CN102393414A - Microelectrode for measuring nitrogen and potassium of greenhouse crops, its measurement method of nitrogen and potassium - Google Patents
Microelectrode for measuring nitrogen and potassium of greenhouse crops, its measurement method of nitrogen and potassium Download PDFInfo
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Abstract
The invention discloses a microelectrode for measuring nitrogen and potassium of greenhouse crops, and a measurement method of nitrogen and potassium. The method comprises the following steps: four micro glass tubes which are respectively filled with a reference solution inner filling liquid, nitrate ion inner filling liquid, ammonium ion inner filling liquid and potassium ion inner filling liquid tightly form multi-tube micro glass tubes in axially parallel, a signal line connected with a same high resistance microelectrode amplifier is inserted in each inner filling liquid, signal voltages of nitrate ion concentration, ammonium ion concentration and potassium ion concentration are respectively generated between the nitrate ion signal line, ammonium ion signal line, potassium ion signal line and the reference signal lines, each ion concentration is calculated by using formula, and the activity of nitrate ions, ammonium ions and potassium ions in greenhouse crops micro area can be rapidly and accurately measured, and the mutual influence among three ions is corrected.
Description
Technical field
The invention belongs to manufacturing technology field, greenhouse, particularly a kind of chamber crop nitrogen potassium measurement microelectrode and measuring method are measured the nitrogen potassium content in the chamber crop.
Background technology
The crop of hothouse production, yield is big, fertilizer requirement is many and soil fertility consumes height, and fertilising the out of proportion and nutritional deficiency symptoms of main nutrient elements such as nitrogen, potassium occur mainly by manual control through regular meeting, directly influence the yield and quality of crop.Some producer is for fear of the generation of nutritional deficiency problem, and excessive nitrogen, the potash fertilizer used not only causes the waste and the environmental pollution of fertilizer, and can cause the reduction of crop quality, even the underproduction.
Traditional crop nutrition diagnosis mode all is to be main with producer's experience and laboratory conventionally test.Diagnose by rule of thumb nutrition whether rich scarce weak point be to need to symptom just can make judgement when apparent in view, and possibly cause injury at this moment to crop.Some is because the excessive or not enough injury that causes of fertilizer is irreversible; Therefore, artificial diagnosis exists subjectivity and individual difference, and mistaken diagnosis takes place easily.Laboratory conventionally test method mainly contains leaf colour atla sheet method, chemical diagnosis, fertilizer window and uses diagnosis and enzymology diagnosis method etc.; These traditional means of testing can destroy making deposits yields; Influence plant growth; And need the human and material resources of labor, poor in timeliness at aspects such as sampling, mensuration, data analyses.
Microelectrode measure nutrient ions concentration fast, convenient, number be 200820228434.7 like Chinese patent, name is called " a kind of nitrate radical ionic selectivity micro-electrode "; Chinese patent number is 200820228429.6, and name is called " a kind of ammonium ion selective composite micro-electrode "; The concentration of ammonium radical ion in disclosed a kind of two resistance ammonium radical ion selectivity micro-electrodes mensuration rice leaf cells of " plant nutrient and fertilizer journal " the 15th the 3rd phase of volume in 2009 such as Yin Xiaoming; Jia Lijun etc. 2005 measure the not concentration of nitrate ion in the balling pakchoi blade cell of live bodies at disclosed a kind of two resistance ion selectivities of " soil journal " the 42nd the 3rd phase of volume; The weak point of above-mentioned these disclosed technical schemes is to detect the concentration of ammonium radical ion or nitrate ion single ionic; And owing to do to exist simultaneously in the object different kinds of ions, other ion to bring interference to electrodes selective, nutritional deficiency can cause that plant endotrophic element ion takes place by significant the variation; And influence each other between the nutrient ion concentration obviously; So detect single ionic concentration, can't eliminate the influence of main interfering ion, can't react the real nutrition condition of crop.
Summary of the invention
The objective of the invention is provides a kind of chamber crop nitrogen potassium measurement microelectrode for the defective that overcomes above-mentioned prior art, can measure the concentration of making tiny area nitrate ion, ammonium radical ion and potassium ion in the object simultaneously.Another object of the present invention provides chamber crop nitrogen potassium measurement method, adopts said microelectrode to detect nitrogen, the potassium content of crop tiny area fast, accurately.
