CN106990174B - SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space - Google Patents
SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space Download PDFInfo
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- CN106990174B CN106990174B CN201710092142.9A CN201710092142A CN106990174B CN 106990174 B CN106990174 B CN 106990174B CN 201710092142 A CN201710092142 A CN 201710092142A CN 106990174 B CN106990174 B CN 106990174B
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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
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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
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Abstract
The invention discloses semi-volatile organic matter (SVOC) rapid detection methods in a kind of cloth velvet sample based on full volatilization head space, include the following steps: to crush cloth velvet sample, it mixes, it places it in ml headspace bottle, acetone solvent is added, ml headspace bottle is sealed rapidly, it is placed in 44 headspace autosamplers, under the conditions of setting head space, SVOC to be measured is evaporated from sample and is quickly formed solid vapor equilibrium in bottle, the partial pressure of SVOC to be measured and its content in the sample are proportional in headspace gas at this time, it is fully transferred to gas phase or part remains in sample, gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection, it is realized by the chromatographic retention and characteristic ion of each substance qualitative, using bare substrate mark-on standard curve standard measure.SVOC rapid detection method has the advantages that easy to operate, time saving, environmental-friendly in cloth velvet sample of the present invention based on full volatilization head space.
Description
Technical field
The present invention relates to inspection and quarantine fields, volatilize more particularly in a kind of cloth velvet sample based on full volatilization head space half
Property organic matter (SVOC) rapid detection method.
Background technique
The detection of organic chemicals in cloth suede class sample, it usually needs pre-treatment is carried out to sample, on the one hand by sample
In determinand extract, on the one hand as far as possible remove impurity component, be present in determinand in cleaner extraction solution.
In common pretreatment technology, ultrasonic extraction and Solid Phase Extraction processing step are more complex, are readily incorporated error and impurity, and consume
A large amount of organic solvents；Though solid phase microextraction sensitivity is high, and more environmentally friendly, reproducibility is relatively poor.Headspace extraction technology behaviour
It is preferable to make simple, high degree of automation, reproducibility, is widely used in the multiple fields such as food, environment, medicine, weaving, especially
Volatile matter (VOC) suitable for boiling point lower than 250 DEG C detects.Head space operation temperature will be generally below the boiling point of bottle internal solvent,
So that determinand forms solution-air dynamic equilibrium in bottle.In common solvent, 100 DEG C of the boiling point of water, 153 DEG C of the boiling point of DMF.
However this has limited the detection of half volatile matter higher for boiling point (SVOC, boiling point is between 250 DEG C~400 DEG C), because
Under the conditions of low-temperature balance, the volatile quantity of half volatile matter is very little, it is difficult to detect.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of easy to operate, time saving, environmental-friendly based on full volatilization top
Semi-volatile organic matter (SVOC) rapid detection method in empty cloth velvet sample.
SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space, includes the following steps: cloth suede sample
Product crush, mix, place it in ml headspace bottle, be added acetone solvent, ml headspace bottle is sealed rapidly, be placed in 44 head spaces automatically into
Sample device, under the conditions of setting head space, SVOC to be measured is evaporated from sample and is quickly formed solid vapor equilibrium in bottle, at this time
The partial pressure of SVOC to be measured and its content in the sample are proportional in headspace gas, are fully transferred to gas phase or part residual
In sample, gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection, passes through the chromatographic retention of each substance
It is qualitative with characteristic ion realization, using bare substrate mark-on standard curve standard measure.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein the method
Specifically comprise the following steps: for cloth velvet sample to be crushed to partial size less than 2mm, mixes, accurately weigh 20mg sample, be accurate to
0.1mg is placed it in 20mL ml headspace bottle, and 20 μ L acetone solvents are added, rapidly seals ml headspace bottle, it is automatic to be placed in 44 head spaces
Sample injector, under the conditions of setting head space, SVOC to be measured is evaporated from sample and is quickly formed solid vapor equilibrium in bottle.This
When headspace gas in SVOC to be measured partial pressure and its content in the sample it is proportional, be fully transferred to gas phase or part be residual
It stays in sample, 1mL gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection, protected by the chromatography of each substance
Time and characteristic ion is stayed to realize qualitative, using bare substrate mark-on standard curve standard measure.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein gas-chromatography-
Mass spectroscopy condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, with 5 DEG C/min rate rises to 210 DEG C after keeping 1min, then with 10 DEG C/
Min rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay: 6min.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein headspace sampling
The head space condition of device is set are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 150~200 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 160~210 DEG C, and the equilibrium temperature than setting is 10 DEG C high；
Transmission line temperature: 170~220 DEG C, and the quantitative loop temperature than setting is 10 DEG C high；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein described to be measured
SVOC is 8 kinds of aromatic, specially allyl isothiocyanate, (R)-4-isopropenyl-1-methyl-1-cyclohexene, anise alcohol, eugenol, hexahydro cumarin, the lily of the valley
Aldehyde, 1- (4- anisyl) -1- penten-3-one and hydroabietyl alcohol.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein gas-chromatography-
Mass spectroscopy condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, with 5 DEG C/min rate rises to 210 DEG C after keeping 1min, then with 10 DEG C/
Min rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition setting are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 200 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 210 DEG C；
Transmission line temperature: 220 DEG C；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, wherein 8 kinds of virtues
The CAS number of pastil, purity, chromatography and mass spectrometry parameters are as shown in table 1:
CAS number, purity, chromatography and the mass spectrometry parameters of 1. 8 kinds of aromatic of table
* quota ion.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, further includes standard solution
Preparation: weigh the standard items 0.1g of each aromatic into 25ml brown volumetric flask, be accurate to 0.1mg, acetone constant volume, respectively
Each substance list mark stock solution for being 4mg/mL to concentration, is placed in 4 DEG C and is kept in dark place, and marks stock solution configuration concentration using single
8 kinds of material mixing stock solutions of 300mg/L are diluted in use, drawing appropriate Standard Stock solutions as needed with acetone
The working solution of respective concentration.
The present invention is based on SVOC rapid detection method differences from prior art in the cloth velvet sample of full volatilization head space to exist
In: the present invention is based in SVOC rapid detection method in the cloth velvet sample of full volatilization head space, cloth suede class sample is not extracted, directly
It is placed in ml headspace bottle, minim organic solvent is added, at a higher temperature, solvent instantaneously vaporizes, and test substance is fast in bottle
Speed reaches solid vapor equilibrium, and the concentration of substance and its content in the sample are proportional in headspace gas at this time.Pass through measurement
Its content in the sample can be obtained in material concentration in gas in turn.Since operation temperature is higher, SVOC volatile quantity in sample
Larger, detection sensitivity is high, to realize the purpose of SVOC in quick, highly sensitive test sample.
There are three the significant advantages of aspect for method tool of the invention: easy to operate (to hardly need before carrying out any sample
Processing, such as ultrasonic extraction, Solid Phase Extraction)；It is time saving that (single sample processing only needs 5min, when headspace autosampler carries out
Multiple samples do not need to expend sample processing time, it can be achieved that continuous sample introduction is analyzed when overlapping sample introduction automatically)；Environmental-friendly (point
Analyse a sample, it is only necessary to consume 20mg sample and 20 μ L organic solvents).The foundation of method of the invention is for cloth suede and weaving
The detection of SVOC has important reference in class sample, is conducive to significantly improve associated sample detection efficiency.
With reference to the accompanying drawing to SVOC rapid detection method in the cloth velvet sample of the invention based on full volatilization head space make into
One step explanation.
