CN112924485B - Method for measuring spinel Fe by electronic probe secondary standard sample correction method3+Method for producing Fe/∑ Fe - Google Patents
Method for measuring spinel Fe by electronic probe secondary standard sample correction method3+Method for producing Fe/∑ Fe Download PDFInfo
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Abstract
The invention provides a method for measuring Fe by using an electronic probe secondary standard sample correction method3+A method of/∑ Fe comprising the steps of: (1) selecting and preparing a standard sample; (2) carrying out electronic probe analysis on a single mineral target sample to calibrate a main quantity element; (3) establishing a spinel electronic probe test condition; (4) testing the main quantity elements of the spinel standard sample, and adjusting the internal standard of the instrument; (5) using spinel standard sample as secondary standard sample, and calculating Fe by using electrovalence balance method3+The ratio of v Fe; (6) fe obtained by calculation in a standard sample3+Fe ratio/mu S Fe and Mossbauer spectra Fe3+Comparing the ratio of the V-Fe and the S-Fe, and establishing a calibration curve; (7) testing the main quantity elements of the spinel sample to be tested, and correcting the Fe of the unknown sample by using the calibration curve in the step (6)3+The ratio of/∑ Fe. The method has the advantages of in-situ performance, high resolution, high efficiency, accuracy and the like, and has very important geological significance and actual demands for ore exploration.
Description
Technical Field
The invention relates to the field of geological sample detection, in particular to a method for determining Fe by using an electronic probe secondary standard sample correction method3+Method of v. Fe.
Background
Oxygen fugacity is an important parameter for controlling the interaction of the earth's various layers (soft-flow, rocky, water and atmospheric) and plays an important role in many geological processes (McCammon, 2005). Valence-changing elements Fe, e.g. ferrous iron (Fe)2+) And ferric iron (Fe)3+) Usually indicated for oxidation state, differences in their geochemical behavior and Fe2+/Fe3+The ratio is the optimum parameter for defining the oxygen fugacity. The oxidation state of iron in minerals is generally expressed as Fe3+Fe, has important indication significance for characterizing the oxidation-reduction condition of a magma source region and the physicochemical process of magma evolution (
and Brey, 2007). All in oneIn time, iron is the transition element with the highest earth content and is mainly present in the mantle, which provides favorable conditions for the research of the oxygen fugacity of the mantle.
The mantle is a critical area for solid geoscience research, and the mantle oxygen fugacity (fO)2) Similar to the temperature and pressure of the mantle, it is an important parameter (Frost and McCammon,2008) that restricts the physical-chemical reaction mode between the mantle source area and the earth's surface and controls the evolution process of the mantle. For example, oxygen fugacity constrains the state of the C-O-H flow/melt composition (Ballhous and Frost, 1994; Holloway, 1998; Kadik, 1997; Taylor and Green,1998), and further affects the mantle solidus and its resulting composition. The oxygen fugacity value of the mantle of the rock ring has a wide variation range, and the temporal and spatial distribution has strong heterogeneity. Inhomogeneity in canopy oxygen fugacity may be associated with factors such as cross-substitution modification, partial melting, and the environment of the earth formation (Wood et al, 1990; Wood and Koch, 2003; Ballhaus, 1993; Parkinson and arcuus, 1999; Frost and McCammon, 2008; Goncharov et al, 2012). In addition, oxygen fugacity is closely related to deposit formation. For example, diamond formation occurs in the mantle of the rocky ring in extremely reducing conditions (Creighton et al, 2010), while large porphyry bronze deposits are formed in oxidizing conditions (Hattori and Keith, 2001; Mungall, 2002). Therefore, accurate acquisition of the oxygen tolerance value of the mantle of the rock ring can greatly promote the deep research on the scientific problems of mantle evolution, material circulation in the deep part of the earth, large-scale metal mineralization and the like.
