CN106855516B - Microscopic quantitative characterization method of organic texture layer - Google Patents
Microscopic quantitative characterization method of organic texture layer Download PDFInfo
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- 238000012512 characterization method Methods 0.000 title claims abstract 6
- 239000005416 organic matter Substances 0.000 claims abstract description 81
- 238000000608 laser ablation Methods 0.000 claims abstract description 36
- 239000011435 rock Substances 0.000 claims abstract description 17
- 238000002474 experimental method Methods 0.000 claims abstract description 7
- 239000013049 sediment Substances 0.000 claims abstract description 7
- 239000011573 trace mineral Substances 0.000 claims abstract description 4
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 230000035945 sensitivity Effects 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052785 arsenic Inorganic materials 0.000 claims description 11
- 229910052770 Uranium Inorganic materials 0.000 claims description 8
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 4
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 238000000918 plasma mass spectrometry Methods 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 238000005422 blasting Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GFRMDONOCHESDE-UHFFFAOYSA-N [Th].[U] Chemical compound [Th].[U] GFRMDONOCHESDE-UHFFFAOYSA-N 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
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- 235000016709 nutrition Nutrition 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000000095 laser ablation inductively coupled plasma mass spectrometry Methods 0.000 abstract 1
- 238000005498 polishing Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 238000004445 quantitative analysis Methods 0.000 description 7
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- 230000007246 mechanism Effects 0.000 description 4
- 241000761557 Lamina Species 0.000 description 3
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- 239000011785 micronutrient Substances 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 238000010219 correlation analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000012615 high-resolution technique Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/68—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using high frequency electric fields
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Abstract
The invention provides a microscopic quantitative characterization method of an organic texture layer. The microscopic quantitative characterization method comprises the following steps: cutting the sediment into samples with regular shapes, and selecting a section with obvious organic texture layer characteristics for polishing treatment to obtain laser ablation target samples; setting proper spot size, scanning speed and the like, and performing a laser ablation-inductively coupled plasma mass spectrometry combined experiment to obtain the signal count of each trace element; and the quantitative characterization of the thickness, concentration and content of the organic matter streak layer in the sediment is realized through the correlation conversion of the content of the nutritional trace elements and the content of the organic matter. The microscopic quantitative characterization method of the organic texture layer can provide quantitative means for researches on fine particle deposition, heterogeneity of source rocks, development environment of the source rocks and the like, and has certain application value in geological foundation fields of source rock research, oil gas resource evaluation, unconventional oil gas and the like.
Description
Technical field
The invention belongs to petroleum geology exploration technical fields, are related to a kind of microcosmic quantitatively characterizing method of organic matter lamina.
Background technique
In contemporary petroleum industry, hydrocarbon source rock is the core of oil exploration, and organic matter is then the core of hydrocarbon source rock research.
As the source of hydrocarbon substance, depositional organic matter determines oil-gas generation type and stock number containing amount and type.Unconventionally
The research on matter basis further demonstrates that the content of organic matter equally affects shale interstitial space and adsorption capacity, to rich organic matter
The air content of shale plays a decisive role.Therefore, the occurrence status and distribution situation for describing organic matter, to determining oil gas product type
Type, assessment petroleum resources amount and shale gas reservoir potentiality to be exploited are of crucial importance.
The organic matter research method of early stage is mostly that whole organic matter abundance measurement and kerogen are carried out to deposit block
Preparation, obtains comprehensive geochemical information.The continuous development of micro- high resolution technique, let us can pass through microscope, field
The equipment such as transmitting Electronic Speculum observe finer organic matter occurrence status, i.e. organic matter lamina.This is current deposit or deposition
Distinguishable minimum or most thin primary deposit layer in rock, thickness is mostly in the micron-scale.Abundant experimental results confirm that the whole world is each main
Marine facies or the organic matter of lacustrine source there is laminated texture more.Continuously or intermittently shape concordant is distributed organic matter lamina, or is in
Short strip shape or it is mottled it is scattered be distributed in other laminas, under fluorescence microscope be in brown color.In petrographic microscope and fluorescence
Under microscope, organic matter lamina is relatively thin, and thickness is generally 5-200 μm.And rich organic matter lamina is interacted with organic-lean lamina
Occur, TOC value can 10-30 times of difference between different laminas.The information such as type, thickness and the content of these organic matter laminas can not only
Enough reflect the variation of depositional environment, and microcosmic source Chu Tezheng and relationship can be probed into.It is suitable from the viewpoint of microcrack arranges hydrocarbon
The organic matter of layer enrichment is more advantageous to hydrocarbon pressurization, and source rock is made locally to generate crunch, causes " gap " microcrack to arrange hydrocarbon, makes
There must be the excellent source rocks of organic matter laminated texture to be more advantageous to the enrichment and discharge of hydrocarbons.
