CN111781285B - Method for simultaneously separating and measuring multiple organic tin and inorganic tin in tobacco - Google Patents
Method for simultaneously separating and measuring multiple organic tin and inorganic tin in tobacco Download PDFInfo
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Abstract
The invention provides a method for simultaneously separating and measuring various organic tin and inorganic tin in tobacco, which comprises the steps of adding a tobacco sample into an extracting solution, vibrating, extracting, centrifuging, taking a sample solution obtained after supernatant liquid is concentrated and filtered, measuring by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry combined method, and calculating the content of various organic tin and inorganic tin in the sample solution by a standard curve method. The method for simultaneously separating and measuring various organic tin and inorganic tin in tobacco can meet the requirement of simultaneous, rapid and reliable detection of organic tin and inorganic tin in complex matrixes such as tobacco and the like, reduce the physical harm to operators and provide technical support for comprehensively and objectively evaluating the harmfulness of tin elements in tobacco.
Description
Technical Field
The invention belongs to the technical field of chromatographic analysis and detection, relates to a method for simultaneously separating and determining various organic tin and inorganic tin in tobacco, and particularly relates to a method for simultaneously separating and determining various organic tin and inorganic tin in tobacco by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS).
Background
Tin is a common heavy metal element and is widely distributed in the natural world, and the compound of tin is also applied to various fields of industry and agriculture. Most inorganic tin compounds belong to low toxicity or micro toxicity, while organic tin compounds have higher neurotoxicity and can be used as pesticides or bacteriostats, and related researches report that the compounds can be used for inhibiting tobacco mosaic virus. However, the research on the separation and quantification of tin element in the tobacco industry is less, and the method is only limited to the total measurement. Because the toxicity difference of different forms of the tin element is obvious, the tin form analysis is more meaningful than the total quantity analysis for measuring the content of the tin element in the tobacco.
At present, the morphological analysis of tin element at home and abroad mostly adopts the mode of combining the separation technology such as Gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), Supercritical Fluid Chromatography (SFC) and the like with the trace metal detection technology such as Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), inductively coupled plasma mass spectrometry (ICP-MS) and the like. The national standard detection method for the tin form in food is based on a GC method, the separation efficiency is high, but the pretreatment of a sample is complex, multi-step purification and derivatization operations are involved, and the recovery rate is unstable. The HPLC method for measuring the sample does not need derivatization treatment, and can analyze most tin forms in ion or neutral forms, and the application range is wider than that of the GC method. And ICP-MS is used as a detector commonly used for trace metal analysis, has low detection limit, high selectivity and wide linear range, and is more suitable for being used together with HPLC for element morphology analysis compared with the traditional ultraviolet detector. For example, a method for measuring various organotins in aquatic products by using HPLC-ICP-MS (cold peach blossom, noble, slug etc. high performance liquid chromatography-inductively coupled plasma mass spectrometry for analyzing the form [ J ] of organotin in aquatic products, 2015,43(4):558-563) is reported by cold peach blossom, etc., and the method can simultaneously detect organotin compounds in aquatic products, but has several important inherent defects: (1) the method cannot simultaneously detect more common inorganic tin and cannot meet the morphological analysis requirement of tin in samples with complex substrates such as tobacco and the like; (2) triethylamine must be added in the mobile phase of the method as a masking agent, otherwise, a chromatographic peak can generate serious tailing, the detection time is greatly increased, and the quantitative accuracy is possibly reduced. Triethylamine is flammable, toxic, low lightning (-7 ℃), and its vapors can form explosive mixtures with air, and is corrosive and highly irritating. In actual use, great potential safety hazard exists, and the operation degree of difficulty is high.
The invention patent with application number 201710204918.1 discloses a method for simultaneously measuring inorganic tin and organic tin compounds by low-pressure ion chromatography-inductively coupled plasma mass spectrometry, which attempts to simultaneously separate inorganic tin and organic tin compounds by replacing liquid chromatography through low-pressure ion chromatography, thereby reducing the analysis cost. The low-pressure ion chromatography utilizes a normal-pressure peristaltic pump to replace a high-pressure pump, has low maintenance and use cost, but has poor actual separation effect (see the attached figure 3 of the specification), and has obvious difference compared with the high-performance liquid chromatography: tin forms such as tricyclohexyltin (TChT), Azocyclotin (ACT) and the like which are more common in tobacco are difficult to separate by low-pressure ion chromatography; when the low-pressure ion chromatography is used for separation, the compounds to be detected are difficult to realize baseline separation, the peak is seriously deformed, and inherent defects such as peak passivation, peak tailing, peak asymmetry and the like (see the attached figure 3 in the specification) which are difficult to solve exist, and especially for the analysis of trace metal elements, an accurate and reliable quantitative result cannot be obtained.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a method for simultaneously separating and measuring multiple kinds of organic tin and inorganic tin in tobacco, which can simultaneously separate and measure 6 kinds of organic tin and inorganic tin in tobacco, is simple and rapid, has low detection limit and good reproducibility, covers tin forms related to tobacco supply chains, has strong universality and practicability, and provides technical support for comprehensively and objectively evaluating the hazard of tin elements in tobacco.
In order to achieve the above objects and other related objects, the present invention provides a method for simultaneously separating and measuring multiple kinds of organic tin and inorganic tin in tobacco, wherein a tobacco sample is added into an extracting solution, subjected to oscillation extraction and centrifugation, and a sample solution obtained after supernatant liquid is concentrated and filtered is measured by a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), and the content of the multiple kinds of organic tin and inorganic tin in the sample solution is calculated by a standard curve method.
