This study was carried out 1) to investigate the pH effect on solubilization of phenanthrene by biosurfactant in aqueous system and 2) to evaluate the pH effect on the biodegradation rate of phenanthrene in the presence and the absence of the biosurfactant by phenanthrene degraders. Tween 80, which is a chemically synthesized surfactant, showed greater solubilizing capacity than rhamnolipid. The solubilization capacity can be expressed as a MSR(molar solubilization ratio=moles of organic compounds solubilized per mole of surfactant). The calculated MSR of Tween 80 and rhamnolipid were 0.1449 and 0.0425 respectively. The kinetic study of phenanthrene solubilization by rhamnolipid showed that solubilization mechanism could reach equilibrium within 24 hours. Addition of 240 ppm rhamnolipid solution, which concentration is 4.3 times of Critical Micelle Concentration(CMC), caused 9 times solubility enhancement compared to water solubility. The highest solubilities were detected around a pH range of 4.5-5.5. Changes in apparent solubility with the changes in pH are possibly related to the fact that the rhamnolipid, an anionic surfactant, can form different structures depending on the pH. Two biodegradation experiments were performed in the absence and the presence of rhamnolipid, with the cell growth investigated using a spread plate method. The specific growth rates at pH 6 and 7 were higher than at the other pH, and the HPLC analysis data, for the total phenanthrene loss, confirmed the trends in the $\mu$(specific growth rate) values. In presence of rhamnolipid, maximum $\mu$ values shifted from around pH 5 which showed maximum enhancement of solubility in the abiotic experiment, compared to the $\mu$ values obtained without the biosurfactant. In this study, the increase in the observed specific grow rate(1.44 times) was not as high as the increase in solubilization(5 times). This was supported by the fact all the solubilized phenanthrene is not bioavailable to microorganisms.
Arsenic contamination around Au-Ag mining areas occurs mainly from the oxidation of arsenopyrite which is frequently contained in mine tailings. In weathered tailings, oxidation of sulfide minerals typically results in the formation of abundant ferric (oxy)hydroxides or (oxy)hydroxysulfates near the tailings surface, and arsenic may be associated with these secondary precipitates. In this study, solid phases of arsenic in weathered tailings of some Au-Ag mines were investigated through the SEM/EDS and sequential extraction analyses. The stability of As solid phases and the leaching potential were assessed with the variation of pH and Eh conditions. Oxidation of sulfides in the tailings samples was indicated by depletion of S molar concentrations compared to As and heavy metals. Under XRD examinations, jarosite as an Fe-oxyhydroxysulfate was found in the tailings of Deokeum, Dongil and Dadeok, and scorodite as an As-bearing crystalline mineral was identified from Dadeok which has the highest concentration of As (4.36 wt.%). Beudantite-like phases and some Pb-arsenates were also found under SEM/EDS analysis, and most of As phases were associated with Fe-(oxy)hydroxides and (oxy)hydroxysulfates despite a few arsenopyrite from Samgwang and Gubong. Sequential extraction analysis also showed that As was present predominantly as coprecipitated with Fe hydroxides from Dongil, Dadeok and Myungbong (72∼99%), and as sulfides (58%) and Fe hydroxide-associated forms (40%) from Samgwang and Gubong. In the tailings leaching experiment, As was released with high amounts by the dissolution of As-bearing Fe(oxy)hydroxysulfates in the lowest pH (2.7) conditions of Deokeum, and by desorption under alkaline conditions of Samgwang and Gubong. Higher leaching rates of arsenite(+3) were found under acidic conditions, which pose a higher risk to water quality. Changes in pH and Eh conditions coupled with microbial processes could influence the stabilities of the As solid phases, and thus, time amendments or landfilling of weathered tailings may result in enhanced As mobilization.
