CN114184711A - Optimization method for headspace solid-phase microextraction conditions of volatile components of eucalyptus shaving boards - Google Patents

Optimization method for headspace solid-phase microextraction conditions of volatile components of eucalyptus shaving boards Download PDF

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CN114184711A
CN114184711A CN202111604488.5A CN202111604488A CN114184711A CN 114184711 A CN114184711 A CN 114184711A CN 202111604488 A CN202111604488 A CN 202111604488A CN 114184711 A CN114184711 A CN 114184711A
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eucalyptus
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文天国
郭兆辉
杨兆金
武波晓
赵平
杜官本
万辉
储键基
金正洪
许文熙
黄鹤鸣
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Yunnan Xinzexing Artificial Board Co ltd
Kunming Xinfeilin Panel Board Co ltd
Southwest Forestry University
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Kunming Xinfeilin Panel Board Co ltd
Southwest Forestry University
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Abstract

The invention relates to a preferable method for headspace solid phase micro-extraction conditions of volatile components of a eucalyptus shaving board, which comprises the following steps: crushing a eucalyptus shaving board, and testing as a sample to be tested; determining an extraction head; determining the influence of the extraction conditions of the headspace solid phase microextraction on the extraction of volatile components of the eucalyptus shaving board by adopting a single-factor test method; analyzing and optimizing operation parameters, and performing gas chromatography-mass spectrometry analysis on volatile components of the eucalyptus shaving board. The optimized method for the headspace solid-phase microextraction condition of the volatile components of the eucalyptus shaving board integrates collection, extraction, concentration, sample introduction and analysis, does not need a solvent, avoids the influence of an organic solvent on detection, greatly simplifies the preparation and analysis processes of the sample, provides an effective way for the detection and identification of VOCs in a complex matrix, and is widely applied to various fields such as food analysis, environmental pollution, pharmacy and the like.

Description

Optimization method for headspace solid-phase microextraction conditions of volatile components of eucalyptus shaving boards
Technical Field
The invention belongs to the field of detection, and particularly relates to a method for optimizing headspace solid-phase microextraction conditions of volatile components in eucalyptus particle boards.
Background
The shaving board is an artificial board which is prepared by drying wood processing residues, small-diameter wood, wood chips and other fragments, mixing with additives such as sizing materials, auxiliaries, curing agents and the like, and pressing at a certain temperature and under a certain pressure, and has the advantages of uniform structure, easiness in automatic continuous production, small volume density and thickness error, pollution resistance, ageing resistance, good sound absorption and sound insulation performance and the like. In recent years, with the rapid development of the interior decoration industry and the artificial board industry, various shaving board products are widely applied to sound insulation walls, interior wall decoration and the like. Because the components contained in the wood shavings are complex, and in addition, a plurality of additives such as sizing materials are used in the production process of the shaving board, a large amount of Volatile Organic Compounds (VOCs) can be released under the conditions of pressurization, heating and the like, so that the wood shavings become one of the main sources of indoor air environmental pollution and bring potential harm to human health. Generally, adhesives such as urea-formaldehyde resin added in the production process can cause formaldehyde residues in the board, so that the formaldehyde in the indoor air exceeds the standard. However, besides formaldehyde, the release of other organic compounds also causes indoor environmental pollution, and the analysis of Melissa and the like on indoor air of newly built residences shows that the artificial board and products thereof are main release sources of indoor terpenes, aldehydes and ketones. Therefore, in recent years, research on the release of VOCs from the sheet material has been receiving attention.
Gas chromatography-mass spectrometry (GC-MS) combined technology is the most commonly used detection method for VOCs, but before detection and analysis, a sample needs to be subjected to proper pretreatment, and different extraction modes bring great difference to the extraction results of the whole VOCs. At the present stage, no method for effectively exploring the headspace solid phase microextraction condition exists.
