CN111638204A - Analysis method for efficiently measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in geochemical sample - Google Patents
Analysis method for efficiently measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in geochemical sample Download PDFInfo
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- CN111638204A CN111638204A CN202010336216.0A CN202010336216A CN111638204A CN 111638204 A CN111638204 A CN 111638204A CN 202010336216 A CN202010336216 A CN 202010336216A CN 111638204 A CN111638204 A CN 111638204A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 52
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 48
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 238000004458 analytical method Methods 0.000 title claims description 20
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 23
- 238000005259 measurement Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002795 fluorescence method Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000012086 standard solution Substances 0.000 claims description 24
- 238000005086 pumping Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
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- 239000012159 carrier gas Substances 0.000 claims description 15
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- MABBGPMUOLWBII-RXSVEWSESA-N (2R)-2-[(1S)-1,2-dihydroxyethyl]-3,4-dihydroxy-2H-furan-5-one thiourea Chemical compound NC(N)=S.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O MABBGPMUOLWBII-RXSVEWSESA-N 0.000 claims description 3
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- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims 1
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- WHEUWNKSCXYKBU-QPWUGHHJSA-N 2-methoxyestrone Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC[C@H]3[C@@H]1CCC1=C2C=C(OC)C(O)=C1 WHEUWNKSCXYKBU-QPWUGHHJSA-N 0.000 description 7
- 239000011573 trace mineral Substances 0.000 description 5
- 235000013619 trace mineral Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- 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
Abstract
The method provides a method for measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury in a geochemical sample by a primary aqua regia sample-inductively coupled plasma spectrum + inductively coupled plasma mass spectrum + atomic fluorescence method, and comprises the steps of pretreatment of the sample, preparation of a liquid to be measured, selection of a standard substance, drawing of a standard working curve and measurement of each element in the sample. The method has the characteristics of simple operation, short measurement time, less sample consumption, less reagent consumption, easy mastering and the like, and has the advantages of wide measurement range, low environmental requirement, strong anti-interference capability and capability of meeting the current standard requirement.
Description
Technical Field
The invention relates to the field of sample element determination and analysis, in particular to an analysis method for determining sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in a geochemical sample.
Background
The geochemistry is a subject for researching the composition, content, distribution and time-space change of chemical elements in various rocks, minerals, ores and various geologic bodies in the crust or on the surface of the earth, and is mainly divided into constant element geochemistry, trace element geochemistry, rare earth element geochemistry and the like according to the content of the chemical elements in the geologic bodies, and has important guiding significance for agricultural development, industrial treatment, environmental detection, environmental protection and geological resource exploration through the research work of geochemical samples.
Sulphur is a common odorless and tasteless non-metal, which is often found in nature in the form of sulphides or sulphates, and is an important essential element for all organisms, being a constituent of a number of amino acids.
Iron is an essential trace element of human content, an important part of hemoglobin, which is required by the human body throughout the body, is present in erythrocytes which supply oxygen to muscles, and is a component of many enzymes and immune system compounds.
Bismuth is mainly used for manufacturing fusible alloys, and is used as a fuse of an automatic fire extinguishing system and an electrical appliance and soldering tin in the fire fighting and electrical industries. Bismuth alloys have the property of not shrinking during solidification, and bismuth oxycarbonate and nitrate are used for the treatment of skin lesions and gastrointestinal disorders.
Lead is a weak metal with softness and strong ductility, is toxic and also a heavy metal, and can be used as a material for resisting sulfuric acid corrosion, resisting ionizing radiation, a storage battery and the like. The alloy can be used for types, bearings, cable jackets, etc.
Antimony is a silvery white shiny hard brittle metal, readily soluble in aqua regia and soluble in concentrated sulfuric acid. The alloy made of antimony, lead and tin can be used to improve the performance of welding materials, bullets and bearings, and the antimony compound is an important additive of chlorine and bromine containing flame retardant with wide application.
Arsenic, a nonmetallic element, exists as three allotropes, namely ash arsenic, black arsenic and yellow arsenic, and is applied to pesticides, herbicides, insecticides and a variety of alloys together with compounds thereof.
Mercury is a transition metal with high density, silver white, liquid at room temperature, toxic, and can be used in thermometers, barometers, pressure gauges, sphygmomanometers, float valves, mercury switches, and other devices, and most of its compounds and salts are very toxic and can cause brain and liver damage after oral administration, inhalation, or contact.
The trace elements are elements which account for less than 0.01 percent of the total mass of the organism and are necessary for the organism, such as iron, arsenic and the like. Trace elements are some elements that are necessary for plants but are in very small demand. When these elements are deficient in soil or unavailable to plants, too little of them causes poor growth of plants, and too much of them causes poisoning. Therefore, the detection of the trace elements is significant to agricultural production, and has high guiding significance to scientific planting and professional fertilization.
