• Title/Summary/Keyword: Chemical Stability

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Highly Doped Nano-crystal Embedded Polymorphous Silicon Thin Film Deposited by Using Neutral Beam Assisted CVD at Room Temperature

  • Jang, Jin-Nyeong;Lee, Dong-Hyeok;So, Hyeon-Uk;Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.154-155
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    • 2012
  • The promise of nano-crystalites (nc) as a technological material, for applications including display backplane, and solar cells, may ultimately depend on tailoring their behavior through doping and crystallinity. Impurities can strongly modify electronic and optical properties of bulk and nc semiconductors. Highly doped dopant also effect structural properties (both grain size, crystal fraction) of nc-Si thin film. As discussed in several literatures, P atoms or radicals have the tendency to reside on the surface of nc. The P-radical segregation on the nano-grain surfaces that called self-purification may reduce the possibility of new nucleation because of the five-coordination of P. In addition, the P doping levels of ${\sim}2{\times}10^{21}\;at/cm^3$ is the solubility limitation of P in Si; the solubility of nc thin film should be smaller. Therefore, the non-activated P tends to segregate on the grain boundaries and the surface of nc. These mechanisms could prevent new nucleation on the existing grain surface. Therefore, most researches shown that highly doped nc-thin film by using conventional PECVD deposition system tended to have low crystallinity, where the formation energy of nucleation should be higher than the nc surface in the intrinsic materials. If the deposition technology that can make highly doped and simultaneously highly crystallized nc at low temperature, it can lead processes of next generation flexible devices. Recently, we are developing a novel CVD technology with a neutral particle beam (NPB) source, named as neutral beam assisted CVD (NBaCVD), which controls the energy of incident neutral particles in the range of 1~300eV in order to enhance the atomic activation and crystalline of thin films at low temperatures. During the formation of the nc-/pm-Si thin films by the NBaCVD with various process conditions, NPB energy directly controlled by the reflector bias and effectively increased crystal fraction (~80%) by uniformly distributed nc grains with 3~10 nm size. In the case of phosphorous doped Si thin films, the doping efficiency also increased as increasing the reflector bias (i.e. increasing NPB energy). At 330V of reflector bias, activation energy of the doped nc-Si thin film reduced as low as 0.001 eV. This means dopants are fully occupied as substitutional site, even though the Si thin film has nano-sized grain structure. And activated dopant concentration is recorded as high as up to 1020 #/$cm^3$ at very low process temperature (< $80^{\circ}C$) process without any post annealing. Theoretical solubility for the higher dopant concentration in Si thin film for order of 1020 #/$cm^3$ can be done only high temperature process or post annealing over $650^{\circ}C$. In general, as decreasing the grain size, the dopant binding energy increases as ratio of 1 of diameter of grain and the dopant hardly be activated. The highly doped nc-Si thin film by low-temperature NBaCVD process had smaller average grain size under 10 nm (measured by GIWAXS, GISAXS and TEM analysis), but achieved very higher activation of phosphorous dopant; NB energy sufficiently transports its energy to doping and crystallization even though without supplying additional thermal energy. TEM image shows that incubation layer does not formed between nc-Si film and SiO2 under later and highly crystallized nc-Si film is constructed with uniformly distributed nano-grains in polymorphous tissues. The nucleation should be start at the first layer on the SiO2 later, but it hardly growth to be cone-shaped micro-size grains. The nc-grain evenly embedded pm-Si thin film can be formatted by competition of the nucleation and the crystal growing, which depend on the NPB energies. In the evaluation of the light soaking degradation of photoconductivity, while conventional intrinsic and n-type doped a-Si thin films appeared typical degradation of photoconductivity, all of the nc-Si thin films processed by the NBaCVD show only a few % of degradation of it. From FTIR and RAMAN spectra, the energetic hydrogen NB atoms passivate nano-grain boundaries during the NBaCVD process because of the high diffusivity and chemical potential of hydrogen atoms.

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Transition Metal Dichalcogenide Nanocatalyst for Solar-Driven Photoelectrochemical Water Splitting (전이금속 디칼코제나이드 나노촉매를 이용한 태양광 흡수 광화학적 물분해 연구)

  • Yoo, Jisun;Cha, Eunhee;Park, Jeunghee;Lim, Soo A
    • Journal of the Korean Electrochemical Society
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    • v.23 no.2
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    • pp.25-38
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    • 2020
  • Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS2, MoSe2, WS2, and WSe2 nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H2SO4; the photocurrent reaches to 20 mA cm-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS2 and MoSe2 is 90% for 3h, which is higher than that (80%) of WS2 and WSe2. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS2 and Si-WSe2 experience more oxidation of Si NWs than Si-MoS2 and Si-MoSe2. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.

