CN110967388A - Soil heavy metal in-situ monitor - Google Patents

Soil heavy metal in-situ monitor Download PDF

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CN110967388A
CN110967388A CN201811160158.XA CN201811160158A CN110967388A CN 110967388 A CN110967388 A CN 110967388A CN 201811160158 A CN201811160158 A CN 201811160158A CN 110967388 A CN110967388 A CN 110967388A
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anode
monitor
soil
cathode
anolyte
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CN110967388B (en
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陈振波
栾胜基
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Shenzhen Beiyan Ecological Environment Technology Co ltd
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Center Of Forecasting And Analysis Peking University Shenzhen Graduate School
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
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    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention discloses a soil heavy metal in-situ monitor. The device comprises a single-chamber bioelectrochemical sensing system and a controller; the single-chamber bioelectrochemical sensing system comprises an anode, an anode chamber, a cathode and an ion exchange membrane, wherein the anode is arranged in the anode chamber or outside the anode chamber, the anode chamber is closed or open, and the ion exchange membrane can be a Proton Exchange Membrane (PEM); the controller comprises an external resistor and a data acquisition device; the anode and the cathode are connected with two ends of an external resistor through a circuit, and the data acquisition device is arranged on the circuit. The monitor can be buried in soil for a long time, can realize continuous real-time monitoring of soil heavy metals, and has high automation degree.

Description

Soil heavy metal in-situ monitor
Technical Field
The invention belongs to the field of soil monitoring and treatment, and particularly relates to a soil heavy metal in-situ monitor.
Background
The heavy metal pollution of the soil is a phenomenon that the content of trace metal elements in the soil exceeds a background value and the content of heavy metals is too high and obviously higher than the original content due to excessive deposition and causes the quality deterioration of the ecological environment mainly due to human activities. With the development of urban industrialization, the activities of mining mineral products and smelting are increased, waste water, waste gas and waste residues are greatly discharged, and heavy metals in soil mainly comprise the following four sources: heavy metals entering the soil along with atmospheric sedimentation, heavy metals entering the soil along with sewage, heavy metals entering the soil along with solid wastes, and heavy metals entering the soil along with agricultural materials.
Heavy metals are used as basic elements of natural composition, cannot be completely removed from soil through the effects of degradation, concentration reduction and the like, and can only be treated and recovered through biological enrichment, transfer, precipitation and the like. The soil polluted by heavy metal has the following characteristics: (1) the soil sample is characterized by outstanding concealment and hysteresis, most heavy metal poisons are concealed, and the poisoning can be discovered only by analyzing and testing soil samples and detecting residues of crops; (2) the soil heavy metal fertilizer has the characteristics of biological accumulation, obvious regional limitation on the heavy metal in the soil, and food chain accumulation; (3) irreversibility, the pollution of heavy metal to soil is basically an irreversible pollution process; (4) the soil heavy metal pollution is difficult to be eliminated through dilution and soil self-purification, and sometimes can be solved through methods of soil replacement, soil washing and the like, so that the cost is high, and the treatment period is long.
As is well known, all heavy metals are toxic to human bodies when exceeding a certain concentration, have serious hazards of carcinogenesis, teratogenesis and mutagenesis, and simultaneously can influence the development of plant roots and leaves to cause the heavy metal content of crops to exceed the standard, and the problems of ecological environment safety, food safety and human health caused by the heavy metals are more and more prominent, so the heavy metals in the soil are always the key points of environmental management and monitoring at home and abroad. Therefore, the treatment and monitoring force on the heavy metal pollution of the soil must be increased, and a comprehensive soil heavy metal pollution monitoring and early warning system is established to eliminate the high harm of the heavy metal pollution of the soil to the ecological environment safety and the human health safety.
In the prior art, methods such as a spectrophotometry, an atomic absorption spectrometry, an atomic fluorescence spectrometry, an inductively coupled plasma atomic emission spectrometry, and an inductively coupled plasma mass spectrometry are usually adopted to analyze and detect heavy metal elements in soil, but the methods usually require pretreatment of heavy metal samples in soil, such as wet digestion, dry ashing, microwave digestion, and the like, the treatment process is complicated, the time consumption is long, and the existing methods are difficult to realize in-situ monitoring of heavy metals in actual soil. Therefore, there is a need to develop an in-situ soil heavy metal monitor to overcome the above problems in the prior art.
