剩余污泥水解酸化过程中胞外聚合物的影响因素研究

为了解胞外聚合物(EPS)对污泥水解酸化处理的影响,采用批量试验研究了污泥厌氧水解酸化处理过程中EPS的变化以及温度、pH值、污泥来源、污泥浓度对其的影响.结果表明,pH值和污泥来源对EPS产率、成分有显著的影响.强酸性和强碱性条件下污泥水解过程中溶解性EPS产率是中性条件下的2倍多;强酸性条件下细胞破裂较多,DNA物质占总EPS含量的20%左右;强碱性条件多糖类物质溶出量占总EPS的80%以上.A/O工艺污泥水解酸化EPS产率最大,平均值为41.1mg/gVSS;其次为SBR、氧化沟(OD)和A2/O工艺污泥,其中OD工艺污泥水解酸化产生的EPS中糖类与蛋白质的质量比(φ)值远小于其他工艺污泥.温度由18℃升高至35℃时,溶解性EPS产率增加近50%,多糖所占比例逐渐增大.污泥浓度由2000mg/L升高至6000mg/L,EPS产率增大至38.1mg/gVSS,当污泥浓度达到8000mg/L时,EPS产率明显减少(23.1mg/gVSS).     

Effects of sludge age on anaerobic acidification of waste activated sludge: Volatile fatty acids production and phosphorus release

Effects of sludge age on volatile fatty acids (VFAs) production and Phosphorus (P) release during anaerobic acidification of waste activated sludge (WAS) were investigated. Sequencing batch reactors (SBR) fed with simulating domestic sewage were applied to produce WAS of different sludge ages, and batch tests were used for anaerobic acidification. The maximum dissolved total organic carbon, release of  ${\text{PO}}_4^{3+}?\mathrm{P}$, and accumulation of acetate (C2), propionate (C3), butyrate (C4), and valerate (C5) decreased by 56.2%, 55.8%, 52.6%, 43.7%, 82.4% and 84.8%, respectively, as the sludge age of WAS increased from 5 to 40 days. Limited degradation of protein played a dominating role in decreasing DTOC and VFAs production. Moreover, the increase in molecular weight of organics and organic nitrogen content in the supernatant after acidification suggested that the refractory protein in WAS increased as sludge age extended. Although the production of C2, C3, C4, and C5 from WAS decreased as the sludge age increased, the proportions of C2 and C3 in VFAs increased, which might be due to the declined production of C5 from protein and the faded genus Dechlorobacter. Keeping sludge age of WAS at a relatively low level (<10 days) is more appropriate for anaerobic acidification of WAS as internal carbon sources and P resource.     

典型酸碱条件下NO2-对剩余污泥水解产酸的影响

控制温度35℃,在典型pH值条件下(酸性5.0,碱性9.0)对比研究了NO2-对剩余污泥水解酸化性能的影响.结果表明:投加亚硝酸盐促进了剩余污泥的水解,提高了总可溶性COD(SCOD)产量,且随着时间的进行,酸性时比碱性时水解程度更高,到第28d时,总SCOD浓度由高到低依次为B1(pH=5且加NO2-),B2(pH=9且加NO2-),B4(pH=9且未加NO2-),B3(pH=5且未加NO2-);B1,B2,B3和B4中总挥发性脂肪酸(TVFAs)最高浓度分别为4476,4303,1350和2921mg/L,表明亚硝酸盐同样增强了污泥的酸化程度,并且酸性条件时促进作用更大.除此之外,酸性且投加NO2-的条件可以有效减少氨氮的释放.     

柠檬酸钠强化剩余污泥酶水解和酸化的研究

厌氧条件下,研究了阳离子络合剂柠檬酸钠(SC)对剩余污泥酶水解和酸化的影响.结果表明:络合剂SC提高了污泥酶水解和酸化的效率,溶解性蛋白质和碳水化合物溶出量增加,SC的最佳投加剂量为0.432 g·g-1(以TS计,下同).络合剂SC可以提高污泥中短链脂肪酸(SCFAs)的积累量,同时减少达到最大SCFAs积累的时间,缩短厌氧消化时间.空白对照组和蛋白酶组的总SCFAs积累量分别在反应第7 d和第6 d达到最大值,而SC+蛋白酶组(SC 0.432 g·g-1)在反应第2 d就达到了最大值.从酶活性的变化和SEM图可知,SC的投加破坏了EPS的网络结构,原来被束缚、隐藏于污泥基体中的水解酶得到释放,从而提高了污泥水解速率.     

