CN104614436B - The detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas - Google Patents
The detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas Download PDFInfo
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- CN104614436B CN104614436B CN201510030971.5A CN201510030971A CN104614436B CN 104614436 B CN104614436 B CN 104614436B CN 201510030971 A CN201510030971 A CN 201510030971A CN 104614436 B CN104614436 B CN 104614436B
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Abstract
The present invention provides a kind of detection method of arsenogen cellulose content in cigarette mainstream flue gas, TPM composition arsenic in cigarette mainstream flue gas is trapped using Electrostatic mode, simultaneously using gas phase composition arsenic in acidic ethanol solution trapping cigarette mainstream flue gas, then the content using arsenic element in inductively coupled plasma mass spectrometry measure cigarette mainstream flue gas.Present invention also offers the detection method of gas phase composition arsenogen cellulose content and its application in a kind of cigarette mainstream flue gas.The detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas of the present invention, reappearance, the rate of recovery are good, be advantageous to tobacco business person skilled and effective quantitative determination control is carried out to the content of arsenic element in cigarette mainstream flue gas, and the harmfulness for arsenic element in the comprehensive objective evaluation cigarette mainstream flue gas of tobacco business provides strong technical support.
Description
Technical field
The invention belongs to chemical analysis detection technique field, and in particular to arsenogen cellulose content in a kind of cigarette mainstream flue gas
Detection method.
Background technology
Arsenic is a Heavy Metallic Elements, in recent years because it has larger harmfulness to human body and environment, has been obtained wide
General concern and research.Arsenic in cigarette smoke is one of source of arsenic in environment, and Hoffmann lists in tobacco business
One of middle harmful components, it includes TPM composition and gas phase composition.When smoking cigarette, arsenic element can be inhaled into branch gas
In pipe, so as to be damaged to the lung, liver, kidney and other organs of human body.Therefore, for more comprehensive and objective appraisal cigarette
The harmfulness of arsenic in flue gas, it would be desirable to which in-depth study is carried out to the measure of arsenic content in cigarette smoke.
At present, determine cigarette mainstream flue gas in content of beary metal method mainly have inductively coupled plasma mass spectrometry,
Hydride generation atomic absorption spectrometry and Atomic fluorophotometry etc..These methods trap volume using filter disc or Electrostatic mode
Cigarette mainstream smoke total particulate matter, and the laggard sample analysis arsenic content of processing such as extracted, cleared up to smoke's total particulate matter.Meanwhile
Gaseous phase of main stream smoke of cigarette composition is trapped with dust technology or diluted acid mixed solution, and is divided after carrying out the pretreatment process of complexity
Arsenic content is analysed, can not realize and directly carry out testing and analyzing arsenic content, and dust technology or diluted acid mixing after flue gas trapping is completed
Solution can not realize trapping completely to the arsenic element in components in cigarette smoke gas phase composition, so as to reduce the accuracy of testing result.
Can be tobacco business harm reduction it can be seen that establishing a kind of detection method of arsenogen cellulose content in accurately and reliably cigarette mainstream flue gas
Tar reduction correlative study and cigarette quality safety assessment system provide strong technical support, have for tobacco business
Important realistic meaning.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide arsenogen in a kind of cigarette mainstream flue gas
The detection method of cellulose content, for solve lack in the prior art accurately and reliably, pre-treatment directly and easily trap cigarette master
The problem of flowing gas phase composition arsenic and total arsenic element in flue gas and analyzing the method for its content.
In order to achieve the above objects and other related objects, the present invention provides arsenogen cellulose content in a kind of cigarette mainstream flue gas
Detection method, TPM composition arsenic in cigarette mainstream flue gas is trapped using Electrostatic mode, at the same it is molten using acidic ethanol
Gas phase composition arsenic in liquid trapping cigarette mainstream flue gas, then determined using inductively coupled plasma mass spectrometry in cigarette mainstream flue gas
The content of arsenic element.
It is preferred that arsenic element includes gas phase composition arsenic and TPM composition arsenic in the cigarette mainstream flue gas.
It is preferred that in a kind of cigarette mainstream flue gas arsenogen cellulose content detection method, comprise the following steps：
1) preparation of trapping solution：Nitric acid, hydrochloric acid are separately added into ethanol, are made into acidic ethanol solution.
Preferably, the ethanol is absolute ethyl alcohol (chromatographically pure).
Preferably, the nitric acid is 65% concentrated nitric acid (v/v).
Preferably, the hydrochloric acid is 35% concentrated hydrochloric acid (v/v).
Preferably, the concentration of each composition is in the acidic ethanol solution：Nitric acid：1-5% (percent by volume v/v)；Salt
Acid：1-3% (percent by volume v/v).
More preferably, the concentration of each composition is in the acidic ethanol solution：Nitric acid：3% (percent by volume v/v)；Hydrochloric acid：
2% (percent by volume v/v).
Preferably, the acidic ethanol solution can preserve for a long time at room temperature.
2) preparation of standard liquid：Prepare germanium72Inner mark solution and arsenic element standard liquid.
2.1st, arsenic element is pipetted, the acidic ethanol solution dilution prepared with step 1) and constant volume, prepares the storage of arsenic element standard
Standby solution；
Preferably, the mass concentration of the arsenic element Standard Stock solutions is 1000.0 μ g/L.
Preferably, the condition of storage of the arsenic element Standard Stock solutions is：Storage temperature：0-4℃；Storage time：1
Month.
2.2nd, germanium is pipetted72Standard substance solution, the acidic ethanol solution dilution prepared with step 1) and constant volume, prepare internal standard
Solution；
Preferably, the germanium72The concentration of standard substance solution is 100.0mg/L.