Preferably, the organic tin is selected from any one or more of triphenyl tin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), and fenbutatin oxide (FBT).
More preferably, the organotin includes triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), and fenbutatin oxide (FBT).
Preferably, the Inorganic Tin (IT) is an inorganic salt solution containing tin (Sn) element. Specifically, the valence of the inorganic tin is IV valence, and the inorganic tin can be SnCl 4 。
Preferably, the tobacco sample is a ground, sieved, equilibrated tobacco sample.
More preferably, the grinding is grinding the tobacco sample into a fine powder. The grinding is carried out by a heavy metal special grinding machine.
More preferably, the mesh opening of the screened screen is 50-150 mesh. Most preferably, the screened mesh opening size is 100 mesh.
More preferably, the conditions of the equilibrium are: the balancing device is a constant temperature and humidity box; the equilibrium temperature is (22 +/-1) DEG C; the equilibrium relative humidity was (60 ± 2)%; the equilibration time is 20-30h, preferably 24 h.
Preferably, the extracting solution is mixed by a volume ratio of 1: 0.5-1.5 of solution A and solution B, wherein the solution A is prepared from the following components in a mass ratio of 100: 60-80: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
More preferably, the sample treatment fluid is a mixture of 1:1 and a solution B, wherein the solution A is a mixture of a solution A and a solution B, and the mass ratio of the solution A is 100: 70: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
Preferably, the ratio of the mass (g) of the tobacco sample added to the volume (mL) of the extract added is 1: 5-15.
More preferably, the ratio of the mass (g) added to the tobacco sample to the volume (mL) of extract added is 1: 10.
Preferably, the shaking extraction is vortex shaking extraction, the temperature of the vortex shaking extraction is 45-55 ℃, and the time of the vortex shaking extraction is 15-25 min.
More preferably, the temperature of the vortex extraction is 50 ℃, and the time of the vortex extraction is 20 min.
Preferably, the conditions of the centrifugation are: the centrifugal rate is more than or equal to 3500 r/min; the centrifugation time is 5-15 min.
More preferably, the conditions of the centrifugation are: the centrifugal rate is 3500 r/min; the centrifugation time was 10 min.
Preferably, the concentration is nitrogen-blown concentration to 1 mL.
Preferably, the filtration is an organic pin filter filtration with a gauge of 0.22 μm.
Preferably, the tobacco sample is subjected to a blank test during the treatment process.
Preferably, the high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) is used for the determination, comprising the following steps:
1) preparing a standard solution: diluting the standard samples of organic tin and inorganic tin step by step to a constant volume to obtain a mixed standard solution;
2) and (3) determination: respectively measuring the sample solution and the mixed standard solution prepared in the step 1) by a high performance liquid chromatography-inductively coupled plasma mass spectrometry combined method, separating various organic tin and inorganic tin components in the sample solution and the mixed standard solution by the high performance liquid chromatography, measuring by the inductively coupled plasma mass spectrometry, comparing retention time to determine various organic tin and inorganic tin components in the sample solution, and calculating the content of various organic tin and inorganic tin in the sample solution by a standard curve method.
More preferably, in the step 1), the stepwise dilution constant volume is to add a solvent into an organotin standard sample to dilute the volume to prepare an organotin mixed standard stock solution, select an inorganic tin standard substance solution as the inorganic tin standard sample, mix the organotin mixed standard stock solution and the inorganic tin standard substance solution, add an extracting solution to dilute the volume to prepare the mixed standard solution.
Further preferably, the concentration of triphenyl tin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), and fenbutatin oxide (FBT) in the organotin mixed standard stock solution are all 1000 mg/L.
Further preferably, the concentration of the tin element (Sn) in the Inorganic Tin (IT) standard substance solution is 10 mg/L.
Further preferably, the solvent is acetonitrile.
Further preferably, the organic tin mixed standard stock solution and the inorganic tin standard substance solution are placed at-20 ℃ and kept away from light for standby.
Further preferably, the volume ratio of the extracting solution is 1: 0.5-1.5 of solution A and solution B, wherein the mass ratio of the solution A is 100: 60-80: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
Most preferably, the extract is in a volume ratio of 1:1, wherein the solution A is a solution A and a solution B, and the mass ratio of the solution A is 100: 70: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
More preferably, in the step 1), the concentration ranges of triphenyl tin (TPhT), tributyl tin (TBT), tricyclohexyl tin (TChT), Azocyclotin (ACT), phenylbutyltin (FBT) and Inorganic Tin (IT) in the mixed standard solution are all more than 0 and less than or equal to 200 mu g/L.
More preferably, in the step 2), in the combination of high performance liquid chromatography and inductively coupled plasma mass spectrometry, the measurement conditions of the high performance liquid chromatography are as follows: a chromatographic column: filling a chromatographic column with a non-silanol material; column temperature: 25-35 ℃; flow rate: 0.5-1.0 mL/min; mobile phase A: the mass ratio of the citric acid to the water to the ammonia water is 100: 60-80: 0.5; mobile phase B: acetonitrile; gradient elution.
