• Analytical Science and Technology
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• v.29 no.5
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• pp.234-241
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• 2016

The approach presented in this article refers to the bioanalytical method validation for the detection and quantitative determination of arsenic species including arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) in dog plasma by high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP/MS). The arsenic species were separated using an agilent As speciation column by a mobile phase of 2 mM sodium phosphate monobasic, 0.2 mM ethylenediaminetetraacetic acid disodium salt dehydrate, 10 mM sodium acetate, 3 mM sodium nitrate and 1 % ethyl alcohol at pH 11 (adjusted with 1M NaOH). The method validation experiment was obtained selectivity, linearity, accuracy, precision, matrix effect, recovery, system suitability, dilution integrity and various stabilities. All calibration curves showed good linearity (R²>0.999) within test ranges. The lower limit of quantitation (LLOQ) was 5 ng/mL for As(III), As(V) and DMA, and 20 ng/mL for MMA. The system suitability and dilution values were within 6.5 % and 7.7 %. Subsequently, the developed and validated HPLC-ICP/MS method was also successfully applied to determine the arsenic speciation in dog plasma samples, and the recoveries for the spiked samples were in the range of 91.5–102.2 %. Therefore, this method could be applied to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies in biological samples.

• Economic and Environmental Geology
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• v.57 no.3
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• pp.305-317
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• 2024

To investigate the effect of changes in microbial communities on arsenic release in soil, experiments were conducted on arsenic-contaminated soils (F1, G7, and G10). The experiments involved three groups of the experimental sets; ① BAC: sterilized soil + Bacillus fungorum, ② IND: indigenous bacteria, and ③ MIX: indigenous bacteria + B. fungorum, and incubated them for seven weeks using lactate as a carbon source under anaerobic conditions. The experimental results showed that higher concentrations of arsenic were released from the IND and MIX soils, where indigenous bacterial communities existed, compared to BAC. Significantly higher levels of arsenic were released from the G10 soil, which showed higher pH, compared to the F1 and G7 soils. In the G10 soil, unlike other soils, the proportion of As(III) among the released arsenic was also low. These results may be attributed to differences in microbial community composition that vary depending on the soil. By the seventh week, the diversity of microbial species in the IND and MIX soils had significantly decreased, with dominant orders such as Eubacteriales and Bacillales thriving. Bacteroidales in the seventh week of the MIX in the F1 soil, Rummeliibacillus in the seventh week of the IND and MIX of the G7 soil, and Enterobacterales in the IND and MIX of the G10 soil were dominant. At present, it is not known which mechanisms of microbial community changes affect the geochemical behavior of arsenic; however, these results indicate that microbiome in the soil may function as one of the factors regulating arsenic release.

• Journal of Soil and Groundwater Environment
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• v.27 no.1
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• pp.25-30
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• 2022

Mackinawite (FeS), as a ubiquitous reduced iron mineral, is known as a key controller of redox reactions in anaerobic subsurface environment. The reaction of FeS with redox-sensitive toxic element such as arsenic is substantially affected by pH conditions of the given environments. In this study, the interaction of As(V) with FeS was studied under strict anaerobic conditions with various pH conditions. The pH-dependent arsenic removal tests were conducted under wide ranges of pH conditions and X-ray absorption spectroscopy (XAS) was applied to investigate the reaction mechanisms under pH 5, 7, and 9. The removal efficiency of FeS for As(V) showed the higher removal of As(V) under low pH conditions and its removal efficiency decreased with increasing pH, and no As(V) reduction was observed in 1 g/L FeS solution. However, XAS analysis indicated the reduction of As(V) to As(III) occurred during reaction between FeS and As(V). The reduced form of As(III) was particularly identified as an arsenic sulfide mineral (As₂S₃) in all pH conditions (pH 5, 7, and 9). As₂S₃ precipitation was more pronounced in pH 5 where the solubility of FeS is higher than in other pH conditions. The linear combination fitting results of XAS demonstrated that As(V) removal mechanism is concerted processes of As₂S₃ precipitation and surface complexation of both arsenic species.

• Journal of Food Hygiene and Safety
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• v.37 no.6
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• pp.385-393
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• 2022

The contamination level of inorganic arsenic, a human carcinogen, was investigated in 87 grains and 66 processed grain foods. Two inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) and four organic arsenic monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine were analyzed using HPLC-ICP/MS with high separation and sensitivity and ICP/MS was used to quantify total arsenic. Inorganic arsenic was detected in all grains. And the total arsenic in grains consists of about 70-85% inorganic arsenic and about 10-20% DMA. The concentration of inorganic arsenic was high in rice and black rice cultivated in paddy soil with irrigated water, while the miscellaneous grain in field was low. Mean concentration of inorganic arsenic in rice germ, brown rice and polished rice was 0.160 mg/kg, 0.135 mg/kg, 0.083 mg/kg, respectively, indicating that rice bran contains more arsenic. In processed grain foods, inorganic arsenic concentration varied according to the kind of ingredients and content, and the detection amount was high in processed food with brown rice and germ. The arsenic content of all samples did not exceed each standard, but the intake frequency is high and it is considered that continuous monitoring is necessary for food safety.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.229-244
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• 2013

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 Environmental Health Sciences
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• v.47 no.6
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• pp.530-539
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• 2021

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.

