CN113466010A - Water pollution detection system based on electrochemical sensor - Google Patents
Water pollution detection system based on electrochemical sensor Download PDFInfo
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Abstract
The invention discloses a water pollution detection system based on an electrochemical sensor, belongs to the field of pollution detection, and relates to a water pollution detection technology, which comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module; the water pollution detection based on the electrochemical sensor is realized through water body collection, water quality analysis, pollution judgment and pollution early warning, concentration determination is carried out on heavy metal ions in the water body, including lead ions, cadmium ions and copper ions, a concentration threshold value is set, and pollution alarm of different levels is realized according to different ion concentration standard exceeding signals through the pollution early warning. The invention adopts the electrochemical sensor, and the sensor has reliable performance and low cost and has good application prospect in the aspect of rapid on-site monitoring of the seawater heavy metal.
Description
Technical Field
The invention belongs to the field of pollution detection, relates to a water pollution detection technology, and particularly relates to a water pollution detection system based on an electrochemical sensor.
Background
The method can accurately monitor the content of heavy metal elements near the sea in time, particularly in the area of the estuary, and is very important for evaluating and effectively preventing the heavy metal pollution of the sea. The seawater has complex components, large matrix effect and low heavy metal content, so the analysis method for determining the heavy metal in the seawater needs to ensure high sensitivity and good selectivity. At present, the detection methods of heavy metals mainly comprise an atomic absorption method, an inductively coupled plasma atomic emission spectrometry and an inductively coupled plasma mass spectrometry. The instruments and devices required by the methods are large in size and high in operation cost, and the requirements of on-site rapid monitoring cannot be met. The electrochemical stripping voltammetry has the obvious advantages of simple instrument and device, high sensitivity, capability of simultaneously analyzing various heavy metal elements and the like, and is successfully used for measuring lead, cadmium, copper and the like in seawater; however, this method has a problem that it is not highly sensitive to the detection of electrochemically irreversible metal ions, and that ion elution is sensitive to vibration of the ship body, and measurement is disturbed by dissolved oxygen.
The low detection limit polymer membrane ion selective electrode is a new technology developed in the last 90 years of the last century, and the detection sensitivity of the low detection limit polymer membrane ion selective electrode is improved by 5-6 orders of magnitude compared with the traditional ion selective electrode; in recent years, high-sensitivity potential detection under the condition of strong body effect has been successfully realized by adopting the technology.
Disclosure of Invention
In order to solve the problems in the scheme, the invention provides a water pollution detection system based on an electrochemical sensor, which comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module, wherein the water body acquisition module is used for acquiring water pollution; the water pollution detection based on the electrochemical sensor is realized through water body collection, water quality analysis, pollution judgment and pollution early warning, concentration determination is carried out on heavy metal ions in the water body, including lead ions, cadmium ions and copper ions, a concentration threshold value is set, and pollution alarm of different levels is realized according to different ion concentration standard exceeding signals through the pollution early warning. The invention adopts the electrochemical sensor, and the sensor has reliable performance and low cost and has good application prospect in the aspect of rapid on-site monitoring of the seawater heavy metal.
The purpose of the invention can be realized by the following technical scheme:
a water pollution detection system based on an electrochemical sensor comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module;
the water body acquisition module is used for acquiring water bodies, the specific acquisition mode comprises a bucket acquisition unit and a water sampler acquisition unit, the bucket acquisition unit is used for acquiring surface seawater, the water sampler acquisition unit is used for acquiring bottom seawater, and the acquired seawater is placed in a refrigerator for freezing and storing.
