Establishment of geochemical thresholds for vanadium throughout Korea and at potential development sites using geochemical map data.

Geochemical maps can be used for a variety of purposes, one of which is to establish regional or local geochemical thresholds for the analyzed elements. In the case of vanadium, as industrial demand and use increase, it is necessary to expand the development of vanadium in Korea. However, the environmental management standards are insufficient. Therefore, in this study, using geochemical data, we derived geochemical threshold values for the entire country and areas with potential for the development of vanadium deposits. The regional (country-wide) threshold value was derived using logarithmic transformation of raw data (N = 23,548) of the first- and second-order stream sediments collected across the country in the late 1990s and the early 2000s. The median + 2 median absolute deviation (MAD) and Tukey inner fence (TIF) values were 116 mg/kg and 200 mg/kg, respectively. Of these, the TIF standard, which showed 0.6% of data exceeding the threshold, was judged to be appropriate for distinguishing clear enrichment or contamination of vanadium. In the case of the Geumsan and Pocheon, areas with potential for vanadium development, the TIF and median + 2 MAD values of 259 mg/kg and 218 mg/kg, respectively, can be used as the criteria for evaluating the impact of environmental pollution before and after deposit development. Likewise, by deriving threshold values of the target elements using geochemical map data, it is possible to provide basic environmental information for geochemical evaluation and follow-up management in advance during large-scale site development.

Aging effects on fractionation and speciation of redox-sensitive metals in artificially contaminated soil.

Artificially contaminated soil is often used in laboratory experiments as a substitute for actual field contaminated soils. In the preparation and use of laboratory contaminated soils, questions remain as to how much and how long metals remain in labile form and in their oxidation state during the contamination process. Therefore, the objectives of this study were to determine if the speciation of added contaminants can be retained in the original form and to observe the change in lability of each element with aging time. In this study, natural soil was artificially polluted with five redox-sensitive toxic elements in their oxidized or reduced forms, i.e., As(III)/As(V), Sb(III)/Sb(V), Cr(III)/Cr(VI), Mo(VI), and W(V). Metal distribution was measured in progressive chemical fractionation using sequential extraction methods in contaminated soils after 3, 100, and 300 days of aging. The results indicated that the more strongly bound fraction of metals increased by day 100; whereas the fractions were not significantly different from those in the 300-day-aged soil. Among five metals, the ratio of weakly-bound fractions remained highest in As- and lowest in Cr-contaminated soils. The W(VI)-contaminated soil showed strong sorption without changes in speciation during aging. The oxidized or reduced metal species converged to occur as a single species under given soil conditions, regardless of the initial form of metal used to spike the soil. Both As and Sb existed as their oxidized form while Cr existed as its reduced form. The results of this study may provide a useful and practical guideline for artificial soil contamination.

Effect of FeS on mercury behavior in mercury-contaminated stream sediment: A case study of Pohang Gumu Creek in South Korea.

This study investigated mercury contamination with respect to the sediment characteristics in Gumu Creek near the Pohang Industrial Complex, South Korea. The contaminated sediment had high levels of Hg, exceeding 250 mg Hg/kg sediment at the sampling position, and high concentrations of iron, sulfur, and organic carbon under extreme anaerobic conditions. The anoxic condition of the sediment produced large amounts of FeS. Hg L3-edge EXAFS analysis revealed that FeS controlled the Hg species in the sediment mainly as ß-HgS like precipitation or Hg-S complexation. We also speculated that the presence of FeS induced the abiotic reduction of Hg(II) to Hg(0) and consequently suppressed the formation of highly toxic methylated mercury species. The results obtained in this study are mostly consistent with those reported in previous studies of geochemical reactions of FeS in controlling Hg(II) under pure FeS mineral systems under laboratory scenarios. This study demonstrates that the laboratory controlled reaction scenarios can explain the field behavior of Hg in the contaminated anoxic sediment of the Gumu Creek site.

Sphingorhabdus pulchriflava sp. nov., isolated from a river.

