This study explored an efficient modified Quick, Easy, Cheap, Effective, Rugged and safe (QuEChERS) method combined with liquid chromatography-electrospray ionization with tandem mass spectrometric detection for the analysis of residues of 76 pesticides in brown rice, barley and corn including acidic sulfonylurea herbicides. Formic acid (1%) acid in acetonitrile and dispersive solid phase extractions used for extraction of pesticides and clean-up of the extract respectively. Two fortified spikes at 50 and 200 ng $g^{-1}$ levels were performed for recovery test. Mean recoveries of majority of pesticides at two spike levels ranged from 73.2 to 132.2, 80.9 to 136.8, 66.6 to 143.5 for brown rice, barley and corn respectively with standard error (CV) less than 10%. Good linearity of calibration curves were achieved with $R^2$ > 0.9907 within the observed concentration ranged. The modified method also provided satisfactory results for sulfonylurea herbicides. The method was applied to the determination of residues of target pesticides in real samples. A total of 26 pesticides in 36 out of 98 tasted samples were observed. The highest concentration was observed for tricyclazole at 1.17 mg $kg^{-1}$ in brown rice. This pesticide in two brown rice samples exceeded their MRLs regulated for rice in republic of Korea. Except tricyclazole none of the observed pesticides' concentration was higher than their MRLs. The results reveal that the method is effectively applicable to routine analysis of residues of target pesticides in brown rice, barley and corn.
Chemical assessment of soil pollution with heavy metals was made by analyzing the changes in pH, ionic strength, cationic concentration and chemical species in the soil solution. Saturated pastes of the unpolluted soils were made by adding solutions containing Cu or Cd and the final Cu or Cd concentrations were in the range of 0 to 400 mg/kg. After equilibrating for 24 hours at $25^{\circ}C$, the soil solution was extracted from the saturated pastes by the vacuum extraction method and analyzed for pH, electrical conductivity, Cu, Cd, cations and inorganic ligands. Chemical species in soil solution were calculated by the GEOCHEM-PC program employing the input variables of pH, ionic strength(${\mu}$), molar concentrations of cations and ligands. Increasing Cu or Cd additions lowered pH of the soil solution but increased concentrations of Ca, Mg and K resulting in increases of ${\mu}$ of the soil solution. Effects of Cu on lowering pH and increasing ${\mu}$ were greater than those of Cd. Concentrations of Cu or Cd in soil solution were relatively very low as compared to those of additions, but increased linearly with increasing additions representing that concentrations of Cu were higher than those of Cd. At 400 mg/kg additions, concentrations of Cu were in the range of 0.51 to 11.70 mg/L but those of Cd were 34.4 to 88.5 mg/L. Major species of Ca, Mg and K were free ions and these species were equivalent to greater than 95 molar % of the existing respective molar concentrations. These cationic species were not changed by Cu or Cd additions. Major species of Cu in lower pH soils such as SiCL and SL were free $Cu^{2+}$ (>95 molar %), but those in LS having a higher pH were free $Cu^{2-}$ and Cu-hydroxide complex. At 100 mg Cu/kg treatment, $Cu^{2+}$ and Cu-hydroxide complex were equivalent to 73 and 22.4 molar %, respectively. These respective percentages were decreased and increased correspondingly with increasing Cu treatments. Major species of Cd in soil solution were free $Cd^{2+}$ and Cd-chloride complex, representing 79 to 85 molar % for $Cd^{2+}$ and 13 to 20% for Cd-chloride complex at 10 mg Cd/kg treatment. With increasing Cd additions to 400 mg/kg, $Cd^{2+}$ species decreased to $40{\sim}47%$ but Cd-chloride complexes increased to $53{\sim}60$ molar %. These results demonstrated that soil contamination with heavy metals caused an adverse effect on the plant nutritional aspects of soil solution by lowering pH, increasing cations temporarily, and increasing free metal concentrations and species enough to be phytotoxic.
