• 제목/요약/키워드: saturated formation

검색결과 191건 처리시간 0.023초

Theoretical Studies of the Gas-Phase Identity Nucleophilic Substitution Reactions of Cyclopentadienyl Halides

  • Lee, Ik-Choon;Li, Hong-Guang;Kim, Chang-Kon;Lee, Bon-Su;Kim, Chan-Kyung;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제24권5호
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    • pp.583-592
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    • 2003
  • The gas phase identity nucleophilic substitution reactions of halide anions (X = F, Cl, Br) with cyclopentadienyl halides (1) are investigated at the B3LYP/6-311+G**, MP2/6-311+G** and G2(+)MP2 levels involving five reaction pathways: σ-attack $S_N2$, β-$S_N$2'-syn, β-$S_N$2'-anti, γ-$S_N$2'-syn and γ-$S_N$2'-anti paths. In addition, the halide exchange reactions at the saturated analogue, cyclopentyl halides (2), and the monohapto circumambulatory halide rearrangements in 1 are also studied at the same three levels of theory. In the σ-attack $S_N2$ transition state for 1 weak positive charge develops in the ring with X = F while negative charge develops with X = Cl and Br leading to a higher energy barrier with X = F but to lower energy barriers with X = Cl and Br than for the corresponding reactions of 2. The π-attack β-$S_N$2' transition states are stabilized by the strong $n_C-{\pi}^{*}_{C=C}$ charge transfer interactions, whereas the π-attack γ-$S_N$2' transition states are stabilized by the strong $n_C-{\sigma}^{*}_{C-X}$ interactions. For all types of reaction paths, the energy barriers are lower with X = F than Cl and Br due to the greater bond energy gain in the partial C-X bond formation with X = F. The β-$S_N$2' paths are favored over the γ-$S_N$2' paths only with X = F and the reverse holds with X = Cl and Br. The σ-attack $S_N2$ reaction provides the lowest energy barrier with X = Cl and Br, but that with X = F is the highest energy barrier path. Activation energies for the circumambulatory rearrangement processes are much higher (by more than 18 kcal $mol^{-1}$) than those for the corresponding $S_N2$ reaction path. Overall the gas-phase halide exchanges are predicted to proceed by the σ-attack $S_N2$ path with X = Cl and Br but by the β-$S_N$2'-anti path with X = F. The barriers to the gas-phase halide exchanges increase in the order X = F < Br < Cl, which is the same as that found for the gas-phase identity methyl transfer reactions.

전통조경공간(傳統造景空間)에서 나타난 동천(洞天)의 조영(造營) 특성(特性) (A Study on the Construction Characteristics of Dongcheon in the Traditional Space of Landscape Architecture)

  • 이혁종;최기수
    • 한국전통조경학회지
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    • 제28권2호
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    • pp.9-22
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    • 2010
  • 본 연구는 선조가 꾸민 전통조경공간 내에서 발견할 수 있는 특징적인 바위글씨인 동천(洞天)을 대상으로 하여 그곳에 담긴 의미는 무엇인지, 어떠한 목적으로 동천을 조영(造營)하였는지, 또한 조영함으로써 무엇을 나타내고자 하였는지를 밝히고자 하였다. 이를 위해 집중적인 연구대상지인 25개소의 동천을 선정하고 이곳에 대한 이해를 뒷받침해줄 수 있는 자료에 대한 문헌분석, 그리고 현지답사를 통해 동천의 경관과 유형을 살펴봄으로써 나타난 조영 특성은 다음과 같다. 첫째, 동천은 조성 목적에 따라 가거지형(家居地型), 은서지형(隱棲地型), 산수유람형(山水遊覽型)에서 승경형(勝景型)과 수신형(修身型), 수도지형(修道地型)으로 나눌 수 있었다. 즉, 동천은 우리의 생활하는 장소에서, 현실의 불합리나 재난을 피하기 위한 은서의 장소에서, 자연과의 화합에 의한 풍류생활의 장소에서, 그럼으로써 자신을 수양하려는 수신의 장소에서, 속세를 벗어난 수도의 장소에서 조영되어 있었다고 볼 수 있다. 둘째, 입지유형에 따라 심산동구형(深山同口型), 계류인접형(溪流隣接型)에서 연계형(連繫型)과 단일영역형(單一領域型), 평지형(平地型)으로 나눌 수 있었다. 특히 심산동구형은 무릉도원, 몽유도원, 오복동에서 보여주는 공간설정과 상당히 유사하게 전개되어 동천이라는 것이 선조가 사유했던 이상향의 공간구조임을 알려준다. 그렇지 않다면 우리나라의 계곡, 승경처에 동천이 조영되었는데, 이는 신선사상에서 말하는 선계의 모습을 원림에서 가꾸어 나감으로써 신선의 경지를 추구하고자 한 바램으로 파악된다. 셋째, 동천이라 명명함으로써 그곳은 이상향이 되며, 그 스스로 선경을 유발시키게 된다. 즉, 눈에 보이는 동천각자를 통해서 이면의 심층에 있는 이상향의 의미를 추구하려는 것이며, 공간을 만든 조영자가 추구했던 이상적 세계에 대한 갈망에 지극히 기여하는 요소가 되고 있다.

