CN106645319A - Soil heavy metal detection method and system based on integrated micro-sensor - Google Patents
Soil heavy metal detection method and system based on integrated micro-sensor Download PDFInfo
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- CN106645319A CN106645319A CN201610899449.5A CN201610899449A CN106645319A CN 106645319 A CN106645319 A CN 106645319A CN 201610899449 A CN201610899449 A CN 201610899449A CN 106645319 A CN106645319 A CN 106645319A
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- G—PHYSICS
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
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Abstract
The invention discloses a soil heavy metal detection method and system based on an integrated micro-sensor. The soil heavy metal detection method disclosed by the invention comprises the following steps: firstly, carrying out extraction treatment on a soil sample, and injecting a filtered soil extraction solution into a sensor sample tank; secondly, carrying out quantitative and qualitative detection on heavy metal including lead and cadmium in soil by adopting a differential pulse stripping voltammetry technology. The soil heavy metal detection method is matched with a heavy metal rapid detector for use, so that rapid and real-time detection on the lead and the cadmium is realized; the soil heavy metal detection method has the characteristics of high practicability, convenience for carrying, high detection precision, rapid analysis speed, easiness of operation and the like, and is very suitable for carrying out on-site rapid detection on heavy metal pollutants in the soil. The soil heavy metal detection system comprises the integrated micro-sensor and the heavy metal rapid detector, is simple and ingenious in design, has high integration, and has the advantages of compact structure, small size, convenience for carrying, low cost, high sensitivity, high anti-interference capability and the like; meanwhile, the cross contamination problem of samples, caused by the fact that a traditional sensor is used for a plurality of times, is avoided.
Description
Technical field
The present invention relates to a kind of heavy metal-polluted soil detection method and system based on integrated microsensor, belongs to environmental pollution
Analyte detection technical field.
Background technology
In recent years, heavy metal pollution of soil problem has attracted increasing attention.Heavy metal has as many as tens of kinds, wherein lead
It is the one-level environmental contaminants that World Health Organization (WHO) is assert with cadmium, primarily as mining, industrial wastewater discharge and containing weight
The use of the fertilizer and pesticide of metal is entered in soil environment.Heavy metal is difficult to decompose in soil, can lead to after being absorbed by plants
Food chain is crossed in human body body, jeopardizes human health.In real time, rapidly the lead and cadmium element in soil detected and is divided
Analysis, for the agriculture home environment safety of guarantee and agricultural product quality and safety have very important significance.
Traditional heavy metal-polluted soil detection method is that Hou Song specialized laboratories are sampled to soil, using atomic absorption light
Spectrometry (AAS), atomic emission spectrometry (AES), inductively coupled plasma mass spectrometry (ICP-MS) etc. are detected.These sides
Method all has preferable detection sensitivity and an accuracy, but major defect be big, expensive equipment instrument, length analysis time,
Flow process is complicated.China's area is vast, is badly in need of a kind of method that is quick, cheap, being easy to operation and heavy metal pollution of soil is entered
Row quick detection and assessment.The sensor that Conventional electrochemical heavy metal analysis are adopted is bar-shaped glass-carbon electrode, and volume is big, cost
Height, needs to be polished before use, is also easy to cause the pollution of sample during reuse.Traditional electrode is needed when in use
Special electrolyzer is equipped with, equipment cost is further increased, the portability of equipment is reduced and for field measurement
Operability.
The content of the invention
For the deficiencies in the prior art, the present invention proposes a kind of heavy metal-polluted soil detection side based on integrated microsensor
Method and system, can not only quickly, accurately, easily carry out the detection of heavy metal, and detection means have be easy to carry, valency
The characteristics of lattice are cheap and easy to use.
The present invention solves its technical problem and adopts the technical scheme that：A kind of heavy metal-polluted soil based on integrated microsensor
Detection method, is characterized in that, including procedure below：
First, soil sample extraction is processed：
First by 80 DEG C of the examined soil Jing drying 1h of collection, crushed using mortar and cross 80 mesh sieves after grinding, made
Uniform powder soil sample；
Then 1g powder soil samples are weighed, acetic acid and citric acid 1 that 40ml concentration is 0.2mol/L is added:1 mixing
Solution, and carry out ultrasound extraction process 1h；
Finally the sample solution after extraction process is filtered twice using 0.2um filters, and adopted 0.2mol/L
Sodium-acetate buffer adjusts sample solution pH value to 4.5；
2nd, heavy metal analysis：
The sample solution that pH value is 4.5 is directly injected in the sample pool of integrated microsensor first, integrated microsensor
Working electrode, reference electrode and to electrode be located at sample pool inner bottom part；
Then the electrode cable of integrated microsensor is connected with heavy metal detector, using differential pulse Stripping Voltammetry skill
Art carries out Electrochemical Detection, and detection parameter is：Deposition potential -1.2V；Sedimentation time：120s, scans take-off potential -1.2V；Sweep
Retouch end current potential 0V；Rate of scanning：20Hz；Scanning impulse amplitude：50mV；Scanning impulse width：20mV；Scan amplitude：50mV；
Scanning stepping potential：5mV；
The Stripping Voltammetry figure and heavy metal analysis result of acquisition are stored and shown by last heavy metal detector.