Preferably, the mass concentration of inner mark solution is 1000.0 μ g/L.
Preferably, the condition of storage of the inner mark solution is：Storage temperature：0-4℃；Storage time：1 month.
2.3rd, the arsenic element Standard Stock solutions in the step 2.1 of different volumes are pipetted respectively, the acid prepared with step 1)
Change ethanol solution dilution and constant volume, be formulated as a series of arsenic element standard liquid of various concentrations respectively.
The standard liquid should cover sample concentration scope, can be i.e. with i.e. use.
3) sample traps：After selecting Cigarette balance, suction, trapped using Electrostatic mode in cigarette mainstream flue gas
TPM composition arsenic sample solution, while the acidic ethanol solution prepared using step 1) traps gas phase in cigarette mainstream flue gas
Composition arsenic sample solution.
Preferably, the Cigarette is according to standard GB/T/T5606.1-2004《Cigarette part 1：Sampling》Carry out
Select.
Preferably, the Cigarette is according to standard GB/T/T 19609-2004《Cigarette is with conventional analysis smoking machine
Determine TPM and tar》It is balanced, aspirates.
Preferably, the sample amount of collected is every time the TPM and gas phase composition of 20 cigarette smokes.
Preferably, it is described that TPM composition arsenic in cigarette mainstream flue gas is trapped using Electrostatic mode including following
Step：
Ith, trap：Trapped using Electrostatic device in cigarette mainstream flue gas after TPM composition arsenic, take out electrostatic and catch
Collector, after the acidic ethanol solution prepared with step 1) elutes, transfer, constant volume, shake up, it is molten to obtain TPM composition arsenic sample
Liquid, it is stand-by；
More preferably, the Electrostatic device is rotating disc type smoking machine Electrostatic device.
IIth, blank test：The blank Electrostatic pipe not trapped separately is taken, the acidic ethanol solution prepared with step 1)
After elution, transfer, constant volume, shake up, obtain TPM composition arsenic blank solution, it is stand-by.
More preferably, in step I, II, the elution is that acidic ethanol solution is eluted into Electrostatic inside pipe wall, by flue gas
TPM composition arsenic elutes dissolving completely.
More preferably, in step I, II, the transfer, constant volume are the solution that will be eluted, and are transferred to certain volume
Container carries out constant volume.
Preferably, gas phase composition arsenic in the trapping cigarette mainstream flue gas using acidic ethanol solution, comprises the following steps：
I, trapping：In collecting trap, trapped in cigarette mainstream flue gas after gas phase composition arsenic, turned using acidic ethanol solution
Shifting, constant volume, shake up, obtain gas phase composition arsenic sample solution, it is stand-by；
II, blank test：The acidic ethanol solution not trapped separately is taken, transfer, constant volume, is shaken up, obtains gas phase composition
Arsenic blank solution, it is stand-by.
More preferably, in step I, II, during the trapping, 2 collecting traps are concatenated.
More preferably, in step I, II, the transfer, constant volume are by the trapping solution in collecting trap, are transferred to certain volume
Container carries out constant volume.
Specifically, the principle of the trapping is：As shown in Fig. 2 cigarette is fixed in cigarette holder, after lighting, lead to
The arsenic crossed in Electrostatic device trapping smoke's total particulate matter, and flue gas gas phase composition is through connecting line, be passed through concatenation 2 catch
Collect in trap, after the arsenic in flue gas gas phase composition is trapped by the acidic ethanol solution in collecting trap, 2 position three-way valves are adjusted, by it
Remaining flue gas is discharged by pump unit.
4) determine：Standard liquid and inner mark solution, the TPM composition of step 3) trapping that step 2) is prepared respectively
Arsenic sample solution and gas phase composition arsenic sample solution carry out icp mses (ICP-MS) detection, using internal standard
Synchronization criterion curve method is quantified, and obtains the content of arsenic element in sample solution.
Preferably, the internal standard synchronization criterion curve method comprises the following steps：
When the internal standard synchronization criterion curve method refers to that ICP-MS is measured, in the neutralization of on-line synchronous bioassay standard solution
Solution is marked, standard working curve, and then on-line synchronous measure inner mark solution and actual sample solution is obtained, is obtained in fact so as to determine
The method of border sample concentration.Due to ICP-MS instrument traits, inner mark solution and sample solution are respectively by two peristaltic pump tubes, together
When synchronous online sample introduction, determined after sampling valve mixes, and unconventional internal standard adds after sample the mode being measured.
A, by inner mark solution in a series of arsenic element standard liquid of various concentrations, the 2.2 of step 2) in the 2.3 of step 2)
Synchronous to carry out ICP-MS detections, the mass-to-charge ratio intensity for obtaining arsenic element/internal standard substance is denseer than with the quality of arsenic element/internal standard substance
The linear relationship of ratio is spent, corresponding standard working curve is drawn, the regression equation of arsenic element standard working curve is calculated.
More preferably, in the standard curve, using the mass-to-charge ratio intensity ratio of arsenic element/internal standard substance as ordinate (Y-axis), its
The mass concentration ratio of corresponding arsenic element/internal standard substance is abscissa (X-axis).
B, by TPM composition arsenic sample solution and its blank solution in step 3) or gas phase composition arsenic sample solution and
Its blank solution, step 2) 2.2 in inner mark solution synchronously carry out ICP-MS detections, by the TPM composition arsenic or gas of acquisition
The mass-to-charge ratio intensity ratio of phase constituent arsenic/internal standard substance, the regression equation of arsenic element standard working curve in step a is substituted into respectively,
And according to the known quality concentration of the inner mark solution synchronously detected, TPM composition arsenic or gas phase in sample solution is calculated
The mass concentration of composition arsenic.
