CN103323548B - Measurement method for residual amount of pentachlorophenol in cigarette paper - Google Patents
Measurement method for residual amount of pentachlorophenol in cigarette paper Download PDFInfo
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Abstract
A measurement method for the residual amount of pentachlorophenol in cigarette paper is characterized by comprising the following steps: cutting cigarette paper into pieces, adding extract liquor into the pieces, conducting ultrasonic extraction and measuring the residual amount of pentachlorophenol in the cigarette paper with liquid chromatography-tandem mass spectrometry (LC-MS/MS) directly after centrifugation of the extract liquor. The method comprises the following steps: a. cutting a cigarette paper sample according to relevant regulations; b. extracting a sample; c. purifying the sample; d. preparing a standard operating solution; e. carrying out liquid chromatography-tandem mass spectrometry (LC-MS/MS) measurement; f. calculating the measured result of the residual amount of pentachlorophenol. In comparison with the prior art, the measurement method has the following advantages: 1. adopting a pre-treatment of cutting the sample to make a solvent contact the sample better. The experiment result shows that such treatment can help to increase the extraction efficiency of pentachlorophenol. 2. measuring the content of pentachlorophenol in the paper with LC-MS/MS without derivatization operation, and the pre-treatment method is simple. 3. The method is accurate in operations, high in sensitivity and good in repeatability.
Description
Technical field
The invention belongs to the residual physical and chemical inspection technical field of objectionable impurities in cigarette paper using, relate generally to the assay method of In Determination of Residual Pentachlorophenol in tobacco lining paper, tipping paper, bar box packaging paper, a kind of employing ultrasonic extraction pentachlorophenol specifically, with the direct method for measuring of liquid chromatography-tandem mass spectrometry.
Background technology
Paper bag is drawn together in the production run of internal lining paper, tipping paper, bar box packaging paper etc., need to add various chemicals as chemicals such as bleaching agent, processing aid, printing-ink, anticorrosion and bactericidal agents, to improve its packaging character and aesthetic property.But research discovery, these chemicals can remain in paper, and then move in cigarette, and some of them migration thing has even carcinogenesis of toxicity, and consumer's health is formed to harm.The developed countries such as the U.S., European Union, Japan are all to having formulated corresponding rules and limit standard with the wrappage of Food Contact, and have implemented strict market access management.Pentachlorophenol (PCP) is used as the anticorrosion and mildewproof agent of wood raw material, can stop the growth of fungi, bacterium, suppresses corrosion.But pentachlorophenol has stronger toxicity, suck or absorb pentachlorophenol through skin and can cause headache, tired, the irritation of eyes, mucous membrane and skin, neuralgia, hidrosis, expiratory dyspnea, liver, renal damage etc. can produce biological accumulation in human body, and Gamma Magnitude just can cause human body reproduction and development toxicity.Environmental Protection Agency and European Union have classified PCP as one of persistence organic pollutant of preferential control.Although PCP still may be present in other local imported raw material, in the product within the scope of European Union, be prohibited at present.
Pentachlorophenol (pentachlorophenol, PCP) is a kind of common easily ionizable, be insoluble in the chlorinated aromatic organic contaminant of water.Pentachlorophenol stable chemical nature, under usual conditions, pentachlorophenol is not oxidized, is also difficult to hydrolysis.Become ionic state form neutral and pentachlorophenol in alkaline solution is dissociable, and in acid solution, it still take molecular state as main.
At present to the mensuration of pentachlorophenol mainly in fields such as water, textile, soil, toy and articles for children, food plastic wrappage and medical supplies.Owing to containing hydroxyl on phenyl ring in chlorinated phenol chemical constitution, the polarity of molecule is strengthened, boiling point, up to 315 ℃, needs just can carry out gas chromatography or GC-MS(gas chromatography-mass spectrography) analysis [mensuration 1st ~ 2 parts of GB/T 18414.1-2-2006 textile chlorinated phenol: vapor-phase chromatography after derivatization; The mensuration gas chromatography-mass spectrography of pentachlorophenol in SN/T 2276-2009 food contact material paper pulp, paper and cardboard aqueous extract; The mensuration of pentachlorophenol in GB/T 25002-2010 paper, cardboard and pulp-water extract; ISO 15320:2011].Derivatization process is complicated, and expends that reagent is many and toxicity is large.It is high that high performance liquid chromatography has separation efficiency, and analysis speed is fast, operates simple and easyly, is particularly suitable for the analysis of higher boiling, poor heat stability, strong polar material.LC-MS/MS method [phenolic compound in Ultra Performance Liquid Chromatography one series connection mass spectrometric determination food wrapper, analytical test journal, 2012,29(12), 1153; Flood Aiwa, Yin Pinghe.Tablets by HPLC-MS is measured the chlorinated phenol in textile, assay laboratory, and 2009,28(11), and 88] without sample is carried out to derivatization, pre-treatment is quick, easy, and detection sensitivity is high, and resolution characteristic is strong.Therefore, be the more efficiently detection method of pentachlorophenol.
