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Development and Validation of an Analytical Method for Fenpropimorph in Agricultural Products Using QuEChERS and LC-MS/MS (QuEChERS법과 LC-MS/MS를 이용한 농산물 중 Fenpropimorph 시험법 개발 및 검증)

  • Lee, Han Sol;Do, Jung-Ah;Park, Ji-Su;Cho, Sung Min;Shin, Hye-Sun;Jang, Dong Eun;Choi, Young-Nae;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.2
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    • pp.115-123
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    • 2019
  • An analytical method was developed for the determination of fenpropimorph, a morpholine fungicide, in hulled rice, potato, soybean, mandarin and green pepper using QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) sample preparation and LC-MS/MS (liquid chromatography-tandem mass spectrometry). The QuEChERS extraction was performed with acetonitrile followed by addition of anhydrous magnesium sulfate and sodium chloride. After centrifugation, d-SPE (dispersive solid phase extraction) cleanup was conducted using anhydrous magnesium sulfate, primary secondary amine sorbents and graphitized carbon black. The matrix-matched calibration curves were constructed using seven concentration levels, from 0.0025 to 0.25 mg/kg, and their correlation coefficient ($R^2$) of five agricultural products were higher than 0.9899. The limits of detection (LOD) and quantification (LOQ) were 0.001 and 0.0025 mg/kg, respectively, and the limits of quantification for the analytical method were 0.01 mg/kg. Average recoveries spiked at three levels (LOQ, $LOQ{\times}10$, $LOQ{\times}50$, n=5) and were in the range of 90.9~110.5% with associated relative standard deviation values less than 5.7%. As a result of the inter-laboratory validation, the average recoveries between the two laboratories were 88.6~101.4% and the coefficient of variation was also below 15%. All optimized results were satisfied the criteria ranges requested in the Codex guidelines and Food Safety Evaluation Department guidelines. This study could serve as a reference for safety management relative to fenpropimorph residues in imported and domestic agricultural products.

Improvement of an Analytical Method for Methoprene in Livestock Products using LC-MS/MS (LC-MS/MS를 이용한 축산물 중 살충제 메토프렌의 잔류분석법 개선)

  • Park, Eun-Ji;Kim, Nam Young;Park, So-Ra;Lee, Jung Mi;Jung, Yong Hyun;Yoon, Hae Jung
    • Journal of Food Hygiene and Safety
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    • v.37 no.3
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    • pp.136-142
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    • 2022
  • The research aims to develop a rapid and easy analytical method for methoprene using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A simple, highly sensitive, and specific analytical method for the determination of methoprene in livestock products (beef, pork, chicken, milk, eggs, and fat) was developed. Methoprene was effectively extracted with 1% acetic acid in acetonitrile and acetone (1:1), followed by the addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. Subsequently, the lipids in the livestock sample were extracted by freezing them at -20℃. The extracts were cleaned using MgSO4, primary secondary amine (PSA), and octadecyl (C18), which were then centrifuged to separate the supernatant. Nitrogen gas was used to evaporate the supernatant, which was then dissolved in methanol. The matrix-matched calibration curves were constructed using 8 levels (1, 2.5, 5, 10, 25, 50, 100, 150 ng/mL) and the coefficient of determination (R2) was above 0.9964. Average recoveries spiked at three levels (0.01, 0.1, and 0.5 mg/kg), and ranged from 79.5-105.1%, with relative standard deviations (RSDs) smaller than 14.2%, as required by the Codex guideline (CODEX CAC/GL 40). This study could be useful for residue safety management in livestock products.

