• Economic and Environmental Geology
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• v.26 no.3
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• pp.311-325
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• 1993

The Ohto and Tohyun copper mine which are located 4 km southeast of Euiseong, Gyeongsangbukdo, Republic of Korea show various common geologic and mineralogic features. Both copper deposits are of hydrothermal-vein types, and associated with fracture system developed during formation of the Geumseong-san caldera in late Cretaceous age. According to structures and mineral assemblages, the mineralization processes have progressed in four stages: three hypogene mineralization stages and one supergene stage. Three hypogene stages are 1) stage I forming $N5{\sim}20^{\circ}E$ veins in the Ohto mine, 2) stage II building $N5^{\circ}W{\sim}N5^{\circ}E$ veins in the Tohyun mine, and 3) stage ill bringing $N80^{\circ}E$ veins which crosscut veins of the stage II. The vein ores consist mainly of pyrite, arsenopyrite, galena and chalcopyrite, minor or trace amounts of magnetite, hematite, pyrrhotite, stannite, bournonite, boulangerite, stibnite, galenobismutite, native bismuth, marcasite, geothite and malachite. The main gangue minerals are quartz and calcite. Wallrock is altered by sericitization, chloritization, pyritization, carbonitization and argillization. Arsenic and copper contents in arsenopyrite increase from stage I to stage III (from 31.28 to 33043 atom.% As) and (from 0.04 to 0040 atom.% Co). Going from stage I to stage III Fe and Mn contents in sphalerite decreases from 12.56 to 0.44 wt.% and from 0.24 to 0.01 wt.%, respectively. The compositional data of arsenopyrite in the early stage I indicate a temperature of $420{\sim}365^{\circ}C$ and sulfur fugacity of $10^{-6.5}{\sim}10^{-8.3}$ atm. Chalcopyrite and pyrrhotite assemblage suggest that Middle stage I was deposited at below $334^{\circ}C$. The compositional data of arsenopyrite in early stage II suggest a temperature range of $425{\sim}390^{\circ}C$ and sulfur fugacity codition of $10^{-6.4}{\sim}10^{-7.3}$ atm. Based on fluid inclusion the Middle stage II was regarded as to be deposited at $420{\sim}337^{\circ}C$ (Chi et al., 1989). Referring composition of sphalerite and stannite middle-late stage II seem to be deposited around $246^{\circ}C$ and $10^{-16.5}$ atm. sulfur fugacity. The ${\delta}^{34}S$ values of sulfide minerals in the Stage I, II, III range from 4.9 to 7.6%0 and indicate igneous ore fluid origin. Based on differences in mineral assemblages, chemical composition and chemical environments of Ohto and Tohyun mine its mineralization are considered to be formed at diffent mineralization ages and by different ore fluids.

• Proceedings of the IEEK Conference
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• 2001.10a
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• pp.264-269
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• 2001

Large amounts of orange juice are produced in Japan every yea.. Accompanied by the production of orange juice, large amount of juice residues are also generated in nearly the same amounts with juice. Although, at present, some of these residues are marketed as a feed for cattle after drying and mixing with lime, the marketing price is lower than its production cost and the difference is paid by the consumers as a part of the price of orange juice. In the present work, we developed new innovative use of orange juice residue, a biomass waste, as adsorption gel for removing toxic heavy metals such as lead. arsenic, selenium and so on as well as radioactive elements such as uranium and thorium from environments. The major components of orange juice residue are cellulose. hemicellulose and pectin, which are converted into pectic. acid, an acidic polysaccharide, by means of saponification with concentrated sodium hydroxide solution. In the previous work, we found that crosslinked pectic acid gel strongly an selectively adsorbs lead over other metals such as zinc an copper. On the other hand. it is well known that polysaccharides such as cellulose can be easily phosphorylated and that phosphorylated polysaccharides have high affinity to uranium and thorium as well as some trivalent metals such as ferric iron and aluminum. Taking account of the noticeable characteristics of these polysaccharides, 2 types of adsorption gels were prepared from orange juice residue: one is the gel which was prepared by saponificating the residue followed by crosslinking with epichlorohydrin and another is that prepared by crosslinking the residue followed by phosphorylation. The former gel exhibited excellent adsorptive separation behavior for lead away from zinc owing to high content of pectic acid while the latter gel exhibited that for uranium and thorium. Both types of adsorption gels exhibited high affinity to ferric iron, which enables selective and strong adsorption for some toxic oxo-anions of arsenic (V and III), . selenium and so on via iron loaded on these gels. These results demonstrate that biomass wastes such as orange juice residue can be effectively utilized fer the purpose of removing toxic heavy or radioactive metals existing in trace or small amounts in environments.

