CN116559247A - Biotoxicity early warning and tracing method and system suitable for industrial park drainage system - Google Patents
Biotoxicity early warning and tracing method and system suitable for industrial park drainage system Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01—MEASURING; TESTING
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a biotoxicity early warning and tracing method and a biotoxicity early warning and tracing system suitable for an industrial park drainage system, which are used for acquiring current signals in all inspection wells in the park; continuously monitoring current signals in all inspection wells, performing early warning according to the current signal changes, and primarily screening out toxic wastewater discharge enterprises; and collecting abnormal characteristic peaks of toxic water quality of the enterprise discharged wastewater corresponding to the primarily screened inspection wells, comparing the abnormal characteristic peaks with the abnormal characteristic peaks of the toxic water quality in the inspection wells of the water inlet of the sewage treatment plant, and judging whether the enterprise is a toxic wastewater discharge enterprise. The biotoxicity early warning and tracing system comprises a plurality of subsystems which are respectively arranged at each inspection well, wherein each subsystem consists of a set of electric signal biological amplifier, a miniature electrochemical workstation and a solar biasing system. The invention not only can effectively identify the water inlet impact, but also can gradually trace the source to search out the impact source, thoroughly solves the problem of the rear end, and has great significance for sewage treatment plants in industrial parks.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a biotoxicity early warning and tracing method and system suitable for an industrial park drainage system.
Background
The wastewater treatment plant in the industrial park has complex water inlet components, mixed industrial wastewater components and harmful substances such as heavy metals, toxic organic matters, acid-base wastewater and the like which are always contained in the wastewater treatment plant exceed the self-monitoring range of the wastewater treatment plant, and some new pollutants such as PPCP, perfluorinated compounds, disinfection byproducts and the like even exceed the monitoring range of common universities and third-party detection institutions. In addition, industrial wastewater often has unknown toxicity, various single pollutants contained in the industrial wastewater have unclear toxicity threshold values for an activated sludge system, and the combined toxicity generated by complex actions such as complexation, chelation and the like among various pollutants is more lack of research. Most importantly, the industrial wastewater has huge fluctuation of water quality, and the types and the amounts of pollutants discharged by various enterprises show huge fluctuation of uncertain time, uncertain types, uncertain discharge capacity along with the adjustment of product types, the fluctuation of process production lines, the requirement of product orders and other factors.
The conventional water toxicity monitoring technologies such as the traditional luminescent bacteria method, the nitrification inhibition method and the zebra fish test have long test time and complex operation, are one-time detection, and do not have an early warning function. The technologies of oxygen consumption rate method, electrochemical test method and the like have low perception precision and high probability of missing report, and are not suitable for industrial/municipal mixed wastewater with complex water inlet components. At present, no effective influent toxicity early warning and monitoring equipment exists, so that the influent water quality toxicity of a sewage treatment plant is difficult to detect, supervise and early warn. In addition, the method is difficult to find for enterprises discharging toxic pollution, and often causes the enterprises to discharge toxic wastewater at regular intervals, thereby causing serious harm to sewage treatment plants.
The Chinese patent application No. CN202122226276.X and the Chinese patent application No. CN201310230554.6 determine the toxicity and inhibition degree of the inflow water to the activated sludge of the biochemical pool by measuring the change of the respiration rate, and the technical equipment is expensive; in addition, the measurement result of the technology has certain delay and the early warning effect is not obvious. The Chinese patent document CN201410020376.9 discloses a preparation method and application of a biological film for a toxicity detection biosensor, wherein the technology utilizes a carrier material to embed and fix microorganisms, the biological film is tightly attached to a polytetrafluoroethylene film of a dissolved oxygen electrode, and then the toxicity of water inflow is judged by monitoring the change condition of the dissolved oxygen; the Chinese patent publication CN201810186395.7 discloses a control method for stably running industrial and urban mixed sewage, which comprises the steps of placing a multi-channel biosensor equipped with a microbial electrode A at the water inlet end of a sewage plant for monitoring the comprehensive toxicity of the water quality of inlet water to activated sludge, taking the outlet water of a secondary sedimentation tank of the sewage plant as a blank control, and adopting a current signal I as a current signal Sewage water /I Reference(s) When the water quality toxicity alarm is not more than 85%, the technology ignores the influence of various indexes such as carbon sources, pH, ammonia nitrogen and the like in the sewage on current signals, and has extremely high false alarm rate.
