• Nuclear Engineering and Technology
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• v.51 no.3
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• pp.755-760
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• 2019

Compound samples based on the mineral-like magnesium potassium phosphate matrix $MgKPO_4{\times}6H_2O$ were synthesized by solidification of high level waste surrogate. Phase composition and structure of synthesized samples were studied by XRD and SEM methods. Compressive strength of the compounds is $12{\pm}3MPa$. Coefficient of thermal expansion of the samples in the range $250-550^{\circ}C$ is $(11.6{\pm}0.3){\times}10^{-6}1/^{\circ}C$, and coefficient of thermal conductivity in the range $20-500^{\circ}C$ is $0.5W/(m{\times}K)$. Differential leaching rate of elements from the compound, $g/(cm^2{\times}day)$: $Mg-6.7{\times}10^{-6}$, $K-3.0{\times}10^{-4}$, $P-1.2{\times}10^{-4}$, $^{137}Cs-4.6{\times}10^{-7}$; $^{90}Sr-9.6{\times}10^{-7}$; $^{239}Pu-3.7{\times}10^{-9}$, $^{241}Am-9.6{\times}10^{-10}$. Leaching mechanism of radionuclides from the samples at the first 1-2 weeks of the leaching test is determined by dissolution ($^{137}Cs$), wash off ($^{90}Sr$) or diffusion ($^{239}Pu$ and $^{241}Am$) from the compound surface, and when the tests continue to 90-91 days - by surface layer depletion of compound. Since the composition and physico-chemical properties of the compound after irradiation with an electron beam (absorbed dose of 1 MGy) are constant the radiation resistance of compound was established.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.1
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• pp.101-108
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• 2005

Because the stone cultural properties located outdoors, they have been altered and deteriorated in external appearance due to environmental factors such as acid rain, extreme change in temperature, and salts. Damage to stone cultural properties is accelerated particularly due to recent industrial development and environmental pollution. An experimental study was conducted to evaluate the effect of environmental contaminants on the weathering of granite. And as part of the developing of conservation method, $TiO_2$ catalyst was prepared and tested. When fresh granite was dipped into the salt and acid solutions, dissolution rate of eight minerals (Si, Mg, Ca, Na, K, Fe, Mn, Al) are abruptly increased at initial stage of reaction and then increased steadily until 100 cycles. After salt and acid solution experiments, the mineral compositions of the granite surface were lower then that of the fresh granite and density of the weathered granite was steadily decreased from $2.60\;g/cm^3$ to $2.56\;g/cm^3$, but Poissions ratio and absorption ratio were slightly increased. It was expected at stone cultural assets could be weathered by salts and acid rain. In the case of $TiO_2$ was coated to the granite, the dissolution rate of minerals and absorption ratio of $TiO_2$ coated granite were decreased. Therefore, the $TiO_2$ coating method tested in this study considered to be a viable method to assist in the conservation of stone cultural properties from environmental contaminants.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.24-29
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• 1999

Naturally-occurring iron minerals, goethite, magnetite, and hydrogen peroxide were used to catalyze and initiate Fenton-like oxidation of silica sand contaminated with mixture of diesel and kerosene in batch system. Optimal reaction conditions were investigated by varying pH(3, 7), $H_2O_2$ concentration(0%, 1%, 7%, 15%, 35%), initial contaminant concentration(0.2, 0.5, 1.0 g-mixture of diesel and kerosene/ kg-soil), and iron mineral contents(1, 5, and 10 wt % magnetite or goethite). Contaminant degradations in silica sand-iron mineral-$H_2O_2$ systems were identified by determining total petroleum hydrocarbon(TPH) concentration. The optimal pH of the system was 3. The system which iron minerals were the only iron source was more efficient than the system with $FeSO_4$ solution due to lower $H_2O_2$ consumption. In case of initial contaminant concentration of 1g-contaminant/kg-soil with 5 wt % magnetite, addition of 0%, 1%, 7%, 15%, and 35% of $H_2O_2$ showed 0%, 24.5%, 44%, 52%, and 70% of TPH reduction in 8 days, respectively. When the mineral contents were varied 0, 1, 5, and 10wt%, removal of contaminants were 0%, 33.5%, 50%, and 60% for magnetite and 0%, 29%, 41%, and 53% for goethite, respectively. Reaction of magnetite system showed higher degradation than that of goethite system due to dissolution of iron and mixed presence of iron(II) and iron(III); however, dissolved iron precipitated on the surface of iron mineral and seemed to cause reducing electron transfer activity on the surface and quenching $H_2O_2$. The system using goethite has better treatment efficiency due to less $H_2O_2$ consumption. When cach system was mixed by shaker, removal of contaminants increased by 41% for magnetite and 30% for goethite. Results of this study showed catalyzed $H_2O_2$ system made in-situ treatment of soil contaminated with petroleum possible without addition of iron source since natural soils generally contain iron minerals such as magnetite and goethite.