The water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and the specific analysis process comprises the following steps:
the method comprises the following steps: dividing surface layer seawater or bottom layer seawater collected by a water body collection module into i parts of T mL seawater samples, wherein i represents the number of the seawater samples; 1,2 … … n;
step two: adjusting the pH value of a T mL seawater sample i to 2.0-2.5 by using concentrated nitric acid; the first pump drives the seawater sample solution i at the flow rate of 0.8-1.2 mL/min to sequentially pass through on-line filtration and ultraviolet digestion and then enter a liquid storage bottle;
step three: pumping the sample in the liquid storage bottle into an enrichment pool by a second pump at the pump speed of 0.5-0.8 mL/min, and controlling the electrode potential to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank;
step three: cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged;
stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential;
step four: completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement;
step five: and calculating the ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module.
Preferably, the pollution determination module is configured to obtain an ion concentration sent by the water quality analysis module, and perform pollution determination, where the specific determination method includes the following steps:
step S1: the pollution judgment module sends an ion acquisition signal to the water quality analysis module, and the water quality analysis module sends the concentration of the heavy metal ions analyzed by the water quality analysis module to the pollution judgment module after receiving the ion acquisition signal;
step S2: after receiving the concentration of the heavy metal ions, the pollution judgment module marks the concentration of the lead ions, the concentration of the cadmium ions and the concentration of the copper ions as Qi, Gi and Ti respectively;
step S3: the pollution judgment module respectively calculates the average concentration of the lead ion concentration, the cadmium ion concentration and the copper ion concentration as the measured concentration, and the calculation formula is
Wherein alpha 1, alpha 2 and alpha 3 are correction coefficients,
the measured concentration of lead ions, the measured concentration of cadmium ions and the measured concentration of copper ions are respectively measured; sending the measured concentration of the lead ions, the measured concentration of the cadmium ions and the measured concentration of the copper ions to a data storage module for storage;
step S4: the pollution judgment module sets a lead ion concentration threshold, a cadmium ion concentration threshold and a copper ion concentration threshold;
when the measured concentration of lead ions
When the lead ion concentration is greater than or equal to the lead ion concentration threshold value, the pollution judgment module judges that the lead ions exceed the standard and sends a lead ion exceeding signal to the pollution early warning module;
when the measured concentration of cadmium ion
When the concentration of the cadmium ions is more than or equal to the concentration threshold of the cadmium ions, the pollution judgment module judges that the cadmium ions exceed the standard and sends a cadmium ion exceeding signal to the pollution early warning module;
when the copper ions are trueMeasuring concentration
And when the concentration of the copper ions is more than or equal to the concentration threshold of the copper ions, the pollution judgment module judges that the copper ions exceed the standard and sends a copper ion exceeding signal to the pollution early warning module.
Preferably, the pollution early warning module is used for early warning of water pollution, and the specific pollution early warning mode comprises the following steps:
step P1: the pollution early warning module receives standard exceeding signals sent by the pollution judging module, wherein the standard exceeding signals comprise lead ion standard exceeding signals, cadmium ion standard exceeding signals and copper ion standard exceeding signals;
step P2: when the pollution early warning module receives an overproof signal, increasing the early warning level by one, and marking the early warning level as j, wherein j is 0, 1,2 and 3 by the pollution early warning module;
step P3: when j is 0, the water quality is pollution-free, and the pollution early warning module does not perform water quality early warning;
when j is 1, indicating that one of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and carrying out primary early warning by a pollution early warning module;
when j is 2, the concentration of two of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and the pollution early warning module performs secondary early warning;
when j is 3, the concentration of lead ions, cadmium ions and copper ions exceeds the standard, and the pollution early warning module performs three-stage early warning;
step P4: when the pollution early warning module carries out early warning of different levels, different solving modes are adopted.
Preferably, the electrochemical sensor comprises a first pump, a filter membrane, an ultraviolet lamp, a liquid storage bottle, a second pump, a reference electrode, a counter electrode, a bismuth membrane electrode, a first switching valve, a second switching valve and an ion selection electrode; the first pump, the filter membrane, the ultraviolet lamp, the liquid storage bottle, the second pump, the reference electrode, the counter electrode, the bismuth membrane electrode, the first switching valve, the second switching valve and the ion selection electrode are connected through a polytetrafluoroethylene tube;
the ion selective electrode comprises a lead ion selective electrode, a cadmium ion selective electrode and a copper ion selective electrode.
