CN111504988A - Method for measuring two-dimensional distribution of available phosphorus content - Google Patents
Method for measuring two-dimensional distribution of available phosphorus content Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 67
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- NGWSAUQBWVWFCU-UHFFFAOYSA-N n-ethyl-2,3-dimethylbutan-2-amine Chemical compound CCNC(C)(C)C(C)C NGWSAUQBWVWFCU-UHFFFAOYSA-N 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/82—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a precipitate or turbidity
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to a method for measuring two-dimensional distribution of available phosphorus content. Putting the DGT device assembled with the precipitated adsorption film into a sediment or soil medium to absorb available phosphorus in a medium longitudinal section, taking out the precipitated adsorption film in the DGT device, soaking the DGT device in a color developing agent to perform color development reaction, and obtaining a surface gray value of the precipitated adsorption film by using a CID method; and converting the gray value into the phosphorus adsorption amount according to the established standard curve of the phosphorus adsorption amount and the gray value of the unit surface area of the precipitation-shaped adsorption film, and calculating by using a formula to obtain two-dimensional distribution of the effective phosphorus content in the sediment or the soil medium. The method has the advantages that the phosphorus is represented by the aid of the high-adsorption-capacity precipitated zirconia adsorption film, the method is suitable for being applied under various environmental scenes such as phosphorus shortage and phosphorus application, particularly under the condition of strong heterogeneity of phosphorus content space distribution, the front side and the back side do not need to be distinguished when the adsorption film is used for loading phosphorus with different amounts to prepare the marked line, only the adsorption film is used instead of a complete DGT device, and complexity in operation is avoided.
Description
Technical Field
The invention belongs to the technical field of element biological effectiveness and spatial distribution representation, and particularly relates to a method for measuring two-dimensional distribution of available phosphorus content.
Background
The average phosphorus content in earth's surface soil is only about 80% of that in the crust, resulting in soil often being deficient in phosphorus and insufficient to maintain the necessary phosphorus supply for crop life. Soil phosphorus application is a common agronomic practice, and the phosphorus applied is typically from phosphate ore in the earth's crust. On the one hand, phosphate rock is a non-renewable resource, and on the other hand, excessive application of phosphate fertilizer to soil to ensure adequate phosphorus supply to crops can cause excessive phosphorus to flow through surface runoff into the surrounding water, possibly resulting in eutrophication of the water. Therefore, for the sustainability of phosphorus resources and the preservation of water and soil ecology, it is necessary to study the microscopic mechanism of phosphorus activation and migration in soil. The convenient and fast determination of the two-dimensional distribution of the soil phosphorus content, particularly the available phosphorus content, is greatly beneficial to the breakthrough of a microscopic mechanism.
The DGT (differential graduations in thin-films) technique is a kind of instrument for measuring the content of effective state of elements (including phosphorus). The DGT technique was invented In 1994 by Davison and Zhang, university of Lankast, UK (Davison, W., and Zhang, H.,1994.In specific measurements of trace elements In natural waters using this-film gels, Nature 367(6463),546-548), was first used to determine trace metal elements In water and sediments, and was first used In 1998 to determine the phosphorus content In water (Zhang, H., Davison, W., Gadi, R.and Kobayashi, T.,1998.In a specific measurements of phosphorus In natural waters using DGT.Analytica Chiacaacta 370 (29-38), also In the same year, T.began to be used In soil media for determining the effective content of elements In soil media (Harison, Harvest, M.76, German. and S., DG. 20. and 2770, moisture, yellow. and yellow. blue, Zhang, K. and Z., S. 20, J. and S. 1, J. Zhang-film gel, K. and S. 1, 29-38, T. and S. In 1998. different samples of soil media, w., Knight, B.and McGrath, S.,1998.In situ measures of concentration and fluxes of trace metals In sources using DGT&Technology 32(5), 704) 710). At present, DGT is widely applied to determination of effective state concentrations of over fifty elements in water, soil and sediments. The DGT technology is based on Fick's first diffusion law, and the physical device mainly comprises a filter membrane, a diffusion membrane, an adsorption membrane and a plastic for fixing the three membranesThe material shell is constituteed, and wherein the filter membrane mainly used obstructs the particulate matter entering device in the environment that awaits measuring, and the diffusion barrier can let the ion follow the first diffusion law of fick and freely diffuse and form the diffusion gradient, and the adsorption film is used for fixing the material of awaiting measuring and can selects specific adsorption material according to the type of adsorption material. The substance to be measured forms a diffusion gradient in the diffusion film, and is captured and immobilized when reaching the adsorption layer, so that the adsorption film is also used as an immobilization film. Matter concentration by DGT measurement (C)DGT) Or flux (F)DGT) Can be calculated by the formula (1) or (2).
