KR20140143967A - Pretreatment method for analyzing dioxins compound and analytical method using the same - Google Patents

Abstract

The present invention relates to a pre-treating method for analyzing a dioxin compound, wherein the pre-treating method comprises the steps of: (a) changing a liquid sample to a solid through a filter including an adsorbent having an octadecyl group; (b) drying the sample which is changed into the solid; (c) adding a first solvent to the dried sample and extracting the same; (d) concentrating the extracted sample; (e) adding a second solvent in the concentrated sample and sequentially passing two or more columns so as to refine the same; and (f) concentrating the refined sample. Moreover, the present invention relates to a method of analyzing a dioxin compound, wherein the method comprises a step of analyzing the sample treated by means of the pre-treating method through an analyzing device.

Description

TECHNICAL FIELD The present invention relates to a pretreatment method for analyzing dioxin compounds and an analytical method using the same.

TECHNICAL FIELD The present invention relates to a pretreatment method for analyzing dioxin compounds and an analytical method using the same.

The dioxin concentration in the wastewater of the VCM (Vinyl Chloride Monomer) manufacturing facility by the Persistent Organic Pollutants Control Act has been reduced from 300 pg I-TEQ / L to 50 pg I-TEQ / L in 2013, the Ministry of Environment's regulations on dioxins are strengthening. Accordingly, there is an increasing demand for quantitative or qualitative analysis of dioxin compounds present in the water.

However, in order to analyze dioxin compounds present in a water quality sample, many pre-treatment steps such as extraction of dioxin compounds, purification process for removing interfering substances, and concentration process are required. Therefore, It takes a long time.

Therefore, in order to analyze the dioxin compounds existing in the water quality sample, it is necessary to use a pretreatment method which does not degrade the quantitative value when analyzing the pretreated sample and the recovery rate of the standard material for purification, .

Residual Organic Pollutants Process Test Method [Enforcement 2007.11.15] [Ministry of Environment notification 2007-165, 2007.11.15, enacted]

The present invention relates to a method for analyzing a dioxin compound having excellent quantitative value and recovery rate of a standard substance for purification when a pretreated sample is analyzed in a time less than a pretreatment method for analyzing a conventional dioxin compound, And a method for analyzing the same.

In the present specification,

(a) converting a liquid sample into a solid phase with a filter comprising an adsorbent having an octadecyl group;

(b) drying the sample converted to the solid phase;

(c) adding a first solvent to the dried sample, and then extracting a component dissolved in the first solvent in the sample;

(d) concentrating the first solvent in the extraction solution;

(e) adding a second solvent to the concentrated sample, and then purifying by passing two or more columns in sequence; And

(f) removing at least a portion of the second solvent from the purified sample solution and concentrating the dioxin compound.

In addition, the present specification provides a method of analyzing a sample treated by the pretreatment method for analyzing dioxin compounds.

The pretreatment method for analyzing dioxin compounds according to the present specification and the method of analyzing the sample treated with the pretreatment method have a short time required and the accuracy of the analysis is excellent.

The dioxin analysis method using the residual organic pollutant process test method of the Korean Ministry of the Environment is limited to a sample amount of 2 L or less since it is based on a liquid-liquid extraction method. However, the pretreatment method for analyzing dioxin compounds and the pretreatment method The analysis method of the sample can be applied to a sample amount of 10 L, so that it can be usefully used for increasing the sample amount for analysis of a trace amount of dioxin.

1 shows a pre-treatment step according to Comparative Example 1 of this specification.
2 shows a pre-processing step according to Embodiment 2 of the present invention.

The present specification provides a pretreatment method for analyzing dioxin compounds.

As used herein, the dioxin compound refers to polychlorinated dibenzo-p-dioxins or polychlorinated dibenzofurans.

According to one embodiment of the present disclosure, the first solvent is toluene.

According to one embodiment of the present disclosure, the second solvent is toluene or n-hexane.

According to one embodiment of the present invention, the filter including the adsorbent having an octadecyl group in the step (a) of the pretreatment method for analyzing dioxin compounds is a glass fiber mixed.

The adsorbent having an octadecyl group may be a compound having a silyl group substituted with an octadecyl group.

According to one embodiment of the present invention, the filter including the adsorbent having an octadecyl group in the step (a) of the pretreatment method for analyzing dioxin compounds includes an adsorbent layer having an oxadecyl group and a glass fiber layer.

