CN101819148A - Three-dimensional fluorescence spectrum method for measuring chlorine disinfection by-product precursor in water - Google Patents
Three-dimensional fluorescence spectrum method for measuring chlorine disinfection by-product precursor in water Download PDFInfo
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Abstract
本发明属于环境监测与分析技术领域。可用于测定水中氯消毒副产物前体物，为其污染控制提供技术支持。针对现有氯消毒副产物前体物测定方法存在步骤繁杂、结果不够明确的问题，研究了三维特征荧光参数表征氯消毒副产物前体物可行性，并确认了氯消毒副产物前体物特征荧光表征参数与其生成势之间的相关性，开发了水中氯消毒副产物前体物简便、快速测定方法。其测定步骤包括：建立氯消毒副产物前体物特征荧光强度与其生成势之间的线性校正方程；三维荧光光谱扫描待测水样；计算氯消毒副产物生成势和结果修正。本发明能够对水中氯消毒副产物前体物进行分类解析；无需复杂的样品处理与检测；平均相对误差在10％左右；不破坏样品结构，易实现在线检测。The invention belongs to the technical field of environmental monitoring and analysis. It can be used to determine the precursors of chlorine disinfection by-products in water and provide technical support for its pollution control. Aiming at the problems of complicated steps and unclear results in the existing methods for the determination of chlorine disinfection by-product precursors, the feasibility of characterizing chlorine disinfection by-product precursors with three-dimensional characteristic fluorescence parameters was studied, and the characteristics of chlorine disinfection by-product precursors were confirmed. A simple and rapid method for the determination of chlorine disinfection by-product precursors in water was developed based on the correlation between fluorescence characterization parameters and their formation potential. The determination steps include: establishing a linear correction equation between the characteristic fluorescence intensity of the chlorine disinfection by-product precursor and its formation potential; scanning the water sample to be tested by three-dimensional fluorescence spectrum; calculating the formation potential of the chlorine disinfection by-product and correcting the result. The invention can classify and analyze the precursors of chlorine disinfection by-products in water; it does not need complex sample processing and detection; the average relative error is about 10%; it does not destroy the structure of samples, and it is easy to realize online detection.
Description
技术领域technical field
本发明属于环境监测与分析，应用于测定再生水中消毒副产物前体物，可用于再生水质安全保障技术研发与氯消毒副产物前体物的控制；也适用于饮用水中氯消毒副产物的控制。The invention belongs to environmental monitoring and analysis, is applied to the determination of disinfection by-product precursors in reclaimed water, can be used for the research and development of regenerated water quality safety assurance technology and the control of chlorine disinfection by-product precursors; it is also suitable for the detection of chlorine disinfection by-products in drinking water control.
背景技术Background technique
(1)饮用水中氯消毒副产物前体物的测定方法(1) Determination of precursors of chlorine disinfection by-products in drinking water
消毒副产物(DBPs，Disinfection by products)是消毒剂与水中溶解性有机物反应生成的对人体有毒害作用的物质。当采用氯消毒剂时，主要生成三卤甲烷(THMs)和卤乙酸(HAAs)氯消毒副产物，水中溶解性有机物则被称为氯消毒副产物前体物。Disinfection by-products (DBPs, Disinfection by products) are substances that are toxic to the human body and are produced by the reaction of disinfectants with dissolved organic matter in water. When chlorine disinfectants are used, trihalomethanes (THMs) and haloacetic acids (HAAs) chlorine disinfection by-products are mainly generated, and dissolved organic matter in water is called chlorine disinfection by-product precursors.
根据国内外文献报道，天然水体中腐殖酸、富里酸等腐殖质类物质是氯消毒副产物的主要前体物质。腐殖质是一种天然的高分子聚合物，主要来源于生物代谢残渣，广泛地存在于水体、土壤及其周围环境中。腐殖酸(HumicAcid，HA)是腐殖质中溶于碱而不溶于酸的部分，富里酸(Fulvic acid，FA)则为即可溶于碱、又可溶于酸的部分。受现有技术水平限制，以天然水体为水源的给水处理系统出水中，不可避免地会残余少量的腐殖质类溶解性有机物，与氯消毒剂作用生成消毒副产物，对饮用水安全和人体健康产生不利影响。为提高饮用水质安全性，必须加强水中消毒副产物前体物的控制。因此，需要通过定性、定量分析测定消毒副产物前体物，判断其物质成分及其来源，以便采取有针对性的措施加以控制。According to domestic and foreign literature reports, humic substances such as humic acid and fulvic acid in natural water bodies are the main precursor substances of chlorine disinfection by-products. Humus is a natural polymer, mainly derived from biological metabolic residues, widely present in water, soil and its surrounding environment. Humic acid (HA) is the part of humic substances that is soluble in alkali but not in acid, while fulvic acid (FA) is the part that is soluble in both alkali and acid. Limited by the existing technical level, a small amount of humus-like dissolved organic matter will inevitably remain in the effluent water of the water supply treatment system using natural water as the water source, which will react with chlorine disinfectants to form disinfection by-products, which will pose a threat to drinking water safety and human health. Negative Effects. In order to improve the safety of drinking water quality, it is necessary to strengthen the control of precursors of disinfection by-products in water. Therefore, it is necessary to determine the precursors of disinfection by-products through qualitative and quantitative analysis, and to judge their composition and source, so as to take targeted measures to control them.
鉴于腐殖酸结构的复杂性，至今，对于腐殖酸的分子组成和化学结构仍处于研究阶段中，由于这种模糊性的存在，对于以腐殖质为主的天然水中消毒副产物前体物的研究控制，也多通过间接的方法来表示此类物质的变化趋势。目前国内外对于天然水中氯消毒副产物前体物的表征多采用消毒副产物生成潜能或称生成势(DBPFP，DBP Formation Potential)、模拟配水管网系统测试(Simulated Distribution System Test)、统一生成条件测试(Uniform FormationCondition)、紫外吸光度和有机碳浓度的比值(SUVA)4种方法进行定量测定，其中，应用广泛的是DBPFP和SUVA。In view of the complexity of the structure of humic acid, the molecular composition and chemical structure of humic acid are still in the research stage. Research and control also use indirect methods to express the changing trend of such substances. At present, for the characterization of chlorine disinfection by-product precursors in natural water at home and abroad, the formation potential of disinfection by-products or formation potential (DBPFP, DBP Formation Potential), simulated distribution system test (Simulated Distribution System Test), and unified generation conditions are mostly used. Test (Uniform Formation Condition), UV absorbance and organic carbon concentration ratio (SUVA) four methods for quantitative determination, among which DBPFP and SUVA are widely used.
