CN116297791A - Ultraviolet laser probe sulfide sulfur isotope micro-region in-situ analysis system and method - Google Patents
Ultraviolet laser probe sulfide sulfur isotope micro-region in-situ analysis system and method Download PDFInfo
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- 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
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- 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
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- 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
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The application relates to an in-situ analysis system and method for sulfide sulfur isotope microdomains of ultraviolet laser probe, wherein the analysis system comprises an analysis gas circuit, and an ultraviolet laser ablation device and a trace SO (SO) are sequentially arranged on the analysis gas circuit along the gas flow direction 2 Gas preparation device, SO 2 The device comprises a gas collection and purification device, a miniature shunt interface and a gas isotope ratio mass spectrometer. The invention changes the traditional laser probe micro-area in-situ sampling and analysis gas preparation from in-situ simultaneous operation to ex-situ sequential operation, thereby avoiding fractionation and influence caused by incomplete reaction and reaction of the reagent and matrix components in the laser ablation-analysis gas preparation process; and is directed to infrared lasersThe fractionation generated in the heating and melting process adopts ultraviolet laser ablation samples without obvious thermal effect and matrix effect, the size of the generated aerosol particles is uniform, the transmission efficiency is high, and the fractionation generated in the laser ablation and transmission process is avoided and reduced.
Description
Technical Field
The application belongs to the technical field of sulfur isotope analysis, and particularly relates to an ultraviolet laser probe sulfide sulfur isotope micro-region in-situ analysis system and method.
Background
The traditional laser probe sulfide sulfur isotope micro-region in-situ analysis method adopts the combination of laser and gas isotope ratio mass spectrometry, and the principle is mainly that O is adopted 2 /F 2 /BrF 5 In the atmosphere, the infrared laser beam is focused on a micro area on the surface of the sulfide sample, and the sample is rapidly heated by the laser beam, SO that the sulfide micro area is heated, melted, gasified and reacted with oxygen or a fluorinating agent to form SO 2 (2FeS 2 +5O 2 ＝2FeO+4SO 2 ) Or SF (sulfur hexafluoride) 6 (2FeS 2 +15F 2 ＝2FeF 3 +4SF 6 ) Gas, SO 2 /SF 6 After the gas is purified and separated by gas chromatography, the gas is led into a gas isotope mass spectrometer sampling system to measure the sulfur isotope composition.
The traditional laser probe micro-region in-situ sulfur isotope analysis technology at present encounters the following technical barriers that are difficult to surmount: (1) laser performance: the effect of laser in the traditional laser probe is micro-zone heating, so that most of adopted laser is infrared laser, the thermal effect of the infrared laser is obvious, obvious fractionation can be generated in the process of micro-zone in-situ heating decomposition and corrosion of a sample, the accuracy of an analysis result is seriously affected, and the accuracy correction is difficult. (2) incomplete reaction: in the process of heating/melting the sample by laser, the reaction of the heated/melted substances is incomplete due to temperature gradient, boundary effect and the like, obvious fractionation occurs, and accurate correction is difficult. (3) reacting the reagent with the matrix component: during laser heating/ablation, the oxidant (O 2 ) Fluorinating agent (F) 2 /BrF 5 ) Not only with the heated/eroded material, but also with unetched components outside the heated zoneThe background is raised, the accuracy of analysis results is obviously affected, and although the former adopts a plurality of measures such as prefluorination, the background is still difficult to thoroughly eliminate. The factors restrict the further improvement of the precision and accuracy of the traditional laser probe stable isotope micro-area in-situ analysis technology, and the requirement of the modern stable isotope micro-area in-situ measurement is difficult to meet, so that the analysis method has been created in 1986 and has not been widely popularized so far.
In addition, two other stable isotope micro-area in-situ analysis technologies are currently applied at home and abroad: (1) Secondary ion probe mass spectrometry (SIMS) micro-area in situ analysis techniques and (2) laser ablation multi-receive inductively coupled plasma mass spectrometry (LA-MC-ICPMS) micro-area in situ analysis techniques. SIMS is expensive and limited in number; the matrix effect is obvious, the analysis sample is required to be strictly matched with the standard, and the isotope standard substance for in-situ analysis of the micro-region is very rare, so that the development difficulty is high. The factors in the two aspects restrict the large-area popularization and application of the ion probe micro-area in-situ isotope analysis technology. The laser ablation multi-receiving inductively coupled plasma mass spectrometry (LA-MC-ICPMS) micro-region in-situ isotope analysis technology has obvious mass discrimination effect and more interference ions, and also faces the problems of rare isotope standard substances and easy pollution during measuring the micro-region in-situ sulfur isotopes.
Disclosure of Invention
In view of the above, the present invention is directed to an in situ analysis system and method for sulfide sulfur isotope of ultraviolet laser probe, which are used to solve one or more of the above-mentioned problems in the prior art.
The purpose of the invention is realized in the following way:
on the one hand, an in-situ analysis system for sulfide sulfur isotope microdomains of an ultraviolet laser probe is provided, which comprises an analysis gas circuit, wherein an ultraviolet laser ablation device and a trace SO are sequentially arranged on the analysis gas circuit along the gas flow direction 2 Gas preparation device, SO 2 The device comprises a gas collection and purification device, a miniature shunt interface and a gas isotope ratio mass spectrometer;
the ultraviolet laser ablation device is provided with a 193nm excimer laser and a sample cell, wherein the sample cell is used for containing sulfide-containing samples; 193nm excimer laser is used to ablate sulfide aerosol particles from sulfide-containing samples in the sample cell;
trace amount of SO 2 The gas preparation device is provided with a reaction tube, sulfide aerosol particles are carried by helium carrier gas and enter the reaction tube, and react in the reaction tube at the high temperature of 1020 ℃ to generate SO 2 A gas;
SO 2 the gas collecting and purifying device is used for collecting and purifying SO in the mixed gas 2 A gas;
through SO 2 SO after purification by gas collection and purification device 2 The gas is supplied to the gas isotope ratio mass spectrometer for detection through the micro split-flow interface.
Further, the reaction tube has a first inlet, a second inlet, and a first outlet; the first inlet is communicated with the air outlet channel of the sample cell and is used for flowing in helium gas flow carrying sulfide aerosol particles; a second inlet connected with an oxygen source for supplying O 2 A gas; helium carrier gas carries sulfide aerosol particles to enter the reaction tube from the first inlet and is supplied with O 2 The SO-containing gas is obtained after the reaction 2 A mixture of gases; containing SO 2 The mixed gas of the gas flows out from the first outlet and enters SO 2 And a gas collection and purification device.
Further, the outer diameter of the reaction tube is 12mm, the inner diameter is 10mm, the reaction tube is made of quartz glass, and the heating temperature of the reaction tube is 1020 ℃; the upper space of the reaction tube forms a reaction space of the mixed gas, and the lower space of the reaction tube is filled with tungsten oxide of 20mm, quartz cotton of 10mm, reduction copper particles of 170mm and quartz cotton of 10mm from top to bottom.
Further, SO 2 The gas collecting and purifying device is provided with a first collecting and purifying component and a second collecting and purifying component which are connected through pipelines SO as to realize the separation of SO in the mixed gas 2 Carrying out enrichment and purification on the gas twice; the air inlet of the first collecting and purifying component is communicated with the first outlet of the reaction tube, and the second collecting and purifying component is used for enriching and purifying the SO after purification of the first collecting and purifying component 2 And the gas is enriched and purified again, and the gas outlet of the second collecting and purifying component is connected with a gas isotope ratio mass spectrometer through a micro split-flow interface.
Further, the first collection and purification assembly comprises a first six-way valve and a first cold trap, and the second collection and purification assembly comprises a second six-way valve and a second cold trap; the gas inlet valve port of the first six-way valve is communicated with the first outlet of the reaction tube, the gas outlet valve port of the first six-way valve is communicated with the gas inlet valve port of the second six-way valve, and the gas outlet valve port of the second six-way valve is connected with the micro diversion interface through a Teflon tube; two valve ports of the first six-way valve are connected with two opening ends of the first cold trap, and two valve ports of the second six-way valve are connected with two opening ends of the second cold trap;
further, the first cold trap comprises a U-shaped Teflon tube, wherein the outer diameter of the U-shaped Teflon tube is 4mm, the inner diameter of the U-shaped Teflon tube is 2mm, and the length of the U-shaped Teflon tube is 60cm; the second cold trap comprises a U-shaped quartz capillary tube and a protective sleeve sleeved outside the U-shaped quartz capillary tube, wherein the inner diameter of the U-shaped quartz capillary tube is 0.32mm, and the length of the U-shaped quartz capillary tube is 60cm.
In one embodiment, the sample cell is an elliptical single sample cell comprising:
the first base is provided with a cavity, and the cross section of the cavity is elliptical;
The cross section of the first target frame is oval, the first target frame is detachably arranged in the cavity, the outer wall surface of the first target frame can be attached to the cavity wall surface of the cavity, the first target frame is provided with a plurality of test points, and the centers of the plurality of test points are equidistantly arranged on the long axis of the oval;
the air inlet channel and the air outlet channel I are coaxially arranged and horizontally arranged at two ends of the base I, and the axes of the air inlet channel and the air outlet channel I are coincident with or parallel to the long axis of the ellipse; the air inlet channel is used for allowing helium carrier gas to flow into the cavity, and the air outlet channel I is used for allowing the helium carrier gas to flow out with sulfide aerosol particles;
MgF 2 the first glass is arranged above the first base and covers and seals the top opening of the cavity arranged on the first base;
a first top cover arranged on MgF 2 And a light-transmitting window is arranged above the first glass, and all the test points are positioned in the longitudinal projection area of the light-transmitting window at the center of the first top cover.
Further, the elliptic long axis of the cavity is 42mm, and the short axis is 15mm; the depth of the cavity is 13mm, and the diameters of the air inlet channel and the air outlet channel I are 3-5mm; the test point is round, and the radius is 4.5mm; the number of the test points is 4, and the gap between two adjacent test points is 0.5mm.
Further, the elliptical single sample cell also comprises a sealing ring, and the sealing ring is an elliptical sealing ring; the sealing ring comprises an elliptic sealing ring main body and an elliptic convex ring arranged on the elliptic sealing ring main body, the top surface of the first base and the bottom surface of the first top cover are both provided with grooves matched with the elliptic convex ring, the grooves are elliptic grooves, and the elliptic convex ring can be arranged in the elliptic grooves; top surface of base one and MgF 2 A first sealing ring is arranged between the first glass and the MgF 2 A second sealing ring is arranged between the first glass and the bottom surface of the first top cover;
further, the groove bottom area of the groove is larger than the notch area of the groove.
