Water quality trace pollutant automatic monitoring method based on online enrichment and voltage focusing compensation

Abstract

The invention relates to sewage detection, and particularly provides a water quality trace pollutant automatic monitoring method based on online enrichment and voltage focusing compensation, which comprises the following steps: A1, collecting sewage and conveying the sewage to a pretreatment device; a2, respectively extracting an interior label and an acid, and feeding the interior label and the acid into a sample pool; a3, extracting a mixed solution in the sample pool, and sending the mixed solution to a second quantitative loop; a4, the pure water pushes the mixed liquid in the quantitative loop to enter the activated enrichment unit; a5, eluting the sample to a mass spectrum analyzer by the mobile phase; a6, the sample is ionized, and ions sequentially pass through the incident lens, the multi-pole rod and the emergent lens; obtaining a compensation voltage E according to the mass of the ions and the charge number; the compensation voltage E is applied to an incident lens and an emergent lens, and ions are focused at an inlet of the incident lens and an outlet of the emergent lens respectively; the ions are received by the detector, and information of forbidden objects in the sewage is output after analysis. The method has the advantages of automation, accuracy and the like.

Description

Technical Field

[0001] This invention relates to wastewater monitoring, and more particularly to an automatic monitoring method for trace pollutants in water quality based on online enrichment and voltage focusing compensation. Background Technology

[0002] "Wastewater drug testing" is a new type of drug control technology that can reverse-engineer data such as the types of drugs abused, the amount consumed, and the scale of drug users in a specific area. It can provide necessary guidance for public security drug control work and is of great significance to promoting the development of drug control work throughout society.

[0003] To accurately estimate drug consumption, a crucial step is to quickly and accurately determine the drug content in wastewater. Current wastewater drug testing is performed in laboratories, and laboratory methods for determining drug content often employ offline SPE extraction and purification. This technique has several limitations, such as: 1. The sample pretreatment process is complex, time-consuming, and inefficient. It requires the regular collection of sewage samples from urban sewage treatment plants and sewage ditches in remote areas. The sampling environment is harsh and sample storage is difficult. The data has a serious lag and cannot achieve real-time traceability.

[0004] 2. Long-term work involving drug testing or samples containing drug components may cause cross-contamination of trace samples, such as biological samples and sewage, and may also have a certain impact on the health of laboratory testing personnel. Summary of the Invention

[0005] To address the shortcomings of the existing technical solutions, this invention provides an automatic monitoring method for trace pollutants in water quality based on online enrichment and voltage focusing compensation.

[0006] The objective of this invention is achieved through the following technical solution: An automatic monitoring method for trace pollutants in water quality based on online enrichment and voltage focusing compensation includes the following steps: A1. Collect wastewater and transport it to a pretreatment device to remove particulate matter from the wastewater, and then send it to a sample cell; A2. By switching the first multi-channel directional valve, the first pump draws the internal standard and acid respectively and sends them into the sample cell; A3. The first multi-channel directional valve and the first multi-way valve switch, the first pump draws the mixture in the sample cell and sends it to the second quantitative loop; A4. The first multi-way valve, the second multi-way valve, the third multi-way valve, and the second multi-channel directional valve are switched. Pure water passes through the second multi-channel directional valve and pushes the mixed liquid in the second metering ring to pass through the first multi-way valve and the second multi-way valve in sequence, and enter the activated enrichment unit. A5. Switching between the second and third multi-port valves, gradient elution, the mobile phase elutes the sample in the enrichment unit to the mass spectrometer; A6. The sample is ionized, and the ions pass sequentially through the incident lens, the multipole, and the exit lens. The compensation voltage E is obtained based on the mass and charge number of the ions; When the compensation voltage E is applied to the incident lens and the exit lens, ions are focused at the inlet of the incident lens and the outlet of the exit lens, respectively. Ions are received by the detector, analyzed, and the information on trace substances in the wastewater is output.

[0007] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. High accuracy; In this invention, ion energy compensation and adjustment are performed for ions with different mass numbers to focus the ions at the exit of the emission lens, thereby achieving greater transmission efficiency.

[0008] Using the periodic focusing difference method, the ion velocity can be controlled within a minimum voltage range (requiring only a few volts). This allows the bias voltage within the transmission rod to be at its limit switching speed, ensuring the number of channels while allowing the focal point to appear at the next stage lens, thus achieving optimal ion transmission efficiency.

[0009] Samples are tested immediately after collection, which can effectively reduce sample degradation; fully automated pretreatment can reduce human error, and the test results are more accurate and closer to the true value.

