CN113899792A - System for monitoring heavy metal and microbial electrochemical sensor - Google Patents
System for monitoring heavy metal and microbial electrochemical sensor Download PDFInfo
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- G—PHYSICS
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Abstract
A system for monitoring heavy metals and a microbial electrochemical sensor comprise the microbial electrochemical sensor, a first liquid storage tank containing anode matrix liquid, a second liquid storage tank containing cathode matrix liquid, a peristaltic pump, an electrochemical workstation, a computer, a resistance-variable box and an external circuit. The microbial electrochemical sensor is an improved MFC, and can automatically output an electric signal without an external power supply.
Description
Technical Field
The invention relates to a system for monitoring heavy metal and a microbial electrochemical sensor, belonging to the technical field of monitoring heavy metal pollution of a water environment.
Background
In recent years, with the development of heavy industry, heavy metal pollution has become one of the most harmful water pollution problems. The monitoring of the heavy metal pollution is an important means for knowing the current situation of water body pollution, and has very important significance for guaranteeing the safety of human life and property and carrying out subsequent water treatment work in a targeted manner. The traditional water quality poison monitoring work is mostly developed by means of an offline physicochemical analysis technology, although the total concentration of heavy metals in a water body can be accurately tested, the method needs complex instruments and equipment for support, the sample pretreatment process is complicated, the professional requirement on operators is high, more importantly, the detection result is obviously delayed, and the real influence of poisons on human health and water environment safety cannot be timely reflected. Therefore, it is very important to develop a sensing system which can meet the online early warning requirement of water quality and can respond in real time after being impacted.
The electrochemical sensor plays an increasingly important role in monitoring water environment safety with the advantages of high reaction speed, high sensitivity, low cost, suitability for on-line monitoring and the like. Electrochemical sensors are generally composed of multiple electrodes, and currently, the most common electrochemical measurement is a three-electrode system composed of a working electrode, a reference electrode and a counter electrode. The three-electrode system has the advantages of high voltage scanning speed, small monitoring error, stable work, capability of compensating ohmic voltage drop in solution and the like.
Electrochemical sensors have the disadvantages: an external power supply is needed for monitoring, and a complete loop is formed; the requirement on the electrode is high, the electrode needs to be chemically modified for increasing the sensitivity, and the operation is complex.
The bioelectricity sensor utilizes the combination of specific biological recognition substances and heavy metals, and converts the change into a monitorable electric signal through a signal converter so as to analyze and judge the heavy metal elements and the content thereof. Common biosensors comprise enzyme biosensors, cell sensors, DNA sensors and other online monitoring methods, and can respond quickly. The bioelectricity sensor relates to the extraction operation of biological active substances such as biological tissues, microorganisms, organelles, enzymes, antibodies, antigens, nucleic acids, DNA and the like, which is generally complex and expensive, and the biological active units have the defects of instability, easy denaturation and the like, so that the stability and the reproducibility of the biosensor are poor. However, a great deal of research work is limited to the initial attempts of methodology, and the gap from the realization of the commercialization requirement of the biosensor is large.
Disclosure of Invention
The invention aims to provide a system for monitoring heavy metal and a microbial electrochemical sensor.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a microbial electrochemical sensor comprising a microbial electrochemical sensor body separated by a diaphragm to form an anode chamber and a cathode chamber, each of the anode chamber and the cathode chamber being filled with carbon felt particles; the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber; the diaphragm is a proton exchange membrane or a cation exchange membrane.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a system for monitoring heavy metals comprises a microbial electrochemical sensor, a first liquid storage tank containing anode matrix liquid, a second liquid storage tank containing cathode matrix liquid, a peristaltic pump, an electrochemical workstation, a computer, a resistance-variable box and an external circuit;
the microbial electrochemical sensor comprises a microbial electrochemical sensor body, wherein the microbial electrochemical sensor body is separated by a diaphragm to form an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are both filled with carbon felt particles; the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber; the anode electrode and the cathode electrode are respectively connected with two poles of the varistor box;
the anode electrode and the carbon felt particles of the anode chamber are both inoculated with anaerobic electrogenic bacteria;
the first liquid storage tank is communicated with an anode water inlet of the anode chamber through a first pipeline, and an anode water outlet of the anode chamber is communicated with the first liquid storage tank through a second pipeline;
the second liquid storage tank is communicated with a cathode water inlet of the cathode chamber through a third pipeline, and a cathode water outlet of the cathode chamber is communicated with the second liquid storage tank through a fourth pipeline;
peristaltic pumps are arranged on the first pipeline and the third pipeline respectively;
the anode electrode and the cathode electrode are electrically connected with an electrochemical workstation, and the electrochemical workstation is in signal connection with a computer.
