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.     

Anthropogenic influence on surface water quality of the Nhue and Day sub-river systems in Vietnam

In order to investigate the temporal and spatial variations of 14 physical and chemical surface water parameters in the Nhue and Day sub-river systems of Vietnam, surface water samples were taken from 43 sampling sites during the dry and rainy seasons in 2007. The results were statistically examined by Mann–Whitney U-test and hierarchical cluster analysis. The results show that water quality of the Day River was significantly improved during the rainy season while this was not the case of the Nhue River. However, the river water did not meet the Vietnamese surface water quality standards for dissolved oxygen (DO), biological oxygen demand (BOD₅), chemical oxygen demand (COD), nutrients, total coliform, and fecal coliform. This implies that the health of local communities using untreated river water for drinking purposes as well as irrigation of vegetables may be at risk. Forty-three sampling sites were grouped into four main clusters on the basis of water quality characteristics with particular reference to geographic location and land use and revealed the contamination levels from anthropogenic sources.     

Uranium Accumulation of Crop Plants Enhanced by Citric Acid

Citric acid was applied to soil to enhance U accumulation in four crop plants. While the highest enhanced U accumulation of aboveground tissues (a.c. 2000 mg kg⁻¹ dry weight) occurred in the leaves of Indian mustard (Brassica juncea), the highest enhanced U accumulation of roots (a.c. 3500 mg kg⁻¹ dry weight) occurred in canola (Brassica napus var. napus). Uranium translocation among tissues of test plants is in the relation of roots>shoots ≅ leaves. The flowers of sunflower (Helianthus annuus) contained similar or higher U concentrations than those found in shoots, but concentrations in seeds are close to zero. In conclusion, Indian mustard is recommended as a potential species for phytoextraction for U-contaminated soil due to its high U accumulation of aboveground biomass (a.c. 2200 μg per plant). There is no evidence that two types of soils cause a significant difference of the enhanced U accumulation (p<0.05). Results, however, indicate that additional citric acid may result in downward U migration that may contaminate groundwater. Speciation of U that is taken up by plants is also discussed in the end.     

Metal contamination of soils and dusts in Seoul metropolitan city,Korea

To investigate the dispersion patterns and the characteristics of heavy metal contamination due to urbanisation and industrialisation, soils and dusts collected from the Seoul area were analysed for Cu, Pb, Zn and Cd. The metal concentrations in most soils and dusts are higher than the world averages. The pollution index (( Metal concentrations in soils/Permissible level for metal)÷(Number of metals)) of soils and dusts is > 1 in most of the Seoul area, a result that concurs with the industrialisation and urbanisation index of the Seoul area. The soils are contaminated with Cu, Zn, Cd and particularly Pb. This suggests that the contamination of the soils in the Seoul area are mainly caused by vehicular emissions. The pollution index of soil is the highest in the Kuro area where Cu and Zn contamination in soils are due to the indigenous brass and bronze factories. From the discriminant analysis, the Seoul area may be partitioned into control, traffic and industrialized areas by the metal concentrations in the order of Zn > Cu > Pb.     

Removal of arsenate from water by adsorbents: a comparative case study

Laboratory and field filtration experiments were conducted to study the effectiveness of As(V) removal for five types of adsorbent media. The media included activated alumina (AA), modified activated alumina (MAA), granular ferric hydroxide (GFH), granular ferric oxide (GFO), and granular titanium dioxide (TiO₂). In laboratory batch and column experiments, the synthetic challenge water was used to evaluate the effectiveness for five adsorbents. The results of the batch experiments showed that the As(V) adsorption decreased as follows at pH 6.5: TiO₂ > GFO > GFH > MAA > AA. At pH 8.5, however, As(V) removal decreased in the following order: GFO = TiO₂ > GFH > MAA > AA. In column experiments, at pH 6.5, the adsorbed As(V) for adsorbents followed the order: TiO₂ > GFO > GFH, whereas at pH 8.5 the order became: GFO = TiO₂ > GFH when the challenge water containing 50 μg/L of As(V) was used. Field filtration experiments were carried out in parallel at a wellhead in New Jersey. Before the effluent arsenic concentration increased to 10 μg/L, approximately 58,000 and 41,500 bed volumes of groundwater containing an average of 47 μg/L of As(V) were treated by the filter system packed with GFO and TiO₂, respectively. The As(V) adsorption decreased in the following sequence: GFO > TiO₂ > GFH > MAA > AA. Filtration results demonstrated that GFO and TiO₂ adsorbents could be used as media in small community filtration systems for As(V) removal.     