Therefore, the technical scheme of the invention is provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preferred method for headspace solid-phase micro-extraction conditions of volatile components of a eucalyptus particle board. The invention takes a eucalyptus shaving board as a research object, optimizes the headspace solid phase microextraction (HS-SPME) extraction condition by adopting a single-factor test combined with a response surface Box-Behnken test design method, establishes an analysis method for rapidly detecting VOCs of the eucalyptus shaving board by combining a GC-MS method, and provides reference for further research of the VOCs of the eucalyptus shaving board.
The scheme of the invention is to provide a preferable method for headspace solid phase micro-extraction conditions of volatile components of eucalyptus particle boards, which comprises the following steps:
(1) crushing a eucalyptus shaving board, and testing as a sample to be tested;
(2) determining an extraction head;
(3) in the test, a single-factor test method is adopted to determine the influence of the extraction conditions of the headspace solid-phase microextraction on the extraction of the volatile components of the eucalyptus shaving board;
(4) analyzing and optimizing operation parameters, and performing gas chromatography-mass spectrometry analysis on volatile components of the eucalyptus shaving board.
Preferably, in step (1), the pulverization is carried out through a 40-mesh sieve.
Preferably, in step (2), the extraction head is selected alternatively between 100 μm PDMS and 75 μm CAR/PDMS.
Preferably, in the step (3), the extraction conditions are extraction temperature, equilibration time, extraction time and resolution time.
Preferably, the extraction temperature is selected from 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃.
Preferably, the balancing time is 25min, 30min, 35min, 40min and 5 min.
Preferably, the extraction time is 20min, 25min, 30min, 35min and 40 min.
Preferably, the analysis time is selected from 1min, 3min, 5min, 7min and 9 min.
The invention has the beneficial effects that:
the optimal selection method of the headspace solid-phase microextraction condition of the volatile components of the eucalyptus shaving board integrates collection, extraction, concentration, sample introduction and analysis, does not need a solvent, avoids the influence of an organic solvent on detection, greatly simplifies the preparation and analysis processes of a sample, provides an effective way for the detection and identification of VOCs in a complex matrix, and is widely applied to the fields of food analysis, environmental pollution, pharmacy and the like. And proved by experiments, the extraction time and the extraction temperature have obvious influence on the extraction of the VOCs of the eucalyptus shaving boards, and the optimal extraction conditions are that the temperature is 91 ℃, the equilibrium time is 34min, the extraction time is 24min and the resolution time is 2.5 min. Under the condition, the relative error between the verification test result and the theoretical prediction value is 0.62%, 54 kinds of VOCs (volatile organic compounds) are detected from the eucalyptus shaving board, including 23 kinds of olefins, 11 kinds of alcohols, 8 kinds of alkanes, 5 kinds of aromatic hydrocarbons, 5 kinds of aldehydes, 1 kind of esters and acids, and reference is provided for further research on the VOCs of the eucalyptus shaving board.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the number and classification of VOCs extracted from 100. mu. mPDMS and 75. mu. mCR/PDMS.
FIG. 2 is a graph showing the effect of different extraction conditions on the number of significant peaks in VOCs in eucalyptus particleboard.
FIG. 3 shows the effect of the interaction of two extraction conditions on the extraction results.
Figure 4 is a total ion diagram of eucalyptus particleboard VOCs.
Figure 5 is the molecular structure of the major VOCs in eucalyptus particleboard.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Examples
This example provides a preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard, comprising the steps of:
(I) preparation of test material, determination apparatus and apparatus
Preparation of test materials: the eucalyptus particle board is provided by Kunming New Feilin artificial board company Limited, the particle board is crushed and sieved by a 40-mesh sieve to be uniform particles, and 1.000g of the particle board is accurately weighed and placed in a 20mL headspace sample bottle for later use.
The instrument and the equipment are as follows: a manual solid phase micro-extraction device (Supelco, USA), 100 mu mPDMS and 75 mu mCRAR/PDMS extraction heads (Supelco, USA), 7090B/5977B type gas chromatography-mass spectrometry (Agilent, USA), and a giant Fengfeng JHF-1000A type high-speed multifunctional pulverizer (Kunming iron trade company, Inc., China).