부식산(腐植酸)-중금속(重金屬) 착화합물형성(錯化合物形成) 반응(反應)에 대한 Mechanism (Mechanisms of Humic Acid-Heavy Metal Complexation)

  • 이정재;장상문;최정
    • 한국토양비료학회지
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    • 제28권2호
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    • pp.114-122
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    • 1995
  • 토양유기물(土壤有機物)에 의한 중금속(重金屬)의 흡착(吸着)현상을 구명(究明)하기 위하여 이탄토(泥炭土)에서 humic acid를 분리정제(分離精製)하여, humid acid-metal complex 생성반응(生成反應)에 대한 mechanism을 조사(調査)하였다. 1. Humic acid-metal complex의 흡광도(吸光度)는 장파장영역(長波長領域)에서 단파장영역(短波長領域)으로 갈수록 Zn-HA > Cd-HA > Cu-HA의 순(順)으로 증가(增加)하였다. 2. Humic acid의 carboxyl group과 phenolic OH group들이 중금속(重金屬) ion들과 반응(反應)하여 complex를 생성(生成)하였으며 그 생성량(生成量)은 Cu > Zn ≧ Cd의 순(順)이었다. 3. Humic acid-medal complex의 안정도(安定度) 상수(常數)는 pH가 증가(增加)함에 따라 增加하였으며 1차(次) 안정도(安定度) 상수(常數)는 Zn>Cd>Cu 순(順)이었고, 2차(次) 안정도(安定度) 상수(常數)는 Cu>Zn>Cd의 순(順)이었으며, 總安定도 常數는 Cu>Zn>Cd의 순(順)이었다. 4. Humlc acid와 중금속(重金屬)ion들 상호(相互) 간(間)의 평균결합수(平均結合數)는 pH가 증가(增加)함에 따라 Cu>Zn>Cd의 順으고 增加하였다. 5. Humic acid에 의한 중금속(重金屬) ion들의 complex생성과정(生成課程)에서 barboxyl group만이 관여(關與)하는 것과 car-boxyl gruup 및 phenolic OH group이 동시(同時)에 관여(關與)하는 두가지 흡착(吸着)mechanlsm을 제안할 수 있었다.

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복합 처분환경 모사조건에서의 KURT 화강암의 역학적 물성 변화 평가 (Evaluation of mechanical properties of KURT granite under simulated coupled condition of a geological repository)

