KR101762215B1 - Method and apparatus for analyzing the binding status of heavy metals in contaminated soils by combining Laser Ablation and Sequential Extraction Analysis - Google Patents

Method and apparatus for analyzing the binding status of heavy metals in contaminated soils by combining Laser Ablation and Sequential Extraction Analysis Download PDF

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KR101762215B1
KR101762215B1 KR1020160008073A KR20160008073A KR101762215B1 KR 101762215 B1 KR101762215 B1 KR 101762215B1 KR 1020160008073 A KR1020160008073 A KR 1020160008073A KR 20160008073 A KR20160008073 A KR 20160008073A KR 101762215 B1 KR101762215 B1 KR 101762215B1
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contaminated soil
quantitative analysis
heavy metal
heavy metals
heavy
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이승학
양중석
박경수
권만재
전수경
최성화
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한국과학기술연구원
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Abstract

In carrying out quantitative analysis of various types of heavy metals present in contaminated soil using continuous extraction method, the present invention quantitatively analyzes the contaminated soil extracted at each step of the continuous extraction method, And a method and apparatus for analysis of heavy metals in contaminated soil by laser ablation and continuous extraction, which can quantitatively analyze the specific types of heavy metals extracted at each stage through the difference of quantitative analysis values As a method for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction according to the present invention, a continuous extraction method is used in which a heavy metal extraction step of a plurality of stages is performed and a heavy metal of a specific type is extracted at each step The quantitative analysis of the contaminated soil obtained through the heavy metal extraction step of each step was carried out. The quantitative analysis of the heavy metals present in each stage of contaminated soil (hereinafter referred to as 'contaminated soil in stage n' and n is a natural number) is measured, and the amount of heavy metals present in the contaminated soil in stage n The quantitative analysis value of each heavy metal is calculated by comparing the analytical value with the quantitative analysis value of the heavy metals present in the contaminated soil in the n-1th stage, And the quantitative analysis value for the n-th type heavy metal.

Description

TECHNICAL FIELD The present invention relates to a method and an apparatus for analyzing heavy metals in contaminated soil by laser ablation and continuous extraction,

The present invention relates to a method and apparatus for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction, and more particularly, to a method and apparatus for analyzing various types of heavy metals present in contaminated soil using a continuous extraction method In carrying out the analysis, the contaminated soil extracted at each step of the continuous extraction method is subjected to quantitative analysis, and the quantitative analysis of the specific type of heavy metals extracted at each step by the difference between the quantitative analysis values at each step and the previous step The present invention relates to a method and an apparatus for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction.

In the analysis of soil contaminated with heavy metals, there is continuous extraction method for analyzing the type of heavy metal present in contaminated soil. The continuous extraction method is a method of sequentially extracting a plurality of types of heavy metals by proceeding a plurality of extraction steps sequentially. The continuous extraction method is used to treat the heavy metals present in the contaminated soil as an exchangeable heavy metal, a bound to carbonate heavy metal, a bound to Fe-Mn oxides heavy metal, bound to organic matter, heavy metals, and residual bound heavy metals.

When the heavy metals are classified into the above-mentioned five types, the continuous extraction method includes a first step of dissolving the contaminated soil in the first solvent to extract an ion exchange heavy metal from the contaminated soil, a step of collecting the contaminated soil, A third step of extracting a metal oxide-bound heavy metal by dissolving the contaminated soil in which the second step is completed in a third solvent, a third step of extracting the metal oxide-bound heavy metal by dissolving the contaminated soil in the third solvent, And a fifth step of extracting the residual bound heavy metal by dissolving the contaminated soil after the fourth step is dissolved in the fifth solvent.

In addition, there are various methods by continuous extraction. In most cases, the types of heavy metals to be extracted are within the above-mentioned five types, and the difference in the detailed processes of extracting each type of heavy metals is shown. (Keon et al., Environ. Sci. Technol. 35 (2001) 2778-2784) and the Tessier method (Tessier et al., Anal. , Wenzel's method (Wenzel et al., Anal. Chim. Acta 436 (2001) 309-323), SM & T method (Rauret et al., J. Environ.

On the other hand, in the conventional continuous extraction method, the contaminated soil is dissolved in a solvent, the supernatant is separated and extracted through solid-liquid separation, and the heavy metal component is analyzed on the extracted supernatant. However, in the conventional continuous extraction method, it is difficult to completely separate the liquid and solid samples by using the pipette in solid-liquid separation. Therefore, there is a great possibility that experimental errors such as the solid samples mixed in the analysis of each step affect the result value, or the sum of the results of the respective concentrations is inconsistent with respect to the total concentration. In addition, in analyzing the result of each step with an analyzer, an appropriate dilution process is additionally required, and there is a problem that the deviation of experimental results is very large depending on the dilution ratio.