According to one embodiment of the present invention, the filter including the adsorbent having an octadecyl group in the step (a) of the pretreatment method for analyzing dioxin compounds is disc-shaped.

The disk-shaped filter including the adsorbate having the silyl group substituted with the oxadecyl group in the step (a) may be a trade name Empore manufactured by 3M Company.

The filter including the adsorbent layer having a silyl group substituted with an oxadecyl group and the glass fiber layer and having a disk shape in the step (a) may be UltraFlow, manufactured by ENVIRONMENTAL EXPRESS.

According to an embodiment of the present invention, the step (c) uses Accelerated Solvent Extraction (ASE).

In this specification, the accelerated solvent extraction method refers to a method in which a sample is put into a sealed container at a specific temperature and a specific pressure and is extracted using a solvent heated to a boiling point or higher.

The temperature of the accelerated solvent extraction method may be from 50 캜 to 200 캜.

The pressure of the accelerated solvent extraction method may be 3000 psi or less.

The device using the accelerated solvent extraction method may be a series product including a product name ASE200 manufactured by Dionex.

According to an embodiment of the present invention, the step (d) is performed using a concentrator compatible with the apparatus using the accelerated solvent extraction method.

The concentrator compatible with the apparatus using the accelerated solvent extraction method may be Turbovap manufactured by Biotage or Turbovap II manufactured by Zymark.

According to one embodiment of the present invention, the column of the step (e) of the pretreatment method for analyzing the dioxin compound may be eluted to be selected from the group consisting of normal hexane, normal hexane containing dichloromethane, and toluene , But is not limited thereto.

According to an embodiment of the present invention, the column of step (e) of the pretreatment method for analyzing dioxin compounds includes a first column, a second column and a third column.

The step (e) of the pretreatment method for analyzing the dioxin compound may be performed by passing the concentrated sample through the first column, the second column and the third column in order.

The first column may be eluted with normal hexane.

The second column may be eluted with normal hexane containing dichloromethane.

The third column may be eluted with toluene.

According to an embodiment of the present invention, the concentration in the step (f) of the pretreatment method for analyzing the dioxin compound may be performed using a rotary evaporator, a concentrator compatible with the apparatus using the accelerated solvent extraction method, and a heating block One or more selected from the group can be used.

The rotary evaporator may be Rotavapor R-205, manufactured by buchi.

A concentrator compatible with the apparatus using the accelerated solvent extraction method may be Turbovap, manufactured by Biotage.

The heating block may be a trade name MG-2200 manufactured by Eyela.

According to one embodiment of the present invention, the column of step (e) of the pretreatment method for analyzing dioxin compounds is selected from the group consisting of silica gel column, alumina column and activated carbon column.

According to an embodiment of the present invention, the step (e) of the pretreatment method for analyzing the dioxin compound is to purify the concentrated sample by passing it through a silica gel column, an alumina column and an activated carbon column in this order.

The purification apparatus including the silica gel column, the alumina column and the activated carbon column is an apparatus for automatically purifying the sample by passing the sample through a silica gel column, an alumina column and an activated carbon column in this order.

The purification apparatus including the silica gel column, the alumina column and the activated carbon column may be PowerPrep (trade name) manufactured by FMS (Fluid Management System).

According to an embodiment of the present invention, an apparatus using an accelerated solvent extraction method of the step (c) and an apparatus for automatically purifying a sample of the step (d) by passing the sample in the order of a silica gel column, an alumina column and a column are connected .

According to an embodiment of the present invention, the pretreatment method for analyzing dioxin compounds further comprises adding an internal standard substance for purification to the sample of step (a) before the step (a).

In the present specification, the internal standard for purification is an organic compound having a chemical structure or chemical property similar to that of the substance to be analyzed and not found in the sample medium. It is added before the sample treatment or extraction to examine the reliability of the analysis method It means to use.

