CN114705831B - Scheelite mineralogy prospecting method for accurately judging type and denudation depth of tungsten polymetallic ore bed - Google Patents
Scheelite mineralogy prospecting method for accurately judging type and denudation depth of tungsten polymetallic ore bed Download PDFInfo
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Abstract
The invention provides a scheelite mineralogy prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore bed, which comprises the following steps: collecting scheelite samples in different types of tungsten deposits, and separating scheelite single particles from the samples; embedding scheelite in epoxy resin, polishing, and shooting a cathode fluorescence image of the CL image; carrying out LA-ICP-MS (laser induced plasma-Mass Spectrometry) trace element analysis on different CL partitions, and carrying out solution method oxygen isotope analysis on the scheelite; the CL image and the trace element characteristics of the scheelite are compared with a database, information such as the type of an ore deposit, the denudation depth and the like is extracted to synthesize the geochemical characteristics of the scheelite, and a scheelite type-ore deposit type-denudation depth comprehensive prospecting model is established; the method has the advantages of directly acquiring mineralogy information and eliminating external interference and multi-solution of element analysis.
Description
Technical Field
The invention relates to the technical field of ore deposit prospecting exploration, in particular to a scheelite mineralogy prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore deposit.
Background
The prior prospecting method for mineral deposits firstly adopts a chemical exploration method, and is carried out by the methods of rock geochemical measurement, soil (rock debris, ditch system, water chemistry, deep penetration earth gas and the like) geochemical measurement and water system sediment measurement. The method determines the geochemical abnormal level and range through the analysis of the element content related to the ore formation and then carries out the verification of the drilling, but the method consumes a great deal of manpower and capital and cannot obtain direct ore deposit information, such as the type of the ore deposit, the burial depth and the like, in addition, the multi-resolution of the chemical exploration method and the interference of surface pollution are also existed, so that the effect of the chemical exploration method for finding the ore is reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a scheelite mineral prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore bed.
In order to achieve the above object, an embodiment of the present invention provides a scheelite mineralogy prospecting method for accurately distinguishing the type and the denudation depth of a tungsten polymetallic ore bed, which includes the following steps:
s1: collecting scheelite samples in different types of tungsten deposits, and sorting scheelite single particles;
s2: embedding the obtained scheelite single particles in epoxy resin, polishing, shooting a cathode fluorescence image of a CL image, and analyzing the CL image characteristics;
s3: performing LA-ICP-MS (laser induced plasma-Mass Spectrometry) trace element analysis on different CL partitions, analyzing the trace element characteristics of the scheelite, and extracting the environment and denudation depth information of scheelite crystal growth according to the trace element content change and the rare earth element distribution type;
s4: carrying out solution method oxygen isotope analysis on the scheelite to obtain the scheelite oxygen isotope content, comparing the scheelite oxygen isotope content with a database, and extracting information such as ore deposit cause types, denudation depths and the like;
s5: by researching the geochemical characteristics of the scheelite minerals, the physicochemical characteristics of the scheelite during crystallization are explored, the comprehensive information of the scheelite type, the deposit type and the denudation depth is obtained, and a deep comprehensive prospecting model is established.
Further, the step S2 specifically includes: the scheelite is embedded in epoxy resin, polished and then photographed by an electronic microscope to obtain a scheelite CL image, the scheelite CL image characteristics are observed, and the scheelite type is preliminarily judged according to the scheelite CL image annulus characteristics.
Further, the step S3 specifically includes: based on scheeliteCL image characteristic, using Geolaspro 193nm laser ablation system to measure the trace element content of different areas of scheelite particles for different CL areas (the Geolaspro laser ablation system is composed of COMPEXPro 102ArF 193nm excimer laser and MicroLas optical system, the model of ICP-MS is Agilent 7700 e), performing off-line processing on the analysis data, using helium as carrier gas and argon as compensation gas to adjust sensitivity in the laser ablation process, mixing the helium and argon before entering ICP through a T-shaped joint, configuring a signal smoothing device for the laser ablation system, wherein the laser beam spot and frequency are respectively 35 μm and 10Hz, using glass standard substances BHVO-2G, BCR-2G and BIR-1G to perform multi-external standard non-internal standard correction in the single mineral trace element content processing, each time resolution analysis data comprises blank signals of about 20-30s and 50s sample signals, and obtaining the content of various trace elements in different areas of scheelite; the trace elements include: 23 Na、 29 Si、 49 Ti、 57 Fe、 65 Cu、 66 Zn、 75 As、 85 Rb、 88 Sr、 89 Y、 91 Zr、 93 Nb、 98 Mo、 118 Sn、 137 Ba、 139 La、 140 Ce、 141 Pr、 143 Nd、 147 Sm、 153 Eu、 157 Gd、 159 Tb、 163 Dy、 165 Ho、 167 Er、 169 Tm、 171 Yb、 175 Lu、 178 Hf、 181 Ta、 182 W、 202 Hg、Pb、 232 Th、 238 and U is added. Off-line processing of the analytical data (including selection of sample and blank signals, instrument sensitivity drift correction, and elemental content calculation) was done using the software ICPMSDataCal.
