CN101650350B - Gaseous arsenic compound instrument combination morphological analysis and determination method - Google Patents
Gaseous arsenic compound instrument combination morphological analysis and determination method Download PDFInfo
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- CN101650350B CN101650350B CN200910075365XA CN200910075365A CN101650350B CN 101650350 B CN101650350 B CN 101650350B CN 200910075365X A CN200910075365X A CN 200910075365XA CN 200910075365 A CN200910075365 A CN 200910075365A CN 101650350 B CN101650350 B CN 101650350B
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Abstract
A gaseous arsenic compound instrument combination morphological analysis and determination method is used for solving the problem of sensitive, rapid and accurate analysis and determination of gaseous arsenic compounds. The technical scheme is as follows: the method is implemented on a gaseous arsenic compound analysis and measurement online coupling system consisting of a standard generation or sample collection device, a low-temperature trapping device, a vacuum heat-insulation separation tank, a gas-carrying pipeline, a hydrogen generation device, an atomic fluorescence spectrometer and a signal recording device, and is carried out according to the following steps: a. arsenic compound generation or sample collection; b. and (3) trapping and separating gaseous arsenic compounds: c. and (3) separating gaseous arsenic compounds: d. and (4) detecting the gaseous arsenic compound. The method has ideal separation effect on the gaseous arsenic compound, good reproducibility, high sensitivity, good linear correlation on the gaseous arsenic compounds with different concentrations, wide linear range, good stability, low cost, simple operation and low analysis cost.
Description
Technical field
The present invention relates to a kind of compound analysis assay method, especially for volatile gaseous arsenic compound AsH
3, CH
3AsH
2, (CH
3)
2AsH, (CH
3)
3The assay determination of As belongs to the chemical detection analysis technical field.
Background technology
Arsenic is the environmental contaminants of severe toxicity, in commercial production and geological movement, has a large amount of arsenic to discharge into environment, and harm humans is healthy.These inorganic arsenic or organoarsenium compounds that are released in the environment can be through the inorganic and organo-arsenic morphologization compound of series of physical chemistry and biological agent process generation different shape.What wherein, cause in the recent period that people pay attention to is in the biomass geochemistry cyclic process of arsenic, can be converted into the bigger gaseous arsenic compound of toxicity.Compare with the arsenic compound of solubility, gaseous arsenic compound not only toxicity is stronger, and high volatility, is difficult to control, and health of human body is had bigger harm and disguise.So it is very necessary to set up quick, sensitive, accurate and cheap gaseous state arsenic analyzing detecting method.The toxicity of gaseous state arsenic is strong, and the gaseous state arsenic of utmost point low content promptly can cause fatal toxic reaction, so higher to the sensitivity and the security requirement of analytical technology.But the method for separating and analyzing of at present relevant arsenic compound is to develop to water-soluble arsenic compound basically, is difficult to satisfy the analyzing and testing of gaseous arsenic compound.The current method that is used for the arsenic compound analysis mainly comprises liquid chromatography-atomic fluorescence spectrophotometry coupling, liquid chromatography-atomic absorption spectrum coupling, liquid chromatography-inductivity coupled plasma mass spectrometry coupling etc.These methods are effectively to the compartment analysis of solubility arsenic compound, analyzing and testing highly sensitive, technical method is ripe, stable.But the target compound of these analytical technologies must be a solution state, and can only carry out compartment analysis to solubility arsenic morphology compound.Though and only a few gaseous state arsenic analytical approach has report, analytical effect is unsatisfactory.Wherein the gas chromatography-mass spectrography report is used to the compartment analysis of gaseous arsenic compound, but because adopt the detecting device of non-exclusive, sensitivity is lower.Though the detection sensitivity of gas chromatography-inductivity coupled plasma mass spectrometry coupling and gas chromatography-mass spectrography specific sensitivity mutually are greatly improved, but instrument costs an arm and a leg, complicated operation, service condition requires high, is unfavorable for applying.In a word; Existing arsenium morphological analysis method can not satisfy the compartment analysis of gaseous arsenic compound mostly; The form separate analytical technique and the on-line analysis that also lack gaseous arsenic compound in gaseous arsenic compound morphological analysis technical field detect combined system, and its sensitivity is difficult to satisfy the analysis requirement of sample.
