Enrichment of potentially toxic elements in areas underlain by black shales and slates in Korea

The Okchon black shale in Korea provides an important example of natural geological materials containing toxic elements; the Chung-Joo, Duk-Pyung, Geum-Kwan, I-Won and Chu-Bu areas are underlain by these black shales and slates of the Guryongsan Formation. This formation is part of the Okchon Group which is found in the central part of Korea. Geochemical surveys were undertaken in these five study areas in the Okchon Zone in order to examine the level of enrichment and dispersion patterns of potentially toxic elements in rocks and soils. After appropriate preparation, samples were analysed by instrumental neutron activation analysis and inductively coupled plasma atomic emission spectrometry for a range of elements. Arsenic, Cu, Mo, V, U and Zn are highly enriched in the Okchon black shales and their mean concentrations are significantly higher than those in black slates. These elements are closely associated with one another from a geochemical viewpoint and may be enriched simultaneously. Mean concentrations of As, Mo and U in soils derived from black shales occurring in the Duk-Pyung and Chu-Bu areas are higher than the permissible level suggested by Kloke (1979), and the enrichment index decreases in the order of Duk- Pyung > Chu-Bu > Chung-Joo > Geum-Kwan = I-Won areas. Uranium-bearing minerals such as uraninite and brannerite have been identified in black shales from the Chung-Joo area by electron probe micro-analysis. Uraninite grains are closely associated with monazite and pyrite with a grain size ranging from 2m to 10m whereas brannerite grains occur as a euhedral form 50m in diameter.     

Inhibition of pyrite oxidation by surface coating: a long-term field study

Pyrite and other iron sulfides are readily oxidized by dissolved oxygen in aqueous phase, producing acidity and Fe²⁺, which causes significant environmental problems. Applications of surface coating agents (Na₂SiO₃ and KH₂PO₄) were conducted at Boeun (Chungbuk, South Korea) outcrop site, and their efficiencies to inhibit the oxidation of sulfide minerals were monitored for a long-term period (449 days). The rock sample showed positive Net Acid Production Potential (NAPP = 20.23) and low Net Acid Generation pH (NAGpH = 2.42) values, suggesting that the rock sample was categorized in the potential acid-forming group. For the monitored time period (449 days), field study results showed that the application of Na₂SiO₃ effectively inhibited the pyrite oxidation as compared to KH₂PO₄. Na₂SiO₃ as a surface coating agent maintained pH 5–6 and reduced oxidation of pyrite surface up to 99.95 and 97.70 % indicated by Fe²⁺ and SO₄ ^2? release, respectively. The scanning electron microscope and energy-dispersive X-ray spectrometer analysis indicated that the morphology of rock surface was completely changed attributable to formation of iron silicate coating. The experimental results suggested that the treatment with Na₂SiO₃ was highly effective and it might be applicable on field for inhibition of iron sulfide oxidation.     

Arsenite oxidation by <Emphasis Type="Italic">Alcaligenes</Emphasis> sp. strain RS-19 isolated from arsenic-contaminated mines in the Republic of Korea

Arsenite [As(III)]-oxidizing bacteria play important roles in reducing arsenic [As] toxicity and mobility in As-contaminated areas. As-resistant bacteria were isolated from the soils of two abandoned mines in the Republic of Korea. The isolated bacteria showed relatively high resistances to As(III) up to 26 mM. The PCR-based 16S rRNA analysis revealed that the isolated As-resistant bacteria were close relatives to Serratia marcescensa, Pseudomonas putida, Pantoea agglomerans, and Alcaligenes sp. Among the five As-resistant bacterial isolates, Alcaligenes sp. strain RS-19 showed the highest As(III)-oxidizing activity in batch tests, completely oxidizing 1 mM of As(III) to As(V) within 40 h during heterotrophic growth. This study suggests that the indigenous bacteria have evolved to retain the ability to resist toxic As in the As-contaminated environments and moreover to convert the species to a less toxic form [e.g., from As(III) to As(V)] and also contribute the biogeochemical cycling of As by being involved in speciation of As.     

Assessment of soil and soil-gas radon activity using active and passive detecting methods in Korea

Radon ((222)Rn) is a carcinogenic gas produced by the radioactive decay of radium ((226)Ra). It has been reported that soil and soil-gas are primary factors that could cause indoor radon problems. Six sites were selected for this study--Sanbook, Gangcheon, Jikyeong, Choojung, Geumsung and Homyoung--each was classified according to bedrock type. In order to investigate soil-gas radon activities and radon emanating power, innovated active and passive detecting methods were developed and applied under both field and laboratory conditions. Statistical analysis of results confirmed that the radon activity values measured using either active or passive methods under field or laboratory conditions could be interchangeable with each other.     