CDGT＝M×Δg/(D×A×t) (1)
FDGT＝M/(A×t) (2)
Wherein M is the adsorption amount (μ g) of the substance to be detected on the adsorption film, Δ g is the thickness (cm) of the diffusion layer, and D is the diffusion rate (cm) of the substance to be detected in the diffusion layer2In/s), A is the sampling area or DGT device opening area (cm)2) And t is the sampling time(s).
DGT technology has been commercialized, and the commercial DGT devices mainly include Piston type (Piston type) and flat type (Flattype), and the construction diagrams are respectively shown in fig. 1 and fig. 2, and the DGT devices directly purchased can be directly used for soil determination without additional treatment. Obtaining CDGTOr FDGTThe data is usually obtained by eluting the adsorption membrane with a suitable chemical solution (such as a dilute acid or a dilute alkali solution), transferring the substance to be tested from the solid phase of the adsorption membrane to the liquid phase of the eluent, and then measuring with a suitable instrument, such as a spectrophotometer after color reaction, to determine the phosphorus content, and then calculating with a formula to obtain the desired result. Using this method, a single DGT device can obtain a CDGTOr FDGTThe data can be obtained by 2 methods, including performing two-dimensional cutting (2D slicing) on the adsorption film, performing the elution and measurement on the obtained small square sheet-shaped film, wherein the element space resolution obtained by the method is millimeter level, and performing drying pretreatment on the adsorption film, and analyzing the two-dimensional element information on the film by using laser ablation-inductively coupled plasma mass spectrometry (L A-ICP-MS) to obtain sub-millimeter level element space resolutionAnalysis of the adsorbent membrane is often cumbersome and time consuming, and may be expensive. Therefore, a rapid, efficient and cheap adsorption membrane analysis method is particularly necessary, and is greatly beneficial to the popularization of DGT.
The color development technology has the advantages of convenience and high efficiency, and is widely applied to the quantitative aspects of orthophosphate, ferrous iron and the like. computer/Colorimetric Imaging Densitometry (CID) is a color development technology that can realize two-dimensional imaging, and can realize rapid characterization of an adsorption film when used together with a DGT technology. DGT-CID method was used for S at the earliest2-Characterization of the content by the principle of S2-Reacting with a light yellow AgI adsorption film to generate Ag2S makes the color of the adsorption film change to black, and the color depth (gray value) and S are2-Content positive correlation (Teasdale, P.R., Hayward, S.and Davison, W.,1999.In site, high-resolution media theory of decomposed sub-using differential graphics In thin films with computer-imagingless graphics, analytical Chemistry 71(11), 2186-one 2 191; DeVries, C.R.and Wang, F.,2003.In site-two-dimensional high-resolution graphics In sub-second-implementation Science&Technology 37(4),792-797；Robertson,D.,Teasdale,P.R.and Welsh,D.T.,2008.A novel gel-based technique for the highresolution,two-dimensional determination of iron(II)and sulfide insediment.Limnology and Oceanography:Methods 6,502-512；Ding,S.,Sun,Q.,Xu,D.,Jia,F.,He,X.and Zhang,C.,2012.High-resolution simultaneous measurements ofdissolved reactive phosphorus and dissolved sulfide:The first observation oftheir simultaneous release in sediments.Environmental Science&Technology 46(15), 8297-8304). The DGT-CID method is then also used for Cu2+(McGifford,R.W.,Seen,A.J.and Haddad,P.R.,2010.Direct colorimetric detection of copper(II)ions in sampling usingdiffusive gradients in thin-films.Analytica Chimica Acta 662(1),44-50)、P(Ding,S.,Wang,Y.,Xu,D.,Zhu,C.and Zhang,C.,2013.Gel-based coloration techniquefor the submillimeter-scale imaging of labile phosphorus in sediments andsoils with diffusive gradients in thin films.Environmental Science&Technology47(14), 7821-7829), and characterization of the same by Chinese patent application, published as CN104048956A and CN104048924A, and Cr (VI) (Yao, Y., Wang, C., Wang, P., Miao, L., Hou, J., Wang, T.and L iu, C.,2016.Zr oxide-based color technique for two-dimensional imaging of laboratory Cr (VI) using differential gradients in thin films, science of the TotalEnvironment 566-1637, 1632-1639).
