Effects of C/N ratio on nitrate removal and floc morphology of autohydrogenotrophic bacteria in a nitrate-containing wastewater treatment process

The effects of C/N ratio of a nitrate-containing wastewater on nitrate removal performed by autohydrogenotrophic bacteria as well as on the morphological parameters of floc such as floc morphology, floc number distribution, mean particle size(MPS), aspect ratio and transparency were examined in this study. The results showed that the nitrate reduction rate increased with increasing C/N ratio from 0.5 to 10 and that the nitrogen removal of up to 95% was found at the C/N ratios of higher than 5(between 0.5–10). Besides, high C/N ratio values reflected a corresponding high nitrite accumulation after 12-hr operation, and a fast decreasing rate of nitrite in the rest of operational time. The final p H values increased with the C/N ratio increasing from 0.5 to 2.5, but decreased with the C/N ratio increasing from2.5 to 10. There were no significant changes in floc morphology with the MPSs ranging from35 to 40 μm. Small and medium-sized flocs were dominant in the sludge suspension, and the number of flocs increased with the increasing C/N ratios. Furthermore, the highest apparent frequency of 10% was observed at aspect ratios of 0.5 and 0.6, while the transparency of flocs changed from 0.1 to 0.7.     

污泥生物沥滤中硫细菌变化和胞外多聚物作用的研究

通过序批试验,分析污泥生物沥滤过程中pH值、异养菌数量变化以及硫细菌的形态,探讨了污泥中重金属在胞外多聚物(EPS)中的分布变化.结果表明,污泥经生物沥滤后异养菌大量死亡.扫描电镜和透射电镜对污泥微生物形态的观测发现,随着生物沥滤时间的延长,生物沥滤污泥明显比对照污泥中的微生物分布紧密,而且杆状和短杆状菌呈现逐渐增多趋势.生物沥滤后期出现受损的细菌胞体以及释放了细胞物质的细菌空壳.污泥沥滤液中EPS含量有所增加,沥滤过程中EPS的松散结合态与紧密结合态的比值呈现先上升后下降趋势,可反映沥滤前期细菌处于加速生长期的居多,而后期处于减速生长期的细菌逐渐增多.污泥EPS中重金属含量在生物沥滤几天后表现持续增长,Cu、Pb和Zn分布于EPS中的最高含量分别占污泥中总量的14.7%、20.3%和24.2%.延长酸化时间,EPS可被水解,而导致其中重金属含量呈现一定下降趋势.     

Insight into the distribution of metallic elements in membrane bioreactor: Influence of operational temperature and role of extracellular polymeric substances

The distribution of metallic elements in a submerged membrane bioreactor(MBR) was revealed at different temperatures using inductively coupled plasma-optical emission spectrometry(ICP-OES), and the role of extracellular polymeric substances(EPS) was probed by integrating scanning electron microscopy(SEM) with confocal laser scanning microscopy(CLSM) over long-term operation. More metallic elements in the influent were captured by suspended sludge and built up in the fouling layer at lower temperature. The concentration of metallic elements in the effluent was 5.60 mg/L at 10°C operational temperature, far lower than that in the influent(51.35 mg/L). The total contents of metallic elements in suspended sludge and the membrane fouling layer increased to 40.20 and 52.19 mg/g at 10°C compared to 35.14 and 32.45 mg/g at 30°C, and were dominated by the organically bound fraction. The EPS contents in suspended sludge and membrane fouling layer sharply increased to 37.88 and 101.51 mg/g at 10°C, compared to 16.87 and 30.03 mg/g at 30°C. The increase in EPS content at lower temperature was responsible for the deposition of more metallic ions. The strong bridging between EPS and metallic elements at lower temperature enhanced the compactness of the fouling layer and further decreased membrane flux. This was helpful for understanding the mechanism of membrane fouling at different operational temperatures and the role of EPS, and also of significance for the design of cleaning strategies for fouled membranes after long-term operation.     

