CN102305779B - Solid sampling-non-dispersion atomic fluorescence photometer collocating device and analyzing method - Google Patents
Solid sampling-non-dispersion atomic fluorescence photometer collocating device and analyzing method Download PDFInfo
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Abstract
The invention relates to a solid sampling-non-dispersion atomic fluorescence photometer collocating device and an analyzing method. The device comprises a solid sampler, an integrated interface, a sample pipe, a peristaltic pump, a tee joint, a gas-liquid separator, a detector and a computer. The method comprises the following steps of: volatilizing an analyzing element in a volatile halide way and absorbing by absorption liquid by adding an auxiliary heat release agent or an ashing auxiliary agent in the solid sampler. The absorption liquid is introduced into a chemical steam generating system for reacting with potassium borohydride (sodium); and the generated volatile hydride or atomic steam is carried into an instrument atomization area for being detected by atomic fluorescence. The invention directly adopts solid sampling, rapidly realizes the detection of toxic elements, such as arsenic, stibium, selenium, mercury, and the like in the samples, such as geology, environment, food, biology, and the like and has the advantages of higher analyzing speed, low analyzing cost, high detecting sensitivity, high device portability, environmental protection, and the like.
Description
Technical field
The invention belongs to light, mechanical, electrical integrated scientific analysis instrument and analytical approach; Be particularly related to a kind of solid sampling-non-dispersive atomic fluorescence photometer logotype device and analytical approach; The present invention directly adopts solid-state sample introduction; Not by means of traditional solubilize sample pretreatment technology, the mensuration of elements such as sample toxic element arsenic, antimony, selenium, mercury such as Rapid Realization geology, environment, food, biology.
Background technology
The specimen preparation and the technology of introducing are important rings of The whole analytical process; Fast development along with Modern Scientific Instruments; Though final measuring technique has reached highly sensitive, quick, high-resolution degree; But sample pre-service and the serious hysteresis of the technology of introducing in earlier stage become " bottleneck " link that present analytical technology develops, seriously restricts the use of multiclass analysis of modernization technology.
The sample that analytical control relates to is formed very complicated; Except nondestructive analysis and partly simply fluid sample can directly be used for analyzing; Common most of sample all will carry out solubilize to sample before analysis handles, and many The pretreatment processes are comparatively complicated.For chemical evapn generation-non-dispersive atomic fluorescence analytical technology (CVG-NDAFS) in actual application; The sample pretreatment technology equally also becomes one of technology of most critical; Nearly all sample all will carry out inorganicization processing, promptly needs the complicated sample preprocessing process.At present common that the sample pretreatment technology mainly comprises: as to open wide system acid decomposition, high pressure sealing sample dissolution, micro-wave digestion decomposition sample and fusion of alkali formula and fritting etc.; Deficiency below these sample pretreatment technology exist: all will use the very strong nitric acid of corrosivity, sulfuric acid, hydrochloric acid, oxyhydroxide, superoxide etc. in (1) sample pretreatment process, environment is caused serious pollution; (2) sample pretreatment process is long, needs 2-6 hour usually; (3) use of a large amount of reagent causes analysis cost high; (4) because there is significant exogenous pollution in the introducing of a large amount of chemical reagent, cause micro-trace elements analysis result deviation bigger; (5) because the adding of hydrochloric acid equal solvent causes arsenic, antimony, selenium etc. with chloride form volatilization loss, mercury is prone to vapor state volatilization loss; (6) element such as antimony, tin makes analysis result on the low side in the easy hydrolysis of sample pretreatment stage.
Famous atomic spectrum expert Weir Mr. thatch points out in its monograph: " systematic error in the atomic absorption; when the overwhelming majority occurs in sample pretreatment and seldom because due to the analysis itself; therefore; the most handy direct method of trace analysis is to avoid sample pretreatment "; When using other atomic spectroscopic analysis technology to the trace heavy metal ultimate analysis, mainly comprise atomic emissions (AES), atomic fluorescence (AFS) and plasma mass (ICP-MS) equally, its analytical error is mainly derived from the sample pretreatment stage equally.Therefore the solid sampling technology of directly introducing based on sample has in recent years obtained research widely.Solid sampling technology present and the atomic spectrum coupling mainly comprises: 1, laser ablation-inductivity coupled plasma mass spectrometry (LA-ICP-MS); 2, solid sampling-electric heating evaporation-inductivity coupled plasma mass spectrometry (SS-ETV-ICP-MS); 3, direct solid sample introduction sampling Graphite Furnace Atomic Absorption analytic approach (SS-GFAAS); Solid sampling plasma spectroscopy (SS-ICP-OES).
