2-Chlorobenzyl alcohol을 이용한 TDI의 가스 크로마토그래피 분석

윤주송,박준호,이규원,엄민용,이은정,유철,최홍순,서동섭,최병길,유호영,임정연,이강명,서종철,노재훈,조영봉 한국EHS평가학회 2004 한국EHS평가학회지 Vol.2 No.2

Isocyanates는 OECD의 high production volume (HPV) chemical list에 등록되어 있다.Isocyanates에 노출시 피부,눈 및 호흡기계의 염증,천식,기관지염,그리고 폐 부종 등을 발생시킨다.TDI의 발암성에 대해서 IARC는 Griop 2B로,그리고 NTP는 Group B로 지정되어있다.1984년 12월 3일 인도 보팔에서 발생한 누출 사고로 인해서 2,800명이 사망하고 200,000명 이상이 부상당했다.TDI에 대한 ACGIH의 TWA는 0.005ppm (0.04 mg/m3)이고,STEL는 0.02 ppm (0.14 mg/m3)이다.NIOSH와 OSHA의 TDI에 대한 HPLC 분석법은 임핀저나 glass fiber filter로 포집하는데 이 방법은 다른 물질의 간섭과 재현성이 좋지 않다.따라서 본 연구는 2-CBA를 이용하여 TDI를 유도체화 및 가수분해하여 GC/ FID 및 GC/ ECD 분석법을 설정하고자 한다.2,4-TDI는 2-CBA와 반응하여 urethane을 합성하였고 수율은 71.74%이었으며,합성된 urethane은 TLC로 확인하였다.2-CBA로 코팅된 glass fiber filter를 87˚C, 20mmHg로 lhr 이상 건조처리 하였을 때 모두 증발하였지만 urethane 코팅된 glass fiber filter를 같은 조건에서 처리하였을 경우 3hr까지 증발하지 않았다.Urethane의 가수분해 수율은 1, 3, 5N HCI 및 l, 3, 5N H2SO4에서 약 100% 이었다.가수분해물인 2-CBA는 GC/FID와 GC/ PD-ECD에서 정량적으로 분석되 었고 LOD는 각각 0.02199 mg/m3 및 0.02503mg/m3이었다.또한 2-CBA 및 urethane의 가수분해물 내의 2-CBA는 GC/MSD에서 정상적으로 확인되었다.그렇지만 GC/FID로 분석한 2-CBA의 최저 농도인 2.5ppm을 적용하였을 때 (1.5 l/min, 6hr 포집)대기 중의 분석 가능한 최저 TDI 농도는 0.00567mg/m3(ACGIH TWA : 0.04 mg/m3) 이었다.만약 좀더 감도가 좋은 알콜류를 사용한다면 GC/PD-ECD로 더 낮은 농도까지 분석 가능할 것이다.따라서 2,4- 및 2,6-TDI의 동시 분석 및 total isocyanate 분석이 GC/FID 및 GC/PD- ECD로 가능할 것이다. Isocyanate is on OECD high production volume(HPV) chemical list. Hazard of TDI are Inflammation of skin, eye and respiratory system, asthma, bronchitis and lung edema etc. Carcinogenicity of TDI are IARC - Group 2B, NTP - Group B. Isocyanate leakage accident in 1984. 12. 03(bopal, India), Union Carbide killed 2,800 man and, injured more than 200,000. TDI's ACGIH TWA is 0.005ppm(0.04 mg/m3) and STEL is 0.02 ppm(0.14 mg/m3). NIOSH and OSHA method of 2,4-TDI is HPLC method collected by impinger or glass fiber filter. These methods have a interference and bad reproducibility. So, this study find new method of GC/FID or GC/ECD by derivation of TDI and hydrolysis using 2-CBA. 2,4-TDI and 2-CBA makes urethane and yield is 71.74% and urethane is verificated by TLC. Glass fiber filter coating 2-CBA is treated in 87˚C and 20mmHg decompression evaporation more than 1 hr and evaporate entirely but, glass fiber filter coating urethane is treated in same condition have no evaporation to 3 hr. Urethane hydrolysis yield in 1, 3, 5N HC1 and H2S04 are about 100%. Hydrolysate the 2-CBA is analyzed by GC/FID and GC/PD-ECD, and LOD is 0.02199 mg/m3 and 0.02503mg/m3 respectively. 2-CBA and 2-CBA in hydrolysate of urethane are identified by GC/MSD. But, Lowest concentration of 2-CBA solution analyzed by GC/FID is 2.5ppm(l.5 l/min, 6hr collect). According to lowest analytical concentration, usual analytical limit of TDI in air is 0.00567mg/m3 (ACGIH TWA : 0.04 mg/m3). If use more sensitive alcohols, a very small amount can be analyzed by GC/PD-ECD. So, simultaneous analysis of 2,4- and 2,6-TDI and total isocyanate analysis can be available by GC/FID and GC/PD-ECD.

