• Toxicological Research
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• 제17권
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• pp.25-35
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• 2001

In 1990, Tolerable Daily Intake (TDI) of 10 pg TCDD/kg/day for dioxins based on carcinogenicity and reproductive toxicity was determined by WHO/EURO, that resulted in the establishment of TDIs in other countries. In Japan, Ministry of Health and Welfare and Environment Agency, respectively established the TDI of 10 pg TCDD/kg/day and Health Risk Assessment Index of 5 pg TCDD/kg/day in 1996. Accumulation of new scientific data, especially by molecular toxicology since 1990, resulted in the reevaluation of TDI by WHO-ECEH and IPCS in May, 1998. At this meeting, it was stressed that \circled1 toxic effects of dioxin is mediated through Ah-receptor in both animals and humans, \circled2 use of ebody burdeni concept is better than the use of traditional NOAEL/UF approach, \circled3 inclusion of coplanar PCBs in the TDI by the use of new WHO-TEF. LOAELs (0.16~200 ng TCDD/kg/day) obtained from reproductive toxicity and immunotoxicity in rats, and neurobehavioral toxicity and induction of endometriosis in rhesus monkeys are calculated to be the body burden of 10~50 ng TCDD/kg that is 14~37 pg TEQ/kg/day as human daily intake. Finally TDI of 1~4 pg TEQ/kg/day was established by applying the UF of 10. In Japan, reproductive toxicity and immunotoxicity in rats were used to obtain LOAELs (100~200 ng TCDD/kg/day). Finally TDI of 4 pg TEQ/kg/day was established in June 1999 by applying the UF of 10 to human daily intake of 43.6 pg TEQ/kg/day which corresponds to the body burden of 86 ng TCDD/kg.

• 한국산업보건학회지
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• 제30권2호
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• pp.134-152
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• 2020

Objectives: The objective of this study was to evaluate volatile organic compounds (VOCs) and toluene diisocyanates (TDIs) exposure among polyurethane waterproofing workers in the construction industry. Methods: Task-based personal air samplings were carried out at seven construction sites using organic vapor monitor for VOCs (n=88) and glass fiber filters coated with 1-(2-pyridyl)piperazine(1-2PP) for TDIs (n=81). The concentration of VOCs and TDIs were shown for four different work types(mixing paint, primer roller painting, urethane resin spread painting, painter assistant) at five different worksites (rooftop, ground parking lot, piloti, bathroom, and swimming pool). The two TDI sampling methods (filter vs impinger) were evaluated in parallel to compare the concentrations. Results: The geometric mean(GM) concentration of VOCs Exposure Index (EI) was highest for primer roller painting (1.4), followed in order by, urethane resin spread painting (0.85), mixing paint (0.53), and painter assistant (0.35) by work types. The GM of VOCs EI was highest for bathroom (1.4) followed in order by, swimming pool (0.85), piloti (0.89), ground parking lot (0.82) and rooftop (0.57) by worksites. The GM of 2,4-/2,6-TDI concentration was 0.052 ppb and 0.432 ppb each. There was no statistical difference in TDIs concentrations among worksites. The concentration of 2,6-TDI was ten times higher than that of 2,4-TDI. The concentration of 2,6-TDI by impinger method was 5.7 times higher than that by filter method. Conclusions: In this study, we found 38.6% of the VOCs samples exceeded the occupational exposure limits and 19.8% of the 2,6-TDI samples exceeded 1 ppb among polyurethane waterproofing workers. The most important determinants that increase the concentration of VOCs and TDIs was indoor environment and primer painting work.