The preferable technical scheme is as follows: the filling amount of the carbon felt particles is 100cm2Filling 40-70 grains; the size of the carbon felt particles is 0.5cm x 1 cm.
The preferable technical scheme is as follows: the domestication method of the anaerobic electrogenesis bacteria comprises the following steps: putting activated sludge in a SBR process sludge collection pool into a first liquid storage tank, mixing an anode substrate liquid and a trace element mixture, introducing nitrogen, adding the mixture into the first liquid storage tank, mounting an aluminum foil gas sampling bag on the first liquid storage tank, placing the first liquid storage tank into a constant-temperature water bath kettle, heating in a water bath at 37.5 ℃ for anaerobic acclimation, and completing acclimation of anaerobic electrogenic bacteria when gas exists in the aluminum foil gas sampling bag; and supernatant in the first liquid storage tank enters the anode chamber from the anode water inlet through the peristaltic pump and then flows back to the first liquid storage tank from the anode water outlet, so that the anaerobic electrogenesis bacteria inoculation can be carried out.
The preferable technical scheme is as follows: 1.65g of CH per liter of the anode matrix solution3COONa·3H2O, 0.31g NH4Cl, 1.93g of NaH2PO4·12H2O, 1.385g of Na2HPO4·2H2O, 0.1g MgSO4·7H2O、1g of NaHCO30.1g of CaCl2And 0.1g of KCl.
The preferable technical scheme is as follows: the mixture of trace elements contains 100mg of FeSO per liter4·7H2O, 70mg ZnCl250mg of MnCl2·4H2O, 6mg of H3BO3100mg of CaCl22mg of CuCl2·2H2O, 24mg of NiCl2·6H2O, 36mg of Na2MoO4·2H2O, 24mg of Na2WO4·2H2O and 238mg of CoCl2·6H2O。
The preferable technical scheme is as follows: per liter of the cathodic matrix liquid: 8.32g of K3[Fe(CN)6]1.93g of NaH2PO4Per L and 1.385g of Na2HPO4。
The preferable technical scheme is as follows: the system comprises a plurality of microbial fuel cell reactors connected in parallel, wherein the plurality of microbial fuel cell reactors connected in parallel share a second liquid storage tank, and each microbial fuel cell reactor uses a first liquid storage tank.
A microbial electrochemical sensor, characterized by: the microbial electrochemical sensor comprises a microbial electrochemical sensor body, wherein the microbial electrochemical sensor body is separated by a diaphragm to form an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are both filled with carbon felt particles (the particle size is 0.5cm multiplied by 1 cm); the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a system for monitoring heavy metals comprises a microbial electrochemical sensor, a first liquid storage tank containing anode matrix liquid, a second liquid storage tank containing cathode matrix liquid, a peristaltic pump, an electrochemical workstation, a computer, a resistance-variable box and an external circuit;
the microbial electrochemical sensor comprises a microbial electrochemical sensor body, wherein the microbial electrochemical sensor body is separated by a diaphragm to form an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are both filled with carbon felt particles; the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber; the anode electrode and the cathode electrode are respectively electrically connected with one end of the varistor box;
the anode electrode and the carbon felt particles of the anode chamber are both inoculated with anaerobic electrogenic bacteria;
the first liquid storage tank is communicated with an anode water inlet of the anode chamber through a first pipeline, and an anode water outlet of the anode chamber is communicated with the first liquid storage tank through a second pipeline;
the second liquid storage tank is communicated with a cathode water inlet of the cathode chamber through a third pipeline, and a cathode water outlet of the cathode chamber is communicated with the second liquid storage tank through a fourth pipeline;
peristaltic pumps are arranged on the first pipeline and the third pipeline respectively;
the anode electrode and the cathode electrode are electrically connected with an electrochemical workstation, and the electrochemical workstation is in signal connection with a computer.
The preferable technical scheme is as follows: the diaphragm is a proton exchange membrane or a cation exchange membrane.
The preferable technical scheme is as follows: the domestication method of the anaerobic electrogenesis bacteria comprises the following steps: putting activated sludge in a SBR process sludge collection pool into a first liquid storage tank, mixing an anode substrate liquid and a trace element mixture, introducing nitrogen, adding the mixture into the first liquid storage tank, mounting an aluminum foil gas sampling bag on the first liquid storage tank, placing the first liquid storage tank into a constant-temperature water bath kettle, heating in a water bath at 37.5 ℃ for anaerobic acclimation, and completing acclimation of anaerobic electrogenic bacteria when gas exists in the aluminum foil gas sampling bag; and supernatant in the first liquid storage tank enters the anode chamber from the anode water inlet through the peristaltic pump and then flows back to the first liquid storage tank from the anode water outlet, so that the anaerobic electrogenesis bacteria inoculation can be carried out. Above or below 37.5 ℃, the activity may be reduced, effected or affected.
