• Analytical Science and Technology
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• v.20 no.1
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• pp.55-60
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• 2007

A sensitive technique for the determination of trace Cu(II) in various samples after the column preconcentration by adsorbing its N-benzoylphenylhydroxylamine (BPHA) onto benzophenone was developed. Several experimental conditions such as the pH of the sample solution, the amount of chelating agent, the amount of benzophenone, and the flowrate of sample solution and so forth were optimized. The interfering effects of diverse concomitant ions were investigated. Fe(III) and $CN^-$ interfered with more seriously than any other ions. However, the interference by these ions could be overcome sufficiently by adjusting the added volume of 0.01M BPHA to 10 mL. The dynamic range, the correlation coefficient ($r^2$) and the detection limit obtained by this proposed technique were 5.0~120 ng/mL, 0.9974, and 2.1 ng/mL, respectively. For validating this proposed technique, the aqueous samples (stream water, reservoir water, and wastewater), the plastic sample and the diluted brass sample were used. Recovery yields of 93~102% were obtained. These measured data were not different from ICP-MS data at 95% confidence level. This method was also validated by the rice flour CRM (normal, fortified) samples. Based on the results from the experiment, it was found that this proposed technique could be applied to the determination of Cu(II) in various real samples.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.153-160
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• 2005

There have been large areas of soil contaminated with high levels of explosives. For this experimental work, 2,4,6-trinitrotoluene (TNT) was tested as a representative explosive contaminant of concern in both aqueous and soil samples and its removal was evaluated using three different chemical treatment methods: 1) the classical Fenton reaction which utilizes hydrogen peroxide ($H_2O_2$) and soluble iron at pH less than 3; 2) a modified Fenton reaction which utilizes chelating agents, $H_2O_2$, and soluble iron at pH 7; and 3) a Fenton-like process which utilizes iron minerals instead of soluble iron and $H_2O_2$, generating a hydroxyl radical. Using classic Fenton reaction, 93% of TNT was removed in 20 h at pH 3 (soil spiked with 300 mg/L of TNT, 3% $H_2O_2$ and 1mM Fe(III)), whereas 21% removed at pH 7. The modified Fenton reaction, using nitrilotriacetic acid (NTA), oxalate, ethylenediaminetetraacetic acid (EDTA), acetate and citrate as representative chelating agents, was tested with 3% $H_2O_2$ at pH 7 for 24 h. Results showed the TNT removal in the order of NTA, EDTA, oxalate, citrate and acetate, with the removal efficiency of 87%, 71%, 64%, 46%, and 37%, respectively, suggesting NTA as the most effective chelating agent. The Fenton-like reaction was performed with water contaminated with 100 mg/L TNT and soil contaminated with 300 mg/L TNT, respectively, using 3% $H_2O_2$ and such iron minerals as goethite, magnetite, and hematite. In the goethite-water system, 33% of TNT was removed at pH 3 whereas 28% removed at pH 7. In the magnetite-water system, 40% of TNT was removed at pH 3 whereas 36% removed at pH 7. In the hematite-water system, 40% of TNT was removed at pH 3 whereas 34% removed at pH 7. For further experiments combining the modified Fenton reaction with the Fenton-like reaction, NTA, EDTA, and oxalate were selected with the natural iron minerals, magnetite and hematite at pH 7, based on the results from the modified Fenton reaction. As results, in case magnetite was used, 79%, 59%, and 14% of TNT was removed when NTA, oxalate, and EDTA used, respectively, whereas 73%, 25%, and 19% removed in case of hematite, when NTA, oxalate, and EDTA used, respectively.

• Economic and Environmental Geology
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• v.42 no.5
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• pp.413-426
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• 2009

