三维荧光光谱结合化学分析评价胞外多聚物的提取方法

采用高速离心法、EDTA法、阳离子交换树脂法(CER)、甲醛法和甲醛 NaOH法提取普通活性污泥和好氧颗粒污泥的胞外多聚物(EPS),结合三维荧光光谱对五种方法进行评价,并对EPS中的成分进行分析.结果表明,5个EPS的三维荧光光谱峰值中,2个是类蛋白峰,2个是类富里酸峰,1个是类腐殖酸峰.匀浆对好氧颗粒污泥EPS的提取必不可少.甲醛严重干扰核酸的化学测定.透析前后的EPS提取液均应作为分析对象.单纯高速离心法无法有效提取EPS.CER法不容易造成细胞破壁,是一种比较有效的方法.虽然甲醛 NaOH法对EPS的提取量最大,但对细胞的破壁程度也最大.EDTA会导致溶胞,并严重污染EPS.甲醛 NaOH法和EDTA法都会严重干扰胞外蛋白的三维荧光光谱分析.     

莱茵衣藻胞外聚合物的提取和红外光谱表征

胞外聚合物(EPS)是微生物细胞代谢过程中产生的高分子物质,其中的多种官能团通过络合、转化等反应改变周围环境的元素形态和活性,在污染生物修复中具有应用前景.以模式微藻——莱茵衣藻为研究材料,采用加热法、NaOH法、EDTA法、阳离子交换树脂(CER)法、高速离心法提取莱茵衣藻的EPS,比较分析每种方法得到的EPS的含量及其组成成分,并结合LIVE/DEAD BacLight染色和激光共聚焦显微镜观察细胞活性,以确定莱茵衣藻EPS最适宜的提取方法.结果表明,不同提取方法得到的EPS各组分含量有显著差异,5种方法的提取总量依次为NaOH法加热法CER法EDTA法离心法.荧光染色和激光共聚焦显微镜检测结果表明,相对于NaOH法,加热法对微藻细胞的破坏程度较小,且傅里叶红外光谱分析结果表明,加热法提取的EPS出现N-H、C=O或C-N(蛋白质)和C-H、C-O-C、RHC(OH)(OR)(糖类)等吸收峰.本研究表明加热法是莱茵衣藻EPS的最适宜提取方法,EPS的官能团信息sk可为后续研究莱茵衣藻EPS与重金属之间的相互作用奠定基础.     

生物絮凝丝状真菌Talaromyces sp.CC-1胞外多聚物的提取及组分分析

以一株高絮凝活性的丝状真菌菌株——糙刺篮状菌(Talaromyces sp.CC-1)为研究对象,考察了热提取法、离心沉淀法、阳离子交换树脂法、NaOH-超声法等4种方法对该菌株胞外多聚物(ECP)的提取效果,结合细胞破坏程度(核酸含量)、ECP的提取效率、化学组成分析对这4种方法进行评价.结果表明,Talaromyces sp.CC-1产生的ECP的化学组成以多糖为主,4种方法中多糖分别占ECP总量的中97%、73%、72%、67%.其中,热提取法既能提高ECP的提取效率(提取量为940 mg·L-1),又不会在提取过程中对菌株细胞造成破坏(核酸仅占ECP总量1%,为离心沉淀法、树脂法和NaOH-超声法的0.06、0.04、0.03倍),是较适宜的ECP提取方法.红外光谱(FI-IR)对热提取的ECP的进一步分析表明,ECP结构中含有较多的羧基、羟基、氨基等絮凝活性基团,凝胶渗透色谱(GPC)分析显示,ECP的分子量分布为1.7×105—3.4×106Da之间,高效液相色谱(HPLC)测定ECP的单糖组成,发现ECP中多糖主要由葡萄糖、甘露糖、木糖和半乳糖等单糖构成(物质的量之比为95.7∶5.8∶1.8∶1).     