Further, in the conventional continuous extraction method, a strong acid such as hydrochloric acid or nitric acid is essentially used in the final step of extracting the residual binding heavy metal, which poses a safety problem.

Tessier et al., Anal. Chem. 51 (1979) 844-851. Keon et al., Environ. Sci. Technol. 35 (2001) 2778-2784. Wenzel et al., Anal. Chim. Acta 436 (2001) 309-323. Rauret et al., J. Environ. Monitor. 1 (1999) 57-61.

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method for quantitatively analyzing various types of heavy metals present in contaminated soil using continuous extraction method, And the contaminated soil that combines continuous abstraction with laser ablation that can quantitatively analyze the specific type of heavy metals extracted at each stage through the difference between the quantitative analysis values of each step and the previous step It is an object of the present invention to provide a method and apparatus for analyzing the presence of heavy metals.

In order to accomplish the above object, the present invention provides a method for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction, comprising the steps of extracting heavy metals in a plurality of stages and extracting specific types of heavy metals In the continuous extraction method, the contaminated soil obtained through the heavy metal extraction step of each step is subjected to quantitative analysis, and the contaminated soil in each step (hereinafter referred to as the "contaminated soil in the n-th stage" and n is a natural number) And comparing the quantitative analysis values of the heavy metals present in the contaminated soil in the n-th stage with the quantitative analysis values of the heavy metals present in the contaminated soil in the n-th stage, And the quantitative analysis value difference of each heavy metal is determined as the quantitative analysis value of the n-th type heavy metal extracted through the n-th step .

The quantitative analysis value of the heavy metals with respect to the contaminated soil at the 0th stage is the quantitative analysis value of the heavy metals with respect to the contaminated soil at the nth stage and the quantitative analysis value of the heavy metals with respect to the contaminated soil at the n- Is the quantitative analysis value for.

In each of the heavy metal extraction steps, the contaminated soil filtered through the heavy metal extraction step of the previous step is injected into the heavy metal extraction solution to extract a specific type of heavy metal corresponding to each heavy metal extraction step from the contaminated soil, It is the process of separating the polluted soil that has been removed.

The heavy metal extraction step of the plurality of stages proceeds in a time-wise manner, and the heavy metals extracted by each heavy metal extraction step are different types of heavy metals.

Quantitatively analyzing the first contaminated soil to quantitatively analyze heavy metals present in the first contaminated soil; The first step of heavy metal extraction step for inducing the reaction of the first contaminated soil and the first heavy metal extraction solution is performed to filter out the contaminated soil of the first step in which the heavy metal of the first type is extracted and separated, To quantitatively analyze heavy metals present in the contaminated soil in the first step; The quantitative analysis values of the heavy metals present in the contaminated soil in the first stage and the quantitative analysis values of the heavy metals present in the initial contaminated soil were compared with each other, 1 < / RTI > type heavy metals; The heavy metal extraction step of the second step for inducing the reaction between the contaminated soil of the first step and the second heavy metal extraction solution is performed to filter the contaminated soil of the second step in which the heavy metal of the second type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the second step by performing quantitative analysis on the contaminated soil of the soil; The quantitative analysis values of the heavy metals present in the contaminated soil in the second stage and the quantitative analysis values of the heavy metals present in the contaminated soil in the first stage are compared with each other, Identifying the extracted second type heavy metals as quantitative analysis values; A third stage heavy metal extraction step of inducing a reaction between the contaminated soil of the second stage and the third heavy metal extraction solution is performed to filter the contaminated soil of the third stage in which the heavy metal of the third type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the third step by performing quantitative analysis on the contaminated soil of the soil; The quantitative analysis value of each heavy metal is compared with the quantitative analysis value of the heavy metals present in the contaminated soil in the third step and the quantitative analysis value of the heavy metals present in the contaminated soil in the second step, Identifying the extracted third type heavy metals as quantitative analysis values; The heavy metal extraction step of the fourth step for inducing the reaction of the contaminated soil of the third step and the fourth heavy metal extraction solution is performed to filter the contaminated soil of the fourth step in which the heavy metal of the fourth type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the fourth step by quantitatively analyzing the contaminated soil; And the quantitative analysis values of the heavy metals present in the contaminated soil in the fourth step and the quantitative analysis values of the heavy metals present in the contaminated soil in the third step are compared with the quantitative analysis value differences of the heavy metals in the fourth step And quantifying the quantitative analysis value of the heavy metals present in the contaminated soil in the fourth step as the quantitative analysis value of the heavy metal of the fifth type by specifying the quantitative analysis value of the fourth type heavy metal extracted through the step ; ≪ / RTI >

Wherein the first type heavy metal is an exchangeable heavy metal and the second type heavy metal is adsorbed to a bound to carbonate heavy metal and the third type heavy metal is a metal oxide bound bound Fe-Mn oxides), the fourth type heavy metal is a bound to organic matter heavy metal, and the fifth type heavy metal may be a residual bound heavy metal.

