• Bulletin of the Korean Chemical Society
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• 제29권2호
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• pp.372-376
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• 2008

The hydrolysis of gallium(III) has been studied using potentiometric techniques under physiological conditions of temperature 37 C and ionic strength 0.15 moldm-3 NaCl and at different metal ion concentrations. Changes in pH were monitored with a glass electrode calibrated daily in hydrogen ions concentrations. The titration data within the pH range of 2.5-9.99 were analyzed to determine stability constants of hydroxide species using the SUPERQUAD program. Several different species were considered during the calculation procedure and the following hydroxides have been characterized: Ga(OH)3, Ga(OH)4- Ga3(OH)112-, Ga4(OH)11+ and Ga6(OH)153+. Speciation calculations based on the determined constants were then used to simulate the species distribution.

• Horticulture, Environment, and Biotechnology : HEB
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• 제59권6호
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• pp.775-786
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• 2018

To test the hypothesis that humic acid (HA), anaerobically digested pig slurry filtrate (APS), and their combination would differently affect the chemical speciation and extractability of metals (cadmium, copper, and zinc) and their uptake by plants, we conducted a pot experiment using wormwood in two texturally contrasting soils (sandy loam and clay loam) collected from a field near an abandoned Cu mine. Four treatments were laid out: HA at $ 23.5g\;kg^{-1}$ (HA), APS at $330mL\;kg^{-1}$ (APS), HA at $ 23.5g\;kg^{-1}$ and APS at $330mL\;kg^{-1}$ (HA + APS), and a control. Each treatment affected the chemical speciation and mobility of the metals, and thereby resulting in variable patterns of plant biomass yield and metal uptake. The APS supported plant growth by increasing nutrient availability. HA supported or hindered plant growth by impacting the soil's water and nutrient retention capacity and aeration, in a soil texture-dependent manner, while consistently enhancing the immobilization of heavy metals. Temporal increases in whole-plant dry matter yield and metal accumulation suggested that the plants were capable of metal hyperaccumulation. The results were discussed in terms of the mobility of metals and plant growth and corroborated by the $^{15}N$ recovery of soil- and plant-N pools under H and HS treatments. Therefore, for effective phytoremediation of polluted soils, an appropriate combination of plant growth promoters (APS) and chelating agents (HA) should be predetermined at the site where chemical stabilization of pollutants is desired.

• 대한환경공학회지
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• 제30권6호
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• pp.621-627
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• 2008

본 연구에서는 물속 As(III)와 As(V)의 종 규명분석에 필요한 HPLC와 DRC-ICP-MS의 최적조건을 설정하고, 이를 이용하여 한강 팔당수계 10개 지류 천으로부터 채취한 시료중의 As(III)와 As(V)를 분석 검토하였다. 종 분리를 위한 HPLC의 이동상으로는 10 mM ammonium nitrate와 10 mM ammonium phosphate monobasic을 사용하였으며, flushing solvent로는 5% v/v 메탄올을 사용하였다. 검출기는 DRC-ICP-MS를, 반응기체는 산소를 사용하였다. 최적 분석조건을 설정하기 위하여 이동상의 pH, 유량 및 시료 주입량과 DRC의 산소 유량을 달리하여 검토한 결과, 이동상의 pH는 9.4, 유량은 1.5 mL/min, 시료 주입량은 100 $\mu$L, 산소의 유량은 0.5 mL/min이었을 때 가장 좋은 분석조건으로 나타났다. 검정곡선은 As(III)와 As(V)에 대해 모두 r$^2$ = 0.998 이상의 선형성을 나타냈으며, As(III)의 검출한계는 0.10 $\mu$g/L, 정확도(RSD)는 4.3%, 회수율은 95.2%, As(V)의 검출한계는 0.08 $\mu$g/L, 정확도(RSD)는 3.6%, 회수율은 96.4%로 나타났다. 분석시간은 4분이었다. 설정된 파라미터를 적용하여 한강 팔당수계 유입 10개 지류 천에서 채수한 시료를 분석한 결과, As(III)는 0.10$\sim$0.22 $\mu$g/L, As(V)는 0.44$\sim$1.19 $\mu$g/L의 범위로 나타났으며, 총 비소의 93.5%가 As(V)의 형태인 것을 확인할 수 있었다.

