• 분석과학
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• 제25권3호
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• pp.178-189
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• 2012

생식독성 및 내분비계 장애물질로 분류되는 프탈레이트가 근자에 유럽 신화학물질관리제도(REACH)의 허가대상 고위험성 물질(SVHC) 목록 및 유럽의 전기전자제품에 함유된 유해물질 규제인 RoHS II의 최우선 고려 물질 등으로 규제가 강화되면서 IEC TC 111에서 분석법 표준화가 진행되고 있으며 KS 개정도 이루어지고 있다. 본 고에서는 프탈레이트 분석법의 KS 개정 및 한국 NC에서 제안하여 진행되고 있는 IEC 62321에 프탈레이트 분석법을 추가함에 있어 기술적 자료로 사용될 수 있도록 현존하는 국가별 표준의 용매 추출 전처리를 비교 및 검증해 보았다. PVC (polyvinyl chloride)에서의 DEHP (diethylhexyl phthalate)의 추출 효율은 메탄올, 톨루엔, 디클로로메테인. 헥세인 순으로 46.9%에서 95.3%까지 증가하였다. DBP (dibutyl phthalate), BBP (butylbenzyl phthalate) 및 DEHP의 속슬렛을 사용한 추출 시간은 6시간이 최적임이 입증되었고, PVC, nitro cellulose, ABS (acrylonitrile butadiene styrene), and EPDM (ethylene propylene diene monomer) rubber 등의 매트리스로부터의 추출 효율도 90%~99%로 측정되었다. 용매추출에 이은 GC-MS 분석법의 검출한계는 용액 및 고분자 샘플에서 각각 0.08 ~0.3 ${\mu}g/mL$ 및 8~30 mg/kg으로 산출되었다. 공산품에서 프탈레이트를 분석하는 국가표준에서 용매 추출 전처리를 사용하는 EN 14372, ASTM D 7083, 일본 후생노동성 시험법(MHLW 0906-4) 및 KS M 1991을 비교한 결과 4개 국가별 표준 모두 98%~99%의 추출효율을 가짐이 검증되었다. 또한, 국내에서 유통되는 어린이 장난감, 전기 코드, 매니큐어의 공산품 3종에서 프탈레이트 함유 여부를 분석한 결과 DBP 및 DEHP가 22~1,910 mg/kg 범위로 검출되었다.

• Toxicological Research
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• 제20권1호
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• pp.71-82
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• 2004

Changes in cell cycle control in the lungs and liver of the B6C3F1 mice (20 males per each group) exposed to ozone (0.5 ppm), 4-(N-methyl-N-nitrosamino)-1-(3-pyridyl)-1-butanone (NNK, 1.0 mg/kg), and dibutyl phthalate (DBP, 5,000 ppm) after 52 weeks were examined through Western, Northern blot, and immunohistochemistry based on alterations in protein expression levels of G1/S checkpoints (cyclin D1, cyclin E, and PCNA), G2/M checkpoints (cyclin B1, cyclin G, and cyclin A), negative regulators (p53, p21, GADD45, and p27), and positive regulator (mdm2). Expression levels of cyclins D1, E, G, PCNA, mutant p53, and mdm2 proteins were higher in the lungs and livers treated with combination of toxicants than in those treated with ozone only. Expression levels of the wild-type and mutant p53, p21, GADD45, p27, and mdm2 proteins and mRNAs were higher in toxicant-treated groups than those of the control. Immunohistochemical analysis revealed staining intensities of the PCNA, cyclin D1, c-myc and mdm2 protein- treated lungs and livers were stronger than those of the control group. Our results showed that combined treatment of ozone with NNK/DBP altered the cell cycle control through instability of the wild-type p53 gene. Such pivotal p53-mediated cell cycle alterations may be responsible for the toxicity observed under our experimental condition. These results may be applied to risk assessment of mixture-induced toxicity.