The researchs such as lamina origin mechanism, palaeoenvironment, oil-gas generation potentiality, source storage proportion potential energy of local pressurization are required to having
The information such as content, the thickness of machine matter lamina are quantitatively described.And at present to the research of organic matter lamina mostly be by microscope,
Electromicroscopic photograph etc. carries out qualitative description to the thickness of organic matter lamina, color, fluorescent characteristics etc., is difficult to accomplish quantification.As opened
It is refreshing et al. to be passed through according to field emission microscopy observation using parameters such as area, perimeter, compactness, elongation percentage as key index
The parameters such as distribution distance, distribution angle are evaluated, to characterize the relativeness that organic matter is distributed in sample, propose description organic matter
Agglomerate degree of scatter and heterogeneity quantitative analysis method (Zhang Shuan, Sui Weibo shale reservoir organic matter be distributed quantitative analysis and
Reconstruction model oil-gas geology and recovery ratio, 2016,23 (2): 22-28).However this quantitative analysis is a kind of based on probability
The organic matter of statistics is distributed reconstruction model, and relies on the identification of organic matter the recognition capability of naked eyes, there is very strong subjectivity,
It is not real quantitative analysis method.
For on the whole, scholars are relatively fewer to the research of organic matter lamina feature, focus mostly in lamina origin mechanism
Aspect is described with feature, still lacks effective quantitative analysis method.This strong influence is to Organic Matter Enrichment mechanism, hydrocarbon
Microcosmicization and quantification of the geological foundations such as source rock developing environment, oil and gas resource evaluation, unconventional oil and gas research.It is therefore proposed that
The microcosmic quantitative analysis method of organic matter lamina is extremely important.
Summary of the invention
Based on it is above-mentioned the problems of in the prior art, the purpose of the present invention is to provide a kind of the micro- of organic matter lamina
See quantitatively characterizing method.
The purpose of the present invention is achieved by the following technical programs:
The present invention provides a kind of microcosmic quantitatively characterizing method of organic matter lamina comprising following steps:
Deposit is cut into the sample of regular shape by step 1；
Step 2 selects the apparent section of organic matter lamina characteristic in sample, and is processed by shot blasting to the section, obtains
Laser ablation target sample；
Step 3, the combined system formed using laser ablation system and icp ms, uses standard
Sample tunes each parameter in combined system；
Laser ablation target sample is placed in the sample cell of laser ablation system of combined system by step 4, is selected organic
The apparent region of matter lamina characteristic is as region to be scanned (by the amplification for adjusting image controller provisioned in laser ablation system
Multiple and focal position, so that the pattern of sample to be scanned can be clearly indicated on computer screen), and adjust laser ablation system
The time unification of system and icp ms；
Step 5, setting spot size, scanning speed, mass spectrographic single element residence time and the micro member of auxotype to be measured
The type of element carries out laser ablation-inductivity coupled plasma mass spectrometry combination experiment, obtains each auxotype microelement signal meter
Number；
Step 6, using laser ablation time or laser ablation distance as abscissa, with the signal of each auxotype microelement
It is counted as ordinate to map, determines the effective peak and the range of laser ablation time in each auxotype microelement map；
The sensitivity that each auxotype microelement detects organic matter lamina is calculated, determines effective element；Calculation of Sensitivity
Formula is as follows:
Each effective peak of effective element is integrated, the thickness of organic matter lamina, concentration and content are carried out microcosmic
Quantitatively characterizing, and the thickness detection limit and concentration detection limit of organic matter lamina are calculated, realize the thickness of Effects of Organic Matter in Sediments lamina
The quantitatively characterizing of degree, concentration and content.