(II) determination of extraction head
Aging the extraction head at a gas chromatography sample inlet until no impurity peak is reserved, and aging the extraction head at 100 mu m PDMS: aging temperature of 250 ℃, aging time: 2 h; 75 μm CAR/PDMS: the aging temperature is 300 ℃, and the aging time is 2 h. Weighing 1.000g of eucalyptus shaving board particles, placing the weighed particles in a 20mL headspace sample bottle, extracting VOCs under the conditions of extraction temperature of 90 ℃, equilibrium time of 35min, extraction time of 25min and resolution time of 3min, detecting according to the following GC-MS analysis conditions, and determining a proper extraction head by taking the effective peak number of the VOCs as an index.
GC-MS analysis conditions: chromatographic conditions are as follows: chromatography column, HP-5MS quartz capillary column (30 m.times.250 μm.times.0.25 μm); the temperature of a sample inlet is 300 ℃; temperature rising procedure: the initial temperature is 60 ℃, the temperature is increased to 120 ℃ at the speed of 10 ℃/min, and the temperature is kept for 10 min; raising the temperature to 180 ℃ at 5 ℃/min; then raising the temperature to 240 ℃ at a speed of 10 ℃/min, and keeping the temperature for 8 min; carrier gas He, the flow rate is 0.8 mL/min; no split-flow sample introduction. Mass spectrum conditions: an Electron Impact (EI) ion source; electron energy 70 eV; the transmission line temperature is 250 ℃; the ion source temperature is 230 ℃; the quadrupole temperature was 150 ℃. The collection mode is as follows: full scanning; the mass range is m/z35-550 u. For VOCs with the matching degree larger than 80 (maximum value 100), performing computer retrieval and qualification by adopting NIST14 standard spectral library; and (3) after eliminating interference of non-target ions by utilizing a quadrupole mass spectrum, performing integration and integration correction on a target spectrum peak, and calculating the relative content of each volatile matter by adopting an area normalization method.
The adsorption of the extraction head on VOCs is mainly based on the principle of 'similarity and compatibility', and the influence of the type and thickness of the coating on the sensitivity of HS-SPME is more critical. Therefore, the adsorption capacities of the extraction heads with two different materials of 100 mu mPDMS and 75 mu mCER/PDMS are compared by taking the detected effective peak as an index. The result shows that 44 VOCs are obtained by extracting the 100 mu m PDMS extraction head, wherein the VOCs comprise 21 olefins, 9 alcohols, 8 alkanes, 3 aromatics, 4 acids and 3 esters; 52 VOCs are extracted by a 75 mu mCAR/PDMS extraction head, wherein 13 olefins, 9 alcohols, 15 alkanes, 6 aromatics, 4 esters, 4 aldehydes and 1 acid (shown in figure 1) are included, which indicates that the 75 mu mCAR/PDMS extraction head is more suitable for extracting VOCs of eucalyptus chipboards.
(III) determining the influence of the extraction conditions of the headspace solid phase microextraction on the extraction of the volatile components of the eucalyptus shaving board by adopting a single-factor test method
Selecting a proper extraction head under the condition of fixing GC-MS, respectively inspecting the influence of 4 factors of extraction temperature (60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃), equilibrium time (25min, 30min, 35min, 40min, 45min), extraction time (20min, 25min, 30min, 35min, 40min) and analysis time (1min, 3min, 5min, 7min, 9min) on the number of effective peaks of the extract, and determining corresponding optimization parameters.
On the basis of a single-factor test, a Box-Behnken test Design scheme is adopted, an optimal extraction head is selected, extraction temperature (A), balance time (B), extraction time (C) and analysis time (D) are taken as test factors, levels of variables are represented by +1, 0 and-1 respectively, a 4-factor 3 horizontal response surface test (table 1) is carried out by taking a detected effective peak as a response value, and regression analysis and response surface analysis are carried out on test data by adopting Design-expert12.0 software.