Further, the lower end face of the first top cover is also provided with a cylindrical side wall, the outer peripheral face of the top of the first base is provided with a yielding space for yielding the cylindrical side wall, the yielding space is provided with a transverse end face, the transverse end face is provided with a threaded hole, the cylindrical side wall can be sleeved and installed at the top of the first base, the cylindrical side wall is provided with a through hole in a penetrating way, and the first top cover is fixedly connected with the transverse end face of the first base by a screw; mgF (MgF) 2 The cross section size of the first glass, the cross section size of the elliptic sealing ring are matched with the size of the cylindrical side wall, and when the first top cover is buckled on MgF 2 After the first glass and the first base are arranged, the inner wall of the cylindrical side wall and MgF 2 The side peripheral wall surface of the first glass and the side peripheral surfaces of the upper sealing ring and the lower sealing ring are contacted.
Further, the air inlet channel is provided with a first gas inlet and a first gas outlet, the first gas inlet is connected with a helium source, and the first gas outlet is communicated with the cavity; the first gas outlet channel is provided with a second gas inlet and a second gas outlet, the second gas inlet is communicated with the cavity, and the second gas outlet is communicated with the first inlet of the reaction tube; the aperture of the air inlet channel gradually becomes larger from the first air inlet to the first air outlet; from the second gas inlet to the second gas outlet, the aperture of the first gas outlet channel is gradually reduced.
On the other hand, an in-situ analysis method of the sulfide sulfur isotope micro-region of the ultraviolet laser probe is provided, and the in-situ analysis system of the sulfide sulfur isotope micro-region of the ultraviolet laser probe is used; the analysis method comprises the following steps:
ablating sulfide aerosol particles from the sulfide-containing sample using a 193nm excimer laser;
carrying the degraded sulfide aerosol particles into trace SO by using He airflow 2 In the gas preparation device, SO-containing is obtained after high-temperature oxidation reaction 2 A gas mixture;
SO 2 SO-containing gas supplied by the gas collecting and purifying device 2 The gas mixture is enriched and purified twice to obtain the target SO 2 A gas;
target SO 2 The gas is carried by the back-blowing helium flow and enters a gas isotope ratio mass spectrometer through a micro-split interface for detection, and a test result is obtained.
Further, the method comprises the following steps: starting a testing instrument, firstly adjusting a first six-way valve to a load mode, adjusting a second six-way valve to an object mode, and immersing a first cold trap into a first liquid nitrogen barrel;
removing sulfide aerosol particles from sulfide-containing samples in a sample cell by using a 193nm excimer laser, carrying the sulfide aerosol particles removed by the laser into a reaction tube by He air flow with the flow speed of 150ml/min through a Teflon tube, and reacting to generate SO 2 After the gas, the target SO is contained 2 The mixed gas of the gases enters a first cold trap to be collected in a freezing way under the purging of He gas, thus completing the target SO 2 Primary enrichment and purification of gas;
then the first six-way valve is switched to an object mode, the second six-way valve is switched to a load mode, the first cold trap is lifted, and the second cold trap is lowered and immersed in the second liquid nitrogen barrel, or the second cold trap is immersed in the second liquid nitrogen barrel before the first cold trap is lowered and immersed in the second liquid nitrogen barrel; the first heating device is started, and the enriched SO is frozen in the first cold trap 2 Sublimating heated SO gas into gas, and sublimating the first cold trap with the first back-blowing helium gas flow through a first six-way valve 2 Carrying and cooling gasFreezing and enriching in a second cold trap to finish the target SO 2 Second enrichment and purification of gas;
after enrichment is completed in the second cold trap, the second six-way valve is switched to an object mode, a second heating device is started after the second cold trap is lifted, and enriched SO is frozen in the second cold trap 2 Sublimating into gas after heating, and enriching purified SO for the second time 2 The gas passes through a low flow rate channel of the miniature shunt interface under the carrying of the second back-blowing helium flow, and finally enters a gas isotope ratio mass spectrometer for detection, so that a test result is obtained;
the flow speed of the first back-blowing helium flow is 26mL/min, and the back-blowing duration time is 180s; the flow rate of the second back-blowing helium flow is 2.2-2.8mL/min.
Compared with the prior art, the ultraviolet laser probe sulfide isotope micro-region in-situ analysis system and method provided by the invention have at least one of the following beneficial effects:
a) Aiming at the two problems of incomplete reaction and reaction of a reagent and a matrix component which restrict the development of the conventional laser probe stable isotope micro-region in-situ analysis technology, the invention adopts a brand new design thought to simultaneously carry out in-situ sampling of the conventional laser probe micro-region and preparation of analysis gas, and changes the in-situ sequential completion into the in-situ sequential completion, thereby avoiding fractionation and influence caused by incomplete reaction and reaction of the reagent and the matrix component in the laser ablation-analysis gas preparation process. Aiming at fractionation generated in the process of infrared laser heating and ablation, ultraviolet laser ablation samples without obvious thermal effect and matrix effect are adopted, aerosol particles generated by ablation are uniform in size and high in transmission efficiency, and the fractionation generated in the process of laser ablation and transmission is avoided and reduced.
b) By adopting the elliptical sample cell without position effect and stable high transmission efficiency, the test points of all parts can be ensured to be influenced by the blowing flow rate identically, thereby effectively avoiding the position effect, ensuring that the degraded sulfide aerosol particles are transmitted to the gas preparation device with maximum efficiency by the small-volume design, and improving the sensitivity.
c) Preparation of analytical gas SO by classical methods 2 Trace SO is improved 2 Gas and its preparation methodThe preparation and enrichment purification device avoids fractionation generated by incomplete reaction, and the sensitivity of the method is greatly improved.
Drawings
In order to more clearly illustrate the embodiments of the present description or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the embodiments of the present description, and other drawings may be obtained according to these drawings for a person having ordinary skill in the art.
FIG. 1 is a schematic diagram of a structure of an in-situ analysis system for sulfide isotope microdomains of ultraviolet laser probes;
FIG. 2 is a schematic structural diagram of an ultraviolet laser ablation apparatus according to the present invention;
FIG. 3 is a schematic view illustrating the disassembly of an elliptical sample cell according to the present invention;
FIG. 4 is a schematic view of a target holder of an elliptical sample cell provided by the invention mounted in a base;
FIG. 5 shows SO provided by the present invention 2 A schematic structural diagram of the gas collection and purification device;
FIG. 6 shows SO provided by the present invention 2 The state schematic diagram of the first six-way valve and the second six-way valve of the gas collection and purification device in the primary enrichment mode;
FIG. 7 shows SO provided by the present invention 2 The state schematic diagram of the first six-way valve and the second six-way valve of the gas collection and purification device in the secondary enrichment mode;
FIG. 8 is a time-signal intensity diagram of a sulfur isotope test provided by the present invention;
FIG. 9 is a graph of calibration equations for three silver sulfide standards provided by the invention;
FIG. 10 is a schematic diagram of a prior art dual chamber sample cell;
FIG. 11 is a schematic diagram of a dual-chamber sample cell according to the present invention;
FIG. 12 is a schematic diagram of a second sample cell of the dual-chamber sample cell provided by the present invention;
FIG. 13 is a schematic view of a base structure of a second sample cell according to the present invention;
FIG. 14 is a top view of the top cover of the second sample cell provided by the present invention;
FIG. 15 is a bottom view of the top cover of the second sample cell provided by the present invention;
FIG. 16 is a schematic diagram of a first temperature-adjustable liquid nitrogen cold trap according to the present invention;
fig. 17 is a schematic structural diagram of a second temperature-adjustable liquid nitrogen cold trap according to the present invention.
Reference numerals:
100. an ultraviolet laser ablation device; 101. 193nm excimer laser; 102. a single sample cell; 1021. an air intake passage; 1022. an air outlet channel I; 1023. a first base; 1024. a chamber; 1025. a first top cover; 1026. MgF (MgF) 2 A first glass; 1027. a first target frame; 1028. a seal ring; 1029. a groove; 1030. testing the point positions; 103. a sample stage; 104. a camera; 105. a first sample cell; 1051. helium carrying gas circuit; 1052. a second target frame; 106', an existing second sample cell; 106. a second sample cell; 1061. an air outlet channel II; 1061a, a channel inlet; 1061b, a channel outlet; 1062. a second base; 1063. a cylindrical chamber; 1064. a second top cover; 1065. MgF (MgF) 2 A second glass; 1067. a third seal ring; 1068. a fourth seal ring; 1069', argon inlet line; 1070', an outlet line; 1070. a Teflon tube;
200. trace amount of SO 2 A gas preparation device; 201. a first inlet; 202. a second inlet; 203. a first outlet; 204. tungsten oxide particles; 205. reducing copper particles; 206. quartz cotton;
300、SO 2 A gas collection and purification device; 301. a first six-way valve; 302. a first cold trap; 303. a second six-way valve; 304. a second cold trap; 305. a first exhaust port; 306. a second exhaust port; 307. a first back-flushing helium flow; 308. a second back-flushing helium flow; 309. a first modified cold trap; 3091. a liquid nitrogen barrel; 3092. an outer tube; 3092a, nitrogen inlet; 3092b, nitrogen outlet; 3093. an inner tube; 3093a, an air inlet; 3093b, air outlet; 3094. sealing the space; 3095. An air supply pipe; 310. a second modified cold trap; 3101. a liquid nitrogen container; 3102. a cylinder; 3103. an exhaust valve; 3104. a U-shaped enrichment tube; 3105. a heating wire; 3106. a thermocouple; 3107. a temperature controller;
400. a miniature shunt interface;
500. a gas isotope ratio mass spectrometer;
600. and the double-path sample injection system.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
For the purpose of facilitating an understanding of the embodiments of the present application, reference will now be made to the following description of specific embodiments, taken in conjunction with the accompanying drawings, in which the embodiments are not intended to limit the embodiments of the present application.