In addition, a large number of patent documents propose a biosensor for early warning the toxicity of water inlet of a sewage treatment plant, but the methods are all end early warning technologies, and can only prevent the problem which cannot be solved.
Disclosure of Invention
Aiming at the problems of complex water inlet components and frequent toxic impact of sewage treatment plants in industrial parks, no effective method is available at present for solving the problems, based on the invention, the biotoxicity early warning technology and the traceability technology are developed, so that the water inlet impact can be effectively identified, the impact source can be gradually traced and detected, the rear-end problem is thoroughly solved, and the method has great significance for the sewage treatment plants in industrial parks.
A biotoxicity early warning and tracing method suitable for an industrial park drainage system comprises the following steps:
acquiring inspection well current signals: the method comprises the steps that an electric signal biological amplifier is respectively arranged in a sewage discharge outlet inspection well of a key industrial enterprise in a park and a water inlet inspection well of a sewage treatment plant in the park, and probes are all immersed in sewage, wherein the electric signal biological amplifier comprises a cathode electrode and a biological anode electrode, and a microbial film formed by conductive strains is attached to the surface of the biological anode electrode; at each inspection well, the electric potential of-0.1 to 0.1V is applied to the biological anode electrode by a miniature electrochemical workstation through the energy supply of a solar photovoltaic panel or a storage battery; after stable operation for 2-5 days, obtaining a stably output current signal;
preliminary screening of toxic wastewater discharge enterprises: continuously monitoring current signals in all inspection wells, when toxic wastewater is contained in water entering the inspection wells, the current signals can rapidly rise or fall, and a change slope A is generated when the current signals rise or fall: a= |i Original current -I Post-change current |/I Original current /t Time of change Wherein I Original current And I Post-change current The unit of (a) is mA, and the unit of t is min; by comparing the A values in all inspection wells in a park pipe network system, performing preliminary screening according to the sorting from large to small of A, searching the inspection wells with the A values of 5% -20% in front, and preliminarily locking the inspection wells as the inspection wells for discharging toxic wastewater, wherein enterprises corresponding to the inspection wells preliminarily identify as toxic wastewater discharging enterprises;
determining a toxic wastewater discharge enterprise: when the inflow current signal in the inspection well of the water inlet of the sewage treatment plant is suddenly changed, the miniature electrochemical working stand immediately starts the linear volt-ampere characteristic curve scanning to obtain an abnormal characteristic peak when toxic water quality in the inspection well of the water inlet of the sewage treatment plant;
scanning a linear volt-ampere characteristic curve of the enterprise discharged wastewater corresponding to the primarily screened inspection well under the same scanning condition as that of the inspection well at the water inlet of the sewage treatment plant to obtain an abnormal characteristic peak of toxic water quality of the enterprise discharged wastewater, and judging whether the enterprise is a toxic wastewater discharge enterprise or not by comparing the abnormal characteristic peak with the abnormal characteristic peak of toxic water quality in the inspection well at the water inlet of the sewage treatment plant. Optionally, the default characteristic peak is judged to be the same when the difference position of the toxic inflow characteristic peak of the sewage treatment plant and the abnormal characteristic peak of the toxic water quality of the wastewater discharged by the enterprises is within 0.03V.
Optionally, the toxicity of the wastewater is determined by a luminescent bacteria or zebra fish experiment in a water sample delivery laboratory aiming at the determined toxicity wastewater discharge enterprises and then immediately sampling.
Optionally, in the step of primarily screening the toxic wastewater discharge enterprises, when the change slope A reaches more than 0.001, early warning is performed. When the signal of the toxic wastewater entering is that the change slope A reaches more than 0.001, the toxic wastewater is considered to be imported into the pipe network water body, and early warning is carried out. When the change slope is less than 0.001, it may be due to the influence of temperature, pH, etc.
