A continuous process of persulfate oxidation and citric acid washing was investigated for ex-situ remediation of complex contaminated soil containing total recoverable petroleum hydrocarbons (TRPHs) and heavy metals (Cu, Pb, and Zn). The batch experiment results showed that TRPHs could be degraded by Fe2+ activated persulfate oxidation and that heavy metals could be removed by washing with citric acid. For efficient remediation of the complex contaminated soil, two-stage and three-stage processes were evaluated. Removal efficiency of the two-stage process (persulfate oxidation - citric acid washing) was 83% for TRPHs and 49%, 53%, 24% for Cu, Zn, and Pb, respectively. To improve the removal efficiency, a three-stage process was also tested; case A) water washing - persulfate oxidation - citirc acid washing and case B) persulfate oxidation - citric acid washing (1) - citric acid washing (2). In case A, 63% of TRPHs, 73% of Cu, 60% of Zn, and 55% of Pb were removed, while the removal efficiencies of TRPHs, Cu, Pb, and Zn were 24%, 68%, 62%, and 59% in case B, respectively. The results indicated that case A was better than case B. The three-stage process was more effective than the two-stage process for the remediation of complex-contaminated soil in therms of overall removal efficiency.

Polycyclic aromatic hydrocarbons (PAHs), which are ubiquitous in the air, are present as volatile and particulate pollutants that result from incomplete combustion. Most PAHs have toxic, mutagenic, and/or carcinogenic properties. Among PAHs, benzo[a]pyrene (B[a]P) and dimethylbenz[a]anthracene (DMBA) are suspected endocrine disruptors. The testis is an important target for PAHs, yet effects on steroidogenesis in Leydig cells are yet to be ascertained. Particularly, disruption of testosterone production by these chemicals can result in serious defects in male reproduction. Exposure to B[a]P reduced serum and intratesticular fluid testosterone levels in rats. Of note, the testosterone level reductions were accompanied by decreased steroidogenic acute regulatory protein (StAR) and 3β-hydroxysteroid dehydrogenase isomerase (3b-HSD) expression in Leydig cells. B[a]P exposure can decrease epididymal sperm quality, possibly by disturbing the testosterone level. StAR may be a key steroidogenic protein that is targeted by B[a]P or other PAHs. Key words : Polycyclic aromatic hydrocarbons, Endocrine disruptor, Steroidogenesis, Leydig cells

본 연구는 호두를 대상으로 감마선을 1-10 kGy 선량으로 조사시켜 생성된 hydrocarbon류와 2-alkylcyclobutanone류를 통해 방사선 조사여부를 확인하였다. 지방은 soxhlet방법으로 n-hexane을 추출용매로 사용하였고 florisil이 충진된 column으로 분리하여 gas chromatography / mass spectrometry(GC/MS)로 확인하였다. 감마선 조사된 호두에서 검출된 주요 hydrocarbon류는 oleic acid에서 유도된 8-heptadecene과 linoleic acid에서 유도된 8,11-Heptadecadiene, 1,7,10-Hexadecatriene이었고, 검출된 주요 2-alkylcyclobutanone류는 linoleic acid와 oleic acid에서 유도된 2-(5',8'-tetradecadienyl)cyclobutanone(5',8'-TCB), 2-(5'-tetradecenyl) cyclobutanone(TECB)가 가장 높은 함량으로 확인되었다. 조사된 호두에서 생성된hydrocarbon류와 2-alkylcyclobutanone류의 생성량은 선량에 비례하여 증가하였으며, 이 화합물들은 1 kGy 이상 조사된 시료에서만 나타났으며 비조사 시료에서는 확인되지 않았다. 따라서 방사선 조사에 의해 oleic acid과 linoleic acid에서 유도된 hydrocarbon류 중 8-heptadecene, 8,11-Heptadecadiene 및 1,7,10-Hexadecatriene, 2-alkylcyclobutanone류 중 5',8'-TCB 및 TECB는 감마선 조사 여부의 확인을 위한 marker로서 활용가능성이 높게 나타났다.