Preferably, in step 4), the icp mses (ICP-MS) are ends of the earth bar collision/reaction
Pond-icp mses (ORS-ICP-MS).
More preferably, the ORS-ICP-MS testing conditions are：Ion gun：ICP source；Radio-frequency power (RF power)：1600W；
RF matching voltages：1.7V；Cool down gas：Argon gas, flow velocity：15.0L/min；Non-user is set；Carrier gas：Argon gas, flow velocity：0.45L/
min；Optional gas：Argon oxygen gas mixture, set amount：30.0% (v/v)；Carrier gas compensates gas：Argon gas, flow velocity：0.1L/min；Touch
Hit/reaction tank gas：Helium, flow velocity：5.0mL/min；It is atomized room temperature：-5.0℃；Atomization gas：Argon gas, flow velocity：0.55L/
min；Ends of the earth bar deflection voltage：-17.6V；Energy is discriminated against：4.0V；Sample feeding speed：0.1rps；Number of repetition：3；Scanning side
Formula：Order jumps peak.
The invention discloses a kind of detection method of arsenogen cellulose content in cigarette mainstream flue gas to be applied to cigarette mainstream flue gas
The purposes of middle arsenic element content detection.
The present invention furthermore provides a kind of detection method of gas phase composition arsenogen cellulose content in cigarette mainstream flue gas, including
Following steps：
A, the preparation of trapping solution：Nitric acid, hydrochloric acid are separately added into ethanol, are made into acidic ethanol solution.
Preferably, the ethanol is absolute ethyl alcohol (chromatographically pure).
Preferably, the nitric acid is 65% concentrated nitric acid (v/v).
Preferably, the hydrochloric acid is 35% concentrated hydrochloric acid (v/v).
Preferably, the concentration of each composition is in the acidic ethanol solution：Nitric acid：1-5% (percent by volume v/v)；Salt
Acid：1-3% (percent by volume v/v).
More preferably, the concentration of each composition is in the acidic ethanol solution：Nitric acid：3% (percent by volume v/v)；Hydrochloric acid：
2% (percent by volume v/v).
Preferably, the acidic ethanol solution can preserve for a long time at room temperature.
B, the preparation of standard liquid：Prepare germanium72Inner mark solution and arsenic element standard liquid.
B1, arsenic element is pipetted, with the step A acidic ethanol solution dilutions prepared and constant volume, prepare arsenic element standard inventory
Solution；
Preferably, the mass concentration of the arsenic element Standard Stock solutions is 1000.0 μ g/L.
Preferably, the condition of storage of the arsenic element Standard Stock solutions is：Storage temperature：0-4℃；Storage time：1
Month.
B2, pipette germanium72Standard substance solution, with the step A acidic ethanol solution dilutions prepared and constant volume, it is molten to prepare internal standard
Liquid；
Preferably, the germanium72The concentration of standard substance solution is 100.0mg/L.
Preferably, the mass concentration of inner mark solution is 1000.0 μ g/L.
Preferably, the condition of storage of the inner mark solution is：Storage temperature：0-4℃；Storage time：1 month.
B3, arsenic element Standard Stock solutions in the step B1 of different volumes, the acidifying second prepared with step A are pipetted respectively
Alcoholic solution dilution and constant volume, a series of arsenic element standard liquid of various concentrations is formulated as respectively.
The standard liquid should cover sample concentration scope, can be i.e. with i.e. use.
C, sample traps：After selecting Cigarette balance, suction, the acidic ethanol solution prepared using step A traps volume
Gas phase composition arsenic sample solution in cigarette main flume.
Preferably, the sample amount of collected is every time the gas phase composition of 20 cigarette smokes.
Preferably, gas phase composition arsenic in the trapping cigarette mainstream flue gas using acidic ethanol solution, comprises the following steps：
I, trapping：In collecting trap, trapped in cigarette mainstream flue gas after gas phase composition arsenic, turned using acidic ethanol solution
Shifting, constant volume, shake up, obtain gas phase composition arsenic sample solution, it is stand-by；
II, blank test：The acidic ethanol solution not trapped separately is taken, transfer, constant volume, is shaken up, obtains gas phase composition
Arsenic blank solution, it is stand-by.
More preferably, in step I, II, during the trapping, 2 collecting traps are concatenated.
More preferably, in step I, II, the transfer, constant volume are by the trapping solution in collecting trap, are transferred to certain volume
Container carries out constant volume.
Specifically, the principle of the trapping is：As shown in Fig. 2 cigarette is fixed in cigarette holder, after lighting, lead to
The arsenic crossed in Electrostatic device trapping smoke's total particulate matter, and flue gas gas phase composition is through connecting line, be passed through concatenation 2 catch
Collect in trap, after the arsenic in flue gas gas phase composition is trapped by the acidic ethanol solution in collecting trap, 2 position three-way valves are adjusted, by it
Remaining flue gas is discharged by pump unit.
D, determine：Respectively by the step B standard liquids prepared and inner mark solution, the gas phase composition arsenic sample of step C trappings
Solution carries out icp mses (ICP-MS) detection, is quantified, obtained using internal standard synchronization criterion curve method
Obtain the content of gas phase composition arsenic element in sample solution.