The two-dimensional distribution of phosphorus content measured by DGT-CID technology mainly comprises the following steps: (1) selecting a proper adsorption film and assembling the adsorption film into a DGT device; (2) adsorbing phosphorus by a DGT device; (3) the adsorption film color reaction, which may also include DGT phosphorus adsorption after adsorption film pretreatment, in order to promote the adsorption film absorbed phosphorus further fixed; (4) and data processing, which mainly comprises scanning the colored adsorption film by using a scanner to obtain an image and establishing a standard curve of a gray value and an adsorption quantity. Currently 3 types of adsorption membranes are used for P characterization based on DGT-CID technology.
The invention patents and documents of publication Nos. CN104048956A and CN104048924A, Ding, S., Wang, Y., Xu, D., Zhu, C.and Zhang, C.,2013.Gel-based color formation Technology for the submillimeter-scale imaging of a simple phosphor in fractions and solids with a differential color in films 47(14),7821-7829 provides a method for determining the phosphor content based on the T-CID technique, which comprises assembling a slurry zirconium oxide adsorption film into a DGT device, placing the slurry into a phosphorus medium for phosphorus absorption, placing the adsorption film into hot water at 85 ℃ for 120h or more, causing the phosphor absorbed by the film to be further fixed, placing the slurry into an adsorption film L, assembling the adsorption film into a color development film with a color development developer at constant temperature, obtaining a color development curve by using a color development conversion scanner, and a color development curve obtained by converting the color development curve of the color development developer into a color development curve of a color development by using a color development time-developed by a thermal-conversion scanner, wherein the color development curve of the color development developer is obtained by using a color development curve of a color development developer, and a color development curve obtained by using a color development curve of a color development curve obtained by using a color development scanner, and a color development curve of a color development curve obtained by using a color development curve of a color development.
Inventive patents and documents CN105548106A and CN105466899A, Han, c, Ren, j, Wang, z, Tang, h.and Xu, d, 2017.a novel hybrid sensor for combined imaging of dissolved oxygen and lipid phosphor fluorine in section and water. water research 108,179-. Firstly, preparing a DGT-PO composite membrane based on a flat Plate Optode (PO) and DGT principles, wherein the DGT composite membrane comprises a transparent support body, a fluorescent sensing layer and a DGT fixing layer, the DGT fixing layer adopts submicron ZrO particles as a fixing agent, polyurethane hydrogel is used as a matrix, and the DGT fixing layer is prepared on the fluorescent sensing layer by a coating method; then, based on the fluorescence analysis principle, acquiring a Dissolved Oxygen (DO) fluorescence intensity image of the PO layer of the composite membrane in real time by adopting an image technology; secondly, the composite film is firstly subjected to 0.1M HNO3Soaking in solution for more than 24h to prevent the composite membrane from cracking and dissociating, soaking in pure water for more than 4h to remove residual acid, placing the composite membrane on an electric hot plate at 80 deg.C for heat treatment for 24h, wherein the heat treatment process needs to pad a humidified filter membrane below the composite membrane and cover the filter membrane with a polyester membrane to prevent the water loss of the composite membrane, placing the composite membrane into a color developing agent, developing at 35 deg.C for 60min, obtaining an image of active phosphorus (SRP) development of the DGT layer by CID analysis, and metering and detecting the SRP and DO according to the obtained image. The method adopts two channels to respectively obtain the information of Dissolved Oxygen (DO) and active phosphorus (SRP), and can realize the in-situ monitoring of active phosphorus and dissolved oxygen in substrates such as water, sediment or soil. The method aims at the slurry adsorption film, and the pretreatment process is extremely complicated due to the adoption of the composite film.
The invention patent with publication number CN109507177A provides a method for monitoring available phosphorus by in-situ color development based on DGT technology, wherein an adsorption film of a DGT device in the method is prepared from a Metsorb material, and the preparation process comprises the following steps: 1) uniformly mixing Metsorb powder with a DGT cross-linking agent, deionized water and an acrylamide monomer aqueous solution to obtain a mixed solution; 2) sequentially adding ammonium persulfate and TEMED into the mixed solution obtained in the step 1), mixing, injecting into a gap between two glass plates, and standing to obtain a molded film; 3) and (3) placing the formed film in deionized water to expand to obtain the adsorption film. The DGT device is adopted to directly contact with a color developing agent for color development after sampling, and an adsorption film after color development is quantitatively analyzed by a CID device. The method is used for directly carrying out color development reaction on the whole DGT device (comprising an adsorption film, a diffusion film, a filter film, a plastic base and a cover, see figure 1) by aiming at a pulpy adsorption film, the consumption of a color developing agent is high, the adsorption film cannot be in full contact with the color developing agent, and insufficient color development possibly occurs.
