少,COD_Cr去除率呈降低趋势. 三维荧光分析表明,进、出水中均含有类富里酸和类蛋白质等DOM物质. HRT为8 h时MBBR对DOM的去除率最高,聚乙烯填料MBBR对有机污染物的去除效果略优于陶粒填料. 综合考虑氮和有机污染物去除效能,聚乙烯和陶粒填料MBBR优化HRT均为8 h.      

两种分子量分级下DOM的组分特征及其生物毒性

分别采用超滤离心管和超滤杯两种方式制备不同分子量的溶解性有机物（DOM）,探究不同的分子量分级方式对获得的DOM组成成分特征及其生物毒性效应的影响,同时判明各组分联合作用方式.DOM分别来源于城市污水厂出水（EfOM）及商品天然腐植酸（SWR-NOM）.结果表明,两种分级方式获得的不同分子量DOM含有相同的荧光峰,腐殖酸类物质是EfOM与SWR-NOM含有的主要荧光类有机质（FDOM）,占FDOM的56%~91%.同种DOM不同分子量组分中FDOM组成相对含量一致.采用超滤离心管分级得到的DOM在不同分子量区间内SUVA₂₅₄和E2/E3的差异较大,而采用超滤杯分级时差异变化较小.对于发光细菌急性毒性,在同一分子量区间内,采用超滤杯分级获得的DOM组分检测到的发光细菌毒性值大于采用超滤离心管分级检测到的结果,但采用超滤杯分级时<1kDa组分的急性毒性效应值低于检测限.利用浓度加和模型（CA）对DOM中各组分的联合作用方式进行判断,发现DOM混合物的联合毒性符合CA模型,预测联合毒性效应占检测到的实际水样毒性的67%~104%.     

制药废水二级出水中溶解性有机物混凝去除特性研究

制药废水二级出水中溶解性有机物(DOM)由于组成复杂、难去除、具有多异质性和分散性,是污水深度处理与回用的主要去除对象和关键限制因子.本论文以发酵制药废水二级出水的DOM为研究对象,采用投加聚合氯化铝(PAC)混凝剂去除DOM,考察混凝剂投加量和混凝pH值对去除效果的影响,并结合分子量分级、亲疏水性分级以及三维荧光光谱-平行因子分析方法等对DOM进行了系统表征和分析,进一步阐述混凝过程DOM的去除特征.结果表明,PAC投加量为250 mg·L~(-1)、pH=7时,混凝沉淀30 min对DOC、UV_(254)、色度和浊度的去除率分别为13.05%±0.29%、23.65%±0.75%、12.66%±1.34%、63.67%±0.89%;混凝对分子量10 kDa的组分和疏水中性(HON)组分去除效果分别为50.33%±0.98%、21.56%±0.42%,而对分子量1 kDa组分去除率较低为2.26%±0.12%;三维荧光光谱-平行因子分析将制药废水二级出水分为2个类腐殖质组分(C1、C3)和1个类蛋白组分(C2),混凝对类腐殖酸组分(C1)最大荧光强度去除率(F_(max))最高为46.22%,而亲水性的小分子和蛋白类物质混凝去除效果较差.     

预臭氧化对二级出水微滤过程中膜有机物污染的影响

在二级出水溶解性有机物（secondary effluent organic matter,EfOM）的微滤过程中,多种因素均与膜的有机污染相关,比如总有机物的含量,溶解性有机物的亲疏水性组成等.本文主要研究了在二级出水微滤过程中溶解性有机物的膜污染,以及预臭氧化对二级出水溶解性有机物性质的影响进而对膜有机污染的影响....     

辽河流域与英国中部河湖水体中溶解有机质的荧光特性

运用三维荧光光谱技术对辽河流域和英国中部水体中溶解有机质(DOM)的荧光光谱特性进行了分析.结果表明,辽河流域各研究水体中DOM包含4种荧光组分,即类色氨酸、类酪氨酸、可见光区和紫外光区类腐殖质,通过对荧光特性定量指标的分析可知,辽河流域各研究断面水体中类腐殖质物质内源作用大于陆源,DOM具有较强的新近自生源,各河流水体中DOM腐殖化程度顺序为:浑河中游海城河中游蒲河下游太子河下游.相比之下,英国河湖中,除了River Tame含有以上4种荧光组分外,其它水体中均没有发现类酪氨酸荧光物质,甚至在River Tern中仅含有类腐殖质荧光物质,河湖中DOM含有较少的新近自生源组分,以陆源影响为主.另外,辽河流域水体中类蛋白与类腐殖质荧光峰强度比值大于英国各河流水体的平均值.由此可以推断,辽河流域各研究断面大量污染物的输入,是造成其严重内源污染的主要原因,从而使水体中DOM含量增加,英国各河流断面其DOM主要来自于水体本身存在的大量微生物和浮游植物的代谢活动以及土壤有机质经雨水的冲刷流入水体的贡献.     

