CN104266888A - Method for separating and measuring arsenic elements with different forms in main stream smoke of cigarettes - Google Patents
Method for separating and measuring arsenic elements with different forms in main stream smoke of cigarettes Download PDFInfo
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- CN104266888A CN104266888A CN201410499263.1A CN201410499263A CN104266888A CN 104266888 A CN104266888 A CN 104266888A CN 201410499263 A CN201410499263 A CN 201410499263A CN 104266888 A CN104266888 A CN 104266888A
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Abstract
The invention provides a method for separating and measuring arsenic elements with different forms in main stream smoke of cigarettes. According to the method, AB-8 resin is adopted for separating, and the content of the arsenic elements with different forms in the main stream smoke of the cigarettes can be measured by an inductively coupled plasma mass spectrometry method, wherein the arsenic elements with different forms are inorganic arsenic and organic arsenic. The method for separating and measuring the arsenic elements with different forms in the main stream smoke of the cigarettes is good in reproducibility and recovery rate, is beneficial to the effective quantitative measurement control of related technical personnel of the tobacco industry for the contents of the arsenic elements with different forms in the main stream smoke of the cigarettes, and provides a powerful technical support for comprehensively and objectively evaluating the harmfulness of the arsenic elements in the main stream smoke of the cigarettes in the tobacco industry.
Description
Technical field
The invention belongs to chemical analysis detection technique field, be specifically related to the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas.
Background technology
Arsenic, as a Heavy Metallic Elements, in recent years because it has larger harmfulness to the mankind and environment, obtains and pays close attention to widely and study.Arsenic in cigarette smoke is one of source of chromium in environment, is also one of objectionable constituent enumerated in Hoffmann list in tobacco business.When smoking cigarette, arsenic element can be inhaled in bronchus, thus works the mischief to the lung of human body, liver, kidney and other organs.From toxicology, the arsenic of different shape has different toxicity, inorganic states arsenic (As
2o
3, AsO
3 3-, AsO
4 3-) toxicity is comparatively strong, organic arsenic toxicity is less, and in inorganic states arsenic, arsenious toxicity is better than pentavalent arsenic.Therefore, in order to the harmfulness of arsenic in more comprehensive and objective appraisal cigarette smoke, we not only need the total amount studying arsenic in cigarette smoke, also need to carry out deep research to the content of different shape arsenic in flue gas.
But, at present the morphological analysis research of arsenic element is mainly concentrated in the sample in the fields such as environmental sample, biological sample, marine products sample and Chinese herbal medicine, only have the report of on a small quantity different shape of arsenic element in tobacco and cigarette smoke being analyzed and researched.As Zhang Jianping etc. adopts ultrasonic solvent extraction, high performance liquid chromatography and inductivity coupled plasma mass spectrometry coupling technique to establish the method for separating and analyzing of arsenious acid, arsenic acid, dimethyl arsenate, methylarsonic acid, arsenocholine, arsenic betaine 6 kinds of form arsenic, but he does not carry out a point analysis of variance to the form of arsenic in cigarette smoke.For another example Liu etc. adopt synchronous radio-and chemotherapy method to analyze the oxidation state of arsenic in pipe tobacco, cigarette ash and Smoke Particulate, and result of study shows containing trivalent arsenic and pentavalent arsenic in Smoke Particulate, but fails to carry out quantitative test.And Taebunpakul etc. analyze the form of arsenic in tobacco leaf and flue gas by HPLC-ICP-MS coupling method, but he also fails quantitatively to detect the arsenic of different shape in flue gas.Therefore, set up that a kind of the separation and detection method of different shape arsenic element is extremely important for tobacco business accurately and reliably, in main flume easy and simple to handle.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas, lacking accurately and reliably for solving in prior art, be separated easy and simple to handlely different shape arsenic element in cigarette mainstream flue gas and carry out the problem of the method analyzed.
For achieving the above object, the invention provides the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas, adopt AB-8 resin isolation, then adopt inductively coupled plasma mass spectrometry to measure the content of different shape arsenic element in cigarette mainstream flue gas.
Preferably, described different shape arsenic element is inorganic states arsenic and organic arsenic.