自养菌和异养菌胞外聚合物对活性污泥絮凝特性的影响

为探讨自养菌和异养菌胞外聚合物(Extracellular polymeric substances,EPS)的差异及其对活性污泥表面及絮凝特性的影响,研究了有机负荷为0、0.30和0.74 kg·kg-1·d-1时,污泥松散附着胞外聚合物(loosely bound EPS,LB-EPS)和紧密粘附胞外聚合物(tightly bound EPS,TBEPS)的组分含量、形态、表面特性以及絮凝性能的差异,并就LB-EPS与TB-EPS对污泥絮凝特性影响的作用机理进行了探讨.结果表明,有机负荷越高,多糖含量越高,EPS总量及蛋白质含量越低.由三维荧光光谱测定结果可知,类富里酸物质为异养菌而非自养菌的代谢产物,且有机负荷越高,TB-EPS中的类富里酸荧光峰强度越大.自养和异养污泥的絮凝机理不同,自养活性污泥通过自养菌菌体自身生物絮凝作用形成密实的污泥絮体,LB-EPS与TB-EPS对其絮体形态、表面及絮凝特性影响较小;异养活性污泥絮体形态在TB-EPS提取后发生明显改变,TB-EPS在异养活性污泥絮体聚集时发挥着主要作用.包裹着LB-EPS的污泥表面负电荷多且疏水性差,不利于异养污泥生物絮凝.有机负荷越高,污泥表面Zeta电位负电性越强,相对疏水性(relative hydrophobity,RH)越小,污泥稳定性越差.     

活性污泥胞外聚合物提取动力学模型

为研究活性污泥胞外聚合物(EPS)提取过程中各参数间的基本关系及优化EPS提取过程,建立了EPS提取过程中浓度随时间变化的动力学模型,并通过前人研究数据和本次试验数据对模型进行验证.结果表明,模型对一些经典文献中的数据拟合效果较好,拟合系数(R2)均大于0.94.对MLSS为(1064.47±298.70)mg/L,MLVSS为(822±147)mg/L的活性污泥进行EPS提取, TOC和蛋白质的拟合效果较好,但多糖和DNA的拟合效果不理想.该模型可以大致估算试验中EPS的最大提取量及任一时间的EPS产量.     

活性污泥胞外聚合物中蛋白质的探针分析方法

应用微相吸附-光谱修正技术(Microsurface adsorption-spectral correction,简称MSASC),利用刚果红(Congo Red,简称CR)探针测定了活性污泥胞外聚合物(Extracellular polymeric substances,简称EPS)中蛋白质(Protein)的含量,与常用的Folin酚法比较,结果一致,蛋白加标回收率为94.5%～107.1%,相对标准偏差(RSD)＜4.5%.对反应机理的分析和产物结合常数的计算结果表明,在pH 2.21时CR-Protein作用符合Langmuir单分子层吸附理论,产物的结合比79∶1,结合常数K=2.17×106,聚集形式为Protein·CR79,摩尔吸收系数ε664r=8.50×105L·mol-1·cm-1.     

Evaluation of the secondary structures of protein in the extracellular polymeric substances extracted from activated sludge by different methods

The changes of protein secondary structures in the extracellular polymeric substances(EPS) extracted from activated sludge by four different methods were studied by analyzing the amide I region(1700–1600 cm-1) of the Fourier transform infrared spectra and model protein test. The results showed the molecular weight distribution of organic matter extracted by centrifugation, heating and cation exchange resin(CER) was similar, while the EPS extracted by centrifugation(Control) and CER had similar fluorescent organic matter. The protein secondary structures of extracted EPS by the four methods were different. The similarities of protein secondary structures between the EPS extracted by CER with the Control were the highest among the four extracted EPS. Although the EPS yield extracted by formaldehyde + NaOH method were the highest, its protein secondary structures had the lowest similarity with those extracted by the Control. Additionally, the effects of centrifugation and CER extraction on the secondary structures of bovine serum albumin were also lower than that of other extraction processes. CER enables the second maximum extraction of EPS and maximum retention of the original secondary structure of proteins.     

Characterization of changes in extracellular polymeric substances and heavy metal speciation of waste activated sludge during typical oxidation solubilization processes

Biopolymer solubilization is considered to be the rate-limiting stage of anaerobic digestion of waste activated sludge(WAS). Oxidation processes have been proven to be effective in disrupting sludge flocs and causing solubilization of the solid biopolymers. In this study,WAS was treated by NaNO2 or H2 O2 oxidation at p H of 2. The changes in extracellular polymeric substances properties and the speciation of heavy metals were investigated. The results revealed that both NaNO2 and H2 O2 treatments were effective in solubilizing organics in WAS, while the conversion of biopolymers in the two treatment processes was different. Free nitrous acid destroyed the gel network structure of EPS, and organic materials were released from the solid phase to the supernatant. Indigenous peroxidase catalyzed H2 O2 to produce hydroxyl radicals which caused significant solubilization of biopolymers, and the protein-like substances were further degraded into micro-molecule polypeptides or amino acids at high dosages of H2 O2. During the oxidation processes, Zn, Cd and Cu, with excellent mobility, tended to migrate to the supernatant, and thus were easy to remove through the liquid–solid separation process. Ni and As showed moderate migration ability, of which the residual fraction tended to transform into reducible and soluble fractions. With poor mobility, Cr and Pb mainly existed in the forms of residual and oxidizable fractions, which were difficult to dissolve and remove from WAS. Both NaNO2 and H2 O2 treatment resulted in the enhancement of sludge solubilization efficiency and heavy metal mobility in WAS, but different heavy metals showed distinct migration and transformation behaviors.     

