Target pollutant and fingerprint collaborative water pollution quantitative traceability technology and system

Abstract

The invention relates to the technical field of environmental monitoring and risk prevention and control, in particular to a target pollutant and fingerprint coordinated water pollution quantitative traceability technology and system, and establishes a water pollution traceability technology coordinated with multi-dimensional fingerprint information of a target pollutant and an environmental matrix thereof. Further constructing databases such as a target pollutant database, a water chemical characteristic fingerprint database, a stable isotope fingerprint database and a soluble organic matter fingerprint database, drawing a multi-dimensional pollution source information puzzle taking the target pollutant as an anchor point, and realizing accurate identification and contribution quantification of the water environment pollution source; the water environment pollution tracing system comprising a data acquisition layer, a feature extraction layer, an information analysis layer and a result output layer is constructed based on the established pollution source information puzzle concept, and the water environment pollution tracing system is complete, simple in process, efficient in output, reliable in result and capable of meeting the water pollution tracing and environmental litigation evidence requirements of various complex environments.

Description

Technical Field

[0001] This invention relates to the field of environmental monitoring and risk control technology, and in particular to a water pollution quantitative tracing technology and system that combines target pollutants with fingerprints. Background Technology

[0002] Water security is crucial to national stability and sustainable development, and a key element in building a beautiful China. However, human production and daily life inevitably discharge pollutants, potentially causing water pollution and threatening human health and aquatic ecosystem security. Therefore, preventing and controlling water pollution is of paramount importance. Accurately identifying pollution sources is a necessary prerequisite for effective control and treatment of water pollution; simultaneously, scientifically and objectively determining the causal relationship between potential pollution sources and water pollution is an important basis for environmental liability claims. Currently, various and numerous pollution sources, including industrial, agricultural, and domestic sources, are overlapping, leading to delayed water pollution phenomena and increasingly complex causes such as risk accumulation, amplification, and sudden changes. This presents significant challenges to accurate source tracing and environmental judicial assessment, and also hinders scientific and efficient water environmental protection and environmental litigation.

[0003] Existing water pollution source tracing technologies have many limitations. For example, hydrochemical characterization methods determine the overall characteristics of water sources and the extent of water pollution based on the ratio of compounds in the water or water quality parameters, focusing on qualitative analysis. Furthermore, hydrochemical equilibrium may be affected by hydrogeochemical processes, leading to the loss of pollution source characteristics. Isotope tracing methods identify pollution sources based on isotope ratios or their variation patterns; their accuracy is affected by isotope fractionation or background values, and their interpretation can sometimes be inconsistent. Fingerprinting methods identify pollution sources based on the characteristic spectra of certain complex substances; however, biochemical degradation altering pollutant composition can distort the spectra. No single source tracing method can comprehensively and holistically solve the complex problem of water pollution source tracing. Therefore, there is an urgent need for a highly efficient water pollution source tracing technology that can compensate for the shortcomings of individual technologies and adapt to complex environments.

[0004] In summary, the shortcomings and deficiencies of existing water pollution source tracing technologies can be categorized into three types. First, the migration and transformation of pollutants are complex, making it difficult for single source tracing technologies to capture the dynamic changes of pollutants in the aquatic environment, resulting in a high rate of misjudgment. Second, while traditional source tracing technologies can identify water pollution characteristics to some extent, their ability to analyze mixed pollution from multiple sources is insufficient. Third, traditional source tracing technologies struggle to distinguish the degree of contribution of different pollution sources to water pollution events.

[0005] To address the above deficiencies and shortcomings, it is necessary to overcome the limitations of single methods, anchor the target pollutants of pollution sources and their dynamic behavior in the aquatic environment, and improve the interpretability of water pollution pathways; comprehensively utilize various information to accurately depict the "profile" of water pollution under multi-source mixed conditions such as point sources and area sources, improve the accuracy of source tracing, and support the quantification of the contributions of multiple pollution sources.

[0006] Therefore, in response to the aforementioned problems, this invention proposes a water pollution quantitative source tracing technology and system that combines target pollutants and fingerprints. Based on target pollutants, it combines multiple source tracing methods to obtain multi-dimensional fingerprint information of the environmental matrix, constructs a "pollution source feature mosaic" of water pollution profile under multi-source mixed conditions, realizes accurate source tracing of water pollution, improves the pertinence and effectiveness of pollution control, and supports the quantitative assessment of pollution source damage in environmental litigation. Summary of the Invention

[0007] To overcome the problems of insufficient accuracy and difficulty in quantifying the contribution of pollution sources in existing water pollution source tracing technologies, this invention proposes a water pollution quantitative source tracing technology and system that combines target pollutants with fingerprints.

[0008] The technical solution of this invention is: a water pollution quantitative source tracing technology that combines target pollutants and fingerprints, including: establishing a water pollution source tracing technology that combines the target pollutant (i.e., "1") with the multi-dimensional fingerprint information (i.e., "N") of the target pollutant and its environmental matrix, stable isotopes, and dissolved organic matter.

[0009] As a preferred method, the method includes the following steps: S1, acquiring water samples from the contaminated site, historical water pollution data and hydrogeological and geomorphological data of the sampling points at the contaminated site, pollution source information around the sampling points at the contaminated site, and potential pollution source samples, thereby obtaining fingerprint information of the target pollutant and various environmental matrices; S2, acquiring data of fingerprint information of the target pollutant and various environmental matrices, and constructing a database of the target pollutant and a fingerprint database of each environmental matrix; S3, based on the target pollutant "1", combining at least one environmental matrix fingerprint information "N" to construct a pollution source feature mosaic Puz for the contaminated site, and based on the target pollutant "1", combining at least one environmental matrix fingerprint information "N" to draw a pollution feature portrait Pic of the potential pollution source; S4, extracting the edge, texture, and local shape features of Puz and Pic, calculating the similarity through the difference in feature spatial distribution, and determining that the pollution source is a single pollution source when the similarity between Puz and a single Pic exceeds the confidence threshold; when the similarity with multiple Pics exceeds the threshold, it is determined to be mixed pollution; S5, for mixed pollution, calculating the contribution ratio of each pollution source based on the relative intensity of the similarity between Puz and each Pic.