Preferably, the internal standard synchronization criterion curve method comprises the following steps：
When the internal standard synchronization criterion curve method refers to that ICP-MS is measured, in the neutralization of on-line synchronous bioassay standard solution
Solution is marked, standard working curve, and then on-line synchronous measure inner mark solution and actual sample solution is obtained, is obtained in fact so as to determine
The method of border sample concentration.Due to ICP-MS instrument traits, inner mark solution and sample solution are respectively by two peristaltic pump tubes, together
When synchronous online sample introduction, determined after sampling valve mixes, and unconventional internal standard adds after sample the mode being measured.
A, it is inner mark solution in a series of arsenic element standard liquid of various concentrations, step B B2 in step B B3 is synchronous
ICP-MS detections are carried out, obtain the mass-to-charge ratio intensity of arsenic element/internal standard substance than the mass concentration ratio with arsenic element/internal standard substance
Linear relationship, draw corresponding standard working curve, the regression equation of arsenic element standard working curve be calculated.
More preferably, in the standard curve, using the mass-to-charge ratio intensity ratio of arsenic element/internal standard substance as ordinate (Y-axis), its
The mass concentration ratio of corresponding arsenic element/internal standard substance is abscissa (X-axis).
B, by gas phase composition arsenic sample solution in step C and its blank solution, step B B2 in inner mark solution synchronously carry out
ICP-MS is detected, and by the mass-to-charge ratio intensity ratio of gas phase composition arsenic/internal standard substance of acquisition, substitutes into arsenic element mark in step a respectively
The regression equation of quasi- working curve, and according to the known quality concentration of the inner mark solution synchronously detected, sample solution is calculated
The mass concentration of middle gas phase composition arsenic.
Preferably, in step D, the icp mses (ICP-MS) be ends of the earth bar collision/reaction tank-
Icp mses (ORS-ICP-MS).
More preferably, the ORS-ICP-MS testing conditions are：Ion gun：ICP source；Radio-frequency power (RF power)：1600W；
RF matching voltages：1.7V；Cool down gas：Argon gas, flow velocity：15.0L/min；Non-user is set；Carrier gas：Argon gas, flow velocity：0.45L/
min；Optional gas：Argon oxygen gas mixture, set amount：30.0% (v/v)；Carrier gas compensates gas：Argon gas, flow velocity：0.1L/min；Touch
Hit/reaction tank gas：Helium, flow velocity：5.0mL/min；It is atomized room temperature：-5.0℃；Atomization gas：Argon gas, flow velocity：0.55L/
min；Ends of the earth bar deflection voltage：-17.6V；Energy is discriminated against：4.0V；Sample feeding speed：0.1rps；Number of repetition：3；Scanning side
Formula：Order jumps peak.
The invention also discloses a kind of detection method of gas phase composition arsenogen cellulose content in cigarette mainstream flue gas to be applied to volume
The purposes of arsenic element content detection in cigarette main flume.
Preferably, the purposes is that a kind of detection method of gas phase composition arsenogen cellulose content in cigarette mainstream flue gas is applied to
The purposes of arsenic element gas phase composition content is detected in cigarette mainstream flue gas.
As described above, the present invention a kind of cigarette mainstream flue gas in arsenogen cellulose content detection method, inhaled using rotating disc type
TPM composition arsenic in cigarette machine Electrostatic device trapping cigarette main flume, while using acidic ethanol solution trapping cigarette master
Gas phase composition arsenic in flue gas is flowed, and using icp mses as determining instrument, establishes cigarette mainstream flue gas
The detection method of middle arsenogen cellulose content.And the detection side of gas phase composition arsenogen cellulose content in cigarette mainstream flue gas is established simultaneously
Method.The standard working curve coefficient R of the inventive method2>0.999, the average recovery rate of object 87.2-96.0% it
Between, relative standard deviation (RSD) is less than 10%, and reappearance, the rate of recovery are satisfactory.The inventive method is advantageous to tobacco business
Person skilled carries out effective quantitative determination control to the content of arsenic element in cigarette mainstream flue gas, and complete for tobacco business
The harmfulness of arsenic element provides strong technical support in the objective evaluation cigarette mainstream flue gas of face.
Brief description of the drawings
Fig. 1 is shown as the schematic flow sheet of the detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas of the present invention
Fig. 2 is shown as trapping the schematic flow sheet of arsenic element in cigarette mainstream flue gas in the present invention, wherein, 1：Cigarette；2：
Cigarette holder；3：Electrostatic pipe；4：End occurs for electrostatic；5：Collecting trap；6：Connecting line；7：2 position three-way valves；8：Suction is single
Member
Embodiment
The present invention is expanded on further with reference to specific embodiment, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
The reagent and instrument that following examples use are as follows：
1st, reagent
Absolute ethyl alcohol (chromatographically pure, German Merck companies)；65% concentrated nitric acid (top pure grade, German Merck companies)；35%
Concentrated hydrochloric acid (top pure grade, German Merck companies)；Arsenic standard solution (10.0mg/L, Agilent Science and Technology Ltd.s of the U.S.)；Germanium72
(100.0mg/L, Agilent Science and Technology Ltd.s of the U.S.)
2nd, instrument
7700X ends of the earth bar collision/reaction tank-icp mses (the limited public affairs of U.S. Agilent science and technology
Department)；Milli-Q ultra-pure waters instrument (Millipore companies of the U.S.)；RM-20H rotating disc types smoking machine (German Borgwaldt companies)
Embodiment 1
1st, assay method
The preparation of 1.1 trapping solutions
A certain amount of 65% concentrated nitric acid, 35% concentrated hydrochloric acid are added in absolute ethyl alcohol, is configured to containing 1-5% nitric acid, 1-
The acidic ethanol solution of 3% hydrochloric acid, the acidic ethanol solution containing 3% nitric acid, 2% hydrochloric acid is preferably configured to, at room temperature
It can preserve for a long time.