TABLE 1 Box-Behnken test factor levels
Figure BDA0003433229300000061
According to the actual needs of test operation, after the optimal extraction conditions obtained by the response surface analysis test are properly adjusted, 1.000g of the optimal extraction conditions are weighed and placed in a 20mL headspace sample bottle for verification test, the verification test is repeated for 3 times, the number of the detected effective peaks of the VOCs is compared with the theoretical predicted value calculated by a regression equation, so that whether the test parameters obtained by the response surface are correct and reliable is verified, and qualitative and quantitative analysis is carried out on the effective peaks of the VOCs.
Effect of extraction temperature on the number of effective peaks of VOCs:
selecting a 75 mu mCAR/PDMS extraction head, fixing the balance time for 35min, the extraction time for 30min and the analysis time for 5min, wherein the influence of different extraction temperatures on the number of effective peaks of VOCs of the eucalyptus shaving board is shown in figure 2 a. At a lower temperature of 60 ℃, the emission of the sample VOCs is slow and is not beneficial to the adsorption of the extraction head to the components of the sample to be detected. Along with the rise of the temperature, the molecular thermal motion is accelerated, the emission speed of VOCs of a sample to be detected is accelerated, the adsorption capacity of an extraction head is enhanced, the quantity of VOCs presents an increasing trend (70-90 ℃), the maximum value is reached at 90 ℃, and 52 VOCs components are detected. At 100 ℃, the number of effective peaks of VOCs is reduced, probably because the distribution coefficient of the substance to be measured in the coating and the substrate is reduced due to too high temperature, resulting in reduced adsorption on the coating, and therefore the extraction temperature is selected to be 90 ℃.
Effect of equilibration time on the number of valid peaks of VOCs:
the effect of different equilibration times on the number of VOCs in eucalyptus particleboard at a fixed extraction temperature of 90 ℃, an extraction time of 30min and an extraction time of 5min is shown in fig. 2 b. When the balance time is 25-35 min, the total peak number shows a growing trend and reaches a maximum value at 35 min. The optimum equilibration time of 35min was chosen because the number of VOCs decreased slightly and did not change significantly as the equilibration time was extended, probably because the headspace volume was fixed and the VOCs saturated in the bottle at 35min, resulting in a relatively stable number of valid peaks.
Effect of extraction time on the number of effective peaks of VOCs:
under the conditions of the fixed extraction temperature of 90 ℃, the equilibrium time of 35min and the analysis time of 5min, the influence of different extraction times on the number of the effective peaks of the VOCs in the eucalyptus shaving board is shown in figure 2c, and the total number of the effective peaks of the VOCs shows a trend of increasing first and then decreasing. The reason may be that the adsorption capacity of the extraction head coating is not saturated when the extraction time is 20-25 min, the adsorption capacity of the extraction head coating is saturated after 25min, and VOCs with low thermal stability begin to decompose into small molecular compounds along with the extension of the extraction time, so that the total peak number is reduced, and therefore, the optimal extraction time is selected to be 25 min.
Influence of the analysis time on the number of effective peaks of VOCs:
under the conditions of the fixed extraction temperature of 90 ℃, the equilibrium time of 35min and the extraction time of 25min, the influence of different analysis times on the number of the effective peaks of the VOCs in the eucalyptus shaving board is shown in fig. 2d, and the total number of the effective peaks of the VOCs shows a trend of increasing first and then decreasing. The length of the analysis time is generally related to the coating thickness of the extraction head, and the analysis time after 3min shows a downward trend probably due to the fact that the high temperature is reduced, the analysis time is too long, and therefore oxidation, isomerization and other reactions of some VOCs occur, and the optimal analysis time is selected to be 3 min.
