1、溶液中有机物分析表征 主要内容主要内容 1.常用有机物表征方法 2.有机物分离方法 3.WR最新难降解有机物研究进展 4.沼液相关研究进展常用有机物表征方法常用有机物表征方法2.简单、单一、未（已）知物1.复杂、混合、未（已）知物宏观分析：COD,MW,FT-IR,NMR,UV,亲疏水性等分离：GC,LC,SEC,IC,SPE分析方法FT-IR,MS,NMR等MW distribution analysis MW distribution analysis has been extensively applied to wastewater samples, and is suitable t
2、o be used as a first step in analyzing complex samples. Size distribution analysis has been widely used, normally carried out using ultrafiltration (UF) or size exclusion chromatography (SEC). UF molecular weight cut-offs: 1 kDa, 3 kDa, 5 kDa,10 kDa, 100 kDa, 300 kDa SEC is useful for MW screening o
3、f samples before using UF to obtain the separated sample for analysis. There are also some drawbacks: the chemical interaction between the column materials, the solvent, a n d t h e o r g a n i c c o m p o u n d s i n S E C c a n overestimate/underestimate the MW profile. Another disadvantage is tha
4、t the peaks from SEC can be very difficult to differentiate between in some samples. GPC is when the mobile phase is an organic solvent, and GFC when the mobile phase is aqueous.gel-filtration-chromatography (GFC) gel-permeation chromatography (GPC)SEC UF is more suitable for identification of compo
5、unds, since large amounts of the sample can be recovered for further characterization. In UF, there are also many factors such as membrane pore size distribution, sample temperature, stirred cell pressure, pH, and membrane materials that can influence the transport of organics through the membranes.
6、 按照Alex et al.提出的有机碳物理尺寸概念 ，有机碳可分为颗粒有机碳(Particulate organic carbon, POC)、胶体有机碳(Colloidal organic carbon, COC)、微胶体有机碳(Fine colloidal organic carbon, FCOC)和溶解性有机碳(Dissolved organic carbon, DOC)。 POC能通过 1.2 m滤膜但0.45 m滤膜截留； COC能通过 0.45 m滤膜但被 0.1 m滤膜截留； FCOC能通过 0.1 m滤膜但被 0.025 m滤膜截留； DOC能通过 0.025 m滤膜。 Ev
7、aluation of on-site biological treatment for landfill leachates and its impact: A size distribution study（WR） Evaluation of on-site biological treatment for landfill leachates and its impact: A size distribution study（WR） HPLC+SEC column: This separation method was effective in revealing the similar
8、ities and differences between microbial products from two different activated sludge plants, and demonstrating the generation and degradation of compounds. Analytical methods for soluble microbial products (SMP) and extracellular polymers (ECP) in wastewater treatment systems: A review（WR）Hydrolysis
9、 of high MW compounds For low MW compounds, GC-MS can be used for identification by matching with existing libraries. For high MW compounds it is more complicated. There is no easy method to identify high MW compounds in complex mixtures. protein/carbohydrates amino acids and monosaccharide GC-MS Hy
10、drolysis: acidic hydrolysis, microwave radiationinduced hydrolysis, alkaline hydrolysis, and enzymatic hydrolysishydrolysisProtein analysis Lowry method excitation-emission matrix spectroscopy（EEM） resonance lights cattering（共振光散射） proteomics（蛋白质组） ion-exchange chromatography Multi-dimensional prote
11、in identification technology (MudPIT) is becoming a prevalent proteomic approach due to its high-throughput separations and accurate mass detection. In-solution digestion involves simultaneous digestion of hundreds or thousands of proteins.（HPLC+tandem MS） Exploring human plasma proteome strategies:
12、 High efficiency in-solution digestion protocol for multi-dimensional protein identification technology（Journal of Chromatography A） Lowry method Reaction: Cu2+peptide bonds（肽键）（pH7） Shortcoming: Proteins are easy to degrade monopeptides, polypeptides, and/or other organic polymers, so the identific
