CN114594077A - High-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox condition change - Google Patents
High-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox condition change Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change, which comprises a soil box ventilation system, an optical polar film working system and an adsorption film treatment analysis system, wherein the soil box ventilation system comprises an oxygen pump, a soil box device and a ventilation hose, the optical polar film working system comprises an oxygen optical polar film, and the adsorption film treatment analysis system comprises a DGT adsorption film; the soil box device comprises a gas-permeable hose, a rear cover plate and a two-dimensional plane which is exposed after the rear cover plate is disassembled and is used for sequentially attaching the DGT adsorption film and the oxygen photoelectrode film, wherein the gas-permeable hose is used for forming an aerobic/anoxic micro interface in soil; the optical electrode film working system is used for analyzing the oxygen concentration of a two-dimensional plane on the oxygen optical electrode film, and the adsorption film processing and analyzing system is used for analyzing the two-dimensional distribution of the metal effective state concentration on the DGT adsorption film.
Description
Technical Field
The invention belongs to the field of polluted soil heavy metal migration and transformation evaluation, and particularly relates to a high-resolution technology-coupled heavy metal in-situ characterization system capable of simulating soil micro-area redox change.
Background
With the rapid development of science and technology, air, soil, water and even food contain heavy metals, and especially sudden heavy metal pollution becomes a worldwide environmental problem, which brings serious threats to ecological environment and food safety. After heavy metals enter soil, due to the obvious spatial heterogeneity of the soil, heavy metals are migrated and transformed in the soil environment in various environmental processes such as rainfall runoff, microbial activities and the like, and serious threats are caused to animals, plants and human health. Various environmental factors such as pH, Eh, organic matters, iron-manganese oxides and the like of the soil environment can influence the migration and transformation of heavy metals, wherein Eh is taken as an important physicochemical property of the soil, and can change in the processes of periodic river water impact leveling, underground water level floating or flooding irrigation, so that the redox environment of the soil is changed, the redox, adsorption-desorption and precipitation dissolution processes of the heavy metals in the soil are influenced, and the effective state concentration of the heavy metals is influenced.
At present, the research on the migration and transformation of heavy metals in soil caused by the change of redox conditions is mainly an ectopic research means, namely, after the soil in a polluted area is collected, the soil is stored and transported to a laboratory, and the soil after the experiment is graded and extracted by adopting a flooded soil column experiment or an anaerobic culture continuous batch experiment. However, the above research methods have certain defects, firstly, in the processes of sample collection, transportation, preservation and pretreatment, redox conditions are easy to change, the form and bioavailability of heavy metals are changed, and the experimental results are deviated; secondly, when a heavy metal migration and transformation mechanism is discussed, higher experiment and time cost are caused to the multi-step analysis process of different heavy metals and the physicochemical properties of soil; finally, the experimental results of most of the current researches are limited to the migration and transformation process of heavy metals on one dimension in the centimeter level, the difference of the effective concentration of the heavy metals caused by Eh change in the microscale is ignored, and the result analysis with higher resolution ratio on a two-dimensional plane is lacked.
The thin film gradient diffusion technology (DGT) is an in-situ passive sampling technology for determining the effectiveness of a solute, the adsorption effect of the DGT can establish a concentration gradient for the surrounding local environment to promote the dissociation in a solid phase, and the measured diffusion flux can reflect the dynamic equilibrium process of heavy metals in soil better. The planar optical electrode film (PO) technology is based on the fluorescent sensing principleAn in-situ high-resolution technique for detecting pH and O in soil or deposit features that a sensing membrane is made of fluorescent dye, a special light source is used to excite the fluorescent image of said sensing membrane, and the two-dimensional quantitative distribution image of the object to be detected can be obtained2、pCO2、NH4Etc. wherein O2Is most widely used. In recent years, with the development of DGT and PO technologies, the combination of two in-situ high-resolution technologies has been gradually applied. The novel two-dimensional high-resolution (millimeter-submillimeter level) sensing technology is established by coupling the high-resolution DGT (HR-DGT) and the planar photoelectrode, so that the concentration and the effectiveness of elements with different valence states can be analyzed in situ, and the influence mechanism of environmental factors on the two-dimensional plane and the micro-area of the soil can be discussed.