• Journal of Soil and Groundwater Environment
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• v.25 no.1
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• pp.95-105
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• 2020

In this study, iron nanoparticles impregnated hydrochar (FeNPs@HC) was synthesized using lignocellulosic waste and simple one-pot synthetic method. During hydrothermal carbonization (HTC) process, the mixture of lignocellulosic waste and ferric nitrate (0.1~0.5 M) as a precursor of iron nanoparticles was added and heated to 220℃ for 3 h in a teflon sealed autoclave, followed by calcination at 600℃ in N₂ atmosphere for 1 h. For the characterization of the as-prepared materials, X-ray diffraction (XRD), cation exchange capacity (CEC), fourier transform infrared spectrometer (FT-IR), Brunauer-Emmett-Teller (BET), transmission electron microscope (TEM), Energy Dispersive X-ray Spectroscopy (EDS) were used. The change of Fe(III) concentration in the feedstock influenced characteristics of produced FeNPs@HC and removal efficiency towards As(V) and Pb(II). According to the Langmuir isotherm test, maximum As(V) and Pb(II) adsorption capacity of Fe_0.25NPs@HC were found to be 11.81 and 116.28 mg/g respectively. The results of this study suggest that FeNPs@HC can be potentially used as an adsorbent or soil amendment for remediation of groundwater or soil contaminated with arsenic and cation heavy metals.

• Economic and Environmental Geology
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• v.55 no.2
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• pp.127-135
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• 2022

Excessive presence of As level in groundwater is a major health problem worldwide. In the Red River Delta in Vietnam, several million residents possess a high risk of chronic As poisoning. The As releases into groundwater caused by natural process through microbially-driven reductive dissolution of Fe (III) oxides. It has been extracted by Red River residents using private tube wells for drinking and daily purposes because of their unawareness of the contamination. This long-term consumption of As-contaminated groundwater could lead to various health problems. Therefore, a predictive model would be useful to expose contamination risks of the wells in the Red River Delta Vietnam area. This study used four machine learning algorithms to predict the As probability of study sites in Red River Delta, Vietnam. The GBM was the best performing model with the accuracy, precision, sensitivity, and specificity of 98.7%, 100%, 95.2%, and 100%, respectively. In addition, it resulted the highest AUC of 92% and 96% for the PRC and ROC curves, with Eh and Fe as the most important variables. The partial dependence plot of As concentration on the model parameters showed that the probability of high level of As is related to the low number of wells' depth, Eh, and SO₄, along with high PO₄^3- and NH₄⁺. This condition triggers the reductive dissolution of iron phases, thus releasing As into groundwater.

• Journal of Environmental Impact Assessment
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• v.29 no.5
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• pp.350-362
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• 2020

In this study, nano Fe°-impregnated biochar (INPBC) was prepared using pruning residues and one-pot synthetic method and evaluated its performance as an amendment agent for the stabilization of arsenic-contaminated soil. For the preparation of INPBC, the mixture of pruning residue and Fe (III) solution was heated to 220℃ for 3hr in a teflon-sealed autoclave followed by calcination at 600℃ under N₂ atmosphere for 1hr. As-prepared INPBC was characterized using FT-IR, XRD, BET, SEM. For the stabilization test of as-prepared INPBC, As-contaminated soils (Soil-E and Soil-S) sampled from agricultural sites located respectively near E-abandoned mine and S-abandoned mine in South Korea were mixed with different of dosage of INPBC and cultivated for 4 weeks. After treatment, TCLP and SPLP tests were conducted to determine the stabilization efficiency of As in soil and showed that the stabilization efficiency was increased with increasing the INPBC dosage and the concentration of As in SPLP extractant of Soil-E was lower than the drinking water standard level of Ministry of Environment of South Korea. The sequential fractionation of As in the stabilized soils indicated that the fractions of As in the 1st and 2nd stages that correspond liable and known as bioavailable fraction were decreased and the fractions of As in 3rd and 4th stages that correspond relatively non-liable fraction were increased. Such a stabilization of As shows that the abundant nano Fe° on the surface of INPBC mixed with As-contaminated soils played the co-precipitation of As leaching from soil by surface complexation with iron. The results of this study may imply that INPBC as a promising amendments for the stabilization of As-contaminated soil play an important role.