Disclosure of Invention
The invention provides a soil heavy metal in-situ monitor, which comprises a single-chamber bioelectrochemical sensing system and a controller;
wherein the single-chamber bioelectrochemical sensing system comprises an anode chamber, an anode, a cathode and an exchange membrane between the anode and the cathode;
the controller comprises an external resistor and a data acquisition device;
the anode and cathode are connected across an external resistance (e.g., a variable resistor) by a circuit, and the data acquisition device is connected to the circuit.
According to an embodiment of the invention, the monitor may be used for monitoring or detection.
According to an embodiment of the present invention, there is no particular limitation on the specific position of the anode, and for example, the anode may be disposed inside the anode chamber or outside the anode chamber.
According to an embodiment of the present invention, the anode chamber may be closed or open.
According to an embodiment of the present invention, a cathode catalyst may also be included on the cathode. For example, the cathode may be coated with a cathode catalyst.
According to an embodiment of the invention, the exchange membrane may be selected from Proton Exchange Membranes (PEM).
According to embodiments of the invention, the exchange membrane may or may not be in contact with the anode and/or the cathode. When in contact, the exchange membrane may be attached to the anode and/or cathode.
According to an embodiment of the invention, the anode chamber comprises a microorganism and an anolyte.
According to an embodiment of the invention, the single-chamber bioelectrochemical sensing system is a system that has been acclimated to an internal resistance after acclimation of 1500 ohms or less, such as 13000 ohms or less, such as 1000 ohms or less or 500 ohms or less, such as 10-500 ohms, 50-100 ohms or 50-200 ohms.
The inoculation and domestication can be carried out in the following way: inoculating the anode of the monitor by adopting anaerobic sludge of a sewage treatment plant, and culturing by adopting anolyte taking sodium acetate as a substrate; after nitrogen is introduced into anolyte to remove air, the anolyte is mixed with anaerobic sludge in the anode chamber, and a circuit between the cathode and the anode is disconnected for a certain time and then is connected; supplementing anolyte to required concentration, and performing acclimation for a certain time.
According to an embodiment of the present invention, the single-compartment bioelectrochemical sensing system may include an anode compartment, an anode located inside or outside the anode compartment, a cathode, and an exchange membrane separating the anode compartment from the cathode.
According to an embodiment of the invention, the membrane may form a closed cavity together with other walls of the anode compartment when the anode is located in the anode compartment.
According to the embodiment of the invention, the distance between the anode and the cathode can be adjusted according to the sample condition, so long as the internal resistance of the single-chamber bioelectrochemical sensing system meets the requirements.
According to an embodiment of the invention, in the single-chamber bioelectrochemical sensing system, the distance between the anode and the cathode is fixed or adjustable. When the distance between the anode and the cathode is fixed, the anode and the cathode can be pressed with an exchange membrane between the anode and the cathode. When the distance between the anode and the cathode is adjustable, the distance can be adjusted in various forms, for example, in one of the following ways: the anode is connected with the cathode through a bracket with adjustable length, the cathode is connected with the anode chamber through a bracket with adjustable length, or the anode is connected with the anode chamber through a bracket with adjustable length.
According to an embodiment of the present invention, the single-compartment bioelectrochemical sensing system further comprises a liquid storage device connected to the anode compartment. Preferably, the liquid storage device contains an anolyte or a concentrate of an anolyte.
According to embodiments of the present invention, the liquid storage device may be fixedly mounted or removably mounted on the anode chamber.
According to an embodiment of the invention, a regulating valve may be provided in the connection of the fluid storage device to the anode chamber to control the rate at which the contents of the fluid storage device enter the anode chamber.
According to an embodiment of the present invention, the two ends of the external resistor connecting the cathode and the anode are respectively connected to the data acquisition device, for example, the two ends are respectively connected to the dc input and the ground port of the data acquisition device.
According to an embodiment of the present invention, there is no particular limitation on the resistance value of the external resistance as long as the presence of the external resistance does not cause the collected data to fall below the detection limit of the data collecting means. As an example, the resistance value of the external resistor may be 10 to 1500 ohms, for example, 100 to 1100 ohms.