In describing embodiments of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the term "coupled" should be interpreted broadly, for example, as being fixedly coupled, detachably coupled, integrally coupled, mechanically coupled, electrically coupled, directly coupled, or indirectly coupled via an intermediary. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Example 1
In one embodiment of the invention, as shown in FIG. 1, an in-situ analysis system for sulfide sulfur isotope microdomains of an ultraviolet laser probe is disclosed, which comprises an analysis gas path, wherein an ultraviolet laser ablation device 100 and a trace SO are sequentially arranged on the analysis gas path along the gas flow direction 2 Gas production apparatus 200, SO 2 Gas collection and purification device 300, micro split-flow interface 400 and gasA body isotope ratio mass spectrometer 500;
wherein, referring to fig. 2, the ultraviolet laser ablation device 100 has a 193nm excimer laser 101 and a sample cell for holding a sulfide-containing sample; 193nm excimer laser 101 is used to ablate sulfide aerosol particles from a sulfide-containing sample in a sample cell; trace amount of SO 2 The gas preparation apparatus 200 has a reaction tube into which sulfide aerosol particles enter with helium carrier gas and are mixed with O in the reaction tube 2 Iso-reaction to form SO 2 A gas; SO (SO) 2 The gas collection and purification device 300 is used for collecting and purifying SO in the mixed gas 2 Gas, via SO 2 Purified SO of gas collection and purification device 300 2 Gas is fed through micro-split interface 400 to gas isotope ratio mass spectrometer 500 for detection.
Unlike the conventional infrared laser heating system, the ultraviolet laser probe sulfide sulfur isotope micro-area in-situ analysis system of the embodiment adopts deep ultraviolet excimer laser, and the sulfide-containing mineral particles fly away from the surface of the sample through electronic excitation, so that the target sulfide mineral particles are degraded, the thermal effect of 193nm ultraviolet laser is small, no obvious matrix effect exists in the laser degrading process, and the size distribution of aerosol particles generated by laser degradation is uniform, the transmission efficiency is high, and the fractionation is small.
In this embodiment, the ultraviolet laser ablation apparatus 100 further includes a camera 104, and the camera 104 is used to observe and determine the position, shape and size of the sulfide to be ablated, so as to realize online real-time observation of the sample ablation process. The main body of the ultraviolet laser ablation device 100 can adopt a RESOUTION excimer ultraviolet laser ablation system produced by Australian ASI company, has the functions of fully-automatic sample collection and rapid laser parameter conversion, comprises rapid parameter conversion of test points, test time, frequency, beam spots, scanning modes and the like, can be suitable for single-point ablation, line scanning and surface scanning, and provides good conditions for different requirements. The software system is a GeoStar operation interface, and can realize that correct particles, phases or growing endless belts are selected on a computer screen for ablation; the method not only supports manual selection of the test points, but also can realize automatic operation after the test points are selected. The operation of gas flow speed adjustment, laser beam focal length (Z axis) ablation, laser energy correction and the like are realized through software.
Referring to FIG. 5, trace SO 2 The reaction tube of the gas preparation device 200 is provided with a first inlet 201, a second inlet 202 and a first outlet 203, wherein the first inlet 201 is communicated with the gas outlet channel of the sample cell for the inflow of helium gas flow carrying sulfide aerosol particles; the second inlet 202 is connected to an oxygen source for supplying O 2 A gas; helium carrier gas carries sulfide aerosol particles into the reaction tube from the first inlet 201, and O is fed in 2 The SO-containing gas is obtained after the high-temperature reaction 2 A mixture of gases; containing SO 2 The mixed gas of the gases flows out from the first outlet 203 and enters SO 2 The gas collection and purification apparatus 300.
Referring to fig. 6 to 7, so 2 The gas collecting and purifying apparatus 300 has a first collecting and purifying unit and a second collecting and purifying unit connected by a pipeline for separating SO in the mixture gas 2 Carrying out enrichment and purification on the gas twice; air inlet of first collection and purification assembly and trace SO 2 The outlet of the gas preparation device 200 is communicated, and the second collecting and purifying component is used for enriching and purifying the purified SO from the first collecting and purifying component 2 The gas is enriched and purified again, and the gas outlet of the second collecting and purifying component is connected with the gas isotope ratio mass spectrometer 500 through the micro-split-flow interface 400.
The sample cell matched with the existing solution excimer ultraviolet laser ablation system is a double-chamber sample cell, referring to fig. 10, the existing double-chamber sample cell comprises a first sample cell 105 and an existing second sample cell 106', the first sample cell 105 is positioned below the existing second sample cell 106', the first sample cell 105 is connected with a helium source through a helium carrier gas path 1051, a sample inlet is arranged at the bottom of the existing second sample cell 106', the sample inlet is communicated with the first sample cell 105, an argon inlet pipeline 1069' and an argon outlet pipeline 1070 'are arranged on the side wall of the existing second sample cell 106', the argon inlet pipeline 1069 'is used for supplying argon to the existing second sample cell 106', the air outlet pipeline 1070 'is communicated with a reaction tube, and helium gas flow containing sulfide aerosol particles enters the reaction tube through the air outlet pipeline 1070'. The first sample cell 105 is internally provided with a second target frame 1052, the second target frame 1052 can move along the X and Y axes, a plurality of sample targets to be degraded are placed on the second target frame 1052, a helium carrier gas path 1051 is communicated with the space of the second target frame 1052, the second target frame 1052 is moved to align a certain sample to be degraded with the second sample cell 106' during testing, sulfide aerosol particles are degraded from the sample to be degraded in the first sample cell 105 by using an excimer laser, the degraded sulfide aerosol particles are located in the first sample cell 105, helium gas is supplied into the first sample cell 105, and the degraded sulfide aerosol particles in the first sample cell 105 are purged and carried into the existing second sample cell 106' by using a helium gas flow, and flow out from the gas outlet pipeline 1070' into a reaction tube. However, the existing second sample cell 106 'of the dual-chamber sample cell structure needs two carrier gases of He and Ar during the test, and needs to purge the sulfide aerosol particles eroded in the first sample cell 105 into the existing second sample cell 106' by using a high-flow helium flow and an argon flow with a flow rate of more than 1000ml/min, wherein the Ar gas has 2 functions: (1) Ar gas is working gas in plasma, which must be provided, or else, the plasma cannot be formed, (2) Ar gas is heavier than He gas, he gas carries aerosol particles to flow from bottom to top, ar gas flows from top to bottom, and the Ar gas are mutually matched to enable the aerosol particles to be intensively blown out from the middle outlet of the second sample pool and enter the reaction tube, but the flow rate of He carrier gas of the laser ablation-gas isotope mass spectrometry stable isotope micro-area in-situ analysis system cannot exceed 200ml/min, so that high-flow helium gas does not meet the requirement of LA-IRMS stable isotope micro-area in-situ analysis, and the aerosol cannot be completely blown out when the flow rate of helium gas is reduced. Based on the above-mentioned problems, the sample cell of the analysis system of the present embodiment adopts the single sample cell 102, the single sample cell 102 is an elliptical sample cell, and degraded aerosol particles can be transferred to the gas preparation device with maximum efficiency by adopting a small carrier gas flow rate, so that the sensitivity is improved, and the position effect in the sample degradation process can be avoided. Referring to fig. 3 to 4, the single sample cell 102 includes:
Base one 1023, base one 1023 is provided with a chamber 1024, and the cross section of chamber 1024 is elliptical;
the cross section of the first target frame 1027 is oval, the first target frame 1027 is detachably arranged in the chamber 1024, the outer wall surface of the first target frame 1027 can be attached to the chamber wall surface of the chamber 1024, the first target frame 1027 is provided with a plurality of test points 1030, and the centers of the test points 1030 are equidistantly arranged on the long axis of the oval;
the air inlet channel 1021 and the air outlet channel 1022 are coaxially arranged, the air inlet channel 1021 and the air outlet channel 1022 are horizontally arranged at two ends of the base 1023, and the axes of the air inlet channel 1021 and the air outlet channel 1022 are coincident with or parallel to the long axis of the ellipse; the inlet passage 1021 supplies helium carrier gas to flow into the chamber 1024, and the outlet passage one 1022 supplies helium carrier gas to flow out with sulfide aerosol particles;
MgF 2 glass one 1026, locate above base one 1023, cover and seal the top opening of cavity 1024 locating in base one 1023;
a top cover 1025 arranged on MgF 2 Above the first glass 1026, a transparent window is provided in the center of the first top cap 1025, and all the test points 1030 are located in the longitudinal projection area of the transparent window.
In this embodiment, the single sample cell 102 is designed with a small volume, the elliptical major axis of the chamber 1024 is 42mm, and the minor axis is 15mm; the test points 1030 are circular, the number of the test points 1030 is 4, and the radius of the circular test points 1030 is 4.5mm; the gap between two adjacent test points 1030 is 0.5mm; the depth of the chamber 1024 is 13mm and the diameters of the inlet passage 1021 and the outlet passage one 1022 are 3-5mm.
During testing, 193nm excimer laser 101 ablates sulfide aerosol particles from sulfide-containing samples in single sample cell 102, he carrier gas is blown into chamber 1024 of the elliptical sample cell from air inlet channel 1021 at one end of the elliptical sample cell at a certain flow rate, and is blown out from air outlet channel one 1022 at the other end into a reaction tube; because the cross section shape of the chamber 1024 is elliptical, the gas flow is smoother, no dead angle exists, the aerosol blowing efficiency is high, the blowing efficiency of each test point 1030 is the same, so that the position effect is effectively avoided, the small-volume design can ensure that degraded aerosol particles are transmitted to the gas preparation device with the maximum efficiency by using the small carrier gas flow rate, and the sensitivity is improved.
In order to improve the tightness of the elliptical sample cell, the elliptical single sample cell 102 further comprises a sealing ring 1028, the sealing ring 1028 is an elliptical sealing ring, preferably a silicone rubber sealing ring, the cross section of the sealing ring 1028 is elliptical, the cross section of the sealing ring 1028 is of a T-shaped structure, and also can be understood that the sealing ring 1028 comprises an elliptical sealing ring main body and an elliptical convex ring arranged on the elliptical sealing ring main body, the top surface of the first base 1023 and the bottom surface of the first top cover 1025 are both provided with grooves 1029 matched with the elliptical convex ring, the grooves 1029 are elliptical grooves, the elliptical convex ring can be filled in the elliptical grooves, and the top surface of the first base 1023 and MgF are provided with grooves 1029 matched with the elliptical convex ring 2 A first sealing ring is arranged between the first 1026 pieces of glass, mgF 2 And a second sealing ring is arranged between the bottom surfaces of the first glass 1026 and the first top cover 1025, and the sealing cavity is sealed by using the two sealing rings 1028, so that the sealing performance is better.
Further, the oval convex ring has a trapezoid cross section, and correspondingly, the oval grooves on the top surface of the first base 1023 and the bottom surface of the first top cover 1025 have a trapezoid cross section, and the groove bottom area of the groove 1029 is larger than the notch area of the groove, and the structure enables the extrusion force between the oval convex ring and the side wall of the oval groove to be increased when the first top cover 1025 and the first base 1023 are fixedly locked, so that the tightness can be further improved, and MgF can be prevented 2 The glass breaks.