Further, the employing differential pulse Stripping Voltammetry technology carries out the process of Electrochemical Detection including following step
Suddenly：
S1. wire and heavy metal analysis are passed through respectively by the working electrode of integrated microsensor, reference electrode and to electrode
Instrument be connected；
S2., detection parameter is set；
S3. heavy metal detector produces voltage excitation signals and is loaded into the reference electrode of integrated microsensor and to electrode
On；
S4. heavy metal detector collecting work electrode is produced in detection process current signal is simultaneously carried out to current signal
Differential pulse voltammetry is detected；
S5. heavy metal detector will obtain Stripping Voltammetry figure and heavy metal analysis result is stored and shown.
Further, the display process of Stripping Voltammetry figure and heavy metal analysis result is：By Stripping Voltammetry figure according to advance
Linear relationship between the heavy metal concentration and peak current of foundation carries out quantitative analyses to lead and cadmium, and is lied prostrate using leaching ability of heavy metal
Pacify curve to represent, the dissolution of the dissolution peak correspondence heavy metal cadmium of -0.8V or so, -0.6V or so on leaching ability of heavy metal volt-ampere curve
Peak correspondence heavy metal lead.
Present invention also offers a kind of heavy metal-polluted soil detecting system based on integrated microsensor, is characterized in that, including
Integrated microsensor and heavy metal detector,
Integrated microsensor is made up of a cylindric sample pool and a lamellar microelectrode, and lamellar microelectrode is using mixing
Printing slurry is made by silk-screen printing technique, working electrode, reference electrode is provided with lamellar microelectrode and to electrode, described
Working electrode is the disc working electrode for being arranged on cylindric sample pool bottom centre position, the periphery of disc working electrode
Be circular arc strip reference electrode and circular arc strip to electrode, the circular arc strip reference electrode and circular arc strip are located at circle to electrode
Both sides of plate-like working electrode and symmetrical with regard to discoid working electrode end；The working electrode, reference electrode and to electrode pair
Electrode cable should be connected with；The surface of the working electrode is respectively arranged with inside-out p-aminobenzene sulfonic acid polymeric membrane and bismuth
Metallic film；
The heavy metal detector includes signal processing circuit, D and D/A converter and controller；The signal processing
Circuit is acquired and is sent to mould to the current signal that the working electrode to integrated microsensor is produced in detection process
Number/digital to analog converter, and it is loaded into the reference electrode of integrated microsensor to the voltage excitation signals for sending controller
With on electrode；The D and D/A converter includes analog-digital converter and digital to analog converter, and the analog-digital converter is to incite somebody to action
The current signal that signal processing circuit sends is carried out being sent to controller after analog digital conversion and carries out differential pulse voltammetry detection；It is described
Digital to analog converter carries out digital-to-analogue conversion and is sent to signal processing circuit to the voltage excitation signals produced to controller；It is described
Controller is producing voltage excitation signals and be sent to signal processing circuit by analog-digital converter, and current signal is entered
Row carries out differential pulse voltammetry detection and obtains Stripping Voltammetry figure and heavy metal analysis result after processing.
Preferably, the signal processing circuit includes voltage follower circuit, current buffering circuit, current/voltage-converted electricity
Road and filter circuit, the voltage follower circuit is connected respectively with reference electrode and digital to analog converter, controller to be sent
Voltage excitation signals be loaded on reference electrode；The current buffering circuit respectively with electrode and controller are connected, to
To the electric current on electrode is conducted and is buffered；One end of the current/voltage converter circuit is connected with working electrode, another
After filtering circuit is connected with analog-digital converter at end, and the weak current produced in detection process to collecting work electrode is believed
Number, and current/voltage-converted and signal amplification, Filtering Processing are carried out to current signal.
Preferably, the voltage follower circuit adopts OPA124 operational amplifiers, to ensure the potential of reference electrode with
Change with the output voltage of voltage excitation signals, while ensureing to pass through without electric current on reference electrode；The current buffering circuit
Using OPA2277 operational amplifiers, to derive and buffering to providing electrode electric current；The current/voltage converter circuit bag
Reverse operational amplification circuit, analog multiplexer and feedback resistive network are included, the reverse amplification circuit adopts OP07 computings
Amplifier, the analog multiplexer adopts MAX308 analog multiplexers, and the feedback resistive network is by a 100K
Ω resistance, a 1M Ω resistance, a 10M Ω resistance and a 100M Ω resistance composition；The filter circuit is by a 10K Ω
Resistance and a 1 μ F electric capacity composition.
Preferably, the controller includes processor, memorizer, display screen and operation button, described memorizer, display
Screen and operation button are connected respectively with processor, and the processor is to produce voltage excitation signals, and the work for receiving collection
Make the current signal that electrode is produced in detection process, and carry out after processing current signal differential pulse voltammetry detection obtain
Obtain Stripping Voltammetry figure and heavy metal analysis result；The memorizer is to store Stripping Voltammetry figure and heavy metal analysis result；Institute
Display screen is stated to show Stripping Voltammetry figure and heavy metal analysis result；The operation button is grasped to arrange parameter and function
Make.
