WO2019205673A1 - 一种基于离子活度核算营养液离子ec贡献率和电导度的方法 - Google Patents

一种基于离子活度核算营养液离子ec贡献率和电导度的方法 Download PDF

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WO2019205673A1
WO2019205673A1 PCT/CN2018/122033 CN2018122033W WO2019205673A1 WO 2019205673 A1 WO2019205673 A1 WO 2019205673A1 CN 2018122033 W CN2018122033 W CN 2018122033W WO 2019205673 A1 WO2019205673 A1 WO 2019205673A1
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ion
nutrient solution
activity
solution
concentration
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贺冬仙
宋金修
徐林
杜维芬
古在丰树
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中国农业大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G31/00—Soilless cultivation, e.g. hydroponics
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/20—Liquid fertilisers
    • C05G5/23—Solutions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/227—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for nitrates or nitrites
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
    • G16C20/20—Identification of molecular entities, parts thereof or of chemical compositions
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
    • G16C20/30—Prediction of properties of chemical compounds, compositions or mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the invention belongs to the technical field of soilless cultivation technology and water and fertilizer integration technology, in particular to a method for calculating nutrient solution ion EC contribution rate and electrical conductivity based on ion activity.
  • Soilless cultivation is widely recognized by the facility vegetable industry for its advantages of water saving, fertilizer saving, labor saving and production promotion.
  • the nutrient solution irrigation system based on electrical conductivity (EC) and pH (pH) can roughly meet the needs of crop growth and development, it is difficult to ensure the demand for specific inorganic ions in different growth stages of crops. Therefore, whether the feedback control of nutrient solution ion concentration can be based on crop growth requirements is the key to achieving efficient and high-quality production of facility vegetables.
  • the inorganic ion dynamic monitoring technology using ion selective electrode still has problems such as poor precision, short life and high price.
  • the nutrient solution irrigation system based on ion concentration regulation has not been applied to production practice, and the mainstream equipment still uses nutrient solution EC and The dynamic regulation of pH is dominant.
  • a new method for controlling the concentration of each component of the nutrient solution by EC and pH feedback is explored for the specific formulation of the nutrient solution for the cultivation of crops, so that the technical constraints of the ion selective electrode can be broken, thereby making use of EC and pH.
  • the nutrient solution irrigation system that dilutes the concentrated mother liquor by the sensor realizes feedback regulation of the main components of the nutrient solution.
  • EC is the result of the combined action of the effective concentration of each inorganic ion in the nutrient solution on the mixed solution.
  • the contribution of each ion to the nutrient solution EC is not only related to the molar concentration of the ion, but also closely related to the charge number and volume parameter of the ion. .
  • Regulating nutrient solution EC can only reflect the change of total salt content or comprehensive ion concentration in nutrient solution, but can not accurately grasp the ion concentration levels of the main components of nutrient solution.
  • the pH of the nutrient solution also indirectly affects the effectiveness of various inorganic ions. Excessive pH will lead to the precipitation of iron, manganese, copper and zinc ions, especially for the activity of iron ions.
  • the lower pH will cause the absorption of calcium ions by crops due to the antagonism of hydrogen ions.
  • the ion contribution rate of the mixed solution can be calculated based on the ion activity of each inorganic ion in the nutrient solution.
  • the ion concentration of the main components of the specific formulation nutrient solution and its EC In order to clarify the quantitative relationship between the ion concentration of the main components of the specific formulation nutrient solution and its EC, and finally provide theoretical basis and technical support for the dynamic feedback regulation of the ion concentration of the nutrient solution.
  • the object of the present invention is to provide a method for calculating the concentration of EC and the EC of the nutrient solution based on the ion activity, and to provide an ion EC for the EC and pH adjustment of the existing nutrient solution irrigation system.
  • Contribution rate and EC actual measurement back-calculation nutrient solution mainly constitutes a new method of ion concentration, which provides theoretical basis and technical support for realizing the feedback regulation of nutrient solution.
  • an index and a calculation method for the contribution rate of the nutrient solution ion EC are proposed, and a statistical regression model based on the ion activity for the EC estimation of the nutrient solution is proposed, thereby grasping the main composition of the nutrient solution between the ion concentration and the EC.
  • Quantitative relationship, using the ion EC contribution rate and nutrient solution EC actual measurement to backcalculate each ion concentration are as follows.
  • EC i is the ion EC contribution rate of ion i, %; Z i is the number of charges carried by ion i; T i is the ion activity of ion i, mol/L; ⁇ ⁇ is the ultimate molar conductivity of ion i , m 2 S/mol;
  • the ion activity T i is used to characterize the effective concentration of ions in the electrolyte solution, and the concentration at which the nutrient solution ions exert an electrostatic effect, calculated from the ion activity coefficient and the ion concentration:
  • T i is the ion activity of ion i, mol/L
  • ⁇ i is the ion activity coefficient of ion i
  • C i is the ion concentration of ion i, mol/L.
