CN112697772A - Method for carrying out garnet source tracing based on micro-confocal laser Raman - Google Patents
Method for carrying out garnet source tracing based on micro-confocal laser Raman Download PDFInfo
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Abstract
The invention provides an analysis method for tracing a debris garnet source based on a confocal laser Raman spectrometer. Garnets comprise 6 end-member components, each having its typical raman spectrum peak. The form and the displacement of the Raman spectrum peak can fully reveal the molecular structure information, and each peak position changes correspondingly along with the difference of molecular components. The method is based on 4 strong spectral peaks (340-‑1) And (3) solving the mole percentage content of each garnet, then carrying out triangular projection, and analyzing the original rock type. Compared with the traditional electronic probe data, the laser Raman technology can be used for nondestructively obtaining garnet quantitative analysis, is a very quick, cheap and effective method for researching garnet chemical components, provides a new technical means for tracing sediment sources, and can be widely applied to the researches of basin mountain effect, regional ancient geographic evolution and the like.
Description
Technical Field
The invention relates to the technical field of sedimentary basin research, in particular to a method for carrying out garnet source tracing by utilizing a micro-confocal laser Raman technology.
Background art:
the source analysis is an important idea for analyzing the ancient geographic evolution of the basin mountain effect and the regional structure, and is also a hotspot of basin dynamics research in recent years. Debris garnet is a common relatively stable heavy mineral in mountainous belt sedimentsA compound (I) is provided. Garnets are relatively complex in chemical composition and comprise 6 end-member components: magnesium aluminum garnet (Mg)3Al2Si3O12) Iron aluminum garnet (Fe)3Al2Si3O12) Manganese aluminum garnet (Mn)3Al2Si3O12) Calcium aluminum garnet (Ca)3Al2Si3O12) Calcium iron garnet (Andradite, Ca)3Fe2Si3O12) And calcium chromium garnet (Uvarovite, Ca)3Cr2Si3O12). Because of the specificity of garnet chemical composition, the garnet composition contained in different types of raw rock has significant differences, and thus the clastic garnet chemical composition is widely used in sediment source tracing research.
Laser raman spectroscopy is a scattering spectroscopy analysis technique, is a molecular vibration spectroscopy, and is an effective nondestructive analysis technique for analyzing molecular components and structures of substances. The micro confocal laser Raman spectrum has the characteristics of microcosmic, in-situ, multi-phase, high resolution, good stability and the like.
At present, the conventional technical method for acquiring the chemical composition of garnet is through an electronic probe technology, but the technology requires that the surface of a sample is flat and conductive, so that pretreatment such as polishing, carbon plating or gold plating is required, the test time is long, and certain destructiveness is generated on the sample.
The invention content is as follows:
the invention aims to rapidly obtain the molecular composition of garnet through a laser Raman spectrometer, and provides a method for carrying out garnet source tracing based on laser Raman.
In order to achieve the above object, the present invention provides a method for garnet source tracing based on confocal laser raman microscopy, the method comprising:
step (1): preparing a sample, and preparing a common sheet or an electronic probe sheet without covering a glass slide;
step (2): performing Raman test analysis on the common sheet; and (3) testing conditions are as follows: the resolution is 2 μm (x 100 objective), 400 μm pinhole, 100 μm slit, 1800 grating, exposure time is 15s, cycle number is 10, test time of each sample point is 180s, and inclusion needs to be avoided during test;
and (3): data processing, namely fitting the Raman peak position through NGSLABSpec software to obtain an accurate peak;
and (4): analyzing the mol percentage content of different garnets, applying an improved Miragem program in Matlab software, inputting Raman typical peak position shift, and obtaining the mol percentage content of the garnets;
and (5): data interpretation, triangle projection was performed in the minimum software, with the three end members of the triangle projection representing the garnet subtype.
Wherein the garnet in the step (1) is more than 100 in total, and each garnet is subjected to a numerical label, thereby ensuring a comparative analysis of the same point.
Wherein, if the individual peak value is lower than the threshold value, the garnet mole percentage content is calculated according to other peak values.