The study was conducted to investigate the effects of indigenous bacteria on geochemical behavior of toxic heavy metals in contaminated paddy soil near an abandoned mine. The effects of sulfate amendment to stimulate microbial sulfate reduction on heavy metal behaviors were also investigated. Batch-type experiments were performed with lactate or glucose as a carbon source to activate indigenous bacteria in the soil under anaerobic condition for 100 days. Sulfate (250 mg/L) was artificially injected at 60 days after the onset of the experiments. In the case of glucose supply, solution pH increased from 4.8 to 7.6 while pH was maintained at 7~8 in the lactate solution. The initial low pH in the case of glucose supply likely resulted in the enhanced extraction of Fe and most heavy metals at the initial experimental period. Lactate supply exerted no significant difference on the amounts of dissolved Zn, Pb, Ni and Cu between microbial and abiotic control slurries; however, lower Zn, Pb and Ni and higher Cu concentrations were observed in the microbial slurries than in the controls when glucose supplied. Sulfate amendment led to dramatic decrease in dissolved Cr and maintenance of dissolved As, both of which had gradually increased over time till the sulfate injection. Black precipitates formed in solution after sulfate amendment, and violarite($Fe^{+2}{Ni^{+3}}_2S_4$) was found with XRD analysis in the microbial precipitates. Conceivably the mineral might be formed after Fe(III) reduction and microbial sulfate reduction with coprecipitation of heavy metal. The results suggested that heavy metals which can be readily extracted from contaminated paddy soils may be stabilized in soil formation by microbial sulfate reduction.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.357-366
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• 2007

Microorganisms participate in a variety of geochemical processes such as weathering and formation of minerals, leaching of precious metals from minerals, and cycling of organic matter The objective of this study was to investigate biogeochemical processes of iron leaching from magnetite ore by iron-reducing bacteria isolated from intertidal flat sediments, southwestern part of Korea. Microbial iron leaching experiments were performed using magnetite ore, Shinyemi magnetite ore, in well-defined media with and without bacteria at room temperature for a month. Water soluble Fe and Mn during the leaching experiments were determined by ICP analysis of bioleached samples, and the resulting precipitated solids were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The extent of iron leaching from magnetite in the aerobic conditions (Fe = 15 mg/L and Mn = 3.41 mg/L) was lower than that in the anaerobic environments (Fe = 32.8 mg/L and Mn = 5.23 mg/L). The medium pH typically decreased from 8.3 to 7.2 during a month incubation. The Eh of the initial medium decreased from +144.9 mV to -331.7 mV in aerobic environments and from -2.3 mV to -494.6 mV in anaerobic environments upon incubation with the metal reducing microorganisms. The decrease in pH is due to glucose fermentation producing organic acids and $CO_2$. The ability of bacteria to leach soluble iron from crystalline magnetite could have significant implications for biogeochemical processes in sediments where Fe(III) in magnetite represents the largest pool of electron acceptor as well as to use as a novel biotechnology for leaching precious and heavy metals from raw materials.

• Korean Journal of Soil Science and Fertilizer
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• v.7 no.2
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• pp.71-97
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• 1974

Many studies on the changes of the materials in the water-logged paddy soil have been reported, but there will be several problems to apply them on the field soil. The main differences between the method of soil packed in beaker or column tube to that of natural field furrow slice are with or without of the rice root and the effect of water percolation. On the other hand, the mechanism of the water percolation on the changes of material in the natural field furrow slice are gradually understood. The purpose of this experiment is to know the effect of the rice cultivation on the chemical and physical changes of material in the water-logged paddy soil. Obtained results are as follows. 1. The physical and chemical changes on the water-logged paddy soil in the non-planted control-plot were nearly the same as the beaker or column tube experiment, while in the planted plot, slightly altered patterns were observed. 2. The relation between the number of tillers and total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, Fe and Mn in the leachate showed very high significance. T hisresult showed that the leaching of those cation was promoted by growing of the rice r- of the rice root. 3. On the other hand, the concentration of the potassium, silica and phosphorus in leachates was gradually decreased and that of $NH_4$-N could not detect after the stage of active tillering. These facts revealed that such components were absorbed by rice plant. 4. The highly significant correlation between the number of tillers and the concentration of the total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$, Fe and Mn in the percolated water was observed except that of $Mg^{{+}{+}}$. It was also showed that the rice root promoted the leaching of those cation. 5. The very high significance in the correlation between $HCO_3{^-}$ and the number of tillers indicated that the higher activity of the rice root was, the more $HCO_3{^-}$ concentration in the leachate was increased. 6. The relationship between the $HCO_3{^-}$ and the total cation, $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$, Fe and Mn was appeared very highly significant. $HCO_3{^-}$, the metabolite of the rice root, promoted the leaching of $Ca^{{+}{+}}$, $Mg^{{+}{+}}$, $Fe^{{+}{+}}$ and Mn. This fact might be a result that these cations were leached as the form of bicarbonate. 7. The iron in the leachate was the form of $Fe^{{+}{+}}$ and the correlation between $Fe^{{+}{+}}$ and $HCO_3{^-}$ was very highly significant. This result indicated that it seemed to be ferrous bicarbonate when it is leached out. 8. In the rhizosphere, ferrous iron was decreased gradually and the concentration of glucose was as high as 2 to 3 times in comparison with the other parts of the soil. These facts were the same as the previous reports in which rhizosphere was oxidized by the oxigen excreted from the root, and was enriched by the organic matter which was also excreted from the root and accumulated residues of the root. 9. ${\beta}$-Glucosidase and phosphatase activity in the rhizosphere was higher than that of the other parts of the soil. This facts might be attributed to the vigorous activity of microorganism in the rhizosphere where glucose concentration was high. 10. The pH in the leachate of the planted plot was lower than that of control, and the Eh on the planted soil was elevated in the last stage.