Furthermore, the lower end surface of the first top cover 1025 is further provided with a cylindrical side wall, the outer peripheral surface of the top of the first base 1023 is provided with a yielding space for yielding the cylindrical side wall, the yielding space is provided with a transverse end surface, the transverse end surface is provided with a threaded hole, the cylindrical side wall of the first top cover 1025 can be sleeved and installed at the top of the first base 1023, the cylindrical side wall of the first top cover 1025 is provided with a through hole in a penetrating manner, and the first top cover 1025 is fixedly connected with the transverse end surface of the first base 1023 by a screw; mgF (MgF) 2 The cross-sectional dimensions of glass one 1026, the oval seal, and the cylindrical side wall match, i.e., when the cap one 1025 is snapped onto the MgF 2 After the first glass 1026 and the first base 1023 are arranged, the inner wall of the cylindrical side wall and MgF 2 Glass 11026, and the side peripheral surfaces of the upper and lower seal rings. The above structure is arranged to make MgF 2 The first 1026 of glass and two upper and lower sealing washer all are located the tubular side wall of top cap one 1025, and a plurality of terminal surfaces of sealing washer all play sealed effect, so the leakproofness is better.
Further, the intake passage 1021 has a first gas inlet connected to a helium source and a first gas outlet in communication with the chamber 1024; the first outlet channel 1022 has a second gas inlet in communication with the chamber 1024 and a second gas outlet in communication with the first inlet 201 of the reaction tube. Wherein, from the first gas inlet to the first gas outlet, the aperture of the gas inlet channel 1021 is gradually increased; the pore size of the first outlet channel 1022 becomes smaller gradually from the second gas inlet to the second gas outlet. It can be also understood that the air inlet channel 1021 and the air outlet channel 1022 are both bell-mouthed, and the opening at one end communicated with the chamber 1024 is large, and the opening at the other end is small, so that helium carrier gas enters the chamber 1024 of the elliptical sample cell in a divergent mode when entering the chamber 1024 from the air inlet channel 1021, and flows into the chamber 1024 as close to the inner wall of the elliptical sample cell as possible, and gas in the chamber 1024 flows into the air outlet channel 1022 as close to the inner wall of the elliptical sample cell as possible, so that the purging blind area of the helium carrier gas can be further reduced, and the purging efficiency is improved.
In this embodiment, the single sample cell 102 is provided with the sample stage 103 in a matching manner, the single sample cell 102 is arranged on the sample stage 103 through a moving mechanism, the moving mechanism is controlled by a computer, the single sample cell 102 can linearly reciprocate along an X-Y axis through the moving mechanism, and the moving precision reaches 0.1um, so that the X and Y axes can rapidly and accurately perform full-automatic positioning on the sample, and the accurate positioning of sulfide targets at any positions in the sample to be degraded is facilitated.
In this example, trace SO 2 The outer diameter of the reaction tube of the gas preparation apparatus 200 is 12mm, the inner diameter is 10mm, the reaction tube is made of quartz glass, the heating temperature of the reaction tube is 1020 ℃, the upper space of the reaction tube forms the reaction space of the mixed gas, and as shown in FIG. 5, the lower space of the reaction tubeTungsten oxide particles 204 and reduced copper particles 205 are filled in the reaction chamber, the tungsten oxide particles and the reduced copper particles are separated by quartz wool 206, and quartz wool 206 can be arranged at the bottom outlet of the reaction tube to prevent the copper particles from entering the bottom outlet to block the gas path. Specifically, the filler is positioned at the lower half part of the reaction tube, and is 20mm tungsten oxide, 10mm quartz cotton, 170mm reduced copper particles and 10mm quartz cotton from top to bottom, and the positions of the tungsten oxide particles are positioned in a high-temperature area of the reaction tube. Wherein, the particle size of the tungsten oxide particles 204 is 0.85-1.7 mm, the reduced copper particles 205 are high-purity copper particles, and the particle size of the reduced copper particles 205 is 1.5-2.5mm, preferably 2mm. Filling with WO 3 Rather than V 2 O 5 Or Cr 2 O 3 The reason for the oxidizing agent is WO 3 More stable at the temperature of more than 1000 ℃ and ensures that the oxidation reaction is complete. The reaction tube adopting the structure can reduce dead volume and further reduce SO in the reaction tube 2 Gas residue; the adoption of the excessive high-purity reduction copper particles can avoid the mixing of other impurities, reduce the background, increase the contact surface area with the reaction gas by adopting the reduction copper particles 205 compared with copper wires, fully absorb the excessive oxygen gas and react the generated SO 3 Reduction to SO 2 Reduction of Cu to SO 3 The reaction is more complete; the quartz wool can lead the generated SO 2 Is homogenized by the oxygen isotope in (2).
In one of the alternative embodiments, the tungsten oxide particles include first particle size tungsten oxide particles having a particle size of 1.2 to 1.7mm and second particle size tungsten oxide particles having a particle size of 0.7 to 1.2mm; the reduced copper particles 205 include third-sized reduced copper particles having a particle size of 3 to 4mm and fourth-sized reduced copper particles having a particle size of 1.8 to 2.2mm. Tungsten oxide particles and reduced copper particles in the reaction tube are filled according to the following structure: the filling materials of the layers are 6-8mm, 10mm, 50-70mm, 10mm, 14-18mm, 10mm, 120-150mm and 10mm in thickness from top to bottom. According to the embodiment, coarse tungsten oxide particles, coarse reduction copper particles, fine tungsten oxide particles and fine reduction copper particles are sequentially filled in the reaction tube, the upper coarse tungsten oxide particles and the upper coarse reduction copper particles can buffer the degraded aerosol, the flow speed of the aerosol in the reaction tube is reduced, the aerosol subsequently enters the fine tungsten oxide particles and the fine reduction copper particles to be instantaneously combusted, and the reaction is more complete.
In this embodiment, SO 2 The gas collection and purification device 300 is positioned in trace SO 2 The gas preparation device 200 and the micro split-flow interface 400 comprise two six-way valves and two liquid nitrogen cold traps. Specifically, as shown in fig. 6 and 7, the first collection and purification assembly includes a first six-way valve 301 and a first cold trap 302, and the second collection and purification assembly has a second six-way valve 303 and a second cold trap 304; the air inlet valve port of the first six-way valve 301 is communicated with the first outlet 203 of the reaction tube, the air outlet valve port of the first six-way valve 301 is communicated with the air inlet valve port of the second six-way valve 303, and the air outlet valve port of the second six-way valve 303 is connected with the micro diversion interface 400 through a Teflon tube; two valve ports of the first six-way valve 301 are connected to two open ends of the first cold trap 302, and two valve ports of the second six-way valve 303 are connected to two open ends of the second cold trap 304.
Due to SO 2 Is easily adsorbed on the inner wall of the pipeline at room temperature, and influences the test result. In one alternative embodiment, first cold trap 302 comprises a U-shaped Teflon tube with an outer diameter of 4mm, an inner diameter of 2mm and a length of 60cm, and first cold trap 302 is filled with nickel wires to increase the contact area to avoid SO generation 2 Loss of gas. The second cold trap 304 comprises a U-shaped quartz capillary and a protective sleeve sleeved outside the U-shaped quartz capillary, wherein the protective sleeve is used for fixing and supporting the quartz capillary, the inner diameter of the U-shaped quartz capillary is 0.32mm, the length of the U-shaped quartz capillary is 60cm, the wall thickness of the quartz capillary is very thin, and the outer diameter of the U-shaped quartz capillary is slightly larger than the inner diameter of the U-shaped quartz capillary. The first cold trap 302 is provided with a first liquid nitrogen barrel and the second cold trap 304 is provided with a second liquid nitrogen barrel. Preferably, the protective sleeve sleeved outside the quartz capillary tube is a stainless steel tube, and the stainless steel tube conducts heat quickly. The materials of the first cold trap 302 and the second cold trap 304 in this embodiment are not easy to adsorb SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The second cold trap 304 adopts a U-shaped quartz capillary with a thin inner diameter for better enrichment of SO 2 Second cold trap 304 is liftedPost-production enriched SO 2 The gas isotope mass spectrometry ion source can be used in a concentrated time period, so that the signal intensity is higher, and tail removal is avoided.
Further, the first cold trap 302 and the second cold trap 304 further comprise heating means for heating the cold traps to rapidly defrost and release SO 2 . In one alternative embodiment, the first cold trap 302 is provided with a first heating device, the second cold trap 304 is provided with a second heating device, the first heating device and the second heating device both comprise a resistance wire and a heating power supply, the resistance wire is wound on a U-shaped Teflon tube of the first cold trap 302 and a stainless steel tube of the second cold trap 304, the length of the resistance wire is 300cm, the resistance is 24 omega, the heating power supply is an 18V direct current power supply, and the resistance wire is used for heating to enable the cold trap to quickly defreeze and release SO 2 。
In this embodiment, the first six-way valve 301 and the second six-way valve 303 have two modes, i.e. an input mode and a load mode, and the free switching of the two modes is realized by switching the communication between the valve ports, as shown in fig. 6 and 7, respectively, are SO 2 The gas collection and purification device is schematically shown in two states of the first six-way valve 301 and the second six-way valve 303 in the primary enrichment mode and the secondary enrichment mode.
As shown in FIG. 6, the first collection and purification module pair SO 2 In the primary enrichment and purification process, the first six-way valve 301 is in load mode, the second six-way valve 303 is in object mode, and in the process, the gas in the first six-way valve 301 does not enter the second six-way valve 303 and is in trace SO 2 SO-containing gas produced by the gas production apparatus 200 2 The mixed gas enters a first cold trap 302 from a first six-way valve 301, so 2 The gas is frozen in the first cold trap 302, and other impurity gases are discharged from the first exhaust gas valve port 305 of the first six-way valve 301;
as shown in FIG. 7, the second collection and purification module pair SO 2 In the second enrichment and purification process, the first six-way valve 301 is in an input mode, the second six-way valve 303 is in a load mode, the first cold trap 302 is taken out of liquid nitrogen, the frozen solid in the first cold trap 302 is sublimated into gas by using the first heating device, and the sublimated gas is carried by the first back-flushing helium gas flow 307 to flow into the air inlet of the second six-way valve 303Valve port, SO 2 Is frozen in a second cold trap 304 for SO 2 The second enrichment and purification are carried out, and the waste gas is discharged from a second waste gas discharge valve port 306 of the second six-way valve 303.
Completion of SO 2 After the second enrichment and purification, the second cold trap 304 is taken out of the liquid nitrogen, and the frozen solid in the second cold trap 304 is sublimated into gas by a second heating device, SO that the sublimated SO 2 The gas is carried by the second flow of back-flushed helium gas 308 into the micro-split interface 400 and further into the gas isotope ratio mass spectrometer 500 for testing.