The preferable technical scheme is as follows: per liter of the above-mentioned Chinese medicinePolar substrate liquid 1.65g of CH3COONa·3H2O, 0.31g NH4Cl, 1.93g of NaH2PO4·12H2O, 1.385g of Na2HPO4·2H2O, 0.1g MgSO4·7H2O, 1g NaHCO30.1g of CaCl2And 0.1g of KCl.
The preferable technical scheme is as follows: the mixture of trace elements contains 100mg of FeSO per liter4·7H2O, 70mg ZnCl250mg of MnCl2·4H2O, 6mg of H3BO3100mg of CaCl22mg of CuCl2·2H2O, 24mg of NiCl2·6H2O, 36mg of Na2MoO4·2H2O, 24mg of Na2WO4·2H2O and 238mg of CoCl2·6H2O。
The preferable technical scheme is as follows: per liter of the cathodic matrix liquid: 8.32g of K3[Fe(CN)6]1.93g of NaH2PO4Per L and 1.385g of Na2HPO4。
The preferable technical scheme is as follows: the system comprises a plurality of microbial electrochemical sensors which are connected in parallel, wherein the plurality of microbial electrochemical sensors which are connected in parallel share a second liquid storage tank, and each microbial fuel cell reactor uses a first liquid storage tank.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
1. the microbial electrochemical sensor is an improved MFC, and can automatically output an electric signal without an external power supply.
2. The microbial electrochemical sensor can directly output an electric signal without a signal converter.
3. The carbon rod and the carbon felt are used as electrode materials, so that the carbon rod and the carbon felt are environment-friendly and low in cost.
4. The electrochemical active bacteria have self-renewal and repair capabilities, so that the microbial sensor is simple to maintain and long in service life.
Drawings
FIG. 1 is a schematic view of a microbial electrochemical sensor.
Fig. 2 is a schematic diagram of a system for heavy metal monitoring.
FIG. 3 is a schematic diagram of a microbial electrochemical sensor for monitoring heavy metal ions.
FIG. 4(A) shows the voltage drop curves for different concentrations of Cu2 +; (B) cu2+And fitting a curve to the change of the voltage suppression rate.
FIG. 5(A) adding different concentrations of Cd2+A voltage droop curve; (B) cd [ Cd ]2+And fitting a curve to the change of the voltage suppression rate.
FIG. 6 shows that (A) Cr with different concentrations is added2+A voltage droop curve; (B) cr (chromium) component2+And fitting a curve to the change of the voltage suppression rate.
FIG. 7 shows the addition of different concentrations of Hg for (A)2+A voltage droop curve; (B) hg is a mercury vapor2+And fitting a curve to the change of the voltage suppression rate.
In the attached drawings, 1, a microbial electrochemical sensor 2 and a peristaltic pump; 3. a first storage tank; 4. a second storage tank; 5. a resistance-changing box; 6. an electrochemical workstation; 7. a computer; 11. a diaphragm; 12. an anode chamber; 121. an anode electrode; 122. an anode water inlet; 123. an anode water outlet; 13. a cathode chamber; 131. a cathode electrode; 132. a cathode water inlet; 133. a cathode water outlet; 14. carbon felt particles.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will be apparent to those skilled in the art from the present disclosure.
Please refer to fig. 1-7. It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are provided for a better understanding of the present invention, and are not intended to limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The experimental materials used in the following examples were all purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1: system for monitoring heavy metal and microbial electrochemical sensor
The microbial electrochemical sensor of the present embodiment is essentially a two-chamber Microbial Fuel Cell (MFC) having carbon rods as an anode and a cathode, and the anode chamber and the cathode chamber are filled with carbon felts to form a microbial membrane. The cathode chamber and the anode chamber are separated by a cation exchange membrane or a proton exchange membrane. The sensor is essentially a double-chamber Microbial Fuel Cell (MFC), can automatically output an electric signal without an external power supply, and can be directly monitored by an electrochemical workstation.
A microbial electrochemical sensor (MFCs sensor) is a device developed based on the characteristics of MFCs electricity generation and applicable to the field of sensing and monitoring of heavy metals in water environment, and generally comprises an anode chamber, a cathode chamber, a proton exchange membrane and an external circuit, as shown in fig. 1.