胞外聚合物EPS在废水生物除磷中的作用

对EPS在废水生物除磷中的作用机理进行系统研究,探讨和完善生物除磷机理.试验结果表明,在生物除磷系统中,EPS贮存了部分磷,在生物除磷中起着重要的作用.在厌氧.好氧交替过程中.EPS中磷含量呈厌氧减少、好氧增加的周期性变化;污泥中的磷有82%左右被聚磷菌吸收,另外18%左右的磷聚集在EPS中;一个运行周期中基质所减少的磷84.3%被聚磷菌过量吸收,15.7%被贮存于EPS中;EPS对磷的去除能力与EPS的含量正相关.此外,泥龄对EPS影响较大,对EPS在生物除磷中的作用影响显著,泥龄越长,EPS含量越高,EPS中所贮存的磷含量越高.而磷负荷对EPS除磷影响不显著.     

含水介质中胞外聚合物的影响因素研究

明确含水介质中微生物胞外聚合物(EPS)生成量的影响因素,是解决含水层生物堵塞的关键问题.本文在现场样品采集和微生物培养的基础上,通过砂柱试验模拟人工回灌过程,系统研究了进水碳、氮、磷浓度、盐度和温度对含水介质中EPS组成和含量的影响.结果表明,砂柱中EPS最主要的成分为多糖和蛋白质,其中多糖占总量的72%~99%;砂柱生物堵塞程度与介质上附着的EPS含量呈正相关关系,当回灌水碳、氮、磷浓度、盐度和温度分别为50 mg·L-1、5 mg·L-1、1 mg·L-1、0.5%和30℃时,微生物EPS生成量最高,砂柱渗透系数降低最显著,堵塞程度最严重.此外,碳、磷浓度、盐度和温度是影响EPS生成量的主要因素,而氮浓度对其影响不大;碳浓度和盐度对EPS中多糖、蛋白质的组成影响较大,而氮、磷以及温度则影响不明显.     

交流电场对生物膜胞外聚合物提取过程的影响

利用电场特性,研究了交流电场的电流、频率大小对生物膜胞外聚合物(EPS)提取过程的影响,当电流密度小于10mA/cm²时,外电场对生物膜内微生物细胞影响较小;提取剂不同则对应的最佳提取频率不同,NaOH提取剂较适合的频率范围是10～100Hz;在电场条件一定的情况下,分别探讨了溶液pH值、提取剂浓度等各因素对提取效果的影响.以EDTA钠盐为提取剂,其浓度为2%时,提取效果较好;以2% EDTA钠盐为提取剂时,pH=10提取效果最佳.     

胞外聚合物对浸没式膜-生物反应器膜过滤性能的影响

通过浸没式膜-生物反应器（SMBR）处理上海市城市内河水的试验,研究了反应器混合液中和2种疏水性不同的膜上污泥胞外聚合物（EPS）的量、组成、污泥特性及对膜过滤性能的影响.结果表明,混合液污泥中的溶解性EPS和固着性EPS比膜上污泥多,不同污泥的固着性EPS组分中蛋白质（EPSP）/多糖（EPSC）的大小顺序依次为混合液污泥〈亲水膜污泥〈疏水膜污泥.疏水膜污泥中溶解性EPS比亲水膜多,溶解性EPS和固着性EPS量及组分均有很大差异.混合液污泥的EPS流动性大,疏水性膜上污泥EPS的流动性较大.溶解性EPS对污泥特性及膜过滤性能影响较大.SMBR中亲、疏水性膜片上黏附的污泥的相对疏水性分别为53%、59%.比较2种膜片通量的变化发现,疏水性膜污染严重.     

胞外聚合物、Ca2+及pH值对生物絮凝作用的影响

应用阳离子交换树脂从活性污泥中提取了胞外聚合物(EPS),考察了EPS、Ca2 及pH值对生物絮凝作用的影响.结果表明,当pH≥7.5, EPS≥70mg/L,[Ca2 ]≥300mg/L时,有利于生物絮体的形成.通过正交试验,得出pH值、EPS和[Ca2 ]对生物絮体形成综合影响的回归方程: h浊度= -901.70 97.35pH 1.96[Ca2 ] 9.08EPS-0.11pH[Ca2 ]-0.91pHEPS-0.02[Ca2 ]EPS 0.0021pH[Ca2 ]EPS.回归分析表明,pH值对生物絮体形成影响最显著,其次是EPS和Ca2 .     