• Korean Journal of Heritage: History & Science
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• v.41 no.1
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• pp.5-19
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• 2008

Thirty six samples of Western asia glass vessel shards which were excavated from South Mound of Hwangnamdaechong were each measured for thickness, pore size and specific gravity and analyzed for ten major compositions and thirteen trace elements. The glass samples with colorless, greenish blue and dark purple blue were well classified by principal component analysis(PCA). All glass shards of Hwangnamdaechong belonged to Soda glass system ($Na_2O-CaO-SiO_2$) which have the range of 14~17% $Na_2O$ and 5~6% CaO. The corelation coefficients of (MgO, $K_2O$) and (MnO, CuO) showed above 0.90. The concentrations of thirteen trace elements apparently differentiated from colorless, greenish blue and dark blue glasses. We found that thirteen trace elements were very important indices for studying raw material of glass and the origin of glass making. Colorless glass : The specific gravity is $1.50{\pm}0.04$. Circle or oval circle pores are observed with regular direction in internal zone and the longest one is about 0.35 mm. The raw material of sodium must be the plant ash because sodium glasses contain HCLA(High CaO, Low $Al_2O_3$) and HMK(high MgO, high $K_2O$) and suggested to Sasanian glass. The total amount of coloring agent of colorless glass is below 1 % which is too small to attribute to the color. Greenish blue glass : The specific gravity is $1.58{\pm}0.04$. The fine pores which are 0.1~0.2mm are dispersed in internal zone. Sodium glasses are distributed to HCLA and HMK. Therefore the greenish blue glass also have used plant ash for raw material of sodium with the same as colorless glass. It was also suggested to the glass of Sasanian. The total amount of coloring agent of greenish blue glass is about 4% under the influence of working MnO, $Fe_2O_3$ and CuO. Dark purple blue glass : The specific gravity is $1.48{\pm}0.19$. There are rarely pores in internal zone. They are distributed to HCLA and LMK(Low MgO, Low $K_2O$) and suggested to Roman glass. The raw material of sodium is estimated to natron. The total amount of coloring agents of greenish blue is about 3% by $Fe_2O_3$ and CuO. These studies for western asia glass shards from South Mound of Hwangnamdaechong could be used in the future as the standard data which could be compared with those of other several graves in Korea and dispersed in foreign areas.

• Economic and Environmental Geology
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• v.12 no.1
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• pp.41-49
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• 1979

A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.

• Journal of Soil and Groundwater Environment
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• v.7 no.3
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• pp.115-132
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• 2002

To distinguish the anthropogenic inputs from the chemical weathering with water-rock interaction on the chemical compositons of groundwater in Kwangju city, four different water groups were established based on the landuse type, lithology and topology. The sample from greenbelt area belongs to Group Ⅰ, whereas those from green buffer zone, urban area and industrial area belong to Group II, Group Ⅲ and Group Ⅳ, respectively. The geology of this city mainly consists of biotite granite and granitic gneiss. The concentration of main cations is subject to the behavior of feldspars, micas and carbonate minerals. Cl$\^$-/ and NO$_3$$\^$-/ are supplied by anthropogenic inputs such as domestic sewage whose concentration of these anions is highest in the Group Ⅲ samples. With the Piper diagram, the groundwaters of Group Ⅲ are mainly plotted in CaSO$_4$-CaCl$_2$ type, whereas those of other groups are plotted in Ca(HCO$_3$)$_2$ type, The calculation for the activities of ions and saturation indices of some minerals shows that most of the minerals are undersaturated and plotted in the area of equlibrium with kaolinite. Three factors were extracted from the factor analysis for chemical data. Factor 1 controlled by HCO$_3$$\^$-/, Ca$\^$2-/, SO$_4$$\^$2-/, Mg$\^$2+/ and Na$\^$+/, explains the dissolution of carbonate minerals. mica and plagioclase. Factor 2, controlled by Cl$\^$-/ and NO$_3$$\^$-/, explains the influence of artificial pollution. Factor 3, controlled by Mn, Fe and Zn is subject to the industrial waste water, but the evidence is not clear. Factor 1 is dominant in the Group I and II, indicating that those samples are subjected to natural chemical weathering, The higher scores of factor 2 in the Group Ⅲ samples indicate the potential artificial pollution.