• Economic and Environmental Geology
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• v.50 no.3
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• pp.215-224
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• 2017

Arsenic (As) is known to be the most toxic element and frequently detected in groundwater environment. Inorganic As exists as arsenite [As(III)] and arsenate [As(V)] in reduced and oxidized environments, respectively. It has been reported that the toxicity of arsenite is much higher than that of arsenate and furthermore arsenite shows relatively higher mobility in aqueous environments. For this reason, there have been numerous researches on the process for oxidation of arsenite to arsenate to reduce the toxicity of arsenic. In particular, photooxidation has been considered to be simple, economical, and efficient to attain such goal. This study was conducted to evaluate the applicability of naturally-occurring goethite as a photocatalyst to substitute for $TiO_2$ which has been mostly used in the photooxidation processes so far. In addition, the effects of several factors on the overall performance of arsenite photocatalytic oxidation process were evaluated. The results show that the efficiency of the process was affected by total concentration of dissolved cations rather than by the kind of those cations and also the relatively higher pH conditions seemed to be more favorable to the process. In the case of coexistence of arsenite and arsenate, the removal tendency by adsorption onto goethite appeared to be different between arsenite and arsenate due to their different affinities with goethite, but any effect on the photocatalytic oxidation of arsenite was not observed. In terms of effect of humic acid on the process, it is likely that the higher concentration of humic acid reduced the overall performance of the arsenite photocatalytic oxidation as a result of competing interaction of activated oxygen species, such as hydroxyl and superoxide radicals, with arsenite and humic acid. In addition, it is revealed that the injection of oxygen gas improved the process because oxygen contributes to arsenite oxidation as an electron acceptor. Based on the results of the study, consequently, the photocatalytic oxidation of aqueous arsenite using goethite seems to be greatly feasible with the optimization of process.

• Journal of Soil and Groundwater Environment
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• v.18 no.3
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• pp.93-108
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• 2013

This study is aimed to prepare the effective detail survey methods(Phase II) of abandoned metal mines through the contamination assessment for mine types and facilities in the abandoned metal mine areas. The study sites of 12 abandoned mines are located in Gyeonggi-do and Gangwon-do and those were chosen among 310 sites that the Phase II survey was conducted from 2007 to 2009 after considering the results of Phase I for abandoned mines scattered all over the country. 12 study sites were classified into four types; Type I sites only have pit mouth. Type II sites have pit mouth and mine-waste field. Type III sites have pit mouth and tailing sorting field. Type IV sites have pit mouth, tailing sorting field and concentrator(s). In forest land, paddy soil and farm land of Type I, As and Cd were showed average concentration, and Cu and Pb were high on the pit mouth area in one mines where the pit mouth was developed within 500 m. In the mines of Type II, Cu and Pb were showed average concentration too, but As and Cd were slightly high in pit mouth and mine-waste field. The mines of Type III which had grinding particle process through physical separation milling or hitting showed similar tendency with Type II. However, mines of Type IV pit mouth, mine-waste field and showed various results depending on defining the contamination sources. For example, if contamination source was pit mouth, the mixed results of Type I, II, II were showed. In tailing sorting field which was regarded as the most important source and having high mobility, however, if there were no facilities or it was difficult to access directly, field sampling was missed occasionally during phase I and phase II survey. For that reason, the assessment for tailing sorting field is missed and it leads to completely different results. In the areas of Type I mines, the concentration of heavy metals exceeded precautionary standards of soil contamination or not within 1,000 meters of pit mouth. Nickel(Ni) was the largest factor of the heavy metal contamination in this type. The heavy metals except Arsenic(As) were shown high levels of concentration in Type II areas, where pit mouth and mine-waste field were operated for making powder in upriver region; therefore, to the areas in the vicinity of midstream and downstream, the high content of heavy metals were shown. The tendency of high level of heavy metals and toxic materials contained in flotation agent used during sorting process were found in soil around sorting and tailing field. In the abandoned-pit-mouth area, drygrinding area and tailing sorting field area, the content of Cupper(Cu) and Zinc(Zn) were higher than other areas. Also, the contaminated area were larger than mine reclamation area(2,000 m) and the location of tailing sorting field was one of the important factors to estimate contaminated area.

• 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.