In conclusion, the high-resolution technology-coupled heavy metal in-situ characterization system for the complex soil environment is set up, and not only is an effective means for discussing the distribution rule of the effective state of the heavy metal and the migration and transformation mechanism in the dynamic change process of the oxidation-reduction condition in the micro-area in-situ discussed, but also is a research focus in the field of the migration and transformation evaluation of the heavy metal in the polluted soil.
Disclosure of Invention
1. Problems to be solved
The research of discussing redox change to heavy metal migration transformation in the prior art is mostly continuous batch experiments of continuous saline water/intermittent flooding or traditional ectopic means such as field earth pillar sampling and grading extraction, the experiment operation is complex, and the destructiveness to the actual soil redox environment is great, the form and the validity of heavy metal are easy to change, the accuracy of the experiment is influenced, and therefore the real-time monitoring and the capturing of the redox condition of the soil dynamic balance process in a two-dimensional plane and a soil micro-area and the effective state concentration of the heavy metal can not be carried out.
The invention aims to provide a high-resolution in-situ characterization system which is simple to operate, high in accuracy and capable of monitoring and capturing the effective concentration of heavy metal in real time.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change, which comprises a soil box ventilation system, an optical polar film working system and an adsorption film treatment analysis system, wherein the soil box ventilation system comprises an oxygen pump, a soil box device and a ventilation hose for introducing oxygen into the soil box device, the adsorption film treatment analysis system comprises a DGT adsorption film and corresponding analysis equipment, and the optical polar film working system comprises an oxygen optical polar film and corresponding analysis equipment; the soil box device comprises an air-permeable hose, a rear cover plate and a two-dimensional plane which is exposed after the rear cover plate is disassembled and used for sequentially attaching the DGT adsorption film and the oxygen photoelectrode film, wherein the air-permeable hose is used for forming an aerobic/anoxic micro interface in soil; the optical pole film working system is used for analyzing the oxygen concentration of a two-dimensional plane on the oxygen optical pole film, and the adsorption film processing and analyzing system is used for analyzing the two-dimensional distribution of the metal effective state concentration on the DGT adsorption film.
The heavy metal micro-area characterization system can simulate the redox micro-interfaces with different oxygen contents, does not damage the solid-liquid phase overall environment of the soil in the dynamic change process, applies the oxygen photoelectrode membrane and the adsorption membrane to the two-dimensional plane of the soil box in situ, synchronously obtains the oxygen concentration and the effective state concentration information of the heavy metal at the aerobic/anoxic micro-interface of the soil, is convenient to operate, and provides an important basis for explaining the migration and transformation of pollutants in the soil.
As a further improvement, the optical polar film working system of the invention utilizes an optical polar film fluorescence sensor and can directly record O in the environment through a camera under the excitation of an LED light source2High resolution two-dimensional measurement of (2). The absorption film processing and analyzing system realizes high-resolution (mum-level) two-dimensional distribution of the concentration of the heavy metal or nonmetal effective state in the soil by the combined use of a DGT absorption film and a laser ablation-inductively coupled plasma mass spectrometry technology.
The DGT adsorption film comprises various adsorption films for different elements known in the prior art, such as S in soil2-A diffusion flux AgI adsorption membrane, said DGT adsorption membrane being manufactured by DGT research Co., Ltd, UK. The oxygen photoelectrode film adopts oxygenThe gas quencher platinum phenylporphyrin, the antenna dye MY, the polystyrene and the dichloromethane are mixed according to a certain proportion to prepare the film, the film has quick response time and uniform dye distribution, and can present different fluorescence responses to different oxygen concentrations. The oxygen optical pole film can also be a purchased optical pole film.
