[논문]Simultaneous detection of five biocides in household products by gas chromatography-mass spectrometry

Choi, Kyeong-Yun; Lim, Hyun-Hee; Shin, Ho-Sang

doi:10.5806/ast.2022.35.5.197

[국내논문] Simultaneous detection of five biocides in household products by gas chromatography-mass spectrometry 원문보기

분석과학 = Analytical science & technology, v.35 no.5, 2022년, pp.197 - 204

Choi, Kyeong-Yun (Department of Environmental Science, Kongju National University) , Lim, Hyun-Hee (Daejeon-Sejong Division, Occupatioanl Safety and Health Agency) , Shin, Ho-Sang (Department of Environmental Education, Kongju National University)

Abstract ▼ AI-Helper

A gas chromatography-mass spectrometric method was developed for determining 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT), 1,2-benzisothiazolin-3-one (BIT), 3-iodo-2-propynyl butyl carbamic acid (IPBC) and benzoic acid (BA) in household products. A 0.5 g sample was placed in a test tube and dissolved with 5 mL water, 5 mL methylene chloride and 1.0 mL methanol. The solution was extracted by ultra-sonication followed by mechanical shaking using the salting out effect. Under the established condition, the lowest quantification limits of all analytes were in the range of 0.04-10 mg/kg and their relative standard deviations were less than 8.0 %. The method was used to analyze 10 household products. As a result of analyzing 10 household products, MIT was detected in the range of 1.2-3.5 mg/kg in 3 of 10 samples, CMIT was detected in the range of 2.6-8.2 mg/kg in 3 of 10 samples, and BA was detected in the range of 5.0-15 mg/kg in 4 of 10 samples. Meanwhile, BIT and IPBC were not detected in any of the products. It has been shown that this method can be used for the simultaneous determination of biocides with various physical and chemical properties in household products.

Keyword

표/그림 (3)

표 Table 1. Comparison of analytical method for determination of biocides in household products and their analytical results
그림 Fig. 1. GC-MS SIM chromatogram of the extract from household product spiked in the concentration of 0.5 mg/kg (Internal standard: 9.335 min, benzoic acid: 10.090 min, MIT: 10.348 min, CMIT: 11.081 min, BIT: 15.508 min, IPBC: 16.602 min).
표 Table 2. Validation results for the analysis of biocides in household chemicals

AI 본문요약
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제안 방법

This paper focuses on the validation of sample preparation and detection methodology. The developed method was used to determine 5 biocides in household products.
Therefore, HP-5MS column, a non-polar stationary phase with the column temperature upper limit of 350 ℃ was used for GC separation of five biocides, and all analytes fortunately showed sharp peaks. For accurate quantification, the internal standard method was used, and it was quantified as the ratio of the area of each peak to the area of the internal standard. After adding the analytes to the control sample, extraction was performed, and as a result of analysis by GC-MS, no additional peaks or interference peaks were observed near the retention time of the analyte as shown in Fig.