The slurry adsorption film is the most common adsorption film type and is obtained by mixing an adsorbent with a cross-linking agent, an acrylamide solution, a tetramethyldiethylamine solution and an ammonium persulfate solution and then heating and curing, and the defects of the adsorption film are that 1) the adsorption film is easy to curl, 2) the adsorption film is easy to shrink during heating treatment, and further the resolution is reduced (Guan, D.X., Williams, P.N., & lTtT translation &. L. & ltTtTtTtTtTtTtTtTtTtTo &. J.,. Zheng, J. L, Xu, H.C., Cai, C.and Ma, L Q. Nonov sludge-precipitated slurry, H.C., Cai, C.and Ma, L Q. & gt, and the precipitation of the like slurry adsorption film is more suitable for the analysis of the adsorption film with the adsorption film type, the adsorption film is more suitable for the adsorption film type, the adsorption film is developed on the adsorption film type, the adsorption film is more suitable for the high-resolution of the adsorption film type, the adsorption film type adsorption film is more suitable for the high-precipitation of the adsorption film type adsorption film, the high-precipitation-resolution, the high-resolution of the adsorption film type adsorption film is developed on the pH-high-resolution of the adsorption film type adsorption film is more suitable for the high-precipitation-pH-resolution and the high-resolution of the high-pH-resolution of the high-precipitation-grade slurry chromatography analytical method, the high-resolution of the high-pH-grade slurry adsorption film analysis, the high-resolution of the high-precipitation of the high-resolution of the adsorption film type adsorption film is more suitable for the high-precipitation of the adsorption film type adsorption film, the high-precipitation of the high-grade of the high-resolution of the adsorption film type adsorption film is more-precipitation of the high-resolution of the high-grade of the high-absorption film type adsorption film of the high-precipitation of the high-absorption film, the high-pH-resolution of the high-pH-precipitation of the adsorption film is more suitable.
Data processing requires a standard curve based on established gray-scale values versus adsorption amounts. The existing methods are that a slurry adsorption film, a diffusion film, a filter membrane, a plastic base and a cover are assembled into a complete DGT device, the DGT device is put into a series of phosphorus solutions with known concentration, the volume of the solution is usually 2 liters or more, the solution needs to be continuously stirred, then the slurry adsorption film is taken out to carry out color reaction and image scanning and conversion, and a standard curve of the relationship between the phosphorus adsorption amount per unit surface area of the slurry adsorption film and the gray value is established. In so doing, not only is the operation complicated but also the phosphorus consumption may be large. The reason for this is that the slurry-like adsorption film has a front side and a back side, and it is necessary to ensure that the adsorption reaction occurs on the front side of the adsorption film during adsorption. Therefore, the data processing process is also expected to be innovative.
From the above analysis, the two-dimensional distribution of the available phosphorus content in the soil cannot be obtained conveniently, quickly and accurately by the prior art means.
Disclosure of Invention
According to the existing problems, the invention provides the idea that a method for representing phosphorus by a precipitation-shaped adsorption film is developed based on a DGT-CID technology, the experimental parameters of a color development process are optimized, a new data processing method is provided, chemical reagents are saved, and the measurement efficiency is improved.
The technical scheme of the invention is as follows:
a method for measuring two-dimensional distribution of available phosphorus content is characterized in that a DGT device assembled with a precipitation-shaped adsorption film is placed in a sediment or soil medium to absorb available phosphorus in a longitudinal section of the medium, the precipitation-shaped adsorption film in the DGT device is taken out and soaked in a color developing agent to perform color development reaction, and a CID method is utilized to obtain a surface gray value of the precipitation-shaped adsorption film; and converting the gray value into the phosphorus adsorption amount according to the established standard curve of the phosphorus adsorption amount and the gray value of the unit surface area of the precipitation-shaped adsorption film, and calculating by using a formula to obtain two-dimensional distribution of the effective phosphorus content in the sediment or the soil medium.
The precipitated adsorption film is a precipitated zirconia adsorption film, and the preparation method is disclosed in patent Z L201510780858.9.
The water content of the sediment or the soil medium is required to be more than or equal to 70 percent.