Preferably, the lead ion-selective electrode composition: 200mg of 1.1% (cw/rw) IV, 0.5% (w/w) NaTFPB, 10.0% (w/w) ETH500, 88.4% (w/w) polymer MMA-DMA were weighed out and dissolved in 2.0mLCH2C2Performing ultrasonic treatment for 10 min;
cadmium and steel ion selective electrode membrane components: 200mg of 1.0% (w/w) ETH1062, 1.0% (w/w) NaTFPB, 10.0% (w/w) ETH500, 88.0% (w/u) polymer MMA-DMA were weighed out and dissolved in 2.0ml of CH2Cl2Performing ultrasonic treatment for 10 min;
adding 10uL of 25mmol/LPOTCH2C12Dripping the solution on the surface of a glassy carbon electrode, dripping 50uL of membrane component solution on the surface of the electrode after complete drying, standing at room temperature for 2-3 h, and volatilizing thousands of CH2C12The electrode is activated by 1d with 1.0mmol/L aqueous solution of ions to be detected and 1.0nmol/L solution of ions to be detected (containing 0.01mol/L NaCl) respectively.
Preferably, the preparation of the bismuth membrane electrode comprises the following steps:
inserting a glassy carbon electrode containing 5X 10mol/LBi (NO)3)3In 0.1mol/LHAc-NaAc buffer solution (pH 4.6), the deposition potential of Bi was selected to be-0.6V, and 240s were deposited under slow stirring.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines the online sample pretreatment technology and the electrochemical enrichment technology with the ion selective electrode potential analysis method with low detection limit, improves the response performance and the analysis efficiency of the system, and develops a novel sensor technology capable of rapidly detecting the concentration of heavy metal in seawater.
2. According to the invention, water pollution detection based on an electrochemical sensor is realized through water body collection, water quality analysis, pollution judgment and pollution early warning, concentration determination is carried out on heavy metal ions in the water body, including lead ions, cadmium ions and copper ions, a concentration threshold is set, and pollution alarm of different levels is realized through pollution early warning according to different ion concentration standard exceeding signals.
3. In a flowing system, the digestion efficiency is reduced along with the increase of the flow rate of the seawater sample; however, too low a flow rate affects the analysis rate, and the flow path temperature is too high, which causes vaporization of a large amount of the sample solution. A flow rate of 0.8mL/min allows for high digestion efficiency and faster digestion rates. In addition, the digestion process produces a large amount of carbonate ions, which can combine with calcium ions, magnesium ions, etc. in the seawater to form precipitates, causing pipeline blockage. The invention uses concentrated nitric acid to adjust the pH value of the seawater sample to 2.0 before digestion, thereby not only eliminating the problem of pipeline blockage, but also preventing the adsorption of metal ions on the pipeline wall.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic block diagram of a water pollution detection system based on an electrochemical sensor according to the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
as shown in fig. 1, a water pollution detection system based on an electrochemical sensor comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module;
the water body acquisition module is used for acquiring water bodies, the specific acquisition mode comprises a bucket acquisition unit and a water sampler acquisition unit, the bucket acquisition unit is used for acquiring surface seawater, the water sampler acquisition unit is used for acquiring bottom seawater, and the acquired seawater is placed in a refrigerator for freezing and storing.
The water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and the specific analysis process comprises the following steps:
the method comprises the following steps: dividing surface layer seawater or bottom layer seawater collected by a water body collection module into i parts of T mL seawater samples, wherein i represents the number of the seawater samples; 1,2 … … n;
step two: adjusting the pH value of a T mL seawater sample i to 2.0 by using concentrated nitric acid; the first pump drives the solution of the seawater sample i at the flow rate of 0.8mL/min to sequentially enter a liquid storage bottle after on-line filtration and ultraviolet digestion;
step three: the second pump pumps the sample in the liquid storage bottle into an enrichment pool at the pump speed of 0.5mL/min, and the electrode potential is controlled to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank;
step three: cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged;
stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential;
step four: completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement;
step five: and calculating the ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module.