The preparation of 1.2 standard liquids
Arsenic element is pipetted, with the 1.1 acidic ethanol solution dilutions prepared and constant volume, prepares arsenic element Standard Stock solutions.
The mass concentration of the arsenic element Standard Stock solutions is 1000.0 μ g/L.Condition of storage can store 1 under the conditions of 0-4 DEG C
Month.
Pipette germanium72Standard substance solution, with the 1.1 acidic ethanol solution dilutions prepared and constant volume, prepare inner mark solution.It is interior
The concentration for marking solution is 1000 μ g/L.Condition of storage can store 1 month under the conditions of 0-4 DEG C.
The arsenic element Standard Stock solutions of different volumes are pipetted respectively, are diluted and are determined with 1.1 acidic ethanol solutions prepared
Hold, be formulated as a series of arsenic element standard liquid of various concentrations respectively.Standard liquid should cover sample size scope, need to match somebody with somebody
Use.The specific concentration of standard liquid is shown in Table 1.
The standard liquid of table 1 is with tabulation (unit：μg/L)
| Sequence number | Arsenic element concentration |
| Lv1 | 0 (reagent blank) |
| Lv2 | 0.5 |
| Lv3 | 1.0 |
| Lv4 | 2.0 |
| Lv5 | 3.0 |
| Lv6 | 5.0 |
| Lv7 | 10.0 |
| Lv8 | 20.0 |
1.3 samples trap
According to standard GB/T/T5606.1-2004《Cigarette part 1：Sampling》Cigarette is selected, and according to standard
GB/T19609-2004《Cigarette conventional analysis determines TPM and tar with smoking machine》Use RM-20H rotating disc type smokings
Machine is balanced, aspirated, with RM-20H rotating disc type smoking machine Electrostatics device trap cigarette mainstream flue gas in TPM into
Divide arsenic sample solution, at the same it is molten using gas phase composition arsenic sample in the 1.1 acidic ethanol solutions trapping cigarette mainstream flue gas prepared
Liquid.The sample amount of collected is every time the TPM and gas phase composition of 20 cigarette smokes.
Trapped using Electrostatic device in cigarette mainstream flue gas after TPM composition arsenic, take out Electrostatic pipe, used
After the 1.1 acidic ethanol solution elution Electrostatic inside pipe walls prepared, after smoke's total particulate matter composition arsenic is eluted into dissolving completely,
It is transferred in 50ml plastics volumetric flasks, constant volume, shakes up, obtains TPM composition arsenic sample solution, it is stand-by.Meanwhile separately take not
The blank Electrostatic pipe trapped, after the 1.1 acidic ethanol solution elution prepared, it is transferred to 50ml plastics volumetric flasks
In, constant volume, shake up, obtain TPM composition arsenic sample solution, it is stand-by.
Using gas phase composition arsenic in the 1.1 acidic ethanol solution trapping cigarette mainstream flue gas prepared, 2 trappings are concatenated respectively
Trap, each collecting trap 50ml are simultaneously equipped with a certain amount of trapping solution.After trapping, it is transferred in 50ml plastics volumetric flasks, constant volume,
Shake up, obtain gas phase composition arsenic sample solution, it is stand-by.Meanwhile the acidic ethanol solution not trapped is separately taken, it is transferred to 50ml
In plastics volumetric flask, constant volume, shake up, obtain gas phase composition arsenic blank solution, it is stand-by.
The measure of 1.4 samples
Standard liquid and inner mark solution, the TPM composition arsenic sample solution of 1.3 trappings that 1.2 are prepared respectively are gentle
Phase constituent arsenic sample solution carries out ORS-ICP-MS detections, is quantified using internal standard synchronization criterion curve method, and it is molten to obtain sample
The content of arsenic element in liquid.
Specifically, a series of arsenic element standard liquid of various concentrations, inner mark solution in table 1 are synchronously first subjected to ORS-
ICP-MS is detected, and obtains line of the mass-to-charge ratio intensity than the mass concentration ratio with arsenic element/internal standard substance of arsenic element/internal standard substance
Sexual intercourse, using the mass-to-charge ratio intensity ratio of arsenic element/internal standard substance as ordinate (Y-axis), the matter of its corresponding arsenic element/internal standard substance
Amount concentration ratio is that abscissa (X-axis) draws corresponding standard working curve, and the recurrence of arsenic element standard working curve is calculated
Equation.
Again by TPM composition arsenic sample solution and its blank solution in 1.3 or gas phase composition arsenic sample solution and its sky
Inner mark solution in white solution, 1.2, it is synchronous to carry out ORS-ICP-MS detections, by the TPM composition arsenic of acquisition or gas phase into
The mass-to-charge ratio intensity ratio of point arsenic/internal standard substance, substitutes into the regression equation of corresponding arsenic element standard working curve respectively, and according to
The known quality concentration of the inner mark solution synchronously detected, TPM composition arsenic or gas phase composition arsenic in sample solution is calculated
Mass concentration.
Wherein, the icp mses (ICP-MS) are ends of the earth bar collision/reaction tank-inductive etc.
Gas ions mass spectrograph (ORS-ICP-MS).