Present invention also offers a kind of lamellar microelectrode manufacture method for being applied to integrated microsensor, is characterized in that, institute
It is the integrated microsensor for being applied to heavy metal-polluted soil detecting system described above to state integrated microsensor, the system of lamellar microelectrode
Make method including procedure below：
A () prepares respectively working electrode, the printing slurry to electrode and reference electrode；
B () prints respectively discoid working electrode, circular arc bar first with screen process press on teflon substrate
Then shape reference electrode and circular arc strip cover layer of polyethylene thin to electrode and corresponding contact conductor on contact conductor
Film, is finally putting in baking oven 100 DEG C and is dried 2h, and room temperature cooling is carried out after taking-up；
C () discoid working electrode, circular arc strip reference electrode and circular arc strip are to electrode surface Jing ethanol and ultra-pure water
After cleaning, p-aminobenzene sulfonic acid polymeric membrane and bismuth metallic film are modified successively in working electrode surface using electro-deposition method；
D () is assembled into one sample pool with microelectrode, the working electrode of its integrated microsensor, reference electrode and to electricity
Pole is located at cylindric sample pool inner bottom part.
Further, in step (a), the printing slurry of the working electrode is by carbon dust, ionic liquid, cellulose acetate
With Ketohexamethylene according to mass ratio be 3:1:1:3 are mixed, and the printing slurry to electrode is by carbon dust, ionic liquid, acetic acid
Cellulose and Ketohexamethylene are 3 according to mass ratio:1:1:3 are mixed, and the printing slurry of the reference electrode is by carbon dust, ionic liquid
Body, cellulose acetate, Ketohexamethylene, argentum powder and silver chloride are 3 according to mass ratio:1:1:3:0.5:0.5 is mixed.
Further, in step (c), working electrode surface modifies successively p-aminobenzene sulfonic acid polymeric membrane and bismuth metal
The process of thin film is：
(c1) working electrode surface is rinsed initially with ethanol, then with ultrapure water, finally using N2Blow
It is dry；
(c2) working electrode is inserted in the PBS containing 2.0mmol/L p-aminobenzene sulfonic acid, using cyclic voltammetric
Technology, makes working electrode enclose to the velocity scanning 10 between 2.0V with 100mV/s -1.5, and N is adopted after taking out2Dry up, make
Working electrode surface one layer of p-aminobenzene sulfonic acid polymeric membrane of polymerization；The concentration of buffer is 0.1mol/L, pH value is 7.0；
(c3) during working electrode is inserted in the acetum of the bismuth chloride of 600 μ g/L, the electro-deposition under -1.4V voltages
180s, and N is adopted after taking out2Dry up, make one layer of bismuth metal film of working electrode surface electro-deposition；The concentration of acetum is
0.1mol/L, pH value are 4.5.
The invention has the beneficial effects as follows：
The heavy metal-polluted soil detection method of the present invention carries out extraction process to soil sample first, then using differential pulse
Stripping Voltammetry technology carries out Electrochemical Detection, and Electrochemical Stripping voltammetry is a kind of internationally recognized micro and trace heavy metal inspection
Survey method, have the advantages that detection sensitivity is high, accuracy is good, speed is fast, can while analyze detection device for multi metallic elements, while
The heavy metal detector small volume of Stripping Voltammetry technique and electrochemical detection is carried out, it is low in energy consumption, simple to operate, it is particularly suitable for carrying out
In real time, field assay.The present invention can not only carry out the quick detection of heavy metal at pollution scene, and easy to operate, sensitive
Degree is high, testing result is accurate, can be used to be used for quickly detecting Heavy Metals In Environment thing.
The heavy metal-polluted soil detecting system design of the present invention is simple exquisite, and Highgrade integration need not be adopted in detection process
With electrochemical investigating pond, eliminate multiple steps such as electrode polishing, activation, with compact conformation, small volume, be easy to carry, into
This low, sensitivity is high, strong antijamming capability the advantages of, while sensor is single use, can abandon after use, it is to avoid pass
System sensor is due to being used for multiple times the sample cross contamination problem for causing.
The integrated microsensor of heavy metal-polluted soil detecting system of the present invention has very high detection sensitivity and anti-interference,
Its principle is：One layer of p-aminobenzene sulfonic acid film polymeric membrane is formed in working electrode surface by electropolymerization method, to amino
Benzenesulfonic acid film polymeric membrane is negatively charged in aqueous, the heavy metal cation such as attraction lead that can be strong and cadmium, improves
Bioaccumulation efficiency of the heavy metal ion on electrode, increase effectively the current-responsive of sensor；The bismuth metallic film of modification is in inspection
Can be co-deposited to electrode surface in the form of alloy with heavy metal ion during survey, heavy metal ion is helped in electrode surface
Enrichment, further enhancing the detection sensitivity of sensor.In addition, the p-aminobenzene sulfonic acid macromolecule of working electrode surface modification
Film can significantly improve sensor to macromolecular particle in sample and impurity capacity of resisting disturbance, and its principle is：Macromole is done
Disturbing material cannot penetrate this layer of polymer membrane participation electrochemical reaction, and the heavy metal ion of small size can be by being somebody's turn to do
Floor height molecular film enters electrode surface and participates in electrochemical reaction.
The lamellar microelectrode of different size can be according to the actual requirements made using the lamellar microelectrode manufacture method of the present invention,
Have the advantages that small volume, low cost and can batch making, preferably solve current tradition heavy-metal electrochemical sensor into
This height, using front grinding process is needed the problems such as；The ionic liquid added in each electrode print slurry has height ion
Activity, can significantly improve the ion and electron conduction of sensor；Cellulose acetate is then a kind of excellent plasticizer, can
Printing slurry is set firmly to be attached on electrode base sheet.
