• 대한화학회지
• /
• 제18권6호
• /
• pp.430-436
• /
• 1974

여러 pH에서 1,1-dicyano-2-p-dimethylaminophenyl-2-chloroethylene(DPC)의 가수분해 속도상수를 측정하고 넓은 pH 범위에서 잘 맞는 반응 속도로식을 구하였다. 이 식에 의하면 넓은 pH 범위에서 DPC에 대한 가수분해 반응메카니즘을 잘 설명할 수 있다. pH3이하와 7.5이상에서는 속도상수는 hydronium ion과 hydroxide ion 농도에 각각 비례한다. 또 pH 3∼7.5 사이에서는 물, hydronium ion 과 hydroxide ion이 DPC의 가수 분해에 촉매 역활을 함을 알았다.

• Korean Chemical Engineering Research
• /
• 제49권5호
• /
• pp.510-515
• /
• 2011

염화탄화수소의 고온열분해 반응에서 생성물 반응경로 특성을 파악하기 위해 $H_2$ 반응분위기에서 1,1-dichloroethylene($CH_2CCl_2$) 열분해반응 실험을 수행하였다. 열분해반응 실험은 등온관형반응기를 이용하여 반응온도 $650{\sim}900^{\circ}C$, 반응시간 0.3~2.0초에서 진행하였으며, 반응물 mole 분율은 전체 실험에서 $CH_2CCl_2:H_2$ = 4:96 일정하게 유지하였다. 반응물 $CH_2CCl_2$가 완전분해온도는(분해율 99% 이상) $825^{\circ}C$(반응시간 1초 기준)였으며, $H_2$ 반응분위기에서 $CH_2CCl_2$ 주요 분해반응경로는 H원자 추출 및 첨가교체치환 연쇄반응으로 파악되었다. $CH_2CCl_2$가 46% 분해되는 $700^{\circ}C$에서 1차 생성물로 $CH_2CHCl$가 28%로 가장 높은 농도로 검출되었다. $775^{\circ}C$ 이상에서는 탈염소화된 $C_2H_4$가 2차 생성물로 가장 많이 생성되었으며, 반응온도가 증가할수록 염소 원자수가 작은 화합물이 생성되었으며 이들 화합물은 열화학적으로 안정된 물질이다. $825^{\circ}C$ 이상의 고온반응영역에서 탈염소반응의 부산물인 HCl과 $C_2H_4$, $C_2H_6$, $CH_4$ $C_2H_2$ 등과 같은 열화학적으로 안정된 탄화수소가 주요생성물로 검출되었다. 본 연구에서 고찰된 반응계에서 분해와 생성물분포 특성을 고려하고 열화학이론 및 반응속도론을 기초로 주요 반응경로를 제시하였다.

• Biotechnology and Bioprocess Engineering:BBE
• /
• 제11권3호
• /
• pp.205-210
• /
• 2006

The widespread use and distribution of chloroethylene organic compounds is of serious concern owing to their carcinogenicity and toxicity to humans and wildlife. In an effort to develop active bacterial consortia that could be useful for bioremediation of chloroethylene-contaminated sites in Africa, 16 combinations of 5 dichloroethylene (DCE)-utilizing bacteria, isolated from South Africa and Nigeria, were assessed for their ability to degrade cis- and trans- DCEs as the sole carbon source. Three combinations of these isolates were able to remove up to 72% of the compounds within 7 days. Specific growth rate constants of the bacterial consortia ranged between 0.465 and $0.716\;d^{-1}$ while the degradation rate constants ranged between 0.184 and $0.205\;d^{-1}$ with $86.36{\sim}93.53\;and\;87.47{\sim}97.12%$ of the stoichiometric-expected chloride released during growth of the bacterial consortia in cis- and trans-DCE, respectively. Succession studies of the individual isolates present in the consortium revealed that the biodegradation process was initially dominated by Achromobacter xylosoxidans and subsequently by Acinetobacter sp. and Bacillus sp., respectively. The results of this study suggest that consortia of bacteria are more efficient than monocultures in the aerobic biodegradation of DCEs, degrading the compounds to levels that are up to 60% below the maximum allowable limits in drinking water.