DBPFP的测定原理是：投加足量的氯，在充分长的时间内与水中的消毒副产物前体物完全反应，然后检测生成的消毒副产物三卤甲烷THMs和卤乙酸HAAs，来间接表征水中潜在的全部前体物，包括三卤甲烷生成潜能和卤乙酸生成潜能。主要测定过程如下：The measurement principle of DBPFP is: adding sufficient amount of chlorine to completely react with the precursors of disinfection by-products in water for a long enough time, and then detect the generated disinfection by-products trihalomethanes THMs and haloacetic acid HAAs to indirectly characterize Potential total precursors in water, including trihalomethane forming potential and haloacetic acid forming potential. The main measurement process is as follows:
①加氯量的确定：由于不同的水体水质情况差别比较大，所需的加氯量不同，所以在测定三卤甲烷生成潜能(THMFP)和卤乙酸生成潜能(HAAFP)前，必须先确定加氯量。确定的原则是反应终点时水样中的游离余氯量为5mg/L。① Determination of the amount of chlorine added: Since the water quality of different water bodies is quite different, the amount of chlorine added is different, so before measuring the trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP), it must be determined first. amount of chlorine. The determined principle is that the amount of free residual chlorine in the water sample at the end of the reaction is 5 mg/L.
②水样的采集：取两个100mL的具反口胶塞的玻璃瓶，在其中一个玻璃瓶中加入1g抗坏血酸(b瓶)，不加抗坏血酸的为a瓶，分别向两个瓶中各加入100mL水样，24h内测定b瓶中的三卤甲烷和卤乙酸量；②Collection of water samples: Take two 100mL glass bottles with anti-mouth rubber stoppers, add 1g of ascorbic acid (bottle b) to one of the glass bottles, and bottle a without ascorbic acid, add 100mL water sample, measure the amount of trihalomethane and haloacetic acid in bottle b within 24h;
③样品氯化处理：a瓶中加入一定量的次氯酸钠溶液，置于(25±2)℃的培养箱中反应5天；③Sample chlorination treatment: add a certain amount of sodium hypochlorite solution to bottle a, and place it in an incubator at (25±2)°C for 5 days;
④测定余氯：从培养箱中取出a瓶，测定余氯并加入1g抗坏血酸；④ Determination of residual chlorine: take out bottle a from the incubator, measure residual chlorine and add 1g of ascorbic acid;
⑤测定三卤甲烷和卤乙酸生成量：采用气相色谱法或气相色谱-质谱方法测定a瓶中的三卤甲烷和卤乙酸生成量。⑤ Determination of the amount of trihalomethanes and haloacetic acids generated: use gas chromatography or gas chromatography-mass spectrometry to measure the amount of trihalomethanes and haloacetic acids generated in bottle a.
DBPFP测试的优点在于大剂量氯和长时间反应可以使水中的前体物质完全反应生成消毒副产物，提供了一个最大值(也就是前体物质生成消毒副产物的潜能)，但是大剂量氯的加入与实际情况相悖，相对误差较大；同时测试时间长及测定过程的繁杂性都影响了该方法的实际应用；另外该方法是通过间接测定DBPS的生成量来表示水样中前体物的含量，不能明确直观地反映前体物的种类及其含量，因而对于实际生产来说，该方法不能有针对性地指导消毒副产物前体物的污染控制。The advantage of the DBPFP test is that a large dose of chlorine and a long reaction time can completely react the precursor substances in the water to form disinfection by-products, providing a maximum value (that is, the potential of the precursor substances to form disinfection by-products), but the large dose of chlorine The addition is contrary to the actual situation, and the relative error is relatively large; at the same time, the long test time and the complexity of the measurement process have affected the practical application of the method; in addition, the method is to indirectly measure the amount of DBPS produced to represent the precursor in the water sample. Therefore, for actual production, this method cannot guide the pollution control of disinfection by-product precursors in a targeted manner.
天然水体中的主要有机物，如腐殖质，是生物质及其代谢残余混合物，分子结构中含有大量苯环及羧基、羟基、杂原子等，研究表明此类物质大部分属于消毒副产物的前体物，它们在紫外光区具有显著地吸收，用紫外吸光度UV254可以表示此类物质在水中的综合含量；有机碳浓度则表示水中全部有机物的含量，两者的比值(SUVA)可以用来表示水中氯消毒副产物前体物所占的比例。其测定方法为：水样经0.45μm滤膜过滤后，分别用紫外分光光度计在紫外光波长254nm处测其吸光度值和总有机碳分析仪测总有机碳TOC，将测定结果进行比较。该方法前处理步骤简单，测定时间短，但是仪器方面除紫外分光光度计之外，还需要总有机碳分析仪，设备要求较为复杂。再者SUVA法是一个综合指标，反映的是水样中在紫外光区有吸收作用的溶解性有机物所占的量，消毒副产物前体物只是其中的一部分，因此该指标属于消毒副产物前体物的非特异性指标，对于消毒副产物前体物污染控制的指导作用仍然不够明确。The main organic matter in natural water bodies, such as humus, is a mixture of biomass and its metabolic residues. The molecular structure contains a large number of benzene rings, carboxyl groups, hydroxyl groups, heteroatoms, etc. Studies have shown that most of these substances are precursors of disinfection by-products , they have significant absorption in the ultraviolet region, and the ultraviolet absorbance UV 254 can be used to indicate the comprehensive content of such substances in water; the organic carbon concentration indicates the content of all organic substances in water, and the ratio of the two (SUVA) can be used to indicate water Proportion of chlorine disinfection by-product precursors. The measurement method is as follows: After the water sample is filtered through a 0.45 μm filter membrane, the absorbance value of the water sample is measured at a wavelength of 254 nm by a UV spectrophotometer and the total organic carbon TOC is measured by a total organic carbon analyzer, and the measurement results are compared. The pretreatment steps of this method are simple and the measurement time is short, but in terms of instruments, in addition to the ultraviolet spectrophotometer, a total organic carbon analyzer is also required, and the equipment requirements are relatively complicated. Furthermore, the SUVA method is a comprehensive indicator, which reflects the amount of dissolved organic matter in the water sample that absorbs in the ultraviolet region, and the precursors of disinfection by-products are only a part of it, so this indicator belongs to the front of disinfection by-products. The guiding role of non-specific indicators for disinfection by-product precursor pollution control is still not clear enough.