[0010] 2. Automation; The entire process is highly automated: automatic water sampling, automatic pretreatment, automatic data processing and uploading, truly realizing unattended detection of trace substances such as prohibited substances in sewage; 3. Real-time and efficient; From water collection to data output, the entire process takes only 40 minutes and can provide real-time feedback on the content of trace substances such as contraband in wastewater, accurately estimating drug consumption. Attached Figure Description

[0011] The disclosure of this invention will become more readily understood with reference to the accompanying drawings. It will be readily understood by those skilled in the art that these drawings are merely illustrative of the technical solutions of this invention and are not intended to limit the scope of protection of this invention. In the drawings: Figure 1 This is a flowchart illustrating the monitoring method according to an embodiment of the present invention; Figure 2 This is a schematic diagram of the ion transport mechanism of the present invention. Detailed Implementation

[0012] Figures 1-2 The following description illustrates optional embodiments of the invention to teach those skilled in the art how to implement and reproduce the invention. Some conventional aspects have been simplified or omitted to explain the technical solutions of the invention. Those skilled in the art should understand that variations or substitutions derived from these embodiments will be within the scope of the invention. Those skilled in the art should understand that the following features can be combined in various ways to form multiple variations of the invention. Therefore, the invention is not limited to the following optional embodiments, but is defined only by the claims and their equivalents. Example 1

[0013] Automatic monitoring methods for trace pollutants in water quality based on online enrichment and voltage focusing compensation, such as Figure 1 As shown, the monitoring method includes the following steps: A1. Wastewater is collected and transported to a pretreatment device, such as sedimentation and multi-stage filtration, to remove particulate matter and other impurities from the wastewater before being sent to a sample tank.

[0014] A2. By using the switching of the first multi-channel directional valve, the first pump extracts the internal standard and acid respectively and sends them into the sample cell; the structure and operation of the multi-channel directional valve are existing technologies in the field.

[0015] A3. The first multi-channel directional valve and the first multi-way valve switch, the first pump draws the mixture in the sample cell and sends it to the second quantitative loop, and the two ends of the second quantitative loop are respectively connected to the ports of the first multi-way valve.

[0016] A4. Switching between the first multi-way valve, the second multi-way valve, and the third multi-way valve, using a carrier liquid to send the mixed liquid in the second metering ring into the activated enrichment unit, the two ends of the enrichment unit being connected to the ports of the second multi-way valve and the third multi-way valve, respectively.

[0017] A5. Switching between the second and third multi-way valves, the mobile phase elutes the sample in the enrichment unit to the mass spectrometer.

[0018] A6. The sample is ionized, such as Figure 2 As shown, ion 41 passes sequentially through incident lens 11, multipole 21 and exit lens 31.

[0019] The compensation voltage E is obtained based on the mass and charge number of the ion 41.

[0020] When the compensation voltage E is applied to the incident lens 11 and the exit lens 31, ions 41 are focused at the inlet 111 of the incident lens 11 and the outlet 311 of the exit lens 31, respectively.

[0021] Ion 41 is received by the detector, and after analysis, information on trace substances such as contraband in the wastewater is output.

[0022] To improve monitoring accuracy, the compensation voltage E further satisfies: , .

[0023] m and q are the mass number and charge number of ion 41, respectively; L is the distance between the inlet 111 and the outlet 311; f is the frequency of the radio frequency voltage on the multipole 21; V is the DC voltage value on the multipole 21; r0 is the distance between the center of the multipole 21 and each pole; E0 is the reference voltage compensation value; z is the charge number of ion 41; and e is the charge of an electron.

[0024] To ensure that monitoring can proceed normally, the monitoring methods further include: The first multi-channel directional valve switches, and the first pump extracts the quality control sample.

[0025] The first multi-channel directional valve and the first multi-way valve switch, and the first pump sends the extracted quality control sample to the second quantitative loop.

[0026] Switching between the first, second, and third multi-way valves, the carrier liquid delivers the quality control sample from the second quantitative loop to the enrichment unit.

[0027] When the third multi-way valve and the second multi-way valve are switched, the mobile phase elutes the quality control sample in the enrichment unit to the analyzer, and the analyzer outputs the quality control sample information.

[0028] If the deviation between the quality control sample information and the nominal information is within the set range, normal monitoring of the wastewater will be carried out.

[0029] To ensure the accuracy of the monitoring results, the first multi-channel directional valve is switched before the first pump extracts the quality control sample or internal standard. The first pump then extracts pure water and cleans the pipeline. After that, the first pump extracts the quality control sample.

[0030] To ensure the reaction proceeds fully, in step (A2), the first multi-channel directional valve switches, the first pump draws in air and sends it into the sample cell, and the mixture is stirred.

