RPLC/DAD를 이용한 Polycyclic Aromatic Hydrocarbon류의 분석에 관한 연구(I)

이원,홍지은,박송자,표희수,Lee, Won,Hong, Jee-Eun,Park, Song-Ja,Pyo, Hee Soo 한국분석과학회 1997 분석과학 Vol.10 No.5

Benzo(a)pyrene을 비롯한 16종의 polycyclic aromatic hydrocarbon(PAHs)과 4종의 nitro-PAHs를 reversed-phase liquid chromatography/diode array detection (RPLC/DAD)를 이용하여 기울기용리법으로 분리하고, PAH류의 머무름거동에 영향을 미치는 인자들, 즉 탄소수, F인자, L/B ratio, 물에 대한 용해도 및 방해수소원자쌍의 수와 시료의 머무름과의 상관관계를 고찰하였다. 대부분의 PAH류는 탄소원자수와 F값이 커질수록 logk'이 증가하는 사실을 확인하였다. 그리고 몇 가지 이성체들과 nitro-PAH류들은 용해도가 크고, L/B값이 작으며, 방해수소원자쌍의 수가 많을수록 먼저 용리됨을 확인하였다. 각 PAH류의 검출한계는 100~500ng/mL 범위로 나타났으며, 실제 물시료에 대한 검출한계(method detection limit, MDL)는 0.1~0.5ng/mL 범위였다. The retention behaviors of 16 PAHs and 4 nitro-PAHs were studied with several parameters involved numbers of carbon atoms, F factor, aqueous solubility, L/B ratio, and numbers of interfering hydrogen atom pairs on the chemical structures of PAHs by using reversed-phase liquid chromatography/diode array detection method (RPLC/DAD) and gradient elution method. It was obtain that the log k' for most of PAHs with increasing the number of carbon and the F factor in their molecules. Chromatographic retention of PAH isomers and nitro-PAHs were examined with aqueous solubility, L/B ratio and number of interfering hydrogen atom pairs. As a result of comparison with these factors and retention times, it was found that those solutes having larger aqueous solubilities and greater L/B ratios were retained longer on stationary phase. This tendency was also occured in the molecules having the more number of interfering hydrogen atom pairs. Detection limits of PAHs which were obtained with three times measurements by RPLC/DAD were in the range of 100~500ng/mL and method detection limit(MDL) for water sample were in the range of 0.1~0.5ng/mL.

Trickle Bed Reactor에서 Pt/Kieselguhr 촉매를 이용한 다환방향족 탄화수소 수소화 반응

오승교,오서현,한기보,정병훈,전종기 한국청정기술학회 2022 청정기술 Vol.28 No.4

The objective of this study is to prepare bead-type and pellet-type Pt (1 wt%)/Kieselguhr catalysts as hydrogenation catalysts for the polycyclic aromatic hydrocarbons (PAHs) included in pyrolysis fuel oil (PFO). The optimal reaction temperature to maximize the yield of saturated cyclic hydrocarbons during the PFO-cut hydrogenation reaction in a trickle bed reactor was determined to be 250 o C. A hydrogen/PFO-cut flow rate ratio of 1800 was found to maximize 1-ring saturated cyclic compounds. The yield of saturated cyclic compound increased as the space velocity (LHSV) of PFO-cut decreased. The difference in hydrogenation reaction performance between the pellet catalyst and the bead catalyst was negligible. However, the catalyst impregnated by Pt after molding the Kieselguhr support (AI catalyst) showed higher hydrogenation activity than the catalyst molded after Pt impregnation on the Kieselguhr powder (BI catalyst), which was a common phenomenon in both the pellet catalysts and bead catalysts. This may be due to a higher number of active sites over the AI catalyst compared to the BI catalyst. It was confirmed that the pellet catalyst prepared by the AI method had the best reaction activity of the prepared catalysts in this study. The majority of the PFO-cut hydrogenation products were cyclic hydrocarbons ranging from C8 to C15, and C11 cyclic hydrocarbons had the highest distribution. It was confirmed that both a cracking reaction and hydrogenation occurred, which shifted the carbon number distribution towards light hydrocarbons. 본 연구의 목적은 열분해연료유(pyrolysis fuel oil, PFO)에 포함된 다환 방향족 탄화수소(polycyclic aromatic hydro, PAHs) 수소화 반응용 촉매로서 Pt(1wt%)/Kieselguhr 비드 촉매 및 펠렛 촉매를 제조하는 것이다. Trickle-bed 반응기에서 PFO-cut 수소화 반응을 통한 포화 고리 화합물(saturated cyclic compound)의 수율을 최대화하기 위한 최적의 반응 온도 및 수소/PFO-cut 유량비는 각각 250o C와 1800으로 결정하였다. PFO-cut의 공간속도(LHSV)가 감소할수록 포화 고리 화합물의 수율이 증가하였다. 펠렛 촉매와 비드 촉매의 수소화 반응 성능 차이는 크지 않았다. Kieselguhr 지지체를 성형한 후에 Pt를 담지한 촉매(AI 촉매)가 kieselguhr 분말에 Pt를 담지한 후에 성형한 촉매(BI 촉매)에 비해 수소화 활성이 높았으며, 이러한 경향은 펠릿 촉매와비드 촉매에서 공통적으로 나타났다. 이는 AI 촉매의 Pt 활성점 수가 BI 촉매 보다 많기 때문이다. 본 연구에서 제조한 촉매 중에서 AI법으로 제조된 펠렛 촉매가 제조된 촉매 중 반응 활성이 가장 우수한 것을 확인하였다. PFO-cut 수소화 반응 생성물 중C8~C15 범위의 고리 화합물이 대부분을 차지했으며, C11 고리 화합물의 분포도가 가장 높았다. 수소화 반응과 더불어서 분해반응도 함께 촉진되어 생성물의 탄소수 분포가 경질 탄화수소 쪽으로 이동함을 확인하였다.