• 한국환경보건학회지
• /
• 제37권5호
• /
• pp.358-368
• /
• 2011

Objectives: In order to evaluate the association between occupational exposure to chloroethylene (TCE) and risk of non-Hodgkin lymphoma (NHL), we conducted a meta-analysis of retrospective cohort studies and casecontrol studies and attempted to summarize the evidence of the association from molecular-epidemiological studies and experiments with human cells. Methods: In the meta-analysis, we restricted the analysis to those studies with data for chlorinated solvents, degreasers, or TCE. Studies involving dry cleaners or launderers were excluded from the analysis because use of TCE as a dry cleaning fluid has been rare since the 1960s. The data were combined using a random-effects model to estimate the summary risks (OR and RR) and 95% confidence intervals (CIs). Molecular evidence of the effect of TCE on human immune system were also reviewed and summarized. Results: Occupational exposure to TCE was strongly associated with NHL among cohort studies (number of studies=13, summary RR=1.33, 95% CI=1.04-1.70) whereas the association was not statistically significant among case-control studies (number of studies=15, summary OR=1.10, 0.98-1.23). When exposure level was considered, it became statistically significant for the highest exposure level (number of studies=5, summary OR=1.70, 1.25-2.32). Molecular evidences showed that TCE exposure in human or cultured human cells may cause a significant decrease immune cell subsets and changes in hormone levels related to immune response. Conclusions: Our results from meta-analysis and additional molecular evidence suggest that occupational exposure to TCE may cause NHL. However, unmeasured potential confounding and unclear dose-response relationships warrant further study on the role of TCE exposure in NHL carcinogenesis.

• Molecular & Cellular Toxicology
• /
• 제1권2호
• /
• pp.99-105
• /
• 2005

Perchloroethylene (tetrachloroethylene, PCE), a dry cleaning and degreasing solvent, can enter ground-water through accidental leak or spills. PCE can be degraded to trichloroethylene (TCE), 1, 1-dichloroethylene (DCE) and vinyl chloride (VC) as potential bio-product. These compounds have been reported that they can cause clinical diseases and cytotoxicity. However, only a little genotoxic information of these compounds has been known. In this study, we investigated DNA single strand breaks of PCE, TCE, DCE and VC by single cell gel electrophoresis assay, (comet assay) which is a sensitive, reliable and rapid method for DNA single strand breaks with mouse lymphoma L5178Y cells. From these results, $37.5\;{\mu}g/ml$ of PCE, $189\;{\mu}g/ml$ of TCE and $56.4\;{\mu}g/ml$ of DCE were revealed significant DNA damages in the absence of S-9 metabolic activation system meaning direct-acting mutagen. And in the presence of S-9 metabolic activation system, $41.5\;{\mu}g/ml$ of PCE, $328.7\;{\mu}g/ml$ of TCE and $949\;{\mu}g/ml$ of DCE were induced significant DNA damage. In the case of VC, it was revealed a significant DNA damage in the presence of S-9 metabolic activation system. Therefore, we suggest that chloroethylene compounds (PCE, TCE, DCE and VC) may be induced the DNA damage in a mammalian cell.

• 한국대기환경학회지
• /
• 제22권6호
• /
• pp.767-778
• /
• 2006

This study was carried out to evaluate the temporal variations of VOCs at an urban site, and to compare the concentrations of VOCs at an urban site in Daegu with those at a suburban site in Gyeongsan. Three hourly VOC samples in the ambient air were collected using a sequential tube sampler (STS 25, Perkin Elmer) throughout two weeks during May and July representing spring and summer seasons, respectively. The VOC concentrations were determined by an automatic thermal desorption apparatus with GC/MS analysis. A total of 12 VOCs of environmental concern were determined, which are chloroform, benzene, trichloroethylene, toluene, tetra-chloroethylene, ethylbenzene, m+p-xylenes, o-xylene, styrene, 1,3,5- and 1,2,4-trimethylbenzenes. Among 12 target VOCs, the most abundant compound appeared to be toluene, being followed by xylenes. The mean concentrations at the urbn site were 1.2 pub for benzene and 20.4 ppb for toluene (n=221) while the mean levels at the suburban site were 0.9 ppb and 4.3 ppb for benzene and toluene (n=96), respectively. The urban site concentrations were typically several-fold higher than those measured at the suburban site. It was found that general trends of VOC levels were significantly dependent on traffic conditions at the sampling site since VOC concentrations were at their maximum during rush hours, i.e. $9{\sim}12a.m$ and $6{\sim}9p.m$. Statistical investigations were conducted to investigate any significant relationships between VOC concentrations and affecting factors. Calculated correlation coefficients among VOCs were positively significant at a level of 0.05 in most cases. Increased concentrations of toluene in the urban site were estimated to reflect the effect of large industrial sources, mainly from textile industry.