Formula a= |i Original current -I Post-change current |/I Original current /t Time of change In (a):
I original current It can be understood as the current before the current jump;
I post-change current It can be understood that the current after the abrupt change is again in the new plateau;
t time of change It can be understood as the time interval from the mutation to the re-entry of the new plateau;
further specifically, I Post-change current It can also be understood as the current after 10 minutes after the mutation, and when the mutation time is less than 10 minutes, the current after the mutation is brought into the new plateau;
t time of change It is also understood that if the mutation time is more than 10 minutes, the time taken to enter the new plateau after the mutation is counted as 10 minutes, and when the mutation time is less than 10 minutes.
A is sorted from large to small, and then the inspection wells with the A value of 5% -20% of the first are searched, alternatively, the first is taken from the end with the maximum A value as a starting point, for example, A1> A2> A3> … > An is taken from the end A1. The first 5% -20% is understood to mean that the a value in the first 5% is taken from the A1 end or the a value in the first 20% is taken from the A1 end, for example, when the total a value is 100, it is understood that the a value is taken from the maximum end in the first 5 (1 st, 1 st to 2 nd, 1 st to 3 rd, 1 st to 4 th, or 1 st to 5 th) or the a value is taken from the maximum end in the first 20 (1 st, 1 st to 2 nd, 1 st to … th, or 1 st to 20 th).
Further alternatively, after sorting from large to small, the inspection wells with the value of a being 20% in front are searched.
The microbial film is a conductive strain cultured on the surface of the bioelectrode in advance, and the microbial film on the surface layer of the bioelectrode is preferably bacillus and Shewanella, and the two strains have strong natural adaptability, good current output performance and the most stable operation effect. Further preferred is Acinetobacter. The conductive strain is cultured on the surface of the bioelectrode by adopting a conventional culture method in the field.
Optionally, the scanning window is-1.0-1.2V, and the scanning speed is 1-10mV s when the abnormal characteristic peak is scanned -1 Partial characteristic peaks can be omitted when the scanning window is too small, and the biological film can be damaged when the window is too large; too slow a scan rate may result in too long a measurement period, and too fast a scan rate may hide some of the fine feature peaks from view.
Preferably, the electrode material needs to consider corrosion resistance, high ductility and high biological facultative property at the same time, and on the basis of the electrode material, the traditional graphite biological electrode is preferable because the traditional graphite biological electrode is poor in conductivity and easy to adsorb a large amount of pollutants in the electrode, so that electric signals are disordered, and the metal electrode is preferable. However, the stainless steel electrode has extremely poor biocompatibility, can be corroded in a waste water link and can undergo oxidation-reduction reaction in a CV scanning process, and therefore, the invention further develops a polyaniline modification technology, so that the stainless steel is thoroughly protected, and a highly conductive and highly ductile electrode interior and a highly corrosion-resistant and highly biocompatible electrode exterior are formed.
Optionally, the biological anode electrode comprises a stainless steel substrate electrode, and the surface of the stainless steel substrate electrode is subjected to polyaniline and hydrophilic composite modification.
Optionally, the polyaniline and hydrophilic complex modification process comprises:
(1) Immersing a stainless steel electrode in aniline electrolyte, and connecting the stainless steel electrode serving as a working electrode to an electrochemical workstation; the aniline electrolyte is H of aniline 2 SO 4 The volume fraction of aniline in the aniline electrolyte is 2-4%, and H is as follows 2 SO 4 The concentration of (C) is 0.03-0.06 mol L -1 。
(2) Starting the sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 10-50mV s -1 Scanning for 10-30 cycles;
(3) Taking out the stainless steel electrode, immersing the stainless steel electrode in clean water for 8-12 minutes;
(4) Immersing the stainless steel electrode treated in the step (3) in hydrophilic modification liquid, and placing the stainless steel electrode in a shaking table with the rotating speed of 100-150 rpm for 30-45 minutes, wherein the hydrophilic modification liquid is sodium alkylbenzenesulfonate aqueous solution with the mass percent of 0.1-0.3%;
(5) Taking out, cleaning and drying to obtain the bioelectrode.
The polyaniline electrode is obtained after the treatment in the step (3), but in order to further improve the biocompatibility of the electrode, the method continues to develop a composite modification technology, and hydrophilic groups are grafted on the surface of the polyaniline again.