The heavy metal-polluted soil detection method of the present invention has that sample process speed is fast, whole pollution-free, detection process is quick,
It is easy to operate, the advantages of analysis precision is high, be suitable for carrying out extensive soil quick heavy metal qualitative and quantitative analysis.This
Bright heavy metal-polluted soil detection method can coordinate heavy metal fast detector to use, and realize the quick real-time inspection of Lead In Soil, cadmium
Survey, with practical, easy to carry, accuracy of detection is high, analyze speed is fast, the features such as easily operation, be very suitable for soil
Heavy metal contaminants in earth carry out field quick detection.
Description of the drawings
Fig. 1 is the heavy metal-polluted soil detection method flow chart of the present invention；
Fig. 2 is the heavy metal-polluted soil detecting system structural representation of the present invention；
Fig. 3 is the overlooking structure figure of integrated microsensor of the present invention；
Fig. 4 is the side block diagram of integrated microsensor of the present invention；
Fig. 5 is the structural representation of signal processing circuit of the present invention；
Fig. 6 is that the present invention carries out the Stripping Voltammetry figure that heavy metal analysis obtain lead and cadmium；
Fig. 7 is that the present invention carries out the concentration linear relationship figure that heavy metal analysis obtain lead and cadmium.
Specific embodiment
Clearly to illustrate the technical characterstic of this programme, below by specific embodiment, and with reference to its accompanying drawing, to this
It is bright to be described in detail.Following disclosure provides many different embodiments or example is used for realizing the different knots of the present invention
Structure.In order to simplify disclosure of the invention, hereinafter the part and setting of specific examples are described.Additionally, the present invention can be with
Repeat reference numerals and/or letter in different examples.This repetition is that for purposes of simplicity and clarity, itself is not indicated
Relation between various embodiments being discussed and/or being arranged.It should be noted that part illustrated in the accompanying drawings is not necessarily to scale
Draw.Present invention omits to the description of known assemblies and treatment technology and process avoiding being unnecessarily limiting the present invention.
As shown in figure 1, a kind of heavy metal-polluted soil detection method based on integrated microsensor of the present invention, needs before detection
Obtain soil sample：Many places soil sample is gathered in farmland using mamoty is adopted, equivalent soil sample mix homogeneously is taken, removes the inside weeds
And rubble, obtain soil sample.The heavy metal-polluted soil detection method of the present invention includes procedure below：
First, soil sample extraction is processed：
First the examined soil sample of collection is put into into 80 DEG C of Jing in drying baker to dry 1 hour, after room temperature cooling, is utilized
Mortar is crushed and crosses 80 mesh sieves after grinding, and makes uniform powder soil sample；
Then 1g powder soil samples are weighed, acetic acid and citric acid 1 that 40ml concentration is 0.2mol/L is added:1 mixing
Solution, and carry out ultrasound extraction process 1 hour；
Finally the sample solution after extraction process is filtered twice using 0.2um filters, and adopted 0.2mol/L
Sodium-acetate buffer adjusts sample solution pH value to 4.5.
2nd, heavy metal analysis：
The 5ml sample solutions that pH value is 4.5 are directly injected in the sample pool of integrated microsensor first, integrated micro sensing
The working electrode of device, reference electrode and sample pool inner bottom part is located to electrode；
Then the electrode cable of integrated microsensor is connected with heavy metal detector, using differential pulse Stripping Voltammetry skill
Art carries out Electrochemical Detection, and detection parameter is：Deposition potential -1.2V；Sedimentation time：120s, scans take-off potential -1.2V；Sweep
Retouch end current potential 0V；Rate of scanning：20Hz；Scanning impulse amplitude：50mV；Scanning impulse width：20mV；Scan amplitude：50mV；
Scanning stepping potential：5mV；
The Stripping Voltammetry figure and heavy metal analysis result of acquisition are stored and shown by last heavy metal detector.
Further, the employing differential pulse Stripping Voltammetry technology carries out the detailed process of Electrochemical Detection including following
Step：
S1. wire and heavy metal analysis are passed through respectively by the working electrode of integrated microsensor, reference electrode and to electrode
Instrument be connected；
S2., detection parameter is set；
S3. heavy metal detector produces voltage excitation signals and is loaded into the reference electrode of integrated microsensor and to electrode
On；
S4. heavy metal detector collecting work electrode is produced in detection process current signal is simultaneously carried out to current signal
Differential pulse voltammetry is detected；
S5. heavy metal detector will obtain Stripping Voltammetry figure and heavy metal analysis result is stored and shown.
Further, the display process of Stripping Voltammetry figure and heavy metal analysis result is：By Stripping Voltammetry figure according to advance
Linear relationship between the heavy metal concentration and peak current of foundation carries out quantitative analyses to lead and cadmium, and is lied prostrate using leaching ability of heavy metal
Pacify curve to represent, the dissolution of the dissolution peak correspondence heavy metal cadmium of -0.8V or so, -0.6V or so on leaching ability of heavy metal volt-ampere curve
Peak correspondence heavy metal lead.
The heavy metal-polluted soil detection method of the present invention carries out extraction process to soil sample first, then using differential pulse
Stripping Voltammetry technology carries out Electrochemical Detection, and Electrochemical Stripping voltammetry is a kind of internationally recognized micro and trace heavy metal inspection
Survey method, have the advantages that detection sensitivity is high, accuracy is good, speed is fast, can while analyze detection device for multi metallic elements, while
The heavy metal detector small volume of Stripping Voltammetry technique and electrochemical detection is carried out, it is low in energy consumption, simple to operate, it is particularly suitable for carrying out
In real time, field assay.The present invention can not only carry out the quick detection of heavy metal at pollution scene, and easy to operate, sensitive
Degree is high, testing result is accurate, can be used to be used for quickly detecting Heavy Metals In Environment thing.