[0010] Preferably, step S1 specifically includes: the core concept of the water pollution source tracing technology is to coordinate the target pollutant ("1") with the environmental matrix fingerprint information ("N") to construct a pollution source feature mosaic ("1+N") for precise pollution source tracing and contribution quantification; obtaining water samples from the polluted site through standardized sampling technology, and acquiring water pollution history and hydrogeological geomorphological data of the sampling points at the polluted site; collecting and acquiring pollution source information around the sampling points at the polluted site through literature review or field survey, the pollution source information including the number of potential pollution sources, emission pollution types, and hydrogeological geomorphology, while acquiring potential pollution source samples through standardized sampling technology; the target pollutant information "1" is key, and pollutant information is acquired through target analysis technology; water chemical characteristics are important environmental matrix fingerprint information "N1", and N1 data is acquired through water chemical characteristic analysis technology; among them, water chemical characteristic technology refers to the comprehensive reflection of the composition, content, proportion, and spatiotemporal variation of dissolved or suspended chemical substances in water, which to a certain extent reflects the source, formation process, evolution history, and relationship with the surrounding environment of the water body. The interaction with the environment is analyzed using chemical characteristic analysis techniques, including compound composition ratios, basic water quality parameters, and comprehensive water quality indicators, to obtain N1 data. Stable isotopes are an important environmental matrix fingerprint, "N2," and their data is obtained through stable isotope analysis. Stable isotopes, as opposed to radioactive isotopes, are atomic forms of the same chemical element with different numbers of neutrons and the same number of protons in their nuclei, and do not spontaneously undergo radioactive decay. N2 data is obtained based on the stable isotope ratios or the changes in isotope ratios caused by isotope fractionation. Dissolved organic matter is an important environmental matrix fingerprint, "N3," and its data is obtained through spectral or mass spectrometric analysis. Dissolved organic matter is a complex mixture existing in water bodies, with diverse structures, and significant differences exist between water bodies from different pollution sources. N3 data is obtained through dissolved organic matter analysis. Other supplementary environmental matrix fingerprint information, "Nx," can be obtained through related analytical techniques. This includes biomarkers and aquatic environmental DNA.

[0011] Preferably, step S2 specifically includes: collecting and acquiring historical water pollution and hydrogeological geomorphological information of sampling points at contaminated sites, and using target analysis techniques to acquire target pollutant data, constructing a target pollutant database Database1; wherein, the historical water pollution and hydrogeological geomorphological information includes local pollution event history records, hydrogeological maps, groundwater flow direction and tidal cycles, and the target analysis techniques include chromatography (gas chromatography, liquid chromatography), and chromatography-mass spectrometry (gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry); using water chemical characteristic analysis techniques to acquire N1 data, constructing a water chemical characteristic fingerprint database DatabaseN1; wherein, the water chemical characteristic analysis techniques include multi-parameter water quality analysis, flow injection analysis, etc. Analysis methods included ion chromatography, inductively coupled plasma mass spectrometry (ICP-MS), and stable isotope analysis techniques. N2 data were acquired using stable isotope ratio mass spectrometry and elemental analysis. N3 data were acquired using dissolved organic matter analysis techniques, constructing a dissolved organic matter fingerprint database, Database N3. Dissolved organic matter analysis techniques included ultraviolet-visible absorption spectroscopy, three-dimensional fluorescence spectroscopy (3D-EEM), Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Nx data were acquired using corresponding analytical techniques to construct other fingerprint databases, Database Nx.

[0012] Preferably, the technology achieves accurate source tracing and contribution quantification by comparing the pollution characteristics of water samples from polluted site sampling points with the pollution characteristics of potential pollution sources. This includes: the polluted site sampling point is the research point where water samples are collected in the area where water pollution occurs, and the sampling point is marked with latitude and longitude coordinates; wherein, the collection volume of the representative water sample from the polluted site is not less than 5 liters, and there are not less than 2 parallel analysis samples. Potential pollution sources are potential discharge outlets that could cause water pollution in the area represented by the sampling point of the contaminated site. Pollution source locations are marked with latitude and longitude coordinates. The volume of representative water samples from potential pollution sources must be no less than 5 liters, and at least two samples must be analyzed in parallel. Multiple potential pollution sources may exist, meaning mixed pollution is possible. Potential pollution sources can be categorized as point sources or area sources. Point sources include fixed and mobile point sources. Fixed point sources are easily located, such as factory discharge outlets, wastewater treatment plant effluents, or landfill leaks. Mobile point sources are dynamically changing, including motor vehicles, whose discharge behavior at a specific time needs to be determined based on their movement trajectories. Area sources, also known as non-point source pollution, are characterized by large areas, dispersion, and difficulty in precise location, including agricultural / forestry non-point source pollution and atmospheric deposition. A combination of multiple single-item source tracing techniques is used to analyze representative water samples from the contaminated site to obtain the target pollutant and its environmental matrix fingerprint information, which forms the composite of pollution source information. The process involves: 1) creating a mosaic (Puz) of pollution source information for a contaminated site; 2) combining multiple single-source tracing techniques to analyze representative water samples from potential pollution sources, obtaining fingerprint information of target pollutants and environmental matrix, and creating a pollution characteristic profile (Pic) of the potential pollution source; 3) comparing the mosaic of pollution source information for the contaminated site with the pollution characteristic profile of the potential pollution source. If the similarity between Puz and a single Pic exceeds a confidence threshold V, the site pollution source represented by Puz can be identified as being related to that single Pic. If the similarity between Puz and multiple Pics exceeds a confidence threshold, the site pollution source represented by Puz originates from multiple Pics. The confidence threshold V is assessed by comparing the differences in the distribution of features in the feature space, extracting features such as edges, textures, and local shapes from the images Puz and Pic; 4) for mixed pollution caused by multiple pollution sources, calculating the relative intensity of the similarity between Puz and multiple Pics, and estimating the contribution percentage of the pollution sources represented by multiple Pics to the pollution represented by Puz.