Study on High Sensitivity Metal Oxide Nanoparticle Sensors for HNS Monitoring of Emissions from Marine Industrial Facilities (해양산업시설 배출 HNS 모니터링을 위한 고감도 금속산화물 나노입자 센서에 대한 연구)

  • Changhan Lee;Sangsu An;Yuna Heo;Youngji Cho;Jiho Chang;Sangtae Lee;Sangwoo Oh;Moonjin Lee
    • Journal of the Korean Society of Marine Environment & Safety
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    • v.28 no.spc
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    • pp.30-36
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    • 2022
  • A sensor is needed to continuously and automatically measure the change in HNS concentration in industrial facilities that directly discharge to the sea after water treatment. The basic function of the sensor is to be able to detect ppb levels even at room temperature. Therefore, a method for increasing the sensitivity of the existing sensor is proposed. First, a method for increasing the conductivity of a film using a conductive carbon-based additive in a nanoparticle thin film and a method for increasing ion adsorption on the surface using a catalyst metal were studied.. To improve conductivity, carbon black was selected as an additive in the film using ITO nanoparticles, and the performance change of the sensor according to the content of the additive was observed. As a result, the change in resistance and response time due to the increase in conductivity at a CB content of 5 wt% could be observed, and notably, the lower limit of detection was lowered to about 250 ppb in an experiment with organic solvents. In addition, to increase the degree of ion adsorption in the liquid, an experiment was conducted using a sample in which a surface catalyst layer was formed by sputtering Au. Notably, the response of the sensor increased by more than 20% and the average lower limit of detection was lowered to 61 ppm. This result confirmed that the chemical resistance sensor using metal oxide nanoparticles could detect HNS of several tens of ppb even at room temperature.

A Study on the Recovery of Lithium from Secondary Resources of Ceramic Glass Containing Li-Al-Si by Ca-based Salt Roasting and Water Leaching Process (Li-Al-Si 함유 유리세라믹 순환자원으로부터 Ca계열 염배소법 및 이에 따른 수침출 공정에 의한 리튬의 회수 연구)

  • Sung-Ho Joo;Dong Ju Shin;Dongseok Lee;Shun Myung Shin
    • Resources Recycling
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    • v.32 no.1
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    • pp.42-49
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    • 2023
  • The glass ceramic secondary resource containing Li-Al-Si is used in inductor, fireproof glass, and transparent cookware and accounts for 14% of the total consumption of Li, which is the second most widely used after Li-ion batteries. Therefore, new Li resources should be explored when the demand for Li is exploding, and extensive research on Li recovery is needed. Herein, we recovered Li from fireproof Li-Al-Si glass ceramic, which is a new secondary resource containing Li. The fireproof glass among all Li-Al-Si glass ceramics was used as raw material that contained 1.5% Li, 9.4% Al, and 28.9% Si. The process for recovering Li from the fireproof glass was divided into two parts: (1) calcium salt roasting and (2) water leaching. In calcium salt roasting, a sample of fireproof glass was crushed and ground below 325 mesh. The leaching efficiency was compared based on the presence or absence of heat treatment of the fireproof glass. Moreover, the leaching rates based on the input ratios of calcium salt, Li-Al-Si glass, and ceramics and the leaching process based on calcium salt roasting temperatures were compared. In water leaching, the leaching and recovery rates of Li based on different temperatures, times, solid-liquid ratios, and number of continuous leaching stages were compared. The results revealed that fireproof glass ceramics containing Li-Al-Si should be heat treated to change phase to beta-type spodumene. CaCO3 salt should be added at a ratio of 6:1 with glass ceramics containing Li-Al-Si, and then leached 4 times or more to achieve a recovery efficiency of Li over 98% from a solution containing 200 mg/L of Li.

The progress in NF3 destruction efficiencies of electrically heated scrubbers (전기가열방식 스크러버의 NF3 제거 효율)