  • the average ion activity T characterizes the ion concentration or comprehensive activity of a single salt in the nutrient solution, and is calculated from the geometric mean of the ion activity of the anion and cation constituting the single salt solution or the mixed solution:
  • T is the average ion activity of a single salt solution or mixed solution, mol/L; T i and T j are the cation activity and anion activity of the composition single salt solution or mixed solution, respectively, mol/L; i and v j are the number of cations and anions constituting the mixed solution of the single salt solution.
  • the ion activity coefficient ⁇ i is used to characterize the correction coefficient of the deviation between the actual solution and the ideal solution. It is the thermodynamic parameter of the solution and is calculated by the Debye-Hückel polar limit law applicable to the nutrient solution:
  • ⁇ i is the ion activity coefficient of ion i;
  • A is a temperature-dependent constant, 0.5091 at 25 ° C;
  • B is a constant related to ion size, 0.328 at 25 ° C;
  • Z i is the ion i Number of charges;
  • r i is the volume parameter of ion i;
  • I is the ionic strength of the solution, mol / L;
  • Ionic strength I characterizes the electric field strength produced by the ions present in the solution, calculated from the concentration of each ion of the constituent solution and the number of charges it carries:
  • I is the ionic strength of the ion i in the solution, mol/L; C i is the ion concentration of the ion i, mol/L; Z i is the number of charges carried by the ion i;
  • the nutrient solution is a nutrient solution prepared based on the general formula of the garden test and the Yamazaki tomato formula.
  • the nutrient solution is configured to have a concentration concentration of 0.20, 0.25, 0.33, 0.50, 0.67, 1.00, 1.33, 1.50, 1.80, and 2.00 times, for a total of 10 concentration gradients.
  • the ions in the formula refer to NO 3 - , H 2 PO 4 - , SO 4 2- , NH 4 + , K + , Ca 2+ , Mg 2+ , Fe 2+ , etc., which are closely related to plant growth.
  • Main inorganic ions refer to NO 3 - , H 2 PO 4 - , SO 4 2- , NH 4 + , K + , Ca 2+ , Mg 2+ , Fe 2+ , etc.
  • the nitrate content was measured spectrophotometrically at 210 nm;
  • Ammonium nitrogen was measured by spectrophotometer at 630 nm based on indophenol blue colorimetric method
  • the effective phosphorus is colorimetrically measured at 680 nm using a spectrophotometer based on the molybdenum blue method;
  • Effective sulfur is measured by turbidity measurement at 535 nm using a spectrophotometer based on barium sulfate precipitation;
  • the effective chloride ion is measured by silver nitrate titration colorimetry
  • the effective potassium ion is measured by an atomic absorption spectrophotometer based on a flame emission method at 766.5 nm;
  • the effective calcium, magnesium and iron ions were measured by flame absorption method using an atomic absorption spectrophotometer at 422.7 nm, 285.2 nm and 248.3 nm, respectively.
  • concentrations of Ca(NO 3 ) 2 ⁇ 4H 2 O, KNO 3 , MgSO 4 ⁇ 7H 2 O, NH 4 H 2 PO 4 , K 2 SO 4 , KCl, and KH are added to each nutrient solution.
  • 2 PO 4 single salt the concentration of the single salt added to the nutrient solution is 0.0, 0.1, 0.2, 0.4 , 0.6, 0.8, 1.0, 1.2, 1.4 , 1.6, 1.8 and 2.0 times, for a total of 12 concentration gradients.
  • T 1-8 respectively represent the ion activities of NO 3 - , H 2 PO 4 - , SO 4 2- , K + , Ca 2+ , Mg 2+ , NH 4 + , Fe 2+ in the nutrient solution.
  • the present invention provides a multiple linear regression model for estimating the nutrient solution EC and pH for the average ion activity of the main constituents of the nutrient solution for a particular formulation.
  • a multiple linear regression model based on the average ion activity of the composition of the garden-based universal nutrient solution and the Yamazaki tomato nutrient solution and its EC and pH is as follows:
  • the present invention also clarifies that the average ion activity after the addition of a particular single salt in the nutrient solution has a linear effect on its EC.
  • the linear regression model of the average ion activity and its EC after adding a specific single salt to the garden test general nutrient solution and the Yamazaki tomato nutrient solution is as follows:
  • the present invention also provides a multiple linear regression model of the average ion activity and nutrient solution EC of each major component after adding a specific single salt to the nutrient solution as follows:
  • T x in the table indicates the average ion activity of the specific single salt added.
  • the technical core of the method of the present invention is a method for calculating the ion EC contribution rate and electrical conductivity of a specific formula nutrient solution based on ion activity, which can be used for facility cultivation management based on nutrient solution formula, and can improve nutrient solution management in facility cultivation from EC level.
  • the tomato yield increase effect is above 15%
  • the strawberry yield increase effect is above 20%.