[0031] To activate the enrichment units, the activation method of the enrichment units is further as follows: By switching between the second multi-channel directional valve, the first multi-way valve, the second multi-way valve, and the third multi-way valve, methanol and pure water are discharged through the second multi-channel directional valve, the second multi-way valve, the enrichment unit, and the third multi-way valve, respectively, thereby activating the enrichment unit.

[0032] To push the mixture, the pure water is discharged through the second multi-channel directional valve, the first multi-way valve, the second multi-way valve, and the third multi-way valve by switching the second multi-channel directional valve, the second multi-way valve, the enrichment unit, and the third multi-way valve, thereby sending the mixture in the second metering loop to the enrichment unit.

[0033] In order to rinse the enrichment unit, further, in step (A4), by switching the second multi-channel directional valve, the first multi-way valve, the second multi-way valve and the third multi-way valve, methanol water is discharged through the second multi-channel directional valve, the second multi-way valve, the enrichment unit and the third multi-way valve, thereby completing the rinsing. Example 2

[0034] An example of the application of the automatic monitoring method for trace pollutants in water quality based on online enrichment and voltage focusing compensation according to Embodiment 1 of the present invention in the monitoring of contraband (drugs) in wastewater.

[0035] In this application example, such as Figure 1 As shown, the monitoring method includes the following steps: A1. Collect wastewater and transport it to the pretreatment device. Let it stand in the sedimentation tank for 10-20 minutes. Then, pass it through filters with filtration accuracies of 100μm and 0.45μm to remove particulate matter and other impurities from the wastewater. Then, send it to the sample cell. While the wastewater is being pretreated, the first multi-channel directional valve switches, the first pump draws pure water, and the pipeline is repeatedly cleaned.

[0036] The first multi-channel directional valve switches, the first pump extracts the quality control sample, and the quality control sample enters the first quantitative loop.

[0037] The first multi-channel directional valve and the first multi-way valve switch, and the first pump sends the quality control sample in the first quantitative loop to the second quantitative loop. The two ends of the second quantitative loop are respectively connected to the ports of the first multi-way valve.

[0038] The first, second, and third multi-way valves are switched to deliver the quality control sample in the second quantitative loop to the activated enrichment unit. The enrichment unit uses an SPE column, with the second and third multi-way valves connected to its two ends, respectively.

[0039] The third multi-way valve and the second multi-way valve are switched. The mobile phase flows through the third multi-way valve, the enrichment unit and the second multi-way valve in sequence. The quality control sample in the enrichment unit is eluted to the analyzer-mass spectrometer. The analyzer outputs the quality control sample information.

[0040] If the deviation between the quality control sample information and the nominal information is within the set range, normal monitoring of the wastewater will be carried out.

[0041] A2. The first multi-channel directional valve switches, the first pump draws pure water, and repeatedly cleans the pipeline.

[0042] By switching the first multi-channel directional valve, the first pump draws internal standard, acid and air respectively and sends them into the sample cell. The air entering the sample stirs the mixture and promotes the reaction. The structure and operation of the multi-channel directional valve are existing technologies in the field.

[0043] A3. The first multi-channel directional valve and the first multi-way valve switch, the first pump draws the mixture in the sample cell and sends it to the second quantitative loop.

[0044] A4. By switching between the first multi-way valve, the second multi-way valve, the third multi-way valve, and the second multi-channel directional valve, methanol and pure water pass through the second multi-channel directional valve, the first multi-way valve, the second multi-way valve, the enrichment unit, and the third multi-way valve in sequence twice to complete the activation of the enrichment unit.

[0045] The first multi-way valve, the second multi-way valve, the third multi-way valve, and the second multi-channel directional valve are switched. Pure water passes through the second multi-channel directional valve, which pushes the mixed liquid in the second metering ring to pass through the first multi-way valve and the second multi-way valve in sequence, and enters the activated enrichment unit.

[0046] A5. By switching between the second multi-channel directional valve, the first multi-way valve, the second multi-way valve, and the third multi-way valve, methanol water is discharged through the second multi-channel directional valve, the second multi-way valve, the enrichment unit, and the third multi-way valve, thereby completing the rinsing of the enrichment unit.

[0047] Switching between the second and third multi-port valves, gradient elution, and the mobile phase elutes the sample in the enrichment unit to the mass spectrometer.

[0048] A6. The sample is ionized, such as Figure 2 As shown, ion 41 passes sequentially through incident lens 11, multipole 21 and exit lens 31.

[0049] The compensation voltage E is obtained based on the mass and charge number of the ion 41.

[0050] For example, the incident ion 41 has a mass m = 490 amu and a q = 1.6e-19C.

[0051] according to This ensures that ions 41 are focused at the exit 311 of the exit lens 31.

[0052] For example, the incident ion mass 41 is m = 474 amu, according to This ensures that ions 41 are focused at the exit 311 of the exit lens 31.

