CN110083585B - Water pollution discharge source database and establishing method thereof - Google Patents
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- 238000003911 water pollution Methods 0.000 title claims abstract description 27
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- G06F16/20—Information retrieval; Database structures therefor; File system structures therefor of structured data, e.g. relational data
- G06F16/21—Design, administration or maintenance of databases
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- G—PHYSICS
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Abstract
A water pollution discharges the source database and its establishment method, this database includes three sub-databases of basic information base of pollution source, conventional water quality database and water quality water wave database; the water quality water streak database comprises three-dimensional molecular weight water streaks, fluorescent water streaks and ultraviolet-visible absorption spectra of a water sample. The database establishment method comprises the steps of pollution source information investigation, sample collection, sample analysis and test and database establishment. The invention firstly provides the concept of the three-dimensional molecular weight water wave and brings the concept into the database, and the method has the characteristics of large water information amount, mature and simple selection index analysis and test method, less required equipment, low cost, strong operability and timeliness and the like, can quickly realize the tracing of the pollution source at low cost, is beneficial to large-scale popularization, and has important significance on the tracing of the water pollution source.
Description
Technical Field
The invention relates to the field of water-related environment supervision, and relates to a water pollution discharge source database and an establishment method thereof.
Background
At present, the sewage overproof steal discharge tracing method mainly depends on 'one-point-one-source' type supervision of a sewage disposal enterprise and manual investigation after an accident occurs. The pollution discharge enterprise is supervised one by one, namely online monitoring equipment is installed at a pollution source discharge port, if the online monitoring equipment detects that the drainage of the enterprise exceeds the pollution discharge standard, the enterprise can be subjected to duty pursuing, but the method is large in investment, the online equipment cannot be prevented from being artificially changed and damaged, and the enterprise cannot be supervised to bypass the illegal stealing and discharging behavior of the online monitoring equipment, so that the effect is relatively limited. The manual investigation mainly refers to the gradual investigation along the water flow direction or upstream of a drainage pipe network after a pollution accident occurs, and the abnormal water sample and the sewage disposal enterprise water sample are detected and compared so as to realize the tracing and responsibility tracing of illegal discharge. However, if there are many upstream enterprises in the pollution accident, the method not only wastes a lot of manpower and material resources, but also loses the timeliness of investigation, and finally, it is difficult to find out the troublemaking enterprises.
The manual investigation method based on the assistance of the water quality database of the sewage disposal enterprise can greatly reduce the workload of the manual investigation after the occurrence of the pollution accident. Meanwhile, the risk that the enterprise changes and damages the online monitoring equipment is avoided, and the problem that whether the enterprise has a hidden sewage outlet or not is also not considered. The method constructs a sewage quality database of a pollution discharge enterprise in advance, and after a pollution accident occurs, the water quality information of a polluted water sample is detected and analyzed and compared with the enterprise water quality database constructed in advance to investigate the accident-causing enterprise. The key point of the method lies in the construction of a water quality database, and theoretically, various water quality indexes (chromaticity, pH value, conductivity, chemical oxygen demand, total nitrogen, total phosphorus, characteristic pollutants, various spectrums, chromatograms, mass spectrums and the like) related to the wastewater can be used for constructing the water quality database of the wastewater. The more the water quality indexes are, the more the included water quality information is, the more beneficial the tracing to the source of the pollution source is, but the larger the workload in the early stage is, the larger and redundant database becomes, and the actual operability is reduced. Before this time, a chemical watermark information database containing pollution sources such as anion types, organic matter types, metal element types, fluorescence information and the like is proposed by Wanpingyu et al, Beijing university of chemical industry for tracing water pollution. However, the database has high requirements for analyzing and testing water quality indexes, expensive instruments, large workload and poor actual operability, and is difficult to apply and popularize in practice.
Disclosure of Invention
The invention provides a water pollution discharge source database and an establishing method thereof, so that the water pollution discharge source database has the characteristics of low cost, large information amount, operability, strong timeliness, high accuracy and the like, is simple to construct, and is beneficial to large-scale popularization and application.