summary of the invention:
The assay method of In Determination of Residual Pentachlorophenol in a kind of cigarette paper using that object of the present invention provides based on above-mentioned current condition just, this method has overcome prior art defect, can fast, accurately detect pentachloro-phenol residual quantity in paper, and measurement result is accurate, mensuration is disturbed few.
The object of the invention is to be achieved through the following technical solutions:
An assay method for In Determination of Residual Pentachlorophenol in cigarette paper using, is to add extract after cigarette paper using is shredded, then ultrasonic extraction, and extract is centrifugal rear directly with the method for pentachloro-phenol residual quantity in liquid chromatography tandom mass spectrometry determination paper, specifically comprises the following steps:
A, cigarette paper using sample is carried out to cutting according to relevant regulations: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, accurately cut long 200 mm, the tipping paper sample of wide 40 mm (should comprise monolateral); The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area approximately 170 cm
2(being equivalent to the internal lining paper area that the soft box packing of regular-size cigarette adopts); The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006; to rigid pack paper; with reference to printing impression, accurately cut master package face; area is 22.0 cm ' 5.5 cm, to soft box packaging paper, gets a soft box packaging paper; area is 15.5 cm ' 10.0 cm; to bar wrapping paper, at packing front middle section, accurately cut the sample of 22.0 cm ' 5.5 cm;
The extraction of b, sample: the sample after cutting is placed on balance and takes (being accurate to 0.01 g); Then with scissors, sample is cut into the fragment that is not more than 0.5 cm * 0.5 cm; Fragment is placed in to 50 mL tool plug triangular flasks, accurately adds 40mL extract (methyl alcohol: water=50:50, volume ratio) and 50 μ L inner mark solutions (2,4,5-T or 2,4-drip, concentration 1.0 μ g/mL), ultrasonic extraction 30 min;
C, sample purification: standing 5 min, pipette extract 8 mL in 10 mL centrifuge tubes, with centrifugal 10 min of 10000 rpm speed.Draw supernatant, through 0.22 μ m organic phase membrane filtration, filtrate is detected through LC-MS/MS;
D, prepare standard operation solution: take respectively 0.01g(PCP) standard items are in 10mL volumetric flask, with methyl alcohol dilution and be finally mixed with the standard operation solution with concentration gradient;
E, liquid chromatography tandom mass spectrometry determination: draw the pesticide standard working solution of the variable concentrations preparing, inject liquid chromatography-tandem mass spectrometer;
The calculating of f, In Determination of Residual Pentachlorophenol measurement result
With internal standard method, carry out quantitative test, with pentachlorophenol and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect pentachlorophenol and interior target quota ion to peak area ratio, substitution typical curve, tries to achieve the residual quantity of the pentachlorophenol in sample.