Studies on the Micelle Formation of Nonionic Surfactant(1) -1NMR Self-Diffusion and Proton Relaxation of Polyoxyethylene Alkyl Ether- (계면활성제 수용액의 미셀형성(제1보) - Polyoxyethylene Alkyl Ether의 자기확산과 프로톤 이완 -)

  • Choi, Seung-Ok;Jeong, Hwan-Kyeong;Lee, Jin-Hee;Nam, Ki-Dae
    • Applied Chemistry for Engineering
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    • v.9 no.6
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    • pp.822-828
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    • 1998
  • Binary system of water and polyoxyethylene dodecyl ether, $C_{12}H_{25}(OCH_2CH_2)nOH$, have been studied by $^1H$ NMR techniques. For n=5($C_{12}EO_5$) and n=8($C_{12}EO_8$), the self-diffusion coefficients of nonionic surfactants in the isotropic phase($L_1$) have been measured by using pulsed field gradient technique for a range of temperature and concentrations. In addition the line widths of the different proton signals have been monitored, and samples of some liquid crystalline characteristic were also studied. Dramatic Broadening of the methylene signals of the alkyl($C_{12}H_{25}$) chain is observed as the hexagonal liquid crystalline phase is approached in the $C_{12}EO_5-$water system, while only small broadening is observed in the $C_{12}EO_8-$water system. It was shown that there was a growth of $C_{12}EO_5$ micelles to rods with increasing concentrations, while the $C_{12}EO_8-$ micelles at low temperature remain small in the concentration range. The self-diffusion coefficients of the surfactants decrease rapidly with increasing concentration until a minimum is reached after which there is slow increase. The location of the minimum point occurs at lower concentrations the temperature is close to the cloud point, where the system separate into two isotropic phase. In the line width studies, broadening is found at a certain temperature interval when the concentration is increased in the $C_{12}EO_5$ system. The results indicate that the surfactant aggregates grow in size at the cloud point is approached. The aggregates seem to be flexible and probably not to be of a definite shape close to the cloud point. In the $C_{12}EO_8$ system, the micelles are much less affected by an increase in temperature and micellar growth can't be unambiguously established. The methylene signals of the ethylene oxide moieties consistantly show narrower $^1H$ signals, showing that in the aggregates they are less ordered than the chain methylenes. The various changes in aggregate size and shape are correlated with the stability ranges of the isotropic and liquid crystalline phases according to phase diagrams from the literature. Both aggregate size and phase structure are in qualitative agreement with concentration based on the effective shape of the molecules at different temperature and concentration.

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Assessment of Soil Contamination and Hydrogeochemistry for Drinking Water Sites in Korea (국내 먹는샘물 개발지역의 토양 오염 평가 및 수리지구화학적 특성)

  • 이두호;전효택
    • Journal of the Korean Society of Groundwater Environment
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    • v.4 no.1
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    • pp.41-53
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    • 1997
  • Geochemical data of soil and water samples were presented in order to assess the environmental impart for drinking water sites. Microscopic observation of rock samples and physical and chemical analysis of soil and water samples were undertaken. The geology of study areas are classified into three groups such as granitic rocks, meta-sedimentary rocks and sedimentary rocks. Enrichment of heavy metals derived from those rocks is not found in this study areas. Soils were analyzed for Cu, Pb, Zn, Cd and Cr using AAS extracted by HNO$_3$+HClO$_4$ and 0.1 N HCl. Heavy metal concentrations in soils are within the range of those in uncontaminated soils. In comparison of metal contents extracted by 0.1 N HCl and HNO$_3$+HC1O$_4$, less than 10% of the heavy metals are present in the exchangeable fraction. In particular, an pollution index has been proposed to assess the degree of soil contamination. Pollution index in soils are between 0.03 and 0.47 therefore, soils are not polluted with heavy metals. Deep groundwaters within granitic rocks have been evolved into Na$\^$+/-HCO$_3$$\^$-/ type, whereas other deep groundwaters evolved into Ca$\^$2+/-HCO$_3$$\^$-/ type. The predominance of Na$\^$+/ over Ca$\^$2+/ in deep groundwaters within granitic rocks is a result of dissolution of plagioclase, but for sedimentary and meta-sedimentary rocks, dissolution of calcite is a dominant factor for their hydrogeochemistry. The pH, conductivity and contents of the most dissolved ions in the water increase with depth. Shallow groundwaters, however, are highly susceptible to pollution owing to agricultural activities, considering the fact that high contents of nitrate, chloride and potassium, and high K/Na ratio are observed in some shallow groundwaters. In a thermodynamic approach, most natural water samples are plotted within the stability fields of kaolinite and smectite. Therefore, microcline and other feldspars will alter to form clay minerals, such as kaolinite and smectite. From the modelling for water-rock interactions based on mass balance equation, models accord well with behavior of the ions and results of thermodynamic studies are derived.

