A method and system for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater

Abstract

The present application belongs to the technical field of environmental pollution detection, and discloses a detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater, which comprises the following protective cover: S1, setting up a multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device; S2, constructing a multi-phase state detection data analysis model; S3, performing a multi-phase state detection experiment; S4, detecting actual samples; the system comprises a cloud server, a management terminal and at least one set of multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device. Through the improvement of the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device and the construction of the multi-phase state detection data analysis model, the present application can realize the synchronous detection of the multi-phase state occurrence concentration of chlorinated hydrocarbons in the soil and groundwater environment, more comprehensively evaluate the soil chlorinated hydrocarbon pollution level, and can be widely applied to the identification of potential risks of soil pollution and the precise prevention and control of soil chlorinated hydrocarbon pollution.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of environmental pollution detection, and particularly relates to a detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater. BACKGROUND

[0002] Chlorinated hydrocarbons are an important class of organic synthesis intermediates, and are starting materials for many organic syntheses. Organic chlorinated hydrocarbons are widely used as solvents, industrial and civilian cleaning agents, but these substances not only damage the skin and cause central nervous system poisoning, but also cause damage to cytoplasm, heart, etc., and have adverse effects on liver, kidney, pancreas, and some compounds may also have carcinogenic effects, so all organic chlorides have greater toxicity. The chlorinated hydrocarbons in the atmosphere are mainly derived from human pollution, except for a small part from natural biological metabolism. The chlorine atoms released by chlorinated hydrocarbons act as catalysts for the decomposition of ozone, destroying the atmospheric ozone layer. Developing the determination of volatile chlorinated hydrocarbons in the environment air will provide basic data for the investigation and control of volatile chlorinated hydrocarbon pollution, and has great significance for protecting the environment and ensuring people's health. However, volatile chlorinated hydrocarbons include many types, and volatile chlorinated hydrocarbons usually refer to halogenated compounds with a boiling point below 200 DEG C. Almost all chlorinated hydrocarbons with 8 carbon atoms or less and 5 halogen atoms or less belong to volatile halogenated hydrocarbons. Depending on the management needs and analysis technical capabilities, the analysis objects are different.

[0003] The detection technology of chlorinated hydrocarbons in soil at the present stage mainly uses chromatography-mass spectrometry instruments, mainly focusing on the detection of single phase state such as residual phase and gas phase. The current detection technology can accurately detect the concentration level of a certain type of chlorinated hydrocarbon in a single phase state in soil, but these technologies ignore the differences in chlorinated hydrocarbon pollutants and the physicochemical properties of soil, resulting in multiple phase states of chlorinated hydrocarbons in different types of soil, and the concentrations of each phase state are different. The current detection technology is difficult to simultaneously detect the concentrations of each phase state under multiple phase states.

[0004] The occurrence phase state of chlorinated hydrocarbons in different types of soil and groundwater mainly includes the following: gas phase: chlorinated hydrocarbons may exist in the form of gas phase in the soil due to their volatility, especially in the soil pores or above the soil surface. The gas phase chlorinated hydrocarbons can enter the atmosphere from the soil by volatilization, or form a dynamic balance between the atmosphere and the soil; free phase: refers to the phase in which chlorinated hydrocarbons exist independently without restriction or mixing with other phases; aqueous phase (dissolved phase): chlorinated hydrocarbons can be dissolved in the aqueous phase of soil pore water, and the migration and transformation of dissolved chlorinated hydrocarbons in soil are affected by factors such as water flow and soil properties; solid phase (residual phase): chlorinated hydrocarbons can also be adsorbed on the surface of soil solid phase, including soil particles, soil organic matter, etc., and adsorption is one of the important existence forms of chlorinated hydrocarbons in soil, which affects the migration and transformation behavior and environmental risk of chlorinated hydrocarbons in soil.

[0005] In actual soil environment, different types of chlorinated hydrocarbons exist in various phase states in different soils, and the concentration distribution of various phase states also has a large difference. Specifically, the occurrence phase state of chlorinated hydrocarbons in different types of soil is different. For example, in sandy soil, due to the large soil particle size and high porosity, chlorinated hydrocarbons are more likely to exist in the form of gas phase and aqueous phase; while in clay soil, due to the small soil particle size and small porosity, chlorinated hydrocarbons are more likely to be adsorbed on the surface of soil solid phase. In addition, factors such as the organic matter content, soil pH value and soil humidity in soil also affect the occurrence phase state of chlorinated hydrocarbons. For example, soil with high organic matter content has strong adsorption capacity for chlorinated hydrocarbons, which may promote the conversion of chlorinated hydrocarbons to solid phase; and the change of soil pH value may affect the solubility and adsorption capacity of chlorinated hydrocarbons in soil, thereby affecting the occurrence phase state thereof.

[0006] The existing detection technology can only detect a single phase state of chlorinated hydrocarbons in soil and groundwater, ignoring the existence of other phase states, which is not conducive to the identification of potential risks of soil pollution and the precise prevention and control of soil chlorinated hydrocarbon pollution, and is not conducive to the precise elimination of potential threats to environmental safety and human health. SUMMARY

[0007] The present application aims to solve the above-mentioned problems, and provides a detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater, which is based on the fact that the occurrence phase state of chlorinated hydrocarbons in different types of soil mainly includes gas phase, aqueous phase, solid phase, free phase and other forms. By improving the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device and constructing a multi-phase state detection data analysis model, the simultaneous detection of the occurrence concentration of chlorinated hydrocarbons in soil and groundwater environment can be realized, and the soil chlorinated hydrocarbon pollution level can be more comprehensively evaluated. The present application can be widely applied to the identification of potential risks of soil pollution and the precise prevention and control of soil chlorinated hydrocarbon pollution, thereby solving the problems of the prior art.

[0008] The application provides the following technical solutions:

[0009] A detection method for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater, characterized by comprising the following steps:

[0010] S1, setting up a multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device

[0011] At least one set of experimental device for detecting the concentration of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater is set up, and the device comprises an upper computer, a soil column experimental platform, and a detection instrument gas chromatography-mass spectrometry (GC-MS) and a capillary column.

