CN107192754A - Farmland nitrate nitrogen detection method and system based on ISE - Google Patents
Farmland nitrate nitrogen detection method and system based on ISE Download PDFInfo
- Publication number
- CN107192754A CN107192754A CN201610147796.2A CN201610147796A CN107192754A CN 107192754 A CN107192754 A CN 107192754A CN 201610147796 A CN201610147796 A CN 201610147796A CN 107192754 A CN107192754 A CN 107192754A
- Authority
- CN
- China
- Prior art keywords
- msub
- mrow
- soil
- response potential
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The present invention relates to a kind of farmland nitrate nitrogen detection method and system based on ISE, this method includes：Detect the first response potential and the second response potential of the master sample solution of various concentrations at different temperatures；According to the first response potential and the second response potential of the master sample solution of each concentration at various temperatures, detection model is set up；Detect first response potential and second response potential of the soil extraction to be detected at a temperature of farm environment；The nitrate ion concentration of the soil extraction is calculated using the detection model；The nitrate nitrogen content of soil to be detected is determined according to the nitrate ion concentration of soil extraction.The detection model that the present invention is set up not only allows for influence of the coexisting ion chlorion to nitrate ion electrode, and also contemplate influence of the temperature to ISE, therefore relative to traditional detection method, the Detection accuracy of soil nitrate-N can be greatly improved.
Description
Technical field
The present invention relates to Soil K+adsorption technical field, ion selectivity is based on more particularly, to one kind
The farmland nitrate nitrogen detection method and system of electrode.
Background technology
China over nearly 20 years population sharply increase, cultivated area is reduced year by year, grain security by
Stern challenge is arrived.However, excessive fertilization, inclined nitrogen fertilizer application cause serious soil dirt
Dye, ecological disruption, seriously threaten human health.The Party Central Committee, State Council are dirty to administering soil
Dye is paid much attention to, and drafts soil temperature and soil moisture content, formulates Soil Pollution Control action meter
Draw.Country start fertilization compositions based on earth measurement project by carrying out soil testing and field test,
Soil supplying nutrient capability, crop regulation of fertilizer requirement etc. are found out, fertilizing constant is proposed, using formula fertilizer.
Wherein, the detection of farmland nitrate nitrogen content is significant to science, economy, the rational application of fertilizer,
It is both to economize on resources, develop agriculture important channel of " two high one is excellent ", is also protection
One important measures of ecological environment, Ensuring Food Safety and human health.
ISE is that one kind can produce specific current potential sound to object ion in solution
The electrochemical sensor answered.More traditional chemical analysis method, ISE has
Quickly, sensitive, accurate, equipment it is simple and can METHOD FOR CONTINUOUS DETERMINATION the advantages of, in every profession and trade especially
It is to be widely used in terms of chemical industry, medical science, environment, and is content of soil nitrate-N analysis
There is provided effective means.
At present, the conventional ion electrodes selective commercialization based on polyvinyl chloride polymer film,
But there is problems with the soil nitrate nitrogen determination based on such electrode：Soil constituent is more complicated,
Nitrate ion electrode is easily by the coexisting ion (especially chlorion) in soil extraction
Interference；Moreover, the temperature change of detection environment can produce influence to sensitive membrane and ionic activity.
However, coexisting ion and environment temperature these factors are considered in actually measurement,
Therefore the detected content of soil nitrate-N degree of accuracy is not high.
The content of the invention
For disadvantages described above, the present invention provides a kind of farmland nitre state based on ISE
Nitrogen detection method and system, it may be considered that to coexisting ion chlorion to nitrate ion electrode
The influence that influence and environment temperature are come to detection band, improves Detection accuracy.
In a first aspect, the farmland nitrate nitrogen detection based on ISE that the present invention is provided
Method includes：
Detect various concentrations master sample solution at different temperatures first response potential and
Second response potential, the first response potential is the response potential of nitrate ion electrode, institute
State the response potential that the second response potential is chlorine ion electrode；
According to the master sample solution of each concentration at various temperatures first response potential and
Second response potential, sets up a detection model, the detection model include the first response potential with
The first function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature and the second response potential
With the second function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature；
Detect the soil extraction of the soil to be detected at a temperature of the farm environment collected
First response potential and second response potential；
According to the first of the soil extraction the response potential, the second sound of the soil extraction
Potential and the farm environment temperature are answered, the soil extraction is calculated using the detection model
Nitrate ion concentration；
The soil to be detected is determined according to the nitrate ion concentration of the soil extraction
Nitrate nitrogen content.