The technical scheme of the invention is as follows:
a water pollution discharges the source database, its characterized in that: the database comprises a pollution source basic information base, a conventional water quality database and a water quality water wave database; the pollution source basic information base comprises a pollution source name, a geographical position, main products, enterprise penalty records, contacts and legal persons; the conventional water quality database comprises pH value, conductivity, chemical oxygen demand, total nitrogen, total phosphorus, ammonia nitrogen, copper, mercury, nickel, cyanide and aniline of a water sample; the water quality water streak database comprises three-dimensional molecular weight water streaks, fluorescent water streaks and ultraviolet-visible absorption spectra of a water sample.
The three-dimensional molecular weight water wave comprises an ultraviolet absorption molecular weight water wave, a multi-excitation fluorescence molecular weight water wave and a multi-emission fluorescence molecular weight water wave; the ultraviolet absorption molecular weight water wave scanning range is 190-900 nm, and the collection interval is 1-5 nm; the multi-excitation fluorescence molecular weight water wave excitation wavelength scanning range is 220-700 nm, and the collection interval is 1-5 nm; the scanning range of the multi-emission fluorescent molecular weight water wave emission wavelength is 230-750 nm, and the collection interval is 1-5 nm. The fluorescence water streak is a fluorescence spectrum obtained by a fluorescence spectrophotometer in a three-dimensional mode, the excitation wavelength scanning range of the fluorescence spectrum is 220-700 nm, the emission wavelength scanning range is 230-750 nm, and the scanning interval is 2-5 nm; the scanning range of the ultraviolet visible absorption spectrum is 190-900 nm, and the scanning interval is 0.2-1 nm.
The ultraviolet absorption molecular weight water streak is a map related to the molecular weight distribution of a sample, which is acquired by a liquid phase size exclusion chromatography under a diode array detector multi-wavelength mode; the multi-excitation molecular weight water streak is a map about the molecular weight distribution of a sample acquired by liquid phase size exclusion chromatography in a multi-excitation mode of a fluorescence detector; the multiple emission molecular weight water streak is a spectrum of the molecular weight distribution of a sample acquired by liquid phase size exclusion chromatography in a fluorescence detector multiple emission mode.
The invention provides a method for establishing a water pollution discharge source database, which is characterized by comprising the following steps:
1) investigation of pollution sources: investigating pollution source names, geographic locations, main products, enterprise penalty records, contacts and legal persons;
2) collecting samples: collecting a wastewater sample of a pollution discharge source;
3) analytical testing of the samples: the pH value, the conductivity, the chemical oxygen demand, the total nitrogen, the total phosphorus, the ammonia nitrogen, the copper, the mercury, the nickel, the cyanide and the aniline of the water sample are tested by adopting a national standard method. Collecting three-dimensional molecular weight water marks of a sample by using a liquid phase size exclusion chromatography, collecting the fluorescent water marks of the sample by using a fluorescence spectrophotometer, and collecting an ultraviolet visible absorption spectrum of the sample by using an ultraviolet visible spectrophotometer;
4) establishing a water pollution discharge source database: the water pollution emission source database consists of a pollution source basic information base, a conventional water quality database and a water quality water wave database. Inputting basic information of the pollution source into a basic information base of the pollution source, inputting conventional water quality data into a conventional water quality database, and inputting three-dimensional molecular weight water wave, fluorescent water wave and ultraviolet visible absorption spectrum data into the water quality water wave database of the pollution source.
Compared with the prior art, the invention has the following advantages and prominent technical effects:
the invention firstly puts forward the concept of three-dimensional molecular weight water marks and brings the concept into a database, and the test of the water marks with various molecular weights can be realized by utilizing one liquid phase size exclusion chromatograph, so that the invention has the advantages of less required equipment, rich information and high accuracy; secondly, the water pollution source database provided by the invention has large water information amount, the selected index analysis and test method is mature and simple, has small workload, low cost and strong operability and timeliness, can quickly realize pollution source tracing at low cost, is beneficial to large-scale popularization, and has important significance for water pollution source tracing.