A facultatively anaerobic and Gram-stain-negative bacterium, strain GY_GT, was isolated from a river (Daedeock-cheon) in Daejeon, Republic of Korea. The isolate was catalase-positive, oxidase-positive and formed yellow colonies. Strain GY_GT was phylogenetically classified as belonging in the genus Sphingorhabdus. Its closely related strains were Sphingorhabdus wooponensis 03SU3-PT (97.1 % similarity), Sphingorhabdus buctiana T5T (96.9 %), Sphingorhabdus contaminans JC216T (96.5 %), Sphingorhabdus rigui 01SU5-PT (96.5 %) and Sphingorhabdus planktonica G1A_585T (96.3 %) based on 16S rRNA gene sequences. The growth conditions for GY_GT were at 10-45 °C (optimum, 25 °C), pH 6-10 (pH 7) and 0-4% NaCl (0.5-1.5 %). Strain GY_GT could utilize turanose, d-fructose-6-phosphate, glucuronamide, α-keto-glutaric acid and acetoacetic acid. The major fatty acids of strain GY_GT were summed features 8 (C18 : 1 ω7c/C18 : 1 ω6c; 40.6 %) and 3 (C16 : 1 ω6c/C16 : 1 ω7c; 24.7 %). The major quinone required for respiration was Q-10. The polar lipids of strain GY_GT were diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine and sphingolipid. The G+C content of the genome was 57.7 mol%. The average nucleotide identity and average amino acid identity values between strains GY_GT and S. wooponensis were 71.0 and 72.7 %, respectively. Based on phylogenetic and phenotypic attributes, we suggest that strain GY_GT is a novel species in the genus Sphingorhabdus and propose the name Sphingorhabdus pulchriflava. The type strain is GY_GT (=KCTC 62791T=JCM 32855T).

Redox transformation of soil minerals and arsenic in arsenic-contaminated soil under cycling redox conditions.

Changes in the saturation degree of aquifers control the geochemical reactions of redox-sensitive elements such as iron (Fe), sulfur (S), and arsenic (As). In this study, the effects of redox conditions and the presence of Fe and S on the behavior of As in a soil environment were investigated by observation in a batch experimental system. Arsenic was stable on Fe(III) solid surface in an oxidizing environment but was easily released into the aqueous phase following the reductive dissolution of Fe during an anoxic period. The alternating redox cycles led to a change in the concentrations of Fe, S, and As in both the aqueous and solid phases. The composition of Fe minerals changed to a less crystalline phase while that of solid phase As changed to a more reduced phase in both the As-contaminated natural soil and FeS-amended soil batch systems. This tendency was more prominent in the batch containing higher amounts of total Fe and S. These results show that a redox cycle can increase the possibility of As contamination of groundwater during dissolution and reprecipitation of Fe minerals and simultaneous microbial reduction of S and/or As species.

Mobility of multiple heavy metalloids in contaminated soil under various redox conditions: Effects of iron sulfide presence and phosphate competition.

The mobility of heavy metalloids including As, Sb, Mo, W, and Cr in soil was investigated under both reducing and oxidizing conditions. The effects of soil mineralogy and the presence of competitive anions were studied as important factors affecting the mobility of these contaminants. Batch experiments conducted with the addition of oxidized and fresh FeS exhibited enhanced sorption rates for As and W under oxidizing conditions, and for Mo under reducing conditions. The inhibitory effect of phosphate on the sorption rates was most apparent for As and Mo under both oxidizing and reducing conditions, while only a small phosphate effect was observed for Sb and W. For Sb and W mobility, pH was determined to be the most important controlling factor. The results of long-term batch experiments revealed that differences in the mobility of metalloids, particularly As, were also influenced by microbial activity in the oxidizing and reducing conditions.

Interaction of Sb(III) with iron sulfide under anoxic conditions: Similarities and differences compared to As(III) interactions.

This study examined the reaction mechanism of arsenite, As(III), and antimonite, Sb(III), with iron sulfide and compared their pH-dependent reaction behaviors under strictly anoxic environments. The comparison of Sb(III) with As(III), based on their chemical similarity, may provide useful insight into understanding the geochemical behavior of the less studied Sb(III). The pH-dependent batch sorption studies revealed that As(III) and Sb(III) displayed similar removal trends with pH in terms of the removal efficiency. However, the aqueous As(III) species transformed to thioarsenite species, while aqueous Sb(III) species remained inert under the highly sulfidic anoxic system. An X-ray absorption spectroscopy study demonstrated the reaction of As(III) and Sb(III) at acidic pH was closely related to the precipitation of sulfide minerals As2S3 and Sb2S3, respectively, as a consequence of the reaction with sulfide produced through mackinawite dissolution. Meanwhile, the removal at basic pH was inferred as a surface reaction, possibly through surface complexation, surface-precipitation, or both. In this study, the pH-dependent Sb(III) uptake mechanisms proved to be similar to the corresponding mechanisms for As(III) uptake, with mackinawite demonstrating a superior capacity to scavenge Sb(III) in ferrous and sulfide-rich reducing environments.

