CN117054293B - Method for measuring movement path of soil colloid in aeration zone - Google Patents

Method for measuring movement path of soil colloid in aeration zone Download PDF

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CN117054293B
CN117054293B CN202311318227.6A CN202311318227A CN117054293B CN 117054293 B CN117054293 B CN 117054293B CN 202311318227 A CN202311318227 A CN 202311318227A CN 117054293 B CN117054293 B CN 117054293B
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colloid
soil
titanium dioxide
sections
section
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CN117054293A (en
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佟洪金
柳强
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Sichuan Ecological Environment Monitoring Station
SICHUAN ACADEMY OF ENVIRONMENTAL SCIENCES
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Sichuan Ecological Environment Monitoring Station
SICHUAN ACADEMY OF ENVIRONMENTAL SCIENCES
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N13/00Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
    • G01N2013/003Diffusion; diffusivity between liquids

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Abstract

The invention provides a method for measuring a movement path of a soil colloid in a gas-covered zone, which comprises the following steps: uniformly injecting a tracer solution containing titanium dioxide colloid into a soil area of the air-packing belt to be detected; after the tracer solution finishes flowing, excavating in the area to form a plurality of longitudinal sections of the soil with the air covering zone, spraying an identification solution containing potassium ferrocyanide on each section formed by excavating, irradiating the section by ultraviolet light, and collecting images of the section after the color of the section changes; and superposing the acquired images of all the sections according to the actual section positions to obtain the motion path. The invention solves the difficult problem of difficult direct measurement in the soil of the gas-covered zone, and has the advantages of clear mechanism, simple operation, high recognition rate and the like.

Description

Method for measuring movement path of soil colloid in aeration zone
Technical Field
The invention belongs to the field of a method for measuring soil in a gas-covered zone, and particularly relates to a method for measuring a colloid movement path of soil in a gas-covered zone.
Background
The aeration zone soil is the basis for maintaining agricultural yield and improving the ecological system, and is also the necessary passage for many pollutants to enter the groundwater system. Because the colloid has the characteristics of small particle size, large specific surface area, charge on the surface, unique double-electric-layer structure, rich surface functional groups and the like, heavy metals, organic pesticides, organic pollutants, phosphorus, bacteria, microorganisms and other pollutants are adsorbed on the colloid and move along with the colloid, and the movement of the movable colloid in the soil can accelerate the movement capability of the pollutants to a great extent. Monitoring data in both laboratory and field conditions indicate that colloid migration occurs mainly in the high flow rate region in the soil pores due to both size exclusion and low diffusivity, and that the migration rate of the colloid in the soil is not lower than that of the solute. Some field test results show that the scale of TP easy to move in soil is more than 10 -6 m (macropores) is less than 10 -9 m (colloidal adsorption) two dimensions, and by less than 10 -9 The TP migration flux formed by the m-pathway is significantly over-dimensioned to be greater than 10 -6 Flux formed by the m-pathway. Therefore, the knowledge of the movement path of the colloid in the air-bag soil has important significance for preventing and controlling the groundwater pollution.
The movement speed of the colloid is influenced by various driving factors such as soil adsorption force, pore hydrodynamic force, LVUO acting force, van der Waals force, brownian acting force, acting force generated by electron transfer and the like, and the physical and chemical properties of the soil such as the water content of the soil, the ionic strength, the pH value and the redox state influence the migration performance of the colloid to a great extent by influencing the migration performance of the colloid, and in addition, the aeration belt takes the soilIn soil, the liquid-water interface in the pores has an important influence on the movement of the moving colloid. Although iodine (I) - ) Bromine (Br) - ) Such solutes propose methods of generating substances of different colors from the background of soil based on chemical reactions or identifying a solute migration path by pH indicators by changing the pH value of soil, however, in unsaturated zone soil, the mechanical properties of colloids and solutes, and the movement conditions are completely different, the movement paths and processes of solutes and colloids are significantly different, and direct measurement of the movement paths of colloids in air-bag soil is still very difficult.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the purposes of the present invention is to provide a colloid tracing method for electron transfer, and the other purpose of the present invention is to provide a measuring method for a colloid movement path of a soil in a gas-enclosed zone.
