• Title/Summary/Keyword: CaO-$Al_2O_3-SiO_2$

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Quantitative Elemental Analysis in Soils by using Laser Induced Breakdown Spectroscopy(LIBS) (레이저유도붕괴분광법을 활용한 토양의 정량분석)

  • Zhang, Yong-Seon;Lee, Gye-Jun;Lee, Jeong-Tae;Hwang, Seon-Woong;Jin, Yong-Ik;Park, Chan-Won;Moon, Yong-Hee
    • Korean Journal of Soil Science and Fertilizer
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    • v.42 no.5
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    • pp.399-407
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    • 2009
  • Laser induced breakdown spectroscopy(LIBS) is an simple analysis method for directly quantifying many kinds of soil micro-elements on site using a small size of laser without pre-treatment at any property of materials(solid, liquid and gas). The purpose of this study were to find an optimum condition of the LIBS measurement including wavelengths for quantifying soil elements, to relate spectral properties to the concentration of soil elements using LIBS as a simultaneous un-breakdown quantitative analysis technology, which can be applied for the safety assessment of agricultural products and precision agriculture, and to compare the results with a standardized chemical analysis method. Soil samples classified as fine-silty, mixed, thermic Typic Hapludalf(Memphis series) from grassland and uplands in Tennessee, USA were collected, crushed, and prepared for further analysis or LIBS measurement. The samples were measured using LIBS ranged from 200 to 600 nm(0.03 nm interval) with a Nd:YAG laser at 532 nm, with a beam energy of 25 mJ per pulse, a pulse width of 5 ns, and a repetition rate of 10 Hz. The optimum wavelength(${\lambda}nm$) of LIBS for estimating soil and plant elements were 308.2 nm for Al, 428.3 nm for Ca, 247.8 nm for T-C, 438.3 nm for Fe, 766.5 nm for K, 85.2 nm for Mg, 330.2 nm for Na, 213.6 nm for P, 180.7 nm for S, 288.2 nm for Si, and 351.9 nm for Ti, respectively. Coefficients of determination($r^2$) of calibration curve using standard reference soil samples for each element from LIBS measurement were ranged from 0.863 to 0.977. In comparison with ICP-AES(Inductively coupled plasma atomic emission spectroscopy) measurement, measurement error in terms of relative standard error were calculated. Silicon dioxide(SiO2) concentration estimated from two methods showed good agreement with -3.5% of relative standard error. The relative standard errors for the other elements were high. It implies that the prediction accuracy is low which might be caused by matrix effect such as particle size and constituent of soils. It is necessary to enhance the measurement and prediction accuracy of LIBS by improving pretreatment process, standard reference soil samples, and measurement method for a reliable quantification method.

Residual Effects of Basic Oxygen Furnace Slag as Soil Conditioner in the Rice Paddy Field (논토양 벼 재배에서 제강슬래그의 토양개량제로서의 시용효과)

  • Lim, June-Taeg;Kim, Young-Sin;Park, Jn-Jin;Lee, Choong-Il;Hyun, Kyu-Hawn;Kwon, Byung-Sun;Kim, Hak-Jin
    • Korean Journal of Soil Science and Fertilizer
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    • v.33 no.3
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    • pp.205-211
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    • 2000
  • This study was conducted to evaluate the residual effects of basic oxygen furnace (BOF) slag applied in rice paddy fields as soil conditioner one year before. The experimental fields of Lim et al. (2000) located in Youjung and Nampyung were used for this purpose. Both variety (Oryza sativa L. cv. Dongjinbyeo) and cultural practices were the same as those in Lim et al. (2000). Soil chemical properties, plant height, number of tillers per plant, yield and yield components were observed. The temporal variation of treatment mean value in soil chemical properties appeared to be similar trends in both Youjung and Nampyung experimental fields. Soil pH and Ca content were still significantly higher than those in control treatment up to July of the second season, but decreased progressively as time passed. However, the effects lasted longer as slag rate became higher. BOF slag seems to have residual effects as a soil conditioner or Ca fertilizer in soil for two years. BOF slag rate of $4Mg\;ha^{-1}$ raised soil pH almost the same as lime rate of $2Mg\;ha^{-1}$. Content of $SiO_2$ in soil applied slag appeared to be higher compared with control. Fe and Mg content in soil with slag treatment was significantly higher than that of control in 1997, but it was almost the same level as that of control in 1998. In YouJung experimental field, rough rice yield of slag teatment became higher as slage rate incresed. Slag rate of $12Mg\;ha^{-1}$ showed the highest rough rice yield of $5,400kg\;ha^{-1}$ among treatment, which was 14% higher than that of control with $4,720kg\;ha^{-1}$. Slag rate of $12Mg\;ha^{-1}$ showed relatively higher plant height and higher number of tillers at the early growth stage compared with other treatments. In NamPyung experimental field, rough rice yield was the highest at the plot of lime rate $2Mg\;ha^{-1}$ and became higher as slag rate increased. There were no significant differences in rough rice yield between lime treatment and slag treatments. Slag rate of $12Mg\;ha^{-1}$ showed the highest rough rice yield of $7,170kg\;ha^{-1}$ among slag treatment, which was 8% significantly higher than that of control with $6,670kg\;ha^{-1}$. Slag rate of $12Mg\;ha^{-1}$ showed relatively slower growth in plant height at the early growth stage, but superior growth at the later growth stage, and significantly higher number of spiklets per panicle and 1000-grain weight than that of control.