Comparison of arsenic co-precipitation and adsorption by iron minerals and the mechanism of arsenic natural attenuation in a mine stream.

Mine stream precipitate collected from Ilkwang mine, Korea, contained high concentrations of arsenic (As), while water collected from the same site had negligible As concentrations, indicating natural attenuation of As occurred in the mine stream. The mechanism of attenuation was explained by comparison of X-ray absorption near edge structure (XANES) of As(V) co-precipitated with or adsorbed to iron (Fe) minerals in mine precipitates. Arsenic in the mine precipitate was present as As(V) and schwertmannite was the main Fe mineral. Arsenic co-precipitation with schwertmannite was the major mechanism of As removal in the mine stream, followed by As adsorption by goethite and As co-precipitation with ferrihydrite. Schwertmannite and ferrihydrite were formed in acid mine drainage and As was incorporated in their structure during formation. Additionally, schwertmannite and ferrihydrite may transform to goethite with As adsorbed onto the goethite surface. Based on the results of batch experiments of As co-precipitation and adsorption, co-precipitation of As with ferrihydrite and schwertmannite was the most effective As sequestration mechanism in the removal of As(V) from acid mine drainage.

Arsenic uptake and speciation in Arabidopsis thaliana under hydroponic conditions.

Arsenic (As) uptake and species in Arabidopsis thaliana were evaluated under hydroponic conditions. Plant nutrient solutions were treated with arsenite [As(III)] or arsenate [As(V)], and aqueous As speciation was conducted using a solid phase extraction (SPE) cartridge. Arabidopsis reduced As(V) to As(III) in the nutrient solution, possibly due to root exudates such as organic acids or the efflux of As(III) from plant roots after in vivo reduction of As(V) to As(III). Arsenic uptake by Arabidopsis was associated with increased levels of Ca and Fe, and decreased levels of K in plant tissues. Arsenic in Arabidopsis mainly occurred as As(III), which was coordinated with oxygen and sulfur based on XANES and EXAFS results. The existence of As(III)O and As(III)S in EXAFS indicates partial biotransformation of As(III)O to a sulfur-coordinated form because of limited amount of glutathione in plants. Further understanding the mechanism of As biotransformation in Arabidopsis may help to develop measures that can mitigate As toxicity via genetic engineering.

Proposed method for controlling turbid particles in solid-phase bioluminescent toxicity measurement.

In the recent half century, numerous methods have been developed to assess ecological toxicity. However, the presence of solid-particle turbidity sometimes causes such tests to end with questionable results. Many researchers focused on controlling this arbitrary turbidity effect when using the Microtox® solid-phase toxicity system, but there is not yet a standard method. In this study, we examined four solid-phase sample test methods recommended in the Microtox® manual, or proposed from the literature, and compared the existing methods with our proposed method (centrifuged basic solid-phase test, c-BSPT). Four existing methods use the following strategies to control turbid particles: complete separation of liquid and solid using 0.45-µm filtration before contacting solid samples and bacteria, natural settlement, moderate separation of large particles using coarser pore size filtration, and exclusion of light loss in the toxicity calculation caused by turbidity after full disturbance of samples. Our proposed method uses moderate centrifugation to separate out the heavier soil particles from the lighter bacteria after direct contact between them. Among the solid-phase methods tested, in which the bacteria and solid particles were in direct contact (i.e., the three existing methods and the newly proposed one, c-BSPT), no single method could be recommended as optimal for samples over a range of turbidity. Instead, a simple screening strategy for selecting a sample-dependent solid-phase test method was suggested, depending on the turbidity of the solid suspension. The results of this study highlight the importance of considering solid particles, and the necessity for optimal selection of test method to reduce errors in the measurement of solid-phase toxicity.

Geochemical occurrences of arsenic and fluoride in bedrock groundwater: a case study in Geumsan County, Korea.