Quantitative analysis of contaminated soil in each heavy metal extraction step can be performed using a laser ablation coupled quantitative analysis device. The laser ablation-coupled quantitative analysis apparatus includes laser ablation-induced plasma-mass spectrometry (LA-ICP-MS), laser ablation-inductively coupled plasma-optical emission spectrometry (LA-ICP-OES) breakdown spectroscopy.

When the heavy metal extracted through each heavy metal extraction step is a cationic heavy metal, the first heavy metal extraction solution is MgCl 2 solution, the second heavy metal extraction solution is CH 3 COONa, and the third heavy metal extraction solution is NH 2 OH HCl And CH 3 COOH. In the heavy metal extraction step of the fourth step, the contaminated soil of the third step is put into a mixed solution of H 2 O 2 and HNO 3 , heated for a predetermined time, and NH 4 OAc and HNO 3 is further added to induce the fourth type of desorption reaction in the contaminated soil in the third stage and to filter out the contaminated soil in the fourth stage in which the heavy metal of the fourth type is removed.

Wherein the first heavy metal extraction solution is (NH 4 ) SO 4 solution, the second heavy metal extraction solution is (NH 4 ) H 2 PO 4 solution, and the second heavy metal extraction solution is The third heavy metal extraction solution and the fourth heavy metal extraction solution may be NH 4 -oxalate butter solutions.

The apparatus for analyzing the presence of heavy metals in contaminated soil, which combines laser ablation and continuous extraction according to an embodiment of the present invention, is characterized by quantitative analysis of heavy metals present in the initial contaminated soil, a quantitative analysis DB of contaminated soil storing quantitative analysis values of heavy metals present in each n contaminant soil; And the quantitative analysis value of the contaminated soil of each step stored in the contaminated soil quantitative analysis DB is used to determine the quantitative analysis value of the heavy metal corresponding to each step, The apparatus for quantitative analysis of heavy metals according to claim 1, wherein the quantitative analysis value of the heavy metals present in the contaminated soil in the n-th stage is compared with the quantitative analysis value of the heavy metals present in the contaminated soil in the The quantitative analysis value difference of each heavy metal is calculated and the quantitative analysis value difference of each heavy metal is specified as the quantitative analysis value of the nth type heavy metal extracted through the nth step.

The method and apparatus for analyzing presence of heavy metals in contaminated soil by laser ablation and continuous extraction according to the present invention have the following effects.

In the quantitative analysis of heavy metals in contaminated soils by continuous extraction method, solid components, that is, non-liquid components, ie, contaminated soil were separated from each step of the continuous extraction method and quantitative analysis was performed on the contaminated soil. The reliability of the analysis can be improved.

In addition, since the difference between the quantitative analysis value of the n-th stage and the quantitative analysis value of the (n-1) -th stage is determined by the quantitative analysis value of the heavy metal corresponding to each step, it is easy to quantitatively analyze each type of heavy metal And the precision of the quantitative analysis can be enhanced.

In addition, in the case of the conventional continuous extraction method, a strong acid such as hydrochloric acid or nitric acid is essentially applied in the extraction step of the last step for extracting the residual bound heavy metal. In the present invention, As the extraction step for extracting heavy metals is omitted, application of strong acids is not required. Further, the possibility of the occurrence of an experimental error due to an artificial action such as extraction of a liquid component and control of dilution drainage, which is a problem of the conventional continuous extraction method, is excluded.

FIG. 1 is a flow chart for explaining a method for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction, according to an embodiment of the present invention. FIG.
FIG. 2 is a schematic view of an apparatus for analyzing presence of heavy metals in contaminated soil by laser ablation and continuous extraction according to an embodiment of the present invention. FIG.

The present invention provides a technique for quantitatively analyzing heavy metals present in contaminated soil by continuous extraction method.

In the present invention, the continuous extraction method refers to a method in which a plurality of heavy metal extraction steps for contaminated soil are carried out in a time-wise manner to extract heavy metals present in various types in the contaminated soil by type, . In addition, each heavy metal extraction step refers to a process in which a contaminated soil is put into an extraction solution to filter out contaminated soil from which each type of heavy metal is removed.

As described in the Background of the Invention, the continuous extraction method may be composed of the heavy metal extraction steps of the first to fifth steps, and the heavy metal extracted at each heavy metal extraction step may be a heavy metal of each type do. In one embodiment, the heavy metal extracted in the first step of the continuous extraction method is an exchangeable heavy metal, the heavy metal extracted in the second step is adsorbed to bound to carbonate heavy metal, Heavy metal is bound to Fe-Mn oxides heavy metal, the heavy metal extracted in the fourth step is bound to organic matter heavy metal, the heavy metal extracted in the fifth step is residual bound, It can mean heavy metal. The continuous extraction method may include a plurality of heavy metal extraction steps other than the five steps described above, and the type of heavy metal extracted in each step may also be set differently from the above-described types. However, in the present invention, the heavy metal extraction step required for the quantitative analysis of the five types of heavy metals is the first to fourth steps.