  • Moon, Dong Min;Lee, Jin Bok;Lee, Jee-Yon;Kim, Dong Hyun;Lee, Suk Hyun;Lee, Myung Gyu;Kim, Jin Seog
    • Analytical Science and Technology
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    • v.19 no.6
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    • pp.535-543
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    • 2006
  • Being used widely in semiconductor and display manufacturing, $NF_3$ is internationally considered as one of the regulated compounds in emission. Numerous companies have been continuously trying to reduce the emissions of $NF_3$ to comply with the global environmental regulation. This work is made to report the destruction and removal efficiency (DRE) of electrically heated scrubbers and the use rate in process chambers installed in three main LCD manufacturing companies in Korea. As the measurement techniques for $NF_3$ emission, mass flow controlled helium gas was continuously supplied into the equipment by which scrubber efficiency is being measured. The partial pressures of $NF_3$ and helium were accurately measured for each sample using a mass spectrometer, as it is emitted from inlet and outlet of the scrubber system. The results show that the DRE value for electrically heated scrubbers installed before 2004 is less than 52 %, while that for the new scrubbers modified based on measurement by scrubber manufacturer has been sigificentely improved upto more than 95 %. In additon, we have confirmed the efficiency depends on such variables as the inlet gas flow rate, water content, heater temperature, and preventative management period. The use rates of $NF_3$ in process chambers were also affected by the process type. The use rate of radio frequency source chambers, built in the $1^{st}$ and $2^{nd}$ generation process lines, was determined to be less than 75 %. In addition, that of remote plasma source chambers for the $3^{rd}$ generation was measured to be aboove 95 %. Therefore, the combined application of improved scrubber and the RPSC process chamber to the semiconductor and display process can reduce $NF_3$ emmision by 99.95 %. It is optimistic that the mission for the reduction of greenhouse gas emission can be realized in these LCD manufacturing companies in Korea.

Influence of Nutritional Supplementation to the Substrate on Vegetative and Reproductive Growth of Winter Mushroom, Flammulina velutipes (Curt. ex Fr.) Sing. and Chemical Changes of the substrates Produced during Growth of the Fungus (톱밥 배지(培地)에 대(對)한 영양첨가(營養添加)가 팽이버섯의 생장(生長)및 배지(培地)의 화학적(化學的) 성분(成分) 변화(變化)에 미치는 영향(影響))

  • Chang, Hak-Gil
    • The Korean Journal of Mycology
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    • v.4 no.1
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    • pp.31-44
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    • 1976
  • The studies were carried out to examine the effects of supplementation of nutritional substances and physical conditions in substrate on the mycelial growth and yield of fresh sporophores of winter mushroom, Flammulina velutipes(Curt. ex Fr.) Sing. and to obtain further informations on the nutritional requirements of the fungus with reference to improvement of substrate through [analysis of chemical composition of the substrates during the cultivation period. The results obtained are summarized as follows: 1. The best yield of fresh sporophores, 84.4 g per 280 g substrate in a bottle, was obtained from the mixture of poplar sawdust 10 and rice bran 3 by volume when Flammulina velutipes was cultivated on the poplar sawdust supplemented by rice bran, wheat bran, cattle manure and various combinations of these materials as nutrient sources. The substrates of poplar sawdust 10 plus rice bran 3 and 2 or wheat bran 3 with a higher yield of fresh sporophores showed a comparatively higher content of total nitrogen. total sugar, and potassium. 2. The mycelial growth of the fungus was compared on the substrates of poplar sawdust supplemented by the several nutrient sources and poplar sawdust alone. The fastest linear growth occurred on substrates of poplar sawdust alone and poplar sawdust plus cattle manure deficient in sugar and nitrogen sources, but mycelial density was more sparse on the substrates. Also, growth in a solution extracted from these substrates was very meager. 3. In the substrates which varied with bulk density and moisture content optimum bulk density and moisture content for mycelial growth was 0.2g/cc and 72% on a dry weight basis, respectively, but the highest yield of fresh sporophores was obtained at the bulk density of 0.3g/cc and moisture content of 67%. 4. By increasing the ratio of rice bran in poplar sawdust the loss of total weight and ash, content at each stage was increased, and during the cultivation period of 75 days, loss of total weight of the substrates at inoculation was 17.8 to 28.8% and ash content increased about 12%. 5. 11 to 14% of the cellulose and 3 to 4% of the lignin content per original substrate were decreased without a great difference depending of the mixing ratio of rice bran. The soluble glucose concentration in the substrates was increased during the same period. 6. In the process of vegetative and reproductive growth of the fungus upon the substrates, the total nitrogen was increased in quantity per dry weight of sample but was reduced in absolute quantity to a minute extent. There is no great changes in content of organic nitrogen including amino acid nitrogen, and hydrolysable ammonium nitrogen during the vegetative growth period, but occurrence of sporophores resulted in a decrease in the nitrogen content of these forms. On the one hand, by an increase of additive amounts of rice bran, nitrogen contents of these forms were higher and the reduction range during the reproductive growth period became wider. 7. Mycelial growth of the fungus was accelerated in various liquid media supplemented with organic nitrogen sources such as peptone and yeast extract in comparison with addition of inorganic nitrogen sources. Furthermore, mycelial growth was mere vigorous in the media with higher content of organic nitrogen sources.