  • 박승훈;김진섭;김건영;권상기
    • 한국터널지하공간학회 논문집
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    • 제21권4호
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    • pp.501-518
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    • 2019
  • 심부 지하환경 조건에서 측정된 암석물성의 사용은 고준위폐기물처분장의 장기 안전성 평가 측면에서 해석의 신뢰성을 향상시킬 수 있다. 본 연구는 지하처분연구시설(Korea atomic energy research institute Underground Research Tunnel, KURT)의 화강암(한국원자력연구원, 대전)을 대상으로 고준위폐기물 처분장에서 예상되는 복합환경 조건을 구현한 후 암석의 역학적 물성 변화를 측정하였다. 실험은 심지층 처분환경이 모사되도록 열-수리-역학적 복합 환경(Thermo-Hydro-Mechanical, THM)이 조절될 수 있는 실험장치를 제작하였다. 다양한 복합 실험조건(M, HM, TM, THM)을 구현하여 일축압축강도와 간접인장강도, 탄성계수, 포와송비 등의 암석물성을 측정한 후 그 결과를 분석하였다. 실험결과, 처분장 근계암반 예상 온도범위 내에서는 KURT 화강암의 역학적 물성이 온도의 영향 보다 포화유무에 따른 변화가 더 큰 것을 확인할 수 있었다. 또한, 동일한 온도 조건에서 포화 유무에 따른 일축압축시험 결과는 최대 약 20%의 상대적인 차이를 보였으며, 간접인장시험 결과는 최대 13%의 차이가 발생하였다. 따라서 처분장의 장기거동에 따른 성능평가 및 안전성 예측을 위해서는 기존의 상온 실내시험을 통해 도출된 암석물성을 사용하기보다 심부 지하환경을 반영한 암석의 복합물성을 활용하는 것이 해석의 신뢰도 향상에 기여할 수 있을 것이다.

Feeding by common heterotrophic protists on the mixotrophic dinoflagellate Ansanella granifera (Suessiaceae, Dinophyceae)

  • Hee Chang Kang;Hae Jin Jeong;An Suk Lim;Jin Hee Ok;Ji Hyun You;Sang Ah Park;Se Hee Eom
    • ALGAE
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    • 제38권1호
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    • pp.57-70
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    • 2023
  • The mortality rate of red-tide dinoflagellates owing to predation is a major parameter that affects their population dynamics. The dinoflagellates Ansanella granifera and Ansanella sp. occasionally cause red tides. To understand the interactions between common heterotrophic protists and A. granifera, we explored the feeding occurrence of nine heterotrophic protists on A. granifera and the growth and ingestion rates of the heterotrophic dinoflagellate Gyrodinium dominans on A. granifera as a function of prey concentration and those of Oxyrrhis marina at a single high prey concentration. The heterotrophic dinoflagellates Aduncodinium glandula, G. dominans, Gyrodinium moestrupii, Luciella masanensis, Oblea rotunda, O. marina, Polykrikos kofoidii, and Pfiesteria piscicida and the naked ciliate Strombidium sp. were able to feed on A. granifera. With increasing mean prey concentrations, the growth and ingestion rates of G. dominans feeding on A. granifera rapidly increased and became saturated or slowly increased. The maximum growth and ingestion rates of G. dominans on A. granifera were 0.305 d-1 and 0.42 ng C predator-1 d-1 (3.8 cells predator-1 d-1), respectively. Furthermore, the growth and ingestion rates of O. marina on A. granifera at 1,700 ng C mL-1 (15,454 cells mL-1) were 0.037 d-1 and 0.19 ng C predator-1 d-1 (1.7 cells predator-1 d-1), respectively. The growth and ingestion rates of G. dominans and O. marina feeding on A. granifera were almost the lowest among those on the dinoflagellate prey species. Therefore, G. dominans and O. marina may prefer A. granifera less than other dinoflagellate prey species. The low mortality rate of A. granifera may positively affect its bloom formation.

건조(乾燥) 갯장어의 저장중(貯藏中) 지방(脂肪)의 산화(酸化)와 유효성(有效性) Lysine의 변화(變化) (Changes in Available Lysine and Lipid Oxidized Products during the Storage of Dried Sea Eel, Muraesox cinereus)

