Pollution tracing method based on watershed water quality fingerprint database

Abstract

The invention discloses a high-precision pollution tracing method based on a watershed water quality fingerprint database. Belongs to the technical field of water pollution traceability. The method comprises the steps of establishing a watershed water quality fingerprint database, establishing an enterprise sewage fingerprint database and tracing pollutants. According to the method, aiming at the characteristics of a water body environment and main characteristic pollutants thereof, the physicochemical properties of the water body environment and the main characteristic pollutants are analyzed, the main source type of the characteristic pollutants is accurately identified, the contribution degree of the characteristic pollutants is determined, a sound water body pollution source analysis technical system is established, and technical support is provided for water environment quality evaluation, water environment risk evaluation and pollutant reduction. Meanwhile, a pollution tracing result can effectively guide water pollution prevention and control work, the pertinence, scientificity and rationality of pollution prevention and control are improved, and the method is an important basis for formulating a water pollution prevention and control plan and a regional industry and energy structure adjustment scheme.

Description

Technical Field

[0001] The present invention belongs to the technical field of water pollution source tracing, and particularly relates to a high-precision pollution source tracing method based on a basin water quality fingerprint database. Background Art

[0002] With the rapid development of the economy and society, a series of problems have emerged in the basin water environment due to the influence of domestic sewage, industrial sewage, and agricultural wastewater. After a water environmental pollution accident occurs, it is an indispensable link to investigate the pollution sources and trace the pollutants. Pollution source tracing is to analyze the physical and chemical properties of a water body environment and its main characteristic pollutants, and use effective technical methods to accurately identify the main source types of the characteristic pollutants and determine their contribution degrees, establish and improve the technical system for analyzing water pollution sources, and provide technical support for water environment quality assessment, water environment risk assessment, and pollutant reduction. At the same time, the results of pollution source tracing can effectively guide water pollution prevention work, improve the pertinence, scientificity, and rationality of pollution prevention, and are also an important basis for formulating water pollution prevention plans and regional industrial and energy structure adjustment plans.

[0003] At present, relatively complete water environment quality monitoring systems have been established in some areas, and online monitoring equipment is used to monitor water quality indicators such as potassium permanganate index, ammonia nitrogen, and total phosphorus in the water environment in real time to reflect the state and changes of the water environment quality. However, these water quality indicators can only reflect the total amount of pollution and are difficult to directly reflect the sources of pollutants. Pollution source analysis methods include isotope method, three-dimensional fluorescence spectroscopy method, chemical fingerprint method, and artificial intelligence method, etc. The chemical fingerprint method can handle the identification problem of similar pollution sources, and can also perform online non-destructive identification, which has a certain reliability for identifying the sources and contribution information of pollutants. In order to quickly respond to water pollution accidents, it is necessary to establish a sewage fingerprint database for upstream sewage discharge enterprises. By analyzing the chemical fingerprint information of polluted water downstream, the enterprises that violate regulations in discharging sewage can be quickly traced. The technology that uses the fingerprint database to complete pollution source tracing can greatly reduce the workload of water pollution source tracing and quickly and timely achieve pollutant source tracing. At the same time, using the fingerprint database to complete pollution source tracing can greatly reduce the number of online automatic monitoring sampling points and the installation quantity of online automatic monitoring equipment, and greatly save the environmental protection supervision cost. By using the existing automatic monitoring equipment in the river and combining with the fingerprint spectrum technology, on the basis of reducing the number of equipment used, the supervision cost is saved, and at the same time, the supervision intensity is strengthened, effectively solving the problems of sewage discharge enterprises discharging secretly through hidden sewage outlets and violating regulations in discharging sewage by destroying equipment parameters.

[0004] Therefore, it is of great significance to develop a high-precision pollution source tracing method based on a basin water quality fingerprint database. Summary of the Invention

[0005] Aiming at the limitation that the water pollution source tracing method in the prior art can only reflect the total amount of pollution and is difficult to directly reflect the source of pollutants, which leads to the technical problem of quickly locating pollution factors, the present invention provides a high-precision pollution source tracing method based on a watershed water quality fingerprint database. The establishment of this method involves three-dimensional fluorescence, ultraviolet spectrophotometry, and gas chromatography-mass spectrometry with solid-phase microextraction to screen characteristic substances. Search for professional characteristic attributes, relatively stable, and distinguishable chemical fingerprints that can reflect the sewage of upstream polluting enterprises, and establish an effective sewage fingerprint database. Under the condition that the composition of the sewage discharged may vary greatly due to the changes in water body flow and the different production processes of polluting enterprises at different times, obtain water quality information quickly and accurately. Based on the physical evidence analysis results of the polluted water samples, identify and trace the pollutants in combination with the sewage fingerprint database.