• Journal of Applied Biological Chemistry
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• v.61 no.4
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• pp.391-395
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• 2018

There is an increasing concern over arsenic (As) contamination of paddy soil and rice with regard to food safety. This study was conducted to investigate total and inorganic As concentration in one hundred husked and polished rice samples collected at the non-contaminated paddy soil in Korea. Arsenic species in rice samples were extracted using 1% nitric acid ($HNO_3$) with a microwave oven and were measured using high performance liquid chromatography coupled with inductively coupled plasma-mass spectrometry. Mean concentrations of total As in husked rice and polished rice were 0.18 and $0.11mg\;kg^{-1}$, respectively. Also, average inorganic As concentrations in husked rice and polished rice were 0.11 and $0.07mg\;kg^{-1}$, respectively. These levels are lower than the standard guideline value 0.35 and $0.2mg\;kg^{-1}$ for inorganic As in husked and polished rice recommended by Codex Committee on Contaminants in Foods and Ministry of Food and Drug Safety, respectively. The mean of the inorganic As ratio for the total amount of As was 0.65 and 0.67 for husked rice and polished rice, respectively, and the range was from 0.08 to 1.0. For health risk assessment, the average value of cancer risk probability was $9.24{\times}10^{-5}$ and ranged from $2.30{\times}10^{-5}$ to $1.90{\times}10^{-5}$. Therefore, human exposure to As through dietary intake of surveyed rice samples might considered to be a low health risk.

• Korean Journal of Soil Science and Fertilizer
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• v.51 no.2
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• pp.90-100
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• 2018

Environmental pollution with arsenic (As) in croplands causes agricultural and health problems worldwide. Rice is an important crop in South Korea, and many studies have evaluated the relationship between As and glutathione (GSH) to alleviate As uptake from the soil into plants. However, information about the relationship between As and ascorbate (AsA) in rice seedlings is still limited with regard to As phytotoxicity. We therefore investigated changes in reactive oxygen species (ROS) and antioxidant levels in rice (Oryza sativa L. cv 'Dasan') seedlings with toxic As and/or AsA application. The exposure of rice seedlings to $15{\mu}M$ As inhibited plant growth and resulted in increased contents of superoxide, hydrogen peroxide, and malondialdehyde, and induced As uptake by the roots and leaves. Application of AsA to As-exposed seedlings ameliorated As-induced oxidative stress by enhancing the capacity of AsA-GSH cycle in applied plants and increasing As transfer from the roots to leaves. These results suggest that AsA application alleviated As-induced oxidative damage by maintaining sufficient levels of AsA and GSH.

• Molecules and Cells
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• v.43 no.9
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• pp.813-820
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• 2020

NB4 cell, the human acute promyelocytic leukemia (APL) cell line, was treated with various concentrations of arsenic trioxide (ATO) to induce apoptosis, measured by staining with 7-amino-actinomycin D (7-AAD) by flow cytometry. 2', 7'-dichlorodihydro-fluorescein-diacetate (DCF-DA) and MitoSOX™ Red mitochondrial superoxide indicator were used to detect intracellular and mitochondrial reactive oxygen species (ROS). The steady-state level of SO₂ (Cysteine sulfinic acid, Cys-SO₂H) form for peroxiredoxin 3 (PRX3) was measured by a western blot. To evaluate the effect of sulfiredoxin 1 depletion, NB4 cells were transfected with small interfering RNA and analyzed for their influence on ROS, redox enzymes, and apoptosis. The mitochondrial ROS of NB4 cells significantly increased after ATO treatment. NB4 cell apoptosis after ATO treatment increased in a time-dependent manner. Increased SO₂ form and dimeric PRX3 were observed as a hyperoxidation reaction in NB4 cells post-ATO treatment, in concordance with mitochondrial ROS accumulation. Sulfiredoxin 1 expression is downregulated by small interfering RNA transfection, which potentiated mitochondrial ROS generation and cell growth arrest in ATO-treated NB4 cells. Our results indicate that ATO-induced ROS generation in APL cell mitochondria is attributable to PRX3 hyperoxidation as well as dimerized PRX3 accumulation, subsequently triggering apoptosis. The downregulation of sulfiredoxin 1 could amplify apoptosis in ATO-treated APL cells.

• Fisheries and Aquatic Sciences
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• v.25 no.3
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• pp.167-174
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• 2022

Despite the beneficial aspect of fish consumption, bioaccumulation of toxic metals such as arsenic (As) and mercury (Hg) can enhance the health risk for the consumers. Arsenic and Hg concentrations were measured in edible tissue and two targeted organs, namely gill and liver of longtail tuna species (Thunnus tonggol) from Terengganu waters, including Kuala Besut, Kuala Terengganu, Dungun and Kemaman. The concentration of As and Hg were analysed by using inductively coupled plasma- mass spectrometry. The mean concentrations of both elements were significantly different (p < 0.05) among the locations and targeted organs. The hierarchy of As and Hg mean concentrations in muscle samples were Dungun > Kuala Besut > Kemaman > Kuala Terengganu. The mean concentration of As in all samples, including muscle, exceeded the permitted level set by Malaysia Food Act. Estimate Weekly Intake (EWI) was conducted to assess the health risk effect, and 63 kg was used as the average body weight of Malaysian adults. However, the EWI values show that the weekly intake of As and Hg does not exceed the provisional tolerable weekly intake limit suggested by Food and Agricultural Organization for the United Nations and is considered safe to be consumed.