  • the yield increase benefit is calculated to be 25000-40000 yuan/hm 2 according to the yield increase effect.
  • the technical core of the method of the invention lies in the method of calculating the ion EC contribution rate and electrical conductivity of the specific formula nutrient solution based on the ion activity, and can be applied to any facility cultivation management based on the nutrient solution formula, not only in the development of the nutrient solution control system.
  • Application promotion can also be applied to the intelligent matching of nutrient solution EC and pH and ion concentration in different growth stages of different crops.
  • the method of the invention can be used not only for the calculation of the electrical conductivity and the pH of the specific formula nutrient solution, but also by using the actual measurement of the electrical conductivity in combination with the ion contribution rate of each ion to inversely infer the ion concentration, and is the nutrient for soilless cultivation and water and fertilizer integration.
  • the theoretical basis and technical support for the dynamic regulation based on ion concentration, which is difficult to achieve by liquid, is provided.
  • the method is simple and easy to operate and has high accuracy. It can be used for the development of nutrient solution control system, and can meet the intelligent control requirements and formula adjustment of the defined EC and pH and ion concentration of nutrient solution in different growth stages of different crops.
  • Fig. 1 is a graph showing changes in the contribution rate of each ion EC in a specific concentration of a nutrient solution of a specific concentration according to the present invention.
  • Fig. 2 is a comparison diagram of EC estimated values and measured values of a specific formula nutrient solution of the present invention.
  • Figure 3 is a graph showing the response of each ion EC contribution rate to a specific single salt addition in a universal nutrient solution for a garden test.
  • the invention is characterized in that the EC and pH regulation of the existing nutrient solution irrigation system is difficult to reflect the concentration level of each inorganic ion, and a method for calculating the ion EC contribution rate and EC of the nutrient solution based on the ion activity is provided, and an ion is explored.
  • EC contribution rate and EC actual measurement of the new method of inverse calculation of nutrient solution ion concentration in order to provide theoretical basis and technical support for the realization of nutrient solution ion concentration feedback regulation.
  • the ion activity EC-based rate calculation based on ion activity and the multiple linear regression model of EC were established for the Japanese garden test general formula and the Yamazaki tomato formula.
  • the method of the invention is applicable to various nutrient solution formulations, and is not limited to the Japanese garden test general formula and the Yamazaki tomato formula.
  • the following examples are intended to illustrate the technical solutions of the present invention, but are not intended to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the materials used are all commercially available.
  • Example 1 Calculates the ion EC contribution rate and EC of a specific formula nutrient solution
  • the garden test general nutrient solution and the Yamazaki tomato nutrient solution are configured to standard concentrations of 0.20, 0.25, 0.33, 0.50, 0.67, 1.00, 1.33, 1.50, 1.80 and 2.00 times.
  • Etc. a total of 10 concentration gradients, the ion contribution rate and EC of each inorganic ion are calculated according to the method of the present invention.
  • the actual measurement of EC and pH of the nutrient solution to be tested was carried out using a portable multi-parameter analyzer (HQ-40D, HACH, USA).
  • the concentration of each ion concentration in the nutrient solution is as follows: the nitrate content is measured by spectrophotometry (UV-3150, Shimadzu Corporation, Japan) at 210 nm (HJ/T 346-2007); ammonium nitrogen is based on Indophenol blue colorimetric method uses a spectrophotometer to perform colorimetric measurement at 630 nm (HJ/T 537-2009); effective phosphorus is measured by spectrophotometer at 680 nm based on molybdenum blue method (HJ/T 593- 2010); effective sulfur based on barium sulfate precipitation method using spectrophotometer to measure turbidity at 535nm (HJ/T 342-2007); effective chloride ion by silver nitrate titration method (GBT 11896-89); effective
  • the nutrient solution of each concentration gradient is weighed to the corresponding content of the reagent (accurate to 1.0mg), fully dissolved and mixed, and added to the corresponding concentration of trace elements to prepare a 1L mixed solution, shaken and stored as a solution to be tested .
  • the EC contribution rate of each ion in the general nutrient solution based on the garden test is within 2%, and only the ion EC contribution rate of Fe 2+ is changed at 5 Within %, the EC contribution rate of each ion in the nutrient solution based on the Yamazaki tomato formula is also within 2%, but the ion EC contribution rate of H 2 PO 4 - and Fe 2+ is 4% and 6% (Fig. 1).
  • the theoretically calculated ion EC contribution rate of each ion in the nutrient solution is about 1%, which is different from the above measured values because the nutrient solution composition and the reagents actually used do not necessarily reach complete dissolution or Fully in line with the boundary conditions of the Debye-Hückel extreme law.
  • the ion concentration, charge amount and ionic radius of each ion in the nutrient solution are different, which results in a large difference in conductivity between ions, so the ion contribution of each ion to the mixed solution is also different.