The color development reaction is that the precipitation-shaped adsorption film which adsorbs the phosphorus is placed in a color development agent in a water bath at 35 +/-2 ℃ for heating and color development, the color development agent refers to a phosphomolybdic blue colorimetric method, and the optimized color development conditions are as follows: the volume ratio of the color developing agent to the precipitation-shaped adsorption film can be as low as 67: 1, the shortest color development time only needs 30 min.
The CID method comprises the steps of scanning a developed precipitation-shaped adsorption film at a resolution of 75-300 dpi by using a scanner, and converting image colors into gray values by using image processing software; and converting the gray value of the image into the adsorption capacity of the unit area according to the established phosphorus adsorption capacity of the unit area and the gray value correction curve.
The standard curve is obtained by placing the precipitation-shaped adsorption film in a group of phosphorus solutions with known concentration gradients for adsorption reaction, measuring the change of phosphorus concentration in the solutions before and after adsorption to obtain the phosphorus adsorption amount of the precipitation-shaped adsorption film, performing color reaction and CID analysis on the precipitation-shaped adsorption film to obtain a gray value, and establishing the relationship between the phosphorus adsorption amount of the precipitation-shaped adsorption film per unit surface area and the gray value.
The concrete description is as follows:
the invention relates to a method for measuring two-dimensional distribution of available phosphorus content, which specifically comprises the following steps:
(1) phosphorus absorption: placing the DGT device assembled with the precipitated zirconia adsorption film in a water system sediment or soil medium to absorb available phosphorus in a medium longitudinal section;
(2) and (3) color development of an adsorption film: placing the precipitated zirconia adsorption film taken out of the DGT device in a color developing agent, wherein the volume ratio of the color developing agent to the precipitated zirconia adsorption film is at least 67: developing at least 30min under the water bath heating condition of 1, 35 +/-2 ℃;
(3) and (3) analysis by a CID method: scanning the developed precipitated zirconia adsorption film by using a scanner, setting the resolution to be 75-300 dpi, and then converting the image color into a gray value by using image processing software;
(4) and (2) data processing, namely firstly establishing a correction curve, namely placing the precipitated zirconia adsorption film in a group of solutions with known concentration gradients, measuring the concentrations of the solutions before and after adsorption by using a spectrophotometer, wherein the volume of the solution with the concentration difference value of × before and after adsorption is the phosphorus adsorption amount of the precipitated zirconia adsorption film, obtaining the gray value of the surface of the precipitated zirconia adsorption film according to the steps 2) and 3), corresponding the gray value to the phosphorus adsorption amount of the unit surface area one by one to obtain the correction curve, converting the gray value of the sample image into the phosphorus adsorption amount of the unit area according to the established calibration curve of the phosphorus adsorption amount of the unit area of the precipitated zirconia adsorption film and the gray value, and converting the gray value into two-dimensional distribution information of the effective phosphorus concentration according to Fick's first diffusion law.
The method has the effects that (1) the precipitation-shaped adsorption film is selected, so that the phosphorus adsorption capacity is high, the film is not easy to curl, the color development process is not easy to shrink, and the method is suitable for being applied under various environmental scenes such as phosphorus deficiency, phosphorus application and the like, especially under the condition of strong heterogeneity of spatial distribution of phosphorus content, and is suitable for measuring two-dimensional distribution of effective phosphorus content under real environmental conditions; (2) the method for establishing the standard curve during data processing is simplified, the front and the back sides are not needed to be distinguished when the precipitated adsorption film is used for loading different amounts of phosphorus to prepare the marking line, and only the precipitated adsorption film is used instead of a complete DGT device, so that the complexity of operation is avoided, and chemical reagents are saved; (3) the CID determination time is shortened, so that the test cost is saved, and the popularization and the application are facilitated.
Drawings
FIG. 1 shows a schematic view of the construction of a piston DGT device.
FIG. 2 is a schematic diagram of a flat DGT device.
Fig. 3, gray scale values of the precipitated adsorption film under different phosphorus concentration conditions.
FIG. 4 is a graph showing the relationship between the phosphorus adsorption amount and the gray level value of the precipitated adsorption film under different phosphorus concentrations.
FIG. 5 is the gray scale values of the precipitated adsorption film at different volume ratios of the color developing agent to the adsorption film.
FIG. 6 is the gray scale values of the precipitated adsorption film at different development times.
Figure 7, two-dimensional concentration distribution of available phosphorus in the deposit of example 1.