According to an embodiment of the present invention, the data acquisition device may include a voltage detection element. Further, the data acquisition device may also include a data recording element, and optionally a data analysis element and/or a display, either present or absent. Preferably, the voltage detecting element and the data recording element can automatically and continuously record the voltage across the resistor. For this purpose, the data acquisition device may also preferably comprise an automatic control element which controls the voltage detection and data recording. As an example, the data acquisition device may include one, two or more of the following: potential monitors for the anode and cathode; a potential adjuster of the cathode; calculating anode and cathode potential difference data; and a transmission device for potential difference data.
Optionally, the monitor of the present invention may further include a wireless transceiver and a remote control terminal, wherein the wireless transceiver is electrically connected to the data acquisition device, and is configured to transmit the data acquired by the data acquisition device to the remote control terminal in real time through a wireless network.
Optionally, the monitor of the present invention may further comprise an anodic biosensor. The biosensor monitors electrolyte conditions and generates a signal when it changes, which can be connected to a data acquisition device. Preferably, when an anodic biosensor is present, a reference electrode connected to the data acquisition device may also be provided.
The monitor according to the invention, wherein the anode material and the cathode material are preferably inert materials. For example, the anode material and the cathode material may be independently selected from carbon, graphite, and specifically may be one, two or more of, for example, carbon cloth, graphite felt, graphite particles, graphite rods, graphite disks, and may also be selected from inert non-metals or metals, for example, one, two or more of inert metals such as carbon, graphite, silver, platinum, and the like.
According to the monitor of the invention, the microorganism is an electrogenic microorganism, preferably an electrogenic anaerobic microorganism, for example one, two or more species selected from the group consisting of α -Proteus, β -Proteus, delta-Proteus, Clostridium, Shewanella (e.g. MR-1, DSP-10), Shewanella putrefaciens (e.g. SR-21, IR-1, MR-1), Aeromonas hydrophila, Clostridium butyricum, Geobacillus (e.g. Thiodermatophilus, Geobacillus KN400), iron-reducing Rhodococcus erythrorhizogenes, Desulfotproprionalis proprionate, Octobiumlessus anthropi YZ-1, Bacillus PTH1, Escherichia coli K12HB101, Corynebacterium, Aeromonas hydrophila MFC03, Pediobolus licheniformis SP-6, Bacillus licheniformis, Bacillus, Thermobacter propriocellus, Spirulina, Bacillus subtilis, enterococcus gallinarum, Acetobacter aceti, Staphylococcus aureus, as examples.
The anolyte of the present invention comprises an aqueous solution of a substrate, a nutrient, and an electrolyte, the substrate comprising a small molecule organic, a large molecule organic, or a mixture thereof. For example, the small molecule organic includes, but is not limited to, one, two or more of glucose, sodium acetate, acetic acid, lactic acid, propionic acid, and the like. For example, the macromolecular organic substance includes, but is not limited to, one, two or more of peptone, beef extract, starch, and cellulose-like substance. For example, the nutrient is one, two or more of a soluble ammonium salt (e.g., ammonium chloride), a soluble phosphate salt (e.g., monopotassium phosphate), a vitamin, and a mineral. For example, the electrolyte includes, but is not limited to, soluble alkali metal salts (e.g., sodium bicarbonate, sodium chloride, potassium chloride), soluble alkaline earth metal salts (e.g., magnesium chloride, calcium chloride), and the like.
As an example, the composition of the anolyte may include sodium acetate, sodium chloride, magnesium chloride, anhydrous disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium chloride, formulated as a solution from distilled water, with a pH between 7.2 and 7.4.
As a specific example, the composition of the anolyte may be: 1536mg/L of sodium acetate, 1500mg/L of sodium chloride, 330mg/L of magnesium chloride, 10442mg/L of anhydrous disodium hydrogen phosphate, 4800mg/L of sodium dihydrogen phosphate and 375mg/L of ammonium chloride, preparing a solution from distilled water, and adjusting the pH to 7.2-7.4.
The concentrated solution concentration of the anolyte may be 2 to 50 times, for example 10 to 20 times, that of the anolyte and subjected to pressure steam sterilization.