Further, step S4 specifically includes: o isotope analysis of scheelite by solution method oxygen isotope analysis method 2 O and BrF 5 Reaction at a constant temperature of 300 ℃ for 20 minutes to produce O purified by freezing 2 (ii) a Reacting oxygen with graphite at 700 ℃ to generate CO under the condition of Pb catalyst 2 Analyzing the oxygen isotope composition by an MAT253 gas isotope mass spectrometer; measuringThe results are based on SMOW and are reported as delta 18 OV-SMOW, the analysis accuracy is better than +/-0.2 per mill, the oxygen isotope reference standard is GBW-04409 and GBW-04410 quartz standard, delta 18 OH 2 O values are respectively 11.11 +/-0.06 thousandths and-1.75 +/-0.08 thousandths; separation of pure O 2 And through O 2 Reacting with carbon rod to produce CO 2 Gas, to collected CO 2 The gas is subjected to mass spectrometry, and the accuracy of a single test is 0.05 per mill.
Further, the step S5 specifically includes: by researching the geochemical characteristics of the scheelite minerals, the physicochemical environmental information of the scheelite during crystallization is obtained according to the characteristics of cathodoluminescence, rare earth elements and oxygen isotopes, the comprehensive characteristics of the scheelite type, the deposit type and the denudation depth in the selected sample are ascertained, and a deep comprehensive prospecting model is established. The scheelite is a heavy mineral, is weather-resistant, can be widely developed in a tungsten deposit of a magma hydrothermal cause, can directly sort scheelite single particles from a sample, and has the following mineral geochemical characteristics that can better reflect the deposit characteristics: (1) The CL image of the scheelite can reflect the environmental characteristics of the scheelite during the growth and crystallization; (2) The trace element characteristics of the scheelite can better reflect the information of the environment, the distance from the rock mass and the like during the crystallization of the scheelite; (3) The O isotope characteristics of the scheelite can accurately invert the characteristics of the deposit type, the denudation depth when the scheelite is formed and the like.
The scheme of the invention has the following beneficial effects:
1) The method of the scheme of the invention can directly obtain mineralogy information, and eliminates external interference and multiresolution of elemental analysis;
2) The invention adopts the chemical element characteristic pair (Y/Ho ratio, eu characteristic) and rare earth distribution type, delta 18 The O value can quantitatively reflect the information such as the crystallization environment, the depth and the like of the scheelite;
3) The information of the type, the denudation depth and the like of the deposit is directly inverted through the geochemical characteristics of the minerals of the scheelite, and the interference of other factors is eliminated.
Drawings
FIG. 1 is a CL image of different types of scheelite in an embodiment of the invention;
FIG. 2 is a rare earth distribution pattern diagram of scheelite at different distances from the rock mass in the embodiment of the invention;
FIG. 3 is a graph showing the difference in the rare earth element content between scheelite of different denudation depths according to the example of the present invention;
FIG. 4 is a graph of O isotope characteristics for different types of scheelite in accordance with an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention; unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The invention provides a scheelite mineralogy prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore bed, aiming at the existing problems.
The samples collected in the embodiment of the invention are mainly from tungsten polymetallic ore beds of different types and causes in south ridge areas, and mainly from tungsten polymetallic ore beds in persimmon bamboo gardens, yao gang Xian, weijia, xiangxi and the like.