In the present invention, quantitative analysis is performed on the contaminated soil separated at each step by the continuous extraction method under the assumption of the type of heavy metal corresponding to each step of the continuous extraction method, and the quantitative determination of the heavy metal present in the contaminated soil at each step The analytical value is calculated and the difference between the quantitative analysis value of each step (for example, the n-th step) and the quantitative analysis value of the previous step (for example, the (n-1) A technique for specifying quantitative analysis values is presented.

In addition, while the conventional continuous extraction method performs solid-liquid separation for each step and quantitative analysis is performed on the separated liquid components, the present invention is characterized in that the solid-liquid separation is carried out for each step and the separated solid component (i.e., contaminated soil) And the quantitative analysis is carried out. In addition, in the present invention, quantitative analysis of contaminated soil is performed using a laser ablation (LA) coupled laser ablation apparatus. Laser ablation-coupled quantitative analysis devices include laser ablation-induced plasma-mass spectrometry (LA-ICP-MS), laser ablation-inductively coupled plasma-optical emission spectrometry (LA-ICP-OES) breakdown spectroscopy) can be used.

As described above, the present invention is characterized in that quantitative analysis is performed on the solid component separated in each of the heavy metal extraction steps, that is, the contaminated soil separated in each step, and the quantitative analysis value of the n-th stage and the quantitative analysis value of the n- Since the difference is regarded as the quantitative analysis value of the heavy metal of the type specified in each heavy metal extraction step, the reliability of the heavy metal quantitative analysis by type is improved. In addition, the possibility of an experiment error due to an artificial action such as extraction of a liquid component and control of dilution drainage, which is a problem of the conventional continuous extraction method, is excluded.

Hereinafter, a method and an apparatus for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction according to an embodiment of the present invention will be described in detail with reference to the drawings.

As described above, in the method for analyzing contaminated soil of the present invention, the quantitative analysis is performed on the solid component, that is, the contaminated soil, which is separated in each heavy metal extraction step of the continuous extraction method, And the quantitative analysis value of the heavy metal of the type corresponding to each heavy metal extraction step through the difference between the quantitative analysis values of the (n-1) and (n-1) stages.

The type of heavy metals extracted through each step of the continuous extraction method may be a known type or a modified type. In the following description, the type of heavy metal that can be present in the contaminated soil in one embodiment is referred to as a first type to a fifth type Type, and the first to fifth types are exchangeable heavy metals, adsorbed bound to carbonate heavy metals, bound to Fe-Mn oxides heavy metals, Bound to organic matter heavy metal, and residual bound heavy metal.

Referring to FIG. 1, a quantitative analysis on the first contaminated soil is performed (S101).

Quantitative analysis of the first contaminated soil can be obtained by quantitative analysis of the heavy metals present in the first contaminated soil. For example, quantitative analysis of heavy metals such as Zn = 100 and Cd = 80 can be obtained by quantitative analysis of the initial contaminated soil. As a quantitative analysis method for the initial contaminated soil, any known quantitative analysis method may be used. Preferably, the laser ablation-coupled quantitative analysis method is an LA-ICP-MS (laser ablation-inducible plasma-mass spectrometry, LA-ICP-OES (laser ablation-inductively coupled plasma-optical emission spectrometry), and LIBS (laser induced breakdown spectroscopy).

In a state where the quantitative analysis on the initially contaminated soil is completed, the first step of the continuous extraction method for extracting the heavy metal of the first type proceeds (S102). The first type of heavy metal may mean an exchangeable heavy metal as described above.

In order to extract the first type of heavy metal from the initially contaminated soil, the first contaminated ore is introduced into the first heavy metal extraction solution to remove the first type heavy metal, e. G., Exchangeable heavy metal, Extraction is carried out through an exchange reaction. When the heavy metal to be extracted is a cationic heavy metal, the first heavy metal extraction solution uses MgCl 2 solution, and when the heavy metal to be extracted is an anionic heavy metal, the (NH 4 ) SO 4 solution is used as the first heavy metal extraction solution . After the ion exchange reaction time has sufficiently elapsed, the first heavy metal extraction solution into which the initially contaminated soil has been introduced is filtered through a filter to filter the solid component, that is, the contaminated soil.

Quantitative analysis is performed on the contaminated soil filtered, i.e., the contaminated soil in the first stage (S103).

Through the quantitative analysis of the contaminated soil in the first stage, the quantitative analysis values of the heavy metals present in the contaminated soil in the first stage are measured. At this time, the quantitative analysis of the contaminated soil in the first step is performed by the same method as the quantitative analysis for the first contaminated soil, that is, the quantitative analysis method combining laser ablation such as LA-ICP-MS and LA-ICP-OES And the same method is applied to the quantitative analysis of the second, third, fourth and fifth steps thereafter.

