CN110208298B - Method for in-situ separation of active components in soil micro-aggregates to characterize microstructure thereof - Google Patents
Method for in-situ separation of active components in soil micro-aggregates to characterize microstructure thereof Download PDFInfo
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- CN110208298B CN110208298B CN201910476008.8A CN201910476008A CN110208298B CN 110208298 B CN110208298 B CN 110208298B CN 201910476008 A CN201910476008 A CN 201910476008A CN 110208298 B CN110208298 B CN 110208298B
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Abstract
The invention discloses a method for realizing in-situ separation of active components in soil micro-aggregates and characterization of the microstructure of the soil micro-aggregates by using a combination of synchrotron radiation scanning transmission microscopy and a mathematical statistics method, which comprises the following steps: grinding the air-dried soil into powder; preparing suspension and air-drying; acquiring X-ray near-edge absorption structure spectrums and stack images of K edges of carbon, aluminum and silicon and L edges of iron by using a synchrotron radiation scanning transmission technology; the stacked images of all elements are combined after image and energy correction, then a superimposed multivariate spectrogram is used for carrying out multi-element main component and cluster analysis to obtain a cluster spectrogram representing different element compositions, contents and structures of carbon, iron and aluminum silicon, so that the in-situ separation of an organic matter component mainly comprising carbon, an iron oxide component mainly comprising iron, a clay mineral component mainly comprising aluminum silicon and the microstructure characteristics of the typical active components in the soil aggregate is realized.
Description
Technical Field
The invention relates to a method for in-situ separation of active components in soil micro-aggregates to characterize the microstructure of the soil micro-aggregates, in particular to a method for in-situ separation of the active components in the soil micro-aggregates to characterize the microstructure of the soil micro-aggregates by using a combination of synchrotron radiation scanning transmission microscopy and a mathematical statistics method.
Background
The soil nutrient management and the heavy metal pollution control are important for the green development of agriculture in China. The soil micro-aggregates are basic constituent units of soil, and nutrients and pollutants enter a soil system and then mainly interact with active components in the soil aggregates, so that the form, distribution, fate and biological effectiveness of the nutrients and pollutants in the soil are influenced. However, the active components of the soil are various, represented by organic matters, iron oxides and clay minerals, so that the distribution of the soil components is uneven, the difference of microstructures is obvious, the understanding of the distribution characteristics, the microscopic forms and the biological effectiveness of soil nutrients and pollutants is greatly limited, the soil nutrients and pollutants cannot be effectively controlled, and the green development of agriculture is limited. Therefore, the effective in-situ separation of the active components of the soil aggregates and the microstructural characterization are the premise for deeply knowing the action mechanism of the soil aggregates and nutrients and pollutants. Currently, for the characterization of active components in soil aggregates, chemical extraction methods are mainly used, for example, an acid-base solution is used for extracting soil humus, a sodium hydrosulfite-citrate-sodium bicarbonate method is used for extracting soil iron oxide and the like, but the chemical extraction process is destructive to the soil active components, and the extraction process is poor in selectivity. In order to overcome the limitation of the chemical extraction method in characterizing the soil aggregate, researchers also report a method for characterizing the soil aggregate by using a synchrotron infrared microscopic imaging technology and combining the synchrotron infrared microscopic imaging technology with a scanning electron microscope, a nano ion probe and other technologies, which specifically comprises the following steps:
patent 1 (application number: CN201610851124. X) reports a method for in-situ research of organic carbon and minerals in soil aggregates by using a synchrotron radiation infrared microscopy imaging technology, and the main functional group of the organic carbon and the mineral distribution characteristics can be obtained.
Patent 2 (application No. 201710896024.3) reports the use of scanning electron microscope, synchrotron radiation infrared microscopy and nano secondary ion probe technology to characterize the distribution of organic and inorganic functional groups in soil aggregates on a submicron scale; the problems of large destructiveness, complexity, poor synchronism, poor visibility, uncoordinated in-situ scale and the like of the traditional soil micro-aggregate research method are solved.