The internal standard for purification is ¹³ C ₁₂ -2,3,7,8-TeCDD, ¹³ C ₁₂ -1,2,3,7,8-PeCDD, ¹³ C ₁₂ -1,2,3,4,7 , 8-HxCDD, ¹³ C ₁₂ -1,2,3,6,7,8-HxCDD, ¹³ C ₁₂ -1,2,3,4,6,7,8-HpCDD, ¹³ C ₁₂ -1,2 , 3,4,6,7,8,9-OCDD, ¹³ C ₁₂ -2,3,7,8, -TeCDF, ¹³ C ₁₂ -1,2,3,7,8-PeCDF, ¹³ C ₁₂ - 2,3,4,7,8-PeCDF, ¹³ C ₁₂ -1,2,3,4,7,8-HxCDF, ¹³ C ₁₂ -1,2,3,6,7,8-HxCDF, ¹³ C ₁₂ -1,2,3,7,8,9-HxCDF, ¹³ C ₁₂ -2,3,4,6,7,8-HxCDF, ¹³ C ₁₂ -1,2,3,4,6,7, 8-HpCDF and ¹³ C ₁₂ -1,2,3,4,7,8,9-HpCDF.

In this specification, TeCDD is TetrachloroDibenzo-ρ-dioxin, TeCDF is Tetrachlorodibenzofuran, PeCDD is PentachloroDibenzo-ρ-dioxin, PeCDF is Pentachlorodibenzofuran, HxCDD is HexachloroDibenzo-ρ-dioxin, HxCDF is Hexachlorodibenzofuran, HpCDD is HeptachloroDibenzo-ρ-dioxin, Heptachlorodibenzofuran, OCDD, OctachloroDibenzo-ρ-dioxin, and OCDF, Octachlorodibenzofuran, respectively.

According to one embodiment of the present disclosure, the dioxin compound is polychlorinated dibenzo-p-dioxins.

According to one embodiment of the present disclosure, it is polychlorinated dibenzofurans.

The present invention provides a method for analyzing a dioxin compound, which comprises the step of analyzing a sample treated with the dioxin pretreatment method described above by an analyzer.

According to one embodiment of the present disclosure, the analyzer is a gas chromatograph / high resolution mass spectrometer.

In this specification, a gas chromatograph / high resolution mass spectrometer is a device in which a gas chromatograph and a high-resolution mass spectrometer are connected to each other and a sample separated from a gas chromatograph is analyzed by a high-resolution mass spectrometer.

According to one embodiment of the present invention, the method for analyzing a dioxin compound further comprises adding an internal standard material for sludge addition to the sample treated by the dioxin pretreatment method before the analysis step.

In this specification, the internal standard material for syringe addition has a chemical structure or chemical property similar to that of the substance to be analyzed, and is an organic compound not found in the sample medium. In order to examine the reproducibility and accuracy of the analytical method, It is added before analysis.

The internal standard for syringe addition may be ¹³ C ₁₂ -1,2,3,4-TeCDD or ¹³ C ₁₂ -1,2,3,7,8,9-HxCDD.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example  One

Sampling

Use a brown glass bottle of Teflon plug that has been cleaned with solvent to collect more than 2 liters of sample below 30 ~ 50 cm below the surface of the water for analysis of dioxin compounds in the water, or if the sampling point is connected to the faucet, After the tank was stirred, the faucet was turned on and after 1 minute, more than 2 L was collected.

Solid-phase extraction  And filter drying

A predetermined amount of the collected samples was collected and 2 ng of the internal standard material for purification was added thereto. The resulting solution was filtered with an Empore filter manufactured by 3M Company, and extracted into a solid phase, followed by drying the filter.

Accelerated solvent extraction

To the dried sample was added toluene 40 mL, and the temperature was 150 ° C. and the pressure was 1500 psi.

Extract concentrate

The extract was concentrated to 1 mL using Turbovap (trade name, manufactured by Zymark), and the final volume of the extract was adjusted to 1 mL.

refine

Each column of the product PowerPrep manufactured by FMS was charged with an acidic silica gel, a basic silica gel and an activated silica gel in a volume corresponding to the EPA1613 method. The alumina column was charged with basic alumina CLDA-BAS-011 11 g. The activated carbon column was charged with 0.34 g of a substance (carbon-labeled product: CLDC-CCE-034 manufactured by FMS) mixed with carbon and celite.

To the concentrated extract, toluene or n-hexane 10 mL, and the silica gel column was loaded with 100 mL of n-hexane at a rate of 8 mL / min, 90 mL of n-hexane containing 2% of dichloromethane was flowed at a rate of 8 mL / min, 100 mL of normal hexane containing dichloromethane was operated at a rate of 8 mL / min, and the activated carbon column was operated at a rate of 5 mL / min with 80 mL of toluene to obtain 80 mL of a purified solution.

concentration

The purified solution was concentrated to 100 μL with a rotary evaporator and a Turbovap concentrator, and finally concentrated in a heating block to obtain a final volume of 10 μL for analysis.