Wherein, the calculation formula of the garnet mole percentage in the step (4) is as follows:
W(i,k)＝∑W(i,j,k)X(j,k)
1＝Xa+Xb+Xc+Xd+Xe+Xf
w: a Raman wave number;
x: the proportion of the end-member components;
1-5 raman peaks;
j is a-f terminal member component;
k is the sample;
a-f magnesium aluminum garnet (Py), iron aluminum garnet (Al), manganese aluminum garnet (Sp), calcium aluminum garnet (Gr), calcium iron garnet (Ad) and calcium chromium garnet (Uv).
In the step (5), the garnet subtypes are classified according to the types of the original rock: type a garnets are mainly derived from high-grade gneiss phase-change sedimentary rock or perilla granite; type B garnet is derived from amphibole phase change sedimentary rock, and the source of the garnet is probably medium-acid magma only when the garnet is thrown into a Type Bi region; type C garnets are mainly derived from advanced metamorphic rocks, with Type Cii produced from ultrabasic rocks; type D garnets are generally derived from alternating metamorphic rocks such as skarn, very low metamorphic rocks or ultra high temperature metamorphic calcareous silicate gnetite.
Wherein the electron probe analysis in the step (6) is completed on a French CAMECA SXFiveFE high-resolution field emission electron probe, the acceleration voltage range of the instrument is 5-30 kV, and the spatial resolution can reach 6 nm.
Wherein the method further comprises: and (4) carrying out comparative analysis on the electronic probe, namely plating carbon on the electronic probe, analyzing the contents of Si, Ti, Al, Cr, Fe, Mn, Mg, Ca and Na elements in the electronic probe piece, and carrying out standard comparative measurement on the result of the electronic probe and the data interpretation in the step (5).
Garnets comprise 6 end-member components, each having its typical raman spectrum peak. The form and the displacement of the Raman spectrum peak can fully reveal the molecular structure information, and each peak position changes correspondingly along with the difference of molecular components. The method of the invention is based on the following method that 4 strong spectrum peaks (340--1) And (3) solving the mole percentage content of each garnet, then carrying out triangular projection, and analyzing the original rock type. Compared with the traditional electronic probe data, the error range of the garnet quantitative analysis result obtained by utilizing the laser Raman technology is less than 8%, the method is a very quick and effective method for researching the chemical components of the garnet, provides a new technical means for tracing the sediment source, and can be widely applied to the researches of the basin mountain effect, the regional ancient geographic evolution and the like.
Drawings
FIG. 1 is a laser Raman spectrum of a garnet.
FIG. 2 is a graph comparing laser Raman analysis results and electron probe analysis results, wherein squares represent Raman spectroscopy (Raman) test data and circles represent Electron Probe (EPMA) test data.
Detailed Description
The following is a more detailed description of the practice of the present invention using 3 representative samples of clastic garnet from the chalk-based sandstone in the Shanxi basin as an example and with reference to the accompanying drawings.
The invention provides an analysis method for carrying out fragment garnet source tracing based on confocal laser Raman microscopy, which comprises the following steps:
(1) sample preparation
Plain film or electronic probe sheet, without cover slip. The garnets analyzed on the SD070-1, SD074-2 and SD080-1 samples totaled more than 100 and were numerically numbered for each garnet to ensure comparative analysis at the same point. The garnet particle size, shape and color were counted during observation. Samples SD070-1, SD074-2 were taken from the middle section of the Chalk series, and sample SD080-1 was taken from the lower section of the Chalk series.
(2) Raman on-machine test analysis
The instrument model is as follows: horiba Jobin-Yvon Labram
And (3) testing conditions are as follows: resolution was 2 μm (x 100 objective), 400 μm pinhole, 100 μm slit, 1800 grating, exposure time 15s, cycle number 10, test time of about 180s per sample spot, test avoiding inclusion.