As shown in Figures 2 to 4, a kind of heavy metal-polluted soil detecting system based on integrated microsensor of the invention, it is wrapped
Include integrated microsensor and heavy metal detector.
As shown in Figure 3 and Figure 4, integrated microsensor is made up of a cylindric sample pool 1 and a lamellar microelectrode 2,
Lamellar microelectrode 2 using mixed printing slurry by silk-screen printing technique make, be provided with lamellar microelectrode 2 working electrode 3,
Reference electrode 4 and to electrode 5, the working electrode 3 is the disc work for being arranged on the bottom centre position of cylindric sample pool 1
Electrode, the periphery of disc working electrode be circular arc strip reference electrode and circular arc strip to electrode, the circular arc strip reference
Electrode and circular arc strip are positioned at the both sides of discoid working electrode and symmetrical with regard to discoid working electrode end to electrode；The work
Make electrode 3, reference electrode 4 and electrode cable 6 is connected with to the correspondence of electrode 5；Distinguish inside-out on the surface of the working electrode 3
It is provided with p-aminobenzene sulfonic acid polymeric membrane and bismuth metallic film.The side of cylindric sample pool 1 can also arrange rule 8,
The injection rate of soil extract can be observed by rule.
As shown in Fig. 2 the heavy metal detector includes signal processing circuit, D and D/A converter and controller；Institute
State signal processing circuit to be acquired to the current signal that the working electrode to integrated microsensor is produced in detection process
And D and D/A converter is sent to, and it is loaded into integrated microsensor to the voltage excitation signals for sending controller
Reference electrode and on electrode；The D and D/A converter includes analog-digital converter and digital to analog converter, and the modulus turns
Parallel operation carries out being sent to controller after analog digital conversion to the current signal for sending signal processing circuit carries out differential pulse volt
Safety check is surveyed；The digital to analog converter carries out digital-to-analogue conversion and is sent at signal to the voltage excitation signals produced to controller
Reason circuit；The controller producing voltage excitation signals and be sent to signal processing circuit by analog-digital converter, and
Differential pulse voltammetry detection is carried out after processing current signal and obtains Stripping Voltammetry figure and heavy metal analysis result.
As shown in figure 5, the signal processing circuit includes voltage follower circuit, current buffering circuit, current/voltage-converted
Circuit and filter circuit, the voltage follower circuit is connected respectively with reference electrode and digital to analog converter, controller to be sent out
The voltage excitation signals sent are loaded on reference electrode；The current buffering circuit respectively with electrode and controller are connected, use
With to the electric current on electrode is conducted and is buffered；One end of the current/voltage converter circuit is connected with working electrode, separately
After filtering circuit is connected with analog-digital converter for one end, and the weak current produced in detection process to collecting work electrode is believed
Number, and current/voltage-converted and signal amplification, Filtering Processing are carried out to current signal.
As shown in figure 5, the voltage follower circuit adopts OPA124 operational amplifiers, to the potential for ensureing reference electrode
The output voltage for following voltage excitation signals changes, while ensureing to pass through without electric current on reference electrode；The current buffering electricity
Road adopts OPA2277 operational amplifiers, to derive and buffering to providing electrode electric current；The current/voltage converter circuit
Including reverse operational amplification circuit, analog multiplexer and feedback resistive network, the reverse amplification circuit is transported using OP07
Amplifier is calculated, the analog multiplexer adopts MAX308 analog multiplexers, and the feedback resistive network is by one
100K Ω resistance, a 1M Ω resistance, a 10M Ω resistance and a 100M Ω resistance composition；The filter circuit is by one
10K Ω resistance and a 1 μ F electric capacity composition.
Preferably, the controller includes processor, memorizer, display screen and operation button, described memorizer, display
Screen and operation button are connected respectively with processor, and the processor is to produce voltage excitation signals, and the work for receiving collection
Make the current signal that electrode is produced in detection process, and carry out after processing current signal differential pulse voltammetry detection obtain
Obtain Stripping Voltammetry figure and heavy metal analysis result；The memorizer is to store Stripping Voltammetry figure and heavy metal analysis result；Institute
Display screen is stated to show Stripping Voltammetry figure and heavy metal analysis result；The operation button is grasped to arrange parameter and function
Make.
The heavy metal-polluted soil detecting system design of the present invention is simple exquisite, and Highgrade integration need not be adopted in detection process
With electrochemical investigating pond, eliminate multiple steps such as electrode polishing, activation, with compact conformation, small volume, be easy to carry, into
This low, sensitivity is high, strong antijamming capability the advantages of, while integrated microsensor is single use, after detection once
Abandon, it is to avoid traditional sensors are due to being used for multiple times the sample cross contamination problem for causing.
