• Journal of the Mineralogical Society of Korea
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• v.14 no.1
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• pp.12-20
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• 2001

충북 영동군 동창광산에서 산출되는 일라이트(illite)광선의 표면화학특성을 전위차 적정 실험과 FITEQL3.2 프로그램을 이용하여 연구하였다. 정량 Xtjs 회절 분석에 의한 일라이트 광석의 광물조석은 석영 46.6% 일라이트 41.6% 카올리나이트(kaolinite) 11.8%이며 $N_2$BET 방법에 의하여 구한 비표면적은 $6.52 m^2$g이다. 전위차 적정 실험결과를 그란(Gran)법을 적용하여 구한 일라이트광석의 영전하점($pH_{pznpc}$ )은 pH 3.9 총표면 자리 밀도는 21.24 sites/$nm^2$이다. 표면 복합체 모델중 일정 용량 모델을 적용해 일라이트 광석의 표변 특성에 알맞는 모델을 찾아보았다. 일라이트 광석의 표면을 사면체 자리와 팔면체 자리로 나누어 설정한 2sites$-3pK_{ a}$s 모델은 변수값이 수렴되지않았으므로 부적절하다고 판단된다. 일라이트 광석의 표면을 하나의 균질한 흡착표면으로 가정해서 설정한 1 site -1 $K_{a}$ 와 1 site -2 $pK_{a}$ s 모델 사이에는 뚜렷한 차이는 없지만, 1 site -1 $pK_{a}$ 모델의 WSOS/DF 값이 17, 1 site - 2 $pK_a{s}$ 모델은 26으로서 앞 모델이 보다 적절하다. 이 결과는 일라이트 광석 표면에서 수소의 해리와 첨가 반응 중 첨가 반응을 무시하여도 표면반응을 설명하는 데 큰 무리가 없음을 시사한다. 가장 적절하다고 판단되는 1 site -1 $pK_{a}$ 모델의 $pK_{a}$ 값은 4.17, specific capacitance는 $6F/m^2$ 표면 자리 농도는 $1.15\Times10^{-3}$ mol/L 이다.

• Journal of the Mineralogical Society of Korea
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• v.28 no.2
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• pp.95-108
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• 2015

Nano-sized iron colloids are formed as acid mine drainage is exposed to surface environments and is introduced into surrounding water bodies. These iron nanomaterials invoke aesthetic contamination as well as adverse effects on aqueous ecosystems. In order to control them, the characteristics of their behaviour should be understood first, but the cumulative research outputs up to now are much less than the expected. Using zero-valent iron (ZVI) and magnetite, this study aims to investigate the behaviour of iron nanomaterials according to the change in the composition and pH of background electrolyte and the concentration of natural organic matter (NOM). The size and surface zeta potential of iron nanomaterials were measured using dynamic light scattering. Characteristic behaviour, such as aggregation and dispersion was compared each other based on the DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory. Whereas iron nanomaterials showed a strong tendency of aggregation at the pH near point of zero charge (PZC) due to electrostatic attraction between particles, their dispersions became dominant at the pH which was higher or lower than PZC. In addition, the behaviour of iron nanomaterials was likely to be more significantly influenced by cations than anions in the electrolyte solutions. Particularly, it was observed that divalent cation influenced more effectively than monovalent cation in electrostatic attraction and repulsion between particles. It was also confirmed that the NOM enhanced the dispersion nanomaterials with increasing the negative charge of nanomaterials by coating on their surface. Under identical conditions, ZVI aggregated more easily than magnetite, and which would be attributed to the lower stability and larger reactivity of ZVI.

• Economic and Environmental Geology
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• v.42 no.2
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• pp.95-105
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• 2009

Systematic studies are performed for arsenic adsorption on synthesized lepidocrocite. The synthesized lepidocrocite with high surface area of $94.8\;g/m^2$ has shown that the point of zero charge(PZC) is 6.57 determined by potentiometric titration, suggestive of high capacity of arsenic removal. Results show that arsenite[As(III)] uptake by synthesized lepidocrocite is greater than that of arsenate[As(V)] at pH $2{\sim}12$, indicating that the lepidocrocite has high affinity toward arsenite rather than arsenate. Adsorption of arsenate decreases with increasing pH from 2 to 12, whereas arsenite sorption increases until pH 8.0, and then decreases dramatically with increasing pH, suggesting that changes in surface charge of the lepidocrocite as a function of pH playa important role in aresinc uptake by the lepidocrocite. Upon kinetic experiments, our results demonstrate that both arsenite and arsenate sorption on the lepidocrocite increases rapidly for the first 4 h followed by little changes during the duration of the experiment, showing that adsorption plays a key role in aresenic uptake by the lepidocrocite. Our results also show that power function and elovich models are the best fit for the adsorption kinetics of arsenite and aesenate on the lepidocrocite.