식품의 방사선 조사는 식품 저장을 위한 성공적인 현대기술의 하나이지만 매우 신중하게 이루어져야 한다. 조사된 식품의 확인은 국제무역에서 소비자의 안전한 선택과 보호를 위해 가장 중요하다. 따라서 본 연구는 건조된 오징어와 문어에 전자선을 조사하여 선량별로 유도 생성되는 hydrocarbon류의 함량 및 분해패턴을 확인하였다. 비조사 시료와 선량별로 전자선 조사된 시료에서 지방을 추출한 뒤 solid phase extraction(SPE)방법을 이용하여 GC/MS로 확인하였다. 1, 3, 5, 7 및 10 kGy의 선량으로 전자선 조사된 건조 오징어와 문어에서 유도된 hydrocarbon류는 동일 선량에서 시료들의 지방산 조성에 따른 다른 생성률을 나타내었으며, 조사선량에 따라 증가하였다. 시료들에 다량 함유되어 있는 palmitic acid와 stearic acid로부터 생성된 1-tetradecene(C14:1), pentadecane(C15:0), 그리고 1-hexadecene(C16:1), heptadecane(C17:0)이 전자선 조사에 의해 유도된 주요 hydrocarbon류로 확인되었으며, 건오징어에서 hydrocarbon류 생성량이 건문어의 hydrocarbon류 생성량 보다 더 많음을 확인하였다. 이는 시료의 지방산 함유량에 따라 hydrocarbon류 생성량이 비례함을 알 수 있었다. 전자선 조사된 건오징어와 건문어에서 분석된 hydrocarbon류 중 1-tetradecene(C14:1), 1-hexadecene(C16:1) 그리고 heptadecane(C17:0)은 전자선 조사여부를 판별할 수 있는 지표로 활용될 수 있을 거라 사료된다.

화석연료의 연소나 유류 오염 등으로 인해 발생하는 PAHs는 우리 주변 어디에서나 존재하는 위험한 오염물질 중 하나로, 생태계에 영향을 끼치며 작물 생육에도 영향을 준다. PAHs는 작물에서도 흡수가 가능하기 때문에, 작물생육에 대한 저해 효과를 알아보기 위해 콩과 벼에 대한 영향을 유묘기부터 검정하였다. PAHs가 처리된 토양에서 자란 벼와 콩의 초장과 건물중은 다소 감소하였고, 벼보다 콩에서 생장 저해가 강하게 발생되었다. 토양에 100 ppm 농도에서 처리된 경우 콩의 초장은 58.9 cm로 처리되지 않은 콩의 87.2% 값을 보였다. 벼의 경우, 처리 후 80일 100 ppm에서 자란 벼가 처리되지 않은 벼의 96.0% 값을 보여, 초장에 있어서 저해 효과가 낮게 나타났다. 광합성과 관련된 엽록소 함량과 엽록소 형광은 PAHs 처리 후 20일부터 70일까지 저해가 약간 되었지만, 출수기 이후는 저해 정도가 약하게 나타났다. 어린 유묘의 한천 배지 실험은 100 ppm phenanthrene 농도일 때, 성숙한 작물의 폿트 실험과 비교시 유묘 길이와 생체중의 저해가 높게 나타났다. 벼에서는 유묘 길이와 생체중이 각 각 54.2%, 33.3% 감소하였고, 콩에서는 각 각 27.9%, 13.2% 감소되었다. 이러한 결과를 통하여 PAHs은 성숙기보다 영양 생장 초기에 저해가 높게 발생하며, 영양생장기의 피해는 콩보다 벼에서 저해가 높게 발생하였다.

본 연구에서는 생물학적 정화기술의 효율향상을 목적으로 유류분해 유용미생물에 의한 TPH 농도 저감효과를 알아보았다. 하절기와 동절기 각 13주간 실제 정화현장의 각 섹터별 유류오염토양에 유용미생물들을 수분, 영양염류 등과 함께 투입하여 주 2회 정기적으로 뒤집기를 실시하였다. 하절기의 경우 유용미생물을 투입한 조건의 경우 평균 60%의 TPH 제거율을 보인 반면에 유용미생물을 투입하지 않은 대조군의 경우 평균 41%의 TPH 제거율을 나타내었다. 동절기의 경우에 유용미생물을 투입한 조건의 경우 평균 41%의 TPH 제거율을 보인 반면에 유용미생물을 투입하지 않은 대조군의 경우 평균 13%의 낮은 TPH 제거율을 나타내었다.결론적으로 하절기와 동절기 모두 유용미생물을 투입하여 TPH의 제거효율의 향상 효과를 얻을 수 있었으며, 하절기에 비하여 동절기의 TPH 제거효과가 낮은 이유는 초기 높은 오염농도와 상대적으로 낮은 기온의 영향인 것으로 판단된다.