The pollution judgment module is used for acquiring the ion concentration sent by the water quality analysis module and judging the pollution, and the specific judgment mode comprises the following steps:
step S1: the pollution judgment module sends an ion acquisition signal to the water quality analysis module, and the water quality analysis module sends the concentration of the heavy metal ions analyzed by the water quality analysis module to the pollution judgment module after receiving the ion acquisition signal;
step S2: after receiving the concentration of the heavy metal ions, the pollution judgment module marks the concentration of the lead ions, the concentration of the cadmium ions and the concentration of the copper ions as Qi, Gi and Ti respectively;
step S3: the pollution judgment module respectively calculates the average concentration of the lead ion concentration, the cadmium ion concentration and the copper ion concentration as the measured concentration, and the calculation formula is
Wherein alpha 1, alpha 2 and alpha 3 are correction coefficients,
the measured concentration of lead ions, the measured concentration of cadmium ions and the measured concentration of copper ions are respectively measured; sending the measured concentration of the lead ions, the measured concentration of the cadmium ions and the measured concentration of the copper ions to a data storage module for storage;
step S4: the pollution judgment module sets a lead ion concentration threshold, a cadmium ion concentration threshold and a copper ion concentration threshold;
when the measured concentration of lead ions
When the lead ion concentration is greater than or equal to the lead ion concentration threshold value, the pollution judgment module judges that the lead ions exceed the standard and sends a lead ion exceeding signal to the pollution early warning module;
when the measured concentration of cadmium ion
When the concentration of the cadmium ions is more than or equal to the concentration threshold of the cadmium ions, the pollution judgment module judges that the cadmium ions exceed the standard and sends a cadmium ion exceeding signal to the pollution early warning module;
when the measured concentration of copper ions
And when the concentration of the copper ions is more than or equal to the concentration threshold of the copper ions, the pollution judgment module judges that the copper ions exceed the standard and sends a copper ion exceeding signal to the pollution early warning module.
Wherein, the pollution early warning module is used for the water body pollution early warning, and the specific pollution early warning mode includes following steps:
step P1: the pollution early warning module receives standard exceeding signals sent by the pollution judging module, wherein the standard exceeding signals comprise lead ion standard exceeding signals, cadmium ion standard exceeding signals and copper ion standard exceeding signals;
step P2: when the pollution early warning module receives an overproof signal, increasing the early warning level by one, and marking the early warning level as j, wherein j is 0, 1,2 and 3 by the pollution early warning module;
step P3: when j is 0, the water quality is pollution-free, and the pollution early warning module does not perform water quality early warning;
when j is 1, indicating that one of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and carrying out primary early warning by a pollution early warning module;
when j is 2, the concentration of two of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and the pollution early warning module performs secondary early warning;
when j is 3, the concentration of lead ions, cadmium ions and copper ions exceeds the standard, and the pollution early warning module performs three-stage early warning;
step P4: when the pollution early warning module carries out early warning of different levels, different solving modes are adopted.
The electrochemical sensor comprises a first pump, a filter membrane, an ultraviolet lamp, a liquid storage bottle, a second pump, a reference electrode, a counter electrode, a bismuth membrane electrode, a first switching valve, a second switching valve and an ion selection electrode; the first pump, the filter membrane, the ultraviolet lamp, the liquid storage bottle, the second pump, the reference electrode, the counter electrode, the bismuth membrane electrode, the first switching valve, the second switching valve and the ion selection electrode are connected through a polytetrafluoroethylene tube;
the ion selective electrode comprises a lead ion selective electrode, a cadmium ion selective electrode and a copper ion selective electrode.