(3) Data processing
The garnet has six typical Raman peaks (FIG. 1), and the peaks 1# to 6# are respectively located at 210-245, 340-368, 369-380, 515-560, 800-870 and 870-920cm-1Each peak position changes accordingly due to the difference in molecular composition. Magnesium aluminum garnet (Mg)3Al2Si3O12) Has six Raman shifts of 211, 363, 377, 563, 868 and 926.2cm-1(ii) a Iron aluminum garnet (Fe)3Al2Si3O12) Are 216, 343, 371, 556, 863 and 915cm-1(ii) a Manganese aluminum garnet (Mn)3Al2Si3O12) Raman shifts of 221, 350, 373, 552, 850 and 907cm-1(ii) a Calcium aluminum garnet (Ca)3Al2Si3O12) Has six Raman shifts of 245.5, 367, 373.3, 547.4, 825 and 879.1cm-1(ii) a Calcium iron garnet (Andradite, Ca)3Fe2Si3O12) Raman shifts of 235.5, 351.6, 369.9, 515.7, 815.7 and 873.6cm-1(ii) a Calcium chromium garnet (Uvarovite, Ca)3Cr2Si3O12) Typical Raman shifts of 241.2, 368, 368, 526, 837.4 and 877.5cm-1. And (4) fitting the Raman peak position by NGSLabSpec software to obtain an accurate peak.
(4) Analysis of different garnet mol percents
The Method modifies and improves the program of the Miragem (Micro-Raman Garnets Evaluation Method), thereby realizing batch processing of data and technically completing the analysis of the mole percentage of garnet more quickly. Then, a modified miragel program is applied in Matlab software, and Raman typical peak position shift is input to obtain the mole percent content of garnet.
The calculation formula is as follows
W(i,k)＝∑W(i,j,k)X(j,k)
1＝Xa+Xb+Xc+Xd+Xe+Xf
W: a Raman wave number;
x: the proportion of the end-member components;
1-5 raman peaks;
j is a-f terminal member component;
k is the sample;
a-f magnesium aluminum garnet (Py), iron aluminum garnet (Al), manganese aluminum garnet (Sp), calcium aluminum garnet (Gr), calcium iron garnet (Ad) and calcium chromium garnet (Uv).
Sometimes peak 1# and peak 3# will be weaker, and if the peak is below the pre-trial threshold, i.e. there is no distinct peak, then to reduce the uncertainty, the garnet mole percentage can be determined from the other 4 strong accurate spectral peaks.
(5) Data interpretation
Triangular projection is carried out in Minpet software, and three end members represent garnet subtypes. Type division is carried out according to the original rock: type a garnets are mainly derived from high-grade gneiss phase-change sedimentary rock or perilla granite; type B garnet is derived from amphibole phase change sedimentary rock, and the source of the garnet is probably medium-acid magma only when the garnet is thrown into a Type Bi region; type C garnets are mainly derived from advanced metamorphic rocks, with Type Cii produced from ultrabasic rocks; type D garnets are generally derived from alternating metamorphic rocks such as skarn, very low metamorphic rocks or ultra high temperature metamorphic calcareous silicate gnetite.
Garnet composition changes in the ruby of the ruhsi basin suggest a shift in the source. The garnet source in the chalk brook basin showed that the dominating deposit in the rutil basin is the zone of sulcus mountains, and fluctuations in the basin source indicate that the rutil ridges may have experienced an increase in the late middle and late middle of the chalky.
(6) Electronic probe contrast analysis
Firstly, plating carbon on an electron probe, completing the analysis of the electron probe on a French CAMECA SXFiveFE high-resolution field emission electron probe, wherein the acceleration voltage range of the instrument is 5-30 kV, the spatial resolution can reach 6nm, and analyzing elements of Si, Ti, Al, Cr, Fe, Mn, Mg, Ca and Na.
Raman vs electron probe results show (fig. 2): the error range of the garnet quantitative analysis result obtained by the laser Raman technology is less than 8 percent. The consistency of the magnalium garnet (Py) is better, the iron aluminum garnet (Al) and the calcium aluminum garnet (Gr) are inferior, and when the content is low, the negative deviation tends to occur; manganese aluminite (Sp) exhibits a positive deviation; overall low calcerolithite (Ad) content values, weak positive deviations. The source of error may be systematic error, which can be eliminated or reduced by standard contrast measurements.