The method of separating and assaying of different shape arsenic element in described a kind of cigarette mainstream flue gas, comprises the following steps:
1) sample pre-treatments: select Cigarette, with the granule phase substance in filter disc trapping cigarette mainstream flue gas after suction, filter the filtrate of acquisition after filter disc is carried out ultrasonic extraction, then adopt the chromatographic column of filling AB-8 resin to be separated, obtain the sample solution of the arsenic element containing different shape respectively.
Preferably, described Cigarette is selected according to standard GB/T/T5606.1-2004 " cigarette part 1: sampling ".
Preferably, described Cigarette traps flue gas according to standard GB/T/T19609-2004 " cigarette conventional analysis smoking machine measures TPM and tar ".
Preferably, described filter disc amount of collected is often open the Smoke Particulate that filter disc traps 20 cigarette.
Preferably, described filter disc is the cambridge filter of Φ 92mm.
Preferably, described ultrasonic extraction comprises the following steps: the filter disc after trapping is put into plastic tube, adds ultrapure water, at room temperature carry out ultrasonic extraction.
Further, described ultrasonic extraction condition is: plastic tube volume: 50ml; Ultrapure water consumption: 30ml; The ultrasonic extraction time: 40min.
Preferably, described filtration adopts membrane filtration.Further, described filter membrane is 0.45 μm of filter membrane.
Preferably, the described chromatographic column of filling AB-8 resin that adopts is separated, and comprises the following steps:
The chromatographic column separation principle of described filling AB-8 resin is: AB-8 resin is to the organic compound effect of withing a hook at the end, aqueous solution of nitric acid is conducive to the wash-out of inorganics in sample solution and cleans chromatographic column, ethanolic solution is better to organic dissolubility, can by the organism wash-out on chromatographic column.
The filling of A, chromatographic column: choose AB-8 resin, insert chromatographic column, adds ultrapure water cleaning chromatographic column, stand-by.
Further, the filling condition of described chromatographic column is: filler: AB-8 resin; Packed height: 5-15cm; Chromatographic column internal diameter: 1.0-2.0cm; Ultrapure water consumption: 250-750ml.
Preferably, the filling condition of described chromatographic column is: filler: AB-8 resin; Packed height: 10cm; Chromatographic column internal diameter: 1.5cm; Ultrapure water consumption: 500ml.
Described ultrapure water refers to by conductivity prepared by Milli-Q ultrapure water instrument to be the pure water of 18.2M Ω cm.
The separation of B, inorganic states arsenic: removing step 1) middle filtrate, add the chromatographic column of a filling AB-8 resin, collect efflux; Pipette aqueous solution of nitric acid again, the chromatographic column of drip washing filling AB-8 resin, continues to collect efflux, obtains inorganic states arsenic sample solution.
Further, the concentration of volume percent of described aqueous solution of nitric acid is 1% (v/v).
Further, described chromatographic column is provided with outlet piston.Described outlet piston controls liquid stream in chromatographic column and has troubles, and regulates outlet piston controllable liquid flow velocity.
Further, described collection efflux refers to, filtrate is added the chromatographic column of a filling AB-8 resin, open the outlet piston on chromatographic column, access collection efflux with a container, when filtrate liquid level is down to resin boundary surface, close outlet piston, add aqueous solution of nitric acid, open outlet piston again, continuation said vesse accesses collection efflux, when efflux reaches certain volume, close outlet piston, namely obtain inorganic states arsenic sample solution.
Preferably, described container is the container having accurate volume markings.
More excellent, described container is volumetric flask.
Optimum, the volume of described volumetric flask is 50ml.Optimum, described volumetric flask is plastics volumetric flask.
Further, described effluent volume is 50ml.
Further, the separation condition of described inorganic states arsenic is: filtrate consumption: 15-25ml; Filtrate pH value: 2.8-3.2; Filtrate crosses column flow rate: 2-4ml/min; Aqueous solution of nitric acid consumption: 30-45ml; Aqueous solution of nitric acid crosses column flow rate: 2-4ml/min.