Chemical evapn generation-non-dispersive atomic fluorescence analytical technology (CVG-NDAFS) is at present unique atomic spectroscopic analysis technology that is unrealized with the direct coupling of solid sampling.The atomic fluorescence analysis technology at first is to be proposed in 1964 by U.S. spectroscopist Winefordner, the measurement mechanism of multiclass based on the atomic fluorescence principle in many decades after this, occurred.The input mode of same atomic fluorescence has also experienced very big variation.Wherein, early stage experimental provision adopts pneumatic nebulization input mode and graphite furnace liquid input mode more.Tsujii in 1974 and Kuga combine the hydride generation technique with the atomic fluorescence analysis technology, started hydride-generation atomic fluorescence coupling technique (HG-AFS).Because this technology adopts chemical evapn sampling technique, in the sample introduction stage analytical element is effectively separated with the coexistence matrix, eliminate the interference problem in the mensuration process, thereby established the most basic technical foundation for the practical application of atomic fluorescence.The initiative research and development of nineteen eighty-three China Guo Xiaowei professor research group have gone out bilateral passage hydride-generation atomic fluorescence photometer; After this this technology has obtained development widely; Form a series of commercial analytical instrument at present; But the sample that these instruments can be measured can only be fluid sample, all will decomposed sample be converted into solution before promptly measuring.
Summary of the invention
In order to overcome the complicated deficiency of existing chemical evapn generation-non-dispersive atomic fluorescence technology (CVG-NDAFS) sample pretreatment process, the invention provides a kind of solid sampling-non-dispersive atomic fluorescence photometer logotype device and analytical approach.
The present invention solves the technical scheme that its technical problem underlying takes and mainly comprises: a kind of solid sampling-non-dispersive atomic fluorescence photometer logotype device; Comprise solid sampler (1), integrated interface (2), sample hose (3), peristaltic pump (4), threeway (7), gas-liquid separator (8), AFS (9) and computing machine (11); Described solid sampler (1), integrated interface (2), sample hose (3), peristaltic pump (4), threeway (7), gas-liquid separator (8), AFS (9) connect successively; The import of threeway (7) connects sample hose (3), carrier gas II enter the mouth (5) and reductive agent H tube inlet (6) respectively; Gas-liquid separator (8) bottom is provided with waste liquid vent pipe (10); Computing machine (11) connects solid sampler (1) and AFS (9) respectively; Described injector (1) is made up of following part with integrated interface (2): carrier gas I (101) is connected with hot releasing tube or little ashing pipe (104) with the fastening interface of carrier gas and sample hose (103) through carrier gas I operation valve (102); Be provided with heat outside hot releasing tube or the little ashing pipe (104) and release heating system (105); Heat is released heating system (105) outside and is provided with cooling fan (106); Hot releasing tube or little ashing pipe (104) are terminal to be connected with absorption tube or trap tube (203) with the fastening interface (201) of integral type interface through sample hose; Absorption tube or trap tube (203) are connected with sample hose (3) with hydride generating system interface (202) through absorption liquid; Absorption tube or trap tube (203) are provided with absorption liquid and cleansing solution introducing port (205), and absorption liquid (208) or cleansing solution (209) are connected with cleansing solution introducing port (205) with absorption liquid with peristaltic pump (206) through threeway valve position (207), and absorption tube or trap tube (203) are provided with exhaust gas evacuation mouth (204).
Described heat is released heating system (105) and is selected one of electrical heating or combustion gas heating for use, and combustion gas heating source of the gas is portable gas-holder or alcohol blast burner.
Described hot releasing tube or little ashing pipe (104) are quartzy or ceramic microminiature straight tube, small U type pipe or small special pipe.
A kind of solid sampling-non-dispersive atomic fluorescence photometer analytical approach comprises the steps:
The first step, accurately take by weighing analytic sample 0.0200-0.3000 gram; Add 2-5 doubly to the auxiliary heat releasing agent of sample size or help fogging agent; Stir and put into quartzy or ceramic hot releasing tube or little ashing pipe (104) of solid sampler (1), and 0.2-25mL absorption liquid (208) is pumped in the absorption tube (203) with peristaltic pump (206);
Second step, release heating system (105) through heat and give hot releasing tube or little ashing pipe (104) heating; Heating-up temperature is 400-1100 ℃; Heated 0.5-10 minute, analytical element evaporates with the volatile halogenated form or the little dry incineration of organic matrix sample in the inorganic matrix sample;
The part of volatilizing when the 3rd step, volatile halogenated or analytical element ashing is taken out of by carrier gas I (101), is absorbed that liquid (208) absorbs and/or gold amalgam captures;
The 4th goes on foot, stops to heat, and opens cooling fan (106), and hot releasing tube or little ashing pipe (104) are fully cooled off;
The 5th step, clean hot releasing tube or little ashing pipe, reduction: with 2-10s/ time frequency through carrier gas operation valve (102) switch carrier gas I; Utilize the switch of carrier gas I pulsed to stir absorption liquid (208) the hot releasing tube of flushing or little ashing pipe (104); The analytical element volatile matter of condensation on hot releasing tube or little ashing pipe (104) wall is dissolved in the absorption liquid (208) fully, and the reductive agent that the while analytical element is absorbed in the liquid (208) fully reduces;
The 6th step, chemical evapn take place and measure: the absorption liquid (208) that has absorbed element to be measured is introduced into chemical evapn generation system by peristaltic pump (4); Analytical element and reductive agent H (6) are through the biochemical reaction of threeway (7) hybrid concurrency in the absorption liquid (208); Produce the volatility chemical evapn and separate through gas-liquid separator (8), steam gets into AFS (9) and is carried out quantitative measurement after the atomization;
The 7th step: clean, T-valve (207) rotates and cleansing solution (209) conducting, and peristaltic pump (206) pumps into cleansing solution (209) absorption tube (203) and reaction pipeline are cleaned, in order to measuring next sample.