Toxicity cutoff of aromatic hydrocarbons for luminescence inhibition of Vibrio fischeri

Lee, S.Y.,Kang, H.J.,Kwon, J.H. Academic Press 2013 Ecotoxicology and environmental safety Vol.94 No.-

Effects of individual petroleum hydrocarbons on the luminescence inhibition of Vibrio fischeri were evaluated according to a standard protocol to develop a quantitative structure-activity relationship and identify the apparent toxicity cutoff. Eighteen aromatic hydrocarbons, including benzene and its derivatives and polycyclic aromatic hydrocarbons (PAHs), were chosen as model compounds with their log K<SUB>ow</SUB> values between 2.7 and 6.4. The obtained values of 50 percent luminescence inhibition (EC<SUB>50</SUB>) showed a good linear correlation with logK<SUB>ow</SUB> up to ~5. However, toxic effects were not observed for more hydrophobic chemicals with logK<SUB>ow</SUB> value >5. The calculated chemical activities that caused EC<SUB>50</SUB> were mostly between 0.01 and 0.1. This agrees with an earlier hypothesis concerning a chemical activity resulting the critical membrane concentration of aromatic hydrocarbons. The highest chemical activities for aromatic hydrocarbons with logK<SUB>ow</SUB> value >5 or melting point >100<SUP>o</SUP>C are <0.01 when they are spiked at their water solubility level according to the standard test protocol; this occurs for two primary reasons: (1) partitioning between organism and the test solution and (2) decreasing fugacity ratio with increasing melting point. Accordingly, luminescence inhibition by petroleum hydrocarbons is well explained by the baseline toxicity model. However, the apparent toxicity cutoff observed for single chemicals is not necessarily valid in a complex mixture, because baseline toxicity is regarded concentration additive.

귀금속/SiO₂-Al₂O₃ 촉매를 이용한 Polycyclic aromatic hydrocarbons으로부터 C₁₀-C₁₃ aromatics 제조 반응 연구

박영서,구희지,오승교,주종현,한기보,정병훈,전종기 한국공업화학회 2021 한국공업화학회 연구논문 초록집 Vol.2021 No.1

식품중 Polycyclic Aromatic Hydrocarbons의 위해성평가

이효민,윤은경,박경아,김윤희,정소영,권기성,김명철,송인상,이철호,양지선,양기화 한국식품위생안전성학회 2004 한국식품위생안전성학회지 Vol.19 No.1