Wherein, the ORS-ICP-MS testing conditions are：Ion gun：ICP source；Radio-frequency power (RF power)：1600W；RF
Matching voltage：1.7V；Cool down gas：Argon gas, flow velocity：15.0L/min；Non-user is set；Carrier gas：Argon gas, flow velocity：0.45L/min；
Optional gas：Argon oxygen gas mixture, set amount：30.0% (v/v)；Carrier gas compensates gas：Argon gas, flow velocity：0.1L/min；Collision/anti-
Answer pond gas：Helium, flow velocity：5.0mL/min；It is atomized room temperature：-5.0℃；Atomization gas：Argon gas, flow velocity：0.55L/min；Eight
Pole bar deflection voltage：-17.6V；Energy is discriminated against：4.0V；Sample feeding speed：0.1rps；Number of repetition：3；Scan mode：It is suitable
Sequence jumps peak.
2nd, result and discussion
The selection of 2.1 different trapping solutions
Same cigarette sample is chosen, according to professional standard YC/T379-2010《Chromium in cigarette mainstream flue gas, nickel, arsenic, selenium,
The measure inductively coupled plasma mass spectrometry of cadmium, lead》From dilute nitric acid solution (nitric acid: volume ratio=1 of water: 10), simultaneously
From 8% (v/v) nitric acid and the diluted acid mixed solution of 2% hydrochloric acid (v/v), at the same it is molten from above-mentioned 1.1 acidic ethanols prepared
Liquid is as trapping solution, according to above-mentioned 1.2 standard liquid and inner mark solution, further according to above-mentioned 1.3 sample trap conditions, difference
TPM composition arsenic sample solution and gas phase composition arsenic sample solution in cigarette mainstream flue gas are trapped, finally uses ORS-ICP-MS
Detected respectively, specific testing result is shown in Table 2.
The testing result of 2 different trapping solutions of table compares
| Trapping solution | Dilute nitric acid solution | Diluted acid mixed solution | Acidic ethanol solution |
| TPM composition arsenic measured value (ng/cig) | 4.58 | 4.39 | 4.50 |
| Gas phase composition arsenic measured value (ng/cig) | 0.38 | 0.44 | 2.66 |
| Arsenic total amount (ng/cig) | 4.96 | 4.83 | 7.16 |
From data in table 2, when being trapped using three kinds of different solvents as trapping solution, the cigarette master of acquisition is trapped
TPM composition arsenic content is more or less the same in stream flue gas, but traps gas phase composition arsenic content difference in the cigarette mainstream flue gas obtained
It is different larger.Wherein, using the acidic ethanol solution in the present invention as trapping solution, gas phase composition in the cigarette mainstream flue gas of acquisition
Arsenic content value is maximum, thus traps arsenic total amount value maximum in the cigarette mainstream flue gas obtained, and trapping effect is most obvious.
2.2 standard working curves, detection limit and quantitative limit
The arsenic element Standard Stock solutions of different volumes are pipetted respectively, with the above-mentioned 1.1 acidic ethanol solution constant volumes prepared
A series of arsenic element standard liquid of various concentrations is formulated as, specific concentration is as shown in table 1 in 1.2.
By a series of standard liquid of the above-mentioned various concentrations prepared progress ORS-ICP- synchronous with inner mark solution difference
MS is detected, using the mass-to-charge ratio intensity ratio of arsenic element/internal standard substance as ordinate (Y-axis), the matter of its corresponding arsenic element/internal standard substance
Amount concentration ratio is abscissa (X-axis), carries out regression analysis, obtains regression equation and its coefficient correlation, as shown in table 3.
As shown in Table 3, the linear relationship of regression equation is good, correlation coefficient r2>0.999.To the target in standard liquid
Thing response signal, sample introduction is repeated 10 times using least concentration standard specimen, ORS-ICP-MS analyses are carried out, using 3 times of signal to noise ratio as method
Detection limit (LOD), 10 times of signal to noise ratio are quantitative limit (LOQ), are scaled after sample size and show that object detection is limited to
0.07ng/cig, quantitative limit have higher sensitivity in 0.23ng/cig.
The working curve of table 3 and detection limit
Y：Mass-to-charge ratio intensity ratio；X：Concentration ratio
2.3 rate of recovery and precision
Respectively in the cigarette sample of concentration known, the arsenic standard solution of concentration known is added, then carries out sample trapping
Analyzed with ORS-ICP-MS, and according to adding scalar sum measured value to calculate its rate of recovery, while to same sample solution parallel determination 6
Secondary (n=6), TPM composition arsenic and the precision determination data of gas phase composition arsenic content are obtained, the results are shown in Table 4,5.By table
4th, 5 as can be seen that object average recovery rate between 87.2-96.0%, relative standard deviation (RSD) be less than 10%, return
It is high income, reproducible.
The sample recovery rate of TPM composition arsenic and gas phase composition arsenic in the cigarette sample main flume of table 4
The precision of TPM composition arsenic and gas phase composition arsenic (n=6) in the cigarette sample main flume of table 5
3rd, the measure of actual sample
The content that arsenic element in the main flume of actual cigarette sample is determined using this method is measured, and is specifically shown in Table 6.
As shown in Table 6, for cigarette sample, this method can effectively determine TPM composition arsenic and gas phase composition arsenic in its main flume
Content, method is easy to operate, applicability is good, as a result accurately, reliably.
The content of arsenic element in 6 actual cigarette sample of table
| Sample sequence number | Grain phase constituent (ng/cig) | Gas phase composition (ng/cig) | Total amount (ng/cig) |
| 1 | 4.92 | 2.03 | 6.95 |
| 2 | 3.36 | 1.32 | 4.68 |
| 3 | 7.47 | 2.42 | 9.89 |
| 4 | 1.39 | 0.66 | 2.05 |
| 5 | 3.48 | 1.45 | 4.93 |
Embodiment 2
1st, assay method
The preparation of 1.1 trapping solutions
With 1.1 related contents in embodiment 1.