综上所述，目前针对天然水体的DBPFP法测定时间长、步骤繁杂，不能明确反映消毒副产物前体物种类和实现在线连续测定；SUVA法针对对象具有笼统性及对仪器设备要求较为复杂等不足之处，上述两种方法均难以有针对性地指导对消毒副产物前体物的污染控制。In summary, the current DBPFP method for natural water bodies takes a long time to measure and has complicated steps, which cannot clearly reflect the types of precursors of disinfection by-products and realize online continuous measurement; the SUVA method is general in terms of objects and has relatively complicated requirements for equipment, etc. Insufficient, the above two methods are difficult to guide the pollution control of the precursors of disinfection by-products.
(2)再生水中氯消毒副产物的测定方法(2) Determination method of chlorine disinfection by-products in reclaimed water
再生水是城市污水经过生物二级处理及深度处理后的出水，可用于市政杂用、城市水景、建筑中水、工业用冷却水等。由于其水源和水处理过程的复杂性，再生水质较为复杂，生物代谢残余的溶解性有机物种类多，含量高。目前针对再生水中氯消毒副产物前体物的测定方法仍然沿用饮用水的测定方法，但是对于水质较天然水体复杂多的再生水，采用上述间接或综合测定方法，无法分类测定各种消毒副产物前体物，其测定结果更具模糊性，不能解析消毒副产物的来源，对于控制再生水中氯消毒副产物缺乏针对性的指导作用。Reclaimed water is the effluent of urban sewage after biological secondary treatment and advanced treatment. It can be used for municipal miscellaneous purposes, urban water features, building reclaimed water, and industrial cooling water. Due to the complexity of its water source and water treatment process, the quality of regenerated water is relatively complicated, and there are many types and high content of dissolved organic substances left by biological metabolism. At present, the determination method of chlorine disinfection by-product precursors in reclaimed water still uses the determination method of drinking water, but for reclaimed water whose water quality is much more complex than that of natural water, the above-mentioned indirect or comprehensive determination method cannot be used to classify and determine the precursors of various disinfection by-products. The determination results are more ambiguous, and the source of disinfection by-products cannot be analyzed, and there is no targeted guidance for the control of chlorine disinfection by-products in reclaimed water.
再生水中的溶解性有机物大多为腐殖质类等生物代谢残余物质，这些物质分子结构中大多有芳香烃或双键、碳基、羧基等共轭体系，具有较强的荧光特性。采用三维荧光光谱(three-dimensional excitation emission matrixfluorescence spectroscopy，3DEEM)技术可以获得激发波长和发射波长同时变化时的特异性荧光信息，非常适合用来研究有机物的化学和物理性质。研究表明，三维荧光光谱法可用于揭示水中有机物的分类情况，表征水中常见有机物的种类和含量。当样品浓度较低时，各种物质的特征荧光强度与其物质浓度成正比，特征荧光强度所对应的激发和发射波长与物质种类有关。国外有应用三维荧光法分析天然水体中溶解有机质的研究，并将其Ex/Em(ExcitationWavelength，Ex；Emission Wavelength，Em)荧光峰位置概述为附图1所示。其中，特征荧光峰I(Ex/Em 350-440/430-510)，称之为类腐殖酸荧光(humic-like)；特征荧光峰II(Ex/Em 310-360/370-450)和特征荧光峰IV(Ex/Em 240-270/370-440nm)均为类富里酸荧光，分别称为可见腐殖质(visible fulvic-like)和UV腐殖质(UV fulvic-like)；特征荧光团III(Ex/Em260-290/300-350)为类蛋白荧光(protein-like)，还可再细分为类色氨酸荧光(tryptophan-like，Ex/Em 270-290/320-350)和类酪氨酸荧光(tyrosine-like，Ex/Em 270-290/300-320)。据此可以得到水中有机污染物的类别信息。Most of the dissolved organic matters in reclaimed water are humic substances and other biological metabolic residues. Most of these substances have aromatic hydrocarbons or double bonds, carbon groups, carboxyl and other conjugated systems in their molecular structures, and have strong fluorescence characteristics. Using three-dimensional excitation emission matrix fluorescence spectroscopy (3DEEM) technology can obtain specific fluorescence information when the excitation wavelength and emission wavelength change simultaneously, which is very suitable for studying the chemical and physical properties of organic matter. Studies have shown that three-dimensional fluorescence spectroscopy can be used to reveal the classification of organic substances in water, and to characterize the types and contents of common organic substances in water. When the sample concentration is low, the characteristic fluorescence intensity of various substances is proportional to the concentration of the substance, and the excitation and emission wavelengths corresponding to the characteristic fluorescence intensity are related to the substance type. There are foreign studies on the application of three-dimensional fluorescence method to analyze dissolved organic matter in natural water bodies, and the position of its Ex/Em (Excitation Wavelength, Ex; Emission Wavelength, Em) fluorescence peak is summarized as shown in Figure 1. Among them, the characteristic fluorescence peak I (Ex/Em 350-440/430-510), called humic acid fluorescence (humic-like); characteristic fluorescence peak II (Ex/Em 310-360/370-450) and The characteristic fluorescence peak IV (Ex/Em 240-270/370-440nm) is fulvic acid-like fluorescence, which are respectively called visible humic substances (visible fulvic-like) and UV humic substances (UV fulvic-like); characteristic fluorophore III (Ex /Em260-290/300-350) is protein-like, which can be subdivided into tryptophan-like (Ex/Em 270-290/320-350) and tyrosine-like Acid fluorescence (tyrosine-like, Ex/Em 270-290/300-320). Based on this, the category information of organic pollutants in water can be obtained.
三维荧光光谱技术具有灵敏度高(10-9数量级)、用量少(1～2mL)、选择性好、不破坏样品结构和操作简单等优点，易于实现在线和连续监测。但是三维荧光光谱法获得的结果只是有机物的种类和含量信息，不能用于直接表示氯消毒副产物前体物，目前亦未见用于间接表示氯消毒副产物生成潜能的报道。Three-dimensional fluorescence spectroscopy has the advantages of high sensitivity (on the order of 10 -9 ), less dosage (1-2mL), good selectivity, no damage to the sample structure, and simple operation. It is easy to realize on-line and continuous monitoring. However, the results obtained by three-dimensional fluorescence spectroscopy are only the type and content of organic matter, and cannot be used to directly represent the precursors of chlorine disinfection by-products, and there is no report on the indirect expression of the potential of chlorine disinfection by-products.
