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Development of Analytical Method for the Determination and Identification of Unregistered Pesticides in Domestic for Orange and Brown Rice(I) -Chlorthal-dimethyl, Clomeprop, Diflufenican, Hexachlorobenzene, Picolinafen, Propyzamide- (식품공전 분석법 미설정 농약의 잔류분석법 확립(I) -Chlorthal-dimethyl, Clomeprop, Diflufenican, Hexachlorobenzene, Picolinafen, Propyzamide-)

  • Chang, Hee-Ra;Kang, Hae-Rim;Kim, Jong-Hwan;Do, Jung-A;Oh, Jae-Ho;Kwon, Ki-Sung;Im, Moo-Hyeog;Kim, Kyun
    • Korean Journal of Environmental Agriculture
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    • v.31 no.2
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    • pp.157-163
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    • 2012
  • BACKGROUND: For the safety of imported agricultural products, the study was conducted to develop the analytical method of unregistered pesticides in domestic. The analytical method of 6 pesticides, chlorthal-dimethyl, clomeprop, diflufenican, hexachlorobenzene, picolinafen, and propyzamide, for a fast multi-residue analysis were established for two different type crops, orange and brown rice by GC-ECD and confirmed by mass spectrometry. METHODS AND RESULTS: The analytical method was evaluated to limit of quantification, linearity and recoveries. The crop samples were extracted with acetonitrile and performed cleanup by liquid-liquid partition and Florisil SPE to remove co-extracted matrix. The extracted samples were analyzed by GC-ECD with good sensitivity and selectivity of the method. The limits of quantification (LOQ) range of the method with S/N ratio of 10 was 0.02~0.05 mg/kg for orange and brown rice. The linearity for targeted pesticides were $R^2$ >0.999 at the levels ranged from 0.05 to 10.0 mg/kg. The average recoveries ranged from 74.4% to 110.3% with the percentage of coefficient variation in the range 0.2~8.8% at two different spiking levels (0.02 mg/kg and 0.2 mg/kg, 0.05 mg/kg and 0.5 mg/kg) in brown rice. And the average recoveries ranged from 77.8% to 118.4% with the percentage of coefficient variation in the range 0.2~6.6% at two different spiking levels (0.02 mg/kg and 0.2 mg/kg, 0.05 mg/kg and 0.5 mg/kg) in orange. Final determination was by gas chromatography/mass spectrometry/selected ion monitoring (GC/MS/SIM) to identify the targeted pesticides. CONCLUSION: As a result, this developed analytical method can be used as an official method for imported agricultural products.

Development and Validation of an Analytical Method for Determination of Fungicide Tridemorph in Agricultural Commodities Using LC-MS/MS (LC-MS/MS를 이용한 농산물 중 살균제 tridemorph의 시험법 개발 및 검증)

  • Pak, Won-Min;Do, Jung-Ah;Lim, Seung-Hee;Park, Shin-Min;Yoon, Ji-Hye;Lee, Dong-seouk;Chang, Moon-Ik
    • Journal of Food Hygiene and Safety
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    • v.32 no.4
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    • pp.290-297
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    • 2017
  • The purpose of this study was developed for the determination of tridemorph in agricultural commodities samples. Tridemorph residues in samples were extracted with acetonitrile, partitioned with saline water, and then purified using and aminopropyl ($NH_2$) SPE catridge. The purified samples were quantified and confirmed via liquid chromatograph-tandem mass spectrometer (LC-MS/MS) in positive ion mode using multiple reaction monitoring (MRM). Matrix-matched calibration curves were linear over the calibration ranges (0.005~2.5 ng) into a blank extract with $r^2$ > 0.999. The limits of detection and quantification were 0.001 and 0.005 mg/kg, respectively. The average recovery ranged between 75.9% and 103.7% at different concentration levels (LOQ, 10 LOQ, 50 LOQ, n = 5) with relative standard deviations (RSDs) less than 9.0%. An interlaboratory study was conducted to validate the method by Korea Advanced Food Research Institute. The average recovery ranged between 87.0% and 109.2% at different concentration levels (LOQ, $10{\times}LOQ$, $50{\times}LOQ$, n = 5) with relative standard deviations (RSDs) less than 8.0%. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL40, 2003) and Food Safety Evaluation Department guidelines (2016). The results prove that the developed analytical methods is accurate, effective and sensitive for tridemorph determination.

