CN106990174A - SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space - Google Patents
SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space Download PDFInfo
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- CN106990174A CN106990174A CN201710092142.9A CN201710092142A CN106990174A CN 106990174 A CN106990174 A CN 106990174A CN 201710092142 A CN201710092142 A CN 201710092142A CN 106990174 A CN106990174 A CN 106990174A
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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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- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
Abstract
The invention discloses semi-volatile organic matter (SVOC) quick determination method in a kind of cloth velvet sample based on full volatilization head space, comprise the following steps：Cloth velvet sample is crushed, mix, it is placed in ml headspace bottle, add acetone solvent, 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 and the quick formation gas-solid equilibrium in bottle from sample, now SVOC to be measured partial pressure and its content in the sample are proportional in headspace gas, it is fully transferred to gas phase or part is residued in sample, gas in quantitative loop is introduced to gas chromatography mass spectrometer and realizes detection, realized by the chromatographic retention and characteristic ion of each material qualitative, using bare substrate mark-on standard curve standard measure.SVOC quick determination methods have the advantages that simple to operate, time saving, environment-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 field, half volatilizees in more particularly to a kind of cloth velvet sample based on full volatilization head space
Property organic matter (SVOC) quick determination method.
Background technology
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 remove impurity component as far as possible, determinand is present in cleaner extraction solution.
In conventional pretreatment technology, ultrasonic extraction and SPE process step are more complicated, are readily incorporated error and impurity, and consumption
A large amount of organic solvents；Though SPME sensitivity is high, again relatively more environmentally friendly, reappearance is relatively poor.Headspace extraction technology is grasped
Make simple, automaticity height, reappearance preferably, be widely used in the multiple fields such as food, environment, medicine, weaving, especially
Volatile matter (VOC) suitable for boiling point less than 250 DEG C is detected.Head space operation temperature will be generally below the boiling point of bottle internal solvent,
To cause determinand to form solution-air dynamic equilibrium in bottle.In common solvent, 100 DEG C of the boiling point of water, 153 DEG C of DMF boiling point.
But this has limited the detection for half higher volatile matter of 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.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of simple to operate, time saving, environment-friendly based on full volatilization top
Semi-volatile organic matter (SVOC) quick determination method in empty cloth velvet sample.
SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space, comprise the following steps：By cloth suede sample
Product are crushed, and are mixed, are placed in ml headspace bottle, are added acetone solvent, are rapidly sealed ml headspace bottle, be placed in 44 head spaces and enter automatically
Sample device, under the conditions of setting head space, SVOC to be measured is evaporated and the quick formation solid vapor equilibrium in bottle from sample, now
SVOC to be measured partial pressure and its content in the sample are proportional in headspace gas, be fully transferred to gas phase or part is remained
In sample, gas in quantitative loop is introduced to gas chromatograph-mass spectrometer and realizes detection, passes through the chromatographic retention of each material
Realized with characteristic ion it is qualitative, using bare substrate mark-on standard curve standard measure.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, wherein, methods described
Specifically include following steps：Cloth velvet sample is crushed to particle diameter less than 2mm, is mixed, is accurately weighed 20mg samples, be accurate to
0.1mg, is placed in 20mL ml headspace bottles, adds 20 μ L acetone solvents, rapidly seals ml headspace bottle, be placed in 44 head spaces automatic
Injector, under the conditions of setting head space, SVOC to be measured is evaporated and the quick formation solid vapor equilibrium in bottle from sample.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
Stay in sample, 1mL gases in quantitative loop are introduced into gas chromatograph-mass spectrometer realizes detection, is protected by the chromatogram of each material
Time and characteristic ion is stayed to realize qualitative, using bare substrate mark-on standard curve standard measure.
SVOC quick determination methods 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 spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature be 40 DEG C, keep 1min after rise to 210 DEG C with 5 DEG C/min speed, then with 10 DEG C/
Min speed rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar mass spectrum；
Ionization mode：EI；
Ionizing energy：70eV；
Monitoring mode：Scan and SIM；
Solvent delay：6min.