• 한국환경과학회지
• /
• 제8권6호
• /
• pp.685-690
• /
• 1999

The pollution characteristics of groundwaters in Taegu City and correlation coefficients(r) between water pollution indicators were investigated for two years from January 1996 to December 1997. Volatile organic compounds such as TCE(tri-chloroethylene), PCE(tetrachloroethylene), l,l,l-trichloroethane, THM(trihalo-methane), dichloromethane, pesticides such as diazinon, parathion, malathion, and toxic inoganic matters such as As, Hg, Se, Pb, Cd, $Cr_6^+,$ CN were not detected in the groundwaters. Mean values of groundwater pollution indicators were below drinking-water standards, but hardness, $KMnO_4-C(potassium$ permanganate consumption), evaporate residues, $SO_4^{-2},\;Fe,\;NO_3^{-}-N,$ color and turbidity exceeded a little in some samples. As groundwater became deeper, hardness and evaporate residues remarkably increased, but $KMnO_4-C,\;NO_3^{-}-N,\;Cl-,$ color, turbity and bacteria decreased. $KMnO_4-C,$ evaporate residues, $Cl^-\;and\;SO_4^{-2}$ were very high at industrial and commercial areas, and $NO_3^--N$ and $NH_4^+-N$ were very high at agricultural and forest areas. It showed high positive significances in the relationships between hardness and each of evaporate residues, $SO_4^{-2}$, Zn and Mn, $KMnO_4-C$ and each of color, turbidity and Zn, color and each of turbidity, Cu, Zn and Mn, turbidity and each of Fe, Cu, Zn and Mn, and evaporate residues and each of $Cl^-,\;SO_4^{-2}$ and Zn.

• 청정기술
• /
• 제16권3호
• /
• pp.198-205
• /
• 2010

염화탄화수소 열분해와 생성물분포 특성을 고찰하기 위해 등온 관형 반응기를 이용해 두 가지 실험을 수행하였다. 첫 번째는 반응분위기에 따른 열분해 특성을 파악하기 위해 $H_2$ 또는 Ar 반응분위기에서 dichloromethane ($CH_2Cl_2$) 분해율과 생성물분포 특성을 고찰하였다. Ar 반응분위기($CH_2Cl_2$/Ar 반응계)에서 보다 $H_2$ 반응분위기($CH_2Cl_2/H_2$ 반응계)에서 $CH_2Cl_2$ 분해율이 더 높았다. 이는 반응성 기체인 $H_2$ 분위기에서 $CH_2Cl_2$ 분해를 촉진시키며 수소 첨가 탈염소반응을 통해 탈염소화된 탄화수소화합물을 생성시키며, 다환방향족탄화수소 (polycyclic aromatic hydrocarbon: PAH)와 soot 생성을 억제하기 때문이다. $CH_2Cl_2/H_2$ 반응계에서 주요생성물로 탈염소화합물인 $CH_3Cl,\;CH_4,\;C_2H_6,\;C_2H_4,\;HCl$ 등이 생성되었으며, 미량 생성물로 chloroethylene이 검출되었다. $CH_2Cl_2$/Ar 반응계에서는 탄소물질수지가 낮았으며 특히 반응온도 $750^{\circ}C$ 이상에서 탄소물질 수지가 더 낮게 나타났다. 주요 생성물로는 chloroethylene과 HCl이 검출되었으며, 미량 생성물로는 $CH_3Cl$과 $C_2H_2$이 검출되었다. 고온 Ar 반응분위기에서 $CH_4$ 주입에 따른 chloroform($CHCl_3$) 분해와 생성물분포 특성을 비교 고찰하였다. $CHCl_3$ 분해율을 비교해 보면 $CH_4$을 주입할 경우($CHCl_3/CH_4/Ar$ 반응계)가 $CH_4$을 주입하지 않았을 경우($CHCl_3$/Ar 반응계)보다 분해율이 낮았다. 이는 $CHCl_3$가 분해되면서 생성되는 활성도가 큰 이중라디칼(diradical)인 :$CCl_2$가 첨가물로 주입된 $CH_4$와 반응하여 소모됨으로써 $CHCl_3$ 분해율이 상대적으로 감소되기 때문이다. Ar 반응분위기에서 $CH_4$ 첨가 여부에 따라 $CHCl_3$이 분해되면서 생성되는 생성물 분포는 큰 차이를 나타내고 있었다. 앞에서 고찰된 각 반응계에서 분해율 비교와 생성물 분포특성을 고려하고 열화학이론 및 반응속도론을 기초로 주요 반응경로를 제시하였다.

