Kim, Soon-Oh;Lee, Woo-Chun;Jeong, Hyeon-Su;Cho, Hyen-Goo
Journal of the Mineralogical Society of Korea
/
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).
The variety and density of entomopathogenic nematodes from the polluted soils of heavy metals were examined. In order to investigate the pollution of heavy metals in soil, 300 sites in kyungsangbuk-do were collected from March to October in 2001. We measured the contents of seven heavy metal elements (Cd, Cu, As, Hg, Pb, Cr^{6+}$, CN) and than cheesed soil of 25 sites with high concentration of heavy metals. The seven strains of nematodes were isolated from seven samples by silkworm host (Bombyx mori mori) and white trap. Isolated nematodes are composed of two families, one order. The members of Rhabditida were isolated in the soil with mean Cd content of 0.870 ppm. And they were isolated in the soil samples with As content less than 0.745 ppm. However they were isolated regardless of concentration of Cu and Pb. The members of Cylindrocorpidae were isolated in the soil samples with Cr^{6+}$ content less than 0.05 ppm. Any entomopathogenic nematode was not detected in the CN polluted soil. Isolated nematodes successfully cultured on the silkworm host and were confirmed the pathogenicity, multiplicity, and tolerance against various condition of preservation. Which proved its potential usefulness as biological agent.
All of the water and stone-dust samples with or without flocculant, in and around quarry mines, were analyzed for total concentrations of heavy metals, cyanide(CN), toxic organic compounds and organic phosphorus. Extraction experiments on stone-dust by EDTA and various pH solutions were also carried out, in order to evaluate the contaminant leaching from the long-term heaped stone-dust within quarry mines. The concentrations of $Cr^{6+}$, Hg, CN, TCE/PCE and total phosphorus in all samples (water and stone-dust) were under detection limits, confirming no environmental contamination from stone-dust in quarry mine areas. Lead and cadmium were not detected in all water samples. Copper and zinc were found in some water samples, and arsenic was detected in a few water samples. But they also showed levels much lower than the drinking water standard. Results of the extraction experiments by EDTA and pH solutions showed that Pb, Cr, Cd, Cu and Zn were leached out in less amounts or under detection limits. Arsenic was detected only at pH 3. From above results, we suggested that environmental contamination by quarry mine development is likely to be minor or negligible.
The purpose of this study was to assess the applicability of acid mine drainage sludge (AMDS) pellets for the arsenic (As) stabilization and to suggest an evaluation method for arsenic stabilization efficiency in soil around abandoned coal mines. The soil samples were collected from the agricultural field around Ham-Tae, Dong-Won, Dong-Hae, and Ok-Dong coal mine. The As concentration in soil was exceeding the criteria of soil pollution level, except for Ham-Tae coal mine. The AMDS pellets are more appropriate to use by reducing dust occurrence during the transport and application process than AMDS powder. In addition, AMDS pellets were maintained the As stabilization efficiency. The application of AMDS pellets for the As stabilization in soil was assessed by column experiments. The AMDS pellets were more effective than limestone and steel slag, which used as the conventional additives for the stabilization process. The As extraction by $0.43M\;HNO_3$ or $1M\;NaH_2PO_4$ solution were appropriate evaluation methods for evaluation of As stabilization efficiency in the soil.
Tailings and contaminated soils from Cheongyang mine and Seobo mine have been analysed by ICP-AES from 5-step sequential extraction method of multielement determination on extraction solutions at each step. As and Co within tailings and contaminated soils from Cheongyang mine and Seobo mine are mainly in the residual phase. In case of Cd, Cu and Zn, the most dominant fraction for tailings of Cheongyang mine is the oxidizable phase, while tailings of Seobo mine is dominated by the residual phase. In contaminated soils from Seobo mine, the predominant fraction for Cd, Cu and Zn is the Fe-Mn oxide phase. The exchangeable fraction of Pb in tailings from Cheongyang mine and Seobo mine is relatively high compared with those of other metals; whereas Pb fraction in contaminated soils from Seobo mine is largely associated with the residual fraction.