Further preferably, the determination conditions of the high performance liquid chromatography are as follows: a chromatographic column: polystyrene-divinylbenzene-packed chromatographic columns (Hamilton PRP-1, 2.1X 100mm, particle size 5 μm) of non-silanol-based material; column temperature: 30 ℃; flow rate: 0.6 mL/min; mobile phase A: the mass ratio of the citric acid to the water to the ammonia water is 100: 70: 0.5; and (3) mobile phase B: acetonitrile; and (4) gradient elution.
Further preferably, the specific procedure of the gradient elution is as follows, table 1:
0-3.5min, phase A: the volume ratio of the phase B is 80:20-35: 65;
3.5-7min, phase A: the volume ratio of the phase B is 35:65-25: 75;
7-8.5min, phase A: the volume ratio of the phase B is 25:75-25: 75;
8.5-12.5min, phase A: the volume ratio of the phase B is 25:75-10: 90;
12.5-14.5min, phase A: the volume ratio of the phase B is 10:90-10: 90;
14.5-15.5min, phase A: the volume ratio of the phase B is 10:90-90: 10;
15.5-17.5min, phase A: the volume ratio of the phase B is 90:10-90: 10.
TABLE 1
| Time (min) | Mobile phase composition (A%: B%) |
| 0 | 80：20 |
| 3.5 | 35：65 |
| 7 | 25：75 |
| 8.5 | 25：75 |
| 12.5 | 10：90 |
| 14.5 | 10：90 |
| 15.5 | 90：10 |
| 17.5 | 90：10 |
More preferably, in the step 2), in the combination of high performance liquid chromatography and inductively coupled plasma mass spectrometry, the high performance liquid chromatography is automatic sample injection, and the sample injection volume is 10 to 30 μ L, preferably 20 μ L.
More preferably, in the step 2), in the method combining high performance liquid chromatography and inductively coupled plasma mass spectrometry, the measurement conditions of the inductively coupled plasma mass spectrometry are as follows:
an ion source: an ICP source; a concentric atomizer; radio frequency power (RF power): 1500-1600W; RF matching voltage: 1.7-1.9V; carrier gas: argon with purity not less than 99.99%, flow rate: 0.4-0.6L/min; temperature of the atomization chamber: -4 to-6 ℃; auxiliary gas: the volume ratio of argon to oxygen is 80:20, flow rate: 0.1-0.2L/min; plasma gas: argon, flow rate: 10-20L/min; waste liquid discharge rate: 0.1-0.5rps (peristaltic pump speed); sampling depth: 6-10 mm; integration time: 0.8-1.2s (m/z 118); the scanning mode comprises the following steps: time resolved mode.
Further preferably, the measurement conditions of the inductively coupled plasma mass spectrometry are as follows:
an ion source: an ICP source; a concentric atomizer; radio frequency power (RF power): 1550W; RF matching voltage: 1.8V; carrier gas: argon with purity more than or equal to 99.99%, flow rate: 0.5L/min; temperature of the atomization chamber: -5 ℃; auxiliary gas: the volume ratio of argon to oxygen is 80:20, flow rate: 0.15L/min; plasma gas: argon, flow rate: 15L/min; waste liquid discharge rate: 0.3rps (peristaltic pump speed); sampling depth: 8 mm; integration time: 1.0s (m/z 118); the scanning mode comprises the following steps: time-resolved mode.
More preferably, in step 2), the standard curve method is: respectively carrying out HPLC-ICP-MS analysis on a series of mixed standard solutions containing various organic tin and inorganic tin components with different concentrations, separating the various organic tin and inorganic tin components in the mixed standard solutions through HPLC, online accessing an effluent liquid to ICP-MS, measuring the contents of the various organic tin and inorganic tin through ICP-MS, thereby obtaining the linear relation between the concentrations of the various organic tin and inorganic tin components and corresponding peak areas, drawing corresponding standard working curves according to the corresponding concentrations of the peak areas of each organic tin and inorganic tin component, and calculating to obtain a regression equation of each standard working curve. And then analyzing the sample solution by using a high performance liquid chromatography-inductively coupled plasma mass spectrometry, separating various organic tin and inorganic tin components in the sample solution by using the high performance liquid chromatography, measuring by using the inductively coupled plasma mass spectrometry to obtain peak areas of the various organic tin and inorganic tin components in the sample solution, and respectively substituting the peak areas into regression equations of the standard working curves to obtain the concentrations of the various organic tin and inorganic tin components in the sample solution.
When the high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) is used for measurement, HPLC is used as a separator, and ICP-MS is used as a detector. Specifically, when a plurality of organic tin and inorganic tin components are separated by HPLC, the retention times of the tin components of different forms are different, the time for the tin components of different forms to flow out of the HPLC is different, the time for the tin components of different forms to flow into the ICP-MS is different, and the time for the ICP-MS to generate a response signal (peak) is different, so that the tin components of different forms are characterized by comparing the retention times. And ICP-MS is adopted to measure various organic tin and inorganic tin components, and the linear relation between the concentration and the corresponding peak area is used for quantification. The elements which are plasmatized are detected during ICP-MS measurement, namely, tin components in different forms are all converted into plasma tin elements at the high temperature (up to 10000K) of ICP.
More preferably, in the step 2), the contents of the organotin and inorganic tin are calculated according to the formula (1),
the formula (1) is:
wherein X is any organotin or none in the tobacco sampleContent of organotin, ng/g; c is the concentration value measured by any organic tin or inorganic tin in the sample solution, and is mu g/L; c 0 The concentration value is the measured concentration value of any organic tin or inorganic tin in the blank solution of the sample, and is mu g/L; v is the volume of the sample solution, mL; m is the mass of the tobacco sample, g.