Described absorption liquid (208) is mineral acid or the organic acid soln of deionized water or 0.1%-50% (v/v); Under acid hydride emergence pattern; Absorption liquid (208) is a kind of acidic mixed solution; Wherein containing acid and the massfraction that volume fraction or massfraction are 0.1-50% is the reductive agent of 0.1-10%, wherein:
Described acid is one of oxalic acid, citric acid, tartrate, halfcystine, hydrochloric acid, sulfuric acid, nitric acid;
Described reductive agent is one of thiocarbamide, ascorbic acid, halfcystine, iodide;
Under alkaline hydride emergence pattern, absorption liquid (208) is that 0.05-2% NaOH or potassium and massfraction are 0.05-5% sodium borohydride or potassium mixed solution for massfraction.
Described auxiliary heat releasing agent is labile halogenide, and the described fogging agent that helps is oxygen, oxygen-enriched air, magnesium oxide (MgO), magnesium nitrate (Mg (NO
3)
2), nitric acid (HNO
3), one of zinc paste (ZnO).
Described auxiliary heat releasing agent is zinc chloride (ZnCl
2), iron chloride (FeCl
3), aluminum chloride (AlCl
3), sal-ammoniac (NH
4Cl), ammonia bromide (NH
4Br) or iodate ammonia (NH
4One of I), helping fogging agent is oxygen or oxygen-enriched air.
Described carrier gas: when sample was inorganic samples, carrier gas was that purity is the 99.9-99.99% argon gas; When sample was organic sample, carrier gas was that purity is the oxygen of 99-99.99%.
Described reductive agent H is a kind of mixed solution, and wherein containing NaOH that volume fraction or massfraction are 0.1-2% or potassium and massfraction is sodium borohydride or the potassium of 0.05-5%.
Described cleansing solution is a 0.1-20% organic or inorganic acid solution for containing volume fraction or massfraction, and described organic acid mainly comprises one of oxalic acid, citric acid, tartrate, halfcystine.
The present invention adopts direct solid sample introduction mode sample introduction to substitute traditional nitric acid, hydrochloric acid, sulfuric acid etc. and analyzes the sample technology, has prevented the pollution problem of these sour uses to environment on the one hand, has shortened the sample pretreatment time on the other hand; The solid sampling stage adopts auxiliary heat to discharge or miniature dry incineration technology; In sample, add hot releasing agent or help fogging agent; Volatile material or fast incineration have been produced through target analysis element in the heated sample and hot releasing agent chemical combination; Realized snap-out release or the ashing under the analytical element cryogenic conditions on the one hand, reduced energy consumption, improved hot release rate on the other hand, shortened release time, improved efficient; The element that discharges through low-temperature heat produces in the chemical evapn generator in the atomizer that is brought into non-dispersive atomic fluorescence behind the chemical evapn separately and measures, and has realized online detection.The present invention has designed incorporate interface; Realized the on-line coupling of solid sampling part, and in interface, realized multi-functionals such as the absorption of analytical element, element morphology are changed, gas stirs automatically, automatic Rapid Cleaning with chemical evapn generation-non-dispersive atomic fluorescence instrument.
The invention has the beneficial effects as follows; Adopt the directly analytical element in the working sample of solid sampling and atomic fluorescence coupling; Sample does not need complicated pretreatment process in early stage; Analysis speed is faster like this, analysis cost is lower, in analytic process, need not use the serious mineral acids of environmental pollution such as a large amount of hydrochloric acid, nitric acid or sulfuric acid, method environmental protection.
Description of drawings
Fig. 1 is solid sampling of the present invention-non-dispersive atomic fluorescence photometer combined apparatus structural representation.
Fig. 2 is the structural representation of solid sampler of the present invention and integrated interface.