The technical scheme that chamber crop nitrogen potassium measurement microelectrode of the present invention adopts is: the little glass tube of multitube is closely to be formed by four little glass tube axially parallel ground; The lower end is drawn into taper; Awl end place, lower end in first, the 3rd, the 4th little glass tube of the little glass tube of multitube is filled with nitrate ion sensitive agent, ammonium radical ion sensitive agent, potassium ion sensitive agent respectively; The whole reference internal-filling liquid that is filled with in second little glass tube, nitrate ion sensitive agent, ammonium radical ion sensitive agent, potassium ion sensitive agent top liquid level conjointly are filled with nitrate ion internal-filling liquid, ammonium radical ion internal-filling liquid, potassium ion internal-filling liquid respectively; Be inserted with nitrate ion signal wire, reference signal line, ammonium radical ion signal wire, potassium ion signal wire in nitrate ion internal-filling liquid, reference internal-filling liquid, ammonium radical ion internal-filling liquid, the potassium ion internal-filling liquid respectively; Each said signal wire stretches into from the little glass tube of multitube outside respectively and is fixedly connected the suitable for reading of the little glass tube of multitube through fluid sealant; Nitrate ion signal wire, ammonium radical ion signal wire, potassium ion signal wire connect high resistant micro-electrode amplifier second channel input end respectively, and the reference signal line connects same high resistant micro-electrode amplifier first passage input end.
The technical scheme that the measuring method of chamber crop nitrogen potassium measurement microelectrode of the present invention adopts is: the lower end awl end with the little glass tube of multitube inserts the chamber crop detected part earlier, at nitrate ion signal wire, ammonium radical ion signal wire (11), potassium ion signal wire respectively and produce nitrate ion concentration signal voltage V1, ammonium radical ion concentration signal voltage V2, potassium concentration signal voltage V3 between the reference signal line; Utilize formula to calculate each ion concentration respectively again:
Lg (nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13; (1)
Lg (ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23; (2)
Lg (potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33; (3)
In the formula: k11 is the nitrate ion sensitivity coefficient; K12 is the interference coefficient of ammonium radical ion to nitrate ion; K13 is the interference coefficient of potassium ion to nitrate ion; E11 is a nitrate ion error term, and e12 is the mushing error item of ammonium radical ion to nitrate ion, and e13 is the mushing error item of potassium ion to nitrate ion; K21 is the interference coefficient of nitrate ion to the ammonium radical ion; K22 is an ammonium radical ion sensitivity coefficient; K23 is the interference coefficient of potassium ion to the ammonium radical ion; E21 is the mushing error item of nitrate ion to the ammonium radical ion, and e22 is an ammonium radical ion error term, and e23 is the mushing error item of potassium ion to the ammonium radical ion; K31 is the interference coefficient of nitrate ion to potassium ion; K32 is the interference coefficient of ammonium radical ion to potassium ion, and k33 is the potassium ion sensitivity coefficient, and e31 is the mushing error item of nitrate ion to potassium ion; E32 is the mushing error item of ammonium radical ion to potassium ion, and e33 is a potassium ion error term.
Definite method of k11, k12, k13, e11, e12, e13, k11 is: utilize the known nitrate ion standard solution of concentration that k11, k12, k13, e11, e12 and e13 in the formula (1) are demarcated earlier, then formula (1) is changed to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (4)
Microelectrode is inserted in the nitrate ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively; Write down 5 groups of nitrate ion concentration of standard solution and corresponding nitrate ion concentration signal voltage V1; There are not ammonium radical ion and potassium ion in the solution; Making the middle k12 of formula (4), k13, e12 and e13 is 0, and then formula (4) is reduced to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+e11 (5)
With V1 value substitution formula (5), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k11 and e11;
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion; Make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value one time; Do not have potassium ion in the solution, make that k13 and e13 are 0, then formula (4) is reduced to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+e11+e12 (6)
With V1 value that measures and V2 value substitution formula (6), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k12 and e12;
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion; Make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time; The fixed k11 of substitution, k12, e11 and e12 are in formula (4); Obtain different nitrate ion concentration calculated values, adopt least square method to calculate k13 and e13;
In like manner, definite method of the definite method of k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 and k11, k12, k13, e11, e12, e13, k11 is similar.
After the present invention adopted technique scheme, the beneficial effect that has was:
1, can measure the concentration of chamber crop tiny area nitrate ion, ammonium radical ion and potassium ion simultaneously apace, accuracy of detection is high, and influencing each other between these three kinds of ions revised.