温度对城市污水厂尾水反硝化MBBR深度脱氮的影响

为解决城市污水厂尾水再生利用时ρ(TN)高的问题,采用反硝化MBBR(移动床生物膜反应器)对城市污水厂尾水进行反硝化脱氮,并重点研究不同温度下分别以聚乙烯和聚丙烯为填料的反硝化MBBR的运行效果. 结果表明:在HRT(水力停留时间)为12 h、温度分别为13、19、25和30 ℃时,NO₃--N去除率和反硝化能力变化不大,聚乙烯和聚丙烯反硝化MBBR的NO₃--N去除率分别为80.1%～85.0%和78.2%～84.0%,二者的反硝化能力分别为6.7～7.1和6.5～7.0 mg/(L·h);较长的HRT弥补了低温时反硝化速率低的不足;随温度增加,生物量逐渐增加,但COD_Cr和DOM(溶解性有机物)的去除率变化不明显. 三维荧光图谱表明,出水中主要的DOM(溶解性有机质)为类色氨酸和类富里酸,聚乙烯和聚丙烯反硝化MBBR对DOM总荧光强度的去除率分别为47.6%～52.5%和24.1%～35.8%. 填料上的微生物以杆菌、丝状菌和球菌为主. 综合考虑脱氮效能和有机物污染物去除效能,聚乙烯和聚丙烯反硝化MBBR深度脱氮的最佳温度均为25 ℃.      

Interactions between lead(II) ions and dissolved organic matter derived from organic fertilizers incubated in the field

This work was to study composition characteristics and the subsequent effect on the lead (Pb) binding properties of dissolved organic matter (DOM) derived from seaweed-based (SWOF) and chicken manure organic fertilizers (CMOF) during a one-year field incubation experiment using the excitation-emission matrix-parallel factor (EEM-PARAFAC) and two-dimensional correlation spectroscopy (2DCOS) analysis. Results showed that high aromatic and hydrophobic fluorescent substances were enriched in CMOF-derived DOM and SWOF-derived DOM and enhanced over time. And phenolic groups in the fulvic-like substances for SWOF-derived DOM and carboxyl groups in the humic-like substances for CMOF-derived DOM had the fastest responses over time, respectively. Moreover, both non-fluorescent polysaccharides and fluorescent humic-like substances or fulvic-like substances with aromatic (C=C) groups first participated in the binding process of Pb to SWOF-derived DOM on day 0 and 180 during the lead binding process. In contrast, humic-like substances associated with aromatic (C=C) and phenolic groups gave a faster response to Pb binding on day 360. Regarding CMOF-derived DOM, the fulvic-like substances associated with aromatic (C=C) and carboxylic groups displayed a faster response to Pb ions on day 0. Nonetheless, polysaccharides and humic-like associated with phenolic groups had a faster response on days 180 and 360. It is noteworthy that the polysaccharides, which participated in Pb binding to CMOF-derived DOM, posed a higher risk of Pb in the environment after 360 days. Therefore, these findings gave new insights into the long-term applications of commercial organic fertilizers for the amendment of soil.     