Detailed description of the invention
Fig. 1 is influence of the quantity of solvent to substance responds value in the present invention；
Fig. 2 is influence of the head space equilibrium temperature to substance responds value in the present invention；
Fig. 3 is influence of the head space equilibration time to substance responds value in the present invention；
Fig. 4 is that head space assists influence of the gas moulding pressure to substance responds value in the present invention；
Fig. 5 is influence of the different sample substrates for aromatic response in the present invention；
Fig. 6 is to extract to detect positive sample Comparative result with ultrasonic extraction two ways using head space in the present invention；
Fig. 7 is the total ion chromatogram of sample S2 and the extraction chromatography of ions figure of detection substance in the present invention；
All substances serial number in FIG. 1 to FIG. 6 of the present invention is the same as table 1.
Specific embodiment
Embodiment 1
SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space, includes the following steps: cloth suede sample
Product are crushed to partial size less than 2mm, mix, accurately weigh 20mg sample, be accurate to 0.1mg, place it in 20mL ml headspace bottle, add
Enter 20 μ L acetone solvents, rapidly seal ml headspace bottle, is placed in 44 headspace autosamplers, it is to be measured under the conditions of setting head space
SVOC is evaporated from sample and is quickly formed solid vapor equilibrium in bottle.At this time in headspace gas the partial pressure of SVOC to be measured with
Its content in the sample is proportional, is fully transferred to gas phase or part remains in sample, by 1mL gas in quantitative loop
It is introduced to gas chromatograph-mass spectrometer and realizes detection, qualitative, use is realized by the chromatographic retention and characteristic ion of each substance
Bare substrate mark-on standard curve standard measure.
Gas Chromatography-Mass Spectrometry condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, with 5 DEG C/min rate rises to 210 DEG C after keeping 1min, then with 10 DEG C/
Min rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min.
The head space condition of head-space sampler is set are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 150~200 DEG C；(depending on suitable boiling point substance and volatility, highest can be to the head space instrumentation upper limit)
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 160~210 DEG C, and the equilibrium temperature than setting is 10 DEG C high；
Transmission line temperature: 170~220 DEG C, and the quantitative loop temperature than setting is 10 DEG C high；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, further includes standard solution
Preparation: weigh the standard items 0.1g of each SVOC to be measured into 25ml brown volumetric flask, be accurate to 0.1mg, acetone constant volume, respectively
Each substance list mark stock solution that concentration is 4mg/mL is obtained, 4 DEG C is placed in and is kept in dark place, configures each object using single mark stock solution
Matter mixes stock solution and is diluted to the work of respective concentration with acetone in use, drawing appropriate Standard Stock solutions as needed
Solution.
Embodiment 2
SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space, includes the following steps: cloth suede sample
Product are crushed to partial size less than 2mm, mix, accurately weigh 20mg sample, be accurate to 0.1mg, place it in 20mL ml headspace bottle, add
Enter 20 μ L acetone solvents, rapidly seal ml headspace bottle, is placed in 44 headspace autosamplers, it is to be measured under the conditions of setting head space
SVOC is evaporated from sample and is quickly formed solid vapor equilibrium in bottle.At this time in headspace gas the partial pressure of SVOC to be measured with
Its content in the sample is proportional, is fully transferred to gas phase or part remains in sample, by 1mL gas in quantitative loop
It is introduced to gas chromatograph-mass spectrometer and realizes detection, qualitative, use is realized by the chromatographic retention and characteristic ion of each substance
Bare substrate mark-on standard curve standard measure.
Gas Chromatography-Mass Spectrometry condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, with 5 DEG C/min rate rises to 210 DEG C after keeping 1min, then with 10 DEG C/
Min rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min.
The head space condition of head-space sampler is set are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 150 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 160 DEG C；
Transmission line temperature: 170 DEG C；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
SVOC rapid detection method in cloth velvet sample of the present invention based on full volatilization head space, further includes standard solution
Preparation: weigh the standard items 0.1g of each SVOC to be measured into 25ml brown volumetric flask, be accurate to 0.1mg, acetone constant volume, respectively
Each substance list mark stock solution that concentration is 4mg/mL is obtained, 4 DEG C is placed in and is kept in dark place, configures each object using single mark stock solution
Matter mixes stock solution and is diluted to the work of respective concentration with acetone in use, drawing appropriate Standard Stock solutions as needed
Solution.