Thermal stabilization of chromium slag by sewage sludge: Effects of sludge quantity and temperature

To investigate the feasibility of detoxifying chromium slag by sewage sludge,synthetic chromium slag containing 3% of Cr(VI) was mixed with sewage sludge followed by thermal treatment in nitrogen gas for stabilizing chromium.The effects of slag to sludge ratio(0.5,1 and 2) and temperature(200,300,500,700 and 900°C) on treatment efficiency were investigated.During the mixing process before thermal treatment,59.8%-99.7% of Cr(VI) was reduced,but Cr could be easily leached from the reduction product.Increasing heating temperature and decreasing slag to sludge ratio strengthened the reduction and stabilization of Cr(VI).When the slag to sludge ratio was 0.5 and thermal treatment temperature was 300°C,the total leached Cr and Cr(VI) declined to 0.55 mg/L and 0.17 mg/L respectively,and 45.5% of Cr in the thermally treated residue existed as residual fraction.A two-stage mechanism was proposed for the reduction and stabilization of Cr.     

A new process to improve short-chain fatty acids and bio-methane generation from waste activated sludge

As an important intermediate product, short-chain fatty acids(SCFAs) can be generated after hydrolysis and acidification from waste activated sludge, and then can be transformed to methane during anaerobic digestion process. In order to obtain more SCFA and methane,most studies in literatures were centered on enhancing the hydrolysis of sludge anaerobic digestion which was proved as un-efficient. Though the alkaline pretreatment in our previous study increased both the hydrolysis and acidification processes, it had a vast chemical cost which was considered uneconomical. In this paper, a low energy consumption pretreatment method, i.e. enhanced the whole three stages of the anaerobic fermentation processes at the same time, was reported, by which hydrolysis and acidification were both enhanced, and the SCFA and methane generation can be significantly improved with a small quantity of chemical input. Firstly, the effect of different pretreated temperatures and pretreatment time on sludge hydrolyzation was compared. It was found that sludge pretreated at 100°C for 60 min can achieve the maximal hydrolyzation. Further, effects of different initial p Hs on acidification of the thermal pretreated sludge were investigated and the highest SCFA was observed at initial p H 9.0with fermentation time of 6 d, the production of which was 348.63 mg COD/g VSS(6.8 times higher than the blank test) and the acetic acid was dominant acid. Then, the mechanisms for this new pretreatment significantly improving SCFA production were discussed. Finally,the effect of this low energy consumption pretreatment on methane generation was investigated.     

Enhanced nitrogen removal upon the addition of volatile fatty acids from activated sludge by combining calcium peroxide and low-thermal pretreatments

This study investigated a combined low-thermal and CaO₂ pretreatment to enhance the volatile fatty acid (VFA) production from waste activated sludge (WAS). The fermentative product was added to a sequencing batch reactor (SBR) as an external carbon source to enhance nitrogen removal. The results showed that the combined pretreatment improved WAS solubilization, releasing more biodegradable substrates, such as proteins and polysaccharides, from TB-EPS to LB-EPS and S-EPS. The maximum VFA production of 3529 ± 188 mg COD/L was obtained in the combined pretreatment (0.2 g CaO₂/g VS + 70 °C for 60 min), which was 2.1 and 1.4-fold of that obtained from the sole low-thermal pretreatment and the control test, respectively. Consequently, when the fermentative liquid was added as an external denitrification carbon source, the effluent total nitrogen decreased to Class A of the discharge standard for pollutants in rural wastewater treatment plants in most areas of China.     

活化方式对过硫酸盐强化剩余污泥发酵的影响

对比考察了二价铁（Fe²⁺）、零价铁（ZVI）、超声波（US）3种活化方式对过硫酸盐（S₂O₈^2-）预处理剩余污泥的溶胞性能,并研究其对污泥厌氧发酵产酸进程的促进效能.结果表明,相对比未预处理污泥,S₂O₈^2-能够明显促进剩余污泥溶胞和发酵产酸进程;同时,活化后的S₂O₈^2-预处理效果明显优于未活化预处理实验组,其中S₂O₈^2-+Fe²⁺预处理体系的促进作用最为明显.Fe²⁺、ZVI和US活化S₂O₈^2-的3组溶胞率分别为42.6%、36.5%和32.9%,相比未活化实验组（22.3%）提高了10.6%～20.3%;3组活化体系最大挥发酸浓度分别为8052,6613,4996mg COD/L,而未活化组仅为3296mg COD/L.此外,不同方式活化S₂O₈^2-预处理对溶解性有机物溶出及挥发酸组分分布也有一定影响.从环境和经济角度来看,S₂O₈^2-+Fe²⁺体系对促进污泥发酵进程具有更大意义.     