[0013] As a preferred method, characteristic pollutants are screened using a priority ranking approach. These include: target pollutants can be categorized into inorganic and organic pollutants, possessing characteristics such as source specificity, environmental stability, detectability, and traceability. Source specificity refers to the pollutant corresponding to certain pollution sources; environmental stability refers to the pollutant's resistance to rapid degradation; detectability refers to the availability of mature analytical methods; and traceability refers to the ability to infer the composition of the original emissions through degradation products. Inorganic pollutants include heavy metals and nutrients, exhibiting high stability in aquatic environments, with emission sources potentially involving metallurgy, agriculture, or natural sources. Organic pollutants include persistent organic pollutants. Pollutants, pharmaceuticals, and personal care products exhibit more complex migration and transformation behaviors in the aquatic environment than inorganic pollutants, and their emission sources may involve chemical, medical, or domestic sources. Inorganic pollutants can be classified according to the background values ​​and quality standard limits of the aquatic environment in the area where the contaminated site is located, and the detection data of pollutants can be prioritized according to the pollution level to screen out at least one inorganic target pollutant. Organic pollutants can be calculated based on the inherent persistence, bioaccumulation, biotoxicity, and exposure level in the environment to determine the environmental health risk, and at least one organic target pollutant can be screened out according to the risk priority.

[0014] Preferably, the pollution source feature mosaic is constructed by combining target pollutants and several types of environmental matrix fingerprint information. Specifically, the target pollutant embodies the key pollution characteristics of the pollution source. If the pollution source can be directly identified through the target pollutant, there is no need to supplement other fingerprint features. If the pollution source cannot be clearly identified solely through the target pollutant, source tracing can be achieved by supplementing environmental matrix fingerprint features. The target pollutant and environmental matrix fingerprint information are combined and matched in multiple dimensions to construct a multi-dimensional pollution source feature mosaic with the target pollutant as the anchor point, thereby achieving accurate source tracing and contribution quantification of water pollution sources.

[0015] Preferably, the target pollutant can be combined with multi-dimensional environmental matrix fingerprint information, including: Based on the target pollutant "1", selecting one more environmental matrix fingerprint feature, including hydrochemical feature "N1", stable isotope "N2", and dissolved organic matter "N3", constructing a pollution source feature mosaic Puz using 1+N1, 1+N2, or 1+N3, and comparing it with the pollution feature profile Pic of potential pollution sources to achieve pollution source tracing or contribution quantification; or based on the target pollutant "1", selecting two more environmental matrix fingerprint features, including hydrochemical feature "N1", stable isotope "N2", and dissolved organic matter "N3", constructing a pollution source feature mosaic Puz using 1+N1+N2, 1+N1+N3, or 1+N2+N3, and comparing it with the potential pollution source profile Pic. By comparing the pollution characteristic profiles (Pic) of potential pollution sources, the source of pollution can be traced or its contribution can be quantified. Based on the target pollutant "1", three environmental matrix fingerprints are selected, including the hydrochemical characteristic "N1", the stable isotope "N2" and the dissolved organic matter "N3". A pollution source characteristic mosaic (Puz) is constructed by 1+N1+N2+N3 and compared with the pollution characteristic profiles (Pic) of potential pollution sources to trace or quantify the source of pollution. Based on the target pollutant "1", other environmental matrix fingerprints (Nx) other than the hydrochemical characteristic "N1", the stable isotope "N2" and the dissolved organic matter "N3" are selected. A pollution source characteristic mosaic (Puz) is constructed and compared with the pollution characteristic profiles (Pic) of potential pollution sources to trace or quantify the source of pollution.

[0016] As a preferred option, the water pollution quantitative tracing system that combines target pollutants and fingerprints includes: a data acquisition layer, which combines multiple individual tracing technologies to acquire pollution characteristic data and constructs Database1, DatabaseN1, DatabaseN2, DatabaseN3, and DatabaseNx; a feature extraction layer, which extracts pollutant data from the database, processes the feature data according to data analysis requirements, mines pollution characteristic data, and extracts key feature information; an information parsing layer, which draws a pollution source feature mosaic Puz and a potential pollution source pollution feature portrait Pic based on the pollution characteristic data, compares the similarity between Puz and Pic, and realizes pollution source tracing and contribution quantification; and a result output layer, which visualizes the pollution source information and pollution contribution ratio that cause water pollution, and provides water pollution control suggestions and environmental litigation evidence chains.

[0017] Preferably, the information parsing layer performs the following operations: when Puz has a similarity greater than the confidence threshold with only a single Pic, it outputs a single pollution source conclusion; when Puz has a similarity greater than the confidence threshold with multiple Pics, it outputs a mixed pollution source conclusion and its contribution percentage.

