• Economic and Environmental Geology
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• v.42 no.5
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• pp.445-455
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• 2009

Microbiological sulfate reduction is the transformation of sulfate to sulfide catalyzed by the activity of sulfate-reducing bacteria using sulfate as an electron acceptor. Low solubility of metal sulfides leads to precipitation of the sulfides in solution. The effects of microbiological sulfate reduction on in-situ precipitation of arsenic and copper were investigated for the heavy metal-contaminated soil around the Songcheon Au-Ag mine site. Total concentrations of As, Cu, and Pb were 1,311 mg/kg, 146 mg/kg, and 294 mg/kg, respectively, after aqua regia digestion. In batch-type experiments, indigenous sulfate-reducing bacteria rapidly decreased sulfate concentration and redox potential and led to substantial removal of dissolved As and Cu from solution. Optimal concentrations of carbon source and sulfate for effective microbial sulfate reduction were 0.2~0.5% (w/v) and 100~200 mg/L, respectively. More than 98% of injected As and Cu were removed in the effluents from both microbial and chemical columns designed for metal sulfides to be precipitated. However, after the injection of oxygen-rich solution, the microbial column showed the enhanced long-term stability of in-situ precipitated metals when compared with the chemical column which showed immediate increase in dissolved As and Cu due to oxidative dissolution of the sulfides. Black precipitates formed in the microbial column during the experiments and were identified as iron sulfide and copper sulfide. Arsenic was observed to be adsorbed on surface of iron sulfide precipitate.

• Economic and Environmental Geology
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• v.56 no.4
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• pp.421-433
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• 2023

The final disposal of spent nuclear fuel(SNF) from nuclear power plants takes place in a deep geological repository. The metal canister encasing the SNF is made of cast iron and copper, and is engineered to effectively isolate radioactive isotopes for a long period of time. The SNF is further shielded by a multi-barrier disposal system comprising both engineering and natural barriers. The deep disposal environment gradually changes to an anaerobic reducing environment. In this environment, sulfide is one of the most probable substances to induce corrosion of copper canister. Stress-corrosion cracking(SCC) triggered by sulfide can carry substantial implications for the integrity of the copper canister, potentially posing a significant threat to the long-term safety of the deep disposal repository. Sulfate can exist in various forms within the deep disposal environment or be introduced from the geosphere. Sulfate has the potential to be transformed into sulfide by sulfate-reducing bacteria(SRB), and this converted sulfide can contribute to the corrosion of the copper canister. Bentonite, which is considered as a potential material for buffering and backfilling, contains oxidized sulfate minerals such as gypsum(CaSO4). If there is sufficient space for microorganisms to thrive in the deep disposal environment and if electron donors such as organic carbon are adequately supplied, sulfate can be converted to sulfide through microbial activity. However, the majority of the sulfides generated in the deep disposal system or introduced from the geosphere will be intercepted by the buffer, with only a small amount reaching the metal canister. Pyrite, one of the potential sulfide minerals present in the deep disposal environment, can generate sulfates during the dissolution process, thereby contributing to the corrosion of the copper canister. However, the quantity of oxidation byproducts from pyrite is anticipated to be minimal due to its extremely low solubility. Moreover, the migration of these oxidized byproducts to the metal canister will be restricted by the low hydraulic conductivity of saturated bentonite. We have comprehensively analyzed and summarized key research cases related to the presence of sulfates, reduction processes, and the formation and behavior characteristics of sulfides and pyrite in the deep disposal environment. Our objective was to gain an understanding of the impact of sulfates and sulfides on the long-term safety of high-level radioactive waste disposal repository.

• Journal of the Korea Organic Resources Recycling Association
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• v.7 no.2
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• pp.25-34
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• 1999

The effects of copper on the anaerobic degradation of propionate were studied using anaerobic batch reactors. The apparent inhibitory effects of copper on the anaerobic degradation of propionate could be observed from behaviors of intermediates, ultimate methane yield(UMY) and specific methanogenic activity(SMA) There was little inhibition at the concentration of $2.5mg\;Cu^{2+}/L$. Beyond this concentration, the inhibitory effects increased with increasing dose of coppers. The 50% inhibition of UMY and SMA occurred at copper dosage of 33.8 and $24.1mg\;Cu^{2+}/gVSS$, respectively. The inhibitory effect based on the UMY was gradually reduced with the operation time dueprobably to the acclimation of microorganisms and/or binding of the added copper by ligands(and possibly ion exchange sites)contained on the cell membrane and extracellular polymer matrix whereas it based on the SMA might exclude the this phenomena. Therefore, the methodology for interpretation of inhibition data based on the SMA was more accurated than the UMY. There was no inhibitory effect in batch reactors supplemented with sulfate due to an antagonistic action of the sulfate reducing bacteria. Propionate degradation was initially retarded for copper inhibited samples but it gradually degraded afterward. Based on the mass removal considering take into account the propionate to acetate conversion, propionate degradation may appeal more affected than acetate. This result revealed that the hydrogenotrophic methanogens were the most affected by copper.