Effect of Ca:Mg ratio and high ammoniacal nitrogen on characteristics of struvite precipitated from waste activated sludge digester effluent

This study revealed the relationship between the presence of calcium impurities and ammoniacal nitrogen concentration upon crystallization of struvite. The research hypothesis was that the presence of both calcium and high concentrations of ammoniacal nitrogen(328–1000 mg/L) in waste activated sludge may influence the struvite quality and acid stability. Hence, we studied the impact of Ca:Mg ratio upon morphology, particle size, purity and dissolution of struvite, in the presence of varying levels of excess ammoniacal nitrogen. X-ray diffraction revealed that up to 31.4%amorphous material was made which was assigned to hydroxyapatite. Increasing the ammoniacal nitrogen concentration and elevation of the Mg:Ca ratio maximized the presence of struvite. Struvite particle size was also increased by ammoniacal nitrogen as was twinning of the crystals. Tests with dilute solutions of organic acid revealed the sensitivity of struvite dissolution to the physical characteristics of the struvite. Smaller particles(21.2 μm) dissolved at higher rates than larger particles(35.86 μm). However,struvite dissolved rapidly as the p H was further reduced irrespective of the physical characteristics. Therefore, addition of struvite to low p H soils was not viewed as beneficial in terms of controlled nutrient release. Overall, this study revealed that waste activated sludge effluent with high ammoniacal nitrogen was prospective for synthesis of high quality struvite material.     

A strategy for enhancing anaerobic digestion of waste activated sludge: Driving anodic oxidation by adding nitrate into microbial electrolysis cell

Cathodic reduction of CO₂ and anodic oxidation of organic matters are crucial to methane-producing microbial electrolysis cell (MEC) applied in anaerobic digestion of waste activated sludge. However, cathodic CO₂ reduction is usually restrained by slow metabolism rates of H₂-utilizing methanogens and low electron-capturing capacity of CO₂, which consequently slows down the anodic oxidation that participates to sludge disintegration. Herein, a strategy with adding nitrate as electron acceptor to foster electronic transfer between the anode and cathode was proposed to improve anodic oxidation. Results showed that the average efficiency of anodic oxidation in the nitrate-added MEC increased by 55.9%. Accordingly, volatile suspended solid removal efficiency in the nitrate-added MEC was 21.9% higher than that of control MEC. Although the initial cumulative methane production in the nitrate-added MEC was lower than that of control MEC, the cumulative methane production in 24?days was 8.9% higher. Fourier transform infrared spectroscopy analysis indicated that anodic oxidation of MEC with nitrate accelerated the disintegration of sludge flocs and cell walls. Calculation on current signal further revealed that anodic oxidation driven by cathodic nitrate reduction was the main mechanism responsible for the improved sludge digestion.     

Kinetic analysis of waste activated sludge hydrolysis and short-chain fatty acids production at pH 10

The accumulation of short-chain fatty acids (SCFAs), a preferred carbon source for enhanced biological phosphorus removal microbes, was significantly improved when waste activated sludge (WAS) was fermented at pH 10. The kinetics of WAS hydrolysis and SCFAs production at pH 10 were investigated. It was observed that during WAS anaerobic fermentation at pH 10 the accumulation of SCFAs was limited by the hydrolysis process, and both the hydrolysis of WAS particulate COD and the accumulation of SCFAs followed first-order kinetics. The hydrolysis and SCFAs accumulation rate constants increased with a increasing of temperature from 10 to 35℃, which could be described by the Arrhenius equation. The kinetic data further indicated that SCFAs production at pH 10 was a biological process. Compared with the experiment of pH uncontrolled (blank test), both the rate constants of WAS hydrolysis and SCFAs accumulation at 20℃ were significantly improved when WAS was fermented at pH 10.     