In order to achieve the above object, the present invention provides a method for measuring a movement path of a soil colloid in a gas-enclosed belt, the method comprising the steps of:
uniformly injecting a tracer solution containing titanium dioxide colloid into a soil area of the air-packing belt to be detected;
after the tracer solution finishes flowing, a plurality of longitudinal sections of the soil with the air covering zone are excavated in the area, identification solution containing potassium ferrocyanide is sprayed to the section formed by each excavation, then ultraviolet light is utilized to irradiate, and after the color of the section changes, an image of the section is acquired;
and superposing the acquired images of all the sections according to the actual section positions to obtain the motion path.
Optionally, the preparation method of the titanium dioxide colloid comprises the following steps:
glacial acetic acid and butyl titanate are mixed according to the molar ratio of not more than 1:2, after fully mixing the components in proportion, carrying out chemical reaction to generate a mixed solution containing titanium dioxide colloid;
mixing hydrochloric acid solution and the mixed solution containing titanium dioxide colloid according to the volume ratio of 1: completely mixing 10-20; adjusting the pH value of the mixed solution to 5-6;
the pH value of the mixed solution is adjusted to 25-35 o And C, standing for 12-24 hours at constant temperature to obtain the stable transparent nanoscale titanium dioxide colloid.
Optionally, the tracer solution is diluted by titanium dioxide colloid and water, and the proportion is not less than 1: 100.
Alternatively, the recognition solution includes an aqueous potassium ferrocyanide solution having a concentration of not less than 0.1 mol/L.
Optionally, the ultraviolet light wavelength is 270-365 nm.
Alternatively, a short arc mercury uv lamp loaded in a sealed quartz glass cylinder, which is filled with an inert gas, is used as the light source for the uv light.
Alternatively, the inert gas includes helium or neon.
Optionally, the cross-section color change comprises: a partial region of the profile exhibits a deep blue color.
Alternatively, the depth of the longitudinal section is not less than the amount of tracer in mm by 50mm.
Alternatively, the profile number density is not less than 1/10 cm.
Compared with the prior art, the invention has the beneficial effects that at least one of the following contents is included:
1) The invention solves the problems of a measurement mechanism and a measurement technology for directly measuring the loss of a colloid movement path in the soil of the air-packing belt.
2) The method measures the movement path of the soil colloid in the air-packing belt through electronic transfer tracing, is simple to operate and high in recognition rate, and has wide application range because the blue area is different from most of the ground colors.
Drawings
The foregoing and other objects and/or features of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings in which:
fig. 1 shows a schematic diagram of a method for measuring a movement path of a soil colloid in an air-bag belt in an exemplary embodiment 1 of the present invention.
Fig. 2 shows an acquired image of a soil profile of a gas-filled zone formed by excavation in example 1 of the present invention.
Fig. 3 shows an image acquired of a soil profile of the air belt of example 1 of the present invention after spraying an identification solution and uv irradiation.
Reference numerals illustrate:
1-image acquisition device, 2-superimposed multiple profiles.
Detailed Description
Hereinafter, the measuring method of the movement path of the air-bag soil colloid of the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
Example embodiment 1
The present exemplary embodiment provides a measurement method of a movement path of a soil colloid of a gas-filled belt, the measurement method including the steps of:
s01: and uniformly injecting the tracer solution containing the titanium dioxide colloid into the area of the air-packing belt soil to be detected.