Human risk assessment of As,Cd, Cu and Zn in the abandoned metal mine site

The cancer risk and the non-cancer hazard index for inhabitants exposed to As, Cd, Cu and Zn in the soils and stream waters of the abandoned Songcheon Au–Ag mine area were evaluated. Mean concentrations of As, Cd, Cu, Pb and Zn in agricultural soils were 230, 2.5, 120, 160, and 164 mg kg⁻¹, respectively. Mean concentrations of As, Cd and Zn of the water in the stream where drinking water was drawn was 246 μg L⁻¹, 161 μg L⁻¹ and 3899 μg L⁻¹, respectively. These levels are significantly higher than the permissible levels for drinking water quality recommended by Korea and WHO. The resulting human health risks to farmers who inhabited the surrounding areas due to drinking water were summarized as follows: (1) the non-cancer health hazard indices showed that the toxic risk due to As and Cd in drinking water were 10 and 4 times, respectively, greater than those induced by the safe average daily dosages of the respective chemicals. (2) the cancer risk of As for exposed individuals through the drinking water pathway was 5 in 1000, exceeded the acceptable risk of 1 in 10,000 set for regulatory purposes.     

Determination of soil contamination sources in mining area using Zn/Cd ratios with mobile Cd

Environmental Geochemistry and Health - Paddy fields near metalliferous mining area are sometimes contaminated by tailings or mine water. In the contaminated paddy fields around the abandoned...     

Study on integrated management of PCB containing waste and PCB contaminated waste: proposal of new congeners for quantification

In the present study, new congeners were selected for the efficient management of PCB containing waste and PCB contaminated waste, and the applicability of these new indicators was confirmed. As a result, 8 indicator congeners and 4 index peaks which were named “Proposed new method 1” and “Proposed new method 2” were selected. For the assessment of a novel quantitative method, comparative tests using conventional methods were conducted, and the factors for total PCB were calculated for each method. Results from these tests showed that the average values for the factors of CEN/TC19/WG22, DIN 51527, and the test method by the disposal regulation for ocean dumping in Korea were 1.86, 3.47, and 2.52, respectively, while those for the proposed new method 1 and proposed new method 2 were 2.98 and 5.56, respectively. For PCB contaminated waste, the factor was found to be 1.99, 3.42, and 3.02 using the conventional methods, 2.67 using the proposed new method 1, and 5.57 using the proposed new method 2. It is expected that, in accordance with the results of the present study, the management of PCB waste can be integrated, regardless of the type of waste involved.     

Interpreting complex geochemistry of groundwater in a coastal paddy field near a mine using isotopic signatures of sulfate and water

Environmental Geochemistry and Health - In the area around the abandoned Seoseong mine, South Korea, coastal paddy fields undergo seawater intrusion and possible sulfate reduction. Here, channel...     

Enhancement of arsenic mobility by indigenous bacteria from mine tailings as response to organic supply

Arsenic leaching by indigenous bacteria in abandoned Au-Ag mine tailings which contained approximately 3200 mg/kg of As was investigated after supply of various organic substrates. Sequential extraction analysis designed to determine the mode of As occurrence in the tailings revealed that most As (90%) was closely associated with the Fe fraction. When glucose was supplied as a C source, indigenous bacteria significantly enhanced the extent of As release from the tailings into solution under both aerobic and anaerobic conditions. Anaerobic indigenous bacteria leached more amount of As from the tailings than aerobes. Highly positive correlation between the extracted amounts of As and Fe implied that microbial dissolution of Fe(III)-oxides, whether it was ligand- and proton-promoted dissolution or reductive dissolution, might be dominantly responsible for the As release. Bacterial strains which were resistant to up to 100 mM As(V) was aerobically isolated from the tailings. One of the isolates appeared to reduce some aqueous As(V) to likely As(III) in a batch type experiment, which indicated that indigenous bacteria can mediate the electrochemical speciation and thus the mobility of As in the tailings. The results suggest that indigenous bacteria in As-contaminated tailings can increase As mobility from the solid media when microbially available organic substrates are supplied, and thus enhance the risk of As dispersion to nearby soil, sediment and groundwater.     

Natural attenuation of arsenic in the wetland system around abandoned mining area

Mechanisms of natural attenuation of arsenic (As) by wetland plants may be classified by plant uptake and adsorption and/or co-precipitation by iron (oxy)hydroxide formed on the root surface of plants or in rhizosediment. A natural Cattail (Typha spp.) wetland impacted by tailings containing high levels of As from the Myungbong abandoned Au Mine, South Korea was selected, and the practical capability of this wetland to attenuate As was evaluated. The As concentrations in the plant tissues from the study wetland were several-fold higher than those from control wetland. SEM-EDX analyses demonstrated that iron plaques exist on the rhizome surface. Moreover, relatively high As contents bonded with hydrous iron oxides were found in the rhizosediments rather than in the bulk sediments. It was revealed through the leaching and sequential extraction analyses that As existed as more stable forms in the wetland sediment compared with adjacent paddy soil, which is also contaminated with As due to input of mine tailings. The As concentration ratios of extracted solution to sediment/soil represented that the wetland sediment showed significant lower values (10-fold) rather than the paddy soil with indicating high As stability. Also, As in the wetland sediment was predominantly bonded with residual phases on the basis of results from sequential extraction analysis. From these results, it is concluded that transformation of As contaminated agricultural field to wetland environment may be helpful for natural attenuation until active remediation action.