[0053] When the compensation voltage E is applied to the incident lens 11 and the exit lens 31, ions 41 are focused at the inlet 111 of the incident lens 11 and the outlet 311 of the exit lens 31, respectively.

[0054] Ion 41 is received by the detector, and after analysis, information on prohibited substances in the wastewater is output.

[0055] The results obtained from multiple tests are shown in the table below. .

[0056] The above embodiments are merely exemplary. If the analyzer is a mass spectrometer, other cases are also possible, such as a combination of a chromatographic column and a mass spectrometer.

Claims

1. A method for automatic monitoring of water quality trace pollutants based on online enrichment and voltage focusing compensation, characterized in that, The monitoring method comprises the following steps: A1. Collecting sewage and transporting it to a pretreatment device to remove particulate matters in the sewage, and then sending the sample to a sample pool; A2. Switching the first multi-channel selector valve, and the first pump respectively draws the internal standard and the acid and sends them into the sample pool; A3. Switching the first multi-channel selector valve and the first multi-channel valve, and the first pump draws the mixed solution in the sample pool and sends it to the second quantitative ring; A4. Switching the first multi-channel valve, the second multi-channel valve, the third multi-channel valve and the second multi-channel selector valve, and the pure water passes through the second multi-channel selector valve to push the mixed solution in the second quantitative ring, which sequentially passes through the first multi-channel valve and the second multi-channel valve and enters the activated enrichment unit; A5. Switching the second multi-channel valve and the third multi-channel valve, and gradient elution, and the mobile phase elutes the sample in the enrichment unit to the mass spectrometer; A6. The sample is ionized, and the ions sequentially pass through the entrance lens, the multipole rod and the exit lens; The compensation voltage E is obtained according to the mass and charge number of the ions; The compensation voltage E is applied to the entrance lens and the exit lens, and the ions are focused at the entrance of the entrance lens and the exit of the exit lens respectively; The ions are received by the detector, and the information of the trace substances in the sewage is output after analysis.

2. The monitoring method according to claim 1, characterized in that, The compensation voltage E satisfies: ， ； m, q are the mass number and charge number of the ions respectively, L is the distance between the entrance and the exit, f is the frequency of the radio frequency voltage on the multipole rod, V is the direct current voltage value on the multipole rod, r0 is the distance between the center of the multipole rod and each pole, E0 is the reference voltage compensation value, z is the charge number of the ions, and e is the charge amount of an electron.

3. The monitoring method according to claim 1, wherein While the sewage is pretreated, the first multi-channel selector valve is switched, the first pump draws the quality control sample, and the quality control sample enters the first quantitative ring; the first quantitative ring is arranged between the common end of the first pump and the second multi-channel selector valve; The first multi-channel selector valve and the first multi-channel valve are switched, the first pump sends the quality control sample in the first quantitative ring to the second quantitative ring, and the two ends of the second quantitative ring are respectively connected to the ports of the first multi-channel valve; The first multi-channel valve, the second multi-channel valve and the third multi-channel valve are switched, and the carrier liquid sends the quality control sample in the second quantitative ring to the activated enrichment unit; the two ends of the enrichment unit are respectively connected to the ports of the second multi-channel valve and the third multi-channel valve; The third multi-channel valve and the second multi-channel valve are switched, the mobile phase sequentially flows through the third multi-channel valve, the enrichment unit and the second multi-channel valve, elutes the quality control sample in the enrichment unit to the analyzer, and the analyzer outputs the quality control sample information; if the deviation between the quality control sample information and the nominal information is within the set range, the normal monitoring of the sewage is performed.

4. The monitoring method of claim 1, wherein, Before the first pump draws the quality control sample or the internal standard, the first multi-channel selector valve is switched, the first pump draws the pure water and cleans the pipeline; then, the first pump draws the quality control sample.

5. The monitoring method of claim 1, wherein, In step A2, the first multi-channel selector valve is switched, the first pump draws the air and sends it into the sample pool to stir the mixed solution.

6. The monitoring method of claim 1, wherein, The activation mode of the enrichment unit is: By switching of the second multi-way selector valve, the first multi-way valve, the second multi-way valve and the third multi-way valve, methanol and pure water are discharged through the second multi-way selector valve, the second multi-way valve, the enrichment unit and the third multi-way valve, respectively, so as to activate the enrichment unit.

7. The monitoring method of claim 1, wherein, In step A4, by switching of the second multi-way selector valve, the first multi-way valve, the second multi-way valve and the third multi-way valve, methanol water is discharged through the second multi-way selector valve, the second multi-way valve, the enrichment unit and the third multi-way valve, so as to complete the elution.

8. The monitoring method of claim 1, wherein, The trace substance is an illicit substance.

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