Embodiment 3
The difference from embodiment 1 is that in the head space condition of head-space sampler:
Equilibrium temperature: 180 DEG C；
Quantitative loop temperature: 190 DEG C；
Transmission line temperature: 200 DEG C；
The other the same as in Example 1.
Embodiment 4
By taking the detection of 8 kinds of fragrance materials in cotton flannel toy sample as an example, detection method is illustrated.
1, sample pre-treatments
Cloth velvet sample is crushed to partial size less than 2mm, is mixed.20mg sample (being accurate to 0.1mg) is accurately weighed, is set
In 20mL ml headspace bottle, be added 20 μ L acetone solvents, rapidly by ml headspace bottle sealing (aluminum bottle cover band PTFE/silicon seal every
Pad), it is placed in 44 headspace autosamplers.Under the conditions of setting head space, aromatic evaporates and fast in bottle from sample
Speed forms solid vapor equilibrium.At this time in headspace gas the partial pressure of fragrance materials with its content in the sample is proportional (can
Can be fully transferred to gas phase, it is also possible to partially remain in sample).1mL gas in quantitative loop is introduced to GC-MS and realizes inspection
It surveys.It is qualitative by chromatographic retention and the characteristic ion realization of each substance, using bare substrate mark-on standard curve standard measure.
2, instrumentation condition
Gas Chromatography-Mass Spectrometry condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, with 5 DEG C/min rate rises to 210 DEG C after keeping 1min, then with 10 DEG C/
Min rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition setting are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 200 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 210 DEG C；
Transmission line temperature: 220 DEG C；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
3, standard items and solution
The standard items of 8 kinds of aromatic are bought from different suppliers, and specifying information includes CAS number, purity and gas phase
Chromatographic mass spectrometry parameter etc. is listed in Table 1 below.The standard items 0.1g (being accurate to 0.1mg) of each substance is weighed to 25ml brown volumetric flask
In, acetone constant volume respectively obtains each substance list mark stock solution that concentration is 4mg/mL, is placed in 4 DEG C and is kept in dark place.Utilize single mark
8 kinds of material mixing stock solutions of stock solution configuration concentration 300mg/L.In use, drawing appropriate standard inventory as needed
Solution is diluted to the working solution of respective concentration with acetone.
4, the title of 8 kinds of aromatic, CAS number, purity, chromatography and mass spectrometry parameters are as shown in table 1:
CAS number, purity, chromatography and the mass spectrometry parameters of 1. 8 kinds of aromatic of table
* quota ion.
Comparative example:
Traditional ultrasonic extracting method:
Sample comminution to partial size is less than 2mm.0.1g sample (being accurate to 0.1mg) is accurately weighed, 25mL cone is placed it in
In shape bottle, 5mL acetone is added as Extraction solvent, stoppers bottle stopper, sealed membrane seals, at room temperature ultrasonic extraction 20min.Absorption mentions
Supernatant in liquid is taken, is crossed after 0.45 μm of micropore PTFE filter membrane for Gas Chromatography-Mass Spectrometry.When extracting solution color is deeper, need
Envi-carb graphitized carbon solid phase extraction column wanted to be purified.
Solid phase extraction process is as follows: using 5mL methanol rinses Envi-carb graphitized carbon solid phase extraction column, will mention
Clear solution in liquid is taken to cross column, the elution of 10mL methanol collects all column liquid of crossing in chicken heart bottle.By solution in 10kPa, 35 DEG C
Under the conditions of revolving to 4mL or so, be transferred in nitrogen blowpipe with a scale, then rinse chicken heart bottle with proper amount of acetone, be incorporated into nitrogen
In blowpipe, it is settled to 5mL (such as solution is more than 5mL, can be blown to slow nitrogen stream less than 5mL, be settled to 5mL).By solution
It crosses after 0.45 μm of micropore PTFE filter membrane for Instrument measuring.