The in situ analysis method of soil aggregate reported above has some defects in the reports above or similar to the above from the aspects of characterization technical accuracy, operability of the method and comprehensiveness of the structural information of the active components:
(1) the spatial resolution of the synchrotron radiation infrared microscopic imaging technology is in a micron level, and the solid phase active components with the size in a nanometer level in the soil aggregate cannot be covered, so that the spatial resolution of the characterization means needs to be further improved.
(2) The scanning electron microscope and the nano ion probe technology are combined to provide nano spatial resolution, so that the defect of the synchrotron radiation infrared microscopic imaging technology in the spatial resolution is overcome, but the electron beams and the ion beams of the scanning electron microscope and the nano ion probe technology can cause sample damage, particularly damage to an organic matter structure, so that the synchrotron radiation infrared microscopic imaging technology cannot represent soil aggregates in situ, and the accuracy of the obtained structural information is questioned; meanwhile, the operation is complex, time-consuming and labor-consuming in the combined use process.
(3) The scanning electron microscope, the nano ion probe and the synchrotron radiation infrared microscopic imaging technology can not carry out quantitative characterization on the element content in the soil components, so that the content of each active component in the tested soil micro-aggregates is evaluated.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides the method which utilizes the combination of synchrotron radiation scanning transmission microscopy and a mathematical statistical method to realize the in-situ separation of the multiple active components of the soil aggregate on the micrometer scale, and utilizes the X-ray near-edge structure spectrum (XANES) of the target element to represent the microstructure of the typical element of the active component, thereby laying an important foundation for the subsequent deep research of the action mechanism of the soil aggregate and the nutrient/pollutant.
The purpose of the invention is realized by the following technical scheme, which comprises the following steps:
(1) preparation of soil micro-aggregates: and collecting soil clay components by using a sedimentation method, and grinding the sample into powder after freeze drying.
(2) Synchrotron radiation scanning transmission microscopy (STXM) test: preparing soil clay components into a suspension by using deionized water, transferring part of the suspension liquid to a silicon nitride window, transferring the suspension liquid to a measurement cavity after drying, introducing helium to maintain 1/6 atmospheric pressure, and then collecting a stack spectrogram of X-ray near-edge absorption structure (XANES) spectrums of K absorption edges of typical elements of soil, namely carbon (C), aluminum (Al) and silicon (Si) and L absorption edges of iron (Fe) in a transmission mode;
(3) in situ separation of soil aggregate reactive multi-components and characterization of their microstructural features by multilateral STXM data processing: performing spectrogram correction on stacked spectrograms of soil typical elements C/Fe/Al/Si, superposing to generate a C-Fe-Al-Si composite spectrogram, then obtaining different clusters by utilizing multi-element principal component analysis and cluster analysis, wherein the appearance of each cluster represents a soil aggregate with specific C/Fe/Al/Si content and form, XANES spectrum of C/Fe/Al/Si in each cluster can represent component structures such as organic carbon, iron oxide valence state, clay minerals or quartz and the like in each separated specific soil aggregate, and main active components in the aggregate are determined by the intensity of main absorption peaks of each XANES spectrum; thus realizing the in-situ separation of soil active solid phase components (soil iron oxide, organic matters, clay minerals and the like) and representing the microstructure of the soil active solid phase components on a submicron scale.
The method for in-situ separation of the active components in the soil micro-aggregates to characterize the microstructure of the soil micro-aggregates comprises the steps of combining stacked images of all elements after image and energy correction, then carrying out multi-element main component and cluster analysis by utilizing a superposed multivariate spectrogram to obtain a cluster spectrogram representing the composition, content and structure of different elements of carbon, iron and aluminum silicon, and realizing in-situ separation of organic matter components mainly comprising carbon, iron oxide components mainly comprising iron and clay mineral components mainly comprising aluminum and silicon in the soil micro-aggregates and the microstructure characteristics of typical active components, thereby having important significance for understanding the action mechanism of nutrients and pollutants in soil micro-domains and the active components (organic matter, iron oxide and clay mineral) and effectiveness control thereof.