• Economic and Environmental Geology
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• v.38 no.5 s.174
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• pp.547-561
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• 2005

General characteristics of groundwater contamination by As were reviewed with several recent researches, and its occurrence in groundwater of Korea was investigated based on a ffw previous studies and a groundwater quality survey in Nonsan and Geumsan areas. In Bangladesh, which has been known as the most serious arsenic calamity country, about $28\%$ of the shallow groundwaters exceeded the Bangladesh drinking water standard, $50{\mu}g/L$, and it was estimated that about 28 million people were exposed to concentrations greater than the standard. Groundwater was characterized by circum-neutral pH with a moderate to strong reducing conditions. Low concentrations of $SO_4^{2-}$ and $NO_3^-$, and high contents of dissolved organic carbon (DOC) and $NH_4^+$ were typical chemical characteristics. Total As concentrations were enriched in the Holocene alluvial aquifers with a dominance of As(III) species. It was generally agreed that reductive dissolution of Fe oxyhydroxides was the main mechanism for the release of As into groundwater coupling with the presence of organic matters and microbial activities as principal factors. A new model has also been suggested to explain how arsenic can naturally contaminate groundwaters far from the ultimate source with transport of As by active tectonic uplift and glaciatiion during Pleistocene, chemical weathering and deposition, and microbial reaction processes. In Korea, it has not been reported to be so serious As contamination, and from the national groundwater quality monitoring survey, only about $1\%$ of grounwaters have concentrations higher than $10{\mu}g/:L.$ However, it was revealed that $19.3\%$ of mineral waters, and $7\%$ of tube-well waters from Nonsan and Geumsan areas contained As concentrations above $10{\mu}g/:L.$. Also, percentages exceeding this value during detailed groundwater quality surveys were $36\%\;and\;22\%$ from Jeonnam and Ulsan areas, respectively, indicating As enrichment possibly by geological factors and local mineralization. Further systematic researches need to proceed in areas potential to As contamination such as mineralized, metasedimentary rock-based, alluvial, and acid sulfate soil areas. Prior to that, it is required to understand various geochemical and microbial processes, and groundwater flow characteristics affecting the behavior of As.

• Economic and Environmental Geology
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• v.38 no.5 s.174
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• pp.499-512
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• 2005

EPMA determined that Fe(Mn)-(oxy)hydroxides and well-crystallized Fe-(oxy)hydroxides and could contain a small amount of As $(0.3-11.0\;wt.\%\;and\;2.1-7.4\;wt.\%\;respectively)$. Amorphous crystalline Fe-(oxy) hydroxide assemblages were identified as the richest in As with $28-36\;wt.\%$. On the ternary $As_2O_5-SO_3-Fe_2O_3$ diagram, these materials were interpreted here as 'scorodite-like'. Dissolved As was attenuated by the adsorption on Fe-(oxy) hydroxides and Fe(Mn)-(oxy) hydroxides and/or the formation of an amorphous Fe-As phase (maybe scorodite: $FeAsO_4\cdot2H_2O$). Leaching tests were performed in order to find out leaching characteristics of As and Fe under acidic conditions. At the initial pHs 3 and 5, As contents dissolved from tailings of the cheongyang mine significantly increased after 7 days due to the oxidation of As-bearing secondary minerals (up to ca. $2.4\%$ of total), while As of Seobo mine-tailing samples was rarely released (ca. $0.0-0.1\%$ of total). Dissolution experiments at an initial pH 1 liberated a higher amount of As (ca. $1.1-4.2\%$ of total for Seobo tailings, $1.5-14.4\%$ of total for Cheongyang tailings). In addition, good correlation between As and Fe in leached solutions with tailings was observed. The kinetic problems could be the important factor which leads to increasing concentrations of As in the runoff water. Release of As from Cheongyang tailings can potentially pose adverse impact to surface and groundwater qualities in the surrounding environment, while precipitation of secondary minerals and the adsorption of As are efficient mechanisms for decreasing the mobilities of As in the surface environment of Seobo mine area.