Polycyclic aromatic hydrocarbons (PAHs) were investigated in seawater and marine sediment from Anmyundo coastal area after oil spill. The concentrations of total PAHs in surface and bottom of seawater at August were 31.1 to 142.6 ng/L and 5.9 to 50.9 ng/L in August and November, respectively. The concentrations of PAHs in sediment were 21.0 to 102.9 ng/g D.W. and 32.3 to 57.4 ng/g D.W. in August and November, respectively. PAHs concentrations in seawater and sediment in August were higher than those in November about 2.5 and 1.4 times, respectively. Diagnostic ratio (PhA/AnT and FluA/Pyr) were investigated to identify source of PAHs in seawater and sediment. The PAHs in seawater originated from pyrolytic source and those in sediment originated from pyrolytic and petrogenic source. The glass, wood and coal origin was higher than petroleum origin on the combustion origin of PAHs in seawater and sediment. The seawater of Anmyundo costal area recovered from oil spill, but the sediments of that were weakly influenced by oil spill until now. Because this area is developed many fishing grounds, demanded Long Term Environmental Monitoring Program (LTEMP). The concentrations of PAHs on depth of sediments were investigated at station 8 and 10. The concentrations of PAHs were decreased with increasing depth.

The present study aims to evaluate the characteristics of atmospheric polycyclic aromatic hydrocarbons (PAHs) pollution in roadside and residential areas of two Korean metropolitan cities (Seoul and Incheon) and a background area (Seokmolee). This purpose was established by analyzing temporal and spacial concentration distribution of total and 7 individual PAHs, which were extracted from ambient particulate matters, and by utilizing a multivariate statistical method (principal component analysis, PCA) for the qualitative determination of potential PAH sources. Target PAHs included benzo(a)anthracene (BaA), benzo(a)pyrene (BaP), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), chrysene (Chr), dibenzo(a,h)anthracene (DahA), and indeno(1,2,3-cd)pyrene (IcdP). For all surveyed sites, the concentrations of total PAHs were higher in winter season than in other seasons. However, the concentrations of individual PAHs varied with surveyed sites. In both residential and roadside sites of Seoul and Incheon, BbF revealed the highest atmospheric levels. For all 7 target PAHs, the ambient concentrations were higher in Seoul and Incheon than in a background area (Seokmolee). In both residential and roadside areas, the concentrations of 4 target PAHs (BaA, BbF, BkF, DahA) were higher in Incheon than in Seoul. However, both the residential and roadside Chr concentrations were comparable in Seoul and Incheon. In addition, the residential IcdP concentrations were higher in Incheon than in Seoul, whereas the roadside concentrations were higher in Seoul. The roadside and residential BaP concentrations exhibited the reverse result to the IcdP concentrations. An PCA analysis suggested that atmospheric PAHs in both residential and roadside areas would be due to combined effects of several potential sources such as gasoline- and diesel-fueled vehicles, coal/oil combustion, and waste incineration.