Optionally, the master sample solution according to each concentration at various temperatures first
Potential and the second response potential are responded, a detection model is set up, including：
The first response potential, the second sound at each temperature are set up using arithmetic of linearity regression
Answer functional relation of the potential respectively with nitric acid Na ion concentration and chlorine ion concentration：
Wherein, E1For the first response potential at this temperature, E2For the second sound at this temperature
Answer potential,For nitrate ion concentration at this temperature,Chlorion at this temperature
Concentration, β01、β11、β21、β02、β12、β22For regression parameter at this temperature；
Each regression parameter and temperature are subjected to unitary linear fit using least square method, obtained
The unitary linear function of the regression parameter and temperature；
According at each temperature first response potential, second response potential respectively with nitric acid sodium ion
The linear letter of unitary of concentration and the functional relation of chlorine ion concentration and each regression parameter and temperature
Number, determines that the detection model is：
Optionally, the nitrate ion concentration according to the soil extraction, it is determined that described
The nitrate nitrogen content of soil to be detected, including：
Set up nitrate ion concentration, soil of the nitrate nitrogen content of soil with corresponding soil extraction
The 3rd functional relation between the volumetric water content of earth；
By the nitrate ion concentration of the soil extraction and the soil to be detected collected
Volumetric water content substitutes into the 3rd functional relation, and the nitrate nitrogen for calculating the soil to be detected contains
Amount.
Optionally, the 3rd functional relation is：
Wherein, ω is the nitrate nitrogen content of soil,For the nitrate ion of soil extraction
Concentration, θvFor the volumetric water content of soil.
Optionally, the master sample solution of the various concentrations is the sodium nitrate of different concentration knowns
The mixed solution of solution and the sodium chloride solution of different concentration knowns.
Optionally, it is described detection various concentrations master sample solution at different temperatures first
Potential and the second response potential are responded, including：
The container for filling master sample solution and deionized water is placed in constant temperature bath of liquid groove；
Set using master sample solution described in nitrate ion electrode detection in constant temperature bath of liquid groove
The first response potential during for different temperatures, detects that the master sample is molten using chlorine ion electrode
Second response potential of the liquid when constant temperature bath of liquid groove is set as different temperatures.
Second aspect, the farmland nitrate nitrogen detection based on ISE that the present invention is provided
System include nitrate ion electrode, chlorine ion electrode, constant temperature bath of liquid groove, data acquisition unit and
Data processor, wherein：
The nitrate ion electrode, for when being positioned over the soil extraction of soil to be detected
Produce the first response potential for characterizing nitrate ion concentration；
The chlorine ion electrode, for when being positioned over the soil extraction produce characterize chlorine from
Second response potential of sub- concentration；
The constant temperature bath of liquid groove, for the first sound in the soil extraction for detecting soil to be detected
When answering potential and the second response potential, the soil extraction is maintained at farm environment temperature
Degree；
The data acquisition unit, the first response electricity for gathering the nitrate ion electrode
The farm environment that gesture, the second response potential of the chlorine ion electrode and temperature sensor are gathered
Temperature, and the data of collection are sent to the data processor；
The data processor, for the data sent according to the data acquisition unit, utilize with
Upper any detection model, calculates the nitrate ion concentration of the soil extraction, and according to institute
The nitrate ion concentration of soil extraction is stated, determines that the nitrate nitrogen of the soil to be detected contains
Amount.
Optionally, the data acquisition unit includes Signal-regulated kinase, analog-to-digital conversion module and place
Module is managed, the system also includes the temperature sensor of detection farm environment temperature and for detecting
The moisture transducer of the volumetric water content of soil to be detected, wherein：
The Signal-regulated kinase, for responding potential to the first of the nitrate ion electrode
Carried out with the second response potential of the chlorine ion electrode defeated after impedance conversion, filtering and amplification
Go out；
The analog-to-digital conversion module, is connected with the output end of the Signal-regulated kinase, for pair
The signal digitlization of the Signal-regulated kinase output；
The processing module, output end, the temperature sensor with the analog-to-digital conversion module
And moisture transducer connection, for will the digitized first response potential, digitized the
Two response potential, the farm environment temperature collected and the volume of the soil to be detected collected contain
Water rate is pre-processed.
Optionally, the data acquisition unit also include power module, display module, input module,
Wireless transport module and/or memory module, wherein：
The power module, with the display module, the processing module and the signal condition
Module is connected, for for the display module, the processing module and the Signal-regulated kinase
Power supply is provided；
The display module, is connected with the processing module, for pretreated data to be entered
Row display；
The input module, is connected with the processing module, for inputting the control processing mould
The control instruction that block is pre-processed；
The wireless transport module, is connected with the processing module, for by the processing module
Pretreated data are sent to the data processor；
The memory module, is connected with the processing module, for pretreated data to be entered
Row storage.
The farmland nitrate nitrogen detection method and system provided according to above technical scheme, the present invention
In, detected by the way of detection model is set up, and the detection model is to include the first sound
Answer the first function relation and second of potential and nitric acid Na ion concentration, chlorine ion concentration and temperature
The second function relation of potential and nitric acid Na ion concentration, chlorine ion concentration and temperature is responded, can
See the detection model set up of the present invention not only allow for coexisting ion chlorion to nitrate anion from
The influence of sub-electrode, and also contemplate influence of the temperature to ISE, therefore phase
For traditional detection method, the Detection accuracy of soil nitrate-N can be greatly improved.