When the quantitative analysis of the contaminated soil in the first stage is completed, the quantitative analysis values of the heavy metals present in the contaminated soil in the first stage and the quantitative analysis values of the heavy metals present in the initial contaminated soil are compared with each other, The difference of the quantitative analysis values of the heavy metals is regarded as the quantitative analysis values of the first type heavy metal extracted through the first step of the continuous extraction method (S104). For example, if the quantitative analysis for the first contaminated soil is Zn = 100, Cd = 80 and the quantitative analysis for the contaminated soil in the first stage is Zn = 70 and Cd = 60, Quantitative analysis values of one type of heavy metal, that is, ion exchange type heavy metals, can be Zn = 30 and Cd = 20.

When the quantitative analysis on the contaminated soil in the first step is completed, the second step of the continuous extraction method for extracting the heavy metal of the second type proceeds (S105). The second type of heavy metal may refer to a heavy metal adsorbed to bound to carbonate as described above.

Specifically, in order to extract the heavy metal of the second type from the contaminated soil of the first stage, the contaminated soil of the first stage is introduced into the second heavy metal extraction solution to remove the heavy metal of the second type present in the contaminated soil of the first stage For example, a carbonate-bound heavy metal is extracted. When the extracted heavy metal is a cationic heavy metal, the second heavy metal extraction solution uses a CH 3 COONa solution. When the extracted heavy metal is an anionic heavy metal, the (NH 4 ) H 2 PO 4 solution Can be used. After the reaction time has sufficiently elapsed, the second heavy metal extraction solution into which the contaminated soil of the first step is introduced is filtered through a filter to filter solid components, that is, contaminated soil.

Then, the contaminated soil of the second stage filtered is subjected to quantitative analysis (S106).

Through the quantitative analysis of the contaminated soil in the second stage, the quantitative analysis values of the heavy metals present in the contaminated soil in the second stage are measured. Then, the quantitative analysis values of the heavy metals present in the contaminated soil in the second stage and the quantitative analysis values of the heavy metals present in the contaminated soil in the first stage are compared with each other, Is regarded as a quantitative analysis value of the second type heavy metal extracted through the second step (S107). For example, if the quantitative analysis values for the contaminated soil in the first stage are Zn = 70 and Cd = 60 and the quantitative analysis values for the contaminated soil in the second stage are Zn = 55 and Cd = 45, The quantitative analysis values of the second type of heavy metal in the polluted soil, that is, carbonate-bound heavy metals, can be Zn = 15 and Cd = 15.

When the quantitative analysis on the contaminated soil in the second step is completed, the third step of the continuous extraction method for extracting the heavy metal of the third type proceeds (S108). The third type of heavy metal may mean heavy metal of bound to Fe-Mn oxides as described above.

Specifically, in order to extract the heavy metal of the third type from the contaminated soil of the second stage, the contaminated soil of the second stage is added to the third heavy metal extraction solution to remove the third type heavy metal present in the contaminated soil of the second stage For example, a metal-bound (bound to Fe-Mn oxides) heavy metal is extracted. If the heavy metal to be extracted is a cationic heavy metal, the third heavy metal extraction solution may be a mixed solution of NH 2 OH ㅇ HCl and CH 3 COOH. If the heavy metal to be extracted is an anionic heavy metal, NH 4 -oxalate butter solution may be used. At this time, in the case of extracting the cationic heavy metal, it is preferable to heat the third heavy metal extraction solution to a certain temperature in order to increase extraction efficiency of the heavy metal of the third type. After the reaction time has sufficiently elapsed, the third heavy metal extraction solution into which the contaminated soil in the second step is introduced is filtered through a filter to filter solid components, that is, contaminated soil.

Then, the contaminated soil in the filtered third stage is quantitatively analyzed (S109).

The quantitative analysis of the contaminated soil in the third step is carried out by quantitative analysis of the contaminated soil. Then, the quantitative analysis values of the heavy metals present in the contaminated soil in the third stage and the quantitative analysis values of the heavy metals present in the contaminated soil in the second stage are compared with each other, Is regarded as a quantitative analysis value of the third type heavy metal extracted through the third step (S110). For example, if the quantitative analysis values for the contaminated soil in the second stage are Zn = 55 and Cd = 45, and the quantitative analysis values for the contaminated soil in the third stage are Zn = 50 and Cd = 45, Quantitative analytical values of the third type of heavy metals, ie, metal oxide-bound heavy metals, present in the contaminated soil may be Zn = 5 and Cd = 0.

When the quantitative analysis on the contaminated soil in the third step is completed, the fourth step of the continuous extraction method for extracting the heavy metal of the fourth type is performed (S111). The fourth type of heavy metal may be a bound to organic matter heavy metal as described above.

