CN106526021B - A kind of method of creosote in measurement woodwork - Google Patents
A kind of method of creosote in measurement woodwork Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention relates to a kind of methods of creosote in measurement woodwork, comprising the following steps: 1) weighs the sample for crushing and being uniformly mixed, Extraction solvent toluene, tracer and internal standard standard solution is added, vortex mixed is uniform, ultrasonic extraction；2) gas chromatography-mass spectrometry is used, the creosote marker in gained sample extraction solution is measured；3) according to the resulting chromatogram of step 2) and mass spectrogram, it is analyzed to identify in sample extraction solution whether containing the distinctive polycyclic aromatic hydrocarbon marker of creosote or phenols marker, to determine whether contain corresponding creosote in sample；The polycyclic aromatic hydrocarbon and phenolic compound that are selected as creosote marker are identified and quantified again；Finally, the content of creosote in sample is obtained through conversion by the content of marker in sample；The method of the present invention quickly, it is simple, the content of 4 kinds of creosotes being forbidden to use by the method for sxemiquantitative to regulation in the sample is determined, and detection limit is 50mg/kg.
Description
[technical field]
The invention belongs to technical field of analytical chemistry, the method for creosote in specifically a kind of measurement woodwork.
[background technique]
Bamboo and wood products are seen everywhere in daily production and life, as the continuous improvement and people of technique are to quality of the life
Continuous pursuit, bamboo and wood products receive the pro-gaze of more and more people.Bamboo and wood materials are widely used in the manufacture of daily necessities,
Wherein more be no lack of the product with direct food contact, as bamboo and wood tableware and kitchen utensils (such as bamboo and wood chopstick production, bowl, dish, bucket,
Food steamer, pot cover, chopping block etc.), natural cork plug, toothpick etc..
Creosote is a kind of strong disinfectant and preservative, has antiseptic and bactericidal effect to bamboo and wood materials, is widely used in wooden
The anti-corrosion of railroad tie, electric pole and fence etc..Creosote is mostly colourless or pale yellow oily liquid, is by timber by heating
What destructive distillation obtained, be to have the mixture of complex component, and form unstable.Wood source is different, and carbonization decomposition temperature is different,
The creosote of different compositions will be all generated, contains a large amount of polycyclic arene compound (PAHs) and phenolic material in composition
Matter.And polycyclic arene compound is a kind of procarcinogen, phenols then has irritation and corrosivity, and the use of creosote can be right
Human body damages, while there is also the risks of pollution environment.
Since two thousand three, consumer has just been prohibited from using creosote.EU Committee passes through on July 26th, 2011
Resolution, the stringent regulation for limiting creosote industrial use came into effect from May 1st, 2013.Creosote does not allow to enter back into Europe
Allied city field, unless company obtains associated authorization.
17 articles of 1907/2006 annex of EC regulations (EC) No, 4 kinds of creosote substances of clear stipulaties must not be used for
The processing of timber, and Related product is there is not allowed that in European market.These substances are mixture, and chemical abstracts number is respectively
8001-58-9,61789-28-4,90640-84-9 and 8021-39-4.Wherein chemical abstracts number be respectively 8001-58-9,
The composition of three kinds of creosotes of 61789-28-4 and 90640-84-9 is close, and main component is polycyclic arene compound；And change
The creosote that digest number is 8021-39-4 is learned, main component is a variety of phenolic compounds.
For creosote, some scholars form it and endanger and studied, and have delivered related academic report.And it closes
The detection method of creosote in bamboo and wood products, but there are no relevant reports.In daily life, the use of bamboo and wood products is increasingly
Extensively, and many products are all used in the daily food and drink of food packaging, processing and people.In view of the harmfulness of creosote, build
The test method for founding creosote content in a kind of bamboo and wood products that Accurate Determining is contacted with food is very important.
[summary of the invention]
It is provided a kind of through toluene ultrasonic extraction, gaschromatographic mass spectrometry present invention aim to solve above-mentioned deficiency
The method of combined instrument measurement and creosote content in food contact bamboo and wood products, this method quickly, simply, pass through the side of sxemiquantitative
The content of 4 kinds of creosotes that method is forbidden to use regulation (EC) No 1907/2006 in the sample is determined, detection limit
It is 50mg/kg.
