WO2015007217A1

WO2015007217A1 - Element analysis method and injection device making use of organic cracking to cause an element to form a volatile

Info

Publication number: WO2015007217A1
Application number: PCT/CN2014/082346
Authority: WO
Inventors: 段旭川
Original assignee: Duan Xuchuan
Priority date: 2013-07-17
Filing date: 2014-07-16
Publication date: 2015-01-22
Also published as: CN103411892B; CN103411892A

Abstract

A method and injection device making use of organic cracking to cause an element to form a volatile for analysis; the injection device comprises a cracking device for heating of a sample, a condensation device for condensing the water and volatile organic material generated during sample heating, and optionally, a dust removal device for removing fine particulate matter; the method comprises the following steps: adding organics to a sample and mixing well; heating the mixture in a carrier gas of an inert gas, causing the hydrogen generated during organic cracking and the sample element to be tested to form an elemental volatile; separating and removing the water vapor in the elemental volatile, the organic volatile, and the fine particulate matter, then sending to the atomic spectrometer for measurement; without sample dissolution, the method directly measures solids and semi-solids, as well as trace elements in a liquid sample, especially trace elements in organic matrix samples such as foods; the method features rapid analysis, high accuracy, low cost of analysis, and no environmental pollution.

Description

The present application claims priority to Chinese Patent Application No. 2013 10299513.2, filed on Jan. 17, 2013, the entire content of

With the rapid development of modern instrumental analysis, the determination of elements, atomic spectrum, fast speed, high accuracy and low detection limit play an increasingly important role. The atomic spectrometer (AFS, AAS, ICP-AES-, ICP-MS, etc.) is used to determine the element in the sample. The first parameter is the entry of the sample (or sample introduction,

The original element was introduced into the spectrometer

The raw absorption or emission spectrum (or fluorescence or mass spectrometry) is measured.

The sample entry system used in atomic spectrometers is currently primarily a pneumatic atomization system.

The dynamic atomizer has two types: a concentric nebulizer and a cross nebulizer. The principle of pneumatic atomization is: Partially atomizing the sample solution by airflow (similar to a nebulizer), and then the aerosol carrying elements are introduced into the spectrometer for measurement. An important disadvantage of the pneumatic atomization method is that the atomization efficiency of the sample is too low. Only about 3 to 5% of the element-containing sample solution is actually entered into the instrument atom (ionizer), so that the sensitivity and detection limit of the instrument are affected. limit. In order to increase the sensitivity of these elements and reduce the detection limit, gaseous injection techniques have also been widely used in atomic spectroscopy. Typical gaseous injection methods are hydride injection and carbon dioxide injection. The former is a mixture of samples and sodium borohydride solution to form volatile hydride-producing elements (such as arsenic, antimony, bismuth, tin, selenium). , ruthenium, osmium, lead, etc.) react with a strong reducing agent sodium borohydride solution to form a volatile elemental hydride; the latter is formed by neutralization of inorganic carbon with a strong acid to form gaseous carbon dioxide. Compared with conventional pneumatic atomization methods, gaseous injection has higher efficiency and is generally considered to be 100%, so it has higher measurement sensitivity and detection limit. In addition, the gaseous sample is still a separation process, which makes 泖 The defined elements are separated from the solution of the coexisting elements of the matrix, avoiding possible matrix interference and spectral interference.

At present, when atomic spectrometry is used to determine the element, whether it is atomized injection or gas injection, in most cases, the sample to be tested needs to be digested (pre-treatment) to convert the sample into a solution, which makes the whole Analysis test process takes a long time (sample pre-processing time usually accounts for the entire analysis time)

50~75%), and because the chemical reagent is used in the pretreatment, the detection limit of the solution is affected, and the blank value is increased to affect the accuracy of the measurement. Furthermore, sample pretreatment creates environmental pollution and increases analytical testing costs.

It is well known that hydrogen is produced in the rapid cracking of raw materials such as coal, petroleum and biomass. This is currently the main method of large-scale hydrogen production. In the rapid cracking hydrogen production process, the organic matter is first cleaved and dehydrogenated to form hydrogen atoms, and then the hydrogen atoms combine to form hydrogen gas. In the present invention, before the hydrogen is dehydrogenated by the organic substance, the element in the sample is reduced to a volatile element hydride by using the generated hydrogen atom to carry out the injection of the element content in the sample.

The inventors have been engaged in the research of atomic spectroscopy gas injection technology. Recently, when attempting to react with an easily dehydrogenated small molecule organic compound such as uranium urate and an element which easily forms a hydride element such as arsenic, cadmium and lead, it has been found that the formic acid pin can be quickly formed and the hydrogenation is easily formed under heating. The elements of the object react to form volatiles, and the elements of the soil and the like can be measured by instruments such as atomic fluorescence. Since such an organic substance is not contained in an inorganic sample such as soil, it is necessary to artificially add such an organic substance before the measurement.

When the inventors further studied the measurement of such elements in food samples such as rice, the inventors were surprised to find that even when there is no artificial addition of a small molecule organic substance such as uranium acid, it is possible to rely on the organic matter contained in the sample itself. Those in samples such as grain can form elements to form volatiles and can be used for these related elemental measurements. Further in-depth exploration, the present inventors were more surprised to find that when a large amount of organic substances such as carbohydrates, water-soluble polymers, water-soluble vitamins, amino acids, and the like are added to these single element standards that easily form volatiles, the relevant elements can be These organic substances form elemental volatiles, and they are easily satisfied by various conditions required for sample introduction during instrumental analysis. Accordingly, the inventors have explored these phenomena by a large number of experiments. The reaction mechanism, which is determined to be because all organic matter can generate hydrogen by rapid cracking in an inert gas. The step of organic cleavage is to form a single hydrogen atom, and then the two hydrogen atoms are combined into hydrogen. When the sample contains an element capable of forming a hydride, a part of the hydrogen atom generated during the cleavage can first react with the element to form an elemental volatile. The inventors have completed the present invention through a large number of experiments. The elemental analysis method and the sample introduction device of the present invention not only do not require pretreatment of the sample, but also do not require expensive reagents such as ffi sodium borohydride, thereby reducing the analysis cost. Since the direct injection is used, the contamination of the reagent is also avoided, and the detection limit is significantly reduced.