Sixteen soil samples around six areas (residental area, traffic area, power plant area, incineration area and factory area) where the stationary and mobile sources of polycyclic aromatic hydrocarbons (PAHs) are estimated to be emitted in Jeju City, were collected during Feburuary to March, 2004, and analyzed for 16 PAHs recommended by US EPA as primary pollutants to investigate their distribution characteristics. The concentrations of total PAHs (t-PAHs) and total carcinogenic PAHs (t−PAHCARC) in soils of Jeju City were in the range of 21.7∼264.2ng/g on a dry weight basis with a mean value of 87.2 ng/g and 6.3∼118.0ng/g with a mean value of 33.4 ng/g, respectively. The concentrations of t-PAHs were low in comparison with those in soils of other domestic and foreign countries. The mean concentrations of t-PAHs and (t−PAHCARC) with area decreased in the following sequences: traffic area> incineration area > factory area > power generation area > harbor area enli residental area. The correlation between t-PAHs and (t−PAHCARC) were very high (γ2=0.9701), indicating that (t−PAHCARC) concentration increases in proportion with t-PAHs. Comparing the distribution ratio of ring PAHs with area among 16 PAHs, it decreased in the order of 4-ring > 5-ring > 6-ring > 3-ring > 2-ring in all the areas except for harbor area. whitens for harbor area it was similar among 3-, 4- and 5-ring with high value. Low and no correlations between t-PAHs and soil compositions (organic matter content and particle size distribution) were observed, which is considered to be caused by the complex factors, such as the loading and characteristics of PAHs and diverse soil environment change, etc. From the examination of the three PAH origin indices, such as LMW/HMW (low molecular weight 2∼3 ring PAHs over high molecular weight 4∼6 ring PAHs), phenanthrene/anthracene ratio and fluoranthene/pyrene ratio, it can be concluded that the soil PAH contaminations were ascribed to strong pyrogenic origin in ail areas except for harbor area and to both pyrogenic and petrogenic origins.

The numerical modeling and comparison with observations are performed to find out the detailed structure of meteorology and the characteristic of related dispersion phenomena of the non-reactive air pollutant at Kyoungin region, South Korea, where several industrial complex including Siwha, Banwol and Namdong is located. MM5 (Fifth Generation NCAR/Penn State Mesoscale Model), 3-D Land/Sea breeze model and 3-D diagnostic meteorological model have been utilized for the meteorological simulation for September, 2002 with each different spatial resolution, while 3-D Eulerian air dispersion model for the air quality study. We can see the simulated wind field shows the very local circulation quitely well compared with in-site observations in shoreline area with complex terrains, at which the circulation of Land/Sea breeze has developed and merged with the mountain and valley breeze eventually. Also it is shown in the result of the dispersion model that the diurnal variation and absolute value of daily mean SO2 concentrations have good agreement with observations, even though the instant concentration of SO2 simulated overestimates around 1.5 times rather than that of observation due to neglecting the deposition process and roughly estimated emission rate. This results may indicate that it is important for the air quality study at shoreline region with the complex terrain to implement the high resolution meteorological model which is able to handle with the complicate local circulation.

Atmospheric bulk (wet and dry) samples were monthly collected in Masan and Heangam areas of Korea, to assess the deposition flux and seasonal variation of polycyclic aromatic hydrocarbons (PAHs). Deposition fluxes of PAHs in bulk samples were determined using gas chromatography coupled to mass spectrometer detector (GC/MSD). Particle deposition fluxes from Masan and Haengam areas varied from 13 to 87 g/m2/year and from 5 to 52 g/m2/year, respectively. PAHs deposition fluxes in atmospheric bulk samples in Masan and Haengam areas ranged from 135 to 464 µg/m2/year and from 62.2 to 194 µg/m2/year, respectively. Atmospheric deposition fluxes of particles and PAHs in this study were comparable to or slightly lower values than those from different locations in Korea and other countries. PAHs profiles of atmospheric deposition bulk samples showed slightly different from two sampling areas, however the predominant species of PAHs were similar. Indeno (1,2,3-c,d)pyrene, benzo(g,h,i)perylene, phenanthrene compounds were the most detected PAHs in deposition bulk samples. Carcinogenic PAHs occupied the contribution of approximately 30-40% of the total PAHs deposition fluxes. The non-metric multi-dimensional scaling (MDS) was used, to assess the differentiation of PAHs source between two sampling areas. The result suggests that PAHs contamination sources were different according to the location and season surveyed. There was no an apparent relationship between the PAHs deposition flux against temperature and rainfall amount, even though summer season with the highest temperature and the largest amount of precipitation showed the lowest PAHs deposition flux. Benzo(e)pyrene/benzo(a)pyrene ratio indicated that the photo-degradation process was one of important factors to the seasonal variation of PAHs with the lower deposition fluxes.