2, three kinds of nutritional labelings are measured simultaneously, can be carried out decoupling zero, detection method and instrument are provided for accurately judging the crop alimentary state to the antagonism between crop nitrate ion, ammonium radical ion and the potassium ion nutrient.
3, can carry out somatometry to crop.
Description of drawings
Fig. 1 is the structural representation of chamber crop nitrogen potassium measurement microelectrode of the present invention.
Among the figure: 1. nitrate ion sensitive agent; 2. ammonium radical ion sensitive agent; 3. potassium ion sensitive agent; 4. the little glass tube of multitube; 5. nitrate ion internal-filling liquid; 6. reference internal-filling liquid; 7. ammonium radical ion internal-filling liquid; 8. potassium ion internal-filling liquid; 9. nitrate ion signal wire; 10. reference signal line; 11. ammonium radical ion signal wire; 12. potassium ion signal wire; 13. fluid sealant.
Embodiment
The present invention closely forms the little glass tube of multitube by four little glass tube axially parallel ground that are filled with reference, nitrate ion, ammonium radical ion, potassium ion internal-filling liquid respectively; Be inserted with the signal wire that connects same high resistant micro-electrode amplifier in every internal-filling liquid respectively; Nitrate ion, ammonium radical ion, potassium ion signal wire are respectively and produce nitrate ion concentration, ammonium radical ion concentration, potassium concentration signal voltage between the reference signal line; Utilize formula to calculate each ion concentration respectively; Can measure the activity of chamber crop tiny area nitrate ion, ammonium radical ion and potassium ion simultaneously quickly and accurately, and influencing each other between these three kinds of ions revised.Specific as follows:
As shown in Figure 1; Four little glass tube axially parallel ground are closely linked together; Form a little glass tube of multitube; Use multitube able to programme to draw the pin device that the little glass tube of multitube is drawn into the lower end and be the little glass tube 4 of the multitube of taper, the minimum diameter at the cone point place of the little glass tube 4 of multitube is 2 μ m～10 μ m.The inwall that draws the good little glass tube 4 of multitube is carried out conventional silanization handle, and under 150 ℃ of temperature, toasted 60 minutes～120 minutes continuously.
Awl end place, lower end in first little glass tube of the little glass tube 4 of multitube is filled with nitrate ion sensitive agent 1; The liquid column length of nitrate ion sensitive agent 1 is 0.1mm～1mm; Nitrate ion sensitive agent 1 top is filled with nitrate ion internal-filling liquid 5; Nitrate ion internal-filling liquid 5 links to each other with nitrate ion sensitive agent 1 liquid level, and the liquid column length of nitrate ion internal-filling liquid 5 is 5mm～30mm.Nitrate ion signal wire 9 stretches into inside from the little glass tube of multitube 4 outsides, and inserts in the nitrate ion internal-filling liquid 5.
The whole reference internal-filling liquid 6 that is filled with in second little glass tube of the little glass tube 4 of multitube, the liquid column length of reference internal-filling liquid 6 is 5mm～31mm, reference signal line 10 stretches into inside from the little glass tube of multitube 4 outsides, and inserts in the reference internal-filling liquid 6.
Awl end place, lower end in the 3rd little glass tube of the little glass tube 4 of multitube is filled with ammonium radical ion sensitive agent 2; The liquid column length of ammonium radical ion sensitive agent 2 is 0.1mm～1mm; Ammonium radical ion sensitive agent 2 tops are filled with ammonium radical ion internal-filling liquid 7; Ammonium radical ion internal-filling liquid 7 links to each other with ammonium radical ion sensitive agent 2 liquid levels, and the liquid column length of ammonium radical ion internal-filling liquid 7 is 5mm～30mm, and ammonium radical ion signal wire 11 stretches into and inserts the ammonium radical ion internal-filling liquid 7 from the little glass tube of multitube 4 outsides.
Awl end place, lower end in the 4th little glass tube of the little glass tube 4 of multitube is filled with potassium ion sensitive agent 3; The liquid column length of potassium ion sensitive agent 3 is 0.1mm～1mm; Potassium ion sensitive agent 3 tops are filled with potassium ion internal-filling liquid 8; Potassium ion internal-filling liquid 8 links to each other with potassium ion sensitive agent 3 liquid levels, and the liquid column length of potassium ion internal-filling liquid 8 is 5mm～30mm, and potassium ion signal wire 12 stretches into and inserts the potassium ion internal-filling liquid 8 from the little glass tube of multitube 4 outsides.