SVOC quick determination methods 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 as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：150~200 DEG C；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：160~210 DEG C, and it is higher 10 DEG C than the equilibrium temperature set；
Transmission line temperature：170~220 DEG C, and it is higher 10 DEG C than the quantitative loop temperature set；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, wherein, it is 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- anisyls) -1- penten-3-ones and hydroabietyl alcohol.
SVOC quick determination methods 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 spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature be 40 DEG C, keep 1min after rise to 210 DEG C with 5 DEG C/min speed, then with 10 DEG C/
Min speed rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar mass spectrum；
Ionization mode：EI；
Ionizing energy：70eV；
Monitoring mode：Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition is set as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：200℃；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：210℃；
Transmission line temperature：220℃；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, wherein, 8 kinds of virtues
The CAS numberings of pastil, purity, chromatogram and mass spectrometry parameters are as shown in table 1：
The CAS numberings, purity, chromatogram and mass spectrometry parameters of 1. 8 kinds of aromatic of table
* quota ion.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, in addition to standard liquid
Preparation：The standard items 0.1g of each aromatic is weighed into 25ml brown volumetric flasks, 0.1mg is accurate to, acetone constant volume is obtained respectively
To each material list mark stock solution that concentration is 4mg/mL, it is placed in 4 DEG C and is kept in dark place, stock solution configuration concentration is marked using single
300mg/L 8 kinds of material mixing stock solutions, in use, drawing appropriate Standard Stock solutions as needed, are diluted to acetone
The working solution of respective concentration.
SVOC quick determination method differences from prior art exist in cloth velvet sample of the present invention based on full volatilization head space
In：In cloth velvet sample of the present invention based on full volatilization head space in SVOC quick determination methods, cloth suede class sample is not extracted, directly
It is positioned in ml headspace bottle, adds minim organic solvent, at a higher temperature, solvent is instantaneously vaporized, test substance is fast in bottle
Speed reaches solid vapor equilibrium, and now the concentration of material and its content in the sample are proportional in headspace gas.By determining
Material concentration in gas and then it can obtain its content in the sample.Because operation temperature is higher, SVOC volatile quantities in sample
Larger, detection sensitivity is high, so as to realize the purpose of SVOC in quick, highly sensitive detection sample.
The method of the present invention has the significant advantage of three aspects：It is simple to operate (with little need for carrying out before any sample
Processing, such as ultrasonic extraction, SPE)；It is time saving that (single sample processing only needs to 5min, when headspace autosampler is carried out
Multiple samples need not expend sample processing time when overlapping sample introduction automatically, and continuous sample introduction analysis can be achieved)；Environment-friendly (point
Analyse a sample, it is only necessary to consume 20mg samples and 20 μ L organic solvents).The foundation of the method for the present invention is for cloth suede and weaving
SVOC detection has important reference in class sample, is conducive to significantly improving associated sample detection efficiency.
SVOC quick determination methods in the cloth velvet sample based on full volatilization head space of the present invention are made below in conjunction with the accompanying drawings into
One step explanation.
Brief description of the drawings
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 influence of the head space auxiliary 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 detects positive Comparative result to be extracted in the present invention using head space with ultrasonic extraction two ways；
Fig. 7 is the total ion chromatogram of sample S2 in the present invention and the extraction chromatography of ions figure of detection material；
All substances sequence number in Fig. 1~Fig. 6 of the present invention is with table 1.
Embodiment
Embodiment 1
SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space, comprise the following steps：By cloth suede sample
Product are crushed to particle diameter less than 2mm, mix, accurately weigh 20mg samples, be accurate to 0.1mg, be placed in 20mL ml headspace bottles, plus
Enter 20 μ L acetone solvents, rapidly seal ml headspace bottle, be placed in 44 headspace autosamplers, it is to be measured under the conditions of setting head space
SVOC is evaporated and the quick formation solid vapor equilibrium in bottle from sample.Now in headspace gas SVOC to be measured partial pressure with
Its content in the sample is proportional, is fully transferred to gas phase or part is residued in sample, by 1mL gases 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 material
Bare substrate mark-on standard curve standard measure.
