CN109060975A - The detection method of cancinogenic dye in a kind of plastic package material - Google Patents
The detection method of cancinogenic dye in a kind of plastic package material Download PDFInfo
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- CN109060975A CN109060975A CN201810733409.2A CN201810733409A CN109060975A CN 109060975 A CN109060975 A CN 109060975A CN 201810733409 A CN201810733409 A CN 201810733409A CN 109060975 A CN109060975 A CN 109060975A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The invention discloses a kind of detection methods of cancinogenic dye in plastic package material, using high performance liquid chromatography and mass spectrometry.The detection method of cancinogenic dye of the present invention is plastic package material using object, and sample pre-treatments are simple, is not necessarily to special purified treatment, can in Accurate Determining target product high-content cancinogenic dye concentration, be suitable for standardization.
Description
Technical field
A kind of carcinogenic substance detection technique field of the present invention, and in particular to the detection method of cancinogenic dye in plastic package material.
Background technique
Influence of the cancinogenic dye to plastic package material safety be mainly manifested in two aspect, be on the one hand directly with human body skin
Skin contact, under the long-term slow effect of the reducing substances caused by human metabolism, if dyestuff generation in plastics
Aromatic amine is one of 24 kinds inside the appendix A of GB/T 18885 (ecological textile technical requirements), then the dyestuff is to the mankind
There is carcinogenicity, or finds to have animal carcinogenicity so far, there may be potential carcinogenicity to the mankind.On the other hand main
It is the plastic package material contacted with food, shows in food contact material cancinogenic dye to food migration situation: colorant
In poisonous and harmful substance include that the cancinogenic dyes such as certain azo dyes are enriched with by migrating into people's food, and then in human body,
Threat will be brought to people's health after reaching sufficient amount.
With the continuous enhancing of people's awareness of environment protection and health, cancinogenic dye is to the shadow in terms of human health and ecological environment
Ring also more and more attention has been paid to.Since German Government in 1994 promulgates disabling some dyes decree, the range of prohibitive dye is not
It is disconnected to expand, many countries, area the prohibitive dye regulation related to continuously publication has been organized including China.It weaves at home
In product supervision and international clothes and footwear trade, cancinogenic dye is also highly important inspection project.Early in 2007, China was big
Scale has formulated the examination criteria of ecological textile, the measurement of GB/T 17595-2006 textile forbidding azo dyes, GB/T
The examination criterias such as the measurement of 20382-2006 textile cancinogenic dye are formally issued and implemented, our ecological spinning detection necks have been constructed
The technical system in domain.But on plastic package material, the potential health threat of cancinogenic dye attracts extensive attention not yet, mesh
It is preceding there is not yet related limit standard or bulletin.Consider plastics as the functional and cheap material of one kind food,
The packaging of clothes and various daily necessities is widely used, and especially Electronic Commerce in China is quickly grown in recent years, on the net
Shopping scale is increasing, people to the contact frequency of plastic package material also more than the past it is very much, these phenomenons may cause
Cancinogenic dye in plastic package material enters human body, endangers the health of the people.Therefore, it is necessary to establish a kind of plastics package material
The detection method of cancinogenic dye in material provides technical support for the later examination and test of products.
Summary of the invention
The purpose of the present invention is to provide a kind of detection methods of cancinogenic dye in plastic package material.
