• Title/Summary/Keyword: Chemical Speciation

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Gallium(III) Ion Hydrolysis under Physiological Conditions

  • Hacht, Brahim
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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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.

Organic amendment-driven removal and speciation of metals using wormwood in two contrasting soils near an abandoned copper mine

  • Ro, Hee-Myong;Choi, Hyo-Jung;Yun, Seok-In;Park, Ji-Suk
    • Horticulture, Environment, and Biotechnology : HEB
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    • v.59 no.6
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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.

Speciation Analysis of Arsenic Species in Surface Water (수중의 비소 종 분리 분석)

  • Jeong, Gwan-Jo;Kim, Dok-Chan
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.6
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    • pp.621-627
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    • 2008
  • In this study, a technique of speciation and determination of the trace inorganic arsenic(As(III) and As(V)) in water sample using HPLC-DRC-ICP-MS has been developed. Isocratic mobile phase of 10 mM ammonium nitrate and 10 mM ammonium phosphate monobasic was used and methanol(5 v/v%) was used as flushing solvent. Selection of the best flow rate of reaction gas, O$_2$, and optimization of the parameters such as pH and flow rate of mobile phase, and injection volume of sample for the separation and detection of arsenic species were carried out. The oxygen flow rate of 0.5 mL/min, pH of 9.4 and flow rate of 1.5 mL/min of mobile phase, and injection volume of sample of 100 $\mu$L were found to be the best parameters for the speciation and determination of arsenic species. The analytical features of the method were detection limit 0.10 and 0.08 $\mu$g/L, precision(RSD) 4.3% and 3.6%, and recovery 95.2% and 96.4% for As(III) and As(V), respectively. Analysis time was 4 minutes per sample. Linear calibration graphs with r$^2$ = 0.998 were obtained for both As(III) and As(V). Speciation analysis of arsenic species in the raw water samples collected from the tributary streams to Han River and main stream of Paldnag were performed by the proposed method. The concentrations of As(III) ranged from 0.10 to 0.22 $\mu$g/L and As(V) concentrations ranged from 0.44 to 1.19 $\mu$g/L, and 93.5% of total arsenic was found to be As(V).

Speciation of Some Heavy Metals in Surface and Core Sediments of Kyeonggi Bay, West Coast of Korea

  • Kim, Bum-Soo;Koh, Chul-Hwan;Lee, Chang-Bok
    • Journal of the korean society of oceanography
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    • v.36 no.1
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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.

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Speciation and Ecological Risk Assessment of Trace Metals in Surface Sediments of the Masan Bay (마산만 표층퇴적물에서 미량금속의 화학적 존재형태 및 생태계 위해도 평가)

  • Sun, Chul-In;Lee, Young-Ju;An, Jung-Hyun;Lee, Yong-Woo
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.19 no.2
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    • pp.155-163
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    • 2014
  • Total concentration and chemical speciation of trace metals (Cu, Pb, Zn, Cd, and Ni) were determined to evaluate pollution level and potential ecological risk in surface sediments of the Masan Bay. The results showed that the trace metal concentrations, except for Ni, were high in the inner Masan Bay. Based on the chemical speciation of metals in sediments, the percentage of total concentrations of Cd and Pb in non-residual fraction was 92% and 88%, respectively, indicating that these metals originated mainly from anthropogenic sources. However, Ni (70%) was dominant in residual fraction. Pollution load index (PLI) and ecological risk index (ERI) values in the inner bay indicate the presence of anthropogenic pollution and considerable-moderate ecological risk, respectively. Ecological index (Ei) value for Cd was high at most stations in the Masan Bay, and Cd content was the highest in acid soluble fraction, which presents the highest ecological risk. The results obtained in this study indicate that Cd presents a high potential ecological risk to benthic biota in the Masan Bay.

The Investigation of a Novel Indicator System for Trace Determination and Speciation of Selenium in Natural Water Samples by Kinetic Spectrophotometric Detection

  • Gurkan, Ramazan;Ulusoy, Halil Ibrahim
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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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).

Speciation of Chromium in Water Samples with Homogeneous Liquid-Liquid Extraction and Determination by Flame Atomic Absorption Spectrometry

  • Abkenar, Shiva Dehghan;Hosseini, Morteza;Dahaghin, Zohreh;Salavati-Niasari, Masoud;Jamali, Mohammad Reza
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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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.

Chemical Speciation of Heavy Metals in Geologic Environments on the Abandoned Jangpoong Cu Mine Area (장풍 폐광산 주변 지질환경에서 중금속의 존재형태)

  • Lee In-Gyeong;Lee Pyeong-Koo;Choi Sang-Hoon;Kim Ji-Soo;So Chil-Sup
    • Economic and Environmental Geology
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    • v.38 no.6 s.175
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    • pp.699-705
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    • 2005
  • In order to identify the speciation of As and trace elements which are contained weathered waste rocks on the abandoned Jangpoong Cu mine area, five fraction sequential extraction was carried out. Concentrations of the extraction solutions which were acquaired each fraction were mesured by ICP-AES. Mineral characters of weathered waste rocks were determinated by XRD. The weathered waste rocks could divide into two types (Type I and type II). Type land type II weathered waste rocks are mainly composed of a quartz and a calcite, respectively. The most dominant speciation of As, Co and Fe is residual phase. Most of the speciation of Cd, Mn and Zn is residual phase for type I and Fe-Mn oxide phase for type II. In case of Cu, residual phase is predominant in type I and sulfide is predominet in type II. The most dominant speciation of Pb for type I and type II is associated with the residual phase and Fe-Mn oxide phase, respectively. At pH 4-7 range, the order of relative mobility considers Zn>Cu>Cd>Pb>Co>AS in type I, and Cd>Cu>Zn>Pb>As>Co in type II.

Modified Ammonia Removal Model Based on Equilibrium and Mass Transfer Principles

  • Shanableh, A.;Imteaz, M.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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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.

Solid-Phase Speciation of Copper in Mine Wastes

  • Jeong, Jae-Bong
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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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.