[0006] To achieve the above invention objective, the embodiments of the present invention adopt the following technical solutions:

[0007] A high-precision pollution source tracing method based on a watershed water quality fingerprint database, including establishing a watershed water quality fingerprint database, establishing an enterprise sewage fingerprint database, and a method for tracing pollutants.

[0008] Furthermore, the establishment of the watershed water quality fingerprint database specifically includes the following steps:

[0009] (1) Divide the watershed into different sections according to the environmental function zoning within the watershed and the influence intensity of various human activities along the main stream and key tributaries, and collect water samples from each section;

[0010] (2) Conduct three-dimensional fluorescence spectral analysis on the water samples in step (1), and find the corresponding pollutant types according to the spectral results corresponding to the three-dimensional fluorescence analysis diagram (see Figure 1 )

[0011] (3) Conduct physical and chemical index analysis on the water samples in step (1) by ultraviolet spectrophotometry; such as nitrogen, phosphorus, sulfide, permanganate index, etc., and record the experimental results;

[0012] (4) After solid-phase microextraction of the water samples in step (1), detect the volatile organic compounds therein by gas chromatography-mass spectrometry and conduct qualitative and quantitative analysis of the results;

[0013] The water sample is detected for volatile organic compounds, and the specific steps are as follows: Transfer 8 mL of the sample into a 15 mL extraction bottle, then add 2.5 g of NaCl and a magnetic stir bar, and then quickly seal it. Age the SPME extraction fiber head in the GC-MS injection port at 250 °C until there are no impurity peaks. Place the sample bottle on the solid-phase microextraction device, set the temperature to 80 °C, and the rotation speed to 1000 rpm; place the sample bottle on the extraction device and preheat it for 15 min; insert the SPME extraction head through the bottle cap into the headspace part of the sample, push out the fiber head, and the extraction head is about 1.0 cm above the upper surface of the sample, and perform headspace extraction for 40 min; withdraw the fiber head, and pull out the extraction head from the sample bottle; then insert the extraction head into the GC-MS injection port, push out the fiber head, and desorb it at 250 °C for 3 min, and then inject for analysis.

[0014] Chromatographic conditions: The chromatographic column is DB-WAX (30.0 m × 250 μm, 0.25 μm); the initial temperature of the chromatographic column is maintained at 40 °C for 5 min, then increased to 120 °C at a rate of 5 °C / min, and then increased to 240 °C at a rate of 10 °C / min and maintained for 5 min; the vaporization chamber temperature is 250 °C; the transfer line temperature is 240 °C; the carrier gas is He; the carrier gas flow rate is 1 mL / min; splitless injection.

[0015] Mass spectrometry conditions: EI source; electron energy 70 eV; ion source temperature 230 °C; quadrupole temperature 150 °C; the scanning mode is Scan; the scanning mass range is 20 - 500 u.

[0016] Qualitative analysis: The detected components are qualitatively analyzed using the MS database NIST11 and retention time; the column bleed peaks, etc. should be deducted from the database screening results.

[0017] Quantitative analysis: The area normalization method is used, that is, the percentage of the peak area of the identified component in the sum of the peak areas of all identified components is used as the quantitative result, and the formula is as follows:

[0018]

[0019] Where: Ci - the content of a certain identified component, %;

[0020] Ai - the peak area corresponding to a certain identified component;

[0021] n - represents the total number of identified components.

[0022] (5)Summarize the quantity, distribution of various pollution sources, as well as the types, concentrations, methods and patterns of pollutant emissions, etc. Rank the pollution sources according to the pollutant emission intensity and impact degree, screen the list of key pollution sources and key pollutants, and confirm the indicators available for constructing the river basin to build a fingerprint database. The main reference standards are the Integrated Wastewater Discharge Standard (GB 8978-1996) (partially replaced by the Water Pollution Discharge Standard for Saponin Industry (GB 20425-2006) and the Pollutant Discharge Standard for Coal Industry (GB 20426-2006)) and the Surface Water Environment Quality Standard (GB 3838-2002).