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Skarn Formation in Metamorphic Rocks of the Chungju Mine Area (충주광산 지역 계명산층의 텅스텐 스카른화작용)

  • Kim, Gun-Soo;Park, Maeng-Eon
    • Economic and Environmental Geology
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    • v.28 no.3
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    • pp.185-197
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    • 1995
  • Tungsten skarns in the Chungju mine which consists mainly of strata-bound type iron ore deposits are found in the vicinity of the contact between the age-unknown Kyemeongsan Formation and granitic rock intrusions of Mesozoic age($134{\pm}2Ma$). Tungsten skarns were formed extensively from alumina and silica-rich schistose rocks by the introduction of calcium and iron from hydrothermal solution. The skarns comprise a metasomatic column and are subdivided into four facies; garnet facies, wollastonite facies, epidote facies and chlorite facies. The skarn process in time-evolutional trend can be divided broadly into the four facies in terms of the paragenetic sequence of calc-silicates and their chemical composition. Skarn and ore minerals were formed in the following sequence; (1) garnet facies, adjacent to biotite granite, containing mainly garnet(>Ad96) and magnetite, (2) wollastonite facies containing mainly wollastonite and garnet(Ad95~60), (3) epidote facies, containing mainly epidote(Ps35~31), quartz, andradite-grossular(Ad63~50), and scheelite, (4) chlorite facies, adjacent to and replacing schist, containing mainly chrolite, muscovite, quartz, calcite, epidote(Ps31~25), hematite and sulfides. The mineral assemblage and mineral compositions. suggest that the chemical potentials of Ca and Fe increased toward the granitic rock, and the component Al, Mg, K, and Si decreased from the host rock to granitic rock. The homogenization temperature and salinity of fluid inclusion in scheelite, quartz and epidote of epidote facies skarn is $300-400^{\circ}C$ and 3-8wt.% eqiv. NaCl, respectively. ${\delta}^{34}S$ values of pyrite and galena associated with chlorite facies skarn is $9.13{\sim}9.51%_{\circ}$ and $5.85{\sim}5.96%_{\circ}$, respectively. The temperature obtained from isotopic com· position of coexisting pyrite-galena is $283{\pm}20^{\circ}C$. Mineral assemblages and fluid inclusion data indicate that skarn formed at low $X_{CO_2}$, approximately 0.01. Temperature of the skarn mineralization are estimated to be in the range of $400^{\circ}C$ to $260^{\circ}C$ and pressure to be 0.5 kbar. The oxygen fugacity($fo_2$) of the skarn mineralization decreased with time. The early skarn facies would have formed at log $fo_2$ values of about -25 to -27, and late skarn facies would have formed at log $fo_2$ values of -28 to -30. The estimated physicochemical condition during skarn formation suggests that the principal causes of scheelite mineralization are reduction of the ore·forming fluid and a decrease in temperature.

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Metamorphism of the Gyeonggi Massif in the Gapyeong-Cheongpyeong area (가평-청평 지역 경기육괴의 변성작용)

  • Lee Kwang Jin;Cho Moonsup
    • The Journal of the Petrological Society of Korea
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    • v.1 no.1
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    • pp.1-24
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    • 1992
  • Precambrian metamorphic rocks of the Gapyeong-Cheongpyeong area consist of banded gneiss, augen gneiss, leucocratic gneiss, quartz schist and quartzite, together with minor intercalations of serpentinite, amphibolite and marble. Mineral assemblages of meta-sedimentary rocks are classified into three types: sillimanite-free; sillimanite-bearing; and sillimanite+K-feldspar-bearing assemblages. Compositions of metamorphic phases depend on the type of mineral assemblages. In particular, the Ca contents of plagioclase and garnet are high in sillimanite-free assemblges. Kyanite occurs in three samples, and coexists with sillimanite in one sample. The presence of kyanite indicates that metamorphic rocks of the study area have experienced the Barrovian type metamorphism. Peak metamorphic conditions estimated from various geothermobarometers and phase equilibria are 618-674$^{\circ}C$ and 6.5${\pm}$2.0 kbar for sillimanite-free assemblages, and 701-740$^{\circ}C$ and 4.4${\pm}$0.8 kbar for sillimanite-bearing assemblages, respectively. Furthermore, a clockwise P-T-time path is deduced for the study area, based on the following observations: (1) the polymorphic transition of kyanite to sillimanite, (2) the occurrence of sillimanite and K-feldspar belonging to the upper amphibolite facies, and finally (3) the retrograde metamorphism characterized by muscovite-, chlorite-, and actinolite-bearing assemblages.