[0012] S2, constructing a multi-phase state detection data analysis model

[0013] A multi-phase state chlorinated hydrocarbon pollutant detection data analysis model is constructed, which is as follows:

[0014] C = C Free phase + C Dissolved phase + C Residual phase + C Gas phase 1

[0015] In the formula:

[0016] C, the concentration of the chlorinated hydrocarbon mixed solution, mg / L;

[0017] C Free phase , the concentration of the free phase chlorinated hydrocarbon, mg / L;

[0018] C Dissolved phase , the concentration of the dissolved phase chlorinated hydrocarbon, mg / L;

[0019] C Residual phase , the concentration of the residual phase chlorinated hydrocarbon, mg / L;

[0020] C Gas phase , the concentration of the gas phase chlorinated hydrocarbon, mg / L;

[0021] S3, performing a multi-phase state detection experiment

[0022] Through the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device, multi-phase state detection experiments are performed under homogeneous and heterogeneous soil column conditions, different chlorinated hydrocarbons are carried out in multiple glass columns in the soil column experimental platform, migration experiments in different soil columns are carried out, and multiple sets of mutually related multi-phase state occurrence experimental data are obtained.

[0023] S4, detecting an actual sample

[0024] The multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device and the multi-phase detection data analysis model are applied to actual sample detection, and through part of the phase detection data obtained by detection, concentration data of other phases are calculated to obtain complete multi-phase chlorinated hydrocarbon pollutant detection data.

[0025] S5, constructing a multi-phase chlorinated hydrocarbon pollutant detection system for synchronous sample detection

[0026] A multi-phase chlorinated hydrocarbon pollutant detection system including a cloud server, a management terminal and a multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is constructed to synchronously detect and analyze multiple samples and output detection results of each detection sample.

[0027] A multi-phase chlorinated hydrocarbon pollutant detection system for soil and groundwater, which is used to implement the detection method, characterized in that,

[0028] The detection system includes a cloud server, a management terminal and at least one multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, and the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device includes an upper computer, a soil column experiment platform and a detection instrument GC.

[0029] The management terminal and the upper computer are connected to the cloud server through the Internet, and the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is connected to the upper computer.

[0030] The cloud server is used to analyze and process the detection data uploaded by the upper computer and output complete multi-phase chlorinated hydrocarbon pollutant concentration detection results.

[0031] The multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is used to detect samples under experimental conditions and actual sampling.

[0032] The upper computer is used to control the operation of the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, receive detection data obtained by the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device and perform data preprocessing.

[0033] The management terminal is used to input data, instructions to the cloud server or display detection results output by the cloud server.

[0034] The soil column experiment platform includes a plurality of detachable glass columns, a plurality of liquid containers and a plurality of Somar cans, the soil columns are formed by filling soil in each glass column, and each glass column and liquid container in the soil column group are connected by pipelines; a peristaltic pump and a flow divider are arranged on the pipeline in front of the water inlet end of each glass column.

[0035] The glass column comprises: a cylindrical hollow glass column body with openings on the upper and lower end faces, an upper glass cover and a lower base, and a liquid outlet pipe, the upper glass cover is arranged on the upper end face of the glass column body and is provided with a gas stripping hole and a liquid inlet hole penetrating the thickness of the glass cover, the lower base is arranged at the lower part of the lower end face of the glass column body, and the liquid outlet pipe communicates with the inner cavity of the glass column body after penetrating the thickness of the lower base.

[0036] The liquid inlet hole of each glass column communicates with the pipeline of the liquid inlet side through a liquid inlet pipe, and a flow control valve is arranged on the liquid inlet pipe.

[0037] The advantages and beneficial effects of the present application at least include the following points:

[0038] 1. The detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the present application can realize the synchronous detection of the multi-phase state occurrence concentration of chlorinated hydrocarbons in soil and groundwater environment, can more comprehensively evaluate the soil chlorinated hydrocarbon pollution level, can be widely applied to the identification of soil pollution potential risk and the precise prevention and control of soil chlorinated hydrocarbon pollution, and can solve the above-mentioned problems of the prior art and make up for the deficiency of the current chlorinated hydrocarbon soil detection technology.

[0039] 2. The detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the present application can screen out three typical chlorinated hydrocarbons (carbon tetrachloride, chlorobenzene and 1,2,4-trichlorobenzene) as target detection substances according to the detectability, toxicity and environmental persistence of high-risk organic toxic substances from a large amount of chlorinated hydrocarbons, and can construct a multi-phase state detection data analysis model according to the phase distribution occurrence change rule of the three chlorinated hydrocarbons in different soil media, so that the occurrence concentration of other phases can be calculated according to the data of part of the phases (such as residual phase) detected in the process of detecting actual samples, thereby greatly simplifying the detection process and difficulty, and meeting the sample detection needs under large quantities, different components and different conditions.

[0040] 3, The detection method and system of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the present application, a soil column experiment model containing homogeneous soil and non-homogeneous soil is newly designed, and the soil sample is quickly and accurately loaded through the optimization of the column design; in the design process, the soil column model is tested and analyzed by three typical chlorinated hydrocarbons, and the detection results are in good conformity with the respective detection results; at the same time, through data analysis, the law or correlation of the phase distribution concentration change of the three chlorinated hydrocarbons in different soil media is found, and the law can be applied to the detection of new soil samples and the simplification of the detection method. The law of phase distribution concentration change mainly includes the basic characteristics of chlorinated hydrocarbons and soil, for example, the more the organic matter content of soil, the smaller the porosity, the stronger the adsorption capacity of chlorinated hydrocarbon pollutants, and the proportion of residual phase chlorinated hydrocarbon is relatively more; if the saturated vapor pressure of chlorinated hydrocarbon is relatively large, it is easy to volatilize, and mainly exists in the form of gas phase in soil, wherein 1,2,4-trichlorobenzene has strong hydrophobicity, and combined with the characteristics of high organic matter content and small porosity of clay, 1,2,4-trichlorobenzene is basically adsorbed and mainly exists in the form of residual phase.

[0041] 4, The detection method and system of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the present application, through the newly designed multi-phase state chlorinated hydrocarbon pollutant concentration detection experiment device and multi-phase state detection data analysis model, accurate and convenient multi-phase state synchronous detection can be realized, and the detection steps are greatly simplified; by layering and sampling different types of soil media, soil column experiment data can be more efficiently obtained in the actual application process, and the chlorinated hydrocarbon pollution characteristic level of the soil environment can be more quickly evaluated.

[0042] 5, The detection method and system of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the present application, the obtained multi-phase state detection data of chlorinated hydrocarbons in soil can distinguish the main existing phase state of different chlorinated hydrocarbons in soil, and provide data basis for the multi-phase state accurate repair of chlorinated hydrocarbon contaminated soil. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 It is a network composition structure schematic diagram of the detection system of the embodiment of the present application;

[0044] Figure 2 It is a composition structure schematic diagram of the soil column experiment platform in the embodiment of the present application;

[0045] Figure 3 It is a structure schematic diagram of the glass column of the embodiment of the present application;

[0046] Figure 4 It is a schematic diagram of the multi-phase state pollutant detection analysis result of the embodiment of the present application.