[0023] Furthermore, the establishment of the enterprise sewage fingerprint database specifically includes the following steps:

[0024] (1)Collect the discharged sewage of different types of enterprises in the river basin. The enterprise types include: printing and dyeing, electroplating, chemical industry / pharmaceutical, food processing, machinery manufacturing, etc.;

[0025] (2)Determine and collate the data of the sewage water samples by three-dimensional fluorescence, ultraviolet spectrophotometry and volatile organic compounds;

[0026] (3)Clarify the basic information of the pollution-related enterprises in the river basin and the three-dimensional fluorescence spectra of the pollution-related enterprises, compare with the three-dimensional fluorescence spectra of the surface water in this river basin to determine the types of main pollutants. At the same time, according to the detection results of ultraviolet and volatile organic compounds, judge the indicators that are likely to characterize the abnormal water quality of the surface water at this point according to the standards of the river basin water quality fingerprint database;

[0027] (4)Collate and analyze the types of pollutants and the index parameters that cause anomalies of various types of enterprises in the river basin, and establish a sewage fingerprint database for all enterprises in combination with the pollutant characteristics and the hydrological conditions of the river basin;

[0028] (5)According to the different sewage discharge types of special enterprises at different times, establish a multi-time fingerprint database for the enterprises to ensure the integrity of the database. On the basis of collecting data such as historical cases, water pollution control project examples, laboratory data, etc., classify and summarize the relevant information of the existing water environment treatment technologies, so as to verify the universality and popularization of the database and build a complete emergency treatment technology library at the same time.

[0029] Furthermore, the method of pollutant tracing specifically includes the following steps:

[0030] (1)Collection of polluted water samples.

[0031] (2)Experimental analysis of the polluted water samples by three-dimensional fluorescence, ultraviolet spectrophotometry and gas chromatography-mass spectrometry with solid-phase microextraction.

[0032] (3) Extract abnormal indicators based on the experimental results, compare with the labels in the enterprise sewage fingerprint database, and quickly find the enterprise where the pollutant source is located.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] (1) Save supervision costs and effectively solve the problems of illegal discharging through hidden sewage outlets by polluting enterprises and illegal discharging by destroying equipment parameters.

[0035] (2) Traceability using the fingerprint database realizes the goal of significantly improving the traceability efficiency on the basis of reducing the workload of pollutant traceability.

[0036] (3) The basin fingerprint database can provide technical support for water environment quality assessment, water environment risk assessment and pollutant reduction.

[0037] (4) The results of pollution traceability can effectively guide the work of water pollution prevention and control, improve the pertinence, scientificity and rationality of pollution prevention and control, and are also an important basis for formulating water pollution prevention and control plans and regional industrial and energy structure adjustment plans. Description of the Drawings

[0038] In order to make the objectives, technical solutions and advantages of the present invention clearer and to more clearly illustrate the technical solutions of the present invention, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0039] Figure 1 It is a three-dimensional fluorescence analysis diagram. Detailed Embodiments

[0040] In order to make the objectives, technical solutions and advantages of the present invention clearer, the following will further describe the present invention in detail with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0041] Embodiment

[0042] Source of the stench at the water outlet of a reservoir dam in Yiwu:

[0043] (1) Daily monitoring of the reservoir water quality: Collect water samples at 8 points in the reservoir (sewage outfall of surrounding enterprises, sewage outfall of rural areas, suspected pollution source points, in the reservoir, at the reservoir dam and at the reservoir tail, etc.) at different times for the determination of three-dimensional fluorescence, ultraviolet (nitrogen, phosphorus, anionic surfactant, sulfide and hexavalent chromium, etc.) and volatile organic compounds. The sampling frequency is twice a day for three days a week.

[0044] (2) Establish a daily fingerprint database for the entire reservoir area: Statistically analyze the detection results, and use the average value of each indicator within the cycle as the reference standard for the fingerprint database.

