• 분석과학
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• 제33권3호
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• pp.125-133
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• 2020

Methylisothiazolinone (MIT) and chloromethylisothiazolinone (CMIT) cause allergic contact dermatitis and are banned cosmetics ingredients, except in rinse-off products. However, their presence has been detected in cosmetics. We report a UPLC-tandem MS/MS screening method for their simultaneous determination in cosmetics. To facilitate extraction from various matrices, pretreatment methods were developed for each sample type. The method was optimized through a series of assessments, including specificity, LOD, LOQ, linearity, recovery, stability, precision, and accuracy. The LODs and LOQs for MIT ranged from 0.054 and 0.163 ㎍ mL^-1 whereas those for CMIT ranged from 0.040 and 0.119 ㎍ mL^-1. The linear correlation coefficients (r²) were higher than 0.999. Relative standard deviations (RSDs) for both intra- and inter-day measurements ranged from 0.3 ~ 13.6 %. Recoveries at three different concentrations were within 87.9 ~ 118.9 %. The RSD for stability measurements of spiked samples was within 7 %. These results confirm the suitability of the developed method for the simultaneous quantitation of MIT and CMIT in cosmetics. Samples of 320 color cosmetics, including eyeshadows, solid lipsticks, liquid lipsticks, and nail polishes were analyzed using the developed method, and two of them were found to contain both MIT and CMIT and one of them was found to contain only MIT. This data and the method will aid the regulation of ingredients used in cosmetics.

• Environmental Engineering Research
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• 제24권1호
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• pp.137-143
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• 2019

In this study, extraction, clean-up and instrumental analytical conditions were optimized for identifying and quantifying methyl-, chloromethylbenzi-, octyl- isothiazolinone (MIT, CMIT, BIT, OIT) and 3-iodo-2-propynyl butyl carbamate (IPBC), widely used biocidal active ingredients in human hygiene consumer products. Accuracy of the developed ultrasonic assisted extraction method followed by HPLC/MS analysis for four isothiazolinones and IPBC ranged between 60.4% and 113% in various types of consumer product samples. Method detection limits ranged 0.011-0.034 mg/kg for wet wipes, 0.57-1.5 mg/kg for liquid detergent and 0.58-1.6 mg/kg for powder detergent. Wet wipes, powder and liquid detergents collected from local market in Korea were analyzed to demonstrate the applicability of the developed method. Even after the regulation of those compounds in wet wipes, CMIT, MIT and IPBC were still frequently detected from complementary wet wipes without brand labels which were distributed to customers at local retail shops and restaurants. The maximum observed concentrations of MIT and CMIT found in those complementary wet wipes were 70.2 mg/kg and 11.3 mg/kg, respectively.

• Environmental Engineering Research
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• 제18권4호
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• pp.253-257
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• 2013

Exposure assessment for three major active ingredients used for humidifier disinfectants, polyhexamethylene guanidine (PHMG), oligo(2-(2-ethoxy)ethoxyethyl guanidinium chloride (PGH), and 5-chloro-2-methylisothiazol-3(2H)-one/2-methylisothiazol-3(2H)-one (CMIT/MIT) mixture, was conducted in a bedroom using an air sampler for a refined risk assessment. The experimental site was selected to reflect consumer exposure conditions. Aerosols formed by a humidifier were sampled during 8 hr at 7.5 L/min. Absorbed PHMG and PGH by the sampler were quantified using a spectrophotometric method, and high performance liquid chromatography-ultraviolet detection was used for CMIT/MIT. Three exposure scenarios were assumed for adding humidifier disinfectants to the humidifier water at 1, 2, and 10 times the volume recommended by the product suppliers, and the humidifier was on at its maximum rate of producing aerosols in order to consider reasonable worst-cases. The sampled mass of PHMG and PGH ranged 200 to $2,800{\mu}g$ and 140 to $1,900{\mu}g$, respectively, under different exposure conditions, whereas the absorbed mass of CMIT/MIT was barely detected at the detection limit of 0.11/0.29 mg/L, only at 10 times the recommended level. The resulting risk quotients for PHMG and PGH ranged 1,400 to 20,000 and 1,000 to 13,000, indicating that health risks could be significant. For CMIT/MIT mixture, risk quotients were much smaller than estimated by assuming that they are conservative in the indoor environment, probably due to oxidative reactions. The refined exposure assessment presented here may provide a useful tool for assessing risks posed by active ingredients in spray-type biocidal products.

• 공기청정기술
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• 제30권2호
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• pp.30-41
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• 2017

• 분석과학
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• 제35권5호
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• pp.197-204
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• 2022

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.

• 한국환경보건학회지
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• 제42권3호
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• pp.147-159
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• 2016

In South Korea, many cases of humidifier disinfectant-associated lung injury (HDLI) have been reported among people who used humidifier products containing humidifier disinfectant (HD). The objective of this study is to characterize exposure to HD among a total of 221 HDLI patients who used HD. Information and data on the HDs used were collected through a structured questionnaire and home environmental investigations. The conditions of these 221 HDLI patients were clinically confirmed to be caused by the use of HD. Children aged under 5 years old made up the highest proportion of HDLI cases (n=125, 56.6 %), followed by pregnant women (n=35, 15.8%). Forty-three percent (n=95) of the victims died. There were three cases of fetuses and 35 pregnant women among the victims. The number of HDLI patients who used only the Oxy Saksak brand of HD was found to be 85 (38.5%), followed by the HD brands Cefu (n=24, 10.9%), Lottemart Wiselect (n=9, 4.1%) and Aekyung (n=3). Patients who exclusively used HD brands containing polyhexamethylene guanidine phosphate (PHMG) (n=13, 55.7%) as an active ingredient made up the largest share, followed by those who exclusively used HD containing only oligo(2-(2-ethoxy) ethoxyethyl guanidinium (PGH) (n=24, 10.9%) and by those who only used a mixture of chloromethylisothiazolinone (CMIT) and methylisothiazolinone (MIT) (n=3, 1.4%). HD products containing PHMG were found to be the most commonly used among the confirmed HDLI patients. Three exposed fetuses who never used HD after birth developed lung injuries, indicating a probability of exposure to HD during gestation. All HDLI patients responded that they used HD while sleeping and for longer than 10 hours per day. In conclusion, the development of HDLI was clinically found to be associated with the use of several HD products containing PHMG, PGH and CMIT/MIT.