The place suitable for reading of the little glass tube 4 of multitube is with fluid sealant 13, and above-mentioned nitrate ion signal wire 9, reference signal line 10, ammonium radical ion signal wire 11 and potassium ion signal wire 12 is all fixing with fluid sealant 13 at the place suitable for reading of the little glass tube 4 of multitube.
Above-mentioned nitrate ion sensitive agent 1 adopts the Ammonium ionophore I-cocktail A of Sigma-Aldrich company; Ammonium radical ion sensitive agent 2 adopts the Nitrate ionophore-cocktail A of Sigma-Aldrich company; Potassium ion sensitive agent 3 adopts the Sodium ionophore I-cocktail A of Sigma-Aldrich company; The little glass tube 4 of multitube adopts the little glass tube of four pipes of Hilgenberg company, and nitrate ion internal-filling liquid 5 adopts the KCl of 50mM and the KNO of 50mM
3Mixed solution; Reference internal-filling liquid 6 adopts the KCl solution of 200mM; Ammonium radical ion internal-filling liquid 7 adopts the KCl solution of 50mM; Potassium ion internal-filling liquid 8 adopts the KCl solution of 50mM; Nitrate ion signal wire 9, reference signal line 10, ammonium radical ion signal wire 11 and potassium ion signal wire 12 are the Ag/AgCl silk; The Ag/AgCl silk uses that purity is 99%, diameter is processed with conventional electro-plating method as the silver-colored line of 0.3mm, and fluid sealant 13 adopts epoxy resin.
With nitrate ion signal wire 9, ammonium radical ion signal wire 11, potassium ion signal wire 12, be connected with high resistant micro-electrode amplifier second channel input end respectively; Reference signal line 10 is connected with same high resistant micro-electrode amplifier first passage input end; Form the difference input mode respectively, can read nitrate ion concentration signal voltage V1, ammonium radical ion concentration signal voltage V2, potassium concentration signal voltage V3 respectively.The SWF-1B type high resistant micro-electrode amplifier that the high resistant micro-electrode amplifier adopts Chengdu Instruement Factory to produce.
Before inserting the standard solution of variable concentrations or heterogeneity, should clean up and dry with the ultrapure water of resistivity earlier greater than 18M Ω cm with chamber crop nitrogen potassium measurement microelectrode of the present invention.
After the lower end awl end insertion chamber crop detected part with the little glass tube 4 of multitube; Between nitrate ion signal wire 9 and reference signal line 10, produce nitrate ion concentration signal voltage V1; Between ammonium radical ion signal wire 11 and reference signal line 10, produce ammonium radical ion concentration signal voltage V2; Between potassium ion signal wire 12 and reference signal line 10, produce potassium concentration signal voltage V3, utilize V1, V2 and V3 to calculate the ion concentration of each electrode part respectively:
Lg (nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (1)
Wherein: k11 is the nitrate ion sensitivity coefficient; K12 is the interference coefficient of ammonium radical ion to nitrate ion; K13 is the interference coefficient of potassium ion to nitrate ion; E11 is a nitrate ion error term, and e12 is the mushing error item of ammonium radical ion to nitrate ion, and e13 is the mushing error item of potassium ion to nitrate ion;
Lg (ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (2)
Wherein: k21 is the interference coefficient of nitrate ion to the ammonium radical ion; K22 is an ammonium radical ion sensitivity coefficient; K23 is the interference coefficient of potassium ion to the ammonium radical ion; E21 is the mushing error item of nitrate ion to the ammonium radical ion, and e22 is an ammonium radical ion error term, and e23 is the mushing error item of potassium ion to the ammonium radical ion;
Lg (potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (3)
Wherein: k31 is the interference coefficient of nitrate ion to potassium ion; K32 is the interference coefficient of ammonium radical ion to potassium ion; K33 is the potassium ion sensitivity coefficient; E31 is the mushing error item of nitrate ion to potassium ion, and e32 is the mushing error item of ammonium radical ion to potassium ion, and e33 is a potassium ion error term.
Definite method of each parameter k11 of nitrate ion electrode part, k12, k13, e11, e12, e13, k11, k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 is following in above-mentioned formula (1)-(3): before microelectrode being inserted the standard solution of variable concentrations or heterogeneity, should clean up and dry with the ultrapure water of resistivity greater than 18M Ω cm earlier.