The preparation of 1.2 standard liquids
With 1.2 related contents in embodiment 1.
1.3 samples trap
According to standard GB/T/T5606.1-2004《Cigarette part 1：Sampling》Cigarette is selected, and according to standard
GB/T19609-2004《Cigarette conventional analysis determines TPM and tar with smoking machine》Use RM-20H rotating disc type smokings
Machine is balanced, aspirated, molten using gas phase composition arsenic sample in the 1.1 acidic ethanol solution trapping cigarette mainstream flue gas prepared
Liquid.The sample amount of collected is every time the gas phase composition of 20 cigarette smokes.
Using gas phase composition arsenic in the 1.1 acidic ethanol solution trapping cigarette mainstream flue gas prepared, 2 trappings are concatenated respectively
Trap, each collecting trap 50ml are simultaneously equipped with a certain amount of trapping solution.After trapping, it is transferred in 50ml plastics volumetric flasks, constant volume,
Shake up, obtain gas phase composition arsenic sample solution, it is stand-by.Meanwhile the acidic ethanol solution not trapped is separately taken, it is transferred to 50ml
In plastics volumetric flask, constant volume, shake up, obtain gas phase composition arsenic blank solution, it is stand-by.
The measure of 1.4 samples
Standard liquid and inner mark solution, the gas phase composition arsenic sample solution of 1.3 trappings that 1.2 are prepared respectively carry out ORS-
ICP-MS is detected, and is quantified using internal standard synchronization criterion curve method, obtains the content of gas phase composition arsenic element in sample solution.
Specifically, a series of arsenic element standard liquid of various concentrations, inner mark solution in table 1 are synchronously first subjected to ORS-
ICP-MS is detected, and obtains line of the mass-to-charge ratio intensity than the mass concentration ratio with arsenic element/internal standard substance of arsenic element/internal standard substance
Sexual intercourse, using the mass-to-charge ratio intensity ratio of arsenic element/internal standard substance as ordinate (Y-axis), the matter of its corresponding arsenic element/internal standard substance
Amount concentration ratio is that abscissa (X-axis) draws corresponding standard working curve, and the recurrence of arsenic element standard working curve is calculated
Equation.
It is synchronous to carry out ORS- again by gas phase composition arsenic sample solution in 1.3 and its inner mark solution in blank solution, 1.2
ICP-MS is detected, and by the mass-to-charge ratio intensity ratio of gas phase composition arsenic/internal standard substance of acquisition, substitutes into corresponding arsenic element standard respectively
The regression equation of working curve, and according to the known quality concentration of the inner mark solution synchronously detected, be calculated in sample solution
The mass concentration of gas phase composition arsenic.
Wherein, the icp mses (ICP-MS) are ends of the earth bar collision/reaction tank-inductive etc.
Gas ions mass spectrograph (ORS-ICP-MS).
Wherein, the ORS-ICP-MS testing conditions are：Ion gun：ICP source；Radio-frequency power (RF power)：1600W；RF
Matching voltage：1.7V；Cool down gas：Argon gas, flow velocity：15.0L/min；Non-user is set；Carrier gas：Argon gas, flow velocity：0.45L/min；
Optional gas：Argon oxygen gas mixture, set amount：30.0% (v/v)；Carrier gas compensates gas：Argon gas, flow velocity：0.1L/min；Collision/anti-
Answer pond gas：Helium, flow velocity：5.0mL/min；It is atomized room temperature：-5.0℃；Atomization gas：Argon gas, flow velocity：0.55L/min；Eight
Pole bar deflection voltage：-17.6V；Energy is discriminated against：4.0V；Sample feeding speed：0.1rps；Number of repetition：3；Scan mode：It is suitable
Sequence jumps peak.
2nd, result and discussion
The selection of 2.1 different trapping solutions
Same cigarette sample is chosen, according to professional standard YC/T379-2010《Chromium in cigarette mainstream flue gas, nickel, arsenic, selenium,
The measure inductively coupled plasma mass spectrometry of cadmium, lead》From dilute nitric acid solution (nitric acid: volume ratio=1 of water: 10), simultaneously
From 8% (v/v) nitric acid and the diluted acid mixed solution of 2% hydrochloric acid (v/v), at the same it is molten from above-mentioned 1.1 acidic ethanols prepared
Liquid is as trapping solution, according to above-mentioned 1.2 standard liquid and inner mark solution, further according to above-mentioned 1.3 sample trap conditions, difference
Gas phase composition arsenic sample solution in cigarette mainstream flue gas is trapped, is finally detected respectively with ORS-ICP-MS, specific detection knot
Fruit is shown in Table 7.
The testing result of 7 different trapping solutions of table compares
| Trapping solution | Dilute nitric acid solution | Diluted acid mixed solution | Acidic ethanol solution |
| Gas phase composition arsenic measured value (ng/cig) | 0.38 | 0.44 | 2.66 |
From data in table 7, when being trapped using three kinds of different solvents as trapping solution, the cigarette master of acquisition is trapped
It is larger to flow gas phase composition arsenic content difference in flue gas.Wherein, obtained using the acidic ethanol solution in the present invention as trapping solution
Cigarette mainstream flue gas in gas phase composition arsenic content value it is maximum, trapping effect is most obvious.
2.2 standard working curves, detection limit and quantitative limit
With the related content in embodiment 1 2.2.