As a further improvement of the invention, the soil box device comprises an organic glass box body, a ventilating hose, a track etching film, a cover plate with a mold, a sealing side plate and a rear cover plate, wherein the cover plate with the mold and the sealing side plate are used for sealing the soil sample before being loaded into the device; and the rear cover plate is disassembled to expose a two-dimensional plane for sequentially attaching the DGT adsorption film and the oxygen optical electrode film.
As a further improvement of the invention, the soil box device can be used for simultaneously filling the soil with different depths in a field, so that synchronous experiments of various kinds of soil are realized. The back shroud and take the mould apron to use and can replace in different stages, use and take the mould apron when filling the soil box, in order to make to form the recess that does benefit to the embedding of ventilative hose in the soil. The back cover plate is used during a ventilation experiment, the two-dimensional plane can be exposed after the back cover plate is detached, the oxygen optical electrode film and the adsorption film can be conveniently attached to detection application, and meanwhile, the stability of oxidation-reduction conditions in the ventilation process is not changed.
As a further improvement of the invention, the cover plate with the die is a cover plate with a U-shaped die; the middle specification of the soil box device is 10 multiplied by 1.5 multiplied by 18.5cm, the ventilation hose is U-shaped expanded polytetrafluoroethylene and has the performances of ventilation and water impermeability, the inner diameter and the outer diameter of the hose are 2 multiplied by 3mm, the hole diameter on the hose is 0.2-0.5 mu m, the air permeability is 60% -80%, and after gas is introduced, the gas can diffuse to soil on two sides through the hose to form an aerobic/anoxic micro interface.
As a further improvement of the invention, the soil box aeration system further comprises an air flow control plate, wherein the air generated by the oxygen pump can be pumped into the air flow control plate through an aeration hose, the air flow control plate comprises a plurality of air flow meters, the air flow meters are provided with regulating valves, and the air flow of each aeration pipeline can be respectively regulated through the regulating valves so as to convey air flows with different sizes to the soil box device.
As a further improvement of the invention, the adsorption film treatment analysis system comprises a DGT adsorption film, a dry glue instrument, a laser ablation and inductively coupled plasma mass spectrometer; the optical film system comprises an oxygen optical film, an LED light source, a camera and a computer.
As a further improvement of the invention, the track-etched membrane has a pore size of 0.2 μm and a thickness of about 10 μm.
As a further improvement, the invention provides a high-resolution technology-coupled heavy metal in-situ characterization method for simulating soil micro-area redox change, which comprises the following steps of:
1) sealing the soil box device, filling the soil sample into the soil box device layer by layer, and compacting;
2) the cover plate of the soil box device is disassembled, the air-permeable hose is buried, the track etching film is attached, the air-permeable hose is fully contacted with the soil layer, and the device is sealed;
3) continuously introducing oxygen, after the soil is stably ventilated, disassembling the rear cover plate to expose a two-dimensional plane, closely attaching the DGT adsorption film to the two-dimensional plane of the soil box device, accurately recording the contact time of the adsorption film and the soil, and analyzing the two-dimensional distribution of the metal effective state concentration obtained on the DGT adsorption film in situ by using corresponding analysis equipment after the adsorption film is taken down;
4) the oxygen optical pole film is tightly attached to the DGT adsorption film, and after the oxygen optical pole film is contacted with soil to be balanced, the oxygen concentration distribution condition of a two-dimensional plane on the oxygen optical pole film is analyzed in situ by using corresponding analysis equipment.
As a further improvement of the invention, the cover plate is a cover plate with a U-shaped mold, the breathable hose is a U-shaped expanded polytetrafluoroethylene hose, the detachable rear cover plate in step 2) is detached to expose the U-shaped groove, and the U-shaped expanded polytetrafluoroethylene hose is embedded and installed in the U-shaped groove.
As a further improvement of the invention, in the step 4), the DGT adsorption membrane is tightly attached to a two-dimensional plane of the soil box device, the contact time between the adsorption membrane and the soil is accurately recorded, the adsorption membrane is taken down and then spread on a polyethersulfone filter membrane, a flat clean plastic film is covered on the adsorption membrane, the adsorption membrane is lightly pressed for 8 hours at room temperature and then dried for 2 hours by using a dry glue instrument, and quantitative analysis is performed by using laser ablation and inductively coupled plasma mass spectrometry to obtain the metal effective state concentration of the two-dimensional plane.