A kind of method for measuring creosote in woodwork is designed to achieve the above object, comprising the following steps:
1) sample pretreatment: weighing the sample for crushing and being uniformly mixed, and Extraction solvent toluene, tracer and internal standard mark is added
Quasi- solution, vortex mixed is uniform, ultrasonic extraction；
2) use gas chromatography-mass spectrometry, to the creosote marker in the resulting sample extraction solution of step 1) into
Row measurement；
3) qualitative analysis: according to the resulting chromatogram of step 2) and mass spectrogram, be analyzed to identify in sample extraction solution whether
Containing the distinctive polycyclic aromatic hydrocarbon marker of creosote or phenols marker, to determine whether contain corresponding creosote in sample；
4) according to the judgement of step 3) as a result, it is that the wood mainly formed evaporates that confirmation, which is contained with polycyclic arene compound,
The sample of oil carries out polycyclic aromatic hydrocarbon marker content and calculates, and quantitative analysis uses internal standard method, uses naphthalene as standard substance to sample
The multiring aromatic hydrocarbon marker that product extract in solution is quantified；
5) according to the judgement of step 3) as a result, for confirming containing the sample for taking phenolic compound as the creosote mainly formed
Product are separated and are detected to the phenolic compound in sample extraction solution using gas chromatograph-mass spectrometer (GC-MS), and quantitative point
Analysis uses external standard method, uses p- methylphenol as standard substance, determines the phenols marker in sample extraction solution
Amount；
6) containing according to multiring aromatic hydrocarbon marker in step 4) and the resulting sample of step 5) or/and phenols marker
Amount converts obtain containing for creosote in sample by a certain percentage according to the content of marker in bought creosote standard substance
Amount.
Further, in step 1), sample is the bamboo and wood products contacted with food, and sample is cut into no more than 2 × 2 × 2mm
Size, tracer are deuterated terphenyl, and inner mark solution is deuterated naphthalene, are vortexed after concussion 1min, under 60 ± 5 DEG C of bath temperature
60 ± 5min of ultrasonic extraction takes out, is cooled to room temperature, sample solution is transferred to sample injection bottle, to be used for gas chromatography-mass spectrometry
It is detected with instrument.
Further, in step 2), the determination condition of gas chromatography-mass spectrometry are as follows:
A) gas chromatographic column use HP-5MS capillary column, specification be column length 30m, column internal diameter 0.25mm, 0.25 μm of film thickness；
B) gas chromatographic sample introduction mouth temperature is set as 290 DEG C, and temperature programming is 70 DEG C of initial temperature, retains 1min, by 70 DEG C/
Min is warming up to 120 DEG C, retains 3min, is warming up to 300 DEG C by 10 DEG C/min, retains 10min；
C) mass spectrum acquisition selection full scan SCAN and ion scan SIM mode, scanning range: m/z 50-650, scan from
Son are as follows:
Further, in step 3), polycyclic aromatic hydrocarbon marker is 7 kinds, and phenols marker is 4 kinds；When containing naphthalene in sample
When with any other 2 polycyclic aromatic hydrocarbon markers, then evaporated in judgement sample containing 3 kinds with polycyclic aromatic hydrocarbon wood as main component
Oil, chemical abstracts number are respectively 8001-58-9,61789-28-4 and 90640-84-9；When in sample contain p- methylphenol
With any other 2 phenols markers, then show in sample containing with phenolic compound creosote as main component, chemistry
Side's number of plucking is 8021-39-4.
Further, in step 5), the determination condition of gas chromatography-mass spectrometry are as follows:
A) gas chromatographic column uses HP-INNOWAX capillary column, and specification is column length 30m, column internal diameter 0.25mm, film thickness
0.50μm；
B) gas chromatographic sample introduction mouth temperature is set as 200 DEG C, and temperature programming is 80 DEG C of initial temperature, retains 1min, by 40 DEG C/
Min is warming up to 180 DEG C, retains 10 minutes min, is warming up to 245 DEG C by 26 DEG C/min, retains 5min；
C) mass spectrum acquisition selection ion scan SIM mode, scans ion are as follows:
| Serial number | Target compound | Scan ion m/z |
| 1 | Ortho-methyl phenol | 107,108,79 |
| 2 | Phenol | 94,66,65 |
| 3 | P- methylphenol | 108,107,77 |
| 4 | M- methylphenol | 108,107,79 |
Further, in step 6), according to the reduction formula between each marker and creosote: creosote content in sample=
Marker content/content of the marker in creosote standard substance in sample is contained by polycyclic aromatic hydrocarbon marker naphthalene in sample
The content of amount or/and the p- methylphenol of phenols marker, conversion obtain the content of creosote in sample.