The current calculation methods of oxygen tolerance value mainly include two types: (1) the oxygen fugacity of the source region is calculated by researching the composition of the mantle source fluid inclusion and the state equation of the fluid system, and the oxygen fugacity is calculated based on the principle that the temperature and the pressure of the fluid inclusion are necessarily fixed in a closed system, which is mainly represented by the point of Taylor (1990). However, the method has the disadvantages that the fluid inclusion is from a source region or a non-source region and is difficult to define, and secondly, the state equation of the complex fluid system at the ultrahigh temperature and the ultrahigh pressure is often subjected to large errors after calculation, so that the accuracy of the calculation result of the oxygen fugacity is necessarily influenced. (2) By the mineral composition of the mantleTo calculate the temperature and pressure conditions and combine the characteristics of the valence-variable elements of the minerals (such as accurate Fe)3+V. Fe value) and an oxygen slip meter to estimate the oxygen slip value for the mantle rock. Spinel is the most common metal oxide in the mantle, has been recognized as a mantle formation cause indicator and is also a key mineral that defines the oxygen fugacity of the mantle of the rocky ring. In addition, the spinel is also the main carrier mineral of the scarce mineral chromite in China, and the spinel is Fe3+The composition of the Fe/Sigma alloy has great guiding significance for judging the chromite formation environment and tracing and searching the ore. Therefore, how to efficiently and accurately determine spinel Fe in situ3+The/∑ Fe has been a technological hotspot and difficulty of great concern in the field of in situ microbeam analysis.
At present, Fe is measured3+The technical method of the/Fe is mainly as follows:
(1) energy-loss spectroscopy (EELS) has the advantage of having the best resolution (Garvie and Craven, 1994; Golla and Putnis, 2001; van Aken and Liebscher, 2002; van Aken et al, 1998, 1999). Energy loss spectroscopy creates the possibility of qualitative analysis of element valence states at nanoscale resolution (Golla and Putnis, 2001). In TEM quantification, a 1 μm beam spot was used to avoid electron beam effect-induced oxidation states (van Aken and Liebscher, 2002). Fe determination by EELS method3+The absolute error of the ratio of Fe/l is within the range of 0.02 to 0.04. However, the method has high sample preparation requirements, so that the application of the method is limited to a certain extent.
(2) X-ray near edge structure spectroscopy (XANES), which is at a moderate level in two-dimensional spatial resolution (Bajt et al, 1994; Berry et al, 2003; Cressey et al, 1993; Delaney et al, 1998; Dyar et al, 2002; O' Neill et al, 2006; Schmid et al, 2003; Wilke et al, 2001). The X-ray beam spot size for X-ray near-edge structural spectroscopy is 10X 15 μm, the spectrum acquisition time is 20-30 minutes, and the error range is + -0.03 to + -0.10 (Dyar et al, 2002).
(3) Mossbauer spectrum (
specroscopy) for estimating Fe of spinel in geoscience3+The most common method for the ratio of v Fe, although this method is highly accurate (<5 percent of spinel monominerals need to be selected to be prepared into samples for spectral line analysis, the process flow is complex, and the resolution is high>50 μm), above all, this method can only test powdery samples and cannot determine the Fe of spinel in situ3+The Fe/l value (McCammon et al, 1991,2001), and therefore the process has been greatly limited in its application to development.
(4) Raman spectroscopy (micro-Raman spectroscopy), which has high requirements on the properties of the measured sample and is not conducive to the development of general research and development applications (Di Muro et al, 2009).
(5) Electron-microprobe techniques (EPMA), the principle of the test is based on Fe2+And Fe3+L alpha and L beta peak shift phenomena of different energies, i.e. from Fe2+To Fe3+The energy of Fe L α and Fe L β will increase, and the intensity of Fe L β will decay preferentially: (
et al.,1994)。
The electronic probe has the advantages of in-situ, high resolution, high efficiency, accuracy and the like by combining the advantages and the disadvantages of the test method, but the electronic probe is selected to test the spinel Fe3+The problem that needs to be solved for the/Fe ratio is the development of a series of standards and the establishment of a calibration curve. Based on the method, an electronic probe-based test spinel Fe is developed3+The/∑ Fe has very important geological significance and realistic demands for prospecting.