The blank solution of the test sample is a solution obtained by oscillating, extracting and centrifuging only by using a sample treatment solution without adding a tobacco sample, and concentrating and filtering supernatant liquor.
The organotin and inorganic tin contents can be expressed as the average of two parallel test determinations to the nearest 1 ng/g.
As described above, according to the method for simultaneously separating and determining multiple organic tin and inorganic tin in tobacco provided by the present invention, the content of multiple organic tin and inorganic tin in tobacco is separated and determined by selecting a chromatography mobile phase as a tin extraction agent, using a chromatography column filled with a non-silanol based material (polystyrene-divinylbenzene) as a stationary phase, using citric acid/water/ammonia water/acetonitrile as a mixed mobile phase, and using a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) through a preferred gradient elution procedure, and the method has the following beneficial effects:
(1) the method for simultaneously separating and measuring various organic tin and inorganic tin in tobacco can realize effective separation of 6 tin forms including organic tin form triphenyl tin (TPhT), tributyl tin (TBT), tricyclohexyl tin (TChT), Azocyclotin (ACT), Fenbutatin (FBT), inorganic tin form IT and the like in a short time, accurately measure the respective contents of the tin forms, can meet the requirement of simultaneous, rapid and reliable detection of organic tin and inorganic tin in complex matrixes such as tobacco and the like, and solves four defects inherent in related reports: incomplete measurement, incomplete separation, inaccurate measurement and long time consumption.
(2) Compared with the traditional method which needs triethylamine which is inflammable, explosive and highly corrosive as a mobile phase additive, the method for simultaneously separating and determining a plurality of organic tin and inorganic tin in tobacco provided by the invention adopts polystyrene-divinylbenzene filled with a chromatographic column without any silanol group material, and can obtain a good separation effect without using triethylamine. The invention is safer and reduces the harm to the body of the operator.
(3) The method for simultaneously separating and measuring various organic tin and inorganic tin in tobacco provided by the invention adopts the mobile phase containing citric acid as the tin extracting agent, and improves the extraction rate of tin in the tobacco strong adsorption matrix through the complexation of the tin extracting agent. Meanwhile, the mobile phase is used as an extracting agent, so that the influence of potential solvent effect on analysis is overcome.
(4) The method for simultaneously separating and measuring various organic tin and inorganic tin in the tobacco provided by the invention has the advantages of low measurement detection limit, good repeatability, high efficiency and high speed, covers all tin forms possibly related to a tobacco supply chain, has strong universality and practicability, is suitable for form analysis of tin in the tobacco, and provides technical support for comprehensively and objectively evaluating the harmfulness of tin elements in the tobacco.
Drawings
FIG. 1 is a chromatogram showing the comparison of a plurality of organotin and inorganic tin components in a tobacco sample and a mixed standard solution in example 1 of the present invention, wherein FIG. 1a is a chromatogram of a plurality of organotin and inorganic tin components in a tobacco sample, and FIG. 1b is a chromatogram of a plurality of organotin and inorganic tin components in a mixed standard solution.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The reagents and equipment used in the following examples are as follows:
1. reagent
Citric acid (british pharmacopoeia, Merck, germany); ammonia (CMOS grade, j.t.baker); acetonitrile (HPLC grade, Merck, germany); triphenyltin chloride (TPhT, AccuStandard, usa); tricyclohexyltin chloride (TChT), fenbutatin oxide (FBT) available from carbofuran technologies ltd; azocyclotin (ACT), tributyltin chloride (TBT) from Dr. Ehrenstontorfer, Germany; inorganic tin standard solutions (IT, national center for standards); deionized water (made by ultrapure water instruments).
2. Instrument for measuring the position of a moving object
1260-, 7700X high performance liquid chromatography-inductively coupled plasma mass spectrometer (Agilent Corp.); hamilton PRP-1 non-silanol based polystyrene-divinylbenzene packed chromatography column (2.1X 100mm, particle size 5 μm) (Agilent Corp., USA); an XS204 electronic balance (accuracy 0.0001g, Mettler, Switzerland); elix3 ultrapure water meter (Millipore, usa); VX-II vortex shaker (TARGIN Corp.); ZM200 heavy metal special mill (Retsch, germany); climacell707L constant temperature and humidity chamber (MMM company, Germany); z300 high speed centrifuge (Hermle, germany); vap II nitrogen blown concentrator (Turbo); a 0.22 μm organic needle filter (polyethersulfone, Shanghai' an spectral scientific instruments Co., Ltd.); PET vials (southern packaging Co., Ltd.).
The specific detection process of the method for simultaneously separating and measuring a plurality of organic tin and inorganic tin in tobacco is as follows.
1. Sample pretreatment
Grinding a tobacco sample by a heavy metal special grinder, sieving the ground tobacco sample by a 50-150-mesh sieve, balancing the ground tobacco sample in a constant-temperature and constant-humidity box with the temperature of (22 +/-1) DEG C and the relative humidity of (60 +/-2)% for 20-30h, accurately weighing a certain amount of the tobacco sample in a container, adding an extracting solution, performing vortex oscillation extraction at the temperature of 45-55 ℃ for 15-25min, centrifuging for 5-15min at the speed of not less than 3500r/min, taking supernatant, and performing nitrogen blowing concentration to 1 mL. And filtering the solution by a 0.22 mu m organic needle filter to obtain a sample solution. Blank control tests were performed simultaneously during the treatment of the tobacco samples.