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Recurrence Analysis of Giant Cell Tumor after Curettage and Cementation (거대 세포종에서 골 소파술 및 시멘트 충전술 후의 재발 분석)

  • Hahn, Soo-Bong;Lee, Won-Jun;Shin, Kyoo-Ho
    • The Journal of the Korean bone and joint tumor society
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    • v.10 no.2
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    • pp.71-78
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    • 2004
  • Purpose: The purpose of this study is to investigate the characteristic of recurred giant cell tumor after bony curettage and cementation, and to review a way to prevent the recurrence. Materials and Methods : Thirty seven cases were analyzed, which were pathologically diagnosed giant cell tumor after diagnostic biopsy or surgical excision, followed by curative curettage, burring and cementation. Location, character, and time interval to recurrence were reviewed. Results: Thirteen out of thirty seven analyzed cases(35%) showed recurrence after primary curettage and cementation. The mean interval to recurrence was sixteen months(5 months to 43 months). Most of recurrence happened within the first two years except two cases. Among the recurred cases, eleven showed recurrence in the vicinity of window area. Two cases recurred in the depth of bone marrow, where cementation was made. The advantage of curettage and cementation is the immediate stability of the operation site, early rehabilitation, and early detection of recurrence. Furthermore, cementation is beneficial in that the cement-producing heat can eradicate the residual tumor burden. In this study, 85% of cases with insufficient curettage (for example, in cases where too small surgical window was made, or where there were anatomical difficulty in approaching the target tumor burden) showed recurrence. Conclusion: Bony curettage, burring and cementation is widely used as the primary curative modality for giant cell tumor. A few other modalities such as chemical cautery using phenol and $H_2O_2$; cryotherapy; and anhydroalcohol have also been introduced, but the benefit of these are still questionable. For some cases that relatively small surgical window was made due to anatomically complicated structures (such as ligament insertion or origin site) over the target tumor burden, unsatisfactory curettage and burring was made. This study showed high chance of recurrence after unsatisfactory curettage, and 85% of recurrence developed in the vicinity of the small window area. Most of the recurrence occurred within the first two years. It is concluded that sufficient window opening, extensive curettage and eradicative burring are key factors to prevent recurrence. Also, it should be reminded that careful and close observation should be made for at least the first two years after initial treatment for early detection of recurrence.

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Potential Benefits of Intercropping Corn with Runner Bean for Small-sized Farming System