In this embodiment, the titanium dioxide colloid is prepared first, specifically comprising the steps of:
glacial acetic acid and butyl titanate Ti (OC 4 H 9 ) 4 According to the molar ratio of glacial acetic acid to butyl titanate not exceeding 1:2, for example 1:1.1, 1:1.5 or 1:1.9, and the like, carrying out chemical reaction to generate a mixed solution containing titanium dioxide colloid, wherein in order to ensure that butyl titanate is fully reacted, glacial acetic acid needs to be excessive;
mixing hydrochloric acid solution and the mixed solution containing titanium dioxide colloid according to the volume ratio of 1: 10-20, for example 1: 11. 1:16 or 1:19, etc.;
adjusting the pH value of the mixed solution to 5-6 to maintain the stability of the colloid;
the mixed solution with the pH value regulated is kept constant for 25-35 in a temperature control box o C is kept stand for 12 to 24 hours, such as 13 hours, 16 hours or 23 hours, etc., to obtain stable and transparent nano-scale titanium dioxide TiO 2 Sol to prepare the tracer colloid.
At the bookIn the examples, potassium ferrocyanide K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 After the concentration is not less than 0.1mol/L, the mixture is fully dissolved and stored in a brown bottle to prepare the identification solution. For example, the concentration of potassium ferrocyanide may be 0.2mol/L, 0.3mol/L, 0.5mol/L, etc., and a lower concentration of the recognition solution may cause insufficient reaction with the colloid.
In this example, a tracer colloid of nano-sized titanium dioxide TiO 2 After the sol is completely diluted in water according to the dilution ratio of not less than 1:100, for example, nano-scale titanium dioxide TiO 2 The ratio of sol to water may be 1:99, 1:95, or 1:80, etc., to ensure that the concentration of titania is not less than the concentration at a 1:100 ratio; the tracer colloid is diluted and then injected into the soil with the air-packing belt along with water flow, the water consumption is tested in the embodiment, namely the diluted colloid consumption can be 20mm, and the area of an experimental area can be 1.0m 2 The earth surface adopts a uniform spraying mode, so that water flows uniformly enter the soil of the air-packing belt, and the movement method of the tracer colloid along with the water flows is mainly influenced by the property of the soil of the air-packing belt. The dosage of the titanium dioxide tracing colloid diluent and the area of the test area can be set according to the soil condition.
S02: after the tracer solution finishes flowing, a plurality of longitudinal sections of the soil with the air covering zone are excavated in the area, after each excavation, identification solution containing potassium ferrocyanide is sprayed to the sections, then the sections are irradiated by ultraviolet light, and after the color of the sections changes, images of the sections are acquired.
In this example, after the fully diluted tracer colloid was sprayed in the test area and flowed with water for 12hr, a working area was excavated on one side of the test area along the colloid movement direction to form a soil profile with a gas-over zone, as shown in fig. 1, which is perpendicular to the surface penetration surface of the test area. Spraying identification solvent onto the section, irradiating with ultraviolet light with wavelength of 270-365 nm, such as 271nm, 280nm, 308nm, 350nm or 367nm, wherein the photochemical effect of titanium dioxide tracer colloid on ultraviolet light is most remarkable in the wavelength range, and the titanium dioxide tracer colloid (nanometer TiO) 2 ) Electron transfer and photochemistry of (a)Under the action, the identification solution changes in color, and appears dark blue, while the area where no colloid movement occurs does not change in color. And taking a picture of the section by using image acquisition equipment such as a CCD camera after the deep blue area is not changed any more.
In this embodiment, the electron transfer and optical effect is that the titanium dioxide generates electron transfer under the irradiation of ultraviolet light to generate electron holes; the hole has stronger electron capturing capability, and after encountering water molecules, the water molecules are deprived of electrons to form hydroxyl:
(TiO 2 )e + +H 2 O→TiO 2 +•OH+H +
wherein e + Represents electrons, OH is hydroxy, H + Is hydrogen ion. Hydroxy groups and oxygen atoms, all of which are capable of binding part of Fe 2+ Oxidation to Fe 3+ Precipitation, chemical reaction equation is:
K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 +4•OH+4H + →Fe 4 3+ [Fe 2+ (CN 6 )] 3 +4K +
K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 +O 2 +4H + →Fe 4 3+ [Fe 2+ (CN 6 )] 3 +4K + +4H 2 O
fe in soil of the aeration zone 4 3+ [Fe 2+ (CN 6 )] 3 The precipitation is changed in color, and the dark blue of the presentation position can be identified, so that the identification of the nano-scale tracer colloid movement path is realized.