Example  2

The procedure of Example 1 was carried out sequentially, except that the filter used for solid phase extraction in Example 1 was the trade name UltraFlow manufactured by ENVIRONMENTAL EXPRESS, and 10 μL volume of the final sample for analysis was obtained.

Comparative Example 1

Sampling

A sample for analyzing dioxin compounds in water was collected by the same method as in Example 1 using a brown glass bottle of Teflon plug which was washed with a solvent.

Sample Filtration and Extraction

After 2 ng of internal standard ³⁷ Cl ₄ -2,3,7,8-TeCDD for sample collection was added to the collected sample, the granular phase was filtered through the filter medium to separate the solid phase and the liquid phase, The flask was placed in a glass filter and extracted with toluene at a rate of 1 drop per second for 16 hours or more. The liquid phase was extracted twice more with normal hexane and the two extracts were combined.

Extract concentrate

The extract is concentrated to about 5 mL using a rotary evaporator, and then the solvent used for extraction is removed as much as possible by blowing nitrogen gas and converted to a sample for purification. The analytical sample was transferred to a 20 mL test tube by converting the solvent to 15 mL of normal hexane, and the final liquid volume was adjusted to 1 mL. 2 ng of the internal reference material for purification was added to the sample concentrated to 1 mL, and purification was carried out.

Tablets - Silica gel tablets

0.9 g of active silica gel, 3 g of basic silica gel, 0.9 g of active silica gel, 4.5 g of 44% acidic silica gel, 6 g of 22% acidic silica gel, 0.9 g of active silica gel, 3 g of 10% silver nitrate silver silica gel, and 6 g of anhydrous sodium sulfate were sequentially charged.

And eluted with 100 mL of normal hexane solution at a rate of 1 drop per second.

The concentrated sample was carefully immersed in the column wall, so that the anhydrous sodium sulfate at the top was not scattered, and then eluted at a rate of one drop per second with 150 mL of normal hexane solution.

The eluate was concentrated to about 5 mL with a concentrator, and then nitrogen gas was blown into it and concentrated to about 1 mL to prepare a sample for purification of alumina.

Purification - Alumina Purification

6 g of active alumina and 2 g of anhydrous sodium sulfate were sequentially charged into a column for purification of 15 mm in inner diameter and 300 mm in length, which were washed with a solvent.

The concentrated sample was carefully placed on the column wall, so that the anhydrous sodium sulfate at the top was not scattered. The sample was eluted at a rate of one drop per second with 100 mL of 2% dichloromethane-containing n-hexane and the eluate was discarded.

150 mL of 50% dichloromethane-containing n-hexane was then eluted at a rate of one drop per second.

The eluate was concentrated to about 1 mL with a concentrator, and then nitrogen gas was blown into the solution to concentrate the solution to about 100 μL. Then, 0.5 mL of toluene was added to convert the solvent to obtain a final volume of 10 μL for analysis.

Experimental Example

The internal standard material for padding added to the analytical final samples of Examples 1 and 2 and Comparative Example 1 was ¹³ C ₁₂ -1,2,3,4-TeCDD or ¹³ C ₁₂ -1,2,7,8,9 After adding 2 ng of HxCDD, the final sample volume was adjusted to 20 μL with nonan.

The final sample was loaded on a gas chromatograph / high-resolution mass spectrometer, and the resolution of the gas chromatograph / high-resolution mass spectrometer was maintained at 10,000 or higher at a 10% valley, and the sample was taken under conditions of an electron energy of 40 eV and a source temperature of 260 ° C As a result of the analysis, the measured concentration of the dioxin compound was obtained.

In order to show the accuracy of the measurement, the recovery rate of the standard material for purification was obtained as follows.

(1) Internal standards for sampling The recovery rates for ³⁷ Cl-2,3,7,8-TeCDD and 15 internal standard substances for purification are ¹³ C-1,2,3, 4-TeCDD and ¹³ C-1,2,3,7,8,9-HxCDD.

② Calibration curves are used to calculate the isotopic substituents for ¹³ C-1,2,3,4-TeCDD and ¹³ C-1,2,3,7,8,9-HxCDD, the internal standard for syringe addition. The relative sensitivity coefficient (RRF) of the standard is calculated as follows.