  • the range of concentration change is limited, so the range of variation of the ion EC contribution rate of the nutrient solution in a certain concentration range is also small. For this reason, within the nutrient solution concentration range of a specific formula, as the relative concentration of the nutrient solution changes, the change in the contribution rate of each ion to its EC is negligible. This result reveals that based on the characteristic that the ion EC contribution rate is relatively stable, it is possible to quantitatively grasp the respective ion concentrations of the specific formulation nutrient solution by using the EC actual measurement.
  • the relative error between the EC estimates of the average ion activity and the multiple linear regression model between the average ion activity and the EC of the nutrient solution of the different concentrations of the garden test nutrient solution and the ECS is equal to 1.4. % and 1.8% ( Figure 2). Therefore, based on the above multiple linear regression model, the average ion activity of the known nutrient solution composition can completely predict the nutrient solution EC, and the measured EC and the ion contribution rate of each ion can be used to calculate the ions of the nutrient solution. concentration.
  • Example 2 Changes in nutrient solution ion EC contribution rate after adding a specific single salt
  • the above-mentioned concentration gradient of the single salt is separately added to the nutrient solution, and then fully mixed, and the volume is adjusted to 1 L of the mixed solution, shaken and stored as a nutrient to be tested. liquid.
  • the multivariate linear regression model was used to estimate the nutrient solution EC after adding a specific single salt, and the results of the comparison with the measured values showed that the EC estimation of the garden test general nutrient solution and the Yamazaki tomato nutrient solution after adding a specific single salt was carried out.
  • the relative deviations of the values from the measured values of EC were between 0.10-0.28% and 0.03-0.33%, respectively (Table 6).

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Abstract

一种基于离子活度核算特定配方营养液的离子EC贡献率和电导度的方法，以期利用电导度实际测量和离子EC贡献率来反算营养液各离子浓度。方法不仅可以用于特定配方营养液的电导度和酸碱度的核算，还可利用营养液电导度的实际测量反向推测各离子浓度，为设施无土栽培中营养液较难实现的基于离子浓度的动态调控提供理论依据和技术支持。方法简单易行、准确度高，可用于营养液调控系统开发，从而满足不同作物在不同生育阶段对营养液既定EC和pH与各离子浓度之间的智能匹配需求和配方调整的自动控制。