  • Bildirici, N.;Aldemir, R.;Karsli, M.A.;Dogan, Y.
    • Asian-Australasian Journal of Animal Sciences
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    • v.22 no.6
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    • pp.836-842
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    • 2009
  • The objectives of this study were to evaluate potential benefits of intercropping of corn with runner bean for a smallsized farming system, based on land equivalent ratio (LER) and silage yield and quality of corn intercropped with runner bean (Phaseolus vulgaris L.), in arid conditions of Turkey under an irrigation system. This experiment was established as a split-plot design in a randomized complete block, with three replications and carried out over two (consecutive) years in 2006 and 2007. Seven different mixtures (runner bean, B and silage corn sole crop, C, 10% B+90% C, 20% B+80% C, 30% B+70% C, 40% B+60%C, and 50% B+50%C) of silage corn-runner bean were intercropped. All of the mixtures were grown under irrigation. The corn-runner bean fields were planted in the second week of May and harvested in the first week of September in both years. Green beans were harvested three times each year and green bean yields were recorded each time. After the 3rd harvest of green bean, residues of bean and corn together were randomly harvested from a 1 $m^{2}$ area by hand using a clipper when the bean started to dry and corn was at the dough stage. Green mass yields of each plot were recorded. Silages were prepared from each plot (triplicate) in 1 L mini-silos. After 60 d ensiling, subsamples were taken from this material for determination of dry matter (DM), pH, organic acids, chemical composition, and in vitro DM digestibility of silages. The LER index was also calculated to evaluate intercrop efficiencies with respect to sole crops. Average pH, acetic, propionic and butyric acid concentrations were similar but lactic acid and ammonia-N levels were significantly different (p<0.05) among different mixtures of bean intercropped with corn. Ammonia-N levels linearly increased from 0.90% to 2.218 as the percentage of bean increased in the mixtures up to a 50:50 seeding ratio. While average CP content increased linearly from 6.47 to 12.45%, and average NDF and ADF contents decreased linearly from 56.17 to 44.88 and from 34.92 to 33.51%, respectively, (p<0.05) as the percentage of bean increased in the mixtures up to a 50:50 seeding ratio, but DM and OM contents did not differ among different mixtures of bean intercropped with corn (p>0.05). In vitro OM digestibility values differed significantly among bean-corn mixture silages (p<0.05). Fresh bean, herbage DM, IVOMD, ME yields, and LER index were significantly influenced by percentage of bean in the mixtures (p<0.01). As the percentage of bean increased in the mixtures up to a 50:50 seeding ratio, yields of fresh bean (from 0 to 24,380 kg/ha) and CP (from 1,258.0 to 1,563.0 kg/ha) and LER values (from 1.0 to 1.775) linearly increased, but yields of herbage DM (from 19,670 to 12,550 kg/ha), IVOMD (from 12,790 to 8,020 kg/ha) and ME (46,230 to 29,000 Mcal/ha) yields decreased (p<0.05). In conclusion, all of the bean-corn mixtures provided a good silage and better CP concentrations. Even though forage yields decreased, the LER index linearly increased as the percentage of bean increased in the mixture up to a 50:50 seeding ratio, which indicates a greater utilization of land. Therefore, a 50:50 seeding ratio seemed to be best for optimal utilization of land in this study and to provide greater financial stability for labor-intensive, small farmers.

Changes in Characteristics of Bark and Piggery Manure By-Product Fertilizers During the Composting (수피${\cdot}$돈분 부산물 비료의 부숙단계별 특성 변화)

  • Yang, Jae-E;Park, Chang-Jin;Yong, Seok-Ho;Kim, Jeong-Je
    • Korean Journal of Environmental Agriculture
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    • v.18 no.4
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    • pp.372-377
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    • 1999
  • Objective of this research was to draw the basic criteria of the compost maturity evaluation, by assessing the stability of chemical and physical properties of the bark and piggery manure byproduct composts during the composting. Colors of the mature composts were black and dark brown for the bark and piggery manure by-product composts, respectively. Good earthy odor was detected for both by-product composts after approximately 40 days composting, by which odors of the original raw materials were disappeared. pH and EC of the mature bark: compost were stabilized at 6.5 and 1dS/m, respectively. The respective values for the piggery compost were stabilized at 7.2 and 6dS/m. Organic matter contents were decreased with time to be stabilized at about 60% at the end of composting. During composting, total N contents of the bark and piggery composts were maintained at $1.1{\sim}1.5%$, and $1.5{\sim}2.2%$, respectively. For both fertilizers, $NH_4-N$ contents were increased at the initial stage bur. decreased after the middle stages of decomposition, resulting in the increase of $NO_3-N$ contents. Total inorganic N contents were increased with time. C/N ratios of both mature composts were stabilized at $25{\sim}27$. CEC of the bark compost was increased logarithmically with time and that of mature compost was 87cmol(+)/㎏. CEC of the piggery manure compost was hyperbolic function with rime and reached at 70cmol(+)/㎏ at the mature stage. Crude fiber analysis indicated that relative contents of lignin were increased with composting by compensating for the decreases of cellulose and hemicellulose contents.

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Quantifying Uncertainty of Vitamin C Determination in Infant Formula by Indophenol Titration Method (인도페놀 적정법에 의한 성장기용조제식 중 비타민 C 함량분석의 측정불확도 산정)