Embodiment
Referring to Fig. 1 and Fig. 2; A kind of solid sampling-non-dispersive atomic fluorescence photometer logotype device; Comprise solid sampler 1, integrated interface 2, sample hose 3, peristaltic pump 4, threeway 7, gas-liquid separator 8, AFS 9 and computing machine 11; Described solid sampler 1, integrated interface 2, sample hose 3, peristaltic pump 4, threeway 7, gas-liquid separator 8, AFS 9 connect successively; The import of threeway 7 connects sample hose 3, carrier gas II inlet 5 and reductive agent H tube inlet 6 respectively; Gas-liquid separator 8 bottoms are provided with waste liquid vent pipe 10; Computing machine 11 connects solid sampler 1 and AFS 9 respectively, and described injector 1 and integrated interface 2 are made up of following part: carrier gas I101 is connected with hot releasing tube or little ashing pipe 104 through the fastening interface 103 of carrier gas I operation valve 102 and carrier gas and sample hose, and described hot releasing tube or little ashing pipe 104 are quartz or ceramic microminiature straight tube, small U type pipe or small special pipe.Be provided with heat outside hot releasing tube or the little ashing pipe 104 and release heating system 105, described heat is released heating system 105 and is selected one of electrical heating or combustion gas heating for use, and combustion gas heating source of the gas is portable gas-holder.Heat is released heating system 105 outsides and is provided with cooling fan 106; Hot releasing tube or little ashing pipe 104 terminal sample hoses that pass through are connected with absorption tube or trap tube 203 with the fastening interface 201 of integral type interface, and absorption tube or trap tube 203 are connected the hydride generating system that get into atomic fluorescence spectrophotometer with hydride generating system interface 202 with sample hose 3 through absorption liquid.Absorption tube or trap tube 203 are provided with absorption liquid and cleansing solution introducing port 205; Absorption liquid 208 or cleansing solution 209 are connected with cleansing solution introducing port 205 with absorption liquid with peristaltic pump 206 through threeway valve position 207, and absorption tube or trap tube 203 are provided with exhaust gas evacuation mouth 204.
Solid sampler of the present invention is controlled by the computing machine 11 that 51 single-chip microcomputers and auxiliary circuit constitute; Import the test sample program in advance; During test sample; Under the control of computing machine 11, be wrapped in heat outside quartzy hot releasing tube or the little ashing pipe 104 and release heating system 105 and heat in good time, cooling fan 106 is released heating system 105 to heat as required in the side that heat is released heating system 105 and is carried out radiating and cooling.Absorption liquid 208 enters into absorption tube or trap tube 203 with cleansing solution 209 timesharing under the control of threeway valve position 207.The waste gas that reaction produces is discharged from exhaust gas evacuation mouth 204.Computing machine output test sample instruction and parameter; The heat of controlling in the integrated interface is released heating system, radiator fan, threeway etc.; Make them consistent in the step of test sample; Realized the on-line coupling of solid sampling part, and in interface, realized multi-functionals such as the absorption of analytical element, element morphology are changed, gas stirs automatically, automatic Rapid Cleaning with chemical evapn generation-non-dispersive atomic fluorescence instrument.Atomic fluorescence appearance atomized chamber adopts the infrared camera monitoring, and software judges automatically whether the atomization oxyhydrogen flame is lighted.The present invention has designed incorporate interface, is the interface of solid sampler and atomic fluorescence chemical evapn generation systems, can make sample pretreatment, chemical evapn generation and measure online once completion through interface; Integrated interface has analytical element capture, reduction, remnant batch (-type) automatic cleaning function.
Solid sampling according to the invention-non-dispersive atomic fluorescence photometer logotype analytical approach mainly comprises following 7 step working routines, sees table 1.
The first step: accurately take by weighing analytic sample 0.0200-0.3000 gram; Add 2-5 doubly to the auxiliary heat releasing agent of sample size or help fogging agent; With the automatic or manual mode uniform mix of analytic sample and 0.05-2.0g auxiliary heat releasing agent is put in quartzy or ceramic hot releasing tube or the little ashing pipe 104 of heat release solid sampler 1, and 0.2-25mL absorption liquid 208 is pumped in the absorption tube 203 with peristaltic pump 206;
Described auxiliary heat releasing agent is labile halogenide, for example halogenide or its potpourris such as zinc chloride, iron chloride, aluminum chloride, sal-ammoniac, ammonia bromide, iodate ammonia, potassium chloride, potassium bromide, potassium iodide, sodium chloride, sodium bromide, sodium iodide.
The described fogging agent that helps is oxygen, oxygen-enriched air, magnesium oxide (MgO), magnesium nitrate (Mg (NO
3)
2), nitric acid (HNO
3), one of zinc paste (ZnO).
Mineral acid or the organic acid soln of described absorption liquid deionized water or 0.1%-50% (v/v); Under acid hydride emergence pattern; Absorption liquid 208 is a kind of acidic mixed solution, and wherein containing acid and the massfraction that volume fraction or massfraction are 0.1-50% is the reductive agent of 0.1-10%.Wherein:
Described acid can be one of oxalic acid, citric acid, tartrate, halfcystine, hydrochloric acid, sulfuric acid, nitric acid;
Described reductive agent can be one of thiocarbamide, ascorbic acid, halfcystine, iodide.