Wherein, the lead ion selective electrode component: 200mg of 1.1% (cw/rw) IV, 0.5% (w/w) NaTFPB, 10.0% (w/w) ETH500, 88.4% (w/w) polymer MMA-DMA were weighed out and dissolved in 2.0mLCH2C2Performing ultrasonic treatment for 10 min;
cadmium and steel ion selective electrode membrane components: 200mg of 1.0% (w/w) ETH1062, 1.0% (w/w) NaTFPB, 10.0% (w/w) ETH500, 88.0% (w/u) polymer MMA-DMA were weighed out and dissolved in 2.0ml of CH2Cl2Performing ultrasonic treatment for 10 min;
adding 10uL of 25mmol/LPOTCH2C12Dripping the solution on the surface of a glassy carbon electrode, dripping 50uL of membrane component solution on the surface of the electrode after complete drying, standing at room temperature for 2-3 h, and volatilizing thousands of CH2C12The electrode is activated by 1d with 1.0mmol/L aqueous solution of ions to be detected and 1.0nmol/L solution of ions to be detected (containing 0.01mol/L NaCl) respectively.
The preparation method of the bismuth membrane electrode comprises the following steps:
inserting a glassy carbon electrode containing 5X 10mol/LBi (NO)3)3In 0.1mol/LHAc-NaAc buffer solution (pH 4.6), the deposition potential of Bi was selected to be-0.6V, and 240s were deposited under slow stirring.
Example 2:
as shown in fig. 1, a water pollution detection system based on an electrochemical sensor comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module;
the water body acquisition module is used for acquiring water bodies, the specific acquisition mode comprises a bucket acquisition unit and a water sampler acquisition unit, the bucket acquisition unit is used for acquiring surface seawater, the water sampler acquisition unit is used for acquiring bottom seawater, and the acquired seawater is placed in a refrigerator for freezing and storing.
The water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and the specific analysis process comprises the following steps:
the method comprises the following steps: dividing surface layer seawater or bottom layer seawater collected by a water body collection module into i parts of T mL seawater samples, wherein i represents the number of the seawater samples; 1,2 … … n;
step two: adjusting the pH value of a T mL seawater sample i to 2.3 by using concentrated nitric acid; the first pump drives the solution of the seawater sample i at the flow rate of 1.0mL/min to sequentially enter a liquid storage bottle after on-line filtration and ultraviolet digestion;
step three: the second pump pumps the sample in the liquid storage bottle into an enrichment pool at the pump speed of 0.7mL/min, and the electrode potential is controlled to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank;
step three: cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged;
stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential;
step four: completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement;
step five: and calculating the ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module.
Example 3:
as shown in fig. 1, a water pollution detection system based on an electrochemical sensor comprises a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module;
the water body acquisition module is used for acquiring water bodies, the specific acquisition mode comprises a bucket acquisition unit and a water sampler acquisition unit, the bucket acquisition unit is used for acquiring surface seawater, the water sampler acquisition unit is used for acquiring bottom seawater, and the acquired seawater is placed in a refrigerator for freezing and storing.
The water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and the specific analysis process comprises the following steps:
the method comprises the following steps: dividing surface layer seawater or bottom layer seawater collected by a water body collection module into i parts of T mL seawater samples, wherein i represents the number of the seawater samples; 1,2 … … n;
step two: adjusting the pH value of a T mL seawater sample i to 2.5 by using concentrated nitric acid; the first pump drives the solution of the seawater sample i at the flow rate of 1.2mL/min to sequentially enter a liquid storage bottle after on-line filtration and ultraviolet digestion;
step three: the second pump pumps the sample in the liquid storage bottle into an enrichment pool at the pump speed of 0.8mL/min, and the electrode potential is controlled to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank;
step three: cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged;
stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential;
step four: completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement;
step five: and calculating the ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module.