盐度变化对厌氧污泥胞外聚合物的影响

为探讨盐度变化对厌氧污泥胞外聚合物的影响,采用三维荧光(3D-EEM)和傅里叶变换红外(FTIR)技术,研究了不同盐度下升流式厌氧污泥流化床(UASB)中污泥的松散结合型胞外聚合物(LB-EPS)与紧密结合型胞外聚合物(TB-EPS)的变化规律,并分析了LB-EPS和TB-EPS与污泥沉降性间的关系.结果表明,进水盐度由0逐渐增加至8%,厌氧污泥LB-EPS和TB-EPS含量分别由4.94和12.25 mg·g~(-1)(以VSS计)增加至41.47和43.04 mg·g~(-1)(以VSS计);LB-EPS和TB-EPS中蛋白(PN)和多糖(PS)含量的比值分别由3.2和3.8降低至1.8和2.3;污泥容积指数(SVI)与LB-EPS、TB-EPS均正相关;3D-EEM光谱显示,色氨酸蛋白和芳环蛋白荧光峰存在于不同盐度下LB-EPS和TB-EPS中,类胡敏酸荧光峰仅存在于盐度高于4%的TB-EPS中;FTIR分析表明,进水盐度的增加导致LB-EPS和TB-EPS中PS的C—O组分相对含量增加.     

Extracellular polymeric substance induces biogenesis of vivianite under inorganic phosphate-free conditions

Vivianite is often found in reducing environments rich in iron and phosphorus from organic debris degradation or phosphorus mineral dissolution. The formation of vivianite is essential to the geochemical cycling of phosphorus and iron elements in natural environments. In this study, extracellular polymeric substances (EPS) were selected as the source of phosphorus. Microcosm experiments were conducted to test the evolution of mineralogy during the reduction of polyferric sulfate flocs (PFS) by Shewanella oneidensis MR-1 (S. oneidensis MR-1) at EPS concentrations of 0, 0.03, and 0.3 g/L. Vivianite was found to be the secondary mineral in EPS treatment when there was no phosphate in the media. The EPS DNA served as the phosphorus source and DNA-supplied phosphate could induce the formation of vivianite. EPS impedes PFS aggregation, contains redox proteins and stores electron shuttle, and thus greatly promotes the formation of minerals and enhances the reduction of Fe(III). At EPS concentration of 0, 0.03, and 0.3 g/L, the produced HCl-extractable Fe(II) was 107.9, 111.0, and 115.2 mg/L, respectively. However, when the microcosms remained unstirred, vivianite can be formed without the addition of EPS. In unstirred systems, the EPS secreted by S. oneidensis MR-1 could agglomerate at some areas, resulting in the formation of vivianite in the proximity of microbial cells. It was found that vivianite can be generated biogenetically by S. oneidensis MR-1 strain and EPS may play a key role in iron reduction and concentrating phosphorus in the oligotrophic ecosystems where quiescent conditions prevail.     

Effects of ultrasonic pretreatment on sludge dewaterability and extracellular polymeric substances distribution in mesophilic anaerobic digestion

Effect of ultrasonic pretreatment on sludge dewaterability was determined and the fate of extracellular polymeric substances (EPS) matrix in mesophilic anaerobic digestion after ultrasonic pretreatment was studied. Characteristics of proteins (PN), polysaccharides (PS), excitation-emission matrix (EEM) fluorescence spectroscopy and molecular weight (MW) distribution of dissolved organic matters (DOM) in different EPS fractions were evaluated. The results showed that after ultrasonic pretreatment, the normalized capillary suction time (CST) decreased from 44.4 to 11.1 (sec·L)/g total suspended solids (TSS) during anaerobic digestion, indicating that sludge dewaterability was greatly improved. The normalized CST was significantly correlated with PN concentration (R2 = 0.92, p 0.01) and the PN/PS ratio (R2 = 0.84, p 0.01) in the loosely bound EPS (LB-EPS) fraction. Meanwhile, the average MW of DOM in the LB- EPS and tightly bound EPS (TB-EPS) fractions also had a good correlation with the normalized CST (R2 0.66, p 0.01). According to EEM fluorescence spectroscopy, tryptophan-like substances intensities in the slime, LB-EPS and TB-EPS fractions were correlated with the normalized CST. The organic matters in the EPS matrix played an important role in influencing sludge dewaterability.     