The present invention provides a method for elemental analysis by using organic matter to cleave an element to form a volatile matter, which comprises the steps of:

Mixing step: adding organic matter to the sample to be tested, and mixing the two to form a mixture; heating step: heating the mixture to 200 Τ>, '900 在 in a carrier gas of an inert gas, directly causing at least a part of hydrogen generated by cracking of the organic matter The element to be tested in the sample reacts to form gaseous elemental volatiles;

The measuring step: the elemental volatile matter is sent from the carrier gas to the atomic spectrometer for elemental determination; wherein, when the sample to be tested itself already contains 20% by mass or more of the organic substance, the mixing step is omitted and the heating step is directly performed.

In one embodiment of the present invention, the method further includes a step of purifying the elemental volatiles before the determining step, wherein the elemental volatiles generated in the heating step are separated from the water vapor, the organic volatiles, and the fine particulate dust. Elemental volatiles are purified.

In one embodiment of the present invention, the organic substance is selected from organic substances having a solubility in water at a temperature of greater than or equal to 10% (m/V), wherein the weight of the organic substance added is at least 0.2 to 100 times the weight of the sample, preferably the weight of the sample. 0,5 to 50 times.

The present invention provides an injection device for analyzing an element to form a volatile substance by cleavage of an organic substance, comprising a cracking apparatus and a condensing apparatus for thermally cracking a sample, characterized in that

A heating chamber is arranged in the cracking device, a detachable liner is arranged in the heating chamber, and a carrier gas inlet pipe and a carrier gas outlet pipe are respectively arranged at the two side walls or openings of the liner; at both ends of the liner A liner sealing plug is arranged; a 坩埚 connecting rod fixed perpendicularly to the liner sealing plug is arranged inside the liner, so that the liner inlet end of the sample is sealed at the same time; by using the chin rest, the chin rest Connecting rod and liner sealing plug, manually or automatically take the sample into or out of the liner; Wherein, by placing the sample containing the element and the organic substance into the sample crucible, the sample and the organic substance are heated by the cracking equipment, the organic substance is cleaved to generate a hydrogen atom and an element to react to generate an elemental volatile substance, and the elemental volatile matter is sent from the carrier gas. Elemental spectrometry was performed on the atomic spectrometer.

In one embodiment of the invention, the analytical sample introduction device further has a dust removal device after the condensing device.

In one embodiment of the present invention, in the analysis sampling device, the heating chamber heats the sample crucible by electricity, microwave or laser, so that the sample is heated from room temperature to a specified temperature for less than 1 minute. , preferably less than 0 seconds.

In one embodiment of the invention, the condensing device is provided with a condensed water storage and discharge pipe, which is condensed using water or/and a semiconductor condensing device.

In an embodiment of the present invention, the dust removing device uses one or a combination of the following: a Scott spray chamber for atomic spectral injection, a cone spray chamber, a drum mist chamber, quartz wool or a mesh filter. device.

In one embodiment of the invention, a liner fastening ring is disposed at one or both ends of the liner of the cracking apparatus and externally connected to the heating chamber, and a thermocouple is disposed inside the heating chamber.

In one embodiment of the invention, the carrier gas is an inert gas, argon, nitrogen, and Z or helium, preferably argon.

The method of the present invention is particularly suitable for direct injection analysis in the case of atomic spectrometry elements, i.e., the sample to be tested is directly determined without being digested into a liquid. Compared with the conventional method, the measurement speed of the method is greatly improved. Since the borohydride which is relatively expensive and easily decomposed is not applicable, the analysis cost is remarkably lowered. At the same time, because the method does not use or use very few reagents, the blank noise is very low, with good sensitivity and detection limit.

Figure 1 is a schematic diagram of the total equipment with both condensing equipment and dust removal equipment (except

After the device);

Figure 2 is a schematic diagram of a heating pyrolysis device when the sample is injected horizontally;

Figure 3 is a schematic view of a device directly inserting a quartz tube containing a sample into a heating system;

Figure 4 (a > f) is a schematic representation of several representative liners. Symbol Description:

1. Cracking equipment; 2. Condensing equipment; 3. Dust removal equipment; 11. Carrier gas intake pipe;

】 2. carrier gas outlet pipe; 13. 坩埚 support; 14. sample 埒埚; 15. liner fastening ring; 16. thermocouple;

17. Liner (The directly inserted test tube is used as a special form of the liner, at which time the liner and the tie are two)

18. A liner gasket secured with a chin rest telescopic rod;

19. 埒埚Connection f (埒埚 When entering from the top opening of the split liner, the connecting rod is connected at the edge

20. 坩埚 connecting rod when entering from the bottom opening of the split liner;

21. Condensate storage and discharge pipe; 22. Heating the heating chamber of the liner.

In one embodiment of the present invention, a sample introduction apparatus for analyzing an element to form a volatile substance by organic matter cracking is disclosed, comprising a cracking apparatus 1 and a condensing apparatus 2 for heating a sample, characterized in that the cracking apparatus 1 is provided The heating chamber 22 is provided with a detachable liner 17 in the heating chamber 22, and a carrier gas inlet pipe 11 and a carrier gas outlet pipe 12 are respectively disposed at the both side walls or openings of the liner pipe 17; inside the liner pipe 17坩埚 connecting rods 19, 20 respectively fixed perpendicularly to the sealing plug 18 of the liner are provided, so that the injection end of the liner placed at the same time is sealed at the same time; a liner fastening ring 15 is provided at one end or both ends of the liner, The sample crucible 14 is manually or automatically removed or removed from the liner 17 by using a chin rest 13, a nipple connection T and a liner sealing plug.

Wherein, by placing the sample containing the element and the organic substance into the sample crucible, the sample and the organic substance are heated by the cracking equipment, the organic substance is cleaved to generate a hydrogen atom and an element to react to generate an elemental volatile substance, and the elemental volatile matter is sent from the carrier gas. Elemental spectrometry was performed on the atomic spectrometer.

Here, the heating may be carried out by electricity, microwave or laser, and the time during which the sample is heated from room temperature to a specified temperature is less than 1 minute, preferably less than 10 seconds, more preferably 2 to 5 seconds.

The carrier gas therein is an inert gas, which is argon gas, nitrogen gas and Z or helium gas, preferably argon gas.

The role of the liner is: (1) used to carry out the cracking reaction and the volatiles generated by the reaction are further purified by the carrier gas (by filling the liner with quartz wool: (2) for depositing carbon deposits generated during cracking, If the 3⁄4 liner is not used, such carbon deposits will deposit on the inner wall of the heating chamber, causing the heating chamber to be quickly contaminated and It makes the cleaning difficult, affects the test results, and the liner is movable and can be disassembled at any time. Therefore, it can be replaced regularly; (3) The liner reduces the dead volume of the reaction, does not contaminate the thermocouple and other The effect, as well as contamination from the heating chamber and other factors contaminate or affect the sample cracking reaction.