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A Rheological Study on Creep Behavior of Clays (점토(粘土)의 Creep 거동(擧動)에 관한 유변학적(流變學的) 연구(研究))

  • Lee, Chong Kue;Chung, In Joon
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.1 no.1
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    • pp.53-68
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    • 1981
  • Most clays under sustained load exhibit time-dependent deformation because of creep movement of soil particles and many investigators have attempted to relate their findings to the creep behavior of natural ground and to the long-term stability of slopes. Since the creep behavior of clays may assume a variety of forms depending on such factors as soil plasticity, activity and water content, it is difficult and complicated to analyse the creep behavior of clays. Rheological models composed of linear springs in combination with linear or nonlinear dashpots and sliders, are generally used for the mathematical description of the time-dependent behavior of soils. Most rheological models, however, have been proposed to simulate the behavior of secondary compression for saturated clays and few definitive data exist that can evaluate the behavior of non-saturated clays under the action of sustained stress. The clays change gradually from a solid state through plastic state to a liquid state with increasing water content, therefore, the rheological models also change. On the other hand, creep is time-dependent, and also the effect of thixotropy is time-function. Consequently, there may be certain correlations between creep behavior and the effects of thixotropy in compacted clays. In addition, the states of clay depend on water content and hence the height of the specimen under drained conditions. Futhermore, based on present and past studies, because immediate elastic deformation occurs instantly after the pressure increment without time-delayed behavior, the factor representing immediate elastic deformations in the rheological model is necessary. The investigation described in this paper, based on rheological model, is designed to identify the immediate elastic deformations and the effects of thixotropy and height of clay specimens with varing water content and stress level on creep deformations. For these purposes, the uniaxial drain-type creep tests were performed. Test results and data for three compacted clays have shown that a linear top spring is needed to account for immediate elastic deformations in the rheological model, and at lower water content below the visco-plastic limit, the effects of thixotropy and height of clay specimens can be represented by the proposed rheological model not considering the effects. Therefore, the rheological model does not necessitate the other factors representing these effects. On the other hand, at water content higher than the visco-plastic limit, although the state behavior of clays is visco-plastic or viscous flow at the beginning of the test, the state behavior, in the case of the lower height sample, does not represent the same behavior during the process of the test, because of rapid drainage. In these cases, the rheological model does not coincide with the model in the case of the higher specimens.

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Development of a Simultaneous Analytical Method for Determination of Insecticide Broflanilide and Its Metabolite Residues in Agricultural Products Using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 살충제 Broflanilide 및 대사물질 동시시험법 개발)