Example 1
S2: the scheelite is embedded in epoxy resin, polished, and then photographed by using a Tescan MIRA 3 field emission Scanning Electron Microscope (SEM) (equipped with a Delmic Sparc cathode fluorescent probe, with a working voltage of 0.5-30kV, a filament emission current of 72 muA. Under energy spectrum analysis test conditions, an acceleration voltage of 20-30kV and a working distance of 9.5-10.5 mm), to obtain a CL image of the scheelite (as shown in FIG. 1). The trace element content in different regions of the same particle leads to significant differences in its cathodoluminescence characteristics, revealing that the microstructure by Cathodoluminescence (CL) can reveal the growth history of the minerals and reflect the crystallization environment (fig. 1). Summarizing the previous study, scheelite CL images in different types of tungsten deposits showed different characteristics: the CL image of scheelite in skarn type deposit generally shows a sector zone with obvious development (as shown in fig. 1 a), the CL image of scheelite in porphyry type deposit usually shows a concussion zone (as shown in fig. 1 b), the quartz vein type scheelite related to magma hydrothermal solution usually shows a changed CL luminescence reaction but has no obvious regular characteristic, and usually shows a relatively uniform CL image characteristic (as shown in fig. 1 c), the CL image of the dolomite type scheelite can show an obvious zone and zone characteristic (as shown in fig. 1 d), the CL image of the breccite type scheelite can show an obvious zone characteristic (as shown in fig. 1 e), and the type of the deposit corresponding to the scheelite can be clearly judged through the CL image characteristic of the scheelite.
Example 2
S2 is the same as in example 2, and S3 is specifically described here: according to the CL image characteristics of the scheelite, the content of trace elements (the laser beam spot and the frequency are respectively 35 mu m and 10 Hz) in different sections of the scheelite particles is determined by using a Geolaspro 193nm laser ablation system for different CL sections, and the content of various trace elements in different areas of the scheelite is obtained by adopting software ICPMSDataCal software to perform off-line processing on analysis data (including selection of sample and blank signals, instrument sensitivity drift correction and element content calculation). The rare earth partition type of the scheelite has important reference significance for judging the type and the characteristics of the scheelite, the rare earth partition type of the scheelite has obvious difference from different distances of a rock body (as shown in figure 2), the distance from the scheelite to the rock body during crystallization can be better judged through the difference of the rare earth partition type, and the scheelite has important reference value for indicating the position and the depth of an ore deposit; meanwhile, the distance between the scheelite and the rock mass can be well indicated by the content of the rare earth element of the scheelite, the farther the scheelite is from the rock mass in the same deposit, the obvious reduction of the content of the rare earth element of the scheelite can be seen (as shown in fig. 3), and the scheelite and the rock mass can meet the obvious linear relationship, wherein the linear relationship is Y = -4.9598x +1777.5 (R = -4.9598x +) 2 = 0.7548), according to the linear relation, the distance between the scheelite particles and the rock mass can be inverted through the measured content of the scheelite rare earth element, the content of the scheelite rare earth element and the rare earth distribution type are synthesized,the method has important indicating significance for judging the type of the scheelite, the type of the deposit and the denudation depth of the deposit.
Example 3
S2-S3 are the same as in example 2, and S4 is specifically described here:
s4: O-Isotope analysis of scheelite was performed using solution-method oxygen-Isotope analysis on a Thermo-Finnigan Delta plus XP Isotope-Ratio Mass Spectrometer (IRMS) instrument, enclosing H in a volume 2 O and BrF 5 Reaction at a constant temperature of 300 ℃ for 20 minutes to produce O purified by freezing 2 . Reacting oxygen with graphite at 700 ℃ under the condition of a Pb catalyst to generate CO 2 And the oxygen isotope composition was analyzed by a MAT253 gas isotope mass spectrometer. The measurement results are based on SMOW and recorded as delta 18OV-SMOW, and the analysis accuracy is better than +/-0.2 per thousand. Oxygen isotope reference standards are GBW-04409 and GBW-04410 quartz standard, delta 18OH 2 The O values are respectively 11.11 +/-0.06 thousandths and-1.75 +/-0.08 thousandths. Separation of pure O 2 And through O 2 Reacting with carbon rod to produce CO 2 A gas. For collected CO 2 The gas was subjected to mass spectrometry. The accuracy of a single test is 0.05 per mill. Obvious differences of O isotopes of different types of scheelite can be seen (figure 4), the O isotope value and the temperature of the porphyry scheelite have no obvious change and are concentrated in metamorphic rock areas; the O isotope value of the skarn type scheelite has no obvious change, the temperature can obviously change, and the O isotope value can be seen in magma rocks, metamorphic rocks and atmospheric water areas; the O isotope value of the quartzite scheelite can be obviously different and is mainly positioned in metamorphic rock and