Wherein the ratio of the added mass (g) of the tobacco sample to the added volume (mL) of the extracting solution is 1: 5-15. The volume ratio of the extracting solution is 1: 0.5-1.5 of solution A and solution B, wherein the mass ratio of the solution A is 100: 60-80: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
2. Preparing standard solution
Adding acetonitrile into an organotin standard sample to dilute and fix the volume to prepare an organotin mixed standard stock solution. Wherein the organotin is triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT) and fenbutatin oxide (FBT). The concentration of triphenyl tin (TPhT), tributyl tin (TBT), tricyclohexyl tin (TChT), Azocyclotin (ACT) and fenbutatin oxide (FBT) in the mixed standard organotin stock solution is 1000 mg/L.
And selecting an inorganic tin standard substance solution as a standard sample of the inorganic tin. Wherein the inorganic tin is an inorganic salt solution containing a tin (Sn) element. The concentration of tin element (Sn) in the inorganic tin standard substance solution is 10 mg/L.
The organic tin mixed standard stock solution and the inorganic tin standard substance solution are placed at minus 20 ℃ and kept away from light for standby.
And adding the organic tin mixed standard stock solution and the inorganic tin standard substance solution into the extracting solution to dilute and fix the volume to prepare a mixed standard solution. In the mixed standard solution, the concentrations of triphenyl tin (TPhT), tributyl tin (TBT), tricyclohexyl tin (TChT), triazol tin (ACT), Fenbutatin (FBT) and tin element (Sn) are all more than 0 and less than or equal to 200 mu g/L. Meanwhile, the extracting solution is taken to prepare a solution with the concentrations of triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), Fenbutatin (FBT) and tin element (Sn) of 0 mu g/L as a solvent blank. It is used as it is.
The volume ratio of the extracting solution is 1: 0.5-1.5 of solution A and solution B, wherein the solution A is prepared from the following components in a mass ratio of 100: 60-80: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
3. Measurement of
Firstly, respectively carrying out HPLC-ICP-MS analysis on a series of mixed standard solutions containing various organic tin and inorganic tin components with different concentrations, separating the various organic tin and inorganic tin components in the mixed standard solutions through HPLC, online connecting an effluent liquid to ICP-MS, measuring the contents of the various organic tin and inorganic tin through ICP-MS, thereby obtaining the linear relation between the concentrations of the various organic tin and inorganic tin components and corresponding peak areas, drawing corresponding standard working curves according to the corresponding concentrations of the peak areas of each organic tin and inorganic tin component, and calculating to obtain a regression equation of each standard working curve.
And then analyzing the sample solution by using a high performance liquid chromatography-inductively coupled plasma mass spectrometry, separating various organic tin and inorganic tin components in the sample solution by using the high performance liquid chromatography, measuring by using the inductively coupled plasma mass spectrometry to obtain peak areas of the various organic tin and inorganic tin components in the sample solution, and respectively substituting the peak areas into regression equations of the standard working curves to obtain the concentrations of the various organic tin and inorganic tin components in the sample solution.
Wherein, the measuring conditions of the high performance liquid chromatography are as follows: a chromatographic column: filling a chromatographic column with a non-silanol material; column temperature: 25-35 ℃; flow rate: 0.5-1.0 mL/min; mobile phase A: the mass ratio of the citric acid to the water to the ammonia water is 100: 60-80: 0.5; mobile phase B: acetonitrile; gradient elution. The high performance liquid chromatography is automatic sample injection, and the sample injection volume is 10-30 μ L.
The specific procedure for gradient elution was:
0-3.5min, phase A: the volume ratio of the phase B is 80:20-35: 65;
3.5-7min, phase A: the volume ratio of the phase B is 35:65-25: 75;
7-8.5min, phase A: the volume ratio of the phase B is 25:75-25: 75;
8.5-12.5min, phase A: the volume ratio of the phase B is 25:75-10: 90;
12.5-14.5min, phase A: the volume ratio of the phase B is 10:90-10: 90;
14.5-15.5min, phase A: the volume ratio of the phase B is 10:90-90: 10;
15.5-17.5min, phase A: the volume ratio of the phase B is 90:10-90: 10.
The measurement conditions of the inductively coupled plasma mass spectrometry are as follows: an ion source: an ICP source; a concentric atomizer; radio frequency power (RF power): 1500-1600W; RF matching voltage: 1.7-1.9V; carrier gas: argon with purity more than or equal to 99.99%, flow rate: 0.4-0.6L/min; temperature of the atomization chamber: -4 to-6 ℃; auxiliary gas: the volume ratio of argon to oxygen is 80:20, flow rate: 0.1-0.2L/min; plasma gas: argon, flow rate: 10-20L/min; waste liquid discharge rate: 0.1-0.5rps (peristaltic pump speed); sampling depth: 6-10 mm; integration time: 0.8-1.2s (m/z 118); the scanning mode is as follows: time resolved mode.
Finally, calculating the content of organic tin and inorganic tin in the tobacco sample according to the formula (1),
the formula (1) is:
in the formula, X is the content of any organic tin or inorganic tin in the tobacco sample, ng/g; c is the measured concentration value of any organic tin or inorganic tin in the sample solution, and the value is mu g/L; c 0 The concentration value is the measured concentration value of any organic tin or inorganic tin in the blank solution of the sample, and the concentration value is mu g/L; v is the volume of the sample solution, mL; m is the mass of the tobacco sample, g.