  • 변대석;송영옥;변재형
    • 한국식품과학회지
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    • 제10권4호
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    • pp.387-393
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    • 1978
  • 수산제품(水産製品)의 품질(品質) 보존(保存)에서 문제점(問題點)으로 되고 있는 지질(脂質)의 산화생성물(酸化生成物)이 단백질(蛋白質)의 영양학적(營養學的) 변화(變化)에 미치는 영향(影響)을 검토(檢討)하였다. 건조(乾燥)갯장어를 재료(材料)로 하였을 때. 저장중(貯藏中)에 생성(生成)되는 지방(脂肪)의 산화생성물(酸化生成物) 즉(卽) malonaldehyde를 포함(包含)하는 carbonyl화물(化物)과 건조육중(乾燥肉中)의 유리(遊離)아미노산(酸) 및 유효성 lysine간(間)의 반응(反應) 및 갈변반응(褐變反應)에 미치는 영향(影響)을 실험(實驗) 검토(檢討)하여 다음의 결론(結論)을 얻었다. 갯장어를 $55^{\circ}C$에서 15시간(時間) 열풍건조(熱風乾燥)하였을 때 TBA가(價)와 carbonyl가(價)는 급격(急激)히 증가(增加)하고 유리(遊離)아미노산(酸) 및 유효성 lysine은 반대(反對)로 감소(減少)하여 열풍건조중(熱風乾燥中)에는 지방(脂肪)의 산화(酸化)에 따라 아미노산(酸)이 상당량(相當量) 불용화(不用化)하는 것으로 판단(判斷)할 수 있었다. 건조(乾燥)갯장어의 저장중(貯藏中)에는 TBA가(價)와 carbonyl가(價)의 증가(增加)에 따라 지방(脂肪)의 산화적(酸化的) 갈변색소(褐變色素)의 양(量)도 계속(繼續)증가(增加)하였으며, 아미노태질소(態窒素)와 유효성 lysine의 양(量)은 역(逆)으로 감소(減少)하였다. 그리고 유효성 lysine의 불용화(不用化)는 포화(飽和) carbonyl 화합물(化合物)보다는 주(主)로 불포화(不飽和) carbonyl 화합물(化合物)에 의하여 영향(影響)을 받는 것으로 보였다. 항산화제(抗酸化劑)의 처리(處理)는 저장중(貯藏中)의 건조(乾燥) 갯장어의 총(總) 유리(遊離) 아미노산(酸)과 유효성 lysine의 손실(損失)을 어느 정도(程度) 막을수 있었다. 이로 미루어 유효성 lysine의 손실(損失)은 지방(脂肪)의 산화반응(酸化反應)과 밀접(密接)한 관계(關係)가 있는 것으로 판단(判斷)되었다.