• 한국독성학회:학술대회논문집
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• 한국독성학회 2005년도 춘계 국제심포지엄 및 학술대회
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• pp.149-150
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• 2005

• Korean Chemical Engineering Research
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• 제47권6호
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• pp.775-780
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• 2009

폐수 방류수 중에 포함될 수 있는 내분비계 장애물질의 제거를 위해 생물학적 영양소 제거 공정에 존재하는 질산화 슬러지의 효용성을 탐색하여 보았다. 질산화 슬러지에 포함된 암모니아 산화균은 ammonia monooxygenase(AMO) 활성에 의해 암모니아 산화를 유발하는데, AMO의 기질 특이성이 낮아 암모니아 산화와 동시에 다양한 화합물이 공산화된다고 알려져 왔다. 본 연구에서는 이러한 공산화 활성이 내분비계 장애물질의 제거에 효과적인지 판단하기 위해, 질산화 슬러지, 유기물산화 슬러지, 멸균 슬러지를 각각 이용하여 3가지의 모델물질(bisphenol A(BPA), nonylphenol(NP), dibutyl phthalate(DBP))에 대한 제거 효율을 비교하였다. 질산화 슬러지에 의한 분해에서는 3가지 모델물질 모두, 배지 중에 질소원으로 아질산염보다 암모늄염을 이용했을 때의 초기 분해속도가 빠르게 나타나서 암모니아 산화 활성과 모델 물질의 분해가 관련이 있는 것으로 나타났다. 반면에 아질산염을 공급한 질산화슬러지에서나 혹은 질산화 활성이 낮은 유기물산화 슬러지를 이용한 경우는 일정한 적응 시간이 지난 이후에 모델 물질들의 분해가 시작되었다. 이는 모델 물질을 탄소원으로 이용하는 균주의 성장 및 활성이 일정한 적응 시간 이후에 나타난 것으로 보인다. 모델 물질의 제거에 슬러지에 의한 물리적 흡착이 어느 정도 기여하는지 확인하기 위해서 멸균 슬러지를 이용한 흡착 제거를 시도하였다. 초기 투입량의 10~20% 내외가 흡착에 의해 상등액에서 제거되었는데, 이를 통해 폐수 슬러지를 이용한 BPA, NP, DBP의 제거에는 물리적 흡착보다는 생물학적 분해 기작이 더 중요한 것으로 보인다.

• 청정기술
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• 제17권2호
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• pp.124-133
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• 2011

2006년 시행되어 온 RoHS 규제에 유해물질을 추가하여 더 강화된 RoHS II의 공표에 대비하여 본 연구에서는 RoHS II의 최우선 규제 물질이면서 2010년 발표된 REACH SVHC 후보목록에도 포함된 물질인 Hexabromocyclododecane (HBCDD) 및 3종 프탈레이트, Dibutyl phthalate (DBP), Butyl benzyl phthalate (BBP), Diethylhexyl phthalate (DEHP)의 국내 전기 전자제품내의 함유 여부를 사전 검토해보려는 목적으로 사례 연구를 진행하였다. 이에 고분자 소재로 구성된 세탁기, 냉장고, 혹은 전자렌지의 부품 20개를 12개 전기전자 부품 생산회사로부터 수거하여 4종 규제 물질을 기체크로마토그래피 질량분석법으로 분석하여 그 함유량을 측정한 결과 Nitrile Butadine Rubber (NBR), Polypropylene (PP), Polybutylene Terephthalate (PBT), Ethylene Propylene Rubber (EPDM), Polyvinyl Chloride (PVC) 등의 소재로 된 부품 중 HBCDD는 NBR 소재로 된 3종 부품에서 42~381 mg/kg 범위로 검출되어 규제값 0.1 wt% (1,000 mg/kg)보다는 적지만 주의를 요한다. DBP 및 BBP는 20개 부품모두에서 검출되지 않고 있어 이 두 물질은 전지전자 제품용 플라스틱 소재에서 넓게 사용되지 않고 있을 가능성을 시사하고 있다. 그러나 DEHP는 40~59,400 mg/kg 범위로 NBR, PP, PBT, EPDM 및 PVC로 이루어진 부품에서 모두 검출되어 광범위하게 사용되고 있음을 알 수 있었고 특히 NBR 및 PVC로 이루어진 8개 부품에서 예상 규제치인 0.1 wt% (1,000 mg/kg)을 훨씬 능가한 0.45~5.94 w%로 검출되고 있어 이에 대한 대비가 필요함을 알 수 있었다. 추가로 REACH SVHC (고위험성 물질)에 속하는 Diarsenic pentaoxide, Diarsenic trioxide, Lead hydrogen arsenate, Triethyl arsenate의 4종 물질의 함유 여부를 ICP에 의한 비소(Arsenic) 분석으로 스크리닝해 본 결과 NBR, PBT 소재의 4개 부품에서 15~700 mg/kg으로 검출되었고 이 중 PBT소재의 부품인 Thermistor에서는 규제되는 비소화합물이 규제값(0.1 wt%, 1,000 mg/kg)을 초과할 가능성이 매우 높다.