• Resources Recycling
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• v.19 no.1
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• pp.33-39
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• 2010

The spheric sintered body with $6{\pm}2mm$ diameter was manufactured in a rotary kiln at $1125^{\circ}C$/15 min using green body formed by pelletizing the batch powder composing of coal bottom ash produced from power plant and dredged soil by 70:30, wt%. And the physical properties of sintered body (BD) were analyzed to confirm the possibility for applying to an absorbent to restore a contaminated soil. The sintered body had a giant pore above 100 ${\mu}m$ and a fine pore below 10 ${\mu}m$, and bulk density was 1.4. Also its specific surface area, porosity and void proportion were $12.0m^2/g$, 30.1% and 38.2% respectively. The crushed body (BD-C), produced by crushing a BD specimen into an irregular shape with a aspect ratio of about 2, was similar to BD specimen at bulk density and pore size distribution. But it had superior values of specific surface area, porosity and void proportion compared with BD specimen owing to a decreased apparent volume due to conversion of closed pore existed at interior of BD to open pore during a crushing process. The IEP of sintered body occurred at about pH=5, so the optimum pH condition of reacting aqueous solution could be known before bonding a microbe to the sintered body. Hence, the optimum void proportion and porosity of an absorbent can be obtained by appropriate mixing a BD with BD-C from the base data calculated in this study.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.197-210
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• 2012

Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).

• Journal of the Mineralogical Society of Korea
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• v.22 no.3
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• pp.177-189
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• 2009

Iron (oxyhydr)oxides commonly form as secondary minerals of high reactivity and large surface area resulting from alteration and weathering of primary minerals, and they are efficient sorbents for inorganic and organic contaminants. Accordingly, they have a great potential in industrial applications and are also of substantial interest in environmental sciences. Goethite (${\alpha}$-FeOOH) is one of the most ubiquitous and stable forms of iron (oxyhydr)oxides in terrestrial soils, sediments, and ore deposits, as well as a common weathering product in rocks of all types. This study focused on adsorption reaction as a main mechanism in scavenging arsenic using goethite. Goethite was synthesized in the laboratory to get high purity, and a variety of mineralogical and physicochemical features of goethite were measured and related to adsorption characteristics of arsenic. To compare differences in adsorption reactions between arsenic species, in addition, a variety of experiments to acquire adsorption isotherm, adsorption edges, and adsorption kinetics were accomplished. The point of zero charge (PZC) of the laboratory-synthesized goethite was measured to be 7.6, which value seems to be relatively higher, compared to those of other iron (oxyhydr)oxides. Its specific surface area appeared to be $29.2\;m^2/g$ and it is relatively smaller than those of other (oxyhydr)oxides. As a result, it was speculated that goethite shows a smaller adsorption capacity. It is likely that the affinity of goethite is much more larger for As(III) (arsenite) than for As(V) (arsenate), because As(III) was observed to be much more adsorbed on goethite than As(V) in equivalent pH conditions. When the adsorption of each arsenic species onto goethite was characterized in various of pH, the adsorption of As(III) was largest in neutral pH range (7.0~9.0) and decreased in both acidic and alkaline pH conditions. In the case of As(V), the adsorption appeared to be highest in the lowest pH condition, and then decreased with an increase of pH. This peculiarity of arsenic adsorption onto goethite might be caused by macroscopic electrostatic interactions due to variation in chemical speciation of arsenic and surface charge of goethite, and also it is significantly affected by change in pH. Parabolic diffusion model was adequate to effectively evaluate arsenic adsorption on goethite, and the regression results show that the kinetic constant of As(V) is larger than that of As(III).