Description

一种基于离子活度核算营养液离子EC贡献率和电导度的方法 技术领域
本发明属于无土栽培技术和水肥一体化技术领域，具体地说，涉及一种基于离子活度核算营养液离子EC贡献率和电导度的方法。
背景技术
无土栽培以其节水、省肥、省工、促产等优点受到设施蔬菜产业的普遍认可。基于电导度(EC)和酸碱度(pH)调控的营养液灌溉系统虽然能够大致满足作物生长发育的需要，但很难保证作物在不同生育阶段对特定无机离子的需求变化。因此，能否根据作物生长需求进行营养液离子浓度的反馈控制是实现设施蔬菜高效优质生产的关键。利用离子选择性电极的无机离子动态监测技术仍存在精度差、寿命短、价格昂贵等问题，导致基于离子浓度调控的营养液灌溉系统还未能应用到生产实际，主流设备仍以营养液EC和pH的动态调控为主。为此，针对设施栽培作物的特定配方营养液应用，探索一种通过EC和pH反馈控制营养液各组成离子浓度的新方法，就可以突破离子选择性电极的技术制约，从而使利用EC和pH传感器对浓缩母液进行稀释的营养液灌溉系统实现营养液主要组成各离子浓度的反馈调控。
EC是组成营养液的各无机离子有效浓度对混合溶液综合作用的结果，各离子对营养液EC的贡献不仅与该离子的摩尔浓度有关，还与离子所带的电荷数与体积参数等密切相关。调控营养液EC仅能反映营养液中总含盐量或综合离子浓度的变化，而不能准确地掌握营养液主要组成的各离子浓度水平。营养液pH亦会间接地影响多种无机离子的有效性。pH过高会导致铁、锰、铜、锌离子的沉淀，尤其是对铁离子活性有显著影响，pH偏低则会由于氢离子的拮抗作用导致作物对钙离子的吸收障碍。为了调控营养液主要组成的各离子浓度以适应不同生育阶段作物对主要无机离子的动态需求，基于营养液中主要组成的各无机离子的离子活度就能计算其对混合溶液的离子EC贡献率，从而明确特定配方营养液主要组成的各离子浓度与其EC之间的定量关系，最终为营养液各离子浓度的动态反馈调控提供理论依据和技术支持。
发明内容
本发明的目的是针对现有营养液灌溉系统的EC和pH调控难以反映各无机离子浓度水平，提供一种基于离子活度核算营养液离子EC贡献率与EC的方法，探索一种利用离子EC贡献率和EC实际测量反算营养液主要组成各离子浓度的新方法，从而为实现营养液的各离子浓度反馈调控提供理论依据和技术支撑。
为了实现本发明目的，提出营养液离子EC贡献率的指标与计算方法，并提出基于离子活度进行营养液EC估测的统计回归模型，从而掌握营养液主要组成各离子浓度与EC之间的定量关系，利用离子EC贡献率和营养液EC实际测量来反算各离子浓度。本发明的具体技术方案如下。
1)离子EC贡献率表征各离子活性影响营养液EC的百分比，由离子活度和极限摩尔电导率计算：
Figure PCTCN2018122033-appb-000001
式中，EC i为离子i的离子EC贡献率，％；Z i为离子i所带电荷数；T i为离子i的离子活度，mol/L；λ ∞为离子i的极限摩尔电导率，m 2S/mol；
2)离子活度T i表征电解质溶液中离子发挥作用的有效浓度，为营养液离子发挥静电作用的浓度，由离子活度系数和离子浓度计算：
T i＝γ iC i
式中，T i为离子i的离子活度，mol/L；γ i为离子i的离子活度系数；C i为离子i的离子浓度，mol/L。
3)平均离子活度T表征营养液中某单盐的离子综合浓度或综合活性，由组成该单盐溶液或混合溶液的阴阳离子的离子活度的几何均值计算：
Figure PCTCN2018122033-appb-000002
式中，T为某单盐溶液或混合溶液的平均离子活度，mol/L；T i和T j分别为组成单盐溶液或混合溶液的阳离子活度和阴离子活度，mol/L；v i和v j为组成单盐溶液混混合溶液的阳离子和阴离子的个数。
4)离子活度系数γ i表征实际溶液与理想溶液之间偏差大小的校正系数，为溶液的热力学参数，由适用于营养液的Debye-Hückel极限定律计算：
Figure PCTCN2018122033-appb-000003
式中，γ i为离子i的离子活度系数；A为与温度有关的常量，25℃时为0.5091；B为与离子大小有关的常量，25℃时为0.328；Z i为离子i所带电荷数；r i为离子i的体积参数；I为溶液的离子强度，mol/L；
5)离子强度I表征溶液中存在的离子所产生的电场强度，由组成溶液的各离子浓度与其所带电荷数计算：
Figure PCTCN2018122033-appb-000004
式中，I为溶液中离子i的离子强度，mol/L；C i为离子i的离子浓度，mol/L；Z i为离子i所带电荷数；
6)基于营养液中各单盐的平均离子活度，采用多元线性回归模型，估测营养液的EC，并利用实测的营养液EC和各离子EC贡献率反算出营养液的各离子浓度。
进一步，所述营养液是基于园试通用配方和山崎番茄配方配制的营养液。
进一步，所述营养液配置成标准浓度的0.20、0.25、0.33、0.50、0.67、1.00、1.33、1.50、1.80和2.00倍，共计10个浓度梯度。
进一步，所述公式中的离子是指与植物生长密切相关的NO 3 -、H 2PO 4 -、SO 4 2-、NH 4 +、K +、Ca 2+、Mg 2+、Fe 2+等主要无机离子。
进一步，所述营养液中各离子浓度的实际测量方法如下：