FIG. 8 shows the two-dimensional concentration distribution of available phosphorus in soil in example 2.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
The method for measuring two-dimensional distribution of available phosphorus content in the embodiment comprises the following specific steps:
(1) phosphorus absorption a sample of a columnar deposit with overlying water was taken from a lake, an elongated DGT device assembled with a precipitated zirconia adsorption film was placed in the deposit medium so that the window of the DGT device was completely exposed to the deposit, the precipitated zirconia adsorption film was prepared by the method disclosed in patent Z L201510780858.9 and the document Guan, d.x., Williams, p.n., <tttranslation = L ">l <t/t >ttuo, J., Zheng, J. L., Xu, h.c., Cai, c.and Ma, L. Q. [ authors ], Novel precipitation zirconia-based DGT Technology for high-resolution imaging of oxidation coatings and technologies [ 9 ] and scientific ] after the sample was taken out of the deposit through a long-term zirconia adsorption film (3653 cm) and the temperature of the deposit was taken out of the deposit under the publication No. 364 & 7 [ 364 ] test No. 364. the deposit was found by the publication No. 3 & 7 publication No. (published by published under the publication of the publication No. 368 & 7 & 8 publication).
(2) And (3) color development of the adsorption film, namely soaking the precipitated zirconia adsorption film in a color developing agent, wherein the volume of the color developing agent is 38m L, the volume ratio of the color developing agent to the adsorption film is 67: 1, and the color development is carried out for 30min under the water bath heating condition at 35 ℃.
(3) And (3) analysis by a CID method: scanning the developed precipitated zirconia adsorption film by using a scanner, setting the resolution to be 300dpi, and then converting the image color into a gray value by using ImageJ image processing software;
(4) data processing: firstly, developing an experiment I, and establishing a correction curve, wherein the method comprises the following specific steps:
step I-a, adsorbing phosphorus by the precipitated zirconia adsorption film, dividing the experimental solution into 9 groups, wherein the phosphorus concentrations are respectively 0, 20, 50, 100, 200, 500, 750, 1000 and 2000 mug/L (marked as C)1) Each set of 3 replicates was set with a solution volume of 20m L (denoted V) and a solution base of 0.01 mol/L NaNO3The solution and 9 groups of solution are respectively placed in 27 centrifuge tubes with the diameter of 50m L, 1 precipitated zirconia adsorption film is respectively placed in each centrifuge tube, the centrifuge tubes with the precipitated zirconia adsorption films are obliquely placed in a shaking table, and are taken out after shaking for 6 hours at the temperature of 25 ℃.
The method comprises the steps of firstly preparing a color developing agent, specifically, measuring 194.6m L concentrated sulfuric acid, slowly pouring the concentrated sulfuric acid into 500m L deionized water, stirring the solution with a glass rod to prepare a solution A, weighing 20.00g of ammonium molybdate, adding 200m L deionized water, heating, stirring and dissolving the ammonium molybdate to prepare a solution B, weighing 0.5g of antimony potassium tartrate, dissolving the antimony potassium tartrate in 50m L deionized water to prepare a solution C, cooling the solutions A and B to room temperature, mixing the A, B and the C solutions, fixing the volume to 1000m L with deionized water, transferring the solution to a brown reagent bottle to be protected from light, storing the solution at 6 ℃ and low temperature, taking 0.6g of ascorbic acid as a color developing agent solution, dissolving the ascorbic acid in 40m L color developing agent stock solution, adding 400m L deionized water, uniformly mixing the solution to obtain a molybdenum blue color developing method phosphorus, adding 10m L into 27 centrifugal tubes, taking out the adsorption film with the phosphorus adsorbing film with a volume ratio of 67: 1, putting the adsorption film which adsorbs phosphorus, placing the phosphorus in the adsorption film, heating the centrifugal tube under a DGT containing the color developing color at 829 temperature for 30min, and heating the centrifugal tube at 30.