本发明获国家自然科学基金项目(50778004)和北京市自然科学基金项目(8082006)的资助。The present invention is funded by the National Natural Science Foundation of China (50778004) and the Beijing Natural Science Foundation of China (8082006).
本发明基于现有氯消毒副产物前体物测定方法所存在的缺陷及三维荧光光谱技术原理，通过筛选再生水中主要氯消毒副产物前体物组成、分析三维特征荧光参数表征氯消毒副产物前体物的可行性、确认了消毒副产物前体物荧光表征参数与其生成势之间的相关关系和修正系数，开发了再生水中氯消毒副产物前体物的简便、快速测定方法，为控制氯消毒副产物前体物，保障再生水质安全，提供一种简便、快速的氯消毒副产物前体物测定方法。The present invention is based on the defects existing in the existing chlorine disinfection by-product precursor determination method and the principle of three-dimensional fluorescence spectroscopy, and characterizes the chlorine disinfection by-product precursor by screening the composition of the main chlorine disinfection by-product precursor in regenerated water and analyzing the three-dimensional characteristic fluorescence parameters. The feasibility of chlorine disinfection by-product precursors was confirmed, the correlation and correction coefficient between fluorescence characterization parameters of disinfection by-product precursors and their formation potential were confirmed, and a simple and rapid determination method for chlorine disinfection by-product precursors in reclaimed water was developed. Disinfection by-product precursors ensure the safety of regenerated water quality and provide a simple and rapid method for the determination of chlorine disinfection by-product precursors.
发明内容Contents of the invention
本发明所要解决的技术问题Technical problem to be solved by the present invention
(1)三维特征荧光光谱分类表征氯消毒副产物前体物的可行性；(1) The feasibility of three-dimensional characteristic fluorescence spectrum classification to characterize the precursors of chlorine disinfection by-products;
(2)腐殖酸、富里酸的三维特征荧光强度与其氯消毒副产物生成势的相关性。(2) The correlation between the three-dimensional characteristic fluorescence intensity of humic acid and fulvic acid and the formation potential of chlorine disinfection by-products.
基于再生水的水质复杂性，本发明选择再生水中几类常见的有机物(腐殖酸、富里酸、类蛋白质)，通过分析各类有机物在不同浓度时的消毒副产物生成能力发现，腐殖酸和富里酸是再生水中主要的氯消毒副产物前体物，它们的消毒副产物生成势与其浓度成正比。Based on the water quality complexity of reclaimed water, the present invention selects several types of common organic substances (humic acid, fulvic acid, proteinoid) in regenerated water, and finds that humic acid and Fulvic acids are the main chlorine disinfection by-product precursors in reclaimed water, and their disinfection by-product formation potential is proportional to their concentration.
腐殖酸、富里酸具有较强的荧光特性。采用三维荧光光谱法可以获得相应的三维特征荧光光谱，其特征荧光峰中心激发/发射波长反映物质的结构特性，具有较强的特异性，可用来表示物质的种类；所对应的特征荧光强度与腐殖酸、富里酸浓度成正比。Humic acid and fulvic acid have strong fluorescence characteristics. Three-dimensional fluorescence spectroscopy can be used to obtain the corresponding three-dimensional characteristic fluorescence spectrum, the excitation/emission wavelength of the characteristic fluorescence peak center reflects the structural characteristics of the substance, has strong specificity, and can be used to represent the type of substance; the corresponding characteristic fluorescence intensity and The concentration of humic acid and fulvic acid is directly proportional.
本发明基于上述理论，通过大量的实验分析，提出三维特征荧光参数能够分类表征氯消毒副产物前体物；并研究确认了腐殖酸、富里酸特征荧光强度与氯消毒副产物生成势之间的相关性。在此基础上建立了三维荧光光谱法测定再生水中氯消毒副产物前体物方法。该方法测定步骤如下：Based on the above-mentioned theory, the present invention proposes that the three-dimensional characteristic fluorescence parameters can classify and characterize the precursors of chlorine disinfection by-products through a large number of experimental analysis; relevance. On this basis, a three-dimensional fluorescence spectrometry method for the determination of precursors of chlorine disinfection by-products in reclaimed water was established. The method determination steps are as follows:
(1)建立特征荧光强度与氯消毒副产物生成势相关方程(1) Establish the correlation equation between the characteristic fluorescence intensity and the formation potential of chlorine disinfection by-products
①配制标准溶液① Preparation of standard solution
腐殖酸标准溶液：浓度控制在1.0～7.0mg/L范围内；Humic acid standard solution: the concentration is controlled within the range of 1.0-7.0mg/L;
富里酸标准溶液：浓度控制在10.0～70.0mg/L范围内。Fulvic acid standard solution: the concentration is controlled within the range of 10.0-70.0mg/L.
尽量选择来源与被测样品相类似的商品腐殖酸、富里酸试剂，也可以通过实验室实际提取与被测样品性质相似的腐殖酸、富里酸。Try to choose commercial humic acid and fulvic acid reagents whose source is similar to the tested sample, or actually extract humic acid and fulvic acid with similar properties to the tested sample through the laboratory.
腐殖酸本身为不溶于水的有机化合物，可溶于KOH的稀溶液。配制时可先用超纯水配成0.01mol/L的KOH稀溶液作为溶剂。Humic acid itself is a water-insoluble organic compound, which is soluble in a dilute solution of KOH. When preparing, first use ultrapure water to make a 0.01mol/L KOH dilute solution as a solvent.
②三维荧光光谱扫描② Three-dimensional fluorescence spectrum scanning
设定三维荧光光谱扫描参数：激发波长扫描范围200nm-450nm，发射波长扫描范围200nm-800nm，激发狭缝10nm，发射狭缝10nm，扫描速度1200nm/min，扫描间隔10nm。Set three-dimensional fluorescence spectrum scanning parameters: excitation wavelength scanning range 200nm-450nm, emission wavelength scanning range 200nm-800nm, excitation slit 10nm, emission slit 10nm, scanning speed 1200nm/min, scanning interval 10nm.