Technical scheme is as follows:
The detection method of cancinogenic dye in a kind of plastic package material, using high performance liquid chromatography and mass spectrometry,
The actual conditions of above-mentioned high performance liquid chromatography are as follows: chromatographic column: C18 chromatographic column；30 DEG C of column temperature；Flow velocity: 0.25mL/
min；Sample volume: 2 μ L；Mobile phase: according to the property of cancinogenic dye to be measured, high performance liquid chromatograph is set and is in ESI cation
Mode or ESI negative ion mode:
Under ESI positive ion mode, mobile phase A is the 5mmol/L ammonium acetate solution of the formic acid containing 0.02wt%, and Mobile phase B is
Acetonitrile；
Under ESI negative ion mode, mobile phase A is 5mmol/L ammonium acetate solution, and Mobile phase B is acetonitrile；
Linear gradient elution program: 0min, 90% mobile phase A；5min, 10% mobile phase A；10min, 10% mobile phase A；
10.1min, 90% mobile phase A；15min, 90% mobile phase A；
Above-mentioned mass spectrographic actual conditions are as follows: the electric spray ion source of use heating, 350 DEG C of ion source heating temperature, capillary
Tube temperature degree is 320 DEG C, sheath atmospheric pressure 30arb, assist gas pressure power 10arb；ESI positive ion mode: spray voltage 3kV, capillary
Tube voltage is 37V, and pipe lens voltage is 100V；ESI negative ion mode: spray voltage is -2.5kV, and capillary voltage is -37V,
Pipe lens voltage is -100V；First mass spectrometric full scan: m/z 150~1000, resolution ratio R are 30000；Second order ms collision lures
Lead dissociation fragment scanning: it is 2.0, ESI cation mould that CID normalization collision energy, which is 35%, Isolation width (m/z),
Formula and ESI negative ion mode acquire data respectively；
Specifically comprise the following steps:
(1) drafting of standard working curve: accurately weighing cancinogenic dye standard items, is dissolved in methanol and constant volume is prepared
It at standard reserving solution, is kept in dark place at 4 DEG C, which is diluted to the standard work of various concentration with methanol by when use
Make liquid, after the standard working solution of the various concentration is purified with the actual conditions of above-mentioned high performance liquid chromatography, then with above-mentioned mass spectrum
Actual conditions obtain standard working solution chromatographic peak, using the mass concentration x in standard working solution as abscissa, above-mentioned standard work
The area y at liquid chromatography peak is ordinate, draws standard working solution regression curve, the unit of x is mg/L, according to gained linear equation
Y=ax+b calculates slope of a curve a and intercept b；
(2) sample detection: being cut into small blade unit for sample, through methylene chloride or tetrahydrofuran ultrasonic extraction, is mentioned
Liquid is taken, by appropriate extracting solution with being dried with nitrogen, with methanol constant volume, analyte sample fluid is obtained after filter membrane, with above-mentioned efficient liquid phase
After the actual conditions purification of chromatography, the area of chromatographic peak to be measured is then obtained with above-mentioned mass spectrographic actual conditions, this is waited for into colour examining
The area of spectral peak substitutes into above-mentioned linear equation y=ax+b, according to step (2) resulting slope a and intercept b, obtains x, i.e., to be measured
The concentration of cancinogenic dye to be measured in sample liquid.
In a preferred embodiment of the invention, the cancinogenic dye include solvent yellow 1, solvent yellow 2, solvent yellow 3,
Disperse blue 1, disperse yellow 3, Acid red 26, alkalinity is red 9, basic violet 14, directly black 38, directly red 28, disperse orange 11 and direct orchid 6.
It is further preferred that the qualitative ion pair and quota ion pair of the cancinogenic dye are as shown in the table:
In a preferred embodiment of the invention, the concentration of the standard reserving solution in the step (2) is 200mg/
L。
In a preferred embodiment of the invention, the temperature of the ultrasonic extraction be room temperature, the time be 15~
25min。
The beneficial effects of the present invention are: the detection method of cancinogenic dye of the present invention is plastics package material using object
Material, sample pre-treatments are simple, are not necessarily to special purified treatment, can in Accurate Determining target product high-content cancinogenic dye it is dense
Degree is suitable for standardization.