Preferably, the separation condition of described inorganic states arsenic is: filtrate consumption: 20ml; Filtrate pH value: 3.0; Filtrate crosses column flow rate: 3ml/min; Aqueous solution of nitric acid consumption: 35ml; Aqueous solution of nitric acid crosses column flow rate: 3ml/min.
The separation of C, organic arsenic: pipette ethanol water again, adds the chromatographic column loading AB-8 resin described in step B,
Collect eluent, obtain organic arsenic sample solution.
Further, the concentration of volume percent of described ethanol water is 70% (v/v).
Further, described collection eluent refers to, ethanol water is continued the chromatographic column adding filling AB-8 resin, open the outlet piston on chromatographic column, access collection eluent with another container, when eluent reaches certain volume, close outlet piston, namely obtain organic arsenic sample solution.
Preferably, described container is the container having accurate volume markings.
More excellent, described container is volumetric flask.
Optimum, the volume of described volumetric flask is 50ml.Optimum, described volumetric flask is plastics volumetric flask.
Further, described effluent volume is 50ml.
Further, the separation condition of described organic arsenic is: ethanol water consumption: 50-60ml; Ethanol water crosses column flow rate: 2-4ml/min.
Preferably, the separation condition of described organic arsenic is: ethanol water consumption: 55ml; Ethanol water crosses column flow rate: 3ml/min.
D, blank test: pipette the chromatographic column that aqueous solution of nitric acid adds another root filling AB-8 resin, collect efflux, obtain inorganic states arsenic blank sample solution; Pipette ethanol water again, add the chromatographic column of filling AB-8 resin, collect eluent, obtain organic arsenic blank sample solution.
Further, the chromatographic column loading AB-8 resin described in step D is identical with the chromatographic column loading AB-8 resin described in step B, C.
Further, to add the condition of the chromatographic column of filling AB-8 resin identical with the condition of aqueous solution of nitric acid in step B for described aqueous solution of nitric acid.
Further, to add the condition of the chromatographic column of filling AB-8 resin identical with the condition of ethanol water in step C for described ethanol water.
2) preparation of standard solution: preparation germanium
72the arsenic element standard solution of inner mark solution and different valence state.
I, arsenic is pipetted, with ultrapure water dilution also constant volume, preparation arsenic Standard Stock solutions.
Further, the mass concentration of described arsenic Standard Stock solutions is 1000 μ g/L.
Further, the condition of storage of described arsenic Standard Stock solutions is: storage temperature: 0-4 DEG C; Storage time: 1 month.
II, germanium is pipetted
72standard substance solution, with aqueous solution of nitric acid dilution also constant volume, preparation inner mark solution.
Further, described germanium
72the concentration of standard substance solution is 100.0mg/L.
Further, the aqueous solution of nitric acid of described aqueous solution of nitric acid to be concentration of volume percent be 1% (v/v).
Further, the mass concentration of described inner mark solution is 1000 μ g/L.
Further, the condition of storage of described inner mark solution is: storage temperature: 0-4 DEG C; Storage time: 1 month.
III, pipette the arsenic Standard Stock solutions in the step I of different volumes respectively, be formulated as the inorganic states arsenic standard solution of a series of variable concentrations with ultrapure water constant volume, be formulated as the organic arsenic standard solution of a series of variable concentrations with ethanol water constant volume.
Further, the solvent that uses of described inorganic states arsenic standard solution and organic arsenic standard solution is consistent with the solvent that respective sample solution uses.
Further, the concentration of volume percent of described ethanol water is 70% (v/v).
Described standard solution should cover sample concentration scope, namely can join and namely use.
3) measure: respectively by step 1) in sample solution, step 2) standard solution prepared and inner mark solution carry out icp ms (ICP-MS) and detect, in adopting, mark synchronization criterion curve method carries out quantitatively, obtains the content of the arsenic element of different shape in sample solution.
Preferably, described interior mark synchronization criterion curve method comprises the following steps:
When described interior mark synchronization criterion curve method refers to that ICP-MS measures, in on-line synchronous bioassay standard solution and inner mark solution, obtain standard working curve, and then on-line synchronous measures inner mark solution and actual sample solution, thus measure the method obtaining actual sample concentration.Due to ICP-MS instrument trait, inner mark solution and sample solution are respectively by two peristaltic pump tubes, and simultaneously synchronous online sample introduction, measures after sampling valve mixing, and unconventional interior mark carries out the mode that measures after adding sample.