In this embodiment, the micro-diversion interface 400 is a low flow channel with a flow rate of 1ml/min. Alternatively, the micro-split interface 400 employs a ConflloIV interface manufactured by ThermoFisher, inc. of America.
In this embodiment, the gas isotope ratio mass spectrometer 500 may be a MAT-253 type gas source isotope ratio mass spectrometer manufactured by ThermoFisher corporation of America, with a Faraday cup set to 3×10 8 Omega high resistance receive 64 (SO) 2 ) Signals, 3×10 10 Omega high resistance receiver 66 (SO) 2 ) A signal.
The embodiment also discloses an in-situ analysis method for the sulfur isotope microdomains of the sulfide by using the in-situ analysis system for the sulfur isotope microdomains of the sulfide by using the ultraviolet laser probe, a time sequence table of a measurement program is shown in fig. 8, and the analysis method comprises the following steps:
ablating sulfide aerosol particles from the sulfide-containing sample using 193nm excimer laser 101;
carrying the degraded sulfide aerosol particles into trace SO by using He airflow 2 In the gas preparation device 200, SO-containing gas is obtained after high-temperature oxidation reaction 2 A gas mixture;
SO 2 The gas collection and purification device 300 is used for supplying SO-containing gas 2 The gas mixture is enriched and purified twice to obtain the target SO 2 A gas;
target SO 2 The gas enters the gas isotope ratio mass spectrometer 500 through the micro-split interface 400 under the carrying of the back-blowing helium gas flow, and the test result is obtained.
The detailed test steps of the ultraviolet laser probe sulfide sulfur isotope micro-area in-situ analysis method are as follows:
(1) Starting the testing instrument, firstly adjusting the first six-way valve 301 to a load mode, adjusting the second six-way valve 303 to an object mode, immersing the first cold trap 302 into a first liquid nitrogen barrel, and at the moment, obtaining the purity in the laboratory steel bottle>99.999% SO 2 The gas enters an ion source through a mass spectrometer double-way sample injection system 600 to be used as reference gas for sulfur isotope test, and meanwhile, the condition parameters of the beam spot diameter of 80 mu m and the denudation time of 30s are selected for single-point denudation.
(2) Sulfide aerosol particles are stripped from sulfide-containing samples in a single sample cell 102 by using a 193nm excimer laser 101, the sulfide aerosol particles stripped by the laser are carried into a reaction tube by He air flow with the flow speed of 150ml/min through a Teflon tube, and SO is generated by high-temperature combustion of the sulfide aerosol particles in an oxygen-injected atmosphere 3 And SO 2 The reaction temperature in the reaction tube is 1020 ℃, the oxygen injection time is 40s, and the flow rate is 20mL/min; SO (SO) 3 Complete reduction to SO by copper particles 2 After the gas, the target SO is contained 2 The mixed gas of the gases enters a first cold trap 302 to be collected under the purging of He gas, the collection time in the first cold trap 302 is 300s, and the target SO is completed 2 And (5) primary enrichment and purification of gas.
(3) Then the first six-way valve 301 is switched to the object mode, the second six-way valve 303 is switched to the load mode, the first cold trap 302 is lifted, the second cold trap 304 is lowered and immersed in the second liquid nitrogen barrel, or the second cold trap 304 is immersed in the second liquid nitrogen barrel before that; the first heating device is activated and the enriched SO is frozen in the first cold trap 302 2 The heated sublimated SO gas is sublimated into gas, and the first path of back-blowing helium gas flow 307 passes through the first six-way valve 301 to sublimate the SO gas in the first cold trap 302 2 The gas is carried and frozen and enriched in the second cold trap 304 to complete the target SO 2 And (3) enriching and purifying the gas for the second time.
(4) Completing the target SO in the second cold trap 304 2 After the second enrichment and purification of the gas, the second six-way valve 303 is switched to an object mode, the second heating device is started after the second cold trap 304 is lifted, the secondFreezing enriched SO in cold trap 304 2 Sublimating into gas by heating SO 2 The gas is carried by the second flow of back-flushing helium 308 through the low flow channel (LF) of the micro-split interface 400 and finally enters the gas isotope ratio mass spectrometer 500 for detection, resulting in a test result.
Preferably, the flow rate of the first back-flushing helium flow 307 is 26mL/min and the back-flushing duration is 180s; the flow rate of the second flow of back-flushing helium stream 308 is 2.2-2.8mL/min. It is generally believed that the smaller the flow rate of the second flow of back-flushed helium, the less SO 2 The higher the utilization, the higher the method sensitivity, but not lower than 0.3mL/min of flow rate into the ion source. However, during the actual test, if the flow rate of the second back-blowing helium flow is too low, it is found that the second back-blowing helium flow is unfavorable for raising SO 2 The utilization rate and sensitivity are also reduced, which is due to: the shunt interface is open and is communicated with the atmosphere, and the background is raised due to the too low flow rate, SO that the SO is caused 2 Dispersing, which is unfavorable for the promotion of SO 2 The utilization of (c) may lead to a decrease in the analysis accuracy. Through a large amount of experimental data, it is verified that the flow rate of the second back-blowing helium flow 308 is 2.2-2.8mL/min, preferably 2.5mL/min, as the optimal parameter, under which SO is generated 2 The utilization rate and the test precision of the test result are both optimal.
Because the laser ablation system, the element analyzer and the mass spectrometer are all signal emitting devices at present and can not receive signals to finish instructions, full-automatic sample measurement is challenged. Based on the above, the embodiment completes the coordination of laser ablation, micro shunt interface start and sample sulfur isotope mass spectrometry according to the time difference, realizes automatic online analysis, namely the laser ablation system sets 870s waiting time after each ablation task is completed, and simultaneously prolongs 300s to effectively reduce SO 2 Memory effect of gas, overall mass spectrometry process about 900s, refer to fig. 8.
In order to verify that the invention can meet the analysis requirement of sulfide sample micro-region in-situ sulfur isotopes, and the test result reaches the international advanced level, three sulfide standard substances are tested by using the ultraviolet laser probe sulfide sulfur isotope micro-region in-situ analysis system and method of the embodiment. By using193nm ultraviolet laser, three silver sulfide standard substances IAEA-S-3, GBW04414, GBW04415 (Ag) under single point ablation condition with beam spot diameter of 80 μm and ablation time of 30S 2 S powder, delta 34 S v-CDT The sulfur isotope test results with the values of-32.3 per mill, -0.07 per mill and 22.15 per mill are shown in table 1, and the deviation value of the test results of three standard substances is 0.26 per mill to 0.5 per mill (1 sigma).
Table 1 test results of three silver sulfide standard substances
FIG. 9 is a graph of three silver sulfide standard substance correction equations using delta of three standard substances, respectively 34 S vs.ref Value (measurement value) and delta 34 S VCDT Fitting the values (true values) to obtain:
δ 34 S vs.ref ＝1.1768δ 34 S V-CDT -4.6501，R 2 ＝0.9996
the slope 1.1768 of the correction equation is close to 1, the correlation coefficient is more than 3 pieces of 9 pieces (0.9996), and the linear relation is good, so that the analysis result is stable and reliable. Correction values (delta) of three standard substances 34 S corrected ) The table 2 shows that the deviation between the correction value of the tested standard substance and the true value is less than 0.36 per mill, the analysis precision and the spatial resolution are completely consistent within the error range, compared with the traditional laser probe, the method achieves the advanced level of the international similar laboratory, can meet the in-situ high-precision, high-resolution and high-efficiency test of the sulfur isotope micro-area of the sulfide sample, and can promote the upgrading and updating of the traditional sulfur isotope analysis technology.
TABLE 2 correction results of sulfur isotope composition of three silver sulfide standard substances
| Standard substance | δ 34 S corrected (‰) | δ 34 S V-CDT (‰) |
| IAEA-S-3 | -32.03±0.58 | -32.3 |
| GBW04414 | -0.07±0.40 | -0.07 |
| GBW04415 | 22.51±0.31 | 22.15 |
By testing three silver sulfide standards, the best parameters for sulfide removal and oxidation reactions using 193nm ultraviolet laser were determined to be: helium flow rate 150ml/min, single point ablation diameter 80 μm, ablation time 30s, oxygen injection time 40s. Standard sample 66 SO 2 The signal intensity was 5000mV, the background was stable below 200mV (negligible effect on test results). For pyrite standard, a 38 μm denuded diameter was used, 66 SO 2 the signal intensity of the obtained product reaches 4000-5000 mV.
Compared with the prior art, the ultraviolet laser probe sulfide sulfur isotope micro-region in-situ analysis system and method provided by the embodiment can at least realize one of the following beneficial effects:
1. aiming at the key problems restricting the development of the conventional laser probe stable isotope micro-area in-situ analysis technology, the LA-IRMS sulfide sulfur isotope micro-area in-situ analysis system adopts a brand new design thought, and performs the conventional laser probe micro-area in-situ sampling and analysis gas preparation in situ simultaneously, so that the in-situ sequential completion is changed into the in-situ sequential completion, the fractionation caused by incomplete reaction and the reaction of the reagent and the matrix component is avoided, the system background is reduced, and the precision and the accuracy of the analysis method are improved. Aiming at fractionation generated in the process of infrared laser heating and ablation, ultraviolet excimer laser without obvious thermal effect and matrix effect is adopted to ablate a sample, aerosol particles generated by ablation are uniform in size and high in transmission efficiency, and the fractionation generated in the process of laser ablation and transmission is avoided and reduced.
2. Elliptical sample cell without position effect and high transmission efficiency, small diameter combustion reaction tube and trace SO 2 The purification and enrichment device and the special interface optimize helium flow parameters of each link, thereby greatly improving SO 2 The spatial resolution of pyrite reaches 38 μm.
Example 2
In still another embodiment of the present invention, a dual-chamber sample cell specifically for stable isotope micro-area in-situ analysis is disclosed, which is different from the dual-chamber sample cell of the existing solution excimer ultraviolet laser ablation system in that the second sample cell 106 adopted in this embodiment has a different structure from the existing second sample cell 106', and in this embodiment, the volume of the second sample cell 106 is smaller, and the blowing efficiency of the laser ablation aerosol is higher under the condition of low flow rate. The dual chamber cuvette of this embodiment may replace the oval cuvette of embodiment 1.