In addition, under alkaline hydride emergence pattern, absorption liquid 208 can be that 0.05-2% NaOH or potassium and massfraction are 0.05-5% sodium borohydride or potassium mixed solution for massfraction.
Second step: release heating system 105 through heat and give hot releasing tube or 104 heating of little ashing pipe, make that analytical element evaporates with the volatile halogenated form or the little dry incineration of organic matrix sample in the inorganic matrix sample; Add hot releasing agent, can make arsenic, antimony, mercury, cadmium etc. analyze element and form volatile matter, to reduce release temperature; Analytical element discharges with volatile halogenated or atomic vapour form; Analytical element and auxiliary heat release reagent heated 0.5-10 minute under 400-1100 ℃ of condition, reacted to generate volatile species AX
M/n, volatile compound is brought in the integrated interface by pure argon.The main chemical reaction that takes place is following in this process:
NH
4X-NH
3+H
++X
- …………………(1)
A
nM
m+X
--nAX
m/n↑…………………(2)
In following formula (1) and (2):
X is the halogens in the hot releasing agent, and A is an element to be analyzed in the sample, M be in sample with the element of analytical element chemical combination, AX
M/nBe volatile halogenide.
Described type of heating can be electrical heating or air-coal gas, air-acetylene, alcohol blast burner heating.
The 3rd step: the heating under the condition that the auxiliary heat releasing agent exists of the analytical element in the sample discharges; The part of volatilizing when volatile halogenated that discharges or analytical element ashing is brought in the absorption tube 203 by carrier gas I101, is absorbed liquid 208 absorptions or gold amalgam and captures.
Volatile species AX
M/nIn integrated interface, being absorbed liquid 208 absorbs; Absorption liquid 208 is mineral acid or the organic acid soln of deionized water or 0.1%-50% (v/v); In absorption liquid, add the reductive agent for preparing in advance, make the form of the easy generation of analytical element generation chemical evapn through the reduction of reductive agent.Wherein: the simple principle in the absorption process is the physics cooling; The conversion of chemical form is in absorption liquid, to add a certain amount of reductive agent or other reagent makes analytical element that the valence state conversion take place, and for example: for As and Sb is in absorption liquid, to add the trivalent ion that As that reductive agent makes high price and Sb convert easy generation hydride reaction into.
Described carrier gas: when sample was inorganic samples such as soil, water system sediment, rock, metal or alloy, carrier gas was that purity is the 99.9-99.99% argon gas; When sample was organic samples such as food, plant, tissue, carrier gas was that purity is the oxygen of 99-99.99%.
The 4th step: stop heating, open cooling fan 106 hot releasing tube or little ashing pipe 104 are fully cooled off;
The 5th step: clean hot releasing tube or little ashing pipe, reduction.In capture, dissolution phase; With 2-10s/ time frequency through the 102 switch carrier gas of carrier gas operation valve; Make carrier gas conducting or cut-out; Utilize the switch of carrier gas I pulsed to stir, it is residual or dissolve the ash of little dry incineration that the pressure official post absorption liquid 208 that produces successively washes the analyte of hot releasing tube or little ashing pipe 104 and interface repeatedly, makes analyte transfer in the absorption liquid fully; Utilize the impulse force of carrier gas to stir, repeatedly wash hot releasing tube 104 with absorption liquid, the analytical element volatile matter that makes heat discharge condensation on the tube wall is dissolved in the absorption liquid fully, and the reductive agent that the while analytical element is absorbed in the liquid fully reduces; For example: As
5+Be reduced to As
3+
The 6th step: chemical evapn takes place and measures; The absorption liquid that has absorbed element to be measured 208 is pumped into the chemical evapn generation systems of atomic fluorescence device through absorption liquid and hydride generating system interface 202 and peristaltic pump 4; Analytical element in the absorption liquid 208 and reductive agent H6 are through the biochemical reaction of threeway 7 hybrid concurrencies; Produce the volatility chemical evapn and separate through gas-liquid separator 8, steam gets into AFS 9 and is carried out quantitative measurement after the atomization.
The sodium borohydride of analytical element and 0.01%-5% (m/v) and potassium borohydride reaction generate the chemical evapn (comprising hydride and cold steam) of analytical element.The main chemical reaction that takes place is following in this process:
NaBH
4+3H
2O+HCl-HBO
3+NaCl+8H
*…………(3)
xH
*+A
n+-AH
n+(x-n)/2H
2…………………(4)
Described reductive agent H is a kind of mixed solution, and wherein containing NaOH that volume fraction or massfraction are 0.1-2% or potassium and massfraction is sodium borohydride or the potassium of 0.05-5%.The analytical element volatile species that in chemical evapn generation system, produces is by argon gas (Ar) or nitrogen (N
2) be brought into the atomic fluorescence atomizer and measure.