Example 1
1. Sample pretreatment
Grinding a tobacco sample by a heavy metal special grinder, sieving the ground tobacco sample by a 100-mesh sieve, balancing the ground tobacco sample in a constant-temperature constant-humidity box with the temperature of (22 +/-1) DEG C and the relative humidity of (60 +/-2)% for 24 hours, accurately weighing 1g (accurate to 0.001g) of the tobacco sample in a 60mL PET bottle, adding 10mL of extracting solution, performing vortex oscillation extraction at 50 ℃ for 20min, centrifuging the extracting solution for 10min at the speed of 3500r/min, taking supernatant, and performing nitrogen blowing concentration to 1 mL. And filtering the solution by a 0.22 mu m organic needle filter to obtain a sample solution. During the treatment of the tobacco samples, blank control tests were performed simultaneously.
Wherein the ratio of the added mass (g) of the tobacco sample to the added volume (mL) of the extracting solution is 1: 10. The volume ratio of the extracting solution is 1:1, wherein the solution A is a solution A and a solution B, and the mass ratio of the solution A is 100: 70: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
2. Preparing standard solution
Adding acetonitrile into an organotin standard sample to dilute and fix the volume to prepare an organotin mixed standard stock solution. Wherein the organotin is triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT) and fenbutatin oxide (FBT). The concentration of triphenyl tin (TPhT), tributyl tin (TBT), tricyclohexyl tin (TChT), Azocyclotin (ACT) and fenbutatin oxide (FBT) in the mixed standard organotin stock solution is 1000 mg/L. And selecting an inorganic tin standard substance solution as a standard sample of the inorganic tin. Wherein the inorganic tin is an inorganic salt solution containing tin (Sn) element. The concentration of tin element (Sn) in the inorganic tin standard substance solution is 10 mg/L. The organic tin mixed standard stock solution and the inorganic tin standard substance solution are placed at minus 20 ℃ and kept away from light for standby.
And adding the organic tin mixed standard stock solution and the inorganic tin standard substance solution into the extracting solution to dilute and fix the volume to prepare a series of mixed standard solutions with different concentrations. The concentrations of triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), Fenbutatin (FBT) and tin element (Sn) in the mixed standard solution were 0.5. mu.g/L, 2.0. mu.g/L, 5.0. mu.g/L, 20.0. mu.g/L, 50.0. mu.g/L and 200.0. mu.g/L, respectively. In addition, a solution with a concentration of 0. mu.g/L of each component was set as a solvent blank, and the specific data are shown in Table 2. It is used as it is.
The volume ratio of the extracting solution is 1:1, wherein the solution A is a solution A and a solution B, and the mass ratio of the solution A is 100: 70: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is methanol.
TABLE 2 series Standard solutions preparation Table (μ g/L)
| Serial number | IT | TPhT | TBT | TChT | | FBT |
| Lv1 | ||||||
| 0 | 0 | 0 | 0 | 0 | 0 | |
| Lv2 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Lv3 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Lv4 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| Lv5 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
| Lv6 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 |
| Lv7 | 200.0 | 200.0 | 200.0 | 200.0 | 200.0 | 200.0 |
3. Measurement of
Firstly, respectively carrying out HPLC-ICP-MS analysis on a series of mixed standard solutions containing 6 organic tin and inorganic tin components with different concentrations, separating the 6 organic tin and inorganic tin components in the mixed standard solutions through HPLC, online connecting an effluent liquid to ICP-MS, measuring the contents of the 6 organic tin and inorganic tin through ICP-MS, thereby obtaining the linear relation between the concentrations of the 6 organic tin and inorganic tin components in the mixed standard solutions and corresponding peak areas, drawing corresponding standard working curves according to the corresponding concentrations of the peak areas of each organic tin and inorganic tin component, and calculating to obtain a regression equation of each standard working curve.
And then analyzing the sample solution by using a high performance liquid chromatography-inductively coupled plasma mass spectrometry, separating 6 organic tin and inorganic tin components in the sample solution by using the high performance liquid chromatography, measuring by using the inductively coupled plasma mass spectrometry to obtain peak areas of the 6 organic tin and inorganic tin components in the sample solution, and substituting the peak areas into regression equations of the standard working curves respectively to obtain the concentrations of the 6 organic tin and inorganic tin components in the sample solution. The specific chromatogram for comparing the 6 organotin and inorganic tin components in the tobacco sample and the mixed standard solution is shown in figure 1, wherein the chromatogram for comparing the 6 organotin and inorganic tin components in the mixed standard solution is shown in figure 1b, and the chromatogram for the specific tobacco sample is shown in figure 1 a.
Wherein, the measuring conditions of the high performance liquid chromatography are as follows: a chromatographic column: polystyrene-divinylbenzene filled chromatographic columns (Hamilton PRP-1, 2.1X 100mm, particle size 5 μm) of non-silanol based material; column temperature: 30 ℃; flow rate: 0.6 mL/min; mobile phase A: the mass ratio of the citric acid to the water to the ammonia water is 100: 70: 0.5; mobile phase B: acetonitrile; gradient elution.