Disclosure of Invention
The invention innovatively provides a secondary standard sample hair test spinel Fe based on an electronic probe3+Method of v. Fe.
Current electronic probe testing of mineral Fe3+The peak-shift method and the peak-shoulder method are mainly used. The peak shift method adopts the peak position of Fe L alpha and Fe3+The calibration of the Fe/V ratio (Fialin et al, 2004), requires confirmation during the testThe exact Fe L α peak position was determined for each sample. The experimental process is complicated, the testing uncertainty is large when the FeO content is lower than 5wt%, and in addition, the method ignores the change of the strength of Fe L alpha and Fe L beta, so the practical application of the peak shift method is not wide. The peak-shoulder method not only fully considers the peak position drift phenomena of Fe L alpha and Fe L beta, but also considers the intensity change between the two. Ratio of Fe L alpha and Fe L beta flank peak intensity to Fe2+The contents are in functional relationship. However, the method has high requirements on instruments and low testing efficiency, and a spinel method is not established at present. The method adopts a secondary standard sample correction method to measure the spinel Fe3+Fe/sigma, different Fe is required3+Chromium spinel of the value of/. SIGMA Fe, according to Mossbauer spectra (
specra) method of Fe3+Value of v sigma Fe
Substantially representing the true value [ (Fe)3+/∑Fe)True]The ratio of the total mass of the particles to the mass of particles analyzed by a conventional electron probe [ (Fe)3+/∑Fe)Probe]The difference and the spinel Al/(Al + Cr) have a certain linear relation, and the (Fe) of the spinel to be measured can be obtained by measuring a series of standard samples3+/∑Fe)True. The method not only avoids the basal effect, but also can determine the spinel Fe more efficiently3+Value of v Fe, Fe3+The error of the/Sigma Fe test is +/-0.02 (1 sigma), and is not lower than the test precision of the peak-shoulder method.
The key of the test by adopting the electronic probe method is the selection of the standard sample, the spinel standard sample utilized by the predecessor is provided abroad, and the electronic probe laboratory in China needs to borrow temporarily, so that the test is extremely inconvenient. Moreover, the series of standards is exhausted, and the calibration of the spinel iron valence state can not be continuously supported. New spinel standards are in need of development. Through homogeneity test, selecting the spinel in the Chinese Apocynum chromite and the American Stillwater serpentine greenstone, analyzing the components by adopting an electronic probe, and determining the Fe by utilizing the Mossbauer spectrum3+The ratio of/∑ Fe.
The purpose of the invention is realized by the following technical scheme:
method for measuring Fe by electronic probe secondary standard sample correction method3+A method of/∑ Fe comprising the steps of:
(1) selecting and preparing a standard sample: selecting spinel standard samples meeting the uniformity, and preparing each standard sample into powder and single mineral targets;
(2) carrying out electronic probe analysis on a single mineral target sample to calibrate a main quantity element; solution method for Fe of powder sample3+Determination of the Fe/V ratio, and simultaneously Fe was measured by Mossbauer Spectroscopy3+The ratio of v Fe;
(3) establishing spinel electronic probe test conditions, and testing all standard samples and corresponding elements within an error range;
(4) testing main quantity elements of the spinel standard sample, and adjusting an instrument internal standard according to the standard component content;
(5) using spinel standard sample as secondary standard sample, and calculating Fe by using electrovalence balance method3+The ratio of v Fe;
(6) fe obtained by calculation in a standard sample3+Fe ratio/mu S Fe and Mossbauer spectra Fe3+Comparing the ratio of the V-Fe and the S-Fe, and establishing a calibration curve;
(7) testing the main quantity elements of the spinel sample to be tested, and correcting the Fe of the unknown sample by using the calibration curve in the step (6)3+The ratio of/∑ Fe.
Preferably, the spinel sample of step (1) is selected from spinel-developed pyrochlore or chromite which provides homogeneity within 5%, preferably within 4%, more preferably within 3%, most preferably within 2% of the variation of each element.