• Journal of the Mineralogical Society of Korea
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• v.19 no.4 s.50
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• pp.265-275
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• 2006

It is in its infancy to use bacteria as a novel biotechnology for leaching precious and heavy metals from raw materials. The objective of this study was to investigate biogeochemical processes of iron leaching from magnetite reduction by iron-reducing bacteria isolated from intertidal flat sediments, southwestern part of Korea. Microbial leaching experiments were performed using commercial magnetite, Aldrich magnetite, in well-defined mediums with and without bacteria. Water soluble Fe production was determined by ICP analysis of bioleached samples in comparison to uninoculated controls, 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 = 107 ppm) was higher than that in the anaerobic environments (Fe = 94 ppm). In the anaerobic conditions, Fe(III) in commercial magnetite was also reduced to Fe(II), but no secondary mineral phases were observed. Amorphous iron oxides formed in the medium under aerobic conditions where there was sufficient supply of oxygen from the atmosphere. SEM observation suggests that the reduction process involves dissolution-precipitation mechanisms as opposed to solid state conversion of magnetite to amorphous iron oxides. The ability of bacteria to leach soluble iron and precipitate amorphous iron oxides from crystalline magnetite could have significant implications for biogeochemical processes in sediments where Fe(III) in magnetite plays an important role in the largest pool of electron acceptor as well as the tool as a novel biotechnology for leaching precious and heavy metals from raw materials.

• Proceedings of the Mineralogical Society of Korea Conference
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• 2001.06a
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• pp.38-39
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• 2001