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.229-244
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• 2013

Arsenic contamination may be brought about by a variety of natural and anthropogenic causes. Among diverse naturally-occurring chemical speciations of arsenic, trivalent (As(III), arsenite) and pentavalent (As(V), arsenate) forms have been reported to be the most predominant ones. It has been well known that the behavior of arsenic is chiefly affected by aluminum, iron, and manganese oxides. For this reason, this study was initiated to evaluate the applicability of manganese slag (Mn-slag) containing high level of Mn, Si, and Ca as an efficient sorbent of arsenic. The main properties of Mn-slag as a sorbent were investigated and the sorption of each arsenic species onto Mn-slag was characterized from the aspects of equilibrium as well as kinetics. The specific surface area and point of zero salt effect (PZSE) of Mn-slag were measured to be $4.04m^2/g$ and 7.73, respectively. The results of equilibrium experiments conducted at pH 4, 7 and 10 suggest that the sorbed amount of As(V) was relatively higher than that of As(III), indicating the higher affinity of As(V) onto Mn-slag. As a result of combined effect of pH-dependent chemical speciations of arsenic as well as charge characteristics of Mn-slag surface, the sorption maxima were observed at pH 4 for As(V) and pH 7 for As(III). The sorption of both arsenic species reached equilibrium within 3 h and fitting of the experimental results to various kinetic models shows that the pseudo-second-order and parabolic models are most appropriate to simulate the system of this study.

• Economic and Environmental Geology
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• v.53 no.4
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• pp.347-362
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• 2020

Iron (hydro)oxides in aqueous environments are primarily formed due to mining activities, and they are known to be typical colloidal particles disturbing surrounding environments. Among them, hematites are widespread in surface environments, and their behavior is controlled by diverse factors in aqueous environments. This study was conducted to elucidate the effect of environmental factors, such as ionic composition and strength, pH, and natural organic matter (NOM) on the behavior of colloidal hematite particles. In particular, two analytical methods, such as dynamic light scattering (DLS) and single-particle ICP-MS (spICP-MS), were compared to quantify and characterize the behavior of colloidal hematites. According to the variation of ionic composition and strength, the aggregation/dispersion characteristics of the hematite particles were affected as a result of the change in the thickness of the diffuse double layer as well as the total force of electrostatic repulsion and van der Walls attraction. Besides, the more dispersed the particles were, the farther away the aqueous pH was from their point of zero charge (PZC). The results indicate that the electrostatic and steric (structural) stabilization of the particles was enhanced by the functional groups of the natural organic matter, such as carboxyl and phenolic, as the NOM coated the surface of colloidal hematite particles in aqueous environments. Furthermore, such coating effects seemed to increase with decreasing molar mass of NOM. On the contrary, these stabilization (dispersion) effects of NOM were much more diminished by divalent cations such as Ca²⁺ than monovalent ones (Na⁺), and it could be attributed to the fact that the former acted as bridges much more strongly between the NOM-coated hematite particles than the latter because of the relatively larger ionic potential of the former. Consequently, it was quantitatively confirmed that the behavior of colloidal hematites in aqueous environments was significantly affected by diverse factors, such as ionic composition and strength, pH, and NOM. Among them, the NOM seemed to be the primary and dominant one controlling the behavior of hematite colloids. Meanwhile, the results of the comparative study on DLS and spICPMS suggest that the analyses combining both methods are likely to improve the effectiveness on the quantitative characterization of colloidal behavior in aqueous environments because they showed different strengths: the main advantage of the DLS method is the speed and ease of the operation, while the outstanding merit of the spICP-MS are to consider the shape of particles and the type of aggregation.

• Economic and Environmental Geology
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• v.46 no.6
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• pp.521-533
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• 2013

This study was initiated to evaluate the applicability of Si slag as an adsorbent via investigation of the main properties of Si slag as an adsorbent aw well as characterization of adsorption features between aqueous arsenic and Si slag. The specific surface area of Si slag was measured to be 6.71 $m^2/g$ which seems to be slightly higher than those of other slags, but relatively lower than those of iron (oxyhydr)oxides extensively used for arsenic controlling processes. The point of zero salt effect (PZSE) of Si slag determined by potentiometric titration appeared to be comparatively high (7.3), indicating the Si slag may be favorably used for adsorption of arsenic which predominantly exists as an oxy-anions. The results of adsorption isotherm indicate that regardless of arsenic species, Langmuir-type isotherm is the most suitable to simulate the adsorption of arsenic onto Si slag. With regard to pH-dependence of arsenic adsorption, the adsorption maxima of arsenite was centered at pH 7, and the adsorption was remarkably decreased in the other pH conditions. In the case of arsenate, on the other hand, the adsorption was highest at the lowest pH (4.0) and then gradually decreased with the increase of pH. Based on the results of kinetic experiments, it is likely that the adsorption of arsenite approached equilibrium within 2 hr, but it took about 8 hr for arsenate adsorption to be equilibrated. In addition, the Pseudo second order was evaluated to be most consistent with the empirical data of arsenic adsorption onto Si slag in this study. Under identical conditions, the affinity of arsenate onto Si slag was estimated to be nearly 6 times higher than that of arsenite.

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