锆负载交联壳聚糖树脂的制备及硫酸根吸附性能

以壳聚糖为原料,利用反相悬浮法制备甲醛-戊二醛交联壳聚糖树脂,后与Zr4+反应制备锆负载交联壳聚糖吸附剂,用于吸附废水中SO2-4.运用红外光谱对吸附剂结构进行表征,采用静态吸附法考察负载条件对吸附量的影响及吸附剂重复使用性能.结果表明,交联反应主要发生在壳聚糖的氨基(—NH2)和一级羟基(C6—OH)上;锆负载过程中锆离子可负载于交联壳聚糖的氨基(—NH2)和羟基(—OH)上;最优条件即当Zr4+初始浓度为500 mg·L-1,体系pH值为3,负载时间为4 h时,锆负载交联壳聚糖吸附剂对SO2-4的吸附量达到最大为55.65 mg·g-1;用NaOH可有效恢复吸附剂,再生后的吸附剂吸附性能良好.     

花生壳活性炭对反渗透(RO)浓水的吸附特性

以花生壳活性炭对RO浓水进行吸附处理,利用傅立叶红外光谱(FTIR)和荧光光谱(EEM)研究花生壳活性炭对不同pH的RO浓水的吸附特性.结果表明,花生壳活性炭对溶解性有机碳(DOC)的吸附遵循准二级吸附动力学方程,特别是碱性条件下,DOC的吸附量随着pH的升高而降低.而且pH越高,达到吸附平衡的时间越长.通过FTIR光谱分析发现,活性炭的芳香结构吸收峰在吸附后红移至1630 cm-1,表明被吸附的有机物在该处有明显的特征吸收峰,而C—O和O—H官能团的吸收峰则因为钙离子等物质的吸附而显著降低.由EEM光谱分析可知,RO浓水的荧光物质主要由腐殖酸类腐殖质和富里酸类腐殖质组成,其荧光强度与DOC之间具有较好的线性相关性.     

聚(氯化二烯丙基铵)基二硫代氨基甲酸钠的合成及其对Cu(Ⅱ)的去除性能

以二烯丙基胺(DAA)、盐酸、偶氮二异丁脒盐酸盐(AIBA)、CS2和NaOH为原料,合成了聚(氯化二烯丙基铵)基二硫代氨基甲酸钠(PDACDTC).探讨了单体、引发剂AIBA和助剂EDTA的浓度对氯化二烯丙基铵(DAAC)聚合的影响,以及n(DAAC):n(NaOH):n(CS2)对PDACDTC中S含量的影响.采用元素分析、红外光谱和紫外光谱对其结构进行表征,并考察了其对模拟含Cu2+废水的去除效果.结果表明,单体浓度≥4.8 mol·L-1,AIBA浓度为0.02 mol·L-1、EDTA浓度为0.5 mmol·L-1时,聚(氯化二烯丙基铵)的特性粘数可达128.5 mL·g-1;当n(DAAC)∶n(NaOH)∶n(CS2)=1∶1.2∶1时,PDACDTC的S含量为32%.对50 mg·L-1和100 mg·L-1的含Cu2+废水的最佳用量分别为205 mg·L-1和415 mg·L-1,PDACDTC中～CSS-与Cu2+物质的量比分别为1.95∶1和1.97∶1,去除率分别为99.51%和99.84%,残余Cu2+浓度均低于国家污水综合排放一级标准(GB8978～1996).     

改性丝胶生物吸附剂对Ag~+的选择性吸附

以蚕丝丝胶(SS)为基材,通过接枝2,5-二硫二脲制备了改性丝胶生物吸附剂(SO),探讨了影响生物吸附的因素,并对比研究了不同体系中生物吸附剂对Ag~+的吸附行为.结果表明,在p H 1.0—6.0范围,吸附率随着p H升高而增大.相同条件下,SO吸附容量和吸附率明显优于SS,在单组分Ag~+溶液中,p H5.0时,SO和SS对Ag~+的吸附率分别为96.2%和57.8%,吸附容量分别为20.8 mg·g~(-1)和12.5 mg·g~(-1).在三组分(Ag~+-Cu~(2+)-Zn~(2+))及五组分(Ag~+-Cu~(2+)-Zn~(2+)-Ni~(2+)-Pb~(2+))溶液中,SO对Ag~+显示出良好的吸附选择性.p H5.0时,SO对其它金属离子很少吸附,而对Ag~+的吸附率分别高达95.8%和93.7%;SS尽管对其它贱金属离子吸附率也较低,但其对Ag~+的吸附率仅为25.4%和23.7%.吸附动力学表明,吸附剂对Ag~+的吸附符合准二级动力学模型,吸附过程为化学吸附,吸附过程活化能Ea(SO)=43.23 k J·mol~(-1),Ea(SS)=59.32 k J·mol~(-1).吸附热力学表明吸附过程为放热的自发过程.25℃吸附平衡时,Ag~+在固液两相的分配系数为K_D~Θ(SO)=5111.K_D~Θ(SS)=273.SO对Ag~+吸附机理主要为配位作用,粒子内扩散为吸附过程的速控步骤.     