• 한국환경보건학회지
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• 제48권1호
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• pp.52-58
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• 2022

Background: Few studies have evaluated the exposure to phthalates via inhalation of floor dust in children's living areas. Objectives: This study evaluated the concentration and exposure level of phthalates emitted from indoor floor dust in children's living areas. Methods: This study utilized the results of a survey conducted by the Ministry of Environment in 2019. Indoor dust was collected from 150 households with children aged 3~7 and 67 daycare centers or local children's centers by using vacuum cleaners. It was analyzed by gas chromatography mass spectrometry. Six types of phthalates were analyzed: Bis (2-ethylhexyl) phthalate (DEHP), Dibutyl phthalate (DBP), Benzyl butyl phthalate (BBP), Di-N-octyl phthalate (DNOP), Diisononyl phthalate (DINP), Di -isodecyl phthalate (DIDP). Results: The medians of DEHP concentrations were 1,028 and 1,937 mg/kg in homes and daycare centers, respectively. The median and maximum values of daily intake were calculated by applying the median and 95th percentile values (the upper 5% of the total concentration) in dust measured in the homes. The DEHP median value was 1.6 ㎍/kg/bw/day, and a maximum A value of 7.8 ㎍/kg/bw/day was calculated. When the childcare center values were applied, the median daily intake of DEHP was 3.1 ㎍/kg/bw/day and the maximum value was 29.2 ㎍/kg/bw/day. As a result of calculating the daily intake by integrating the values of home and childcare facilities, the median and maximum values of daily intake were 1.9 and 10.9 ㎍/kg/bw/day, respectively. Conclusions: This study derives phthalate concentrations among the floor dust in homes and childcare facilities where children mainly spend time, and suggests their intake of phthalates through this. In particular, it was newly suggested that the phthalate concentrations in homes and childcare facilities are different, resulting in differences in intake.

• 한국환경보건학회지
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• 제36권6호
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• pp.510-517
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• 2010

Phthalates, such as di (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP) have been proved to be teratogenics and endocrine disruptors, metabolized rapidly and excreted in the urine. In this study, a simultaneous analytical method for 10 phthalate metabolites, MnBP, MiBP, MBzP, MCHP, MEHP, MEHHP, MEOHP, MnOP, MiNP and MiDP, in human urines, based on switching system with on-line pretreatment column using HPLC-MS/MS has been developed. This method was validated according to the guideline of bioanalytical method validation of National Institute of Toxicological Research. Limits of detection range between 0.2 and 0.9 ng/ml for 10 phthalate metabolites. The calibration curves showed linearity in the range 0.997~0.999, and the results of the intra- and inter-day validations were in the range from 0.4 to 14.7% RSD and from 0.3 to 9.4% RSD, respectively. Recoveries of phthalate metabolites varied from 87.0 to 116.1%. This analytical method showed high accuracy and stable precision for all metabolites, and seems to be suitable for biomonitoring of phthalates in human urine.