The volume of the liner can be large or small according to actual needs. In general, a quartz liner having an inner diameter of 10 to 40 mm and a length of 150 mm to 400 mm is preferable. The opening of the liner can be provided with only one end opening or an opening at both ends according to the actual situation. There are various methods for the position of the opening when the carrier gas enters the liner and is output from the liner. The method and position of the carrier gas in and out of several typical liners can be matched with the sample. (a) ~4(f).

As a special case of the liner, the unit can replace the sample crucible and the liner with the ffi tube, where the bottom of the tube is equivalent to the crucible and the upper portion of the bottom of the tube is equivalent to the liner.

The sample heating device is to put a test tube or a test tube containing a sample into a liner or a test tube which is passed through an inert gas (carrier gas), and is heated to a specified temperature by heating; or a crucible or a test tube containing the sample. , put into the already-constant liner with the carrier gas in advance; or make the 3⁄4 laser directly irradiate the sample through the liner (also with the carrier gas in advance) for heating. The specified heating temperature is between 2001 and 850 ° C, preferably between 350 ° C and 700 ° C, more preferably between 450 ° C and 650 ° C.

When the element forms volatiles during cracking, the volatiles sandwich the water vapor, volatile organic compounds and fine-grained dust generated during the cracking. These entrained large amounts of water vapor and the like will produce the gas pipeline and the final measurement. Contamination and clogging, etc., so the condensing and dedusting equipment should be removed. Such devices use water or (and) semiconductor condensing equipment to remove water vapor and volatile organic compounds. Condensing tubes can be used with small or micro U-condensing tubes, spiral condensing tubes, straight tube condensing tubes, etc., condensed water and organic matter. There are special collection and discharge pipes, which can not make the condensate flow back into the liner; for dust removal equipment, the drum type mist chamber or / and Scott fog chamber device, fiber cotton or mesh filter for atomic spectrum pneumatic atomization injection are mainly used. The device can also use a bubble dedusting device (ie, the carrier gas passes through the aqueous solution container, so that fine particles of dust are absorbed by the water).

In one embodiment of the present invention, there is provided a method for elemental analysis in which an organic material is cleaved to form a volatile matter, which is characterized by the following steps:

(1) adding organic matter to the sample to be tested, so that the two are uniformly mixed to form a mixture;

(2) heating: heating the mixture to 200 Torr to 900 Torr in a carrier gas of an inert gas, and hydrogen generated during the cracking of the organic matter directly forms gaseous elemental volatiles with the element to be tested in the sample; (3) Purification of elemental volatiles: Separation of elemental volatiles generated during heating from water vapor, organic volatiles and fine particulate dust, so that elemental volatiles are purified;

(4) Determination: The purified elemental volatiles are sent to the atomic spectrometer for detection by the carrier gas; when the sample itself already contains more than or equal to 20% of the organic matter, the method starts directly from step (2).

The organic substance is selected from organic substances having a solubility of less than or equal to 10% (m/V) in water at room temperature or under heating, wherein the weight of the organic substance added is at least 0.2 to 100 times the weight of the sample, preferably 0.5 of the weight of the sample. ~50 times.

In one embodiment, the heating temperature is 200 Ό 850 Ό, preferably 350 Ό to 700 Ό, more preferably 450. C ~ 650 ° C.

In one embodiment of the invention, the method of performing elemental analysis is performed as follows:

(1) Accurately weigh 0.0010~1.0000g sample and put it in sample tube or crucible; When the content of organic matter in the sample is less than 20%, mix organic matter in the sample, so that the total amount of organic matter is greater than the total mass of the mixed sample. 20%;

(2) The test tube or crucible containing the sample is heated to 350 Ό to 700 Torr in a carrier gas of an inert gas _;

(3) 3) the inert gas is used as a carrier gas, and the volatile matter of the element to be tested generated during the heating process is purified to remove water vapor, organic volatile matter and fine particulate dust;

(4) The purified elemental volatiles are sent to the atomic spectrometer atomic or ionization system for detection by the carrier gas.

In one embodiment, the elements measured in the present invention are: arsenic, mercury, antimony, bismuth, antimony, antimony, tin, lead, antimony, gold, silver, copper, palladium, platinum, rhodium, iridium, ruthenium, osmium, iridium , zinc, cadmium, cobalt, nickel, manganese, iron, vanadium, niobium, zirconium, hafnium, boron, gallium, indium, niobium, silicon, titanium.

In one embodiment, when the elements to be measured are arsenic, mercury, antimony, bismuth, selenium, tellurium, tin, lead, antimony, and the organic matter contained in the sample itself is less than or equal to 20%, the sample may be further extended to the sample. Thiourea or L-cysteine is added as a sensitizing masking agent in an amount of 0.2 to 100 times the weight of the sample.

In one embodiment, when the measured sample is an inorganic sample in the soil, sludge, and geological fields, a strong inorganic acid other than nitric acid and perchloric acid may be further added to the sample as a decomposition reagent, and the amount is the sample weight. 0.5 to 50 times. In one embodiment, the elemental analysis injection method for forming elements to form volatiles of the present invention is mainly used to detect traces in samples of food, biological, soil, geological, environmental, agricultural, and water quality fields. In one embodiment of the present invention The detection method is an analytical injection method for the formation of volatiles by elemental pyrolysis, including the following steps:

(1) adding organic matter to the sample to be tested, so that the two are uniformly mixed;

(2) Heating: The mixture is directly heated in a carrier gas of an inert gas to a specified temperature between 200 ° C and 850 ° C, so that the hydrogen generated when the organic matter is cleaved directly forms a gaseous state with the element to be tested in the sample. Elemental volatiles;

(3) Purification of elemental volatiles: The elemental volatiles generated during the heating process are separated from water vapor, organic volatiles and fine particulate dust to purify the elemental volatiles.

(4) Measurement: The purified elemental volatiles are sent to the atomic spectrometer for detection by the carrier gas.

The organic substance to be added is selected from organic substances which are soluble in water at a normal temperature, wherein the weight of the organic substance added is at least 0.2 to 100 times the weight of the sample, preferably 0.5 to 50 letters of the weight of the sample. When the sample itself already contains more than or equal to 20% organic matter, the method starts directly from step (2), that is, the reaction is carried out directly after weighing the sample. For example, in the determination of food, vegetables, fruits, aquatic products, meat and other samples are directly cracked to produce elemental volatiles.