Brief description of the drawings
The characteristic information and advantage of the present invention, accompanying drawing can be more clearly understood from by reference to accompanying drawing
It is schematical and should not be construed as carrying out the present invention any limitation, in the accompanying drawings：
Fig. 1 is shown according to farmland nitrate nitrogen detection side of the present invention based on ISE
The schematic flow sheet of the embodiment of method one；
Fig. 2 is shown according to farmland nitrate nitrogen detection system of the present invention based on ISE
The structured flowchart of unified implementation example.
Embodiment
In order to be more clearly understood that the above objects, features and advantages of the present invention, tie below
The drawings and specific embodiments are closed the present invention is further described in detail.Need explanation
It is that, in the case where not conflicting, the feature in embodiments herein and embodiment can be mutual
Combination.
Elaborate many details in the following description to facilitate a thorough understanding of the present invention, but
It is that the present invention can also be different from other modes described here to implement using other, therefore,
Protection scope of the present invention is not limited by following public specific embodiment.
The present invention provides a kind of farmland nitrate nitrogen detection method based on ISE, such as
Shown in Fig. 1, this method includes：
S1, detect various concentrations master sample solution at different temperatures first response potential
With the second response potential, the first response potential is the response potential of nitrate ion electrode,
The second response potential is the response potential of chlorine ion electrode；
S2, the first response potential according to the master sample solution of each concentration at various temperatures
With the second response potential, a detection model is set up, the detection model includes the first response potential
With the first function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature and the second response electricity
Gesture and the second function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature；
S3, the soil extraction of the detection soil to be detected are in the farm environment temperature collected
Under first response potential and second response potential；
S4, according to the first of the soil extraction the response potential, the soil extraction the
Two response potentials and the farm environment temperature, calculate the soil using the detection model and soak
The nitrate ion concentration of extract；
S5, the soil to be detected determined according to the nitrate ion concentration of the soil extraction
Nitrate nitrogen content.
In the farmland nitrate nitrogen detection method that the present invention is provided, by the way of detection model is set up
Detected, and the detection model is to include the first response potential and nitric acid Na ion concentration, chlorine
Ion concentration and the first function relation of temperature and the second response potential and nitric acid Na ion concentration,
The second function relation of chlorine ion concentration and temperature, it is seen that the detection model that the present invention is set up is not
Influence of the coexisting ion chlorion to nitrate ion electrode is only accounted for, and also contemplates temperature
The influence to ISE is spent, therefore relative to traditional detection method, can be significantly
Improve the Detection accuracy of soil nitrate-N.
In the specific implementation, the master sample solution of various concentrations can be different concentration knowns
In the mixed solution of sodium nitrate solution and the sodium chloride solution of different concentration knowns, such as table 1 below
Several master sample solution：
The master sample solution of several various concentrations of table 1
From upper table 1 as can be seen that different concentration knowns sodium nitrate solution and Bu Tong known to it is dense
The sodium chloride solution of degree constitutes the master sample solution of various concentrations.
In the specific implementation, the master sample solution of various concentrations is detected at different temperatures in S1
First response potential and second response potential detailed process can include：
S11, the container for filling master sample solution and deionized water is placed in constant temperature bath of liquid groove；
S12, using master sample solution described in nitrate ion electrode detection in constant temperature bath of liquid groove
It is set as the first response potential during different temperatures, the standard sample is detected using chlorine ion electrode
Second response potential of this solution when constant temperature bath of liquid groove is set as different temperatures.
Here every time after the complete master sample solution of electrode detection, it is both needed to using deionized water cleaning
Electrode can avoid electrode from producing intersecting for potential memory and master sample solution to baseline potential
Pollution.
The detailed process of above-mentioned detection is illustrated with four groups of master sample solution in table 1：
First, the temperature of constant temperature bath of liquid groove is set as 5 DEG C, and by numbering, the master sample for being 1-1 is molten
Liquid is placed in constant temperature bath of liquid groove, when the temperature of master sample solution is basicly stable, and insertion is lived
The nitrate ion electrode and chlorine ion electrode of change, gather corresponding response electricity after electrode is stable
Gesture.After the completion of detection, two electrodes are taken out, cleaned with deionized water, and electricity is blotted with filter paper
The moisture of pole remained on surface.In the same way, detection numbering is 1-2,1-3,1-4 standard
The response potential of sample solution and remaining three groups of master sample solution.
Then, the temperature of constant temperature bath of liquid groove is respectively set as 15 DEG C, 25 DEG C, 30 DEG C, use
Above-mentioned method detects four groups of master sample solution.
