CN109406616A - A method of sulfate mineral sulfur isotope is measured by standard specimen of YF-2 barite - Google Patents
A method of sulfate mineral sulfur isotope is measured by standard specimen of YF-2 barite Download PDFInfo
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- CN109406616A CN109406616A CN201811158308.3A CN201811158308A CN109406616A CN 109406616 A CN109406616 A CN 109406616A CN 201811158308 A CN201811158308 A CN 201811158308A CN 109406616 A CN109406616 A CN 109406616A
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 144
- 229910052601 baryte Inorganic materials 0.000 title claims abstract description 127
- 239000010428 baryte Substances 0.000 title claims abstract description 127
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 107
- 239000011593 sulfur Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052600 sulfate mineral Inorganic materials 0.000 title claims abstract description 20
- 238000005259 measurement Methods 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000004575 stone Substances 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000002775 capsule Substances 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 10
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Inorganic materials [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000004364 calculation method Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- -1 barytocelestite Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001819 mass spectrum Methods 0.000 claims 1
- 238000000100 multiple collector inductively coupled plasma mass spectrometry Methods 0.000 abstract description 26
- 238000005103 elemental analyser isotope ratio mass spectroscopy Methods 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 86
- 238000004458 analytical method Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XUBKPYAWPSXPDZ-UHFFFAOYSA-N [Ba].OS(O)(=O)=O Chemical compound [Ba].OS(O)(=O)=O XUBKPYAWPSXPDZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000010430 carbonatite Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002307 isotope ratio mass spectrometry Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N2001/2893—Preparing calibration standards
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明提供一种以YF‑2重晶石为标样测定硫酸盐矿物硫同位素的方法，步骤如下：筛选YF‑2重晶石样品，研磨，利用EA‑IRMS法测得YF‑2重晶石样品中硫同位素δ34S值；分别取一块YF‑2重晶石样品和一块待测矿石样品制成YF‑2重晶石标样靶样和待测矿石靶样；利用LA‑MC‑ICP‑MS法先测量YF‑2重晶石标样靶样得到YF‑2重晶石标样靶样中第一样品点硫同位素34S/32S的比值，接着测量待测矿石靶样得到待测矿石靶样样品中硫同位素34S/32S的比值，再测量YF‑2重晶石标样靶样得到YF‑2重晶石标样靶样中第二样品点硫同位素34S/32S的比值；计算得到待测矿石样品中硫同位素δ34S值。本发明提供的方法能够精准确定硫酸盐矿物中硫同位素，为LA‑MC‑ICP‑MS法原位测定同位素提供均一且基体匹配标准样品，有效校正测量时的质量歧视。
The invention provides a method for measuring sulfur isotope of sulfate minerals by using YF-2 barite as a standard sample. The steps are as follows: screening a YF-2 barite sample, grinding, and using EA-IRMS method to measure the YF-2 barite The δ 34 S value of the sulfur isotope in the stone sample; take a YF-2 barite sample and an ore sample to be tested to make a YF-2 barite target sample and an ore target sample to be tested; use LA-MC- The ICP-MS method first measures the YF-2 barite standard target sample to obtain the ratio of sulfur isotope 34 S/ 32 S at the first sample point in the YF-2 barite standard target sample, and then measures the ore target to be tested Obtain the ratio of sulfur isotope 34 S/ 32 S in the ore target sample to be tested, and then measure the YF-2 barite standard sample to obtain the second sample point of sulfur isotope 34 S in the YF-2 barite standard target sample / 32 S ratio; calculate the sulfur isotope δ 34 S value in the ore sample to be tested. The method provided by the invention can accurately determine sulfur isotopes in sulfate minerals, provide a uniform and matrix-matched standard sample for the in-situ determination of isotopes by the LA-MC-ICP-MS method, and effectively correct the mass discrimination during measurement.
