• Economic and Environmental Geology
• /
• v.43 no.2
• /
• pp.137-148
• /
• 2010

The Myoungbong mine located in Boseong-gun, Jellanamdo consists of Au-Ag bearing quartz veins which filled the fissures of Bulguksa granitic rocks of Cretaceous. The tailings obtained from the Myungbong mine were used to investigate the effects of various processes, such as oxidation of primary sulfides and formation(alteration) of secondary and/or tertiary minerals, on arsenic immobilization in tailings. This study was conducted via both mineralogical and chemical methods. Mineralogical methods used included gravity and magnetic separation, ultrasonic cleaning, and instrumental analyses(X-ray diffractometry, energy-dispersive spectroscopy, and electron probe microanalyzer) and aqua regia extraction technique for soils was applied to determine the elemental concentrations in the tailings. Iron (oxy)hydroxides formed as a result of oxidation of tailings were identified as three specific forms. The first form filled in rims and fissures of primary pyrites. The second one precipitated and coated the surfaces of gangue minerals and the final form was altered into yukonites. Initially, large amounts of acid-generating minerals, such as pyrite and arsenopyrite, might make the rapid progress of oxidation reactions, and lots of secondary minerals including iron (oxy)hydroxides and scorodite were formed. The rate of pH decrease in tailings diminished, in addition, as the exposure time of tailings to oxidation environments was prolonged and the acid-generating minerals were depleted. Rather, it is speculated that the pH of tailings increased, as the contribution of pH neutralization reactions by calcite contained in surrounding parental rocks became larger. The stability of secondary minerals, such as scorodite, were deteriorated due to the increase in pH, and finally arsenic might be leached out. Subsequently, calcimn and arsenic ions dissociated from calcites and scorodites were locally concentrated, and yukonite could be grown tertiarily. It is confirmed that this tertiary yukonite which is one of arsenate minerals and contains arsenic in high level plays a crucial role in immobilizing arsenic in tailings. In addition to immobilization of arsenic in yukonites, the results indicate that a huge amount of iron (oxy)hydroxides formed by weathering of pyrite which is one of typical primary minerals in tailings can strongly control arsenic behavior as well. Consequently, this study elucidates that through a sequence of various processes, arsenic which was leached out as a result of weathering of primary minerals, such as arsenopyrite, and/or redissolved from secondary minerals, such as scorodite, might be immobilized by various sorption reactions including adsorption, coprecipiation, and absorption.

• Journal of the Mineralogical Society of Korea
• /
• v.21 no.4
• /
• pp.425-434
• /
• 2008

Arsenic contamination in soil and groundwater has recently been one of the most serious environmental concerns. This arsenic contamination can be originated from natural or anthropogenic sources. It has been well known that arsenic behavior in geo-environmental is controlled by various oxides or hydroxides, such as those of iron, manganese, and aluminum, and clay minerals. Among those, particularly, iron (oxy)hydroxides are the most effective scavengers for arsenic. For this reason, this study characterized arsenic adsorption of magnetite which is a kind of iron oxide in nature. The physicochemcial features of the magnetite were investigated to evaluate adsorption of arsenite [As(III)] and arsenate [As(V)] onto magnetite. In addition to experiments on adsorption equilibria, kinetic experiments were also conducted. The point of zero charge (PZC) and specific surface area of the laboratory-synthesized magnetite used as an arsenic adsorbent were measured 6.56 and $16.6\;g/m^2$, which values seem to be relatively smaller than those of the other iron (oxy)hydroxides. From the results of equilibria experiments, arsenite was much more adsorbed onto magnetite than arsenate, indicating the affinity of arsenite on magnetite is larger than arsenate. Arsenite and arsenate showed adsorption maxima at pHs 7 and 2, respectively. In particular, adsorption of arsenate decreased with increase in pH as a result of electrical repulsion caused by anionic arsenate and negatively-charged surface of magnetite. These results indicate that the surface charge of magnetite and the chemical speciation of arsenic should be considered as the most crucial factors in controlling arsenic. The results of kinetic experiments show that arsenate was adsorbed more quickly than arsenite and adsorption of arsenic was investigated to be mostly completed within the duration of 4 hours, regardless of chemical speciation of arsenic. When the results of kinetic experiments were fitted to a variety of kinetic models proposed so far, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto magnetite.

• Journal of the Mineralogical Society of Korea
• /
• v.22 no.4
• /
• pp.359-370
• /
• 2009