In the specific implementation, the process of detection model is set up in S2 to be included：
S21, using arithmetic of linearity regression set up at each temperature first response potential,
Second response potential is respectively many with the functional relation of nitric acid Na ion concentration and chlorine ion concentration
First regression model：
Wherein, E1For the first response potential at this temperature, unit is mV；E2For the temperature
Under second response potential, unit is mV；For nitrate ion concentration at this temperature,
Unit is mol/L；Chlorine ion concentration at this temperature, unit is mol/L；β01、β11、
β21、β02、β12、β22For regression parameter at this temperature.
It is understood that first in above-mentioned group of functions is the first response potential E1With nitric acid
The first linear function between the logarithm of Na ion concentration, the logarithm of chlorine ion concentration, second
For the second response potential E2The logarithm of logarithm, chlorine ion concentration with nitric acid Na ion concentration it
Between the second linear function.
Each regression parameter of table 2 at each temperature
As can be seen that the value of same regression parameter at different temperatures is that have trickle from upper table 2
Difference, it is therefore desirable to the relation set up between regression parameter and temperature.
S22, using least square method unitary linear fit is carried out to each regression parameter and temperature,
Obtain the unitary linear function of the regression parameter and temperature；
According at each temperature first response potential, second response potential respectively with nitric acid sodium ion
The linear letter of unitary of concentration and the functional relation of chlorine ion concentration and each regression parameter and temperature
Number, determines that the detection model is：
For example, setting up the first response potential at 5 DEG C, 15 DEG C, 25 DEG C, 30 DEG C respectively first
Functional relation, the second response potential and sodium nitrate with nitric acid Na ion concentration and chlorine ion concentration
The functional relation of ion concentration and chlorine ion concentration.Then according to β under different temperatures01、β11、
β21、β02、β12、β22In each regression parameter concrete numerical value, be fitted each regression parameter with
The relation of temperature, and then obtain above-mentioned detection model.
For example, the occurrence of each regression parameter in above-mentioned table 2 carries out regression parameter and temperature
Substituted into after the fitting of degree in regression model, obtained detection model is：
It can be seen that, the detection model finally obtained is the first response potential and temperature, nitrate ion
The logarithm of concentration and the functional relation of the logarithm of chlorine ion concentration and the second response potential and temperature,
The functional relation of the logarithm of nitrate ion concentration and the logarithm of chlorine ion concentration, wherein temperature are
It can detect, therefore be a binary quadratic equation group, when actually detected, first
Respond potential and second response potential be also to detect, and then calculate nitrate anion from
Sub- concentration and chlorine ion concentration.
It is understood that the farm environment temperature in S3 should be farmland where soil to be detected
Environment temperature.
In the prior art, traditional soil pre-treatment link includes：Air-dry → crushing → sieving →
Sample → liquid feeding → stirring → filtering is measured, it is excessively cumbersome, it is impossible to meet soil nutrient detection ageing
Requirement, wherein air dry operation is the most time-consuming.To improve the ageing of detection, the present invention is used
Be the volumetric water content for detecting fresh soil to be detected first, it is then the soil to be detected is direct
Liquid feeding makes the mode as soil extraction, and detailed process can be：In several sampled points
Fresh wet soil sample 10mL is gathered respectively, is separately added into deionized water 50mL extractions, you can
Obtain several pieces soil extraction.But directly extracted and surveyed by fixed soil ratio with fresh soil sample
During amount, soil moisture is also to influence one of factor of content of soil nitrate-N accuracy in detection, therefore
S5 detailed process can include in the present invention：
S51, the nitrate nitrogen content for setting up soil and the nitrate ion of corresponding soil extraction are dense
The 3rd functional relation between degree, the volumetric water content of soil；
S52, by the nitrate ion concentration of the soil extraction and the soil to be detected collected
The volumetric water content of earth substitutes into the 3rd functional relation, calculates the nitre state of the soil to be detected
Nitrogen content.
Advantage of this is that, it is contemplated that the influence that soil moisture content is caused to detection process, enter
One step improves the degree of accuracy of detection.Furthermore, it is possible to simplify soil pre-treatment step, greatly improve
That detects is ageing.
In the specific implementation, the 3rd functional relation is the nitrate nitrogen content updating formula,
Can be：
Wherein, ω is the nitrate nitrogen content of soil, and unit is mg/L；For soil extraction
Nitrate ion concentration, unit is mol/L；14 be the molal weight of nitrogen, and unit is
g/mol；103For unit conversion coefficient, unit is mg/g；θvFor the volumetric water content of soil；
5 be extraction soil ratio (volume ratio).
Table 3 respectively detects the contrast table of parameter and soil nitrate-N measured value and reference value
Each detection parameter in upper table 3 is substituted into model, nitrate ion concentration is calculated,
And obtain content of soil nitrate-N using nitrate nitrogen content updating formula.It can be seen that relative error is maximum
5% or so, its accuracy of detection meets the required precision that scene speed is surveyed.Meanwhile, because removing soil from
Earth air dry operation, the time that detection is spent was shorten within 1 hour from 1~2 day, was substantially increased
Detection is ageing.