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FIG. 1 is a graph of the morphology (a-f), content and microstructure (g-j) of typical active components of soil aggregates characterized by synchrotron radiation STXM technology, wherein Aromatic-C, Phenolic-C, Aliphatic-C and Carboxyl-C in the g-diagram represent Aromatic carbon, Phenolic carbon, Aliphatic carbon and Carboxyl carbon; FeCl in h diagram3And FeCl2Represents trivalent and divalent iron; muscovite in panels i and j represents a mica mineral; the soil micro-aggregates represented by the clusters 6 and 10 can be presumed to be mainly organic matters according to the height of main peaks in the carbon, iron, aluminum and silicon XANES spectra in g-j; the soil micro-aggregates represented by cluster 9 are mainly trivalent ferriteA compound; the soil micro-aggregates represented by cluster 1 are mainly mica minerals.
Detailed Description
The present invention will now be more fully described with reference to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein.
In the embodiment, the in-situ separation of active components in the soil micro-aggregates and the characterization of the microstructure of the soil micro-aggregates are realized by combining the synchrotron radiation scanning transmission microscopy with a mathematical statistics method; the method comprises the following specific steps:
(1) preparing soil micro-aggregates: selecting air-dried soil passing through a 2 mm sieve, separating and obtaining clay components of the soil by using a sedimentation method, and grinding the clay components into powder for later use after freeze drying.
(2) Preparation of STXM samples: mixing the soil clay component with deionized water to prepare a soil suspension, dripping the soil suspension on a silicon nitride window for air drying, moving the silicon window into an STXM measuring cavity, and introducing helium to maintain 1/6 atmospheric pressure; stacked spectra of K absorption edge of soil typical elements carbon (C), aluminum (Al), silicon (Si), and L absorption edge X-ray near edge absorption structure (XANES) spectra of iron (Fe) were collected using transmission mode, as shown in fig. 1 a-f.
(3) Multilateral STXM data processing: overlapping stacked spectrograms of soil typical elements C/Fe/Al/Si by using Axis2000 software to generate a composite spectrogram of C-Fe-Al-Si; performing spectrum correction by using a software Stack-Analyze 2.7 (C. Jacobsen, SUNY Stony Brook) by taking a stacked spectrum of the first energy point position as a reference; and finally, performing multi-element principal component analysis and cluster analysis on the corrected composite spectrogram by utilizing PCA GUI 1.1.1 software to obtain cluster graphs and XANES spectrums with different distributions.
(4) Characterizing the active components of the soil micro-aggregates by using the clustering analysis result: the morphology of each Cluster (Cluster) obtained by the clustering analysis represents the two-dimensional morphology of the soil aggregate with specific C/Fe/Al/Si content and morphology, XANES spectrum of C/Fe/Al/Si element in each Cluster is used for analyzing the structure of active components such as organic carbon, iron oxide valence state, clay mineral and the like in each separated specific soil aggregate, and the relative abundance of the active fixed components in the aggregate is determined by the intensity of main absorption peak of XANES spectrum of each element; thus realizing the in-situ separation of soil active solid phase components (soil iron oxide, organic matters, clay minerals and the like) on a micro-nano scale, and representing the composition abundance and microstructure of the components; as shown in g-j in figure 1.
The above examples are only for illustrating the present invention, and besides, there are many different embodiments, which can be conceived by those skilled in the art after understanding the idea of the present invention, and therefore, they are not listed here.