The present invention compared with the existing technology, provides a kind of through toluene ultrasonic extraction, gas chromatography-mass spectrometry measurement
With the method for creosote content in food contact bamboo and wood products, not only measuring method is quick, simple, but also can be realized regulation
(EC) measurement for 4 kinds of creosote contents in bamboo and wood products being forbidden to use in No 1907/2006, and with polycyclic aromatic hydrocarbon
It is quantified respectively for main component and with phenolic compound creosote as main component, detection limit is 50mg/kg；Meanwhile
In view of creosote is the changeable mixture of composition, after carrying out careful consider to the component in creosote, multiple marks are selected
Object is remembered to detect to creosote.Method of the present invention according in relation to creosote product analysis correlation technique data and
The composition of creosote standard substance selects the frequency of occurrences and the higher naphthalene of content and p- methylphenol to determine for creosote
Amount, the calculation method of the content consider what the worst situation was made, and content is semi-quantitative results, are worthy of popularization.
[Detailed description of the invention]
Fig. 1 is that the chromatograms of 7 polycyclic aromatic hydrocarbons and tracer and internal standard compound, (deuterated naphthalene is internal standard using instrumental method I
Object, deuterated terphenyl are tracer)；
Fig. 2 be using instrumental method I to the chromatograms of 4 phenols markers (under the conditions of instrumental method I, m- methylbenzene
Phenol and p- methylphenol cannot be separated)；
Fig. 3 (using instrumental method II, can be separated m- using chromatogram of the instrumental method II to 4 phenols markers
Methylphenol and p- methylphenol)；
Fig. 4 is evaporated using instrumental method I using polycyclic aromatic hydrocarbon as main component and with phenolic compound wood as main component
Oil standard substance chromatogram (uses instrumental method I, with the feature in phenolic compound creosote standard substance as main component
The m- methylphenol of substance and p- methylphenol cannot be separated)；
Fig. 5 is using instrumental method II with phenolic compound creosote standard substance chromatogram as main component；
Fig. 6-1 is the mass spectrogram of naphthalene in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-2 is the mass spectrogram of acenaphthene in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-3 is the mass spectrogram of dibenzofurans in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-4 is the mass spectrogram of fluorenes in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-5 is the mass spectrogram of 7 polycyclic aromatic hydrocarbon marker China and Philippines；
Fig. 6-6 is the mass spectrogram of fluoranthene in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-7 is the mass spectrogram of pyrene in 7 polycyclic aromatic hydrocarbon markers；
Fig. 6-8 is the mass spectrogram of the deuterated naphthalene of internal standard compound；
Fig. 6-9 is the mass spectrogram of the deuterated terphenyl of tracer；
Fig. 6-10 is the mass spectrogram of ortho-methyl phenol in 4 phenols markers；
Fig. 6-11 is the mass spectrogram of phenol in 4 phenols markers；
Fig. 6-12 is the mass spectrogram of m- methylphenol in 4 phenols markers；
Fig. 6-13 is the mass spectrogram of p- methylphenol in 4 phenols markers；
Fig. 7 is cork sample creosote content gas chromatography-mass spectrum detection chromatogram.
[specific embodiment]
The invention belongs to the measurement in analytical chemistry field to creosote in bamboo and wood products is contacted with food, principles are as follows:
Sample is detected with gas chromatography-mass spectrometry, is evaporated wood is selected as through toluene ultrasonic extraction, gained sample extraction solution
The polycyclic aromatic hydrocarbon and phenolic compound of oily marker are identified and are quantified.Finally, by the content of marker in sample through converting
Obtain the content of creosote in sample.