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Crystal Structure of Fully Dehydrated Partially Cs+-Exchanged Zeolite X, Cs52Na40-X (The Highest Cs+-Exchanged Level Achieved by Conventional Method and Confirmation of Special Site Selectivity)

  • Bae, Myung-Nam
    • Bulletin of the Korean Chemical Society
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    • v.28 no.2
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    • pp.251-256
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    • 2007
  • The crystal structure of fully dehydrated partially Cs+-exchanged zeolite X, [Cs52Na40Si100Al92O384], a = 24.9765(10) A, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21 °C. The crystal was prepared by flow method for 5 days using exchange solution in which mole ratio of CsOH and CsNO3 was 1 : 1 with total concentration of 0.05 M. The crystal was then dehydrated at 400 °C and 2 × 10-6 Torr for 2 days. The structure was refined to the final error indices, R1 = 0.051 and wR2 (based on F2) = 0.094 with 247 reflections for which Fo > 4σ (Fo). In this structure, about fifty-two Cs+ ions per unit cell are located at six different crystallographic sites with special selectivity; about one Cs+ ion is located at site I, at the centers of double oxygen-rings (D6Rs), two Cs+ ions are located at site I', and six Cs+ ions are found at site II'. This is contrary to common view that Cs+ ions cannot pass sodalite cavities nor D6Rs because six-ring entrances are too small. Ring-opening by the formation of ?OH groups and ring-flexing make Cs+ ions at sites I, I', and II' enter six-oxygen rings. The defects of zeolite frameworks also give enough mobility to Cs+ ions to enter sodalite cavities and D6Rs. Another six Cs+ ions are found at site II, thirty-six are located at site III, and one is located at site III' in the supercage, respectively. Forty Na+ ions per unit cell are located at two different crystallographic sites; about fourteen are located at site I, the centers of D6Rs and twenty-six are also located at site II in the supercage. Cs+ ions and Na+ ions at site II are recessed ca. 0.34(1) A and 1.91(1) A into the supercage, respectively. In this work, the highest exchange level of Cs+ ions per unit cell was achieved in zeolite X by conventional aqueous solution methods and it was also shown that Cs+ ion could pass through the sixoxygen rings.

Studies on the Physico-chemical Properties and Characterization of Soil Organic Matter in Jeju Volcanic Ash Soil (제주도(濟州道) 화산회토양(火山灰土壌)의 이화학적(理化学的) 특성(特性) 및 유기물(有機物) 성상(性状)에 관(関)한 연구(硏究))

  • Lee, Sang-Kyu;Cha, Kyu-Seuk;Kim, In-Tak
    • Korean Journal of Soil Science and Fertilizer
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    • v.16 no.1
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    • pp.20-27
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    • 1983
  • A series of laboratory experiment was conducted to find out the chemical composition, characterization of humic substances by physical and chemical methods and reaction of Na-pyrophosphate, $Ca(OH)_2$ and rice straw with albumin on the degradation of soil organic matter in the volcanic ask soils of the Jeju Island. Results obtained were summarized as follows: 1. The contents of organic matter, available silicon, active iron and aluminum concentration in volcanic ash the soils were remarkably higher but available phosphorous was comparatively lower than the mineral soils. In volcanic ash soil, the contents of potassium, calcium and magnessium were higher in upland soil than that of forest soil. The ratios of active $Al^{{+}{+}{+}}/Fe^{{+}{+}}$, C/P and $K/Ca^+$ Mg were apparently high in volcanic ash soils while that of $SiO_2$/O.M. was high in mineral soil. 2. The carbon/nitrogen ratio in humin, humic acid content in organic matter, and carbon contents of humin in total carbon of soil organic matter were apparently higher in the volcanic ash soils than in the mineral soils, The total nitrogen and fractions of acid or alkali soluble nitrogen were remarkably high in volcanic ash soils while mineralizable nitrogen ($NH_4$-N and $NO_3$) contents were high in mineral soils. 3. The values of K600, RF and log K were also higher in volcanic ash soils than those in mineral soils, and the absorbance in the visible range were high and color was dark in the soil of which humification was progressed Extracted humic acid from volcanic ash soil was less reactive to the oxidizing chemical reagent and was persistance to the acid or alkali hydrolysises. 4. The major oxygen-containing functional groups in humic substances of volcanic ash soils were phenolic-OH alcoholic-OH and carboxyl groups while those in mineral soil were methoxyl and carbonyl groups. 5. Absorption spectra of alkaline solution of humic acid ranged from 200 nm to maxima 500 nm. Visible spectra peaks of from humic substances in the visible region were recognized at 350, 420, 450 and 480 nm. Only one single absorbance peak was observed in the visible region at 362 nm for Heugag series and two absorbance Peak were also at 360 nm and 390 nm for Yeungrag series. 6. Evolution of carbon as $Co_2$ was increased with addition of Na-pyrophosphate in Namweon and Heugag series, and "priming effects" took place on the soil organic matter decomposition by addition of rice straw with albumin in Ido series.

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