The specific procedure for gradient elution was:
0-3.5min, phase A: the volume ratio of the phase B is 80:20-35: 65;
3.5-7min, phase A: the volume ratio of the phase B is 35:65-25: 75;
7-8.5min, phase A: the volume ratio of the phase B is 25:75-25: 75;
8.5-12.5min, phase A: the volume ratio of the phase B is 25:75-10: 90;
12.5-14.5min, phase A: the volume ratio of the phase B is 10:90-10: 90;
14.5-15.5min, phase A: the volume ratio of the phase B is 10:90-90: 10;
15.5-17.5min, phase A: the volume ratio of the phase B is 90:10-90: 10.
The measurement conditions of the inductively coupled plasma mass spectrometry are as follows: an ion source: an ICP source; a concentric atomizer; radio frequency power (RF power): 1550W; RF matching voltage: 1.8V; carrier gas: argon with purity not less than 99.99%, flow rate: 0.5L/min; temperature of the atomization chamber: -5 ℃; auxiliary gas: the volume ratio of argon to oxygen is 80:20, flow rate: 0.15L/min; plasma gas: argon, flow rate: 15L/min; waste liquid discharge rate: 0.3rps (peristaltic pump speed); sampling depth: 8 mm; integration time: 1.0s (m/z 118); the scanning mode is as follows: time-resolved mode.
Finally, calculating the content of organic tin and inorganic tin in the tobacco sample according to the formula (1),
the formula (1) is:
in the formula, X is the content of any organic tin or inorganic tin in the tobacco sample, ng/g; c is the concentration value measured by any organic tin or inorganic tin in the sample solution, and is mu g/L; c 0 The concentration value is the measured concentration value of any organic tin or inorganic tin in the blank solution of the sample, and is mu g/L; v is the volume of the sample solution, mL; m is the mass of the tobacco sample, g. The above-mentioned contents of organotin and inorganic tin can be expressed as an average value of two parallel test measurements to the nearest 1 ng/g.
Example 2
As shown in the above example 1 and 2, the organic tin mixed standard stock solution and the inorganic tin standard stock solution are accurately transferred and added into the extracting solution to be diluted and prepared into a series of mixed standard solutions with different concentrations. The concentrations of triphenyltin (TPhT), tributyltin (TBT), tricyclohexyltin (TChT), Azocyclotin (ACT), Fenbutatin (FBT) and tin element (Sn) contained in the same mixed standard solution are the same, namely a series of mixed standard solutions with the components of 0.5 mu g/L, 2.0 mu g/L, 5.0 mu g/L, 20.0 mu g/L, 50.0 mu g/L and 200.0 mu g/L are respectively prepared. Meanwhile, the extracting solution is added to prepare a solution with the concentration of 6 organic tin and inorganic tin components being 0 mu g/L as a solvent blank.
And (3) respectively carrying out high performance liquid chromatography-inductively coupled plasma mass spectrometry combined analysis on the prepared series of mixed standard solutions with different concentrations, and carrying out regression analysis by taking the peak area ratio of the 6 organic tin and inorganic tin components as a vertical coordinate (Y axis) and the concentration of the 6 organic tin and inorganic tin components as a horizontal coordinate (X axis) to obtain a regression equation and a correlation coefficient thereof. Specific results are shown in Table 3. As can be seen from Table 3, the regression equation has good linearity and the correlation coefficient R 2 ≥0.999。
Meanwhile, for target substance response signals in the standard solution, sampling is repeatedly carried out for 10 times by adopting a standard sample with the lowest concentration, and 3 times of standard deviation of a measurement result is taken as a detection limit. The specific results are shown in Table 3. As is clear from Table 3, the detection limit of tin in each form was 0.27 to 0.59ng/g, and the method had high sensitivity.
TABLE 3
y: peak area; x: concentration of
Example 3
According to the pretreatment and measurement steps in the example 1, three standard adding levels of low, medium and high of the tobacco sample are selected, the standard adding recovery rate of the sample is measured, the standard adding levels are respectively 10ng/g, 50ng/g and 200ng/g, and the corresponding recovery rates are shown in the table 4. And calculating the recovery rate according to the difference between the concentration of the known sample and the standard sample relative to the amount of the standard sample, wherein the recovery rate is 72.6-96.4%, and the recovery rate of 6 tin components is better.
Meanwhile, the recovery rates of the 6 types of tin components were continuously measured in parallel for 6 times, and the corresponding relative standard deviation data are shown in Table 4. The Relative Standard Deviation (RSD) of the tin components of the 6 forms was 8.0% or less, indicating that the precision of the method was good.
TABLE 4
Example 4
By adopting the detection conditions of the embodiment 1 in the method, 6 kinds of organic tin and inorganic tin in the actual tobacco sample are measured, and the content of the organic tin and the inorganic tin can be represented by the average value of two times of parallel test measurement and is accurate to 1 ng/g. The specific data are shown in Table 5. As can be seen from Table 5, the tin in the actual tobacco samples of this batch was present primarily as inorganic tin with trace amounts of organotin. The method has the advantages of good separation effect, low detection limit and high sensitivity, and can be used for objectively evaluating the distribution condition of different forms of tin elements in tobacco.