分别对不同浓度的腐殖酸、富里酸标准溶液进行三维荧光扫描，得到腐殖酸、富里酸的三维特征荧光光谱图，记录对应的腐殖酸、富里酸特征荧光峰中心激发/发射波长(Ex/Em)及其特征荧光强度fEX/EM。Carry out three-dimensional fluorescence scanning to humic acid and fulvic acid standard solution of different concentrations respectively, obtain the three-dimensional characteristic fluorescence spectrum figure of humic acid and fulvic acid, record corresponding humic acid, fulvic acid characteristic fluorescence peak central excitation/emission wavelength ( Ex/Em) and its characteristic fluorescence intensity f EX/EM .
③测定氯消毒副产物生成势③ Determination of the formation potential of chlorine disinfection by-products
按照DBPFP测定方法分别测定腐殖酸、富里酸不同浓度的系列标准溶液的消毒副产物生成势值，并记录各自的三卤甲烷生成势和卤乙酸生成势值。According to the DBPFP determination method, the disinfection by-product formation potential values of series of standard solutions with different concentrations of humic acid and fulvic acid were respectively measured, and the respective trihalomethane formation potentials and haloacetic acid formation potential values were recorded.
④建立标准溶液的特征荧光强度与消毒副产物生成势之间的相关校正方程④ Establish a correlation correction equation between the characteristic fluorescence intensity of the standard solution and the generation potential of disinfection by-products
以特征荧光强度为自变量，三卤甲烷生成势(THMFP)或卤乙酸生成势(HAAFP)为因变量，分别建立腐殖酸、富里酸标准溶液的特征荧光强度fEX/EM1、fEX/EM2与THMFP、HAAFP的相关线性校正方程。With the characteristic fluorescence intensity as the independent variable and the trihalomethane formation potential (THMFP) or haloacetic acid formation potential (HAAFP) as the dependent variable, the characteristic fluorescence intensities f EX/EM1 and f EX/ Correlation linear correction equations of EM2 and THMFP, HAAFP.
腐殖酸特征荧光强度与消毒副产物生成势之间的相关校正方程为：The correlation correction equation between the characteristic fluorescence intensity of humic acid and the generation potential of disinfection by-products is:
THMFPHA＝a1 fEX/EM1+b1 (1)THMFP HA =a 1 f EX/EM1 +b 1 (1)
HAAFPHA＝a2 fEX/EM1+b2 (2)HAAFP HA = a 2 f EX/EM1 + b 2 (2)
富里酸特征荧光强度与消毒副产物生成势之间的相关校正方程为：The correlation correction equation between the characteristic fluorescence intensity of fulvic acid and the generation potential of disinfection by-products is:
THMFPFA＝a3 fEX/EM2+b3 (3)THMFP FA =a 3 f EX/EM2 +b 3 (3)
HAAFPFA＝a4 fEX/EM2+b4 (4)HAAFP FA = a 4 f EX/EM2 + b 4 (4)
式中，THMFPHA、THMFPFA、HAAFPHA、HAAFPFA分别为腐殖酸、富里酸的三卤甲烷和卤乙酸生成势(μg/L)；In the formula, THMFP HA , THMFP FA , HAAFP HA , and HAAFP FA are the trihalomethane and haloacetic acid formation potentials of humic acid and fulvic acid, respectively (μg/L);
fEX/EM1、fEX/EM2分别为腐殖酸、富里酸的特征荧光强度(A.U)；f EX/EM1 and f EX/EM2 are the characteristic fluorescence intensity (AU) of humic acid and fulvic acid respectively;
a1、a2、a3、a4、b1、b2、b3、b4均为校正系数，可通过线性回归法获得。a 1 , a 2 , a 3 , a 4 , b 1 , b 2 , b 3 , and b 4 are all correction coefficients, which can be obtained by linear regression.
(2)测定实际水样中的氯消毒副产物生成势(2) Determination of the formation potential of chlorine disinfection by-products in actual water samples
①进行三维荧光光谱扫描① Three-dimensional fluorescence spectrum scanning
先将水样经过0.45μm滤膜过滤，以去除水样中的颗粒性不溶有机物，然后对水样进行三维荧光光谱扫描，扫描参数同上。根据腐殖酸、富里酸标准溶液所确定的三维特征荧光峰中心位置Ex/Em，分别记录水样中腐殖酸、富里酸的特征荧光强度fEX/EM。First filter the water sample through a 0.45 μm filter membrane to remove particulate insoluble organic matter in the water sample, and then perform three-dimensional fluorescence spectrum scanning on the water sample, and the scanning parameters are the same as above. According to the center position Ex/Em of the three-dimensional characteristic fluorescence peak determined by the standard solution of humic acid and fulvic acid, record the characteristic fluorescence intensity f EX/EM of humic acid and fulvic acid in the water sample respectively.
②利用相关校正方程分类计算消毒副产物生成势②Calculate the formation potential of disinfection by-products by using the relevant correction equations
利用相关校正方程和水样中腐殖酸、富里酸的三维特征荧光强度，可分别求得水样中腐殖酸、富里酸的三卤甲烷和卤乙酸生成势值；还可以通过加和方法分别求出水样总的三卤甲烷、卤乙酸生成势，即：Using the relevant correction equations and the three-dimensional characteristic fluorescence intensity of humic acid and fulvic acid in water samples, the trihalomethane and haloacetic acid formation potential values of humic acid and fulvic acid in water samples can be obtained respectively; Calculate the total trihalomethane and haloacetic acid formation potential of the water sample respectively, namely:
∑THMFP＝THMFPHA+THMFPFA (5)∑ THMFP = THMFP HA + THMFP FA (5)
∑HAAFP＝HAAFPHA+HAAFPFA (6)∑HAAFP＝HAAFP HA +HAAFP FA (6)
(3)结果的修正(3) Correction of results
腐殖酸、富里酸均非单一组分，它们都是没有确定分子量，在组成、结构上均较为模糊的复杂的混合物，因而不同来源的腐殖酸或富里酸，在分子结构、官能团、分子量等方面存在差异，其三维荧光特性也会有不同。因此当用以配置标准溶液的腐殖酸、富里酸与水样中的腐殖酸、富里酸的三维荧光特征激发/发射波长有显著差异时，应引入修正系数对计算结果进行修正。建议配置标准溶液的腐殖酸、富里酸来源应尽可能与被测定水样相近，以减少测定误差。Neither humic acid nor fulvic acid is a single component, they are complex mixtures with unclear molecular weight and relatively vague composition and structure. Therefore, humic acid or fulvic acid from different sources have different molecular structures, functional groups, and There are differences in other aspects, and their three-dimensional fluorescence characteristics will also be different. Therefore, when there are significant differences in the three-dimensional fluorescence characteristic excitation/emission wavelengths of humic acid and fulvic acid used to configure standard solutions and humic acid and fulvic acid in water samples, a correction factor should be introduced to correct the calculation results. It is suggested that the source of humic acid and fulvic acid in the standard solution should be as close as possible to the water sample to be measured to reduce the measurement error.