Specifically, as shown in fig. 11 to 15, the dual-chamber sample cell of the present embodiment includes:
the first sample cell 105, the first sample cell 105 is connected with helium source through helium carrier gas path 1051, the first sample cell 105 is provided with movable target frame two 1052, the target frame two 1052 can move along X and Y axes, the stepping resolution is <1 μm; the second target frame 1052 is used for placing a plurality of sample targets to be degraded, and can be used for placing sample targets with different sizes and shapes, so that the sample targets do not need to be replaced frequently, and the working efficiency is improved;
A second sample cell 106, the second sample cell 106 is positioned above the first sample cell 105, the second sample cell 106 is provided with a cylindrical cavity 1063, two ends of the cylindrical cavity 1063 are opened, and the bottom end opening of the cylindrical cavity 1063 is a sample inletThe sample inlet is communicated with the inner space of the first sample pool 105, and the top opening of the cylindrical cavity 1063 is hermetically provided with MgF 2 Glass two 1065; the second sample cell 106 is provided with a second air outlet channel 1061, an argon inlet pipeline 1069' for argon to enter is not arranged, the second air outlet channel 1061 is obliquely upwards arranged, the second air outlet channel 1061 is provided with a channel inlet 1061a and a channel outlet 1061b, the channel inlet 1061a is positioned on the inner wall of the cylindrical chamber 1063 and communicated with the cylindrical chamber 1063, the channel outlet 1061b is positioned on the top end surface of the second base 1062, the channel outlet 1061b is connected with the Teflon tube 1070, and the channel outlet 1061b is communicated with the first inlet 201 of the reaction tube through the Teflon tube 1070.
Further, the inclination angle of the second air outlet channel 1061 is 40-50 °, which indicates the included angle between the axis of the second air outlet channel 1061 and the axis of the cylindrical chamber 1063, the second air outlet channel 1061 is bell-mouth-shaped, the diameter of the channel inlet 1061a is larger than that of the channel outlet 1061b, the channel inlet 1061a is uniformly variable-diameter from the channel outlet 1061b to the channel outlet 1061a, the diameter of the channel outlet 1061b is 2mm, the diameter of the channel inlet 1061a is 4mm, and the second air outlet channel 1061 with bell-mouth-shaped structure can make the purged aerosol particles blow out of the sample cell more easily.
In this embodiment, the second sample cell 106 includes a second base 1062 and MgF 2 A second glass 1065 and a second top cover 1064, a cylindrical chamber 1063 disposed within the second base 1062, mgF 2 The second glass 1065 is fixed on the top end surface of the second base 1062 through the second top cover 1064, mgF 2 The second glass 1065 can completely transmit 193nm ultraviolet light, the second base 1062 is made of aluminum alloy, the inner wall of the cylindrical cavity 1063 is smooth, and the degraded aerosol particles can be ensured to be completely blown out of the second sample cell 106, so that the influence of the residue of the degraded sample on the next test result is effectively avoided.
In this embodiment, the diameter of the cylindrical chamber 1063 of the second sample cell 106 is 4mm, and the volume of the cylindrical chamber 1063 of the second sample cell 106 is 0.15ml, so that the dead volume can be reduced, and the sample transfer efficiency can be effectively increased. The distance between the bottom opening of the cylindrical chamber 1063 and the top surface of the sample target is reduced from-2 mm to-1 mm, further improving the blowing efficiency of aerosol particles.
In the present embodiment，MgF 2 A third sealing ring 1067 is arranged between the second glass 1065 and the second base 1062, the third sealing ring 1067 is a circular sealing ring, the top surface of the second base 1062 is provided with a first circular groove, and the third sealing ring 1067 is arranged in the first circular groove; the second top cover 1064 is fixedly connected with the second base 1062 through a bolt, a containing groove is formed in the lower end face of the second top cover 1064, and MgF is arranged on the lower end face of the second top cover 2 The diameter of the second glass 1065 is smaller than the diameter of the accommodating groove, and MgF is formed when the second top cover 1064 is fixed on the second base 1062 2 The second glass 1065 is secured within the receiving slot of the second top cover 1064. Alternatively, mgF 2 A sealing ring is also arranged between the second glass 1065 and the bottom of the accommodating groove of the second top cover 1064 so as to further improve the sealing performance and prevent MgF 2 Glass two 1065 is crushed.
Further, a mounting groove is formed in the top end surface of the first sample cell 105, a top sample outlet of the first sample cell 105 is formed in the bottom surface of the mounting groove, the second sample cell 106 is mounted in the mounting groove of the first sample cell 105, the outer contour of a second base 1062 of the second sample cell 106 is matched with the shape of the groove wall of the mounting groove, and a bottom sample inlet of the cylindrical cavity 1063 is aligned and communicated with the sample outlet of the first sample cell 105; in order to improve the tightness, the installation groove of the first sample tank 105 is a stepped groove, the lower diameter of the installation groove is small, the upper diameter of the installation groove is large, the installation groove is provided with an upward stepped end face, correspondingly, the lower diameter of the second base 1062 of the second sample tank 106 is small, the upper diameter of the installation groove is large, the installation groove is provided with a downward stepped end face, a fourth sealing ring 1068 is installed between the stepped end face of the installation groove of the first sample tank 105 and the stepped end face of the second base 1062, and optionally, a second circular groove is arranged on the stepped end face of the second base 1062, and the fourth sealing ring 1068 is installed in the second circular groove.
Compared with the prior art, the double-chamber sample cell provided by the embodiment adopts a micro-volume straight-through design, the chamber of the second sample cell is in a horn shape with a large upper part and a small lower part, and the structure of a step at the middle outlet is obviously different from that of the original chamber of the second sample cell, the diameter, the height and the volume of the inner chamber of the second sample cell are reduced, the diameter is reduced from 30mm to 4mm, the height is reduced from 40mm to 12mm, the volume is reduced from about 35ml to 0.15ml, the distance between the bottom end of the second sample cell and the top surface of a sample target is reduced from 2mm to 1mm, the carrier gas is changed from 2 paths to 1 path, ar carrier gas is removed, the inclination angle of an air outlet channel II is 40-50 degrees, the structural design ensures that the flow rate of the He carrier gas is reduced from above original 1000ml/min to about 150ml/min, the degraded aerosol sample can be rapidly taken away from the sample chamber of the second sample cell into a reaction tube, and the requirements of micro-IRMS stable isotope area in-situ analysis are met.
Example 3
In yet another embodiment of the present invention, a first modified cold trap 309, particularly a temperature adjustable liquid nitrogen cold trap, is disclosed, which may replace the first cold trap 302 and/or the second cold trap 304 of embodiment 1. Specifically, as shown in fig. 16, the temperature-adjustable liquid nitrogen cold trap includes a liquid nitrogen barrel 3091, and an outer tube 3092 and an inner tube 3093 which are sleeved; wherein, the containing space in the liquid nitrogen barrel 3091 is a first freezing space, the inner space of the outer tube 3092 is a second freezing space, and the inner space of the inner tube 3093 is a third freezing space; wherein the first cryogen space is configured to hold a first cryogen medium; the second cryogen space is disposed within the first cryogen space and configured to receive a second cryogen medium, and the third cryogen space is disposed within the second cryogen space and configured to pass a gas mixture comprising a target gas. The temperature of the second freezing medium is higher than that of the first freezing medium, the first freezing medium is liquid nitrogen, the temperature of the liquid nitrogen is-196 ℃, and the second freezing medium is normal-temperature nitrogen.
Specifically, the outer tube 3092 and the inner tube 3093 are both U-shaped tubes, a sealed space 3094 is formed between the inner wall of the outer tube 3092 and the outer wall of the inner tube 3093, the tube orifice of the outer tube 3092 is connected with the outer wall of the inner tube 3093 in a sealing manner, and the two end tube orifices of the inner tube 3093 extend out of the two end tube orifices of the outer tube 3092; wherein, the side wall of the outer tube 3092 is provided with a nitrogen inlet 3092a and a nitrogen outlet 3092b which are communicated with the sealed space 3094, and the nitrogen provided by the nitrogen source flows into the sealed space 3094 from the nitrogen inlet 3092a and flows out from the nitrogen outlet 3092 b; one end of the inner tube 3093 is provided with an air inlet 3093a, the other end is provided with an air outlet 3093b, the air inlet 3093a is used for flowing in mixed gas containing target gas, the air outlet 3093b is connected with a downstream test gas path, unfrozen gas flows out from the air outlet 3093b, and gas obtained by sublimating frozen solid after being heated flows out from the air outlet 3093 b.
If the adjustable liquid nitrogen cold trap of the embodiment replaces the first cold trap 302, the air inlet 3093a and the air outlet 3093b of the adjustable liquid nitrogen cold trap are two open ends of the first cold trap 302; if the second cold trap 304 is replaced, the inlet 3093a and outlet 3093b of the temperature-adjustable liquid nitrogen cold trap are the two open ends of the second cold trap 304.
In this embodiment, the temperature-adjustable liquid nitrogen cold trap further includes a nitrogen source connected to the nitrogen inlet 3092a of the second cryogen space through a gas supply tube 3095. Optionally, the nitrogen temperature that the nitrogen gas source provided is normal atmospheric temperature, and in the use was arranged nitrogen gas air supply line 5 coiled part in liquid nitrogen, make normal atmospheric temperature nitrogen cooling to need not to additionally set up thermal power and just can realize adjusting the freezing temperature in the second freezing space, can realize freezing the sublimation that is heated of solid.
In one alternative embodiment, the air supply pipe 3095 is provided with a flow valve, and the flow valve can control the flow rate and the flow velocity of nitrogen in the air supply pipe 3095 according to the pipe diameters of the inner pipe 3093 and the outer pipe 3092, and simultaneously, the temperature of the nitrogen in the air supply pipe 3095 is controlled in a matched manner, so that the freezing temperature in the second freezing space is accurately, continuously and dynamically adjusted, namely the temperature in the third freezing space is adjusted, the temperature adjusting range is-90 ℃ to-160 ℃, and the adjusting precision is not higher than 1 ℃, thereby meeting the purpose of accurate temperature adjustment.
In one alternative embodiment, at least a portion of the gas supply tube 3095 is located within the liquid nitrogen of the first cryogen space. If the gas supply pipe 3095 with the length of at least about 60cm is immersed in a liquid nitrogen barrel with the temperature of minus 196 ℃, the gas supply pipe 3095 is in contact refrigeration with liquid nitrogen, nitrogen with the temperature reduced is supplied into a sealed space 3094 between the outer pipe 3092 and the inner pipe 3093 through a nitrogen inlet 3092a and flows out from a nitrogen outlet 3092b, liquid nitrogen medium in the first freezing space and the supplied low-temperature nitrogen jointly cool the inner pipe 3093, so that target gas is frozen in the inner pipe 3093, in the process, the supplied nitrogen plays a role of heating, and the freezing temperature is more stable by immersing part of the gas supply pipe into the liquid nitrogen to reduce the heating speed. In this embodiment, a part of the gas supply pipe 3095 is placed in liquid nitrogen, and the nitrogen flowing in the gas supply pipe 3095 is cooled by using the liquid nitrogen, so that the temperature difference between the nitrogen temperature and the set target temperature is reduced, and the low-temperature of the third freezing space is more stable.