As a further improvement of the invention, in step 4), after the oxygen optical polar film is in contact with the soil and balanced, the LED light source is turned on to emit excitation light with a corresponding wavelength to uniformly irradiate the oxygen optical polar film, the oxygen optical polar film is excited to generate fluorescence with a specific wavelength, the fluorescence image of the whole soil box device is captured by the camera, the whole process is controlled by the computer, and the fluorescence image can be stored in the computer to perform data processing according to the response curve of the oxygen optical polar film to the oxygen to obtain a monitoring result.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change, a designed aeration soil box system can simulate different aeration conditions, so that an aerobic/anoxic micro interface is formed in soil of a soil box and is coupled with an oxygen optical polar film-DGT technology, a two-dimensional distribution high-resolution image of the oxygen content of the soil and the effective state concentration of heavy metal in the soil during the dynamic balancing process of the aerated soil can be synchronously obtained in situ on the premise of not damaging the soil redox environment, and the migration and conversion mechanism of the heavy metal in the soil micro-area during the dynamic balancing process promoted by oxidation and reduction can be more comprehensively explained.
(2) The high-resolution technology-coupled heavy metal in-situ characterization system for simulating the soil micro-area redox change, provided by the invention, can form an aerobic/anoxic micro interface of the micro area in the soil aeration process, and can be conveniently detached; and meanwhile, the two-dimensional optical polar film and the high-resolution DGT adsorption film are assembled, so that the soil physicochemical property and the two-dimensional distribution high-resolution image of the soil heavy metal effective state are simultaneously obtained in the oxidation-reduction dynamic change process on the premise of not damaging the soil oxidation-reduction environment, quantitative analysis is carried out on the images, the environmental risk of the heavy metal in the soil environment can be more accurately and effectively evaluated, and the migration and transformation mechanism of the heavy metal is discussed. However, in the conventional research on redox and heavy metal migration transformation, the change of soil redox conditions in a micro-area is mostly ignored, and Eh of one point in a centimeter scale and heavy metal concentration monitoring can only be realized, if high-resolution two-dimensional data is obtained, a large number of electrodes or experiments are needed, so that the cost is increased to a great extent undoubtedly, and the measurement process is complicated.
Drawings
FIG. 1 is an overall schematic view of an in situ characterization system of the present invention;
FIG. 2 is a three-dimensional perspective view of the soil box assembly of the present invention;
FIG. 3 is a standard curve of the oxygen photoelectrode film analysis system of example 2;
FIG. 4 is a standard curve of the target element Cr (VI) in the DGT adsorption film analysis system in example 2;
FIG. 5 is a two-dimensional image of an oxygen gas optical polar film in the soil box of example 3 after introducing (A) air and (B) oxygen gas;
FIG. 6 is a graph showing the percentage of dissolved oxygen in the soil in the oxygen photoelectrode film around the hose before and after the introduction of oxygen in example 3;
FIG. 7 is a view showing S around the hose obtained by adsorbing the adhesive before and after aeration in example 32-A diffusion flux distribution trend;
in the figure: 1. an oxygen pump; 2. an air hose; 3. an airflow control panel; 4. a gas flow meter; 5. a soil box device; 6. etching the mold by the track; 7. a DGT adsorption film; 8. an oxygen gas optical pole film; 9. an LED light source; 10. a camera; 11. a computer; 12. a polyethersulfone filter membrane; 13. a glue drying instrument; 14. laser ablation; 15. an inductively coupled plasma mass spectrometer; 16. a puffed polytetrafluoroethylene hose; 17. an organic glass box body; 18. a rear cover plate; 19. sealing the side plate; 20. and (5) fastening the screw.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings. The following description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art can modify the technical content disclosed below to equivalent embodiments with equivalent changes. Any simple modifications or equivalent changes made to the following examples according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Example 1
The embodiment provides a high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change, which consists of a soil box ventilation system, an optical polar film working system and an adsorption film processing and analyzing system.