Optionally, the cathode is a stainless steel electrode without any modification.
Optionally, the distance between the bioanode electrode and the cathode electrode is 0.5-1.0 cm. Too small electrode spacing can cause electrode gaps to be blocked by garbage, too large electrode spacing can cause excessive internal resistance, and unstable liquid internal resistance can cause great fluctuation of current signals.
The invention also provides a biotoxicity early warning and tracing system suitable for the industrial park drainage system, which comprises the following components:
the electric signal biological amplifier is respectively arranged in a sewage discharge port inspection well of a key industrial enterprise in the park and a water inlet inspection well of a sewage treatment plant in the park; the electric signal biological amplifier comprises a cathode electrode and a biological anode electrode, and a microbial film formed by conductive strains is attached to the surface of the biological anode electrode;
the miniature electrochemical workstations are respectively arranged at each inspection well and are correspondingly connected to the cathode electrode and the biological anode electrode of the electric signal biological amplifier;
the solar biasing system comprises a solar photovoltaic panel and a storage battery, and is respectively arranged at each inspection well and is used for supplying power to the miniature electrochemical workstation.
The biotoxicity early warning and tracing system comprises a plurality of subsystems which are respectively arranged at each inspection well, wherein each subsystem consists of a set of electric signal biological amplifier, a miniature electrochemical workstation and a solar biasing system. Optionally, in each subsystem, the solar photovoltaic panel is connected with a storage battery, the storage battery supplies power for a micro electrochemical workstation, and the micro electrochemical workstation is connected with a cathode electrode and a biological anode electrode
The system of the invention is various, the data acquisition and comparison of each subsystem can be realized through manual processing, and optionally, the system can also be automatically processed through a data processing end, for example, the system can also comprise a data processing base station or a control system, and the control system can be realized through a PLC and the like. The data collection collected by each subsystem is processed only in the data processing base station or the control system.
Optionally, the cathode is an unmodified stainless steel electrode.
Optionally, the distance between the biological anode and the cathode is 0.5-1.0 cm.
Optionally, the preparation process of the biological anode electrode comprises the following steps:
(1) Immersing a stainless steel electrode in aniline electrolyte, and connecting the stainless steel electrode serving as a working electrode to an electrochemical workstation; the aniline electrolyte is H of aniline 2 SO 4 The volume fraction of aniline in the aniline electrolyte is 2-4%, and H is as follows 2 SO 4 The concentration of (C) is 0.03-0.06 mol L -1 。
(2) Starting the sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 10-50mV s -1 Scanning for 10-30 cycles;
(3) Taking out the stainless steel electrode, immersing the stainless steel electrode in clean water for 8-12 minutes;
(4) Immersing the stainless steel electrode treated in the step (3) in hydrophilic modification liquid, and placing the stainless steel electrode in a shaking table with the rotating speed of 100-150 rpm for 30-45 minutes, wherein the hydrophilic modification liquid is sodium alkylbenzenesulfonate aqueous solution with the mass percent of 0.1-0.3%;
(5) Taking out, cleaning and drying to obtain the bioelectrode.
The system is mainly arranged in areas such as a water inlet of a sewage treatment plant in a park, a main inlet inspection well on a trunk sewage pipe network, a key wading enterprise sewage discharge port and the like, and forms a distribution network taking the sewage treatment plant as a root, the trunk pipe network as a stem and an enterprise water discharge port as a branch.
The traditional pollutant tracing is mainly that the water inlet problem is discovered after the problem occurs in a sewage treatment plant, and then the traditional investigation success rate is extremely low due to volatility and concealment of the theft investigation through the technologies of manual sampling, luminescent bacteria investigation and the like. The existing inspection well mounting probes and tracing modes are mainly confirmed through indexes such as conductivity, pH and the like, the detection conditions of the technology are limited, and toxic substances cannot be found.
Based on the above, the invention has no similar products at present, and compared with the prior art, the invention has at least one of the following beneficial effects:
(1) Corrosion resistance, self energy supply and low maintenance, and subsequent maintenance management is performed without inputting manpower and material resources;
(2) Compared with the traditional biological probe which analyzes through the absolute value of the current, the invention adopts the slope of the change of the relative value to analyze, and can shield the slow influencing factors such as temperature, pH, dissolved oxygen and the like;
(3) The device monitors and analyzes the total toxicity index, and has universal monitoring capability for most toxic pollutants.