(IV) analyzing and optimizing operation parameters, and carrying out gas chromatography-mass spectrometry combined analysis on volatile components of the eucalyptus shaving board
Response surface analysis test results:
the results of the 4-factor 3 horizontal center combination test according to table 1 are shown in table 2. The multivariate regression analysis is carried out on the test data of the table 2 by using the software DesignExpert12.0, the analysis result of the variance of a regression model is shown in the table 3, and the binary regression equation for obtaining the quantity (Y) of the effective peaks of the VOCs of the eucalyptus shaving boards is as follows: y ═ 53.4+2.33A-1.17B-2.5C-1.33D-1.5AB-3.76AC-0.75AD +3.25BC-0.25BD-2CD-12.37A2-5.37B2-6.87C2-1.87D2. Wherein A, B, C, D are the level values of extraction temperature, equilibration time, extraction time and analysis time, respectively.
As can be seen from Table 3, the model P values were < 0.0001, indicating that the regression model was very significant (P < 0.01). And the mismatching term is not significant (P-0.1131) and R2The model can be used to analyze and predict the number of significant peaks in eucalyptus chipboard VOCs, indicating good fit of the regression equation 0.9414. As can also be seen from Table 3, A, C, A2、B2、C2The effect on the results was very significant (P < 0.01), the effect on the results was significant for the interaction terms AC and BC (P < 0.05), and the magnitude order of the effect on the number of VOCs from the F value in Table 3 is the extraction time (C)>Extraction temperature (A)>Analysis time (D)>The balance time (B), the extraction time and the extraction temperature are very obvious for extracting VOCs from the eucalyptus shaving boards.
Table 2 response surface test design and results
Figure BDA0003433229300000081
Figure BDA0003433229300000091
TABLE 3 regression model analysis of variance results
Figure BDA0003433229300000092
Figure BDA0003433229300000101
Note: "x" indicates that the difference was extremely significant (P < 0.01); "" indicates significant difference (P < 0.05).
Interaction between two factors:
the three-dimensional response surface drawn by using the design expert12.0 software is shown in fig. 3. As can be seen from fig. 3, the response surface graph formed by the influencing factors of each test is open downwards, the central part of the response surface graph is provided with a certain bulge, and the highest point exists in the surface and is within the range of the test design, which indicates that the response value has the maximum value. The degree of steepness of the response surface can reflect the influence degree of each factor, and the influence is larger when the surface is steeper, and vice versa. From the steepness of the two-factor response surface in fig. 3, AC > BC > CD > AB > AD > BD, where the curve of the change of the extraction temperature and the extraction time is steepest, i.e. has a large influence on the number of effective peaks of the VOCs, and the curve of the change of the equilibrium time and the analysis time is gentler, has a small influence on the number of effective peaks of the VOCs, which is also consistent with the data analysis in table 3.
Determination and verification of optimal extraction conditions:
and predicting the regression model by combining the analysis result of the quadratic regression model to obtain the optimum extraction conditions for analyzing the VOCs of the eucalyptus shaving board by the HS-SPME-GC-MS, wherein the optimum extraction conditions comprise the extraction temperature of 91.49 ℃, the equilibrium time of 34.03min, the extraction time of 23.84min and the analysis time of 2.50min, and the number of effective peaks of the VOCs of the eucalyptus shaving board under the conditions is predicted to be 54.14. On the basis of a response surface test, by combining with the consideration of actual operation, 3 parallel verification tests are carried out by selecting the extraction temperature of 91 ℃, the balance time of 34min, the extraction time of 24min and the analysis time of 2.5min, the number of the obtained VOCs effective peaks is respectively 55, 54 and 54, the relative error with the predicted value is 0.62%, and the fact that the extraction parameters obtained by optimizing the response surface are accurate and reliable is proved.