  • Park, Ji-Su;Do, Jung-Ah;Lee, Han Sol;Park, Shin-min;Cho, Sung Min;Kim, Ji-Young;Shin, Hye-Sun;Jang, Dong Eun;Jung, Yong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.2
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    • pp.124-134
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    • 2019
  • An analytical method was developed for the determination of broflanilide and its metabolites in agricultural products. Sample preparation was conducted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and LC-MS/MS (liquid chromatograph-tandem mass spectrometer). The analytes were extracted with acetonitrile and cleaned up using d-SPE (dispersive solid phase extraction) sorbents such as anhydrous magnesium sulfate, primary secondary amine (PSA) and octadecyl ($C_{18}$). The limit of detection (LOD) and quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. The recovery results for broflanilide, DM-8007 and S(PFP-OH)-8007 ranged between 90.7 to 113.7%, 88.2 to 109.7% and 79.8 to 97.8% at different concentration levels (LOQ, 10LOQ, 50LOQ) with relative standard deviation (RSD) less than 8.8%. The inter-laboratory study recovery results for broflanilide and DM-8007 and S (PFP-OH)-8007 ranged between 86.3 to 109.1%, 87.8 to 109.7% and 78.8 to 102.1%, and RSD values were also below 21%. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food and Drug Safety Evaluation guidelines (2016). Therefore, the proposed analytical method was accurate, effective and sensitive for broflanilide determination in agricultural commodities.

The Variation of Natural Population of Pinus densiflora S. et Z. in Korea (III) -Genetic Variation of the Progeny Originated from Mt. Chu-wang, An-Myon Island and Mt. O-Dae Populations- (소나무 천연집단(天然集團)의 변이(變異)에 관(關)한 연구(硏究)(III) -주왕산(周王山), 안면도(安眠島), 오대산(五臺山) 소나무집단(集團)의 차대(次代)의 유전변이(遺傳變異)-)