Disclosure of Invention
The invention relates to an analysis method for measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in a geochemical sample by one-time royal water digestion and sample dissolution of the sample and combining an inductively coupled plasma spectrometer, an inductively coupled plasma mass spectrometer and an atomic fluorescence spectrometer.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an analysis method for efficiently measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in a geochemical sample comprises the following steps:
1) pretreatment of samples
Weighing 0.2500g of sample to be detected, adding the sample into a test tube, adding 5ml (1+1) of aqua regia to be fully mixed with the sample, sealing, heating in a water bath to dissolve the sample, taking out after the water is boiled for 1 hour, taking out, placing to room temperature, metering the volume, shaking up, and standing for more than 4 hours to obtain a sample for later use.
2) Preparation of liquid to be tested
Dividing and taking 5ml of the sample into a small beaker, quantitatively adding 1ml (1+1) of aqua regia, and then quantitatively adding 4ml (5% thiourea-5% ascorbic acid) thiourea-ascorbic acid mixed solution to obtain a first solution to be detected for detecting arsenic and antimony elements by using a hydride atomic fluorescence method;
dividing 5mL of the sample into 50mL volumetric flasks, adding water to a constant volume of 50mL, and shaking up to obtain a second solution to be detected for determining bismuth and lead elements by using an inductively coupled plasma mass spectrometry;
absorbing 2mL of the sample as a solution III to be detected for detecting the mercury element by a cold atomic fluorescence method;
and taking the rest of the sample as a to-be-detected liquid IV for directly detecting iron and sulfur elements by using an inductively coupled plasma spectrometry.
3) Selection of standard substances
a) Preparing a mixed solution of 2% of potassium borohydride and 0.5% of potassium hydroxide: weighing 20g of analytically pure potassium borohydride reagent, pouring the reagent into a 1000mL volumetric flask, adding 5g of potassium hydroxide reagent, diluting the reagent to 1000mL with distilled water, and shaking up for later use.
b) Preparing a 10% stannous chloride-2% hydrochloric acid mixed solution: weighing 50g of analytically pure stannous chloride reagent, pouring the reagent into a heat-resistant beaker, adding 20mL of high-grade pure concentrated hydrochloric acid reagent, placing the beaker on a low-temperature furnace, heating the beaker to boil, taking the beaker down, naturally cooling the beaker to room temperature, transferring all the beaker to a 500mL volumetric flask, using distilled water to fix the volume to 500mL, and shaking the beaker uniformly for later use.
4) Concentration of standard working curve of each element
The standard working curve concentrations of the elements are prepared, and the elements tested under the same condition can be directly prepared into mixed standards, so that the measurement is convenient.
5) Instrument operating condition setting
Adjusting an inductively coupled plasma mass spectrometer (Series2 type), an inductively coupled plasma spectrometer (Icap7400), an atomic fluorescence spectrometer (SK-sharp analysis) and an atomic fluorescence spectrometer (XGY-1011A) to an optimal working state according to the operation rules of the instrument.
6) Drawing of standard working curve of each element
a) Pumping standard solutions with different concentrations of bismuth and lead elements into the inductively coupled plasma mass spectrometer (Series2 type) by using a sample inlet pipe, measuring the strength values of bismuth and lead in each standard solution, and drawing a standard working curve of the bismuth and lead elements;
b) pumping standard solutions with different concentrations of sulfur and iron elements into the inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the intensity values of the sulfur and the iron in each standard solution, and drawing a standard working curve of the sulfur and the iron elements;
c) pumping standard solutions with different concentrations of antimony and arsenic elements into the atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, measuring fluorescence intensity values of the antimony and the arsenic in the standard solutions, and drawing standard working curves of the antimony and the arsenic elements;
d) pumping standard solutions with different concentrations of mercury elements into an atomic fluorescence spectrometer (XGY-1011A) by using a sample inlet pipe, measuring the fluorescence intensity value of mercury in the standard solutions, and drawing a standard working curve of the mercury elements.
7) Measurement of respective solutions to be measured
a) Pumping the liquid to be detected into an atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, reducing by using the mixed solution of 2% potassium borohydride and 0.5% potassium hydroxide, measuring the intensity of antimony and arsenic elements in the solution, respectively substituting the measured intensity values into standard working curves of the antimony and arsenic elements, and calculating the content of the antimony and arsenic in the first liquid to be detected;
b) pumping the sample tube for the liquid II to be detected into an inductively coupled plasma mass spectrometer (Series2 type), measuring the strength of bismuth and lead elements in the solution, respectively substituting the measured strength values into the standard working curves of the bismuth and lead elements, and calculating the content of bismuth and lead in the liquid II to be detected;
c) absorbing 2mL of the liquid three-purpose pipette gun of the liquid to be detected, injecting the liquid into an atomic fluorescence spectrometer (XGY-1011A), adding 5mL of the prepared 10% stannous chloride-2% hydrochloric acid mixed solution for reduction, measuring the strength of mercury elements in the solution, substituting the measured strength value into the standard working curve of the mercury elements, and calculating the content of mercury in the liquid three to be detected;
d) pumping the liquid to be detected into an inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the strength of iron and sulfur elements in the solution, respectively substituting the measured strength values into standard working curves of the iron and sulfur elements, and calculating the content of the iron and sulfur in the liquid to be detected.