Further, the air supply pipe 3095 is a hose, the air supply pipe 3095 is coiled in the first freezing space, the coiling part is positioned in the liquid nitrogen, the cooling time of the nitrogen in the air supply pipe 3095 can be prolonged, the temperature of the nitrogen fed into the second freezing space can reach a lower target temperature, and the temperature of the low-temperature nitrogen fed into the second freezing space can be kept consistent.
In this embodiment, the pipe diameter of the outer pipe 3092 is 20-40mm, the pipe diameter of the inner pipe 3093 is 5-7mm, and the pipe diameter of the air supply pipe 3095 is 2-3mm. For example, the tube diameter of the inner tube 3093 is 6.35mm and the tube diameter of the gas supply tube 3095 is 1.6mm.
In one alternative embodiment, the plurality of annular plenums are of different volumes, each of which is independent and non-contiguous. The inner wall spacing between two adjacent second freezing spaces is sequentially reduced from outside to inside. Through the volume differentiation setting with a plurality of annular ventilation spaces, and increase in proper order between the inner wall in annular ventilation space from inside to outside, the annular ventilation space that is close to more is narrower, is more sensitive by its inside nitrogen gas temperature, velocity of flow, flow influence, consequently, can promote the accurate regulation to the freezing temperature in the third freezing space through adjusting nitrogen gas temperature, velocity of flow, the flow in annular ventilation space from outside to inside in proper order, further promotes temperature control precision.
In one alternative embodiment, a first temperature sensor is provided on the outer wall of the inner tube 3093 for monitoring the temperature within the inner tube 3093 in real time.
In practice, nitrogen at normal temperature is supplied into a sealed space 3094 between an outer tube 3092 and an inner tube 3093 by a nitrogen source, because a part of an air supply tube 3095 is positioned in liquid nitrogen, the nitrogen is cooled by the liquid nitrogen before being supplied into the sealed space 3094, the flow rate of the nitrogen in the air supply tube 3095 is controlled by adjusting a flow valve, and the nitrogen supplied into the sealed annular space 3094 can be maintained at a specific temperature in cooperation with the temperature of the nitrogen, so that a freezing environment for the inner tube 3093 is formed; the mixed gas containing the target gas enters the inner tube 3093 through the gas inlet 3093a, and the target gas is frozen in the bottom of the inner tube 3093 while the mixed gas flows through the inner tube 3093 because the inner tube 3093 is in the low-temperature environment of the sealed space 3094, and the remaining non-target gas flows out through the gas outlet 3093 b. When it is desired to sublimate the solid material into a gaseous state, the outer tube 3092, the inner tube 3093 and the gas supply tube 3095 are taken out of the liquid nitrogen barrel and placed in air, and sublimated into a gaseous state at room temperature, or the flow rate of nitrogen in the gas supply tube 3095 is adjusted by a flow valve, and the temperature of the cold trap is raised to sublimate into a gaseous state.
Compared with the prior art, the adjustable temperature liquid nitrogen cold trap that this embodiment provided, outer tube and inner tube including liquid nitrogen bucket and cover are established, form sealed space between inner tube and the outer tube, nitrogen in the liquid nitrogen bucket carries out the direct cooling to nitrogen gas in the air supply pipe and sealed space, low temperature nitrogen in the annular space freezes the gaseous mixture in the inner tube, and through adjusting the nitrogen flow rate, the realization freezes the sublimation of being heated of solid moreover, but the structure of adjustable temperature liquid nitrogen cold trap is simple, and convenient operation, with low costs can realize unmanned on duty moreover. Can be based on the target gas SO 2 And the difference of the freezing temperature of the impurity gas and the temperature of the adjustable liquid nitrogen cold trap is accurately set, so that the impurity gas is more effectively separated and the target gas is purified.
Example 4
In yet another embodiment of the present invention, a second modified cold trap 310, specifically a temperature adjustable liquid nitrogen cold trap, is disclosed that may replace the first cold trap 302 and/or the second cold trap 304 of embodiment 1. Specifically, as shown in fig. 17, the temperature-adjustable liquid nitrogen cold trap includes:
The U-shaped enrichment tube 3104, the U-shaped enrichment tube 3104 is provided with an air inlet and an air outlet, a U-shaped enrichment section is arranged between the air inlet and the air outlet, the U-shaped enrichment section passes through the closed end of the cylinder body and is arranged in the inner space of the cylinder body, at least one part of the U-shaped enrichment section can be positioned in liquid nitrogen, the air inlet and the air outlet are positioned outside the cylinder body, the air inlet is used for inflow of mixed gas containing target gas, and the air outlet is used for outflow of impurity gas in the freezing process and target gas after freezing enrichment purification; the U-shaped enrichment section is wound with a heating wire 3105, the heating wire 3105 is a nichrome heating wire, and the heating wire 3105 is used for heating the U-shaped enrichment section; the U-shaped enrichment section is also provided with a thermocouple 3106 for monitoring the temperature of the U-shaped enrichment section;
the temperature controller 3107 is electrically connected to the heating wire 3105 and the thermocouple 3106, and is capable of controlling the heating temperature and time of the heating wire 3105 based on temperature information monitored by the thermocouple 3106.
In this embodiment, the open end of the cylinder 3102 is provided with a reduced diameter, the diameter of the opening of the cylinder 3102 is smaller than the diameter of the main body of the cylinder 3102, and the diameter of the main body of the cylinder 3102 is the same as the diameter of the closed end of the cylinder 3102.
In this embodiment, the cylinder 3102 is made of teflon material, the wall of the cylinder 3102 has a certain thickness, preferably, the thickness of the wall of the cylinder 3102 is 3-5cm, and the heat transfer between the inside and the outside of the cylinder 3102 can be reduced as much as possible by the thickness of the cylinder 3102, so that the liquid nitrogen outside the cylinder 3102 is prevented from being sublimated by heating.
In this embodiment, the U-shaped enrichment tube 3104 has an outer diameter of 1.5mm, an inner diameter of 1.0mm, and a length of 20cm, and may be made of stainless steel tube or quartz glass tube, which may be specifically selected according to practical needs.
In one alternative embodiment, the heating wire 3105 is wound on a U-shaped enrichment section, the U-shaped enrichment section including parallel first and second vertical sections and an arc section connecting the first and second vertical sections, the winding density of the heating wire 3105 on the arc section being greater than the winding density of the heating wire 3105 on the first and second vertical sections. The structure is arranged in such a way that the frozen matters frozen in the U-shaped enrichment section are also in a U shape, and the frozen matters are mainly concentrated in the arc-shaped section of the U-shaped enrichment section, so that the frozen matters in each part of the U-shaped enrichment section can be sublimated rapidly by winding the heating wires with high density on the arc-shaped section.
In implementation, liquid nitrogen with a certain liquid level is filled in a liquid nitrogen container 3101, a cylinder 3102 provided with an exhaust valve 3103 and a U-shaped enrichment tube 3104 is inverted in the liquid nitrogen container 3101, the open end of the cylinder 3102 is placed below the liquid nitrogen level of the liquid nitrogen container 3101, the closed end of the cylinder is placed above the liquid nitrogen level, the lower part of a U-shaped enrichment section of the U-shaped enrichment tube 3104 is placed below the liquid nitrogen level, and the U-shaped enrichment section is frozen by liquid nitrogen; the air inlet and the air outlet of the U-shaped enrichment tube 3104 are respectively connected into a system pipeline; in the initial state, the heating wire 3105 is de-energized, in the unheated state, and the top vent valve 3103 is opened to cool the temperature of the U-shaped enrichment tube 3104 to the same temperature as the liquid nitrogen (-196 ℃). When the temperature of the U-shaped enrichment tube 3104 needs to be raised, the top exhaust valve 3103 is closed, the heating wire 3105 is electrified to heat, liquid nitrogen in the inner space of the cylinder 3102 begins to boil, and part of liquid nitrogen sublimates from liquid to gaseous N 2 Thereby increasing the gas pressure in the inner space of the cylinder 3102, sublimated N 2 The pressure will apply downward pressure to the liquid level of the liquid nitrogen inside barrel 3102, causing the liquid nitrogen inside barrel 3102 to be expelled from the bottom open end of barrel 3102, and eventually from the opening of the liquid nitrogen container to the atmosphere, with the temperature of the interior space of barrel 3102 being controlled by the low temperature nitrogen gas vaporized from the liquid nitrogen inside barrel 3102. The heating wire 3105 is continuously heated, and the thermocouple monitors the temperature of the U-shaped enrichment tube 3104 in real time until the temperature of the U-shaped enrichment tube 3104 reaches a set temperature and maintains the set temperature for a predetermined time. When the temperature of the U-shaped enrichment tube 3104 needs to be reduced, the heating wire 3105 is powered off to stop heating, the top exhaust valve 3103 is opened, nitrogen in the inner space of the cylinder 3102 is discharged, the liquid level of liquid nitrogen in the cylinder 3102 is increased, the U-shaped enrichment section is placed below the liquid level of liquid nitrogen again, and the U-shaped enrichment section is frozen by liquid nitrogen. The low-temperature freezing temperature or the heating temperature of the U-shaped enrichment section is controlled by a programmable microprocessor using a thermocouple, so that the automatic temperature rising and lowering process can be realized.
Compared with the prior art, the adjustable device provided by the embodimentThe temperature liquid nitrogen cold trap adopts a triple freezing space design, a cylinder body provided with an exhaust valve and a U-shaped enrichment pipe is arranged in a liquid nitrogen container in an inverted mode, a space between the outer wall of the cylinder body and the inner wall of the liquid nitrogen container is a first freezing space, a space between the outer wall of the U-shaped enrichment pipe and the inner wall of the cylinder body is a second freezing space, the inner space of the U-shaped enrichment pipe is a third freezing space, one end of the cylinder body is closed, the other end of the cylinder body is open, the open end of the cylinder body is located below the liquid nitrogen liquid level of the liquid nitrogen container, liquid nitrogen in the second freezing space is heated and sublimated by utilizing the electric heating wire, the liquid nitrogen liquid level in the cylinder body is lowered, sublimated gas is discharged from the open end of the cylinder body, therefore the freezing temperatures of the second freezing space and the third space are improved, the temperature of the cold trap is adjustable, the whole process can be controlled automatically, and the temperature adjusting precision is controllable. Can be based on the target gas SO 2 And the difference of the temperature and the freezing temperature of the impurity gas can accurately set the temperature of the adjustable liquid nitrogen cold trap, the freezing time and the six-way valve switching time, so that the impurity gas can be effectively separated, and the target gas can be purified.