The anode potential monitor and the cathode potential monitor can take various forms according to the requirements of different test environments. For example, an anode potential monitor for monitoring the anode potential and an anode potential monitor for monitoring the cathode potential and a cathode potential monitor for monitoring the cathode potential, respectively, may be provided; or alternatively, the anode potential monitor and the cathode potential monitor may be integrated into one monitor.
According to one embodiment of the invention, the potential monitor and the potential regulator may optionally be integrated in the same device.
The cathode catalyst may be selected from one, two or more of manganese dioxide, a conductive polymer, a polyelectrolyte, or a composite catalyst thereof with a carbon nanomaterial, the manganese dioxide may be selected from one or more of α -manganese dioxide, β -manganese dioxide, gamma-manganese dioxide, the conductive polymer may be one, two or more of polypyrrole, polythiophene, polyphenyl, polyacetylene, polyaniline, polyphenylacetylene, etc., the polyelectrolyte may be, for example, polyquaternium such as polydiallyldimethylammonium chloride, polyquaternium urea-containing polymers, etc., inorganic species such as polyphosphates, etc., and natural nucleic acids, proteins, etc.
According to an embodiment of the invention, the heavy metals include, but are not limited to, cations or their oxyanion forms selected from one, two or more of the following: fe. Ni, Zn, Hg, Cr, As, Co, Cu, U, Mn, Mo, Cd, Pb, Ag, Au, Pd, Pt, Rh, Ir, Re.
According to embodiments of the present invention, the cations of the heavy metal include cations containing any possible valence state of the heavy metal element, including but not limited to one, two or more selected from the group consisting of: fe3+、Ni2+、Zn2+、Hg2+、Hg+、Cr6+、Cr5+、Cr4+、Cr3+、Cr2+、As5+、As3+、Co2+、Co3+、Cu2+、Cu+、UO2 2+、Mn2+、Mn7+、Mo6+、Cd2+、Pb2+、Ag+、Au2+、Au+、Pd4+、Pd2+、Pt4+、Pt2+、Rh2+、Ir3+、Re3+
According to an embodiment of the invention, the heavy metal in the form of an oxygen-containing cation may be, for example, VO2 +、Cr2O7 2-And the like.
The invention also provides a using method of the soil heavy metal in-situ monitor, which comprises the following steps:
a) inoculating the anode of the monitor by adopting anaerobic sludge of a sewage treatment plant, and culturing by adopting anolyte taking sodium acetate as a substrate; after nitrogen is introduced into the anolyte to remove air, the anolyte is mixed with anaerobic sludge in the anode chamber, and a circuit between the cathode and the anode is disconnected for 2 days and then is connected; supplementing anolyte to required concentration, and performing acclimation for 3 weeks to obtain an acclimated and started monitor;
b) adjusting the humidity of the tested soil sample if necessary;
c) burying the acclimatized and started monitor in a tested soil sample, and compacting the soil to ensure that the soil is fully contacted with a cathode;
d) the voltage in the circuit is measured using a data acquisition device.
According to the using method of the invention, after the system generates the response signal, the type and the concentration of the heavy metal can be judged by the molar ratio of the output electric quantity to the metal ions.
The moisture content of the soil is 15% or more, for example, 20% or more, 40% or more. If necessary, the soil can be moistened by water when the water content is insufficient.
The invention also provides application of the soil heavy metal in-situ monitor in-situ monitoring of soil heavy metal content.
Advantageous effects
The single-chamber bioelectrochemical sensing system technology is applied to actual soil monitoring containing various heavy metal ions, a device capable of carrying out in-situ monitoring on an actual soil sample is developed for the first time, and the single-chamber bioelectrochemical sensing system has the advantages of low cost, energy conservation, low consumption, environmental friendliness, easiness in practicability and the like. On the basis of researching the MFC cathode reduction reaction influence factors, the invention quantifies the MFC cathode reduction reaction influence factors by means of a mathematical model, deeply discusses the MFC cathode reduction heavy metal mechanism, further optimizes the MFC design and operation parameters, and enlarges the application range of the MFC cathode reduction reaction influence factors in the aspects of soil pollution monitoring and treatment.
The technical scheme of the invention combines experimental chemistry and mathematical simulation, verifies each other and has the function of selectively monitoring the target heavy metal pollutants; and the monitor is directly inserted into the soil, so that the heavy metal concentration of the soil can be detected without pretreating the soil. The monitoring instrument can be buried in soil for a long time, can realize continuous real-time monitoring of soil heavy metals, is high in automation degree, and can transmit monitoring data to a remote control terminal in real time by utilizing a data acquisition device.