Drawings
Fig. 1 is a flowchart of a method for establishing a water pollution discharge source database according to the present invention.
FIGS. 2a, 2b, and 2c show typical fluorescent patterns of pre-treated wastewater from certain electroplating industrial parks (a) YL, (b) BD, and (c) TD, respectively.
FIGS. 3a, 3b and 3c show multi-wavelength UV absorption molecular weight water marks of pre-treated wastewater from (a) YL, (b) BD and (c) TD in a certain electroplating industrial park, respectively.
FIGS. 4a, 4b, and 4c are typical multi-excitation fluorescent molecular weight water marks of pretreated wastewater from (a) YL, (b) BD, and (c) TD, respectively, in certain electroplating industry parks.
FIGS. 5a, 5b, and 5c are typical multiple emission fluorescent molecular weight water marks of pretreated wastewater from certain electroplating industrial parks (a) YL, (b) BD, and (c) TD, respectively.
Detailed Description
The invention provides a water pollution discharge source database, which is a water pollution source database consisting of three sub-databases, namely a pollution source basic information database, a conventional water quality database and a water quality water wave database; the pollution source basic information base comprises a pollution source name, a geographical position, main products, enterprise penalty records, contacts and legal persons; the conventional water quality database comprises pH value, conductivity, chemical oxygen demand, total nitrogen, total phosphorus, ammonia nitrogen, copper, mercury, nickel, cyanide and aniline of a water sample; the conventional water quality database can be added with pollutant indexes in the integrated wastewater discharge standard (GB8978-1996) table 6 according to actual conditions; the water quality water streak database comprises three-dimensional molecular weight water streaks, fluorescent water streaks and ultraviolet-visible absorption spectra of a water sample.
The three-dimensional molecular weight water wave comprises an ultraviolet absorption molecular weight water wave, a multi-excitation fluorescence molecular weight water wave and a multi-emission fluorescence molecular weight water wave; the ultraviolet absorption molecular weight water wave scanning range is 190-900 nm, and the collection interval is 1-5 nm; the multi-excitation fluorescence molecular weight water wave excitation wavelength scanning range is 220-700 nm, and the collection interval is 1-5 nm; the scanning range of the multi-emission fluorescent molecular weight water wave emission wavelength is 230-750 nm, and the collection interval is 1-5 nm. The ultraviolet absorption molecular weight water streak is a map related to the molecular weight distribution of a sample acquired by a liquid phase size exclusion chromatography in a diode array detector multi-wavelength mode; the multi-excitation molecular weight water streak is a map about the molecular weight distribution of a sample acquired by liquid phase size exclusion chromatography in a multi-excitation mode of a fluorescence detector; the multiple emission molecular weight water streak is a spectrum of the molecular weight distribution of a sample acquired by liquid phase size exclusion chromatography in a fluorescence detector multiple emission mode. The fluorescence water streak is a fluorescence spectrum obtained by a fluorescence spectrophotometer in a three-dimensional mode, the excitation wavelength scanning range of the fluorescence spectrum is 220-700 nm, and the emission wavelength scanning range is 230-750 nm. The ultraviolet-visible absorption spectrum is obtained by adopting an ultraviolet-visible spectrophotometer in a spectrum scanning mode, the scanning range of the absorption spectrum is 190-900 nm, and the scanning interval is 0.2-1 nm.
The construction of the water pollution source database mainly comprises the following steps (as shown in figure 1):
1) investigation of pollution sources: investigating pollution source names, geographic locations, main products, enterprise penalty records, contacts and legal persons;
2) collecting samples: collecting a wastewater sample of a pollution discharge source;
3) analytical testing of the samples: the conventional water quality indexes including pH value, conductivity, chemical oxygen demand, total nitrogen, total phosphorus, ammonia nitrogen, copper, mercury, nickel, cyanide and aniline are respectively tested by adopting a national standard method. Respectively collecting three-dimensional molecular weight water waves, fluorescent water waves and ultraviolet visible absorption spectra of a water sample.