Description
Technical field
The present invention relates to barite analysis determining technology fields, more particularly to one kind to measure sulphur by standard specimen of YF-2 barite
The method of hydrochlorate mineral sulfur isotope.
Background technique
Sulfate is common sulfur-rich mineral, and sulfur isotope composition has many undeveloped potential value information, this
A little information facilitate us and understand magma, hydrothermal solution and deposition process.Mine is increasingly interested in recently as geological research
Geochemical alteration on object microcell scale, LA-MC-ICP-MS in-site detecting Isotope Analysis Method application are also more and more.
This method being used widely in terms of sulfide sulfur isotope, but the research for determining sulphate is compared
It is few, one of the main reasons for this is that lacking than more uniform and Matrix Match standard sample.It is first when measuring lightweight with MC-ICP-MS
When the isotopics of element, quality discrimination is the important potential error source of accuracy and accuracy.Standard specimen sample cross method
(Sample-Standard-Bracketing, SSB) is to be usually used in LA-MC-ICP-MS sulfur isotope quality in recent years to discriminate against school
Positive method.SSB method can correct the quality betided in MC-ICP-MS and laser ablation simultaneously and discriminate against.However, this method
Generally require the solid standard specimen of suitable Matrix Match.The solid standard specimen can be natural minerals, pressed powder either other
Artificial synthesized solid sample.National Institute of Standards and Technology (NIST) and US Geological Survey (USGS) it is artificial
Synthesis sulfate sulfur isotope is used in studying previous.However, currently without suitable puritan filler salt electron probe
It can be used for sulfur isotope analysis in situ.
Summary of the invention
In view of this, the present invention provides a kind of sides for measuring sulfate mineral sulfur isotope using YF-2 barite as standard specimen
Method, this method meet the needs of LA-MC-ICP-MS method analysis sulfate mineral sulfur isotope, bring for numerous analysts
It is convenient, while being also to study origin of ore deposit, tracking BIFhosted gold deposit source, look for mine and magmatic evolution etc. to provide advantageous means.
The present invention provides a kind of method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite, including following
Step:
S1 screens YF-2 barite samples, and grinding, then measurement obtains sulfur isotope δ in YF-2 barite samples34S value；
S2, take respectively one piece of YF-2 barite samples and one piece of ore sample to be measured be made YF-2 barite standard specimen target sample and
Ore target sample to be measured；
S3, measurement YF-2 barite standard specimen target sample obtain the first sample spot sulfur isotope in YF-2 barite standard specimen target sample34S/32The ratio of S then measures ore target sample to be measured and obtains sulfur isotope in all product of ore target to be measured34S/32The ratio of S, then
Measurement YF-2 barite standard specimen target sample obtains the second sample spot sulfur isotope in YF-2 barite standard specimen target sample34S/32The ratio of S；
S4, according to sulfur isotope δ in the YF-2 barite samples34First sample in S value, YF-2 barite standard specimen target sample
Point sulfur isotope34S/32Sulfur isotope in the ratio of S, all product of ore target to be measured34S/32The ratio and YF-2 barite standard specimen of S
Second sample spot sulfur isotope in target sample34S/32The ratio calculation of S obtains sulfur isotope δ in ore sample to be measured34S value.
Further, in step S1, sulfur isotope δ in YF-2 barite samples is measured34The process of S value are as follows: by YF-2 weight
Spar sample is ground to 200 mesh, then weighs YF-2 barite samples and barium sulfate standard sample is individually positioned in tin capsule, to
Oxidation catalyst is added in tin capsule, then tin capsule is placed in sample injector by tin capsule closed impaction, by sample injector by tin capsule
It puts into combustion reactor, while injecting purity oxygen into combustion reactor, YF-2 barite samples and barium sulfate standard sample
It burns in combustion reactor, the gas generated after processing burning, by SO2Gas is separated with other gases, SO2Gas is passed into
Measurement obtains sulfur isotope δ in YF-2 barite samples in isotope ratio mass spectrometer34S value.