The method of the present invention is to every head space parameter, such as head space solvent volume, equilibrium temperature, equilibration time, auxiliary gas pressurization
Pressure carries out carefully optimization to reach higher sensitivity.Different sample substrates has been investigated for the interference feelings of testing result
Condition, the results showed that sample substrate influences detection unobvious.By the method established of the present invention and traditional ultrasonic extraction into
Row comparison, discovery testing result is consistent, and the method for the present invention various aspects are better than conventional ultrasound extractive technique.Method of the invention will
There is important reference to the detection of SVOC in cloth suede and textile sample.
Results and discussion:
1, GC-MS condition optimizing
Take by single mark working solution of every kind of substance carried out under full scan Scan mode one by one sample introduction to be determined
Chromatographic peak elution order and retention time.Several characteristic ions of each target substance can be obtained simultaneously, respectively as it is qualitative from
Son and quota ion.All substances are considered with kurtosis simultaneously compared with the strong and larger two aspects factor of karyoplasmic ratio, selection is suitable
Ion is as quota ion and qualitative ion.Chromatography and mass spectrometry parameters are specifically shown in Table 1.
2, the optimization of head space condition
For quantitative analysis, obtain higher extraction efficiency be it is critically important, i.e., determinand is nearly completely by sample
Product are transferred to head space.Therefore, head space operating parameter should be investigated carefully.To extract self-control cloth suede positive sample (by 2g sample
8 kinds of substances for being placed in 100mL 30mg/L mix entirely to be impregnated in acetone soln, is taken out after vibrating 3h in natural air drying in ventilating kitchen) in
For 6 kinds of aromatic allyl isothiocyanates, (R)-4-isopropenyl-1-methyl-1-cyclohexene, eugenol, hexahydro cumarin, lilial and hydroabietyl alcohol, ginseng
Number optimization process is as follows.
(1) influence of quantity of solvent
Using calibration curve method quantified when, a certain amount of standard solution is inevitably added in ml headspace bottle, into
Row actual sample when measuring is also required to that a certain amount of solvent is added in the sample, to keep the consistency of environmental system with standard curve
To obtain accurate quantitative result.In theory, solvent cannot reach in a closed bottle absolutely volatilizees completely,
Even environment temperature is higher than its boiling point.But it for micro solvent (< 100 μ L), can be obtained at a relatively high temperature
Almost complete volatilization.The volatilization of solvent will affect the pressure in bottle, though it is foreseeable that with the increase of quantity of solvent, bottle internal pressure
Power increases, this will make the partial pressure of determinand in bottle become smaller, and then deterioration of sensitivity, may cause ml headspace bottle what is more and collapse
It splits.In this research, equilibrium temperature, equilibration time and moulding pressure are fixed as 200 DEG C, 20min and 70kPa, are placed in advance
Different amounts of acetone solvent (0~100 μ L) is added in the ml headspace bottle of 20mg positive sample, to investigate quantity of solvent to each substance responds
Influence.The result shows that, with the increase of quantity of solvent, each substance peak area shows downward trend in Fig. 1, and 20 μ L is selected to use
Amount carries out follow-up study, and relatively satisfactory sensitivity not only can be obtained, be also convenient for that liquid is taken to operate.