The above formulas are all calculated by removing dimensions and taking numerical values thereof, the formula is a formula which is obtained by acquiring a large amount of data and performing software simulation to obtain the closest real situation, and the preset parameters and the preset threshold value in the formula are set by the technical personnel in the field according to the actual situation or obtained by simulating a large amount of data.
The working principle of the invention is as follows:
water body collection: the specific collection mode comprises a bucket collection unit and a water sampler collection unit, wherein the bucket collection unit is used for collecting surface seawater, the water sampler collection unit is used for collecting bottom seawater, and the collected seawater is placed in a refrigerator for freezing and storing;
water quality analysis: the water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and dividing the surface layer seawater or the bottom layer seawater collected by the water body collection module into i parts of T mL seawater samples; adjusting the pH value of a T mL seawater sample i to 2.0 by using concentrated nitric acid; the first pump drives the solution of the seawater sample i at the flow rate of 0.8mL/min to sequentially enter a liquid storage bottle after on-line filtration and ultraviolet digestion; the second pump pumps the sample in the liquid storage bottle into an enrichment pool at the pump speed of 0.5mL/min, and the electrode potential is controlled to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank; cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged; stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential; completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement; calculating ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module;
and (3) pollution judgment: the pollution judgment module is used for acquiring the ion concentration sent by the water quality analysis module and judging pollution, the pollution judgment module sends an ion acquisition signal to the water quality analysis module, and the water quality analysis module sends the concentration of the heavy metal ions analyzed by the water quality analysis module to the pollution judgment module after receiving the ion acquisition signal; after receiving the concentration of the heavy metal ions, the pollution judgment module marks the concentration of the lead ions, the concentration of the cadmium ions and the concentration of the copper ions as Qi, Gi and Ti respectively; the pollution judgment module respectively calculates the average concentration of the lead ion concentration, the cadmium ion concentration and the copper ion concentration as the measured concentration, and the calculation formula is
The measured concentration of lead ions, the measured concentration of cadmium ions and the measured concentration of copper ions are respectively measured; sending the measured concentration of the lead ions, the measured concentration of the cadmium ions and the measured concentration of the copper ions to a data storage module for storage; the pollution judgment module sets a lead ion concentration threshold, a cadmium ion concentration threshold and a copper ion concentration threshold; when the measured concentration of lead ions
When the lead ion concentration is greater than or equal to the lead ion concentration threshold value, the pollution judgment module judges that the lead ions exceed the standard and sends a lead ion exceeding signal to the pollution early warning module; when the measured concentration of cadmium ion
When the concentration of the cadmium ions is more than or equal to the concentration threshold of the cadmium ions, the pollution judgment module judges that the cadmium ions exceed the standard and sends a cadmium ion exceeding signal to the pollution early warning module; when the measured concentration of copper ions
And when the concentration of the copper ions is more than or equal to the concentration threshold of the copper ions, the pollution judgment module judges that the copper ions exceed the standard and sends a copper ion exceeding signal to the pollution early warning module.
Pollution early warning: the pollution early warning module is used for early warning water body pollution, and receives standard exceeding signals sent by the pollution judging module, wherein the standard exceeding signals comprise lead ion standard exceeding signals, cadmium ion standard exceeding signals and copper ion standard exceeding signals; when the pollution early warning module receives an overproof signal, increasing the early warning level by one, and marking the early warning level as j by the pollution early warning module; when j is 0, the water quality is pollution-free, and the pollution early warning module does not perform water quality early warning; when j is 1, indicating that one of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and carrying out primary early warning by a pollution early warning module; when j is 2, the concentration of two of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and the pollution early warning module performs secondary early warning; and when j is 3, the concentration of lead ions, cadmium ions and copper ions exceeds the standard, and the pollution early warning module performs three-level early warning.