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.     

Contamination of groundwater and risk assessment for arsenic exposure in Ha Nam province, Vietnam

The characteristics of arsenic-contaminated groundwater and the potential risks from the groundwater were investigated. Arsenic contamination in groundwater was found in four villages (Vinh Tru, Bo De, Hoa Hau, Nhan Dao) in Ha Nam province in northern Vietnam. Since the groundwater had been used as one of the main drinking water sources in these regions, groundwater and hair samples were collected in the villages. The concentrations of arsenic in the three villages (Vinh Tru, Bo De, Hoa Hau) significantly exceeded the Vietnamese drinking water standard for arsenic (10 microg/L) with average concentrations of 348, 211, and 325 microg/L, respectively. According to the results of the arsenic speciation testing, the predominant arsenic species in the groundwater existed as arsenite [As(III)]. Elevated concentrations of iron, manganese, and ammonium were also found in the groundwater. Although more than 90% of the arsenic was removed by sand filtration systems used in this region, arsenic concentrations of most treated groundwater were still higher than the drinking water standard. A significant positive correlation was found between the arsenic concentrations in the treated groundwater and in female human hair. The risk assessment for arsenic through drinking water pathways shows both potential chronic and carcinogenic risks to the local community. More than 40% of the people consuming treated groundwater are at chronic risk for arsenic exposure.     

Bioaccumulation and the soil factors affecting the uptake of arsenic in earthworm, Eisenia fetida

To better understand arsenic (As) bioaccumulation, a soil invertebrate species was exposed to 17 field soils contaminated with arsenic due to mining activity. Earthworms (Eisenia fetida) were kept in the soils for 70 days under laboratory conditions, as body burden increased and failed to reach equilibrium in all soils. After 70 days of exposure, XANES spectra determined that As was biotransformed to a highly reduced form. Uptake kinetics for As was calculated using one compartment model. Stepwise multiple regression suggested that sorbed As in soils are bioaccessible, and uptake is governed by soil properties (iron oxide, sulfate, and dissolved organic carbon) that control As mobility in soils. As in soil solution are highly related to uptake rate except four soils which had relatively high chloride or phosphate. The results imply that uptake of As is through As interaction with soil characteristics as well as direct from the soil solution. Internal validation showed that empirically derived regression equations can be used for predicting As uptake as a function of soil properties within the range of soil properties in the data set.     

Comparative toxicity of silver nanoparticles and silver ions to Escherichia coli

With the increase in silver(Ag)-based products in our lives, it is essential to test the potential toxicity of silver nanoparticles(Ag NPs) and silver ions(Ag ions) on living organisms under various conditions. Here, we investigated the toxicity of Ag NPs with Ag ions to Escherichia coli K-12 strain under various conditions. We observed that both Ag NPs and Ag ions display antibacterial activities, and that Ag ions had higher toxicity to E. coli K-12 strain than Ag NPs under the same concentrations. To understand the toxicity of Ag NPs at a cellular level, reactive oxygen species(ROS) enzymes were detected for use as antioxidant enzymatic biomarkers. We have also studied the toxicity of Ag NPs and Ag ions under various coexistence conditions including: fixed total concentration, with a varied the ratio of Ag NPs to Ag ions; fixed the Ag NPs concentration and then increased the Ag ions concentration; fixed Ag ions concentration and then increasing the Ag NPs concentration.Exposure to Ag NPs and Ag ions clearly had synergistic toxicity; however, decreased toxicity(for a fixed Ag NPs concentration of 5 mg/L, after increasing the Ag ions concentration) to E. coli K-12 strain. Ag NPs and Ag ions in the presence of L-cysteine accelerated the bacterial cell growth rate, thereby reducing the bioavailability of Ag ions released from Ag NPs under the single and coexistence conditions. Further works are needed to consider this potential for Ag NPs and Ag ions toxicity across a range of environmental conditions.Environmental Significance Statement: As silver nanoparticles(Ag NPs)-based products are being broadly used in commercial industries, an ecotoxicological understanding of the Ag NPs being released into the environment should be further considered. Here, we investigate the comparative toxicity of Ag NPs and silver ions(Ag ions) to Escherichia coli K-12 strain, a representative ecotoxicological bioreporter. This study showed that toxicities of Ag NPs and Ag ions to E. coli K-12 strain display different relationships when existing individually or when coexisting, and in the presence of L-cysteine materials. These findings suggest that the toxicology research of nanomaterials should consider conditions when NPs coexist with and without their bioavailable ions.