Bedrock groundwaters in Geumsan County, Korea, were surveyed to investigate the distribution and geochemical behaviors of arsenic and fluoride, mobilized through geogenic processes. The concentrations were enriched up to 113 µg/L for arsenic and 7.54 mg/L for fluoride, and 16% of 150 samples exceeded World Health Organization drinking water guidelines for each element. Simple Ca-HCO(3) groundwater types and positive correlations with pH, Ca, SO(4), and HCO(3) were characteristics of high (>10 µg/L) As groundwaters. The oxidation reaction of sulfide minerals in metasedimentary rocks and locally mineralized zones seems to be ultimately responsible for the existence of arsenic in groundwater. Desorption process under high pH conditions may also control the arsenic mobility in the study area. High (>1.5 mg/L) F groundwaters were found in the Na-HCO(3) type and with greater depth. Fluoride seemed to be enriched by deep groundwater interaction with granitic rocks, and continuous supply to shallow Ca-HCO(3)-type groundwater kept the concentration high. In the study area, drinking water management should include periodic As and F monitoring in groundwater.

An engineered cover system for mine tailings using a hardpan layer: a solidification/stabilization method for layer and field performance evaluation.

A cover system for mine tailings with a solidified layer (called an engineered hardpan) was developed in this study to reduce water infiltration, acid generation and sulfide oxidation. Hydrated lime and waterglass were used to produce calcium silicate, which can serve as a binder when constructing a hardpan layer. The compressive strength of each solidified/stabilized material was found to be sufficient in the lab, and the amounts of heavy metals were significantly reduced in chemical leaching tests. Various characteristics of tailings may affect the layer's mechanical strength early on, but a long curing period is capable of compensating for these effects. Heavy metals were stabilized as carbonate-bound phases and sulfide minerals were surrounded by calcium silicate matrix, thereby preventing further reaction. To evaluate the field performance of the system, a hardpan layer was installed on top of tailings on a pilot scale. Leachate with high salt content was generated in the tailings layer in the early stages of monitoring, but after approximately 6 months, the objective was achieved as the hardpan layer gradually stabilized. Notably, during the heavy rainfall season of the later monitoring stage, water infiltration was continuously prevented by the system.

Phosphate removal using sludge from fuller's earth production.

This study assesses the phosphate removal capacity and mechanism of precipitation or adsorption from aqueous solutions in batch experiments by an industrial sludge containing gypsum (CaSO(4).2H(2)O) obtained as a by-product from a fuller's earth process. The potential capacity for phosphate removal was tested using various solution concentrations, pH values, reaction times, and amount of sludge. The maximum phosphate adsorption capacity calculated using the Langmuir equation was 2.0 g kg(-1). The pH for the maximum adsorption by the sludge was neutral to alkaline (pH 7-12). Over 99% of phosphate was removed from a phosphate solution of 30 mg L(-1) using 0.15 g of sludge in a 9-h reaction. Sulfate (SO(4)(2-)) concentration increased with increasing initial phosphate concentration, possibly because of dissolution of gypsum and adsorption of both sulfate and phosphate. At high phosphate concentration (>1000 mg L(-1)), relative constant concentration of Ca(2+) was not consistent with adsorption of the most important phosphate removal mechanism. Results suggest that precipitation of calcium phosphate is principally responsible for phosphate removal under its high concentration. Agglomerated precipitate in the reaction sludge was observed by SEM and identified as brushite (CaHPO(4).2H(2)O) by XRD, FT-IR, and DTA. Based on thermodynamic considerations, it is suggested that the brushite will readily transform to more stable phases, such as hydroxyapatite (Ca(5)(PO(4))(3).OH).

Mineralogical and geochemical characterization of arsenic in an abandoned mine tailings of Korea.