Three-dimensional molecular weight water marks comprising three types of ultraviolet absorption molecular weight water marks, multi-excitation fluorescent molecular weight water marks and multi-emission fluorescent molecular weight water marks are collected by liquid phase size exclusion chromatography. Ultraviolet absorption molecular weight water waves are collected in a diode array detector multi-wavelength mode, the scanning range is 190-900 nm, and the collection interval is 1-5 nm. The multi-excitation fluorescence molecular weight water wave and the multi-emission fluorescence molecular weight water wave are respectively collected in a multi-excitation mode and a multi-emission mode of a fluorescence detector, the multi-excitation fluorescence molecular weight water wave excitation wavelength scanning range is 220-700 nm, the collection interval is 1-5 nm, the multi-emission fluorescence molecular weight water wave emission wavelength scanning range is 230-750 nm, and the collection interval is 1-5 nm. The fluorescence water streak is collected in a three-dimensional mode through a fluorescence spectrophotometer, the scanning range of the excitation wavelength is 220-700 nm, the scanning range of the emission wavelength is 230-750 nm, and the scanning interval is 2-5 nm. The ultraviolet-visible absorption spectrum is collected through a wavelength scanning mode of an ultraviolet-visible spectrophotometer, the scanning range is 190-900 nm, and the scanning interval is 0.2-1 nm.
4) Establishing a water pollution discharge source database: the water pollution emission source database consists of a pollution source basic information base, a conventional water quality database and a water quality water wave database. Inputting basic information of the pollution source into a basic information base of the pollution source, inputting conventional water quality data into a conventional water quality database, and inputting three-dimensional molecular weight water wave, fluorescent water wave and ultraviolet visible absorption spectrum data into the water quality water wave database of the pollution source.
According to the invention, the basic information of the pollution source, such as geographical position, main products and the like, can also provide effective information for the identification of the pollution source, and the information can be obtained through field investigation and literature investigation without consuming a large amount of manpower and material resources, so that the basic information of the pollution source is used as an auxiliary tool for identifying the pollution source; the pH value in the conventional water quality database reflects the pH value of the wastewater, the conductivity reflects the salt content of the wastewater, the chemical oxygen demand reflects the total organic matter level of the wastewater, the total nitrogen, total phosphorus and ammonia nitrogen reflect the nutrient salt level of the wastewater, the copper, mercury and nickel reflect the heavy metal concentration level of the wastewater, and the cyanide and aniline reflect the characteristic organic pollutant level of the wastewater. The conventional water quality indexes are simple to test, mature in method and low in investment, and the conventional indexes are used as auxiliary tools for waste water identification; the three-dimensional molecular weight water wave, the fluorescent water wave and the ultraviolet visible absorption spectrum of the wastewater have stability and distinguishability, and can be used for identifying the characteristic water wave of different wastewater, so that the three indexes are constructed into a water quality water wave database.
In conclusion, the analysis shows that the pollution source database established by the method comprises a pollution source basic information base, a conventional water quality database and a water quality water wave database. When a pollution accident occurs, the general situation of pollution is investigated, a polluted water sample is collected, conventional water quality indexes and water quality water marks are analyzed and tested, and the conventional water quality indexes and the water quality water marks are compared with a database, so that the pollution source can be rapidly investigated.
The invention is further illustrated with reference to specific embodiments and figures. The examples are given solely for the purpose of illustration and are not intended to be limiting.
Example 1
A plurality of electroplating enterprises exist in an industrial park, and the electroplating enterprises can generate a large amount of waste water in the electroplating pretreatment process. The wastewater before electroplating treatment contains salt, free acid or free alkali, various electroplating additives such as various anionic or cationic surfactants, coumarin, ethanolamine and other additives, so that the wastewater before electroplating treatment is difficult to treat, and the risk of stealing the wastewater is high. The method for establishing the pollution source database is described in detail by taking three household electrical appliance plating enterprises of YL, BD and TD as classes.