MIEX中试实验对二级出水中有机物去除的3DEEM解析

利用三维荧光光谱研究了磁性离子交换树脂（magnetic ion exchange resin,MIEX）对污水厂二级出水中有机物的去除特征.结果表明,磁性树脂处理二级出水过程中,两级反应过程和进水流量对DOC和UV254有较显著的去除效果,去除率分别达到25.5%～53.5%和27.6%～52.2%,其中50 L.h-1流量条件下,出水中DOC和UV254浓度分别为3.29 mg.L-1和0.057cm-1.水中芳香族蛋白质或酚类物质和类腐殖酸物质荧光强度较高,磁性树脂使二级出水中色氨酸类芳香族蛋白质、芳香族蛋白质、腐殖酸类荧光强度分别下降38.2%、85.8%和85.7%,腐殖酸和富里酸峰消失,并露出溶解性微生物代谢产物荧光峰.不同进水流量条件下,色氨酸类芳香族蛋白质荧光强度下降率和芳香族蛋白质或酚类物质荧光强度下降率与进水流量的负相关性最好,50～100 L.h-1流量条件对各类荧光物质的去除率影响最大.磁性树脂与二级出水中色氨酸类芳香族蛋白质和芳香族蛋白质或酚类物质有更好的线性置换关系（R2=0.834 8）,磁性树脂对二级出水中芳香族蛋白质或酚类物质的置换作用则最显著（a=850.2）.     

电凝聚臭氧化耦合工艺的有机物处理特性及去除机制解析

以污水厂二级出水溶解性有机物强效去除为目的,本研究构建了电凝聚臭氧化耦合（E-HOC）体系,明确了该体系对污水厂二级出水及布洛芬的处理特性,探明了有机物的强化去除机制.结果表明,在pH5条件下,E-HOC工艺对二级出水溶解性有机物的去除效果更优,相较于臭氧氧化、电絮凝工艺、预臭氧化-电絮凝工艺、电絮凝串联臭氧工艺以及化学混凝工艺分别提高了46.4%、20.0%、19.4%、36.1%和49.7%.为进一步明确该耦合工艺去除溶解性有机物的机制,基于淬灭实验和EPR特征峰谱图分析,证实了金属盐混凝剂可作为催化剂有效地提高羟基自由基（·OH）的产量,揭示了该耦合体系存在臭氧混凝协同增效（SOC）反应.傅立叶红外的分析结果表明,Al阳极电解产生的混凝剂水解物表面羟基为SOC反应中产生·OH的活性位点.基于有机物在E-HOC体系中的动力学特性,解析了耦合体系中有机物的去除机制,SOC反应和臭氧氧化反应在E-HOC体系的有机物去除过程中作用显著,SOC反应为·OH的生成提供了一种新的途径.     

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.     

河北洨河溶解性有机物光谱学特性

基于荧光光谱、紫外吸收光谱与水质基本化学指标,联合主成分分析与相关性分析,对典型城市纳污河流——河北洨河的溶解性有机物(DOM)进行光谱学特性研究.结果表明,河流水体中DOM主要有类蛋白和类腐殖质两类,其中含氮化合物及DOM与水体COD之间相关性较高,尤其以氨氮对类腐殖质贡献较大.因此降低洨河水体中COD可通过减少氨氮与DOM来实现,同时此两类指标也应作为日后水体监控指标.干流水体样品中DOM下游相对上游类蛋白逐渐减少,而类腐殖质则呈现增加的趋势,并以类胡敏酸为主要存在形式.代表支流4种样品中,S1、S2水体DOM主要以类胡敏酸为重要成分,其组成有机物多为大分子量、芳香性高的有机物质,而S3、S6水体中主要为相对易降解的类蛋白,其相对分子质量相对较小、芳香性程度较低.针对代表支流的4个污水处理单位出水水体中的DOM特征,建议S1与S2应添加或改进对大分子物质有较好去除效果的膜处理设备,以加强对水体中相对难降解类腐殖质物质的去除;S3与S6应优化相关厌氧与好氧生物处理工艺,从而提高易降解的类蛋白物质的去除能力.     

腐蚀电池-Fenton处理渗滤液溶解性有机物光谱特征

为了研究垃圾渗滤液中溶解性有机物（DOM）在腐蚀电池-Fenton（CCF）深度处理过程中的去除特性,采用XAD-8和XAD-4树脂将DOM分成5种组分（亲水性有机物HPI、疏水性有机酸HPO-A、过渡亲水性有机酸TPI-A、疏水性中性有机物HPO-N、过渡亲水性中性有机物TPI-N）,并用紫外和荧光光谱对各组分的降解...     