The 16 priority PAHs (Polycyclic Aromatic Hydrocarbons) designated by US Environmental Protection Agency were analyzed for some digested sludges from wastewater treatment plants in Korea. PAHs are an important group of organic contaminants present in sewage sludge due to their persistence and toxic potential. PAHs were extracted from freeze-dried sludges using a methylene chloride-methanol (2:1) mixture in a soxhlet extractor. The extracts were cleaned-up by silica gel/alumina combination column and subsequently fed into gas chromatograph/mass spectrometer (GC/MS) for determining PAH contents. The sum of the 16 PAHs in the sewage sludge varied from 534.8 to 5754.5 ㎍/kg, dry wt.. In the sewage sludge, phenanthrene appears as the most abundant PAHs, followed by naphthalene, pyrene, fluoranthene. Source of the investigated sewage sludges relatively predominated pyrogenic. PAHs levels of sewage sludges in Korea appeared to be lower than those in other countries.

The surface sediments inside Songsanpo and Seogwipo Harbors, major harbors of Jeju Island, were collected three times (June, September and December, 2001) and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs) recommended by US-EPA as priority pollutants to assess their distribution levels and their biological effects on the marine organisms, and to suggest their possible origins. The concentrations of total PAHs inside Songsanpo and Seogwipo Harbors ranged from 41 to 288 ng/g on a dry weight basis with a mean value of 121 ng/g and from 14 to 268 ng/g with a mean value of 119 ng/g, respectively, and the levels were low as compared with those in other areas of the world. The sedimentary PAHs may be correlated with organic carbon and mud content to some extent. Based on comparisons of individual and total concentrations with effects-based sediment quality guidelines, the potential for the biological effects on the marine organisms were expected to be very low. From the examinations of the four PAH origin indices, such as LMW/HMW (low molecular weight 2-3 ring PAHs over high molecular weight 4-6 ring PAHs), phenanthrene/anthracene ratio, fluoranthene/pyrene ratio, chrysene/benzo[a]anthracene ratio, it can be concluded that the sediment PAH contaminations were ascribed to both of pyrolytic and petrogenic origins.

The number of cases exceeding environmental standards of atmospheric ozone in the major cities in Korea has steadily increased during the past decades. In order to understand and analyze the atmospheric reactions in the atmosphere, especially the secondary photochemical reactions, smog chambers studies have been performed very actively by many research groups worldwide. However, these studies have focused on the mechanism of photochemical reactions in high concentration conditions, not at the ambient levels. Therefore, in-depth studies in these conditions are essentially needed to realize exact mechanism in the atmosphere near the earth surface, especially at Korean atmospheric conditions. In this experiment, the mechanism of photochemical smog was examined through a comparative experiment of smog chambers under sun light and black light conditions. The results of our study indicated that concentrations of ozone, aldehyde, and PAN increased as the radiation of light source increases. Photochemical reaction patterns can be considered quite similar for both black light and sun light experiments. Based on our experiments using toluene as a reactant which is present at significant high levels in ambient air relative to other VOCs, it was found that toluene could contribute notably to oxidize NO to NO2, this reaction can eventually generate some other photochemical oxidants such as ozone, aldehyde, and PAN. The results of simulation and experiments generally showed a good agreement quite well except for the case of O3. The restriction of oxidization of NO to NO2 seems to cause this difference, which is mainly from the reaction of peroxy radical itself and other reactants in the real gas.

Soil is one of the most fundamental elements as well as with water and air in studies associated with the environment, in addition, it is one of the important environmental mediums that constructs a basis of the biological system and performs various roles of matter circulation. This study was carried out in Seoul, in May 2000 to evaluate variation in the concentration levels and distribution characteristics for PAH compounds in soil. Soil samples were collected from 33 sites covering traffic, factory, incineration and mountain groups and the PAHs were analyzed. The results show a wide distribution range of PAHs concentrations between 14.66 ng/g and 1,219.35 ng/g. The highest concentration levels exist at Sungsu-2 of the factory group (FS-2). Daemo-3 of the Mountain group (MD-3) presents the lowest levels as compared with the other sites. PAH compounds including mutagenic and carcinogenic materials show high concentrations in the traffic and factory groups and a high ratio in the mountain group. Besides, these compounds absorbed with micro particles might be spread out over a wide region associated with particles' movement and diffusion. After principal component analysis of the soil samples, the results indicated that the sources of PAHs in the soil were divided into two groups, pesticides and vehicles.