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ATHEROSCLEROSIS, CHOLESTEROL AND EGG - REVIEW -

  • Paik, I.K.;Blair, R.
    • Asian-Australasian Journal of Animal Sciences
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    • 제9권1호
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    • pp.1-25
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    • 1996
  • The pathogenesis of atherosclerosis can not be summarized as a single process. Lipid infiltration hypothesis and endothelial injury hypothesis have been proposed and investigated. Recent developments show that there are many points of potential interactions between them and that they can actually be regarded as two phases of a single, unifying hypothesis. Among the many risk factors of atherosclerosis, plasma homocysteine and lipoprotein(a) draw a considerable interest because they are independent indicators of atherogenicity. Triglyceride (TG)-rich lipoproteins (chylomicron and VLDL) are not considered to be atherogenic but they are related to the metabolism of HDL cholesterol and indirectly related to coronary heart disease (CHD). LDL can of itself be atherogenic but the oxidative products of this lipoprotein are more detrimental. HDL cholesterol has been considered to be a favorable cholesterol. The so-called 'causalist view' claims that HDL traps excess cholesterol from cellular membranes and transfers it to TG-rich lipoproteins that are subsequently removed by hepatic receptors. In the so-called 'noncausalist view', HDL does not interfere directly with cholesterol deposition in the arterial wall but instead reflects he metabolism of TG-rich lipoproteins and their conversion to atherogenic remnants. Approximately 70-80% of the human population shows an effective feedback control mechanism in cholesterol homeostasis. Type of dietary fat has a significant effect on the lipoprotein cholesterol metabolism and atherosclerosis. Generally, saturated fatty acids elevate and PUFA lower serum cholesterol, whereas MUFA have no specific effect. EPA and DHA inhibit the synthesis of TG, VLDL and LDL, and may have favourable effects on some of the risk factors. Phospholipids, particularly lecithin, have an antiatherosclerotic effect. Essential phospholipids (EPL) may enhance the formation of polyunsaturated cholesteryl ester (CE) which is less sclerotic and more easily dispersed via enhanced hydrolysis of CE in the arterial wall. Also, neutral fecal steroid elimination may be enhanced and cholesterol absorption reduced following EPL treatment. Antioxidants protect lipoproteins from oxidation, and cells from the injury of toxic, oxidized LDL. The rationale for lowering of serum cholesterol is the strong association between elevation of plasma or serum cholesterol and CHD. Cholesterol-lowing, especially LDL cholesterol, to the target level could be achieved using diet and combination of drug therapy. Information on the link between cholesterol and CHD has decreased egg consumption by 16-25%. Some clinical studies have indicated that dietary cholesterol and egg have a significant hypercholesterolemic effect, while others have indicated no effect. These studies differed in the use of purified cholesterol or cholesterol in eggs, in the range of baseline and challenge cholesterol levels, in the quality and quantity of concomitant dietary fat, in the study population demographics and initial serum cholesterol levels, and clinical settings. Cholesterol content of eggs varies to a certain extent depending on the age, breed and diet of hens. However, egg yolk cholesterol level is very resistant to change because of the particular mechanism involved in yolk formation. Egg yolk contains a factor of factors responsible for accelerated cholesterol metabolism and excretion compared with crystalline cholesterol. One of these factors could be egg lecithin. Egg lecithin may not be as effective as soybean lecithin in lowering serum cholesterol level due probably to the differences of fatty acid composition. However, egg lecithin may have positive effects in hypercholesterolemia by increasing serum HDL level and excretion of fecal cholesterol. The association of serum cholesterol with egg consumption has been widely studied. When the basal or control diet contained little or no cholesterol, consumption of 1 or 2 eggs daily increased the concentration of plasma cholesterol, whereas that of the normolipemic persons on a normal diet was not significantly influenced by consuming 2 to 3 eggs daily. At higher levels of egg consumption, the concentration of HDL tends to increase as well as LDL. There exist hyper-and hypo-responders to dietary (egg) cholesterol. Identifying individuals in both categories would be useful from the point of view of nutrition guidelines. Dietary modification of fatty acid composition has been pursued as a viable method of modifying fat composition of eggs and adding value to eggs. In many cases beneficial effects of PUFA enriched eggs have been demonstrated. Generally, consumption of n-3 fatty acids enriched eggs lowered the concentration of plasma TG and total cholesterol compared to the consumption of regular eggs. Due to the highly oxidative nature of PUFA, stability of this fat is essential. The implication of hepatic lipid accumulation which was observed in hens fed on fish oils should be explored. Nutritional manipulations, such as supplementation with iodine, inhibitors of cholesterol biosynthesis, garlic products, amino acids and high fibre ingredients, have met a limited success in lowering egg cholesterol.

저콘 포화온도로 추정한 남한 현생이언 화강암의 상대적인 마그마 생성온도 (Relative Magma Formation Temperatures of the Phanerozoic Granitoids in South Korea Estimated by Zircon Saturated Temperature)