Effects of Thermal Wastewater Effluent and Hydrogen Ion Potential (pH) on Water Quality and Periphyton Biomass in a Small Stream (Buso) of Pocheon Area, Korea (포천지역 계류 (부소천)의 수질과 부착조류 생물량에 온배수와 수소이온농도 (pH) 영향)

  • Jeon, Gyeonghye;Eum, Hyun Soo;Jung, Jinho;Hwang, Soon-Jin;Shin, Jae-Ki
    • Korean Journal of Ecology and Environment
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    • v.50 no.1
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    • pp.96-115
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    • 2017
  • Understanding effects of thermal pollution and acidification has long been a concern of aquatic ecologists, but it remains largely unknown in Korea. This study was performed to elucidate the effects of thermal wastewater effluent (TWE) and acid rain on water quality and attached algae in a small mountain stream, the Buso Stream, a tributary located in the Hantan River basin. A total of five study sites were selected in the upstream area including the inflowing point of hot-spring wastewater (HSW), one upstream site (BSU), and three sites below thermal effluent merged into the stream (1 m, 10 m and 300 m for BSD1, BSD2, and BSD3, respectively). Field surveys and laboratory analyses were carried out every month from December 2015 to September 2016. Water temperature ranged $1.7{\sim}28.8^{\circ}C$ with a mean of $15.0^{\circ}C$ among all sites. Due to the effect of thermal effluent, water temperature at HSW site was sustained at high level during the study period from $17.5^{\circ}C$ (January) to $28.8^{\circ}C$ (September) with a mean of $24.2{\pm}3.7^{\circ}C$, which was significantly higher than other sites. Thermal wastewater effluent also brought in high concentration of nutrients(N, P). The effect of TWE was particularly apparent during dry season and low temperature period (December~March). Temperature effect of TWE did not last toward downstream, while nutrient effect seemed to maintain in longer distance. pH ranged 5.1~8.4 with a mean of 6.9 among all sites during the study period. The pH decrease was attributed to seasonal acid rain and snow fall, and their effects was identified by acidophilic diatoms dominated mainly by Eunotia pectinalis and Tabellaria flocculosa during March and August. These findings indicated that water quality and periphyton assemblages in the upstream region of Buso Stream were affected by thermal pollution, eutrophication, and acidification, and their confounding effects were seasonally variable.

Development of Black Garlic Yakju and Its Antioxidant Activity (흑마늘 발효주 개발 및 항산화 활성)

  • Lee, Hyo-Hyung;Kim, Ig-Jo;Kang, Sang-Tae;Kim, Yeong-Hoon;Lee, Jeong-Ok;Ryu, Chung-Ho
    • Korean Journal of Food Science and Technology
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    • v.42 no.1
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    • pp.69-74
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    • 2010
  • Black garlic has recently received significant attention due to its various health functional properties, and there has been an increase in demand for its use as a functional food. This study was performed to determine the optimum concentration for the fermentation of black garlic yakju. In addition, the antioxidant activity of the fermented black garlic yakju was examined. The alcohol content in the black garlic yakju significantly increased for 6 days and the pH gradually increased as the concentration of black garlic increased. The reducing sugar content at each black garlic concentration was maximal when it was fermented for 24 hours, and then rapidly decreased at longer fermentation periods. The main organic acids were lactic, citric, malic and oxalic acid. Also, the lactic acid content increased as the concentration of the black garlic increased where as the content of other organic acids decreased. The total polyphenol content, ferric ion reducing antioxidant power (FRAP) activity and DPPH (1,1-diphenyl-2-picryl-hydrazyl) free radical scavenging activity of black garlic yakju increased as the concentration of black garlic increased. The sensory characteristics of fermented black garlic yakju were evaluated in terms of color, flavor, taste and overall acceptability, and the highest overall acceptability value was obtained for yakju containing a black garlic concentration of 1-3%. Therefore, the optimum concentration of black garlic was determined to be 1% for the production of high quality black garlic yakju.

Time Dependent Evaluation of Corrosion Free Life of Concrete Tunnel Structures Based on the Reliability Theory (해저 콘크리트 구조물의 신뢰성 이론에 의한 시간 의존적 내구수명 평가)