(2) influence of equilibrium temperature
Equilibrium temperature for method sensitivity have important influence because its directly determine aromatic from sample to
Volatile quantity in headspace gas.Typically, the higher release for aromatic of temperature and quickly to form dynamic equilibrium be more to have
Benefit, but the tolerable temperature of head space is limited, and seals dottle pin and transmission line especially for bottle.Equilibration time and pressurization pressure
Power is set to 20min and 70kPa, investigates 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C of equilibrium temperature.By result
As it can be seen that substance lower for boiling point (No. 1 and No. 2 substances, boiling point are respectively 151 DEG C and 177 DEG C), peak area does not almost have Fig. 2
Change, and substance higher for boiling point (especially No. 8 substances, 375.5 DEG C of boiling point), peak area with temperature increase by
It is cumulative big, reach high value at 200 DEG C.In order to which ensuring method has higher sensitivity to all substances, temperature is set to
200℃。
(3) influence of equilibration time
Equilibration time is that head space balances another important parameter, it is related to that substance is put down in the two alternate dynamics that whether reach
Weighing apparatus.Traditional Static Headspace equilibration time is generally longer, in this method, micro solvent transient evaporation under 200 DEG C of high temperature,
Stable air pressure is formed in bottle, this is conducive to fragrance materials and is rapidly reached balance.As seen from Figure 3, when equilibrium temperature and pressurization
When pressure is set to 200 DEG C and 70kPa, each substance peak area changes smaller between 5min to 20min, it is meant that head space balances very
It can realize fastly.When the time being greater than 20min, peak area is in reduction trend as time increases, it may be possible to due to head space
Bottle through a long time baking air-tightness starts the reason being deteriorated.Equilibration time is finally set to 5min.
(4) influence of moulding pressure
Insufficient pressure in ml headspace bottle is to be full of quantitative loop, it usually needs adds additional auxiliary gas (He gas or N2Gas),
And gas is assisted to will affect the partial pressure of aromatic in bottle namely its concentration in the gas phase.Equilibrium temperature and time are fixed herein
Under the conditions of 200 DEG C and 10min, the influence that moulding pressure responds aromatic is investigated.Based on The Ideal-Gas Equation PV=
NRT, P are the partial pressure that acetone generates, unit Pa；V is bottle body product, unit m3；N is the amount of substance, unit mol；R is that gas is normal
Number, 8.314J/ (mol*K)；T is thermodynamic temperature, unit K.When acetone volume is 20 μ L, n=20 μ L × 0.788g mL-1
(density of acetone at 25 DEG C) ÷ 58.08g mol-1=0.0002713mol, T=473K, V=20mL acquires P and is approximately equal to
53kPa (judges its actual value in 60~70kPa) by subsequent result.
From fig. 4, it can be seen that the peak area of aromatic gradually increases, especially when moulding pressure increases to 70kPa by 50kPa
It is for high boiling substance (No. 5, No. 6 and No. 8 substances).Speculate that reason is that can produce when moulding pressure is less than the pressure in the bottle
Raw suck-back phenomenon causes material concentration in bottle to reduce.When moulding pressure increases to 110kPa by 70kPa, the response of each substance
Value is obviously gradually reduced, this may be to cause the partial pressure of test substance in bottle to become smaller since too many auxiliary gas introduces, thus ring
It should be worth and become smaller.From the experimental results, 70kPa is optimal moulding pressure for all substances.
(5) investigation of matrix interference
In order to investigate influence of the different sample substrates for testing result, 5 sections of polyester fiber cotton flannel toys are randomly choosed
Sample (the cotton flannel toy sample material overwhelming majority is polyester fiber), 8 kinds of material mixing standards that 20 μ L 60mg/L are added are molten
Liquid, and be measured using the Parameter Conditions of optimization.As seen from Figure 5, testing result is influenced smaller, different substrates by sample substrate
Testing result deviation it is unobvious, thus it is speculated that this is mainly due to aromatic to form stable gas-solid equilibrium in bottle, when cloth suede sample
When kind class is consistent, this gas-solid equilibrium environment is consistent, thus will not have an impact to the distribution of the concentration of determinand.Therefore in reality
In the sample detection of border, the accuracy that can quantitatively guarantee testing result is carried out using bare substrate mark-on calibration curve method.