The working principle of the microbial electrochemical sensor (MFCs sensor) is that anode anaerobic electrogenesis bacteria are used as a catalyst and are attached to the surface of an anode to form a biomembrane, organic matters are degraded on the surface of the anode after entering an anode chamber to form an intermediate product, protons and electrons, the protons reach a cathode chamber after passing through a proton or ion exchange membrane, the electrons are transferred to the anode and then reach a cathode through an external circuit to generate current, and the electrons, the protons and an electron acceptor (such as oxygen) are subjected to reduction reaction (combined to generate water) on the surface of the cathode. When the MFCs are used as the biosensor to monitor the heavy metals, the heavy metal substances enter the anode chamber and can inhibit anaerobic electrogenesis bacteria at the anode of the MFCs, so that the metabolism rate is reduced, the activity of the anaerobic electrogenesis bacteria is inhibited, the electrogenesis capability is finally reduced, the toxicity of the heavy metals can be reflected by monitoring the change of an electric signal (usually selecting current or voltage), and the online monitoring and early warning effect on the heavy metal pollution of a water body is realized.
Construction of microbial electrochemical sensors (MFCs reactors):
as shown in FIG. 1, electrochemical treatment of microorganismsThe chemical sensor (MFCs reactor) consists of an anode chamber 12, a cathode chamber 13 and a membrane 11 between the anode chamber 12 and the cathode chamber 13. The anode chamber 12 and the cathode chamber 13 are filled with carbon felt particles 14, which play a role in conducting electricity and attaching electrochemically active bacteria of microorganisms. The volumes of the anode chamber 12 and the cathode chamber 13 are 64cm3. The anode chamber 12 and the cathode chamber 13 are separated by a diaphragm, 35 carbon felts with the grain size of 0.5cm multiplied by 1cm are respectively arranged in the two chambers,
the anode chamber is provided with an anode water inlet 122 and an anode water outlet 123 for anode liquid or simulated heavy metal waste liquid to enter and exit; an anode electrode 121 is provided. The cathode chamber is provided with a cathode water inlet 132 and a cathode water outlet 133 for cathode liquid to enter and exit; a cathode electrode 131 is provided.
Four corners of the anode chamber baffle, the rubber pad, the anode chamber, the diaphragm 11, the cathode chamber and the cathode chamber baffle are all provided with screw holes, and all parts are fixed by long screws in sequence. An anode electrode insertion opening and a cathode electrode insertion opening are provided, and a cylindrical anode electrode 121 and a cylindrical cathode electrode 131 are vertically inserted into the bottom portions of the anode chamber 12 and the cathode chamber 13 through the anode electrode insertion opening and the cathode electrode insertion opening, respectively, as an anode electrode and a cathode electrode.
The system for monitoring the heavy metals comprises a microbial electrochemical sensor 1(MFCs reactor), a first storage tank 3 containing anode matrix liquid, a second storage tank 4 containing cathode matrix liquid, a peristaltic pump 2, an electrochemical workstation 6, a computer 7, a variable resistance box 5, an external circuit, an ammeter 8 and an external circuit. In order to increase the accuracy, a plurality of groups of microbial electrochemical sensors 1(MFCs reactors) are set to run in parallel, the plurality of groups of microbial electrochemical sensors (MFCs reactors) share the same second storage tank 4, and errors caused by catholyte are reduced. The anode substrate liquid is respectively arranged in different first storage tanks 3, so that respective data monitoring is facilitated. The first storage tank 3 is arranged in a constant-temperature water bath for heating, and the activity of the microbial electrochemical active bacteria is increased. The water inlet pipes of the anode chamber and the cathode chamber feed water into the MFCs reactor through the peristaltic pump 2, the discharged water flows back to the first storage tank 3, and the counter-flow water feeding ensures that the liquid is fully contacted with the attached electrochemical active bacteria in the anode chamber 12. The external varistor box 5 is connected to the anode electrode 121 and the cathode electrode 131 of the reactor, and receives an electric signal through the electrochemical workstation 6. A system for heavy metal monitoring is shown in figure 2.
The microbial electrochemical active bacteria inoculated on the anode indoor electrode and the carbon felt are taken from the active sludge of the SBR process sludge collecting tank of the sewage treatment plant, and the acclimation process of the anaerobic electrogenesis bacteria is as follows: putting 400mL of sludge into a 1L liquid storage tank, adding 600mL of anolyte into 12.5mL of trace elements, mixing, introducing nitrogen for 15min, adding into the liquid storage tank, mounting an aluminum foil gas sampling bag on the liquid storage tank, and placing in a digital display constant temperature water bath kettle at 37.5 ℃ for water bath heating for anaerobic acclimation. When the anaerobic bacteria is operated at constant temperature until gas exists in the sampling bag, the anaerobic fermentation of the anaerobic bacteria is explained to generate methane, the sludge on the appearance is changed into black bottom sludge from red brown turbid liquid and is deposited at the bottom of the liquid storage tank, and the supernatant is arranged at the upper part, namely the acclimation of the anaerobic electrogenic bacteria is completed, and the anaerobic electrogenic bacteria is placed in a constant temperature box for culture and standby.