[0047] In the figure:

[0048] 1, soil column experiment platform; 2, glass column; 3, pipeline; 4, CHCs mixed liquid container; 5, peristaltic pump; 6, hard tube group; 7, flow control valve; 8, waste liquid container; 9, dissolved phase CHCs container; 10, sumar tank; 21, hollow glass column body; 22, upper glass cover; 23, lower bottom support; 24, liquid inlet hole; 25, gas stripping hole; 26, liquid outlet hole; 27, fixed rubber ring. DETAILED DESCRIPTION

[0049] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the present application.

[0050] Embodiment 1

[0051] Referring to the accompanying drawings, Figures 1 to 4 The detection method for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the embodiment includes the following steps:

[0052] S1, setting up a multi-phase state chlorinated hydrocarbon pollutant concentration detection experiment device

[0053] A set of experimental device for detecting the concentration of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater is set up, and the device includes an upper computer, a soil column experiment platform, and detection instruments such as a gas chromatograph-mass spectrometer and a capillary column. Specifically, the device includes:

[0054] S1-1, setting up a soil column experiment platform

[0055] Each soil column experiment platform 1 includes a plurality of detachable glass columns 2, a plurality of liquid containers (CHCs mixed liquid container 4, waste liquid container 8, and dissolved phase CHCs container 9), and a plurality of sumar tanks 10. After the soil is filled in each glass column 2 to form a soil column group, each glass column 2 and the liquid container in the soil column group are connected by a pipeline 3. A peristaltic pump 5 and a flow divider (not shown in the figure) are arranged on the pipeline 4 in the front section of the water inlet end of each glass column 2. A section of the pipeline 4 is a hard tube group 6, the flow divider is built-in, and the CHCs mixed liquid is divided into each glass column 2.

[0056] The glass column 2 comprises: a cylindrical hollow glass column body 21 with openings on the upper and lower end faces, an upper glass cover 22 and a lower bottom support 23, a liquid inlet pipe and a liquid outlet pipe, the upper glass cover 22 is arranged on the upper end face of the glass column body 21 and seals the opening at the end face, and is provided with a gas stripping hole 25 and a liquid inlet hole 24 penetrating the thickness of the upper glass cover 22; the liquid inlet pipe passes through the liquid inlet hole 24 and communicates with the inner cavity of the glass column body 21; the lower bottom support 23 is arranged at the lower part of the lower end face of the glass column body 21, and the liquid outlet pipe passes through the thickness of the lower bottom support and then passes through the liquid outlet hole 26 to communicate with the inner cavity of the glass column body 21; the liquid inlet hole 24 of each glass column 2 is communicated with the pipeline 4 on the liquid inlet side through the liquid inlet pipe, and a flow control valve 7 is further arranged on the liquid inlet pipe; each part of the glass column 2 is detachably connected; a fixed rubber ring 27 is arranged around the glass column body 21 and used for auxiliary fixing of the glass column body 21;

[0057] S1-2, setting a detection instrument

[0058] An upper computer, a gas chromatograph-mass spectrometer and a capillary column are arranged, the gas chromatograph-mass spectrometer, the capillary column and the upper computer are connected, and the gas chromatograph-mass spectrometer, the capillary column and each soil column experimental platform are connected;

[0059] S1-3, from a large number of chlorinated hydrocarbons, three typical chlorinated hydrocarbons, carbon tetrachloride, chlorobenzene and 1,2,4-trichlorobenzene, are selected as target detection substances for soil column experiments according to the detectability, toxicity and environmental persistence of high-risk organic toxic substances;

[0060] S2, constructing a multi-phase state detection data analysis model

[0061] Specifically, it comprises:

[0062] S2-1, defining the multi-phase state concentration of chlorinated hydrocarbons

[0063] The concentration of free phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons existing independently in a state without restriction or mixing with other phases, which is obtained by using the concentration conservation law;

[0064] The concentration of dissolved phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons dissolved in soil pore water, which is obtained by using CHCs soil column transport experiments and detection;

[0065] The concentration of residual phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons adsorbed on the surface of soil solid phase, which is obtained by using CHCs soil column transport experiments and detection;

[0066] The concentration of gas phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons existing in the form of gas in soil, which is obtained by using CHCs soil column transport experiments and detection;

[0067] S2-2, determining the relationship model between the multi-phase states in the CHCs soil column transport experiment

[0068] Analyzing the rules in the CHCs soil column transport experiment, determining the relationship model between the multi-phase state chlorinated hydrocarbon pollutant detection data, for the following formula 1:

[0069] C = C Free phase + C Dissolved phase + C Residual phase + C Gas phase Formula 1

[0070] In the formula:

[0071] C, the concentration of chlorinated hydrocarbon mixed solution, mg / L;

[0072] C Free phase , the concentration of free phase chlorinated hydrocarbon, mg / L;

[0073] C Dissolved phase , the concentration of dissolved phase chlorinated hydrocarbon, mg / L;

[0074] C Residual phase , the concentration of residual phase chlorinated hydrocarbon, mg / L;

[0075] C Gas phase , the concentration of gas phase chlorinated hydrocarbon, mg / L;

[0076] S2-3, verifying the applicability of the detection experiment device and the model

[0077] The comsol is used to simulate the transport behavior of dissolved phase CHCs in soil, the physical field control equation is used, and the multi-phase state chlorinated hydrocarbon pollutant concentration detection experiment device and formula 1 are verified.