The method of creosote in the measurement woodwork, comprising the following steps:
1) sample pretreatment: weighing and crush and uniformly mixed sample, Extraction solvent toluene is added, and tracer and interior is added
Standard solution is marked, vortex mixed is uniform, ultrasonic extraction；
2) gas chromatography-mass spectrometry is used, using instrumental method I in the resulting sample extraction solution of step 1)
Creosote marker is measured；
3) qualitative analysis: according to the resulting chromatogram of step 2) and mass spectrogram, be analyzed to identify in sample extraction solution whether
Containing the distinctive polycyclic aromatic hydrocarbon marker of creosote or phenols marker, to determine whether contain corresponding creosote in sample；
4) according to the judgement of step 3) as a result, it is that the wood mainly formed evaporates that confirmation, which is contained with polycyclic arene compound,
The sample of oil carries out polycyclic aromatic hydrocarbon marker content and calculates.Quantitative analysis uses internal standard method, uses naphthalene as standard substance to sample
The multiring aromatic hydrocarbon marker that product extract in solution is quantified；
5) according to the judgement of step 3) as a result, for confirming containing the sample for taking phenolic compound as the creosote mainly formed
Product divide the phenolic compound in sample extraction solution using instrumental method II using gas chromatograph-mass spectrometer (GC-MS)
From and detection.Quantitative analysis uses external standard method, uses p- methylphenol as standard substance, to the phenol in sample extraction solution
Class marker is quantified；
6) according to the content of step 4) and multiring aromatic hydrocarbon marker and phenols marker in 5) resulting sample, according to institute
The content of marker in creosote standard substance is bought, conversion obtains the content of creosote in sample by a certain percentage.
In step 1), sample is to contact woodwork with food, is cut into 2mm × 2mm × 2mm size (or smaller szie), adds
Enter 20mL toluene, tracer (deuterated terphenyl) and internal standard (deuterated naphthalene) solution.It is vortexed after concussion 1min, in 60 ± 5 DEG C of water
60 ± 5min of ultrasonic extraction under bath temperature.It takes out, is cooled to room temperature, sample solution is transferred to sample injection bottle, be used for gas-chromatography-
Mass spectrometer detection.
In step 2), the determination condition (i.e. instrumental method I) of gas chromatography-mass spectrometry are as follows:
A) gas chromatographic column use HP-5MS capillary column, specification be column length 30m, column internal diameter 0.25mm, 0.25 μm of film thickness；
B) gas chromatographic sample introduction mouth temperature is set as 290 DEG C, and temperature programming is 70 DEG C of initial temperature, retains 1min, by 70 DEG C/
Min is warming up to 120 DEG C, retains 3min, is warming up to 300 DEG C by 10 DEG C/min, retains 10min；
C) mass spectrum acquisition selection full scan (SCAN) and ion scan (SIM) mode, scanning range: m/z50-650, scanning
Ion are as follows:
In step 3), whether contain the distinctive polycyclic aromatic hydrocarbon marker of creosote by being analyzed to identify in sample extraction solution
Or phenols marker, to determine whether contain corresponding creosote in sample.Wherein, polycyclic aromatic hydrocarbon marker is 7 kinds, phenols mark
Remember that object is 4 kinds.When containing naphthalene and any other 2 polycyclic aromatic hydrocarbon markers in sample, then contain 3 kinds in judgement sample with more
Cycloaromatics creosote as main component, their chemical abstracts number are respectively 8001-58-9,61789-28-4 and 90640-
84-9.When containing p- methylphenol and any other 2 phenols markers in sample, then show in sample containing with phenol generalization
Object creosote as main component is closed, chemistry side's number of plucking is 8021-39-4.