Summary of the invention
Technical matters to be solved by this invention is to set up a kind of instrument coupled speciation measuring method of gaseous arsenic compound, fast, accurately reaches low-cost assay determination with what satisfy gaseous arsenic compound in the environmental sample.
The alleged problem of the present invention is solved by following technical scheme:
A kind of instrument coupled speciation measuring method of gaseous arsenic compound; Its special feature is; It utilizes gaseous arsenic compound assay determination on-line coupled system to measure; Said gaseous arsenic compound assay determination on-line coupled system is made up of standard generation or sample collection device, cryogenic trapping device, vacuum insulation separating tank, gas-carrier pipeline, hydrogen formation apparatus, AFS and signal recording apparatus, and determination step is following:
A. arsenic compound generates or sample collection: reaction produces and collects gaseous arsenic compound in said standard generation or sample collection device;
B. gaseous arsenic compound captures and separates: with above-mentioned gaseous arsenic compound, bring the cryogenic trapping device into through carrier gas, the gaseous arsenic compound that is captured is captured and is condensate on the separating column of cryogenic trapping device;
C. gaseous arsenic compound separates: after capturing completion, rapidly separating column is transferred in the vacuum insulation separating tank, makes its slow intensification, the gaseous arsenic compound that is captured on the separating column is released at low temperatures, realizes quick baseline separation;
D. the detection of gaseous arsenic compound: the hydrogen that separated gaseous arsenic compound produces with said hydrogen formation apparatus under the effect of carrier gas and the carrier gas of said AFS mix; Get into atomic fluorescence spectrometer atomizer; At high temperature carry out atomization; Generate gaseous state arsenic atom, the arsenic atom that is excited deactivates and sends atomic fluorescence, and the photosignal that is produced obtains testing result by the signal recording apparatus record.
Above-mentioned instrument coupled speciation measuring method of gaseous arsenic compound; Said standard generation or sample collection device comprise the reaction vessel jar and the lid of PTFE material; Lid is provided with solution of potassium borohydride pipeline, helium inlet and gas vent; The solution of potassium borohydride pipeline connects peristaltic pump, is provided with magnetic agitation in the reaction vessel jar.
Above-mentioned instrument coupled speciation measuring method of gaseous arsenic compound, said cryogenic trapping device is made up of liquid nitrogen container and separating column; The separating column cylinder length 50-60cm of PTFE material, filling length in it is the absorbent cotton of 20-30cm, the absorbent cotton quality is 0.5-1.0g; Cylinder external diameter 6.0mm; Internal diameter 4.0mm, separating column insert in the liquid nitrogen container, make to fill 3-5cm under the complete submergence liquid nitrogen liquid level of absorbent cotton part.
Above-mentioned instrument coupled speciation measuring method of gaseous arsenic compound; Said hydrogen formation apparatus comprises Mixed liquid T-branch, is respectively equipped with aqueous slkali pipeline and acid solution pipeline, hydrogen pipeline, gas-carrier pipeline, auxiliary air pipe and the gas-liquid separator of peristaltic pump; Said Mixed liquid T-branch connects aqueous slkali pipeline, acid solution pipeline and one-level hydrogen pipeline respectively; Said gas-carrier pipeline is communicated with the one-level hydrogen pipeline; The terminal one-level gas-liquid separator that is communicated with of one-level hydrogen pipeline; One-level gas-liquid separator gas vent pipeline is communicated with the secondary gas-liquid separator, and auxiliary air pipe is communicated with one-level gas-liquid separator gas vent pipeline, the atomizer of secondary gas-liquid separator gas vent pipeline and separating column export pipeline, AFS) entering the mouth is communicated with.