[0018] The beneficial effects of this invention are as follows: 1. This invention combines multiple individual source tracing technologies, effectively reducing the uncertainty and misjudgment rate of individual technology source tracing results through mutual verification and supplementation of multiple methods. It has a stronger adaptability to complex environments (mixed pollution, migration and transformation) and interfering factors (such as background value fluctuations). At the same time, based on the target pollutant, it coordinates with the multi-dimensional fingerprint information of the environmental matrix, enhancing the interpretability of the source tracing results. 2. This invention can generate a comprehensive "pollution source feature mosaic" of water samples from contaminated sites, pointing to the most likely pollution source type, location, or specific emitter in the area represented by the water sample, and providing a credibility assessment of the source tracing results, visual display (such as GIS map marking hotspot sources, contribution rate pie charts, feature matching degree charts) and / or structured report output of source tracing conclusions. 3. This invention facilitates the preservation of evidence in litigation, providing support for environmental management, environmental justice, and environmental liability claims. In litigation or other non-litigation dispute resolution, it helps determine the extent of liability for water pollution damage, particularly by scientifically and objectively assessing the causal relationship between water pollution and its sources, and determining the amount of compensation for water pollution damage. This has significant legal implications and enforcement reference value. This invention can provide decision support for environmental management or judicial departments, enabling the development of targeted pollution control measures based on source tracing results, such as strict supervision of key pollution sources, the development of pollutant reduction plans, and the planning of pollution control projects, achieving precise pollution control. 4. The water pollutant source tracing system proposed in this invention is a structured and process-oriented application of water pollution source tracing technology that coordinates target pollutants with environmental matrix fingerprint information. It is expected to improve the efficiency of source tracing work and lay the foundation for reducing response time and technical barriers in water pollution source tracing. Attached Figure Description

[0019] Figure 1 The diagram shown is a schematic representation of the core technical framework of this invention. Figure 2 The diagram illustrates a water pollution combined source tracing strategy and its method system as an application example of the present invention. Figure 3 The diagram illustrates a workflow for water pollution source tracing, representing an application example of the present invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Please see Figure 1 The present invention provides an embodiment: a water pollution quantitative tracing technology and system that combines target pollutants and fingerprints, comprising:

[0022] This document explains the spatiotemporal definition of water pollution and the investigation of potential pollution sources. Specifically, water pollution refers to the phenomenon where water bodies undergo changes in their physical, chemical, or biological characteristics due to one or more substances, i.e., "target pollutants," exceeding a certain level, thereby affecting water safety. Water pollution has a wide range of sources. Some water pollution incidents have relatively clear sources that can be directly identified through the target pollutant; others have complex causes, and the source of the target pollutant is unclear. To address these water pollution incidents, the temporal and spatial boundaries of the pollution event should first be defined, i.e., "when and where did the water pollution occur," and then potential pollution sources should be screened under certain temporal and spatial constraints. If the hydrological model shows that the pollution discharge from a certain source cannot reach the sampling point, then that source should not be considered a potential pollution source. When a water pollution event originates from mixed pollution from multiple sources, further clarifying the contribution ratio of each pollution source based on accurate source tracing plays a crucial role in water pollution control.

[0023] This invention describes a water pollution source tracing technology that combines target pollutants with environmental matrix fingerprints. Specifically, single-item source tracing technologies typically have limitations, while combining multiple single-item source tracing technologies helps improve the accuracy of the tracing results. Target pollutants can establish a causal chain between water pollution and pollution sources, providing a scientific basis for precise source tracing, and their mass balance model helps decouple mixed contributions. This invention uses the target pollutant (“1”) as a foundation, and combines it with multi-dimensional fingerprint information such as the hydrochemical characteristics (“N1”), stable isotopes (“N2”), and dissolved organic matter (“N3”) of the environmental matrix to construct a pollution source feature mosaic (“1+N”), aiming to achieve precise source tracing and contribution quantification of pollution sources.

[0024] The pollution characteristic database serves as a scientific basis for determining the sources and migration / transformation pathways of pollutants. By systematically collecting and organizing pollution characteristic data from different pollution sources and polluted water bodies, the database provides comparable, archived, and retrospective information for precise source tracing and contribution quantification, promoting the standardization of source tracing technologies and the scientification of environmental forensic identification. When combining multiple individual source tracing technologies to analyze water samples, various classification data can be obtained, correspondingly forming a target pollutant database (Database1), a water chemical characteristic fingerprint database (DatabaseN1), a stable isotope fingerprint database (DatabaseN2), a dissolved organic matter fingerprint database (DatabaseN3), and other fingerprint databases (DatabaseNx).

[0025] The pollution source feature mosaic (“1+N”) is explained as follows: Based on the target pollutant (“1”), multi-dimensional environmental matrix fingerprint features are selected as needed, including water chemical features (“N1”), stable isotopes (“N2”), and dissolved organic matter (“N3”). If the pollution source can be identified through the target pollutant (“1”), there is no need to supplement other environmental matrix fingerprint features; otherwise, by selecting more than one fingerprint feature, pollution source feature mosaics of 1+N1, 1+N2, 1+N3, 1+N1+N2, 1+N1+N3, 1+N2+N3, and “1+N1+N2+N3” can be formed. These mosaics are then compared with the pollution feature profiles of potential pollution sources to achieve pollution source tracing or contribution quantification.

[0026] The water pollution source tracing system is described in detail below: This system is a structured and procedural application of water pollution source tracing technology that coordinates target pollutants with extended fingerprint information. Its core function is to provide specific implementation schemes for each key process of water pollution source tracing technology, consisting of four system layers: data acquisition layer (S01), feature extraction layer (S02), information parsing layer (S03), and result output layer (S04). With the deep integration of environmental big data models and the Internet of Things, the water pollution source tracing system will further improve the efficiency of source tracing work, reduce the response time and technical threshold of water pollution source tracing, and promote the development of water environment management from "passive emergency response" to "proactive early warning."