• Journal of the Society of Cosmetic Scientists of Korea
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• v.31 no.4 s.54
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• pp.289-293
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• 2005

Nowadays there are many sun protection cosmetics including organic or inorganic UV filter as an active ingredient. Chemically stable inorganic sunsEreen agents, usually metal oxides, we widely employed in high SPF products. Titanium dioxide is one of the most frequently used inorganic UV filters. It has been used as pigments for a long period of cosmetic history. With the development of micronization techniques, it becomes possible to incorporate titanium dioxide in sunscreen formulations without whitening effect and it becomes an important research topic. However, there are very few works related to quantitations of titanium dioxide in sunscreen products. In this research, we analyzed amounts of titanium dioxide in sunscreen cosmetics by adapting redof titration, reduction of Ti(IV) to Ti(III) and reoxidation to Ti(IV). After calcification of other organic ingredients of cosmetics, titanium dioxide is dissolved by hot sulfuric acid. The dissolved Ti(IV) is reduced to the Ti(III) by adding aluminum metals. The reduced Ti(III) is titrated against a standard oxidizing agent, Fe(III) (ammonium iron(III) sulfate), with potassium thiocyanate as an indicator In order to test accuracy and applicability of the proposed method, we analyzed the amounts of titanium dioxide in four types of sunscreen cosmetics, such as cream, make-up base, foundation and powder, after adding known amounts of titanium dioxide $(1{\sim}25w/w%)$. The percent recoveries of the titanium dioxide in four types of formulations were in the range between 96 and 105%. We also analyzed 7 commercial cosmetic products labeled titanium dioxide as an ingredient and compared the results with those of obtained from ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry), one of the most powerful atomic analysis techniques. The results showed that the titrated amounts were well coincided with the analyzed amounts of titanium dioxide by ICP-AES. Although instrumental analytical methods, ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) and ICP-AES, are the best for the analysis of titanium, it is hard to adopt because of their high prices for small cosmetic companies. It was found that the volumetric method presented here gat e quantitative and reliable results with routine lab-wares and chemicals.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.481-490
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• 2003

The objectives of this study are (1) to determine the extent and degree of As contamination of the water and sediments influenced by mining activity of the abandoned Au-Ag mines, (2) to examine As speciation In contaminated water, (3) to monitor variation of As contamination in water system throughout the dry and wet seasons, and (4) to investigate the As chemical form in the sediments through the sequential extraction analyses. Natural water(mine water, surface water and groundwater) and sediments were collected in six abandoned Au-Ag mine(Au-bearing quartz veins) areas. The contamination level of As in mine water of the Dongil(524${\mu}m$/L) is more higher than the tolerance level(500 ${\mu}m$/L) for waste water of mine area in Korea. Elevated levels of As in stream water were also found in the Dongil(range of 63.7∼117.6 ${\mu}m$/L.) and Gubong(range of 56.1∼62.9 ${\mu}m$/L) mine areas. Arsenic contamination levels in groundwater used by drinking water were more significant in the Dongil(11.3∼63.5 ${\mu}m$/L), Okdong(0.2∼68.9 ${\mu}m$/L) and Gubong(2.0∼101.0${\mu}m$/L) mine areas. Arsenate[As(V), $H_2AsO_4^-$] is more dominant than arsenite[As(III), $H_3AsO_3$] in water system of the most mine areas. The concentration ratios of As(III) to As(total), however, extend to the 95% in stream water of the Okdong mine area and 70∼82% in groundwater of the Okdong and Dongjung mine areas. As a study of seasonal variation in the water system, relatively high levels of As from the dongil mine area were found in April rather than in September. Sequential extraction analysis showed that As was predominantly present as coprecipitated with Fe hydroxides from sediment samples of the Dongjung and Gubong mine(35.9∼40.5%), which indicates its possibility of re-extraction and inducing elevated contamination of As in the reductive condition. In sediments from the Dongil, Okdong and Hwachon mine area, high percentage(55.2∼83.4%) of As sulfide form was found.