The seasonal changes in pH, Fe, Al and SO$_4$$\^$2-/ contents of acid drainage released from coal mine dumps play a major role in precipitation of metal hydroxides in the Taebaek coal field area, southeastern Korea. Precipitates in the creeks underwent a cycle of the color change showing white, reddish brown and brownish yellow, which depends on geochemical factors of the creek waters. White precipitates consist of Al-sulfate (basaluminite and hydrobasaluminite) and reddish brown ones are composed of ferrihydrite and brownish yellow ones are of schwertmannite. Goethite coprecipitates with ferrihydrite and schwertmannite. Ferrihydrite formed at higher values than pH 5.3 and schwertmannite precipitated below pH 4.3, and goethite formed at the intermediate pH range between the two minerals. With the pH being increased from acid to intermediate regions, Fe is present both as schwertmannite and goethite. From the present observation, the most favorable pH that basauluminte can precipitate is in the range of pH 4.45-5.95. SEM examination of precipitates at stream bottom shows that they basically consist of agglomerates of spheroid and rod-shape bacteria. Bacteria species are remarkably different among bottom precipitates and, to a less extent, there are slightly different chemical compositions even within the same bacteria. The speciation and calculation of the mineral saturation index were made using MINTEQA2. In waters associated with yellowish brown precipitates mainly composed of schwertmannite, So$_4$ species is mostly free So$_4$$\^$2-/ ion with less AlSo$_4$$\^$+/, CaSo$\sub$(aq)/, and MgSo$\sub$4(aq)/. Ferrous iron is present mostly as free Fe$\^$2+/, and FeSo$\sub$4(aq)/ and ferric iron exists predominantly as Fe(OH)$_2$$\^$+/, with less FeSo$\sub$4(aq)/, Fe(OH)$_2$$\^$-/, FeSo$_4$$\^$-/ and Fe$\^$3+/, respectively Al exists as free Al$\^$3+/, AlOH$_2$$\^$-/, (AlSo$_4$)$\^$+/, and Al(So$_4$)$\^$2-/. Fe is generally saturated with respect to hematite, magnetite, and goethite, with nearly saturation with lepidocrocite. Aluminum and sulfate are supersaturated with respect to predominant alunite and less jubanite, and they approach a saturation state with respect to diaspore, gibbsite, boehmite and gypsum. In the case of waters associated with whitish precipitates mainly composed of basaluminite, Al is present as predominant Al$\^$3+/ and Al(SO$_4$)$\^$+/, with less Al(OH)$\^$2+/, Al(OH)$_2$$\^$+/ and Al(SO$_4$)$\^$2-/. According to calculation for the mineral saturation, aluminum and sulfate are greatly supersaturated with respect to basaluminite and alunite. Diaspore is flirty well supersaturated while jubanite, gibbsite, and boehmite are already supersaturated, and gypsum approaches its saturation state. The observation that the only mineral phase we can easily detect in the whitish precipitate is basaluminite suggests that growth rate of alunite is much slower than that of basaluminite. Neutralization of acid mine drainage due to the dilution caused by the dilution effect due to mixing of unpolluted waters prevails over the buffering effect by the dissolution of carbonate or aluminosilicates. The main factors to affect color change are variations in aqueous geochemistry, which are controlled by dilution effect due to rainfall, water mixng from adjacent creeks, and the extent to which water-rock interaction takes place with seasons. pH, Fe, Al and SO$_4$ contents of the creek water are the most important factors leading to color changes in the precipitates. A geochemical cycle showing color variations in the precipitates provides the potential control on acid mine drainage and can be applied as a reclamation tool in a temperate region with four seasons.

• 한국석유지질학회:학술대회논문집
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• autumn
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• pp.63-65
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• 2001

The Chosen Supergroup (Cambro-Ordovician), mid-east Korea consists mainly of shallow marine carbonates and contains a variety of limestone conglomerates. These conglomerates largely comprise oligomictic, rounded lime-mudstone clasts of various size and shape (equant, oval, discoidal, tabular, and irregular) and dolomitic shale matrices. Most clasts are characterized by jigsaw-fit (mosaic), disorganized, or edgewise fabric and autoclastic lithology. Each conglomerate layer is commonly interbedded with limestone-dolomitic shale couplets and occasionally underlain by fractured limestone layer, capped by calcareous shale. According to composition, characteristic sedimentary structures, and fabric, limestone conglomerates in the Hwajol, Tumugol, Makkol, and Mungok formations of Chosen Supergroup can be classified into 4 types: (1) disorganized polymictic conglomerate (Cd), (2) horizontally stratified polymictic conglomerate (Cs), (3) mosaic conglomerate (Cm), and (4) disorganized/edgewise oligomictic conglomerate (Cd/e). These conglomerates are either depositional (Cd and Cs) or diagenetic (Cm and Cd/e) in origin. Depositional conglomerates are interpreted as storm deposits, tidal channel fills, or transgressive lag deposits. On the other hand, diagenetic conglomerates are not deposited by normal sedimentary processes, but formed by post-depositional diagenetic processes. Diagenetic conglomerates in the Chosen Supergroup are characterized by autoclastic and oligomictic lithology of lime-mudstone clasts, jigsaw-fit (mosaic) fabric, edgewise fabric, and a gradual transition from the underlying bed (Table 1). Autoclastic and oligomictic lithologies may be indicative of subsurface brecciation (fragmentation). Consolidation of lime-mudstone clasts pre-requisite for brecciation may result from dissolution and reprecipitation of CaCO3 by degradation of organic matter during burial. Jigsaw-fit fabric has been considered as evidence for in situ fragmentation. The edgewise fabric is most likely formed by expulsion of pore fluid during compaction. The lower boundary of intraformational conglomerates of depositional origin is commonly sharp and erosional. In contrast, diagenetic conglomerate layers mostly show a gradual transition from the underlying unit, which is indicative of progressive fragmentation upward (Fig. 1). The underlying fractured limestone layer also shows evidence for in situ fragmentation such as jigsaw-fit fabric and the same lithology as the overlying conglomerate layer (Fig, 1). Evidence from the conglomerate beds in the Chosen Supergroup suggests that diagenetic conglomerates are formed by in situ subsurface fragmentation of limestone layers and rounding of the fragments. In situ subsurface fragmentation may be primarily due to compaction, dewatering (upward-moving pore fluids), and dissolution, accompanying volume reduction. This process commonly occurs under the conditions of (1) alternating layers of carbonate-rich and carbonate-poor sediments and (B) early differential cementation of carbonate-rich layers. Differential cementation commonly takes place between alternating beds of carbonate-rich and clay-rich layers, because high carbonate content promotes cementation, whereas clay inhibits cementation. After deposition of alternating beds and differential cementation, with progressive burial, upward-moving pore fluid may raise pore-pressure in the upper part of limestone layers, due to commonly overlying impermeable shale layers (or beds). The high pore-pressure may reinforce propagation of fragmentation and cause upward-expulsion of pore fluid which probably produces edgewise fabric of tabular clasts. The fluidized flow then extends laterally, causing reorientation and further rounding of clasts. This process is analogous to that of autobrecciation, which can be analogously termed autoconglomeration. This is a fragmentation and rounding process whereby earlier semiconsolidated portions of limestone are incorporated into still fluid portions. The rounding may be due mainly to immiscibility and surface tension of lime-mud. The progressive rounding of the fragmented clasts probably results from grain attrition by fluidized flow. A synthetic study of limestone conglomerate beds in the Chosen Supergroup suggests that very small percent of the conglomerate layers are of depositional origin, whereas the rest, more than $80\%$, are of diagenetic origin. The common occurrence of diagenetic conglomerates warrants further study on limestone conglomerates elsewhere in the world.