Further, the oxidation catalyst selects V2O5, by the process of tin capsule closed impaction are as follows: will with curved tweezers
Tin capsule is placed on clean flat magnetic sheet, and is allowed to be closed with the side wall of the tweezers gently tight tin capsule of tweezer；By tin capsule side horizontal, with one
Tweezers push down its bottom, with the flat horizontal surface of another tweezers suitably firmly scrape tin capsule be allowed to side wall be fully closed into it is flat；
Then tin capsule is built up into square or spherical shape, and compressed it.
Further, in step S4, sulfur isotope δ in the ore sample to be measured34The calculation formula of S value are as follows:
In formula, δ34SsampleFor sulfur isotope δ in ore sample to be measured34S value, δ34SYF-2For sulphur in YF-2 barite samples
Isotope δ34S value,For sulfur isotope in ore sample target sample to be measured34S/32The ratio of S,For YF-2 barite
First sample spot sulfur isotope in standard specimen target sample34S/32The ratio of S and the second sample spot sulfur isotope34S/32The ratio of S is averaged
Value.
Further, the ore to be measured includes barite, barytocelestite, celestine and gypsum.
Further, the YF-2 barite samples pick up from Guangxi Yongfu baryte deposit, white or colourless crystal
Particle.
Further, in step S3, YF-2 barite standard specimen target sample and ore target sample to be measured are placed on to the sample of laser
In product pond, the first sample spot sulfur isotope in plasma mass spectrograph measurement YF-2 barite standard specimen target sample is then utilized34S/32S
Ratio, sulfur isotope in all product of ore target to be measured34S/32Second sample spot in the ratio and YF-2 barite standard specimen target sample of S
Sulfur isotope34S/32The ratio of S.
Further, the laser is RESOLution laser, the laser parameter of the RESOLution laser
Are as follows: laser beam spot diameter is 50 μm, laser energy 8.9Jcm-2, laser frequency 8Hz.
Further, the laser is GeoLasHD laser, the laser parameter of the GeoLasHD laser are as follows: is swashed
Light beam spot diameter is 60 μm, laser energy 5Jcm-2, laser frequency 10Hz.
Technical solution provided by the invention has the benefit that method provided by the invention can precisely determine sulfuric acid
Salt mineral sulfur isotope provides uniform and Matrix Match standard sample for LA-MC-ICP-MS method in-site detecting isotope, has
Effect corrects existing quality when measurement and discriminates against, and YF-2 barite can be used as standard specimen in LA-MC-ICP-MS analysis to correct
Other barites, barytocelestite, celestine and gypsum sulfur isotope, be widely used, meet LA-MC-ICP-MS analysis
The needs of sulfate mineral sulfur isotope are brought conveniently for numerous analysts, while being also research origin of ore deposit, tracking into mine
Fluid origin looks for mine and magmatic evolution etc. and provides advantageous means.
Detailed description of the invention
Fig. 1 is that the present invention is a kind of to be shown by the process of the method for standard specimen measurement sulfate mineral sulfur isotope of YF-2 barite
It is intended to.
Fig. 2 is LA-MC-ICP-MS analysis YF-2 barite sulfur isotope result schematic diagram of the present invention.
Fig. 3 is that LA-MC-ICP-MS of the present invention analyzes other barite sulfur isotope result schematic diagrams.
Fig. 4 is that LA-MC-ICP-MS of the present invention analyzes other sulfate sulfur isotope result schematic diagrams.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Sulfate mineral sulphur is measured by standard specimen of YF-2 barite referring to FIG. 1, the embodiment provides one kind
The method of isotope, comprising the following steps:
Step S1 screens YF-2 barite samples, is ground to 200 mesh or so, then measures YF-2 weight using EA-IRMS method
Sulfur isotope δ in spar sample34S value, YF-2 barite samples pick up from Guangxi Yongfu baryte deposit, and white or colourless is big
Crystal grain is up to 1 centimetre, and quality is more crisp.