The soil box ventilation system comprises an oxygen pump 1, an airflow control plate 3, a ventilation hose 2 and a soil box device 5, wherein gas generated by the oxygen pump can be pumped into the airflow control plate 3 through the ventilation hose 2, the airflow control plate comprises a plurality of gas flow meters, the gas flow meters are provided with regulating valves, the gas flow of each ventilation pipeline can be respectively regulated through the regulating valves, and airflows with different sizes are transmitted to the soil box device 5.
The middle specification of the soil box device 5 is 10 multiplied by 1.5 multiplied by 18.5cm, the air-permeable hose is U-shaped expanded polytetrafluoroethylene and has air-permeable and water-impermeable performances, the inner diameter multiplied by the outer diameter of the hose is 2 multiplied by 3mm, the hole diameter on the hose is 0.2-0.5 mu m, the air permeability is 60% -80%, and after gas is introduced, the air can diffuse to soil at two sides through the hose to form an aerobic/anoxic micro interface.
Adsorption film treatment analysis system: the absorption film processing and analyzing system comprises a DGT absorption film 7, a dry glue instrument 13, a laser ablation 14 and an inductively coupled plasma mass spectrometer 15. In the adsorption film treatment analysis system, a DGT adsorption film 7 is tightly attached to a two-dimensional plane of a soil box, the contact time of the DGT adsorption film 7 and soil is accurately recorded, the DGT adsorption film 7 is taken down and then is flatly laid on a polyether sulfone filter membrane 12, a layer of flat clean plastic film is covered on the DGT adsorption film, a dry glue instrument 13 is used for drying for 2 hours after light pressing is carried out for 8 hours at room temperature, quantitative analysis is carried out by using a laser ablation 14 and an inductively coupled plasma mass spectrum 15 in a combined mode, and the metal effective state concentration of the two-dimensional plane of the soil box is obtained.
The working system of the optical pole film comprises: the optical pole film working system comprises an oxygen optical pole film 8, an LED light source 9, a camera 10 and a computer 11; in the photoelectrode membrane working system, an oxygen photoelectrode membrane 8 is tightly attached to a two-dimensional plane of a soil box, after the oxygen photoelectrode membrane is contacted with soil and the gas flow is balanced, an LED lamp light source 9 with the wavelength of 455nm is started to emit exciting light with the corresponding wavelength to uniformly irradiate the oxygen photoelectrode membrane 8, the oxygen photoelectrode membrane 8 is excited to generate fluorescence, a fluorescence image of the whole soil box is captured through a camera 10, the whole process is controlled by a computer 10, and the fluorescence image can be stored in the computer to perform data processing according to a response curve of the oxygen photoelectrode membrane 8 to the oxygen concentration to obtain a monitoring result.
Example 2
This example is the stability verification of the oxygen photoelectrode system and the DGT adsorption film analysis system
1) Calibrating the oxygen photoelectrode film: before the optical electrode film is used, the optical electrode film needs to be calibrated, namely a strip film with a proper size is cut out and attached to the inner side of a quartz glass box with the size close to that of the soil box. The tap water saturated with oxygen can be filled with nitrogen/oxygen mixed gas or Na2SO3So as to adjust the content of dissolved oxygen in the water body. After the oxygen concentration had stabilized, pictures were taken under excitation of 455nm LEDs. The fluorescence intensity value of the optical polar film under each oxygen content is compared with the intensity value under the upper absolute oxygen concentration to be used as a vertical coordinate, the oxygen content value is used as a horizontal coordinate to carry out nonlinear fitting, and R can be seen20.991, as shown in fig. 3, which determines O in subsequent studies2Stability of the optode film and data reliability. Therefore, in the subsequent use of the optical pole film, the obtained fluorescence intensity ratio is substituted into the standard curve, and the corresponding oxygen concentration value can be obtained.