• 한국환경보건학회지
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• 제42권6호
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• pp.365-374
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• 2016

Objectives: Studies are needed to examine the characteristics of health effects reported by people who used humidifier disinfectant (HD), including the distribution of victims. Methods: We analyzed the distribution of health effects including lung injury that were asserted by a total of 699 individuals who registered with the first through third national programs to determine health effects associated with the use of HD. Results: We found that HD-associated lung injury (HDLI) occurred every year from 2002 through 2011, and in 2011 for 37.2% (n=96) of the total of 258 clinically evaluated HDLI victims. More than half of the victims responded that they were victimized between 2010 and 2011. This was consistent among all classifications by sex, age, HD brand and HD chemical ingredient. Conclusion: This study assumed that the major reason for the outbreak of the health effect between 2010 and 2011 could be the variations in concentrations and physical properties related to polyhexamethylene guanidine (PHMG). Further studies are necessary to examine if some factors related to the chemical disinfectants contained in HD brands may have caused the massive outbreak of health effects including HDLI.

• 한국환경보건학회지
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• 제46권5호
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• pp.481-494
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• 2020

Objectives: No study has been conducted to review characteristics of humidifier disinfectants (HD) products, such as real numbers, levels and types of HD substances contained, or the volume marketed. We aimed to review the characteristics of HD through a literature review. Methods: We collected literature reporting the names, numbers, and ingredients of HD and discussed them with a focus on the number of HD products and the chemicals used as a disinfectant. Results: A total of eight publications has reported the names of HD brands or types of disinfectants from 2011 to 2020. To date, a total of 40 HD products have been used, excluding four products. Eight HD products used polyhexamethylene guanidine phosphate (PHMG) and 14 used a mixture of chloromethylisothiazolinone (CMIT) and methylisothiazolinone (MIT) as disinfectants. Benzalkonium chloride (BKC) and sodium dichloroisocyanurate (NaDCC) were also used as a disinfectant in several HD products. A total of 19 HD products were associated with the development of HD associated lung injury (HDLI). The Oxy Saksak HD product containing PHMG showed the highest number of HD associated health effects. The type of disinfectant from a total of 14 HD products has not been identified. Conclusions: A total of 40 HD products have been marketed in South Korea since 1994. Further studies should be conducted to identify the association of product characteristics, including type of HD ingredients, with health effects.

• 한국환경보건학회지
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• 제46권2호
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• pp.128-135
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• 2020

Objective: The objectives of this study are to report the number of humidifier disinfectant (HD) associated health problems, including HD associated lung injury (HDLI), by year. This data was analyzed by the type of HD and HD brand. Methods: A total of 530 patients registered with the national program on HD through its third round were distributed based on the year when they developed their first health problem including HDLI (N=221). The distribution of health problems at diagnosis was clinically evaluated in order to examine the association between their lung injury and the use of HD. Results: The number of HD associated victims and HDLI patients was found to rise sharply from 2008 to 2011, with a peak in 2011. This trend was found not only for HD brands containing polyhexamethylene guanidine phosphate (PHMG), but also chloromethylisothiazolinone/methylisothiazolinone (CMIT/MIT). The number of patients who responded as developing health problems in the specific year was 35 for 2008, 51 for 2009, 108 for 2010 and 182 for 2011. Other types of HD brands and HD chemicals did not follow the trend of abrupt increase in HD associated patients since 2008. Conclusion: This study found the number of HD associated victims and HDLI patients who used HD brands containing PHMG sharply increased starting in 2008. A significant change in the process of manufacturing PHMG can be suspected with the abrupt rise in HD associated patients in specific years.

• 한국산업보건학회지
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• 제29권1호
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• pp.13-20
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• 2019

Objective: This study was performed to propose a domestic occupational exposure limit(OEL) following a health hazard assessment, calculation of a non-carcinogenicity reference concentration worker($RfC_{worker}$) value, and examination of international agencies' exposure limits. It also recommends legal management within the Occupational Safety and Health Act for PHMG-Phosphate(CAS No. 89697-78-9), It is a humidifier disinfectant that generated many lung injuries. Methods: We have investigated the recommendation or guidelines of foreign OEL for PHMG-Phosphate and the actual state of legal management in Korea. To examine the procedures and methods for recommendation OEL. Toxicological hazard and health hazard classifications were examined and a non-carcinogenicity $RfC_{worker}$ value was calculated for PHMG-Phosphate. An OEL and the necessity of legal management were recommended as well. Results and Conclusions: The OEL for PHMG-Phosphate is recommended to be $0.01mg/m^3$. The recommended OEL is close to 10 times the RfCworker value of $0.000833mg/m^3$ calculated from the chemical dose-response hazard assessment, which is a 2017 study. The CMIT/MIT(3:1) mixture, which was a social issue as a humidifier disinfectant substance, was also exposed to the same ratio in March 2018, establish the OEL. It is recommended to establish OEL for PHMG-Phosphate to prevent worker health hazards and for chemical safety management.