Further, the concentrations of the standard working curves of the elements of sulfur, iron, bismuth, lead, antimony, arsenic and mercury are as follows:
sulfur: 0ug/mL, 0.5ug/mL, 1ug/mL, 5ug/mL, 10ug/mL, 20 ug/mL;
iron: 0ug/mL, 25ug/mL, 50ug/mL, 250ug/mL, 500ug/mL, 1000 ug/mL;
bismuth: 0ng/mL, 0.25ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10 ng/mL;
lead: 0ng/mL, 25ng/mL, 50ng/mL, 100ng/mL, 500ng/mL, 1000 ng/mL;
arsenic: 0ng/mL, 2.5ng/mL, 10ng/mL, 50ng/mL, 75ng/mL, 100 ng/mL;
antimony: 0ng/mL, 0.25ng/mL, 1ng/mL, 5ng/mL, 7.5ng/mL, 10 ng/mL;
mercury: 0ng/mL, 0.05ng/mL, 0.2ng/mL, 0.5ng/mL, 1ng/mL, 1.5 ng/mL.
Further, the best operation parameters of each instrument are as follows:
the best operating parameters for an inductively coupled plasma mass spectrometer (Series type 2) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 20s, scanning mode peak jump, integration time: 1s, resolution 100, sampling depth 100step, sampling cone aperture 1.2mm, intercepting cone aperture 1mm, and isotope measured208Pb、209Bi, the carrier gas is high-purity argon with the purity of 99.9 percent;
the best operating parameters for the inductively coupled plasma spectrometer (Icap7400) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 15s, optical cell temperature: 38 ℃, Camera temperature: at-40 ℃, the characteristic wavelength of the measured elements is S182.0nm and Fe259.9nm, and the carrier gas is high-purity argon with the purity of 99.9 percent;
the optimal working parameters of the atomic fluorescence spectrometer (SK-sharp analysis) are as follows: the main gas flow is 600mL/min, the auxiliary gas flow is 800mL/min, the arsenic lamp current: 30mA, antimony lamp current: 60mA, negative high voltage: 300V, pump speed: 100r/min, integration time: and 5 s. Wavelength of arsenic lamp: 193.7nm, antimony lamp wavelength: 217.6nm, and the carrier gas is high-purity argon with the purity of 99.9%;
the optimal working parameters of the atomic fluorescence spectrometer (XGY-1011A) are as follows: carrier gas flow rate 800mL/min, mercury lamp current: 50mA, negative high voltage: -260V, furnace temperature: 200 ℃, integration time: and 8 s. Mercury lamp wavelength: 253.7nm, and the carrier gas is high-purity argon with the purity of 99.9 percent.
Compared with the prior art, the invention has the following beneficial effects:
the method provides a method for measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury in a geochemical sample by a primary aqua regia sample-inductively coupled plasma spectrum + inductively coupled plasma mass spectrum + atomic fluorescence method, and comprises the steps of pretreatment of the sample, preparation of a liquid to be measured, selection of a standard substance, drawing of a standard working curve and measurement of each element in the sample. The method has the characteristics of simple operation, short measurement time, less sample consumption, less reagent consumption, easy mastering and the like, and has the advantages of wide measurement range, low environmental requirement, strong anti-interference capability and capability of meeting the current standard requirement.
Drawings
FIG. 1 is a standard operating curve for elemental sulfur.
Fig. 2 is a standard working curve of the iron element.
FIG. 3 is a standard working curve of bismuth element.
Fig. 4 is a standard working curve for lead element.
FIG. 5 is a standard operating curve for antimony.
FIG. 6 is a standard operating curve for elemental arsenic.
Fig. 7 is a standard operating curve for elemental mercury.
Detailed Description
The technical solution of the present invention is further illustrated in detail by the following specific examples.
An analysis method for efficiently measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in a geochemical sample comprises the following steps:
1) pretreatment of samples
Weighing 0.2500g of sample to be detected, adding the sample into a polyvinyl chloride test tube, firstly adding 5ml (1+1) of aqua regia and fully mixing the sample, covering a layer of safety film, pressing the mixture by using a plastic plate, placing the mixture into a 95-100 ℃ temperature-control water bath pot for heating and dissolving the sample, taking out the mixture after 1 hour after the water is boiled, shaking the mixture for 3-4 times at intervals in the decomposition process, taking out the mixture, placing the mixture to room temperature, fixing the volume, shaking the mixture uniformly, and standing the mixture for more than 4 hours to obtain a sample for later use.