In addition, the system can also operate by itself or provide energy to each other under the condition of no external power supply. The invention does not need to use toxic reagents and can realize continuous monitoring.
Drawings
FIG. 1 is a schematic structural diagram of the in-situ soil heavy metal monitor according to embodiment 1, wherein the reference numerals have the following meanings: 1-anode, 2-cathode, 3-proton exchange membrane, 4-microorganism, 5-external resistance, 6-data acquisition device, 7-anode chamber, 8-liquid storage device and 10-reference electrode.
Fig. 2 is a schematic structural diagram of the soil heavy metal in-situ monitor according to embodiment 2, wherein the reference numerals have the following meanings: 1-anode, 2-cathode, 3-proton exchange membrane, 4-microorganism, 5-external resistance, 6-data acquisition device, 7-anode chamber, 8-liquid storage device, 9-length-adjustable support and 10-reference electrode.
Fig. 3 and 4 are graphs of the test results of example 3, in which the upper point and curve (#3) are for 1000 ohm sampled data and the lower point and curve (#1) are for 1250 ohm sampled data.
FIG. 5 is a graph showing the test results of example 4.
Detailed Description
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents described are all commercially available products.
Example 1
The structure of the in-situ soil heavy metal monitor of the embodiment is shown in fig. 1, and the in-situ soil heavy metal monitor comprises a single-chamber bioelectrochemical sensing system and a controller.
The single-chamber bioelectrochemical sensing system comprises an anode 1, a cathode 2, an anode chamber 7 and a proton exchange membrane (PEM, Nafion 117)3, wherein the anode 1 is a graphite felt, the cathode 2 is carbon cloth, and the anode chamber 7 is a cavity made of a five-faced acrylic material and contains microorganisms and anolyte.
The anode 1 is arranged outside the anode chamber 7 and connected with the anode chamber through a lead, the proton exchange membrane 3 is arranged between the anode 1 and the cathode 2, and the anode 1, the proton exchange membrane 3 and the cathode 2 are pressed together and arranged outside the anode chamber 7 and are connected and sealed with the cavity and the square end plate through rubber gaskets. The openings of the end plates are within the chamber opening of the anode chamber 7 so that gas and liquid inside and outside the chamber can communicate through the electrodes and the membrane.
The controller comprises an external resistor 5 and a data acquisition device 6; the anode 1 and the cathode 2 are connected to both ends of an external resistor 5 through a circuit, and a data acquisition device 6 is connected to the circuit. The data acquisition device is additionally connected to a reference electrode 10 in the anode compartment.
The liquid storage device 8 is a sterilized container which contains concentrated solution of the anode liquid. The liquid storage device 8 is connected to the anode chamber 7 and a flow rate regulating valve is provided at the connection to control the concentration of the anolyte in the anode chamber by controlling the flow rate of the concentrate.
In this example, the concentrations of each substance in the anolyte were 1536mg/L sodium acetate, 1500mg/L sodium chloride, 330mg/L magnesium chloride, 10442mg/L disodium hydrogenphosphate, 4800mg/L sodium dihydrogenphosphate, and 375mg/L ammonium chloride, and the anolyte was prepared as a solution in distilled water, and the pH was adjusted to 7.2 to 7.4. The concentrated solution concentration of the anolyte is 10 times of that of the anolyte, and the anolyte is sterilized by pressure steam at 121 ℃ for 20 min.
Example 2
The structure of the in-situ soil heavy metal monitor of the embodiment is shown in fig. 2, and the in-situ soil heavy metal monitor comprises a single-chamber bioelectrochemical sensing system and a controller.
The single-chamber bioelectrochemical sensing system comprises an anode 1, a cathode 2, an anode chamber 7 and a Proton Exchange Membrane (PEM)3, wherein the anode 1 is a graphite felt, the cathode 2 is a carbon rod, and the anode chamber 7 is a cavity made of a five-faced acrylic material and contains microorganisms and anolyte.