The measurement process of EA-IRMS method are as follows:
It weighs suitable YF-2 barite samples and barium sulfate standard sample is respectively placed in small tin capsule, then into tin capsule
The V more than twice is added2O5Powder, V2O5Powder serves as oxidation catalyst；After having weighed sample and oxidation catalyst in tin capsule,
Tin capsule is placed on clean flat magnetic sheet with curved tweezers, and gently the tight tin capsule side wall of tweezer is allowed to be closed with tweezers；It is flat with side
Tin capsule is set, pushes down its bottom with a tweezers, suitably firmly scraping tin capsule with the flat horizontal surface of another tweezers, to be allowed to side wall complete
It is closed into flat；Then tin capsule is built up into small cube or small spherical shape, and compressed it；Then, tin capsule is placed in sample injector
In, a tin capsule is put into combustion reactor every time by sample injector, while certain flow is injected into combustion reactor
Purity oxygen makes YF-2 barite samples and barium sulfate standard sample burn at 1050 DEG C, the institute then generated after processing burning
There is gas (SO2、SO3、SO、H2O、CO2、N2), all gas for generation of burning is brought under helium carrier gas stream and by being filled with height
Pure oxygen agent WO3In the single redox quartz ampoule of reducing agent Cu, high-purity oxidant WO3With reducing agent Cu by SO3, SO also
It is former and be oxidized to SO2, moisture is by filled with Mg (ClO4)210cm long drier (i.e. water trap) when be removed；Finally, gas
Body is heated to 70 DEG C of 50-80 mesh Porapack column for SO by one2With CO2、N2It is separated etc. other gases, by separated
SO2It under the drive of helium carrier gas stream, enters in isotope ratio mass spectrometer, obtains sulfur isotope in YF-2 barite samples through measurement
δ34S value, 1-3 point of general measure are averaged when measuring at multiple, and sample injector selects 200 autosampler of AS
(Fisons Instruments), isotope ratio mass spectrometer select Thermo Fisher Scientific Delta V Plus
Isotope ratio mass spectrometer.
YF-2 barite deposit composition granule sample δ34The analysis precision of S is about ± 0.4 ‰ (2s), which is based on repeating
Analyze 8557 (δ of NIST SRM34‰) S=21.17 ± 0.09 is obtained with the barium sulfate standard specimen of International Atomic Energy Agency (IAEA)
(IAEA-05,δ34S=0.5 ‰ and IAEA-06, δ34S=-34.1 ‰).
In the measurement process of EA-IRMS method, if it is barium-free sulfate sample, sulfur isotope value needs further true
It is fixed, barium-free sulfate (celestine, barytocelestite and anhydrite) is first converted into barium sulfate (BaSO4), method particularly includes: it weighs
30mg celestine, barytocelestite and anhydrite are dissolved in 50mmol L-1Diethylene triamine pentacetic acid (DTPA) (DTPA) in, and with HCl acid
Change, adjusts pH < 2, be heated to boiling；Then, the 8.5%BaCl of about 25mL is added2Solution makes it sufficiently be precipitated as sulfuric acid
Barium.The sulfur isotope value of barite and the barium sulfate of conversion is measured by EA-IRMS, and the long-term reproducibility of measured value is excellent
In 0.2 ‰.
Step S2 takes a fritter YF-2 barite samples and fritter ore sample to be measured to be placed in epoxy resin and make respectively
At about 1 inch of rounded YF-2 barite standard specimen target sample and ore target sample to be measured.
