Assessment of Young Dong tributary and Imgok Creek impacted by Young Dong coal mine, South Korea

An initial reclamation of the Young Dong coal mine site, located in northeastern South Korea, was completed in 1995. Despite the filling of the adit with limestone, acid rock drainage (ARD) enters Young Dong tributary and is then discharged to Imgok Creek. This ARD carries an average of 500 mg CaCO(3)/l of mineral acidity, primarily as Fe(II) and Al. Before spring runoff, the flow of Imgok Creek is 3.3-4 times greater than that of the tributary and has an alkalinity of 100 mg CaCO(3)/l, which is sufficient to eliminate the mineral acidity and raise the pH to about 6.5. From April through September 2008, there were at least two periods of high surface flow that affects the flow of ARD from the adit. Flow of ARD reaches 2.8 m(3)/min during spring runoff. This raised the concentrations of Fe and Al in the confluence with Imgok Creek. However, by 2 km downstream the pH of the Imgok Creek is 6.5 and only dissolved Fe is above the Korean drinking water criteria (0.30 mg/l). This suggests only a minor impact of Young Dong Creek water on Imgok Creek. Acid digestion of the sediments in Imgok Creek and Young Dong Tributary reveals considerable abundances of heavy metals, which could have a long-term impact on water quality. However, several water-based leaching tests, which better simulate the bioavailable metals pool, released only Al, Fe, Mn, and Zn at concentrations exceeding the criteria for drinking water or aquatic life.     

Distribution and structure of heterotrophic protist communities in the northeast equatorial Pacific Ocean

The distribution and structure of heterotrophic protist communities and size-fractionated chlorophyll a were studied during the Korea Deep Ocean Study 98 (KODOS 98) research expedition (July 1998) in the northeast equatorial Pacific Ocean (5–11°N). Areas of convergence and divergence formed at the boundaries of the South Equatorial Current (SEC), North Equatorial Current (NEC), and North Equatorial Counter Current (NECC) during the expedition. Water column physicochemical characteristics significantly influenced the size structure of heterotrophic protist communities. Intense vertical mixing and high nutrient and chlorophyll a concentrations characterized SEC and NECC areas, which were affected by converging and diverging water masses, respectively. Nanophytoplankton dominated in SEC and NECC areas; both areas also had relatively high heterotrophic protist biomasses (average 743 µg C m^–2). NEC areas were characterized by a stratified vertical structure, low nutrient and chlorophyll a concentrations, and picophytoplankton dominance. The heterotrophic protist biomass in NEC areas averaged 414 µg C m^–2; nanoprotists (<20 µm) dominated the community. The nanoprotist biomass comprised 49–54% of the total heterotrophic protist biomass in SEC/NECC areas and 67–72% in NEC areas. The biomass of heterotrophic protists was higher in SEC/NECC areas than in NEC areas, but the relative importance of nanoprotists was greater in NEC areas than in SEC/NECC areas. Heterotrophic dinoflagellates were dominant components of the <20 µm and >20 µm size classes in both water columns. The biomass of heterotrophic protists significantly correlated with the net-, nano-, and picophytoplankton biomass in SEC/NECC areas and with the nano- and picophytoplankton biomass in NEC areas. Heterotrophic protists and phytoplankton also showed strong positive correlation in the study area. The size structure of the phytoplankton biomass coincided with that of heterotrophic protists; the heterotrophic protist biomass positively correlated with the protists prey source. These relationships suggest that the community structure of heterotrophic protists and the microbial food web depended on size classes within the phytoplankton biomass. Microzooplankton grazing and phytoplankton growth rates were higher in SEC/NECC areas than in NEC areas. In contrast, the potential primary production grazed by microzooplankton was relatively high in NEC areas (127.3%) compared with SEC/NECC areas (94.6%). Our results indicate that the relative importance and size structure of heterotrophic protists might vary according to two distinct water column structures.Communicated by T. Ikeda, Hakodate     

Hydrochemical Monitoring and Heavy Metal Contaminations at the Narim Mine Creek in the Sulcheon District, Republic of Korea