The anode 1 is arranged in the anode chamber 7, and the proton exchange membrane 3 closes the cavity of the anode chamber 7. The cathode 2 is positioned outside the anode chamber 7 and is connected with the anode chamber 7 through a bracket 9 with adjustable length so as to adjust the distance between the anode and the cathode according to the condition of a sample to be measured.
The controller comprises an external resistor 5 and a voltage data acquisition Device (DAQ) 6; the anode 1 and the cathode 2 are connected to both ends of an external resistor 5 through a circuit, and a data acquisition device 6 is connected to the circuit. The data acquisition device is additionally connected to a reference electrode 10 in the anode compartment.
The anolyte and anolyte concentrate were the same as in example 1.
Example 3 in situ monitoring of soil heavy metal content using the monitor of example 2
Inoculation and domestication: the monitor of example 2 was used, and the monitor anode was inoculated with two types of anaerobic sludge from a sewage treatment plant and cultured in anolyte with sodium acetate as substrate. And introducing nitrogen into the anolyte to remove air, mixing the anolyte with anaerobic sludge in the anode chamber, disconnecting a circuit between a cathode and an anode, connecting the anolyte after 2 days, supplementing the anolyte with sodium acetate with the concentration lower than 500mg/L to keep the concentration of sodium acetate between 500 plus materials and 1000mg/L, inoculating and domesticating for 3 weeks, and measuring the open-circuit voltage of the device to be 550mV and 620mV respectively to obtain a domesticated and started monitor, wherein the internal resistances of the monitor after two kinds of sewage treatment plant anaerobic sludge domestication are 1250 ohm and 1000 ohm respectively.
The humidity of the tested soil sample is 15%, and the acclimatized and started monitoring instrument is buried in the soil sample containing copper ions (Cu) with different concentrations2 +) Compacting the soil to be detected to ensure that the soil is fully contacted with the cathode. Cu2+The concentration is 0-65mg/L, wherein 0 is a baseline control sample. 1010 ohm external resistance is connected between the cathode and the anode, the voltage at two ends of the resistance is measured, and after the data correction of the reference electrode, the test result is shown in figures 3 and 4, wherein the upper point and the curve in the figures are used for data of 1000 ohm, and the lower point and the curve are used for data of 1250 ohm. The data show that the output voltage signal of the monitor changes with the concentration of copper ions in soil, and the linear range is 0-65 mg/L.
Example 4 in situ monitoring of soil heavy metal content using the monitor of example 1
Inoculation and domestication: the monitor of example 1 was used, and the monitor anode was inoculated with anaerobic sludge from a sewage treatment plant and cultured with anolyte solution containing sodium acetate as a substrate. And (3) introducing nitrogen into the anolyte to remove air, mixing the anolyte with anaerobic sludge in the anode chamber, disconnecting a circuit between the cathode and the anode, connecting the anolyte after disconnecting the circuit for 2 days, supplementing the anolyte with sodium acetate concentration lower than 500mg/L to keep the sodium acetate concentration between 500 and 1000mg/L, inoculating and domesticating for 3 weeks, measuring the open-circuit voltage of the device to be 600mV, and obtaining a monitor started by domestication, wherein the internal resistance of the monitor is 95 ohms.
The humidity of the tested soil sample is 20%, and the acclimatized and started monitor is buried in the soil sample containing copper ions (Cu) with different concentrations2 +) Compacting the soil to be detected to ensure that the soil is fully contacted with the cathode. Cu2+The concentration is 0-200mg/L, wherein 0 is a baseline control sample. The 1000 ohm external resistance is connected between the cathode and the anode, the voltage at two ends of the resistance is measured, and after the data correction of the reference electrode, the result is shown in figure 5, and the result shows that: the output voltage signal of the monitor changes with the concentration of copper ions in soil, and the linear range is 0-150 mg/L.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A soil heavy metal in-situ monitor comprises a single-chamber bioelectrochemical sensing system and a controller;
wherein the single-chamber bioelectrochemical sensing system comprises an anode chamber, an anode, a cathode and an exchange membrane between the anode and the cathode;
the controller comprises an external resistor and a data acquisition device;
the anode and cathode are connected across an external resistance (e.g., a variable resistor) by a circuit, and the data acquisition device is connected to the circuit.