Jo, WooJin;Jeong, SooHwa;Park, SungJin;Choi, YoungTai;Lee, DongHyun
Korean Chemical Engineering Research
/
v.53
no.6
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pp.783-791
/
2015
A fluidized-bed reactor with an inside diameter of 0.1 m and a height of 1.2 m was used to study the effect of steam and catalyst additions to air-blown biomass gasification on the production of producer gas. The equipment consisted of a fluidized bed reactor, a fuel supply system, a cyclone, a condenser, two receivers, steam generator and gas analyzer. Silica sand with a mean particle diameter of $380{\mu}m$ was used as a bed material and calcined dolomite ($356{\mu}m$), which is effective in tar reduction and producer gas purification, was used as the catalyst. Both of Korea wood pellet (KWP) and a pellet form of EFB (empty fruit bunch) which is the byproduct of Southeast Asia palm oil extraction were examined as biomass feeds. In all the experiments, the feeding rates were 50 g/min for EFB and 38 g/min for KWP, respectively at the reaction temperature of $800^{\circ}C$ and an ER (equivalence ratio) of 0.25. The mixing ratio (0~100 wt%) of catalyst was applied to the bed material. Air or an air-steam mixture was used as the injection gas. The SBR (steam to biomass ratio) was 0.3. The composition, tar content, and lower heating value of the generated producer gas were measured. The addition of calcined dolomite decreased tar content in the producer gas with maximum reduction of 67.3 wt%. The addition of calcined dolomite in the air gasification reduced lower heating value of the producer gas. However The addition of calcined dolomite in the air-steam gasification slightly increased its lower heating value.
In order to understand the chemical binding forms of Cd in terms of its binding strength in wood, the radial distribution of it through dendroanalysis and its different chemical fractions in trunk wood of mature red pine(Pinus densiflora L.) trees grown in a relatively unpolluted area, in Kangwon-Province, were examined. Total Cd concentration in stem wood was determined by dry digestion and $H_2O$ and 0.01 M solutions of citric acid, malic acid, $CaCl_2$, $MgCl_2$, $Na_2EDTA$ were used as extracting solutions for Cd. Extracting efficiencies of applied solutions were expressed as % of Cd concentration extracted by $Na_2EDTA$ which extracted all Cd instead of Cd total concentration. Total concentration of Cd decreased from the innermost rings near pith towards the the outermost rings near cambium. Especially through the transition zone this tendency was observed clearly. $H_2O$ was the least effective extractant of Cd, then extracting efficiency increased in the order $MgCl_2$ < $CaCl_2$$Na_2EDTA$ (extracted all Cd). According to the radial position, extracting efficiency of Cd was ranging from 7 to 30% by $H_2O$ and even from 60 to 95% by citric acid. The Cd extracting efficiencies of $H_2O$ and organic acids increased continuously from the stem center to outermost annual rings, whereas salts showed somewhat different tendency, suddenly decreasing near the outermost ring. The results are discussed with regard to the different chemical binding forms of Cd and the mobility of Cd in wood and comparable with ones in previous studies on Pinus sylvestris and Quercus patraea. According to the results, usefulness of radial distribution pattern of Cd in pine tree trunks for retrosective biomonitoring is questioned.
Composting animal manure is one of feasible treatments that reserves some portion of nutrients of manure. Although the application of compost to arable land has many advantages, the repeated cultivation of the agriculture land will accumulate the level of heavy metals in the soil which is potentially hamful to people and animals. Therefore it is important to know the characteristics concentration and species of heavy metals in a variety of chemical fonns than just total content of the metal. Because the metals in different forms have different mobilities and bioavailabilites. The aim of this study was to examine the total content and the chemical forms of the heavy metals; Cr, Ni, Cu, Zn, As, Cd and Pb in the animal manure composted with sawdust or rice hull as a bulking agent. A total of 75 compost samples were collected throughout the country and classified into the three groups in accordance with the characteristics of raw materials: swine manure, poultry manure, and mixed(swine + poultry + cattle)manure. The compost samples were analyzed for total metal content and fractionated by sequential chemical extractions to estimate the quantities of metals: exchangeable, adsorbed, organically bound, carbonate and residual. The results showed that the heavy metal concentrations in all compost samples were lower than the maximum acceptable limits by the Korea Compost Quality Standards. The concentrations of heavy metals in the swine manure compost were higher than those of both the poultry and the mixed manure compost except for Cr. Zn and Cu concentrations of three different compost ranged from 157 to 839 mg Zn/kg DM(dry matter) and from 47 to 458 mg Cu/kg DM, depending on the composition of animal manures. The predominant forms for extracted metals were Cr, Ni, Zn, As and Ph, residual; Cu, organic; and Cd, carbonate. The results suggested that the legal standards for composts should be reexamined to revise the criteria on the total metal content as well as metal speciation.