  • Yim, Kyong Bin;Kwon, Ki Won
    • Journal of Korean Society of Forest Science
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    • v.32 no.1
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    • pp.36-63
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    • 1976
  • The purpose of this study is to elucidate the genetic variation of the natural forest of Pinus densiflora. Three natural populations of the species, which are considered to be superior quality phenotypically, were selected. The locations and conditions of the populations are shown in table 1 and 2. The morphological traits of tree and needle and some other characteristics were presented already in our first report of this series in which population and family differences according to observed characteristics were statistically analyzed. Twenty trees were sampled from each populations, i.e., 60 trees in total. During the autumn of 1974, matured cones were collected from each tree and open-pollinated seeds were extracted in laboratory. Immediately after cone collection, in closed condition, the morphological characteristics were measured. Seed and seed-wing dimensions were also studied. In the spring of 1975, the seeds were sown in the experimental tree nursery located in Suweon. And in the April of 1976, the 1-0 seedlings were transplanted according to the predetermined experimental design, randomized block design with three replications. Because of cone setting condition. the number of family from which progenies were raised by populations were not equal. The numbers of family were 20 in population 1. 18 in population 2 and 15 in population 3. Then, each randomized block contained seedlings of 53 families from 3 populations. The present paper is mainly concerned with the variation of some characteristics of cone, seed, needle, growth performance of seedlings, and chlorophyll and monoterpene compositions of needles. The results obtained are summerized as follows. 1. The meteorological data obtained by averaging the records of 30 year period, observed from the nearest station to each location of populations, are shown in Fig. 3, 4, and 5. The distributional pattern of monthly precipitation are quite similar among locations. However, the precipitation density on population 2, Seosan area, during growing season is lower as compared to the other two populations. Population 1. Cheong-song area, and population 3, Pyong-chang area, are located in inland, but population 2 in the western seacoast. The differences on the average monthly air temperatures and the average monthly lowest temperatures among populations can hardly be found. 2. Available information on the each mother trees (families) studied, such as age, stem height, diameter at breast height, clear-bole-length, crown conditions and others are shown in table 6,7, and 8. 3. The measurements of fresh cone weight, length and the widest diameter of cone are given in Tab]e 9. All these traits arc concerned with the highly significant population differences and family differences within population. And the population difference was also found in the cone-index, that is, length-diameter ratio. 4. Seed-wing length and seed-wing width showed the population differences, and the family differences were also found in both characteristics. Not discussed in this paper, however, seed-wing colours and their shapes indicate the specificity which is inherent to individual trees as shown in photo 3 on page 50. The colour and shape are fully the expression of genetic make up of mother tree. The little variations on these traits are resulted from this reason. The significant differences among populations and among families were found in those characteristics, such as 1000-seed weight, seed length, seed width, and seed thickness as shown in table 11. As to all these dimensions, the values arc always larger in population 1 which is younger in age than that of the other two. The population differences evaluated by cone, seed and seed-wing sizes could partly be attributed to the growth vigorousity. 5. The values of correlation between the characteristics of cone and seed are presented in table 12. As shown, the positive correlations between cone diameter and seed-wing width were calculated in all populations studied. The correlation between seed-wing length and seed length was significantly positive in population 1 and 3 but not in population 2, that is, the r-value is so small as 0.002. in the latter. The correlation between cone length and seed-wing length was highly significant in population 1, but not in population 2. 6. Differences among progenies in growth performances, such as 1-0 and 1-1 seedling height and root collar diameter were highly singificant among populations as well as families within population(Table 13.) 7. The heritability values in narrow sense of population characteristics were estimated on the basis of variance components. The values based on seedling height at each age stage of 1-1 and 1-0 ranged from 0.146 to 0.288 and the values of root collar diameter from 0.060 to 0.130. (Table 14). These heritability values varied according to characteristics and seedling ages. Here what must be stated is that, for calculation of heritability values, the variance values of population was divided by the variance value of environment (error) and family and population. The present authors want to add the heritability values based on family level in the coming report. It might be considered that if the tree age is increased in furture, the heritability value is supposed to be altered or lowered. Examining the heritability values studied previously by many authors, in pine group at age of 7 to 15, the values of height growth ranged from 0.2 to 0.4 in general. The values we obtained are further below than these. 8. The correlation between seedling growth and seed characteristics were examined and the values resulted are shown in table 16. Contrary to our hypothetical premise of positive correlation between 1-0 seedling height and seed weight, non-significance on it was found. However, 1-0 seedling height correlated positively with seed length. And significant correlations between 1-0 and 1-1 seedling height are calculated. 9. The numbers of stomata row calculated separately by abaxial and adaxial side showed highly significant differences among populations, but not in serration density. On serration density, the differences among families within population were highly significant. (Table 17) A fact must be noted is that the correlation between stomata row on abaxial side and adaxial side was highly significant in all populations. Non-significances of correlation coefficient between progenies and parents regarding to stomata row on abaxial side were shown in all populations studied.(Table 18). 10. The contents of chhlorophyll b of the needle were a little more than that of chlorophyll a irrespective of the populations examined. The differences of chlorophyll a, b and a plus b contents were highly significant but not among families within populations as shown in table 20. The contents of chlorophyll a and b are presented by individual trees of each populations in table 21. 11. The occurrence of monoterpene components was examined by gas liquid chromatography (Shimazu, GC-1C type) to evaluate the population difference. There are some papers reporting the chemical geography of pines basing upon monoterpene composition. The number of populations studied here is not enough to state this problem. The kinds of monoterpene observed in needle were ${\alpha}$-pinene, camphene, ${\beta}$-pinene, myrcene, limonene, ${\beta}$-phellandrene and terpinolene plus two unknowns. In analysis of monoterpene composition, the number of sample trees varied with population, I.e., 18 families for population 1, 15 for population 2 and 11 for population3. (Table 22, 23 and 24). The histograms(Fig. 6) of 7 components of monoterpene by population show noticeably higher percentages of ${\alpha}$-pinene irrespective of population and ${\beta}$-phellandrene in the next order. The minor Pinus densiflora monoterpene composition of camphene, myrcene, limonene and terpinolene made up less than 10 percent of the portion in general. The average coefficients of variation of ${\alpha}$-pinene and ${\beta}$-phellandrene were 11 percent. On the contrary to this, the average coefficients of variation of camphene, limonene and terpinolene varied from 20 to 30 percent. And the significant differences between populaiton were observed only in myrcene and ${\beta}$-phellandrene. (Table 25).

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