Polycyclic aromatic hydrocarbons(PAHs)의 인체에 대한 위해성 정도를 판단하기 위해 PAHs의 대표독성물질인 benzo(a)pyrene의 독성을 기준으로 하는 TEFs를 적용하여, PAHs의 주요노출식품에 의한 위해성 평가를 수행하였다. 숯불구이쇠고기, 숯불구이돼지공기, 숯불구이닭고기, 햄, 베이컨, 및 식용유지 등을 대상으로 PAHs 오염도를 모니터링한 결과 숯불구이닭고기에서 총 PAHs농도가 9.3 ppb로 가장 높게 검출되었으며 각각의 congener들 모두 다른 식품에서 보다 높게 나타났다. 반면에 숯불구이쇠고기, 베이컨, 숯불구이돼지고기, 햄 및 식용유지의 총 PAHs는 각각 0.2 ppb, 0.3 ppb, 0.7 ppb, 0.8 ppb 및 1.2 ppb로 비교적 낮은 값을 나타냈다. TEFs값을 적용하여 환산된 오염도 값의 경우에서도 숯불구이닭고기가 가장 높은 값을 보였고, congener들의 농도를 비교했을 때 숯불구이닭고기, 숯불구이돼지고기, 베이컨, 숯불구이쇠고기 및 햄에서 모두 BaP의 농도가 각각 1.88 ㎍-TEQ_BaP/kg, 0.19 ㎍-TEQ_BaP/kg, 0.08 ㎍-TEQ_BaP/kg, 0.04 ㎍-TEQ_BaP/kg 및 0.02 ㎍-TEQ_BaP/kg로 congener들 중 가장 높게 나타났고 식용유지에서는 dibenzo(a, h)anthracene의 농도가 0.21㎍-TEQ_BaP/kg으로 가장 높은 값을 나타냈다. 우리나라 사람들의 PAHs 주요노출식품 섭취로 인한 만성1일인체노출량은 4.32×10^-4 ㎍/kg/day으로 산출되었으며 선정된 식품 중에서 숯불구이닭고기의 노출기여도가 가장 높았다. PAHs의 초과발암위해도는 만성1일인체노출량과 BaP의 발암력인 7.3 (mg/kg/day)^-1을 고려하였을 때 3.44×10^-6, 백만명동 3~4명 수준이어다. 우리나라 대표식단을 통한 PAHs 노출량을 반영할 수 있는 위해성 평가각 추후 계속되어야 할 것으로 사료된다. This study was executed to determine the cumulative dietary risk of PAHs exposed by food ingestion. Food samples including barbecued beef, barbecued pork, grilled chicken, ham, bacon and vegetable oil which were collected from food markets. These samples were saponified, extracted and cleaned up to purify PAHs, and then the purified sample solutions were analyzed by HPLC-FL. Generally, the levels of total PAHs in barbecued beef (0.2 ppb), bacon (0.3 ppb), barbecued pork (0.7 ppb), ham (0.8 ppb), and vegetable oil (1.2 ppb) were low, whereas the level of total PAHs in grilled chicken (9.3 ppb) was significantly high. For the exposure assessment of PAHs due to food ingestion, PAHs levels converted into TEQ_BaP. the average body weight for 20-73 age group and consumed levels of food proposed from report on the National Health and Nutrition Survey were used. The estimated lifetime average daily intake of dietary PAHs was 4.32×10^-4 ㎍-THQ_BaP/kg/day as the mean value. The dietary risk adjusted to cancer potency of benzo(a)pyrene as 7.3 (mg/kg/day)^-1 was 3.44×10^-6 based on current data.

Polycyclic aromatic hydrocarbons로부터 BTXE와 C10-C13 aromatics 제조

박영서,구희지,전아름,오승교,한기보,정병훈,전종기 한국공업화학회 2022 한국공업화학회 연구논문 초록집 Vol.2022 No.-

Exosomes released by polycyclic aromatic hydrocarbon-treated keratinocytes enhance inflammatory cytokine/chemokine response in recipient keratinocytes depending on the aryl hydrocarbon receptor

( Jinseo Park ),( Soyeon Lee ),( Jincheol Kim ),( Seokyoung Kang ),( Hyeran Kim ),( Hyeone Kim ),( Chunwook Park ),( Boyoung Chung ) 대한피부과학회 2022 대한피부과학회 학술발표대회집 Vol.74 No.1

Molecularly Controlled Stark Effect Induces Significant Rectification in Polycyclic-Aromatic-Hydrocarbon-Terminated <i>n</i>-Alkanethiolates

Cho, Soo Jin,Kong, Gyu Don,Park, Sohyun,Park, Jeongwoo,Byeon, Seo Eun,Kim, Taekyeong,Yoon, Hyo Jae American Chemical Society 2019 NANO LETTERS Vol.19 No.1