另外，由于再生水质较为复杂，一些共存物质，比如金属离子也有可能影响消毒副产物前体物的荧光特性，因此也需要对测定结果进行修正。In addition, due to the complexity of the regenerated water quality, some coexisting substances, such as metal ions, may also affect the fluorescence characteristics of the precursors of disinfection by-products, so the measurement results also need to be corrected.
根据实验结果分析发现，利用相关校正方程计算出的水样总的三卤甲烷、卤乙酸生成势与实测值具有一致的变化趋势，存在着相对稳定的倍数关系。According to the analysis of the experimental results, it is found that the total trihalomethanes and haloacetic acid formation potentials of the water samples calculated by the relevant calibration equations have a consistent trend with the measured values, and there is a relatively stable multiple relationship.
需要修正时，可根据DBPFP测定方法实际测定5～7个水样的三卤甲烷、卤乙酸生成势，并与相应的计算值进行线性回归分析，回归系数即为修正系数。When correction is required, the formation potential of trihalomethanes and haloacetic acids in 5 to 7 water samples can be actually measured according to the DBPFP determination method, and linear regression analysis is performed with the corresponding calculated values, and the regression coefficient is the correction coefficient.
(4)准确度与适用范围(4) Accuracy and scope of application
采用上述方法测定了百余个再生水样品，平均相对误差在10％左右。More than one hundred reclaimed water samples were measured by the above method, and the average relative error was about 10%.
本方法适用于再生水中氯消毒副产物生成势的测定，同时也适用于天然水体或自来水中氯消毒副产物生成势测定。This method is applicable to the determination of the formation potential of chlorine disinfection by-products in reclaimed water, and also applicable to the determination of formation potential of chlorine disinfection by-products in natural water or tap water.
本发明关键技术是提出用三维特征荧光参数来分类表征消毒副产物前体物，并确认了三维特征荧光强度与消毒副产物生成势之间的相关性。The key technology of the present invention is to use three-dimensional characteristic fluorescence parameters to classify and characterize the precursors of disinfection by-products, and confirm the correlation between the three-dimensional characteristic fluorescence intensity and the generation potential of disinfection by-products.
本发明与现有技术相比主要特点如下：The present invention compares main features as follows with prior art:
(1)实现氯消毒副产物前体物的分类定量分析：现有DBPFP测定方法不能区分消毒副产物生成势的来源，现有SUVA法测定结果表示的是各类有机物的综合含量。本方法通过对水样进行三维荧光扫描以获取水样的特征荧光参数，利用各类物质的特征荧光强度与其消毒副产物生成势的相关方程，可以直接得到各类有机物的消毒副产物生成势，能够实现对消毒副产物前体物的分类解析，有针对性地开展污染控制。(1) Realize the classification and quantitative analysis of the precursors of chlorine disinfection by-products: the existing DBPFP determination method cannot distinguish the source of the generation potential of disinfection by-products, and the determination results of the existing SUVA method represent the comprehensive content of various organic substances. In this method, the characteristic fluorescence parameters of the water sample are obtained by performing three-dimensional fluorescence scanning on the water sample, and the correlation equation between the characteristic fluorescence intensity of various substances and the generation potential of disinfection by-products can be used to directly obtain the generation potential of disinfection by-products of various organic substances. It can realize the classification and analysis of the precursors of disinfection by-products, and carry out targeted pollution control.
(2)操作简单，测定迅速，无需复杂的样品处理和检测过程。而现有DBPFP测定方法需要复杂的样品处理和5天恒温培养过程，需要消耗较多的化学试剂和药品。(2) The operation is simple, the determination is rapid, and there is no need for complicated sample processing and detection processes. However, the existing DBPFP determination method requires complex sample processing and a 5-day constant temperature incubation process, and consumes more chemical reagents and drugs.
(3)相对误差小，平均相对误差在10％左右。有国外研究表明，现有DBPFP方法测定结果的相对误差达到25％。(3) The relative error is small, and the average relative error is about 10%. Some foreign studies have shown that the relative error of the measurement results of the existing DBPFP method reaches 25%.
(4)荧光分析法具有灵敏度高，样品用量少，选择性好的特点。(4) The fluorescence analysis method has the characteristics of high sensitivity, less sample consumption and good selectivity.
(5)本方法不破坏样品结构，易于实现在线检测。(5) This method does not destroy the sample structure, and it is easy to realize online detection.
附图说明Description of drawings
图1溶解有机质三维荧光光谱图中Ex/Em峰出现的常见位置Figure 1 The common positions of Ex/Em peaks in the three-dimensional fluorescence spectrum of dissolved organic matter
图2a三卤甲烷生成势计算值、修正值与实测值.Figure 2a The calculated value, corrected value and measured value of trihalomethane formation potential.
图2b卤乙酸生成势计算值、修正值与实测值Figure 2b The calculated value, corrected value and measured value of haloacetic acid formation potential
图3a修正后的三卤甲烷生成势计算值与实测值误差分析Figure 3a The error analysis between the calculated value and the measured value of the trihalomethane formation potential after correction
图3b修正后的卤乙酸生成势计算值与实测值误差分析Figure 3b The error analysis between the calculated value and the measured value of the corrected haloacetic acid formation potential
具体实施方式Detailed ways
采用上述方法连续测定某实验室再生水处理装置出水中氯消毒副产物生成势，主要测定过程如下：Using the above method to continuously measure the formation potential of chlorine disinfection by-products in the effluent water of a laboratory reclaimed water treatment device, the main measurement process is as follows:
(1)建立特征荧光强度与氯消毒副产物生成势相关方程(1) Establish the correlation equation between the characteristic fluorescence intensity and the formation potential of chlorine disinfection by-products
①配制标准溶液① Preparation of standard solution
腐殖酸：生化试剂，上海巨枫化学科技有限公司Humic acid: biochemical reagent, Shanghai Jufeng Chemical Technology Co., Ltd.