The Narim gold mine is located approximately 200km southeast of Seoul within the Sulcheon mineralised district in the Yeongnam massif, Korea. In this study, environmental geochemical analyses were undertaken for soil, sediment and water samples collected in April, September and November in 1998 from the Narim mine creek. The mine area consists mainly of granitic gneiss; however, mineral constituents of soil and sediment near the mine were mainly composed of quartz, feldspar, mica, amphibole, some pyrite and clay minerals. Also were found some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite, various hydroxide and unidentified secondary minerals. Generally, high concentrations of heavy metals in the soil and sediment are correlated with a high proportion of secondary minerals. Hydrochemical compositions of water samples are characterised by relative significant enrichment of Na⁺+K⁺ and alkali metals in the ground water, whereas the surface and mine waters are relatively enriched in Ca²⁺+Mg²⁺ and heavy metals. Anion contents of the ground waters are typically enriched in HCO₃ ^–, NO₃ ^– and Cl^–, whereas the surface and mine waters are highly enriched in HCO₃ ^– and SO₄ ^2–. The pH and EC values of the surface water from the non-mine creek are relatively lower compared with those of the surface water around the mine and waste dump. The range of D and ¹⁸O values (d parameters) of the water samples are shown in distinct two groups for the April waters of 10.1–13.1, and for the November waters of 5.8–7.9, respectively. This range variation indicates that two group water were composed of distinct waters because of seasonal difference. Geochemical modelling showed that mostly heavy toxic metals may exist largely in the form of free metal (M²⁺) and metal-sulphate (MSO₄ ^2–), and SO₄ ^2– concentration influenced the speciation of heavy metals in the mine water. These metals in the ground water could be formed of CO₃ ^– and OH^– complex ions. Using a computer program, saturation indices of albite, calcite, dolomite in mostly surface water show undersaturated and progressively evolved toward the saturation state, however, ground and mine waters are nearly saturated. The gibbsite, kaolinite and smectite are supersaturated in the surface and ground water, respectively. Calculated water-mineral reaction and stabilities suggest that the weathering of silicate minerals may be stable kaolinite. The clay minerals of K-illite and Na-smectite will be transformed to more stable kaolinite owing to the continuous reaction.     

Stabilization of Cu-contaminated army firing range soils using waste oyster shells

A stabilization/solidification (S/S) process was used to immobilize Cu in contaminated soils obtained from two army firing ranges sites (A and B) with total Cu concentrations of 520 and 380 mg/kg, respectively. Both waste oyster shells (WOS) and pretreated oyster shells (POS) were used to immobilize Cu in the contaminated soils. Waste oyster shells passing the #10 mesh and #20 mesh were used for the Sites A and B, respectively. WOS- and POS-treated soil samples cured for 28 days were evaluated for Cu leaching by the Korean Standard Leaching Test (KSLT) method. Slurry suspensions were prepared to investigate the Cu immobilization mechanism using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy (EDX) analyses. The treatment results showed that the POS treatment was more effective than the WOS treatment of 28 days. For Site A, 10 wt% WOS and 3 wt% POS dosages were required to pass the Korean warning standard of 50 mg/kg, while 10 wt% WOS and 5 wt% POS dosages were required for the Site B treatment. The XRPD and SEM-EDX results showed that Cu immobilization was strongly linked to both CSH/CAH and ettringite. Overall, the POS treatment was effective at immobilizing the Cu in the contaminated soils, very likely due to its CaO content.     

Solubility of organic acids in various methanol and salt concentrations: the implication on organic acid sorption in a cosolvent system

The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (K_m) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the K_m and methanol volume fraction (f_c). However, the K_m of carboxylic acids increased with increasing f_c. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl₂ concentrations and the salting constant (K^s) became smaller as f_c increased. However, the σ value at a given salt concentration and the K^s value at a given f_c were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of f_c and CaCl₂ concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between K_m and f_c for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f _c ≤ 0.4) and ionic compositions (CaCl₂ and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K _m values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f _c. However, the K _m values of 1-NAPA with both ionic compositions remained relatively constant over the f _c range. For the model sorbent, the K _m values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f _c, while the sorption of 1-NAPA with kaolinite for the CaCl₂ system was increased with f _c. From the solubility data of 1-NAPA with f _c, no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.