In one embodiment, the organic substance soluble in water according to the present invention is selected from organic substances which are soluble in water at normal temperature, including but not limited to:

(1) 11:

(a) - alkoxide: cyclohexanol, tetraethylene glycol, hexahexol, ethyl carbitol.

(b) Polyol: ethylene glycol, glycerol, sorbitol, xylitol, pentaerythritol, butanediol, mannitol.

(2) Aldehydes and ketones: Propionaldehyde, lactaldehyde, diacetyl, 2,4-pentanedione, cyclohexanone.

(3) Carboxylic acids and their salts with potassium, sodium and ammonia:

(a) Fatty acids less than 5 carbons: formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, acetoacetic acid.

(b) Dicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, hydroxysuccinic acid.

(c) Polycarboxylic acids: tartaric acid, oxalic acid, malic acid, tartaric acid, ascorbic acid, EDTA (uranium: K tannic acid, pantothenic acid, gluconic acid, lactobionic acid). (e) Substituted acid: lactic acid (2~hydroxypropionic acid), malic acid (hydroxysuccinic acid), tartaric acid (2,3~'dihydroxysuccinic acid), citric acid (3~hydroxy~3~carboxypentane) Acid), glyoxylic acid, pyruvic acid, gallic acid.

(f) «Amino acids.

(4) Sulfur-containing organic compounds: DDTC, cysteine, acetylcysteine, mercaptobutyric acid, dimercaptopropionic acid, sulfosalicylic acid, sodium saccharin.

(5) Urea: Thiourea, biuret, semicarbazide.

(6) Sugar (carbohydrate: h

( _a ) Monosaccharides: glucose, sucrose, galactose, fructose, arabinose, xylose, amino sugar, propionose, acetonide, butyral, butanulose, oleyl aldehyde, erythritol, sul sugar.

b) Oligosaccharides: Disaccharide (cellobiose, maltose, sucrose, lactose, sucrose, rhamnose: K ring

(a) Ammonium salts of amines having less than 6 carbons and hydrochloric acid: ethylenediamine, butanediamine, hexamethylenediamine, tetramethylammonium chloride, cyclohexylamine, antipyrine.

(b) An amine salt of an alcohol amine of less than 6 carbons with hydrochloric acid or sulfuric acid: ethanolamine, diethanolamine, triethanolamine.

(c) dihydropyrrole tetrahydropyrrole, hydrazine, formamidine, ::: benzoquinone.

(8) Heterocyclic compounds: pyroxane, azole, pyrazole,

(9) Synthetic and semi-synthetic synthetic water-soluble polymers (reagent grade: h polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol (PEG, molecular weight between 190 and 7000), carboxymethyl Base starch, starch acetate, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose.

(10) Surfactant: an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant having a reagent grade of 9 to 40.

(a) anionic; potassium oleate, sodium oleate, ammonium oleate, triethanolamine oleate.

(b) cationic; cetyltrimethylammonium bromide, benzylammonium chloride, benzylammonium bromide, chlorinated (brominated) cetylpyridinium, tetradecyldimethylbenzylammonium chloride , methylbenzylammonium chloride, cetylpyridinium bromide.

(c) Amphoteric type: dodecyl dimethyl betaine.

(d) Non-ionic: 1 fatty alcohol polyoxyethylene ether series: RO (- CH2CH20 ) n H, R = C12 or C12 ~ C18, n = 7~20.

2 fatty acid alkanolamide, lauric acid diethanolamide.

3 fli: temperature - 20, Tween 40, Tween - 60, Tween 80, Tween - 65, Tween 85.

In one embodiment, the organic substance is preferably a salt of formic acid with an alkali metal or ammonia, a salt of gluconic acid with an alkali metal, and/or a polyol.

The atomic spectrometer of the present invention includes an atomic fluorescence spectrometer, an atomic emission spectrometer, an atomic absorption spectrometer, and an inorganic mass spectrometer.

The method for elemental analysis by using organic matter cracking to form a volatile substance by using an organic substance, and when the sample to be measured is an inorganic sample in soil, sludge and geological fields, nitric acid and perchloric acid may be further added to the sample. The inorganic strong acid other than the decomposition reagent is used in an amount of 0, 5 to 50 times the weight of the sample.

The inorganic acid according to the present invention means: hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, preferably hydrochloric acid. The features and advantages of the present invention are set forth in the <RTIgt;

A first preferred embodiment of the present invention is

(1) Device: Select the vertical inserting tube (inner diameter 40mm, length 300mm) in the drawing of Figures 1 and 4(d): The crucible is fed to the lining by the chin rest and its bracket placed in the lower part of the liner In the tube, the lower part of the bracket of the chin rest is connected with the sealing plug of the lower opening of the liner. When the raft carries the 坩埚 to the heated part in the middle of the liner, the sealing plug connected to the lower part of the bracket just seals the lower mouth of the liner. The carrier gas outlet on the cracking unit is connected to a straight tube condenser, and the carrier gas cluster condenser is connected to a Scott mist chamber connected to an inductively coupled plasma atomic emission spectrometer for atomization injection. The condenser is used to condense water vapor and organic volatiles generated during the cracking of organic matter; the Scott-shaped mist chamber is used for dust removal!: ffi is used to remove a small amount of water mist). 3⁄4 non-dispersive atomic fluorescence as a detection instrument, the instrument atomizer carrier gas (argon, 300 ml / min) inlet tube (the purified carrier gas outlet tube containing elemental volatiles in the present invention) also occurs with hydrogen The device (hydrogen flow rate 450 ml/min) is connected, and the hydrogen produced by the carrier gas and the hydrogen generator is merged and then entered into the atomizer of the atomic fluorometer for igniting the hydrogen argon flame.

(2) Determination method: Under the above conditions, in the quartz crucible (1CK30 ml), accurately add 5~20 mg of grain sample, because the food itself is an organic matrix sample, so do not add Machine. Then, under the introduction of a carrier gas, the fault is placed in the liner from the upper or lower portion of the liner through the chin rest and the chin rest bracket. When the device is connected and stable, turn on the heating switch, and quickly heat the tube to 500 4 in 4~10 seconds. Determine the toxic and harmful elements (arsenic, etc. in the sample such as grain according to the matrix matching external standard method or other (quantitative) method. The content of lead, mercury and cadmium).