After the MFCs sensor is built, a layer of biomembrane needs to be attached to the graphite electrode and the carbon felt in the double-chamber MFCs anode chamber, and the microbial electrochemical active bacteria on the biomembrane convert chemical energy into electric signals and transmit the electric signals to a computer, so that the anode liquid storage tank of the constructed microbial electrochemical sensor is replaced by domesticated activated sludge. The MFCs are acclimated for a long time because microorganisms are slowly attached, cathode electrodes are not modified by catalysts, and electrons need to repeatedly accumulate on the surfaces of the electrodes. Inoculating the anode of the reactor, flowing supernatant in an activated sludge bottle into the reactor through a pump, and finishing the attachment of anaerobic electrogenesis bacteria after the output voltage collected by an electrochemical workstation is stabilized to about 0.45V for 3 consecutive days, namely replacing the acclimated sludge with an anode substrate solution.
Anode matrix liquid: in the process of starting and operating the microbial electrochemical sensor reactor, the anode substrate solution needs to be replaced once a day, 1000mL of trace element solution is prepared and added every time, nitrogen is introduced for 15-20min to meet the requirement of anaerobic environment required by anaerobic electrogenesis bacteria, 1/3 bottles of anode substrate solution need to be uniformly and slowly moved and replaced by a rubber tube every day for a 1L liquid storage tank, and a large amount of oxygen is prevented from being dissolved in the anode solution. The anode matrix liquid is not easy to store, and needs to be prepared at present for preventing organic matter loss. The anolyte formulation is shown in the table below.
| Composition (I) | content/(g/L) |
| CH3COONa·3H2O | 1.65 |
| NH4Cl | 0.31 |
| NaH2PO4·12H2O | 1.93 |
| Na2HPO4·2H2O | 1.385 |
| MgSO4·7H2O | 0.1 |
| |
1 |
| CaCl2 | 0.1 |
| KCl | 0.1 |
Note: the solute is water.
Cathode matrix liquid: k3[Fe(CN)6]8.32g/L，NaH2PO4 1.93g/L，Na2HPO4 1.385g/L。
In the starting operation process of the microbial electrochemical sensor reactor, the 2L liquid storage tank of the cathode matrix liquid is replaced once a week.
Trace elements: the formulation of the trace element solution is shown in the following table.
| Composition (I) | content/(mg/L) |
| FeSO4·7H2O | 100 |
| |
70 |
| MnCl2·4H2O | 50 |
| H3BO3 | 6 |
| |
100 |
| CuCl2·2H2O | 2 |
| NiCl2·6H2O | 24 |
| Na2MoO4·2H2O | 36 |
| Na2WO4·2H2O | 24 |
| CoCl2·6H2O | 238 |
Note: the solute is water.
Matrix liquid: NaAc 1.65g/L, NH4Cl 0.31.31 g/L, and nitrogen is introduced for 15-20 min.
The matrix liquid is used for preparing artificial heavy metal wastewater and used as flushing liquid. 2L of the washing liquid is prepared every day, 1L of the washing liquid is used for preparing artificial waste water, and 1L of the washing liquid is used as the washing liquid, so that the preparation on site needs to be used.
Washing liquid: the MFC anode chamber needs to be washed after the heavy metal monitoring is completed every time, the purpose is to prevent the influence of residual heavy metal on the next monitoring, and the MFC anode chamber is not suitable for being washed by deionized water in order to meet the nutritional requirements of anaerobic electrogenic bacteria in the anode chamber and reduce the death of microorganism infiltration. The washing liquid adopted in the experiment only contains sodium acetate and ammonium chloride, and the washing liquid is not easy to store and needs to be prepared at present.
Liquid to be detected: the liquid to be detected is matrix liquid added with heavy metals with different concentrations.
Method for monitoring heavy metal ions by microbial electrochemical sensor
When the heavy metal ion monitoring and the washing are completed, the water discharged from the anode chamber is directly discharged to a waste liquid bottle without returning, as shown in fig. 3.
The inhibition rate of different heavy metal ions on the electricity generation performance of the microbial electrochemical sensor is examined by utilizing microbial electrochemical active bacteria in the microbial fuel cell anode reaction chamber. The concentration gradient of the wastewater is configured by monitoring artificially configured simulated heavy metal wastewater, and the same heavy metal wastewater with the same concentration gradient is monitored in the same reactor. The variation of the output voltage value (Potential) and the anode voltage suppression ratio (Inhibition ratio) were examined. The main experimental procedure is as follows.
1. Before the experiment was started, it was checked whether the four sensor voltages on the Device Test function on the DAQNavi software dropped to around 0.05V.
2. Preparing 2L of anode substrate solution, adding 25mL of trace element solution, oscillating by ultrasonic wave, mixing uniformly, and introducing nitrogen for 15-20 min.