(6) head space and ultrasonic testing results compare
The method of foundation and classical ultrasonic extraction are compared further to investigate its accuracy.By homemade two
The positive sample of a distinct fragrance agent content is extracted with two kinds of extracting modes, GC-MS detection.As seen from Figure 6, it mentions for two kinds
It takes the testing result of mode very close, is consistent, it was demonstrated that the testing result of this method is accurate.It can also find out, head space
The relative standard deviation of technology is smaller (n=5), and repeatability is slightly better than ultrasonic extraction.For two methods, ultrasonic extraction consumption
A large amount of organic solvent, takes a long time, and generates biggish noise and harmful Ultrasonic Radiation, in addition if extract liquor color
Also need to carry out more complicated Solid phase extraction operation if heavier.And before head space extraction method does not need complicated sample
Reason, it is easy to operate, the time is saved, and only need to expend minim organic solvent, it is more environmentally friendly.Therefore, for cloth velvet sample
The detection of middle VOC and SVOC substance, head space extraction method various aspects are better than ultrasonic extraction.
(7) methodological study
Under the chromatographic condition of setting, standard working solution is successively measured from low to high by concentration, with what is obtained
The peak area of quantitative ion chromatography peak is ordinate, and the sample introduction concentration of corresponding each substance is abscissa mapping, draws standard work
Make curve.The result shows that each substance, in 0.2~300mg/kg of its range of linearity, concentration value has good linear with peak area
Relationship, linearly dependent coefficient are all larger than 0.9984.Corresponding content of material is as quantitatively when using response signal greater than 10 times of noise
Limit, obtains 0.02~1.0mg/kg of quantitative limit of each substance.The quantitative limit of all substances is far below European Union 2009/48/EC and refers to
Limitation (100mg/kg) in order.We set 3 addition concentration for every kind of substance, by experiment item determined by this method
Part repeats 6 tests to each addition concentration.As can be seen from the results, method is for the rate of recovery of different material 88.6%
Between~123.5%, relative standard deviation (RSD) is between 1.1%~9.1%.Specific data are shown in Table 2.
The TIANZHU XINGNAO Capsul and relative standard deviation (n=6) of 2. 8 kinds of aromatic of table
(8) actual sample is analyzed
Using this method, 20 kinds of commercially available cotton flannel toy samples are measured.In these samples, S2
Sample detects eugenol and hexahydro cumarin, content are respectively 10mg/kg and 6mg/kg；S6 sample detects hexahydro cumarin, contains
Measure 263.6mg/kg；S9 sample detects eugenol, content 23.4mg/kg；S13 sample detects eugenol, content 2.3mg/kg.Its
Excess matter is not detected.Fig. 7 gives the total ion chromatogram of sample S2 and detects the extraction chromatography of ions figure of substance.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (6)
1. SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space, characterized by the following steps:
Cloth velvet sample is crushed, mixes, places it in ml headspace bottle, acetone solvent is added, ml headspace bottle is sealed rapidly, is placed in 44 tops
Gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection by empty autosampler, is retained by the chromatography of each substance
Time and characteristic ion realization are qualitative, using bare substrate mark-on standard curve standard measure；
The head space condition of head-space sampler is set are as follows:
Instrument configuration: 86.50 headspace autosampler of DANI, 44；
Equilibrium temperature: 150~200 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 160~210 DEG C, and the equilibrium temperature than setting is 10 DEG C high；
Transmission line temperature: 170~220 DEG C, and the quantitative loop temperature than setting is 10 DEG C high；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s；
Gas Chromatography-Mass Spectrometry condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, rises to 210 DEG C after holding 1min with 5 DEG C/min rate, then with 10 DEG C/min speed
Rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min.