In above-mentioned microcosmic quantitatively characterizing method, the rhythm structure that " organic matter lamina characteristic is obvious " refers mainly to lamina is brighter
It is aobvious.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that in step 1, regular shape include rectangular cubic structure or
Cylindrical structure.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that the rectangular cubic structure and specification is length≤76mm, width
≤ 26mm, thickness≤3mm；The specification of the cylindrical structure is diameter≤26mm, thickness≤3mm.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that the deposit may include black shale, silicalite and carbonic acid
One of rock salt etc. or a variety of combinations.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that in step 3, each parameter of combined system is tuned with standard sample,
Ensure under standard sample tuning mode, auxotype trace element chromium, uranium (52Cr、238U respective counting) is not less than 1000/ respectively
Ppm, 5000/ppm, uranium thorium ratio (238U/232Th) be 1.00 ± 0.10, and in 1min chromium, uranium and thorium (52Cr、238U and232Th)
The relative standard deviation respectively counted be below 10%.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that in step 4, after determining region to be scanned, further include into
The step of row degrades in advance.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that degrade in advance and degrade mode in advance including selection laser, or certainly
Row setting large spot, the laser parameter that quickly scanning and high frequency quickly degrade, realize that fast laser degrades in advance, both may be implemented fast
Speed removal surface contaminant and the purpose for not damaging target sample.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that in step 4, adjust laser ablation system and inductive coupling etc.
The mass spectrometric time unification of gas ions comprises determining that laser starts to degrade sample when providing required for signal-count to mass spectrum
Between, it is synchronized to out when degrading by laser ablation system by setting mass spectrographic counting trigger signal and realize, and determine
Laser ablation sample cell clean required for the time, with uranium (238U counting) is blown required for being brought down below 300 higher than 300,000
Subject to flyback time, according to the interval of time, adjustment time uniformity.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that in step 5, set spot size >=1 μm, scanning speed
Spend >=1 μm/s, mass spectrographic single element residence time >=0.001s, auxotype microelement to be determined type >=8.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that the auxotype microelement may include vanadium, chromium, nickel, copper,
It is at least eight kinds of in zinc, arsenic, selenium, caesium, molybdenum and uranium, but not limited to this.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that determine the foundation at effective peak are as follows: micro at least four auxotype
Element is determined above higher than 3 times of baseline amplitude for effective peak in the peak height of same position.
In above-mentioned microcosmic quantitatively characterizing method, it is preferable that determine the foundation of effective element are as follows: with sensitivity 90% or more
Auxotype microelement be determined as effective element.
In above-mentioned microcosmic quantitatively characterizing method, formed using laser ablation system and icp ms
Combined system is different from common LIBS system (induced with laser loses spectrometer thoroughly), the mass spectrum that combined system of the invention uses
Instrument is wider to the inspection range of effective element, it is easier to which quantitative, the quantitative detection limit of organic matter concentration is lower, can be realized trace
The detection of organic matter lamina.
In above-mentioned microcosmic quantitatively characterizing method, peak width represents organic matter lamina thickness；It is maximum that peak height represents organic matter lamina
Concentration；Peak area represents the content of organic matter of organic matter lamina.Wherein, the quantitative effect of the content of organic matter is maximum better than organic matter
Concentration.Stimulated light degrades spot size control, and organic matter lamina thickness detection limit is minimum to can reach 1 μm.The detection of organic matter concentration
Limiting by organic matter lamina micronutrient levels, mutual crumb layer micronutrient levels and mass signal response condition indicates, one
As can reach 5ppm or less (indicating with micronutrient levels).
Above-mentioned microcosmic quantitatively characterizing method can be realized the identification of effective element and effective peak and quantify, and not expand to
The quantitatively characterizing of machine matter lamina.It is total to enrichment mechanism based on organic and inorganic, according to Organic Matter Enrichment degree and auxotype microelement
Positive correlation, the member of multiple auxotype microelements is quantitative determined by laser ablation-inductivity coupled plasma mass spectrometry
Plain concentration variation, after excluding mineral signal interference, peak width, peak height and the peak area at the comprehensive effective peak for obtaining effective element, point
The thickness of organic matter lamina, the maximum concentration of organic matter and the content of organic matter are not represented, to realize Effects of Organic Matter in Sediments lamina
Microcosmic quantitatively characterizing.
The microcosmic quantitatively characterizing method of organic matter lamina provided by the invention can quantitatively characterizing analysis deposit in it is organic
Thickness, concentration and the content of lamina；It can be provided for researchs such as fine-grained sediment, hydrocarbon source rock heterogeneity, source rock development environment
Quantitative means have certain application valence in the geological foundations fields such as hydrocarbon source rock research, oil and gas resource evaluation, unconventional oil and gas
Value.