富里酸：生化试剂。Fulvic acid: biochemical reagent.
上述试剂的制备来源于天然腐殖酸，如泥炭、褐煤或某些土壤中。The above reagents are prepared from natural humic acids, such as peat, lignite or some soils.
称取0.1000g腐殖酸，用0.01mol/L的KOH作为溶剂溶解，配制成浓度为100mg/L的储备溶液，再将其依次稀释为1.0mg/L、2.0mg/L、3.0mg/L、4.0mg/L、5.0mg/L、6.0mg/L、7.0mg/L的标准溶液；Weigh 0.1000g humic acid, dissolve it with 0.01mol/L KOH as a solvent, prepare a stock solution with a concentration of 100mg/L, and then dilute it successively to 1.0mg/L, 2.0mg/L, 3.0mg/L , 4.0mg/L, 5.0mg/L, 6.0mg/L, 7.0mg/L standard solutions;
称取1.0g富里酸，配制成浓度为1000mg/L的储备溶液，再逐级稀释成10.0mg/L、20.0mg/L、30.0mg/L、40.0mg/L、50.0mg/L、60.0mg/L、70.0mg/L一系列浓度的标准溶液。Weigh 1.0g of fulvic acid, prepare a stock solution with a concentration of 1000mg/L, and then dilute it step by step to 10.0mg/L, 20.0mg/L, 30.0mg/L, 40.0mg/L, 50.0mg/L, 60.0mg /L, 70.0mg/L series of standard solutions.
②三维荧光光谱扫描② Three-dimensional fluorescence spectrum scanning
设定三维荧光光谱扫描参数：激发波长扫描范围200nm-450nm，发射波长扫描范围200nm-800nm，激发狭缝10nm，发射狭缝10nm，扫描速度1200nm/min，扫描间隔10nm。Set three-dimensional fluorescence spectrum scanning parameters: excitation wavelength scanning range 200nm-450nm, emission wavelength scanning range 200nm-800nm, excitation slit 10nm, emission slit 10nm, scanning speed 1200nm/min, scanning interval 10nm.
分别对不同浓度的腐殖酸、富里酸标准溶液进行三维荧光扫描，得到腐殖酸、富里酸的三维特征荧光光谱图，记录对应的腐殖酸、富里酸特征荧光峰中心激发/发射波长(Ex/Em)及其特征荧光强度fEX/EM，其中腐殖酸有一个特征荧光峰，富里酸有两个特征荧光峰。表1为腐殖酸、富里酸特征荧光峰中心波长以及特征荧光强度与浓度的相关性，从表上可以看出，腐殖酸、富里酸浓度与其三维特征荧光强度具有很好的线性相关性。Carry out three-dimensional fluorescence scanning to humic acid and fulvic acid standard solution of different concentrations respectively, obtain the three-dimensional characteristic fluorescence spectrum figure of humic acid and fulvic acid, record corresponding humic acid, fulvic acid characteristic fluorescence peak central excitation/emission wavelength ( Ex/Em) and its characteristic fluorescence intensity f EX/EM , wherein humic acid has one characteristic fluorescence peak, and fulvic acid has two characteristic fluorescence peaks. Table 1 shows the correlation between the central wavelength of the characteristic fluorescence peak of humic acid and fulvic acid and the characteristic fluorescence intensity and concentration. It can be seen from the table that the concentration of humic acid and fulvic acid has a good linear correlation with its three-dimensional characteristic fluorescence intensity .
表1腐殖酸、富里酸浓度与其三维特征荧光强度的相关性Table 1 Correlation between concentrations of humic acid and fulvic acid and their three-dimensional characteristic fluorescence intensity
③测定氯消毒副产物生成势③ Determination of the formation potential of chlorine disinfection by-products
采用DBPFP的测定步骤，分别测定腐殖酸、富里酸的不同浓度的系列标准溶液的消毒副产物生成势值，并记录各自的三卤甲烷生成势和卤乙酸生成势值。表2为腐殖酸、富里酸浓度与其消毒副产物生成势的相关性，反映了腐殖酸、富里酸浓度与其消毒副产物生成势也具有线性相关性。Using the determination procedure of DBPFP, measure the disinfection by-product formation potential values of series standard solutions of different concentrations of humic acid and fulvic acid respectively, and record the respective trihalomethane formation potentials and haloacetic acid formation potential values. Table 2 shows the correlation between the concentration of humic acid and fulvic acid and the formation potential of disinfection by-products, which reflects that the concentration of humic acid and fulvic acid and the formation potential of disinfection by-products also have a linear correlation.
表2腐殖酸、富里酸浓度与其消毒副产物生成势的相关性Table 2 The correlation between the concentration of humic acid and fulvic acid and the formation potential of disinfection by-products
④建立标准溶液的特征荧光强度与消毒副产物生成势之间的相关校正方程④ Establish a correlation correction equation between the characteristic fluorescence intensity of the standard solution and the generation potential of disinfection by-products
表3为标准溶液的特征荧光强度与消毒副产物生成势之间的相关校正方程。从表3看出，腐殖酸、富里酸的三维特征荧光强度与三卤甲烷、卤乙酸生成势具有显著的线性相关性，相关系数均达到0.9以上，表明腐殖酸、富里酸的三维特征荧光强度能够表示其相应的氯消毒副产物生成势。Table 3 shows the correlation correction equation between the characteristic fluorescence intensity of the standard solution and the generation potential of disinfection by-products. It can be seen from Table 3 that the three-dimensional characteristic fluorescence intensity of humic acid and fulvic acid has a significant linear correlation with the formation potential of trihalomethane and haloacetic acid, and the correlation coefficients are all above 0.9, indicating that the three-dimensional characteristics of humic acid and fulvic acid Fluorescence intensity can represent its corresponding chlorine disinfection by-product formation potential.