• The Journal of the Petrological Society of Korea
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• v.9 no.4
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• pp.211-237
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• 2000

Major element zoning has been analyzed in garnet porphroblasts obtained from the Grt-St and Ky-Grt-St grade assemblages in Zones I on the northern flank of the Pelham Dome, north central Massachusetts. These porphyroblasts grew during multiple phases of deformation and meta-morphism revealed by the inclusion trail geometry plus the chemical zoning patterns within garnet porphyroblasts. Unusual zoning patterns, including zoning reversals and gradient changes in XMn, zlgzag patterns in Fe/(Fe +Mg) and staircase-shaped patterns in XCa, are coincident with textural truncations and other changes in microstructure within the garnet porphrublasts. Chemical variations in plagioclase, biotite, muscovite and staurolite combined with inclusion trail geometry and petrography reveal that the garnet zoning patterns are modified by combinations of the following. (1) Uni-and divariant reactions involving garnet consumption(Grt+ Chl+Ms=St+Bt+Qtz + $H_2$O) and production(St+Ms + Qtz= Bt+ Grt +A1$_2$$SiO_{5}$ + $H_2$O). (2) Deformation induced episudic ionit dissolution, preferential diffusion and re-distribution during foliation development. (3) P-T changes during growth of the porphyroblasts. The P-T paths combined with petrographic and inclusion trail morphology observations consist of two pattens; (1) heating/compression during NW-SE shortening; and (2) decompression with cooling during NNW-SSE shortening. Based on temperature-time(T-t) geochronological data and late-Paleozoic tectonic model, Alleghanian metamorphism, which is the result of heterogeneous shearing concentrated along the boundary between the Abalone Terrane(Pelham dome) and cover rocks(Bronson Hill Terrane), has produced Ky-St-Ms mineral assemblage during Pennsylvanian(290-300 Ma) in Shutesbury area. However, temperature of alleghanian metamorphism was not high enough to form garnet and staurolite in the Northfiled syncline area. Alleghanian metamorphism has affected only the matrix due to heterogeneous shearing in the study area.

• 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.