• 한국환경보건학회지
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• 제22권2호
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• pp.32-42
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• 1996

This study was performed to evaluate accuracy and precision of filter method and impinger method for analyzin airborne isocyanates in mixture (2, 6-TDI, HDI, 2, 4-TDI, MDI). Filter method was performed using the OSHA Method 42 and impinger method using the NIOSH Method 5521. The samples were analyzed by high performance liquid chromatography-ultraviolet detector (HPLC-UVD). After the optimum operating conditions for each method were investigated, samples with various concentration levels were quantified at the conditions. The precision was expressed by the pooled coefficient of variation(C.V.) and the accuracy by overall accuracy. The results are summarized as follows: 1. The optimum condition of filter method was determined at 35/65 ACN/buffer (0.01 M ammonium acetate) in mobile phase. And in case of impinger method, it was at 30/70 ACN/buffer(0.2 M sodium acetate). The effect of concentrations of acetate on the separation of the peaks was not significant, but, the effect of ACN/buffer ratio was significant. 2. The correlation coefficients for the two methods were above 0.9 in all isocyanate compounds. Average recovery efficiencies for 2, 6-TDI, HDI, 2, 4-TDI and MDI in filter method were 92.4%, 102.6%, 87.3% and 101.0%, respectively. Those in impinger method were 106.6%, 106.7%, 99.0% and 103.6%, respectively. As a result, the recovery efficiency of impinger method was higher than those of filter method in analyzing isocyanate compounds. 3. The pooled coefficients of variations of the methods were slightly higher than expected. The overall accuracies of the methods were within $\pm 25%$ for each isocyanate compound. Since these results satisfy NIOSH criteria, the accuracy of the experiment is appropriate. 4. As seen above, impinger method is more efficient than filter method. But, there are many disadvantages in impinger method. Therefore, solid sorbent such as a glass fiber filter must be developed in order to have the high efficiency not less than that of impinger method in the future.

• 환경생물
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• 제27권4호
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• pp.414-424
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• 2009

본 연구는 2008년 6월부터 2009년 3월까지 남한강 지류인 복하천과 달천의 이화학적 수질 및 부착규조를 이용한 생물학적 수질평가를 하였다. 그 결과 복하천은 영양염의 총인이 $0.041{\sim}0.886\;mg\cdot}L^{-1}$ 총질소가 $0.336{\sim}10.532\;mg\cdot}L^{-1}$의 범위로 매우 높게 나타났으며, BOD의 농도도 일부지점을 제외하고 $2{\sim}5\;mg\cdot}L^{-1}$의 범위로 수질이 다소 오염된 것으로 나타났다. 달천은 하류 정점 및 일부 지점을 제외하고 총인이 $0.06\;mg\cdot}L^{-1}$ 이하, 총 질소가 $2.0\;mg\cdot}L^{-1}$ 이하, BOD가 $2.0\;mg\cdot}L^{-1}$ 이하로 수질이 매우 양호한 것으로 나타났다. 조사기간 동안 복하천과 달천 총 12개 정점에서 출현한 부착규조류는 총 98분류군으로 2목 2아목 8과 22속 85종 13변종이 출현하였으며, 복하천이 총 67분류군, 달천이 78분류군 출현 하였다. 생물학적 수질평가 결과 복하천은 대부분 $\alpha$-중부수성이고, TDI 80 이상으로 오염이 심각한 것으로 나타났으며, 달천은 하류를 제외한 전 정점에서 극빈부수성 및 $\alpha$-중부수성, TDI 50 이하로 생물학적 수질이 양호한 것으로 나타났다. 상관분석 결과 DAIpo와 TDI의 상관성이 상관계수 0.83로 높게 나타났으며, 수질이 양호한 하천일수록 이화학적 수질평가와 생물학적 수질평가의 상관성이 높은 것으로 나타났다. 또한 DAIpo보다 넓은 범위의 규조류를 대상으로 하는 TDI지수가 안정적인 결과를 도출하는 것으로 나타났다.