2) Quantification of DGT adsorption membranes in adsorption gel analysis systems: before the adsorption film analysis system is adopted to obtain the effective state concentration of heavy metal on the adsorption film, the DGT adsorption glue with the standard concentration is prepared in advance for debugging the parameters of an instrument and finally carrying out quantitative analysis. Preparing enough common disc type DGTs, putting the disc type DGTs into a target element solution with a certain concentration, stirring the solution at a constant temperature, taking 6 DGTs out of the solution at different time, eluting the absorbent according to a DGT conventional method, measuring the concentration of the target element by utilizing ICP-MS, and calculating the mass and the density of the target element on the adsorption film. The other three reference sorbent membrane analytical systems were run dry for LA analysis. According to the data, a linear relation between the signal value of the LA test sample and the amount of the target element on the adsorption film is established, and R can be obtained by data fitting 20.998, as shown in fig. 4. In subsequent analysis, the signal value of the sample adsorption film can be substituted into the linear relation for calculation, so that the in-situ quantitative calculation of the element flux of the adsorption film is realized.
Example 3
The device of example 1 is adopted to develop the law of the influence of the process of changing the oxidation-reduction conditions on the change of the oxygen content of the soil and the element migration and transformation at the aerobic/anoxic micro-interface of the soil.
The method comprises the following steps: the lower half part of the soil box device 5 is filled with soil at a certain place depth of 3m in the upper sea, the upper half part is filled with soil at a certain place depth of 1m in the upper sea, and the density at each place is kept uniform and consistent as far as possible in the filling process. Then the cover plate of the soil box with the U-shaped mould is removed without breakingUnder the condition of bad soil, a U-shaped expanded polytetrafluoroethylene hose 16 is filled, a track etching film 6 with the aperture of 0.2 mu m and the thickness of about 10 mu m is attached to the hose and is fully contacted with the soil layer, a rear cover plate 18 is filled back after the hose is sealed by a waterproof tape, and then a slow gravity water-passing tool is used for slowly wetting the soil block at a constant speed until the saturated water content is reached. The filled soil box is wrapped by aluminum foil and placed in a dark place, the soil box is stabilized for two weeks under a moisture state, and then oxygen/air is introduced into a hose of the soil box. During the aeration process, the fluorescence pictures of the oxygen photoelectrode membrane are observed and taken regularly. After the aerobic/anoxic micro-interface of the soil is basically stabilized, the oxygen content of the aerobic/anoxic micro-interface (around the hose) in the soil is changed by using the photoelectrode film and the adsorption glue 2And carrying out two-dimensional in-situ characterization on the effective state concentration of the element.
A, B in FIG. 5 are two-dimensional images of dissolved oxygen in two-dimensional planes of soil box captured by oxygen photoelectrode film after air and oxygen are introduced respectively, it can be seen that, for the soil from different depths, the continuous air introduction makes the oxygen content around the hose diffuse and present obvious difference, the obvious oxygen content increase around the hose can be observed in the soil from 1m depth (upper part of soil box), forming obvious aerobic/anoxic micro interface, but the oxygen content change in the soil from 3m depth (lower part of soil box) is not obvious. Comparing the change of the dissolved oxygen percentage of the oxygen photoelectrode membrane soil around the hose before and after the oxygen introduction (figure 6), it can be seen that the hose extends to the surrounding soil to present obvious gradient change of the oxygen content, and the oxygen content is obviously increased after the oxygen introduction. Before oxygen is introduced, the dissolved oxygen saturation percentage of soil at the far position of the hose is lower than 25%, and the dissolved oxygen saturation percentage of soil at the near position of the hose is about 111% at most. However, after the oxygen gas was introduced, the percent dissolved oxygen saturation increased to 265%. It can be seen that O2The photoelectrode film can accurately capture the distribution and migration of oxygen content at the oxygen/oxygen-poor micro-interface at two sides of the hose in situ.