Detailed description of the invention
The standard working solution regression curve of basic violet 14 in Fig. 1 present invention.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
In following embodiments:
The actual conditions of high performance liquid chromatography are as follows: chromatographic column: C18 chromatographic column；30 DEG C of column temperature；Flow velocity: 0.25mL/min into
Sample amount: 2 μ L；Mobile phase: according to the property of cancinogenic dye to be measured, be arranged high performance liquid chromatograph be in ESI positive ion mode or
ESI negative ion mode:
Under ESI positive ion mode, mobile phase A is the 5mmol/L ammonium acetate solution of the formic acid containing 0.02wt%, and Mobile phase B is
Acetonitrile；
Under ESI negative ion mode, mobile phase A is 5mmol/L ammonium acetate solution, and Mobile phase B is acetonitrile；
Linear gradient elution program: 0min, 90% mobile phase A；5min, 10% mobile phase A；10min, 10% mobile phase A；
10.1min, 90% mobile phase A；15min, 90% mobile phase A；
Mass spectrographic actual conditions are as follows: the electric spray ion source of use heating, 350 DEG C of ion source heating temperature, capillary tube temperature
Degree is 320 DEG C, sheath atmospheric pressure 30arb, assist gas pressure power 10arb；ESI positive ion mode: spray voltage 3kV, capillary electricity
Pressure is 37V, and pipe lens voltage is 100V；ESI negative ion mode: spray voltage is -2.5kV, and capillary voltage is -37V, and pipe is saturating
Mirror voltage is -100V；First mass spectrometric full scan: m/z 150~1000, resolution ratio R are 30000；Second order ms collision-induced solution
Scanned from fragment: CID normalization collision energy be 35%, Isolation width (m/z) be 2.0, ESI positive ion mode with
ESI negative ion mode acquires data respectively；
Specifically comprise the following steps:
(1) drafting of standard working curve: accurately weighing cancinogenic dye standard items, is dissolved in methanol and constant volume is prepared
It at standard reserving solution, is kept in dark place at 4 DEG C, which is diluted to the standard work of various concentration with methanol by when use
Make liquid, after the standard working solution of the various concentration is purified with the actual conditions of above-mentioned high performance liquid chromatography, then with above-mentioned mass spectrum
Actual conditions obtain standard working solution chromatographic peak, using the mass concentration x in standard working solution as abscissa, above-mentioned standard work
The area y at liquid chromatography peak is ordinate, draws standard working solution regression curve, the unit of x is mg/L, according to gained linear equation
Y=ax+b calculates slope of a curve a and intercept b；
(2) sample detection: being cut into small blade unit for sample, through methylene chloride or tetrahydrofuran ultrasonic extraction, is mentioned
Liquid is taken, by appropriate extracting solution with being dried with nitrogen, with methanol constant volume, analyte sample fluid is obtained after filter membrane, with above-mentioned efficient liquid phase
After the actual conditions purification of chromatography, the area of chromatographic peak to be measured is then obtained with above-mentioned mass spectrographic actual conditions, this is waited for into colour examining
The area of spectral peak substitutes into above-mentioned linear equation y=ax+b, according to step (2) resulting slope a and intercept b, obtains x, i.e., to be measured
The concentration of cancinogenic dye to be measured in sample liquid.
The cancinogenic dye includes solvent yellow 1, solvent yellow 2, solvent yellow 3, disperse blue 1, disperse yellow 3, Acid red 26, alkalinity
Red 9, basic violet 14, directly black 38, directly red 28, disperse orange 11 and directly blue 6.The qualitative ion pair of the cancinogenic dye and fixed
It is as shown in the table to measure ion pair:
The method for drafting of cancinogenic dye (by taking basic violet 14 as an example) solution standard curve in following embodiments are as follows: accurately weigh
The sterling type basic violet 14 standard items 66.7mg that mass fraction is 30.0% is dissolved into 100mL volumetric flask with Chromatographic Pure Methanol
And constant volume, it is configured to the standard items stock solution that concentration is 200mg/L, is placed in 4 DEG C of refrigerators and saves.Accurately pipette alkalescence purple deposit
Liquid 1.0mL is transferred in 10mL volumetric flask, and with Chromatographic Pure Methanol constant volume, purple 14 concentration of this standard items intermediate fluid neutral and alkali are
20mg/L；Suitable intermediate fluid is pipetted, is configured to the series standard that concentration is 0.05,0.1,0.2,0.5,1.0mg/L with methanol
Working solution.It is detected by above-mentioned instrument condition, with the mass concentration (x, mg/L) of basic violet 14 for abscissa, chromatographic peak face
Product (y) is ordinate, draws standard working solution regression curve (as shown in Figure 1), obtains the functional relation of standard curve are as follows: y=
4.61×106x+5.86×104, linearly dependent coefficient R2=0.9999.In addition to basic violet 14, the standard of other 11 kinds of objects
Drawing of Curve step is identical as basic violet 14.Standard curve is linearly good, can be used for the analysis of object in extracting solution.
Embodiment 1
An igelite packaging bag about 20g is taken, is cut into 0.5cm × 0.5cm or less size small pieces with scissors, it is quasi-
It really weighs and cuts sample 1g in tool cover glass bottle, the methylene chloride of 20mL is added, ultrasound 20min under room temperature.Pipette the extraction of 2mL
Liquid is dried with nitrogen at normal temperature, and residue is dissolved with methanol and constant volume is 1mL, and after filter membrane, liquid phase chromatograph-mas spectrometer is surveyed
It is fixed.Each sample is measured in parallel twice.In the content detection of 12 kinds of objects, detect containing cancinogenic dye disperse yellow 3, not
Detect other 11 kinds of cancinogenic dyes.The testing result of disperse yellow is shown in Table 1.