A second preferred embodiment of the invention is:

(1) Device: Select the ffi specification stage 1 and 3 horizontal inserting pipe (inner diameter 40mm, length 300mm) cracking equipment: where the fault is caused by the lower part of the liner and its support into the liner, The lower part of the bracket is connected with the sealing plug of the right opening of the liner. When the crucible carries the crucible to reach the heated portion in the middle of the liner, the sealing plug connected to the right side of the bracket is just sealed to the right opening of the liner. The carrier gas outlet on the cracking device is connected to a U-tube condenser (there is a drain in the lower part of the U-shaped condenser), and the carrier gas is discharged from the condenser and then infused into an inductively coupled plasma atomic emission spectrometer. The drum type mist chambers used in the sample are connected. The condenser ffi is used to remove water from the condensed organic matter and organic volatiles; the drum-type mist chamber is used for dust removal (also used to continue to remove a small amount of water mist). Using a non-dispersive atomic fluorescence as a detection instrument, the instrument atomizer carrier gas (argon, 400 ml Z minutes) inlet tube (the purified carrier gas outlet tube containing elemental volatiles in the present invention) is also coupled with a hydrogen generator! : Hydrogen flow 450 ml Z minutes) Connected, the hydrogen produced by the carrier gas and the hydrogen generator merges and enters the atomic fluorometer atomizer to ignite the hydrogen argon flame.

(2) Measurement method: Under the above device conditions, 5 to 20 mg of vegetable samples are accurately added to a 5 ml quartz crucible. Since the vegetables themselves are organic matrix samples, do not add any organic matter. Then put ±ίί埚 into the furnace under the carrier gas. When the device is connected and stable, immediately turn on the heating switch, and quickly heat the tube to 550 °C in 4~15 seconds. Determine the toxic and harmful elements in the vegetable sample according to the matrix matching external standard method or the standard addition method. Containing lead, mercury and cadmium) A third preferred embodiment of the invention is:

(1) Device: Select the manual for the cracking equipment of the quartz tube (25 ml, inner diameter 18 mm, length i80 mm) in the drawings 1 and 3, and insert a 25 ml quartz tube sealing rubber stopper with a carrier gas inlet and carrier gas. The outlet, wherein the carrier gas outlet is connected to two U-tube condensers (secondary condensation), and the carrier gas exits the condenser and then enters a fine particle filter tube containing quartz wool. The condenser is used to condense water vapor and organic volatiles generated during the cracking of organic matter; quartz wool is used for dust removal. Use No-dispersion atomic fluorescence as a detection instrument, the carrier gas of the instrument atomizer (argon, 500 ml / min: after the cracker and purification equipment (including condensing equipment and dust removal equipment), and then with the hydrogen generator!: hydrogen flow Connected to the 450 cc / min), the carrier gas and hydrogen generators merge and enter the atomic fluorometer atomizer ffi to ignite the hydrogen argon flame.

(2) Measurement method: Under the above conditions, in the quartz tube (10~20 ml), accurately add 5~20 mg of milk powder sample. Since the milk powder itself is an organic matrix sample, do not add any organic matter. The test tube is then quickly inserted into a furnace that has been previously heated to 500 degrees Celsius under a carrier gas supply, and the instrument is started for measurement. Determine the content of harmful and beneficial elements (arsenic, lead, selenium, cadmium) in samples such as milk powder according to the matrix matching external standard method or standard addition method.

A fourth preferred embodiment of the invention is:

(1) Device: Select the vertical insertion tube (40 mm inner diameter, 300 mm length) of the cracking equipment in the steps 1 and 4 (a) of the manual: where the crucible is fed to the lining by the chin rest and its bracket placed on the upper part of the liner In the tube, the bracket of the chin rest is fed from the upper opening of the liner, and is connected with the sealing plug of the upper opening of the liner. When the raft carries the raft to reach the heated portion in the middle of the liner, the sealing plug connected to the upper portion of the bracket Just seal the opening on the liner. The carrier gas outlet on the cracking equipment is connected to a vertically placed spiral tube condenser (there is a drain in the lower part of the condenser), and the carrier gas condenser is discharged and then infused into an inductively coupled plasma atomic emission spectrometer. When the sample is connected, the 3⁄4 Scott mist chamber is connected, and then enters a fine particle filter tube containing quartz wool. The condenser is used for water vapor and organic volatiles generated when condensing organic matter is cracked; the Scott mist chamber and quartz cotton tube are mainly used for dust removal. Using achromatic atomic fluorescence as a detection instrument, the instrument atomizer carrier gas (argon, 500 ml/min) inlet tube (the purified carrier gas outlet tube containing elemental volatiles in the present invention) is also coupled with a hydrogen generator ( The hydrogen flow rate of 450 ml/min is connected, and the hydrogen produced by the carrier gas and the hydrogen generator merges and enters the atomizer of the atomic fluorometer to ignite the hydrogen argon flame.

(2) Determination method: Under the above device conditions, accurately add 5~10 mg of animal tissue or blood sample in a 10 ml quartz crucible. Since the animal tissue or blood itself is an organic matrix sample, do not add organic matter. . The crucible is then placed in a furnace under the introduction of a carrier gas. When the device is connected and stable, immediately turn on the heating switch, heat the tube to 600 4 in 4~15 seconds, and measure the toxic and harmful elements in the sample such as grain according to the matrix matching external standard method or other methods.

(lead, cadmium) content A fifth preferred embodiment of the invention is:

(1) Apparatus: As shown in Figs. 1 and 3, the same horizontal heating cracking apparatus as in the second preferred embodiment was employed, in which a liner (inner diameter 40 mm, length 300 mm) was horizontally placed in the middle of the heating furnace. Connect the carrier gas outlet on the cracking unit to a vertically placed, (here _three ) u-type condensers in series with a condenser unit (one drain for each U-shaped condenser), using a semiconductor The refrigeration device ffi is condensed. After the carrier gas condenser is out, it enters a fine particle filter tube filled with quartz wool. The condenser is used for the water vapor and organic volatiles generated when the condensed organic matter is cracked; the quartz cotton tube ffi is used for dust removal. Using ffi non-dispersive atomic fluorescence as a detection instrument, the instrument atomizer carrier gas (argon gas, 300 ml/min) inlet tube (the purified carrier gas outlet tube containing elemental volatiles in the present invention) is also coupled with a hydrogen generator (Hydrogen flow rate 450 ml/min) is connected, and the hydrogen produced by the carrier gas and the hydrogen generator merges and enters the atomizer of the atomic fluorometer for igniting the hydrogen argon flame.