[0078] S3, multi-phase state detection experiment

[0079] Through the multi-phase state chlorinated hydrocarbon pollutant concentration detection experiment device, the multi-phase state detection experiment is carried out under the conditions of homogeneous and heterogeneous soil columns, a plurality of glass columns in the soil column experiment platform are used to carry out the transport experiment of different chlorinated hydrocarbons in different soil columns, and a plurality of groups of experimental data of multi-phase state occurrence related to each other are obtained; Specifically including:

[0080] S3-1, filling of soil column

[0081] After filling soil in each glass column, the soil column is formed, the filling of soil column adopts dry filling method; After filling a plurality of soil columns, the soil column group is formed; Through filling soil with different properties, the filling of soil column obtains homogeneous and heterogeneous soil column models, and after subsequent detection steps, the detection data of multi-phase state chlorinated hydrocarbon pollutants in complex soil and groundwater environment are obtained;

[0082] S3-2, pretreatment of the soil column

[0083] Before the soil column transport experiment begins, the filled experimental column is saturated with a CaCl2 solution from the bottom up until it is submerged, the air in the column is discharged, and a stable saturated flow field is formed;

[0084] S3-3, collection of dissolved-phase chlorinated hydrocarbons

[0085] The experimental carbon tetrachloride, chlorobenzene, and 1,2,4-trichlorobenzene mixture is introduced into the soil column, and the filtrate is taken from the bottom end of the column at a certain time sequence and collected in a brown glass sample bottle, without leaving a gap and immediately sealing and storing at low temperature after being taken;

[0086] S3-4, collection of gas-phase chlorinated hydrocarbons

[0087] During the introduction of CHCs, at certain time intervals, a cleaned and installed sampler is used to sample, and gas is drawn from the top end of the soil column at a certain flow rate, and after the end, nitrogen gas is introduced to fill the tank to dilute the gas;

[0088] S3-5, collection of residual-phase chlorinated hydrocarbons

[0089] After the end of the pollutant leaching, the soil column is disassembled and the soil sample is taken out as much as possible to maintain the original state, and the cylindrical soil sample is cut into soil samples of different depths with a tool knife, and each part of the soil sample is detected after extraction pretreatment.

[0090] S3-6, machine detection

[0091] The collected samples are detected for the concentration of each pollutant using a gas chromatograph-mass spectrometer, a capillary column, and an upper computer, respectively, to obtain multiple sets of correlated multi-phase chlorinated hydrocarbon pollutant concentration experimental data;

[0092] S3-7, repeating steps S3-1 to S3-6, under homogeneous and heterogeneous soil column conditions, respectively, using the experimental device to perform multi-phase detection experiments, using multiple glass columns in the soil column experiment platform to carry out transport experiments of different chlorinated hydrocarbons in different soil columns, and obtaining multiple sets of interrelated multi-phase experimental data; analyzing the experimental data to obtain the main influencing parameters, factors, and trends of multi-phase chlorinated hydrocarbon pollutants in soil and groundwater.

[0093] S4, detection of actual samples

[0094] The multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device and the multi-phase detection data analysis model are applied to the detection of actual samples, and the concentration data of other phases are calculated based on part of the phase detection data obtained by detection, to obtain complete multi-phase chlorinated hydrocarbon pollutant detection data; specifically including:

[0095] S4-1, fill the actual sample to be detected into each organic glass column in the soil column experiment platform, repeat step S3, and detect the concentration of the partial phase of the chlorinated hydrocarbon pollutant in the actual sample by using the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device;

[0096] S4-2, substitute the detected concentration data of the partial phase of the chlorinated hydrocarbon pollutant into the multi-phase detection data analysis model formula 1, and obtain the concentration data of other phases by calculation to obtain complete multi-phase chlorinated hydrocarbon pollutant detection data, that is, the occurrence concentration of the multi-phase chlorinated hydrocarbon pollutant in the soil and groundwater is obtained by one detection.

[0097] S5, construct a multi-phase chlorinated hydrocarbon pollutant detection system for synchronous sample detection

[0098] A multi-phase chlorinated hydrocarbon pollutant detection system including a cloud server, a management terminal and a multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is constructed, synchronous detection and analysis are performed on multiple samples, and the detection results of each detection sample are output, which specifically includes:

[0099] S5-1, construct a multi-phase chlorinated hydrocarbon pollutant detection system

[0100] A multi-phase chlorinated hydrocarbon pollutant detection system including a cloud server, a management terminal and at least one set of multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is constructed,

[0101] S5-2, perform multi-connection synchronous sample detection

[0102] The multiple samples respectively filled into each organic glass column in the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device are synchronously detected and analyzed, and the detection results of each detection sample are output.

[0103] A multi-phase chlorinated hydrocarbon pollutant detection system in soil and groundwater for implementing the foregoing detection method, including: a cloud server, a management terminal and at least one set of multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device including an upper computer, a soil column experiment platform and a detection instrument gas chromatography-mass spectrometer, and a capillary column;

[0104] The management terminal and the upper computer are connected with the cloud server through the Internet respectively; the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is connected with the upper computer;

[0105] The cloud server is used for analyzing and processing the detection data uploaded by the upper computer, and outputting complete multi-phase chlorinated hydrocarbon pollutant concentration detection results;

[0106] The multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device is used for detecting samples under experimental conditions and actual sampling;

[0107] The upper computer is used for controlling the working of the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device, receiving detection data obtained by the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device, and performing data preprocessing;

[0108] The management terminal is used for inputting data and instructions to the cloud server or displaying detection results output by the cloud server;

[0109] The soil column experimental platform comprises a plurality of detachable glass columns, a plurality of liquid containers and a plurality of Somar cans.

[0110] The glass column comprises a cylindrical hollow glass column body with openings on upper and lower end faces, an upper glass cover and a lower base, and a liquid outlet pipe.

[0111] The liquid inlet hole of each glass column is communicated with the pipeline on the liquid inlet side through a liquid inlet pipe, and a flow control valve is further arranged on the liquid inlet pipe.

[0112] The embodiment of the present application focuses on improving the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device and constructing a multi-phase detection data analysis model, which can realize synchronous detection of the concentration of multi-phase chlorinated hydrocarbons in soil and groundwater environment, more comprehensive evaluation of the pollution level of soil chlorinated hydrocarbons, and wide application in the identification of potential risks of soil pollution and precise prevention and control of soil chlorinated hydrocarbon pollution.

[0113] Embodiment 2

[0114] The detection method and system for multi-phase chlorinated hydrocarbon pollutants in soil and groundwater provided in the embodiment are specific on the basis of embodiment 1, which are basically the same as embodiment 1, and the difference lies in that:

[0115] Referring to Figure 2 The soil column experimental platform designed in the embodiment comprises a pipeline, a single-channel peristaltic pump, a flow divider, a corrosion-resistant hard pipe set, a plurality of experimental glass columns (soil column group), a plurality of containers for storing pollutants and effluent.