I, by step 2) III in the inorganic states arsenic standard solution of a series of variable concentrations and organic arsenic standard solution, step 2) II in inner mark solution synchronously carry out ICP-MS detection, obtain the linear relationship of inorganic states arsenic or the mass-to-charge ratio strength ratio of organic arsenic/internal standard compound matter and the mass concentration ratio of inorganic states arsenic or organic arsenic/internal standard compound matter respectively, draw corresponding standard working curve, calculate the regression equation of inorganic states arsenic or organic arsenic standard working curve respectively.
Further, in described typical curve, with the mass-to-charge ratio strength ratio of inorganic states arsenic or organic arsenic and internal standard compound matter for ordinate (Y-axis), the mass concentration ratio of its corresponding inorganic states arsenic or organic arsenic and internal standard compound matter is horizontal ordinate (X-axis).
II, by step 1) in inorganic states arsenic sample solution and blank solution thereof or organic arsenic sample solution and blank solution, step 2) II in inner mark solution synchronously carry out ICP-MS detection, by the inorganic states arsenic of acquisition or the mass-to-charge ratio strength ratio of organic arsenic/internal standard compound matter, substitute into the regression equation of corresponding inorganic states arsenic or organic arsenic standard working curve in step I, and according to the known quality concentration of the synchronous inner mark solution detected, calculate the mass concentration of inorganic states arsenic or organic arsenic in sample solution.
Preferably, step 3) in, described icp ms (ICP-MS) is ends of the earth bar collision/reaction tank-icp ms (ORS-ICP-MS), and is furnished with machine oxygenation sampling system.
The principle of described organic oxygenation sampling system is: due to common sampling system meet organic solvent after plasma flame can be caused to stop working, and organic oxygen-enrichment system adopts the less quarter bend of internal diameter and pass into argon oxygen gas mixture and assist burning.Under normal circumstances in sample solution as just can sample introduction analysis after must being removed by the mode such as heating, rotary evaporation containing organic solvent, operate comparatively loaded down with trivial details and easily cause unnecessary loss and pollution for heavy metal element trace analysis, and can directly the sample containing organic solvent be analyzed after adopting organic oxygen-enrichment system, the accuracy of testing result can better be ensured.
Further, described ORS-ICP-MS to the testing conditions of inorganic states arsenic is: ion gun: ICP source; Radio-frequency power: 1550W; RF matching voltage: 1.8V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.85L/min; Carrier gas complemental air: argon gas, flow velocity: 0.3L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature: 2.0 DEG C; Atomization gas: argon gas, flow velocity: 1.15L/min; Ends of the earth bar deflection voltage :-18.0V; Energy is discriminated against: 1.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
Further, described ORS-ICP-MS to the testing conditions of organic arsenic is: ion gun: ICP source; Radio-frequency power (RF power): 1600W; RF matching voltage: 1.7V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.45L/min; Optional gas: argon oxygen gas mixture, set amount: 30.0%; Carrier gas complemental air: argon gas, flow velocity: 0.1L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature :-5.0 DEG C; Atomization gas: argon gas, flow velocity: 0.55L/min; Ends of the earth bar deflection voltage :-17.6V; Energy is discriminated against: 2.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
As mentioned above, the method of separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas of the present invention, the chromatographic column of filling AB-8 resin is adopted to be separated the arsenic element of different shape in main flume, using icp ms as determining instrument, measure the content of different shape arsenic element in cigarette mainstream flue gas.The standard working curve coefficient R of the inventive method
2>0.999, the average recovery rate of object is between 87.7-107.2%, and relative standard deviation (RSD) is less than 5%, and reappearance, the recovery are all satisfactory.The inventive method is conducive to tobacco business person skilled and carries out effective quantitative measurement control to the content of different shape arsenic element in cigarette mainstream flue gas, and provides strong technical support for the harmfulness of arsenic element in tobacco business comprehensive objective evaluation cigarette mainstream flue gas.