The manner of formulation of standard operation solution is as follows in the present invention: take 0.01g PCP standard items to 100 mL volumetric flasks in, be accurate to 0.0001g, with methyl alcohol, dilute constant volume, be mixed with the standard reserving solution that concentration is about 100 μ g/mL; Pipette standard reserving solution 1mL in 100mL volumetric flask, with methyl alcohol, dilute constant volume, obtain the working solution that concentration is about 1 μ g/mL; Pipette respectively the working solution of certain volume in 50 mL volumetric flasks, and add 50 μ L inner mark solutions (2,4,5-T, 1.0 μ g/mL).With methyl alcohol, dilute constant volume, be mixed with the pesticide standard working solution of variable concentrations, series standard working solution concentration is respectively: 2 ng/mL, 4 ng/mL, 6 ng/mL, 10 ng/mL, 20 ng/mL and 40 ng/mL;
The liquid phase chromatogram condition adopting is: chromatographic column: Atiantis dC18 (150 mm * 2.1 mm, 3 μ m, U.S. Waters company); Mobile phase: acetonitrile/0.1 % aqueous formic acid (volume ratio 95:5), flow velocity: 200 μ L/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition adopting: scan mode: negative ion scanning; Electric spray ion source (ESI); Atomization gas flow is 60 psi; Gas curtain airshed 18 psi; Auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; Collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, detection mode: negative ion polyion reaction monitoring (MRM), MRM parameter is in Table 1.
Method of the present invention has overcome the deficiency of prior art sample treatment, for cigarette tipping paper, internal lining paper and tobacco shred and box packaging paper sample, has optimized sample-pretreating method and instrument testing conditions.Compared with prior art the inventive method has following excellent results:
(1) the present invention takes the pretreatment mode that sample is shredded, and makes solvent better contact sample, and experimental result shows, processing can improve the extraction efficiency of pentachlorophenol like this.
(2) the inventive method utilizes LC-MS/MS to measure the content of pentachlorophenol in paper, and without carrying out derivatization operation, pre-treating method is simple.
(3) the inventive method has advantages of that operation is accurate, highly sensitive and reproducible.
1. the detectability of the inventive method:
The pentachloro-phenol standard operation solution of variable concentrations is injected to LC-MS/MS, with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), calculate detectability (LOD), detect and be limited to 0.005 μ g/g.
2. the repeatability of the inventive method and recovery of standard addition:
The standard solution that adds pentachloro-phenol in blank sample, then carries out respectively pre-treatment and LC-MS/MS and analyzes, and calculate its recovery according to adding scalar sum measured value, the results are shown in Table 2.As can be seen from Table 2, the recovery of pentachloro-phenol reaches more than 95%, and average relative standard deviation (RSD) is less than between 5%, illustrates that the recovery of the inventive method is high, reproducible.
Accompanying drawing explanation
Fig. 1 is assay method process flow diagram of the present invention (this figure is as Figure of abstract).
Embodiment
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Example 1:
1. instrument and reagent:
Pentachlorophenol, methyl alcohol, acetic acid is chromatographic grade reagent; Distilled water, meets the requirement of one-level water in GB/T 6682.
API 4000 quadrupole rod tandem mass spectrometers; Switzerland Mettler AE 163 electronic balance (sensibility reciprocals: 0.0001g).
2. sample preparation:
First sample is carried out to cutting: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, accurately cut long 200 mm, the tipping paper sample of wide 40 mm (should comprise monolateral); Sample after cutting is placed on balance and is weighed; Then with scissors, sample is cut into the fragment that is not more than 0.5 cm * 0.5 cm; Fragment is placed in to 50 mL tool plug triangular flasks, accurately adds 40mL extract and 50 μ L inner mark solutions (2,4,5-T, 1.0 μ g/mL), ultrasonic extraction 30 min; Standing 5min, gets 8 mL supernatant liquors in 10 mL tool plug centrifuge tubes, centrifugal 10 min of 10000 rotary speeds, and getting supernatant is liquid to be measured;
3. prepare standard operation solution: take 0.01g PCP standard items to 100 mL volumetric flasks in, be accurate to 0.0001g, with methyl alcohol, dilute constant volume, be mixed with the standard reserving solution that concentration is about 100 μ g/mL; Pipette standard reserving solution 1mL in 100mL volumetric flask, with methyl alcohol, dilute constant volume, obtain the working solution that concentration is about 1 μ g/mL; Pipette respectively the working solution of certain volume in 50 mL volumetric flasks, and add 50 μ L inner mark solutions (2,4,5-T, 1.0 μ g/mL).With methyl alcohol, dilute constant volume, be mixed with the pesticide standard working solution of variable concentrations, series standard working solution concentration is respectively: 2 ng/mL, 4 ng/mL, 6 ng/mL, 10 ng/mL, 20 ng/mL and 40 ng/mL;
4. assay method: carry out quantitative test with internal standard method, with pentachlorophenol and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect pentachlorophenol and interior target quota ion to peak area ratio, substitution typical curve, the content of trying to achieve the pentachloro-phenol in this tipping paper sample is respectively 0.05 μ g/g.