  • Pack, Seung Woo;Jung, Min Sun
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.15 no.3
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    • pp.142-154
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    • 2011
  • This study predicted the probability of corrosion initiation of reinforced concrete tunnel boxes structures using the Monte Carlo Simulation. For the inner wall and outer wall in the tunnel boxes, exposed to airborne chloride ion and seawater directly respectively, statistical values of parameters like diffusion coefficient D, surface chloride content $C_s$, cover depth c, and the chloride threshold level $C_{lim}$ were examined from experiment or literature review. Their average values accounted for $3.77{\times}10^{-12}m^2/s$, 3.0% by weight of cement, 94.7mm and 45.5mm for outer wall and inner wall, respectively, and 0.69% by weight of cement for D, $C_s$, c, and $C_{lim}$, respectively. With these parametric values, the distribution of chloride contents at rebar with time and the probability of corrosion initiation of the tunnel boxes, inner wall and outer wall, was examined by considering time dependency of chloride transport. From the examination, the histogram of chloride contents at rebar is closer to a gamma distribution, and the mean value increases with time, while the coefficient of variance decreases with time. It was found that the probability of corrosion initiation and the time to corrosion were dependent on the time dependency of chloride transport. Time independent model predicted time to corrosion initiation of inner wall and outer wall as 8 and 12 years, respectively, while 178 and 283 years of time to corrosion was calculated by time dependent model for inner wall and outer wall, respectively. For time independent model, the probability of corrosion at 100 years of exposure for inner wall and outer wall was ranged 59.5 and 95.5%, respectively, while time dependent model indicated 2.9 and 0.2% of the probability corrosion, respectively. Finally, impact of $C_{lim}$, including values specified in current codes, on the probability of corrosion initiation and corrosion free life is discussed.

A STUDY ON IN VIVO AND IN VITRO AMALGAM CORROSION (아말감의 구강내 부식 및 인공 부식에 관한 연구)

  • Lim, Byong-Mok;Kwon, Hyuk-Choon;Um, Chung-Moon
    • Restorative Dentistry and Endodontics
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    • v.22 no.1
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    • pp.1-33
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    • 1997
  • The objective of this study was to analyze the in vitro and in vivo corrosion products of low and high copper amalgams. The four different types of amalgam alloy used in this study were Fine cut, Caulk spherical, Dispersalloy, and Tytin. After each amalgam alloy and Hg were triturated according to the directions of the manufacturer by means of the mechanical amalgamator(Amalgam mixer. Shinhung Co. Korea), the triturated mass was inserted into a cylindrical metal mold which was 12mm in diameter and 10mm in height. The mass was condensed by 150Kg/cm compressive force. The specimen was removed from the mold and aged at room temperature for about seven days. The standard surface preparation was routinely carried out by emery paper polishing under running water. In vitro amalgam specimens were potentiostatically polarized ten times in a normal saline solution at $37^{\circ}C$(potentiostat : HA-301. Hukuto Denko Corp. Japan). Each specimen was subjected to anodic polarization scan within the potential range -1700mV to+400mV(SCE). After corrosion tests, anodic polarization curves and corrosion potentials were obtained. The amount of component elements dissolved from amalgams into solution was measured three times by ICP AES(Inductive Coupled Plasma Atomic Emission Spectrometry: Plasma 40. Perkim Elmer Co. U.S.A.). The four different types of amalgam were filled in occlusal and buccal class I cavities of four human 3rd molars. After about five years the restorations were carefully removed after tooth extraction to preserve the structural details including the deteriorated margins. The occlusal surface, amalgam-tooth interface and the fractured surface of in vivo amalgam corrosion products were analyzed. In vivo and in vitro amalgam specimens were examined and analyzed metallographically by SEM(Scanning Electron Microscope: JSM 840. Jeol Co. Japan) and EDAX(Energy Dispersive Micro X-ray Analyser: JSM 840. Jeol Co. Japan). 1. The following results are obtained from in vitro corrosion tests. 1) Corrosion potentials of all amalgams became more noble after ten times passing through the in vitro corrosion test compared to first time. 2) After times through the test, released Cu concentration in saline solution was almost equal but highest in Fine cut. Ag and Hg ion concentration was highest in Caulk spherical and Sn was highest in Dispersalloy. 3) Analyses of surface corrosion products in vitro reveal the following results. a)The corroded surface of Caulk spherical has Na-Sn-Cl containing clusters of $5{\mu}m$ needle-like crystals and oval shapes of Sn-Cl phase, polyhedral Sn oxide phase. b)In Fine cut, there appeared to be a large Sn containing phase, surrounded by many Cu-Sn phases of $1{\mu}m$ granular shapes. c)Dispersalloy was covered by a thick reticular layer which contained Zn-Cl phase. d)In Tytin, a very thin, corroded layer had formed with irregularly growing Sn-Cl phases that looked like a stack of plates. 2. The following results are obtained by an analysis of in vivo amalgam corrosion products. 1) Occlusal surfaces of all amalgams were covered by thick amorphous layers containing Ca-P elements which were abraded by occlusal force. 2) In tooth-amalgam interface, Ca-P containing products were examined in all amalgams but were most clearly seen in low copper amalgams. 3) Sn oxide appeared as a polyhedral shape in internal space in Caulk spherical and Fine cut. 4) Apical pyramidal shaped Sn oxide and curved plate-like Sn-Cl phases resulted in Dispersalloy. 5) In Tytin, Sn oxide and Sn hydroxide were not seen but polyhedral Ag-Hg phase crystal appeared in internal space which assumed a ${\beta}_l$ phase.