The present invention also provides a kind of farmland nitrate nitrogen detecting system based on ISE,
As shown in Fig. 2 the system include nitrate ion electrode, chlorine ion electrode, constant temperature bath of liquid groove,
Data acquisition unit and data processor, wherein：
The nitrate ion electrode, for when being positioned over the soil extraction of soil to be detected
Produce the first response potential for characterizing nitrate ion concentration；
The chlorine ion electrode, for when being positioned over the soil extraction produce characterize chlorine from
Second response potential of sub- concentration；
The constant temperature bath of liquid groove, for the first sound in the soil extraction for detecting soil to be detected
When answering potential and the second response potential, the soil extraction is maintained at farm environment temperature
Degree；
The data acquisition unit, the first response electricity for gathering the nitrate ion electrode
The farm environment that gesture, the second response potential of the chlorine ion electrode and temperature sensor are gathered
Temperature, and the data of collection are sent to the data processor；
The data processor, for the data sent according to the data acquisition unit, using upper
The detection model stated calculates the nitrate ion concentration of the soil extraction, and according to the soil
The nitrate ion concentration of earth leaching liquor, determines the nitrate nitrogen content of the soil to be detected, example
Such as host computer.
Detected due to using above-mentioned detection model in the nitrate nitrogen detecting system of farmland,
And detection model is to include the first response potential and nitric acid Na ion concentration, chlorine ion concentration and temperature
The first function relation of degree and the second response potential and nitric acid Na ion concentration, chlorine ion concentration and
The second function relation of temperature, it is seen that the detection model that the present invention is set up not only allows for coexisting
Influence of the ion chlorion to nitrate ion electrode, and temperature is also contemplated to ion selection
The influence of property electrode, therefore relative to traditional detection method, soil nitrate can be greatly improved
The Detection accuracy of nitrogen.
In the specific implementation, as shown in Fig. 2 the data acquisition unit can include signal condition
Module, analog-to-digital conversion module and processing module, the system also include detection farm environment temperature
Temperature sensor and for the moisture transducer for the volumetric water content for detecting soil to be detected, its
In：
The Signal-regulated kinase, for responding potential to the first of the nitrate ion electrode
Carried out with the second response potential of the chlorine ion electrode defeated after impedance conversion, filtering and amplification
Go out；
The analog-to-digital conversion module, is connected with the output end of the Signal-regulated kinase, for pair
The signal digitlization of the Signal-regulated kinase output, the analog-to-digital conversion module of such as 12；
The processing module, output end, the temperature sensor with the analog-to-digital conversion module
And moisture transducer connection, for will the digitized first response potential, digitized the
Two response potential, the farm environment temperature collected and the volume of the soil to be detected collected contain
Water rate is pre-processed, for example C8051F020 microprocessors.
In the specific implementation, as shown in Fig. 2 the data acquisition unit can also include power supply mould
Block, display module, input module, wireless transport module and/or memory module, wherein：
The power module, with the display module, the processing module and the signal condition
Module is connected, for for the display module, the processing module and the Signal-regulated kinase
Power supply is provided；
The display module, is connected with the processing module, for pretreated data to be entered
Row display, such as liquid crystal display device；
The input module, is connected with the processing module, for inputting the control processing mould
The control instruction that block is pre-processed, such as keyboard；
The wireless transport module, is connected with the processing module, for by the processing module
Pretreated data are sent to the data processor, such as GPRS communication modules；
The memory module, is connected with the processing module, for pretreated data to be entered
Row storage, such as USB flash disk.
Using any of the above farmland nitrate nitrogen detecting system when being detected, with it is simple, into
This is low, stably, accuracy rate is high, quick advantage, available for instructing fertilising or field management.
In the present invention, term " first ", " second " are only used for describing purpose, and can not manage
Solve to indicate or imply relative importance.Term " multiple " refers to two or more, unless
Separately there is clear and definite restriction.
Although being described in conjunction with the accompanying embodiments of the present invention, those skilled in the art can
To make various modifications and variations without departing from the spirit and scope of the present invention, so
Modifications and variations each fall within and be defined by the appended claims within the scope of.
Claims (9)
1. a kind of farmland nitrate nitrogen detection method based on ISE, its feature exists
In, including：
Detect various concentrations master sample solution at different temperatures first response potential and
Second response potential, the first response potential is the response potential of nitrate ion electrode, institute
State the response potential that the second response potential is chlorine ion electrode；
According to the master sample solution of each concentration at various temperatures first response potential and
Second response potential, sets up a detection model, the detection model include the first response potential with
The first function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature and the second response potential
With the second function relation of nitric acid Na ion concentration, chlorine ion concentration and temperature；
Detect the soil extraction of the soil to be detected at a temperature of the farm environment collected
First response potential and second response potential；
According to the first of the soil extraction the response potential, the second sound of the soil extraction
Potential and the farm environment temperature are answered, the soil extraction is calculated using the detection model
Nitrate ion concentration；
The soil to be detected is determined according to the nitrate ion concentration of the soil extraction
Nitrate nitrogen content.