Above-mentioned instrument coupled speciation measuring method of gaseous arsenic compound; Feeding concentration is 4% solution of potassium borohydride in the said aqueous slkali pipeline; Feeding concentration is 10% hydrochloric acid in the said acid solution pipeline; Feed purity in said gas-carrier pipeline, the auxiliary air pipe respectively and be 99.99% argon gas, argon flow amount is 500mL/min; The helium that feeds in said standard generation or the sample collection device is high-purity helium, and purity is 99.999%, and flow velocity is 50-80mL/min, nebulizer gas pressure 0.1-0.15Mpa.
The present invention is directed to sensitive, the gaseous arsenic compound analysis determining method problem fast and accurately of present shortage; A kind of simple to operate, with low cost, sensitive and accurate gaseous arsenic compound analysis determining method has been proposed; This method is carried out on-line analysis by means of the combined system of being made up of cryogenic trapping, separation, AFS and signal recording apparatus to volatile gaseous arsenic.This method is utilized the special efficacy detecting device of the cheap relatively AFS of cost as gaseous arsenic compound, and highly sensitive, selectivity is strong, technology maturation, stable performance.Process operations such as the capture of gaseous arsenic compound, separation are simple, with low cost, avoided the use of large-scale chromatographic apparatus and chromatograph packing material, utilize absorbent cotton and temperature control equipment to replace traditional chromatography packed column, greatly reduce the difficulty of analytical test; Because filling material adopts absorbent cotton, entire separation system pipeline gaseous tension is very little, makes tripping device be more prone to carry out on-line coupling with atomic fluorescence spectrophotometry, and the pipeline of having avoided the air pressure height to cause is simultaneously revealed.Experiment shows, adopts the inventive method, can in 3 minutes, reach baseline separation for the volatile gaseous arsenic compound of different shape; Separating effect to gaseous arsenic compound is desirable, favorable reproducibility (n=7, relative standard deviation (RSD)≤8%), highly sensitive (detection limit DL is 0.005ng As); To variable concentrations gaseous arsenic compound linear dependence good (more than the r=0.99), the range of linearity wide (0.05ng-200ngAs), good stability; With low cost, simple to operate, analysis cost is low.
Description of drawings
Fig. 1 is a gaseous arsenic compound assay determination on-line coupled system synoptic diagram of the present invention;
Fig. 2 is that gaseous arsenic compound separates spectrogram.
Label is following in the accompanying drawing: 1. aqueous slkali pipeline, 2. acid solution pipeline, 3. Mixed liquid T-branch, 4. one-level hydrogen pipeline, 5. gas-carrier pipeline; 6. one-level gas-liquid separator, 7. one-level gas-liquid separator gas vent pipeline, 8. auxiliary air pipe, 9. secondary gas-liquid separator, 10. separating column export pipeline; 11. secondary gas-liquid separator gas vent pipeline, 12. AFSs, 12-1. atomizer, 13. signal recording apparatus, 14. vacuum insulation separating tanks; 15. liquid nitrogen container, 16. separating columns, 17. liquid nitrogen, 18. reaction vessel jars, 19. magnetic agitation; 20. lid, 21. solution of potassium borohydride pipelines, 22. helium inlet, 23. gas vents, 24. peristaltic pumps.