Gas Chromatography-Mass Spectrometry condition is as follows：
Instrument configuration：Agilent 6890-5975 gas chromatograph-mass spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature be 40 DEG C, keep 1min after rise to 210 DEG C with 5 DEG C/min speed, then with 10 DEG C/
Min speed rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar 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 as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
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；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：160~210 DEG C, and it is higher 10 DEG C than the equilibrium temperature set；
Transmission line temperature：170~220 DEG C, and it is higher 10 DEG C than the quantitative loop temperature set；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, in addition to standard liquid
Preparation：Each SVOC to be measured standard items 0.1g is weighed into 25ml brown volumetric flasks, 0.1mg, acetone constant volume, difference is accurate to
Each material list mark stock solution that concentration is 4mg/mL is obtained, 4 DEG C is placed in and is kept in dark place, each thing is configured using single mark stock solution
Matter mixes stock solution, in use, drawing appropriate Standard Stock solutions as needed, the work of respective concentration is diluted to acetone
Solution.
Embodiment 2
SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space, comprise the following steps：By cloth suede sample
Product are crushed to particle diameter less than 2mm, mix, accurately weigh 20mg samples, be accurate to 0.1mg, be placed in 20mL ml headspace bottles, plus
Enter 20 μ L acetone solvents, rapidly seal ml headspace bottle, be placed in 44 headspace autosamplers, it is to be measured under the conditions of setting head space
SVOC is evaporated and the quick formation solid vapor equilibrium in bottle from sample.Now in headspace gas SVOC to be measured partial pressure with
Its content in the sample is proportional, is fully transferred to gas phase or part is residued in sample, by 1mL gases 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 material
Bare substrate mark-on standard curve standard measure.
Gas Chromatography-Mass Spectrometry condition is as follows：
Instrument configuration：Agilent 6890-5975 gas chromatograph-mass spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature be 40 DEG C, keep 1min after rise to 210 DEG C with 5 DEG C/min speed, then with 10 DEG C/
Min speed rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar 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 as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：150℃；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：160℃；
Transmission line temperature：170℃；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
SVOC quick determination methods in cloth velvet sample of the present invention based on full volatilization head space, in addition to standard liquid
Preparation：Each SVOC to be measured standard items 0.1g is weighed into 25ml brown volumetric flasks, 0.1mg, acetone constant volume, difference is accurate to
Each material list mark stock solution that concentration is 4mg/mL is obtained, 4 DEG C is placed in and is kept in dark place, each thing is configured using single mark stock solution
Matter mixes stock solution, in use, drawing appropriate Standard Stock solutions as needed, the work of respective concentration is diluted to acetone
Solution.
Embodiment 3
Difference with embodiment 1 is, in the head space condition of head-space sampler：
Equilibrium temperature：180℃；
Quantitative loop temperature：190℃；
Transmission line temperature：200℃；
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.
1st, sample pre-treatments
Cloth velvet sample is crushed to particle diameter less than 2mm, mixed.20mg samples (being accurate to 0.1mg) accurately are weighed, are put
In 20mL ml headspace bottles, add 20 μ L acetone solvents, ml headspace bottle is sealed rapidly (aluminum bottle cover band PTFE/silicon seal every
Pad), it is placed in 44 headspace autosamplers.Under the conditions of setting head space, aromatic is evaporated and fast in bottle from sample
Speed forms solid vapor equilibrium.Now 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 partly residue in sample).1mL gases in quantitative loop are introduced to GC-MS and realize inspection
Survey.Realized by the chromatographic retention and characteristic ion of each material it is qualitative, using bare substrate mark-on standard curve standard measure.