表3 fEx/Em与DBPFP的相关方程Table 3 Correlation equations of f Ex/Em and DBPFP
(2)再生水样品测定(2) Determination of recycled water samples
①三维荧光扫描① Three-dimensional fluorescence scanning
水样经过0.45μm滤膜过滤，以去除水样中不溶性有机物，然后分别进行三维荧光扫描。荧光光谱分析仪的参数设定：激发波长扫描范围200nm-450nm，发射波长扫描范围200nm-800nm，激发狭缝10nm，发射狭缝10nm，扫描速度1200nm/min，扫描间隔10nm。得到The water samples were filtered through a 0.45 μm filter membrane to remove insoluble organic matter in the water samples, and then three-dimensional fluorescence scanning was performed respectively. The parameter setting of the fluorescence spectrum analyzer: the scanning range of the excitation wavelength is 200nm-450nm, the scanning range of the emission wavelength is 200nm-800nm, the excitation slit is 10nm, the emission slit is 10nm, the scanning speed is 1200nm/min, and the scanning interval is 10nm. get
根据已经确定的特征荧光峰中心位置Ex/Em，记录相应腐殖酸、富里酸的特征荧光强度。表4为10个水样的三维特征荧光强度值。According to the determined central position of the characteristic fluorescence peak Ex/Em, record the characteristic fluorescence intensity of the corresponding humic acid and fulvic acid. Table 4 shows the three-dimensional characteristic fluorescence intensity values of 10 water samples.
表4水样的三维特征荧光强度值Table 4 Three-dimensional characteristic fluorescence intensity values of water samples
②利用校正方程计算水样中的三卤甲烷生成势和卤乙酸生成势值② Using the calibration equation to calculate the trihalomethane formation potential and haloacetic acid formation potential in water samples
将腐殖酸、富里酸三维特征荧光强度分别带入相应的校正方程，求得腐殖酸的三卤甲烷生成势值和卤乙酸生成势值，以及富里酸的三卤甲烷生成势值和卤乙酸生成势值；也可以通过加和，求得水样总的三卤甲烷、卤乙酸生成势值。Bring the three-dimensional characteristic fluorescence intensity of humic acid and fulvic acid into the corresponding calibration equations respectively, and obtain the trihalomethane formation potential value and haloacetic acid formation potential value of humic acid, as well as the trihalomethane formation potential value and haloacetic acid formation potential value of fulvic acid. Acetic acid formation potential value; can also be obtained by adding the total trihalomethane and haloacetic acid formation potential value of the water sample.
(3)结果修正(3) Result correction
由于本实施例中配置标准溶液的腐殖酸、富里酸试剂为生化试剂，来源于天然腐殖质，如泥炭、褐煤或某些土壤，与再生水样品中的腐殖质在分子结构、官能团特性、分子量等方面有一定的差异。另外，再生水样品背景比标准溶液复杂，共存物质也有一定影响。因此需要对计算结果进行修正。Since the humic acid and fulvic acid reagents configured in the standard solution in this example are biochemical reagents, they are derived from natural humus, such as peat, lignite or certain soils, and the humic substances in the regenerated water sample are different in terms of molecular structure, functional group characteristics, molecular weight, etc. There are certain differences. In addition, the background of the regenerated water sample is more complicated than that of the standard solution, and the coexisting substances also have a certain influence. Therefore, the calculation results need to be corrected.
根据多次实验检验发现，通过相关校正方程计算出的消毒副产物生成势与实测值具有一致的变化趋势，存在着相对稳定的倍数关系。本实施例中，三卤甲烷生成势的修正系数为0.36，卤乙酸生成势的修正系数为0.47。附图2为三卤甲烷、卤乙酸生成势计算值、修正值与实测值对比。According to multiple experiments, it is found that the generation potential of disinfection byproducts calculated by the relevant correction equation has a consistent trend with the measured value, and there is a relatively stable multiple relationship. In this embodiment, the correction coefficient for the formation potential of trihalomethanes is 0.36, and the correction coefficient for the formation potential of haloacetic acids is 0.47. Accompanying drawing 2 is the comparison of the calculated value, corrected value and measured value of trihalomethane and haloacetic acid formation potential.
(4)结果验证与误差分析(4) Result verification and error analysis
①相关性分析① Correlation analysis
采用相关分析法对修正后的消毒副产物生成势计算值和实测值进行相关性分析，分析结果见表5。The correlation analysis method was used to analyze the correlation between the calculated value and the measured value of the revised disinfection by-product formation potential. The analysis results are shown in Table 5.
表5消毒副产物生成势计算值和实测值相关分析结果Table 5 Correlation analysis results between the calculated value and the measured value of the generation potential of disinfection by-products
从表中可以看出，三卤甲烷、卤乙酸消毒副产物生成势计算值与实测值的相关系数分别达0.992、0.984，均具有较强的相关性；双侧检验的显著性概率均小于0.01，因此否定零假设，认为相关系数通过显著性检验，即认为卤乙酸和三卤甲烷消毒副产物均存在计算值与实际测量值之间的正相关性。It can be seen from the table that the correlation coefficients between the calculated and measured values of the disinfection by-product formation potentials of trihalomethanes and haloacetic acids are 0.992 and 0.984 respectively, both of which have strong correlations; the significance probabilities of the two-sided tests are all less than 0.01 , so the null hypothesis was rejected, and the correlation coefficient passed the significance test, that is, there was a positive correlation between the calculated value and the actual measured value of haloacetic acid and trihalomethane disinfection by-products.
②误差检验② Error checking
对修正后的计算值与实测值进行误差分析，结果见附图3。The error analysis between the corrected calculated value and the measured value is carried out, and the results are shown in Figure 3.
附图3中标出了10个水样对应的数据点。其中直线y＝x表示了计算值与实测值的完全一致性，分配在y＝x左右两侧的直线表示计算值与实测值的误差为10％，左侧直线表示计算值超出实测值，右侧直线表示计算值小于实测值。由附图3可以看出，计算值与实测值的误差在10％左右。The data points corresponding to the 10 water samples are marked in accompanying drawing 3. Among them, the straight line y=x represents the complete consistency between the calculated value and the measured value. The straight line distributed on the left and right sides of y=x means that the error between the calculated value and the measured value is 10%. The left straight line means that the calculated value exceeds the measured value. A straight line on the side indicates that the calculated value is smaller than the measured value. It can be seen from Figure 3 that the error between the calculated value and the measured value is about 10%.
因此，采用上述方法测定的消毒副产物生成势结果可靠。Therefore, the formation potential of disinfection by-products determined by the above method is reliable.
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