  • Jun, Jang-Young;Kwak, Byung-Man;Ahn, Jang-Hyuk;Kong, Un-Young
    • Korean Journal of Food Science and Technology
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    • v.37 no.3
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    • pp.352-359
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    • 2005
  • Uncertainty involved during determination of vitamin C content in infant formula was quantified by indophenol titration method. Uncertainty sources in measurand, such as purity, weight, final volume of standard, volume of standard solution used for titration, sample weight, final volume of sample, extraction solution used for titration, titration of extraction solution and standard solution by indophenol solution were identified and used as parameters for combined standard uncertainty based on Guide to the expression of uncertainty in measurement (GUM) and Draft EURACHEM/CITAC Guide. Uncertainty parameters of each source in measurand were identified as resolution, reproducibility and stability of chemical balance, standard material purity, repeatability, reproducibility, end point of titration, 1 mL pipet, 5 mL autopipet, and 100 mL mass flask. Each uncertainty component was evaluated by types A and B and included to calculate combined uncertainty. Analytical test result for traceability under laboratorial conditions using Certified Reference Material (CRM) test was certified as $108.4{\pm}1.7mg/100g$, which was within CRM certification range of $114.6{\pm}6.6mg/100g$. Uncertainty test result of vitamin C content of 5 g sampling was $56.7{\pm}2.44mg/100g$. Uncertainty could be reduced by identification of uncertainty sources and components related with vitamin C determination by indophenol titration method and by decreasing uncertainty sources and components.

Chemo-Mechanical Analysis of Bifunctional Linear DGEBA/Linear Amine (DDM, DDS) Resin Casting Systems (DGEBA/방향족 아민(DDM, DDS) 경화제의 벤젠링 사이의 관능기 변화가 물성 변화에 미치는 영향에 대한 연구)

  • 명인호;정인재;이재락
    • Composites Research
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    • v.12 no.4
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    • pp.71-78
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    • 1999
  • To determine the effect of chemical structure of linear amine curing agents on thermal and mechanical properties, standard epoxy resin DGEBA was cured with diaminodiphenyl methane (DDM), diaminodiphenyl sulphone (DDS) in a stoichiometrically equivalent ratio. From this work, the effect of aromatic amine curing agents. In contrast, the results show that the DGEBA/DDS cure system having the sulfone structure between the benzene rings had higher values in the conversion of epoxide, density, shrinkage (%), glass transition temperature, tensile modulus and strength, flexural modulus and strength than the DGEBA/DDM cure system having methylene structure between the benzene rings, whereas the DGEBA/DDM cure system presented higher values in the maximum exothermic temperature, thermal expansion coefficient, and thermal stability. These results are caused by the relative effects of sulfone group having strong electronegativity and methylene group having (+) repulsive property and stem from the effect of the conversion ratio of epoxide group. The result of fractography shows that the each grain size of the DDM/DGEBA system with feather-like structure is larger than that of the DDS/DGEBA system.

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Regeneration Processes of Nutrients in the Polar Front Area of the last Sea IV. Chlorophyll a Distribution, New Production and the Vertical Diffusion of Nitrate (동해 극전선역의 영양염류 순환과정 IV. Clorophyll a 분포, 신생산 및 질산염의 수직확산)

  • MOON Chang-Ho;YANG Sung-Ryull;YANG Han-Soeb;CHO Hyun-Jin;LEE Seung-Yong;KIM Seok-Yun
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.31 no.2
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    • pp.259-266
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    • 1998
  • A study on the biological and chemical characteristics in the middle last Sea of Korea was carried out at 31 stations in October $11\~18$, 1995 on board the R/V Tam-Yang. The chlorophyll a concentration, new and regenerated production, and the vertical diffusion of nitrate from the thermocline structure were investigated. From the vertical distribution of chlorophyll a, subsurface maxima were observed near the thermorline at most stations including the frontal zone, except at the southern stations where the maximum chloropyll a concentration occurred at the surface, The nanophytoplankton was the most dominant fraction comprising $83.5\%$ of total phytoplankton cell numbers, but netphytoplankton were common at the southern stations where the dominant species were Rhizosolenia sp. Nitrogenous new production and regenerated productions were measured using the stable isotope $^{15}N$ nitrate and ammonia uptake method. The vertically integrated nitrogen production varied between 8.470 and $72.945\;mg\;N\;m^{-2}\;d^{-1}$. The f-ratio, which is the traction of new production from primary production, waried between 0.03 and 0.72, indicating that $3\%$ to $72\%$ of primary production was supported by the input of nutrients from below the euphotic zone and the rest are supported by ammonia recycled within the euphotic layer. This range of f-ratio encompasses from extremely oligotrophic to eutrophic area characteristics. The differences in productivity and f-ratio among stations were related to frontal structure and the bottom topography. The values were high near the frontal zone and low outside of it, and the station near Ulleng Island showed the highest f-ratio. Vertical diffusion coefficients were calculated from both the water column stability (Kz-1) of King and Devol's equation (1979) and new nitrogen requirement (Kz-2). The values of Kz-2 ($0.11\~0.55\;cm^2/s$) were relatively low compared to the values reported previously.

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