The integrated microsensor of heavy metal-polluted soil detecting system of the present invention has very high detection sensitivity and anti-interference,
Its principle is：One layer of p-aminobenzene sulfonic acid film polymeric membrane is formed in working electrode surface by electropolymerization method, to amino
Benzenesulfonic acid film polymeric membrane is negatively charged in aqueous, the heavy metal cation such as attraction lead that can be strong and cadmium, improves
Bioaccumulation efficiency of the heavy metal ion on electrode, increase effectively the current-responsive of sensor；The bismuth metallic film of modification is in inspection
Can be co-deposited to electrode surface in the form of alloy with heavy metal ion during survey, heavy metal ion is helped in electrode surface
Enrichment, further enhancing the detection sensitivity of sensor.In addition, the p-aminobenzene sulfonic acid macromolecule of working electrode surface modification
Film can significantly improve sensor to macromolecular particle in sample and impurity capacity of resisting disturbance, and its principle is：Macromole is done
Disturbing material cannot penetrate this layer of polymer membrane participation electrochemical reaction, and the heavy metal ion of small size can be by being somebody's turn to do
Floor height molecular film enters electrode surface and participates in electrochemical reaction.
Present invention also offers a kind of lamellar microelectrode manufacture method for being applied to integrated microsensor, integrated micro- biography
Sensor is the integrated microsensor for being applied to heavy metal-polluted soil detecting system described above, and the manufacture method of lamellar microelectrode includes
Procedure below：
A () prepares respectively working electrode, the printing slurry to electrode and reference electrode；
B () prints respectively discoid working electrode, circular arc bar first with screen process press on teflon substrate
Then shape reference electrode and circular arc strip cover layer of polyethylene thin to electrode and corresponding contact conductor on contact conductor
Film, is finally putting in baking oven 100 DEG C and is dried 2h, and room temperature cooling is carried out after taking-up；
C () discoid working electrode, circular arc strip reference electrode and circular arc strip are to electrode surface Jing ethanol and ultra-pure water
After cleaning, p-aminobenzene sulfonic acid polymeric membrane and bismuth metallic film are modified successively in working electrode surface using electro-deposition method；
D () is assembled into one sample pool with microelectrode, the working electrode of its integrated microsensor, reference electrode and to electricity
Pole is located at cylindric sample pool inner bottom part.
Further, in step (a), the printing slurry of the working electrode is by carbon dust, ionic liquid, cellulose acetate
With Ketohexamethylene according to mass ratio be 3:1:1:3 are mixed, and the printing slurry to electrode is by carbon dust, ionic liquid, acetic acid
Cellulose and Ketohexamethylene are 3 according to mass ratio:1:1:3 are mixed, and the printing slurry of the reference electrode is by carbon dust, ionic liquid
Body, cellulose acetate, Ketohexamethylene, argentum powder and silver chloride are 3 according to mass ratio:1:1:3:0.5:0.5 is mixed.
Further, in step (c), working electrode surface modifies successively p-aminobenzene sulfonic acid polymeric membrane and bismuth metal
The process of thin film is：
(c1) working electrode surface is rinsed initially with ethanol, then with ultrapure water, finally using N2Blow
It is dry；
(c2) working electrode is inserted in the PBS containing 2.0mmol/L p-aminobenzene sulfonic acid, using cyclic voltammetric
Technology, makes working electrode enclose to the velocity scanning 10 between 2.0V with 100mV/s -1.5, and N is adopted after taking out2Dry up, make
Working electrode surface one layer of p-aminobenzene sulfonic acid polymeric membrane of polymerization；The concentration of buffer is 0.1mol/L, pH value is 7.0；
(c3) during working electrode is inserted in the acetum of the bismuth chloride of 600 μ g/L, the electro-deposition under -1.4V voltages
180s, and N is adopted after taking out2Dry up, make one layer of bismuth metal film of working electrode surface electro-deposition；The concentration of acetum is
0.1mol/L, pH value are 4.5.
The lamellar microelectrode of different size can be according to the actual requirements made using the lamellar microelectrode manufacture method of the present invention,
Have the advantages that small volume, low cost and can batch making, preferably solve current tradition heavy-metal electrochemical sensor into
This height, using front grinding process is needed the problems such as；The ionic liquid added in each electrode print slurry has height ion
Activity, can significantly improve the ion and electron conduction of sensor；Cellulose acetate is then a kind of excellent plasticizer, can
Printing slurry is set firmly to be attached on electrode base sheet.
In order to obtain accurate testing result, integrated microsensor adopts disposable integrated microsensor, i.e., carries out every time
Using new integrated microsensor when heavy metal-polluted soil is detected, re-replace when inspection next time after the completion of detection new integrated micro-
Sensor, such integrated microsensor is single use in detection process, it is to avoid traditional sensors are due to being used for multiple times
The sample cross contamination problem for causing.
Fig. 6 and Fig. 7 are that the present invention carries out Stripping Voltammetry figure and corresponding concentration line that heavy metal analysis obtain lead and cadmium
Sexual intercourse figure.The present invention carries out Electrochemical Detection using differential pulse Stripping Voltammetry technology, and to obtain heavy metal as shown in Figure 6 molten
Go out volt-ampere curve, the dissolution peak correspondence heavy metal lead of the dissolution peak correspondence heavy metal cadmium of -0.8V or so, -0.6V or so on curve.
The height at measurement dissolution peak, lead and cadmium in sample are obtained using the linear relationship between the heavy metal concentration and peak height set up
Concentration, as shown in fig. 7, wherein the equation of linear regression of cadmium be y=0.6132x-0.1923 (x:μgL-1,y:μ A), phase relation
Number is 0.9948；The equation of linear regression of lead is y=0.4011x-0.2426, and correlation coefficient is 0.9918.