The bioleaching experiment under $42^{\circ}C$ was effectively carried out to leach the more valuable element ions from the pyrite in the Gangyang mine waste. Bacteria can survive at this temperature, as indigenous acidophilic bacteria were collected in the Hatchobaru acidic hot spring, in Japan. To enhance the bacterial activity, yeast extract was added to the pyrite-leaching medium. The indigenous acidophilic bacteria appeared to be rod-shaped in the growth-medium which contained elemental sulfur and yeast extract. The rod-shaped bacteria ($0.7\times2.6\;{\mu}m$, $0.6\times7\;{\mu}m$, $0.8\times5\;{\mu}m$ and $0.7\times8.4\;{\mu}m$) were attached to the pyrite surface. The colonies of the rod-shaped bacteria were selectively attached to the surroundings of a hexagonal cavity and the inner wall of the hexagonal cavity, which developed on a pyrite surface. Filament-shaped bacteria ranging from $4.92\;{\mu}m$ to $10.0\;{\mu}m$ in length were subsequently attached to the surrounding cracks and inner wall of the cracks on the pyrite surface. In the XRD analysis, the intensity of (111), (311), (222) and (320) plane on the bacteria pyrite sample relatively decreased in plane on the control pyrite sample, whereas the intensity of (200), (210) and (211) increased in these samples. The microbiological leaching content of Fe ions was found to be 3.4 times higher than that of the chemical leaching content. As for the Zn, microbiological leaching content, it was 2 times higher than the chemical leaching content. The results of XRD analysis for the bioleaching of pyrite indicated that the indigenous acidophilic bacteria are selectively attacked on the pyrite specific plane. It is expected that the more valuable element ions can be leached out from the mine waste, if the temperature is increased in future bioleaching experiments.
In order to remediate heavy metal contaminated Nong island, Maehyang-ri shooting range soils through the batch reactor scale washing were evaluated. The experiment texture soil of N3 in the Nong island at north side incline was (g)mS containing 12.9% gravel, 47.0% sand, 35.1% silt and 5.0% clay. And the N3 soil area was contaminated with Cd($22.5\pm1.9$ ppm), Cu($35.5\pm4.0$ ppm), Pb($1,279.0\pm5.1$ ppm) and Zn($403.4\pm9.8$ ppm). The EDTA(ethylene diamine tetra acetic acid, $C_{10}H_{16}N_2O_8$) in the N3 soil was observed as most effective extractants among the 5 extractants(citric acid, EDTA, phosphoric acid, potassium phosphate and oxalic acid) tested. And chemical partitioning of heavy metals after washing N3 soil with EDTA was evaluated. Removal efficiency of residual fractions was higher than that of non-residual fractions. To choose EDTA extractant which is the most effective in soil washing technology using batch reactor process cleaning Pb and Zn contaminated sits; Pb and Zn removal rates were investigated 92.4%, 94.0% removal(1,000 mM, soil:solution=5, $20^{\circ}C$, 24 hour shaking, pH=2, 200 RPM), respectively. The results of the batch test showed that the removal efficiency curve was logarithmic in soil was removal. Thus, EDTA washing process can be applied to remediate the Pb and Zn contaminated soil used in this study.
The rates of oxidative degradation of perchloroethene (PCE) and trichloroethene (TCE) using $KMnO_4$ solution were evaluated under the flow condition using a bench-scale transport experimental setup. Parameters which are considered to affect the reaction rates tested in this study were the contact time (or retention time), and the concentration of oxidizing agent. A glass column packed with coarse sand was used for simulating the aquifer condition. Contact time between reactants was controlled by changing the flow rate of the solution through the column. The inflow concentrations of PCE and TCE were controlled constant within the range of $0.11{\sim}0.21\;mM$ and $1.3{\sim}1.5\;mM$, respectively. And the contact time was $14{\sim}125$ min for PCE and $15{\sim}36$ min for TCE. The $KMnO_4$ concentration was controlled constant during experiment in the range of $0.6{\sim}2.5\;mM$. It was found that the reduction of PCE and TCE concentrations were inversely proportional to the contact time. The exact reaction order for the PCE and TCE degradation reaction could not be determined under the experimental condition used in this study. However, the estimated reaction rate constants assuming pseudo-1st order reaction agree with those reported based on batch studies. TCE degradation rate was proportional to $KMnO_4$ concentration. This was considered to be the result of using high inflow concentrations of reactant, which might be the case at the vicinity of the source zones in aquifer. The results of this study, performed using a dynamic flow system, are expected to provide useful information for designing and implementing a field scale oxidative removal process for PCE/TCE-contaminated sites.