3 content measuring result (n=6) of cancinogenic dye disperse yellow in 1 igelite packaging bag of table
The recovery of standard addition for further investigating this detection method weighs 1g and cuts 3 parts of sample, is separately added into 0.05,0.1 and
The disperse yellow 3 of the 200mg/L of 0.5mL is used as mark-on sample, and every kind of mark-on sample prepares 3 parts in parallel.By the processing side of above-mentioned test specimens
Method processing mark-on sample, then uses high performance liquid chromatography tandem mass spectrometry analysis detection, and each sample is measured in parallel 2 times, calculates and adds
The rate of recovery is marked, the results are shown in Table 2.As shown in Table 2, the rate of recovery 93.7-109.0%, RSD of three kinds of mark-on levels be under 5%, this
Illustrate that this method accuracy and precision are more reliable.
2 recovery of standard addition measurement result (n=3) of table
| Spiked levels (mg/kg) | It measures concentration (mg/kg) | The rate of recovery (%) | RSD (%) |
| 10 | 10.51 | 105.1 | 3.36 |
| 20 | 18.74 | 93.7 | 2.18 |
| 100 | 101.8 | 101.8 | 1.05 |
Embodiment 2
A vinyon packaging bag about 20g is taken, 0.5cm × 0.5cm or less size small pieces is cut with scissors, then locates
With case 1, sample liquid measures reason through high performance liquid chromatography tandem mass spectrum instrument.In the content detection of 12 kinds of objects, detect to contain
There is cancinogenic dye solvent yellow 1, other 11 kinds of cancinogenic dyes are not detected.The testing result of solvent yellow 1 is shown in Table 3.As shown in Table 4,6
The average concentrations of Duplicate Samples dissolution Huang 1 are 5.37mg/kg, and average relative standard's deviation (RSD) is 4.68%, and precision is good
It is good.
1 content measuring result (n=6) of cancinogenic dye solvent yellow in 3 vinyon packaging bag of table
The recovery of standard addition for further investigating this detection method weighs 1g and cuts 3 parts of sample, is separately added into 0.5mL, 1mL
As mark-on sample, every kind of mark-on sample is prepared in parallel for 3 titer of disperse yellow of 1mg/L and 3 titer of 200mg/L disperse yellow of 25 μ L
3 parts.Pre-treatment step is with case 1, and with high performance liquid chromatography tandem mass spectrometry analysis detection, each sample is measured in parallel 2 times, meter
Recovery of standard addition is calculated, the results are shown in Table 4.As shown in Table 4, the rate of recovery 94.4-103.0%, RSD of three kinds of mark-on levels 5% it
Under, this illustrates that this method accuracy and precision are more reliable.
4 recovery of standard addition measurement result (n=3) of table
| Spiked levels (mg/kg) | It measures concentration (mg/kg) | The rate of recovery (%) | RSD (%) |
| 0.5 | 0.472 | 94.4 | 4.17 |
| 1.0 | 1.03 | 103.0 | 2.85 |
| 5.0 | 4.815 | 96.3 | 3.91 |
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (5)
1. the detection method of cancinogenic dye in a kind of plastic package material, it is characterised in that: use high performance liquid chromatography and mass spectrum
Combination,
The actual conditions of above-mentioned high performance liquid chromatography are as follows: chromatographic column: C18 chromatographic column；30 DEG C of column temperature；Flow velocity: 0.25mL/min；Into
Sample amount: 2 μ L；Mobile phase: according to the property of cancinogenic dye to be measured, be arranged high performance liquid chromatograph be in ESI positive ion mode or
ESI negative ion mode:
Under ESI positive ion mode, mobile phase A is the 5mmol/L ammonium acetate solution of the formic acid containing 0.02wt%, and Mobile phase B is acetonitrile；
Under ESI negative ion mode, mobile phase A is 5mmol/L ammonium acetate solution, and Mobile phase B is acetonitrile；
Linear gradient elution program: 0min, 90% mobile phase A；5min, 10% mobile phase A；10min, 10% mobile phase A；
10.1min, 90% mobile phase A；15min, 90% mobile phase A；
Above-mentioned mass spectrographic actual conditions are as follows: the electric spray ion source of use heating, 350 DEG C of ion source heating temperature, capillary tube temperature
Degree is 320 DEG C, sheath atmospheric pressure 30arb, assist gas pressure power 10arb；ESI positive ion mode: spray voltage 3kV, capillary electricity
