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 c...
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.
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.
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제안 방법
Target compounds were analyzed by high performance liquid chromatography (Agilent 1200 series HPLC; Agilent Technologies, Santa Clara, CA, USA) coupled with mass spectrometry (1100 MS; Agilent Technologies, Santa Clara, CA, USA) with C18 column (Hypersil gold; 4.6 mm x 250 mm, 5 μm; Thermo Fisher Scientific, Waltham, MA, USA) and Eclipse XDB C18 guard column (4.6 mm x 12.5 mm, 5 μm; Agilent Technologies).
The detailed procedure was as follows:50 mg of detergent sample (20 mg for fabric softener) was diluted into 25 mL water and the whole mixture solution was extracted by using 25 mL of MC:EtAC (9:1) for 10 min sonication (200 watt, 15°C) and shaking for 5 min (300 rpm, 25°C).
5 g of sample was diluted (1/50 fold) from the raw material by pure water, loaded onto each of two cartridges, respectively, and eluted with 12 mL of MC. The identical operating conditions used for wet wipes were applied for optimizing UAE condition for detergents, while experiments were performed to select an optimal extracting solvent among MeOH, EtAC, MTBE, MC, and their mixtures based on the solubility for the target compounds. 0.
Therefore, in this study, analytical method for simultaneous identification and quantifications of MIT, CMIT, BIT, OIT and IPBC using high performance liquid chromatography/mass spectrometry (HPLC/MS) system with widened coverage of sample matrix was developed especially for determination of trace amount of biocides included in human hygiene biocidal products (Product type (PT) 01 class of the European Union Biocidal Products Directive [EU BPD]) comprising wet wipes and detergents [2]. The accuracy of the method was verified by analyzing matrix spike per each targeted sample type.
This study presented a simple simultaneous analytical method for five emerging concern biocidal active ingredients that are frequently used in consumer products, with a special focus on MIT and CMIT in wet wipes and detergents. Of the three pre-treatment methods we tested, UAE had the highest extraction efficiency with MC:EtAC (9:1) for detergents and with MC:Tol (9:1) for wet wipes that were cleaned up with alumina cartridge.
The items selected for testing analytical method in this study were 21 wet wipes (WW), three powder type (PD) and five liquid type (LD) laundry detergents (including two fabric softeners, Table S3). To compare and optimize the extraction and purification conditions per sample type, one each powder and liquid detergent (PD 1 and LD 2), and three wet wipes (WW 1-3) were analyzed.
The 500 μL homogenate was passed through syringe filter to remove any residual fibers and particles, transferred to a clean 2 mL vial and injected into the instrument. To configure appropriate SPE cartridge with the right conditioning and eluting solvent, experiment was performed with using various cartridge types, sample pH condition and by utilizing Ac, ACN and MeOH as mobile phase referring from previous studies [3, 4]. Sample was pH adjusted to 2 and 7, respectively, by adding 2 N hydrochloric acid and loaded onto each one of cartridge A (combination of 200 mg HLB and 500 mg C18 cartridge) and cartridge B (500 mg ENVI-Chrom P).
The method was validated by analyzing 21 wet wipes and 8 detergents collected from local market in Korea. To the best of our knowledge, this is the first study to report on a simultaneous extraction and quantitative analysis by using HPLC/MS system for the four major isothiazolinones in various household products based on an internal standard method.
대상 데이터
Oasis HLB cartridges (200 mg, 6 cc) were purchased from Waters (Milford, USA). Aluminum oxide (98% purity) was purchased from Sigma-Aldrich. The polytetrafluoroethylene (PTFE) syringe filter (0.
Baker (Philipsburg, NJ, USA). Supelclean ENVI-carb, ENVI-Chrom P cartridges (500 mg, 6 cc) and filtration tubes (empty cartridge, 6 cc) were purchased from Supelco (Bellefonte, USA). Oasis HLB cartridges (200 mg, 6 cc) were purchased from Waters (Milford, USA).