Detailed description of the invention
Fig. 1 is the microcosmic quantitatively characterizing method flow chart of organic matter lamina in the embodiment of the present invention；
Fig. 2 is auxotype microelement in the embodiment of the present invention60Ni time resolution map；
Fig. 3 is auxotype microelement in the embodiment of the present invention75As time resolution map；
Fig. 4 is auxotype microelement in the embodiment of the present invention95Mo time resolution map；
Fig. 5 is auxotype microelement in the embodiment of the present invention65Cu time resolution map；
Fig. 6 is auxotype microelement in the embodiment of the present invention66Zn time resolution map；
Fig. 7 is auxotype microelement in the embodiment of the present invention238U time resolution map；
Fig. 8 is auxotype microelement in the embodiment of the present invention51V time resolution map；
Fig. 9 is auxotype microelement in the embodiment of the present invention52Cr time resolution map；
Figure 10 is auxotype microelement in the embodiment of the present invention82Se time resolution map；
Figure 11 is the correlation comparison diagram of peak height between effective peak of effective element Ni, As and Mo in the embodiment of the present invention.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Laser ablation system as used in the following examples is U.S. Photo Machines Inc. company
Analyte Excite 193nm gaseous state excimer laser degrades system；Used icp ms are beauty
The iCAPQ icp ms of Thermo Fisher company, state；Used standard sample is NIST 612；Institute
The data processing software used is the Origin 8.5 of U.S. OriginLab company.
Embodiment
The present embodiment provides a kind of the microcosmic of organic matter lamina (the organic matter lamina of the steep mountain a small bay in a river group black shale of ZK102 well)
Quantitatively characterizing method, process are as shown in Figure 1, comprising the following steps:
Step 1 uses rock according to the sample cell of used laser ablation system to the size of sample and the requirement of thickness
It is 76mm × 26mm, the sample of the cube structure of the glass slide of thickness 2mm that black shale is cut into length and width by anxious cutting mill.
Step 2 selects the apparent section of organic matter lamina characteristic in rectangle sample, and is processed by shot blasting to the section,
Laser ablation target sample is obtained, 5 minutes, 50 DEG C of baking oven drying are cleaned in supersonic wave cleaning machine, are then cleaned again with acetone, really
Protect the clean surface of laser ablation target sample to be analyzed.
Step 3, the combined system formed using laser ablation system and icp ms, is passed through
NIST612 glass standard sample tuning optimization laser ablation-inductively coupled plasma mass spectrometer coupling system test parameter,
Specific tuner parameters are as shown in table 1: under standard sample tuning mode,52Cr、238U counts the average counter difference in 1min
It is 41595,205493, relative standard deviation is respectively 6.8%, 9.1%, it is ensured that spirit when different quality number Element detection
Sensitivity.Helium-uranium ratio (232Th/238It U is) 1.02 in the average value of 1min, standard deviation 9.5% can be effectively reduced quality discrimination
Effect.
Table 1
Laser ablation target sample is placed in HelExII laser ablation sample cell by step 4, selects organic matter lamina characteristic
Apparent region is as region to be scanned, length 1mm.By tuning it is experimentally confirmed that every time the line end of scan return it is next
Secondary scan position, required time are about 0.5s, and the HelExII sample cell of laser ablation system is dropped from > 30 ten thousand grades of signal-counts
As low as < 0.1% blank intensity, required time is about 2s, and the aerosol particle after degrading is transferred to ICP-MS from sample cell,
And the counting of elemental signals intensity is provided, required time is about 2s.Therefore the laser of 10s is set after each line end of scan
Degrade time out, the total time of the time-resolved mode of ICP-MS 20ss more compared with the laser ablation time, it is ensured that laser ablation system
With the time unification of mass spectrometer system, the signal message that each line of ICP-MS complete documentation is scanned, and do not intersect
Pollution.
Step 5 sets the spot diameter of laser ablation as 20 μm, scanning speed according to the instrument condition of table 1 coordinated
10 μm/s of rate, 0.01 second mass spectrographic single element residence time etc., auxotype microelement selection to be measured51V、52Cr、60Ni、65Cu
、66Zn、75As、82Se、95Mo、2389 kinds of U etc..