Step S3, using LA-MC-ICP-MS method to the YF-2 barite standard specimen target sample of step S2 and ore target sample to be measured into
The analysis of row original position sulfur isotope, in order to study influence of the matrix effect to result, the present invention uses two in the analysis process
A 193nm ArF excimer laser ablation system progress check analysis, respectively RESOLution laser (Resonetics,
Canberra, Australia) and GeoLasHD laser (Coherent, German), two laser systems all with Nu Plasma
Reception more than II-icp ms (MC-ICP-MS；Nu instruments, Britain) combination, RESOLution
Laser, GeoLasHD laser, the instrument setting of plasma mass spectrograph and instrument parameter are shown in Table 1.
Wherein, the laser parameter setting of RESOLution laser are as follows: laser beam spot diameter is 50 μm, corresponding laser energy
Amount is 8.9Jcm-2, laser parameter in laser frequency 8Hz, GeoLasHD laser are as follows: laser beam spot diameter is 60 μm,
Laser frequency is 10Hz, laser energy 5Jcm-2。
When being measured using LA-MC-ICP-MS method, YF-2 barite standard specimen target sample and ore target sample to be measured are placed on
In the sample cell of RESOLution laser and GeoLasHD laser, YF-2 barite standard specimen target sample and ore target sample quilt to be measured
Laser distinguishes calcination into aerosol, and aerosol is under the current-carrying of high-purity He gas, with Ar gas and a small amount of N2Gas mixing after enter etc. from
Daughter mass spectrograph measures, and first measures YF-2 barite standard specimen target sample and obtains the first sample spot in YF-2 barite standard specimen target sample
Sulfur isotope34S/32Then the ratio of S measures ore target sample to be measured and obtains sulfur isotope in all product of ore target to be measured34S/32S
Ratio, then measure YF-2 barite standard specimen target sample and obtain the second sample spot sulfur isotope in YF-2 barite standard specimen target sample34S
/32The ratio of S, the present invention measure simultaneously34S、33S and32The ion signal of S obtains under the mode of time resolution analysis (TRA)
Obtain data.Each sample acquisition includes the washing time for degrading data acquisition and 50s of the background measurement of 30s, 40s.32The back of S
Scape intensity is 0.2-0.5V, according to laser ablation beam spot size, the difference of laser frequency and laser intensity, the signal strength of sample
For 3-25V, ore sample to be measured measures 5 points or so, and YF-2 barite generally measures 1-3 point every time, when measuring at multiple,
It is averaged respectively.
Ore sample to be measured includes barite, barytocelestite, celestine and gypsum.
The instrument parameter of 1 RESOLution laser of table, GeoLasHD laser and plasma mass spectrograph is arranged
Step S4, sulfur isotope δ in the YF-2 barite samples obtained according to step S1 measurement34S value, step S3 are measured
To YF-2 barite standard specimen target sample in the first sample spot sulfur isotope34S/32Sulphur is same in the ratio of S, all product of ore target to be measured
Position element34S/32Second sample spot sulfur isotope in the ratio and YF-2 barite standard specimen target sample of S34S/32The ratio calculation of S obtain to
Survey sulfur isotope δ in ore mineral particle34S value；
Sulfur isotope δ in ore sample to be measured34The calculation formula of S value are as follows:
In formula, δ34SsampleFor sulfur isotope δ in ore sample to be measured34S value, δ34SYF-2For sulphur in YF-2 barite samples
Isotope δ34S value,For sulfur isotope in ore sample target sample to be measured34S/32The ratio of S,For YF-2 barite
First sample spot sulfur isotope in standard specimen target sample34S/32The ratio of S and the second sample spot sulfur isotope34S/32The ratio of S is averaged
Value.
The same position of sulfate mineral sulphur is measured by standard specimen of YF-2 barite to provided by the invention below with reference to verification test
The accuracy of the method for element is illustrated.