Preferably, the spinel standard Cr/Cr + Al ratio of the step (1) is 4.2-71.6, Fe3+The ratio of Fe/S is between 0.08 and 0.26.
Preferably, the major constituent element in step (2) includes at least one of Mg, Ca, Si, Na, K, Al, Ti, Mn, Ni, V and Cr.
Preferably, in step (3), the error range is not more than 1.5wt% different from the recommended value of the standard sample.
Preferably, in the step (5), the electrolytic equilibrium method is according to the following calculation formula:
Fe3+/∑Fe＝(2-ECr*3-EAl*3)/E∑Fe
wherein E represents the number of elemental cation electrons, ECr＝(Cr2O3/75.996)/∑mol，EAl＝(Al2O3/50.982)/∑mol， E∑Fe＝(FeO/71.845)/∑mol，∑mol＝MgO/40.305+FeO/71.845+NiO/74.693+ZnO/81.39+
Al2O3/50.982+Cr2O3/75.996+SiO2/60.086+TiO2/79.867
Preferably, after the correction, the linear relation of the standard curve in the step (6) is as follows:
representing Mossbauer spectra Fe3+The value of v-Fe can be considered to represent the true valueEPMARepresents Fe calculated by the electrovalence equilibrium method3+The ratio of/∑ Fe.
Drawings
FIG. 1 is a standard curve of a secondary standard sample of the present invention before and after calibration.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test of the invention adopts a JEOL JXA-8100 electronic probe instrument. The test conditions were: voltage: 15kV, beam current: 20nA, beam spot: 1 μm. The test elements are MgO and SiO2,TiO2,Al2O3,Cr2O3,V2O3,FeO,MnO,CaO,NiO, Na2O, and K2And O. Internal standards for each element utilize natural minerals or synthetic metals as follows: diopside (Ca, Si, and Mg), albite (Na and Al), rutile (Ti), spodumene (Mn), potash feldspar (K), NiO (Ni), Fe2O3(Fe),Cr2O3(Cr) and V2O5(V) absorption spectra of the respective elements are as follows: na (129.503), Mn (146.445), K (120.157), Mg (107.451), Si (77.329), Fe (134.921), Al (90.517), Ca (108.315), Ti (89.115), Cr (159.574), V (81.426) Ni (115.453). The data result adopts ZAF correction, wherein Z represents the comprehensive atomic number correction coefficient of each element in the sample, A represents the comprehensive absorption correction coefficient of each element, F represents the correction coefficient of fluorescence effect of mutual excitation of characteristic X-rays among each element, and Z, A, F washing is related to the content, atomic number, acceleration voltage and X-ray detection angle of each element in the sample matrix.
Example 1
1) Selection and composition calibration of spinel standards
1.1 homogeneity test
Selecting nearly three hundred spinel samples from a plurality of serpentine green rocks or chromite in spinel development, grinding probe sheets, carrying out uniformity test on main elements one by one, and selecting samples with each element variation range within 2%;
1.2 selection and preparation of standards
The spinel Cr # value (Cr/(Cr + Al)) can reflect the state of the mantle when the mineral is crystallized, such as the material composition, the physical and chemical properties, the melting degree of the mantle and the like, and the information has important significance for discussing the cause and the construction environment of the rock. And Fe3+The value of the/Fe ratio has important indication significance for characterizing the oxidation-reduction condition of a magma source region and the physicochemical process of magma evolution. Therefore, different Cr # values and Fe were selected3+/∑FThe e-ratio standard provides comprehensive monitoring and more accurate determination of spinel of various compositions. In spinel samples with uniform components, the Cr # value of the standard sample selected by the method is 4.2-71.6, and Fe3+The ratio of Fe/S is between 0.08 and 0.26, and basically covers geological samples with various complex components. Selecting spinel monominerals from rocks, and respectively making 200-mesh powder and monominerals as targets;
1.3 calibration of Standard Components
Electron probe analysis on a single mineral target for the major element (Al)2O3,Cr2O3FeO, MgO) for calibration; the powder was subjected to Fe using a solution method (plasma Mass Spectrometry PE300D)3+Determination of the Fe/S ratio and also Mossbauer Spectroscopy measurements, the Fe determined3+Comparing the Fe/Sigma ratio with a solution method, and determining the final main component and Fe of each standard sample3+The ratio of/∑ Fe.
