• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.185-195
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• 2012

Due to the high reduction and sorption capacity as well as the large specific surface area, nanosized mackinawite (FeS) is useful in reductively transforming chlorinated organic pollutants and sequestering toxic metals and metalloids. Due to the dynamic nature in its colloid stability, however, nanosized FeS may be washed out with the groundwater flow or result in aquifer clogging via particle aggregation. Thus, these nanoparticles should be modified such as to be built into permeable reactive barriers. This study employed coating methods in efforts to facilitate the installation of permeable reactive barriers of nanosized mackinawite. In applying the methods, nanosized mackinawite was coated on non-treated silica sand (NTS) and chemically treated silica sand (CTS). For both silica sands, the maximum coating of mackinawite occurred around pH 5.4, the condition of which was governed by (1) the solubility of mackinawite and (2) the surface charge of both silica and mackinawite. Under this pH condition, the maximum coating by NTS and CTS were found to be 0.101 mmol FeS/g and 0.043 mmol FeS/g respectively, with such elevated coatings by NTS likely linked with impurities (e.g., iron oxides) on its surface. Arsenite sorption experiments were performed under anoxic conditions using uncoated silica sands and those coated with mackinawite at the optimal pH to compare their reactivity. At pH 7, the relative sorption efficiency between uncoated NTS and coated NTS changed with the initial concentration of arsenite. At the lower initial concentration, uncoated NTS showed the higher sorption efficiency, whereas at the higher concentration, coated NTS exhibited the higher sorption efficiency. This could be attributed to different sorption mechanisms as a function of arsenite concentration: the surface complexation of arsenite with the iron oxide impurity on silica sand at the low concentration and the precipitation as arsenic sulfides by reaction with mackinawite coating at the high concentration. Compared to coated NTS, coated CTS showed the lower arsenite removal at pH 7 due to its relatively lower mackinawite coating. Taken together, our results indicate that NTS is a more effective material than CTS for the coating of nanosized mackinawite.

• Journal of the Mineralogical Society of Korea
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• v.26 no.2
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• pp.101-110
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• 2013

Due to the large specific surface area and great reactivity toward environmental contaminants, nanocrystalline mackinawite (FeS) has been widely applied for the remediation of contaminated groundwater and soil. Furthermore, nanocrystalline FeS is rather thermodynamically stable against anoxic corrosion, and its reactivity can be regenerated continuously by the activity of sulfate-reducing bacteria. However, nanocrystalline mackinawite is prone to either spread out along the groundwater flow or cause pore clogging in aquifers by particle aggregation. Accordingly, this mineral should be modified for the application of permeable reactive barriers (PRBs). In this study, coating methods were investigated by which mackinawite nanoparticles were deposited on the surface of alumina or activated alumina. The amount of FeS coating was found to significantly vary with pH, with the highest amount occurring at pH ~6.9 for both minerals. At this pH, the surfaces of mackinawite and alumina (or activated alumina) were oppositely charged, with the resultant electrostatic attraction making the coating highly effective. At this pH, the coating amounts by alumina and activated alumina were 0.038 and 0.114 $mmol{\cdot}FeS/g$, respectively. Under anoxic conditions, arsenite sorption experiments were conducted with uncoated alumina, uncoated activated alumina, and both minerals coated with FeS at the optimal pH for comparison of their reactivity. Uncoated activated alumina showed the higher arsenite removal compared to uncoated alumina. Notably, the arsenite sorption capacity of activated alumina was little changed by the coating with FeS. This might be attributed to the abundance of highly reactive hydroxyl functional groups (${\equiv}$AlOH) on the surface of activated alumina, making the arsenite sorption by the coated FeS unnoticeable. In contrast, the arsenite sorption capacity of alumina was found to increase substantially by the FeS coating. This was due to the consumption of the surface hydroxyl functional groups on the alumina surface and the subsequent occurrence of As(III) sorption by the coated FeS. Alumina, on the surface area basis, has about 8 times higher FeS coating amount and higher As(III) sorption capacity than silica. This study indicates that alumina is a better candidate than silica for the coating of nanocrystalline mackinawite.

• Nuclear Engineering and Technology
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• v.51 no.4
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• pp.1041-1046
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• 2019

In terms of long-term safety for radioactive waste disposal, the anionic iodide (I-129) with a long half-life ($1.6{\times}10^6yr$) is of a critical importance because this radionuclide migrates in geological media with limited interactions. Various studies have been performed to retard the iodide migration. Recently, some minerals that are likely generated from waste container corrosion, have been suggested to have a considerable chemical interaction with iodide. In this study, chalcocite and mackinawite were selected as candidate minerals for underground corrosion materials, and an iodide sorption experiment were carried out. The experiment was performed under anoxic and alkaline conditions and the pH effects on the iodide sorption were investigated in the range of pH 8 to 12. The results showed that both minerals demonstrated a noticeable sorption capacity on iodide, and the distribution coefficient ($K_d$) decreased as the pH increased in the experimental condition. In addition, when the alkalinity increased higher than a pH of 12, the sorption capacity of both minerals decreased dramatically, likely due to the competition of hydroxy ions with the iodide. This result confirmed that chalcocite was an especially good sorbing media for iodide under alkaline conditions with a pH value of less than 12.