游离氨对热水解联合中温厌氧消化处理剩余污泥的影响

热水解预处理强化了污泥厌氧消化过程,但同时增加了微生物受游离氨抑制的风险.对比传统工艺,在有机容积负荷率1.74~4.27gVS/(L·d)条件下,研究了游离氨(FA)对热水解联合中温厌氧消化工艺性能的影响.结果表明,组合工艺甲烷产量较传统反应器提高89%~121%,有机去除率提高1.21~1.46倍.但同时导致系统中游离氨浓度达89~382mgN/L,显著高于传统工艺中37~84mgN/L的范围.游离氨毒性测试显示,传统工艺中FA浓度从43mgN/L升至84mgN/L,没有抑制解乙酸产甲烷途径,而组合工艺中FA升至264mgN/L时,表现出抑制作用,尽管厌氧菌对高浓度FA表现更强的驯化趋势.结合氮负荷试验, FA浓度与基质利用能力,解乙酸产甲烷途径抑制程度和挥发性有机酸积累的关系表明,高有机负荷条件下组合工艺效率可通过控制氮负荷优化.     

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb2+and Zn2+in aqueous single-metal solutions. A p H value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients(above 0.99 for both metal ions) and insignificant lack of fit(p = 0.0838 and 0.0782 for Pb2+and Zn2+, respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation(between –NH2,-CN and metal ions) and ion-exchange(between –COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions.     

超声与碱预处理对剩余污泥磷及有机物释放的影响

为了回收污泥所含的磷,采用碱和超声波对3种剩余污泥进行预处理以释放磷,考察了处理前后PO3-4-P(正磷酸盐)、TP(总磷)、SCOD(可溶性COD)、TOC(总有机碳)、TS(总固体)、VS(挥发性固体)的释放规律及溶解性有机物的三维荧光特性变化.结果表明,碱和超声波处理均能有效破解污泥,释放磷和有机物;城市污泥比制药污泥更容易破解;城市污泥无机磷的释放高于有机磷,而工业污泥的有机磷释放高于无机磷;采用生物脱氮除磷工艺的城市污泥释放磷最多,释放有机物最少,有利于磷的进一步回收.碱处理和超声处理都不会从根本上改变污泥上清液中有机物的组分,但碱处理能促进污泥蛋白质类、腐殖酸类和富里酸类有机物的释放.     

Responses of protists with different feeding habits to the changes of activated sludge conditions: A study based on biomass data

Changes of protists, which were categorized into different functional groups primarily according to their feeding habits, in two full-scale municipal wastewater treatment systems experiencing sludge bulking were investigated over a period of 14 months. Protist biomass represented 3.7% to 5.2% of total biomass on average under normal sludge conditions, and the percentage increased significantly (p < 0.05) under sludge bulking conditions. The biomass of Chilodonella spp., capable of eating filamentous bacteria, tended to decrease in both systems when sludge bulking occurred, showing that the abnormal growth of filamentous bacteria did not lead to a biomass bloom of this group of protists. On the other hand, the bactivorous protists represented more than 96% of total protist biomass, and the biomass of this group, particularly the attached ciliates, increased significantly (p < 0.05) when sludge bulking occurred. The significant increase of the attached ciliates may have possibly facilitated the growth of filamentous bacteria through selectively preying on non-filamentous bacteria and further exacerbated sludge bulking. The redundancy analysis and correlation analysis results showed that the biomass changes of the attached ciliates were primarily related to the sludge volume index and to some extent related to five-day biochemical oxygen demand loading and hydraulic retention time.     

环境浓度双氯芬酸对活性污泥处理性能和微生物群落的影响

双氯芬酸(Diclofenac,DCF)是水环境中高频检出的新兴污染物,随着DCF的广泛使用,城市污水中的DCF逐年增加,对污水生物处理系统可能产生不利影响.本研究在序批式活性污泥反应器(SBR)中进行了连续120 d的DCF暴露实验,考察了环境浓度DCF(5和50μg·L~(-1))对SBR出水水质、微生物活性及微生物群落结构的影响.结果表明,DCF可降低COD的去除效果,但对氨氮和总氮的去除几乎没有影响.在微生物生理生化性能方面,5μg·L~(-1) DCF可促进超氧化物歧化酶(SOD)和琥珀酸脱氢酶(SDH)活性升高,但50μg·L~(-1) DCF导致SOD和SDH活性下降,DCF胁迫使胞外聚合物(EPS)含量增加.DCF会对微生物群落结构造成影响,其中,革兰氏阴性菌丰度增加,革兰氏阳性菌在5μg·L~(-1) DCF压力下丰度无明显变化,但在50μg·L~(-1) DCF压力下丰度显著降低(p0.05),微生物群落多样性在5μg·L~(-1) DCF下增加但在50μg·L~(-1) DCF下降低.16S rRNA基因焦磷酸测序结果表明,Proteobacteria是活性污泥群落中的优势门.随着DCF浓度的升高,Proteobacteria丰度不断增加,Chloroflexi、OD1和Firmicutes丰度则受到一定程度的抑制.高浓度DCF(50μg·L~(-1))刺激导致特定菌属如Nakamurella、Micropruina等丰度增加.研究结果揭示了环境浓度的DCF对活性污泥微生物处理能力和群落结构的影响特征,可为DCF的风险评估和污水处理工艺的优化提供借鉴.     

