Hematite-coated sand was examined for the application of the PRB (permeable reactive barrier) to the arsenic-contaminated subsurface in the metal mining areas. The removal efficiency of As in a batch and a flow system was investigated through the adsorption isotherm, removal kinetics and column experiments. Hematite-coated sand followed a linear adsorption isotherm with high adsorption capacity at low level concentrations of As (<1.0 mg/L). In the column experiments, high content of hematite-coated sand enhanced the removal efficiency, but the amount of the As removal decreased due to the higher affinity of As (V) than As (III) and reduced adsorption kinetics in the flow system. Therefore. the amount of hematite-coated sand, the adsorption affinity of As species and removal kinetics determined the removal efficiency of As in a flow system.
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.
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.
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.
Kim, Soon-Oh;Lee, Woo-Chun;Jeong, Hyeon-Su;Cho, Hyen-Goo
Journal of the Mineralogical Society of Korea
/
v.22
no.3
/
pp.177-189
/
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).
Kim, Kwang-Seob;Song, Ki-Hoon;Yang, Jae-Kyu;Chang, Yoon-Young
Journal of Korean Society of Environmental Engineers
/
v.28
no.8
/
pp.878-883
/
2006
Removal efficiency of As(III) was investigated with a pilot-scale filtration system packed with an equal amount(each 21.5 kg) of manganese-coated sand(MCS) in the bottom and iron-coated sand(ICS) in the top. Height and diameter of the used column was 200 cm and 15 cm, respectively. The As(III) solution was introduced into the bottom of the filtration system with a peristaltic pump at a speed of $5{\times}10^{-3}$ cm/s over 148 days. Breakthrough of total arsenic in the mid-sampling position(end of the MCS bed) and final-sampling position(end of the ICS bed) was started after 18 and 44 days, respectively, and then showed a complete breakthrough after 148 days. Although the breakthrough of total arsenic in the mid-sampling position was started after 18 days, the concentration of As(III) in this effluent was below 50 ppb up to 61 days. This result indicates that MCS has a sufficient oxidizing capacity to As(III) and can oxidize 92 mg of As(III) with 1 kg of MCS up to 61 days. When a complete breakthrough of total arsenic occurred, the removed total arsenic by MCS was calculated as 79.0 mg with 1 kg MCS. As variation of head loss is small at each sampling position over the entire reaction time, it was possible to operate the filtration system with ICS and MCS for a long time without a significant head loss.
Kim, Seong Hee;Lee, Woo Chun;Cho, Hyen Goo;Kim, Soon-Oh
Journal of the Mineralogical Society of Korea
/
v.25
no.4
/
pp.197-210
/
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).
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.
Journal of Korean Society of Environmental Engineers
/
v.28
no.11
/
pp.1186-1191
/
2006
Removal efficiency of As(III) through oxidation and adsorption in column reactors was investigated at different ratios of manganese-coated sand(MCS) and iron-coated sand(ICS) : MCS-alone, ICS-alone and both of ICS and MCS. The breakthrough of arsenic immediately occurred from a column reactor with MCS-alone. However, most of the arsenic present in the effluent was identified as As(V) due to the oxidation of As(III) by MCS. While five-times delayed breakthrough of arsenic was observed from a column reactor with ICS-alone. At a complete breakthrough of arsenic, the removed As(III) was 36.1 mg with 1 kg ICS. To find an optimum ratio of ICS and MCS in the column packed with both ICS and MCS, the removal efficiency of As(III) was investigated at three different ratios of ICS/MCS with a fixed amount of ICS. The breakthrough time of arsenic was quite similar in the different ratios ICS/MCS. However, much slower breakthrough of arsenic was observed as the ratio of ICS/MCS decreased. As the ratio of ICS/MCS decreased the concentration of As(III) in the effluent decreased and then showed below 50 ppb at an equal amount of ICS and MCS, suggesting more efficient oxidation of As(III) by greater amount of MCS. When a complete breakthrough of arsenic occurred, the removed total arsenic with an equal amount of ICS and MCS was 68.5 mg with 1 kg of filter material.
Kim, Seong Hee;Seol, Jeong Woo;Lee, Woo Chun;Kim, Soon-Oh
Economic and Environmental Geology
/
v.46
no.6
/
pp.521-533
/
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.
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