관능법과 기기분석법을 접목한 악취원인물질 평가방법

김만구,정영림,박정진,서영민,윤인구 한국냄새환경학회 2002 실내환경 및 냄새 학회지 Vol.1 No.1

The objective method, combined sensory and instrumental analysis, was desired to evaluation of intensity as well as odor-active compounds because malodor is sensory pollution. In this study, the odor-activecompounds were analysed by Cryofocusing- GC/FID/Olfactometry and GC/MSD in the Sihwa-Banwoul industrial area. The major odor-active compounds related to solvent were methyl ethyl ketone, methyl isobutyl ketone and n-butyl acetate. As well as a novel evaluation method of odor-active compounds were proposed. The evaluation method base on the quality of odor in a sampling site by human nose, a retention time and an quality of odor detected by GC/ FID/Olfactometry, and a retention time and a mass spectrum obtained by GC/MSD. This evaluation method is expected to identify not only odor-active compounds in the industrial area also flavors and stench of food, polymer, cosmetics and a related odor industry. 악취는 감각오염이므로 악취의 세기, 원인물질들의 평가에 기기분석법과 관능법을 병행한 객관적인 평가방법이 절실히 요구된다. 이 연구에서는 기기분석법과 관능법을 접목시킨 Cryofocusing-GC/FID/Olfactometry와 GC/MSD를 이용하여 시화․반월공단지역의 악취물질을 분석하였다. 공단지역의 악취는 여러 가지 물질에서 기인한 복합취였지만, 시화․반월공단 내에서 용제에 기인한 주요 냄새원인물질은 methyl ethyl ketone, methyl isobutyl ketone, n-butyl acetate 등으로 확인되었다. 그리고, 현장에서 맡은 냄새의 질과 GC/FID/Olfactometry에서 얻은 냄새의 질과 머무름 시간 그리고 GC/MSD에서 얻은 머무름 시간과 mass spectrum을 연관지어 냄새원인물질을 평가하는 새로운 방법을 제안하였다. 이 평가법은 공단지역의 악취원인물질 뿐만 아니라 식품의 향과 이취, 고분자, 화장품 그리고 냄새와 관련된 산업 등에 널리 활용될 것으로 기대된다.

기체 크로마토그래피/불꽃 이온화 검출/후각 검출법의 패널선정과 응답특성

김만구,정영림,박정진 한국냄새환경학회 2003 실내환경 및 냄새 학회지 Vol.2 No.1

Panel selection play a very important role in analysis of odor-active compounds using GC/FID/Olfactometry combine sensory method with instrumental analysis. This is because quite often humans respond differently to odors have an effect on olfactometry results. In this paper, to identify factors affecting olfactometry panel selection in the measurement of odor, a data bank of odor intensity and description of odor 21 individual panel tests on acetic acid, trimethylamine, phenol, methylcyclopentenone, β-phenylethylalcohol were investigated and response character were analysed statistically. The major factor is health condition that sex, smoking, health condition have effect on odor intensity in panel selection. Analysis result of the malodor standard gas using Cryofocusing-GC/FID/Olfactometry showed description for odorant diversely and describe a noun than an epithet for same odorant. The time gap between FID and ODP responses was dependent on physical property such as odor threshold, vapor pressure and solubility in water of odorant. Lower odor threshold odorant showed a narrow time gap. 관능법과 기기분석법을 접목시킨 GC/FID/Olfactometry를 이용하여 냄새원인물질을 분석하는데 패널의 선정이 중요하다. 이는 냄새를 판정하는 패널의 응답특성이 분석결과에 많은 영향을 미치기 때문이다. 이 논문에서는 21명의 피험자를 대상으로 아세트산, 트라이메틸아민, 페놀, 메틸사이클로 펜테노른, β-페닐에틸알코올 등 5가지 표준시험액에 대한 냄새강도와 냄새질의 응답을 조사하여 특성을 분석하였다. 패널의 선정에 있어 패널들의 성별, 흡연유무, 건강상태가 냄새 판정에 미치는 영향을 검토해 본 결과 건강상태가 냄새강도에 가장 많은 영향을 주는 것으로 나타났다. 악취표준물질을 저온농축-GC/FID/Olfactometry로 분석한 결과 동일한 물질이라도 패널간의 냄새표현이 다양하게 나타났으며, 주로 형용사보다는 명사에 붙어서 표현하였다. 표준물질에 대한 FID와 ODP 신호차이는 물질의 후각최소감지농도, 증기압, 수용성 등 물질적 특성에 영향을 받았으며, 후각최소감지농도가 낮은 물질일수록 패널들간의 FID와 ODP 신호차이가 적게 나타났다.

