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.     

Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO?) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0-5% powdered eggshell waste and curing the soil (1,246 mg Pb kg?1 soil and 17 mg Cd kg?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl?), 1 M CaCl?, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH?COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO? and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO? and eggshell waste, regardless of extractant. Using CaCl? extraction, the lowest Cd concentration was achieved upon both CaCO? and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH?COOH or EDTA in soils treated with CaCO? and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO? for the immobilization of heavy metals in soils.     

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     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.     

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.     

Amelioration of acidic soil using various renewable waste resources

In this study, improvement of acidic soil with respect to soil pH and exchangeable cations was attempted for sample with an initial pH of approximately 5. Acidic soil was amended with various waste resources in the range of 1 to 5 wt.% including waste oyster shells (WOS), calcined oyster shells (COS), Class C fly ash (FA), and cement kiln dust (CKD) to improve soil pH and exchangeable cations. Upon treatment, the soil pH was monitored for periods up to 3 months. The exchangeable cations were measured after 1 month of curing. After a curing period of 1 month, a maize growth experiment was conducted with selected-treated samples to evaluate the effectiveness of treatment. The treatment results indicate that in order to increase the soil pH to a value of 7, 1 wt.% of WOS, 3 wt.% of FA, and 1 wt.% of CKD are required. In the case of COS, 1 wt.% was more than enough to increase the soil pH value to 7 because of COS's strong alkalinity. Moreover, the soil pH increases after a curing period of 7 days and remains virtually unchanged thereafter up to 1 month of curing. Upon treatment, the summation of cations (Ca, Mg, K, and Na) significantly increased. The growth of maize is superior in the treated samples rather than the untreated one, indicating that the amelioration of acidic soil is beneficial to plant growth, since soil pH was improved and nutrients were replenished.     

Distributions of heavy metals in the sediments of South Korean harbors

Bottom sediments of harbors in the South Korea have been long suspected for metal contamination due to ship-based and urban-based activities for the past several decades. A number of areas have been suspected to impair ecosystem services to the local residents and drawn complaints from main stakeholders. Twelve contamination suspected harbors were subject to evaluate the level of contamination of Cr, Ni, Cu, Zn, As, Cd, Pb and Hg. The level of sediment contamination for each metal was evaluated comparing the relative enrichment of a given metal to pollution-insensitive aluminum. Regional background concentration of a given metal was also determined based on its down core measurement and sediment texture. Ecological risk posed by the presence of heavy metals was evaluated using the sediment quality guidelines (SQGs) developed by United States National Ocean and Atmosphere Administration (US NOAA) as benchmarks for evaluating sediment chemistry to aquatic organisms. Cu, Zn, Cd, Pb and Hg in the surface sediment were found to be higher than a factor of 1.5 than background sediments, and the overall metal contaminations of surface sediment can be regarded as medium–high- to high-priority sites in the sense of SQGs.     

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces

This study examines the adsorption isotherms, kinetics and mechanisms of Pb2(+) sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb2(+) in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb2(+) with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca2(+) and PO?3? concentrations during the metal sorption processes. The Pb2(+) sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb(+). The sorption isotherm results indicated that Pb2(+) sorption onto the Langmuir and Freundlich constant q(max) and K( F ) is 9.52 and 8.18 mg g?1, respectively. Sorption kinetics results indicated that Pb2(+) sorption onto WCBP was pseudo-second-order rate constants K? was 1.12 g mg?1 h?1. The main mechanism is adsorption or surface complexation (≡POPb(+): 61.6%), co-precipitation or ion exchange [Ca?(.)?? Pb?(.)?? (PO?)? (OH): 21.4%] and other precipitation [Pb 50 mg L?1 and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb2(+) removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb2(+) indicates its potential as another promising way to remediate Pb2(+)-contaminated media.     

Occurrence of estrogenic chemicals in South Korean surface waters and municipal wastewaters

Broad scale monitoring of estrogenic compounds was performed at 19 sampling points throughout the Yeongsan and Seomjin river basins and 5 wastewater treatment plants (WWTPs) adjacent to the Gwangju area, Korea, from December 2005 to August 2007. The concentrations of estrogenic compounds, including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), bisphenol-A, nonylphenol (NP) and 4-octylphenol (OP), in the samples was measured with gas chromatography/mass spectrometry (GC-MS). In addition, the estrogenic activities throughout the river were investigated using the E-screen assay. Of the six estrogenic chemicals, NP (114.6-336.1 ng L(-1)) and EE2 (0.23-1.90 ng L(-1)) were detected at the highest and lowest levels, respectively in both the river waters and the WWTP effluents. Bisphenol-A showed the largest concentration range, from 7.5 to 335 ng L(-1). The concentrations of E1, E2 and octylphenol ranges were 3.6-69.1, 1.2-10.7, and 2.2-16.9 ng L(-1), respectively. According to the calculated estradiol equivalent concentration (EEQ); however, no estrogenic contribution was observed due to the phenolic compounds in the river waters and effluents. E1 and E2 dominated in both the river water and effluent samples, with contributions to the calculated EEQ of over 79 and 77%, respectively. Conversely, EE2 was rarely detected in the river waters (21%) and effluents (0%). The largest contribution of EE2 to the calculated EEQ was 21% in the river water at S-7. The levels of E1, E2, and EE2 were remarkably decreased in the effluents, indicating that the 5 WWTPs did not contribute to the estrogenic effect of the receiving streams. Overall, the WWTPs did not contributed to the estrogenic activity of the receiving waters, but the livestock industry or wildlife may play an important role in the estrogenic contribution to river water.     

Evaluating the PM damage cost due to urban air pollution and vehicle emissions in Seoul, Korea

This study evaluated the prospective damage costs of PM(2.5) inhalation. We performed a health risk assessment based on an exposure-response function to estimate the annual population risk in the Seoul metropolitan city, Korea. Also, we estimated a willingness-to-pay (WTP) amount for reducing the mortality rate in order to evaluate a statistical life value. We combined the annual population risk and the value-of-statistical-life to calculate the damage cost estimate. In the health risk assessment, we applied the PM(2.5) relative risk to evaluate the annual population risk. We targeted an exposure population of 5,401,369 persons who were over the age of 30. Using a Monte-Carlo simulation for uncertainty analysis, we estimated that the population risk of PM(2.5) inhalation during a year in Seoul is 2181 premature deaths for acute exposure and 18,510 premature deaths for chronic exposure. The monthly average WTP for 5/1000 mortality reduction over ten years is $20.20 USD (95% C.I: $16.60-24.50) and the implied value-of-statistical-life (VSL) is $485,000 USD (95% C.I: $398,000-588,000). The damage cost estimate due to risk from PM(2.5) inhalation in Seoul is about $1057 million USD per year for acute exposure, and $8972 million USD per year for chronic exposure. It is important to note that this cost estimate does not reflect all health damage cost estimates in this urban area. This recommendation is a model for evaluating a mortality risk reduction and as such we must re-evaluate an integrated application of morbidity risk.