2nd, instrumentation condition
Gas Chromatography-Mass Spectrometry condition is as follows：
Instrument configuration：Agilent 6890-5975 gas chromatograph-mass spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature be 40 DEG C, keep 1min after rise to 210 DEG C with 5 DEG C/min speed, then with 10 DEG C/
Min speed rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar mass spectrum；
Ionization mode：EI；
Ionizing energy：70eV；
Monitoring mode：Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition is set as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：200℃；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：210℃；
Transmission line temperature：220℃；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
3rd, standard items and solution
The standard items purchase of 8 kinds of aromatic is from different suppliers, and its specifying information includes CAS numberings, 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 material is weighed to 25ml brown volumetric flasks
In, acetone constant volume respectively obtains each material list mark stock solution that concentration is 4mg/mL, is placed in 4 DEG C and is kept in dark place.Utilize single mark
Stock solution configuration concentration 300mg/L 8 kinds of material mixing stock solutions.In use, drawing appropriate standard inventory as needed
Solution, the working solution of respective concentration is diluted to acetone.
4th, the title of 8 kinds of aromatic, CAS numberings, purity, chromatogram and mass spectrometry parameters are as shown in table 1：
The CAS numberings, purity, chromatogram and mass spectrometry parameters of 1. 8 kinds of aromatic of table
* quota ion.
Comparative example：
Traditional ultrasonic extracting method：
Sample comminution to particle diameter is less than 2mm.0.1g samples (being accurate to 0.1mg) accurately are weighed, 25mL cones are placed on
In shape bottle, 5mL acetone is added as Extraction solvent, bottle stopper is stoppered, and sealed membrane is sealed, at room temperature ultrasonic extraction 20min.Absorption is carried
Supernatant in liquid is taken, crosses and Gas Chromatography-Mass Spectrometry is supplied after 0.45 μm of micropore PTFE filter membrane.When extract solution color is deeper, need
Envi-carb graphitized carbons solid phase extraction column was wanted to be purified.
Solid phase extraction process is as follows：With 5mL methanol rinses Envi-carb graphitized carbon solid phase extraction columns, it will carry
Settled solution in liquid is taken to cross post, the elution of 10mL methanol collects all post liquid of crossing in heart bottle.By solution 10kPa, 35 DEG C
Under the conditions of rotate to 4mL or so, be transferred in nitrogen blowpipe with a scale, then rinse 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
Cross and Instrument measuring is supplied after 0.45 μm of micropore PTFE filter membrane.
The inventive method 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.Interference feelings of the different sample substrates for testing result are investigated
Condition, as a result shows that sample substrate is not obvious for detection influence.The method that the present invention is set up is entered with traditional ultrasonic extraction
Row contrast, it is found that testing result is consistent, and the inventive method many-side is better than conventional ultrasound extractive technique.The method of the present invention will
There is important reference to the detection of SVOC in cloth suede and textile sample.
As a result with discussion：
1st, GC-MS condition optimizings
Take by single mark working solution of every kind of material carried out under full scan Scan patterns one by one sample introduction to be determined
Chromatographic peak elution order and retention time.Can obtain several characteristic ions of each target substance simultaneously, respectively as it is qualitative from
Son and quota ion.Kurtosis is considered simultaneously compared with the strong and larger two aspects factor of karyoplasmic ratio for all substances, and selection is suitable
Ion is as quota ion and qualitative ion.Chromatogram and mass spectrometry parameters are specifically shown in Table 1.
2nd, the optimization of head space condition
For quantitative analysis, it is critically important to obtain higher extraction efficiency, 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 (by 2g samples
It is placed in 100mL 30mg/L 8 kinds of materials and mixes entirely in acetone soln and soak, is taken out after vibration 3h in natural air drying in ventilating kitchen) in
Exemplified by 6 kinds of aromatic allyl isothiocyanates, (R)-4-isopropenyl-1-methyl-1-cyclohexene, eugenol, hexahydro cumarin, lilial and hydroabietyl alcohols, ginseng
Number optimization process is as follows.