2. SVOC rapid detection method in the cloth velvet sample according to claim 1 based on full volatilization head space, feature exist
In: the method specifically comprises the following steps: for cloth velvet sample to be crushed to partial size less than 2mm, mixes, accurately weighs 20mg sample
Product are accurate to 0.1mg, place it in 20mL ml headspace bottle, and 20 μ L acetone solvents are added, rapidly seals ml headspace bottle, is placed in 44
1mL gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection, passes through each substance by position headspace autosampler
Chromatographic retention and characteristic ion realization are qualitative, using bare substrate mark-on standard curve standard measure.
3. SVOC rapid detection method in the cloth velvet sample according to claim 2 based on full volatilization head space, feature exist
In: SVOC to be measured is 8 kinds of aromatic, specially allyl isothiocyanate, (R)-4-isopropenyl-1-methyl-1-cyclohexene, anise alcohol, eugenol, hexahydro tonka-bean
Element, lilial, 1- (4- anisyl) -1- penten-3-one and hydroabietyl alcohol.
4. SVOC rapid detection method in the cloth velvet sample according to claim 3 based on full volatilization head space, feature exist
In:
Gas Chromatography-Mass Spectrometry condition is as follows:
Instrument configuration: Agilent 6890-5975 gas chromatograph-mass spectrometer；
Capillary chromatographic column: Agilent DB-35MS capillary column, 30m × 0.25mm × 0.25 μm；
Temperature programming: initial temperature is 40 DEG C, rises to 210 DEG C after holding 1min with 5 DEG C/min rate, then with 10 DEG C/min speed
Rate rises to 300 DEG C；
Carrier gas: high-purity helium, flow velocity 1.0mL/min；
Injector temperature: 280 DEG C；
Sample introduction mode: Splitless injecting samples；
Detector: level four bars mass spectrum；
Ionization mode: EI；
Ionizing energy: 70eV；
Monitoring mode: Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition setting are as follows:
Instrument configuration: DANI86.50 headspace autosampler, 44；
Equilibrium temperature: 200 DEG C；
Equilibration time: 5min；
Assist gas moulding pressure: 70kPa；
Quantitative loop temperature: 210 DEG C；
Transmission line temperature: 220 DEG C；
Pressing time: 10s；
Quantitative loop volume: 1mL；
Quantitative loop equilibration time: 10s；
Sample injection time: 20s.
5. SVOC rapid detection method in the cloth velvet sample according to claim 4 based on full volatilization head space, feature exist
It is as shown in table 1 in the CAS number of: 8 kinds of aromatic, purity, chromatography and mass spectrometry parameters:
CAS number, purity, chromatography and the mass spectrometry parameters of 1. 8 kinds of aromatic of table
* quota ion.
6. SVOC rapid detection method in the cloth velvet sample according to claim 5 based on full volatilization head space, feature exist
In: further include the preparation of standard solution: weighing the standard items 0.1g of each aromatic into 25ml brown volumetric flask, be accurate to
0.1mg, acetone constant volume respectively obtain each substance list mark stock solution that concentration is 4mg/mL, are placed in 4 DEG C and are kept in dark place, utilize
8 kinds of material mixing stock solutions of single mark stock solution configuration concentration 300mg/L, in use, drawing appropriate standard as needed
Stock solution is diluted to the working solution of respective concentration with acetone.
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| CN114487248A (en) * | 2020-10-27 | 2022-05-13 | 天津市职业大学 | Method for measuring total volatile organic compounds in disposable mask |
| CN112557564B (en) * | 2020-12-09 | 2021-10-22 | 苏州博莱特新材料有限公司 | Method for determining content of benzene solvent in solvent type acrylate adhesive |
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| CN114814031A (en) * | 2022-04-29 | 2022-07-29 | 中国检验检疫科学研究院 | High-sensitivity environment-friendly detection method for 14 chemical substances in medical mask |
| CN115166069B (en) * | 2022-06-13 | 2024-04-19 | 徐州市检验检测中心 | Detection method and application of migration quantity of volatile organic compounds in water toy |
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