And I-c, analyzing by a CID method. Taking out the precipitated zirconia adsorption film after color development, and immediately washing the film with deionized water at 6 ℃ to stop color development; absorbing water on the surface of the precipitated zirconia adsorption film by using filter paper, scanning the precipitated zirconia adsorption film by using a scanner at the resolution of 300dpi to obtain a color Image, and then converting the color of the Image into a gray value by using Image J software, as shown in figure 3;
preparing phosphorus standard solutions with phosphorus concentrations of 0, 0.05, 0.1, 0.2, 0.3, 0.4 and 0.5 mg/L by using a phosphorus standard substance, measuring an absorbance value at a wavelength of 700nm by using an ultraviolet-visible spectrophotometer, establishing a phosphorus concentration (mg/L) -absorbance value standard curve, and obtaining a standard curve y which is 0.410085x +0.00531266 and a correlation coefficient r20.998, measuring absorbance of the 4 groups of residual solution after adsorbing phosphorus at 700nm, and calculating residual phosphorus concentration C after adsorbing corresponding to phosphorus concentration (mg/L) -absorbance standard curve2(mg/L) using the formula f ═ 10-3C1-C2)V](S), calculating the phosphorus adsorption amount f (mu g/cm) of the unit area of the surface of the adsorption film2) In the formula, C1The concentration of phosphorus in each group of solutions before adsorption (. mu.g/L), C2The concentration of the residual phosphorus in the solution after adsorption (mg/L) is shown, V is the volume of the phosphorus-containing solution (m L), the difference of the volumes of the solutions before and after adsorption is extremely small and can be ignored, and S is the surface area of the adsorption film (S is 9.3117 cm)2) (ii) a Respectively calculating the phosphorus adsorption amount of the precipitated zirconia adsorption film in unit area of three parallel samples of each group of solution, establishing a phosphorus adsorption amount-gray value correction curve in unit area corresponding to respective gray value to obtain y-0.2974 +215.8534[1-exp (-0.0193x)]1.4810Coefficient of correlation r20.9993; according to the established calibration curve of the phosphorus adsorption amount per unit surface area and the gray value of the precipitated zirconia adsorption film, see fig. 4.
The standard curve establishing process has two parameters needing to be optimized, one is the volume ratio of the color developing agent to the adsorption film, and the other is the color developing reaction time. Therefore, two additional experiments, experiment II and experiment III, respectively, were set up to obtain the best quality of the two parameters.
Experiment II was as follows:
step II-a phosphorus absorption the experimental solutions were divided into 4 groups, the phosphorus concentrations were all 500. mu.g/L, and the other conditions were the same as in experiment I.
And step II-b, developing the adsorption film, preparing a color developing agent, wherein the specific method is the same as that of experiment I, adding 10, 20, 30 and 40m L phosphorus color developing agents into 4 centrifugal tubes respectively, wherein the volume ratios of the corresponding color developing agents to the adsorption film are 67: 1, 133: 1, 200: 1 and 267: 1 respectively, taking out 4 groups of precipitated zirconium oxide adsorption films adsorbing phosphorus, putting the zirconium oxide adsorption films into centrifugal tubes containing 10, 20, 30 and 40m L phosphorus color developing agents respectively, and heating in water bath for 30min at 35 ℃ to develop color.
Step II-c, CID method analysis, the same experiment I, the gray values of 4 groups of precipitated zirconia adsorption membranes which develop color respectively at the color developing agent to adsorption membrane volume ratios of 67: 1, 133: 1, 200: 1 and 267: 1 are 134.112, 136.877, 133.626 and 126.634 respectively, as shown in figure 5, it can be seen that the color developing agent volume is increased from 10m L to 40m L, and no significant influence is caused on the color development of the precipitated zirconia adsorption membranes, so that good colorimetric effect can be obtained when the color developing agent to adsorption membrane volume ratio reaches 67: 1.
Experiment III was as follows:
step III-a: and (4) phosphorus absorption. As in experiment II.
And step III-b, performing color development on the adsorption film, preparing a color developing agent by the same method as experiment I, adding 10m L phosphorus color developing agents into 4 centrifugal tubes respectively, taking out 4 groups of precipitated zirconia adsorption films adsorbing phosphorus, placing the adsorption films into 4 centrifugal tubes containing 10m L color developing agents respectively, and performing water bath heating for 10min, 20 min, 30min and 40min at the temperature of 35 ℃ to perform color development.
Step III-c: and (4) analyzing by a CID method. The gray values of 4 groups of precipitated zirconia adsorption membranes developed by heating in water bath for 10, 20, 30 and 40min were 63.034, 108.583, 136.830 and 141.634, respectively, as in experiment I, see fig. 6. Therefore, when the water bath heating color development time is increased from 10min to 40min, the color development degree of the precipitated zirconia adsorption film is gradually increased, but the color development degree of the precipitated zirconia adsorption film which develops color after 30min and 40min is not greatly different, so that the good color comparison effect can be obtained when the color development time reaches 30 min.