竹子生物质废弃物前处理技术比较研究

为开发高效、低成本的预处理技术,促进竹子生物质及其废弃物资源的能源化利用,采用3种不同纤维素预处理方法分别对竹子生物质废弃物——笋壳和竹叶(茎)进行比较研究,同时与玉米秸秆相比较.结果表明,在稀H2SO4–酶解工艺、浓H3PO4–酶解工艺和NaOH–酶解工艺条件下,几种样品水解液中分别存在3、4和5种糖类组分.在稀H2SO4–酶解工艺中,木糖为主要成分,其次为葡萄糖;在浓H3PO4–酶解工艺中,葡萄糖为主要成分,其次为木糖;而在NaOH–酶解工艺,葡萄糖和木糖含量基本相当.同时对样品处理前后的表面结构变化分析表明,不同处理工艺均改变了竹叶(茎)、笋壳和秸秆等样品的表面结构,其结构更为松散,从而有利于纤维素的酶解.     

皇竹草生物炭的结构特征及对重金属吸附作用机制

本研究以皇竹草秸秆为生物质原料,在不同温度(400—700℃)下利用限氧热解法烧制一系列秸秆生物炭.利用扫描电镜(SEM)、X射线衍射(XRD)和拉曼光谱对所得生物炭样品进行分析,结果表明,500℃可使皇竹草秸秆生物炭充分热解,所得的生物炭晶体构成主要由半晶体结构涡轮层碳和一些矿物晶体组成,表面含有芳香类化合物、不饱和的醚类物质、无定形碳和C—C、C—O、C—OH等官能团.吸附实验表明,不同热解温度的皇竹草秸秆生物炭对混合重金属(Cr(Ⅵ)、Cu~(2+)、Cd~(2+))的吸附效果差异显著.在EDTA共存的条件下,皇竹草秸秆生物炭对Cr(Ⅵ)的吸附量远高于Cu~(2+)、Cd~(2+),其中500℃下热解得到的生物炭对Cr(Ⅵ)的吸附量达1.525 mg·g-1,而对Cu~(2+)和Cd~(2+)的吸附量约在0.05—0.15 mg·g-1.p H影响实验表明,在酸性条件(p H 1—4)下有利于Cr(Ⅵ)的吸附,其吸附量最高可达1.836 mg·g-1,在碱性条件(p H 9—13)下有利用于Cu~(2+)的去除,其吸附量最高可达0.836 mg·g-1.Cu~(2+)和Cd~(2+)在生物炭的吸附作用主要发生在C—C/C—H、C—O/C—OH等官能团上,重金属与生物炭中C—O官能团中的氧原子可能存在配位作用.     

胞外聚合物物理法提取过程的优化

对物理法提取活性污泥中的胞外聚合物(EPS)进行了优化.分别考察了超声时间、振摇时间、离心速度和时间以及加热时间对EPS的松散附着(LB)和紧密粘附(TB)提取的影响,得出污泥EPS物理法提取的优化方案.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

强力霉素在凹凸棒土上的吸附行为

通过等温吸附平衡法研究了强力霉素在凹凸棒土上的吸附行为,考察了pH、反应时间、离子强度和离子类型等因素对吸附的影响,探讨了吸附机理.结果表明,pH=8.5时,饱和吸附容量最大,为293.35μmol.g-1;强力霉素在凹凸棒土上的吸附可用Langmuir型等温方程和准二级动力学方程很好地拟合;离子强度对强力霉素的吸附影响不是很明显;0.05 mol.L-1NaOH能显著地将强力霉素从凹凸棒土上解吸下来.红外表征结果说明凹凸棒土对强力霉素的吸附可能是化学吸附,酸性条件下,强力霉素主要通过阳离子交换、静电作用、氢键作用等吸附在凹凸棒土上,部分H+可能通过强力霉素质子化吸附到凹凸棒土上.弱碱性条件下主要通过水桥接,与凹凸棒土层间阳离子配位以及结合于凹凸棒土边缘吸附位点达到吸附.     