Verification test 1:
Using isotope uniform and Matrix Match normative mineral to the sulfur isotope of SSB method in-site detecting barite especially
It is important.In order to verify potential sulfate standard sample sulfur isotope homogeneity and reproducibility (LA-MC-ICP-MS and EA-
IRMS), the present invention carries out replicate analysis to the sulfur isotope of YF-2 barite samples.For EA-IRMS method, reproducibility is measured
Refer to the consistency for the result for taking different piece to carry out multiple measurement from bulk sample.The present invention repeats to have surveyed YF-2 in CAS
Three times, sulfur isotope value is 18.31 ± 0.06 ‰ (2s) to the sub-fraction sample of barite；YF-2 barite has been surveyed in CUG
11 different pieces, obtain sulfur isotope average value be 18.1 ± 0.4 ‰ (2s), the result measured respectively in two units
It is consistent in range of uncertainty.In addition to this, the present invention determines the δ of YF-2 barite also by LA-MC-ICP-MS34S
Value, the interior result measured is as shown in Table 2 and Fig. 1 in different times, and table 2 is the sulfur isotope value of different minerals sulfate, Fig. 2
YF-2 barite sulfur isotope is analyzed as a result, can be seen that the δ of YF-2 barite from table 2 and Fig. 2 for LA-MC-ICP-MS method34S
Value is 18.0 ± 0.4 ‰ (2s), uncertainty < 0.5 ‰ (2s), and the solid line in Fig. 2 indicates average value.
In conclusion either EA-IRMS method either LA-MC-ICP-MS method, i.e. complete analysis or microcell scale, YF-2
The sulfur isotope of barite shows good homogeneity.Therefore, YF-2 barite can be used as LA-MC-ICP-MS analysis
The standard specimen of the sulfur isotope of other barite samples can be used as a new sulfur isotope standard specimen.
The sulfur isotope value of 2 sulfate of table
In table 2, number is YF-1 and the barite of YF-2 picks up from Yongfu (Guangxi) baryte deposit, and the weight that number is WC is brilliant
Stone picks up from Wu Chuan (Guizhou) hydrothermal deposit, and the barite of Yongfu YF-1, Yongfu YF-2 and river WC hydrothermal deposit of being engaged in is white or nothing
The big crystal grain (being up to 1 centimetre) of color, quality is more crisp；Number is DGD and the barite of GTS picks up from Mianning-Dechang carbonatite
Granitic Complex (Sichuan), Mianning-Dechang rare earth mineral deposit DGD and GTS barite contain a small amount of fluorite in light yellow；Number is DSG
Barytocelestite pick up from Huanglong paving carbonic acid lithotype rare earth-molybdenum deposit (Shaanxi), barytocelestite DSG be in light brown rhomboidan, matter
Brittleness；The celestine that number is BK picks up from Bayan Khushu rare earth mineral deposit, and celestine BK is light blue color；The admant that number is LX
Cream picks up from Hubei Ling Xiang iron ore-deposit, and clever township's anhydrite LX is colourless transparent crystal.
Verification test 2:
In LA-MC-ICP-MS analytic approach, in order to verify the applicability of YF-2 barite standard specimen, with YF-2 barite work
For standard specimen, using SSB method, to correct the more uniform barite samples of other sulfur isotope ratios (YF-1, DGD and GTS barite),
Fig. 3 is that LA-MC-ICP-MS method analyzes other barite sulfur isotope result schematic diagrams, the analysis of YF-1, DGD and GTS barite
It the results are shown in Table 2 and Fig. 3 A, 3B, 3C.The result of LA-MC-ICP-MS measurement is consistent with EA-IRMS measurement result, analysis essence
Degree is 0.5 ‰.In addition, according to EA-IRMS measurement as a result, discovery WC barite samples sulfur isotope value change greatly, because
This also demonstrates its variation on microcell scale, using YF-2 barite as standard specimen, with LA-MC-ICP-MS to the same position of its sulphur
Element is measured, and as the result is shown in a small region, sulfur isotope is varied widely, obtained value difference 4 ‰ (see
Fig. 3 D and 3E), and what is measured with traditional EA-IRMS analysis method is an average value.Therefore, the advantage of micro-region analysis technique
Obviously.