직독식 측정기 PID와 능동식 시료채취기에 의한 GC-FID 정량분석법의 VOCs 농도 비교 연구

여진희 ( Jin-hee Yeo ),최광민 ( Kwang-min Choi ) 한국산업보건학회 (구 한국산업위생학회) 2016 한국산업보건학회지 Vol.26 No.3

Objectives: Direct-reading instrument(Photoionization detectors, PID) and quantitative analysis using active type air sampling (Gas chromatography-flame ionization detector, GC-FID) were tested to evaluate their ability to detect volatile organic compounds(VOCs) in a semiconductor manufacturing plant. Methods: The organic compounds used were acetone and ethanol which are normally used as cleaning solutions in the semiconductor manufacturing. The evaluation was based on the preparation of test solutions of known acetone and ethanol concentration in a chamber(600×600×1150 ㎜). Samples were prepared that would be equivalent to 5~100 ppm for acetone and 10~ 200 ppm ethanol. GC-FID and PID were evaluated simultaneously. Quantitative analysis was performed after sampling and the direct-reading instrument was checked using real-time data logging. Results: Positive correlations between PID and GC-FID were found for acetone and ethanol at 0.04~2.4% for acetone(TLV: 500 ppm) and 0.1~8.3% for ethanol(TLV: 1000 ppm). When the sampling time was 15 min, concentration of test solution was the most similar between measurement methods. However, the longer the sampling time, the less similar the results. PID and GC-FID had similar exposure patterns. Conclusions: The results indicate that PID and GC-FID have similar exposure pattern and positive correlation for detection of acetone and ethanol. Therefore, PID can be used for exposure monitoring for VOCs in the semiconductor manufacturing industry. This study has significance in that it validates measuring occupational exposure using a portable device.

Development of Analytical Technology Using the HS-SPME-GC/FID for Monitoring Aromatic Solvents in Urine

( Mi-young Lee ),( Yun Kyung Chung ),( Kyong-sok Shin ) 한국질량분석학회 2013 Mass spectrometry letters Vol.4 No.1

Headspace solid phase micro-extraction gas chromatography/flame ionization detection (HS-SPME-GC/FID) method was compared with headspace gas chromatography/mass selective detection (HS-GC/MS). Organic solvent-spiked urine as well as urine samples from workspace was analyzed under optimal condition of each method. Detection limit of each compound by HS-SPME-GC/FID was 3.4-9.5 μg/L, which enabled trace analysis of organic solvents in urine. Linear range of each organic solvent was 10-400 μg/L, with fair correlation coefficient between 0.992 and 0.999. The detection sensitivity was 4 times better than HS-GC/MS in selected ion monitoring (SIM) mode. Accuracy and precision was confirmed using commercial reference material, with accuracy around 90% and precision less than 4.6% of coefficient of variance. Among 48 urine samples from workplace, toluene was detected from 45 samples in the range of 20-324 μg/L, but no other solvents were found. As a method for trace analysis, SPME HS GC/FID showed high sensitivity for biological monitoring of organic solvent in urine.

Development of Analytical Technology Using the HS-SPME-GC/FID for Monitoring Aromatic Solvents in Urine

이미영,정윤경,신경석 사단법인 한국질량분석학회 2013 Mass spectrometry letters Vol.4 No.1

Headspace solid phase micro-extraction gas chromatography/flame ionization detection (HS-SPME-GC/FID) method was compared with headspace gas chromatography/mass selective detection (HS-GC/MS). Organic solvent-spiked urine as well as urine samples from workspace was analyzed under optimal condition of each method. Detection limit of each compound by HS-SPME-GC/FID was 3.4-9.5 μg/L, which enabled trace analysis of organic solvents in urine. Linear range of each organic solvent was 10-400 μg/L, with fair correlation coefficient between 0.992 and 0.999. The detection sensitivity was 4 times better than HS-GC/MS in selected ion monitoring (SIM) mode. Accuracy and precision was confirmed using commercial reference material, with accuracy around 90% and precision less than 4.6% of coefficient of variance. Among 48 urine samples from workplace, toluene was detected from 45 samples in the range of 20-324 μg/L, but no other solvents were found. As a method for trace analysis, SPME HS GC/FID showed high sensitivity for biological monitoring of organic solvent in urine.