TABLE 5 measurement of tin content (ng/g) in different forms in the samples
| Serial number | IT | TPhT | TBT | | ACT | FBT | |
| 1 | 163 | ND * | ND | 20 | 18 | ND | |
| 2 | 185 | ND | ND | 26 | 12 | ND | |
| Mean value of | 174 | ND | ND | 23 | 15 | ND |
Note: ND indicates no detection
In conclusion, the method for simultaneously separating and determining various organic tin and inorganic tin in tobacco provided by the invention can meet the requirement of simultaneously, quickly and reliably detecting the organic tin and the inorganic tin in complex matrixes such as tobacco and the like, reduces the physical harm to operators, and provides technical support for comprehensively and objectively evaluating the harmfulness of tin elements in the tobacco. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A method for simultaneously separating and measuring various organic tin and inorganic tin in tobacco comprises the steps of adding a tobacco sample into an extracting solution, oscillating, extracting, centrifuging, taking a sample solution obtained after supernatant liquid is concentrated and filtered, measuring by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry combined method, and calculating the content of various organic tin and inorganic tin in the sample solution by a standard curve method;
the organic tin is selected from any one or combination of more of triphenyl tin, tributyl tin, tricyclohexyl tin, azocyclotin and fenbutatin oxide; the inorganic tin is an inorganic salt solution containing a tin element;
the high performance liquid chromatography-inductively coupled plasma mass spectrometry combined method for determination comprises the following steps:
1) preparing a standard solution: diluting the standard samples of organic tin and inorganic tin step by step to a constant volume to obtain a mixed standard solution;
2) and (3) determination: respectively measuring the sample solution and the mixed standard solution prepared in the step 1) by a high performance liquid chromatography-inductively coupled plasma mass spectrometry combined method, separating multiple organic tin and inorganic tin components in the sample solution and the mixed standard solution by the high performance liquid chromatography, measuring by using an inductively coupled plasma mass spectrometry, comparing retention time to determine the multiple organic tin and inorganic tin components in the sample solution, and calculating the content of the multiple organic tin and inorganic tin in the sample solution by a standard curve method;
in the step 2), the determination conditions of the high performance liquid chromatography are as follows:
a chromatographic column: hamilton PRP-1 polystyrene-divinylbenzene filled chromatographic column of non-silanol material; column temperature: 25-35 ℃; flow rate: 0.5-1.0 mL/min; mobile phase A: the mass ratio of the citric acid to the water to the ammonia water is 100: 60-80: 0.5;
mobile phase B: acetonitrile; gradient elution;
the specific procedure of the gradient elution is as follows:
0-3.5min, phase A: the volume ratio of the phase B is 80:20-35: 65;
3.5-7min, phase A: the volume ratio of the phase B is 35:65-25: 75;
7-8.5min, phase A: the volume ratio of the phase B is 25:75-25: 75;
8.5-12.5min, phase A: the volume ratio of the phase B is 25:75-10: 90;
12.5-14.5min, phase A: the volume ratio of the phase B is 10:90-10: 90;
14.5-15.5min, phase A: the volume ratio of the phase B is 10:90-90: 10;
15.5-17.5min, phase A: the volume ratio of the phase B is 90:10-90: 10.
2. The method for simultaneously separating and measuring multiple kinds of organic tin and inorganic tin in tobacco according to claim 1, wherein the extracting solution is prepared by mixing the components in a volume ratio of 1: 0.5-1.5 of solution A and solution B, wherein the mass ratio of the solution A is 100: 60-80: 0.5 of a mixed solution of citric acid, water and ammonia water, wherein the solution B is acetonitrile.
3. The method for simultaneously separating and measuring multiple organotin and inorganic tin in tobacco according to claim 1, wherein the ratio of the added mass of the tobacco sample to the added volume of the extracting solution is 1:5-15 g/mL.
4. The method for simultaneously separating and measuring a plurality of organotin and inorganic tin in tobacco according to claim 1, wherein the oscillation extraction is vortex oscillation extraction, the temperature of the vortex oscillation extraction is 45-55 ℃, and the time of the vortex oscillation extraction is 15-25 min; the centrifugation conditions were: the centrifugal speed is more than or equal to 3500r/min, and the centrifugal time is 5-15 min.
5. The method for simultaneously separating and measuring a plurality of organotin and inorganic tin in tobacco according to claim 1, wherein in the step 2), the measurement conditions of the inductively coupled plasma mass spectrometry are as follows:
an ion source: an ICP source; a concentric atomizer; radio frequency power: 1500-1600W; RF matching voltage: 1.7-1.9V; carrier gas: argon with purity more than or equal to 99.99%, flow rate: 0.4-0.6L/min; temperature of the atomization chamber: -4 to-6 ℃; auxiliary gas: the volume ratio of argon to oxygen is 80:20, flow rate: 0.1-0.2L/min; plasma gas: argon, flow rate: 10-20L/min; waste liquid discharge rate: 0.1 to 0.5 rps; sampling depth: 6-10 mm; integration time: 0.8-1.2s, m/z 118; the scanning mode is as follows: time-resolved mode.
6. The method for simultaneously separating and measuring a plurality of organotin and inorganic tin in tobacco according to claim 1, wherein in the step 2), the content of the organotin and the inorganic tin is calculated according to the formula (1),
the formula (1) is:
in the formula, X is the content of any organic tin or inorganic tin in the tobacco sample, ng/g; c is the concentration value measured by any organic tin or inorganic tin in the sample solution, and is mu g/L; c 0 The concentration value is the measured concentration value of any organic tin or inorganic tin in the blank solution of the sample, and is mu g/L; v is the volume of the sample solution, mL; m is the mass of the tobacco sample, g.
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