(2) Determination method: Under the above conditions, in the quartz crucible (10~30 ml), accurately add 10~20 mg of soil sample. Because the soil itself is an inorganic matrix sample, it is necessary to add organic matter. For example, add 50% sodium formate solution 0J ml, add 10% thiourea (ml as a sensitizing masking agent, and add 1 drop of concentrated hydrochloric acid as a cosolvent at the same time. Then put the sputum into the heating furnace under the carrier gas When the device is connected and running stably, immediately turn on the heating switch, and quickly heat the tube to 650 °C in 4~15 seconds. Determine the toxic and harmful elements in the soil sample according to the matrix matching external standard method or other methods (arsenic, The content of bismuth, mercury, lead).

A sixth preferred embodiment of the present invention is

(1) Device: As shown in Fig. 1 and Fig. 4(b), the upper part is directly inserted into a cracking device of a quartz tube (25 ml, inner diameter i8 mm, length 180 mm). The test tube sealing rubber plug is provided with a carrier gas inlet and a carrier gas outlet, wherein the carrier gas outlet is connected to a U-tube condenser (there is a drainage device in the lower part of the U-shaped condenser), and the carrier gas is discharged from the condenser. It enters a conical mist chamber equipped with an inductively coupled plasma atomic emission spectrometer for further purification of fine particles. Using achromatic atomic fluorescence as a detection instrument, the instrument atomizer carrier gas (argon, 350 ml/min) inlet tube (the purified carrier gas outlet tube containing elemental volatiles in the present invention) is also coupled with a hydrogen generator ( The hydrogen flow rate is 450 ml/min), and the hydrogen produced by the carrier gas and the hydrogen generator merges and enters the atomizer of the atomic fluorometer] 3⁄4 to ignite the hydrogen argon flame.

(2) Determination method: Under the above device conditions, in the quartz test tube (10~20 ml), accurately Into 200 microliters of surface water sample, because the surface water itself does not contain or contains very few organic matrix samples, so add organic matter. In this embodiment, 0.1 ml of a 50% formic acid solution was added, and 0.1 ml of 10% thiourea was added as a sensitizing masking agent. The crucible is then placed in a furnace under the introduction of a carrier gas. When the device is connected and stable, immediately turn on the heating switch, heat the tube to 450 °C in 4~15 seconds, determine the toxic and harmful element arsenic in the sample according to the matrix matching external standard method or other methods. The seventh preferred embodiment is:

(1) Apparatus: As shown in Fig. 1 and Fig. 4(d), the same vertical lower liner cracking apparatus and purification apparatus as in the second preferred embodiment are employed.

(2) Measurement method: Under the above apparatus conditions, 10 to 20 mg of sludge sample was accurately added to a 10 ml quartz crucible. Since the sample belongs to an inorganic matrix sample, it is necessary to add an organic substance. In this embodiment, 0.1 ml of 50% oxalic acid solution was added, and 0.1 ml of 10% thiourea was added as a sensitizing masking agent. Then place the 3⁄4 埚 into the furnace while the carrier gas is being supplied while sealing the liner. When the device is connected and stable, immediately turn on the heating switch, heat the tube to 500 4 in 4~ 0 seconds, and determine the content of toxic and harmful elements (lead and strontium) in the soil sample according to the matrix matching external standard method or other methods. .

An eighth preferred embodiment of the present invention is

(!) 3⁄4*: The same horizontal liner cracking equipment and purification equipment as the second preferred embodiment.

(2) Determination method: Under the above device conditions, accurately add 10 mg of ore sample in 5 ml of quartz 3⁄4 ,, and add 0.1 ml of 50% glycerol solution, and add 10 ml of 10% thiourea as sensitization mask. At the same time, add 1 drop of hydrofluoric acid as a cosolvent. After the rubber plug that has been ventilated is placed, the carrier gas is introduced and the furnace temperature is heated to 500 Torr in 5 seconds, and the content of toxic and harmful elements (arsenic arsenic) in the soil sample is determined according to the matrix matching external standard method or the other method.

The elemental analysis sampling device and method disclosed in the present invention for utilizing organic matter cleavage dehydrogenation to form volatiles of elements have advantages over the prior art in that: (1) the trace elements in the sample can be directly determined without digesting the sample. This saves the overall measurement time of the sample, improves the detection speed, and also reduces the detection limit deterioration caused by the contamination of the reagent by the reagent digestion method and the environmental pollution of the reagent when the sample digestion method is used, and the analysis test is lowered. cost. (2) Avoid the use of boron hydride in the traditional method When sodium is used as a reducing agent, the acidity interferes with other coexisting ions. (3) Since the sample is directly analyzed without introducing any additional reagent, the measurement sensitivity is significantly improved and the detection limit is lowered. (4) When the sample amount is very small, if the method of digesting and re-sizing is adopted, it may be impossible to detect because the sample element is diluted, and the method can be detected because it is directly determined. (5) The present invention can directly measure trace elements in a sample, particularly toxic and harmful elements in foods and organic chemicals, without sample digestion (pretreatment). It has the advantages of very fast analysis speed, low detection limit and high accuracy. It also reduces the cost of analysis and has no environmental pollution.

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that these examples are merely illustrative of the invention and are not intended to limit the scope of the invention. Various reagents used in the present invention are commercially available.

Example h Analysis of the content of rice in rice

In a 20 ml quartz tube, accurately add 10 mg of rice sample, then cover and plug a rubber stopper with a carrier gas (argon, flow 300 ml / min) inlet and outlet into the test tube. The carrier gas outlet tube carrying the elemental volatiles is connected in series with a U-shaped condenser (water and organic volatiles) and a plastic tube containing quartz wool (removing particulate matter), and the purified carrier gas and atomic fluorescent atoms The catalyst is connected, and the atomic fluorescence atomizer is also connected to a hydrogen generator (hydrogen generation amount of 450 ml/min) to provide a hydrogen source for normal atomization of the atomizer. The carrier gas inlet is connected to the atomic fluorescent carrier gas supply pipe. When the device is connected and stable, immediately insert the test tube into a constant temperature furnace that has been heated to 550 预先 in advance, determine the arsenic content in the rice according to the external standard method, and use another rice standard (GB W 3⁄4080684) as the external standard. The curve, the arsenic content was determined to be 110 ppb. The arsenic in the sample was determined to be 105 ppb by the non-dispersive atomic fluorescence method using hydride formation after digestion with a normal nitric acid-perchloric acid method. This method is in good agreement with the conventional method.

