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).
INTRODUCTION : Arsenic is a ubiquitous element present in various compounds throughout the earth's crust. The use of arsenic compounds increased greatly during the 18th and 19th centuries, including its use in pigments and dyes, as a preservative of animal hides, in glass manufacture, agricultural pesticides, and various pharmaceutical substances. The causal association between human arsenic exposure, usually in the form of inorganic compounds containing trivalent arsenite (As$^{III}$) or pentavalent arsenate (As$^V$), and various forms of human cancer has been known for many years.
Lee, Kyo Suk;Shim, Ho Young;Lee, Dong Sung;Chung, Doug Young
Korean Journal of Soil Science and Fertilizer
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v.48
no.2
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pp.73-80
/
2015
Arsenic which is found in several different chemical forms and oxidation states and causes acute and chronic adverse health effects is a toxic trace element widely distributed in soils and aquifers from both geologic and anthropogenic sources. Arsenic which has a mysterious ability to change color, behavior, reactivity, and toxicity has diverse chemical behavior in the natural environment. Arsenic which has stronger ability to readily change oxidation state than nitrogen and phosphorus due to a consequence of the electronic configuration of its valence orbitals with partially filled states capable of both electron donation and acceptance although the electronegativity of arsenic is greater than that of nitrogen and similar to that of phosphorus. Arsenate (V) is the thermodynamically stable form of As under aerobic condition and interacts strongly with solid matrix. However, it has been known that adsorption and oxidation reactions of arsenite (III) which is more soluble and mobile than As(V) in soils are two important factors affecting the fate and transport of arsenic in the environment. That is, the movement of As in soils and aquifers is highly dependent on the adsorption-desorption reactions in the solid phase. This article, however, focuses primarily on understanding the fate and speciation of As in soils and what fate arsenic will have after it is incorporated into soils.
Lin, Chai-Ching;Huang, Chia-Cherng;Chen, Ming-Cheng;Huang, Andrew Jeng-Fang;Chiou, Hung-Yi
Asian-Australasian Journal of Animal Sciences
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v.15
no.1
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pp.19-25
/
2002
The objectives of this study were to understand the possible mechanism of duck sperm toxicity induced by arsenic exposure in vivo, and to investigate the roles of the antioxidant L-ascorbic acid in ameliorating the arsenic-induced sperm impairment. To test the acute toxicity, the percentages of mortality of mature drakes treated with different concentrations of trivalent sodium arsenite, As (III), and pentavalent sodium arsenate, As (V) were measured. The LD50 value of As (III) for mature drakes was $4.89{\pm}1.49$ ppm. Although As (V) didn't cause any deaths even at a concentration of 40 ppm, the chronic toxicity of As (V) on sperm quality was shown by a decreased fertilization rate. When the concentrations of As (V) were above 0.4 ppm, fertilization rates were lower than those of 0.04 ppm and control. Drakes treated with 40 ppm of As (V) had the highest malondialdehyde (MDA) level in the testis tissue, $3.100{\pm}0.218{\mu}mole/g$ testis. This showed that 40 ppm of As (V) significantly induced lipid peroxidation in testis tissue. For the 1.2 ppm As (III) treatment, several significant effects were observed: (1) sperm motility was decreased most dramatically by $52.0{\pm}9.1$% after three days of incubation; (2) fertilization rate of artificially inseminated semen was the lowest, $26.4{\pm}15.4$; (3) the MDA concentration in testis tissue, $7.846{\pm}0.246{\mu}mole/g$ testis, was significantly higher than the others (p<0.05); (4) the sperm number, $1.17{\pm}0.40({\times}10^9)$, was significantly lower than with the 60 ppb and control treatments (p<0.05); (5) a black appearance and soft texture was observed in the testis tissue. The antioxidant L-ascorbic acid administered along with 1.2 ppm As (III) decreased the toxicity of arsenic. The ameliorating effects included: improved sperm motility, increased sperm number and fertilization rate, and decreased MDA concentration in the testis tissue. This study suggests that the toxicity of the trivalent arsenic on sperm quality is partly from free radicals generated by its metabolic pathway, and the antioxidant ascorbic acid ameliorates arsenic-caused sperm impairment.
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.
The ecosystems of certain abandoned mines contain arsenic-resistant bacteria capable of performing detoxification when an ars gene is present in the bacterial genome. The ars gene has already been isolated from Pseudomonas putida and identified as a member of the membrane transport regulatory deoxyribonucleic acid family. The arsenite-oxidizing bacterial strains isolated in the present study were found to grow in the presence of 66.7 mM sodium arsenate($V;\;Na_2HAsO_4{\cdot}7H_2O$), yet experienced inhibited growth when the sodium arsenite($III;\;NaAsO_2$) concentration was higher than 26 mM. Batch experiment results showed that Pseudomonas putida strain OS-5 completely oxidized 1 mM of As(III) to As(V) within 35 h. An arsB gene encoding a membrane transport regulatory protein was observed in arsenite-oxidizing Pseudomonas putida strain OS-5, whereas arsB, arsH, and arrA were detected in strain OS-19, arsD and arsB were isolated from strain RW-18, and arsR, arsD, and arsB were found in E. coli strain OS-80. The leader gene of arsR, -arsD, was observed in a weak acid position. Thus, for bacteria exposed to weak acidity, the ars system may cause changes to the ecosystems of As-contaminated mines. Accordingly, the present results suggest that arsR, arsD, arsAB, arsA, arsB, arsC, arsH, arrA, arrB, aoxA, aoxB, aoxC, aoxD, aroA, and aroB may be useful for arsenite-oxidizing bacteria in abandoned arsenic-contaminated mines.