This study was conducted to investigate the effect of maturity scores [2 (bull), 2 (steer), 3-9 (cow)] and the number of extractions (up to 4 times) on the chemical properties of water extract from Hanwoo shank bones (arm, fore shank, round and hind shank). The turbidity, meat color (CIE L value), collagen, protein, caloric and chondroitin sulfate contents of samples were observed. The turbidity and lightness were higher for water extract of Hanwoo shank bones with a maturity score of 2 (bull and steer) than maturity scores of 3-9 (cow) (p<0.05). The turbidity and lightness of water extract from shank bones of all Hanwoo maturity scores significantly increased with the 1st and 2nd extractions, but significantly decreased with 3rd and 4th extractions (p<0.05). The collagen and protein contents were highest for water extract from Hanwoo shank bones of maturity score 2 (bull and steer) (p<0.05). The caloric and chondroitin sulfate contents were higher for water extract from Hanwoo shank bones of maturity score 2 (bull and steer) than maturity scores of 3-9 (cow) (p<0.05). As the number of extractions increased, the chondroitin sulfate content significantly decreased (p<0.05). Based on these results, differences correlating with maturity scores were found only with collagen and protein contents. Therefore, further studies should be considered to address whether different maturity scores affect the price of shank bones in the meat industry.
Fluoxastrobin a fungicide developed from Strobilurus species mushroom extracts, can be used as an effective pesticide to control fungal diseases. In this study, we optimized the extraction and purification of fluoxastrobin according to its physical and chemical properties using the QuEChERS method and developed an LC-MS/MS-based analysis method. For extraction, we used acetonitrile as the extraction solvent, along with MgSO4 and PSA. The limit of quantitation of fluoxastrobin was 0.01 mg/kg. We used 0.01, 0.1, and 0.5 mg/kg of five representative agricultural products and treated them with fluoxastrobin. The coefficients of determination (R2) of fluoxastrobin and fluoxastrobin Z isomer were > 0.998. The average recovery rates of fluoxastrobin (n=5) and fluoxastrobin Z isomer were 75.5-100.3% and 75.0-103.9%, respectively. The relative standard deviations (RSDs) were < 5.5% and < 4.3% for fluoxastrobin and fluoxastrobin Z isomer, respectively. We also performed an interlaboratory validation at Gwangju Regional Food and Drug Administration and compared the recovery rates and RSDs obtained for fluoxastrobin and fluoxastrobin Z isomer at the external lab with our results to validate our analysis method. In the external lab, the average recovery rates and RSDs of fluoxastrobin and fluoxastrobin Z isomer at each concentration were 79.5-100.5% and 78.8-104.7% and < 18.1% and < 10.2%, respectively. In all treatment groups, the concentrations were less than those described by the 'Codex Alimentarius Commission' and the 'Standard procedure for preparing test methods for food, etc.'. Therefore, fluoxastrobin is safe for use as a pesticide.
Hyun, Sun Hee;Kim, Eun Sun;Lee, Sang Min;Kyung, Jong Soo;Lee, Sang Myung;Lee, Jong Won;Kim, Mee Ree;Hong, Jin Tae;Kim, Young Sook
Journal of the Korean Society of Food Science and Nutrition
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v.43
no.11
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pp.1665-1673
/
2014
The objective of this study was to compare the compositions and immuno-enhancing effects of 6-year-old red ginseng powder (RGP) with those of its fractions. RGP was subjected to extraction with 100% ethanol to obtain an ethanol fraction (E) and residue 1 (R1). Then, R1 was subjected to extraction with distilled water to obtain water fraction (W) and residue 2 (R2). Chemical compositions were as follows: 4.94% acidic polysaccharides and 1.56% ginsenosides (amounts of Rg1, Re, Rf, Rg2, Rb1, Rc, Rd, and Rg3) in RGP, 0.11% acidic polysaccharides and 6.99% ginsenosides in E, 4.93% acidic polysaccharides and 0.40% ginsenosides in R1, 0.50% acidic polysaccharides and 0.30% ginsenosides in R2, and 7.46% acidic polysaccharides and 0.61% ginsenosides in W. Immuno-enhancing effects of fractions from RGP were examined based on suppression of immune responses by cyclophosphamide. In the first fraction test, the antibody response to SRBCs increased significantly in the R1-treated group, but not the E-treated group. In the second fraction test, W showed higher immuno-enhancing effect than R1 and R2. W, which contained the highest amount of acidic polysaccharides, restored numbers of T and B cells, macrophages, as well as $CD4^+$ and $CD8^+$ T cells in the spleen suppressed by cyclophosphamide. These results suggest that acidic polysaccharides from red ginseng may be more effective than saponin in enhancing immune functions and reducing immunotoxicity of cyclophosphamide.