As shown in FIG. 7A, S is calculated at any position in the vertical direction of the soil with two depths2-Diffusion flux, air aeration clearly visible S from 1m depth soil and from 3m depth soil2-Diffusion flux difference of (1 m depth)S in soil2-Diffusion flux at 27 μmol cm-2h-1To 39. mu. mol cm-2h-1Fluctuates between the two, and is only 17 to 27 mu mol cm in the soil with the depth of 3m-2h-1In the meantime. While observing the air input, S2-The flux of (A) is in a clear gradient from the hose to the soil on both sides, in FIG. 7B, the hose S is filled with air2-The minimum value reaches 17 mu mol cm-2h-1Soil S on both sides of the hose2-Can be up to 40 mu mol cm-2h-1. However, in the oxygen introducing group, the S in the soil is generated due to higher net oxygen introduction amount2-Probably most oxidized, AgI adsorbs S on the glue2-Has a weak gradient of S2-The diffusion flux is lower than 20 mu mol cm in the soil at two depths-2h-1In the transverse direction S2-The diffusion flux also did not change significantly from the center of the hose to the soil on both sides. The results show that the system is used for treating S at the aerobic/anoxic micro-interface of the soil2-The diffusion flux is characterized, and the aerobic/anoxic micro-interfaces at different soil properties can be quantitatively analyzed.
Claims (10)
1. A heavy metal in-situ characterization system for simulating soil micro-area redox change and coupling with high resolution technology is characterized in that: the device comprises a soil box ventilation system, an optical polar film working system and an adsorption film treatment analysis system, wherein the soil box ventilation system comprises an oxygen pump (1), a soil box device (5) and a ventilation hose (2) for introducing oxygen into the soil box device (5), the adsorption film treatment analysis system comprises a DGT adsorption film (7), and the optical polar film working system comprises an oxygen optical polar film (8); the soil box device (5) comprises an air-permeable hose, a rear cover plate (18) and a two-dimensional plane which is exposed after the rear cover plate (18) is disassembled and used for sequentially attaching the DGT adsorption film (8) and the oxygen photoelectrode film (7), and the air-permeable hose is used for enabling the interior of soil to form an aerobic/anoxic micro interface; the optical pole film working system is used for analyzing the oxygen concentration of a two-dimensional plane on the oxygen optical pole film (7), and the adsorption film processing and analyzing system is used for analyzing the two-dimensional distribution of the metal effective state concentration on the DGT adsorption film (8).
2. The high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change according to claim 1, wherein: the soil box device (5) comprises an organic glass box body (17), a ventilating hose, a track etching film (6), a cover plate with a mold, a sealing side plate (19) and a rear cover plate (18), wherein the cover plate with the mold and the sealing side plate (19) are used for sealing a soil sample before being loaded into the device, the cover plate with the mold is also used for generating a groove matched with the shape of the ventilating hose in the soil sample, the track etching film (6) is tightly attached to a two-dimensional soil plane containing the ventilating hose, and the rear cover plate (18) is used for sealing the soil box device (5) after being loaded into the ventilating hose and the track etching film (6); and the rear cover plate (18) is disassembled to expose a two-dimensional plane for sequentially attaching the DGT adsorption film (7) and the oxygen optical pole film (8).
3. The high-resolution technology-coupled in-situ characterization system for heavy metals, which simulates the redox changes of soil micro-regions, according to claim 1 or 2, wherein: the air-permeable hose is an expanded polytetrafluoroethylene hose (16), the aperture of the hose is 0.2-0.5 mu m, the air permeability is 60% -80%, and after air is introduced, the air can diffuse from the expanded polytetrafluoroethylene hose (16) to soil on two sides to form an aerobic/anoxic micro interface.
4. The high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change according to claim 3, wherein: the cover plate with the die is a cover plate with a U-shaped die, and the expanded polytetrafluoroethylene hose (16) is U-shaped.
5. The high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change according to claim 1, wherein: the soil box ventilation system further comprises an airflow control plate (3), gas generated by the oxygen pump (1) can be pumped into the airflow control plate (3) through the ventilation hose (2), the airflow control plate (3) comprises a plurality of gas flow meters (4), the gas flow meters (4) are provided with regulating valves, the flow rate of each ventilation pipeline can be respectively regulated through the regulating valves, and airflow with different sizes is conveyed to the soil box device (5).