2. according to the method described in claim 1, it is characterised in that described according to each concentration
Master sample solution at various temperatures first response potential and second response potential, set up
One detection model, including：
The first response potential, the second sound at each temperature are set up using arithmetic of linearity regression
Answer functional relation of the potential respectively with nitric acid Na ion concentration and chlorine ion concentration：
<mfenced open = "{" close = "">
<mtable>
<mtr>
<mtd>
<msub>
<mi>E</mi>
<mn>1</mn>
</msub>
<mo>=</mo>
<msub>
<mi>&beta;</mi>
<mn>01</mn>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>11</mn>
</msub>
<mi>lg</mi>
<msub>
<mi>C</mi>
<mrow>
<msubsup>
<mi>NO</mi>
<mn>3</mn>
<mo>-</mo>
</msubsup>
</mrow>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>21</mn>
</msub>
<mi>lg</mi>
<msub>
<mi>C</mi>
<mrow>
<msup>
<mi>Cl</mi>
<mo>-</mo>
</msup>
</mrow>
</msub>
</mtd>
</mtr>
<mtr>
<mtd>
<msub>
<mi>E</mi>
<mn>2</mn>
</msub>
<mo>=</mo>
<msub>
<mi>&beta;</mi>
<mn>02</mn>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>12</mn>
</msub>
<mi>lg</mi>
<msub>
<mi>C</mi>
<mrow>
<msubsup>
<mi>NO</mi>
<mn>3</mn>
<mo>-</mo>
</msubsup>
</mrow>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>22</mn>
</msub>
<mi>lg</mi>
<msub>
<mi>C</mi>
<mrow>
<msup>
<mi>Cl</mi>
<mo>-</mo>
</msup>
</mrow>
</msub>
</mtd>
</mtr>
</mtable>
</mfenced>
Wherein, E1For the first response potential at this temperature, E2For the second sound at this temperature
Answer potential,For nitrate ion concentration at this temperature,Chlorion at this temperature
Concentration, β01、β11、β21、β02、β12、β22For regression parameter at this temperature；
Each regression parameter and temperature are subjected to unitary linear fit using least square method, obtained
The unitary linear function of the regression parameter and temperature；
According at each temperature first response potential, second response potential respectively with nitric acid sodium ion
The linear letter of unitary of concentration and the functional relation of chlorine ion concentration and each regression parameter and temperature
Number, determines that the detection model is：
<mrow>
<mfenced open = "{" close = "">
<mtable>
<mtr>
<mtd>
<mrow>
<msub>
<mi>E</mi>
<mn>1</mn>
</msub>
<mo>=</mo>
<msub>
<mi>&beta;</mi>
<mn>01</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>11</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<msub>
<mi>lgC</mi>
<mrow>
<msubsup>
<mi>NO</mi>
<mn>3</mn>
<mo>-</mo>
</msubsup>
</mrow>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>21</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<msub>
<mi>lgC</mi>
<mrow>
<msup>
<mi>Cl</mi>
<mo>-</mo>
</msup>
</mrow>
</msub>
</mrow>
</mtd>
</mtr>
<mtr>
<mtd>
<mrow>
<msub>
<mi>E</mi>
<mn>2</mn>
</msub>
<mo>=</mo>
<msub>
<mi>&beta;</mi>
<mn>02</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>12</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<msub>
<mi>lgC</mi>
<mrow>
<msubsup>
<mi>NO</mi>
<mn>3</mn>
<mo>-</mo>
</msubsup>
</mrow>
</msub>
<mo>+</mo>
<msub>
<mi>&beta;</mi>
<mn>22</mn>
</msub>
<mrow>
<mo>(</mo>
<mi>T</mi>
<mo>)</mo>
</mrow>
<msub>
<mi>lgC</mi>
<mrow>
<msup>
<mi>Cl</mi>
<mo>-</mo>
</msup>
</mrow>
</msub>
</mrow>
</mtd>
</mtr>
</mtable>
</mfenced>
<mo>.</mo>
</mrow>
3. according to the method described in claim 1, it is characterised in that described according to the soil
The nitrate ion concentration of leaching liquor, determines the nitrate nitrogen content of the soil to be detected, including：
Set up nitrate ion concentration, soil of the nitrate nitrogen content of soil with corresponding soil extraction
The 3rd functional relation between the volumetric water content of earth；
By the nitrate ion concentration of the soil extraction and the soil to be detected collected
Volumetric water content substitutes into the 3rd functional relation, and the nitrate nitrogen for calculating the soil to be detected contains
Amount.