To compare heavy metal phytoavailability in paddy soils near five abandoned mining areas, 4 different soil extractants such as 0.1M-HCl, $0.1M-HNO_3$, 0.05M-EDTA, and 0.005M-DTPA were used. Total acid digestion method $(H_2SO_4:HClO_4:HNO_3)$ was also employed to analyze heavy metal content in 30 paddy soils and brown rice. The rates of extracted heavy metal to total content were in the range of $12.1{\sim}39.1%$ for Cd, $20.5{\sim}45.5%$ for Cu, $10.6{\sim}30.7%$ for Pb, and $6.7{\sim}13.0%$ for Zn. 0.1M-HCl and $0.1M-HNO_3$ extractable both Cu and Pb were relatively less extracted at the high soil pH and extractable calcium site(Mine D) whereas 0.05M-EDTA and 0.005M-DTPA extractable Pb were strongly extracted at the same soils. In case of Cd, Cu, and Zn in soil, 4 types of extractable heavy metals and total content were highly correlated with each other. However, there were positive correlations between 0.1 M-HCl and $0.1M-HNO_3$ extractable Pb as well as between 0.05M-EDTA and 0.005M-DTPA extractable Pb, which were relatively similar extractants in chemical properties. The rates of heavy metals in brown rice to total contents in soils were in the order Zn>Cd>Cu>Pb. Specially, the rate of Cd, Pb, and Zn were lower at the highest level of soil pH and Ex. Ca. Both Cd and Zn in brown rice were positively correlated with those of all soil extractants. It was estimated that the solubility following to the plant uptake of Cd and Zn were higher than those of Cu and Pb considering relationships between all kinds of heavy metal contents in soil and those in brown rice.
The objectives of this study we to assess the extent and degree of environmental contamination and to draw general conclusions on the fate of toxic elements derived from mining activities in Korea. 인t abandoned mines with four base-metal mines and four Au-Ag mines were selected and the results of environmental surveys in those areas were discussed. In the base-metal mining areas, the Sambo Pb-Zn-barite, the Shinyemi Pb-Zn-Fe, the Geodo Cu-Fe and the Shiheung Cu-Pb-Zn mine, significant levels of Cd, Cu, Pb and Zn were found in mine dump soils developed over mine waste materials, tailings and slag. Furthermore, agricultural soils, stream sediments and stream water near the mines were severely contaminated by the metals mainly due to the continuing dispersion downstream and downslope from the sites, which was controlled by the feature of geography, prevailing wind directions and the distance from the mine. In e Au-Ag mining areas, the Kubong, the Samkwang, the Keumwang and the Kilkok mines, elevated levels of As, Cd, Cu, Pb and Zn were found in tailings and mine dump soils. These levels may have caused increased concentrations of those elements in stream sediments and waters due to direct dis-charge downstream from tailings and mine dumps. In the Au-Ag mines, As would be the most characteristic contaminant in the nearby environment. Arsenic and heavy metals were found to be mainly associated with sulfide gangue minerals, and mobility of these metals would be enhanced by the effect of oxidation. According to sequential extraction of metals in soils, most heavy metals were identified as non-residual chemical forms, and those are very susceptible to the change of ambient conditions of a nearby environment. As application of pollution index (PI), giving data on multi-element contamination in soils, over 1.0 value of the PI was found in soils sampled at and around the mining areas.
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