The heavy metal-polluted soil detection method of the present invention has that sample process speed is fast, whole pollution-free, detection process is quick,
It is easy to operate, the advantages of analysis precision is high, be suitable for carrying out extensive soil quick heavy metal qualitative and quantitative analysis.This
Bright heavy metal-polluted soil detection method can coordinate heavy metal fast detector to use, and realize the quick real-time inspection of Lead In Soil, cadmium
Survey, with practical, easy to carry, accuracy of detection is high, analyze speed is fast, the features such as easily operation, be highly suitable for soil
Heavy metal contaminants in earth carry out field quick detection.
The above is the preferred embodiment of the present invention, for those skilled in the art,
Without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also regarded as this
Bright protection domain.
Claims (10)
1. a kind of heavy metal-polluted soil detection method based on integrated microsensor, is characterized in that, including procedure below：
First, soil sample extraction is processed：
First by 80 DEG C of the examined soil Jing drying 1h of collection, crushed using mortar and cross 80 mesh sieves after grinding, made uniform
Powder soil sample；
Then 1g powder soil samples are weighed, acetic acid and citric acid 1 that 40ml concentration is 0.2mol/L is added:1 mixed solution,
And carry out ultrasound extraction process 1h；
Finally the sample solution after extraction process is filtered twice using 0.2um filters, and using 0.2mol/L acetic acid
Sodium buffer adjusts sample solution pH value to 4.5；
2nd, heavy metal analysis：
The sample solution that pH value is 4.5 is directly injected in the sample pool of integrated microsensor first, the work of integrated microsensor
Make electrode, reference electrode and sample pool inner bottom part is located to electrode；
Then the electrode cable of integrated microsensor is connected with heavy metal detector, is entered using differential pulse Stripping Voltammetry technology
Row Electrochemical Detection, detects that parameter is：Deposition potential -1.2V；Sedimentation time：120s, scans take-off potential -1.2V；Scanning knot
Fasciculation potential 0V；Rate of scanning：20Hz；Scanning impulse amplitude：50mV；Scanning impulse width：20mV；Scan amplitude：50mV；Scanning
Stepping potential：5mV；
The Stripping Voltammetry figure and heavy metal analysis result of acquisition are stored and shown by last heavy metal detector.
2. a kind of heavy metal-polluted soil detection method based on integrated microsensor as claimed in claim 1, is characterized in that, described
The process for carrying out Electrochemical Detection using differential pulse Stripping Voltammetry technology is comprised the following steps：
S1. by the working electrode of integrated microsensor, reference electrode and to electrode respectively by wire and heavy metal detector
It is connected；
S2., detection parameter is set；
S3. heavy metal detector produces voltage excitation signals and is loaded into the reference electrode of integrated microsensor and on electrode；
S4. heavy metal detector collecting work electrode is produced in detection process current signal simultaneously carries out difference to current signal
Pulse Voltammetry is detected；
S5. heavy metal detector will obtain Stripping Voltammetry figure and heavy metal analysis result is stored and shown.
3. a kind of heavy metal-polluted soil detection method based on integrated microsensor as claimed in claim 1 or 2, is characterized in that,
The display process of Stripping Voltammetry figure and heavy metal analysis result is：By Stripping Voltammetry figure according to the heavy metal concentration that pre-builds with
Linear relationship between peak current carries out quantitative analyses to lead and cadmium, and is represented using leaching ability of heavy metal volt-ampere curve, heavy metal
The dissolution peak correspondence heavy metal lead of the dissolution peak correspondence heavy metal cadmium of -0.8V or so, -0.6V or so on Stripping Voltammetry curve.
4. a kind of heavy metal-polluted soil detecting system based on integrated microsensor, is characterized in that, including integrated microsensor and weight
Metal detector,
Integrated microsensor is made up of a cylindric sample pool and a lamellar microelectrode, and lamellar microelectrode adopts mixed printing
Slurry is made by silk-screen printing technique, working electrode, reference electrode is provided with lamellar microelectrode and to electrode, the work
Electrode is the disc working electrode for being arranged on cylindric sample pool bottom centre position, and the periphery of disc working electrode is round
, to electrode, the circular arc strip reference electrode and circular arc strip are located at discoid to electrode for arc strip reference electrode and circular arc strip
Both sides of working electrode and symmetrical with regard to discoid working electrode end；The working electrode, reference electrode and electrode pair should be connected
It is connected to electrode cable；The surface of the working electrode is respectively arranged with inside-out p-aminobenzene sulfonic acid polymeric membrane and bismuth metal
Thin film；
The heavy metal detector includes signal processing circuit, D and D/A converter and controller；The signal processing circuit
The current signal produced in detection process to the working electrode to integrated microsensor is acquired and is sent to modulus/number
Weighted-voltage D/A converter, and it is loaded into the reference electrode of integrated microsensor and to electricity to the voltage excitation signals for sending controller
Extremely go up；The D and D/A converter includes analog-digital converter and digital to analog converter, and the analog-digital converter is to by signal
The current signal that reason circuit sends is carried out being sent to controller after analog digital conversion and carries out differential pulse voltammetry detection；The digital-to-analogue turns
Parallel operation carries out digital-to-analogue conversion and is sent to signal processing circuit to the voltage excitation signals produced to controller；The controller
To produce voltage excitation signals and be sent to signal processing circuit by analog-digital converter, and current signal is processed
After carry out differential pulse voltammetry detection and obtain Stripping Voltammetry figure and heavy metal analysis result.