In the embodiment, since the object of measurement is a soil profile, a short arc mercury ultraviolet lamp loaded in a sealed quartz glass cylinder is used as an ultraviolet light source, and inert gas is injected into the cylinder to improve the irradiation area and uniformity of ultraviolet light; the inert gas may be helium or neon.
S03: and superposing the acquired images of all the sections according to the actual section positions to obtain the moving path.
Fig. 1 shows a schematic diagram of the method for measuring the movement path of the soil colloid in the air-bag type belt of the present invention. Wherein 1 in the figure is an image acquisition device, which may include a camera; 2 in the figure represents a plurality of overlapped sections, and a 3-dimensional colloid motion path can be identified after the overlapped sections are overlapped; arrows in the figure indicate the section excavation direction.
In this embodiment, a plurality of longitudinal sections of the soil in the air-packing zone of the working area, such as the sections shown in fig. 1, are excavated in the direction of the colloid movement in the test area. The number density of the sections is not less than 1/10 cm, for example, the distance between the sections may be 9cm, 7cm, 5cm, or the like, and if the distance between the sections is more than 10cm, the error of the superimposed image path increases. The depth of the section excavation is not less than the dosage x 50 of the diluted tracer colloid, the unit is mm, for example, when the dosage of the diluted tracer colloid can be 20mm, the depth of the longitudinal section is not less than 20mm x 50, namely, the depth is not less than 100mm; so as to cover the maximum movement depth of the colloid and avoid the loss of colloid migration information. The horizontal dimension of the section is not smaller than that of the test area, continuous section excavation is carried out along the flowing direction along the surface penetrating plane perpendicular to the test area, so that the colloid movement path is determined in a superposition mode. And (3) irradiating the area of the trace colloid movement of each soil section with ultraviolet light, identifying colloid paths of the section pictures after the deep blue area is not changed, measuring the area with color change layer by layer, namely the migration area of the trace colloid, and superposing all sections according to the actual section positions of the sampling to obtain the movement paths of the trace colloid.
For a better understanding of the above-described exemplary embodiments of the present invention, they are further described below in conjunction with specific examples.
Example 1
Glacial acetic acid and butyl titanate Ti (OC 4 H 9 ) 4 According to the mole ratio of 1:2, adding hydrochloric acid solution with the volume ratio of 1:20 after fully mixing, adjusting the pH value of the mixed solution to 5-6 by glacial acetic acid after fully mixing, and keeping the pH value constant for 30 in a temperature control box o C for 24 hours to obtain stable and transparent nano-scale titanium dioxide (TiO) 2 ) Sols, i.e. tracer gumsA body.
368.3g of potassium ferrocyanide K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 Dissolving in 1L water, and storing in brown bottle to obtain identification solvent.
The method comprises the steps of tracing a colloid motion path in a gas-wrapping belt by using a tracing colloid, testing in a Wansheng farmland in the glabella city in 2021 month, wherein the experimental gas-wrapping belt soil is clay with a broken structure, the contents of clay particles, powder particles and sand particles are 42.1%,10.7% and 47.2%, after the earth surface is leveled, selecting a rectangular area of 1.0mx1.0m as an experimental area, fully diluting 400mL of nano-scale titanium dioxide sol in 40L of reclaimed water, uniformly injecting the diluted nano-scale titanium dioxide into the experimental area, and enabling the nano-scale titanium dioxide to enter the gas-wrapping belt soil along with water flow.