Here, A1 _n , A2 _n : the peak area of the first and second selected ions of the reference material for quantification

A1 _l , A2 _l : The peak area of primary and secondary selective ions in internal reference material for syringe addition

C _l : Concentration of internal reference material for syringe addition

C _n : concentration of reference material for quantification

③ Using the calculated RRF value and sample analysis data, the internal standards for sampling and purification of 4, 5-chlorides were identified by ¹³ C-1,2,3,4-TeCDD as 6, 7, 8 chloride For ¹³ C-1,2,3,7,8,9-HxCDD were calculated as follows.

Here, A1 _n , A2 _n : the peak area of the first and second selective ions of the reference material for purification

A1 _l , A2 _l : Peak area of primary and secondary selective ions in internal reference material for syringe addition

C _l : Concentration of internal reference material for syringe addition

C _n : concentration of reference material for quantification

RRF: relative sensitivity coefficient

Measured quantities of actual concentrations of dioxins in the samples obtained in Examples 1 and 2 and Comparative Example 1, recovery rates of the standard substances for purification, and pretreatment and analysis time are shown in Table 1 below.

Quantitative value
(pg I-TEQ / L) Recovery rate of standard substances for purification (%) Pre-treatment and analysis time (days) Example 1 597 ± 48 71 ~ 94 3 Example 2 604 ± 44 58 ~ 72 3 Comparative Example 1 577 ± 40 67 ~ 89 15

The quantitative values in Table 1 are values obtained by multiplying the measured toxic equivalents (TEQ) by the toxicity equivalence conversion coefficient using the international toxicity equivalency factor (I-TEF).

As shown in the above table, the pretreatment and analysis time required for Examples 1 and 2 were shortened to 1/5 level compared to Comparative Example 1 using the conventional pretreatment method, and the recovery rates of standard substances for purification were 50 %, Indicating that it is an effective method for quantitatively analyzing dioxin compounds.

Therefore, it can be seen that the methods of Examples 1 and 2 are more effective than the pretreatment method of Comparative Example 1, which is a pre-processing method for effective analysis while shortening the analysis time.

In addition, the pretreatment method of Example 1 has a higher recovery rate of the standard material for purification than the pretreatment method of Example 2, and is similar to the pretreatment method of Comparative Example 1, while the analysis time is shortened to 1/5 , And it is a preprocessing method of analysis that maintains similar accuracy.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention.

Therefore, the embodiments disclosed in the present invention are not intended to limit the scope of the present invention but to explain the scope of protection of the present invention should be construed according to the following claims, and all technical ideas Should be construed as being included in the scope of the present invention.

Claims (11)

(a) converting a liquid sample into a solid phase with a filter comprising an adsorbent having an octadecyl group;
(b) drying the sample converted to the solid phase;
(c) adding a first solvent to the dried sample, and then extracting a component dissolved in the first solvent in the sample;
(d) concentrating the first solvent in the extraction solution;
(e) adding a second solvent to the concentrated sample, and then purifying by passing two or more columns in sequence; And
(f) removing at least a portion of the second solvent from the purified sample solution and concentrating the dioxin compound. The pretreatment method for analyzing a dioxin compound according to claim 1, wherein the filter comprising the adsorbent having an octadecyl group in the step (a) is a mixture of glass fibers. The pretreatment method for analyzing a dioxin compound according to claim 1, wherein the filter including the adsorbent having an octadecyl group in the step (a) comprises an adsorbent layer having an oxadecyl group and a glass fiber layer. The pretreatment method according to claim 1, wherein the filter including the adsorbent having an octadecyl group in step (a) is disc-shaped. The pretreatment method according to claim 1, wherein the column of step (e) is selected from the group consisting of silica gel column, alumina column and activated carbon column. The pretreatment method according to claim 1, wherein the step (e) is performed by passing the concentrated sample through a silica gel column, an alumina column and an activated carbon column in order. The pretreatment method according to claim 1, further comprising the step of adding the internal standard for purification to the sample of step (a) before the step (a). The pretreatment method according to claim 1, wherein the dioxin compound is any one of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. A method for analyzing a dioxin compound, the method comprising the step of analyzing a sample treated by the dioxin pretreatment method of any one of claims 1 to 8 with an analyzer. The method according to claim 9, wherein the analyzer is a gas chromatograph / high-resolution mass spectrometer. [Claim 12] The method according to claim 9, further comprising adding an internal standard material for sludge addition to the sample treated by the dioxin pretreatment method prior to the analysis step.

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