Specifically, in order to extract the heavy metal of the fourth type from the contaminated soil of the third stage, the contaminated soil of the third stage is put into the fourth heavy metal extraction solution, and the heavy metal of the fourth type For example, to extract bound to organic matter heavy metals. If the heavy metal to be extracted is an anionic heavy metal, the fourth heavy metal extraction solution may be an NH 4 -oxalate butter solution. If the heavy metal to be extracted is an anionic heavy metal, it may be added to a mixed solution of H 2 O 2 and HNO 3 After heating for a certain period of time, NH 4 OAc and HNO 3 are added to induce the desorption reaction of the organic-bonded heavy metals present in the contaminated soil in the third step. After the reaction time has sufficiently elapsed, the reaction solution into which the contaminated soil in the third step is put is filtered through the filter to filter the solid component, that is, the contaminated soil in the fourth step.

Then, the contaminated soil of the filtered fourth stage is quantitatively analyzed (S112).

Through quantitative analysis of the contaminated soil in the fourth step, the quantitative analysis values of the heavy metals present in the contaminated soil in the fourth step are measured. Next, the quantitative analysis values of the heavy metals present in the contaminated soil in the fourth step and the quantitative analysis values of the heavy metals present in the contaminated soil in the third step are compared with each other, Is regarded as a quantitative analysis value of the fourth type heavy metal extracted through the fourth step (S113). For example, if the quantitative analysis values for the contaminated soil in the third step are Zn = 50 and Cd = 45 and the quantitative analysis values for the contaminated soil in the fourth step are Zn = 25 and Cd = 20, The quantitative analysis values of the fourth type of heavy metals present in contaminated soil, that is, organic binding type heavy metals, can be Zn = 25 and Cd = 25.

On the other hand, since the contaminated soil in the fourth stage at the time when the fourth step of the continuous extraction method is completed is that all the heavy metals of the first to fourth types are extracted and separated, in the contaminated soil of the fourth step, Only. Therefore, the quantitative analysis values of the heavy metals present in the contaminated soil in the fourth step measured by the quantitative analysis of the contaminated soil in the fourth step are as follows: a fifth type heavy metal, for example, a residual bound heavy metal (Step S114). Accordingly, it is not necessary to carry out the fifth step for extracting the heavy metal of the fifth type.

In the case of the conventional continuous extraction method, five stages of heavy metal extraction step are required for quantitative analysis of five types of heavy metals. However, in the case of the present invention, only the four heavy metal extraction steps as described above are used for quantitative determination of five types of heavy metals Analysis is possible. Further, in the case of the conventional continuous extraction method, a strong acid such as hydrochloric acid or nitric acid is essentially applied in the extraction step of the last step for extracting the heavy metal of the fifth type (for example, residual bound heavy metal) In the present invention, since the extraction step for extracting the residual bound heavy metal (i.e., the heavy metal extraction step in the fifth step) is omitted, application of strong acid is not required.

The method of analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction according to an embodiment of the present invention has been described above. Meanwhile, the method of analyzing the presence of heavy metals in the contaminated soil by laser ablation and continuous extraction according to an embodiment of the present invention can be implemented as a computerized apparatus and can be implemented by the following contaminated soil analysis apparatus.

Referring to FIG. 2, an apparatus for analyzing the presence of heavy metals in contaminated soil, which combines laser ablation and continuous extraction according to an embodiment of the present invention, includes a contaminated soil quantitative analysis DB 220 and a heavy metal quantitative analysis control apparatus 210).

The contaminated soil quantitative analysis DB 220 stores the quantitative analysis values of the heavy metals present in the contaminated soil of the first stage, the quantitative analysis values of the heavy metals present in the contaminated soil of the first stage to the contaminated soil of the n-th stage do. The quantitative analysis values of the initially contaminated soil and the contaminated soil at each stage are transmitted from the quantitative analysis apparatus 250 communicating with the contaminated soil analysis apparatus of the present invention and stored in the contaminated soil quantitative analysis DB 220 or separately May be input and stored via the client 230 via an external device of the client 200. [

The quantitative analysis device 250 is a device for quantitatively analyzing the contaminated soil separated at each step of the continuous extraction method. The laser ablation-coupled quantitative analysis device 250 includes LA-ICP-MS, LA-ICP -OES, or LIBS.

The heavy metal quantitative analysis controller 210 analyzes quantitative analysis values of the contaminated soil of the first contaminated soil stored in the contaminated soil quantitative analysis DB 220 and the contaminated soil of each step, And the like.

Specifically, the type-specific heavy metal quantitative analysis control device 210 compares the quantitative analysis values of the heavy metals present in the contaminated soil in the n-th stage with the quantitative analysis values of the heavy metals present in the contaminated soil in the (n-1) And the quantitative analysis value difference of each heavy metal is determined as a quantitative analysis value of the n-th type heavy metal extracted through the n-th step. At this time, the quantitative analysis value of the heavy metals with respect to the contaminated soil in the n-th stage is specified as the quantitative analysis value with respect to the heavy metal of the n + 1 type.