Drawings
FIG. 1 is a schematic diagram of an assembly of a device at one of the inspection wells in the biotoxicity early warning and tracing system of the present invention.
FIG. 2 is a scanning electron microscope image of a bioelectrode modified: a1-2 stainless steel raw electrode and B1-2 modified bioelectrode.
FIG. 3 is a graph showing the comparison of the scanning results of abnormal characteristic peaks of the inlet water of a primary screening toxic wastewater discharge enterprise and a sewage treatment plant in an application example.
FIG. 4 is a microscopic photograph of the development of fish eggs in the application example for determining the wastewater discharge enterprises and the wastewater treatment plant water inflow (A: wastewater treatment plant water inflow; B: C enterprise water discharge).
The reference numerals shown in fig. 1 are as follows:
1-solar photovoltaic panel 2-inspection well 3-miniature electrochemical workstation
4-sewage pipe network 5-electric signal biological amplifier 6-storage battery
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
A biotoxicity early warning and traceability system suitable for an industrial park drainage system comprises a plurality of subsystems, wherein each subsystem is respectively installed at a water inlet inspection well of a park sewage treatment plant and a sewage discharge outlet inspection well of each key industrial enterprise, as shown in fig. 1, the subsystem at the water inlet inspection well of the park sewage treatment plant is taken as an example for explanation.
The subsystem shown in fig. 1 comprises an electric signal biological amplifier 5, a miniature electrochemical workstation 3 and a solar biasing system, wherein the electric signal biological amplifier 5 is arranged in a water inlet inspection well 2 of a sewage treatment plant in a park, and the electric signal biological amplifier 5 comprises a cathode electrode and a biological anode electrode; the miniature electrochemical workstation 3 is a commercially available mature product and is connected with a cathode electrode and a biological anode electrode of the electric signal biological amplifier 5 through leads; the solar biasing system comprises a solar photovoltaic panel 1 and a storage battery 6, wherein the solar photovoltaic panel 1 is connected with the storage battery 6, and the storage battery 6 is connected with the miniature electrochemical workstation 3.
The arrangement of the sewage discharge inspection wells of each key industrial enterprise in the park pipe network system is also shown in fig. 1.
The bioelectrode is used as an anode, the cathode is a stainless steel electrode which is not subjected to any modification, and the electrode spacing is 5-10mm.
The electrode material needs to consider corrosion resistance, high ductility and high biological facultative, and on the basis of the electrode material, the traditional graphite bioelectrode is preferable because the traditional graphite bioelectrode is poor in conductivity and easy to adsorb a large amount of pollutants in the electrode, so that electric signals are disordered, and the metal electrode is preferable. However, the stainless steel electrode has extremely poor biocompatibility, can be corroded in a waste water link and can undergo oxidation-reduction reaction in a CV scanning process, and therefore, the invention further develops a polyaniline modification technology, so that the stainless steel is thoroughly protected, and a highly conductive and highly ductile electrode interior and a highly corrosion-resistant and highly biocompatible electrode exterior are formed.
In one embodiment, the preparation process of the bioanode electrode comprises:
(1) Immersing a stainless steel electrode in aniline electrolyte, and connecting the stainless steel electrode serving as a working electrode to an electrochemical workstation; the aniline electrolyte is H of aniline 2 SO 4 The volume fraction of aniline in the aniline electrolyte is 2-4%, and H is as follows 2 SO 4 The concentration of (C) is 0.03-0.06 mol L -1 。
(2) Starting the sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 10-50mV s -1 Scanning for 10-30 cycles;
(3) Taking out the stainless steel electrode, immersing the stainless steel electrode in clean water for 8-12 minutes;
(4) Immersing the stainless steel electrode treated in the step (3) in hydrophilic modification liquid, and placing the stainless steel electrode in a shaking table with the rotating speed of 100-150 rpm for 30-45 minutes, wherein the hydrophilic modification liquid is sodium alkylbenzenesulfonate aqueous solution with the mass percent of 0.1-0.3%;
(5) Taking out, cleaning and drying to obtain the bioelectrode.