硝态氮含量采用分光光度法在210nm处进行比色测量；
铵态氮基于腚酚蓝比色法采用分光光度计在630nm处进行比色测量；
有效磷基于钼蓝法采用分光光光度计在680nm处进行比色测量；
有效硫基于硫酸钡沉淀法采用分光光度计在535nm处进行比浊测量；
有效氯离子采用硝酸银滴定显色法测量；
有效钾离子基于火焰发射法采用原子吸收分光光度计，在766.5nm处进行测量；
有效钙、镁和铁离子基于火焰吸收法采用原子吸收分光光度计分别在422.7nm、285.2nm和248.3nm处进行测量。
进一步，所述每种营养液中添加不同浓度的Ca(NO 3) 2·4H 2O、KNO 3、MgSO 4·7H 2O、NH 4H 2PO 4，K 2SO 4、KCl、及KH 2PO 4单盐，添加到营养液中的单盐浓度为0.0、0.1、0.2、0.4、0.6、0.8、1.0、1.2、1.4、1.6、1.8和2.0倍，共计12个浓度梯度。
进一步，基于营养液各离子的离子活度，利用多元线性回归模型估测营养液EC的结果如下：
表1特定配方营养液的各离子活度与其EC和pH的多元线性回归模型
Figure PCTCN2018122033-appb-000005
其中T 1-8分别表示营养液中NO 3 -、H 2PO 4 -、SO 4 2-、K +、Ca 2+、Mg 2+、NH 4 +、Fe 2+的离子活度。
本发明提供针对特定配方的营养液主要组成成分的平均离子活度用来估测营养液EC和pH的多元线性回归模型。例如，基于园试通用营养液和山崎番茄营养液的组成成分的平均离子活度与其EC和pH的多元线性回归模型如下：
表2营养液组成的单盐平均离子活度与其EC和pH的多元线性回归模型
Figure PCTCN2018122033-appb-000006
Figure PCTCN2018122033-appb-000007
本发明还明确了在营养液中添加某特定单盐后的平均离子活度对其EC的影响是线性的。例如，在园试通用营养液和山崎番茄营养液中添加特定单盐后的平均离子活度与其EC的线性回归模型如下：
表3营养液中添加特定单盐后的平均离子活度对其EC的影响
Figure PCTCN2018122033-appb-000008
本发明同样提供了在营养液中添加特定单盐后各主要组成的平均离子活度与营养液EC的多元线性回归模型如下：
表4营养液中添加特定单盐后的平均离子活度与其EC的多元线性回归模型
Figure PCTCN2018122033-appb-000009
Figure PCTCN2018122033-appb-000010
Figure PCTCN2018122033-appb-000011
注：表中的T x表示所添加特定单盐的平均离子活度。
本发明的有益效果
本发明方法的技术核心在于基于离子活度核算特定配方营养液的离子EC贡献率和电导度的方法，可用于基于营养液配方的设施栽培管理，可以将设施栽培中营养液管理从EC水平提高到离子浓度水平，番茄增产效果在15％以上，草莓的增产效果在20％以上。在营养液智能管理水平上按照增产效果计算其增产效益为25000-40000元/hm 2。
本发明方法的技术核心在于基于离子活度核算特定配方营养液的离子EC贡献率和电导度的方法，可适用于任何基于营养液配方的设施栽培管理，不仅可以在营养液调控系统开发中进行应用推广，也可为不同作物在不同生育阶段进行营养液EC和pH与各离子浓度之间的智能匹配中进行应用推广。
本发明方法不仅可以用于特定配方营养液的电导度和酸碱度的核算，还可利用电导度的实际测量结合各离子EC贡献率反向推测各离子浓度，为无土栽培和水肥一体化中营养液较难实现的基于离子浓度的动态调控提供理论依据和技术支持。该方法简单易行、准确度高，可用于营养液调控系统开发，可以满足不同作物在不同生育阶段对营养液既定EC和pH与各离子浓度之间的智能匹配需求和配方调整的自动控制。
附图说明
图1为本发明不同浓度的特定配方营养液中各离子EC贡献率的变化图。
图2为本发明特定配方营养液的EC估测值与实测值的比较图。
图3为园试通用营养液中各离子EC贡献率对特定单盐添加的响应图。
具体实施方式
本发明的特点在于针对现有营养液灌溉系统的EC和pH调控难以反映各无机离子浓度水平，提供一种基于离子活度核算营养液的离子EC贡献率与EC的方法，探索一种利用离子EC贡献率和EC实际测量反算营养液各离子浓度的新方法，从而为实现营养液的离子浓度反馈调控提供理论依据和技术支撑。本发明为了测试该理论与方案的正确性，针对日本园试通用配方和山崎番茄配方，进行了基于离子活度的离子EC贡献率核算和EC的多元线性回归模型建立。本发明方法适用于各种营养液配方，并不局限于日本园试通用配方和山崎番茄配方。以下实施例用于说明本发明的技术方案，但不用来限制本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段，所用原料均为市售商品。
实施例1核算特定配方营养液的离子EC贡献率与EC
根据作物在各生育阶段对营养液浓度的不同需求，将园试通用营养液和山崎番茄营养液配置成标准浓度的0.20、0.25、0.33、0.50、0.67、1.00、1.33、1.50、1.80和2.00倍等，共10个浓度梯度，根据本发明的方法核算各无机离子的离子EC贡献率和EC。待测营养液使用Ca(NO 3) 2·4H 2O、KNO 3、MgSO 4·7H 2O、NH 4H 2PO 4、MnSO 4·H 2O、CuSO 4·5H 2O、ZnSO 4·7H 2O、H 3BO 3、(NH 4) 6Mo 7O 24·4H 2O的分析纯(西陇化工化学试剂，广东)和蒸馏水(EC值为11±2μS/cm，pH值为5.82±0.08)配制，螯合铁采用7％含量的DTPA-Fe-7(上海永通化工有限公司，上海)。K +溶液的离子EC贡献率测量增加了K 2SO 4、KCl和KH 2PO 4分析纯试剂。