[0027] The system comprises: S01, a data acquisition layer, which collects water environment samples, combines various single-item source tracing technologies to obtain pollution characteristic data, and constructs multiple databases such as Database1, DatabaseN1, DatabaseN2, DatabaseN3, and DatabaseNx; S02, a feature extraction layer, which extracts pollutant data from the databases, processes the feature data according to data analysis requirements, and, after preprocessing such as standardization and normalization, mines pollution characteristic data and extracts key feature information, such as characteristic pollutant concentrations, isotope ratios, and time series patterns; S03, an information parsing layer, which uses specific algorithms or strategies (such as multivariate statistical analysis, Bayesian inference, machine learning models, weight allocation optimization, etc.) to analyze the extracted feature information, draws a pollution source feature mosaic and a pollution feature profile of potential pollution sources based on the pollution characteristic data, compares the similarity between the two, and realizes pollution source tracing and contribution quantification; S04, a result output layer, which identifies the correlation, consistency, or contradictions between features, visualizes the pollution source information and pollution contribution ratio of water pollution, and provides water pollution control suggestions and environmental litigation evidence chains.

[0028] The technical solution of the present invention will be further described below with reference to specific application examples.

[0029] Please see Figure 2According to embodiments of the present invention, a methodological system for tracing groundwater pollution sources in the marine-terrestrial interaction zone is established. The marine-terrestrial interaction zone is influenced by both the ocean and land, resulting in highly complex groundwater pollution conditions. Considering the fragility of the marine-terrestrial interaction zone ecosystem and the concealed, delayed, and complex nature of groundwater pollution, accurate and timely pollution source tracing is crucial and extremely challenging. This application provides an efficient combined source tracing strategy and its methodological system to accurately and rapidly identify groundwater pollution sources in the marine-terrestrial interaction zone and quantify the pollution contribution rate of each source, including: A01~A03, and potential pollution source investigation. Mastering information on potential pollution sources in the marine-terrestrial interaction zone is crucial for accurate pollution source tracing and can significantly improve tracing efficiency. Potential pollution sources leading to groundwater pollution in the marine-terrestrial interaction zone are numerous. Based on geographical spatial division, they can be divided into marine sources and terrestrial sources. Marine sources include shipping, offshore oil extraction, and marine aquaculture, where pollutants enter groundwater through tidal pathways; terrestrial sources include domestic, industrial, agricultural, and aquaculture activities, where pollutants pollute groundwater through direct discharge, surface water infiltration, and soil seepage. Based on the stationary nature of pollution sources, they can be divided into point sources and area sources. Point sources have fixed discharge points, such as the centralized discharge of industrial wastewater and urban sewage; area sources do not have fixed discharge points, such as agricultural pollution or atmospheric deposition. In addition, mobile sources and historical sources are two special types of pollution sources. Mobile sources are pollutants emitted by mobile facilities such as vehicles and ships, while historical sources are the continued pollution of the current environment caused by past pollution events. Methods for collecting information on potential groundwater pollution sources in the land-sea interface include literature review and field surveys, combining multiple methods to comprehensively understand potential pollution sources.

[0030] A04, Groundwater Sample Analysis in the Land-Sea Interchange Zone. Collecting and analyzing environmental samples targeting potential pollution sources is crucial for subsequent assessment of groundwater pollution characteristics. Environmental samples from different pollution sources typically contain unique chemical information, which is an important clue for accurate source tracing. However, these chemical information do not always correspond one-to-one with the pollution source. When chemical information specifically points to a particular pollution source, this chemical information can be called the characteristic pollutant of that source. In this case, by applying target pollutant analysis techniques, detecting the target pollutant in the groundwater can identify the pollution source. When chemical information is shared by multiple pollution sources, a more comprehensive analysis of chemical information is needed to achieve accurate source tracing. In this case, a combination of target pollutant analysis and comprehensive water quality analysis should be used to understand the pollution characteristics of groundwater in the land-sea interchange zone.

[0031] A05, Pollution source characteristic mosaic and pollution source contribution rate. Analytical detection of target pollutants includes gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). Comprehensive water quality analysis techniques for auxiliary fingerprints include hydrochemical characterization, stable isotope techniques, and dissolved organic matter fingerprinting techniques.

[0032] (1) Water chemical characterization method: In this application example, eight major ions such as Na+, K+, Ca2+, Mg2+, Cl-, SO42-, HCO3- and NO3-, and metal elements such as Cd, Cr, Cu, Fe, Ni and Ti are selected as water quality parameters. The water quality is comprehensively characterized by pipe tri-line diagrams, ion ratios (such as NO3- / Cl-, Na+ / Cl-) and principal component analysis. (2) In some cases, stable isotope technology can be used to reflect the biochemical processes of the earth based on isotope ratios and their changes, thereby describing the overall characteristics of water quality. (3) Dissolved organic matter (DOM) is ubiquitous in environmental water bodies and deeply participates in various physical, chemical and biological processes in water bodies, carrying rich environmental information. In view of this, when the water chemical characteristics are the same or similar, 3D-EEM or FT-ICR-MS can be used to obtain DOM fingerprint spectra in environmental samples to reflect the compositional characteristics of DOM in water.

[0033] A06, Characteristics of Groundwater Pollution. On one hand, based on literature review, the potential sources of groundwater pollution in the marine-terrestrial transition zone of the study area are investigated. On the other hand, water quality index analysis and target pollutant analysis are used to clarify the characteristics of groundwater pollution in the marine-terrestrial transition zone. Through qualitative comparison or quantitative analysis of the relationship between groundwater pollution characteristics and potential pollution sources, pollution sources are ultimately identified or the pollution contribution of each source is quantified.