2) Preparation of liquid to be tested
Dividing and taking 5ml of the sample into a small beaker, quantitatively adding 1ml (1+1) of aqua regia, and then quantitatively adding 4ml (5% thiourea-5% ascorbic acid) thiourea-ascorbic acid mixed solution to obtain a first solution to be detected for detecting arsenic and antimony elements by using a hydride atomic fluorescence method;
dividing 5mL of the sample into 50mL volumetric flasks, adding water to a constant volume of 50mL, and shaking up to obtain a second solution to be detected for determining bismuth and lead elements by using an inductively coupled plasma mass spectrometry;
absorbing 2mL of the sample as a solution III to be detected for detecting the mercury element by a cold atomic fluorescence method;
and taking the rest of the sample as a to-be-detected liquid IV for directly detecting iron and sulfur elements by using an inductively coupled plasma spectrometry.
3) Selection of standard substances
a) Preparing a mixed solution of 2% of potassium borohydride and 0.5% of potassium hydroxide: weighing 20g of analytically pure potassium borohydride reagent, pouring the reagent into a 1000mL volumetric flask, adding 5g of potassium hydroxide reagent, diluting the reagent to 1000mL with distilled water, and shaking up for later use.
b) Preparing a 10% stannous chloride-2% hydrochloric acid mixed solution: weighing 50g of analytically pure stannous chloride reagent, pouring the reagent into a heat-resistant beaker, adding 20mL of high-grade pure concentrated hydrochloric acid reagent, placing the beaker on a low-temperature furnace, heating the beaker to boil, taking the beaker down, naturally cooling the beaker to room temperature, transferring all the beaker to a 500mL volumetric flask, using distilled water to fix the volume to 500mL, and shaking the beaker uniformly for later use.
4) Concentration of standard working curve of each element
The concentration of the standard working curve of each element of sulfur, iron, bismuth, lead, antimony, arsenic and mercury is as follows:
sulfur: 0ug/mL, 0.5ug/mL, 1ug/mL, 5ug/mL, 10ug/mL, 20 ug/mL;
iron: 0ug/mL, 25ug/mL, 50ug/mL, 250ug/mL, 500ug/mL, 1000 ug/mL;
bismuth: 0ng/mL, 0.25ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10 ng/mL;
lead: 0ng/mL, 25ng/mL, 50ng/mL, 100ng/mL, 500ng/mL, 1000 ng/mL;
arsenic: 0ng/mL, 2.5ng/mL, 10ng/mL, 50ng/mL, 75ng/mL, 100 ng/mL;
antimony: 0ng/mL, 0.25ng/mL, 1ng/mL, 5ng/mL, 7.5ng/mL, 10 ng/mL;
mercury: 0ng/mL, 0.05ng/mL, 0.2ng/mL, 0.5ng/mL, 1ng/mL, 1.5 ng/mL.
The working curves of the elements are prepared, and the elements tested under the same condition can be directly prepared into mixed standards, so that the measurement is convenient.
5) Instrument operating condition setting
Adjusting an inductively coupled plasma mass spectrometer (Series2 type), an inductively coupled plasma spectrometer (Icap7400), an atomic fluorescence spectrometer (SK-sharp analysis) and an atomic fluorescence spectrometer (XGY-1011A) to an optimal working state according to the operation rules of the instrument.
Wherein, working parameters of each instrument are:
the best operating parameters for an inductively coupled plasma mass spectrometer (Series type 2) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 20s, scanning mode peak jump, integration time: 1s, resolution 100, sampling depth 100step, sampling cone aperture 1.2mm, intercepting cone aperture 1mm, and isotope measured208Pb、209Bi and the carrier gas is high-purity argon with the purity of 99.9 percent.
The best operating parameters for the inductively coupled plasma spectrometer (Icap7400) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 15s, optical cell temperature: 38 ℃, Camera temperature: at-40 ℃ and the characteristic wavelength of the measured element is S182.0nm,Fe259.9nm, and the carrier gas is high-purity argon with the purity of 99.9 percent.
The optimal working parameters of the atomic fluorescence spectrometer (SK-sharp analysis) are as follows: the main gas flow is 600mL/min, the auxiliary gas flow is 800mL/min, the arsenic lamp current: 30mA, antimony lamp current: 60mA, negative high voltage: 300V, pump speed: 100r/min, integration time: and 5 s. Wavelength of arsenic lamp: 193.7nm, antimony lamp wavelength: 217.6nm, and the carrier gas is high purity argon with a purity of 99.9%.
The optimal working parameters of the atomic fluorescence spectrometer (XGY-1011A) are as follows: carrier gas flow rate 800mL/min, mercury lamp current: 50mA, negative high voltage: -260V, furnace temperature: 200 ℃, integration time: and 8 s. Mercury lamp wavelength: 253.7nm, and the carrier gas is high-purity argon with the purity of 99.9 percent.