13、ation of “proteins” is very likely to be an overestimation. The result should be confirmed with a proteomic study, or ion exchange chromatography. Proteomics Proteomics is the large-scale study of proteins, particularl their structure and function. Steps： 1.fractionation and/or protein concentration
14、 2.digestion 3.separation(HPLC) 4.detection(MS) However, there is a scarcity of proteomic studies applied to aerobic and anaerobic biological treatment systems.Carbohydrate analysis titration gravimetric colorimetric enzymatic chromatographic Colorimetric use Anthrone and Phenol-Sulfuric Acid for qu
15、antification of carbohydrates Chromatographic methods are alternative techniques for analyzing monosaccharides(单糖) and oligosaccharides(多糖).Carbohydrates can be separated based on their differential adsorption characteristics. There are several types of columns which can be used for the analysis of
16、sugars, such as ion-exchange, amino, and reversed-phase columns Using a resonance light-scattering technique low concentration of proteins and carbohydrates can be determined. Congo red and Neutral red dyes were used for the determination of proteins and carbohydrates, respectively.UV-Vis spectromet
17、ry Humic substances in bioreactor effluents were characterized by having a high degree of aromaticity. specific UVA: The ratio of UV absorbance at 254 nm and the DOC of the sample. This represents a measure of aromaticity of the organics in the sample. Researchers have have used specific UVA to eval
18、uate the aromaticity of SMPs and ECPsd and suggested that aromaticity can increase after anaerobic treatment.Fluorescence excitation-emission matrixspectroscopy (EEM) EEM has been applied as a substitute for some chemical analysis to identify compounds in the sample by comparing their EEM spectral f
19、ingerprints. Each EEM presents spectral information about the chemical composition of the samples. EEM technique can only detect fluorescence active compounds, whereas other components such as polysaccharides were not detectableFourier transform infrared spectrometry (FTIR) FTIR has been used to det
20、ermine the functional groups of organic matter, and to predict the major components in wastewater treatment systems. But is not suitable for compound identification. It is not easy to use FTIR as a quantitative analytical technique due to the difficulties related to sample preparation.NMR NMR可检测的核素有
21、很多,如1H、13C、15N、19F、23Na、31P等。由于大多数药物都含有质子,最常用的是1H-NMR和13C-NMR。对于一些含有氟、磷等原子的化合物,可借助于19F谱、31P谱为研究手段。 通过化学位移及其峰面积等可以得到相应的官能团、化学官能团、化学键键信息。13C-NMR图谱图谱 Characteristic transformation of humic acid during photoelectrocatalysis process and its subsequent disinfection byproduct formation potential（WR）DOM fra
22、ctionEffective removal of effluent organic matter (EfOM) from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer（WR） Contribution of effluent organic matter (EfOM) to ultrafiltration (UF) membrane fouling: Isolation, characterization, and fouling effect of EfOM fractio
23、ns（WR）有机物提纯、分离方法有机物提纯、分离方法 固相萃取 毛细管电泳 超临界流体色谱固相萃取（固相萃取（SPE） 固相萃取是采用用固体物质作为萃取剂 ,采用高效、高选择性的固定相 进行萃取的样品预处理技术。 SPE是一种吸附剂萃取，样品通过填充吸附剂的一次性萃取柱，分析物和杂质被保留在柱上，然后分别用选择性溶剂去除杂质，洗脱出分析物，从而达到分离的目的。SPE的分离模式主要取决于填充剂的类型和溶剂的性质。 SPE柱的填料粒径填料粒径（40m）要比HPLC填料（310m）大。由于短的柱床和大的粒径，SPE柱效比HPLC色谱柱低得多。因此，用SPE只能分开保留性质有很大差别的化合物，且SPE