And (3) identifying a colloid migration path, excavating a working area on one side of a test area after the flow is completed, and excavating along the colloid movement direction to form a soil profile of the air-packing zone, as shown in figure 2. Spraying identification solvent to the profile, adopting a short arc mercury ultraviolet lamp loaded in a sealed quartz glass cylinder as an ultraviolet light source, injecting helium into the cylinder to improve the irradiation area and uniformity of ultraviolet light, and emitting 280nm ultraviolet light to irradiate the profile. Under the irradiation of ultraviolet light, the titanium dioxide generates electron transfer and generates electron holes. The hole has stronger electron capturing capability, and after encountering water molecules, the water molecules are deprived of electrons to form hydroxyl:
(TiO 2 )e + +H 2 O→TiO 2 +•OH+H +
wherein e + Represents electrons, OH is hydroxy, H + Is hydrogen ion. Hydroxy groups and oxygen atoms, all of which are capable of binding part of Fe 2+ Oxidation to Fe 3+ Precipitation, chemical reaction equation is:
K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 +4•OH+4H + →Fe 4 3+ [Fe 2+ (CN 6 )] 3 +4K +
K 4 Fe 4 2+ [Fe 2+ (CN) 6 ] 3 +O 2 +4H + →Fe 4 3+ [Fe 2+ (CN 6 )] 3 +4K + +4H 2 O
the colloid trace colloid movement area, under the electron transfer and photochemical action of colloid, fe 4 3+ [Fe 2+ (CN 6 )] 3 The precipitate will change in color and appear dark blue. After the dark blue region appears unchanged, the CCD camera NikonD90 may be used to photograph the cross section, and the resulting photograph is shown in FIG. 3, where the upper dark region actually appears dark blue, for example, the circled portion of the figure is a portion of the dark region.
The same method is adopted to excavate the next section and identify the colloid path, and the experimental area is 1m 2 According to the square development perpendicular to the surface seepage water plane of the test area, each section is spaced by 10cm, and 11 sections are formed by excavation; and measuring the color change area layer by layer, namely tracing the migration area of the colloid, and superposing all sections according to the actual section positions of the sampling to obtain the migration path of the colloid.
Although the present invention has been described above with reference to the exemplary embodiments and the accompanying drawings, it should be apparent to those of ordinary skill in the art that various modifications can be made to the above-described embodiments without departing from the spirit and scope of the claims.

Claims (8)

1. The method for measuring the movement path of the soil colloid in the aeration zone is characterized by comprising the following steps of:
uniformly injecting a tracer solution containing titanium dioxide colloid into a soil area of the air-packing belt to be detected;
after the tracer solution finishes flowing, a plurality of longitudinal sections of the soil with the air covering zone are excavated in the area, the number density of the sections is not less than 1/10 cm, identification solution containing potassium ferrocyanide is sprayed to the sections formed by each excavation, then ultraviolet light is used for irradiation, and after the color of the sections changes, images of the sections are acquired;
overlapping all acquired images of the sections according to the actual section positions to obtain the motion path;
the preparation method of the titanium dioxide colloid comprises the following steps: glacial acetic acid and butyl titanate are mixed according to the molar ratio of not more than 1:2, after fully mixing the components in proportion, carrying out chemical reaction to generate a mixed solution containing titanium dioxide colloid; mixing hydrochloric acid solution and titanium dioxide colloid-containing mixed solution according to a volume ratio of 1: 10-20, completely mixing; the pH value of the mixed solution is adjusted to be between 5 and 6; and standing the mixed solution with the regulated pH value at the constant temperature of 25-35 ℃ for 12-24 hours to obtain the stable transparent nanoscale titanium dioxide colloid.
2. The method according to claim 1, wherein the tracer solution is a titanium dioxide colloid diluted with water in a ratio of not less than 1: 100.
3. The measurement method according to claim 1, wherein the identification solution comprises an aqueous potassium ferrocyanide solution having a concentration of not less than 0.1 mol/L.
4. The method according to claim 1, wherein the ultraviolet light has a wavelength of 270 to 368nm.
5. The method according to claim 1, characterized in that a short-arc mercury ultraviolet lamp loaded in a sealed quartz glass cylinder, into which an inert gas is injected, is used as the light source of the ultraviolet light.
6. The method of measurement according to claim 5, wherein the inert gas comprises helium or neon.
7. The measurement method of claim 1, wherein the cross-section color change comprises: a partial region of the profile exhibits a deep blue color.
8. The method of measuring according to claim 1, wherein the depth of the longitudinal section is not less than the tracer liquid amount x 50 in mm.
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