Example 2; Analysis of cadmium in spinach

The cadmium content in spinach was determined using the full set of equipment and parameters of the second preferred embodiment. In a quartz crucible (10 ml), accurately add 20 mg of spinach sample. Since the vegetable itself is an organic matrix sample, do not add organic matter. Then, under the carrier gas, the 3⁄4 埚 is placed in a constant temperature furnace which has been heated to 550 Torr in advance, and the atomic fluorescence of the instrument is started to start measurement. The external standard standard curve is compared with another spinach standard GBW10015, and the result is 88 ppb. . However, the results of the normal nitrous-perchloric acid digestion of the sample and the cadmium in the sample by hydride generation were 83 ppb, which shows that the method is in good agreement with the conventional method. Example 3: Analysis of lead in blood

In a 25 ml tube, add 20 mg of blood sample, then cover and plug a rubber stopper with a carrier gas (argon) inlet and outlet into the tube. The carrier gas outlet tube carrying the elemental volatiles is connected in series with a condenser (except water and organic volatiles), and the purified carrier gas is connected to an atomic fluorescence atomizer. At this time, the atomic fluorescence atomizer is also connected to the hydrogen generator to provide a hydrogen source ffi to the atomizer for normal ignition. The carrier gas inlet is connected to the atomic fluorescent carrier gas supply pipe. When the device is connected and stable, immediately insert the test tube into a constant temperature oven that has been heated to 500 °C. Determine the lead content in the serum according to the external standard method, and use another serum standard GBW(E)09003. Standard standard curve, the measurement result is 5.3 ppb. The content of mercury in the sample was 5.00 ppb after the sample was digested by normal nitric acid ~ 'perchloric acid method. The method was in good agreement with the conventional method.

Example 4: Determination of gold in gold-plated resin

In a 25 ml tube, add 10 mg of powdered dry gold-adsorbed resin sample and then add 1 ml of 50% thiourea solution. After mixing, cover and insert a rubber stopper with a carrier gas (argon) inlet and outlet into the tube. The carrier gas outlet is then coupled to an atomic fluorescence atomizer, where the atomic fluorescence atomizer is also coupled to a hydrogen generator to provide a source of hydrogen for normal atomization of the atomizer. The carrier gas inlet is connected to the atomic fluorescent carrier gas supply pipe. Immediately after the device is connected and stabilized, the test tube is inserted into a constant temperature oven that has been previously heated to 650 Torr, and the gold content of the resin is determined according to the matrix matching external standard method. The result of the measurement was 5 ppm, and the result of the dispersive atomic fluorescence sodium borohydride reduction method of 3⁄4 borohydride hydrogenated hydride was 4.7 ppm, which shows that the method is in good agreement with the conventional method.

Example 5; comparative test

Taking Example 1 as an example, the arsenic content in the same standard substance (rice, GBW(E) 080684) was determined by this method and nitric acid-perchloric acid digestion borohydride hydrogenation-non-dispersive atomic fluorescence spectrometry (HG AFS). The test results are shown in Table 1. RSD (%) calibration curve phase sample entry mode analysis, all the time used to form the sample to separate the cost of the invention 0,0002 less than 3 direct injection 5 minutes method

HG~A: FS 0.0004 less than 2 requires sample digestion for at least 3 hours.

Example 6

The test was carried out using the apparatus of the fifth preferred embodiment. In a 10 ml quartz crucible, accurately add 20 mg of the tailings sample, add 20% of cetyltrimethylammonium bromide 0.2 ml, then add 10% thiourea 0.2 ml, 1 drop of hydrochloric acid solution. When the device is connected and stable, the crucible is immediately sent to a constant temperature furnace that has been heated to 650"C in advance, using a similar tailings standard material as the external standard curve, and the crucible is determined by electrothermal quartz tube atomic absorption spectrometry. The results were similar to those obtained by the mixed acid digestion-hydride atomic absorption method, which were 5.72 ppm and 6.13 ppm, respectively.

Example 7

In a 25 ml tube, add 20 mg of sandstorm sample, then add 10% of Tween-60 aqueous solution 0.3 ml, mix and place one with a carrier gas (argon, flow 400 ml / min) inlet and outlet The rubber stopper covers and plugs the tube. The carrier gas outlet is connected to a U-tube condenser (there is a drain in the lower part of the U-type condenser), and the carrier gas is discharged from the condenser to the drum-type mist chamber for inductively coupled plasma atomization. Connected. The atomic fluorescence atomizer is also coupled to the hydrogen generator to provide a source of hydrogen for the normal ignition carrier gas inlet of the atomizer to be coupled to the atomic fluorescent carrier gas supply. The carrier gas outlets are then separately coupled to an atomic fluorescence atomizer. When the device is connected and stable, immediately insert the test tube into a thermostat that has been heated to 550 Torr in advance, and determine the lead content in the sample sink according to the external standard method. The results were in agreement with the results obtained by the sodium borohydride reduction method, which was usually 26 ppb and 25.7 ppb, respectively.

Example 8

The test was carried out using the apparatus of the fourth preferred embodiment. In a 10 ml quartz crucible, accurately add 20 mg of soil sample, then add 50 ml of 50% glucose, then add 10 ml of 10% thiourea, and mix well with the sample. When the device is connected and stable, the crucible is immediately sent to a constant temperature furnace that has been heated to 500 预先 in advance, so that the content of the monument can be determined by the external standard method. The results were similar to those obtained by hydride atomic fluorescence, and were 18 ppb and 16.5 ppb, respectively. Example 9

The test was carried out using the apparatus of the third preferred embodiment. In a 10 ml quartz crucible, accurately add 0.2 ml of drinking water sample, then add 50 ml of triethanolamine hydrochloride 0.1 ml, then add 0% thiourea 0.2 ml, and mix with the sample. When the device is connected and stable, the crucible is immediately sent to a constant temperature furnace that has been heated to 550' Torr beforehand, and the cadmium content is determined by external standard method without dispersive atomic fluorescence. The results were similar to those obtained by ICP-MS, which were 23 ppb and 22,5 ppb, respectively.

Example 10

The test was carried out using the apparatus of the fourth preferred embodiment. In a 10 ml quartz '埚, accurately add 20 mg of the burned dust sample, then add 50% of sorbitol 0.1 ml, then add 0% thiourea 0.2 ml, and mix with the sample. When the device is connected and stable, the crucible is immediately sent to a constant temperature furnace that has been heated to 450 Torr in advance, and the ffi external standard method is used to determine the lead content. The results were similar to those obtained by hydride atomic fluorescence, and were 18 ppb and 16.5 ppb, respectively.

The above is only the preferred embodiments and examples of the present invention, and it should be noted that those skilled in the art can make thousands of improvements and retouchings without departing from the principles of the present invention. Improvements and retouching are also subject to the scope of protection of the present invention.