有机磷酸酯阻燃剂降解方法的研究进展

有机磷阻燃剂(OPFRs)已取代溴代阻燃剂广泛应用于各行业,并很容易通过挥发、磨损等方式进入各环境介质中.目前,已在水体、土壤等环境介质中检测到了OPFRs的存在.本文总结了目前已有的OPFRs在环境中的降解方式,据其原理主要可分为化学法和生物法,化学法主要包含Fenton/类Fenton氧化法、紫外-双氧水法(UV/H2O2)、光催化法、过硫酸盐活化法和水解光解等,能够产生大量具有强氧化性的自由基(·OH、SO4·-等)破坏烃链使其降解.但该方法容易受到实际水体中的复杂成分影响,导致效果降低.生物法则是利用不同的细菌将OPFRs作为碳源或磷源在生长过程中将其消耗或和微生物体内的特异性酶发生酶促反应从而降解.通过总结归纳目前OPFRs的降解方法,了解现有方法存在的优点和缺点,为高效去除OPFRs提供理论基础.     

Biosorption of Cu(II) to extracellular polymeric substances (EPS) from Synechoeystis sp.: a fluorescence quenching study

Biosorption of extracellular polymeric substances (EPS) from Synechocystis sp. (cyanobacterium) with Cu(II) was investigated using fluorescence spectroscopy. Three fluorescence peaks were found in the excitation-emission matrix (EEM) fluorescence spectra of EPS. Fluorescence of peak A (Ex/Em = 275/452 nm) and peak C (Ex/Em = 350/452 nm) were originated from humic-like substances and fluorescence of peak B (Ex/ Em = 275/338 nm) was attributed to protein-like substances. Fluorescence of peaks A, B, and C could be quenched by Cu(II). The effective quenching constants (lg K_a) were 2.8?C5.84 for peak A, 6.4?C9.24 for peak B, and 3.48?C6.68 for peak C, respectively. The values of lg K_a showed a decreasing trend with increasing temperature, indicating that the quenching processes were static in nature. The binding constants (lg K_b) followed the order of peak A>peak B>peak C, implying that the humic-like substances in EPS have greater Cu(II) binding capacity than the protein-like substances. The binding site number, n, in EPS-Cu(II) complexes for peaks A, B, and C was less than 1. This suggests the negative cooperativity between multiple binding sites and the presence of more than one Cu binding site.     

三维荧光光谱技术在水环境修复和废水处理中的应用

近年来我国水环境污染问题情况日益严重,其引发的水华问题频发,藻类生长代谢过程释放的各类衍生物对水生生态系统及原水处理工艺性能造成影响。为此,分析环境水体、废水处理系统中溶解性有机污染物（DOM）的组成、性质和来源,对水环境安全及水污染控制具有重要意义。三维荧光光谱技术通过在不同的激发波长上扫描发射荧光谱以获得激发．发射矩阵（EEM）,基于EEM数据构建三维立体图或等高线（指纹图）描绘监测对象特性,可分析水体溶解性有机物、藻类及藻毒素等,近年来已在饮用水源水质监测、湖库富营养化成因分析及废水生物处理性能评价等方面得到应用。与传统分析方法相比,该技术具有灵敏度高、操作简便、检测快速、试剂消耗量少等优点。文章从荧光光谱分析技术基本原理出发,对三维荧光峰的分类、影响因素及其在水环境中的应用进行了综述,并对今后该技术在环境领域的研究方向进行了展望,以期为水污染控制、污染环境修复提供先进可靠的分析方法。     

Chemical additives affect sulfate reducing bacteria biofilm properties adsorbed on stainless steel 316L surface in circulating cooling water system