atmospheric water areas, the temperature value has no obvious change, and the O isotope value and the temperature of the quartz vein scheelite related to hydrothermal solution can be obviously changed but are concentrated in a smaller range and are mainly positioned in magma and atmospheric water areas; the oxygen isotope value and the temperature of the hillmaking breccia type scheelite can be obviously changed and are relatively continuous, the change is mainly concentrated in metamorphic rock and atmospheric water areas, the positive correlation relationship (shown as figure 4) is displayed between the O isotope value and the temperature on the whole, the information such as the type of the scheelite can be better obtained through a relation diagram of the O isotope content and the temperature of the scheelite, and meanwhile, the scheeliteThe O isotope has important significance for judging the source of the fluid for forming the scheelite, and according to the characteristics of the source of the fluid, the type and the environmental characteristics of the scheelite can be better judged, and the denudation depth of an ore deposit can be well indicated.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A scheelite mineralogy prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore bed is characterized by comprising the following steps:
s1: collecting scheelite samples in different types of tungsten deposits, and sorting scheelite single particles;
s2: embedding scheelite in epoxy resin, polishing, shooting a cathode fluorescence image of a CL image, and analyzing the CL image characteristics;
s3: performing LA-ICP-MS (laser induced plasma ionization-mass spectrometry) trace element analysis on different CL partitions, analyzing the trace element characteristics of the scheelite, and extracting the environment and denudation depth information of the scheelite crystal growth according to the trace element content change and the rare earth element distribution type;
s4: carrying out solution method oxygen isotope analysis on the scheelite to obtain the scheelite oxygen isotope content, comparing the scheelite oxygen isotope content with a database, and extracting the deposit cause type and denudation depth information;
s5: researching the geochemical characteristics of the scheelite minerals, exploring the physicochemical characteristics of the scheelite when in crystallization, acquiring the comprehensive information of scheelite type-deposit type-denudation depth, and establishing a deep comprehensive prospecting model;
the step S4 specifically comprises the following steps: o isotope analysis of scheelite by solution method oxygen isotope analysis method 2 O and BrF 5 Reaction at a constant temperature of 300 ℃ for 20 minutes to produce O purified by freezing 2 (ii) a Reacting oxygen with graphite at 700 ℃ under the condition of a Pb catalyst to generate CO 2 And is combined withAnalyzing oxygen isotope composition by an MAT253 gas isotope mass spectrometer; the measurement results are based on SMOW and are recorded as delta 18 OV-SMOW with analysis accuracy better than +/-0.2 ‰, oxygen isotope reference standard of GBW-04409 and GBW-04410 quartz standard, delta 18 OH 2 O values are respectively 11.11 +/-0.06 thousandths and-1.75 +/-0.08 thousandths; separation of pure O 2 And through O 2 Reacting with carbon rod to produce CO 2 Gas to collected CO 2 The gas is subjected to mass spectrometry, and the accuracy of a single test is 0.05 per mill.
2. The scheelite mineralogy prospecting method for accurately distinguishing the type and the denudation depth of a tungsten polymetallic ore bed according to claim 1, wherein the step S2 specifically comprises the following steps: the scheelite is embedded in epoxy resin, polished and then shot by an electronic microscope to obtain a scheelite CL image, and the scheelite CL image zone characteristics are analyzed through the scheelite CL image characteristics to preliminarily judge the type of the scheelite.
3. The scheelite mineralogy prospecting method for accurately judging the type and the denudation depth of a tungsten polymetallic ore bed according to claim 1, wherein the step S3 specifically comprises the following steps: according to the CL image characteristics of scheelite, the content of trace elements in different areas of scheelite particles is measured by a Geolaspro 193nm laser ablation system for different CL areas, analysis data is processed in an off-line mode, helium is used as carrier gas and argon is used as compensation gas in the laser ablation process to adjust the sensitivity, the helium and the argon are mixed through a T-shaped connector before entering ICP, the laser ablation system is provided with a signal smoothing device, the laser beam spot frequency is 35 mu m and 10Hz respectively, glass standard substances BHVO-2G, BCR-2G and BIR-1G are used for multi-external-standard internal standard-free correction in single-mineral trace element content processing, each time-resolved analysis data comprises about 20-30s signals and 50s sample blank signals, the content of various trace elements in different areas of the scheelite is obtained, and the trace elements comprise: 23 Na、 29 Si、 49 Ti、 57 Fe、 65 Cu、 66 Zn、 75 As、 85 Rb、 88 Sr、 89 Y、 91 Zr、 93 Nb、 98 Mo、 118 Sn、 137 Ba、 139 La、 140 Ce、 141 Pr、 143 Nd、 147 Sm、 153 Eu、 157 Gd、 159 Tb、 163 Dy、 165 Ho、 167 Er、 169 Tm、 171 Yb、 175 Lu、 178 Hf、 181 Ta、 182 W、 202 Hg、Pb、 232 Th、 238 U。
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