5. a kind of heavy metal-polluted soil detecting system based on integrated microsensor according to claim 4, is characterized in that, institute
Signal processing circuit is stated including voltage follower circuit, current buffering circuit, current/voltage converter circuit and filter circuit, it is described
Voltage follower circuit is connected respectively with reference electrode and digital to analog converter, to the voltage excitation signals loading for sending controller
To on reference electrode；The current buffering circuit respectively with electrode and controller are connected, to entering to the electric current on electrode
Row conduction and buffering；One end of the current/voltage converter circuit is connected with working electrode, the other end circuit and mould after filtering
Number converter connects, and to the low current signal that collecting work electrode is produced in detection process, and current signal is carried out
Current/voltage-converted and signal amplify, Filtering Processing.
6. a kind of heavy metal-polluted soil detecting system based on integrated microsensor according to claim 5, is characterized in that, institute
Voltage follower circuit is stated using OPA124 operational amplifiers, to ensure that the potential of reference electrode follows the defeated of voltage excitation signals
Go out change in voltage, while ensureing to pass through without electric current on reference electrode；The current buffering circuit adopts OPA2277 operation amplifiers
Device, to derive and buffering to providing electrode electric current；The current/voltage converter circuit include reverse operational amplification circuit,
Analog multiplexer and feedback resistive network, the reverse amplification circuit adopts OP07 operational amplifiers, the Multipexer
Transducer adopts MAX308 analog multiplexers, the feedback resistive network by a 100K Ω resistance, 1M Ω resistance,
One 10M Ω resistance and a 100M Ω resistance composition；The filter circuit is by a 10K Ω resistance and a 1 μ F capacitance group
Into.
7. a kind of heavy metal-polluted soil detecting system based on integrated microsensor according to claim 4 to 6 any one,
It is characterized in that, the controller includes processor, memorizer, display screen and operation button, described memorizer, display screen and behaviour
Make button to be connected with processor respectively, the processor is to produce voltage excitation signals, and the working electrode for receiving collection
The current signal produced in detection process, and differential pulse voltammetry detection acquisition dissolution is carried out after processing current signal
Voltammogram and heavy metal analysis result；The memorizer is to store Stripping Voltammetry figure and heavy metal analysis result；The display
Screen is to show Stripping Voltammetry figure and heavy metal analysis result；The operation button is to arrange parameter and feature operation.
8. a kind of lamellar microelectrode manufacture method for being applied to integrated microsensor, is characterized in that, the integrated microsensor is
The integrated microsensor of heavy metal-polluted soil detecting system described in claim 4 is applied to, the manufacture method of lamellar microelectrode includes
Procedure below：
A () prepares respectively working electrode, the printing slurry to electrode and reference electrode；
B () prints respectively discoid working electrode, circular arc strip ginseng first with screen process press on teflon substrate
Than electrode and circular arc strip to electrode and corresponding contact conductor, layer of polyethylene thin film is then covered on contact conductor, most
After be put in baking oven 100 DEG C and be dried 2h, room temperature cooling is carried out after taking-up；
C () discoid working electrode, circular arc strip reference electrode and circular arc strip are cleaned to electrode surface Jing ethanol and ultra-pure water
Afterwards, p-aminobenzene sulfonic acid polymeric membrane and bismuth metallic film are modified successively in working electrode surface using electro-deposition method；
D () is assembled into one sample pool with microelectrode, the working electrode of its integrated microsensor, reference electrode and to electrode position
In cylindric sample pool inner bottom part.
9. a kind of lamellar microelectrode manufacture method for being applied to integrated microsensor according to claim 8, is characterized in that,
In step (a), the printing slurry of the working electrode is by carbon dust, ionic liquid, cellulose acetate and Ketohexamethylene according to quality
Than for 3:1:1:3 are mixed, and the printing slurry to electrode is pressed by carbon dust, ionic liquid, cellulose acetate and Ketohexamethylene
It is 3 according to mass ratio:1:1:3 are mixed, and the printing slurry of the reference electrode is by carbon dust, ionic liquid, cellulose acetate, ring
Hexanone, argentum powder and silver chloride are 3 according to mass ratio:1:1:3:0.5:0.5 is mixed.
10. a kind of lamellar microelectrode manufacture method for being applied to integrated microsensor according to claim 8, its feature
It is that in step (c), working electrode surface modifies successively p-aminobenzene sulfonic acid polymeric membrane and the process of bismuth metallic film is：
(c1) working electrode surface is rinsed initially with ethanol, then with ultrapure water, finally using N2Dry up；
(c2) working electrode is inserted in the PBS containing 2.0mmol/L p-aminobenzene sulfonic acid, using cyclic voltammetric skill
Art, makes working electrode enclose to the velocity scanning 10 between 2.0V with 100mV/s -1.5, and N is adopted after taking out2Dry up, make work
Make electrode surface one layer of p-aminobenzene sulfonic acid polymeric membrane of polymerization；The concentration of buffer is 0.1mol/L, pH value is 7.0；
(c3) during working electrode is inserted in the acetum of the bismuth chloride of 600 μ g/L, the electro-deposition 180s under -1.4V voltages,
And using N after taking out2Dry up, make one layer of bismuth metal film of working electrode surface electro-deposition；The concentration of acetum be 0.1mol/L,
PH value is 4.5.
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| CN111982998A (en) * | 2020-08-25 | 2020-11-24 | 上海第二工业大学 | Heavy metal electrochemical analyzer and detection method thereof |
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