(1) influence of quantity of solvent
When application calibration curve method carries out quantitative, ml headspace bottle inevitably adds a certain amount of standard liquid, is entering
Row actual sample is also required to add a certain amount of solvent in the sample when determining, to keep the uniformity of environmental system with standard curve
So as to obtain accurate quantitative result.In theory, solvent can not reach in a closed bottle definitely volatilizees completely,
Even environment temperature is higher than its boiling point.But for micro solvent (<100 μ L), it can obtain at a relatively high temperature
Almost complete volatilization.The volatilization of solvent can influence the pressure in bottle, though it is foreseeable that with the increase of quantity of solvent, bottle internal pressure
Power increases, and this will cause the partial pressure of determinand in bottle to diminish, and then deterioration of sensitivity, ml headspace bottle may be caused to collapse what is more
Split.In this research, equilibrium temperature, equilibration time and moulding pressure are fixed as 200 DEG C, 20min and 70kPa, are placed with advance
Different amounts of acetone solvent (0~100 μ L) is added in the ml headspace bottle of 20mg positives, to investigate quantity of solvent to each substance responds
Influence.Result shows in Fig. 1, with the increase of quantity of solvent, and each material peak area shows downward trend, and 20 μ L of selection are used
Amount carries out follow-up study, not only can obtain relatively satisfactory sensitivity, is also convenient for taking liquid to operate.
(2) influence of equilibrium temperature
Equilibrium temperature has important influence for the sensitivity of method 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
Profit, but the tolerable temperature of head space is limited, and dottle pin and transmission line are sealed especially for bottle.Equilibration time and pressurization are pressed
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
Fig. 2 is visible, and for the relatively low material of boiling point (No. 1 and No. 2 materials, boiling point is respectively 151 DEG C and 177 DEG C), peak area does not almost have
Change, and for the higher material of boiling point (particularly No. 8 materials, 375.5 DEG C of boiling point), peak area with temperature raise 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, and it is related to that material is dynamically put down in two alternate whether reach
Weighing apparatus.Traditional Static Headspace equilibration time is general longer, in this method, the micro solvent transient evaporation under 200 DEG C of high temperature,
Stable air pressure is formed in bottle, this is conducive to fragrance materials to be rapidly reached balance.As seen from Figure 3, when equilibrium temperature and pressurization
When pressure is set to 200 DEG C and 70kPa, each material peak area changes smaller between 5min to 20min, it is meant that head space is balanced very
It can just realize soon.When the time being more than 20min, peak area is increased over time in reduction trend, it may be possible to due to head space
The reason that bottle starts to be deteriorated through long-time baking air-tightness.Most equilibration time is set to 5min at last.
(4) influence of moulding pressure
Insufficient pressure in ml headspace bottle is with full of quantitative loop, it usually needs plus extra auxiliary gas (He gas or N2Gas),
And aid in gas to influence 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 is responded to aromatic is investigated.Based on The Ideal-Gas Equation PV=
NRT, P are the partial pressure that acetone is produced, unit Pa；V is bottle product, unit m3；N is the amount of material, 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, try to achieve P and are approximately equal to
53kPa (judges its actual value in 60~70kPa) by subsequent result.
From fig. 4, it can be seen that when moulding pressure increases to 70kPa by 50kPa, the peak area of aromatic gradually increases, especially
It is for high boiling material (No. 5, No. 6 and No. 8 materials).It is that, when moulding pressure is less than the pressure in the bottle, can produce to speculate reason
Raw suck-back phenomenon, causes material concentration in bottle to reduce.When moulding pressure increases to 110kPa by 70kPa, the response of each material
Value is substantially gradually reduced, and this is probably to cause the partial pressure of test substance in bottle to diminish because too many auxiliary gas is introduced, thus is rung
It should be worth and diminish.It was found from experimental result, 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 of random selection
Sample (the cotton flannel toy sample material overwhelming majority is polyester fiber), 8 kinds of material mixing standards for adding 20 μ L 60mg/L are molten
Liquid, and be measured using the Parameter Conditions of optimization.As seen from Figure 5, testing result is influenceed smaller by sample substrate, different substrates
Testing result deviation it is unobvious, thus it is speculated that this forms in bottle stable gas-solid equilibrium mainly due to aromatic, when cloth suede sample
When kind class is consistent, this gas-solid equilibrium environment is consistent, thus will not produce influence to the concentration distribution of determinand.Therefore in reality
In the sample detection of border, the accuracy of testing result is quantitatively ensure that using bare substrate mark-on calibration curve method.