2) Establishment of spinel test conditions
2.1 adopting a JEOL JXA-8100 electronic probe instrument, setting the test condition to be 15kV, 20nA and 1 μm;
2.2 selection of test Element SiO under Element Condition2,TiO2,Al2O3,Cr2O3,V2O3,FeO,MnO,CaO, NiO,Na2O, and K2O；
2.3 internal standards of each element are selected in turn under the Standard Condition, which is as follows: diopside (Ca, Si, and Mg), albite (Na and Al), rutile (Ti), spodumene (Mn), potash feldspar (K), NiO (Ni), Fe2O3(Fe),Cr2O3(Cr) and V2O5(V)；
2.4 before starting the test, searching peaks for corresponding elements under each internal standard mineral, and determining and storing peak positions;
2.5 in Stage condition, sequentially selecting a standard sample containing a target element, focusing, selecting points, and then sequentially testing;
2.6 after the test is finished, the data is checked in Summary, and if the test result is consistent with the recommended value of the standard sample within the error range (<1.5 wt.%), the next step is carried out. If the error is too large, the error of which element exists is found out, in the Standard Analysis, the counting of the element is re-determined, and then the external Standard test Analysis is carried out until all the Standard samples and the corresponding element tests are consistent within the error range.
3. Test of spinel standard sample and establishment of correction curve
3.1 under the test condition, testing the main quantity elements of the spinel standard sample, and adjusting the internal standard of the instrument according to the standard component content;
3.2 taking the spinel standard sample as a secondary standard sample, sequentially testing eight spinel standard samples, testing 20 points for each sample, and calculating Fe by using electrovalence balance3+The ratio of Fe/S, then taking the average value;
Fe3+/∑Fe＝(2-ECr*3-EAl*3)/E∑Fe
wherein E represents the number of elemental cation electrons
ECr＝(Cr2O3/75.996)/∑mol
EAl＝(Al2O3/50.982)/∑mol
E∑Fe＝(FeO/71.845)/∑mol
∑mol＝MgO/40.305+FeO/71.845+NiO/74.693+ZnO/81.39+Al2O3/50.982+
Cr2O3/75.996+SiO2/60.086+TiO2/79.867
3.3 calculating the Fe from the standards3+Mean value of the/∑ Fe ratio and Mossbauer spectrum Fe3+V. Fe ratio (room temperature transmission)57Fe、119Sn mossbauer spectra test) were compared one by one to establish a suitable calibration curve (as shown in fig. 1) as a calibration curve to calibrate Fe for unknown spinel samples3+The ratio of/∑ Fe. Through calculation verification, the secondary standard sample correction method is adopted to test the Fe of the spinel3+The ratio of v-Fe not only has a high accuracy (σ ═ 0.02), but also has a high degree of accuracyThe effect and the characteristic can be more widely used for spinel Fe in magma rocks and metamorphic rocks3+And (6) measuring the ratio of the Fe/Sigma.
4. Determination of unknown samples
Testing unknown spinel samples under identical conditions for Fe3+The ratio of the v-Fe is corrected by the calibration curve, and the final accurate Fe is obtained3+The ratio of/∑ Fe. The method comprises the following specific steps:
firstly testing spinel standard samples, selecting proper internal standard for counting according to standard sample components, and calculating theoretical Fe of each standard sample by using an electricity price balance method3+the/Fe ratio, data is shown in Table 1 below:
TABLE 1
Calculating theoretical Fe according to the average value of each spinel standard sample component3+The ratio of v sigma Fe to the Mossbauer spectrum Fe3+And (4) comparing the values of the V and the E to establish the optimal linear relation, wherein the left graph of the figure 1 is a standard curve before correction, and the right graph is a standard curve after correction. Obtaining a corrected linear relationship:
the variance of the correction relationship was 0.9789, indicating that the method of the present invention has a high degree of accuracy.