• Journal of the korean society of oceanography
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• 제36권1호
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• pp.9-18
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• 2001

Chemical speciation of five heavy metals (Cr, Cu, Ni, Pb, Zn) has been analyzed from 37 surface and 2 core sediments of Kyeonggi Bay, using the modified sequential extraction method based on Tessier et at. (1979). The results show that heavy metals in the Kyeonggi Bay surface sediments are associated dominantly with the crystal lattice fraction. But in the polluted sediments of the Incheon North Harbor, the importance of the labile fractions increased while that of the lattice fraction decreased. In particular, the adsorbed and the easily reducible fractions showed a noticeable increase. In the core samples emerged a speciation pattern which differed significantly from that of the surface sediments. A sharp increase in the percentage of the reducible and organic/sulfide fractions and a decrease in the lattice fraction were observed. Throughout the vertical column, however, the metal contents in the lattice fraction showed stability while those of the labile fractions showed an upward increase. The strong association of heavy metals with the organic/sulfide fraction could be attributed in part to the sulfate reduction prevailing in the polluted harbor sediments.

• 한국해양학회지:바다
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• 제19권2호
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• pp.155-163
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• 2014

마산만 표층퇴적물에서 미량금속의 오염도 및 잠재적 생태계 위해도를 평가하기 위하여 미량금속(Cu, Pb, Zn, Cd, Ni)의 총 농도 및 화학적 존재형태를 분석하였다. 미량금속의 농도는 Ni을 제외한 모든 금속이 만의 내측에 위치한 마산항 주변에서 높게 나타났다. 미량금속의 화학적 존재형태 중 Cd과 Pb은 비잔류 부분이 각각 92%, 88%로 인위적 기원에 의해서 주로 공급되는 것으로 나타난 반면, Ni은 잔류 부분이 70%로 주로 자연적 기원에 의해서 공급된 것으로 나타났다. 미량금속의 오염도 및 생태계 위해도를 다양한 지수로 평가한 결과, pollution load index (PLI)는 만의 바깥쪽 정점을 제외한 모든 정점에서 1을 초과하여 인위적 오염 상태를 보였다. Ecological risk index (ERI)는 만의 내측에서 considerable 또는 moderate risk 수준이었으며, 만의 바깥쪽에서는 low risk 수준이었다. Cd의 ecological index (Ei) 값은 대부분의 정점에서 높게 나타났으며, Cd이 산가용성 부분에서 가장 높은 농도를 보여 Cd이 마산만에서 저서생물에게 잠재적으로 높은 위해도를 미칠 것으로 판단된다.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1907-1914
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• 2010

A novel catalytic kinetic method is proposed for the determination of Se(IV), Se(VI) and total inorganic selenium in water based on the catalytic effect of Se(IV) on the reduction of bromate by p-nitrophenylhydrazine at pH 3.0. The generated bromine, $Br_2$ or $Cl_2$ plus $Br_2$ in 0.1 M NaCl (or NaBr) environment efficiently decolorized Calmagite and the reaction was monitored spectrophotometrically at 523 nm as a function of time. In this indicator reaction, bromide acted as an activator for the catalysis of selenium (IV) and a reducing agent for selenium (VI) at pH 3.0, which allowed the determination of total selenium. The fixed time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the calibration graph are linear in the range 1 - 35 ${\mu}gL^{-1}$ of Se(IV) for the fixed time method at $25^{\circ}C$. The detection limit based on statistical $3S_{blank}$/m-criterion was 0.215 ${\mu}gL^{-1}$ for the fixed time method (7 min). All of the variables that affect the sensitivity at 523 nm were investigated, and the optimum conditions were established. The interference effect of various cations and anions on the Se (IV) determination was also studied. The selectivity of the selenium determination was greatly improved with the use of the strongly cation exchange resin such as Amberlite IR120 plus. The proposed kinetic method was validated statistically and through recovery studies in natural water samples. The RSDs for ten replicate measurements of 5, 15 and 25 ${\mu}gL^{-1}$ of Se(IV) and Se(VI) was changed between 2.1 - 4.85%. Analyses of a certified standard reference material (NIST SRM 1643e) for selenium using the fixed-time method showed that the proposed kinetic method has good accuracy. Se(IV), Se(VI) and total inorganic selenium in environmental water samples have been successfully determined by this method after selective reduction of Se(VI) to Se(IV).

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2813-2818
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• 2010

A novel method was developed for the speciation of chromium in natural water samples based on homogeneous liquid-liquid extraction and determination by flame atomic absorption spectrometry (FAAS). In this method, Cr(III) reacts with a new Schiff's base ligand to form the hydrophobic complex, which is subsequently entrapped in the sediment phase, whereas Cr(VI) remained in aqueous phase. The Cr(VI) assay is based on its reduction to Cr(III) by the addition of sodium sulfite to the sample solution. Thus, separation of Cr(III) and Cr(VI) could be realized. Homogeneous liquid-liquid extraction based on the pH-independent phase-separation process was investigated using a ternary solvent system (water-tetrabutylammonium ion ($TBA^+$)-chloroform) for the preconcentration of chromium. The phase separation phenomenon occurred by an ion-pair formation of TBA and perchlorate ion. Then sedimented phase was separated using a $100\;{\mu}L$ micro-syringe and diluted to 1.0 mL with ethanol. The sample was introduced into the flame by conventional aspiration. After the optimization of complexation and extraction conditions such as pH = 9.5, [ligand] = $1.0{\times}10^{-4}\;M$, [$TBA^+$] = $2.0{\times}10^{-2}\;M$, [$CHCl_3$] = $100.0\;{\mu}L$ and [$ClO_4$] = $2.0{\times}10{-2}\;M$, a preconcentration factor (Va/Vs) of 100 was obtained for only 10 mL of the sample. The relative standard deviation was 2.8% (n = 10). The limit of detection was sufficiently low and lie at ppb level. The proposed method was applied for the extraction and determination of chromium in natural water samples with satisfactory results.