3. The peristaltic pump is closed to replace the anode substrate solution, each of the four anode liquid storage tanks is replaced by 330mL, and the peristaltic pump and the electrochemical workstation are restarted.
4. 2L of prepared matrix liquid is evenly mixed by ultrasonic oscillation, and dissolved oxygen in the matrix liquid is blown off by introducing nitrogen for 15-20 minutes. Then the mixture is put into a constant temperature water bath kettle at 37.5 ℃ and poured into a 250mL liquid storage tank for standby.
5. And restarting the Electrochemical workstation and recording the voltage value after 300s after the CH Instruments electronic Software of the desktop computer selects an OCPT- (Open Circuit Potential-Time) function to monitor the voltage stability of the sensor.
6. And (5) suspending the peristaltic pump and the electrochemical workstation, switching the liquid inlet pipe from the anode matrix liquid to the matrix liquid, and switching the liquid outlet pipe to the waste liquid tank. And (4) restarting the peristaltic pump and operating the electrochemical workstation for 450s, so as to discharge the anode substrate liquid in the anode chamber of the reactor, and recording the recorded voltage value of the electrochemical workstation.
7. After 450s, the liquid outlet pipe is connected into the matrix liquid to smoothly run for 6400 s. The voltage drop should be stable and gentle, the voltage value is recorded, and the peristaltic pump and the electrochemical workstation are suspended.
8. Pouring out 1000mL of the residual matrix liquid in the water bath to a beaker, adding the heavy metal solution into the beaker by using a liquid transfer gun, uniformly mixing for later use, and adding a rotor.
9. Putting 1000mL beaker into 37.5 ℃ heat collection type constant temperature heating magnetic stirrer, connecting liquid inlet pipe, and restarting peristaltic pump and electrochemical workstation. The voltage value, the voltage drop amount and the voltage drop rate are recorded every 10 min.
10. And after the operation time reaches 10000s, stopping the peristaltic pump and the electrochemical workstation, and storing the measured data image.
11. And (4) connecting the liquid inlet pipe into the residual matrix liquid, flushing for 30min to completely flush the reactor with the residual matrix liquid, and restarting the electrochemical workstation.
12. After the washing is finished, the peristaltic pump and the electrochemical workstation are suspended, the liquid inlet and outlet pipe is connected back to the anode liquid storage tank, and the peristaltic pump and the electrochemical workstation are restarted.
Cu is used separately in this experiment2+Cu is added into artificial wastewater with the concentration of 1mg/L, 2mg/L, 4mg/L, 6mg/L and 10mg/L2+Inhibition of microbial electrochemical poison sensor voltage. Adding Cu of different concentrations2+In the time, the monitoring time of the heavy metal toxicity sensing test is 60 minutes, and the change trend of the voltage of the microbial electrochemical sensor and the linear fitting curve of the voltage inhibition rate are shown in fig. 4.
With Cu in the experimental process2+The increase of the concentration and the decrease rate of the output voltage become faster, which shows that the Cu concentration is high2+Can inhibit the activity of anaerobic electrogenesis bacteria in the anode reaction chamber or lead the enzyme of microorganism to be inactivated, and lead the output voltage of the microbial fuel cell to be reduced. Cu2+Suppression Ratio of voltage (Inhibition Ratio) and Cu2+The concentration is directly proportional. In Cu2+When the concentration is too high, the sensor is considered to be failed when the voltage suppression rate is substantially unchanged. The experiment is carried out on Cu2+When the concentration reaches 10mg/L, the inhibition rate of the copper alloy on voltage is 92.95 percent, and the Cu content is improved2+The voltage inhibition rate is basically unchanged at concentration, so Cu is used in the experiment2+The monitoring range of (A) is 0-10mg/L, Cu2+The maximum inhibition rate of the compound reaches 92.95 percent. Cu2+The linear fit equation in the monitoring range is:
YCu＝13.66+7.89XCu
in the formula: y isCuIs Cu2+The output voltage inhibition rate of the microbial electrochemical sensor; xCuIs Cu2+Concentrations, represented by unknowns in the following formula, were consistent. Coefficient of correlation R2A value of 1.00 indicates good correlation performance of the sensor. Cu2+The output voltage rejection ratio for the sensor is shown in fig. 4.
Example 2: system for monitoring heavy metal and microbial electrochemical sensor
The other method is the same as example 1, except that Cd is used in the experiment2+The artificial wastewater with the concentration of 0.25mg/L, 0.5mg/L, 0.75mg/L, 1mg/L and 1.25mg/L is used for researching the addition of Cd2+The inhibition ratio of the voltage of the microbial electrochemical sensor. Adding Cd with different concentrations2+In the time, the monitoring time of the heavy metal toxicity sensing test is 60 minutes, and the change trend of the voltage of the microbial electrochemical sensor and the linear fitting curve of the voltage inhibition rate are shown in fig. 5.