축산시설의 악취 특성에 관한 연구

박귀환,오길영,정경훈,정선용,차규석 한국냄새환경학회 2005 실내환경 및 냄새 학회지 Vol.4 No.4

이 연구는 GC/PFPD, GC/FID, 분광광도계(UV)를 이용하여 축사내 악취물질을 측정하였으며, 대상 시설은 광주 근교에 위치한 축산시설 중 돈사(7), 우사(2), 계사(1)를 선정하여 2004년 7월부터 10월까지 일부 악취물질에 대해 측정․분석하였다. 측정대상 물질에 대한 표준물질분석은 낮은 수준의 검량 범위에서 결정계수(R2)가 0.98이상, 분석재현성이 10% 이내였으며, 최소검출한계는 시료 100mL 일 때 0.99ppb로 검출되었다. 연구대상 시설 중 가장 높은 악취물질농도는 암모니아 성분 이였으며, 각각 돈사 2.31ppm, 우사 1.32ppm, 계사 1.88ppm으로 조사 되었다. 또한, 황화합물 중 황화수소는 돈사 17.53ppb, 우사 8.41ppb 였으며, 메틸메르캅탄은 계사에서 32.06ppb로 나타났다. 대상 악취물질에 최소감지 농도를 이용한 예상 악취농도는 황화수소, 암모니아가 돈사에서 각각 74%, 24%, 우사에서는 70%, 29%로 영향을 미치는 것으로 나타났으나, 계사에서는 메틸메르캅탄 88%로 주요 기여물질로 조사되었다. 예상악취강도와 희석영향을 비교해보면, 황화합물은 축산시설로부터 악취 민원을 감소시키기 위한 원인물질이 될 것으로 사료된다. In this study, odor compounds from 10 livestock raising facility(pigpen, cowshed, henhouse) located in adjacent Kwangju-city were analyzed using GC/PFPD, GC/FID and spectrophotometer(UV) from July to October 2004 for identifying odorants. The analytical method gave good linearity(R2=0.98 above) in calibration range of low ppb level, and good reproducibility of 10%. Minimum detection limit(within run) of the method could reach to 0.99ppb when 100ml was sampled. The highest odorant was ammonia showing 2.31ppm at pigpen, 1.32ppm at cowshed, and 1.88ppm at henhouse respectively. Among the sulfur compounds, H2S was 17.53ppb at pigpen and 8.41ppb at cowshed, and methylmercaptan was 32.06ppb at henhouse, respectively. Predicted Odor Concentration based on odor threshold showed that the major odor active compounds were H2S and NH3 showing 74%, 24% at pigpen and 70%, 29% at cowshed respectively. But methylmercaptan was the major compound at henhouse(88%). Comparing Predicted Odor Intensity and dilution effect, sulfur compounds will be the target compound to reduce the complaints related with odors from livestock raising facility.

Development of Analytical Technology Using the HS-SPME-GC/FID for Monitoring Aromatic Solvents in Urine

Lee, Mi-Young,Chung, Yun Kyung,Shin, Kyong-Sok Korean Society for Mass Spectrometry 2013 Mass spectrometry letters Vol.4 No.1

Headspace solid phase micro-extraction gas chromatography/flame ionization detection (HS-SPME-GC/FID) method was compared with headspace gas chromatography/mass selective detection (HS-GC/MS). Organic solvent-spiked urine as well as urine samples from workspace was analyzed under optimal condition of each method. Detection limit of each compound by HS-SPME-GC/FID was $3.4-9.5{\mu}g/L$, which enabled trace analysis of organic solvents in urine. Linear range of each organic solvent was $10-400{\mu}g/L$, with fair correlation coefficient between 0.992 and 0.999. The detection sensitivity was 4 times better than HS-GC/MS in selected ion monitoring (SIM) mode. Accuracy and precision was confirmed using commercial reference material, with accuracy around 90% and precision less than 4.6% of coefficient of variance. Among 48 urine samples from workplace, toluene was detected from 45 samples in the range of $20-324{\mu}g/L$, but no other solvents were found. As a method for trace analysis, SPME HS GC/FID showed high sensitivity for biological monitoring of organic solvent in urine.