In order to evaluate the geochemical behaviors of elements with waste rocks in the abandoned Jangpoong Cu mine area, total concentration analysis and leaching experiments were performed. The content of elements within waste rocks compared with background values decreased in order of As>>Cu>Pb>Cd>Co. Leaching experiments were carried out at various extraction environments, considering the acid rain ($0.00001{\sim}0.001N\;HNO_3$) and the acid mine drainage ($0.001{\sim}0.1N$ HNO3). After 24 hours of reaction with different acidic solution, the leaching characteristics of waste rocks were classified into three types according to final pH of leaching solution. Type I refers to the case that the final pH of leaching solution was lower than that of the reaction solution due to the dissolution of acidic minerals from rocks, while type 2 and 3 refer to the case that the final pH maintained higher than that of the reaction solution. Theses types include in acid buffering minerals such as clay minerals and carbonate minerals. The leaching characteristics of the elements after the reaction could be categorized into As-Co-Fe, Cu-Mn-Cd-Zn, and Pb. As-Co-Fe started to get leached under 2.5 of pH regardless of changes in the final pH, and Cu-Mn-Cd-Zn showed different initial leaching pH according to the types of final pH changes. Based on the pH value where leaching started regardless of leaching concentration, the relative mobility of each element was in the order of Mn Zn>Cd>Cu>>Fe Co>As>Pb. Thus, more higher mobility elements(Zn, Mn and Cu) were leached by reacting with acid rain water. Acid mine drainage may result in distributions of elements having relatively less mobility(As, Fe, Co and Pb).
The stabilization process using limestone ($CaCO_3$) and steel making slag as the immobilization amendments was investigated for As contaminated farmland soils around Chonam abandoned mine, Korea. Batch and continuous column experiments were performed to quantify As-immobilization efficiency in soil and the analyses using XRD and SEM/EDS for secondary minerals precipitated in soil were also conducted to understand the mechanism of Asimmobilization by the amendments. For the batch experiment, with 3% of limestone and steel making slag, leaching concentration of As from the contaminated soil decreased by 62% and 52% respectively, compared to that without the amendment. When the mixed amendment (2% of limestone and 1% of steel making slag) was used, As concentration in the effluent solution decreased by 72%, showing that the mixed of limestone and steel making slag has a great capability to immobilize As in the soil. For the continuous column experiments without the amendment, As concentration from the effluent of the column ranged from 50 to $80\;{\mu}g/L$. However, with 2% limestone and 1% steel making slag, more than 80% diminution of As leaching concentration occurred within 1 year and maintained mostly below $10\;{\mu}g/L$. Results from XRD and SEM/EDS analysis for the secondary minerals created from the reaction of the amendments with $As^{+3}$ (arsenite) investigated that portlandite ($Ca(OH)_2$), calcium-arsenite (Ca-As-O) and calcite ($CaCO_3$) were main secondary minerals and the distinct As peaks in the EDS spectra of the secondary minerals can be observed. These findings suggest that the co-precipitation might be the major mechanisms to immobilize As in the soil medium with limestone and steel making slag.