(6) head space is contrasted with ultrasonic testing results
The method of foundation is contrasted further to investigate its accuracy with classical ultrasonic extraction.By homemade two
The positive of individual distinct fragrance agent content, is extracted with two kinds of extracting modes, GC-MS detections.As seen from Figure 6, two kinds carry
The testing result for taking mode closely, 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
Substantial amounts of organic solvent, it is time-consuming longer, and larger noise and harmful Ultrasonic Radiation are produced, if extract color in addition
Also need to carry out more complicated Solid phase extraction operation if heavier.And head space extraction method need not be located before the sample of complexity
Reason, it is simple 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 classes material, head space extraction method many-side is better than ultrasonic extraction.
(7) methodological study
Under the chromatographic condition of setting, standard working solution is measured successively from low to high by concentration, with what is obtained
The peak area of quota ion chromatographic peak is ordinate, and the sample introduction concentration of corresponding each material is mapped for abscissa, draws standard work
Make curve.As a result show, each material is in 0.2~300mg/kg of its range of linearity, and concentration value and peak area have good linear
Relation, linearly dependent coefficient is all higher than 0.9984.Corresponding content of material is as quantitative when being more than 10 times of noise using response signal
Limit, obtains 0.02~1.0mg/kg of quantitative limit of each material.The quantitative limit of all substances refers to far below European Union 2009/48/EC
Limitation (100mg/kg) in order.We set 3 addition concentration for every kind of material, and bar is tested as determined by this method
Part, 6 experiments are repeated to each addition concentration.From result, method for different material the rate of recovery 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, and content is respectively 10mg/kg and 6mg/kg；S6 samples detect hexahydro cumarin, contain
Measure 263.6mg/kg；S9 samples detect eugenol, content 23.4mg/kg；S13 samples detect eugenol, content 2.3mg/kg.Its
Excess matter is not detected.Fig. 7 gives sample S2 total ion chromatogram and detects the extraction chromatography of ions figure of material.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
In various modifications and improvement that case is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (8)
1. SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space, it is characterised in that：Comprise the following steps：
Cloth velvet sample is crushed, mixes, is placed in ml headspace bottle, acetone solvent is added, ml headspace bottle is sealed rapidly, 44 tops are placed in
Empty automatic sampler, under the conditions of setting head space, SVOC to be measured is evaporated from sample and is quickly formed gas-solid flat in bottle
Weighing apparatus, now SVOC to be measured partial pressure and its content in the sample are proportional in headspace gas, be fully transferred to gas phase or
Part is residued in sample, and gas in quantitative loop is introduced into gas chromatograph-mass spectrometer realizes detection, passes through the chromatogram of each material
Retention time and characteristic ion realize it is qualitative, using bare substrate mark-on standard curve standard measure.
2. SVOC quick determination methods in the cloth velvet sample according to claim 1 based on full volatilization head space, its feature exists
In：Methods described specifically includes following steps：Cloth velvet sample is crushed to particle diameter less than 2mm, mixes, accurately weighs 20mg samples
Product, are accurate to 0.1mg, are placed in 20mL ml headspace bottles, add 20 μ L acetone solvents, rapidly seal ml headspace bottle, be placed in 44
Position headspace autosampler, under the conditions of setting head space, SVOC to be measured evaporated from sample and in bottle it is quick formed gas-
Gu balance.Now SVOC to be measured partial pressure and its content in the sample are proportional in headspace gas, are fully transferred to gas
Mutually or partly residue in sample, 1mL gases in quantitative loop are introduced into gas chromatograph-mass spectrometer realizes detection, passes through each thing
The chromatographic retention and characteristic ion of matter realize it is qualitative, using bare substrate mark-on standard curve standard measure.