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present application, and are not meant to limit the scope of the invention, but to limit the scope of the invention.
Claims (10)
1. The in-situ analysis system for the sulfide sulfur isotope microdomains of the ultraviolet laser probe is characterized by comprising an analysis gas path, wherein an ultraviolet laser ablation device (100) and a trace SO are sequentially arranged on the analysis gas path along the gas flow direction 2 Gas preparation device (200) and SO 2 The device comprises a gas collection and purification device (300), a miniature shunt interface (400) and a gas isotope ratio mass spectrometer (500);
wherein the ultraviolet laser ablation device (100) has a 193nm excimer laser (101) and a sample cell for holding a sulfide-containing sample; the 193nm excimer laser (101) is configured to ablate sulfide aerosol particles from a sulfide-containing sample in the sample cell;
Trace amount of SO 2 The gas preparation device (200) is provided with a reaction tube, sulfide aerosol particles are carried by helium carrier gas and enter the reaction tube, and react in the reaction tube at the high temperature of 1020 ℃ to generate SO 2 A gas;
SO 2 the gas collection and purification device (300) is used for collecting and purifying SO in the mixed gas 2 A gas;
through SO 2 SO purified by the gas collection and purification device (300) 2 Gas is fed into a gas isotope ratio mass spectrometer (500) through a micro-split interface (400).
2. The ultraviolet laser probe sulfide sulfur isotope micro-scale in situ analysis system of claim 1, wherein the reaction tube has a first inlet (201), a second inlet (202), and a first outlet (203); wherein, the first inlet (201) is communicated with the air outlet channel of the sample cell, so that helium gas flow carrying sulfide aerosol particles flows in; a second inlet (202) connected to a source of oxygen for supplying O 2 A gas; helium carrier gas carries sulfide aerosol particles into the reaction tube from the first inlet (201), and the supplied O 2 The SO-containing gas is obtained after the reaction 2 A mixture of gases; containing SO 2 The mixed gas of the gases flows out from the first outlet (203) and enters SO 2 A gas collection and purification device (300).
3. The ultraviolet laser probe sulfide sulfur isotope micro-zone in situ analysis system of claim 2, wherein SO 2 The gas collecting and purifying device (300) is provided with a first collecting and purifying component and a second collecting and purifying component which are connected through pipelines SO as to realize the separation of SO in the mixed gas 2 Carrying out enrichment and purification on the gas twice; the air inlet of the first collecting and purifying component is communicated with the first outlet (203), and the second collecting and purifying component is used for enriching and purifying the SO after the purification of the first collecting and purifying component 2 The gas is enriched and purified again, and the gas outlet of the second collecting and purifying component passes through the micro-scale deviceThe shunt interface (400) is connected with a gas isotope ratio mass spectrometer (500).
4. The ultraviolet laser probe sulfide sulfur isotope micro-zone in situ analysis system of claim 3, wherein the first collection and purification assembly comprises a first six-way valve (301) and a first cold trap (302), and the second collection and purification assembly has a second six-way valve (303) and a second cold trap (304); the air inlet valve port of the first six-way valve (301) is communicated with the first outlet (203) of the reaction tube, the air outlet valve port of the first six-way valve (301) is communicated with the air inlet valve port of the second six-way valve (303), and the air outlet valve port of the second six-way valve (303) is connected with the micro diversion interface (400) through a Teflon tube; two valve ports of the first six-way valve (301) are connected with two opening ends of the first cold trap (302), and two valve ports of the second six-way valve (303) are connected with two opening ends of the second cold trap (304).
5. A uv laser probe sulfide sulfur isotope micro-zone in situ analysis system according to claim 2 or 3, characterized in that the sample cell is an elliptical single sample cell (102), the single sample cell (102) comprising:
the first base (1023), the first base (1023) is provided with a cavity (1024), and the cross section of the cavity (1024) is elliptical;
the cross section of the first target frame (1027) is elliptical, the first target frame (1027) is detachably arranged in the cavity (1024), the outer wall surface of the first target frame (1027) can be attached to the cavity wall surface of the cavity (1024), the first target frame (1027) is provided with a plurality of test points (1030), and the centers of the test points (1030) are arranged on the long axis of the ellipse at equal intervals;
the air inlet channel (1021) and the air outlet channel (1022) are coaxially arranged and horizontally arranged at two ends of the base (1023), and the axes of the air inlet channel (1021) and the air outlet channel (1022) are coincident with or parallel to the long axis of the ellipse; an air inlet channel (1021) for helium carrier gas to flow into the chamber (1024), and an air outlet channel (1022) for helium carrier gas to flow out with sulfide aerosol particles;
MgF 2 glass one (1026),the cover is arranged above the first base (1023) and covers and seals the top opening of the cavity (1024) arranged on the first base (1023);
A first top cover (1025) arranged on the MgF 2 And a light transmission window is arranged above the first glass (1026), the center of the first top cover (1025), and all test points (1030) are positioned in the longitudinal projection area of the light transmission window.
6. The ultraviolet laser probe sulfide sulfur isotope micro-zone in situ analysis system of claim 5, wherein the chamber (1024) has an elliptical major axis of 42mm and a minor axis of 15mm; the depth of the chamber (1024) is 13mm, and the diameters of the air inlet channel (1021) and the air outlet channel (1022) are 3-5mm.
7. The ultraviolet laser probe sulfide sulfur isotope micro-scale in situ analysis system of claim 5, wherein the elliptical single sample cell (102) further comprises a sealing ring (1028), the sealing ring (1028) being an elliptical sealing ring.
8. An in-situ analysis method of a sulfur isotope micro-region of a sulfide by using an ultraviolet laser probe according to any one of claims 1 to 7; the analysis method comprises the following steps:
ablating sulfide aerosol particles from the sulfide-containing sample using a 193nm excimer laser (101);
carrying the degraded sulfide aerosol particles into trace SO by using He airflow 2 In the gas preparation device (200), SO-containing gas is obtained after high-temperature oxidation reaction 2 A gas mixture;
SO 2 the gas collection and purification device (300) is used for supplying SO-containing gas 2 The gas mixture is enriched and purified twice to obtain the target SO 2 A gas;
target SO 2 The gas enters a gas isotope ratio mass spectrometer (500) for detection through a micro shunt interface (400) under the carrying of back-blowing helium gas flow, and a test result is obtained.
9. The method for in-situ analysis of sulfide sulfur isotope by using an ultraviolet laser probe according to claim 8, wherein the method comprises the following steps: starting a testing instrument, firstly adjusting a first six-way valve (301) to a load mode, adjusting a second six-way valve (303) to an object mode, and immersing a first cold trap (302) into a first liquid nitrogen barrel;
sulfide aerosol particles are stripped from a sulfide-containing sample in a sample cell by using a 193nm excimer laser (101), and the sulfide aerosol particles stripped by the laser are carried into a reaction tube by He air flow with the flow speed of 150ml/min through a Teflon tube to react to generate SO 2 After the gas, the target SO is contained 2 The mixed gas of the gases enters a first cold trap (302) to be collected in a freezing way under the purging of He gas, thus completing the target SO 2 Primary enrichment and purification of gas;
Then the first six-way valve (301) is switched to an object mode, the second six-way valve (303) is switched to a load mode, the first cold trap (302) is lifted, the second cold trap (304) is lowered and immersed in the second liquid nitrogen barrel, or the second cold trap (304) is immersed in the second liquid nitrogen barrel before the first cold trap is lowered and immersed in the second liquid nitrogen barrel; the first heating device is started, and enriched SO is frozen in the first cold trap (302) 2 Sublimating heated SO gas into gas, and sublimating the sublimated SO gas in the first cold trap (302) by a first back-blowing helium gas flow (307) through a first six-way valve (301) 2 Carrying and freeze-concentrating the gas in a second cold trap (304) to complete the target SO 2 Second enrichment and purification of gas;
after enrichment is completed in the second cold trap (304), the second six-way valve (303) is switched to an object mode, a second heating device is started after the second cold trap (304) is lifted, and enriched SO is frozen in the second cold trap (304) 2 Sublimating into gas after heating, and enriching purified SO for the second time 2 The gas is carried by the second back-blowing helium flow (308) and passes through the low-flow-rate channel of the miniature shunt interface (400), and finally enters the gas isotope ratio mass spectrometer (500) for detection, so that a test result is obtained.
10. The method for in-situ analysis of sulfide sulfur isotope microdomains by using an ultraviolet laser probe according to claim 9, wherein the flow rate of the first back-blowing helium gas flow (307) is 26mL/min, and the back-blowing duration is 180s; the flow rate of the second back-flushing helium flow (308) is 2.2-2.8mL/min.
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| CN102455317A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Micro component laser ablation isotope analyzing device and method |
| CN210956595U (en) * | 2020-02-15 | 2020-07-07 | 中国科学院地球化学研究所 | Sample ablation pool for laser ablation inductively coupled plasma mass spectrometer |
| CN111551650A (en) * | 2020-06-16 | 2020-08-18 | 中国地质科学院矿产资源研究所 | System and method for analyzing trace sulfur isotopes in sulfide and sulfate |
| CN111965282A (en) * | 2020-08-18 | 2020-11-20 | 中国地质科学院矿产资源研究所 | Ultra-micro sulfur isotope analysis system and analysis method |
| CN114544746A (en) * | 2022-03-28 | 2022-05-27 | 山东省地质科学研究院 | Small-volume ablation pool for laser ablation of multiple targets at same position and working method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102455317A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Micro component laser ablation isotope analyzing device and method |
| CN210956595U (en) * | 2020-02-15 | 2020-07-07 | 中国科学院地球化学研究所 | Sample ablation pool for laser ablation inductively coupled plasma mass spectrometer |
| CN111551650A (en) * | 2020-06-16 | 2020-08-18 | 中国地质科学院矿产资源研究所 | System and method for analyzing trace sulfur isotopes in sulfide and sulfate |
| CN111965282A (en) * | 2020-08-18 | 2020-11-20 | 中国地质科学院矿产资源研究所 | Ultra-micro sulfur isotope analysis system and analysis method |
| CN114544746A (en) * | 2022-03-28 | 2022-05-27 | 山东省地质科学研究院 | Small-volume ablation pool for laser ablation of multiple targets at same position and working method |
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