Step 6 is tested using laser ablation-inductivity coupled plasma mass spectrometry combined system, to region to be measured into
Row laser ablation sample introduction determines according to the 10 μm/s of scanning speed of setting and always effectively degrades time 100s, synchronization settings ICP-MS
Bulk analysis time 120s, pass through the counting response of icp ms synchronous recording auxotype microelement.
Using Origin8.5, using time and distance as abscissa, using each auxotype microelement signal-count as ordinate
It carries out doing figure, determines the effective peak and the range of laser ablation time in each auxotype microelement map；Calculate each auxotype
The sensitivity that microelement detects organic matter lamina, determines effective element；Calculation of Sensitivity formula is as follows:
Peak height at least four element in same position is higher than 3 times of effective peaks of determination of baseline amplitude, with sensitivity 90%
Above auxotype microelement is determined as effective element.
As a result as shown in Fig. 2 to Figure 10 and table 2, Fig. 2 is auxotype microelement in the embodiment of the present invention60Ni time resolution
Map；Fig. 3 is auxotype microelement in the embodiment of the present invention75As time resolution map；Fig. 4 is nutrition in the embodiment of the present invention
Type microelement95Mo time resolution map；Fig. 5 is auxotype microelement in the embodiment of the present invention65Cu time resolution map；
Fig. 6 is auxotype microelement in the embodiment of the present invention66Zn time resolution map；Fig. 7 is that auxotype is micro- in the embodiment of the present invention
Secondary element238U time resolution map；Fig. 8 is auxotype microelement in the embodiment of the present invention51V time resolution map；Fig. 9 is this
Auxotype microelement in inventive embodiments52Cr time resolution map；Figure 10 is the micro member of auxotype in the embodiment of the present invention
Element82Se time resolution map；Table 2 is effective identification and sensitivity of the auxotype microelement signal peak to organic matter lamina.By
For 2 data of table it is found that effectively peak represents organic matter lamina, final determining effective peak number mesh is 15, that is, represents 15 organic matters
Lamina.Finally determining effective element is Ni, As and Mo.
Table 2
Each effective peak of Ni, As and Mo are integrated, organic matter lamina thickness is represented with peak width, peak height represents organic
The maximum concentration of matter lamina, peak area represent the content of organic matter of organic matter lamina, carry out the microcosmic quantitative table of organic matter lamina
Sign, the results are shown in Table 3.Table 3 is peak width, peak height and the peak area at the effective peak effective element Ni, As and Mo.
Table 3
The peak area at each peak Ni, As and Mo and peak height are subjected to correlation analysis respectively, as a result as shown in Figure 11 and table 4,
Table 4 peak height relative coefficient and peak area relative coefficient between the effective peak effective element Ni, As and Mo.By Figure 11 and table 4
It can be seen that the correlation of peak area is better than peak height, show that the accuracy that quantitative analysis is carried out by the content of organic matter is better than
The maximum concentration of organic matter.In addition, relative coefficient (the R of the good relationship of Ni and As, peak area and peak height2) reachable
The correlation of 0.8 or more, Ni and Mo, As and Mo are slightly poor, but also meet the requirement (P < 0.01) of correlation statistically.Therefore, should
Ni and As is better than Mo to the sensitivity of organic matter lamina and dosing accuracy in experiment.
Table 4
The experiment detection elements 9, single element mass spectroscopy residence time 0.01s, single element data retention over time
0.001s, therefore the time interval of mass spectrum record data is 0.1s, according to the scanning speed of 10 μm/s, and effectively needed for peak identification
The data point wanted 5 determines that the thickness detection of organic matter lamina is limited to 5 μm.
Standard content due to NIST612 standard sample only containing Ni and Mo, the not standard content of As, therefore the experiment
Mo and Ni are utilized respectively to calculate the content of organic matter.60Ni and95Signal strength under Mo experiment condition be respectively 372/ppm and
509/ppm, method, which quantitatively detects, is limited to 10 times of baseline amplitudes, and the quantitative detection limit that organic matter is thus calculated is respectively
10.5ppm and 4.3ppm (being shown in Table 5).
Table 5
| Effective element | Baseline amplitude | Signal sensitivity | Quantitative detection limit |
| Ni | 389 | 372/ppm | 10.5ppm |
| Mo | 217 | 509/ppm | 4.3ppm |
In conclusion the microcosmic quantitatively characterizing method of organic matter lamina provided by the invention being capable of quantitatively characterizing analysis deposition
The thickness of organic lamina, concentration and content in object；It can be fine-grained sediment, hydrocarbon source rock heterogeneity, source rock development environment etc.