[0045] (3) Water quality monitoring of the sewage outfalls of enterprises around the reservoir: According to the distribution of industrial enterprises around the reservoir area, sample and detect the sewage of enterprises upstream of the reservoir and around the reservoir. The sampling frequency is twice a day for two consecutive days.

[0046] (4) Establish a fingerprint database for enterprise sewage: Analyze the quantity, distribution of various pollution sources, as well as the types, concentrations, methods, and patterns of pollutant emissions, etc. According to the pollutant emission intensity and impact degree, compare with the reservoir fingerprint database standard, and use the indicators with large deviations for each enterprise as the key attention labels for the enterprise.

[0047] (5) Analysis of malodorous water samples: According to the determination results of the three-dimensional fluorescence, ultraviolet, and volatile organic compounds of the malodorous water samples, quickly identify that the malodor is caused by a surrounding enterprise's perennial illegal discharge of poultry and livestock manure by comparing the abnormal indicators with the enterprise labels in the sewage fingerprint database.

[0048] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, or improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high-precision pollution source tracing method based on a watershed water quality fingerprint database, characterized in that, It includes establishing a river basin water quality fingerprint database, establishing an enterprise sewage fingerprint database, and a pollutant tracing method.

2. The high-precision pollution source tracing method based on the basin water quality fingerprint database according to claim 1, wherein The establishment of the river basin water quality fingerprint database specifically includes the following steps: (1) Divide the river basin into different sections and collect water samples from each section; (2) Conduct three-dimensional fluorescence spectroscopy analysis on the water samples in step (1) and find the corresponding pollutant types according to the spectral results; (3) Conduct physical and chemical index analysis on the water samples in step (1) by ultraviolet spectrophotometry; (4) After solid-phase microextraction of the water samples in step (1), detect the volatile organic compounds in them by gas chromatography-mass spectrometry and conduct qualitative and quantitative analysis of the results; (5) Organize the quantity, distribution of pollution sources and the types, concentrations, methods, and laws of pollutant emissions in steps (1) to (4), rank the pollution sources according to the pollutant emission intensity and influence degree, screen the list of key pollution sources and key pollutants, and confirm the indicators that can be used to construct the river basin to construct the river basin water quality fingerprint database.

3. The high-precision pollution source tracing method based on the watershed water quality fingerprint database according to claim 1, characterized in that The establishment of the enterprise sewage fingerprint database specifically includes the following steps: (1) Collect the external sewage discharged by different types of enterprises in the river basin; (2) Conduct three-dimensional fluorescence, ultraviolet spectrophotometry, and determination of volatile organic compounds on the sewage water samples in step (1) and organize the data; (3) Clarify the basic information of pollution-related enterprises in the river basin and the three-dimensional fluorescence spectra of pollution-related enterprises, compare the three-dimensional fluorescence spectra of surface water in this river basin to determine the main pollutant types, and at the same time, according to the detection results of ultraviolet spectrophotometry and volatile organic compounds, judge the indicators that are likely to characterize the abnormal water quality of the surface water at this point according to the river basin water quality fingerprint database standard; (4) Organize and analyze the pollutant types and index parameters that will cause abnormalities of various types of enterprises in the river basin, and combine the pollutant characteristics and river basin hydrological conditions to establish an enterprise sewage fingerprint database for all; (5) According to the different sewage discharge types of special enterprises at different times, establish a multi-time fingerprint database for enterprises to ensure the integrity of the database. On the basis of investigating historical cases, collecting data such as water pollution control project examples and laboratory data, classify and summarize the relevant information of existing water environment treatment technologies to verify the universality and popularization of the database while constructing a complete emergency treatment technology library.

4. The high-precision pollution source tracing method based on the basin water quality fingerprint database according to claim 1, characterized in that, The method for tracing pollutants specifically includes the following steps: (1) Collection of polluted water samples; (2) Conduct experimental analysis of the polluted water samples by three-dimensional fluorescence, ultraviolet spectrophotometry, and gas chromatography-mass spectrometry after solid-phase microextraction; (3) Extract abnormal indicators according to the experimental results, compare with the enterprise sewage fingerprint database, and quickly find the enterprise where the pollutants come from.

5. The high-precision pollution source tracing method based on the basin water quality fingerprint database according to any one of claims 2-4, characterized in that The water sample sources are one or more of rivers, lakes, reservoirs, and sewage treatment plants.

Images