In step 5), the determination condition (i.e. instrumental method II) of gas chromatography-mass spectrometry are as follows:
A) gas chromatographic column uses HP-INNOWAX capillary column, and specification is column length 30m, column internal diameter 0.25mm, film thickness
0.50μm；
B) gas chromatographic sample introduction mouth temperature is set as 200 DEG C, and temperature programming is 80 DEG C of initial temperature, retains 1min, by 40 DEG C/
Min is warming up to 180 DEG C, retains 10 minutes min, is warming up to 245 DEG C by 26 DEG C/min, retains 5min；
C) mass spectrum acquisition selection ion scan (SIM) mode, scans ion are as follows:
| Serial number | Target compound | It scans ion (m/z) |
| 1 | Ortho-methyl phenol | 107,108,79 |
| 2 | Phenol | 94,66,65 |
| 3 | P- methylphenol | 108,107,77 |
| 4 | M- methylphenol | 108,107,79 |
In step 6), according to the reduction formula between each marker and creosote, (creosote content=sample is got the bid in sample
Remember object content/content of the marker in creosote standard substance), by the content of polycyclic aromatic hydrocarbon marker naphthalene in sample or (/
With) content of the p- methylphenol of phenols marker, conversion obtains the content of creosote in sample.With polycyclic aromatic hydrocarbon be mainly at
Divide and quantitative respectively with phenolic compound creosote as main component, detection limit is 50mg/kg.
The present invention is made combined with specific embodiments below further explained below:
Embodiment 1: the measurement of creosote in bamboo chopsticks
1. the preparation of sample:
Bamboo chopsticks are shredded as 2mm × 2mm × 2mm size, and are uniformly mixed, are deposited in the hermetic bag of clean dried.Claim
It takes uniformly mixed 2.0 ± 0.02g of sample in 40mL reagent bottle, the deuterated terphenyl (tracer of 20mL toluene, 10mg/L is added
Agent) 200 μ L of standard solution 200 μ L and 50mg/L deuterated naphthalene (internal standard) standard solution.After the concussion 1min that is vortexed is mixed, in 60 ± 5
DEG C bath temperature under 60 ± 5min of ultrasonic extraction.It takes out, is cooled to room temperature, sample solution is transferred to sample injection bottle, uses gas phase
Chromatograph-mas spectrometer analysis.
2. extracting solution to bamboo chopsticks using instrumental method I to analyze
This method for confirm in sample whether the polycyclic aromatic hydrocarbon containing creosote and phenols marker and in confirmation sample
In containing being the creosote substance mainly formed with polycyclic aromatic hydrocarbon after, such creosote substance in sample is quantified.Tool
Body gas chromatograph-mass spectrometer (GC-MS) detection parameters are as follows:
1) gas chromatograph condition
Gas chromatograph: Agilent 7890
Chromatographic column: HP-5MS capillary column, 0.25mm × 30m, 0.25 μm
Injector temperature: 290 DEG C
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction mode: Splitless injecting samples
Sampling volume: 1 μ L
Temperature programming: temperature programming is 70 DEG C of initial temperature, retains 1min, is warming up to 120 DEG C by 70 DEG C/min, retains 3min,
300 DEG C are warming up to by 10 DEG C/min, retains 10min.
2) Mass Spectrometry Conditions
Solvent delay: 3min
Ion source temperature: 230 DEG C
Quadrupole rod temperature: 150 DEG C
Scan pattern: full scan (SCAN) and selection ion scan (SIM) mode,
Full scan range: m/z 50-650 scans ion are as follows:
3. initial characterization is analyzed
The retention time of the compound, characteristic ion and abundance of ions ratio in solution are extracted according to sample, to 7 polycyclic aromatic hydrocarbons
Whether marker and 4 phenols markers carry out qualitative analysis, to determine in sample containing as main component with polycyclic aromatic hydrocarbon
Whether containing with phenolic substances creosote substance as main component in creosote substance and preliminary judgement sample.
If 1) contain naphthalene and any other 2 polycyclic aromatic hydrocarbon markers in sample, show in sample containing with polycyclic
Aromatic hydrocarbons creosote as main component.
If 2) in sample contain p- methylphenol and any other 2 phenols markers, show in sample containing with
Phenolic compound creosote as main component.Because using instrumental method I, p-methyl phenol and m- methylphenol can not be separated,
Instrumental method II need to be used to extract solution to sample further to be separated and confirmed.