For nitrate ion potential electrode part, utilize the known nitrate ion standard solution of concentration that k11, k12, k13, e11, e12 and e13 in the formula (1) are demarcated earlier, then formula (1) is changed to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (4)
The chamber crop nitrogen potassium measurement microelectrode of making is inserted in the nitrate ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively; After treating that nitrate ion concentration signal voltage V1 is stable; Record nitrate ion concentration of standard solution and corresponding V1 value, totally 5 groups of nominal datas.Do not have ammonium radical ion and potassium ion in the solution, can make the middle k12 of formula (4), k13, e12 and e13 is 0, and then formula (4) is reduced to
Lg (nitrate ion concentration of standard solution)=k11 * V1+e11 (5)
Like this, formula (5) is converted into confirms k11 and e11, and with the V1 value substitution formula (5) that measures, different k11 and e11 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the nitrate ion concentration calculated value of 5 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k11 and e11.
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion; Make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value, totally 25 groups of nominal datas one time.Do not have potassium ion in the solution, can make middle k13 of formula (4) and e13 is 0, and then formula (4) is reduced to
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+e11+e12 (6)
Owing to above-mentionedly confirmed k11 and e11, like this, formula (6) turns to confirms k12 and e12.With V1 value that measures and V2 value substitution formula (6), different k12 and e12 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the nitrate ion concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k12 and e12.
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion; Make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time; Totally 25 groups of nominal datas; The fixed k11 of substitution, k12, e11 and e12 are in formula (4), and problem is converted into confirming of k13 and e13.With the V1 value that measures, V2 value and V3 value substitution formula (4), different k13 and e13 can obtain different nitrate ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the nitrate ion concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding nitrate ion concentration of standard solution, calculates k13 and e13.
In like manner, definite method of the definite method of parameter k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 and above-mentioned k11, k12, k13, e11, e12, e13, k11 is similar, below explains respectively:
Ammonium radical ion potential electrode part utilizes the known ammonium radical ion standard solution of concentration that k21, k22, k23, e21, e22 and e23 in the formula (2) are confirmed that formula (2) is changed to
Lg (ammonium radical ion concentration of standard solution)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23 (7)
The chamber crop nitrogen potassium measurement microelectrode of making is inserted in the ammonium radical ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively; After treating that ammonium radical ion concentration signal voltage V2 is stable; Record ammonium radical ion concentration of standard solution and corresponding V2 value, totally 5 groups of nominal datas.Do not have nitrate ion and potassium ion in the solution, can make the middle k21 of formula (7), k23, e21 and e23 is 0, and then formula (7) is reduced to
Lg (ammonium radical ion concentration of standard solution)=k22 * V2+e22 (8)
Be converted into and confirm k22 and e22.With the V2 value substitution formula (8) that measures, different k22 and e22 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the ammonium radical ion concentration calculated value of 5 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k22 and e22;
In the ammonium radical ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add nitrate ion; Make that nitrate ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down ammonium radical ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value, totally 25 groups of nominal datas one time.Do not have potassium ion in the solution, can make middle k23 of formula (7) and e23 is 0, and then formula (7) is reduced to:
Lg (ammonium radical ion concentration of standard solution)=k21 * V1+k22 * V2+e21+e22 (9)
K22 and e22 confirm that problem is converted into confirms k21 and e21.With V1 value that measures and V2 value substitution formula (9), different k21 and e21 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the ammonium radical ion concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k21 and e21;
In the ammonium radical ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion; Make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down ammonium radical ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time; Totally 25 groups of nominal datas; The fixed k21 of substitution, k22, e21 and e22 are in formula (7), and problem is converted into confirming of k23 and e23.With the V1 value that measures, V2 value and V3 value substitution formula (7), different k23 and e23 can obtain different ammonium radical ion concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the ammonium radical ion concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding ammonium radical ion concentration of standard solution, calculates k23 and e23;
Potassium ion potential electrode part utilizes the known potassium ion standard solution of concentration that k31, k32, k33, e31, e32 and e33 in the formula (3) are confirmed that formula (3) is changed to
Lg (potassium ion concentration of standard solution)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33 (10)