[0034] B01 utilizes the synergistic (1+N) water pollution source tracing technology of target pollutant and environmental matrix fingerprint as described in this invention to achieve precise source tracing and contribution quantification of groundwater pollution in the marine-terrestrial interaction zone. When the target pollutant initially indicates a potential pollution source (such as petroleum, coal combustion, etc.), the environmental matrix fingerprint further distinguishes subclasses or verifies the source (such as different oil fields, different coal types). If the results are consistent, the credibility is enhanced; otherwise, the cause needs to be investigated or more information needs to be introduced.

[0035] B02 represents a fragment of the pollution source characteristics in groundwater samples from the marine-terrestrial transition zone. First, target pollutants in the groundwater of the marine-terrestrial transition zone were identified. Using index classification and evaluation methods and the analytic hierarchy process (AHP), all pollutant indicators were preliminarily ranked, and NH4+, petroleum hydrocarbons (C10~40), and F- were initially identified as target pollutants. For these three target pollutants, the pollution source could not be directly determined; therefore, environmental matrix fingerprinting was required for source tracing.

[0036] B03, Source Tracing Puzzle. The land-sea interaction zone is simultaneously influenced by both land and ocean sources, and groundwater pollution exhibits significant concealment and lag, posing a substantial challenge to accurate pollution source tracing. While the target pollutant, petroleum hydrocarbons (C10-40), can roughly indicate that a sample is contaminated by a chemical company, it cannot pinpoint the exact chemical plant. Furthermore, the target pollutants NH4+ and F- also fail to pinpoint specific pollution sources. Based on field research, the companies in the application case study area, categorized by industry, include loading and unloading and warehousing, chemical raw materials and chemical products manufacturing, electricity and heat production and supply, and non-metallic mineral products manufacturing. Therefore, further optimization of the target pollutants or the construction of a pollution source characteristic puzzle is needed to achieve accurate source tracing.

[0037] Please see Figure 3 Furthermore, to achieve the above objectives, according to embodiments of the present invention, a standardized workflow for tracing groundwater pollution sources in the land-sea interaction zone is further established. This application example provides a standardized workflow for the systematic implementation of water pollution source tracing technology that combines target pollutants with environmental matrix fingerprints, including: S05, determining the scope of the investigation. Based on the basic requirements of tracing the source of groundwater pollution in the land-sea interaction zone, various relevant data were systematically collected to clarify and verify the following contents: (1) geological and hydrogeological data of the land-sea interaction zone, including the geological structure of the coastal zone, the lithology and spatial characteristics of aquifers and impermeable layers; (2) marine dynamics and hydrological data, covering the tidal variation law, tidal current velocity and direction, wave characteristics, and historical and current data of seawater intrusion; (3) data on potential pollution sources from land and sea, sorting out the distribution and discharge characteristics of pollution sources such as industrial wastewater discharge outlets, domestic sewage pipe networks, marine aquaculture areas, and offshore oil platforms along the coast; (4) data on the interaction between fresh and salt water, as well as historical monitoring data; (5) the boundary of the groundwater system in the target area, and the conditions for groundwater recharge, runoff and discharge; (6) the water quantity, water quality, water level and its temporal and spatial variation law of groundwater in the target area; (7) the main hydrogeological parameters of the target aquifer.

[0038] S06, Sampling Points. Based on the collected data, sampling points are scientifically and rationally deployed, and the distribution and number of sampling points are clarified, including: (1) Sampling points are deployed in a gradient along the coastal-land transition zone, covering freshwater areas, brackish water mixed areas, and saline water areas, to ensure coverage of areas with different hydrodynamic conditions and pollution risks; (2) Sampling points are deployed densely around potential pollution sources, distinguishing between land-based point sources (such as factory sewage outlets), non-point sources (such as agricultural irrigation areas), and marine pollution sources (such as mariculture areas), and clarifying the depth and frequency of each type of sampling point; (3) Considering the impact of marine dynamic factors such as tides and storm surges on groundwater, dynamic monitoring sampling points are added near the high tide line, low tide line, and estuary area, and the sampling scheme is optimized in combination with numerical models to ensure that the data can accurately reflect the migration and transformation laws of pollution sources. For areas where sampling work in the land-sea transition zone has not been carried out before, or where existing schemes cannot meet the requirements for pollution source apportionment, the design and optimization of sampling point layout schemes should be carried out with reference to relevant standards such as the "Specification for Geological Investigation and Evaluation of Groundwater Pollution" (DZ / T 0288-2015) and the "Guidelines for Groundwater Environmental Status Investigation and Evaluation" (Huanban Tutu Han

[2019] No. 770). Water, soil, air, or biological samples should be collected according to standard methods, and necessary preservation, transportation, and pretreatment (filtration, extraction, digestion, etc.) should be carried out. The sample testing content is planned to include characteristic pollutants, water chemical characteristics, stable isotopes, and dissolved organic matter.

[0039] S07, Pollution Source Analysis. Applying the "1+N" water source tracing technology, and combining potential pollution sources in the land-sea interaction zone (such as land-based sewage discharge, seawater intrusion carrying pollutants, pollution from tidal flat aquaculture, and pollution from coastal industries), groundwater pollution sources are identified. Specific steps include: First, determining whether tracing can be performed based solely on the target pollutant ("1"). If so, the pollution source is identified and a pollution source tracing report is generated. If not, initiate the 1+N combined source tracing procedure, which involves constructing a pollution source feature mosaic based on the target pollutant ("1") and combining 1 to 3 fingerprints from water chemical characteristics ("N1"), stable isotopes ("N2"), and dissolved organic matter ("N3"). Then, progressively determine whether the target pollutant can be traced by combining 1 environmental matrix fingerprint (1+1N), 2 environmental matrix fingerprints (1+2N), or 3 environmental matrix fingerprints (1+3N). If the above procedures cannot achieve source tracing, other supplementary methods are required. Finally, if the above procedures can achieve source tracing, provide the confidence level of the source tracing conclusion and obtain a deterministic source tracing report and a quantification of the pollution source contribution.