6. The high-resolution technology-coupled heavy metal in-situ characterization system for simulating soil micro-area redox change according to claim 1, wherein: the absorption film processing and analyzing system comprises a DGT absorption film (7), a dry glue instrument (13), a laser ablation instrument (14) and an inductively coupled plasma mass spectrometer (15); the optical film system comprises an oxygen optical film (8), an LED light source (9), a camera (10) and a computer (11).
7. A high-resolution technology-coupled heavy metal in-situ characterization method for simulating soil micro-area redox change by using the system of claim 1, which is characterized in that: the method comprises the following steps:
1) sealing the soil box device (5), filling the soil sample into the soil box device (5) layer by layer, and compacting;
2) the cover plate of the soil box device is disassembled, the air-permeable hose is buried, the track etching film (6) is attached to the air-permeable hose and fully contacts with the soil layer, and the device is sealed;
3) continuously introducing oxygen, after the soil is stably ventilated, detaching the rear cover plate (18) to expose a two-dimensional plane, tightly attaching the DGT adsorption film (7) to the two-dimensional plane of the soil box device (5), accurately recording the contact time of the adsorption film and the soil, and analyzing the two-dimensional distribution of the metal effective state concentration obtained on the DGT adsorption film (7) in situ by using corresponding analysis equipment after taking down the adsorption film;
4) the oxygen optical polar film (8) is tightly attached to the DGT adsorption film (7), and after the oxygen optical polar film is contacted with soil to be balanced, the oxygen concentration distribution condition of a two-dimensional plane on the oxygen optical polar film (8) is analyzed in situ by using corresponding analysis equipment.
8. The high-resolution technology-coupled in-situ characterization method for heavy metals for simulating soil micro-area redox changes according to claim 7, wherein the method comprises the following steps: the apron is the apron of taking U type mould, the gas permeability hose is popped polytetrafluoroethylene hose (16) of U type, can dismantle in step 2) that the back shroud unpacks apart the back and expose U type recess, the popped polytetrafluoroethylene hose (16) of U type imbed and install to U type recess in.
9. The high-resolution technology-coupled heavy metal in-situ characterization method for simulating soil micro-area redox change according to claim 7, characterized in that: in the step 4), the DGT adsorption film (7) is tightly attached to a two-dimensional plane of the soil box device (5), the contact time of the adsorption film and soil is accurately recorded, the adsorption film is taken down and then is flatly laid on a polyether sulfone filter membrane, a layer of smooth clean plastic film is covered on the adsorption film, a dry glue instrument (13) is used for drying after the adsorption film is lightly pressed for a period of time at room temperature, and quantitative analysis is carried out by using the combination of laser ablation (14) and an inductively coupled plasma mass spectrometer (15) to obtain the metal effective state concentration of the two-dimensional plane.
10. The high-resolution technology-coupled in-situ characterization method for heavy metals for simulating soil micro-area redox changes according to claim 7, wherein the method comprises the following steps: in the step 5), after the oxygen optical polar film (8) is in contact with the soil to be balanced, the LED lamp light source (9) is started to emit exciting light with corresponding wavelength to uniformly irradiate the oxygen optical polar film (8), the oxygen optical polar film (8) is excited to generate fluorescence with specific wavelength, a camera (10) is used for capturing an integral fluorescence image of the soil box device (5), the integral process is controlled by a computer, and the fluorescence image can be stored in the computer to be subjected to data processing according to a response curve of the oxygen optical polar film (8) to the oxygen to obtain a monitoring result.
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| CN114486824A (en) * | 2021-12-27 | 2022-05-13 | 南京大学 | Soil system-oriented high-resolution technology-coupled heavy metal in-situ characterization system for simulating pH change |
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| CN114486824A (en) * | 2021-12-27 | 2022-05-13 | 南京大学 | Soil system-oriented high-resolution technology-coupled heavy metal in-situ characterization system for simulating pH change |
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