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Hydrogeochemical Characteristics and Contamination of Dissolved Major ions and Heavy Metals in Waters and Sediments from the Tancheon River (탄천의 하상퇴적물과 하천수내 주요 용존 이온과 중금속의 수리지구화학적 특성과 오염)

  • 이성은;김규한;이진수;전효택
    • Economic and Environmental Geology
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    • v.35 no.1
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    • pp.25-41
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    • 2002
  • In order to investigate the hydrogeochemical characteristics and contamination of dissolved major ions and heavy metals in the Tancheon River, river water and sediment samples were collected at 18 locations, along a distance of 69 km, between Yongin-si in Kyunggi-do and Samsung-dong in Seoul on October in 2000 and April in 2001. After appropriate sample preparation, waters were analyzed for the dissolved constituents and sediments. The pH values of river waters were in the range of 7.0 to 9.3 and could be plotted in the area of surface environment. The level of $Ca^{2+}$, , CI-, sol-, N0$_{3}$ and HC0$_{3}$ in the Tancheon River were higher than those in world average river water. Most of dissolved constituents in the river waters increased toward downstream from upstream. In particular, high concentrations of Zn2+, Na$_{+}$, CI$^{-}$, SO$_{4}^{2-}$ and N03- were found near densely residential areas and the Sungnam waste water treatment plant. The relative ion enrichment was caused by the inflow of local domestic and industrial sewages. Also, Ca2+ and HC03- concentrations were enriched in the middle of the Tancheon River due to the dissolution of cements. This indicates that the apartment complexes were built on a large scale in the upriver since these ten years and large amounts of construction materials such as cements were flowed into the Tancheon River. Concentrations of heavy metals (Mn, Cd, Cu, Pb, Zn) in sediments from the Tancheon River exceeded the lower limit of tolerence level in bottom sediment established by the Ontario Ministry of the Environment (OME) of Canada. In particular, these metals were highly elevated in sediment (TSM-12) collected from near the Sungnam waste water treatment plant. Heavy metals were higher enriched in sediments collected from dry period rather than wet period.

Hydrogeochemistry of Groundwater Occurring in Complex Geological Environment of Yeongdong Area, Chungbuk, Korea (충북 영동군 복합 지질지역에서 산출되는 지하수의 수리지화학적 특성)

  • Moon, Sang-Ho
    • Economic and Environmental Geology
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    • v.50 no.6
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    • pp.445-466
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    • 2017
  • Yeongdong area is located in the contact zone between central southeastern Ogcheon belt and Yeongnam massif, in which Cretaceous Yeongdong basin exists. Therefore, the study area has complex geological environment of various geological age and rock types such as Precambrian metamorphic rocks, age-unknown Ogcheon Supergroup, Paleozoic/Mesozoic sedimentary rocks, Mesozoic igneous rocks and Quaternary alluvial deposits. This study focuses on the link between the various geology and water type, and discussed the source of some major ions and their related water-rock interaction. For this study, the field parameters and ion concentrations for twenty alluvial/weathered and eighty bedrock aquifer wells were used. Statistical analysis indicates that there was no significant differences in groundwater quality between wet and dry seasons. Although various types were observed due to complex geology, 80 to 84 % of samples showed $Ca-HCO_3$ water type. Some wells placed in alluvial/weathered aquifers of Precambrian metamorphic and Jurassic granitic terrains showed somewhat elevated $NO_3$ and Cl concentrations. $Mg-HCO_3$ typed waters prevailed in Cretaceous Yeongdong sedimentary rocks. The deeper wells placed in bedrock aquifers showed complicated water types varying from $Ca-HCO_3$ through $Ca-Cl/SO_4/NO_3$ to $Na-HCO_3$ and Na-Cl type. Groundwater samples with $Na-HCO_3$ or Na-Cl types are generally high in F concentrations, indicating more influences of water-rock interaction within mineralized/hydrothermal alteration zone by Cretaceous porphyry or granites. This study revealed that many deep-seated aquifer had been contaminated by $NO_3$, especially prominent in Jurassic granites area. Based on molar ratios of $HCO_3/Ca$, $HCO_3/Na$, Na/Si, it can be inferred that Ca and $HCO_3$ components of most groundwater in alluvial/weathered aquifer wells were definitely related with dissolution of calcite. On the other hand, Ca and $HCO_3$ in bedrock aquifer seem to be due to dissolution of feldspar besides calcite. However, these molar ratios require other mechanism except simple weathering process causing feldspar to be broken into kaolinite. The origin of $HCO_3$ of some groundwater occurring in Cretaceous Yeongdong sedimentary rock area seems to be from dissolution of dolomite($MgCO_3$) or strontianite($SrCO_3$) as well.