A preferred specific modification method comprises:
the polyaniline modification steps are as follows:
(1) preparing an aniline electrolyte: 0.05mol L -1 H 2 SO 4 3% by volume of aniline liquid.
(2) The stainless steel electrode is immersed in the aniline electrolyte and used as a working electrode to be connected with an electrochemical workstation.
(3) Starting a sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 30mV s -1 A total of 20 cycles was scanned.
(4) The stainless steel electrode was removed and immersed in clear water for 10 minutes.
The polyaniline electrode is obtained through the steps, but in order to further improve the biocompatibility of the electrode, the invention continues to develop a composite modification technology, and hydrophilic groups are grafted on the surface of polyaniline again.
The hydrophilic modification steps are as follows: preparing 0.2% sodium alkylbenzenesulfonate hydrophilic modifying liquid, immersing the electrode in the hydrophilic modifying liquid, and placing in a shaking table with a rotating speed of about 150rpm for 40 minutes.
The scanning electron microscope image pairs before and after modification are shown in fig. 2. Wherein A-1 and A-2 are unmodified stainless steel electrodes, and B-1 and B-2 are modified electrodes.
The surface of the modified biological anode electrode is subjected to microorganism culture according to a conventional method in the field, surface microorganisms, preferably bacillus and Shewanella, are strong in natural adaptation force, good in current output performance and most stable in operation effect. Further preferred is Acinetobacter.
The system is mainly arranged in areas such as a water inlet of a sewage treatment plant, a main inlet inspection well on a main sewage pipe network, a key wading enterprise sewage discharge outlet and the like, and forms a distribution network taking the sewage treatment plant as a root, the main pipe network as a stem and an enterprise water discharge outlet as a branch.
A specific implementation method for carrying out biotoxicity early warning and tracing on an industrial park drainage system through the early warning and tracing system comprises the following steps:
(1) the electric signal biological amplifier is arranged at the bottom of each inspection well in the park, and the probe is completely immersed in sewage.
(2) The micro electrochemical workstation applies electric potential of-0.1 to 0.1V to the anode of the bioelectrode system by the energy of the solar panel.
(3) After stable operation for 2-5 days, a stable output current signal is obtained.
(4) When the wastewater from the sewage treatment plant contains toxic wastewater, the current signal can rise or fall rapidly. The rising and falling of the current signal will generate a change slope a, a= |i Original current -I Post-change current |/I Original current /t Time of change (I Original current And I Post-change current The unit of (t) is mA and the unit of t is min), comparing the A values in all inspection wells in a pipe network system, sorting according to the A from large to small, performing preliminary screening, searching the inspection wells with the A values of 5% -20% in front, and preliminarily locking the inspection wells as the inspection wells for discharging toxic wastewater, wherein enterprises corresponding to the inspection wells are preliminarily identified as toxic wastewater discharging enterprises;
in the step, when the A in the inspection well without the water inlet of the water treatment plant reaches more than 0.001, early warning is carried out simultaneously.
In this embodiment, I Original current Understood as the current before the graph changes, I Post-change current It is understood that the current after 10 minutes after the mutation, when the mutation time is less than 10 minutes, the current after the mutation enters a new plateau; t is t Time of change It is understood that if the mutation time is more than 10 minutes, the time taken to enter the new plateau after the mutation is counted as 10 minutes, and when the mutation time is less than 10 minutes.
(5) When the current signal in the inspection well of the water inlet of the sewage treatment plant is suddenly changed, the miniature electrochemical working stand immediately starts the linear volt-ampere characteristic curve scanning to obtain an abnormal characteristic peak when toxic water quality is obtained.
(6) And (3) scanning a linear volt-ampere characteristic curve of the wastewater discharged by the primarily screened thief discharge enterprises under the same condition as the condition (5), obtaining an abnormal characteristic peak of the toxic wastewater enterprises, and comparing the abnormal characteristic peak obtained in the condition (5), thereby identifying the thief discharge condition of the enterprises.
(7) And then immediately sampling, and determining the toxicity condition of the water sample by a water sample delivery laboratory through technologies such as luminescent bacteria, zebra fish experiments and the like.