1) Investigation of pollution sources: and researching the geographic position, main products, enterprise penalty records, contact persons and legal persons of YL, BD and TD household electrical appliance plating enterprises.
2) Collecting samples: collecting pretreatment wastewater of YL, BD and TD household electrical appliance plating enterprises.
3) And (3) conventional water quality index analysis and test: the samples were tested for pH, conductivity, chemical oxygen demand and total phosphorus immediately after transport to the laboratory. The test results show that the water quality of the pretreatment wastewater of different electroplating enterprises has certain difference, which shows that the conventional indexes have certain auxiliary effect on wastewater identification. The pH value of YL is between 4 and 5, the pH value of BD is between 7 and 9, and the pH value of TD is more than 13. The conductivity of YL is 3000-4400 mu S/cm, the conductivity of BD is 400-1200 mu S/cm, and the conductivity of TD is 110000-130000 mu S/cm. The chemical oxygen demand of YL is between 150 and 350mg/L, the chemical oxygen demand of BD is between 500 and 600mg/L, and the chemical oxygen demand of TD is between 2500 and 3500 mg/L. Total phosphorus of YL is between 15 and 25mg/L, total phosphorus of BD is between 1 and 3mg/L, and total phosphorus of TD is between 60 and 70 mg/L.
4) And collecting the ultraviolet visible absorption spectrum, the fluorescent water wave and the three-dimensional molecular water wave of the sample.
The ultraviolet visible absorption spectrum test conditions are as follows: the scanning range is 190 nm and 800nm, and the interval is 0.2 nm.
And (3) acquiring the fluorescent water marks: the excitation wavelength is 220-500 nm, the emission wavelength is 230-550 nm, the scanning interval is 5nm, the scanning speed is 12000nm/min, the slit width is 5nm, and the voltage of the photomultiplier is 700V. Typical fluorescence spectra of wastewater from three electroplating plant pre-treatment plants, YL, BD and TD, are shown in FIG. 2a, FIG. 2b and FIG. 2 c.
The three-dimensional molecular weight water wave test conditions are as follows: agilent 1260 series high performance liquid chromatography, protective column (60mm × 7.5mm,8 μm), size exclusion chromatography column (300mm × 7.5mm,8 μm), column temperature 35 deg.C, mobile phase is phosphate buffer (1.0336g/L KH)2PO4+2.8272g/L K2HPO4·3H2O, pH 7.0)), mobile phase flow rate 1mL/min, scan time 20 min. Diode array detector for multi-wavelength ultraviolet absorption molecular weight water waveCollecting, wherein the scanning range is 200-500 nm, and the collection interval is 2 nm; collecting multi-excitation fluorescence molecular weight water marks by using a fluorescence detector in a multi-excitation mode, wherein the excitation wavelength range is set to be 200-400 nm, the collection interval is 5nm, the emission wavelengths of YL and BD are set to be 305nm, and the emission wavelength of TD is set to be 340 nm; the multi-emission fluorescence molecular weight water streak is collected by using a fluorescence detector in a multi-emission mode, the emission wavelength range is set to be 300-500 nm, the collection interval is 5nm, the YL and BD excitation wavelengths are set to be 225nm, and the TD excitation wavelength is set to be 275 nm. Typical multi-wavelength ultraviolet absorption molecular weight water waves of the pretreatment wastewater of the three household electrical appliance plating enterprises are shown in figures 3a, 3b and 3 c; multiple excitation fluorescent molecular weight water wave patterns are shown in fig. 4a, 4b and 4 c; multiple emission fluorescent molecular weight water marks are shown in FIGS. 5a, 5b and 5 c.