• 생태와환경
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• 제45권3호
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• pp.289-301
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• 2012

본 연구는 강원도 정선군에 위치한 조양강 및 유입천을 대상으로 총 9개 정점을 선정하고 2008년 6월부터 2010년 9월까지 총 6회에 걸쳐 이화학적 환경요인과 생물량 및 부착규조류의 현존량을 조사하였다. 또한 부착규조류의 군집구조를 분석하고 생물학적 평가를 통해 수질을 평가하였다. 1. 조양강 일대는 석회암으로 구성되어 pH가 7.4~10.2로 중성~알칼리성의 범위를 보였다. 2. 조양강 수계에서 출현한 부착규조류는 2목 6과 23속 95종 15변종 2품종 5미동정종으로 총 117분류군이 출현하였고, 산성수역의 지표종은 출현하지 않았으며 중성~알칼리성의 pH에서 생육하는 Achnanthes laterostrata, Cymbella delicatula 등 11분류군이 출현하였다. 3. 특히 알칼리성 수역의 지표종인 Cymbella delicatula는 I3과 I4 정점의 일부 시기를 제외하고 10% 이상의 상대출현빈도를 나타냈다. 4. 조양강 및 유입천에 DAIpo를 적용한 결과 조양강은 평균 77.03로 A등급을 나타냈으며, 유입천은 평균 65.84로 B 등급으로 나타났다. TDI를 이용한 생물학적 평가시 조양강은 A~B 등급을 나타냈으며, 유입천은 A~D 등급에 걸쳐 나타남으로써, 조양강 본류가 유입천보다 수질이 양호한 것으로 나타났다. 5. 본 연구에서 유입천의 수질이 조양강에 미치는 영향은 낮은 것으로 나타났으나, 2009년 9월의 경우에는 본류인 J2와 J3 정점이 유입천 I1 정점의 영향으로 수질이 저하되었다.

• 한국산업보건학회지
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• 제26권2호
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• pp.178-187
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• 2016

Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.

• 한국산업보건학회지
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• 제23권2호
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• pp.95-102
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• 2013

Objectives: The aim of this study is to present an appropriate sampling method for individual exposure assessment based on a comparison of toluene diisocyanate (TDI) concentrations collected through different sampling methods by work process type. Methods: Two plants handling TDIs in the Incheon area were selected. The samplings were taken during respective processes of spray painting, drying, grinding, and foaming, in which the production of TDIs took on different forms. For the sampling methods for airborne TDIs, open-face cassette holder, modified 2-piece cassette holder, and impinger were used, and the sampling was performed simultaneously at the same locations. Results: The comparison of TDI collection concentrations by each process depending on the sampling method showed high concentrations in the order of the impinger, modified 2-piece cassette holder, and open-face cassette holder for spray painting and foaming. In all processes with the exception of drying, TDI collection concentrations were higher for sampling done with the modified 2-piece cassette holder than with the open-face cassette holder. Conclusions: Based on these results, the modified 2-piece cassette holder was found to be a more appropriate sampling method than the open-face cassette holder when taking individual samples of TDIs from spray painting, grinding, and foaming processes. In particular, for individual exposure assessment of the spray painting process, which features comparatively high collection concentrations compared to the other processes, the use of a modified 2-piece cassette holder is considered appropriate.

• Tuberculosis and Respiratory Diseases
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• 제39권6호
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• pp.490-501
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• 1992

TDI 기관지 유발검사상 TDI-천식으로 확진된 환자 22명을 대상으로 이들의 임상적 특징에 관한 고찰과 함께 메타콜린 기관지유발검사 및 TDI-, MDI-, HDI-HSA conjugate에 대한 특이 IgE 항체를 측정하여 다음과 같은 결과를 얻었다. 1) TDI 기관지유발검사상에서는 조기 반응형이 11예(50%), 후기단독 반응형이 6예(27%), 그리고 이중 반응형이 5예(23%)였다. 2) 메타콜린 기관지유발검사상 19예(86.4%)가 양성반응을, 3예(13.6%)가 음성반응을 보였으며, 이들 음성반응자들은 TDI 기관지유발검사 24시간후에 다시 시행한 메타콜린 기관지유발검사에서는 기도과민성을 나타내었다. 3) Isocyanate에 대한 특이 IgE 항체의 측정 결과 TDI-HSA에 대해서는 12예(54.5%), MDI-HSA에 대해서는 7예(31.8%), 그리고 HDI-HSA conjugate에 대해서는 9예(40.9%)가 양성반응을 보였으며, 특이 IgE의 양성률은 잠복기, 아토피유무 및 흡연상태와는 상관관계가 없었다. 4) 추적검사가 가능했던 12예에서 기도과민증의 호전을 보였던 예는 8예였는데, 이 중 7예는 isocyanate 노출에의 회피가 가능했던 경우였고 1예는 계속적으로 노출되어 있었음에도 불구하고 호전된 경우였으며, 악화되었던 4예 중 2예는 계속적으로 노출되어 있었던 경우, 그리고 2예는 회피에도 불구하고 악화을 보인 경우였다. 이상의 결과로 isocyanate에 의한 직업성 천식 환자의 59.1%에서 IgE 매개에 의한 기관지 수축반응이 의심되었으며, 메타콜린 기관지유발검사상 음성반응을 보인다고 하더라도 병력상 isocyanate에 의한 직업성 천식이 의심되면 isocyanate-기관지유발검사를 시행하고 그 이후 지도 과민증의 변화를 관찰하는 것이 진단에 유용할 것으로 여겨진다.