Converting the gray value of the sample image into the phosphorus adsorption capacity (M/A, mu g/cm) of the unit area according to the calibration curve of the phosphorus adsorption capacity and the gray value of the unit area of the precipitated zirconia adsorption film established in the step I-d2) According to FickOne law of diffusion, equation CDGTM × Δ g/(D × a × t) is converted into two-dimensional distribution information of phosphorus concentration, where Δ g is the thickness of the diffusion layer (0.088cm), and D is the diffusion rate of the substance to be measured in the diffusion layer (0.00000605 cm)2And/s), and t is the sampling time (43200 s). As a result, as shown in FIG. 7, it is understood that the distribution of available phosphorus in the deposit is highly heterogeneous, and a "hot zone" of a local high available phosphorus concentration distribution exists.
Example 2
The method for measuring two-dimensional distribution of available phosphorus content in the embodiment comprises the following specific steps:
(1) collecting a columnar soil sample with water from a certain rice field, placing a long DGT device assembled with a precipitated zirconia adsorption film in the soil medium, wherein the preparation method of the precipitated zirconia adsorption film is shown in patent Z L201510780858.9, controlling the indoor temperature to be 25 +/-2 ℃ in the experimental process, standing for 12h, recovering the DGT device, and taking out the precipitated zirconia adsorption film to obtain the precipitated zirconia adsorption film with the size of 8.6cm (length) × 1.8cm (width) × 0.04.04 cm (thickness).
(2) And (3) color development of the adsorption film, namely soaking the precipitated zirconia adsorption film in a color developing agent, wherein the volume of the color developing agent is 41m L, the volume ratio of the color developing agent to the adsorption film is 67: 1, and the color development is carried out for 30min under the water bath heating condition at 35 ℃.
(3) And (3) analysis by a CID method: scanning the developed precipitated zirconia adsorption film by using a scanner, setting the resolution to be 300dpi, and then converting the image color into a gray value by using ImageJ image processing software;
(4) data processing: according to the calibration curve of the phosphorus adsorption amount per unit area and the gray value of the precipitated zirconia adsorption film established in the first embodiment, the gray value of the sample image is converted into the phosphorus adsorption amount per unit area (M/A, mu g/cm)2) Then according to Fick's first diffusion law, i.e. formula CDGTM × Δ g/(D × a × t) is converted into two-dimensional distribution information of phosphorus concentration, where Δ g is the thickness of the diffusion layer (0.088cm), and D is the diffusion rate of the substance to be measured in the diffusion layer (0.00000605 cm)2And/s), and t is the sampling time (43200 s). As a result, as shown in FIG. 8, it can be seen that the distribution of available phosphorus in soil is highly heterogeneous, and that the available phosphorus is localizedThe higher concentration forms a "hot zone" effect.
The method is based on a DGT-CID technology, utilizes a precipitated adsorption film to represent phosphorus, has high adsorption capacity, is suitable for being applied under various environmental scenes such as phosphorus shortage, phosphorus application and the like, particularly under the condition of strong heterogeneity of phosphorus content spatial distribution, simultaneously shortens the CID measuring time to within 1 hour, does not need to distinguish the front side and the back side when the adsorption film is used for loading different amounts of phosphorus to prepare the marked line, only uses the adsorption film instead of a complete DGT device, and avoids the complexity of operation.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (6)
1. A method for measuring two-dimensional distribution of available phosphorus content is characterized in that a DGT device assembled with a precipitation-shaped adsorption film is placed in a sediment or soil medium to absorb available phosphorus in a longitudinal section of the medium, the precipitation-shaped adsorption film in the DGT device is taken out and soaked in a color developing agent to perform color development reaction, and a CID method is utilized to obtain a surface gray value of the precipitation-shaped adsorption film; and converting the gray value into the phosphorus adsorption amount according to the established standard curve of the phosphorus adsorption amount and the gray value of the unit surface area of the precipitation-shaped adsorption film, and calculating by using a formula to obtain two-dimensional distribution of the effective phosphorus content in the sediment or the soil medium.
2. The method according to claim 1, wherein the precipitated adsorbent film is a precipitated zirconia adsorbent film.
3. The method of claim 1, wherein the sediment or soil medium has a moisture content of 70% or more.
4. The method as set forth in claim 1, wherein the color development reaction is carried out by heating the precipitate-like adsorption film adsorbed with phosphorus in a water bath at 35 ± 2 ℃ in a color developing agent according to phosphomolybdic blue colorimetry.
5. The method as set forth in claim 1, wherein the volume ratio of the color-developing agent to the precipitated adsorption film is at least 67: 1, the shortest color development time only needs 30 min.
6. The method of claim 1, wherein the CID method comprises scanning the developed precipitated adsorption film with a scanner at a resolution of 75-300 dpi, and converting the image color into gray scale values with image processing software.
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