5) Inputting basic information of a pollution source into a constructed pollution source basic information base, inputting conventional water quality data into a constructed conventional water quality database, constructing a water quality water wave database of the pollution source by using ultraviolet-visible spectrum, fluorescence water wave and three-dimensional molecular weight water wave data, and finally combining the pollution source basic information base, the conventional water quality database and the water quality water wave database into a water pollution source database.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A water pollution discharges the source database, its characterized in that: the database comprises a pollution emission source basic information base, a conventional water quality database and a water quality water wave database; the pollution source basic information base comprises a pollution source name, a geographical position, main products, enterprise penalty records, contacts and legal persons; the conventional water quality database comprises pH value, conductivity, chemical oxygen demand, total nitrogen, total phosphorus, ammonia nitrogen, copper, mercury, nickel, cyanide and aniline of a water sample; the water quality water streak database comprises three-dimensional molecular weight water streaks, fluorescent water streaks and ultraviolet-visible absorption spectra of a water sample;
the three-dimensional molecular weight water wave comprises an ultraviolet absorption molecular weight water wave, a multi-excitation fluorescence molecular weight water wave and a multi-emission fluorescence molecular weight water wave; the ultraviolet absorption molecular weight water wave scanning range is 190-900 nm, and the collection interval is 1-5 nm; the multi-excitation fluorescence molecular weight water wave excitation wavelength scanning range is 220-700 nm, and the collection interval is 1-5 nm; the scanning range of the multi-emission fluorescent molecular weight water wave emission wavelength is 230-750 nm, and the collection interval is 1-5 nm;
the ultraviolet absorption molecular weight water streak is a map related to the molecular weight distribution of a sample acquired by a liquid phase size exclusion chromatography in a diode array detector multi-wavelength mode; the multi-excitation fluorescence molecular weight water streak is a map which is collected by a liquid phase size exclusion chromatography under a multi-excitation mode of a fluorescence detector and relates to the molecular weight distribution of a sample; the multiple emission fluorescent molecular weight water streak is a spectrum which is collected by a liquid phase size exclusion chromatography under a multiple emission mode of a fluorescence detector and relates to the molecular weight distribution of a sample.
2. The water pollution discharge source database of claim 1, wherein: the scanning range of the excitation wavelength of the fluorescent water wave is 220-700 nm, the scanning range of the emission wavelength is 230-750 nm, and the scanning interval is 2-5 nm.
3. The water pollution discharge source database of claim 1, wherein: the scanning range of the ultraviolet visible absorption spectrum is 190-900 nm, and the scanning interval is 0.2-1 nm.
4. A method for establishing a source database of water pollution discharge sources as claimed in any one of claims 1 to 3, characterized in that the method comprises the steps of:
1) investigation of pollution sources: investigating pollution source names, geographic locations, main products, enterprise penalty records, contacts and legal persons;
2) collecting samples: collecting a wastewater sample of a pollution discharge source;
3) analytical testing of the samples: testing the pH value, the conductivity, the chemical oxygen demand, the total nitrogen, the total phosphorus, the ammonia nitrogen, the copper, the mercury, the nickel, the cyanide and the aniline of a water sample by adopting a national standard method; collecting three-dimensional molecular weight water marks of a sample by using a liquid phase size exclusion chromatography, collecting the fluorescent water marks of the sample by using a fluorescence spectrophotometer, and collecting an ultraviolet visible absorption spectrum of the sample by using an ultraviolet visible spectrophotometer;
4) establishing a water pollution discharge source database: the water pollution emission source database consists of a pollution source basic information base, a conventional water quality database and a water quality water wave database; inputting basic information of the pollution source into a basic information base of the pollution source, inputting conventional water quality data into a conventional water quality database, and inputting three-dimensional molecular weight water wave, fluorescent water wave and ultraviolet visible absorption spectrum data into the water quality water wave database of the pollution source.
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| CN113311081B (en) * | 2021-05-17 | 2023-08-11 | 清华大学 | Pollution source identification method and device based on three-dimensional liquid chromatography fingerprint |
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