Embodiment
The present invention forms gaseous arsenic compound assay determination on-line coupled system by standard generation or sample collection device, cryogenic trapping device, vacuum insulation separating tank, gas-carrier pipeline, hydrogen formation apparatus, AFS, signal recording apparatus, utilizes this system to the volatile gaseous arsenic compound assay determination.Said system is with the special efficacy detecting device of AFS as assay determination, adopts cryogenic trapping technology and low temperature separation technology, and the separating column through being filled with absorbent cotton and the form of vacuum insulation separating tank realization volatile gaseous arsenic compound are separated.Utilize said system following to the volatile gaseous arsenic compound analysis determining method: at first reaction produces and collects gaseous arsenic compound in said standard generation or sample collection device; Gaseous arsenic compound standard that generates or sample are brought into the cryogenic trapping device under the effect of helium.Gaseous arsenic compound is trapped on the separating column under low temperature liquid nitrogen, and behind the capture 3-6min, all gaseous arsenic compounds are brought into separating column fully.Having the separating column of gaseous arsenic compound to be transferred in the vacuum insulation separating tank capture rapidly then slowly heats up; Because temperature rises slowly, control easily, each heating rate error is less; The separating behavior favorable reproducibility of gaseous arsenic compound on separating column; Retention time is stable, and the gaseous arsenic compound that is captured on the separating column is released at low temperatures, realizes quick baseline separation.Subsequently; Separated gaseous arsenic compound mixes with the hydrogen that argon gas and said hydrogen formation apparatus produce; Get into atomic fluorescence spectrometer atomizer, at high temperature carry out atomization, generate gaseous state arsenic atom; The arsenic atom that is excited deactivates and sends atomic fluorescence, behind the photosignal that is produced by the signal recording apparatus record.
Referring to Fig. 1, said standard generates or sample collection device can be that the sample culturing device also can be the gaseous arsenic compound gathering-device.It comprises the reaction vessel jar 18 and lid 20 of PTFE material; Lid is provided with solution of potassium borohydride pipeline 21, helium inlet 22 and gas vent 23; The solution of potassium borohydride pipeline connects peristaltic pump 24; Be provided with magnetic agitation 19 in the tank body, under the effect of magnetic stirring apparatus, hydride reacts stable more, rapid.
Still referring to Fig. 1, said cryogenic trapping device is made up of liquid nitrogen container 15 and separating column 16; The separating column cylinder length 50-60cm of PTFE material, filling length in it is the absorbent cotton of 20-30cm, the absorbent cotton quality is 0.5-1.0g; Cylinder external diameter 6.0mm; Internal diameter 4.0mm, separating column insert in the liquid nitrogen container, make to fill 3-5cm under complete submergence liquid nitrogen 17 liquid levels of absorbent cotton part.Used separating column selects to have flexible PTFE material cylinder, and the filling material in the cylinder is an absorbent cotton.Said PTFE is a kind of (per) fluoropolymer that is made by tetrafluoroethene free radical polymerization, is a kind of crystalline polymer.PTFE has excellent chemical-resistant, and loss factor is low, stable performance, and good mechanical property, friction factor is low, and is nonflammable, has certain thermal adaptability scope, the material physicochemical property are stable.Another fundamental purpose of selecting this material for use be the PTFE tube Louis in bending, be convenient to be connected with the carrier gas gas circuit of AFS.The separating column inner stuffing is selected absorbent cotton for use; The agent structure of absorbent cotton is a cotton fiber; Has strong polarity adsorptive power; Have fluffy reticulate texture simultaneously, in the compound separation process, can play the effect that gaseous state arsenide and the intensification of stabilization column internal temperature are resolved in absorption simultaneously, guaranteed that gaseous arsenic compound reaches quick baseline separation.In addition, the selected AFS of the present invention needs the carrier gas of certain pressure, regime flow, if adopt the conventional chromatogram filler, line pressure is too high in cryogenic trapping and separating process, and the situation that carrier gas and separator leak takes place easily.Simultaneously; In the process that captures, the air in the sample or other gases also have been trapped in the separation cylinder simultaneously, if captured gas on normal temperature or the higher temperature separating column;, analyte is easy to generate big release air-flow of moment when gasifying; Water down the argon hydrogen stream, cause the argon hydrogen flame cancellation in the atomizer, greatly hinder the stability and normal assay determination of system.Separating column of the present invention captures the back and in vacuum insulation separating tank 14, slowly heats up; Gasification is slowly carried out to greatest extent; Under the effect of carrier gas, steadily discharge and separate, both guaranteed separating effect and reappearance, kept the stability of atomizer argon-hydrogen flame again.