Arsenic and heavy metals leached out as a result of oxidation of tailings exposed to the surface pose a serious environmental contamination of mine areas. This study investigated how arsenic behavior is controlled by a variety of processes, such as oxidation of sulfides and formation or alteration of secondary minerals, based on mineralogical methods. The study was carried out using the tailing samples obtained from Nakdong mine located in Jeongseongun, Gangwondo. After separating magnetic and non-magnetic minerals using pretreated tailing samples, each mineral sample was classified according to their colors and metallic lusters observed by the stereoscopic microscope. Subsequently, the mineralogical properties were determined using various instrumental analyses, such as x-ray diffractometer (XRD), energy dispersive spectroscopy (EDS), and electron probe micro analyzer (EPMA). The literature review confirmed that various ore minerals were identified in the Nakdong ore deposits. In this study, however, there were observed a few original ore minerals as well as secondary and/or tertiary minerals newly formed as a result of weathering including oxidation. In particular, we did not recognize pyrrhotite which has been known to originally exist in a large abundance, but peculiarly colloform-type iron (oxy)hydroxides were identified, which indicates most of pyrrhotite has been altered by rapid weathering due to its large reactivity. In addition, a secondary scorodites filling the fissure of weathered primary arsenopyrites were identified, and it is speculated that arsenic is immobilized through such a alteration reaction. Also, we observed tertiary iron (oxy)hydroxides were formed as a result of re-alteration of secondary jarosites, and it suggests that the environment of tailing has been changed to high pH from low pH condition which was initiated and developed by oxidation reactions of diverse primary ore minerals. The environmental change is mainly attributed to interactions between secondary minerals and parental rocks around the mine. As a result, not only was the stability of secondary minerals declined, but tertiary minerals were newly formed. As such a process goes through, arsenic which was immobilized is likely to re-dissolve and disperse into surrounding environments.

• Journal of the Mineralogical Society of Korea
• /
• v.21 no.3
• /
• pp.227-237
• /
• 2008

Arsenic has recently become of the most serious environmental concerns, and the worldwide regulation of arsenic fur drinking water has been reinforced. Arsenic contaminated groundwater and soil have been frequently revealed as well, and arsenic contamination and its treatment and measures have been domestically raised as one of the most important environmental issues. Arsenic behavior in geo-environment is principally affected by oxides and clay minerals, and particularly iron (oxy)hydroxides have been well known to be most effective in controlling arsenic. Among a number of iron (oxy)hydroxides, for this reason, 2-line ferrihydrite was selected in this study to investigate its effect on arsenic behavior. Adsorption of 2-line ferrihydrite was characterized and compared between As(III) and As(V) which are known to be the most ubiquitous species among arsenic forms in natural environment. Two-line ferrihydrite synthesized in the lab as the adsorbent of arsenic had $10\sim200$ nm for diameter, $247m^{2}/g$ for specific surface area, and 8.2 for pH of zero charge, and those representative properties of 2-line ferrihydrite appeared to be greatly suitable to be used as adsorbent of arsenic. The experimental results on equilibrium adsorption indicate that As(III) showed much stronger adsorption affinity onto 2-line ferrihydrite than As(V). In addition, the maximum adsorptions of As(III) and As(V) were observed at pH 7.0 and 2.0, respectively. In particular, the adsorption of As(III) did not show any difference between pH conditions, except for pH 12.2. On the contrary, the As(V) adsorption was remarkably decreased with increase in pH. The results obtained from the detailed experiments investigating pH effect on arsenic adsorption show that As(III) adsorption increased up to pH 8.0 and dramatically decreased above pH 9.2. In case of As(V), its adsorption steadily decreased with increase in pH. The reason the adsorption characteristics became totally different depending on arsenic species is attributed to the fact that chemical speciation of arsenic and surface charge of 2-line ferrihydrite are significantly affected by pH, and it is speculated that those composite phenomena cause the difference in adsorption between As(III) and As(V). From the view point of adsorption kinetics, adsorption of arsenic species onto 2-line ferrihydrite was investigated to be mostly completed within the duration of 2 hours. Among the kinetic models proposed so for, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto 2-line ferrihydrite.

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.4
• /
• pp.409-421
• /
• 2022

Achieving a highly resolved spatial distribution of Mn-bearing minerals and elements in the natural ferromanganese nodules can provide detailed knowledge of the temporal variations of geochemical conditions affecting the formation processes of nodules. While a recent study utilizing Raman spectroscopy has reported the changes in the manganate mineral phases with growth for spherical nodules from the Arctic Sea, the distributions of minerals and elements in the nodules from the shallow Arctic Sea with non-spherical forms have not yet fully elucidated. Here, we reported the micro-laser Raman spectra with varying data acquisition points along three different profiles from the center to the outermost rim of the non-spherical ferromanganese nodules collected from the East Siberian Sea (~73 m). The elemental distributions in the nodule (such as Mn, Fe, etc.) were also investigated by energy dispersive X-ray spectroscopy (EDS) analysis to observe the internal structure and mineralogical details. Based on the microscopic observation, the internal structures of a non-spherical nodule can be divided into three different regions, which are sediment-rich core, iron-rich substrate, and Mn-Fe layers. The Raman results show that the Mn-bearing mineral phases vary with the data acquisition points in the Mn-Fe layer, suggesting the changes in the geochemical conditions during nodule formation. In addition, we also observe that the mineral composition and structural characteristics depend on the profile direction from the core to the rim. Particularly, the Raman spectra obtained along one profile show the lack of Fe-(oxy)hydroxides and the noticeably high crystallinity of Mn-bearing minerals such as birnessite and todorokite. On the other hand, the spectra obtained along the other two profiles present the presence of significant amount of amorphous or poorly-ordered Fe-bearing minerals and the low crystallinity of Mn-bearing minerals. These results suggest that the diagenetic conditions varied with the different growth directions. We also observed the presence of halite in several layers in the nodule, which can be evidence of the alteration of seawater after nodule formation. The current results can provide the opportunity to obtain detailed knowledge of the formation process and geochemical environments recorded in the natural non-spherical ferromanganese nodule.

• Journal of the Korean Society of Groundwater Environment
• /
• v.7 no.3
• /
• pp.103-115
• /
• 2000

The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.