待测营养液的EC和pH的实际测量采用便携式多参数分析仪(HQ-40D，HACH公司，美国)。营养液各离子浓度的测量方法为：硝态氮含量采用分光光度法(UV-3150，岛津制作所，日本)在210nm处进行比色测量(HJ/T 346-2007)；铵态氮基于腚酚蓝比色法采用分光光度计在630nm处进行比色测量(HJ/T 537-2009)；有效磷基于钼蓝法采用分光光光度计在680nm处进行比色测量(HJ/T 593-2010)；有效硫基于硫酸钡沉淀法采用分光光度计在535nm处进行比浊测量(HJ/T 342-2007)；有效氯离子采用硝酸银滴定显色法测量(GBT 11896-89)；有效钾离子基于火焰发射法采用原子吸收分光光度计(AA-7002，北京东西分析仪器 有限公司，北京)在766.5nm处进行测量(GB 11904-1989)；有效钙、镁(GB 11905-1989)和铁离子(GB 11911-1989)基于火焰吸收法采用原子吸收分光光度计分别在422.7nm、285.2nm和248.3nm处进行测量。
表5无土栽培常用的日本园试通用配方和山崎番茄配方
Figure PCTCN2018122033-appb-000012
各浓度梯度的营养液分别称取相应含量的试剂(精确至1.0mg)进行充分溶解后混合，并加入相应浓度的微量元素后配制为1L的混合溶液，摇匀后避光保存作为待测溶液。
在特定配方营养液浓度为标准浓度的0-2.0倍时，基于园试通用营养液中各离子EC贡献率的变化范围均在2％以内，仅有Fe 2+的离子EC贡献率变化在5％以内；基于山崎番茄配方的营养液中各离子EC贡献率的变化范围也在2％以内，但H 2PO 4 -和Fe 2+的离子EC贡献率的变化为4％和6％(图1)。营养液中各离子在一定浓度范围内理论计算的离子EC贡献率的变化均在1％左右，与上述实测值的差异是因为营养液组成及其实际使用的试剂并不一定能够达到完全溶解或者完全符合Debye-Hückel极限定律的边界条件。营养液中每种离子的离子浓度、带电荷量和离子半径等不尽相同，这导致离子之间的导电性存在很大差异，故各离子对混合溶液的离子EC贡献量也不同。由于作物栽培所用营养液是较稀的电解质溶液，其浓度变化的范围也有限，故在一定浓度范围的营养液的离子EC贡献率的变化范围也较小。为此，在特定配方的营养液浓度范围内，随着营养液相对浓度的变化，各离子对其EC的贡献率的变化可以忽略不计。该结果揭示了基于该离子EC贡献率相对稳定的特性可以利用EC实际测量定量地掌握特定配方营养液的各离子浓度。
利用不同浓度的园试通用营养液和山崎番茄营养液组成成分的平均离子活度与EC之间的多元线性回归模型核算的EC估测值，与EC实测值之间的相对误差分别仅为1.4％和1.8％(图2)。因此，基于上述多元线性回归模型，利用已知的营养液组成成分的平均离子活度完全可以准确地预测营养液EC，亦可利用实测的EC和各离子EC贡献率反算出营养液的各离子浓度。
实施例2添加特定单盐后的营养液离子EC贡献率的变化
为了测试在园试通用营养液和山崎番茄营养液中添加不同浓度的Ca(NO 3) 2·4H 2O、KNO 3、MgSO 4·7H 2O、NH 4H 2PO 4，K 2SO 4、KCl、及KH 2PO 4单盐后，混合溶液中主要离子成分的离子EC贡献率的变化，每种单盐的添加量设置成标准浓度(以配方离子浓度为标准)的0.0、0.1、0.2、0.4、0.6、0.8、1.0、1.2、1.4、1.6、1.8和2.0倍等，共计12个浓度梯度。基于园试通用配方和山崎番茄配方配制100L标准营养液后，在营养液中分别添加上述浓度梯度的单盐后进行充分混合，定容为1L混合液，摇匀后避光保存作为待测营养液。
在园试通用营养液和山崎番茄营养液中添加12种不同浓度梯度的特定单盐后的营养液中，该特定单盐各离子的离子EC贡献率有所增加，但其他离子的离子EC贡献率相应下降(图3)。添加营养液中已存在的Ca(NO 3) 2·4H 2O、KNO 3、MgSO 4·7H 2O和NH 4H 2PO 4时，各离子EC贡献率相对变化幅度较小的是NH 4H 2PO 4，MgSO 4·7H 2O和NH 4H 2PO 4中的阳离子和阴离子，其离子EC贡献率的上升幅度相近，而Ca(NO 3) 2·4H 2O和KNO 3中的阳离子上升幅度却是阴离子的5-6倍。这说明不同离子因本身特性的不同对离子EC贡献率影响的差异很大，这为区分营养液动态调控过程中的特定离子的调控或添加方式提供了理论依据。
在添加相同K +浓度的KNO 3、K 2SO 4、KCl、和KH 2PO 4时，K +的离子EC贡献率的变化相似，但不同阴离子的离子EC贡献率各有不同，其中阴离子EC贡献率相对变化幅度最大的是Cl -，其次是H 2PO 4 -，变化最小的是NO 3 -。这说明离子之间不存在近相互作用，离子EC贡献率只与该离子的离子活度有关。