4. method according to claim 3, it is characterised in that the 3rd functional relation
For：
<mrow>
<mi>&omega;</mi>
<mo>=</mo>
<msub>
<mi>C</mi>
<mrow>
<msubsup>
<mi>NO</mi>
<mn>3</mn>
<mo>-</mo>
</msubsup>
</mrow>
</msub>
<mo>&times;</mo>
<mn>14</mn>
<mo>&times;</mo>
<msup>
<mn>10</mn>
<mn>3</mn>
</msup>
<mo>&times;</mo>
<mrow>
<mo>(</mo>
<msub>
<mi>&theta;</mi>
<mi>v</mi>
</msub>
<mo>+</mo>
<mn>5</mn>
<mo>)</mo>
</mrow>
</mrow>
Wherein, ω is the nitrate nitrogen content of soil,For the nitrate ion of soil extraction
Concentration, θvFor the volumetric water content of soil.
5. according to the method described in claim 1, it is characterised in that the mark of the various concentrations
Quasi- sample solution is the sodium nitrate solution of different concentration knowns and the sodium chloride of different concentration knowns
The mixed solution of solution.
6. according to the method described in claim 1, it is characterised in that the detection various concentrations
Master sample solution at different temperatures first response potential and second response potential, bag
Include：
The container for filling master sample solution and deionized water is placed in constant temperature bath of liquid groove；
Set using master sample solution described in nitrate ion electrode detection in constant temperature bath of liquid groove
The first response potential during for different temperatures, detects that the master sample is molten using chlorine ion electrode
Second response potential of the liquid when constant temperature bath of liquid groove is set as different temperatures.
7. a kind of farmland nitrate nitrogen detecting system based on ISE, its feature exists
In, including nitrate ion electrode, chlorine ion electrode, constant temperature bath of liquid groove, data acquisition unit and
Data processor, wherein：
The nitrate ion electrode, for when being positioned over the soil extraction of soil to be detected
Produce the first response potential for characterizing nitrate ion concentration；
The chlorine ion electrode, for when being positioned over the soil extraction produce characterize chlorine from
Second response potential of sub- concentration；
The constant temperature bath of liquid groove, for the first sound in the soil extraction for detecting soil to be detected
When answering potential and the second response potential, the soil extraction is maintained at farm environment temperature
Degree；
The data acquisition unit, the first response electricity for gathering the nitrate ion electrode
The farm environment that gesture, the second response potential of the chlorine ion electrode and temperature sensor are gathered
Temperature, and the data of collection are sent to the data processor；
The data processor, for the data sent according to the data acquisition unit, exploitation right
Profit requires the detection model in any described methods of 1-6, calculates the nitre of the soil extraction
Acid ion concentration, and according to the nitrate ion concentration of the soil extraction, it is determined that described
The nitrate nitrogen content of soil to be detected.
8. system according to claim 7, it is characterised in that the data acquisition unit bag
Signal-regulated kinase, analog-to-digital conversion module and processing module are included, the system also includes detection agriculture
The temperature sensor of field environment temperature and for the water for the volumetric water content for detecting soil to be detected
Sub-sensor, wherein：
The Signal-regulated kinase, for responding potential to the first of the nitrate ion electrode
Carried out with the second response potential of the chlorine ion electrode defeated after impedance conversion, filtering and amplification
Go out；
The analog-to-digital conversion module, is connected with the output end of the Signal-regulated kinase, for pair
The signal digitlization of the Signal-regulated kinase output；
The processing module, output end, the temperature sensor with the analog-to-digital conversion module
And moisture transducer connection, for will the digitized first response potential, digitized the
Two response potential, the farm environment temperature collected and the volume of the soil to be detected collected contain
Water rate is pre-processed.
9. system according to claim 8, it is characterised in that the data acquisition unit is also
Including power module, display module, input module, wireless transport module and/or memory module,
Wherein：
The power module, with the display module, the processing module and the signal condition
Module is connected, for for the display module, the processing module and the Signal-regulated kinase
Power supply is provided；
The display module, is connected with the processing module, for pretreated data to be entered
Row display；
The input module, is connected with the processing module, for inputting the control processing mould
The control instruction that block is pre-processed；
The wireless transport module, is connected with the processing module, for by the processing module
Pretreated data are sent to the data processor；
The memory module, is connected with the processing module, for pretreated data to be entered
Row storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610147796.2A CN107192754B (en) | 2016-03-15 | 2016-03-15 | Farmland nitrate nitrogen detection method and system based on ion selective electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610147796.2A CN107192754B (en) | 2016-03-15 | 2016-03-15 | Farmland nitrate nitrogen detection method and system based on ion selective electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107192754A true CN107192754A (en) | 2017-09-22 |