Claims

A method for elemental analysis by using organic matter to cleave an element to form a volatile matter, the method comprising the steps of:

Mixing step: adding organic matter to the sample to be tested, and mixing the two to form a mixture; heating step: heating the mixture to 2 (Χ) 'Ό~900Ό in a carrier gas of an inert gas to cause at least a part of the organic matter to be cracked Hydrogen directly reacts with the element to be tested in the sample to form gaseous elemental volatiles;

2. The method according to claim 1, further comprising a purification step before the determining step, wherein the elemental volatiles generated in the heating step are separated from water vapor, organic volatiles and fine particulate dust to make an element The volatiles are purified.

3. The method according to claim 1 or 2, wherein the organic substance is selected to have an organic substance having a solubility in water of greater than or equal to 10% (m/V) at room temperature, and the weight of the organic substance is the weight of the sample (12 to ί00 times .

4. The method according to claim 3, characterized in that the weight of the organic substance is 0, 5 to 50 times the weight of the sample.

The method according to any one of claims 1 to 3, wherein in the heating step, the mixture is heated by microwave, microwave or laser, so that the time during which the sample is heated from room temperature to a specified temperature is less than 1 minute.

6. The method of claim 5, wherein the sample plexus is heated to rise to a specified temperature for less than 10 seconds.

7. The method according to claim 2, wherein the dust removing device selects one or a combination of the following: a Scott spray chamber for atomic spectral injection, a cone spray chamber, a drum type mist chamber, and quartz wool. Or wire mesh filtration equipment.

8. A method according to any one of claims 1 to 7, characterized in that the carrier gas is argon, nitrogen and/or helium.

9. The method according to claim 1, wherein the following steps are performed:

(]) Accurately weigh 0.0010~L0000g sample and put it in sample tube or crucible; When the content of organic matter in the sample is less than 20%, mix organic matter in the sample, so that the total amount of organic matter is greater than the total mass of the mixed sample. 20%;

(2) Heat the test tube or crucible containing the sample in a carrier gas of inert gas to 350Ό~700'Ό

(3) using an inert gas as a carrier gas to purify the volatile matter of the element to be tested generated during the heating process, so that water vapor, organic volatile matter and fine particulate dust are removed;

10. The method according to claim 9, characterized in that in the step (2), the test tube containing the sample or the crucible is heated to 450 "C to 650 ° C in a carrier gas of an inert gas.

The method according to any one of claims 1 to 10, wherein the organic substance is a salt of formic acid with an alkali metal or ammonia, a salt of gluconic acid with an alkali metal, and a Z or a polyhydric alcohol.

The method according to any one of claims 1 to 5, wherein the element means: monument, mercury, strontium, barium, selenium, tellurium, tin, lead, antimony, gold, silver, copper, palladium, Platinum, rhodium, ruthenium, osmium, iridium, zinc, cadmium, cobalt, nickel, manganese, iron, vanadium, niobium, zirconium, hafnium, boron, gallium, indium, lanthanum, silicon, titanium.

13. The method according to claim 12, wherein when the measured element is arsenic, mercury, antimony, bismuth, selenium, tellurium, tin, antimony, when the sample itself contains less than or equal to 20% by weight of organic matter, Further, thiourea or L-cysteine may be added to the sample as a sensitizing masking agent in an amount of 0.2 to 100 times the weight of the sample.

14. The method according to any one of claims 1 to 13, wherein when the sample to be measured is an inorganic sample in the soil, sludge or geological field, a mineral acid other than nitric acid and perchloric acid may be further added to the sample as a decomposition reagent. It is used in an amount of 0.5 to 50 times the weight of the sample.

15. The method according to claim 14, wherein the inorganic acid refers to; hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid.

16. A sample introduction device for performing analysis by using organic matter to cleave an element to form a volatile matter, comprising a cracking device and a condensing device for thermally cracking a sample, characterized in that

A heating chamber is arranged in the cracking device, a detachable liner is arranged in the heating chamber, and a carrier gas inlet pipe and a carrier gas outlet pipe are respectively arranged at the two side walls or openings of the liner; at both ends of the liner Setting lining Pipe sealing plug; inside the liner, respectively, a connecting rod fixed perpendicularly to the sealing plug of the liner, so that the inlet end of the liner after the sample is placed is sealed at the same time; by using the chin rest, the connecting rod and the lining Pipe sealing plug, manually or automatically take the sample 坩埚 into or out of the liner;

The sample introduction device according to claim 14, further comprising a dust removal device after the condensation device.

A method according to claim 16 or 17, characterized in that in the cracking apparatus, the sample and the organic matter are heated to 350 Torr >, '700 Torr in a carrier gas of an inert gas.

A method according to claim 18, characterized in that in the cracking apparatus, the sample and the organic substance are heated to 450 Ό to 650 Torr in a carrier gas of an inert gas.

The sample introduction device according to any one of claims 16 to 19, wherein the heating chamber heats the sample crucible by electricity, microwave or laser to increase the temperature of the sample from room temperature to a specified temperature. Less than 1 minute

21. The sample introduction device of claim 20, wherein the sample is heated from room temperature to a specified temperature for less than 10 seconds.

The sample introduction device according to any one of claims 16 to 21, characterized in that the condensation device is provided with a condensed water storage and discharge pipe.

23. The sample introduction device according to claim 17, wherein the dust removal device is selected from one or a combination of the following: a Scott spray chamber for atomic spectral injection, a cone spray chamber, a drum type mist chamber, Quartz cotton or wire mesh filtration equipment.

The sample introduction device according to any one of claims 16 to 23, characterized in that, in the cracking device, a liner fastening ring is disposed at a position where one or both ends of the liner contact the outside of the heating chamber, A thermocouple is provided inside the heating chamber.

The sample introduction device according to any one of claims 16 to 24, characterized in that the carrier gas is an inert gas and is argon gas, nitrogen gas and/or helium gas.

The sample introduction device according to any one of claims 16 to 25, wherein the element means: arsenic, mercury, antimony, bismuth, bismuth, antimony, tin, lead, antimony, gold, silver, copper , palladium, platinum, rhodium, ruthenium, 锇, 铱, Zn, cadmium, cobalt, nickel, manganese, iron, vanadium, niobium, zirconium, hafnium, boron, gallium, radium, lanthanum, silicon titanium.

The sample introduction device according to any one of claims 16 to 26, wherein the organic substance is a salt of formic acid with an alkali metal or ammonia, a salt of gluconic acid and an alkali metal, and/or a polyhydric alcohol.