Representing Mossbauer spectra Fe3+The value of v-Fe can be considered to represent the true valueEPMAIndicating passing through the electricity priceFe calculated by the balance method3+The ratio of/∑ Fe.
Then, the components of the spinel sample are tested under the condition, and theoretical Fe is calculated by using the electrovalence balance3+After the Fe ratio is divided by the sum of the equation, correcting according to the correction formula to obtain Fe after correction3+The ratio of v Fe is the true value, and part of the data is shown in the following table 2:
TABLE 2
Fe is measured by the electron probe secondary standard sample calibration method provided by the invention3+The method of the Fe/∑ can test the ore sample without the ability of the Mussbauer spectrum in situ and simply and quickly obtain the Fe of the spinel sample3+The ratio of/∑ Fe.
Claims (3)
1. Method for measuring Fe by electronic probe secondary standard sample correction method3+A method of/∑ Fe comprising the steps of:
(1) selecting and preparing a standard sample: selecting spinel standard samples meeting the uniformity, and preparing each standard sample into powder and a single mineral target sample; the spinel standard sample is spinel in Chinese Apocynum chromite and American Stillwater snake greenstone, the Cr/Cr + Al ratio of the spinel standard sample is 4.2-71.6, and Fe3+The ratio of Fe/S is between 0.08 and 0.26, and the variation range of each element is within 2 percent;
(2) carrying out electronic probe analysis on a single mineral target sample, and calibrating a main quantity element; solution method for Fe of powder sample3+Determination of the Fe/V ratio while obtaining Fe by means of Mossbauer Spectroscopy3+The ratio of v Fe;
(3) establishing spinel electronic probe test conditions, and testing all standard samples and corresponding elements within an error range;
(4) testing main quantity elements of the spinel standard sample, and adjusting an instrument internal standard according to the standard component content;
(5) using spinel standard sample as secondary standard sample, and calculating Fe by using electrovalence balance method3+The ratio of v Fe; the electricity price balance method is according to the following calculation formula:
Fe3+/∑Fe =(2 - ECr *3- EAl*3)/ E∑Fe
wherein E represents the number of elemental cation electrons, ECr = (Cr2O3/75.996)/ ∑mol，EAl = (Al2O3/50.982)/ ∑mol，E∑Fe = (FeO/71.845)/ ∑mol，∑mol = MgO/40.305 + FeO/71.845 + NiO/74.693 + ZnO/81.39 + Al2O3/50.982 + Cr2O3/75.996 + SiO2/60.086 + TiO2/79.867；
(6) Fe obtained by calculation in the secondary standard sample3+Fe/sigma Fe ratio and Fe obtained from Mossbauer Spectroscopy test3+Comparing the Fe ratio and establishing a calibration curve; the linear relation of the calibration curve is as follows: fe3+/∑FeEPMA = 1.0455Fe3+/∑FeMöss -0.0687，Fe3+/∑FeMössRepresents Fe obtained by Mossbauer Spectroscopy test3+V. Fe ratio, Fe3+/∑FeEPMARepresents Fe calculated by the electrovalence equilibrium method3+The ratio of v Fe;
(7) testing the main quantity elements of the spinel sample to be tested, and correcting the Fe of the unknown sample by using the calibration curve in the step (6)3+The ratio of/∑ Fe.
2. The method of claim 1, wherein the majority element in step (2) comprises at least one of Mg, Ca, Si, Na, K, Al, Ti, Mn, Ni, V, and Cr.
3. The method of claim 1, wherein the error range is no more than 1.5wt% difference between the test result and the recommended value for the standard.
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| Revisiting the electron microprobe method of spinel-olivine-orthopyroxene oxybarometry applied to spinel peridotites;Fred A. Davis et al.;《American Mineralogist》;20171231;第102卷;第421-428页，图1-5，表1-4 * |
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