GC/FID/액상주입 system의 장치간 VOCs 검출한계 비교

심녕주(Nyeong-Ju Sim),김수미(Su-Mi Kim),김선태(Sun-Tae Kim) 대전대학교 환경문제연구소 2010 환경문제연구소 논문집 Vol.14 No.-

According to the development of GC equipment, it has been possible to analyze the low level of ambient VOCs concentration. In this study, the limit of detection and the limit of quantitation were estimated for two GC equipments of the VOCs analysis, which would contribute to improve the quality of VOCs analysis results. The results of %RSD for ten standard solutes showed a great reproducibility in terms of detection time and detection area. The limit of detection and the limit of quantitation in SRI GC appeared to be 0.175 ppb and 0.583 ppb for benzene, and 0.223 ppb and 0.743 ppb for toluene, respectively. On the other hand, The limit of detection and the limit of quantitation in FISON GC appeared to be 0.149 ppb and 0.496 ppb for benzene, and 0.094 ppb and 0.313 ppb for toluene, respectively.

국내 사업장폐기물의 폐유기용제 분석방법 연구

황동건,홍수연,김용준,정미정,김기헌,신선경 한국폐기물자원순환학회(구 한국폐기물학회) 2016 한국폐기물자원순환학회 추계학술발표논문집 Vol.2016 No.-

유기용제는 어떤 물질을 녹일 수 있는 액체상태의 유기화학물질을 총칭한 것으로 기름 및 지방 등을 잘 녹이고 휘발성이 강한 것이 특징이다. 폐기물 관리법에서는 사업장에서 발생하는 폐유기용제의 독성, 인화성, 발화성 등으로 인한 인체 및 생태계에 미치는 유해한 영향을 최소화하기 위해 지정폐기물로 관리하고 있다. 또한, 폐유기용제의 종류가 다양하고 혼합되어 배출되는 특성상, 함량에 관계없이 지정폐기물로 관리하고 있다. 그 중에서도 할로겐족 유기용제에 함유된 염소, 브롬 등을 포함하는 유기용제는 소각 할 경우 다이옥신과 같은 독성이 높은 유기염소계 화합물이 생성되므로 1,100℃ 이상에서 고온소각하고, 비의도적 발생을 줄이고자 할로겐화 유기물질 17항목을 설정하고 5%의 함유량 기준을 두고 있으며, 할로겐족을 제외한 그 밖의 폐유기용제는 850℃ 이상에서 일반소각하여 처리하고 있다. 유기용제 분석방법으로 국내의 폐기물공정시험기준 ES. 06601.1 할로겐화 유기물질-기체크로마토그래피-질량분석법과 미국 EPA 8260B(고형폐기물 중 휘발성유기화합물 측정방법, GC/MS), EPA 8015C(비할로겐족유기물질, GC/MS), EPA 5021a의 헤드스페이스법을 검토하였으며, 또한 일본 JIS K 0125 폐유기용제 중 휘발성유기 화학물 분석법 등의 유기용제 분석방법을 검토하였다. 본 연구에서는 국내 사업장에서 배출되는 그 밖의 폐유기용제의 관리대상 항목 및 관리기준을 마련하여 지정폐기물의 적정 처리 방안을 제시하기 위해, 분석 방법을 검토하였다. 폐기물공정시험기준 ES 06601.1에 준하여 분석하였으며, 분석 장비와 컬럼 조건 등을 비교하여 검토하였다. 희석법으로 전처리한 시료 중 24항목은 VOCOL 컬럼을 사용하여 GC/FID로 분석하였고, 14항목에 대해서는 DB-5MS 컬럼을 사용하여 GC/MSD로 분석하였으나, 14 항목 중 8개의 항목만 분석되었다. 이 중 확인이 어려웠던 항목에 대해서는, 쉽게 휘발되는 유기용제의 성질을 고려하여 전처리 단계가 없는 HS-GC/MSD 방법을 도입하여 추가 검토하였다. 헤드스페이스법을 도입하여 분석한 결과, 확인이 어려웠던 항목 중 몇몇 항목에 대해서는 추가로 검출되었다. MSD의 분석 조건은 거의 동일했기 때문에, 사용된 컬럼의 특성이나 전처리 과정에서의 휘발로 인한 손실등의 영향이 있을 것으로 보이며, 헤드스페이스법 도입에 대해서는 폐기물 특성에 따른 제한조건 등의 추가적인 검토가 필요할 것으로 판단된다.