• 한국잠사곤충학회지
• /
• 제26권2호
• /
• pp.16-25
• /
• 1984

수용성염의 존재하에서 여러 가지 용매상에 소정시간, 소정온도로 epoxy수지에 의한 견직물의 sericin정착을 행하였다. Potassium thiocyanate염의 촉매하에서 glycero1 glycidyl ether(EX-313)와 ethylene glycol diglycidylether(EX-810)의 4염화탄소용액중에서의 반응에서 높은 수지부착률을 얻었으며, 정착효과가 뛰어난 것을 알 수 있었다. 얻어진 결과를 요약하면 다음과 같다. 1. 사용한 두 수지는 반응 거동이 유사하였으며, EX-810이 수지부착률이나 정착효과면에서 뛰어 났다. 2. 수지부착률은 반응온도나 반응미간에 따라 증가하였고, 90분 7$0^{\circ}C$에서 연감률은 평형에 도달하였다. 3. 수지부착률과 연감률은 3~5%의 수지농도에서 평형에 달하였다. 4. 촉매의 N농도에 따라 부착률은 현저하게 증가하고 0.5N에서 연감률은 평형에 달하였다. 5. 침지시간의 증가와 더불어 부착률은 완만하게 증가하지만 연감률은 15분간 침지에 평형에 도달하였다. 6. 건조온도의 영향은 없는 것으로 보인다. 7. 수분율의 감소는 미약하여, epoxy 수지에 의한 sericin 정착시 수분율을 유지할 수 있는 가능성을 시사하는 것이라 생각된다. 8. 소수성이 강한 용매인 4염화탄소, p-chloroeth-ylene, cyclohexane, xylene, toluene 등이 정착효과가 뛰어남을 알 수 있다. 9. Sericin 정착포의 물성을 시험한 결과 정착효과가 뛰어날 수록, 유연도는 감소하고, 방추도도 감소하며 강도와 신도는 증가하는 것을 알 수 있었다.

• 한국산업보건학회지
• /
• 제22권3호
• /
• pp.175-183
• /
• 2012

Objectives: This study developed a harmonized method for risk assessment based on the Hazard & Risk Evaluation of Chemicals (HREC) according to the Industrial Safety and Health Act (ISHA). Methods: Three preliminary studies, performed during 2010 and 2011 by the Occupational Safety and Health Research Institute and three academic research groups, were compared. The differences in risk assessment, especially in the dose-response assessment method, were analyzed. A new harmonized method for dose-response assessment was suggested and its applicability for the HREC was examined. Results: Considering the various steps of each dose-response assessment, the equivalent steps in quantitative correction, uncertainty factor 2 (UF2) for intra-species uncertainty, and UF3 for the experimental period in the uncertainty correction were relatively high. Using our new method, the total correction values (quantitative correction plus uncertainty correction) ranged from 72~15,789 to 30~60, and the ratio of the threshold limit value (TLV) to the reference concentration decreased from 12.8~1900 to 5.4~11.8. Furthermore, when we performed risk characterization by our new method, hazard quotient (HQ) values for chloroethylene, epichlorohydrin, and barium sulfate became 3.0, 14.1, and 1.13 respectively, whereas three previous studies reported HQ values of 7.1, 4580, and 87.3 considering reasonable maximum exposure (RME) conditions. HQs of the three chemicals were calculated to be 0.6, 2.4, and 0.1 respectively, when compared to their TLVs. Conclusions: Our new method could be applicable for the HREC because the total correction values and the ratio of TLVs were within reasonable ranges. It is also recommended that additional risk management measures be applied for epichlorohydrin, for which the HQ values were greater than 1 when compared with both reference values and the TLV. Our proposed method could be used to harmonize dose-response assessment methods for the implementation of risk assessment based on the HREC according to ISHA.