[0040] S08, Technological Achievements. Through the above standardized workflow, a pollution source tracing report is finally obtained, and appendices and tables for key data in the source tracing process are compiled, along with evidence stored on the environmental judicial chain.

[0041] In the description of this invention, unless otherwise stated, "target pollutant" refers to a chemical pollutant that can be matched with a specific pollution source, and in special scenarios, it can also be a biological pollutant, such as a virus; "fingerprint" means a unique, identifiable, and stable characteristic feature exhibited by a water environment sample, used to establish a causal mapping relationship or correlation between the pollution source and the pollutants in the water environment medium; "environmental matrix fingerprint" refers to information that is complementary to the target pollutant and can be used to present a more comprehensive picture of water pollution characteristics; single-item source tracing technology includes a variety of technologies and methods that can be used to identify pollution sources, and is not limited to the few examples given; specific source tracing technologies can employ a variety of analytical methods or instruments, and the specific technologies or methods listed in this specification, such as LC-MS, GC-MS, FT-ICR-MS, etc., are only a part of them, and also include other technologies or methods with similar functions.

[0042] The embodiments of this invention can be applied to pollution source tracing in various scenarios, and can be used for more types of pollutants, environmental media, and complex sites. This is achieved through scheme adjustments, technology optimization, and system modeling to adapt to research needs. Those skilled in the art will understand that the above-described technologies and systems can be implemented in a variety of situations.

[0043] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments that can be applied to other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention shall still fall within the protection scope of the technical solution of the present invention.

Claims

1. A water pollution quantification and tracing technique of target pollutants in coordination with fingerprints, characterized in that, The application relates to a water pollution tracing technology which comprises the following steps: S1, obtaining water samples of a pollution site, water pollution history and hydrogeological data of a sampling point of the pollution site, pollution source information around the sampling point of the pollution site and potential pollution source samples; S2, obtaining data of target pollutants and various environmental matrix fingerprint information, and constructing a target pollutant database and a fingerprint database of each environmental matrix; S3, combining at least one environmental matrix fingerprint information N with the target pollutant 1 to construct a pollution source feature puzzle Puz, and combining at least one environmental matrix fingerprint information N with the target pollutant 1 to draw a potential pollution source pollution feature image Pic; S4, extracting edge, texture and local shape features of Puz and Pic, calculating similarity through feature space distribution difference, and determining that the pollution source is a single pollution source when the similarity of Puz and a single Pic exceeds a confidence threshold value; when the similarity with multiple Pics all exceeds the threshold value, the pollution is determined to be mixed pollution; S5, for the mixed pollution, calculating the contribution proportion of each pollution source according to the relative intensity of the similarity of Puz and each Pic.

2. The target pollutant and fingerprint coordinated water pollution quantification tracing technology according to claim 1, characterized in that, The step S1 specifically comprises the following: the core concept of the water pollution tracing technology is that the target pollutant 1 is coordinated with the environmental matrix fingerprint information N, a pollution source feature puzzle 1+N is constructed for precise pollution tracing and contribution quantification; water samples of the pollution site are obtained through standardized sampling technology, and water pollution history and hydrogeological data of the sampling point of the pollution site are obtained; pollution source information around the sampling point of the pollution site is collected and obtained through literature research or field investigation, the pollution source information comprises the number of potential pollution sources, pollution discharge types and hydrogeological conditions, and meanwhile, potential pollution source samples are obtained through standardized sampling technology; target pollutant information 1 is key, and the pollutant information is obtained through target analysis technology; water chemical characteristics are important environmental matrix fingerprint information N1, and N1 data are obtained through water chemical characteristic analysis technology; stable isotopes are important environmental matrix fingerprint information N2, and N2 data are obtained through stable isotope analysis technology; dissolved organic matter is important environmental matrix fingerprint information N3, and N3 data are obtained through spectral or mass spectrometric dissolved organic matter analysis technology; other environmental matrix fingerprint information Nx can be obtained through related analysis technology. ​ 3. The target pollutant and fingerprint coordinated water pollution quantification tracing technology according to claim 2, characterized in that, ​ 4. The target pollutant and fingerprint coordinated water pollution quantification tracing technology according to claim 2, characterized in that, The step S2 specifically comprises: collecting and acquiring water pollution history and hydrogeological information of the sampling point of the contaminated site, and acquiring target pollutant data by using target analysis technology to construct a target pollutant database Database1; acquiring N1 data by using water chemical characteristic analysis technology to construct a water chemical characteristic fingerprint library DatabaseN1; acquiring N2 data by using stable isotope analysis technology to construct a stable isotope fingerprint library DatabaseN2; acquiring N3 data by using dissolved organic matter analysis technology to construct a dissolved organic matter fingerprint library DatabaseN3; acquiring Nx data by using corresponding analysis technology to construct other fingerprint libraries DatabaseNx.