According to the invention, water pollution detection based on an electrochemical sensor is realized through water body collection, water quality analysis, pollution judgment and pollution early warning, concentration determination is carried out on heavy metal ions in the water body, including lead ions, cadmium ions and copper ions, a concentration threshold is set, and pollution alarm of different levels is realized through pollution early warning according to different ion concentration standard exceeding signals. In a flowing system, the digestion efficiency is reduced along with the increase of the flow rate of the seawater sample; however, too low a flow rate affects the analysis rate, and the flow path temperature is too high, which causes vaporization of a large amount of the sample solution. A flow rate of 0.8mL/min allows for high digestion efficiency and faster digestion rates. In addition, the digestion process produces a large amount of carbonate ions, which can combine with calcium ions, magnesium ions, etc. in the seawater to form precipitates, causing pipeline blockage. The invention uses concentrated nitric acid to adjust the pH value of the seawater sample to 2.0 before digestion, thereby not only eliminating the problem of pipeline blockage, but also preventing the adsorption of metal ions on the pipeline wall.
In the embodiments provided by the present invention, it should be understood that the disclosed apparatus, device and method can be implemented in other ways. For example, the above-described apparatus embodiments are merely illustrative, and for example, the division of the modules is only one logical functional division, and there may be other divisions when the actual implementation is performed; the modules described as separate parts may or may not be physically separate, and parts displayed as modules may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the modules may be selected according to actual needs to achieve the purpose of the method of the embodiment.
It will also be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof.
The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference signs in the claims shall not be construed as limiting the claim concerned.
Furthermore, it is obvious that the word "comprising" does not exclude other elements or steps, and the singular does not exclude the plural. A plurality of units or means recited in the system claims may also be implemented by one unit or means in software or hardware. The terms second, etc. are used to denote names, but not any particular order.
Finally, it should be noted that the above examples are only intended to illustrate the technical process of the present invention and not to limit the same, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical process of the present invention without departing from the spirit and scope of the technical process of the present invention.
Claims (4)
1. A water pollution detection system based on an electrochemical sensor is characterized by comprising a water body acquisition module, a water quality analysis module, a pollution judgment module, a data storage module and a pollution early warning module;
the water body acquisition module is used for acquiring water bodies, and the specific acquisition mode comprises a bucket acquisition unit and a water sampler acquisition unit, wherein the bucket acquisition unit is used for acquiring surface seawater, the water sampler acquisition unit is used for acquiring bottom seawater, and the acquired seawater is placed in a refrigerator for freezing and storing;
the water quality analysis module is used for analyzing heavy metal ions of the surface layer seawater or the bottom layer seawater collected by the water body collection module by using the electrochemical sensor, and the specific analysis process comprises the following steps:
the method comprises the following steps: dividing surface layer seawater or bottom layer seawater collected by a water body collection module into i parts of T mL seawater samples, wherein i represents the number of the seawater samples; 1,2 … … n;
step two: adjusting the pH value of a T mL seawater sample i to 2.0-2.5 by using concentrated nitric acid; the first pump drives the seawater sample solution i at the flow rate of 0.8-1.2 mL/min to sequentially pass through on-line filtration and ultraviolet digestion and then enter a liquid storage bottle;
step three: pumping the sample in the liquid storage bottle into an enrichment pool by a second pump at the pump speed of 0.5-0.8 mL/min, and controlling the electrode potential to enrich the heavy metal to be detected to the surface of the electrode; discharging the first waste liquid into a first waste liquid tank;
step three: cleaning the system for 1min by 0.01mol/L NaCl solution at the flow rate of 1.2mL/mind under the condition of keeping the enrichment potential unchanged;
stopping the pump, and dissolving the ions to be detected by adopting differential pulse volt-ampere normal linear scanning (50mV/s) to a dissolving potential;
step four: completely transferring the metal ions to be detected dissolved out from the enrichment pool to a detection pool for potential measurement;
step five: and calculating the ion concentration through the measured potential, and sending the ion concentration to a pollution judgment module.