In this study, bio-electrokinetics was used to increase migration of arsenic by activating endemic microorganisms in the soil. In this technology, bio-electrokinetics which the cultured soil microorganisms and nutrients injected combines with biological technology. This technology using electrical movement of microorganisms could overcome the weakness of late degradation speed and low removal efficiency. And, various soil microorganisms reduce ferreous, manganese, etc., using organic matter by as an electron donor by injecting mixture of soil microorganisms and nutrients instead of using electrolyte of the electrode. Accordingly, surrounding metal oxide microorganisms convert arsenic (III) to arsenic (V) to increase migration of arsenic (III), in consequence, migration of arsenic increased in 60 to 70% compared to about 30% of conventional electrokinetics.
Arsenic contamination around Au-Ag mining areas occurs mainly from the oxidation of arsenopyrite which is frequently contained in mine tailings. In weathered tailings, oxidation of sulfide minerals typically results in the formation of abundant ferric (oxy)hydroxides or (oxy)hydroxysulfates near the tailings surface, and arsenic may be associated with these secondary precipitates. In this study, solid phases of arsenic in weathered tailings of some Au-Ag mines were investigated through the SEM/EDS and sequential extraction analyses. The stability of As solid phases and the leaching potential were assessed with the variation of pH and Eh conditions. Oxidation of sulfides in the tailings samples was indicated by depletion of S molar concentrations compared to As and heavy metals. Under XRD examinations, jarosite as an Fe-oxyhydroxysulfate was found in the tailings of Deokeum, Dongil and Dadeok, and scorodite as an As-bearing crystalline mineral was identified from Dadeok which has the highest concentration of As (4.36 wt.%). Beudantite-like phases and some Pb-arsenates were also found under SEM/EDS analysis, and most of As phases were associated with Fe-(oxy)hydroxides and (oxy)hydroxysulfates despite a few arsenopyrite from Samgwang and Gubong. Sequential extraction analysis also showed that As was present predominantly as coprecipitated with Fe hydroxides from Dongil, Dadeok and Myungbong (72∼99%), and as sulfides (58%) and Fe hydroxide-associated forms (40%) from Samgwang and Gubong. In the tailings leaching experiment, As was released with high amounts by the dissolution of As-bearing Fe(oxy)hydroxysulfates in the lowest pH (2.7) conditions of Deokeum, and by desorption under alkaline conditions of Samgwang and Gubong. Higher leaching rates of arsenite(+3) were found under acidic conditions, which pose a higher risk to water quality. Changes in pH and Eh conditions coupled with microbial processes could influence the stabilities of the As solid phases, and thus, time amendments or landfilling of weathered tailings may result in enhanced As mobilization.
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
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v.28
no.11
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pp.1186-1191
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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.
There are several remediation technologies for heavy metal contaminated soils but increasing cost limits the application of the technology if the contaminated area is large. Therefore, stabilization, which blocks the release of heavy metals or makes slow the release, is one of the applicable technology for the heavy metal contaminated soil. Current study is an applicability test for a smelter area with various stabilizer such as magnetite, hematite, zeolite-A, zeolite-X, zeolite-Y, zinc oxide, calcium oxide, carbon trioxide, manganese oxide, manganese dioxide, fish bone, sodium phosphate. The soil contaminated with arsenic, lead, copper, nickel, and zinc could not be stabilized only one stabilizer which is known to have stability for certain metal. Many of the stabilizer works for a few metal but not all of the heavy metal. In several cases, stabilizers increase the release of the other metals while they stabilize some metals. In general, the stabilizing efficiency was increased with time. For Ni, Pb, calcium oxide, carbon trioxide, manganese oxide had good stabilizing effect in water extractable portion. For Cu, manganese oxide, zeolite showed good results especially in the exchangeable portion of the sequential extraction. For As, magnetite had good ability but most of the metal oxide which showed good result for other heavy metals increased with the release of As. Current study suggest that multiple stabilizers are needed for the contaminated soil and dose of the stabilizer and stabilizing time should be carefully considered for the soil contaminated with various metals.
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