  • 사공희;권성택;조등룡;좌용주
    • 암석학회지
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    • 제14권2호
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    • pp.83-92
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    • 2005
  • 최근 화강암의 옛저콘(inherited zircon)의 존재여부로써 마그마 생성온도를 상대적으로 저온화강암과 고온화강암으로 구분할 수 있음이 제안되었으며, 이는 저콘 포화온도와 밀접하게 관련이 있음이 밝혀졌다. $SiO_2-Zr$ 그림에서 남한의 현생이언 화강암들은 고Zr 화강암과 저Zr 화강암으로 구분된다. 이들 구분은 관입시기와 관련된 것으로 보인다. 트라이아스-쥬라기 화강암들은 거의 대부분 저Zr 화강암에 속한다. 반면 백악기-제3기초 화강암들은 대부분 고Zr 화강암에 해당하나, 마산-진해 화강암은 저Zr 화강암에 속하여 지리적 차이를 보인다. 주성분원소와 Zr 함량을 이용하여 저콘 포화온도를 계산하면 저Zr 화강암(마산진해 화강암, 평균 $759\times16^{\circ}C$)을 제외한 경상분지의 백악기-제3기초 화강암 $(608-834^{\circ}C,\;평균\;782\times31^{\circ}C$)이 트라이아스_쥬라기 화강암 ($642-824^{\circ}C$, 평균 $756\pm31^{\circ}C$)보다 높은 온도를 지시한다. 현재까지 알려진 트라이아스-쥬라기 화강암의 U-Pb 저콘 연대 자료는 모두 콘코디아 그림에서 디스코디아를 정의하는데 이는 옛저콘의 존재를 지시하며 낮은 저콘 포화온도와 조화적이다. 반면에 상대적으로 높은 저콘 포화온도를 가지는 백악기-제3기초 화강암의 경우 옛저콘의 존재에 대하여 아직 알려진 바가 없기 때문에 고온 혹은 저온 화강암에 해당하는지를 판단할 수 없다. 그럼에도 불구하고 저콘 포화온도는 마그마 생성, 온도를 어느 정도 반영하기 때문에 백악기-제3기초 화강암은 트라이아스-쥬라기 화강암보다 높은 온도에서 생성되었음을 시사한다.

계면활성제가 공극 구조 내 비혼성 유체의 거동과 분포에 미치는 영향 (The Effect of the Surfactant on the Migration and Distribution of Immiscible Fluids in Pore Network)

  • 박규령;김선옥;왕수균
    • 자원환경지질
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    • 제54권1호
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    • pp.105-115
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    • 2021
  • 대규모로 포집된 이산화탄소를 고갈된 석유·가스 저류층, 대염수층과 같은 심부 지질구조에 주입하는 이산화탄소 지중저장은 대기중 CO2 배출을 저감하기 위한 가장 유망한 기술 중 하나로 연구되고 있다. 이산화탄소 지중저장은 공극수로 포화된 다공성 지질 구조 내부로 초임계상 이산화탄소를 주입함으로써 그 흐름이 공극수와 비혼성 대체를 일으키며 진행된다. 따라서, 공극 구조 내에서 초임계상 이산화탄소와 공극수의 거동과 분포, 그리고 그 결과로 나타나는 대체효율은 두 유체의 상호작용에 의해 좌우되는데, 특히, 점성력과 모세관력은 지질 구조 내부의 환경 조건과 주입 조건에 의해 결정된다. 본 연구에서는 상온상압조건에서 대체유체를 수적법에 적용하여 고온고압조건에서 계면활성제가 초임계상 이산화탄소와 공극수 간 계면장력에 미치는 영향을 산정하였다. 또한, 다공성 매체 내에서의 비혼성 유체의 거동과 분포 양상을 관찰함으로써 계면활성제 농도가 초임계상 이산화탄소의 대체율에 미치는 영향을 분석하였다. 이를 위하여 초임계상 이산화탄소와 공극수의 대체 유체로서 헥산과 탈이온수를 적용하는 마이크로모델 실험을 수행하였으며, 공극 구조 내로의 헥산 주입에 의한 탈이온수의 대체 과정을 정량적으로 분석하기 위하여 이미징 시스템을 통해 두 유체의 비혼성 대체 양상에 관한 이미지를 확득하여 분석하였다. 실험의 결과는 계면활성제의 첨가는 낮은 농도에서도 헥산과 탈이온수 간 계면장력을 급격하게 감소시키며 이후 농도가 증가함에 따라 일정한 값에 접근하는 양상을 보여주었으며, 이러한 변화는 다공성 매체 내부의 공극 규모에서 진입 유체의 흐름 경로에 직접적인 영향을 미침으로써 평형 상태에서 헥산의 대체율에도 동일한 효과를 나타내는 것으로 나타났다. 본 연구의 결과는 다공성 매체 내에서 일어나는 비혼성 유체의 대체에 관한 중요한 정보를 제공하며, 계면활성제의 적용이 이산화탄소 지중저장의 효율을 향상시킬 수 있는 가능성을 보여주었다.

Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • 한국지하수토양환경학회:학술대회논문집
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    • 한국지하수토양환경학회 2004년도 총회 및 춘계학술발표회
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    • pp.3-4
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    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

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