Accuracy for determination methods, the pentachlorophenol standard solution that adds 0.05 μ g in this sample, carry out the same sample pre-treatments, with LC-MS/MS, record the selection quasi-molecular ions area of pentachlorophenol, substitution typical curve, the pentachlorophenol content of trying to achieve in sample is now 0.096 μ g/g, and the recovery of standard addition of pentachlorophenol is 96.0%, illustrates that the method is accurately.
Example 2:
As described in Example 1, select another cigarette tipping paper sample, recording pentachlorophenol content in sample is 0.
Example 3:
As described in Example 1, select another tobacco lining paper sample, the content that records pentachlorophenol in sample is 0.
Claims (4)
1. the assay method of In Determination of Residual Pentachlorophenol in a cigarette paper using, it is characterized in that: be to add extract after cigarette paper using is shredded, then ultrasonic extraction, extract is centrifugal rear directly with the method for pentachloro-phenol residual quantity in liquid chromatography tandom mass spectrometry determination paper, specifically comprises the following steps:
A, cigarette paper using sample is carried out to cutting according to relevant regulations;
The extraction of b, sample: the sample after cutting is placed on balance and is taken, be accurate to 0.01 g; Be cut into fragment; Fragment is placed in to 50 mL tool plug triangular flasks, accurately adds 40mL extract and 50 μ L inner mark solutions, ultrasonic extraction 30 min, extract is methyl alcohol: water=50:50, volume ratio; Described inner mark solution is 2,4,5-T, and concentration is 1.0 μ g/mL;
C, sample purification: standing 5 min, pipette extract 8 mL in 10 mL centrifuge tubes, with centrifugal 10 min of 10000 rpm speed; Draw supernatant, through 0.22 μ m organic phase membrane filtration, filtrate is detected through LC-MS/MS;
D, preparation standard operation solution: take respectively 0.01g pentachlorophenol standard items in 10 mL volumetric flasks, with methyl alcohol dilution, be also finally mixed with the standard operation solution with concentration gradient;
E, liquid chromatography tandom mass spectrometry determination: draw the pesticide standard working solution of the variable concentrations preparing, inject liquid chromatography-tandem mass spectrometer; The liquid phase chromatogram condition adopting is: chromatographic column: Atiantis dC18, specification 150 mm * 2.1 mm, 3 μ m; Mobile phase: acetonitrile/0.1 % aqueous formic acid, volume ratio 95:5, flow velocity: 200 μ L/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition adopting: scan mode: negative ion scanning; Electric spray ion source (ESI); Atomization gas flow is 60 psi; Gas curtain airshed 18 psi; Auxiliary heating airshed is 60 psi; 500 ℃ of ionization temperature; Collision airshed is 10 psi; 4 kinds of gases are nitrogen; The residence time is 100 msec; Ionization voltage 5500 V, detection mode: negative ion polyion reaction monitoring (MRM);
The calculating of f, In Determination of Residual Pentachlorophenol measurement result
With internal standard method, carry out quantitative test, with pentachlorophenol and interior target quota ion, peak area is carried out to regretional analysis to its respective concentration, obtain typical curve, related coefficient is more than or equal to 0.999, sample after extracting is measured, record and detect pentachlorophenol and interior target quota ion to peak area ratio, substitution typical curve, tries to achieve the residual quantity of the pentachlorophenol in sample.
2. the assay method of In Determination of Residual Pentachlorophenol in cigarette paper using according to claim 1, is characterized in that: described cigarette paper using is tobacco lining paper, tipping paper, bar box packaging paper.
3. the assay method of In Determination of Residual Pentachlorophenol in cigarette paper using according to claim 1, it is characterized in that: the relevant regulations in step a refers to: the cutting method of cigarette tipping paper carries out according to the regulation of YC 171-2008, accurately cut long 200 mm, the tipping paper sample of wide 40 mm, should comprise one monolateral; The cutting method of tobacco lining paper carries out according to the regulation of YC 264-2008, i.e. cutting area approximately 170 cm
2, be equivalent to the internal lining paper area that the soft box packing of regular-size cigarette adopts; The cutting method of tobacco shred and box packaging paper carries out according to the regulation of YC/T 207-2006, to rigid pack paper, with reference to printing impression, accurately cut master package face, area is 22.0 cm * 5.5 cm, to soft box packaging paper, gets a soft box packaging paper, area is 15.5 cm * 10.0 cm, to bar wrapping paper, at packing front middle section, accurately cut the sample of 22.0 cm * 5.5 cm.