The chamber crop nitrogen potassium measurement microelectrode of making is inserted in the potassium ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively; After treating that potassium concentration signal voltage V3 is stable; Record potassium ion concentration of standard solution and corresponding V3 value, totally 5 groups of nominal datas.Do not have nitrate ion and ammonium radical ion in the solution, can make the middle k31 of formula (10), k32, e31 and e32 is 0, and then formula (10) is reduced to
Lg (potassium ion concentration of standard solution)=k33 * V3+e33 (11)
Problem is converted into confirms k33 and e33.With the potassium concentration signal voltage V3 value substitution formula (11) that measures, different k33 and e33 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the potassium concentration calculated value of 5 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k33 and e33;
In the potassium ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add nitrate ion; Make that nitrate ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down potassium concentration, nitrate ion concentration signal voltage V1 value and potassium concentration signal voltage V3 value, totally 25 groups of nominal datas one time.Do not have the ammonium radical ion in the solution, can make middle k32 of formula (10) and e32 is 0, and then formula (10) is reduced to
Lg (potassium ion concentration of standard solution)=k31 * V1+k33 * V3+e31+e33 (12)
K33 and e33 confirm that problem is converted into confirms k31 and e31.With V1 value that measures and V3 value substitution formula (12), different k31 and e31 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the potassium concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k31 and e31;
In the potassium ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion; Make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down potassium concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time; Totally 25 groups of nominal datas; The fixed k31 of substitution, k33, e31 and e33 are in formula (10), and problem is converted into confirming of k32 and e32.The acquired k31 of substitution, k33, e31 and e33, with the V1 value that measures, V2 value and V3 value substitution formula (10), different k32 and e32 can obtain different potassium concentration calculated values.Adopting least square method, is principle with the error sum of squares minimum, and promptly the potassium concentration calculated value of 25 groups of nominal datas is a principle with the quadratic sum minimum of the difference of corresponding potassium ion concentration of standard solution, calculates k32 and e32.
Confirmed after parameter k11, k12, k13, e11, e12, e13, k11, k21, k22, e21, e22, e23, k31, k32, e31, e32, the e33; The most advanced and sophisticated chamber crop detected part of inserting of lower end awl end with the little glass tube 4 of multitube; Treat to read nitrate ion concentration signal voltage V1, ammonium radical ion concentration signal voltage V2 and potassium concentration signal voltage V3 after reading is stablized; In the parameter k11 that confirms, k12, k13, e11, e12, e13, k11, k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 difference substitution aforementioned formula (1)-(3), calculate the nitrate radical, ammonium radical ion and the potassium concentration information that obtain the crop detected part.
Claims (5)
1. chamber crop nitrogen potassium measurement microelectrode; Has a little glass tube of multitube (4); The little glass tube of multitube (4) is closely to be formed by four little glass tube axially parallel ground; The lower end is drawn into taper; It is characterized in that: the awl end place, lower end in first, the 3rd, the 4th little glass tube of the little glass tube of multitube (4) is filled with nitrate ion sensitive agent (1), ammonium radical ion sensitive agent (2), potassium ion sensitive agent (3) respectively; The whole reference internal-filling liquid (6) that is filled with in second little glass tube, nitrate ion sensitive agent (1), ammonium radical ion sensitive agent (2), potassium ion sensitive agent (3) top liquid level conjointly are filled with nitrate ion internal-filling liquid (5), ammonium radical ion internal-filling liquid (7), potassium ion internal-filling liquid (8) respectively; Be inserted with nitrate ion signal wire (9), reference signal line (10), ammonium radical ion signal wire (11), potassium ion signal wire (12) in nitrate ion internal-filling liquid (5), reference internal-filling liquid (6), ammonium radical ion internal-filling liquid (7), the potassium ion internal-filling liquid (8) respectively; Each said signal wire stretches into from the little glass tube of multitube (4) outside respectively and is fixedly connected the suitable for reading of the little glass tube of multitube (4) through fluid sealant (13); Nitrate ion signal wire (9), ammonium radical ion signal wire (11), potassium ion signal wire (12) connect high resistant micro-electrode amplifier second channel input end respectively, and reference signal line (10) connects same high resistant micro-electrode amplifier first passage input end.
2. a kind of chamber crop nitrogen potassium measurement microelectrode according to claim 1; It is characterized in that: the fluid column length of nitrate ion sensitive agent (1), ammonium radical ion sensitive agent (2), potassium ion sensitive agent (3) all is 0.1mm～1mm; The liquid column length of nitrate ion internal-filling liquid (5), ammonium radical ion internal-filling liquid (7), potassium ion internal-filling liquid (8) all is 5mm～30mm, and the liquid column length of reference internal-filling liquid (6) is 5mm～31mm.