210: Heavy metal quantitative analysis control device by type
220: Quantitative analysis of contaminated soil DB
230: Client
240: Interface module
250: Quantitative analysis device

Claims (13)

In the continuous extraction method of extracting a heavy metal of a specific type at each step by proceeding to a heavy metal extraction step of a plurality of stages,
Quantitative analysis of the contaminated soils separated through the heavy metal extraction step of each stage was carried out to determine the amount of heavy metals present in the contaminated soil in each step (hereinafter referred to as "contaminated soil in the n-th stage" and n in the natural number) The analytical values were measured,
The quantitative analysis value of each heavy metal is calculated by comparing the quantitative analysis value of the heavy metals present in the contaminated soil in the n-th stage with the quantitative analysis value of the heavy metals present in the contaminated soil in the (n-1)
The quantitative analysis value difference of each heavy metal is specified as the quantitative analysis value of the n-th type heavy metal extracted through the n-th step,
A quantitative analysis of contaminated soil in each heavy metal extraction step is performed using a laser ablation coupled quantitative analysis apparatus. A method for analysis of heavy metals in contaminated soil by laser ablation and continuous extraction.
The method according to claim 1, wherein the quantitative analysis value of the heavy metals with respect to the contaminated soil in the 0th step is a quantitative analysis value of heavy metals with respect to the first contaminated soil,
The quantitative analysis value of the heavy metals with respect to the contaminated soil in the n-th stage is the quantitative analysis value of the heavy metal of the n + 1 type. Analysis of the heavy metals in the contaminated soil by laser ablation and continuous extraction Way.
The method according to claim 1,
The contaminated soil filtered through the heavy metal extraction step of the previous step is injected into the heavy metal extraction solution to extract a specific type of heavy metal corresponding to each heavy metal extraction step from the contaminated soil and to separate the contaminated soil from which a specific type of heavy metal is removed The method according to any one of claims 1 to 5, wherein the laser ablation is continuous and continuous extraction is performed.
The method according to claim 1, wherein the heavy metal extraction step of the plurality of stages is performed in a time-series manner, and heavy metals extracted by each heavy metal extraction step are heavy metals of different types. Analytical methods for presence of heavy metals in contaminated soil.
The method of claim 1, further comprising: quantitatively analyzing the first contaminated soil to measure quantitative analysis of heavy metals present in the first contaminated soil;
The first step of heavy metal extraction step for inducing the reaction of the first contaminated soil and the first heavy metal extraction solution is performed to filter out the contaminated soil of the first step in which the heavy metal of the first type is extracted and separated, To quantitatively analyze heavy metals present in the contaminated soil in the first step;
The quantitative analysis values of the heavy metals present in the contaminated soil in the first stage and the quantitative analysis values of the heavy metals present in the initial contaminated soil were compared with each other, 1 < / RTI > type heavy metals;
The heavy metal extraction step of the second step for inducing the reaction between the contaminated soil of the first step and the second heavy metal extraction solution is performed to filter the contaminated soil of the second step in which the heavy metal of the second type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the second step by performing quantitative analysis on the contaminated soil of the soil;
The quantitative analysis values of the heavy metals present in the contaminated soil in the second stage and the quantitative analysis values of the heavy metals present in the contaminated soil in the first stage are compared with each other, Identifying the extracted second type heavy metals as quantitative analysis values;
A third stage heavy metal extraction step of inducing a reaction between the contaminated soil of the second stage and the third heavy metal extraction solution is performed to filter the contaminated soil of the third stage in which the heavy metal of the third type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the third step by performing quantitative analysis on the contaminated soil of the soil;
The quantitative analysis value of each heavy metal is compared with the quantitative analysis value of the heavy metals present in the contaminated soil in the third step and the quantitative analysis value of the heavy metals present in the contaminated soil in the second step, Identifying the extracted third type heavy metals as quantitative analysis values;
The heavy metal extraction step of the fourth step for inducing the reaction of the contaminated soil of the third step and the fourth heavy metal extraction solution is performed to filter the contaminated soil of the fourth step in which the heavy metal of the fourth type is extracted and separated, Measuring quantitative analysis of heavy metals present in the contaminated soil in the fourth step by quantitatively analyzing the contaminated soil; And
The quantitative analysis values of the heavy metals present in the contaminated soil in the fourth step and the quantitative analysis values of the heavy metals present in the contaminated soil in the third step are compared with each other, And quantitatively analyzed values of the extracted fourth type heavy metals,