[0116] Referring to Figure 3The organic glass column 2 designed in the embodiment is used for the experiment, the cylindrical hollow glass column body 21 has the following specifications: an inner diameter of 5 cm, a total length of 30 cm, and a solid filling length of 20 cm; a tin paper wrapped rubber plug with two holes is designed in the top of the column, the inner wall of the experimental column is fully polished with coarse paper to reduce the purpose of preferential flow; the soil column experiment device includes multiple glass column bodies 21, can be split longitudinally, and the interfaces are designed in a nested manner, facilitating the loading and taking of soil samples before and after the experiment; after chlorinated hydrocarbons are adsorbed by soil in a heterogeneous soil column, in order to more accurately obtain the residual phase distribution characteristics of the three chlorinated hydrocarbons in each soil medium, the glass column 2 is designed in a form facilitating splicing and disassembly.

[0117] The soil column experiment detection step includes the following specific steps:

[0118] (I) Soil column experiment platform construction

[0119] The embodiment of the application carries out the migration experiment of chlorinated hydrocarbons in different soil columns by using the organic glass column 2. The experimental column has the following specifications: an inner diameter of 5 cm, a total length of 30 cm, and a solid filling length of 20 cm. A tin paper wrapped rubber plug with two holes is designed in the top of the column, and the inner wall of the experimental column is fully polished with coarse paper to reduce the purpose of preferential flow. The entire experimental system device includes a pipeline, a single-channel peristaltic pump, a flow divider, a corrosion-resistant hard tube set, a soil column set, a pollutant container, and an effluent container.

[0120] The soil column is filled by dry filling. First, a piece of gauze with a hole diameter of 0.1 mm is placed at the bottom of the column, and 5 cm of treated quartz sand is filled. Then, the soil sample is filled into the column in multiple layers according to different soil column filling methods, and each layer is compacted with a tool and the layers are roughened with a glass rod during the process. After the soil column is filled, 5 cm of quartz sand is filled again. Before the column experiment starts, the filled experimental column is saturated with water from bottom to top using 0.01 mol / L CaCl2 solution until it is higher than the soil column, the air in the column is discharged, and a stable saturated flow field is formed.

[0121] (II) Sample collection and storage

[0122] 1. Collection of dissolved phase chlorinated hydrocarbons

[0123] 10 mg / L of a mixture of carbon tetrachloride, chlorobenzene, and 1,2,4-trichlorobenzene is introduced into the soil column at a flow rate of 1.5 mL / min, and the filtrate is collected from the bottom of the glass column 2 in a certain time sequence and collected into a 1 mL brown glass sample bottle. There is no gap and it is immediately sealed and stored at low temperature after being taken.

[0124] 2. Collection of gaseous phase chlorinated hydrocarbons

[0125] During the passage of CHCs, a canister 10 was used to draw gas from the top of the column at a certain flow rate (24 h) for 5 min every certain time (0 h, 2 h, 6 h, 12 h, 24 h, 48 h, 72 h…), and after the end of the passage of CHCs, nitrogen was passed into the canister to dilute the gas.

[0126] The canister sampling process was as follows: a 3.2 L canister was heated to 70 ℃, and vacuum was drawn by a canister cleaning device (Entech 3100A) and then high-purity nitrogen was filled in, and the cleaning was repeated 5 times, and vacuum was drawn at the end of the last cleaning for standby. The cleaned canister was installed with a sampler, and the sampling flow rate was set to 2.1 ml / min. The gas in the column was collected for 5 min, and then a high-precision diluter was connected to fill in nitrogen, and the valve of the canister was closed after the dilution was completed. The sample was stored at room temperature and analyzed within 20 days.

[0127] 3. Collection of residual phase chlorinated hydrocarbons

[0128] After the end of the leaching of the pollutants, the soil column was disassembled to take out the soil sample, and the original state was maintained as much as possible. The cylindrical soil sample was cut into soil samples of different depths of 0 cm (close to the top of the column), 4 cm, 8 cm, 12 cm, 16 cm and 20 cm by a tool knife, and 1 g of each soil sample was pretreated (extracted) and then detected by a machine.

[0129] (Three) sample analysis

[0130] The collected samples were detected by Agilent 7890A-3172A gas chromatography-mass spectrometry, DB-624 capillary column (60 m x 0.32 mm x 1.8 μm) to detect the concentration of pollutants.

[0131] 1. Detection working conditions of samples collected from dissolved phase and residual phase chlorinated hydrocarbons

[0132] (1) Chromatographic working conditions: programmed temperature: 35 ℃ (4 min)→5 ℃ / min→120 ℃→10 ℃ / min→220 ℃ (2 min); carrier gas: helium, flow rate 1.0 mL / min; injection mode: split injection (split ratio 10:1), front injection port temperature: 220 ℃.

[0133] (2) Mass spectrometry working conditions: ion source, EI source; ion source temperature, 230 ℃; quadrupole temperature, 150 ℃; ionization energy, 70 eV; scanning mode, selected ion scanning (SIM); solvent delay 4 min.

[0134] 2. Detection working conditions of gaseous chlorinated hydrocarbons

[0135] (1) Pre-concentration conditions

[0136] Primary cold trap. Trap temperature: -150 °C; trap flow rate: 100 mL / min; desorption temperature: 10 °C; valve temperature 100 °C; bake temperature: 120 °C; bake time: 20 min

[0137] Secondary cold trap. Trap temperature: -15 °C; trap flow rate: 10 mL / min; trap time: 5 min; desorption temperature: 180 °C; bake temperature: 220 °C; bake time: 20 min.

[0138] Tertiary focus. Focus temperature: -165 °C; desorption temperature: 80 °C; desorption time: 2.5 min, bake temperature: 220 °C; bake time: 20 min.

[0139] (2) Chromatographic conditions

[0140] Chromatographic column 1 (30 m x 320 μm x 20 μm, Agilent, HP Plot Q)

[0141] Chromatographic column 2 (60 m x 250 μm x 1 μm, Agilent, DB-1)

[0142] Chromatographic column temperature program: 35 °C for 10 min; increase to 180 °C at 10 °C / min, hold for 8 min; increase to 220 °C at 15 °C / min, hold for 15 min.

[0143] Detector: FID; temperature: 250 °C; air flow: 400 mL / min; hydrogen flow: 35 mL / min; center cut time: 11.2 min

[0144] (3) Mass spectrometric conditions

[0145] Ion source temperature 230 °C; MS quadrupole temperature: 150 °C. Scanning mode: full scan (SCAN); scan range: 35-300 m / z.

[0146] (4) Data processing

[0147] The measured gas phase and dissolved phase chlorocarbons are plotted as concentration-time curves, while the residual phase chlorocarbons are plotted as concentration-depth curves, and finally the migration rules of the three phase chlorocarbons in the soil column can be observed.