3. a kind of chamber crop nitrogen potassium measurement microelectrode according to claim 1 is characterized in that: the minimum diameter at the awl end place, lower end of the little glass tube of multitube (4) is 2 μ m～10 μ m.
4. nitrogen potassium measurement method that adopts the said microelectrode of claim 1; It is characterized in that: earlier the lower end awl end with the little glass tube of multitube (4) inserts the chamber crop detected part, at nitrate ion signal wire (9), ammonium radical ion signal wire (11), potassium ion signal wire (12) respectively and produce nitrate ion concentration signal voltage V1, ammonium radical ion concentration signal voltage V2, potassium concentration signal voltage V3 between the reference signal line (10); Utilize formula to calculate each ion concentration respectively again:
Lg (nitrate ion concentration)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13; (1)
Lg (ammonium radical ion concentration)=k21 * V1+k22 * V2+k23 * V3+e21+e22+e23; (2)
Lg (potassium concentration)=k31 * V1+k32 * V2+k33 * V3+e31+e32+e33; (3)
In the formula: k11 is the nitrate ion sensitivity coefficient; K12 is the interference coefficient of ammonium radical ion to nitrate ion; K13 is the interference coefficient of potassium ion to nitrate ion; E11 is a nitrate ion error term, and e12 is the mushing error item of ammonium radical ion to nitrate ion, and e13 is the mushing error item of potassium ion to nitrate ion; K21 is the interference coefficient of nitrate ion to the ammonium radical ion; K22 is an ammonium radical ion sensitivity coefficient; K23 is the interference coefficient of potassium ion to the ammonium radical ion; E21 is the mushing error item of nitrate ion to the ammonium radical ion, and e22 is an ammonium radical ion error term, and e23 is the mushing error item of potassium ion to the ammonium radical ion; K31 is the interference coefficient of nitrate ion to potassium ion; K32 is the interference coefficient of ammonium radical ion to potassium ion, and k33 is the potassium ion sensitivity coefficient, and e31 is the mushing error item of nitrate ion to potassium ion; E32 is the mushing error item of ammonium radical ion to potassium ion, and e33 is a potassium ion error term.
5. nitrogen potassium measurement method according to claim 4; It is characterized in that: definite method of said k11, k12, k13, e11, e12, e13, k11 is: utilize the known nitrate ion standard solution of concentration that k11, k12, k13, e11, e12 and e13 in the formula (1) are demarcated earlier, then formula (1) is changed to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+k13 * V3+e11+e12+e13 (4)
Microelectrode is inserted in the nitrate ion standard solution that concentration is 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in order successively; Write down 5 groups of nitrate ion concentration of standard solution and corresponding nitrate ion concentration signal voltage V1; There are not ammonium radical ion and potassium ion in the solution; Making the middle k12 of formula (4), k13, e12 and e13 is 0, and then formula (4) is reduced to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+e11 (5)
With V1 value substitution formula (5), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k11 and e11;
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add the ammonium radical ion; Make that ammonium radical ion concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value and ammonium radical ion concentration signal voltage V2 value one time; Do not have potassium ion in the solution, make that k13 and e13 are 0, then formula (4) is reduced to:
Lg (nitrate ion concentration of standard solution)=k11 * V1+k12 * V2+e11+e12 (6)
With V1 value that measures and V2 value substitution formula (6), obtain different nitrate ion concentration calculated values, adopt least square method to calculate k12 and e12;
In the nitrate ion standard solution of 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM, add potassium ion; Make that potassium concentration reaches 0.01mM, 0.1mM, 1 mM, 10 mM and 100 mM in the solution; Under every kind of concentration combination, all write down nitrate ion concentration, nitrate ion concentration signal voltage V1 value, ammonium radical ion concentration signal voltage V2 value and potassium concentration signal voltage V3 value one time; The fixed k11 of substitution, k12, e11 and e12 are in formula (4); Obtain different nitrate ion concentration calculated values, adopt least square method to calculate k13 and e13;
In like manner, definite method of the definite method of k21, k22, e21, e22, e23, k31, k32, e31, e32, e33 and k11, k12, k13, e11, e12, e13, k11 is similar.
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