성능/효과

The ratios of the peak areas of the standards to that of the internal standard were used to quantify the analytes. The lowest limit of detection (LOD) and limit of quantification (LOQ) were determined as the lowest concentration of the standard solution resulting in a signal-to-noise ratio of 3:1 and 10:1.
Full-scan mass spectra (m/z 35-400) were recorded for the identification of analytes at a high concentration. Confirmation of trace chemicals was completed by three MS characteristic ions and the ratio of the three MS characteristic ions, and the GC-retention time matched the known standard compound. The ions selected in this study were as shown in Table 2.
So far, the simultaneous analysis of five biocides with chemically diverse properties has been separated by LC or HPLC, as shown in Table 1. In this study, a GC-MS method that can simultaneously and sensitively measure theses five biocides was developed. In order to analyze water-soluble analytes, including benzoic acid, contained in household chemical products by GC-MS, the analytes must be extracted to organic solvent from the sample to obtain a final solution that does not contain water.
In order to analyze water-soluble analytes, including benzoic acid, contained in household chemical products by GC-MS, the analytes must be extracted to organic solvent from the sample to obtain a final solution that does not contain water. In addition, it is necessary to find GC conditions with symmetric, sharp, and quantitative peak shapes, and to establish MS conditions through ion selection with high sensitivity.
Initially, we tested direct extraction of analytes from household products using chloroform, methylene chloride, acetonitrile and methanol to achieve optimal extraction conditions. As a result, high extraction efficiency close to 100% was obtained with all organic solvents for 5 biocides, but matrix interference was very severe. Therefore, it was determined that the turbid extraction method was suitable for achieving optimal extraction conditions for multiple analytes with strong and weak water solubility.
As a result, high extraction efficiency close to 100% was obtained with all organic solvents for 5 biocides, but matrix interference was very severe. Therefore, it was determined that the turbid extraction method was suitable for achieving optimal extraction conditions for multiple analytes with strong and weak water solubility. Cloudy extraction is a method of extracting an analyte using an extraction solvent and a dispersion solvent at the same time, and a turbid solution is formed as a microemulsion in which the extraction solvent is dispersed in an aqueous solution sample.
Cloudy extraction is a method of extracting an analyte using an extraction solvent and a dispersion solvent at the same time, and a turbid solution is formed as a microemulsion in which the extraction solvent is dispersed in an aqueous solution sample. In a turbid solution, the contact surface between the sample and the extraction solvent is dramatically improved due to the formation of a microemulsion, after which equilibration is achieved very quickly, thereby improving the extraction efficiency of the target analyte.
To increase the extraction efficiency, an excess of salt was added to give a salting-out effect. As a result, the method of using methylene chloride as an extraction solvent, methanol as a dispersion solvent, and pure water for purification purposes at the same time was a very efficient extraction method for the analysis of biocides in household products. Spike samples were prepared at two different concentrations for 5 analytes and recovery was calculated as the percentage of analyte recovered.
The recovery of the biocide in the household product samples was greater than 57 %, as shown in Table 2. The recoveries of biocides from household products were 57-59 % for MIT, 76-82 % for BIT, and nearly 100 % for other biocides. Because MIT has very high water solubility, the extraction efficiency by LLE is generally low at 20-30 %, but the extraction efficiency was improved to 57 % by combining cloudy extraction using ultrasonication and mechanical extraction using salting-out effect.
The recoveries of biocides from household products were 57-59 % for MIT, 76-82 % for BIT, and nearly 100 % for other biocides. Because MIT has very high water solubility, the extraction efficiency by LLE is generally low at 20-30 %, but the extraction efficiency was improved to 57 % by combining cloudy extraction using ultrasonication and mechanical extraction using salting-out effect.
For GC separation of five biocides including benzoic acid, the use of semipolar stationary phases such as Wax or InnoWax was initially attempted, but BIT and IPBC could not be analyzed at the column temperature upper limit of 260 ℃. Therefore, HP-5MS column, a non-polar stationary phase with the column temperature upper limit of 350 ℃ was used for GC separation of five biocides, and all analytes fortunately showed sharp peaks. For accurate quantification, the internal standard method was used, and it was quantified as the ratio of the area of each peak to the area of the internal standard.
For accurate quantification, the internal standard method was used, and it was quantified as the ratio of the area of each peak to the area of the internal standard. After adding the analytes to the control sample, extraction was performed, and as a result of analysis by GC-MS, no additional peaks or interference peaks were observed near the retention time of the analyte as shown in Fig. 1.
The standard curve was obtained by computing the regression line of the peak area ratios of the analytes versus concentration using a least-squares fit and demonstrates a linear relationship. The calibration curves were linear in two to four orders of magnitude with correlation coefficients higher than 0.99 in all cases. The line of best fits for biocides are as described in Table 2.
The reproducibility of the assay was very good. For five independent determinations in the two different concentration, the accuracy was in the range of 96.
The reproducibility of the assay was very good. For five independent determinations in the two different concentration, the accuracy was in the range of 96.0-110 %, and the precision was less than 8.0 % (Table 2). It can be seen that the accuracy of the method developed in this study is superior to those of other methods as shown in Table 2.
We used the proposed method to analyze the target biocides in ten household products. As a result of analyzing biocides, MIT was detected in the range of 1.2-3.5 mg/kg in 3 of 10 samples, CMIT was detected in the range of 2.6-8.2 mg/kg in 3 of 10 samples, and benzoic acid was detected in the range of 5.0-15 mg/kg in 4 of 10 samples. They are mainly detected in children's toy products made in China, so a more detailed investigation is needed for children's toys.
In this paper, we tried to combine cloudy extraction using ultrasonication and mechanical extraction using salting-out effect for the detection of biocides in household products. The recoveries of biocides were greatly improved, many interfering substances were removed. The peaks of biocides showed good chromatographic properties and a sensitive response for the EI-MS (SIM).
The recoveries of biocides were greatly improved, many interfering substances were removed. The peaks of biocides showed good chromatographic properties and a sensitive response for the EI-MS (SIM).
The major advantages of this method are described as follows: 1) The method allows simultaneous determination of trace levels of MIT, CMIT, BIT, IPBC and BA in household products. 2) Although this method requires only a small amount of 0.
The major advantages of this method are described as follows: 1) The method allows simultaneous determination of trace levels of MIT, CMIT, BIT, IPBC and BA in household products. 2) Although this method requires only a small amount of 0.5 g, the LODs determined by this study were less than or similar to the previously reported LOD values using HPLC or GC-MS. 3) The cloudy extraction method developed in this study is simple and fast, and therefore, it can be easily applied to many household product analyses.
5 g, the LODs determined by this study were less than or similar to the previously reported LOD values using HPLC or GC-MS. 3) The cloudy extraction method developed in this study is simple and fast, and therefore, it can be easily applied to many household product analyses.
For GC separation of five biocides including benzoic acid, the use of semipolar stationary phases such as Wax or InnoWax was initially attempted, but BIT and IPBC could not be analyzed at the column temperature upper limit of 260 ℃. Therefore, HP-5MS column, a non-polar stationary phase with the column temperature upper limit of 350 ℃ was used for GC separation of five biocides, and all analytes fortunately showed sharp peaks.

후속연구

They are mainly detected in children's toy products made in China, so a more detailed investigation is needed for children's toys.

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