Pressure is 37V, and pipe lens voltage is 100V；ESI negative ion mode: spray voltage is -2.5kV, and capillary voltage is -37V, and pipe is saturating
Mirror voltage is -100V；First mass spectrometric full scan: m/z 150~1000, resolution ratio R are 30 000；Second order ms collision-induced solution
Scanned from fragment: CID normalization collision energy be 35%, Isolation width (m/z) be 2.0, ESI positive ion mode with
ESI negative ion mode acquires data respectively；
Specifically comprise the following steps:
(1) drafting of standard working curve: accurately weighing cancinogenic dye standard items, is dissolved in methanol and constant volume is configured to mark
Quasi- stock solution is kept in dark place at 4 DEG C, the standard that the standard reserving solution is diluted to various concentration is worked with methanol when use
Liquid, after the standard working solution of the various concentration is purified with the actual conditions of above-mentioned high performance liquid chromatography, then with above-mentioned mass spectrographic
Actual conditions obtain standard working solution chromatographic peak, using the mass concentration x in standard working solution as abscissa, above-mentioned standard working solution
The area y of chromatographic peak is ordinate, draws standard working solution regression curve, the unit of x is mg/L, according to gained linear equation y
=ax+b calculates slope of a curve a and intercept b；
(2) sample detection: being cut into small blade unit for sample, through methylene chloride or tetrahydrofuran ultrasonic extraction, obtains extracting solution,
By appropriate extracting solution with being dried with nitrogen, with methanol constant volume, analyte sample fluid is obtained after filter membrane, with above-mentioned high performance liquid chromatography
After actual conditions purification, the area of chromatographic peak to be measured is then obtained with above-mentioned mass spectrographic actual conditions, by the chromatographic peak to be measured
Area substitutes into above-mentioned linear equation y=ax+b, according to step (2) resulting slope a and intercept b, obtains x, i.e. analyte sample fluid
In cancinogenic dye to be measured concentration.
2. detection method as described in claim 1, it is characterised in that: the cancinogenic dye includes solvent yellow 1, solvent yellow 2, molten
Agent Huang 3, disperse blue 1, disperse yellow 3, Acid red 26, alkalinity is red 9, basic violet 14, directly black 38, directly red 28,11 and of disperse orange
Directly orchid 6.
3. detection method as claimed in claim 2, it is characterised in that: the qualitative ion pair and quota ion of the cancinogenic dye
To as shown in the table:
4. detection method as described in claim 1, it is characterised in that: the concentration of the standard reserving solution in the step (2) is
200mg/L。
5. detection method as described in claim 1, it is characterised in that: the temperature of the ultrasonic extraction is room temperature, time 15
~25min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109738534A (en) * | 2019-01-10 | 2019-05-10 | 安徽省阜阳市国泰彩印包装有限公司 | A kind of color printing packing solvent method for detecting residue |
| CN113418829A (en) * | 2021-06-01 | 2021-09-21 | 厦门市产品质量监督检验院 | Method for detecting migration volume of 4, 4' -biphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108132311A (en) * | 2017-12-25 | 2018-06-08 | 上海微谱化工技术服务有限公司 | The qualitative and quantitative analysis method of disperse dyes in weaving |
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2018
- 2018-07-05 CN CN201810733409.2A patent/CN109060975A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108132311A (en) * | 2017-12-25 | 2018-06-08 | 上海微谱化工技术服务有限公司 | The qualitative and quantitative analysis method of disperse dyes in weaving |
Non-Patent Citations (1)
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| 方荣谦: "UPLC-LTQ/Orbitrap MS法测定塑料袋中35种致敏致癌染料", 《福建分析测试》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109738534A (en) * | 2019-01-10 | 2019-05-10 | 安徽省阜阳市国泰彩印包装有限公司 | A kind of color printing packing solvent method for detecting residue |
| CN113418829A (en) * | 2021-06-01 | 2021-09-21 | 厦门市产品质量监督检验院 | Method for detecting migration volume of 4, 4' -biphenol |
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Application publication date: 20181221 |