Through the embodiment, the garnet source analysis can be rapidly and accurately carried out by utilizing the confocal laser Raman spectroscopy, so that the sedimentology basis is provided for the understanding of the regional structure-ancient geographic evolution.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for garnet source tracing based on micro confocal laser Raman comprises the following steps:
step (1): preparing a sample, namely preparing garnet into a common thin sheet or an electronic probe sheet;
step (2): performing Raman test analysis on the common sheet; and (3) testing conditions are as follows: the resolution is 2 μm (x 100 objective), 400 μm pinhole, 100 μm slit, 1800 grating, exposure time is 15s, cycle number is 10, test time of each sample point is 180s, and inclusion needs to be avoided during test;
and (3): data processing, namely fitting the Raman peak position through NGSLABSpec software to obtain an accurate peak;
and (4): analyzing the mol percentage content of different garnets, applying a Miragem program in Matlab software, inputting Raman typical peak position displacement, and obtaining the mol percentage content of the garnets;
and (5): data interpretation, triangle projection was performed in the minimum software, with the three end members of the triangle projection representing the garnet subtype.
2. The method of claim 1, wherein the garnets in step (1) are greater than 100 in total and each garnet is numerically labeled to ensure a same point of comparative analysis.
3. The method of claim 2, wherein in step (3), if the individual spectral peaks are below a threshold, the garnet mole percentage is determined from the other spectral peaks.
4. The method as claimed in claim 2, wherein the molar percentage of garnet in the step (4) is calculated as follows:
W(i,k)＝∑W(i,j,k)X(j,k)
1＝Xa+Xb+Xc+Xd+Xe+Xf
w: a Raman wave number;
x: the proportion of the end-member components;
1-5 raman peaks;
j is a-f terminal member component;
k is the sample;
a-f magnesium aluminum garnet (Py), iron aluminum garnet (Al), manganese aluminum garnet (Sp), calcium aluminum garnet (Gr), calcium iron garnet (Ad) and calcium chromium garnet (Uv).
5. The method according to claim 1 or 4, wherein, in step (5), the garnet subtypes are classified according to the type of the proto-rocks: type a garnets are mainly derived from high-grade gneiss phase-change sedimentary rock or perilla granite; type B garnet is derived from amphibole phase change sedimentary rock, and the source of the garnet is probably medium-acid magma only when the garnet is thrown into a Type Bi region; type C garnets are mainly derived from advanced metamorphic rocks, with Type Cii produced from ultrabasic rocks; type D garnets are generally derived from alternating metamorphic rocks such as skarn, very low metamorphic rocks or ultra high temperature metamorphic calcareous silicate gnetite.
6. The method according to any of claims 1 to 5, wherein the electron probe analysis in step (6) is performed on a CAMECA SXFiveFE high resolution field emission electron probe, France, with an instrument acceleration voltage in the range of 5-30 kV and a spatial resolution of 6 nm.
7. The method of claim 1, wherein the method further comprises:
and (4) carrying out comparative analysis on the electronic probe, namely plating carbon on the electronic probe, analyzing the contents of Si, Ti, Al, Cr, Fe, Mn, Mg, Ca and Na elements in the electronic probe piece, and carrying out standard comparative measurement on the result of the electronic probe and the data interpretation in the step (5).
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| CN103698312A (en) * | 2013-12-31 | 2014-04-02 | 中国科学院地质与地球物理研究所 | Method for measuring order degree of dolomite based on laser Raman |
| CN104122244A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Application of Au-polyaniline nano-composite particle in surface enhanced Raman spectrum |
| CN109856106A (en) * | 2017-11-30 | 2019-06-07 | 核工业北京地质研究院 | A method of identification garnet kind |
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Patent Citations (4)
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| CN104122244A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Application of Au-polyaniline nano-composite particle in surface enhanced Raman spectrum |
| CN103698312A (en) * | 2013-12-31 | 2014-04-02 | 中国科学院地质与地球物理研究所 | Method for measuring order degree of dolomite based on laser Raman |
| CN109856106A (en) * | 2017-11-30 | 2019-06-07 | 核工业北京地质研究院 | A method of identification garnet kind |
| CN110223912A (en) * | 2019-06-20 | 2019-09-10 | 中国科学院上海微系统与信息技术研究所 | The preparation method of oxygen-containing monocrystal thin films |
Non-Patent Citations (3)
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| DANILO BERSANI ET AL.: "Micro-Raman spectroscopy as a routine tool for garnet analysis", 《SPECTROCHIMICA ACTA PART A》 * |
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