The 7th step: clean, T-valve 207 rotates and cleansing solution 209 conductings, and peristaltic pump 206 pumps into 209 pairs of absorption tubes of cleansing solution 203 and cleans with the reaction pipeline, in order to measuring next sample.At wash phase, through of the frequency switching carrier gas of automatic control electromagnetic valve, make carrier gas conducting or cut-out with 2-10s/ time, the pressure official post cleaning fluid that produces successively washes hot releasing tube and interface pipeline repeatedly, eliminates measured last time residual, stops cross pollution.
Described cleansing solution is a 0.1-20% organic or inorganic acid solution for containing volume fraction or massfraction, and described organic acid mainly comprises one of oxalic acid, citric acid, tartrate, halfcystine.
Table 1 solid sampling and non-dispersive atomic fluorescence coupling technique working routine
Annotate:, clean transfer conduit with 2-10s/ time frequency switching carrier gas.
The present invention adopts solid sample directly to introduce as the photometric input mode of non-dispersive atomic fluorescence, (1) sample in solid sampler directly through hot releasing agent or help that fogging agent is auxiliary to be discharged or little dry incineration; (2) analytical element volatile species (comprising volatile halogenated, atomic vapour and effumability compound) is trapped in absorption liquid and the trap tube; (3) trap analytical element volatile species in the absorption liquid and be absorbed reductive agent reduction conversion in the liquid for being prone to that the valence state of hydride takes place and being introduced in the chemical evapn generation systems and sodium borohydride (potassium) reaction generation hydride or atomic vapour separately; The mercury heating that traps on the trap tube discharges generation mercury atom steam; (4) hydride that produces and atomic vapour take place with the atomic fluorescence analysis principle analytical element to be carried out quantitative measurement after the atomization in hydrogen-argon flame after being brought into the atomization district by carrier gas.
For the feasibility of verifying the present invention technology and the accuracy of method, adopt dissimilar country-level standard substances, adopt apparatus and method of the present invention to measure.
Embodiment one: the analysis of inorganic matrix samples such as soil, rock
Standard model is analyzed data, comprises 2 rock standard models (GBW 07104 and GBW07113) and 1 soil standard model (GBW 07402)
The first step, take by weighing selected standard model 0.1000g respectively, and in each appearance, add heat and release agent ammonia bromide 0.200g, put into hot releasing tube after mixing.
Second step, heating discharges under 800 ± 50 ℃ of conditions, and wherein heat is released heating system and selected heating wire and liquefied gas-air flame respectively, and wherein to select the portable liquified gas compressed tanks for use be source of the gas to liquefied gas.
The 3rd the step, with 5% (v/v) H
2SO
4+ 1% (m/v) thiocarbamide+1% (m/v) ascorbic acid mixed solution 5mL absorbs the analytical element that discharges as absorption liquid.
The 4th the step, with 5% (v/v) H
2SO
4+ 1% (m/v) thiocarbamide+ascorbic acid mixed solution 5mL absorbs the analytical element that discharges as absorption liquid, and absorbed arsenic, antimony volatile compound absorb and be reduced to the lower valency of easy generation hydride in absorption liquid.
The 5th step, absorption liquid are fed to the chemical evapn generation systems, with 1.3% (m/v) potassium borohydride generation hydride reaction, produce volatile hydride.
The 6th step, mensuration, the atomization district that the analytical element hydride of generation is sent carrier gas to bring atomic fluorescence into takes place to measure after the atomization in the immersion flame of hydrogen argon oxygen.Condition determination sees the following form:
Table 2: the condition of solid sampling-hydride generation-atom fluorimetry arsenic and antimony
| Total current (mA) | 40-80 | Flow rate of carrier gas (mL/min) | 300-500 |
| Major-minor |
1∶1 | Shield gas flow speed (mL/min) | 600-1200 |
| Negative high voltage (V) | 230-320 | Time delay (s) | 0-3 |
| Stove high (mm) | 7-10 | Integral time (s) | 6-12 |
| Sample size (mL) | 1-3 | Reading mode | Peak area |
The typical curve of method is to use the solid standard substance, is to be mixed with hybrid standard series with releasing agent and arsenic, antimony standard, and the standard of arsenic is respectively 0.0,1.0,5.0,10.0,15.0 μ g/g.In same standard point, the concentration of arsenic is 10 times of antimony concentration, and promptly the concentration of antimony is respectively 0.0,0.1,0.5,1.0,1.5 μ g/g.See table 3 with the typical curve equation of this series standard drafting and the characteristic of method:
Table 3: the characteristic of typical curve equation and method
With this method 3 country-level standard models such as rock, soil are measured, each sample replicate determination 3 times, analysis result is as shown in table 4.
Table 4: soil, rock standard model analysis result
Embodiment two: the analysis of organic component samples such as food, plant, biological sample
Choose GBW10010 (rice), GBW07601 (people sends out) and GBW07605 (tealeaves).
The first step, take by weighing selected standard model 0.1000g respectively, put into hot releasing tube.