With Cd in the experimental process2+The concentration is increased, the output voltage drop rate is increased, and the high concentration Cd is shown2+Can inhibit the activity of anaerobic electrogenesis bacteria in the anode reaction chamber or lead the enzyme of microorganism to be inactivated, and lead the output voltage of the microbial fuel cell to be reduced. Cd [ Cd ]2+The suppression Ratio (Inhibition Ratio) for voltage is proportional to the ion concentration. In Cd2+When the concentration is too high, the sensor is considered to be failed when the voltage suppression rate is substantially unchanged. This experiment is in Cd2+When the concentration reaches 1.25mg/L, the inhibition rate of the nano-particles on voltage is 73.11 percent, and the Cd content is improved2+The voltage inhibition rate is basically unchanged at concentration, so Cd in the experiment2+The monitoring range of (1) is 0-1.25mg/L, and the maximum inhibition rate reaches 73.11%. Cd [ Cd ]2+The linear fit equation in the monitoring range is:
YCd＝7.09+52.96XCd
in the formula: y isCdIs Cd2+The output voltage inhibition rate of the microbial electrochemical sensor; xCdIs Cd2+Concentration, coefficient of correlation R2A value of 0.98 indicates a sensor pair Cd2+The monitoring performance of (2) is better. Cd [ Cd ]2+The output voltage rejection rate for the sensor is shown in fig. 5.
Example 3: system for monitoring heavy metal and microbial electrochemical sensor
The other method is the same as that of example 1, except that Cr is contained in the alloy6+The artificial wastewater with the concentration of 0.3mg/L, 0.5mg/L, 0.75mg/L, 1mg/L and 1.25mg/L is added for researchInto Cr6+The inhibition ratio of the voltage of the microbial electrochemical sensor. Adding Cr with different concentrations6+The monitoring time of the heavy metal toxicity sensing test is 60 minutes.
With Cr in the experimental process6+The increase of the concentration and the decrease rate of the output voltage become faster, which shows that a certain concentration of Cr6+Can inhibit the activity of anaerobic electrogenesis bacteria in the anode reaction chamber or lead to the enzyme inactivation of microorganisms. Suppression ratio of voltage and Cr6+The concentration is directly proportional. When Cr is present6+When the concentration is too high, the sensor is considered to be failed when the voltage suppression rate is substantially unchanged. This experiment was carried out on Cr6+When the concentration reaches 1.25mg/L, the inhibition rate of the alloy on voltage is 82.76 percent, and the Cr content is improved6+The voltage inhibition rate is basically unchanged at concentration, so Cr in the experiment6+The monitoring range of (A) is 0-1.25mg/L, Cr6+The maximum inhibition rate of the compound reaches 82.76 percent. Cr (chromium) component6+The linear fit equation in the monitoring range is:
YCr＝3.55+65.86XCr
in the formula: y isCrIs Cr6+The output voltage inhibition rate of the microbial electrochemical sensor; xCrIs Cr6+Concentration, coefficient of correlation R20.97, indicating sensor pair Cr6+The real-time monitoring performance is good. Cr (chromium) component6+The output voltage suppression ratio for the sensor is shown in fig. 6.
Example 4: system for monitoring heavy metal and microbial electrochemical sensor
Otherwise, the same procedure as in example 1 was followed, except that the low Hg concentration was used in this example2+The experiment was carried out with artificial wastewater containing Hg2+The addition of Hg was investigated for artificial wastewater concentrations of 0.25mg/L, 0.5mg/L, 0.75mg/L, 1mg/L2+The inhibition ratio of the voltage of the microbial electrochemical sensor. Different concentrations of Hg were added2+The monitoring time of the wastewater and heavy metal toxicity sensing test is 60 minutes, data is recorded every ten minutes, and the change trend of the voltage of the microbial electrochemical sensor and a linear fitting curve of the voltage inhibition rate are shown in figure 7.
During the experiment, the Hg is accompanied with the Hg2+The increase in concentration and the increase in the rate of decrease in output voltage indicate Hg2+Can inhibit the activity of anaerobic electrogenesis bacteria in the anode reaction chamber or lead the enzyme of microorganism to be inactivated, and lead the output voltage of the microbial fuel cell to be reduced. Hg is a mercury vapor2+Suppression ratio of output voltage to Hg2+The concentration is directly proportional. The experiment is in Hg2+When the concentration reaches 1.00mg/L, strong biological toxicity is generated to anaerobic electrogenesis bacteria in the sensor, the electrogenesis performance is reduced, the inhibition rate of the concentration on voltage is 75.8%, therefore, the monitoring range in the experiment is 0-1.00mg/L, and the maximum inhibition rate reaches 75.8%. Hg is a mercury vapor2+The linear fit equation in the monitoring range is:
YHg＝19.02+57.60XHg
in the formula: y isHgIs Hg2+The output voltage inhibition rate of the microbial electrochemical sensor; xHgIs Hg2+Concentration, coefficient of correlation R20.96, indicating sensor pair Hg2+The real-time on-line monitoring performance is good. Hg is a mercury vapor2+The output voltage suppression ratio for the sensor is shown in fig. 7.