The final extraction method selected for the detergent samples was UAE coupled with purification using a combination of alumina and ENVI-Carb cartridges. The detailed procedure was as follows:50 mg of detergent sample (20 mg for fabric softener) was diluted into 25 mL water and the whole mixture solution was extracted by using 25 mL of MC:EtAC (9:1) for 10 min sonication (200 watt, 15°C) and shaking for 5 min (300 rpm, 25°C).
The type and brand of consumer product samples were chosen based on published market analysis report of products with containing high content of biocidal active ingredients and domestic market survey of reporting approximate usage and production volume. The items selected for testing analytical method in this study were 21 wet wipes (WW), three powder type (PD) and five liquid type (LD) laundry detergents (including two fabric softeners, Table S3). To compare and optimize the extraction and purification conditions per sample type, one each powder and liquid detergent (PD 1 and LD 2), and three wet wipes (WW 1-3) were analyzed.
The accuracy of the method was verified by analyzing matrix spike per each targeted sample type. The method was validated by analyzing 21 wet wipes and 8 detergents collected from local market in Korea. To the best of our knowledge, this is the first study to report on a simultaneous extraction and quantitative analysis by using HPLC/MS system for the four major isothiazolinones in various household products based on an internal standard method.
성능/효과
To minimize ion suppression due to sample matrix, ENVI-carb cartridge (500 mg, 6 cc) and activated alumina cartridge (2 g alumina and 1 g sodium sulfate) was connected in order and preconditioned with 12 mL MC prior to pass through the extractant. After purification, the extraction efficiency of both compounds was improved (MIT: 80.0-80.9%, CMIT; 80.2-99.7%; Table 3). From Alvarez-Rivera et al.
The recovery results for MIT and CMIT were shown in Table 3. The average recovery of direct injection method after 5 times dilution of original sample was 35% (19-50%) for MIT and 128% (50-170%) for CMIT, respectively. Over than 45% of relative standard deviation (RSD) was observed when the method was applied to different brands of wet wipes.
The MDL for five target biocides of proposed analytical method is sufficient to analyze target compounds lower than guideline values. The observed concentration level of MIT, CMIT, and IPBC in complementary wet wipes without brand labels was surprisingly high and detected from more than 60% of collected samples even after regulation. Therefore, human exposure to isothiazolinone class biocides is highly suspected and further researches are strongly recommended for continuous monitoring of consumer products to assess human health risk related with exposure through consumer products usage.
The extracts were passed through an activated alumina cartridge (690 mg) that was preconditioned by 12 mL MC. The recovery of MIT and CMIT was lot improved to 100% (87-110%) and 90% (77-102%), respectively, and the standard deviation of recoveries was below 15% for all three types of test sample. The extraction efficiency of MIT or CMIT from wet wipes were not reported so far but compared with water sample results including tap water [3], distilled water [4], river water and sewage effluents [6] using SPE and large-volume direct injection method (Table S4).
The extraction efficiency of MIT or CMIT from wet wipes were not reported so far but compared with water sample results including tap water [3], distilled water [4], river water and sewage effluents [6] using SPE and large-volume direct injection method (Table S4). The reported recoveries of CMIT were 49-98% and the recoveries of MIT showed wide range (5-92%). Wittenberg et al.
, household and cosmetic products, adhesives, river and tap water, distilled water) were compared with our result. The reported recoveries were 5-103% for MIT, 49-103% for CMIT, 15-103% for BIT, 89% for IPBC, and 85-99% for OIT which were similar to or lower than the recovery values by using our method [3-5, 20, 21].
후속연구
Recently, analytical method for targeting metabolites of isothiazolinones in human urine recently reported [27-29]. To fill the gap between wide occurrence of isothiazolinones and human health risk derived from exposure to biocides, further studies of monitoring human specimens with matched information about life style (e.g. consumer product usage and frequency) questionnaires will be recommended.
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