利用上述多元线性回归模型对添加特定单盐后的营养液EC进行估测，并与实测值进行比较的结果表明：园试通用营养液和山崎番茄营养液在添加特定单盐后的EC估测值与EC实测值相比的相对偏差分别介于0.10-0.28％和0.03-0.33％(表6)。 因此，尽管基于特定配方营养液中的离子EC贡献率的影响有所差异，但通过对所添加单盐的离子EC贡献率的核算和EC实际测量完全可以掌握营养液的各离子浓度，从而为基于营养液的EC实际测量而实现离子浓度水平的动态调控提供了理论依据与技术支持。
表6添加特定单盐后的营养液EC估测值与实测值的比较
Figure PCTCN2018122033-appb-000013
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (6)

  1. 一种基于离子活度核算营养液离子EC贡献率和电导度的方法，其特征在于，包括以下步骤：
    1)基于离子活度提出离子EC贡献率，用于表征营养液中各离子活性影响其EC的百分比，由离子活度和极限摩尔电导率计算：
    Figure PCTCN2018122033-appb-100001
    式中，EC i为离子i的离子EC贡献率，％；Z i为离子i所带电荷数；T i为离子i的离子活度，mol/L；λ ∞为离子i的极限摩尔电导率，m 2 S/mol；
    2)离子活度表征电解质溶液中离子发挥作用的有效浓度，为营养液离子发挥静电作用的浓度，由离子活度系数和浓度计算：
    Figure PCTCN2018122033-appb-100002
    式中，T i为离子i的离子活度，mol/L；γ i为离子i的离子活度系数；C i为离子i的离子浓度，mol/L；
    3)平均离子活度表征某一单盐溶液或混合溶液的离子综合活度或综合活性，由该组成单盐溶液或混合溶液的阴阳离子的离子活度的几何均值计算：
    Figure PCTCN2018122033-appb-100003
    式中，T为某单盐溶液或混合溶液的平均离子活度，mol/L；T i和T j分别为组成单盐溶液或混合溶液的阳离子活度和阴离子活度，mol/L；v i和v j为组成组成单盐溶液或混合溶液的阳离子和阴离子的个数；
    4)离子活度系数为衡量实际溶液与理想溶液之间偏差大小的校正系数，由适用于营养液特性的Debye-Hückel极限定律计算：
    Figure PCTCN2018122033-appb-100004
    式中，γ i为离子i的离子活度系数；A为与温度有关的常量，25℃时为0.5091；B为与离子大小有关的常量，25℃时为0.328；Z i为离子i所带电荷数；r i为离子i体积参数；I为营养液的离子强度，mol/L；
    5)离子强度表征营养液中存在的离子所产生的电场强度，由营养液中各离子浓度与其所带电荷数计算：
    Figure PCTCN2018122033-appb-100005
    式中，I为营养液的离子强度，mol/L；C i为离子i的离子浓度，mol/L；Z i为离子i所带电荷数；
    6)基于营养液中各单盐的平均离子活度，利用多元线性回归模型估测营养液电导度，并利用实测电导度和离子EC贡献率反算离子浓度。
  2. 根据权利要求1所述的方法，其特征在于，所述离子是指营养液中与植物生长密切相关的NO 3 -、H 2PO 4 -、SO 4 2-、NH 4 +、K +、Ca 2+、Mg 2+、Fe 2+主要无机离子，基于上述主要无机离子的离子活度建立特定配方营养液的电导度(EC)和酸碱度(pH)的多元线性回归模型；基于园试通用配方和山崎番茄配方建立的各离子活度与其营养液EC和pH的多元线性回归模型如下：
    Figure PCTCN2018122033-appb-100006
    其中T 1-8分别表示营养液中NO 3 -、H 2PO 4 -、SO 4 2-、K +、Ca 2+、Mg 2+、NH 4 +、Fe 2+的离子活度。
  3. 根据权利要求1或2所述的方法，其特征在于，利用特定配方营养液主要组成成分的平均离子活度来估测营养液EC和pH的多元线性回归模型；基于园试通用营养液和山崎番茄营养液的组成成分的平均离子活度与其EC和pH的多元线性回归模型如下：
    Figure PCTCN2018122033-appb-100007
  4. 根据权利要求1或2所述的方法，其特征在于，根据特定配方营养液中添加特定单盐后的平均离子活度与EC的线性回归模型用于EC估测；基于园试通用营养液和山崎番茄营养液中添加特定单盐的平均离子活度与其EC的多元线性回归模型如下：
    Figure PCTCN2018122033-appb-100008
    Figure PCTCN2018122033-appb-100009
  5. 根据权利要求1或2所述的方法，其特征在于，根据特定配方营养液中添加特定单盐的平均离子活度与其他单盐的平均离子活度与其EC建立多元线性回归模型；基于园试通用营养液和山崎番茄营养液中添加特定单盐的平均离子活度与其他组成的平均离子活度与其EC的多元线性回归模型如下：
    Figure PCTCN2018122033-appb-100010
    Figure PCTCN2018122033-appb-100011
    注：表中的T x表示所添加特定单盐的平均离子活度。
  6. 根据权利要求1或2所述方法，其特征在于，所述方法测试用营养液为基于园试通用营养液配方和山崎番茄营养液配方而配制的营养液。
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