<P>The variation of the electronic structure of individual molecules as a function of the applied bias matters for the performance of molecular and organic electronic devices. Understanding the structure-electric-field relationship, however, remains a challenge because of the lack of in-operando spectroscopic technique and complexity arising from the ill-defined on-surface structure of molecules and organic-electrode interfaces within devices. We report that a reliable and reproducible molecular diode can be achieved by control of the conjugation length in polycyclic-aromatic-hydrocarbon (PAH)-terminated <I>n</I>-alkanethiolate (denoted as SC<SUB>11</SUB>PAH), incorporated into liquid-metal-based large-area tunnel junctions in the form of a self-assembled monolayer. By taking advantage of the structural simplicity and tunability of SC<SUB>11</SUB>PAH and the high-yielding feature of the junction technique, we demonstrate that the increase in the conjugation length of the PAH terminal group leads to a significant rectification ratio up to ∼1.7 × 10<SUP>2</SUP> at ±740 mV. Further study suggests that the Stark shift of the molecular energy resonance of the PAH breaks the symmetry of the energy topography across the junction and induces rectification in a temperature-independent charge-transport regime.</P> [FIG OMISSION]</BR>

낙동강 하구 인근 해양 퇴적토 중의 PAHs 농도 및 발생원 산정 연구

이준호,양찬근,한경수,이태윤 한국지반환경공학회 2019 한국지반환경공학회논문집 Vol.20 No.1

The main objective of this study was to analyse polycyclic aromatic hydrocarbons in surface sediments obtained from near Nakdong estuary, and to estimate ecological risks of PAHs using PAHs concentrations. The main constituents of sediments were SiO2, Al2O3, CaO, Fe2O3, and ignition loss of sediments ranged from 2.97% and 8.39%. Total concentrations of PAHs ranged from 128.4 ng g-1 and 507.4 ng g-1, and the major PAHs were 2 ring and 4 ring aromatic hydrocarbons. Each concentrations of PAHs are all below effect range low, which indicated that each PAHs in 8 studying sites show low ecological risk. From M-ERM-Q analyses, M-ERM-Q values of 8 studying sites are below 0.1 indicating low ecological risk. From source apportionment analyses, PAHs come from grass, wood, charcoal combustion for N-1 and N-7, petroleum combustion for N-5 and N-6, petroleum pollution for N-2, N-3, N-4, N-8. 본 연구는 낙동강 하구 인근의 해양퇴적토에 포함된 PAHs의 농도를 분석하여 퇴적토의 생태학적 위해성을 평가하고자 하였다. 퇴적토의 주성분은 SiO2, Al2O3, CaO, Fe2O3였으며, 강열감량은 2.97%에서 8.39%의 분포를 보였다. 총 PAHs의 농도는 128.4 ng g-1에서 507.4 ng g-1의 범위를 가졌으며 2고리와 4고리 형태의 PAHs로 주로 구성이 되어있었다. 8개 지역의 각각의 PAHs의 농도는 모두 ERL 이하로 생태학적 위해성은 낮은 것으로 판단되었다. 지역별 PAHs의 생태학적 위해성 평가는 M-ERM-Q를 사용하여 이루어졌고, 계산 값 모두 0.1 이하로 생태학적 위해성은 낮음으로 분류되었다. 발생원 분석을 통해 각 지역의 PAHs의 발생원은 N-1과 N-7은 풀, 나무, 석탄 등의 연소이며, N-5와 N-6는 석유연소, N-2, N-3, N-4, N-8은 석유오염인 것으로 판단되었다.

Monitoring Nutrient Impact on Bacterial Community Composition during Bioremediation of Anoxic PAH-Contaminated Sediment

Myungsu Kim,Seung Seob Bae,Mijin Seol,Jung-Hyun Lee,오영숙 한국미생물학회 2008 The journal of microbiology Vol.46 No.6

Marine harbor sediments are frequently polluted with significant amount of polycyclic aromatic hydrocarbons (PAHs) some of which are naturally toxic, recalcitrant, mutagenic, and carcinogenic. To stimulate biodegradation of PAHs in PAH-contaminated sediments collected from near Gwangyang Bay, Korea, lactate was chosen as a supplementary carbonaceous substrate. Sediment packed into 600 ml air-tight jar was either under no treatment condition or lactate amended condition (1%, w/v). Microbial community composition was monitored by bacteria-specific and archaea-specific PCR-terminal restriction fragment length polymorphism (T-RFLP), in addition to measuring the residual PAH concentration. Results showed that lactate amendment enhanced biodegradation rate of PAHs in the sediment by 4 to 8 times, and caused a significant shift in archaebacterial community in terms of structure and diversity with time. Phylogenetic analysis of 23 archaeal clones with distinctive RFLP patterns among 288 archaeal clones indicated that majority of the archaeal members were closest to unculturable environmental rDNA clones from hydrocarbon-contaminated and/or methanogenesis-bearing sediments. Lactate amendment led to the enrichment of some clones that were most closely related to PAH-degrading Methanosarcina species. These results suggest a possible contribution of methanogenic community to PAH degradation and give us more insights on how to effectively remediate PAH-contaminated sediments.