[0148] For the phase distribution characteristics of chlorinated hydrocarbons in the six different soil columns, the equilibrium concentrations of the dissolved phase, the gas phase and the residual phase are used. The concentration of the free phase is calculated by the concentration conservation method. According to the law of concentration conservation, the original concentration of a component should be equal to the sum of the concentrations of all the existing forms in the solution. Through the CHCs soil column transport experiment, the transport concentrations of the dissolved phase, the residual phase and the gas phase are obtained, and the concentration of the free phase is calculated according to the following formula 1:

[0149] C = C Free phase + C Dissolved phase + C Residual phase + C Gas phase 1

[0150] In the formula:

[0151] C, the concentration of the chlorinated hydrocarbon mixture, mg / L;

[0152] C Free phase , the concentration of the free phase chlorinated hydrocarbon, mg / L;

[0153] C Dissolved phase , the concentration of the dissolved phase chlorinated hydrocarbon, mg / L;

[0154] C Residual phase , the concentration of the residual phase chlorinated hydrocarbon, mg / L;

[0155] C Gas phase , the concentration of the gas phase chlorinated hydrocarbon, mg / L.

[0156] (V) Verification of the applicability of the device and the model

[0157] Finally, more chlorinated hydrocarbon components are selected to verify the applicability of the device and the model through experiments. The experimental process refers to the steps (ii), (iii) and (iv) described above. The analysis results show that most of the CHCs exist in the form of free phase in the six soil columns (about 50%), in addition to the free phase, carbon tetrachloride mainly exists in the form of gas phase (about 28%), 1,2,4-trichlorobenzene mainly exists in the form of residual phase (about 35%), and chlorobenzene mainly exists in the form of dissolved phase (about 25%), and the detection trends of other chlorinated hydrocarbon components are basically consistent with those of the three components. The specific results are shown in Table 1. Figure 4 .

[0158] The experimental parameters are as follows:

[0159] 1. Soil column experiment parameters

[0160] (1) Initial concentration: CT concentration is 5 mg / L; CB concentration is 8 mg / L; TCB concentration is 8 mg / L

[0161] Table 1: Basic parameters of three chlorinated hydrocarbons

[0162]

[0163] a Relative density refers to the density relative to water

[0164] b Chinese drinking water health standards (GB5749-2006)

[0165] Table 2: Retardation factor

[0166]

[0167] Table 3: Basic parameters of soil column

[0168]

[0169] Table 4: Simulation migration parameters

[0170]

[0171]

[0172] Table 5: Phase distribution concentration ratio table

[0173]

[0174] The embodiment of the application obtains a large amount of experimental data through the test device, and obtains the analysis model formula 1. In the detection process of the actual sample, according to the determined concentration data of part of the phase state (such as residual phase, dissolved phase), after substituting formula 1, the detection data of other phase states can be obtained, so that the detection process is greatly simplified, and a set of correlation detection data with high accuracy and reliability can be obtained.

[0175] Embodiment 3

[0176] The soil and groundwater multi-phase state chlorinated hydrocarbon pollutant detection method and system provided in the embodiment is a specific embodiment based on embodiments 1 and 2, which is basically the same as embodiments 1-2, and the difference is that:

[0177] Referring to Figure 1 The soil and groundwater multi-phase state chlorinated hydrocarbon pollutant detection method and system includes multiple sets of multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental devices 1~N to meet the needs of large quantities of sample experiments or detection.

[0178] The step S5 of the detection method further comprises: constructing an AI model, obtaining a pre-trained AI model through deep learning, adding the correlation between more components, parameters and factors, and then applying it to the detection and analysis of the actual sample in step S4.

[0179] The cloud server of the detection system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater further has a multi-phase state data analysis module, a multi-phase state data AI processing module (with an AI model), and a multi-phase state detection result output module.

[0180] The multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device has multiple sets, and each set of the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device is connected to an upper computer, and the upper computer has a multi-phase state data acquisition module.

[0181] The upper computer collects the detection data of the detection sample filled in each glass column in each set of the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device, and sends the detection data to the multi-phase state data analysis module of the cloud server. The multi-phase state data analysis module processes the data and sends the processed data to the multi-phase state data AI processing module. The data processed by the multi-phase state data AI processing module is finally output through the multi-phase state detection result output module.

[0182] Through the soil column experiment platform test device, actual detection data and trend analysis results, the total amount of different pollutants, the content of each phase state pollutant, and the change data between soil media can be obtained. An AI model (such as DNN) is constructed. After processing each group of data, the AI model is pre-trained to obtain a pre-trained multi-phase state pollutant content detection AI model. The AI model automatically adjusts related parameters according to the input changes. The AI model can further include generalization, verification and optimization of the model. Through learning of the parameter change law that has a greater impact on chlorinated hydrocarbons during the migration process in the soil column, the model can be applied to the actual environment to more comprehensively and accurately determine the factors that have a greater impact on the migration process and phase distribution characteristics. Then, the soil column experiment platform and the AI model are combined to be applied to rapid detection of actual samples, which can greatly simplify the difficulty and process of detecting actual samples and reduce the required test instruments and consumables.

[0183] In this embodiment, the characteristics of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater can be analyzed according to the available external data, experimental data, etc. in advance. A suitable AI algorithm set is constructed based on a deep learning algorithm as a basic framework. The system optimizes the deep learning algorithm as a basic framework, and trains the optimized deep learning framework model. The model performance is evaluated during the training, and the optimal model basic framework and AI algorithm set are selected.

[0184] The optional AI algorithm set includes: machine learning algorithms, deep learning algorithms, spatio-temporal analysis algorithms, convolutional neural networks, random forests, logistic regression, linear regression, ensemble learning methods (such as Bagging, Boosting, etc.), generative adversarial networks, etc.; in the specific model construction process, the system iterates through multiple algorithms, compares their performance, and selects the optimal algorithm; considering adaptability and nonlinear processing capability, the embodiment takes a deep learning algorithm (such as a neural network) as the basic architecture; further, a suitable deep learning architecture model is selected, such as a deep neural network (DNN), a convolutional neural network (CNN), a recurrent neural network (RNN), etc., and the model architecture is customized according to specific monitoring requirements, layers are added or reduced, activation functions are adjusted, etc.; the preprocessed data is used to train the model, and the model parameters are optimized. In the training process, methods such as cross-validation (CV) can also be used to evaluate model performance, and the optimal model basic architecture and AI algorithm set are selected. The steps of AI model training and verification include data division, dividing the preprocessed data into a training set, a validation set, and a test set, adjusting the parameters of the model during training to obtain optimal performance; the training set is used for model training, the validation set is used for model verification and hyperparameter adjustment, and the test set is used for final model evaluation; then the experimental results are checked, corrected, and the data processing method is optimized according to and through actual measurement.