6) Drawing of standard working curve of each element
a) Pumping standard solutions with different concentrations of bismuth and lead elements into the inductively coupled plasma mass spectrometer (Series2 type) by using a sample inlet pipe, measuring the strength values of bismuth and lead in each standard solution, and drawing a standard working curve of the bismuth and lead elements;
b) pumping standard solutions with different concentrations of sulfur and iron elements into the inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the intensity values of the sulfur and the iron in each standard solution, and drawing a standard working curve of the sulfur and the iron elements;
c) pumping standard solutions with different concentrations of antimony and arsenic elements into the atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, measuring fluorescence intensity values of the antimony and the arsenic in the standard solutions, and drawing standard working curves of the antimony and the arsenic elements;
d) pumping standard solutions with different concentrations of mercury elements into an atomic fluorescence spectrometer (XGY-1011A) by using a sample inlet pipe, measuring the fluorescence intensity value of mercury in the standard solutions, and drawing a standard working curve of the mercury elements.
7) Measurement of respective solutions to be measured
a) Pumping the liquid to be detected into an atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, reducing by using the mixed solution of 2% potassium borohydride and 0.5% potassium hydroxide, measuring the intensity of antimony and arsenic elements in the solution, respectively substituting the measured intensity values into standard working curves of the antimony and arsenic elements, and calculating the content of the antimony and arsenic in the first liquid to be detected;
b) pumping the sample tube for the liquid II to be detected into an inductively coupled plasma mass spectrometer (Series2 type), measuring the strength of bismuth and lead elements in the solution, respectively substituting the measured strength values into the standard working curves of the bismuth and lead elements, and calculating the content of bismuth and lead in the liquid II to be detected;
c) absorbing 2mL of the liquid three-purpose pipette gun of the liquid to be detected, injecting the liquid into an atomic fluorescence spectrometer (XGY-1011A), adding 5mL of the prepared 10% stannous chloride-2% hydrochloric acid mixed solution for reduction, measuring the strength of mercury elements in the solution, substituting the measured strength value into the standard working curve of the mercury elements, and calculating the content of mercury in the liquid three to be detected;
d) pumping the liquid to be detected into an inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the strength of iron and sulfur elements in the solution, respectively substituting the measured strength values into standard working curves of the iron and sulfur elements, and calculating the content of the iron and sulfur in the liquid to be detected.
The test results of sulfur, iron, bismuth, lead, antimony, arsenic and mercury in the geochemical samples are shown in tables 1-8.
TABLE 1 elemental sulfur
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△LgC） |
| 1 | GSS-24 | 2000 | 1933 | -3.39 | -0.01 |
| 2 | GSS-25 | 170 | 177 | 4.04 | 0.02 |
| 3 | GSS-26 | 162 | 158 | -2.26 | -0.01 |
| 4 | GSS-27 | 254 | 244 | -4.19 | -0.02 |
| 5 | GSS-28 | 281 | 288 | 2.43 | 0.01 |
| 6 | GSS-29 | 266 | 253 | -4.89 | -0.02 |
| 7 | GSS-30 | 244 | 247 | 1.18 | 0.01 |
| 8 | GSS-31 | 180 | 182 | 0.87 | 0.00 |
| 9 | GSS-32 | 77 | 74 | -4.07 | -0.02 |
| 10 | GSS-33 | 268 | 258 | -3.96 | -0.02 |
| 11 | GSS-34 | 431 | 446 | 3.41 | 0.01 |
| 12 | GSS-35 | 344 | 356 | 3.40 | 0.01 |
TABLE 2 iron element
| Serial number | Standard substance | Standard value (%) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 4.97 | 4.84 | -2.74 | -0.01 |
| 2 | GSS-25 | 4.3 | 4.23 | -1.71 | -0.01 |