(IV) analyzing and optimizing operation parameters, and carrying out gas chromatography-mass spectrometry combined analysis on volatile components of the eucalyptus shaving board
The HS-SPME-GC-MS technology after the optimization of the extraction conditions is used for analyzing VOCs in the eucalyptus shaving board, the total ion diagram is shown in figure 4, and the chemical composition and the relative content are shown in table 4. As can be seen from table 4, after response surface optimization, the HS-SPME-GC-MS detects 54 types of eucalyptus particleboard VOCs including 23 types of olefins, 11 types of alcohols, 8 types of alkanes, 5 types of aromatics, 5 types of aldehydes, 1 type of esters and acids, and the relative content ratios are 37.18%, 33.84%, 20.02%, 5.30%, 2.97%, 0.39% and 0.30%, respectively. Wherein, the relative contents of (+) -coumarine, (-) -eudesmol, n-eicosane, (+) -horn alkene and lachrymal are high, respectively 18.99%, 17.46%, 5.32%, 4.25% and 3.81%, and the relative contents thereof account for 49.86% (fig. 5), which should be the main VOCs in the eucalyptus shaving board.
TABLE 4 composition and relative content of VOCs in eucalyptus particleboards
Figure BDA0003433229300000111
Figure BDA0003433229300000121
Figure BDA0003433229300000131
Figure BDA0003433229300000141
And (4) conclusion:
on the basis of a single-factor test, the HS-SPME extraction conditions of VOCs in a eucalyptus shaving board are analyzed and optimized by applying a Box-Behnken design method and a response surface method, and the VOCs in the eucalyptus shaving board are analyzed by combining a GC-MS technology. The result shows that the optimal extraction conditions of the VOCs of the eucalyptus wood shaving board are that a 75 mu mCAR/PDMS extraction head is selected, the extraction temperature is 91 ℃, the equilibrium time is 34min, the extraction time is 24min and the analysis time is 2.5 min. Under the condition, 54 kinds of VOCs are detected from the eucalyptus shaving board, wherein the content of the olefins is the highest, the alcohols and the alkanes are the second most, the relative content of the aromatic hydrocarbons, the aldehydes, the esters and the acids is less, and the (+) -citronene, (-) -eudesmol, n-eicosane, (+) -trumpet alkene and tear fir alcohol are the main VOCs in the eucalyptus shaving board. The relative error between the test result and the model prediction result is 0.62%, which shows that the extraction parameters obtained by response surface optimization are accurate and reliable, and provides reference for further research of the VOCs of the eucalyptus shaving boards.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (8)

1. A preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard, characterized in that it comprises the following steps:
(1) crushing a eucalyptus shaving board, and testing as a sample to be tested;
(2) determining an extraction head;
(3) in the test, a single-factor test method is adopted to determine the influence of the extraction conditions of the headspace solid-phase microextraction on the extraction of the volatile components of the eucalyptus shaving board;
(4) analyzing and optimizing operation parameters, and performing gas chromatography-mass spectrometry analysis on volatile components of the eucalyptus shaving board.
2. The preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particle boards as claimed in claim 1 wherein in step (1) said grinding is done through a 40 mesh screen.
3. The preferred method of claim 1 wherein in step (2) said extraction head is selected alternatively between 100 μm PDMS and 75 μm CAR/PDMS.
4. The preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard according to claim 1, wherein in step (3), said extraction conditions are extraction temperature, equilibration time, extraction time and resolution time.
5. The preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard according to claim 4 wherein said extraction temperature is selected from 60 ℃, 70 ℃, 80 ℃, 90 ℃ and 100 ℃.
6. The preferred method of headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard as claimed in claim 4 wherein said equilibration time is selected from 25min, 30min, 35min, 40min and 5 min.
7. The preferred method of the headspace solid phase microextraction conditions for volatile components of eucalyptus particle boards as claimed in claim 4 wherein said extraction time is selected from 20min, 25min, 30min, 35min and 40 min.
8. The preferred method of the headspace solid phase microextraction conditions for volatile components of eucalyptus particleboard according to claim 4, wherein said resolving time is selected from 1min, 3min, 5min, 7min and 9 min.
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