Research provides quantitative means, has in the geological foundations fields such as hydrocarbon source rock research, oil and gas resource evaluation, unconventional oil and gas certain
Application value.
Claims (12)
1. a kind of microcosmic quantitatively characterizing method of organic matter lamina comprising following steps:
Deposit is cut into the sample of regular shape by step 1；
Step 2 selects the apparent section of organic matter lamina characteristic in sample, and is processed by shot blasting to the section, obtains laser
Degrade target sample；
Step 3, the combined system formed using laser ablation system and icp ms, with standard sample tune
Each parameter in humorous combined system；
Laser ablation target sample is placed in the sample cell of laser ablation system of combined system by step 4, selects organic matter line
Layer characteristic apparent region as region to be scanned, and adjust laser ablation system and icp ms when
Between uniformity；
Step 5 sets spot size, scanning speed, mass spectrographic single element residence time and auxotype microelement to be measured
Type carries out laser ablation-inductivity coupled plasma mass spectrometry combination experiment, obtains each auxotype microelement signal-count；
Step 6, using laser ablation time or laser ablation distance as abscissa, with the signal-count of each auxotype microelement
It maps for ordinate, determines the effective peak and the range of laser ablation time in each auxotype microelement map；
The sensitivity that each auxotype microelement detects organic matter lamina is calculated, determines effective element；Calculation of Sensitivity formula
It is as follows:
Each effective peak of effective element is integrated, the thickness of organic matter lamina, concentration and content are carried out microcosmic quantitative
Characterization, and calculates the thickness detection limit and concentration detection limit of organic matter lamina, realizes the thickness, dense of Effects of Organic Matter in Sediments lamina
The quantitatively characterizing of degree and content.
2. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: the deposit include black shale,
One of silicalite and carbonate rock or a variety of combinations.
3. microcosmic quantitatively characterizing method according to claim 2, it is characterised in that: in step 1, regular shape includes
Rectangular cubic structure or cylindrical structure.
4. microcosmic quantitatively characterizing method according to claim 3, it is characterised in that: the rectangular cubic structure and specification is
Length≤76mm, width≤26mm, thickness≤3mm；The specification of the cylindrical structure is diameter≤26mm, thickness≤3mm.
5. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: in step 3, tuned with standard sample
When each parameter of combined system, need to ensure under standard sample tuning mode, auxotype trace element chromium, uranium respective counting respectively not
Lower than 1000/ppm, 5000/ppm, uranium thorium ratio is 1.00 ± 0.10, and in 1min chromium, uranium, thorium the opposite mark respectively counted
Quasi- deviation is below 10%.
6. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: to be scanned determining in step 4
Behind region, further include the steps that being degraded in advance.
7. microcosmic quantitatively characterizing method according to claim 6, it is characterised in that: degrade in advance pre- including selection laser
Mode or self-setting large spot, the laser parameter that quickly scanning and high frequency quickly degrade are degraded, realizes that fast laser is shelled in advance
Erosion.
8. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: in step 4, adjust laser ablation
The time unification of system and icp ms includes determining that laser starts to degrade sample to provide letter to mass spectrum
Time required for number counting and determine time required for laser ablation sample cell cleans, according to the interval of time, adjustment
Time unification.
9. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: in step 5, set hot spot
Size >=1 μm, scanning speed >=1 μm/s, mass spectrographic single element residence time >=0.001s, auxotype microelement kind to be determined
Class >=8.
10. according to claim 1 or microcosmic quantitatively characterizing method described in 9, it is characterised in that: the auxotype microelement packet
It includes at least eight kinds of in vanadium, chromium, nickel, copper, zinc, arsenic, selenium, caesium, molybdenum and uranium.
11. microcosmic quantitatively characterizing method according to claim 1, it is characterised in that: determine the foundation at effective peak are as follows: so that
Few 4 auxotype microelements are determined above higher than 3 times of baseline amplitude for effective peak in the peak height of same position.
12. according to claim 1 or microcosmic quantitatively characterizing method described in 11, it is characterised in that: determine the foundation of effective element
Are as follows: effective element is determined as in 90% or more auxotype microelement with sensitivity.
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