Still referring to Fig. 1; Said hydrogen formation apparatus comprises Mixed liquid T-branch 3, is respectively equipped with the aqueous slkali pipeline 1 and acid solution pipeline 2, hydrogen pipeline 4, gas-carrier pipeline 5, auxiliary air pipe 8 and the gas-liquid separator that connect peristaltic pump; Said Mixed liquid T-branch connects aqueous slkali pipeline, acid solution pipeline and one-level hydrogen pipeline 4 respectively; Said gas-carrier pipeline is communicated with the one-level hydrogen pipeline; The terminal one-level gas-liquid separator 6 that is communicated with of one-level hydrogen pipeline; One-level gas-liquid separator gas vent pipeline 7 is communicated with secondary gas-liquid separator 9, and auxiliary air pipe is communicated with one-level gas-liquid separator gas vent pipeline, and secondary gas-liquid separator gas vent pipeline 11 is communicated with the atomizer 12-1 inlet of separating column export pipeline 10, AFS 12.AFS need be kept stable flame when measuring arsenic, Gaseous Hydrogen and the burning of carrier gas argon gas that said combined system utilizes hydrogenation to react and generates generate argon-hydrogen flame, to guarantee the required temperature and the energy of atomization of arsenic.In hydrogenation reacts; Feed the reductive agent solution of potassium borohydride in the aqueous slkali pipeline 1; Feed dilute hydrochloric acid solution in the acid solution pipeline 2; Both react and generate a large amount of Gaseous Hydrogens, and hydrogen mixes the back at the atomizer 12-1 generation argon-hydrogen flame that burns with argon gas, for the atomization of arsenic compound provides condition.The atomizer that gaseous arsenic compound after the separation is brought AFS into carrier gas carries out atomization, under the exciting of hollow cathode lamp, sends fluorescence, through the signal Processing and the amplification of photomultiplier, at last by computing machine and workstation record and processing.
Still referring to Fig. 1, practical implementation process of the present invention is following: with 4%KBH
4(0.3%KOH) and 10%HCl (v/v) feeds aqueous slkali pipeline 1 respectively, 2, two kinds of solution of acid solution pipeline are written into Mixed liquid T-branch 3 by pipeline, at this, acid-base solution mixes and hydrogenation takes place reacts, and produces a large amount of Gaseous Hydrogens and waste liquid.The hydrogen that generates is brought into one-level gas-liquid separator 6 with carrier gas in the gas-carrier pipeline 5, and gas-liquid reaches to greatest extent separates.Gaseous Hydrogen is brought into secondary gas-liquid separator 9 again with carrier gas, gets into the gas of secondary gas-liquid separator, under auxiliary air pipe 8 auxiliary gas effects, steadily gets into atomizer 12-1 burning.Above-mentioned carrier gas and auxiliary gas are argon gas, and its purity is 99.99%, and flow is 500mL/min.Simultaneously, in the gaseous arsenic compound separating process, the gaseous arsenic compound standard of generation or sample are brought into the cryogenic trapping device under the effect of helium, and helium is high-purity helium, and purity is 99.999%, and flow velocity is 50-80mL/min, and pressure is 0.1-0.15Mpa.During reaction, in reaction vessel jar 18, add a certain amount of different shape arsenic compound, the oxalic acid that adds 5mL5% subsequently is as reaction medium and reaction reagent, 5%KBH
4Solution is pumped in the reaction vessel jar by the solution of potassium borohydride pipeline, and through the reaction of 5-6min, the gaseous arsenic compound standard of generation all is captured, is condensate on the separating column 16 under the stirring of magnetic agitation 19.After capturing fully; Separating column is transferred to vacuum insulation separating tank 14 and slowly heats up; The separating column carrier gas inlet connects sample collection device or gaseous arsenic compound standard deriving device; The separating column gas vent is through the atomizer of threeway connection AFS, and gaseous arsenic compound successively gets into AFS in separated back and detects, and testing result is by the signal recording apparatus record.Gaseous arsenic compound AsH
3, CH
3AsH
2, (CH
3)
2AsH, (CH
3)
3A can reach baseline separation in 3min, separate spectrogram and see accompanying drawing 2.
