• 한국환경농학회지
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• 제32권3호
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• pp.171-178
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• 2013

BACKGROUND: Consensus of heavy metal phytoavailability in soils needs to be introduced for soil management protocols in relation to safer food production in the contaminated agricultural soils. For this, setting up the method for evaluation of metal phytoavailability in soil is an essential prerequisite. METHODS AND RESULTS: The current study was carried to select a proper single extraction method for determination of phytoavailable metal concentration in soil. Two extraction methods were examined including 1 M $NH_4NO_3$ extraction and 0.01 M $Ca(NO_3)_2$ extraction methods using 142 soil samples collected from the agricultural soils nearby abandoned mining area in Korea. Corelation analysis was conducted between phytoavailable metal concentrations and soil properties potentially influencing on the metal phytoavailability. Both methods showed similar significance (p<0.001) in correlation with soil properties such as soil pH. However, higher correlation coefficients between phytoavailable metal concentrations and soil properties were observed when used $Ca(NO_3)_2$ extraction rather than using $NH_4NO_3$ extraction. CONCLUSION(S): It appeared that 0.01 M $Ca(NO_3)_2$ extraction was better option for determination of phytoavailable metals in soils and further study to test the efficiency of this method is required in combination with plant uptake.

• 한국토양비료학회지
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• 제47권6호
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• pp.464-472
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• 2014

The Codex Committee of Contaminants in Food (CCCF) has been discussing a new standard for arsenic (As) in rice since 2010 and a code of practice for the prevention and reduction of As contamination in rice since 2013. Therefore, our current studies focus on setting a maximum level of As in rice and paddy soil by considering bioavailability in the remediation of As contaminated soils. This study aimed to select an appropriate single chemical extractant for evaluating the mobility of As in paddy soil and the bioavailability of As to rice. Nine different extractants, such as deionized water, 0.01 M $Ca(NO_3)_2$, 0.1 M HCl, 0.2 M $C_6H_8O_7$, 0.43 M $HNO_3$, 0.43 M $CH_3COOH$, 0.5 M $KH_2PO_4$, 1 M HCl, and 1 M $NH_4NO_3$ were used in this study. Total As content in soil was also determined after aqua regia digestion. The As extractability of the was in the order of: Aqua regia > 1 M HCl > 0.5 M $KH_2PO_4$ > 0.43 M $HNO_3$ > 0.2 M $C_6H_8O_7$ > 0.1 M HCl > 0.43 M $CH_3COOH$ > deionized water > 1 M $NH_4NO_3$ > 0.01 M $Ca(NO_3)_2$. Correlation between soil extractants and As content in rice was in the order of : deionized water > 0.01 M $Ca(NO_3)_2$ > 0.43 M $CH_3COOH$ > 0.1 M HCl > 0.5 M $KH_2PO_4$ > 1 M $NH_4NO_3$ > 0.2 M $C_6H_8O_7$ > 0.43 M $HNO_3$ > 1M HCl > Aqua regia. BCF (bioconcentration factor) according to extractants was in the order of : 0.01M $Ca(NO_3)_2$ > 1 M $NH_4NO_3$ > deionized water > 0.43 M $CH_3COOH$ > 0.1 M HCl > 0.43 M $HNO_3$ > 0.2 M $C_6H_8O_7$ > 0.5 M $KH_2PO_4$ > 1 M HCl > Aqua regia. Therefore, 0.01 M $Ca(NO_3)_2$ ($r=0.78^{**}$) was proven to have the greatest potential for predicting As bioavailability in soil with higher correlation between As in rice and the extractant.

• 자원환경지질
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• 제38권6호
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• pp.657-662
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• 2005

Extractions fro fertilizer and soil samples were performed to yield the operationally defined fractions 'soluble' chromate (extractable with $NH_4NO_3$), 'exchangeable' chromate (extractable with phosphate buffer pH 7.2), and these results were compared with the data obtained by extractions with ammonium sulfate, borate buffer pH 7.2, saturated borax pH 9.6, and polyphosphate (Graham's salt). In order to maintain the pH of extractant solution about constant, the concentration of extractant buffer had to be raised to at least 0.5 M. The results strongly depended on the kind of extractant, and the solid: liquid ratio. For most of the samples investigated, the extraction efficiency increased in the order borate-sulfate-nitrate-phosphate. Whereas the recovery of $K_2CrO_4\;and\;CaCrO_4$ added to the samples of basic slags prior to the extraction was about complete, the recovery of added $PbCrO_4$ was highly variable. In soil extracts, the color reaction was interfered from co-extracted humics, which react with the chromate in weak acid solution during the time period necessary for color reaction (1 hour). However, this problem can be overcome by standard addition and subtraction of the color of the extractant solution. In soil extract of about pH < 7, organic material reduced chromate during the extraction period also, and standard addition of soluble chromate is recommended to prove recovery and the stability of chromate in the samples. In admixtures of soils and basic slags, results for hexavalent chromium were lower than from the mere basic slags. This effect was more pronounced in phosphate than in nitrate extracts. As a proficiency test, samples low in organic carbon from contaminated sites in Hungary were tested. The results from $NH_4NO_3$ extracts satisfactorily matched the results of the Hungarian labs obtained from $CalCl_2$ extractants.

• Journal of Industrial and Engineering Chemistry
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• 제68권
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• pp.153-160
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• 2018

An environmentally favorable (chlorine-free) solid oxidizer, guanidinium dinitramide [GDN; $NH_2C(NH_2)NH_2N(NO_2)_2$], was newly synthesized from guanidine carbonate [$NH_2C(=NH)NH_2{\cdot}1/2H_2CO_3$]. Two different crystalline forms (${\alpha}-type$ and ${\beta}-type$) appeared according to the applied solvents and synthesis conditions. Moisture, during extraction, might become trapped in a crystal between inner molecules. Therefore, despite having the same chemical composition, Raman-IR and TGA-DSC revealed different physical characteristics of the two forms. Peaks of Raman shift near $1000cm^{-1}$ implied different chemical structures. Thermal analysis revealed an exothermic temperature $155.7^{\circ}C$ for ${\alpha}-type$ but one of $191.6^{\circ}C$ for ${\beta}-type$. The caloric value of ${\alpha}-type$ was 536.4 J/g, which was 2.5 times larger than that of the ${\beta}-type$, which was 1310 J/g. While the synthesized GDN of ${\alpha}-type$ showed a steep exothermic decomposition, the ${\beta}-type$ was slowly decomposed after melting through an endothermic process. This work implied that despite of the same molecular formula some different core thermal properties would appear depending on synthesis conditions.

• Environmental Engineering Research
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• 제19권3호
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• pp.229-240
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• 2014

Rain events are extremely important for phosphorus (P) dynamics in rivers since large portions of annual river P loads can be transported in particulate forms during only a few major events. Despite their importance, a precise estimation of P contribution in river sediments after rainy seasons has rarely been reported. This study estimated the longitudinal variation in the concentrations of different inorganic P fractions in bed sediments of the South Han River over a rainy season, through using the sequential extraction method. Non-apatite P was the dominant form, representing more than 60% of total inorganic P (TIP) content in sediments. Although no significant variation of TIP contents was observed, the proportion of bioavailable P in TIP pools decreased after the rainy season. The concentrations of individual inorganic P fractions ($NH_4Cl-P$, $NH_4F-P$, NaOH-P, and $H_2SO_4-P$) were significantly different across sites and after the rainy season (p < 0.05, two-way ANOVA). $NH_4F-P$ and NaOH-P concentrations in sediments increased in a downstream direction. After the rainy season, $NH_4Cl-P$ concentrations in sediments decreased whereas $NH_4F-P$ and $H_2SO_4-P$ concentrations increased. The redistribution of individual P fractions in sediments observed after rainy seasons were possibly due to the changing contribution of various sources of runoff and the variation in flow related particle size. Current estimation of P in bed sediments of the South Han River suggests a lower potential of internal P loading from sediments after the rainy season.

• 자원리싸이클링
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• 제9권2호
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• pp.11-17
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• 2000

니켈의 소비량은 계속 중가 추세에 있으며, 이와 함께 2차전지, 페라이트 페촉매는 사용 후의 폐기물이 연속적으로 발생하고 있다. 이들 중 본 연구에서는 Ni-Cd 2차전지 폐기물을 이용하여 니켈 회수를 수행하였다 폐전지의 구성은 니켈이 24wt% 칠이 30wt%, 카드뮴이 18.5wt%, 그리고 산소와 절연물 등으로 이루어져 있었다. 금속 회수의 방법은 침출 후 용매 추출법을 적용하였다. 염산침출에서는 1N 이상의 농도에서 카드뮴이 100% 침출되었고, 니켈은 20,000ppm이상 침출되어 70%이상의 침출율을 보였다. 산침출에서 얻은 침출액은 30vol%의 MSP-8로서 카드뮴만 추출하고 니켈은 잔류액으로 분리할 수 있었다. 그리고 암모늄염에 의한 침출에서는 $NH_4NO_3$에 의한 침출 시 니켈과 카드뮴만을 선택적으로 침출하는데 우수하였다. 질산암모늄에 의해 얻은 침출액 중의 Ni LIX계 추출제를 이용하여 100% 회수할 수 있었고, 잔류액 중의 카드뮴은 D2EHPA로 75% 이상 회수할 수 있었다.

• 한국환경농학회지
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• 제33권4호
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• pp.271-281
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• 2014

BACKGROUND: Application of the transfer functions derived from local soil data is necessary in order to develop proper management protocols for agricultural soils contaminated with heavy metals through phytoavailability control of the heavy metals. The aim of this study was to derive the transfer functions of Korean agricultural soils affected by the abandoned mining sites and evaluate suitability of the derived transfer functions. METHODS AND RESULTS: 142 agricultural soils affected by the abandoned mining sites were collected and analyzed. Two extraction methods, including 1 M $NH_4NO_3$ extraction and 0.01 M $Ca(NO_3)_2$ extraction were applied to determine phytoavailable metal pools in soils. Multiple stepwise regression of phytoavailable metal pools against the corresponding total metal concentration and soil properties was conducted to derive suitable transfer functions for estimating phytoavailable heavy metal pools. Applicability of the derived transfer functions was examined by calculating NME and NRMSE. CONCLUSION: Soil pH and organic matter were valid variables for derivation of the transfer functions which were applicable for estimating phytoavailable metal concentrations in the soils being contaminated by heavy metals. In addition, it was confirmed that transfer functions need to be developed based on local soil conditions to accurately estimate heavy metal-phytoavailability.

• 한국토양비료학회지
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• 제14권4호
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• pp.242-249
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• 1982

카드뮴의 해독(害毒)을 경감(輕減)하는데 필요(必要)한 기초지식(基礎知識)을 얻기 위(爲)하여 카드뮴이 처리(處理)된 토양(土壤)에 석회물질(石灰物質)과 개량제(改良劑)를 사용(使用)한 것과 이미 석회(石灰)가 사용(使用)된 토양(土壤)에 Cd를 처리(處理)한 것을 분(盆)에 담아서 1981년(年) 여름 또는 가을에 자연토양수분조건하(自然土壤水分條件下)에 묻고 처리후(處理后) 40일(日)~70일(日)사이에 토양시료(土壤試料)를 채취분석(採取分析)한 결과(結果)는 다음과 같다. 1. 카드뮴은 토양(土壤)을 0.1N-HCl나 2%구연산으로 침출(浸出)했을 때에 많고, $N-AcNH_4$로 침출(浸出)했을때 적었으며 물로 침출(浸出)했을 때는 나오지 않았다. 침출(浸出)된 카드뮴의 처리간(處理間) 차이(差異)는 $N-NH_4A$ 침출(浸出)에서 가장 뚜렷하여 이것을 유효카드뮴으로 할 수 있을 것 같다. 2) 치환성(置換性)카드뮴을 줄이는데 가장 유효한 것은 수산화(水酸化)카드뮴이며 탄산(炭酸)카드뮴, 규산(珪酸)카드뮴의 순서(順序)로 효과가 적어졌다. 3. 과석(過石)도 치환성(置換性)카드뮴을 줄였는데 인산(燐酸)카드뮴을 침전(沈澱)시키기 때문으로 판단(判斷)되었다. 4. 치환성(置換性)카드뮴은 토양(土壤)의 pH 6.0~6.5에서 많고 그 이하(以下)나 이상(以上)에서 적었다. pH 5.0이하(以下)에서는 $Mn^{+{+}}$으로 인(因)한 $Cd^{+{+}}$의 침전(沈澱)때문이고, pH 6.0이상(以上)에서는 수산화(水酸化)카드뮴의 침전(沈澱)때문으로 판단(判斷)되었다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제21권6호
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• pp.56-66
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• 2016

Generally, the contribution of crop-intake pathway (CIP) is remarkable in human health assessment (HHA) of heavy metal contamination. Although the crop exposure concentrations (Cp) should directly be used for calculating the average daily dose (ADD) of CIP, the soil exposure concentration (Cs) multiplied by soil-crop bio-concentration factor (BCF) has frequently been used instead of using Cp values. Thus, the BCF values are significant in the HHA, and care should be taken to ensure the reasonable acquisition of BCF values. Meanwhile, the BCF values are known to be significantly affected by analytical methods. Nevertheless, they have been calculated from the concentrations of soil and crop analyzed by only one method: total digestion (aqua regia extraction). For this reason, this study was initiated to seek appropriate soil analysis methods for effective computation of the ADD of CIP. The concentrations of 5 metal contaminants (As, Cd, Cu, Pb, and Zn) in 127 soil samples obtained from 4 abandoned metal mine areas were analyzed by several methods including total digestion and partial digestions using 0.1/1 N HCl, 1M $NH_4NO_3$, 0.1 M $NaNO_3$, and 0.01M $CaCl_2$. The heavy metal concentrations in 127 crop samples (rice grains) were analyzed by total digestion as well. Using the concentrations of soils and crops, the BCF values of each contaminant were calculated according to the kind of soil extraction methods applied. Finally, the errors between Cp and $C_s{\times}BCF$ were computed to evaluate the relevance of each method. The results indicate that the partial extraction using 0.1 N and 1 N HCl was superior or equivalent to total digestion. In addition, the 0.1M $NaNO_3$ method combined with total digestion is recommended for improving the reliability of BCF values.

• 한국환경농학회지
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• 제16권3호
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• pp.239-244
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• 1997

토양중 tightly bound paraquat의 효과적인 추출방법을 모색코자 HCl 및 $H_2O_2$첨가 그리고, keldahl 분해장치를 이용하여 회수율 및 여과시간의 단축을 조사하였으며, ammonium chloride와 calcium chloride의 농도와 진탕 시간을 달리하여 loosely bound paraquat의 유출정도를 조사한 결과는 다음과 같다. 1. 토양 50g에 70ml의 conc. HCl을 첨가하여 시간별로 진탕하고 여기에 진한 황산을 가하여 1시간동안 환류 추출한 결과, 60분간 진탕할때 기존의 추출방법에 비해 A토양은 1.15배 높은 96.7%의 회수율과 4.64배 단축된 14분의 여과 시간을, B토양은 1.09배 높은 84.0%의 회수율과 4.91배 단축된 11분의 여과시간을 나타냈다. 아울러, 이러한 결과는 회수율의 증가는 물론 여과시간의 단축, pH조정과정에서 과다한 NaOH사용을 통한 총용량의 증가 방지, 그리고 전체적인 실험시간의 단축을 꾀할 수 있었다. 2. HCl의 첨가에 의한 진탕과정 없이 $H_2O_2$만을 첨가하는 경우, $H_2O_2$ 30ml첨가하여 30분간의 환류 재추출하는 것이 적정 수준이었는데, 회수율은 증대하였으나 여과시간의 단축은 거의 없었다. 반면, 50ml의 $H_2O_2$ 첨가만으로도 회수율의 증대는 있었으나 실험의 위험성을 고려시 적절하지 못하다고 생각된다. 3. Kjeldahl 분해장치를 이용한 방법으로 회수율의 증대를 나타내는 경향은 있었으나, 반복간의 큰 오차를 나타내었으므로 추출방법으로 적합하지 못하다고 생각된다. 4. Loosely bound paraquat의 추출을 위해 0.01, 0.1, 1, 10M ammonium chloride와 calcium chloride를 이용하여 1.5, 3, 6, 12, 24시간으로 진탕시간을 달리하여 분석한 결과, 시간, 농도, 추출액의 변화에도 불구하고 모든 처리구에서 paraquat은 검출한계 미만의 수준이었다.