2.3 rate of recovery and precision
Respectively in the cigarette sample of concentration known, the arsenic standard solution of concentration known is added, then carries out sample trapping
Analyzed with ORS-ICP-MS, and according to adding scalar sum measured value to calculate its rate of recovery, while to same sample solution parallel determination 6
Secondary (n=6), the precision determination data of gas phase composition arsenic content is obtained, the results are shown in Table 8,9.The target it can be seen from table 8,9
The average recovery rate of thing is between 87.2-96.0%, and relative standard deviation (RSD) is less than 10%, and the rate of recovery is high, reproducible.
The sample recovery rate of gas phase composition arsenic in the cigarette sample main flume of table 8
The precision (n=6) of gas phase composition arsenic in the cigarette sample main flume of table 9
3rd, the measure of actual sample
The content that gas phase composition arsenic element in the main flume of actual cigarette sample is determined using this method is measured, and is had
Body is shown in Table 10.As shown in Table 10, for cigarette sample, this method can effectively determine containing for gas phase composition arsenic in its main flume
Amount, method is easy to operate, applicability is good, as a result accurately, reliably.
The content of gas phase composition arsenic in 10 actual cigarette mainstream flue gas of table
| Sample sequence number | Gas phase composition (ng/cig) |
| 1 | 2.03 |
| 2 | 1.32 |
| 3 | 2.42 |
| 4 | 0.66 |
| 5 | 1.45 |
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (4)
1. the detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas, cigarette mainstream flue gas is trapped using Electrostatic mode
Middle TPM composition arsenic, while using gas phase composition arsenic in acidic ethanol solution trapping cigarette mainstream flue gas, then using inductance
The content of arsenic element in coupled plasma mass measure cigarette mainstream flue gas；
Comprise the following steps：
1) preparation of trapping solution：Nitric acid, hydrochloric acid are separately added into ethanol, are made into acidic ethanol solution；
2) preparation of standard liquid：Prepare germanium72Inner mark solution and arsenic element standard liquid；
3) sample traps：After selecting Cigarette balance, suction, total grain in cigarette mainstream flue gas is trapped using Electrostatic mode
Phase thing composition arsenic sample solution, while the acidic ethanol solution prepared using step 1) traps gas phase composition in cigarette mainstream flue gas
Arsenic sample solution；
4) determine：Standard liquid and inner mark solution, the TPM composition arsenic sample of step 3) trapping that step 2) is prepared respectively
Product solution and gas phase composition arsenic sample solution carry out icp mses detection, using internal standard synchronization criterion curve
Method is quantified, and obtains the content of arsenic element in sample solution；
In step 1), the concentration of each composition is in the acidic ethanol solution：Nitric acid：1-5%；Hydrochloric acid：1-3%；
It is described that TPM composition arsenic in cigarette mainstream flue gas, including following step are trapped using Electrostatic mode in step 3)
Suddenly：
A) trap：Trapped using Electrostatic device in cigarette mainstream flue gas after TPM composition arsenic, take out Electrostatic pipe,
After being eluted with acidic ethanol solution, transfer, constant volume, shake up, obtain TPM composition arsenic sample solution, it is stand-by；
B) blank test：Separately take the blank Electrostatic pipe not trapped, after being eluted with acidic ethanol solution, transfer, constant volume,
Shake up, obtain TPM composition arsenic blank solution, it is stand-by；
In step 3), gas phase composition arsenic in the trapping cigarette mainstream flue gas using acidic ethanol solution, comprise the following steps：
A) trap：In collecting trap, trapped in cigarette mainstream flue gas after gas phase composition arsenic, transfer, determined using acidic ethanol solution
Hold, shake up, obtain gas phase composition arsenic sample solution, it is stand-by；
B) blank test：The acidic ethanol solution not trapped separately is taken, transfer, constant volume, is shaken up, obtains gas phase composition arsenic blank
Solution, it is stand-by；
The principle of the trapping is：Cigarette is fixed in cigarette holder, after lighting, flue gas is trapped by Electrostatic device
Arsenic in TPM, and flue gas gas phase composition is passed through in 2 collecting traps of concatenation, by collecting trap through connecting line
After arsenic in acidic ethanol solution trapping flue gas gas phase composition, 2 position three-way valves are adjusted, remaining flue gas is arranged by pump unit
Go out.
2. the detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas according to claim 1, it is characterised in that step
It is rapid 4) in, the icp mses are ends of the earth bar collision/reaction tank-icp mses.
3. the detection method of arsenogen cellulose content in a kind of cigarette mainstream flue gas according to claim 2, it is characterised in that institute
Stating ends of the earth bar collision/reaction tank-icp mses testing conditions is：Ion gun：ICP source；Radio-frequency power：
1600W；RF matching voltages：1.7V；Cool down gas：Argon gas, flow velocity：15.0L/min；Carrier gas：Argon gas, flow velocity：0.45L/min；Can
Select gas：Argon oxygen gas mixture, set amount：30.0%；Carrier gas compensates gas：Argon gas, flow velocity：0.1L/min；Collision/reaction tank gas
Body：Helium, flow velocity：5.0mL/min；It is atomized room temperature：-5.0℃；Atomization gas：Argon gas, flow velocity：0.55L/min；Ends of the earth bar is inclined
Turn voltage：-17.6V；Energy is discriminated against：4.0V；Sample feeding speed：0.1rps；Number of repetition：3；Scan mode：Order jumps peak.
4. volume is applied to according to the detection method of arsenogen cellulose content in a kind of any described cigarette mainstream flue gas of claim 1-3
The purposes of arsenic element content detection in cigarette main flume.
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