In order to study the matrix effect between different sulfate, standard specimen is made with YF-2 barite, to measure other sulfate
The sulfur isotope of (DSG barytocelestite, BK celestine and LX anhydrite) finds the sulphur between YF-2 barite and these sulfate
Isotope fractionation be it is negligible, LA-MC-ICP-MS measurement result and EA-IRMS measurement result are in error range
It is consistent, is shown in Table 2 and Fig. 4, wherein Fig. 4 is that LA-MC-ICP-MS analyzes other sulfate sulfur isotope result schematic diagrams, figure
4A is DSG sulfur isotope result schematic diagram, and Fig. 4 B is BK sulfur isotope result schematic diagram, and Fig. 4 C is the signal of LX sulfur isotope result
Figure.It can be seen that YF-2 barite can also serve as other sulfate sample sulfur isotope measurement standard specimens, the scope of application is non-
Normal is wide.
Solid line in Fig. 3 and Fig. 4 indicates average value.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite, which is characterized in that including following
Step:
S1 screens YF-2 barite samples, and grinding, then measurement obtains sulfur isotope δ in YF-2 barite samples34S value；
S2 takes one piece of YF-2 barite samples and one piece of ore sample to be measured that YF-2 barite standard specimen target sample and to be measured is made respectively
Ore target sample；
S3, measurement YF-2 barite standard specimen target sample obtain the first sample spot sulfur isotope in YF-2 barite standard specimen target sample34S/32S
Ratio, then measure ore target sample to be measured and obtain sulfur isotope in all product of ore target to be measured34S/32The ratio of S, then measure
YF-2 barite standard specimen target sample obtains the second sample spot sulfur isotope in YF-2 barite standard specimen target sample34S/32The ratio of S；
S4, according to sulfur isotope δ in the YF-2 barite samples34First sample spot sulphur in S value, YF-2 barite standard specimen target sample
Isotope34S/32Sulfur isotope in the ratio of S, all product of ore target to be measured34S/32The ratio and YF-2 barite standard specimen target sample of S
In the second sample spot sulfur isotope34S/32The ratio calculation of S obtains sulfur isotope δ in ore sample to be measured34S value.
2. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as described in claim 1, feature
It is, in step S1, measures sulfur isotope δ in YF-2 barite samples34The process of S value are as follows: grind YF-2 barite samples
To 200 mesh, then weighs YF-2 barite samples and barium sulfate standard sample is individually positioned in tin capsule, oxygen is added into tin capsule
Change catalyst then tin capsule is placed on tin capsule closed impaction in sample injector to, tin capsule is put by combustion reaction by sample injector
In device, while purity oxygen is injected into combustion reactor, YF-2 barite samples and barium sulfate standard sample are in combustion reactor
Middle burning, the gas generated after processing burning, by SO2Gas is separated with other gases, SO2Gas is passed into isotope ratio mass spectrum
Measurement obtains sulfur isotope δ in YF-2 barite samples in instrument34S value.
3. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as claimed in claim 2, feature
It is, the oxidation catalyst selects V2O5, by the process of tin capsule closed impaction are as follows: tin capsule is placed in cleaning with curved tweezers
On flat magnetic sheet, and it is allowed to be closed with the side wall of the tweezers gently tight tin capsule of tweezer；By tin capsule side horizontal, its bottom is pushed down with a tweezers
Portion, with the flat horizontal surface of another tweezers suitably firmly scrape tin capsule be allowed to side wall be fully closed into it is flat；Then tin capsule is folded
At square or spherical shape, and compress it.
4. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as described in claim 1, feature
It is, in step S4, sulfur isotope δ in the ore sample to be measured34The calculation formula of S value are as follows:
In formula, δ34SsampleFor sulfur isotope δ in ore sample to be measured34S value, δ34SYF-2For the same position of sulphur in YF-2 barite samples
Plain δ34S value,For sulfur isotope in ore sample target sample to be measured34S/32The ratio of S,For YF-2 barite standard specimen
First sample spot sulfur isotope in target sample34S/32The ratio of S and the second sample spot sulfur isotope34S/32The average value of the ratio of S.
5. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as described in claim 1, feature
It is, the ore to be measured includes barite, barytocelestite, celestine and gypsum.
6. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as described in claim 1, feature
It is, the YF-2 barite samples pick up from Guangxi Yongfu baryte deposit, white or colourless crystal grain.
7. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as described in claim 1, feature
It is, in step S3, YF-2 barite standard specimen target sample and ore target sample to be measured is placed in the sample cell of laser, it is then sharp
With the first sample spot sulfur isotope in plasma mass spectrograph measurement YF-2 barite standard specimen target sample34S/32The ratio of S, mine to be measured
Sulfur isotope in all product of stone target34S/32Second sample spot sulfur isotope in the ratio and YF-2 barite standard specimen target sample of S34S/32S
Ratio.
8. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as claimed in claim 7, feature
It is, the laser is RESOLution laser, the laser parameter of the RESOLution laser are as follows: laser beam spot is straight
Diameter is 50 μm, laser energy 8.9Jcm-2, laser frequency 8Hz.
9. the method for measuring sulfate mineral sulfur isotope as standard specimen using YF-2 barite as claimed in claim 7, feature
It is, the laser is GeoLasHD laser, the laser parameter of the GeoLasHD laser are as follows: laser beam spot diameter is
60 μm, laser energy 5Jcm-2, laser frequency 10Hz.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111638266A (en) * | 2020-07-09 | 2020-09-08 | 中国测试技术研究院化学研究所 | ICP-MS detection method for measuring total sulfur in natural gas based on constant-current control sample injection device |
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| CN112730581A (en) * | 2021-01-18 | 2021-04-30 | 天津师范大学 | Sulfur monoxide ion method for detecting sulfur stable isotope in atmosphere |
| CN113087007A (en) * | 2021-02-25 | 2021-07-09 | 广州海洋地质调查局 | Device for extracting protogenic carbonate crystal lattice sulfate in carbonate rock |
| CN114994163A (en) * | 2022-06-10 | 2022-09-02 | 贵州大学 | Method for judging position of barite deposition center by using sulfur isotope value |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108051468A (en) * | 2018-01-23 | 2018-05-18 | 中国地质科学院矿产综合利用研究所 | X-ray fluorescence spectrum method for simultaneously analyzing fluorite, barite and celestite |
| CN108152099A (en) * | 2017-12-13 | 2018-06-12 | 中国科学院地质与地球物理研究所 | The extracting method of organic sulfur in the carbonate rock of the low content of organic matter |
-
2018
- 2018-09-30 CN CN201811158308.3A patent/CN109406616A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108152099A (en) * | 2017-12-13 | 2018-06-12 | 中国科学院地质与地球物理研究所 | The extracting method of organic sulfur in the carbonate rock of the low content of organic matter |
| CN108051468A (en) * | 2018-01-23 | 2018-05-18 | 中国地质科学院矿产综合利用研究所 | X-ray fluorescence spectrum method for simultaneously analyzing fluorite, barite and celestite |
Non-Patent Citations (4)
| Title |
|---|
| ADINA PAYTAN 等: "Origin of marine barite deposits：Sr and S isotope characterization", 《GEOLOGY》 * |
| ROBERT R.SEAL: "Sulfur Isotope Geochemistry of Sulfide Minerals", 《REVIEWS IN MINERALOGY ＆ GEOCHEMISTRY》 * |
| 丁悌平 等: "六氟化硫法测量33S/32S、34S/32S和36S/32S的方法研究", 《矿床地质》 * |
| 朱祥坤 等: "铁同位素的MC-ICP-MS测定方法与地质标准物质的铁同位素组成", 《岩石矿物学杂质》 * |
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