And quantifying the quantitative analysis value of the heavy metals present in the contaminated soil in the fourth step as the quantitative analysis value of the heavy metal of the fifth type. Analysis method of existence type of heavy metals in soil.
6. The method of claim 5, wherein the first type heavy metal is an exchangeable heavy metal, the second type heavy metal is adsorbed to bound to carbonate heavy metal, and the third type heavy metal is metal Wherein the fourth type of heavy metal is a bound to organic matter heavy metal and the fifth type heavy metal is a residual bound heavy metal. Analysis of the presence of heavy metals in contaminated soil by laser ablation and continuous extraction.
delete 2. The apparatus according to claim 1, wherein the laser ablation-coupled quantitative analysis device is a laser ablation-induced plasma-mass spectrometry (LA-ICP-MS), a laser ablation-inductively coupled plasma-optical emission spectrometry ), And laser induced breakdown spectroscopy (LIBS). The present invention relates to a method for analyzing the presence of heavy metals in contaminated soil by laser ablation and continuous extraction.
The method according to claim 5, wherein the first heavy metal extraction solution is a MgCl 2 solution, the second heavy metal extraction solution is CH 3 COONa, the third heavy metal extraction solution is a mixed solution of NH 2 OH HCl and CH 3 COOH,
In the heavy metal extraction step of the fourth step, the contaminated soil of the third step is put into a mixed solution of H 2 O 2 and HNO 3 , heated for a predetermined time, NH 4 OAc and HNO 3 are further added, Characterized in that the fourth type of desorption reaction in the contaminated soil is induced and the contaminated soil in the fourth step in which the heavy metal of the fourth type is removed is filtered out. Analysis method for existence type.
The method according to claim 5, wherein the first heavy metal extraction solution is (NH 4 ) SO 4 solution, the second heavy metal extraction solution is (NH 4 ) H 2 PO 4 solution, and the third heavy metal extraction solution and fourth heavy metal extraction Characterized in that the solution is an NH 4 -oxalate butter solution. A method for analysis of heavy metals in contaminated soil by laser ablation and continuous extraction.
A quantitative analysis DB of the contaminated soil storing the quantitative analysis value of the heavy metals present in the contaminated soil in the first stage, the quantitative analysis value of the heavy metals present in the contaminated soil in the contaminated soil in the first stage, And
A heavy metal quantitative analysis control device for identifying the quantitative analysis value of the heavy metal of the type corresponding to each step using the quantitative analysis values of the first contaminated soil stored in the contaminated soil quantitative analysis DB and the contaminated soil at each step ; ≪ / RTI >
The heavy metal quantitative analysis control apparatus of the type compares the quantitative analysis value of the heavy metals present in the contaminated soil in the n-th stage and the quantitative analysis values of the heavy metals present in the contaminated soil in the n-1 st stage, And the quantitative analysis value difference of each heavy metal is specified as the quantitative analysis value of the n-th type heavy metal extracted through the n-th step,
Quantitative analysis values for the initial contaminated soil and contaminated soil at each stage are measured by a quantitative analyzer,
The quantitative analysis apparatus is a device for performing quantitative analysis on the contaminated soil separated at each step of the continuous extraction method, and is a quantitative analysis apparatus combined with laser ablation. The quantitative analysis apparatus includes LA-ICP-MS, LA-ICP-OES and LIBS Which is characterized in that the laser ablation and continuous extraction are combined.
12. The method according to claim 11, wherein the quantitative analysis value of the heavy metals with respect to the contaminated soil in the n-th stage is specified by the quantitative analysis value of the heavy metal of the n + 1 type. An apparatus for analyzing the presence of heavy metals.
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KR1020160008073A 2016-01-22 2016-01-22 Method and apparatus for analyzing the binding status of heavy metals in contaminated soils by combining Laser Ablation and Sequential Extraction Analysis KR101762215B1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013064603A (en) 2011-09-15 2013-04-11 Gunma Univ Heavy metal analyzer and heavy metal analysis method
KR101349306B1 (en) * 2013-09-13 2014-01-09 한국지질자원연구원 Method for resolving sources of heavy metal contaminants by sequential extraction scheme and isotope analysis
KR101511292B1 (en) 2014-12-30 2015-04-13 한국지질자원연구원 Method for resolving contribution ratio for soil contamination through sequential extraction scheme and analysis of stable isotope
JP2015114240A (en) * 2013-12-12 2015-06-22 住友金属鉱山株式会社 Gold distribution rate analysis method of ore

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013064603A (en) 2011-09-15 2013-04-11 Gunma Univ Heavy metal analyzer and heavy metal analysis method
KR101349306B1 (en) * 2013-09-13 2014-01-09 한국지질자원연구원 Method for resolving sources of heavy metal contaminants by sequential extraction scheme and isotope analysis
JP2015114240A (en) * 2013-12-12 2015-06-22 住友金属鉱山株式会社 Gold distribution rate analysis method of ore
KR101511292B1 (en) 2014-12-30 2015-04-13 한국지질자원연구원 Method for resolving contribution ratio for soil contamination through sequential extraction scheme and analysis of stable isotope

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