Accompanying drawing explanation
Fig. 1 is shown as the method for separating and assaying schematic flow sheet of different shape arsenic element in a kind of cigarette mainstream flue gas of the present invention
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this instructions can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this instructions also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Embodiment 1
1 reagent and instrument
1.1 reagent
AB-8 macroporous absorbent resin (particle size range 0.3 ~ 1.25mm>=95%, Tianjin recovery fine chemistry industry research institute); Arsenic standard solution (10.0mg/L, Agilent Science and Technology Ltd. of the U.S.); Germanium
72(100.0mg/L, Agilent Science and Technology Ltd. of the U.S.); NaOH (analyzing pure, German Merck company); Ethanol (analyzing pure, German Merck company); 65% nitric acid (top grade is pure, German Merck company)
1.2 instrument
RM200A rotating disc type smoking machine (German Borgwaldt company); Cambridge filter (diameter 92mm, German Borgwaldt company); Filter membrane (0.45 μm, Town in Shanghai spectrum Science and Technology Ltd.); SW12H ultrasonic cleaning machine (SONO SWISS company of Switzerland); Milli-Q ultrapure water instrument (Millipore company of the U.S.); 7700X ends of the earth bar collision/reaction tank-icp ms (Agilent Science and Technology Ltd. of the U.S.)
2, assay method
2.1 sample pre-treatments
Cigarette is selected according to standard GB/T/T5606.1-2004 " cigarette part 1: sampling ", and use RM200A rotating disc type smoking machine to aspirate according to standard GB/T19609-2004 " cigarette conventional analysis smoking machine measures TPM and tar ", with the granule phase substance in cambridge filter trapping cigarette mainstream flue gas, often open the Smoke Particulate that filter disc collects 20 cigarette.After cigarette smoking, take out filter disc and put into 50ml plastic tube, and add 30ml ultrapure water, ultrasonic extraction 40min under room temperature, then by extract 0.45 μm of membrane filtration, filtrate saves backup.
Choose the chromatographic column filling AB-8 resin that internal diameter is 1.5cm, resin height is 10cm, has loaded rear 500mL ultrapure water cleaning chromatographic column, has saved backup.
Accurately pipette the chromatographic column that 20ml filtrate (adding NaOH regulates pH to be 3.0) adds a filling AB-8 resin, open and regulate the outlet piston of chromatographic column, coutroi velocity is at 3ml/min, collection efflux is accessed with 50mL plastics volumetric flask, when filtrate liquid level drops to resin boundary surface, close outlet piston, add 1% (v/v) aqueous solution of nitric acid, open outlet piston again, coutroi velocity, at 3ml/min, continues to access collection efflux, when efflux reaches 50.0ml, close outlet piston, obtain inorganic states arsenic sample solution.In chromatographic column, add 70% (v/v) ethanol water again, open and regulate the outlet piston of chromatographic column, coutroi velocity is at 3ml/min, efflux is accessed with another 50ml plastics volumetric flask, when eluent reaches 50.0ml, close outlet piston, obtain organic arsenic sample solution.
Simultaneously, pipette the chromatographic column that 1% (v/v) aqueous solution of nitric acid adds another root filling AB-8 resin, open and regulate the outlet piston of chromatographic column, coutroi velocity is at 3ml/min, collection efflux is accessed with 50mL plastics volumetric flask, when efflux reaches 50.0ml, close outlet piston, obtain inorganic states arsenic blank sample solution.70% (v/v) ethanol water is added again in chromatographic column, open and regulate the outlet piston of chromatographic column, coutroi velocity is at 3ml/min, efflux is accessed with another 50ml plastics volumetric flask, when eluent reaches 50.0ml, close outlet piston, obtain organic arsenic blank sample solution.Detailed process as shown in Figure 1.
The preparation of 2.2 standard solution
Pipette arsenic, dissolve and constant volume with ultrapure water, preparation arsenic Standard Stock solutions.The concentration of arsenic Standard Stock solutions is 1000 μ g/L.Condition of storage, under 0-4 DEG C of condition, can store 1 month.