This study evaluated the technical feasibility of the application of TiO2 photocatalysis for the removal of volatile hydrocarbons(VHC) at low ppb concentrations commonly associated with non-occupational indoor air quality issues. A series of experiments was conducted to evaluate five parameters (relative humidity (RH), hydraulic diameter (HD), feeding type (FT) of VHC, photocatalytic oxidation (PCO) reactor material (RM), and inlet port size (IPS) of PCO reactor) for the PCO destruction efficiencies of the selected target VHC. None of the target VHC presented significant dependence on the RH, which are inconsistent with a certain previous study that reported that under conditions of low humidity and a ppm toluene inlet level, there was a drop in the PCO efficiency with decreasing humidity. However, it is noted that the four parameters (HD, RM, FT and IPS) should be considered for better VHC removal efficiencies for the application of TiO2 photocatalytic technology for cleansing non-occupational indoor air. The PCO destruction of VHC at concentrations associated with non-occupational indoor air quality issues can be up to nearly 100%. The amount of CO generated during PCO were a negligible addition to the indoor CO levels. These abilities can make the PCO reactor an important tool in the effort to improve non-occupational indoor air quality.

Polycyclic aromatic hydrocarbons(PAHs) in sediments of Kwangyang bay on Korea, have been investigated by gas chromatography-mass spectrometery (GC/MS). The average content of total PAHs in all samples was 2,211ppb, and the range was from 36 to 22,699ppb. The higher concentrations were found in sediment sampled near Kwangyang iron processing plant, Taeindo. The resulting distributions of PAHs according to the number of aromatic ring and molecular ratios of specific aromatic compounds (phenanthrene, anthracene, fluoranthene and pyrene) have been discussed in terms of sample location, origin of the organic matter. Four, five and six rings of PAHs were mainly found near to Kwangyang iron processing plant, and three and four rings near to Yeosu chemical kombinat. This result typically indicated the local characteristics, depending on the origin of PAHs.

Polycyclic aromatic hydrocarbons (PAHs) are an important group of organic contaminants present in sewage sludge, due to their persistence, toxic, bioaccumulative and long range transfer. These characters make themselves as Persistent Organic Pollutants(POPs) in Long Range Transboundary Air Pollutions convention(LRTAP) of Europe. A method of the gas chromatographicmass spectrometric (GCMS) determination of PAHs present in sewage sludge was developed and applied to analyzed samples from five sewerage treatment plants (SWTPs), having different treatment types. PAHs were extracted from freeze-dried samples by toluene 16 hours in a soxhlet extraction system. The sludge extracts were cleaned-up by an activated silica gel column chromatography. The sum of the 16 US Environmental Protection Agency PAHs sewage sludge samples varied from 2.44 to 4.82 ㎍/ g. Concentration of emission carcinogen PAHs(PAHcarc), such as Benzo(a)anthracene, Benzo(b)fluoran- thene, Benzo(k)fluoranthene, Benzo(a)pyrene, Dibenzo(a,h)anthracene and Indeno(1,2,3-cd)pyrene ranged from 0.62 to 1.03 ㎍/g. The total amount of PAHs emission from sewage sludge in Korea was calculated as a top-down approach. PAHs and ∑PAHcarc from sewage treatment plants had emitted to environment by several pathway. The highest amount of emission to the environment was remarked in the ocean dumping(PAHs and ∑PAHcarc emissions were 1155.95 kg/year and 5040.32 kg/year, respectively).

The surface sediments inside Hallim Harbor, one of the major harbors of Jeju Island, were sampled three times (June, September and December, 2001) and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), recommended by US-EPA as priority pollutants, to assess their distribution levels and to suggest their possible origins. The concentrations of PAHs ranged from 19 to 496 ng/g on a dry weight basis with a mean value of 245 ng/g, and the levels were low to moderate in comparison with other areas in the world. Based on comparisons of individual and total PAH concentrations with effects-based and equilibrium partitioning-based on sediment quality guidelines, the potential for the biological effects were expected to be low. The sedimentary PAHs may be correlated with organic carbon and mud contents to some extent. From the examinations of the four PAH origin indices, such as LMW/HMW (low molecular weight 2-3 ring PAHs over high molecular weight 4-6 ring PAHs), phenanthrene/anthracene ratio, fluoranthene/pyrene ratio, chrysene/benzo[a]anthracene ratio, it can be concluded that the sediment PAH contaminations were ascribed to both pyrolytic and petrogenic origins.