Analysis and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in seafood from oil contaminated bay (유류 오염지역의 수산물 중 다환방향족탄화수소류 (PAHs) 분석 및 위해평가)

  • Jeong, Ji-Yoon;Choi, Chan-Woong;Ryeom, Tai-Kyung;Cho, Kyoung-Hee;Park, Se-Ryung;Shin, Ho-Sang;Lee, Kwang-Ho;Lee, Hyo-Min
    • Analytical Science and Technology
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    • v.23 no.2
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    • pp.187-195
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    • 2010
  • To assess health risk for the intake among residents after the Hebei Spirit oil spill, 16 Polycyclic Aromatic Hydrocarbons (PAHs) in seafood samples from oil contaminated bay were determined by Gas Chromatography-Mass Spectrometry (GC-MSD) and samples were personally collected and purchased by residents. Samples were hydrolyzed with KOH and extracted with methylene chloride. The extracted solution were cleaned up using silica/florisil column and 16 PAHs were eluted by methylene chloride : n-hexane (1:9) mixture and determined by GC-MSD in Selected Ion Monitoring (SIM) mode. The mean recoveries for 16 PAHs ranged from 79% to 85%. The 16 PAHs levels in 126 samples ranged from 0.17 to $6.04\;{\mu}g$/kg and the TEQBaP (Toxic EQuivalents) levels in 126 samples were calculated using benzo(a)pyrene toxic equivalency factor for individual 16 PAHs and ranged from 0 to $0.91\;{\mu}gTEQ$/kg. The average Benzo(a)pyrene dietary exposure of residents was $5.5{\times}10^{-8}\;mg/kg$ bw/day and the average PAHs chronic dietary exposure was $1.3{\times}10^{-5}\;mg$ TEQ/kg bw/day. The margin of exposure (MOE) and the excess cancer risk and were $1.8{\times}10^6$ and $9.8{\times}10^{-8}$, respectively. Therefore, the assessment result was considered as low concern for health risk.

Risk Analysis of Inorganic Arsenic in Foods (식품 중 무기비소의 위해 분석)

  • Yang, Seung-Hyun;Park, Ji-Su;Cho, Min-Ja;Choi, Hoon
    • Journal of Food Hygiene and Safety
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    • v.31 no.4
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    • pp.227-249
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    • 2016
  • Arsenic and its compounds vary in their toxicity according to the chemical forms. Inorganic arsenic is more toxic and known as carcinogen. The provisional tolerable weekly intake (PTWI) of $15{\mu}g/kg$ b.w./week established by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) has been withdrawn, while the EFSA panel suggested $BMDL_{0.1}$ $0.3{\sim}8{\mu}g/kg\;b.w./day$ for cancers of the lung, skin and bladder, as well as skin lesions. Rice, seaweed and beverages are known as food being rich in inorganic arsenic. As(III) is the major form of inorganic arsenic in rice and anaerobic paddy soils, while most of inorganic arsenic in seaweed is present as As(V). The inorganic arsenic in food was extracted with solvent such as distilled water, methanol, nitric acid and so on in heat-assisted condition or at room temperature. Arsenic speciation analysis was based on ion-exchange chromatography and high-performance liquid chromatography equipped with atomic absorption spectrometry and inductively coupled plasma mass spectrometry. However, there has been no harmonized and standardized method for inorganic arsenic analysis internationally. The inorganic arsenic exposure from food has been estimated to range of $0.13{\sim}0.7{\mu}g/kg$ bw/day for European, American and Australian, and $0.22{\sim}5{\mu}g/kg$ bw/day for Asian. The maximum level (ML) for inorganic arsenic in food has established by EU, China, Australia and New Zealand, but are under review in Korea. Until now, several studies have conducted for reduction of inorganic arsenic in food. Inorganic arsenic levels in rice and seaweed were reduced by more polishing and washing, boiling and washing, respectively. Further research for international harmonization of analytical method, monitoring and risk assessment will be needed to strengthen safety management of inorganic arsenic of foods in Korea.