Second step, after earlier feeding the argon gas destructive distillation under 800 ± 50 ℃ of conditions, feed the sample dry incineration again, in the process of ashing, in order to prevent the volatilization loss of Hg and As, Sb, Se, follow-up have gold amalgam capturing device and an absorption tube absorption.The mode that wherein adds has been selected heating wire and liquefied gas-air flame respectively, and wherein to select the portable liquified gas compressed tanks for use be source of the gas to liquefied gas.
The 3rd step, with 1% (v/v) HCl+1% (m/v) thiocarbamide+ascorbic acid mixed solution 2mL as absorption liquid, the analytical element that discharges of absorption.
The 4th step, treat that heat is released pipe cooling after, with 5% (v/v) H
2SO
4+ 1% (m/v) thiocarbamide+ascorbic acid mixed solution 3mL releases ash content remaining in the pipe with heat and thoroughly incorporates in the absorption liquid after the dissolving.
The 5th step, absorption liquid are fed to the chemical evapn generation systems, with 1.3% (m/v) potassium borohydride generation hydride reaction, produce volatile hydride.Mercury trap tube heating simultaneously discharges the mercury that adsorbs.
The 6th step, mensuration, the analytical element hydride of generation and the atomization district that the mercury vapour that discharges is sent carrier gas to bring atomic fluorescence into take place to measure after the atomization in the immersion flame of hydrogen argon oxygen.Condition determination sees the following form:
Table 5: solid sampling-hydride generation-atomic fluorescence is measured the condition of arsenic, antimony, selenium and mercury simultaneously
| Total current (mA) | 40-80 | Flow rate of carrier gas (mL/min) | 300-500 |
| Major-minor |
1∶1 | Shield gas flow speed (mL/min) | 600-1200 |
| Negative high voltage (V) | 230-320 | Time delay (s) | 0-3 |
| Stove high (mm) | 7-10 | Integral time (s) | 6-12 |
| Sample size (mL) | 0.5-2 | Reading mode | Peak area |
The typical curve of method is to use the solid standard substance, is to be mixed with hybrid standard series with high pure carbon powder and arsenic, antimony, selenium and mercury standard, and standard series concentration is as shown in table 6:
Table 6: arsenic, antimony, selenium and mercury standard series
With this method 3 country-level standard models of biological sample are measured, each sample replicate determination 3 times, analysis result is as shown in table 7.
Table 7: biological standard sample analysis result
Claims (10)
1. solid sampling-non-dispersive atomic fluorescence photometer logotype device; Comprise solid sampler (1), integrated interface (2), sample hose (3), peristaltic pump (4), threeway (7), gas-liquid separator (8), AFS (9) and computing machine (11); Described solid sampler (1), integrated interface (2), sample hose (3), peristaltic pump (4), threeway (7), gas-liquid separator (8), AFS (9) connect successively; The import of threeway (7) connects sample hose (3), carrier gas II enter the mouth (5) and reductive agent H tube inlet (6) respectively; Gas-liquid separator (8) bottom is provided with waste liquid vent pipe (10); Computing machine (11) connects solid sampler (1) and AFS (9) respectively; It is characterized in that: described injector (1) is made up of following part with integrated interface (2): carrier gas I (101) is connected with hot releasing tube or little ashing pipe (104) with the fastening interface of carrier gas and sample hose (103) through carrier gas I operation valve (102); Be provided with heat outside hot releasing tube or the little ashing pipe (104) and release heating system (105); Heat is released heating system (105) outside and is provided with cooling fan (106); Hot releasing tube or little ashing pipe (104) are terminal to be connected with absorption tube or trap tube (203) with the fastening interface (201) of integral type interface through sample hose, and absorption tube or trap tube (203) are connected with sample hose (3) with hydride generating system interface (202) through absorption liquid, and absorption tube or trap tube (203) are provided with absorption liquid and cleansing solution introducing port (205); Absorption liquid (208) or cleansing solution (209) are connected with cleansing solution introducing port (205) with absorption liquid with peristaltic pump (206) through threeway valve position (207), and absorption tube or trap tube (203) are provided with exhaust gas evacuation mouth (204).
2. solid sampling as claimed in claim 1-non-dispersive atomic fluorescence photometer logotype device is characterized in that: described heat is released heating system (105) and is selected one of electrical heating or combustion gas heating for use, and combustion gas heating source of the gas is portable gas-holder or alcohol blast burner.
3. solid sampling as claimed in claim 1-non-dispersive atomic fluorescence photometer logotype device is characterized in that: described hot releasing tube or little ashing pipe (104) are quartzy or ceramic microminiature straight tube, small U type pipe or small special pipe.