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, and any modifications or variations thereof that fall within the spirit of the invention are intended to be included within the scope thereof.
Claims (8)
1. A microbial electrochemical sensor, characterized by: the microbial electrochemical sensor comprises a microbial electrochemical sensor body, wherein the microbial electrochemical sensor body is separated by a diaphragm to form an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are both filled with carbon felt particles; the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber; the diaphragm is a proton exchange membrane or a cation exchange membrane.
2. A system for heavy metal monitoring, characterized by: the device comprises a microbial electrochemical sensor, a first liquid storage tank for containing anode matrix liquid, a second liquid storage tank for containing cathode matrix liquid, a peristaltic pump, an electrochemical workstation, a computer, a resistance-variable box and an external circuit;
the microbial electrochemical sensor comprises a microbial electrochemical sensor body, wherein the microbial electrochemical sensor body is separated by a diaphragm to form an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are both filled with carbon felt particles; the anode chamber is provided with an anode water inlet and an anode water outlet, and an anode electrode is inserted in the anode chamber; the cathode chamber is provided with a cathode water inlet and a cathode water outlet, and a cathode electrode is inserted in the cathode chamber; the anode electrode and the cathode electrode are respectively connected with two poles of the varistor box;
the anode electrode and the carbon felt particles of the anode chamber are both inoculated with anaerobic electrogenic bacteria;
the first liquid storage tank is communicated with an anode water inlet of the anode chamber through a first pipeline, and an anode water outlet of the anode chamber is communicated with the first liquid storage tank through a second pipeline;
the second liquid storage tank is communicated with a cathode water inlet of the cathode chamber through a third pipeline, and a cathode water outlet of the cathode chamber is communicated with the second liquid storage tank through a fourth pipeline;
peristaltic pumps are arranged on the first pipeline and the third pipeline respectively;
the anode electrode and the cathode electrode are electrically connected with an electrochemical workstation, and the electrochemical workstation is in signal connection with a computer.
3. The system for heavy metal monitoring of claim 2, wherein: the filling amount of the carbon felt particles is 100cm2Filling 40-70 grains; the size of the carbon felt particles is 0.5cm x 1 cm.
4. The system for heavy metal monitoring of claim 2, wherein: the domestication method of the anaerobic electrogenesis bacteria comprises the following steps: putting activated sludge in a SBR process sludge collection pool into a first liquid storage tank, mixing an anode substrate liquid and a trace element mixture, introducing nitrogen, adding the mixture into the first liquid storage tank, mounting an aluminum foil gas sampling bag on the first liquid storage tank, placing the first liquid storage tank into a constant-temperature water bath kettle, heating in a water bath at 37.5 ℃ for anaerobic acclimation, and completing acclimation of anaerobic electrogenic bacteria when gas exists in the aluminum foil gas sampling bag; and supernatant in the first liquid storage tank enters the anode chamber from the anode water inlet through the peristaltic pump and then flows back to the first liquid storage tank from the anode water outlet, so that the anaerobic electrogenesis bacteria inoculation can be carried out.
5. The system for heavy metal monitoring of claim 4, wherein: 1.65g of CH per liter of the anode matrix solution3COONa·3H2O, 0.31g NH4Cl, 1.93g of NaH2PO4·12H2O, 1.385g of Na2HPO4·2H2O, 0.1g MgSO4·7H2O, 1g NaHCO30.1g of CaCl2And 0.1g of KCl.
6. The system for heavy metal monitoring of claim 2, wherein: the mixture of trace elements contains 100mg of FeSO per liter4·7H2O, 70mg ZnCl250mg of MnCl2·4H2O, 6mg of H3BO3100mg of CaCl22mg of CuCl2·2H2O, 24mg of NiCl2·6H2O, 36mg of Na2MoO4·2H2O, 24mg of Na2WO4·2H2O and 238mg of CoCl2·6H2O。
7. The system for heavy metal monitoring of claim 2, wherein: per liter of the cathodic matrix liquid: 8.32g of K3[Fe(CN)6]1.93g of NaH2PO4 Per L and 1.385g of Na2HPO4。
8. The system for heavy metal monitoring of claim 2, wherein: the system comprises a plurality of microbial electrochemical sensors which are connected in parallel, wherein the plurality of microbial electrochemical sensors which are connected in parallel share a second liquid storage tank, and each microbial fuel cell reactor uses a first liquid storage tank.
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