This paper studied the biofilm properties and corrosion behavior of sulfate reducing bacteria (SRB) on stainless steel 316L (SS316L) surface in circulating cooling water system with and without additives including hydroxy ethyl fork phosphonic acid (HEDP), dodecyl dimethyl benzyl ammonium chlotide (1227) and NaClO. Biochemical technique, electrochemical technology, X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used. The results show that the extracellular polymeric substance (EPS) in biofilm attached on the SS316L surface mainly contain proteins and polysaccharides, the contents are 98 ug·cm^-2 and 635ug·cm^-2, respectively. The polysaccharides were cut by 1227 about 80%, while 55% by NaClO. The proteins were reduced by NaClO about 53%, while only 30% by 1227. The potentiodynamic polarization shows that the corrosion potential of SS316L was enhanced from -0.495 V to -0.390 V by the chemical additives, delaying the occurrence of the corrosion. And the corrosion rate was also reduced from 5.19 × 10^-3 mm·a^-1 to 2.42 × 10^-3 mm·a^-1. But NaClO still caused pitting corrosion after sterilizing the bacteria, while 1227 can form a protective film on the surface of SS316L. Though HEDP contribute to the bacteria activity, it can enhance the breakdown potential. XPS results confirmed that 1227 can change the value of C:O in the biofilm attached on metal surface, and NaClO can eliminate the existence of amidogen. This study would provide some recommendations for the selection of chemical additives in the thermal power plant.

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Investigate of in situ sludge reduction in sequencing batch biofilm reactor: Performances,mechanisms and comparison of different carriers

Biofilm is an effective simultaneous denitrification and in situ sludge reduction system, and the characteristics of different biofilm carrier have important implications for biofilm growth and in situ sludge reduction. In this study, the performance and mechanism of in situ sludge reduction were compared between FSC-SBBR and SC-SBBR with constructed by composite floating spherical carriers (FSC) and multi-faceted polyethylene suspension carriers (SC), respectively. The variation of EPS concentration indicated that the biofilm formation of FSC was faster than SC. Compared with SCSBBR, the FSC-SBBR yielded 0.16 g MLSS/g COD, almost 27.27% less sludge. The average removal rates of COD and NH₄⁺-N were 93.39% and 96.66%, respectively, which were 5.21% and 1.43% higher than the average removal rate of SC-SBBR. Investigation of the mechanisms of sludge reduction revealed that, energy uncoupling metabolism and sludge decay were the main factors for sludge reduction inducing 43.13% and 49.65% less sludge, respectively, in FSC-SBBR. EEM fluorescence spectroscopy and SUVA analysis showed that the hydrolytic capacity of biofilm attached in FSC was stronger than those of SC, and the hydrolysis of EPS released more DOM contributed to lysis-cryptic growth metabolism. In additional, Bacteroidetes and Mizugakiibacter associated with sludge reduction were the dominant phylum and genus in FCS-SBBR. Thus, the effect of simultaneous in situ sludge reduction and pollutant removal in FSC-SBBR was better.

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ZnO薄膜光电催化降解乙酰甲胺磷

采用溶胶-凝胶法制备了ZnO薄膜,并通过光电流响应、EIS、SEM、XRD等分析方法对其光电化学性能、表面形貌和结构进行表征.以制备的ZnO薄膜为工作电极对乙酰甲胺磷进行光电催化降解.实验表明,ZnO薄膜电极在UV照射下能够有效地光电催化降解乙酰甲胺磷,加入适量H2O2后具有一定的协同作用.在H2O2浓度为9.908 mmol.L-1,外加电压为1.2 V,支持电解液Na2SO4浓度为0.01 mol.L-1,溶液pH值为5.4的条件下,对0.1 mmol.L-1的乙酰甲胺磷180 min的降解率可达到89.6%.     

Characterization of the dissolved organic matter in sewage effluent of sequence batch reactor: the impact of carbon source

Dissolved organic matter (DOM) transformation in sequence batch reactor (SBR) fed with carbon sources of different biodegradability was investigated. During the biologic degradation process, the low molecular weight (MW) fraction (< 1 kDa) gradually decreased, while the refractory compounds with higher aromaticity were aggregated. Size exclusion chromatography (SEC) and fluorescence of excitation emission matrices (EEM) demonstrated that more biopolymers (polysaccharides or proteins) and humic-like substances were presented in the extracellular polymeric substance (EPS) extracted from the SBR fed with sodium acetate or glucose, while the EPS from SBR fed with slowly biodegradable dissolved organic carbon (DOC) substratestarch had relatively less biopolymers. Comparing the EfOM in sewage effluent of three SBRs, the effluent from SBR fed with starch is more aromatic. Organic carbon with MW>1 kDa as well as the hydrophobic fraction in DOM gradually increased with the carbon sources changing from sodium acetate to glucose and starch. The DOC fractionation and the EEM all demonstrated that EfOM from the effluent of the SBR fed with starch contained more fulvic acid-like substances comparing with the SBR fed with sodium acetate and glucose.