24、柱是一次性使用。一个完整的固相萃取步骤包括固相萃取柱的预处理、上样、洗去干扰物质、洗脱及收集分析物四个步骤。毛细管电泳毛细管电泳 一、毛细管区带电泳一、毛细管区带电泳(CZE) capillary zone electrophoresis 二、胶束电动毛细管色谱二、胶束电动毛细管色谱(MEKC) micelle electrokinetic chromatography 三、毛细管凝胶电泳（三、毛细管凝胶电泳（CGE） capillary gel electrophoresis 四、毛细管电色谱四、毛细管电色谱(CEC) capillary electrochromatography毛细管区带
25、电泳毛细管区带电泳 带电粒子的迁移速度=电泳和电渗流速度的矢量和。 正离子：两种效应的运动方向一致，在负极最先流出； 中性粒子：无电泳现象，受电渗流影响，在阳离子后流出； 阴离子：两种效应的运动方向相反；电渗流 电泳时,阴离子在负极最后流出,在这种情况下,不但可以按类分离,同种类离子由于差速迁移被相互分离。 这是最基本、应用广的分离模式； 1.1.缓冲溶液中加入离子型表面活性剂，其浓度达到临界缓冲溶液中加入离子型表面活性剂，其浓度达到临界浓度，形成一疏水内核、外部带电的胶束。浓度，形成一疏水内核、外部带电的胶束。 在电场力的作用在电场力的作用下，胶束在柱中移下，胶束在柱中移动。动。胶束电动毛细
26、管色谱胶束电动毛细管色谱2. 电泳流和电渗流的方向相反，且u电渗流 u电泳 ，负电胶束以较慢的速度向负极移动；3.中性分子在胶束相和溶液（水相）间分配，疏水性强的组分与胶束结合的较牢，流出时间长；4.可用来分离中性物质，扩展了高效毛细管电泳的应用范围； 5.色谱与电泳分离模式的结合。毛细管凝胶电泳毛细管凝胶电泳 将聚丙烯酰胺等在毛细管柱内交联生成凝胶。 其具有多孔性，类似分子筛的作用，试样分子按大小分离。能够有效减小组分扩散，所得峰型尖锐，分离效率高。 蛋白质、DNA等的电荷/质量比与分子大小无关，CZE模式很难分离，采用CGE能获得良好分离，DNA排序的重要手段。 特点：抗对流性好，散热性好
27、，分离度极高。 无胶筛分技术：采用低粘度的线性聚合物溶液代替高粘度交联聚丙烯酰胺。柱便宜、易制备。毛细管电色谱毛细管电色谱 将细粒径固定相填充到毛细管中或在毛细管内壁键合固定相，毛细管两端施加高电压，以电渗流驱动操作缓冲液。它也包含了电泳和色谱两种机制，溶质根据它们在流动相和固定相中的分配系数不同和自身淌度的差异得以分离。 整合了毛细管电泳与微径液相色谱的优点，大大提高了样品的分离能力，代表了分析学界高效微分离的趋势，尤其适用于复杂生物及化学体系的研究。超临界流体色谱超临界流体色谱 与高效液相色谱法比较与高效液相色谱法比较 实验证明SFC法的柱效一般比HPLC法要高：当平均线速度为0.6cmS
28、-1时，SFC法的柱效可为HPLC法的3倍左右，在最小板高下载气线速度是4倍左右；因此SFC法的分离时间也比HPLC法短。这是由于流体的低粘度使其流动速度比HPLC法快，有利于缩短分离时间。 与气相色谱法比较与气相色谱法比较 出于流体的扩散系数与粘度介于气体和液体之间，因此SFC的谱带展宽比GC要小；另外，SFC中流动相的作用类似LC中流动相，流体作流动相不仅载带溶质移动，而且与溶质会产生相互作用力，参与选择竞争。 如果我们把溶质分子溶解在超临界流体看作类似于挥发，这样，大分子物质的分压很大，因此可应用比GC低得多的温度，实现对大分子物质、热不稳定性化合物、高聚物等的有效分离。 下图描绘了SF
29、C与其他色谱方法测定相对分子质量范围的比较。由图看出SFC比起GC法测定相对分子质量的范围要大出好几个数量级，基本与LC法相当。超临界流体色谱的应用超临界流体色谱的应用 超临界流体色谱法被广泛应用于糖类、蛋白质、氨基酸、天然产物、药物、表面活性剂、高聚物、多聚物、农药、炸药和火箭推进剂等物质的分离和分析。WR中难降解有机物研究中难降解有机物研究NumTitleContent1Removal of micropollutants during tertiary wastewater treatment by biofiltration: Role of nitrifiers and remova
30、l mechanisms反硝化细菌处理微污染2Treatment of olive oil millwastewater by combined process electro-Fenton reaction and anaerobic digestion电芬顿与厌氧消化处理油厂废水3Textile wastewater treatment: Aerobic granular sludge vs activated sludge systems好氧颗粒污泥与活性污泥处理印染废水的对比4Biogenic metals for the oxidative and reductive removal
31、 of pharmaceuticals, biocides and iodinated contrast media in a polishing membrane bioreactor膜反应器氧化还原处理制药等废水5Solar photocatalytic oxidation of recalcitrant natural metabolic by-products of amoxicillin biodegradation先用微生物处理AMX，代谢产物没有了抗菌性，但依然难降解，后采取光催化方式去除副产物。NumTitleContent1New chlorinated amphetamin
32、e-type-stimulants disinfection-by-products formed during drinking water treatment自来水消毒中产生的新的副产物2Treatment of municipal solid waste leachate using a submerged anaerobic membrane bioreactor at mesophilic and psychrophilic temperatures: Analysis of recalcitrants in the permeate using GC-MS不同温度对SAMBR处理污
33、泥渗滤液的影响及其MS对难降解有机物的分析38.Photooxidation and subsequent biodegradability of recalcitrant tri-alkyl phosphates TCEP and TBP in water光催化联合生物方法处理难降解有机物4Characterisation and removal of recalcitrants in reverse osmosis concentrates from water reclamation plants反渗透浓液中有机物特别是有色及含氮有机物的表征及去除，去除研究了铁、铝絮凝去除及其高级氧化去
34、除。5Ultrasonic treatment of water contaminated with ibuprofen超声处理含布洛芬的废水44写在最后写在最后成功的基础在于好的学习习惯成功的基础在于好的学习习惯The foundation of success lies in good habits 结束语当你尽了自己的最大努力时，失败也是伟大的，所以不要放弃，坚持就是正确的。When You Do Your Best, Failure Is Great, So DonT Give Up, Stick To The End演讲人：XXXXXX 时 间：XX年XX月XX日 46写在最后写在最后成功的基础在于好的学习习惯成功的基础在于好的学习习惯The foundation of success lies in good habits 结束语当你尽了自己的最大努力时，失败也是伟大的，所以不要放弃，坚持就是正确的。When You Do Your Best, Failure Is Great, So DonT Give Up, Stick To The End演讲人：XXXXXX 时 间：XX年XX月XX日