4. extracting solution to bamboo chopsticks using instrumental method II to analyze
This method is used to further confirm that the phenols marker in sample, and quantifies to it.Specific gas phase
Chromatograph-mass spectrometer detection parameters are as follows:
1) gas chromatograph condition
Gas chromatograph: Thermo DSQII spectrometer
Chromatographic column: HP-INNOWAX capillary column, 30m × 0.25mm, 0.50 μm
Injector temperature: 200 DEG C
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction mode: Splitless injecting samples
Sampling volume: 1 μ L
Temperature programming: temperature programming is 80 DEG C of initial temperature, retains 1min, is warming up to 180 DEG C by 40 DEG C/min, retains 10min,
245 DEG C are warming up to by 26 DEG C/min, retains 5min.
2) Mass Spectrometry Conditions
Solvent delay: 3min
Ion source temperature: 230 DEG C
Quadrupole rod temperature: 150 DEG C
Scan pattern: selection ion scan mode (SIM) scans ion:
| Serial number | Target compound | It scans ion (m/z) |
| 1 | Ortho-methyl phenol | 107,108,79 |
| 2 | Phenol | 94,66,65 |
| 3 | P- methylphenol | 108,107,77 |
| 4 | M- methylphenol | 108,107,79 |
5. marker quantitative analysis
1) polycyclic aromatic hydrocarbon marker quantifies
Using standard curve inner mark method ration, the content of polycyclic aromatic hydrocarbon marker naphthalene in sample is calculated.
2) phenols marker quantifies
Using standard curve quantified by external standard method, the content of the p- methylphenol of phenols marker in sample is calculated.
6. the calculating of creosote content in bamboo chopsticks
According between each marker and creosote reduction formula (marker content in creosote content=sample in sample/
Content of the marker in creosote standard substance), it is marked by the content of polycyclic aromatic hydrocarbon marker naphthalene in sample or (/ and) phenols
The content of the p- methylphenol of object, conversion obtain the content of creosote in sample.Through detecting, evaporated in the bamboo chopsticks sample without containing wood
Oil.
Embodiment 2: the measurement of creosote in cork
1. the preparation of sample:
Cork is shredded as 2mm × 2mm × 2mm size, and is uniformly mixed, is deposited in the hermetic bag of clean dried.
Uniformly mixed 2.0 ± 0.02g of sample is weighed in 40mL reagent bottle, 20mL toluene is added, the deuterated terphenyl of 10mg/L (shows
Track agent) 200 μ L of standard solution 200 μ L and 50mg/L deuterated naphthalene (internal standard) standard solution.After the concussion 1min that is vortexed is mixed, in 60
60 ± 5min of ultrasonic extraction under ± 5 DEG C of bath temperature.It takes out, is cooled to room temperature, sample solution is transferred to sample injection bottle, uses gas
The analysis of phase chromatograph-mas spectrometer.
2. extracting solution to cork using instrumental method I to analyze
This method for confirm in sample whether the polycyclic aromatic hydrocarbon containing creosote and phenols marker.And in confirmation sample
In containing being the creosote substance mainly formed with polycyclic aromatic hydrocarbon after, such creosote substance in sample is quantified.Tool
Body gas chromatography-mass spectrometry detection parameters are as follows:
1) gas chromatograph condition
Gas chromatograph: Agilent 7890
Chromatographic column: HP-5MS capillary column, 0.25mm × 30m, 0.25 μm
Injector temperature: 290 DEG C
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction mode: Splitless injecting samples
Sampling volume: 1 μ L
Temperature programming: temperature programming is 70 DEG C of initial temperature, retains 1min, is warming up to 120 DEG C by 70 DEG C/min, retains 3min,
300 DEG C are warming up to by 10 DEG C/min, retains 10min.
2) Mass Spectrometry Conditions
Solvent delay: 3min
Ion source temperature: 230 DEG C
Quadrupole rod temperature: 150 DEG C
Scan pattern: full scan (SCAN) and selection ion scan (SIM) mode,
Full scan range: m/z 50-650 scans ion are as follows:
3. initial characterization is analyzed
The retention time of the compound, characteristic ion and abundance of ions ratio in solution are extracted according to sample, to 7 polycyclic aromatic hydrocarbons
Whether marker and 4 phenols markers carry out qualitative analysis, to determine in sample containing as main component with polycyclic aromatic hydrocarbon
Whether containing with phenolic substances creosote substance as main component in creosote substance and preliminary judgement sample.
If 1) contain naphthalene and any other 2 polycyclic aromatic hydrocarbon markers in sample, show in sample containing with polycyclic
Aromatic hydrocarbons creosote as main component.