| 3 | GSS-26 | 4 | 4.18 | 4.43 | 0.02 |
| 4 | GSS-27 | 6.12 | 6.30 | 2.84 | 0.01 |
| 5 | GSS-28 | 6.5 | 6.43 | -1.10 | 0.00 |
| 6 | GSS-29 | 5.44 | 5.44 | -0.08 | 0.00 |
| 7 | GSS-30 | 3.81 | 3.87 | 1.64 | 0.01 |
| 8 | GSS-31 | 5.92 | 6.17 | 4.09 | 0.02 |
| 9 | GSS-32 | 5.52 | 5.78 | 4.53 | 0.02 |
| 10 | GSS-33 | 4.73 | 4.95 | 4.52 | 0.02 |
| 11 | GSS-34 | 5.76 | 5.82 | 0.96 | 0.00 |
| 12 | GSS-35 | 4.09 | 3.98 | -2.80 | -0.01 |
TABLE 3 bismuth element
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 0.98 | 1.02 | 4.28 | 0.02 |
| 2 | GSS-25 | 0.32 | 0.34 | 4.68 | 0.02 |
| 3 | GSS-26 | 0.28 | 0.29 | 3.58 | 0.02 |
| 4 | GSS-27 | 0.79 | 0.80 | 1.19 | 0.01 |
| 5 | GSS-28 | 1.53 | 1.56 | 2.24 | 0.01 |
| 6 | GSS-29 | 0.37 | 0.36 | -2.65 | -0.01 |
| 7 | GSS-30 | 1.2 | 1.24 | 3.64 | 0.02 |
| 8 | GSS-31 | 0.67 | 0.67 | 0.25 | 0.00 |
| 9 | GSS-32 | 0.34 | 0.33 | -4.28 | -0.02 |
| 10 | GSS-33 | 0.34 | 0.34 | 1.11 | 0.00 |
| 11 | GSS-34 | 0.38 | 0.38 | 0.84 | 0.00 |
| 12 | GSS-35 | 0.3 | 0.31 | 4.82 | 0.02 |
TABLE 4 lead element
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 40.0 | 40.6 | 1.53 | 0.01 |
| 2 | GSS-25 | 22.0 | 21.7 | -1.59 | -0.01 |
| 3 | GSS-26 | 21.0 | 20.1 | -4.48 | -0.02 |
| 4 | GSS-27 | 41.0 | 39.1 | -4.69 | -0.02 |
| 5 | GSS-28 | 61.0 | 62.2 | 1.92 | 0.01 |
| 6 | GSS-29 | 32.0 | 30.6 | -4.64 | -0.02 |
| 7 | GSS-30 | 43.0 | 44.3 | 2.95 | 0.01 |
| 8 | GSS-31 | 28.0 | 27.2 | -2.99 | -0.01 |
| 9 | GSS-32 | 26.0 | 25.1 | -3.38 | -0.01 |
| 10 | GSS-33 | 22.0 | 21.3 | -3.21 | -0.01 |
| 11 | GSS-34 | 26.0 | 26.8 | 2.97 | 0.01 |
| 12 | GSS-35 | 22.0 | 21.8 | -0.95 | 0.00 |
TABLE 5 antimony elements
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 1.05 | 1.09 | 3.92 | 0.02 |
| 2 | GSS-25 | 1.13 | 1.16 | 2.47 | 0.01 |
| 3 | GSS-26 | 0.86 | 0.84 | -2.06 | -0.01 |
| 4 | GSS-27 | 1.21 | 1.27 | 4.78 | 0.02 |
| 5 | GSS-28 | 3.6 | 3.62 | 0.53 | 0.00 |
| 6 | GSS-29 | 1.16 | 1.10 | -5.05 | -0.02 |
| 7 | GSS-30 | 0.82 | 0.82 | -0.06 | 0.00 |
| 8 | GSS-31 | 1.27 | 1.27 | 0.16 | 0.00 |
| 9 | GSS-32 | 1.08 | 1.10 | 1.75 | 0.01 |
| 10 | GSS-33 | 1.14 | 1.13 | -0.53 | 0.00 |
| 11 | GSS-34 | 1.08 | 1.11 | 2.52 | 0.01 |
| 12 | GSS-35 | 0.8 | 0.79 | -1.18 | -0.01 |
TABLE 6 arsenic element
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 15.8 | 16.5 | 4.28 | 0.02 |
| 2 | GSS-25 | 12.9 | 13.4 | 3.95 | 0.02 |
| 3 | GSS-26 | 8.9 | 9.0 | 1.65 | 0.01 |
| 4 | GSS-27 | 13.3 | 13.2 | -0.63 | 0.00 |
| 5 | GSS-28 | 28.5 | 27.8 | -2.40 | -0.01 |
| 6 | GSS-29 | 9.3 | 9.6 | 3.34 | 0.01 |
| 7 | GSS-30 | 10 | 10.4 | 3.86 | 0.02 |
| 8 | GSS-31 | 13 | 12.5 | -3.97 | -0.02 |
| 9 | GSS-32 | 12.7 | 12.3 | -3.46 | -0.02 |
| 10 | GSS-33 | 13.7 | 14.4 | 4.82 | 0.02 |
| 11 | GSS-34 | 13.7 | 13.8 | 0.89 | 0.00 |
| 12 | GSS-35 | 9.2 | 8.9 | -3.05 | -0.01 |
TABLE 7 elemental mercury
| Serial number | Standard substance | Standard value (ug/g) | Measured value | Relative standard deviation (%) | Accuracy (△ LgC) |
| 1 | GSS-24 | 0.075 | 0.076 | 1.27 | 0.01 |
| 2 | GSS-25 | 0.043 | 0.043 | -0.20 | 0.00 |
| 3 | GSS-26 | 0.03 | 0.031 | 4.33 | 0.02 |
| 4 | GSS-27 | 0.116 | 0.116 | 0.20 | 0.00 |
| 5 | GSS-28 | 0.143 | 0.147 | 2.77 | 0.01 |
| 6 | GSS-29 | 0.15 | 0.152 | 1.63 | 0.01 |
| 7 | GSS-30 | 0.091 | 0.093 | 2.17 | 0.01 |
| 8 | GSS-31 | 0.081 | 0.080 | -0.65 | 0.00 |
| 9 | GSS-32 | 0.026 | 0.027 | 2.01 | 0.01 |
| 10 | GSS-33 | 0.019 | 0.020 | 4.14 | 0.02 |
| 11 | GSS-34 | 0.053 | 0.055 | 3.52 | 0.02 |
| 12 | GSS-35 | 0.042 | 0.041 | -1.59 | -0.01 |
TABLE 8 detection limits of the elements
| Serial number | Element(s) | Detection limit (ug/g) | Remarks for |
| 1 | Sulfur | 30 | |
| 2 | |
400 | |
| 3 | Bismuth (III) | 0.05 | |
| 4 | Lead (II) | 1.0 | |
| 5 | Antimony (Sb) | 0.05 | |
| 6 | Arsenic (As) | 1.0 | |
| 7 | Mercury | 0.0005 |
While the invention has been described in detail, it is to be understood that the invention is not limited to the precise form disclosed, and that various changes and modifications can be effected therein without departing from the scope of the invention.