Application example
Aiming at a pipe network system of an industrial park, the early warning and tracing system is installed in a water inlet inspection well of a sewage treatment plant and a wastewater discharge outlet inspection well of 15 key discharge enterprises in the park for pilot test, and the early warning and tracing are carried out by adopting the specific implementation method.
When the slope A is found to be rapidly increased by the inflow water of the sewage treatment plant, slope changes of all inspection wells are immediately monitored, and the values are sequentially ordered from large to small as shown in the following table (the value A is close to 0):
table 1A value change procedure
Scanning abnormal characteristic peaks of three enterprises A\B\C with the largest slope, wherein the scanning window for scanning the abnormal characteristic peaks is-1.0-0.4V, and the scanning speed is 5mV s -1 The results are shown in fig. 3, and the results show that the drainage of the enterprise C is the same as the characteristic peak of the inflow water of the sewage treatment plant.
The results of the luminescent bacteria test and the zebra fish test performed on the wastewater of the enterprise C are shown in the table 2 and the figure 4, and the results show that the wastewater of the enterprise C does have serious biotoxicity.
TABLE 2 toxicity test of tail water of sewage treatment plant
| Blank value | Standard sample | Inlet water of sewage plant | Enterprise C drainage | |
| Initial light quantity | 3539068 | 3330826 | 3489712 | 3440253 |
| 15min luminescence amount | 3372800 | 737903 | 1959505 | 711022 |
| Toxicity value | 0.95(CF) | 75% (quality control) | 43.8％ | 79.3％ |
The above examples merely represent a few embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it would be apparent to those skilled in the art that various modifications and improvements could be made without departing from the spirit of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.
Claims (10)
1. A biotoxicity early warning and tracing method suitable for an industrial park drainage system is characterized by comprising the following steps:
acquiring inspection well current signals: the method comprises the steps that an electric signal biological amplifier is respectively arranged in a sewage discharge outlet inspection well of a key industrial enterprise in a park and a water inlet inspection well of a sewage treatment plant in the park, and probes are all immersed in sewage, wherein the electric signal biological amplifier comprises a cathode electrode and a biological anode electrode, and a microbial film formed by conductive strains is attached to the surface of the biological anode electrode; at each inspection well, the electric potential of-0.1 to 0.1V is applied to the biological anode electrode by a miniature electrochemical workstation through the energy supply of a solar photovoltaic panel or a storage battery; after stable operation for 2-5 days, obtaining a stably output current signal;
preliminary screening of toxic wastewater discharge enterprises: continuously monitoring current signals in all inspection wells, and when toxic wastewater is contained in water entering the inspection wells, rapidly rising or falling the current signals to generate a change slope A: a= |i Original current -I Post-change current |/I Original current /t Time of change Wherein I Original current And I Post-change current The unit of (a) is mA, and the unit of t is min; by comparing the A values in all inspection wells in a park pipe network system, performing preliminary screening according to the sorting from large to small of A, searching the inspection wells with the A values of 5% -20% in front, and preliminarily locking the inspection wells as the inspection wells for discharging toxic wastewater, wherein enterprises corresponding to the inspection wells preliminarily identify as toxic wastewater discharging enterprises;
determining a toxic wastewater discharge enterprise: when the inflow current signal in the inspection well of the water inlet of the sewage treatment plant is suddenly changed, the miniature electrochemical working stand immediately starts the linear volt-ampere characteristic curve scanning to obtain an abnormal characteristic peak when toxic water quality in the inspection well of the water inlet of the sewage treatment plant;
scanning a linear volt-ampere characteristic curve of the enterprise discharged wastewater corresponding to the primarily screened inspection well under the same scanning condition as that of the inspection well at the water inlet of the sewage treatment plant to obtain an abnormal characteristic peak of toxic water quality of the enterprise discharged wastewater, and judging whether the enterprise is a toxic wastewater discharge enterprise or not by comparing the abnormal characteristic peak with the abnormal characteristic peak of toxic water quality in the inspection well at the water inlet of the sewage treatment plant.