[0185] In summary, the detection method and system for multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater provided by the above embodiments of the present application focus on the actual situation that chlorinated hydrocarbons exist in different types of soil in the form of gas phase, aqueous phase, solid phase, free phase and other forms. By improving the multi-phase state chlorinated hydrocarbon pollutant concentration detection experimental device and constructing a multi-phase state detection data analysis model, the simultaneous detection of the concentration of chlorinated hydrocarbons in different phases in the soil and groundwater environment can be realized, and a more comprehensive evaluation of the chlorinated hydrocarbon pollution level in the soil can be carried out. The method can be widely used in the identification of potential risks of soil pollution and the precise prevention and control of soil chlorinated hydrocarbon pollution, and can simplify the detection steps and process, improve the detection efficiency and accuracy.

[0186] It should be noted that in other embodiments of the present application, other different schemes obtained by making specific choices within the scope of the steps, systems, thresholds, parameters, instruments, etc. described in the present application can achieve the technical effects described in the present application, and therefore the present application will not list them one by one.

[0187] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application in any form. Any person skilled in the art, without departing from the technical scheme of the present application, can make many possible changes and modifications to the technical scheme of the present application, or modify equivalent embodiments, by using the disclosed methods and technical contents. Any equivalent changes made according to the components, proportions and processes of the present application should be covered within the protection scope of the present application.

Claims

1. A method for detecting multi-phase state chlorinated hydrocarbon contaminants in soil and groundwater, characterized by, The method comprises the following steps: S1, setting up a multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device At least one set of experimental device for detecting the concentration of multi-phase chlorinated hydrocarbon pollutants in soil and groundwater is set up, and the device comprises an upper computer, a soil column experimental platform, and a detection instrument gas chromatography-mass spectrometry (GC-MS) and a capillary column. S2, constructing a multi-phase detection data analysis model A multi-phase chlorinated hydrocarbon pollutant detection data analysis model is constructed, which is as follows: C = C Free phase + C Dissolved phase + C Residual phase + C Gas phase 1 In the formula: C, the concentration of chlorinated hydrocarbon mixed solution, mg / L; C Free phase , concentration of free phase chlorinated hydrocarbon, mg / L; C Dissolved phase , concentration of the dissolved phase chlorinated hydrocarbon, mg / L; C Residual phase Concentration of residual phase chlorinated hydrocarbons, mg / L; C Gas phase , concentration of gas-phase chlorinated hydrocarbons, mg / L; S3, multi-phase detection experiment Through the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device, multi-phase detection experiments are carried out under homogeneous and heterogeneous soil column conditions, different chlorinated hydrocarbons are carried out in the multiple glass columns in the soil column experimental platform, the migration experiments in different soil columns are carried out, and multiple sets of experimental data of multi-phase occurrence are obtained. S4, detection of actual samples The multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device and the multi-phase detection data analysis model are applied to the detection of actual samples, and the concentration data of other phases are calculated by using part of the detection data of the phases obtained by detection, and complete multi-phase chlorinated hydrocarbon pollutant detection data are obtained.

2. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 1, characterized by, It further comprises the following steps: S5, constructing a multi-phase chlorinated hydrocarbon pollutant detection system for synchronous sample detection A multi-phase chlorinated hydrocarbon pollutant detection system comprising a cloud server, a management terminal and a multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device is constructed, multiple samples are detected and analyzed synchronously, and the detection results of each detection sample are output.

3. Method for the detection of multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 1 or 2, characterized in that, The step S1 specifically comprises: S1-1, setting up a soil column experimental platform Each soil column experimental platform comprises a plurality of detachable glass columns, a plurality of liquid containers, and a plurality of Somacan tanks. After the soil columns are filled with soil, a soil column group is formed, and then each glass column and liquid container in the soil column group is connected by a pipeline. A peristaltic pump and a flow divider are arranged on the pipeline in front of the water inlet end of each glass column. S1-2, setting up a detection instrument An upper computer, a detection instrument GC-MS and a capillary column are set up, the GC-MS and the capillary column are connected to the upper computer, and the GC-MS and the capillary column are connected to each soil column experimental platform. S1-3, from a large number of chlorinated hydrocarbons, according to the detectability, toxicity and environmental persistence of high-risk organic toxic substances, three typical chlorinated hydrocarbons, carbon tetrachloride, chlorobenzene and 1,2,4-trichlorobenzene, are selected as the target detection substances for the soil column experimental platform.

4. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 1 or 2, characterized by, The step S2 of constructing a multi-phase detection data analysis model specifically comprises: S2-1, defining the multi-phase concentration of chlorinated hydrocarbons The concentration of free-phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons existing independently in a state without restriction or mixing with other phases, which is obtained by using the concentration conservation law; The concentration of dissolved-phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons dissolved in soil pore water, which is obtained by using CHCs soil column migration experiments and detection; The concentration of residual-phase chlorinated hydrocarbons is the phase concentration of chlorinated hydrocarbons adsorbed on the surface of soil solid phase, which is obtained by using CHCs soil column migration experiments and detection; Concentration of gas-phase chlorinated hydrocarbon: the phase concentration of chlorinated hydrocarbon existing in the soil in the form of gas, obtained by using CHCs soil column migration experiment and detection; S2-2, determining the relationship model between the multiple phases in the CHCs soil column migration experiment By analyzing the rules in the CHCs soil column migration experiment, the relationship model between the detection data of the multiple-phase chlorinated hydrocarbon pollutants is determined, and the following formula 1 is obtained: C = C Free phase + C Dissolved phase + C Residual phase + C Gas phase 1 In the formula: C, concentration of chlorinated hydrocarbon mixed solution, mg / L; C Free phase , concentration of free phase chlorinated hydrocarbon, mg / L; C Dissolved phase , concentration of the dissolved phase chlorinated hydrocarbon, mg / L; C Residual phase , concentration of residual phase chlorinated hydrocarbon, mg / L; C Gas phase , concentration of gas-phase chlorinated hydrocarbons, mg / L; S2-3, verifying the applicability of the detection experiment device and the model The migration behavior of the dissolved-phase CHCs in the soil is simulated by using comsol, and the physical field control equation is used to verify the detection experiment device of the multiple-phase chlorinated hydrocarbon pollutants and formula 1.

5. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 1, characterized in that, The step S3 for the multiple-phase detection experiment specifically includes: S3-1, soil column filling After filling the soil in each glass column to form a soil column, the soil column is filled by using a dry method; after filling a plurality of soil columns, a soil column group is formed; S3-2, soil column pretreatment Before the start of the soil column migration experiment, the filled experimental column is fully saturated with water from bottom to top using a CaCl2 solution until it is above the soil column, the air in the column is discharged, and a stable saturated flow field is formed; S3-3, collection of dissolved-phase chlorinated hydrocarbon The experimental carbon tetrachloride, chlorobenzene, and 1,2,4-trichlorobenzene mixed solution is introduced into the soil column, and the filtrate is taken from the bottom end of the column in a certain time sequence and collected in a brown glass sample bottle. There is no gap, and it is immediately sealed and stored at low temperature after being taken out; S3-4, collection of gas-phase chlorinated hydrocarbon During the introduction of CHCs, every certain time, a cleaned and installed sampler is used to sample, and gas is extracted from the top of the soil column at a certain flow rate. After the end, nitrogen is introduced into the tank to fill the gas for dilution; S3-5, collection of residual-phase chlorinated hydrocarbon After the end of the pollutant leaching, the soil sample is taken out while maintaining the original state as much as possible. The cylindrical soil sample is cut into soil samples of different depths with a tool knife, and each part of the soil sample is detected after extraction pretreatment; S3-6, machine detection The collected samples are detected by gas chromatography-mass spectrometry, capillary column, and upper computer, respectively, to detect the concentration of each pollutant, and to obtain multiple sets of correlated multiple-phase chlorinated hydrocarbon pollutant concentration experimental data; S3-7, repeating steps S3-1 to S3-6, by using the experimental device, multiple-phase detection experiments are carried out under the conditions of homogeneous and heterogeneous soil columns, respectively. Different chlorinated hydrocarbons are used in the soil column experiment platform to carry out migration experiments in different soil columns, and multiple sets of interrelated multiple-phase experimental data are obtained. By analyzing the experimental data, the main influencing parameters, factors, and trends of the multiple-phase chlorinated hydrocarbon pollutants in the soil and groundwater are obtained.

6. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 5, characterized by, The step S3-1 for soil column filling is carried out by filling soil with different properties to obtain homogeneous and heterogeneous soil column models. After the subsequent detection steps, the detection data of the multiple-phase chlorinated hydrocarbon pollutants in the complex soil and groundwater environment are obtained.

7. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 1 or 2, characterized by, The step S4 for detecting actual samples specifically includes: S4-1, fill the actual sample to be detected into each organic glass column in the soil column experiment platform, repeat step S3, and detect the concentration of the partial phase of the chlorinated hydrocarbon pollutant in the actual sample by using the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device; S4-2, substitute the detected concentration data of the partial phase of the chlorinated hydrocarbon pollutant into the multi-phase detection data analysis model formula 1, and obtain the concentration data of other phases by calculation to obtain complete multi-phase chlorinated hydrocarbon pollutant detection data, and obtain the occurrence concentration of the multi-phase chlorinated hydrocarbon pollutant in the soil and groundwater by one detection.

8. The method for detecting multi-phase state chlorinated hydrocarbon pollutants in soil and groundwater according to claim 2, characterized by, The step S5 further comprises: S5-1, constructing a multi-phase chlorinated hydrocarbon pollutant detection system Constructing a multi-phase chlorinated hydrocarbon pollutant detection system comprising a cloud server, a management terminal and at least one set of multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, S5-2, performing multi-connection synchronous sample detection The detection system detects and analyzes a plurality of samples filled into each organic glass column in the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device synchronously, and outputs the detection results of each detection sample.

9. A system for detecting multi-phase state chlorinated hydrocarbon contaminants in soil and groundwater, comprising: The detection system comprises a cloud server, a management terminal and at least one set of multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device comprises an upper computer, a soil column experiment platform and a detection instrument GC; The management terminal and the upper computer are connected with the cloud server through the Internet; the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is connected with the upper computer; The cloud server is used for analyzing and processing the detection data uploaded by the upper computer, and outputting complete multi-phase chlorinated hydrocarbon pollutant concentration detection results; The multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device is used for detecting samples under experimental conditions and actual sampling; The upper computer is used for controlling the work of the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, receiving the detection data obtained by the multi-phase chlorinated hydrocarbon pollutant concentration detection experiment device, and performing data preprocessing; The management terminal is used for inputting data, instructions or displaying the detection results output by the cloud server; The soil column experiment platform comprises a plurality of detachable glass columns, a plurality of liquid containers and a plurality of Somar cans, a soil column group is formed after the soil is filled into each glass column, then the glass columns and the liquid containers in the soil column group are connected by pipelines; a peristaltic pump and a flow divider are arranged on the pipeline in front of the water inlet end of each glass column; The glass column comprises a cylindrical hollow glass column body with openings on the upper and lower end faces, an upper glass cover and a lower base, and a liquid outlet pipe, the upper glass cover is arranged on the upper end face of the glass column body and is provided with a gas stripping hole and a liquid inlet hole penetrating the thickness of the glass cover; the lower base is arranged at the lower part of the lower end face of the glass column body, and the liquid outlet pipe communicates with the inner cavity of the glass column body after penetrating the thickness of the lower base; The liquid inlet hole of each glass column communicates with the pipeline on the liquid inlet side through a liquid inlet pipe, and a flow control valve is further arranged on the liquid inlet pipe. ​ 10. The system for detecting multi-phase chlorinated hydrocarbon pollutants in soil and groundwater according to claim 9, characterized in that, The cloud server is also built-in with a multi-phase data analysis module, a multi-phase data AI processing module, and a multi-phase detection result output module. The multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device has multiple sets, and each set of the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device is connected to an upper computer, and the upper computer is built-in with a multi-phase data acquisition module. The upper computer collects the detection data of the detection sample filled in each glass column in each set of the multi-phase chlorinated hydrocarbon pollutant concentration detection experimental device, and sends the detection data to the multi-phase data analysis module of the cloud server; the multi-phase data analysis module processes the data and sends the processed data to the multi-phase data AI processing module; and the multi-phase data AI processing module processes the data and finally outputs the processed data through the multi-phase detection result output module.

Images