• 분석과학
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• 제18권6호
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• pp.511-519
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• 2005

식품 포장재에 사용되는 접착제의 원료로 사용되는 우레탄의 주원료인 톨루엔 디이소시아네이트(TDI)는 인체에 노출될 경우에 독성을 일으킬 수 있다. GC/MS를 사용하여 식품 포장재에 잔류하는 TDI를 분석하기 위한 시료 전처리 조건과 분석조건을 확립하였다. 포장재 중에 포함된 TDI는 n-헵탄, 4%아세트산 등과 같은 식품유사용매를 사용하여 추출된 후, 기체 크로마토그래프/질량분석기 (GC/MS)에 의해 분석되었다. 26개의 식품 포장재를 측정한 결과 10개의 시료에서 $0.51{\sim}60.88{\mu}g/ml$ 농도 범위에서 TDI가 검출되었다. 포장재의 절단된 면에 대한 추출 용매의 접촉을 피하고 포장재 면만이 접촉하도록 한 후 추출시간을 달리하면서 실험한 결과 2시간 추출 조건에서도 0.7% 수준으로 감소되어 실제 식품 조리시에 TDI가 다량 검출될 위험은 미미한 것으로 평가되었다. 본 연구에서 확립된 톨루엔 디이소시아네이트에 대한 분석법은 외국의 유해물질에 대한 관리기준을 만족시키는 정량한계를 확보한 신뢰성 있는 방법으로 추후 관련 연구를 위한 기초 분석기술로 활용도가 높을 것으로 예상된다.

• 한국염색가공학회지
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• 제8권2호
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• pp.1-7
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• 1996

Thermotropic liquid-crystalline polyurethanes were synthesized by the polyaddition reaction of such para-substiuted diisocyanate monomer as 1,4-phenylene diisocyanate(1,4-PDI) and 2,5-tolylene diisocyanate(2,5-TDI), with 4,4'-bis($\omega$-hydroxyalkoxy)biphenyls(BPm: $HOC_{m}OC_{6}H_{4}C_{6}H_{4}OC_{m}H_{2m}OH$; m is the carbon number of the hydroxyalkoxy group). These polyurethanes have mesogenic biphenyl units in the main chain. Properties of polymers were studied by differential scanning calorimetry, wide-angle X-ray scattering, thermogravimetic analysis, polarizing microscopy, and infraed spectroscopy. DSC thermograms for these polymers exhibited two endothermic peaks corresponding to phase transitions of melting and isotropization. Mesomorphic behavior of the polyurethanes were also observed under the polarizing microscope. For example, polyurethane 2,5-YDI/BP5 with [$\theta$]=0.44 prepared from 2,5-TDI and BP5 exhibited a liquid crystalline phase from 194 to 205$^{\circ}C$. Infrared spectrum study indicated that the hydrogen bonding between urethane linkages affected the mesomorphism. The thermostabilities of polyurethanes 2,5-TDI/BP5 and 1,4-PDI/BP5 were measured at a heating rate of 1$0^{\circ}C$/min in air. The temperatures of 5% weight loss for 2,5-TDI/BP5 and 1,4-PDI/BP5 were 297 and 334$^{\circ}C$, respectively.