| CN107192754B CN107192754B (en) | 2019-11-08 |
Family
ID=59872013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610147796.2A Expired - Fee Related CN107192754B (en) | 2016-03-15 | 2016-03-15 | Farmland nitrate nitrogen detection method and system based on ion selective electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107192754B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112147202A (en) * | 2020-09-18 | 2020-12-29 | 河南农业大学 | Soil nitrate nitrogen real-time detection system and method based on electrochemistry |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811255A (en) * | 1995-09-20 | 1998-09-22 | Yellowstone Environmental Science | Apparatus and method for anaerobic respirometry |
| CN102175737A (en) * | 2010-12-30 | 2011-09-07 | 中国科学技术大学 | Correction method and device for cross sensitivity of ion-selective electrode for on-line detection of nutrient solution components |
| CN102435656A (en) * | 2011-09-13 | 2012-05-02 | 中国农业大学 | Sensor array and method for quickly detecting soil nitrate nitrogen |
| JP2013167567A (en) * | 2012-02-16 | 2013-08-29 | Taiheiyo Material Kk | Method for measuring soil salinity concentration |
| US20130304395A1 (en) * | 2010-12-23 | 2013-11-14 | Ravendra Naidu | Analyte ion detection method and device |
| CN104198419A (en) * | 2014-08-14 | 2014-12-10 | 河南农业大学 | Soil nitrate nitrogen extracting agent and method for rapid determination of soil nitrate nitrogen |
-
2016
- 2016-03-15 CN CN201610147796.2A patent/CN107192754B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811255A (en) * | 1995-09-20 | 1998-09-22 | Yellowstone Environmental Science | Apparatus and method for anaerobic respirometry |
| US20130304395A1 (en) * | 2010-12-23 | 2013-11-14 | Ravendra Naidu | Analyte ion detection method and device |
| CN102175737A (en) * | 2010-12-30 | 2011-09-07 | 中国科学技术大学 | Correction method and device for cross sensitivity of ion-selective electrode for on-line detection of nutrient solution components |
| CN102435656A (en) * | 2011-09-13 | 2012-05-02 | 中国农业大学 | Sensor array and method for quickly detecting soil nitrate nitrogen |
| JP2013167567A (en) * | 2012-02-16 | 2013-08-29 | Taiheiyo Material Kk | Method for measuring soil salinity concentration |
| CN104198419A (en) * | 2014-08-14 | 2014-12-10 | 河南农业大学 | Soil nitrate nitrogen extracting agent and method for rapid determination of soil nitrate nitrogen |
Non-Patent Citations (3)
| Title |
|---|
| PU PAN 等: "《ANN model optimization for reducing interference of Cl- on NO3- ion selective electrode》", 《农业工程学报》 * |
| 杜尚丰 等: "《电极法检测土壤硝态氮的干扰因素与测量模型研究》", 《农业机械学报》 * |
| 杜尚丰 等: "《电极法测定土壤硝态氮精度的提高方法》", 《农业机械学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112147202A (en) * | 2020-09-18 | 2020-12-29 | 河南农业大学 | Soil nitrate nitrogen real-time detection system and method based on electrochemistry |
| CN112147202B (en) * | 2020-09-18 | 2024-03-22 | 河南农业大学 | Electrochemical-based soil nitrate nitrogen real-time detection system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107192754B (en) | 2019-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2936132B1 (en) | Soil chemistry sensor | |
| US10684241B2 (en) | Method for detecting clogging of subsurface flow constructed wetland | |
| Gartley | Recommended methods for measuring soluble salts in soils | |
| CN100429519C (en) | Method for detecting plant electric signal in green house and special equipment thereof | |
| CN104820003A (en) | Paper-based micro-fluidic system and method for detection of pesticide residues | |
| CN104215672A (en) | Rapid soil nutrient detection method | |
| CN107941989A (en) | A kind of Kiwi berry cold hardness evaluation and the method for evaluation | |
| CN107064409A (en) | A kind of soil fast determining method | |
| Govindasamy et al. | Comparison of low-cost methods for soil water holding capacity | |
| CN105806731A (en) | Method for determining decomposition rate of straws in field | |
| CN104488432A (en) | High-yield drop irrigation maize soil nutrient diagnosis and nitrogen fertilizer recommendation method | |
| CN205374443U (en) | Soil sample test device | |
| CN107192754A (en) | Farmland nitrate nitrogen detection method and system based on ISE | |
| CN103235216B (en) | A kind of aerator Auto-Test System based on LabVIEW | |
| CN205665171U (en) | Soil pH quick test device | |
| Thayer et al. | Runoff nutrient loads as affected by residue cover, manure application rate, and flow rate | |
| CN201993242U (en) | Farmland test soil collecting bag | |
| CN207764212U (en) | A kind of soil and fertilizer nutrient detector | |
| Tanriverdi | Using TDR in the agricultural water management | |
| CN207650207U (en) | A kind of plant root soil humidity prospecting apparatus | |
| CN103267664B (en) | Soil standard sample and applications thereof | |
| Erickson | Field experience validates on-the-go soil pH sensor | |
| CN103197045B (en) | A kind of method of solid geometry knowledge analysis soil three-phase ratio data | |
| ur Rehman et al. | IoT based smart farming using decision support system | |
| CN106979969A (en) | The Intelligent bowl of concentration of heavy metal ion in a kind of detection food liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191108 Termination date: 20210315 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |