• Korean Journal of Soil Science and Fertilizer
• /
• v.47 no.1
• /
• pp.41-47
• /
• 2014

Agricultural soils surrounding mine areas in South Korea are often contaminated with multiple metals such as Cd, Pb and Zn. It poses potential risks to plants, soil organisms, groundwater, and eventually human health. The aim of this study was to examine the changes in phytoavailability of Cd, Cu, Pb and Zn after application with calcined eggshell (CES; 0, 1, 3, and 5% W/W) in an agricultural soil contaminated by mine tailings. The contents of Cd, Cu, Pb and Zn in soils were 8.79, 65.4, 1602, and $692mgkg^{-1}$ (aqua regia dissolution), respectively. The experiments were conducted with lettuce (Lactuca sativa L. var. longifolia) grown under greenhouse conditions during a 30-d period. $NH_4NO_3$ solution was used to examine the mobile fraction of these metals in soil. The application of CES dramatically increased soil pH and inorganic carbon content in soil due to CaO and $CaCO_3$ of CES. The increased soil pH decreased the mobile fraction of Cd, Pb, Zn: from 3.49 to < $0.01mgkg^{-1}$ for Cd, from 79.4 to $1.75mgkg^{-1}$ for Pb, and from 29.6 to $1.13mgkg^{-1}$ for Zn with increasing treatment of CES from 0 to 5%. In contrast, the mobile fraction of Cu was increased from 0.05 to $3.08mgkg^{-1}$, probably due to the formation of soluble $CuCO_3{^0}$ and Cu-organic complex. This changes in the mobile fraction resulted in a diminished uptake of Cd, Pb and Zn by lettuce and an increased uptake of Cu: from 4.19 to < $0.001mgkg^{-1}$ dry weight (DW) for Cd, from 0.78 to < $0.001mgkg^{-1}$ DW for Pb, and from 133 to $50.0mgkg^{-1}$ DW for Zn and conversely, from 3.79 up to $8.21kg^{-1}$ DW for Cu. The increased contents of Cu in lettuce shoots did not exceed the toxic level of $>25mgkg^{-1}$ DW. The mobile contents of these metals in soils showed a strong relationship with their contents in plant roots and shoots. These results showed that CES effectively reduced the phytoavailability of Cd, Pb, and Zn to lettuce but elevated that of Cu in consequence of the changed binding forms of Cd, Cu, Pb, and Zn in soils. Based on these conclusions, CES can be used as an effective immobilization agent for Cd, Pb and Zn in contaminated soils. However, the CES should be applied in restricted doses due to too high increased pH in soils.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.14 no.8
• /
• pp.3597-3601
• /
• 2013

In this study, a wet cleaning process, P II, using aqua-regia and sulfuric acid mixture with oxidant agent ($K_2S_2O_8$, $P_2O_5$, $KMnO_4$, $H_2O_2$ etc) is proposed to remove the metastable phase of graphite such as graphene and DLC for high quality synthetic diamonds. The process employed the conventional acid cleaning process (P I) as well as P I+P II to remove the graphite related impurities from the 200um-diamond powders synthesized at 7GPa-$1500^{\circ}C$-5minutes. The degree of cleaning after P I and P I+P II has been observed by naked-eye, optical microscopy, micro-Raman spectroscopy, and TGA-DTA. After P I+P II, the color of diamond became more vividly yellow with enhanced saturation with naked eye and optical microscopy analysis. Moreover, the disappearance of diamond-like-carbon (DLC) peak ($1440cm^{-1}$) observed by Raman spectroscopy confirmed the decrease in amount of remaining impurities. TGA-DTA results showed that the graphite impurities first started to dissolve at $770.91^{\circ}C$ after PI process. However, the pyrolysis started at $892.18^{\circ}C$ after P I+P II process because of the dissolution of pure diamonds. This result proved the effective dissolution of the metastable phase of graphite. We expect that the proposed P II process may enhance the quality of diamonds through effective removal of surface impurities.

• Journal of Soil and Groundwater Environment
• /
• v.17 no.3
• /
• pp.1-9
• /
• 2012

According to the agreement on WTO/TBT, we are under the situation to adopt international standard (ISO standard) as a national standard if it exists. However, in case of environmental area, it is a domestic legal obligation to use Korean environmental standard method(KESM) for analyzing various contaminants. Therefore it is necessary to assess the comparability between KEM and ISO standard prior to apply ISO standard to soil conservation law in Korea. The main purpose of this study is to assess the comparability of both methods for analyzing heavy metals in soil. We looked over various aspects like pre-treatment, calibration curve range, detection wavelength, soil organic matter content and so on. Apparently, the procedure of both methods is almost same. However in details, both methods are different in stationary time before aqua-regia extraction using reflux system, calibration curve range for Cu, Pb, Ni and measuring wavelength for Pb. According to the results of comparison test, the results were significantly different when the different calibration range was used. In case that all the extracts independent of methods were reanalyzed with the same calibration range of each method, both methods showed statistically same results. Other conditions like different stationary time, measuring wavelength of AAS and soil organic matter content did not have any influence on the analytical result. Therefore, we suggest to extend the calibration curve range to 0~8 mg/L which is used in KS I ISO standard(Korean standard related with environment which is translation version of ISO standard without any technical change). In case of $Cr^{6+}$, the results showed no significant differences between two methods even though the pretreatment, instrumentation and other analysis conditions were different. In addition to UV/Visble spectrometry of KESM for soil contamination, we suggest to adopt ion chromatography of ISO 15192(US EPA method 7199) for analyzing $Cr^{6+}$ with the consideration of laboratory work efficiency.

• Economic and Environmental Geology
• /
• v.51 no.4
• /
• pp.371-379
• /
• 2018

In many countries, recycling coal ashes as backfill materials for subsided lands, abandoned mine tunnels, and road pipeline constructions by making low-strength concretes with minimal amounts of cement is frequently considered for massive treatment of coal ashes. This study investigates the variation of heavy metals in the concrete test pieces prepared for the cases of using only Portland cement as binding material, fly ash as a replacement of the cement, sand as aggregates, and disposed ashes in the ash ponds as a replacement of aggregates. Heavy metal contents were measured based on the aqua regia extraction technique following the Korean Standard for Fair Testing of Soil Contamination and the influences of each materials on the total heavy metal contents were also assessed. Results show that the cement has the highest Cu, Pb, and Zn concentrations than any other materials. Therefore, the test pieces show significant concentration decreases for those metals when the cement was replaced by fly ash. Ponded ash shows low concentrations relative to fly ash in most of the parameters but shows higher Cu and Ni, and lower Pb levels than the sand aggregate. In overall, heavy metal levels of the test pieces are regulated by mixing among the used materials. Test pieces prepared during this study always show concentrations much lower than the Worrisome Level of Soil Contamination (Area 1), which was designated by the Soil Environment Conservation Act of Korea.

• Analytical Science and Technology
• /
• v.30 no.5
• /
• pp.252-261
• /
• 2017

Naturally occurring radioactive materials (NORMs) increase radiation exposure to the public as these materials are concentrated through artificial manufacturing processes by human activities. This study focuses on the development of a method for the quantitative analysis of $^{232}Th$, $^{235}U$, and $^{238}U$ in building materials. The accuracy and precision of inductively coupled plasma mass spectrometry (ICP-MS) for determination of digestion processes was evaluated for certified reference materials (CRMs) digested using various mixed acid (e.g., aqua regia, hydrofluoric acid, and perchloric acid) digestions and a $LiBO_2$ fusion method. The method validation results reveal that a $LiBO_2$ fusion and $Fe(OH)_3$ co-precipitation should be applied as the optimal sample digestion process for the quantitative analysis of radionuclides in building materials. The radioactivity of $^{232}Th$, $^{235}U$, and $^{238}U$ in a total of 51 building material (e.g., board, brick, cement, paint, tile, and wall paper) samples was quantitatively analyzed using an established process. Finally, the values of $^{238}U$ and $^{232}Th$ radioactivity were comprehensively compared with those from the indirect method using ${\gamma}$-spectrometry.

• Economic and Environmental Geology
• /
• v.42 no.5
• /
• pp.445-455
• /
• 2009

Microbiological sulfate reduction is the transformation of sulfate to sulfide catalyzed by the activity of sulfate-reducing bacteria using sulfate as an electron acceptor. Low solubility of metal sulfides leads to precipitation of the sulfides in solution. The effects of microbiological sulfate reduction on in-situ precipitation of arsenic and copper were investigated for the heavy metal-contaminated soil around the Songcheon Au-Ag mine site. Total concentrations of As, Cu, and Pb were 1,311 mg/kg, 146 mg/kg, and 294 mg/kg, respectively, after aqua regia digestion. In batch-type experiments, indigenous sulfate-reducing bacteria rapidly decreased sulfate concentration and redox potential and led to substantial removal of dissolved As and Cu from solution. Optimal concentrations of carbon source and sulfate for effective microbial sulfate reduction were 0.2~0.5% (w/v) and 100~200 mg/L, respectively. More than 98% of injected As and Cu were removed in the effluents from both microbial and chemical columns designed for metal sulfides to be precipitated. However, after the injection of oxygen-rich solution, the microbial column showed the enhanced long-term stability of in-situ precipitated metals when compared with the chemical column which showed immediate increase in dissolved As and Cu due to oxidative dissolution of the sulfides. Black precipitates formed in the microbial column during the experiments and were identified as iron sulfide and copper sulfide. Arsenic was observed to be adsorbed on surface of iron sulfide precipitate.

• Korean Journal of Soil Science and Fertilizer
• /
• v.29 no.2
• /
• pp.113-123
• /
• 1996

This experiment was carried out to compare with the physico-chemical properties of granular fused magnesium phosphates which were two domestic products(Pungnong Biryo Industrial Co., LTD and Kyunggi Chemical Industrial Co., LTD) and a imported Chinese product. The changes of pH, distribution of particle size, disintegration in water and in soil, hardness in soil, chemical composition, and dissolution rates in water, in soil and in 2% citric acid solution were investigated. The changes in pH were bigger in Jungmun series(black volcanic soil), in the imported chinese product, and in Jungmun series with the larger quantities applied. The domestic products were lower in pH, calcium, alkalinity and 1/2N-HCl soluble silicate than the Chinese product but total(Aqua regia) soluble phosphate, 2% citric acid soluble phosphate, 1/2N-HCl soluble and 2% citric acid soluble magnesium, and 2% citric acid soluble manganese concentration were similar among the domestic products and the imported product. In particle sizes, Chinese product was the biggest, Kyunggi product was the next, and Pungnong product was the smallest. The changes of disintegration rate in water and in soil were smaller in Pungnong and Kyunggi products at the early days of dissolution, and there were decreased with the order of Kyunggi product> Chinese product> Pungnong product at the latter days. The hardness of the products in soil was the strongest in Kyunggi product, the next was Pungnong product and Chinese product was the weakest so as to hardly measurable. The changing dissolution rates of 2% citric acid soluble phosphate concentration of granular fused magnesium phosphate products were the highest in Kyunggi product and the lowest in Pungnong product at the early days, the three products were dissolved over 90% within 50 days, and there were no clear difference among the products after 70 days of dissolution. The dissolution rates of 2% citric acid soluble phosphate concentration of granular fused magnesium phosphate products in soil were the highest in Pungnong product and Chinese product was the lowest, but they were less than 60% in 100 days of dissolution.

• Journal of Korean Society of Environmental Engineers
• /
• v.27 no.1
• /
• pp.25-35
• /
• 2005

This study analyzed total concentrations and existing forms of heavy metals in soils of Ulsan using a sequential extraction method. Soil samples were collected from 6 categorized areas including green, residential, heavy traffic, petrochemical industrial complex(IC), mechanical and shipbuilding IC, and non-ferrous metal IC areas. which represent different emission characteristics. The highest total concentrations of heavy metals by a sequential extraction analysis were observed in the soils collected from the non-ferrous metal IC area, followed by the mechanical and shipbuilding IC and heavy traffic areas. Dominant(> 50%) existing forms of Cd, Cr and Ni were residual forms followed by Fe and Mn oxides in almost areas. Residual fractions in the non-ferrous metal IC areas were relatively lower than those in other areas. However, the fractions of organic and sulphides in the IC areas were higher. The dominant farms of Cu were much different with the investigated areas. In most areas, the dominant forms of Pb and Zn were Fe and Mn oxides, followed by residual fraction for Pb. The exchangeable and carbonate fractions represent mobility of metallic elements in soils. They are also significantly affected by the environmental renditions, such as pHs of soil and rainfall. In this study the exchangeable and carbonate fractions were lower than other fractions. Because the total concentrations of heavy metals in the soils of the non-ferrous metal IC area were extremely high, however, the mobile fractions of heavy metals in the IC area would be significant. Thus a large amount of heavy metals can be released into plants, water bodies, and soils. Therefore, urgent measures, such as source control for soil remediation of heavy metals, in the non-ferrous metal IC areas are essentially required. Analysis results obtained from the sequential extraction and the aqua regia extraction showed a high correlation, whose determination coefficients(R2) of heavy metals except Cd approximately ranged from 0.7 to 0.9.

• Economic and Environmental Geology
• /
• v.43 no.2
• /
• pp.137-148
• /
• 2010

The Myoungbong mine located in Boseong-gun, Jellanamdo consists of Au-Ag bearing quartz veins which filled the fissures of Bulguksa granitic rocks of Cretaceous. The tailings obtained from the Myungbong mine were used to investigate the effects of various processes, such as oxidation of primary sulfides and formation(alteration) of secondary and/or tertiary minerals, on arsenic immobilization in tailings. This study was conducted via both mineralogical and chemical methods. Mineralogical methods used included gravity and magnetic separation, ultrasonic cleaning, and instrumental analyses(X-ray diffractometry, energy-dispersive spectroscopy, and electron probe microanalyzer) and aqua regia extraction technique for soils was applied to determine the elemental concentrations in the tailings. Iron (oxy)hydroxides formed as a result of oxidation of tailings were identified as three specific forms. The first form filled in rims and fissures of primary pyrites. The second one precipitated and coated the surfaces of gangue minerals and the final form was altered into yukonites. Initially, large amounts of acid-generating minerals, such as pyrite and arsenopyrite, might make the rapid progress of oxidation reactions, and lots of secondary minerals including iron (oxy)hydroxides and scorodite were formed. The rate of pH decrease in tailings diminished, in addition, as the exposure time of tailings to oxidation environments was prolonged and the acid-generating minerals were depleted. Rather, it is speculated that the pH of tailings increased, as the contribution of pH neutralization reactions by calcite contained in surrounding parental rocks became larger. The stability of secondary minerals, such as scorodite, were deteriorated due to the increase in pH, and finally arsenic might be leached out. Subsequently, calcimn and arsenic ions dissociated from calcites and scorodites were locally concentrated, and yukonite could be grown tertiarily. It is confirmed that this tertiary yukonite which is one of arsenate minerals and contains arsenic in high level plays a crucial role in immobilizing arsenic in tailings. In addition to immobilization of arsenic in yukonites, the results indicate that a huge amount of iron (oxy)hydroxides formed by weathering of pyrite which is one of typical primary minerals in tailings can strongly control arsenic behavior as well. Consequently, this study elucidates that through a sequence of various processes, arsenic which was leached out as a result of weathering of primary minerals, such as arsenopyrite, and/or redissolved from secondary minerals, such as scorodite, might be immobilized by various sorption reactions including adsorption, coprecipiation, and absorption.

• Analytical Science and Technology
• /
• v.23 no.5
• /
• pp.485-491
• /
• 2010

A certified reference material (CRM) of KRISS 109-03-SSD was developed for the analysis of hazardous elements in soil. The target elements were As, Cd, Cr, Cu, Hg, Ni, Pb, Zn being regulated by the Soil Environment Conservation Act. Starting material was collected from tailing dump of an unworked tungsten mine at Sangdong (Gangwon-do, Korea). The starting material under-went through a series of fabricating process steps of screening, drying, grinding, sieving, blending, bottling, sterilization and was certified according to the ISO Guide 35. Isotope dilution-inductively coupled mass spectrometry (ID-ICP/MS) and instrumental neutron activation analysis (INAA) were used for the measurement. Homogeneity was tested according to ISO 13528 annex B. The certified values were determined using the results from two different methods or from two independent measurements using a method. Finally, certified values of seven elements of arsenic, cadmium, chromium, copper, lead, nickel and zinc were determined. Mercury did not satisfied the criteria of homogeneity and the result would be provided for information only, together with iron and tungsten. It was also studied, the extractable fraction of elements by aqua regia according to the ISO 11466 protocol being frequently studied for the purpose of environmental monitoring. It was performed as a inter-laboratory study by 6 laboratories of a public institute and universities. Standard deviation among the laboratories was much bigger than the uncertainty of the certified value. The result of inter-laboratory study on the extractable fraction will be provided for information, only.