活性污泥降解四溴双酚A的特性、途径及毒性评估

电子行业典型污染物溴代阻燃剂对环境的污染引起了广泛关注.本文以产量最大、应用最广的典型溴代阻燃剂四溴双酚A(Tetrabromobisphenol A,TBBPA)为研究对象,考察了活性污泥降解四溴双酚A的特性、影响因素、降解途径并进行毒性评估.结果显示:活性污泥能有效降解水体中的TBBPA;在初始接菌量OD_(600)=0.77,TBBPA浓度为2.50 mg·L~(-1),温度为40℃,pH值为6.0时,经6 h反应后降解率可达58.46%,脱溴率达43.80%;在自然水体中活性污泥对TBBPA的降解受到抑制,尤其在腐殖质含量较高时;自然光能促进TBBPA降解,紫外光则抑制其降解活性;利用LC-Q-TOF-MS/MS检测到3种中间产物,推测TBBPA可能通过以下两种路径降解:①TBBPA发生甲基化和脱溴反应,产生甲基化的二溴双酚A,随后发生羟基化反应生成5-[1-(3-溴-4-甲氧基-苯基)-1-甲基-乙基]-2-甲氧基-苯酚;②TBBPA发生羟基化反应生成5-[1-(3-溴-4,5-二羟基-苯基)-1-甲基-乙基]-苯-1,2,3-三醇,随后发生脱溴、羟基化和甲基化反应,生成5-[1-(3-羟基-4,5-二甲氧基-苯基)-1-甲基-乙基]-2-甲氧基-苯-1,3-二醇;最后,利用发光细菌对该降解过程进行毒性评价,结果表明,活性污泥降解TBBPA的过程中其毒性未被完全去除,仍存在一定的环境风险.     

Dynamic membrane bioreactor performance enhancement by powdered activated carbon addition: Evaluation of sludge morphological, aggregative and microbial properties

The effects of powdered activated carbon(PAC) addition on sludge morphological, aggregative and microbial properties in a dynamic membrane bioreactor(DMBR) were investigated to explore the enhancement mechanism of pollutants removal and filtration performance. Sludge properties were analyzed through various analytical measurements. The results showed that the improved sludge aggregation ability and the evolution of microbial communities affected sludge morphology in PAC-DMBR, as evidenced by the formation of large, regularly shaped and strengthened sludge flocs. The modifications of sludge characteristics promoted the formation process and filtration flux of the dynamic membrane(DM) layer. Additionally, PAC addition did not exert very significant influence on the propagation of eukaryotes(protists and metazoans)and microbial metabolic activity. High-throughput pyrosequencing results indicated that adding PAC improved the bacterial diversity in activated sludge, as PAC addition brought about additional microenvironment in the form of biological PAC(BPAC), which promoted the enrichment of Acinetobacter(13.9%), Comamonas(2.9%), Flavobacterium(0.31%) and Pseudomonas(0.62%), all contributing to sludge flocs formation and several(such as Acinetobacter) capable of biodegrading relatively complex organics. Therefore, PAC addition could favorably modify sludge properties from various aspects and thus enhance the DMBR performance.     

活性污泥系统生物场-水力场-温度场耦合模型(FCASM3-Hydro-Temp)Ⅱ:模型校验

以采用AAO工艺的德清县狮山污水处理厂作为生物场-水力场-温度场耦合模型校验的现场试验基地.针对AAO工艺的特点,按照物料平衡原理分别对厌氧池、缺氧池、好氧池等各反应池内物质变化关系进行数学表征,建立了AAO工艺生物场-水力场-温度场耦合模型(FCASM3-Hydro-Temp)以及生物场-水力场耦合模型(FCASM3-Hydro).以若丹明B作为示踪剂于该厂进行了现场示踪实验,测得厌氧池、缺氧池和好氧池的水力弥散系数.依据试验所得数据,实现了对FCASM3-Hydro耦合模型以及FCASM3一Hydro-Temp耦合模型的现场模拟校验.校验结果表明,FCASM3-Hydre-Temp耦合模型能够实现活性污泥系统污染物质生物去除与水力场和温度场耦合变化过程的动态模拟.