• Journal of the Mineralogical Society of Korea
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• v.25 no.3
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• pp.155-162
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• 2012

We observed characteristic oxidation and dissolution phenomena induced by dissolved oxygen for mackinawite that is produced via sulfate-reducing bacteria (SRB) living in anaerobic environments such as soils and groundwater. We tried to recognize the role of the sulfide minerals that usually coexist with some stabilized radionuclides (e.g., reduced uranium), which can be reoxidized and redissolved by an oxygen-rich groundwater invaded into a contaminated area. The mackinawite produced by 'Desulfovibrio desulfuricans', a sulfate-reducing bacterium, was conducted to be dissolved for 2 weeks by some oxidants such as 'hydrogen peroxide' and 'sodium nitrite'. Although mineralogical oxidation and dissolution characteristics were different from each other according to the oxidants, the initially oxidized solution was early stabilized through the oxygen consumption by ${\mu}m$-sized sulfide particles and the resultant increase of sulfate in solution. From these results, we can anticipate that the large amount of sulfide minerals generated by SRB can not only repress the anoxic environment to be disturbed by the consumption of oxygen in groundwater, but also contribute to stabilize the reduced/precipitated radionuclides as a buffer material for a long time.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2018.11a
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• pp.199-200
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• 2018

• Journal of the Mineralogical Society of Korea
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• v.24 no.4
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• pp.279-287
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• 2011

In order to identify if bacteria surviving in soils and groundwater can change the oxidation/reduction potential of groundwater, Eh values of solution that contained bacteria were measured for 2 weeks. The Eh values of the solution reacted with sulfate-reducing bacteria decreased from -120 mV to -500 mV in 5 days, and $Desulfuricans$ was superior to $Vulgaris$ in reducing the solution. The Eh value was relatively higher for the solution containing $Shewanella$, iron-reducing bacteria, showing -400 mV. During the Eh decrease by the metal-reducing bacteria, a sulfide mineral such as mackinawite (FeS) started precipitating through the microbial reducing process for sulfate and ferric iron. These results show that the ORP of natrual groundwater may be sensitive to the geomicrobial respiration. In addition, a subsurface environment where groundwater is highly reduced and sulfide minerals are largely biogenerated may be a good place to retard the migration of oxidized radionu-clides by making them precipitated as reduced forms.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.1
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• pp.73-81
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• 2020

Strontium (⁹⁰Sr) and nickel (⁵⁹Ni) have been considered as key radionuclides in the safety assessment of radioactive waste disposal. Through various efforts to impede the migration of radioactive nuclides underground, it has been established that some minerals generated from the corrosion of the waste containers have a positive chemical interaction with these radionuclides. Among these minerals we selected mackinawite (FeS), an iron and sulfur compound, and performed a sorption experiment for the Sr and Ni in FeS under anoxic and alkaline conditions by reflecting deep underground environments. The effects of pH on sorption were likewise investigated in the pH range of 8 ~ 12. As a result, it was found that strontium failed to exhibit a good sorption capacity in a weak alkaline range, while nickel showed a noticeably higher sorption affinity over the entire experimental pH range. Moreover, we determined that as the pH increased in the solution, the distribution coefficients (K_d) were increased for both nuclides, which reflects when an alkalinity increses, the surface of the mineral charges much negatively by detaching the hydrogen or cations on the mineral surface. Thus, it can be concluded that the cationic nuclides of Sr and Ni can attach easily to the mineral under strong alkalinity.

• Journal of the Mineralogical Society of Korea
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• v.24 no.2
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• pp.83-90
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• 2011

Removal of dissolved uranium by D. baculatum, a sulfate-reducing bacterium, and effects of trace metals such as manganese, copper, nickel, and cobalt were investigated. Total concentrations of dissolved uranium and trace metals were used by $50\;{\mu}M$ and $200\;{\mu}M$, respectively. Most dissolved uranium decreased up to a non-detectable level (< 10 ppb) MS during the experiments. Most of the heavy metals did nearly not affect the bioremoval rates and amounts of uranium, but copper restrained microbial activity. However, it is found that dissolved uranium rapidly decreased after 2 weeks, showing that the bacteria can overcome the copper toxicity and remove the uranium. It is observed that nickel and cobalt were readily coprecipitated with biogenic mackinawite.

• 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.

• Journal of Soil and Groundwater Environment
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• v.27 no.1
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• pp.25-30
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• 2022

Mackinawite (FeS), as a ubiquitous reduced iron mineral, is known as a key controller of redox reactions in anaerobic subsurface environment. The reaction of FeS with redox-sensitive toxic element such as arsenic is substantially affected by pH conditions of the given environments. In this study, the interaction of As(V) with FeS was studied under strict anaerobic conditions with various pH conditions. The pH-dependent arsenic removal tests were conducted under wide ranges of pH conditions and X-ray absorption spectroscopy (XAS) was applied to investigate the reaction mechanisms under pH 5, 7, and 9. The removal efficiency of FeS for As(V) showed the higher removal of As(V) under low pH conditions and its removal efficiency decreased with increasing pH, and no As(V) reduction was observed in 1 g/L FeS solution. However, XAS analysis indicated the reduction of As(V) to As(III) occurred during reaction between FeS and As(V). The reduced form of As(III) was particularly identified as an arsenic sulfide mineral (As₂S₃) in all pH conditions (pH 5, 7, and 9). As₂S₃ precipitation was more pronounced in pH 5 where the solubility of FeS is higher than in other pH conditions. The linear combination fitting results of XAS demonstrated that As(V) removal mechanism is concerted processes of As₂S₃ precipitation and surface complexation of both arsenic species.