2. The electrochemical sensor-based water pollution detection system of claim 1, wherein the pollution determination module is configured to obtain the ion concentration sent by the water quality analysis module and determine pollution, and the specific determination method includes the following steps:
step S1: the pollution judgment module sends an ion acquisition signal to the water quality analysis module, and the water quality analysis module sends the concentration of the heavy metal ions analyzed by the water quality analysis module to the pollution judgment module after receiving the ion acquisition signal;
step S2: after receiving the concentration of the heavy metal ions, the pollution judgment module marks the concentration of the lead ions, the concentration of the cadmium ions and the concentration of the copper ions as Qi, Gi and Ti respectively;
step S3: the pollution judgment module respectively calculates the average concentration of the lead ion concentration, the cadmium ion concentration and the copper ion concentration as the measured concentration, and the calculation formula is
Wherein alpha 1, alpha 2 and alpha 3 are correction coefficients,
the measured concentration of lead ions, the measured concentration of cadmium ions and the measured concentration of copper ions are respectively measured; sending the measured concentration of the lead ions, the measured concentration of the cadmium ions and the measured concentration of the copper ions to a data storage module for storage;
step S4: the pollution judgment module sets a lead ion concentration threshold, a cadmium ion concentration threshold and a copper ion concentration threshold;
when the measured concentration of lead ions
When the lead ion concentration is greater than or equal to the lead ion concentration threshold value, the pollution judgment module judges that the lead ions exceed the standard and sends a lead ion exceeding signal to the pollution early warning module;
when the measured concentration of cadmium ion
When the concentration of the cadmium ions is more than or equal to the concentration threshold of the cadmium ions, the pollution judgment module judges that the cadmium ions exceed the standard and sends a cadmium ion exceeding signal to the pollution early warning module;
when the measured concentration of copper ions
And when the concentration of the copper ions is more than or equal to the concentration threshold of the copper ions, the pollution judgment module judges that the copper ions exceed the standard and sends a copper ion exceeding signal to the pollution early warning module.
3. The electrochemical sensor-based water pollution detection system as claimed in claim 1, wherein the pollution pre-warning module is used for pre-warning water pollution, and the specific pollution pre-warning mode comprises the following steps:
step P1: the pollution early warning module receives standard exceeding signals sent by the pollution judging module, wherein the standard exceeding signals comprise lead ion standard exceeding signals, cadmium ion standard exceeding signals and copper ion standard exceeding signals;
step P2: when the pollution early warning module receives an overproof signal, increasing the early warning level by one, and marking the early warning level as j, wherein j is 0, 1,2 and 3 by the pollution early warning module;
step P3: when j is 0, the water quality is pollution-free, and the pollution early warning module does not perform water quality early warning;
when j is 1, indicating that one of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and carrying out primary early warning by a pollution early warning module;
when j is 2, the concentration of two of the lead ion concentration, the cadmium ion concentration and the copper ion concentration exceeds the standard, and the pollution early warning module performs secondary early warning;
when j is 3, the concentration of lead ions, cadmium ions and copper ions exceeds the standard, and the pollution early warning module performs three-stage early warning;
step P4: when the pollution early warning module carries out early warning of different levels, different solving modes are adopted.
4. The electrochemical sensor-based water pollution detection system of claim 1, wherein the electrochemical sensor comprises a first pump, a filter membrane, an ultraviolet lamp, a liquid storage bottle, a second pump, a reference electrode, a counter electrode, a bismuth membrane electrode, a first switching valve, a second switching valve, and an ion selective electrode; the first pump, the filter membrane, the ultraviolet lamp, the liquid storage bottle, the second pump, the reference electrode, the counter electrode, the bismuth membrane electrode, the first switching valve, the second switching valve and the ion selection electrode are connected through a polytetrafluoroethylene tube;
the ion selective electrode comprises a lead ion selective electrode, a cadmium ion selective electrode and a copper ion selective electrode.
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