Take the germanium that concentration is 100.0mg/L
72standard substance solution, dissolves and constant volume with 1% aqueous solution of nitric acid, preparation inner mark solution.The concentration of inner mark solution is 1000 μ g/L.Condition of storage, under 0-4 DEG C of condition, can store 1 month.
Pipette the arsenic Standard Stock solutions of different volumes respectively, be formulated as the inorganic states arsenic standard solution of a series of variable concentrations with ultrapure water constant volume, be formulated as the organic arsenic standard solution of a series of variable concentrations with the ethanol water constant volume of 70% (v/v).Standard solution should cover sample size scope, namely need join and namely use.The concrete concentration of standard solution is in table 1.
Table 1 standard solution preparation table (unit: μ g/L)
| Sequence number | Inorganic states arsenic | Organic arsenic |
| Lv1 | 0 (reagent blank) | 0 (reagent blank) |
| Lv2 | 0.5 | 0.5 |
| Lv3 | 1.0 | 1.0 |
| Lv4 | 2.0 | 2.0 |
| Lv5 | 3.0 | 3.0 |
| Lv6 | 5.0 | 5.0 |
| Lv7 | 10.0 | 10.0 |
| Lv8 | 15.0 | 15.0 |
| Lv9 | 20.0 | 20.0 |
2.3 sample tests
Respectively 2.1 sample solutions prepared and 2.2 Plays solution are carried out ORS-ICP-MS detection, in adopting, mark synchronization criterion curve method carries out quantitatively, obtains the content of inorganic states arsenic and organic arsenic in sample solution.
Specifically, first by the inorganic states arsenic standard solution of variable concentrations a series of in table 1 and organic arsenic standard solution, inner mark solution synchronously carries out ORS-ICP-MS detection, obtain the linear relationship of inorganic states arsenic or the mass-to-charge ratio strength ratio of organic arsenic/internal standard compound matter and the mass concentration ratio of inorganic states arsenic or organic arsenic/internal standard compound matter respectively, with the mass-to-charge ratio strength ratio of inorganic states arsenic or organic arsenic and internal standard compound matter for ordinate (Y-axis), the mass concentration ratio of its corresponding inorganic states arsenic or organic arsenic and internal standard compound matter is horizontal ordinate (X-axis), draw corresponding standard working curve, calculate the regression equation of inorganic states arsenic or organic arsenic standard working curve respectively.
Wherein, the capillary inner diameter measuring inner mark solution due to ORS-ICP-MS is 1/20 of the capillary inner diameter of working sample, and the concentration of its inner mark solution is without the need to dilution, and the actual sample introduction concentration of inner mark solution is 1/20 of inner mark solution concentration.
Again by inorganic states arsenic sample solution and blank solution thereof or organic arsenic sample solution and blank solution, inner mark solution, synchronously carry out ORS-ICP-MS detection, by the inorganic states arsenic of acquisition or the mass-to-charge ratio strength ratio of organic arsenic/internal standard compound matter, substitute into the regression equation of corresponding inorganic states arsenic or organic arsenic standard working curve, and according to the known quality concentration of the synchronous inner mark solution detected, calculate the mass concentration of inorganic states arsenic or organic arsenic in sample solution.
Wherein, ends of the earth bar collision/reaction tank-icp ms (ORS-ICP-MS) is furnished with machine oxygenation sampling system.
Wherein, described ORS-ICP-MS to the testing conditions of inorganic states arsenic is: ion gun: ICP source; Radio-frequency power: 1550W; RF matching voltage: 1.8V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.85L/min; Carrier gas complemental air: argon gas, flow velocity: 0.3L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature: 2.0 DEG C; Atomization gas: argon gas, flow velocity: 1.15L/min; Ends of the earth bar deflection voltage :-18.0V; Energy is discriminated against: 1.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
Described ORS-ICP-MS to the testing conditions of organic arsenic is: ion gun: ICP source; Radio-frequency power (RF power): 1600W; RF matching voltage: 1.7V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.45L/min; Optional gas: argon oxygen gas mixture, set amount: 30.0%; Carrier gas complemental air: argon gas, flow velocity: 0.1L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature :-5.0 DEG C; Atomization gas: argon gas, flow velocity: 0.55L/min; Ends of the earth bar deflection voltage :-17.6V; Energy is discriminated against: 2.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
3, result and discussion
3.1 standard working curves, detection limit and quantitative limit
Pipette the arsenic Standard Stock solutions of different volumes respectively, the inorganic states arsenic standard solution of a series of variable concentrations is formulated as with ultrapure water constant volume, be formulated as the organic arsenic standard solution of a series of variable concentrations with ethanol water constant volume, concrete concentration is as shown in table 1 in 2.2.