• Journal of the Mineralogical Society of Korea
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• v.24 no.3
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• pp.217-224
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• 2011

Removal of dissolved selenium by D. michiganensis, a iron-reducing bacterium, and effects of dissolved metal elements such as iron, sulfate, and copper were investigated. Selenide that was reduced from selenite (2 mM) by D. michiganensis was gradually removed from the aqueous medium. As the reduced selenide was combined with aqueous iron, it was precipitated as a nanoparticulate iron-selenide. Sulfate and copper negatively affected the microbial selenite reduction, and the copper was especially toxic to the bacterium, inhibiting a microbial removal of dissolved selenite. These results show that it should be carefully biotreated for a selenium-contaminated site considering in situ sulfate or copper distribution and concentration. Consequently, the formation of iron-selenide by bacteria will be an important measure for preventing a long-distance migration of selenium in the subsurface environments.

• Journal of the Mineralogical Society of Korea
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• v.19 no.3 s.49
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• pp.129-138
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• 2006

In this study, we identified the secondary precipitates from Samsan-jeil and Sambong mine, Goseong, Gyeongnam by means of scanning electron microscopy, electron probe microanalysis and X-ray powder diffraction analysis. Copper sulfide minerals had been produced from the mines during last few decades, however they are not worked. White and blue precipitates were found at the downstream of mine rock dump at Sambong mine and green one was at Samsan-jeil mine. The white precipitate covered the host rock surface with thickness of $30{\mu}m$, and is a kind of diatom with $10{\mu}m$ in length and $3{\mu}m$ in width. It is a species Fragilaria constuens, which is contained a order Pennales(pennate diatom) and lives in fresh water. The blue precipitate is the alteration product of chalcopyrite. It resultes in the increase in the ratio Cu:Fe from 5 to 13. The green precipitate has worm-like morphology with $10{\sim}20nm$ in diameter and $200{\sim}300nm$ in length. It is mainly composed of secondary copper sulfate such as woodwardite. However, it could be formed by the activity of microorganism, because the copper content is more than any secondary copper sulfate reported in copper sulfide mine. In order to identity the green precipitate exactly, the further research is needed.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.219-228
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• 2013

To understand characteristics of biogeochemical corrosion for the metal canisters that usually contain the radioactive wastes for a long-term period below the ground, some metal materials consisting of cast iron and copper were reacted for 3 months with D. desulfuricans, a sulfate-reducing bacterium, under a reducing condition. During the experiment, concentrations of dissolved metal ions were periodically measured, and then metal specimen and surface secondary products were examined using the electron microscopy to know the chemical and mineralogical changes of the original metal samples. The metal corrosion was not noticeable at the absence of D. desulfuricans, but it was relatively greater at the presence of the bacterium. In our experiment, darkish metal sulfides such as mackinawite and copper sulfide were the final products of biogeochemical metal corrosion, and they were easily scaled off the original specimen and suspended as colloids. For the copper specimen, in particular, there appeared an accelerated corrosion of copper in the presence of dissolved iron and bacteria in solution, probably due to a weakening of copper-copper binding caused by a growth of other phase, iron sulfide, on the copper surface.

• Membrane Journal
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• v.23 no.1
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• pp.92-99
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• 2013

In this study the nanofiltration (NF) membrane treatment of a sulfuric acid waste solutions containing copper ion ($Cu^{+2}$) discharging from the etching processes of the printed circuit board (PCB) manufacturing industry has been studied for the recycling of acid etching solution. SelRO MPS-34 4040 NF membrane from Koch company was tested to obtain the basic NF data for recycling of etching solution and separation efficiency (total rejection) of copper ion. NF experiments were carried out with a dead-end membrane filtration laboratory system. The pure water flux was increased with the increasing storage time in sulfuric acid solution and lowering pH of acid solution because of the enhancement of NF membrane damage by sulfuric acid. The permeate flux of acid solution was decreased with the increasing copper ion concentration. Total rejection of copper ion was decreased with the increasing storage time in sulfuric acid solution and copper ion concentration, and lowering the pH of acid solution. The total rejection of copper ion was decreased from initial 37% to 15% minimum value.