The mineralogical and chemical characteristics of As solid phases in arsenic-rich mine tailings from the Nakdong As-Bi mine in Korea was investigated. The tailings generated from the ore roasting process contained 4.36% of As whereas the concentration was up to 20.2% in some tailings from the cyanidation process for the Au extraction. Thin indurated layers and other secondary precipitates had formed at the surfaces of the tailings piles and the As contents of the hardened layers varied from 2.87 to 16.0%. Scorodite and iron arsenate (Fe3AsO7) were the primary As-bearing crystalline minerals. Others such as arsenolamprite, bernardite and titanium oxide arsenate were also found. The amorphous As-Fe phases often showed framboidal aggregates and gel type textures with desiccation cracks. Sequential extraction results also showed that 55.7-91.1% of the As in tailings were NH(4)-oxalate extractable As, further confirmed the predominance of amorphous As-Fe solid phases. When the tailings were equilibrated with de-ionized water, the solution exhibited extremely acidic conditions (pH 2.01-3.10) and high concentrations of dissolved As (up to 29.5 mg L(-1)), indicating high potentials for As to be released during rainfall events. The downstream water was affected by drainage from tailings and contained 12.7-522 microg L(-1) of As. The amorphous As-Fe phases in tailings have not entirely been stabilized through the long term natural weathering processes. To remediate the environmental harms they had caused, anthropogenic interventions to stabilize or immobilize As in the tailings pile should be explored.

Investigation and risk assessment modeling of As and other heavy metals contamination around five abandoned metal mines in Korea.

Tailings, agricultural soils, vegetables and groundwater samples were collected from abandoned metal mines (Duckum, Dongil, Dongjung, Myoungbong and Songchun mines) in Korea. Total concentrations of arsenic (As) and heavy metals (Cd, Cu, Pb and Zn) were analyzed to investigate the contamination level. Several digestion methods (Toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), 0.1 N/1 N HCl) and sequential extraction analysis for mine tailings were conducted to examine the potential leachability of As and heavy metals from the tailings. The order of urgent remediation for the studied mines based on the risk assessment and remedial goals was suggested. The Songchun mine tailings were most severely contaminated by As and heavy metals. Total concentrations of As and Pb in the tailings were 38,600-58,700 mg/kg (av. 47,400 mg/kg) and 11,800-16,800 mg/kg (av. 14,600 mg/kg), respectively. Agricultural soils having high As concentrations were found at the all mines. Average concentrations of Cd in the vegetables exceeded the normal value at all mines areas, while As only at the Dongjung, Myoungbong, and Songchun mine area. One groundwater sample each from the Dongil and Myoungbong mines, and 4 groundwater samples from the Songchun mine had values above 10 mug/L of As concentration. The TCLP method revealed that only Pb in the Songchun tailings, 6.49 mg/L, exceeded the regulatory level (5 mg/L). Employing the 1-N HCl digestion method, the concentration of As in the Songchun mine tailings, 4,250 mg/kg, was up to 3,000 times higher than its Korean countermeasure standard. Results from the sequential extraction of As in the tailings showed that the easily releasable fraction in the Myoungbong and Songchun mine tailings was more than 30% and the residual fraction was less than 40%. Based on results showing the exposure health risk employing the hazard quotient and cancer risk of As, Cd and Zn, the Dongil mine needs the most urgent remedial action. The concentration reduction factor (CRF) of As in both soil and groundwater follows the order: Songchun>Dongjung>Dongil>Myoungbong>Duckum mine.

Arsenic removal using steel manufacturing byproducts as permeable reactive materials in mine tailing containment systems.

Steel manufacturing byproducts were tested as a means of treating mine tailing leachate with a high As concentration. Byproduct materials can be placed in situ as permeable reactive barriers to control the subsurface release of leachate from tailing containment systems. The tested materials had various compositions of elemental Fe, Fe oxides, Ca-Fe oxides and Ca hydroxides typical of different steel manufacturing processes. Among these materials, evaporation cooler dust (ECD), oxygen gas sludge (OGS), basic oxygen furnace slag (BOFS) and to a lesser degree, electrostatic precipitator dust (EPD) effectively removed both As(V) and As(III) during batch experiments. ECD, OGS and BOFS reduced As concentrations to <0.5mg/l from 25mg/l As(V) or As(III) solution in 72 h, exhibiting higher removal capacities than zero-valent iron. High Ca concentrations and alkaline conditions (pH ca. 12) provided by the dissolution of Ca hydroxides may promote the formation of stable, sparingly soluble Ca-As compounds. When initial pH conditions were adjusted to 4, As reduction was enhanced, probably by adsorption onto iron oxides. The elution rate of retained As from OGS and ECD decreased with treatment time, and increasing the residence time in a permeable barrier strategy would be beneficial for the immobilization of As. When applied to real tailing leachate, ECD was found to be the most efficient barrier material to increase pH and to remove As and dissolved metals.