4. the assay method of In Determination of Residual Pentachlorophenol in cigarette paper using according to claim 1, it is characterized in that: take 0.01g PCP standard items to 100 mL volumetric flasks in, be accurate to 0.0001g, with methyl alcohol, dilute constant volume, be mixed with the standard reserving solution that concentration is about 100 μ g/mL; Pipette standard reserving solution 1mL in 100mL volumetric flask, with methyl alcohol, dilute constant volume, obtain the working solution that concentration is about 1 μ g/mL; Pipette respectively the working solution of certain volume in 50 mL volumetric flasks, and add 50 μ L inner mark solutions, with methyl alcohol, dilute constant volume, be mixed with the pesticide standard working solution of variable concentrations, series standard working solution concentration is respectively: 2 ng/mL, 4 ng/mL, 6 ng/mL, 10 ng/mL, 20 ng/mL and 40 ng/mL.
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| CN104820053B (en) * | 2015-05-06 | 2016-08-24 | 宁波市海洋与渔业研究院 | 19 kinds of chlorinated phenols and the method for sodium salt thereof in Gas Chromatography-Mass Spectrometry aquatic animal |
| CN108872336B (en) * | 2018-06-22 | 2021-03-12 | 上海烟草集团有限责任公司 | Method for detecting content of pentachlorophenol in paper packaging material |
| CN113281287B (en) * | 2021-05-18 | 2023-10-31 | 福建中烟工业有限责任公司 | Pretreatment method for paper surface layer and method for determining saccharin sodium content in paper surface layer |
| CN115508470B (en) * | 2022-09-21 | 2023-05-30 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for detecting pentachlorophenol content in milk powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102346174A (en) * | 2010-08-04 | 2012-02-08 | 江苏天瑞仪器股份有限公司 | Method for determining content of chlorine-containing phenol in leather by liquid chromatogram-ultraviolet detector |
-
2013
- 2013-06-08 CN CN201310227443.XA patent/CN103323548B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102346174A (en) * | 2010-08-04 | 2012-02-08 | 江苏天瑞仪器股份有限公司 | Method for determining content of chlorine-containing phenol in leather by liquid chromatogram-ultraviolet detector |
Non-Patent Citations (9)
| Title |
|---|
| C. Domeno等.Development of a solid-phase microextraction method for direct determination of pentachlorophenol in paper and board samples：Comparison with conventional extraction method.《Journal of Chromatography A》.2005,第1095卷(第1-2期),第8-15页. * |
| 区棋铭等.纸制品中五氯苯酚的高效液相色谱测定方法.《科技与企业》.2012,(第3期), |
| 李中皓等.气相色谱/质谱联用测定纸质材料中五氯苯酚的残留量.《现代食品科技》.2012,第28卷(第12期),第1818-1821页. |
| 气相色谱/质谱联用测定纸质材料中五氯苯酚的残留量;李中皓等;《现代食品科技》;20121231;第28卷(第12期);第1818-1821页 * |
| 王天娇等.超高效液相色谱-串联质谱法测定食品包装纸中的酚类化合物.《分析测试学报》.2010,第29卷(第12期), |
| 皮革及其皮革制品中五氯苯酚的检测;童成豹;《西部皮革》;20130430;第35卷(第8期);第37-40页 * |
| 童成豹.皮革及其皮革制品中五氯苯酚的检测.《西部皮革》.2013,第35卷(第8期),第37-40页. |
| 纸制品中五氯苯酚的高效液相色谱测定方法;区棋铭等;《科技与企业》;20120228(第3期);第220页第1.4节 * |
| 超高效液相色谱-串联质谱法测定食品包装纸中的酚类化合物;王天娇等;《分析测试学报》;20101231;第29卷(第12期);第1154页第1节和第1156页第2.5节 * |
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