• Journal of Pharmaceutical Investigation
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• 제17권3호
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• pp.111-126
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• 1987

Methyl methacrylate-butyl methacrylate copolymer (MMBM)-dibutyl phthalate (DBP) films were investigated as a potential topical drug delivery system for the controlled release of nitrofurazone. The kinetic analysis of release data indicated that drug release followed a diffusion-controlled granular matrix model, where the quantity released per unit area is proportional to the square root of time. DBP of several hydrophobic plasticizers selected was found to give the highest release of nitrofurazone. However, hydrophilic plasticizers such as propylene glycol and polyethylene glycol 400 had no controlled release properties and acceptable film formation. The effects of changes in film composition, drug concentration, film thickness, pH of release medium, and temperature on the in vitro release of nitrofurazone were analyzed both theoretically and experimentally. The release rate constant (k') was found to be proportional to DBP content, pH, and the temperature of release medium, but independent of film thickness, and drug concentration in a range of 0.1-0.4% by weight. The linear relationship was found to exist between the log k' and DBP content. The release of nitrofurazone from MMBM-DBP (8:2) films was found to be an energy-linked process. Two energy terms were calculated ; the activation energy for matrix diffusion was 13.45 kcal/mole, and the heat of drug crystal solvation was 27.26-29.34 kcal/mole. Observation of scanning electron micrographs and microscopic photographs showed that the incorporation of DBP in films increased markedly the particle size of nitrofurazone dispersed in the film matrix, comparing with the fine dispersion of nitrofurazone in pure MMBM film alone.

• 한국환경보건학회지
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• 제44권1호
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• pp.76-89
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• 2018

Background: Exposure to endocrine disrupting chemicals (EDCs) has been considered one of the main causes of a range of endocrine diseases in modern society. An EDC priority list considering exposure, toxicity, and societal concern should be established for EDC management. Methods: The chemical ranking and scoring (CRS) system for EDCs was based on exposure, toxicity,and societal concern. The exposure score system was based on usage, circulation volume, bioaccumulation, and detection in consumer products. The toxicity score system was based on carcinogenicity and reproductive and developmental toxicity. The societal concern score system was based on domestic or international regulations and mass media reports. Results: A total of 165 EDCs were considered in the CRS system. The top-five priority EDCs were Bis(2-ethylhexyl) phthalate (DEHP), Benzene, Bisphenol A, Dibutyl phthalate (DBP) and Trichloroethylene. Phthalates, bisphenols and parabens were identified as priority chemical groups. Conclusion: We developed a CRS system for EDCs to identify priority EDCs for management. This will be a foundation to provide an EDC management plan based on scientific decision-making.

• Environmental Analysis Health and Toxicology
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• 제19권2호
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• pp.177-182
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• 2004

Alcohol consumption and exposure to endocrine disruptors and industrial solvents have been implicated in impaired spermatogenesis, increase in the incidence of malformed sperm and decrease in the percentage of moving sperm. The aim of this study was to determine and compare the direct effects of some organic solvents(bisphenol A; BPA, dibutyl phthalate; DBP, formaldehyde; HCHO, dimethylsulphoxide; DMSO, ethanol) on mucus penetration distance, motility and survival rate of human sperm in vitro. Semen samples from 3 health subjects were prepared using swim-up method and 0.0005-0.5% organic solvents were added to the test medium. BPA, DBP, HCHO and DMSO produced significant decreases in the motility and survival rate with a different potency. The most potent inhibition of mucus penetration distance, motility and survival rate was observed after exposure to HCHO. A concentration of 0.0005% HCHO significantly inhibited sperm motility. When ethanol m.: added directly to sperm, at concentrations equivalent to that in serum after heavy drinking, these damaging effects were lowest compared with other solvents. Present study shows that each compound has different toxic potency to human sperm and we need special caution for the use of HCHO.