Claims (3)
1. An analysis method for efficiently measuring sulfur, iron, bismuth, lead, antimony, arsenic and mercury elements in a geochemical sample comprises the following steps:
1) pretreatment of samples
Weighing 0.2500g of sample to be detected, adding the sample into a test tube, adding 5ml (1+1) of aqua regia to be fully mixed with the sample, sealing, heating in a water bath to dissolve the sample, taking out after the water is boiled for 1 hour, taking out, placing to room temperature, metering the volume, shaking up, and standing for more than 4 hours to obtain a sample for later use;
2) preparation of liquid to be tested
Dividing and taking 5ml of the sample into a small beaker, quantitatively adding 1ml (1+1) of aqua regia, and then quantitatively adding 4ml (5% thiourea-5% ascorbic acid) thiourea-ascorbic acid mixed solution to obtain a first solution to be detected for detecting arsenic and antimony elements by using a hydride atomic fluorescence method; dividing 5mL of the sample into 50mL volumetric flasks, adding water to a constant volume of 50mL, and shaking up to obtain a second solution to be detected for determining bismuth and lead elements by using an inductively coupled plasma mass spectrometry;
absorbing 2mL of the sample as a solution III to be detected for detecting the mercury element by a cold atomic fluorescence method;
the residual sample is used as a liquid IV to be detected for directly detecting iron and sulfur elements by utilizing an inductively coupled plasma spectrometry;
3) selection of standard substances
a) Preparing a mixed solution of 2% of potassium borohydride and 0.5% of potassium hydroxide: weighing 20g of analytically pure potassium borohydride reagent, pouring the reagent into a 1000mL volumetric flask, adding 5g of potassium hydroxide reagent, diluting the reagent to 1000mL with distilled water, and shaking up for later use;
b) preparing a 10% stannous chloride-2% hydrochloric acid mixed solution: weighing 50g of analytically pure stannous chloride reagent, pouring the reagent into a heat-resistant beaker, adding 20mL of high-grade pure concentrated hydrochloric acid reagent, putting the beaker on a low-temperature furnace, heating the beaker to boil, taking the beaker down, naturally cooling the beaker to room temperature, completely transferring the beaker to a 500mL volumetric flask, using distilled water to fix the volume to 500mL, and shaking the beaker uniformly for later use;
4) concentration of standard working curve of each element
The standard working curve concentrations of the elements are prepared, and the elements tested under the same condition can be directly prepared into mixed standards, so that the measurement is convenient;
5) instrument operating condition setting
Adjusting an inductively coupled plasma mass spectrometer (Series2 type), an inductively coupled plasma spectrometer (Icap7400), an atomic fluorescence spectrometer (SK-sharp analysis) and the atomic fluorescence spectrometer (XGY-1011A) to an optimal working state according to instrument operation rules;
6) drawing of standard working curve of each element
a) Pumping standard solutions with different concentrations of bismuth and lead elements into the inductively coupled plasma mass spectrometer (Series 2) by using a sample inlet pipe, measuring the strength values of bismuth and lead in each standard solution, and drawing a standard working curve of the bismuth and lead elements;
b) pumping standard solutions with different concentrations of sulfur and iron elements into the inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the intensity values of the sulfur and the iron in each standard solution, and drawing a standard working curve of the sulfur and the iron elements;
c) pumping standard solutions with different concentrations of antimony and arsenic elements into the atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, measuring fluorescence intensity values of the antimony and the arsenic in the standard solutions, and drawing standard working curves of the antimony and the arsenic elements;
d) pumping standard solutions with different concentrations of mercury elements into an atomic fluorescence spectrometer (XGY-1011A) by using a sample inlet pipe, measuring the fluorescence intensity value of mercury in the standard solutions, and drawing a standard working curve of the mercury elements;
7) measurement of respective solutions to be measured