If 2) in sample contain p- methylphenol and any other 2 phenols markers, show in sample containing with
Phenolic compound creosote as main component.Because using instrumental method I, p-methyl phenol and m- methylphenol can not be separated,
Instrumental method II need to be used to extract solution to sample further to be separated and confirmed.
4. extracting solution to cork using instrumental method II to analyze
This method is used to further confirm that the phenols marker in sample, and quantifies to it.Specific gas-chromatography-matter
It is as follows to compose combined instrument detection parameters:
1) gas chromatograph condition
Gas chromatograph: Thermo DSQII spectrometer
Chromatographic column: HP-INNOWAX capillary column, 30m × 0.25mm, 0.50 μm
Injector temperature: 200 DEG C
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction mode: Splitless injecting samples
Sampling volume: 1 μ L
Temperature programming: temperature programming is 80 DEG C of initial temperature, retains 1min, is warming up to 180 DEG C by 40 DEG C/min, retains 10min,
245 DEG C are warming up to by 26 DEG C/min, retains 5min.
2) Mass Spectrometry Conditions
Solvent delay: 3min
Ion source temperature: 230 DEG C
Quadrupole rod temperature: 150 DEG C
Scan pattern: selection ion scan mode (SIM) scans ion:
| Serial number | Target compound | It scans ion (m/z) |
| 1 | Ortho-methyl phenol | 107,108,79 |
| 2 | Phenol | 94,66,65 |
| 3 | P- methylphenol | 108,107,77 |
| 4 | M- methylphenol | 108,107,79 |
5. marker quantitative analysis
1) polycyclic aromatic hydrocarbon marker quantifies
Using standard curve inner mark method ration, the content of polycyclic aromatic hydrocarbon marker naphthalene in sample is calculated.
2) phenols marker quantifies
Using standard curve quantified by external standard method, the content of the p- methylphenol of phenols marker in sample is calculated.
6. the calculating of creosote content in cork
According between each marker and creosote reduction formula (marker content in creosote content=sample in sample/
Content of the marker in creosote standard substance), it is marked by the content of polycyclic aromatic hydrocarbon marker naphthalene in sample or (/ and) phenols
The content of the p- methylphenol of object, conversion obtain the content of creosote in sample.Through detecting, evaporated in the cork sample containing wood
Oily 52mg/kg.
The present invention is simultaneously not limited to the embodiments described above, other any without departing from spiritual essence and principle of the invention
Changes, modifications, substitutions, combinations, simplifications made by lower, should be equivalent substitute mode, are included in protection model of the invention
Within enclosing.
Claims (5)
1. a kind of method of creosote in measurement woodwork, which comprises the following steps:
1) sample pretreatment: weighing the sample for crushing and being uniformly mixed, and it is molten that Extraction solvent toluene, tracer and internal standard standard is added
Liquid, vortex mixed is uniform, ultrasonic extraction；
2) gas chromatography-mass spectrometry is used, the creosote marker in the resulting sample extraction solution of step 1) is surveyed
It is fixed；
In step 2), the determination condition of gas chromatography-mass spectrometry are as follows:
A) gas chromatographic column use HP-5MS capillary column, specification be column length 30m, column internal diameter 0.25mm, 0.25 μm of film thickness；
B) gas chromatographic sample introduction mouth temperature is set as 290 DEG C, and temperature programming is 70 DEG C of initial temperature, retains 1min, by 70 DEG C/min liter
Temperature retains 3min to 120 DEG C, is warming up to 300 DEG C by 10 DEG C/min, retains 10min；
C) mass spectrum acquisition selection full scan SCAN and ion scan SIM mode, scanning range: m/z 50-650 scans ion are as follows:
3) it qualitative analysis: according to the resulting chromatogram of step 2) and mass spectrogram, is analyzed to identify in sample extraction solution and whether contains
The distinctive polycyclic aromatic hydrocarbon marker of creosote or phenols marker, to determine whether contain corresponding creosote in sample；
4) according to the judgement of step 3) as a result, it is the creosote mainly formed that confirmation, which is contained with polycyclic arene compound,
Sample carries out polycyclic aromatic hydrocarbon marker content and calculates, and quantitative analysis uses internal standard method, and naphthalene is used to mention as standard substance to sample
The multiring aromatic hydrocarbon marker in solution is taken to be quantified；
5) according to the judgement of step 3) as a result, for confirming containing the sample for taking phenolic compound as the creosote mainly formed,
Using gas chromatograph-mass spectrometer (GC-MS), the phenolic compound in sample extraction solution is separated and detected, quantitative analysis is adopted
With external standard method, uses p- methylphenol as standard substance, the phenols marker in sample extraction solution is quantified；
6) according to the content of multiring aromatic hydrocarbon marker or/and phenols marker in step 4) and the resulting sample of step 5), according to
According to the content of marker in bought creosote standard substance, conversion obtains the content of creosote in sample by a certain percentage.