2. The monitor of claim 1, wherein the anode is disposed within the anode chamber or outside the anode chamber; the anode chamber is closed or opened; the exchange membrane is selected from Proton Exchange Membranes (PEM).
3. The monitor of claim 1 or 2, wherein the anode chamber includes microorganisms and anolyte;
preferably, the microorganism is an electrogenic microorganism, preferably an electroanaerobic microorganism, for example one, two or more species selected from the group consisting of α -Proteus, β -Proteus, delta-Proteus, Clostridium, Shewanella (e.g., MR-1, DSP-10), Shewanella putrefaciens (e.g., SR-21, IR-1, MR-1), Aeromonas hydrophila, Clostridium butyricum, Geobacillus (e.g., Acinetobacter thioredoxin, Geobacillus KN400), Rhodorhizogenes ferrugineus, sulfolobus propionicum, Xanthium anthropi YZ-1, Bacillus PTH1, Escherichia coli K12HB101, Corynebacterium, Aeromonas hydrophila MFC03, Fibrobacter licheniformis SP-6, Bacillus subtilis, Bacillus thermotolerant Bacillus, Spirulina, Bacillus gallinarum, Acetobacter aceticus, Staphylococcus aureus;
preferably, the anolyte comprises an aqueous solution of a substrate, a nutrient and an electrolyte,
preferably, the substrate comprises a small molecule organic, a large molecule organic, or a mixture thereof;
preferably, the nutrient is one, two or more of soluble ammonium salt, soluble phosphate, vitamin and mineral;
preferably, the electrolyte includes, but is not limited to, one, two or more of soluble alkali metal salts and soluble alkaline earth metal salts.
4. The monitor according to any one of claims 1 to 3, wherein the single-chamber bioelectrochemical sensing system is an inoculated and acclimated system, and the internal resistance after inoculation and acclimation is below 1500 ohms.
5. The monitor according to any one of claims 1 to 4, wherein the distance between the anode and the cathode is fixed or adjustable.
6. The monitor according to any one of claims 1-5, wherein the single-compartment bioelectrochemical sensing system further comprises a liquid storage device, the liquid storage device being connected to the anode compartment;
preferably, the liquid storage device contains an anolyte or a concentrate of an anolyte;
preferably, a regulating valve may be provided in the connection passage between the fluid storage means and the anode chamber to control the rate at which the contents of the fluid storage means enter the anode chamber;
preferably, the composition of the anolyte may include sodium acetate, sodium chloride, magnesium chloride, anhydrous disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium chloride, formulated as a solution from distilled water, with a pH between 7.2 and 7.4.
7. The monitor according to any one of claims 1 to 6, wherein the external resistor is connected with the data acquisition device at two ends of the cathode and the anode respectively;
the data acquisition device comprises a voltage detection element;
preferably, the monitor further comprises a wireless transceiver and a remote control terminal, wherein the wireless transceiver is electrically connected with the data acquisition device and is used for transmitting the data acquired by the data acquisition device to the remote control terminal in real time through a wireless network;
preferably, the monitor further comprises an anodic biosensor which monitors electrolyte conditions and generates a signal when there is a change in the electrolyte conditions.
8. A method of using the monitor of any one of claims 1 to 7, comprising:
a) inoculating the anode of the monitor by adopting anaerobic sludge of a sewage treatment plant, and culturing by adopting anolyte taking sodium acetate as a substrate; after nitrogen is introduced into the anolyte to remove air, the anolyte is mixed with anaerobic sludge in the anode chamber, and a circuit between the cathode and the anode is disconnected for 2 days and then is connected; supplementing anolyte to required concentration, and performing acclimation for 3 weeks to obtain an acclimated and started monitor;
b) adjusting the humidity of the tested soil sample if necessary;
c) burying the acclimatized and started monitor in a tested soil sample, and compacting the soil to ensure that the soil is fully contacted with a cathode;
d) the voltage in the circuit is measured using a data acquisition device.
9. Use according to claim 8, wherein the moisture content of the soil is above 15%, preferably above 40%, and the soil is wettable with water when the moisture content is insufficient.
10. Use of the monitor according to any one of claims 1 to 7 for in situ monitoring of the heavy metal content of soil.
CN201811160158.XA 2018-09-30 2018-09-30 Soil heavy metal in-situ monitor Active CN110967388B (en)

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