自然光和UV辐照下二级出水DOM及毒性的变化

为了探明自然光和紫外光（UV）对二级处理出水中溶解性有机物（DOM）及其毒性效应的削减特性，研究了在自然光和UV两种不同光源的辐照条件下，二级处理出水中DOM的光谱特性、遗传毒性和植物毒性变化，阐明了毒性效应变化的成因.结果表明：相比于自然光照，UV辐照可以明显降低二级处理出水的UV₂₅₄，并达到21%矿化.自然光和UV均可降低二级处理出水中有色溶解性有机物（CDOM），但去除的组分有所差异.同时，自然光照与UV辐照均可降低二级处理出水的遗传毒性，其削减率分别达到92%和61%.遗传毒性的变化与CDOM荧光强度变化有显著相关性.UV辐照可降低二级处理出水的植物毒性，削减率达到81%，而自然光照对二级处理出水植物毒性的削减率仅为19%，削减效果较差.利用UPLC-MS检测二级出水中的除草剂，发现植物毒性削减的差异主要是由于自然光照下二级处理出水中的阿特拉津降解缓慢，表观降解速率常数为0.0033h^-1；但是UV辐照下二级处理出水中的阿特拉津可快速降解，其表观速率常数为0.2225h^-1.这为污水厂排放水毒性效应控制及生态安全保障提供了一定的依据.     

Effects of duckweed (Spriodela polyrrhiza) remediation on the composition of dissolved organic matter in effluent of scale pig farms

The swine effluent studied was collected from scale pig farms, located in Yujiang County of Jiangxi Province, China, and duckweed (Spriodela polyrrhiza) was selected to dispose the effluent. The purpose of this study was to elucidate the effects of duckweed growth on the dissolved organic matter composition in swine effluent. Throughout the experiment period, the concentrations of organic matter were determined regularly, and the excitation–emission matrix (3DEEM) spectroscopy was used to characterize the fluorescence component. Compared with no-duckweed treatments (controls), the specific ultra-violet absorbance at 254 nm (SUVA₂₅₄) was increased by a final average of 34.4% as the phytoremediation using duckweed, and the removal rate of DOC was increased by a final average of 28.0%. In swine effluent, four fluorescence components were identified, including two protein-like (tryptophan, tyrosine) and two humic-like (fulvic acids, humic acids) components. For all treatments, the concentrations of protein-like components decreased by a final average of 69.0%. As the growth of duckweed, the concentrations of humic-like components were increased by a final average of 123.5% than controls. Significant and positive correlations were observed between SUVA₂₅₄ and humic-like components. Compared with the controls, the humification index (HIX) increased by a final average of 9.0% for duckweed treatments. Meanwhile, the duckweed growth leaded to a lower biological index (BIX) and a higher proportion of microbial-derived fulvic acids than controls. In conclusion, the duckweed remediation not only enhanced the removal rate of organic matter in swine effluent, but also increased the percent of humic substances.     

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix(EEM) coupled with parallel factor analysis(PARAFAC) was performed for a total of 18 water samples taken from three water sources(two lakes and one wastewater treatment plant(WWTP) secondary effluent),with the purpose of identifying the major ultrafiltration(UF) membrane foulants in different water sources. Three fluorescent components(C1, C2 and C3) were identified,which represented terrestrially derived humic-like substances(C1), microbially derived humic-like substances(C2), and protein-like substances(C3). The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components(C1, C2 and C3) made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.     

pH值对SBR生物反应器出水溶解态有机质含量与构成的影响

为探讨污水二级生化出水中有机物(EfOM)的构成特点和变化规律,采用配置生活污水,对不同pH值运行条件下, SBR生物反应器出水中的溶解态有机质(DOM)含量和构成进行了比较研究.结果表明,运行期间pH值的调节对SBR反应器出水DOM含量与构成的影响均较大.初始pH为6.5的SBR反应器, pH值降低为6.0后,出水DOC由原来的4.0mg·L-1不断升高,进一步提高pH值,能够起到一定的缓解作用;初始pH为8.0的SBR反应器,出水DOC从4.0mg·L-1快速降低并保持在2mg·L-1左右, pH值降低为6.5后, DOC变化不大.单宁酸和蛋白质、碳水化合物、DNA等微生物代谢产物(SMPs)是出水DOM的主要组成部分, pH值对SMPs生成的影响是一个长期的过程,运行过程中降低pH值,造成出水SMPs含量不断升高. pH值对整个循环过程中溶解态有机物降解情况的影响,在厌氧阶段发挥了主要作用,较高pH值有利于厌氧阶段有机物的降解,而好氧阶段的有机物降解受pH值影响不大.