2. the method as described in claim 1, it is characterised in that: in step 1), sample is the bamboo and wood products contacted with food, sample
Product are cut into no more than 2 × 2 × 2mm size, and tracer is deuterated terphenyl, and inner mark solution is deuterated naphthalene, are vortexed after concussion 1min,
60 ± 5min of ultrasonic extraction under 60 ± 5 DEG C of bath temperature takes out, is cooled to room temperature, sample solution is transferred to sample injection bottle,
To be detected for gas chromatograph-mass spectrometer (GC-MS).
3. the method as described in claim 1, it is characterised in that: in step 3), polycyclic aromatic hydrocarbon marker is 7 kinds, phenols label
Object is 4 kinds；When containing naphthalene and any other 2 polycyclic aromatic hydrocarbon markers in sample, then contain 3 kinds in judgement sample with polycyclic
Aromatic hydrocarbons creosote as main component, chemical abstracts number are respectively 8001-58-9,61789-28-4 and 90640-84-9；When
Contain p- methylphenol and any other 2 phenols markers in sample, then shows in sample containing based on phenolic compound
The creosote of ingredient is wanted, chemistry side's number of plucking is 8021-39-4.
4. the method as described in claim 1, which is characterized in that in step 5), the determination condition of gas chromatography-mass spectrometry
Are as follows:
A) gas chromatographic column use HP-INNOWAX capillary column, specification be column length 30m, column internal diameter 0.25mm, 0.50 μm of film thickness；
B) gas chromatographic sample introduction mouth temperature is set as 200 DEG C, and temperature programming is 80 DEG C of initial temperature, retains 1min, by 40 DEG C/min liter
Temperature retains 10 minutes min to 180 DEG C, is warming up to 245 DEG C by 26 DEG C/min, retains 5min；
C) mass spectrum acquisition selection ion scan SIM mode, scans ion are as follows:
。
5. the method as described in claim 1, which is characterized in that in step 6), by weight of between each marker and creosote
Formula: marker content/content of the marker in creosote standard substance in creosote content=sample in sample, by sample
The content of middle polycyclic aromatic hydrocarbon marker naphthalene or/and the content of the p- methylphenol of phenols marker, conversion obtain creosote in sample
Content.
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| JP2005127932A (en) * | 2003-10-27 | 2005-05-19 | Hywood Co Ltd | Optical method and instrument for detecting wood preservative |
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| JP2005127932A (en) * | 2003-10-27 | 2005-05-19 | Hywood Co Ltd | Optical method and instrument for detecting wood preservative |
| CN104132905A (en) * | 2014-05-05 | 2014-11-05 | 河南科技大学 | Detection method for adulterated sesame oil |
Non-Patent Citations (4)
| Title |
|---|
| Inventory and Emission Factors of Creosote, Polycyclic Aromatic Hydrocarbons (PAH), and Phenols from Railroad Ties Treated with Creosote;MARTIN KOHLER 等;《Environ.Sci.Technol.》;20001231;第34卷(第22期);第4766-4772页 * |
| VOCs and PAHs emissions from creosote-treated wood in a field storage area;E. Gallego 等;《SCIENCE OF THE TOTAL ENVIRONMENT》;20080527;第402卷(第1期);第130-138页 * |
| 木焦油及其馏分有机成分分析;隋海清 等;《太阳能学报》;20141130;第35卷(第11期);第2204-2209页 * |
| 阔叶树皮木醋液与木焦油有机成分的气相色谱分析;李元祥 等;《分析科学学报》;20120229;第28卷(第1期);第58-62页 * |
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