The standard solution of the above-mentioned a series of variable concentrations prepared and inner mark solution are synchronously carried out ORS-ICP-MS detection respectively, with the mass-to-charge ratio strength ratio of inorganic states arsenic or organic arsenic and internal standard compound matter for ordinate (Y-axis), the mass concentration ratio of its corresponding inorganic states arsenic or organic arsenic and internal standard compound matter is horizontal ordinate (X-axis), carry out regretional analysis, obtain regression equation and related coefficient thereof, as shown in table 2.
As shown in Table 2, the linear relationship of regression equation is good, correlation coefficient r
2>0.999.To the object response signal in standard solution, least concentration standard specimen is adopted to repeat sample introduction 10 times, carry out ORS-ICP-MS analysis, the detection limit being method with 3 times of signal to noise ratio (S/N ratio)s (LOD), 10 times of signal to noise ratio (S/N ratio)s are quantitative limit (LOQ), show after being scaled sample size that object detects and be limited to 0.05-0.09ng/cig, quantitative limit, at 0.18-0.30ng/cig, has higher sensitivity.
Table 2 working curve and detection limit
Y: mass-to-charge ratio strength ratio; X: concentration ratio
3.2 recovery and precision
Respectively in the inorganic states arsenic sample solution and organic arsenic sample solution of concentration known, add the standard solution of concentration known, then sample pre-treatments is carried out and ORS-ICP-MS analyzes, and calculate its recovery according to adding scalar sum measured value, simultaneously to same sample solution replicate determination 5 times (n=5), obtain the precision determination data of inorganic states arsenic and organic arsenic sample size, the results are shown in Table 3,4.As can be seen from table 3,4, the average recovery rate of object is between 87.7 ~ 107.2%, relative standard deviation (RSD) is less than 5%, owing to belonging to trace analysis category in the present invention, in sample, object content is lower, detectable concentration is ng/ml rank, so accuracy of the present invention and repeatability are better, can meet quantitative needs.
Inorganic states arsenic and organic arsenic sample recovery rate in table 3 cigarette sample main flume
The precision (n=5) of inorganic states arsenic and organic arsenic sample in table 4 cigarette sample main flume
The mensuration of 3.3 actual samples
The content adopting this method to measure inorganic states arsenic and organic arsenic in the main flume of actual cigarette sample measures, specifically in table 5.As shown in Table 5, for cigarette sample, the method effectively can measure the content of inorganic states arsenic and organic arsenic in its main flume, and method is easy and simple to handle, applicability good, and result accurately, reliably.
The content of inorganic states arsenic and organic arsenic in the actual cigarette sample of table 5
| Sample | Inorganic states arsenic (ng/cig) | Organic arsenic (ng/cig) |
| Sample 1 | 4.34 | 1.25 |
4, conclusion
In sum, the present invention utilizes AB-8 resin to be separated the arsenic element of different shape in main flume, and measures in conjunction with icp ms, establishes the method for separating and assaying of different shape arsenic element in cigarette mainstream flue gas.The method is easy and simple to handle, applicability good, and result accurately, reliably.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. the method for separating and assaying of different shape arsenic element in cigarette mainstream flue gas, adopts AB-8 resin isolation, then adopts inductively coupled plasma mass spectrometry to measure the content of different shape arsenic element in cigarette mainstream flue gas.
2. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 1, it is characterized in that, described different shape arsenic element is inorganic states arsenic and organic arsenic.
3. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 1, is characterized in that, comprise the following steps:
1) sample pre-treatments: select Cigarette, with the granule phase substance in filter disc trapping cigarette mainstream flue gas after suction, filter the filtrate of acquisition after filter disc is carried out ultrasonic extraction, then adopt the chromatographic column of filling AB-8 resin to be separated, obtain the sample solution of the arsenic element containing different shape respectively;
2) preparation of standard solution: preparation germanium
72the arsenic element standard solution of inner mark solution and different valence state;
3) measure: respectively by step 1) in sample solution, step 2) standard solution prepared and inner mark solution carry out icp ms detection, in adopting, mark synchronization criterion curve method carries out quantitatively, obtains the content of the arsenic element of different shape in sample solution.
4. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 3, is characterized in that, step 1) in, the described chromatographic column of filling AB-8 resin that adopts is separated, and comprises the following steps:
The filling of A, chromatographic column: choose AB-8 resin, insert chromatographic column, adds ultrapure water cleaning chromatographic column, stand-by;
The separation of B, inorganic states arsenic: removing step 1) middle filtrate, add the chromatographic column of a filling AB-8 resin, collect efflux; Pipette aqueous solution of nitric acid again, the chromatographic column of drip washing filling AB-8 resin, continues to collect efflux, obtains inorganic states arsenic sample solution;
The separation of C, organic arsenic: pipette ethanol water again, adds the chromatographic column loading AB-8 resin described in step B, collects eluent, obtains organic arsenic sample solution;
D, blank test: pipette the chromatographic column that aqueous solution of nitric acid adds another root filling AB-8 resin, collect efflux, obtain inorganic states arsenic blank sample solution; Pipette ethanol water again, add the chromatographic column of filling AB-8 resin, collect eluent, obtain organic arsenic blank sample solution.
5. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 4, it is characterized in that, in steps A, the filling condition of described chromatographic column is: filler: AB-8 resin; Packed height: 5-15cm; Chromatographic column internal diameter: 1.0-2.0cm; Ultrapure water consumption: 250-750ml.
6. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 4, it is characterized in that, in step B, the separation condition of described inorganic states arsenic is: filtrate consumption: 15-25ml; Filtrate pH value: 2.8-3.2; Filtrate crosses column flow rate: 2-4ml/min; Aqueous solution of nitric acid consumption: 30-45ml; Aqueous solution of nitric acid crosses column flow rate: 2-4ml/min.
7. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 4, it is characterized in that, in step C, the separation condition of described organic arsenic is: ethanol water consumption: 50-60ml; Ethanol water crosses column flow rate: 2-4ml/min.
8. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 3, it is characterized in that, step 3) in, described icp ms is ends of the earth bar collision/reaction tank-icp ms, and is furnished with machine oxygenation sampling system.
9. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 8, it is characterized in that, described ORS-ICP-MS to the testing conditions of inorganic states arsenic is: ion gun: ICP source; Radio-frequency power: 1550W; RF matching voltage: 1.8V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.85L/min; Carrier gas complemental air: argon gas, flow velocity: 0.3L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature: 2.0 DEG C; Atomization gas: argon gas, flow velocity: 1.15L/min; Ends of the earth bar deflection voltage :-18.0V; Energy is discriminated against: 1.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
10. the method for separating and assaying of different shape arsenic element in a kind of cigarette mainstream flue gas according to claim 8, it is characterized in that, described ORS-ICP-MS to the testing conditions of organic arsenic is: ion gun: ICP source; Radio-frequency power (RF power): 1600W; RF matching voltage: 1.7V; Cold gas: argon gas, flow velocity: 15.0L/min; Carrier gas: argon gas, flow velocity: 0.45L/min; Optional gas: argon oxygen gas mixture, set amount: 30.0%; Carrier gas complemental air: argon gas, flow velocity: 0.1L/min; Collision/reaction tank gas: helium, flow velocity: 4.3mL/min; Spray chamber temperature :-5.0 DEG C; Atomization gas: argon gas, flow velocity: 0.55L/min; Ends of the earth bar deflection voltage :-17.6V; Energy is discriminated against: 2.0V; Sample feeding speed: 0.1rps; Multiplicity: 3; Scan mode: order jumps peak.
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| CN113405865A (en) * | 2021-06-30 | 2021-09-17 | 上海电力大学 | Coal-fired flue gas arsenic sampling device |
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