Claims (1)
1. A method for in-situ separation of active components in soil micro-aggregates to characterize the microstructure of the soil micro-aggregates is characterized by comprising the following steps:
(1) preparation of soil micro-aggregates: collecting soil clay components by using a sedimentation method, and grinding a sample into powder after freeze drying;
(2) synchrotron radiation scanning transmission microscopy (STXM) test: preparing soil clay components into a suspension by using deionized water, transferring part of the suspension liquid to a silicon nitride window, transferring the suspension liquid to a measurement cavity after drying, introducing helium to maintain 1/6 atmospheric pressure, and then collecting a stack spectrogram of X-ray near-edge absorption structure (XANES) spectrums of K absorption edges of typical elements of soil, namely carbon (C), aluminum (Al) and silicon (Si) and L absorption edges of iron (Fe) in a transmission mode;
(3) in situ separation of soil aggregate reactive multi-components and characterization of their microstructural features by multilateral STXM data processing: performing spectrogram correction on stacked spectrograms of soil typical elements C/Fe/Al/Si, superposing to generate a C-Fe-Al-Si composite spectrogram, then obtaining different clusters by utilizing multi-element principal component analysis and cluster analysis, wherein the appearance of each cluster represents a soil aggregate with specific C/Fe/Al/Si content and form, the XANES spectrum of the C/Fe/Al/Si element in each cluster can represent the component structure of organic carbon, iron oxide valence state, clay mineral or quartz in each separated specific soil aggregate, and the main active component in the aggregate is determined by the intensity of the main absorption peak of each XANES spectrum; thus realizing the in-situ separation of the soil active solid phase component and the representation of the microstructure on the submicron scale.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134549A (en) * | 1989-10-19 | 1991-06-07 | Rigaku Corp | Method and apparatus for x-ray analysis |
| WO2014088051A1 (en) * | 2012-12-06 | 2014-06-12 | 住友ゴム工業株式会社 | Method for analyzing degradation |
| CN104122260A (en) * | 2014-07-29 | 2014-10-29 | 中国科学院生态环境研究中心 | In-situ visualized analysis method of organic bromine compound in soil |
| CN106370615A (en) * | 2016-09-26 | 2017-02-01 | 南京农业大学 | Soil aggregate analysis method |
| CN106680306A (en) * | 2017-01-17 | 2017-05-17 | 肖健 | Method for submicron-scale in-situ characterization of soil microaggregate |
| CN108907209A (en) * | 2018-07-27 | 2018-11-30 | 中南大学 | A kind of oxide dispersion intensifying iron(-)base powder and its characterizing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8804897B2 (en) * | 2006-07-21 | 2014-08-12 | Areva Inc. | Integrated method to analyze crystals in deposits |
| CN101738383A (en) * | 2008-11-07 | 2010-06-16 | 中国农业科学院农业环境与可持续发展研究所 | Mid-infrared spectrum-based method for quickly detecting contents of heavy metal elements in soil |
| CN109697427A (en) * | 2018-12-25 | 2019-04-30 | 中南大学 | The analysis method and system that aggregate structure quantifies during a kind of red mud soil |
-
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- 2019-06-03 CN CN201910476008.8A patent/CN110208298B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03134549A (en) * | 1989-10-19 | 1991-06-07 | Rigaku Corp | Method and apparatus for x-ray analysis |
| WO2014088051A1 (en) * | 2012-12-06 | 2014-06-12 | 住友ゴム工業株式会社 | Method for analyzing degradation |
| CN104122260A (en) * | 2014-07-29 | 2014-10-29 | 中国科学院生态环境研究中心 | In-situ visualized analysis method of organic bromine compound in soil |
| CN106370615A (en) * | 2016-09-26 | 2017-02-01 | 南京农业大学 | Soil aggregate analysis method |
| CN106680306A (en) * | 2017-01-17 | 2017-05-17 | 肖健 | Method for submicron-scale in-situ characterization of soil microaggregate |
| CN108907209A (en) * | 2018-07-27 | 2018-11-30 | 中南大学 | A kind of oxide dispersion intensifying iron(-)base powder and its characterizing method |
Non-Patent Citations (3)
| Title |
|---|
| Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy for mapping nano-scale distribution of organic carbon forms in soil: Application to black carbon particles;Johannes Lehmann 等;《GLOBAL BIOGEOCHEMICAL CYCLES》;20050216;第19卷;参见摘要，第4页"2.4. Data Analyses" * |
| Organic carbon distribution, speciation, and elemental correlations within soil micro aggregates: Applications of STXM and NEXAFS spectroscopy;Jiamin Wan 等;《GEOCHIMICA ET COSMOCHIMICA ACTA》;20070915;第71卷;参见摘要，第5440-5448页 * |
| STXM-NEXAFS 研究铁(III)离子诱发柠檬酸在高岭石表面的固定机制;刘瑾 等;《化学学报》;20171231;第75卷;617-620 * |
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