• Korean Chemical Engineering Research
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• v.52 no.2
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• pp.272-277
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• 2014

In this study the nanofiltration (NF) membrane treatment of a sulfuric acid waste solutions containing copper ion ($Cu^{+2}$) discharging from the etching processes of the printed circuit board (PCB) manufacturing industry has been studied for the recycling of acid etching solution. SelRO MPS-34 4040 NF membrane from Koch company was tested to obtain the basic NF data for recycling of etching solution and separation efficiency (total rejection) of copper ion. NF experiments were carried out with a cross-flow membrane filtration laboratory system. The permeate flux was decreased with the increasing copper ion concentration in sulfuric acid solution and lowering pH of acid solution, and its value was the range of $4.5{\sim}23L/m^2{\cdot}h$. Total rejection of copper ion was decreased with the increasing copper ion concentration, lowering pH of acid solution and decreasing cross-flow rate. The total rejection of copper ion was more than 70% at the experimental condition. The SelRO MPS-34 4040 NF membrane was represented the stable flux and rejection for 1 year operation.

• Proceedings of the Korean Geotechical Society Conference
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• 2010.09a
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• pp.1225-1230
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• 2010

본 연구는 군부대 사격장의 중금속 오염토양에 대하여 생물학적 용출기술(BT)과 전기동력학적 기술(ET)의 통합공정의 적용성 평가 연구에 대한 것이다. 사격장 오염 토양의 경우 사격에 의해 탄두가 피탄지에 박히면서 오염토양 내에 잔존하여 탄두를 구성하는 주성분인 납과 구리 등에 의해 지속적인 오염원으로 작용하는 특징을 가진다. 따라서 사격장 토양오염정화를 위해서는 이 탄두를 물리적으로 선별하는 물리적 선별공정을 전처리공정으로 수행한 후 인공적으로 조성된 셀에 통합공정 적용성 평가를 위한 현장실증시험을 수행하였다. 생물학적 용출을 통해 토양내 잔류하는 중금속을 이온화시켜 이동성을 크게 한후 전기동력학적 기술을 통해 토양내에서 전해질로 이동시켜 최종적으로 전해질을 처리하는 시스템으로써 공정 모니터링결과 납과 구리 모두 주목할 만한 제거효율을 얻을수 있었다. 오염물질별 공정 적용성 평가결과 납의 경우 황산화박테리아에 의해 이온화가 되지만 황산화박테리아의 생장 부산물인 황산염이온(${SO_4}^{2-}$)과 반응하여 안정성이 큰 Anglesite($PbSO_4 $)를 형성하므로 전체적인 제거효율이 저하되는 것을 확인하였고 기타 미생물을 이용한 생물학적 용출기술 연구의 필요성을 확인하였다. 구리의 경우 황산염박테리아를 이용한 생물학적 용출공정 및 전기동력학적 처리공정의 통합공정을 통해 주목할 만한 제거효율을 얻을수 있었으며 통합공정의 효율성을 확인할 수 있었다. 본 연구를 통하여 미생물학적 용출기술과 전기동력학적 기술의 통합공정은 현장특이성(Site-specific) 확인후 적용가능성이 있음을 확인하였다.

• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.645-652
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• 1997

Electrochemical characteristics and kinetic parameters of copper ion reduction were investigated with a platinum rotating disk electrode (RDE) in a diffusion controlled region. Reduction of Cu(II) in sulfate had one-step two-xelectron process, while the reduction of Cu(II) in chloride solution was involved two one-electron processes. The transfer coefficient of Cu(II) in sulfate solution was lowest, and the transfer coefficient of Cu(I) in halide solutions had the value of nearly one. In chloride solutions, electrodeposition rate of Cu(II) was about one hundred times faster than Cu(I). Diffusion coefficient increased in the order of Cu(II) in chloride solution, Cu(I) in the iodide, bromide, chloride solution, Cu(II) in sulfate solution. The calculated ionic radii and activation energy for diffusion decreased in the same order as above. Morphological study on the copper electrodeposition indicated that the electrode surface became rougher as both concentration and reduction potential increases, and the roughness of the surface was analyzed with UV/VIS spectrophotometer.