3. SVOC quick determination methods in the cloth velvet sample according to claim 2 based on full volatilization head space, its feature exists
In：Gas Chromatography-Mass Spectrometry condition is as follows：
Instrument configuration：Agilent 6890-5975 gas chromatograph-mass spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature is 40 DEG C, and 210 DEG C are risen to 5 DEG C/min speed after keeping 1min, then with 10 DEG C/min speed
Rate rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar mass spectrum；
Ionization mode：EI；
Ionizing energy：70eV；
Monitoring mode：Scan and SIM；
Solvent delay 6min.
4. SVOC quick determination methods in the cloth velvet sample according to claim 3 based on full volatilization head space, its feature exists
In：
The head space condition of head-space sampler is set as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：150~200 DEG C；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：160~210 DEG C, and it is higher 10 DEG C than the equilibrium temperature set；
Transmission line temperature：170~220 DEG C, and it is higher 10 DEG C than the quantitative loop temperature set；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
5. SVOC quick determination methods in the cloth velvet sample according to claim 4 based on full volatilization head space, its feature exists
In：The SVOC to be measured is 8 kinds of aromatic, and specially allyl isothiocyanate, (R)-4-isopropenyl-1-methyl-1-cyclohexene, anise alcohol, eugenol, hexahydro is fragrant
Legumin, lilial, 1- (4- anisyls) -1- penten-3-ones and hydroabietyl alcohol.
6. SVOC quick determination methods in the cloth velvet sample according to claim 5 based on full volatilization head space, its feature exists
In：
Gas Chromatography-Mass Spectrometry condition is as follows：
Instrument configuration：Agilent 6890-5975 gas chromatograph-mass spectrometers；
Capillary chromatographic column：Agilent DB-35MS capillary columns, 30m × 0.25mm × 0.25 μm；
Temperature programming：Initial temperature is 40 DEG C, and 210 DEG C are risen to 5 DEG C/min speed after keeping 1min, then with 10 DEG C/min speed
Rate rises to 300 DEG C；
Carrier gas：High-purity helium, flow velocity is 1.0mL/min；
Injector temperature：280℃；
Sample introduction pattern：Splitless injecting samples；
Detector：Level Four bar mass spectrum；
Ionization mode：EI；
Ionizing energy：70eV；
Monitoring mode：Scan and SIM；
Solvent delay 6min；
The headspace autosampler condition is set as：
Instrument configuration：The headspace autosamplers of DANI 86.50,44；
Equilibrium temperature：200℃；
Equilibration time：5min；
Aid in gas moulding pressure：70kPa；
Quantitative loop temperature：210℃；
Transmission line temperature：220℃；
Pressing time：10s；
Quantitative loop volume：1mL；
Quantitative loop equilibration time：10s；
Sample injection time：20s.
7. SVOC quick determination methods in the cloth velvet sample according to claim 6 based on full volatilization head space, its feature exists
In：The CAS numberings of 8 kinds of aromatic, purity, chromatogram and mass spectrometry parameters are as shown in table 1：
The CAS numberings, purity, chromatogram and mass spectrometry parameters of 1.8 kinds of aromatic of table
* quota ion.
8. SVOC quick determination methods in the cloth velvet sample according to claim 7 based on full volatilization head space, its feature exists
In：Also include the preparation of standard liquid：The standard items 0.1g of each aromatic is weighed into 25ml brown volumetric flasks, is accurate to
0.1mg, acetone constant volume respectively obtains each material list mark stock solution that concentration is 4mg/mL, is placed in 4 DEG C and is kept in dark place, utilizes
Single mark stock solution configuration concentration 300mg/L 8 kinds of material mixing stock solutions, in use, drawing appropriate standard as needed
Stock solution, the working solution of respective concentration is diluted to acetone.
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