5. The target pollutant and fingerprint co-banded water pollution quantification and tracing technology according to claim 4, characterized in that, The technology realizes accurate tracing and contribution quantification by comparing the water sample pollution characteristics of the sampling point of the contaminated site with the pollution characteristics of the potential pollution source information, including: the sampling point of the contaminated site is a research point of collecting water samples in a water pollution phenomenon area, and the sampling point is marked by longitude and latitude coordinates; the potential pollution source is a potential pollution outlet causing water pollution in the area represented by the sampling point of the contaminated site, and the pollution source point is marked by longitude and latitude coordinates; there can be multiple potential pollution sources, meaning that mixed pollution can occur; a plurality of single tracing technologies are combined to analyze representative water samples of the contaminated site to acquire target pollutants and environmental matrix fingerprint information, which is used as a puzzle piece of pollution source information to acquire a pollution source information puzzle Puz of the contaminated site; a plurality of single tracing technologies are combined to analyze representative water samples of the potential pollution source to acquire target pollutants and environmental matrix fingerprint information, and a pollution characteristic portrait Pic of the potential pollution source is drawn; the pollution source information puzzle of the contaminated site and the pollution characteristic portrait of the potential pollution source are compared, when the similarity of Puz to a single Pic exceeds a confidence threshold V, it is determined that the pollution source of the site represented by Puz is the pollution source represented by Puz, when the similarity of Puz to multiple Pics all exceeds the confidence threshold, it is determined that the pollution source of the site represented by Puz is the pollution sources represented by multiple Pics; the confidence threshold V is the edge, texture, local shape and other characteristics of the extracted image Puz and Pic, which are compared to evaluate the distribution difference of the characteristic space; for mixed pollution caused by multiple pollution sources, the relative strength of the similarity of Puz to multiple Pics is calculated to estimate the contribution proportion of the pollution sources represented by multiple Pics to the pollution represented by Puz.

6. The target pollutant and fingerprint co-banded water pollution quantification and tracing technology according to claim 5, characterized in that, The characteristic pollutants are screened by a prioritization method, including: the target pollutants can be divided into inorganic pollutants and organic pollutants, which have source specificity, environmental stability, detectability and traceability, etc.; the inorganic pollutants can be classified according to the water environmental background value and the quality standard limit value of the area where the contaminated site is located, and the detection data of the pollutants are prioritized according to the pollution degree level to screen at least one inorganic target pollutant with high ranking; the environmental health risk of the organic pollutants can be calculated according to the inherent persistence, biological accumulation, biological toxicity and exposure level of the environment, and at least one organic target pollutant with high ranking is screened according to the risk prioritization.

7. The target pollutant and fingerprint coordinated water pollution quantification tracing technology according to claim 6, characterized in that, The pollution source characteristic puzzle is constructed by combining target pollutants and several environmental matrix fingerprint information, and specifically includes: the target pollutants embody the key pollution characteristics of the pollution source, if the pollution source can be directly identified through the target pollutants, no other fingerprint characteristics need to be supplemented, and if the pollution source cannot be clearly identified through the target pollutants alone, the traceability can be achieved by supplementing the environmental matrix fingerprint characteristics; the target pollutants are combined with the environmental matrix fingerprint information in multiple dimensions, a multi-dimensional pollution source characteristic puzzle with the target pollutants as the anchor point is constructed, and the precise traceability of the water pollution source and the quantification of the contribution are realized.

8. The target pollutant and fingerprint coordinated water pollution quantification tracing technology according to claim 7, characterized in that, The target pollutants can be combined with multi-dimensional environmental matrix fingerprint information, including: based on the target pollutant "1", one environmental matrix fingerprint characteristic is selected, including water chemical characteristics "N1", stable isotopes "N2" and dissolved organic matter "N3", a pollution source characteristic puzzle Puz is constructed through 1+N1 or 1+N2 or 1+N3, compared with the pollution characteristic image Pic of the potential pollution source, the pollution source traceability or contribution quantification is realized; based on the target pollutant "1", two environmental matrix fingerprint characteristics are selected, including water chemical characteristics "N1", stable isotopes "N2" and dissolved organic matter "N3", a pollution source characteristic puzzle Puz is constructed through 1+N1+N2 or 1+N1+N3 or 1+N2+N3, compared with the pollution characteristic image Pic of the potential pollution source, the pollution source traceability or contribution quantification is realized; based on the target pollutant "1", three environmental matrix fingerprint characteristics are selected, including water chemical characteristics "N1", stable isotopes "N2" and dissolved organic matter "N3", a pollution source characteristic puzzle Puz is constructed through 1+N1+N2+N3, compared with the pollution characteristic image Pic of the potential pollution source, the pollution source traceability or contribution quantification is realized; based on the target pollutant "1", other environmental matrix fingerprint "Nx" except water chemical characteristics "N1", stable isotopes "N2" and dissolved organic matter "N3" is selected, a pollution source characteristic puzzle Puz is constructed, compared with the pollution characteristic image Pic of the potential pollution source, the pollution source traceability or contribution quantification is realized.

9. Water pollution quantification and tracing system of target pollutants in synergy with fingerprints, according to the water pollution quantification and tracing technology of target pollutants in synergy with fingerprints according to any one of claims 1-8, characterized by, It includes: A data acquisition layer combines multiple single traceability technologies to obtain pollution characteristic data and construct Database1, DatabaseN1, DatabaseN2, DatabaseN3 and DatabaseNx; a characteristic extraction layer extracts pollutant data from the database, processes characteristic data according to data analysis requirements, mines pollution characteristic data, and extracts key characteristic information; An information analysis layer draws a pollution source characteristic puzzle Puz and a pollution characteristic image Pic of a potential pollution source according to pollution characteristic data, compares the similarity of Puz and Pic, realizes pollution source traceability and contribution quantification; a result output layer visualizes the pollution source information causing water pollution and the pollution contribution proportion, and gives water pollution control suggestions and environmental litigation evidence chain.

10. The target contaminant and fingerprint co-banded water pollution quantification and tracing system according to claim 9, characterized in that, The information analysis layer performs the following operations: when Puz is only similar to a single Pic similarity > confidence threshold, a single pollution source conclusion is output; when Puz is similar to multiple Pic similarities > confidence threshold, a mixed pollution source conclusion and a contribution ratio are output.

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