a) Pumping the liquid to be detected into an atomic fluorescence spectrometer (SK-sharp analysis) by using a sample inlet pipe, reducing by using the mixed solution of 2% potassium borohydride and 0.5% potassium hydroxide, measuring the intensity of antimony and arsenic elements in the solution, respectively substituting the measured intensity values into standard working curves of the antimony and arsenic elements, and calculating the content of the antimony and arsenic elements in the first liquid to be detected;
b) pumping the sample tube for the liquid II to be detected into an inductively coupled plasma mass spectrometer (Series2 type), measuring the strength of bismuth and lead elements in the solution, respectively substituting the measured strength values into the standard working curves of the bismuth and lead elements, and calculating the content of the bismuth and lead elements in the liquid II to be detected;
c) absorbing 2mL of the liquid three-purpose pipette gun of the liquid to be detected, injecting the liquid into an atomic fluorescence spectrometer (XGY-1011A), adding 5mL of the prepared 10% stannous chloride-2% hydrochloric acid mixed solution for reduction, measuring the strength of mercury elements in the solution, substituting the measured strength value into the standard working curve of the mercury elements, and calculating the content of the mercury elements in the liquid three to be detected;
d) pumping the liquid to be detected into an inductively coupled plasma spectrometer (Icap7400) by using a sample inlet pipe, measuring the strength of iron and sulfur elements in the solution, respectively substituting the measured strength values into standard working curves of the iron and sulfur elements, and calculating the content of the iron and sulfur elements in the liquid to be detected;
8) detection limits of respective elements
a) Detection limit of sulfur element: 30 ug/g;
b) detection limit of iron element: 400 ug/g;
c) detection limit of bismuth element: 0.05 ug/g;
d) detection limit of lead element: 1.0 ug/g;
e) detection limit of antimony element: 0.05 ug/g;
f) detection limit of arsenic element: 1.0 ug/g;
g) detection limit of mercury element: 0.0005 ug/g.
2. The method of claim 1, wherein: in the step 4), the concentrations of the standard working curves of the elements of sulfur, iron, bismuth, lead, antimony, arsenic and mercury are as follows:
sulfur: 0ug/mL, 0.5ug/mL, 1ug/mL, 5ug/mL, 10ug/mL, 20 ug/mL;
iron: 0ug/mL, 25ug/mL, 50ug/mL, 250ug/mL, 500ug/mL, 1000 ug/mL;
bismuth: 0ng/mL, 0.25ng/mL, 0.5ng/mL, 1ng/mL, 5ng/mL, 10 ng/mL;
lead: 0ng/mL, 25ng/mL, 50ng/mL, 100ng/mL, 500ng/mL, 1000 ng/mL;
arsenic: 0ng/mL, 2.5ng/mL, 10ng/mL, 50ng/mL, 75ng/mL, 100 ng/mL;
antimony: 0ng/mL, 0.25ng/mL, 1ng/mL, 5ng/mL, 7.5ng/mL, 10 ng/mL;
mercury: 0ng/mL, 0.05ng/mL, 0.2ng/mL, 0.5ng/mL, 1ng/mL, 1.5 ng/mL.
3. The method of claim 1, wherein: in the step 5), the maximum working parameters of each instrument are as follows:
the best operating parameters for an inductively coupled plasma mass spectrometer (Series type 2) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 20s, scanning mode peak jump, integration time: 1s, resolution 100, sampling depth 100step, sampling cone aperture 1.2mm, intercepting cone aperture 1mm, and isotope measured208Pb、209Bi, the carrier gas is high-purity argon with the purity of 99.9 percent;
the best operating parameters for the inductively coupled plasma spectrometer (Icap7400) are: incident power of 1150W and cooling gas flow of 13.5L.min-1Auxiliary air flow rate of 1.0L.min-1And the flow rate of atomized gas: 1.0L.min-1And the sampling pump speed is as follows: 50rpm, sample washing time 15s, optical cell temperature: 38 ℃, Camera temperature: at-40 ℃, the characteristic wavelength of the measured elements is S182.0nm and Fe259.9nm, and the carrier gas is high-purity argon with the purity of 99.9 percent;
the optimal working parameters of the atomic fluorescence spectrometer (SK-sharp analysis) are as follows: the main gas flow is 600mL/min, the auxiliary gas flow is 800mL/min, the arsenic lamp current: 30mA, antimony lamp current: 60mA, negative high voltage: 300V, pump speed: 100r/min, integration time: and 5 s. Wavelength of arsenic lamp: 193.7nm, antimony lamp wavelength: 217.6nm, and the carrier gas is high-purity argon with the purity of 99.9%;
the optimal working parameters of the atomic fluorescence spectrometer (XGY-1011A) are as follows: carrier gas flow rate 800mL/min, mercury lamp current: 50mA, negative high voltage: -260V, furnace temperature: 200 ℃, integration time: and 8 s. Mercury lamp wavelength: 253.7nm, and the carrier gas is high-purity argon with the purity of 99.9 percent.
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