Claims (2)
1. instrument coupled speciation measuring method of gaseous arsenic compound; It is characterized in that; It utilizes gaseous arsenic compound assay determination on-line coupled system to measure; Said gaseous arsenic compound assay determination on-line coupled system is made up of standard generation or sample collection device, cryogenic trapping device, vacuum insulation separating tank, gas-carrier pipeline, hydrogen formation apparatus, AFS and signal recording apparatus, and determination step is following:
A. arsenic compound generates or sample collection: reaction produces and collects gaseous arsenic compound in said standard generation or sample collection device;
B. gaseous arsenic compound captures and separates: with above-mentioned gaseous arsenic compound, bring the cryogenic trapping device into through carrier gas, the gaseous arsenic compound that is captured is captured and is condensate on the separating column of cryogenic trapping device;
C. gaseous arsenic compound separates: after capturing completion, rapidly separating column is transferred in the vacuum insulation separating tank, makes its slow intensification, the gaseous arsenic compound that is captured on the separating column is released at low temperatures, realizes quick baseline separation;
D. the detection of gaseous arsenic compound: the hydrogen that separated gaseous arsenic compound produces with said hydrogen formation apparatus under the effect of carrier gas and the carrier gas of said AFS mix; Get into atomic fluorescence spectrometer atomizer; At high temperature carry out atomization; Generate gaseous state arsenic atom, the arsenic atom that is excited deactivates and sends atomic fluorescence, obtains testing result by the signal recording apparatus record behind the photosignal that is produced;
Said standard generation or sample collection device comprise the reaction vessel jar (18) and the lid (20) of PTFE material; Lid is provided with solution of potassium borohydride pipeline (21), helium inlet (22) and gas vent (23); The solution of potassium borohydride pipeline connects peristaltic pump (24), is provided with magnetic agitation (19) in the reaction vessel jar;
Said cryogenic trapping device is made up of liquid nitrogen container (15) and separating column (16), the separating column cylinder length 50-60cm of PTFE material; Filling length in it is the absorbent cotton of 20-30cm; The absorbent cotton quality is 0.5-1.0g, cylinder external diameter 6.0mm, internal diameter 4.0mm; Separating column is inserted in the liquid nitrogen container, makes to fill 3-5cm under complete submergence liquid nitrogen (17) liquid level of absorbent cotton part;
Said hydrogen formation apparatus comprises Mixed liquid T-branch (3), is respectively equipped with aqueous slkali pipeline (1) and acid solution pipeline (2), hydrogen pipeline, gas-carrier pipeline (5), auxiliary air pipe (8) and the gas-liquid separator of peristaltic pump; Said Mixed liquid T-branch connects aqueous slkali pipeline, acid solution pipeline and one-level hydrogen pipeline (4) respectively; Said gas-carrier pipeline is communicated with the one-level hydrogen pipeline; The terminal one-level gas-liquid separator (6) that is communicated with of one-level hydrogen pipeline; One-level gas-liquid separator gas vent pipeline (7) is communicated with secondary gas-liquid separator (9); Auxiliary air pipe is communicated with one-level gas-liquid separator gas vent pipeline, and secondary gas-liquid separator gas vent pipeline (11) is communicated with atomizer (12-1) inlet of separating column export pipeline (10), AFS (12).
2. instrument coupled speciation measuring method of gaseous arsenic compound according to claim 1; It is characterized in that; Feeding concentration is 4% solution of potassium borohydride in the said aqueous slkali pipeline (1); Feed concentration in the said acid solution pipeline (2) and be 10% hydrochloric acid, feed purity in said gas-carrier pipeline (5), the auxiliary air pipe (8) respectively and be 99.99% argon gas, argon flow amount is 500mL/min; The helium that feeds in said standard generation or the sample collection device is high-purity helium, and purity is 99.999%, and flow velocity is 50-80mL/min, nebulizer gas pressure 0.1-0.15Mpa.
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