• 자원환경지질
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• 제38권6호
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• pp.699-705
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• 2005

폐광된 장풍광산의 풍화된 폐광석에 함유된 중금속의 존재형태를 규명하기 위해 5단계 연속추출법을 수행하였다. 각 단계에서 용출된 용액은 ICP-AES로 분석하였다. XRD로 풍화된 폐광석 시료들의 광물조성을 파악한 결과, 시료는 산성 환경에서 pH에 대한 완충작용을 할 수 있는 방해석의 유무에 따라 두 유형(type I and type II)으로 나눌 수 있었다. Type I 시료의 주 구성광물은 석영으로 방해석이 산출되지 않으며, type II 시료의 주 구성광물은 방해석이었다. 모든 시료에서 비소, 코발트, 철은 잔류형태로 존재하는 것이 가장 우세하였다. 카드뮴, 망간, 아연의 경우 type I 시료에서는 잔류형태가, type II 시료에서는 산화철망간형태가 우세하였다. 구리는 type I 시료의 경우 잔류형태가 가장 우세하였고, type II의 경우 황화광물형태가 우세하였다. 납은 type I시료에서는 잔류형태가 가장 우세하였고, type II시료에서 산화철망간 형태가 우세하였다. pH 4-7 사이에서 중금속의 상대적인 이동성은 type I시료의 경우 아연>구리>카드뮴>납>코발트>비소의 순서였으며, type II시료에서는 카드뮴>구리>아연>납>비소>코발트의 순서로 확인되었다.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1920-1926
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• 2010

Yoon et $al.^1$ presented an approximate mathmatical model to describe ammonia removal from an experimental batch reactor system with gaseous headspace. The development of the model was initially based on assuming instantaneous equilibrium between ammonia in the aqueous and gas phases. In the model, a "saturation factor, $\beta$" was defined as a constant and used to check whether the equilibrium assumption was appropriate. The authors used the trends established by the estimated $\beta$ values to conclude that the equilibrium assumption was not valid. The authors presented valuable experimental results obtained using a carefully designed system and the model used to analyze the results accounted for the following effects: speciation of ammonia between $NH_3$ and $NH^+_4$ as a function of pH; temperature dependence of the reactions constants; and air flow rate. In this article, an alternative model based on the exact solution of the governing mass-balance differential equations was developed and used to describe ammonia removal without relying on the use of the saturation factor. The modified model was also extended to mathematically describe the pH dependence of the ammonia removal rate, in addition to accounting for the speciation of ammonia, temperature dependence of reactions constants, and air flow rate. The modified model was used to extend the analysis of the original experimental data presented by Yoon et $al.^1$ and the results matched the theory in an excellent manner.

• Bulletin of the Korean Chemical Society
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• 제24권2호
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• pp.209-218
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• 2003

Ecosystems in the Keweenaw Peninsula region of Lake Superior, USA, were disturbed by over 500 million tons of copper-rich mine tailings during the period 1850-1968. Metals leaching from these mine residues have had dramatic effects on the ecosystems. Vast acreages of exposed tailings that are over 100 years old remain unvegetated because of the combination of metal toxicity, absence of nutrients, and temperature and water stress. Therefore, it is important to characterize and fractionate solid copper phases for assessing labile forms of copper in soils and sediments contaminated by the mining wastes. X-ray diffraction analyses indicate that calcite, quartz, hematite, orthoclase, and sanidine minerals are present as major minerals, whereas cuprite,tenorite, malachite, and chalcopyrite might be present as copper minerals in the mining wastes. Sequential extraction technique revealed that carbonate and oxide fractions were the largest pools of copper (ca. 50-80%) in lakeshore and wetland stamp sands whereas the organic matter fraction was the largest reservoir (ca. 32%) in the lake sediments. The concentrations of iron and copper were inversely correlated in the oxide fraction suggesting that copper may occur as a surface coating on iron oxides. As particle size and water contents decrease, the percent of the copper bound to the labile carbonate fraction increases.