Batch experiments were performed to develop the method for the pH reduction of recycled aggregate by using $scCO_2$ (supercritical $CO_2$), maintaining the pH of extraction water below 9.8. Three different aggregate types from a domestic company were used for the $scCO_2$-water-recycled aggregate reaction to investigate the low pH maintenance of aggregate during the reaction. Thirty five gram of recycled aggregate sample was mixed with 70 mL of distilled water in a Teflon beaker, which was fixed in a high pressurized stainless steel cell (150 mL of capacity). The inside of the cell was pressurized to 100 bar and each cell was located in an oven at $50^{\circ}C$ for 50 days and the pH and ion concentrations of water in the cell were measured at a different reaction time interval. The XRD and SEM-EDS analyses for the aggregate before and after the reaction were performed to identify the mineralogical change during the reaction. The extraction experiment for the aggregate was also conducted to investigate the pH change of extracted water by the $scCO_2$ treatment. The pH of the recycled aggregate without the $scCO_2$ treatment maintained over 12, but its pH dramatically decreased to below 7 after 1 hour reaction and maintained below 8 for 50 day reaction. Concentration of $Ca^{2+}$, $Si^{4+}$, $Mg^{2+}$ and $Na^+$ increased in water due to the $scCO_2$-water-recycled aggregate reaction and lots of secondary precipitates such as calcite, amorphous silicate, and hydroxide minerals were found by XRD and SEM-EDS analyses. The pH of extracted water from the recycled aggregates without the $scCO_2$ treatment maintained over 12, but the pH of extracted water with the $scCO_2$ treatment kept below 9 of pH for both of 50 day and 1 day treatment, suggesting that the recycled aggregate with the $scCO_2$ treatment can be reused in real construction sites.
Laboratory leaching experiment study carried out to estimate a extent of heavy metals that could be leached out when acid rain(pH 5.0-3.0) and strong acidic solution(pH 2.5-1.0) reacted with tailings and contaminated soils from abandoned metal mines. In slightly to moderately acid conditions(pH 5.0-3.0), As, Pb and Zn dissolutions became significantly increased with decreased pH in tailing, while dissolution of these elements was very limited in contaminated soil. These results suggested that moderately acid rainwater leaches Pb, As and Zn from the tailings, while these elements would remain fixed in contaminated soil. In the pH range of 2.5-1.0(strongly acid condition), Zn, Cd and Cu concentrations of leachate rapidly increased with decreased pH in contaminated soil, while Pb, As and Co dissolutions became importantly increased in tailings. The experimental solubility of Zn. Cd and Cu was very low even at very low pH values(up to pH 1), except for CY4(Cheongyang mine). These can result from an incomplete dissolution or the presence of less soluble mineral phases. So, the solubility of heavy metals depends not only on the pH values of leachate but also on the speciation of metals associated with contaminated soils and tailings. The relative mobility of each element within failings at the pH 5.0-3.0 of the reaction solution was in the order of Pb>Zn>Cd>Co=Cu>As. In case of pH 2.5-1.0 of the reaction solution, the relative mobility of each element within contaminated soils and tailings were in the order of Zn>Cd>Cu>Co>Pb=As for contaminated soils, and Pb>Zn>Cd>hs>Co>Cu for tailings. The obtained results could be useful for assessing the environmental effects and setting up the restoration plan in the areas.
This study was conducted to explain degree of injury caused by P. panopealis larva which is the key component to develop economic injury level or control threshold in green perilla and was carried out in polyvinyl houses at Yuseong Daejeon, Geumsan and Yesan Chungnam from 2004 to 2006. Of 5 major pests in green perilla polyvinyl house, P. panopealis larva injured green perilla leaf by 48.5% on average under no insecticides application. The peak occurrence of P. panopealis adult was early August and late September in 2004 and 2005 studies. The feeding amount of P. panopealis larva among 1st to 3rd instar was not different, but from the 4th instar the feeding amount greatly increased and this result was consistent with daily feeding experiment in which the amount greatly increased from seventh day. The degree of injury which was investigated with different larval infestation levels showed that the degree of injury increased a little but was not dim ε rent significantly as the density increased. The density of P. panopealis larva in damaged green perilla plant was less than three individuals/plant. This result indicates that P. panopealis adult lays egg on green perilla leaf dispersedly and larva hatched from egg injures only the leaf which egg is layed. These preliminary data seems to be very useful to design economic injury level and control threshold studies for P. panopealis in green perilla polyvinyl house.
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