The total arsenic and 6 arsenic species were investigated in 56 fish collagen products using ICP-MS (Inductively coupled plasma-mass spectrometer) and HPLC-ICP-MS(High performance liquid chromatography-Inductively coupled plasma-mass spectrometer). The mean concentrations of total arsenic and arsenic species were 40.103±81.133 ㎍/kg (N.D.~586.686) and 30.070±50.378 ㎍/kg (N.D.~313.871), respectively. The mean concentration of inorganic arsenic was 24.610±32.706 ㎍/kg (N.D.~129.331), and the As(V) (Arsenate) was the most dominant. The standards and specifications of arsenic have not been established for fish collagen products. Our study presents that arsenic levels are relatively safe compared with not only previous studies but also domestic and international standards. However, in one sample, the total arsenic concentration was 586.686 ㎍/kg, showing the inorganic was 8.119 ㎍/kg, and the DMA was 305.752 ㎍/kg, which was high than the Canadian standard for organic arsenic. In conclusion, it is necessary to monitor arsenic levels consistently and establish standards and specifications of arsenic in fish collagen products to assure consumer safety.
Background: In South Korea, areas around abandoned metal mines are designated as regions with high arsenic (As) contamination. However, studies assessing urinary As exposure, As metabolism, and relevant genetic polymorphisms in residents of these metal mine areas are lacking. Objectives: To identify factors associated with As exposure and evaluate the effects of MTHFR, As3MT, and GSTO1 genetic polymorphisms on As metabolism in residents of abandoned metal mine areas by measuring urinary As species. Methods: Urinary As species (arsenite [As3+], arsenate [As5+], monomethyl arsonic acid, and dimethylarsinic acid) were isolated using high-performance liquid chromatography in combination with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Four genetic polymorphisms (MTHFR A222V, MTHFR E429A, GSTO1 A140D, As3MT M287T) were analyzed in 144 residents of four areas around abandoned metal mines. Results: The study sample was comprised of 34.7% men and 65.3% women, with a mean age of 70.7±10.9 years. The urinary inorganic As concentration was higher among those consuming more than half locally produced rice (0.31 ㎍/L) than those consuming less than half such rice (0.18 ㎍/L). The urinary dimethylarsinic acid concentration was higher in the group that had consumed seafood in the past day (31.68 ㎍/L) than in those who had not (22.37 ㎍/L). Furthermore, individuals heterozygous in the MTHFR A222V and GSTO1 A140D polymorphism had higher urinary arsenic species concentrations than did individuals with a wild type or homozygous for the variant allele. Conclusions: Consumption of locally produced rice was associated with inorganic As exposure, whereas seafood consumption was associated with organic As exposure among residents of abandoned metal mine areas. There was no clear association between MTHFR A222V and GSTO1 A140D polymorphisms and As metabolism.
The objectives of this study are (1) to determine the extent and degree of As contamination of the water and sediments influenced by mining activity of the abandoned Au-Ag mines, (2) to examine As speciation In contaminated water, (3) to monitor variation of As contamination in water system throughout the dry and wet seasons, and (4) to investigate the As chemical form in the sediments through the sequential extraction analyses. Natural water(mine water, surface water and groundwater) and sediments were collected in six abandoned Au-Ag mine(Au-bearing quartz veins) areas. The contamination level of As in mine water of the Dongil(524${\mu}m$/L) is more higher than the tolerance level(500 ${\mu}m$/L) for waste water of mine area in Korea. Elevated levels of As in stream water were also found in the Dongil(range of 63.7∼117.6 ${\mu}m$/L.) and Gubong(range of 56.1∼62.9 ${\mu}m$/L) mine areas. Arsenic contamination levels in groundwater used by drinking water were more significant in the Dongil(11.3∼63.5 ${\mu}m$/L), Okdong(0.2∼68.9 ${\mu}m$/L) and Gubong(2.0∼101.0${\mu}m$/L) mine areas. Arsenate[As(V), $H_2AsO_4^-$] is more dominant than arsenite[As(III), $H_3AsO_3$] in water system of the most mine areas. The concentration ratios of As(III) to As(total), however, extend to the 95% in stream water of the Okdong mine area and 70∼82% in groundwater of the Okdong and Dongjung mine areas. As a study of seasonal variation in the water system, relatively high levels of As from the dongil mine area were found in April rather than in September. Sequential extraction analysis showed that As was predominantly present as coprecipitated with Fe hydroxides from sediment samples of the Dongjung and Gubong mine(35.9∼40.5%), which indicates its possibility of re-extraction and inducing elevated contamination of As in the reductive condition. In sediments from the Dongil, Okdong and Hwachon mine area, high percentage(55.2∼83.4%) of As sulfide form was found.
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.
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