厌氧氨氧化颗粒污泥胞外聚合物金属元素特性

为探究厌氧氨氧化颗粒污泥胞外金属元素特性,将厌氧氨氧化颗粒污泥根据粒径筛分为0.5~1.4mm、1.4~2.8mm、>2.8mm 3组,提取不同粒径厌氧氨氧化颗粒污泥胞外聚合物（EPS）,研究EPS金属元素特性.结果表明,蛋白质（PN）是厌氧氨氧化颗粒污泥EPS的主要成分,占EPS含量的84.2%以上.随着粒径的增大,EPS中Na、K、Ca、Mg元素含量均增多,且与EPS中蛋白质含量变化一致.EPS中K、Ca、Mg元素的离子形式占比分别为68.6%、56.2%、94.7%.EPS经过阳离子交换树脂（CER）处理后,0.5~1.4mm、1.4~2.8mm、>2.8mm组EPS Zeta电位分别减小了4.7,7.2,9.1mV,EPS中的金属离子可通过压缩双电层作用促进颗粒污泥的聚集,金属离子对大粒径颗粒污泥EPS Zeta电位的影响幅度更大.     

厌氧氨氧化颗粒污泥胞外聚合物金属元素特性

为探究厌氧氨氧化颗粒污泥胞外金属元素特性,将厌氧氨氧化颗粒污泥根据粒径筛分为0.5~1.4mm、1.4~2.8mm、>2.8mm 3组,提取不同粒径厌氧氨氧化颗粒污泥胞外聚合物（EPS）,研究EPS金属元素特性.结果表明,蛋白质（PN）是厌氧氨氧化颗粒污泥EPS的主要成分,占EPS含量的84.2%以上.随着粒径的增大,EPS中Na、K、Ca、Mg元素含量均增多,且与EPS中蛋白质含量变化一致.EPS中K、Ca、Mg元素的离子形式占比分别为68.6%、56.2%、94.7%.EPS经过阳离子交换树脂（CER）处理后,0.5~1.4mm、1.4~2.8mm、>2.8mm组EPS Zeta电位分别减小了4.7,7.2,9.1mV,EPS中的金属离子可通过压缩双电层作用促进颗粒污泥的聚集,金属离子对大粒径颗粒污泥EPS Zeta电位的影响幅度更大.     

Functions and behaviors of activated sludge extracellular polymeric substances (EPS): a promising environmental interest

Extracellular polymeric substances （EPS） are the predominant constituents of activated sludge and represent up to 80% of the mass of activated sludge. They play a crucial role in the flocculation, settling and dewatering of activated sludge. Furthermore, EPS also show great efficiency in binding heavy metals. So EPS are key factors influencing reduction in sludge volume and mass, as well as activity and utilization of sludge. EPS are of considerable environmental interest and hundreds of articles on EPS have been published abroad, while information on EPS in China is limited. In this paper, results of over 60 publications related to constituents and characteristics of EPS and their influences on flocculation, settling and dewatering of sludge are compiled and analyzed. Metal-binding ability of EPS is also discussed, together with a brief consideration of possible research interests in the future.     

受四环素影响的活性污泥胞内外聚合物特征

利用离心加超声的方法对处理四环素抗生素废水的活性污泥胞外聚合物(EPS)和胞内聚合物(IPS)进行提取,将其分为-溶解型胞外聚合物(slime)、松散附着型胞外聚合物(LB)、紧密附着型胞外聚合物(TB)、胞内聚合物(IPS).用BCA法和蒽酮-硫酸法测定了各层EPS和IPS溶液中的蛋白质和多糖含量,同时用三维荧光光谱扫描(EEM)和同步荧光光谱扫描(SFS)对其中的溶解性有机物(DOM)进行定性和定量分析,结果表明在EPS中的蛋白质和多糖的含量高于IPS,且蛋白质含量均比多糖含量高,而在slime和IPS中的蛋白质和多糖的含量高于LB和TB;低激发波长类色氨酸和高激发波长类色氨酸是EPS和IPS溶液的主要成分,且溶液中的溶解性代谢产物和芳香蛋白类物质相对含量在slime、LB、TB和IPS逐渐增加,而难降解有机物-腐殖酸类物质的相对含量逐渐降低;进水四环素浓度与污泥各层EPS和IPS溶液中DOM也具有较好的相关性;三维荧光法检测溶液中的DOM与化学分析测试出的蛋白质含量具有较好的相关性.