2. The method for early warning and tracing biotoxicity according to claim 1, wherein the determined toxicity of the wastewater is determined by a luminescent bacteria or zebra fish experiment in a water sample delivery laboratory by immediately sampling the wastewater after the determined toxicity is discharged from the enterprise.
3. The method for early warning and tracing biological toxicity according to claim 1, wherein in the step of primarily screening the toxic wastewater discharge enterprises, early warning is performed when the change slope a reaches more than 0.001.
4. The method of claim 1, wherein the conductive species comprises geobacillus or shiveri.
5. The method for early warning and tracing biotoxicity according to claim 1, wherein the scanning window is-1.0-1.2V and the scanning speed is 1-10mV s when scanning abnormal characteristic peaks -1 。
6. The method for early warning and tracing of biotoxicity according to claim 1, wherein the bioanode electrode comprises a stainless steel base electrode, and the surface of the stainless steel base electrode is modified by polyaniline and hydrophilic composite.
7. The method for early warning and tracing of biotoxicity according to claim 6, wherein the polyaniline and hydrophilic complex modification process comprises:
(1) Immersing a stainless steel electrode in aniline electrolyte, and connecting the stainless steel electrode serving as a working electrode to an electrochemical workstation; the aniline electrolyte is anilineH 2 SO 4 The volume fraction of aniline in the aniline electrolyte is 2-4%, and H is as follows 2 SO 4 The concentration of (C) is 0.03-0.06 mol L -1 。
(2) Starting the sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 10-50mV s -1 Scanning for 10-30 cycles;
(3) Taking out the stainless steel electrode, immersing the stainless steel electrode in clean water for 8-12 minutes;
(4) Immersing the stainless steel electrode treated in the step (3) in hydrophilic modification liquid, and placing the stainless steel electrode in a shaking table with the rotating speed of 100-150 rpm for 30-45 minutes, wherein the hydrophilic modification liquid is sodium alkylbenzenesulfonate aqueous solution with the mass percent of 0.1-0.3%;
(5) Taking out, cleaning and drying to obtain the bioelectrode.
8. The method of claim 1, wherein the cathode is a stainless steel electrode without any modification; the distance between the biological anode electrode and the cathode electrode is 0.5-1.0 cm.
9. Biotoxicity early warning and traceability system suitable for industrial park drainage system, characterized by comprising:
the electric signal biological amplifier is respectively arranged in a sewage discharge port inspection well of a key industrial enterprise in the park and a water inlet inspection well of a sewage treatment plant in the park; the electric signal biological amplifier comprises a cathode electrode and a biological anode electrode, and a microbial film formed by conductive strains is attached to the surface of the biological anode electrode;
the miniature electrochemical workstations are respectively arranged at each inspection well and are correspondingly connected to the cathode electrode and the biological anode electrode of the electric signal biological amplifier;
the solar biasing system comprises a solar photovoltaic panel and a storage battery, and is respectively arranged at each inspection well and is used for supplying power to the miniature electrochemical workstation.
10. The system of claim 9, wherein the cathode is an unmodified stainless steel electrode;
the distance between the biological anode and the cathode is 0.5-1.0 cm;
the preparation process of the biological anode electrode comprises the following steps:
(1) Immersing a stainless steel electrode in aniline electrolyte, and connecting the stainless steel electrode serving as a working electrode to an electrochemical workstation; the aniline electrolyte is H of aniline 2 SO 4 The volume fraction of aniline in the aniline electrolyte is 2-4%, and H is as follows 2 SO 4 The concentration of (C) is 0.03-0.06 mol L -1 。
(2) Starting the sweep volt-ampere characteristic curve, wherein the window is-0.1-0.8V, and the sweep rate is 10-50mV s -1 Scanning for 10-30 cycles;
(3) Taking out the stainless steel electrode, immersing the stainless steel electrode in clean water for 8-12 minutes;
(4) Immersing the stainless steel electrode treated in the step (3) in hydrophilic modification liquid, and placing the stainless steel electrode in a shaking table with the rotating speed of 100-150 rpm for 30-45 minutes, wherein the hydrophilic modification liquid is sodium alkylbenzenesulfonate aqueous solution with the mass percent of 0.1-0.3%;
(5) Taking out, cleaning and drying to obtain the bioelectrode.
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