4. solid sampling-non-dispersive atomic fluorescence photometer analytical approach is characterized in that: comprise the steps:
The first step, accurately take by weighing analytic sample 0.0200-0.3000 gram; Add 2-5 doubly to the auxiliary heat releasing agent of sample size or help fogging agent; Stir and put into quartzy or ceramic hot releasing tube or little ashing pipe (104) of solid sampler (1), and 0.2-25mL absorption liquid (208) is pumped in the absorption tube (203) with peristaltic pump (206);
Second step, release heating system (105) through heat and give hot releasing tube or little ashing pipe (104) heating; Heating-up temperature is 400-1100 ℃; Heated 0.5-10 minute, analytical element evaporates with the volatile halogenated form or the little dry incineration of organic matrix sample in the inorganic matrix sample;
The part of volatilizing when the 3rd step, volatile halogenated or analytical element ashing is taken out of by carrier gas I (101), is absorbed that liquid (208) absorbs and/or gold amalgam captures;
The 4th goes on foot, stops to heat, and opens cooling fan (106), and hot releasing tube or little ashing pipe (104) are fully cooled off;
The 5th step, clean hot releasing tube or little ashing pipe, reduction: with 2-10s/ time frequency through carrier gas operation valve (102) switch carrier gas I; Utilize the switch of carrier gas I pulsed to stir absorption liquid (208) the hot releasing tube of flushing or little ashing pipe (104); The analytical element volatile matter of condensation on hot releasing tube or little ashing pipe (104) wall is dissolved in the absorption liquid (208) fully, and the reductive agent that the while analytical element is absorbed in the liquid (208) fully reduces;
The 6th step, chemical evapn take place and measure: the absorption liquid (208) that has absorbed element to be measured is introduced into chemical evapn generation system by peristaltic pump (4); Analytical element and reductive agent H (6) are through the biochemical reaction of threeway (7) hybrid concurrency in the absorption liquid (208); Produce the volatility chemical evapn and separate through gas-liquid separator (8), steam gets into AFS (9) and is carried out quantitative measurement after the atomization;
The 7th step: clean, T-valve (207) rotates and cleansing solution (209) conducting, and peristaltic pump (206) pumps into cleansing solution (209) absorption tube (203) and reaction pipeline are cleaned, in order to measuring next sample.
5. solid sampling as claimed in claim 4-non-dispersive atomic fluorescence photometer analytical approach; It is characterized in that: described absorption liquid (208) is mineral acid or the organic acid soln of deionized water or 0.1%-50% (v/v); Under acid hydride emergence pattern; Absorption liquid (208) is a kind of acidic mixed solution, and wherein containing acid and the massfraction that volume fraction or massfraction are 0.1-50% is the reductive agent of 0.1-10%, wherein:
Described acid is one of oxalic acid, citric acid, tartrate, halfcystine, hydrochloric acid, sulfuric acid, nitric acid;
Described reductive agent is one of thiocarbamide, ascorbic acid, halfcystine, iodide;
Under alkaline hydride emergence pattern, absorption liquid (208) is that 0.05-2% NaOH or potassium and massfraction are 0.05-5% sodium borohydride or potassium mixed solution for massfraction.
6. solid sampling as claimed in claim 4-non-dispersive atomic fluorescence photometer analytical approach; It is characterized in that: described auxiliary heat releasing agent is labile halogenide, and the described fogging agent that helps is oxygen, oxygen-enriched air, magnesium oxide (MgO), magnesium nitrate (Mg (NO
3)
2), nitric acid (HNO
3), one of zinc paste (ZnO).
7. solid sampling as claimed in claim 6-non-dispersive atomic fluorescence photometer analytical approach is characterized in that: described auxiliary heat releasing agent is zinc chloride (ZnCl
2), iron chloride (FeCl
3), aluminum chloride (AlCl
3), sal-ammoniac (NH
4Cl), ammonia bromide (NH
4Br) or iodate ammonia (NH
4One of I), helping fogging agent is oxygen or oxygen-enriched air.
8. solid sampling as claimed in claim 4-non-dispersive atomic fluorescence photometer analytical approach is characterized in that: described carrier gas: when sample was inorganic samples, carrier gas was that purity is the 99.9-99.99% argon gas; When sample was organic sample, carrier gas was that purity is the oxygen of 99-99.99%.
9. solid sampling as claimed in claim 4-non-dispersive atomic fluorescence photometer analytical approach; It is characterized in that: described reductive agent H is a kind of mixed solution, and wherein containing NaOH that volume fraction or massfraction are 0.1-2% or potassium and massfraction is sodium borohydride or the potassium of 0.05-5%.
10. solid sampling as claimed in claim 4-non-dispersive atomic fluorescence photometer analytical approach; It is characterized in that: described cleansing solution is a 0.1-20% organic or inorganic acid solution for containing volume fraction or massfraction, and described organic acid mainly comprises one of oxalic acid, citric acid, tartrate, halfcystine.
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| CN101776585B (en) * | 2010-03-09 | 2011-07-20 | 四川大学 | Photochemical steam generating-atomic spectrometry for determining trace iron |
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