Jinsung An

Effect of dissolved humic acid on the Pb bioavailability in soil solution and its consequence on ecological risk.

Current risk characterization in ecological risk assessment does not consider bioavailability of heavy metals, which highly depends on physicochemical properties of environmental media. This study was set to investigate the effect of humic acid (HA), used as a surrogate of organic matter, on Pb toxicity and the subsequent effect on risk characterization in ecological risk assessment. Pb toxicity was assessed using Microtox(®) in the presence and absence of two different forms of HA, particulate HA (pHA) and dissolved HA (dHA). With increasing contact time, the EC10 values increased (i.e., the toxic effects decreased) and the dissolved Pb concentrations of the filtrates decreased. The high correlation (R = 0.88, p < 0.001) between toxic effects determined using both the mixture and its filtrate as exposure media leads us to conclude that the Pb toxicity highly depends on the soluble fraction. Also, reduced Pb toxicity with increasing dHA concentrations, probably due to formation of Pb-dHA complexes, indicated that Pb toxicity largely comes from free Pb ions. Overall, this study shows the effect of HA on metal toxicity alleviation, and emphasizes the need for incorporating the bioavailable heavy metal concentrations in environmental media as a point of exposure in ecological risk assessment.

A simplified analysis of dimethylarsinic acid by wavelength dispersive X-ray fluorescence spectrometry combined with a strong cation exchange disk.

Dimethylarsinic acid (DMA(V)) was pre-concentrated from water samples using a strong cation exchange (SCX) disk functionalized with sulfonic groups, before being analyzed by wavelength dispersive X-ray fluorescence spectrometry (WDXRF). The adsorption of DMA(V) occurred preferentially on the surface of the SCX disk, regardless of pH levels, probably due to interactions with the sulfonic functional groups. However, no other arsenic species, such as arsenate (iAs(V)), arsenite (iAs(III)), and monomethylarsonic acid (MMA(V)), were retained. The SCX-WDXRF method produced a strongly linear calibration curve (R(2)=0.9996) with its limit of detection at 0.218 μgL(-1) when a one-liter water sample was used for pre-concentration. The As intensity of the system was sensitive to the Pb content retained on the SCX disk owing to the proximity of the As-Kα and Pb-Lα lines. To compensate for this interference, a correction factor was developed by considering the calibration slope ratio between the X-ray intensity measured at a Bragg angle of 48.781° and the Pb content of the SCX disks. The results of spike tests for iAs(V), iAs(III), MMA(V), and DMA(V) with and without the addition of Pb in synthetic landfill leachate exhibited reasonable recoveries (i.e., 98-105%) after the spectral adjustment for the Pb interference.

Study on Heavy Metal Contamination Characteristics and Plant Bioavailability for Soils in the Janghang Smelter Area

Potential risk of heavy metals to various receptors including humans depends on the bioavailability of the heavy metals in soil. In this study, the heavy metal extraction methods using 0.1N HCl and aqua regia were compared with the Tessier`s sequential extraction method to assess whether these two methods can be used to determine the plant-available heavy metal concentrations. The contamination characteristics of copper (Cu), cadmium (Cd), lead (Pb), and arsenic (As) found in soils collected from 75 sites around the closed Janghang smelter were analyzed by extracting heavy metals using 0.1 N HCl, aqua regia, and the Tessier`s sequential extraction method. The portion of metals bioavailable to plants is considered as the sum of the fraction 1 (exchangeable) and the fraction 2 (carbonates binding) of the Tessier`s 5-step sequential extraction method, which were determined to be 3.1 3.82, 0.6 0.15, 20.6 18.78, and 7.0 6.48 mg/kg for Cu, Cd, Pb, and As, respectively, in this study. When the extraction using aqua regia and the Tessier`s extraction method were compared, the extracted Cu and Pb concentrations did not show significant differences, whereas the extracted Cd and As concentrations showed significant differences. These results indicate that the portion of Cd and As in the fraction 5 of the Tessier`s sequential extraction can not be extracted using aqua regia. Using aqua regia, which is the official test method, higher concentrations of Cu, Cd, Pb and As were extracted than the sum of the fraction 1 and 2. The results show that only 9, 40, 39 and 10% of Cu, Cd, Pb and As using aqua regia can be uptaken by plants (i.e., plant-available). Using 0.1N HCl, the portion of Cd equivalent to about 66% the fraction 1 could be extracted, while, with Pb, the portion of the fraction 1 and about 90% of the fraction 2 could be extracted. With As, the portion equivalent to the fraction 1, 2 and 79% of the fraction 3 was extracted, while with Cu, the portion equivalent to the fraction 1, 2, 3 and 20% of the fraction 4 was extracted using 0.1N HCl.

Effectiveness of activated carbon disk for the analysis of iodine in water samples using wavelength dispersive X-ray fluorescence spectrometry.

A novel approach using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry combined with an activated carbon (AC) disk was developed for the determination of total iodine concentrations in water samples. Dissolved iodine species (i.e., I(-) and IO3(-)) in water samples were preconcentrated on the AC disk and directly analyzed by WDXRF spectrometry. The adsorption behavior of I(-) and IO3(-) on the AC disk was assessed at varying pH levels (4, 6, and 8). The AC disks completely retained the I(-) and IO3(-) for all the pH levels tested. The calibration curve obtained from the iodine concentrations (i.e., 0, 20, 200, and 400 μg) of AC disks and the measured X-ray intensity from the WDXRF analysis showed a good linearity (R(2)=0.9960), with a relatively low limit of detection (0.575 μg). The durability of the AC disk for repeatable measurements was also assessed to validate the sustainability of the proposed method and consequently the measured X-ray intensity for the AC disks was constant until 8d of analysis time. The accuracy of the proposed AC-WDXRF method was confirmed by measuring iodine concentration spiked in drinking water using inductively coupled plasma-mass spectrometry (ICP-MS). The proposed method is simple, rapid, efficient, and environmental friendly for iodine analysis in water samples. As a precursor of disinfection by products (DBPs), it is important to determine the total iodine concentrations in raw water.

Formation of dimethyldithioarsinic acid in a simulated landfill leachate in relation to hydrosulfide concentration

Abstract Dimethyldithioarsinic acid (DMDTAV), present in such intense sources as municipal landfill leachate, has drawn a great deal of attention due to its abundant occurrence and different aspect of toxicity. The hydrosulfide (HS−) concentration in leachate was studied as a major variable affecting the formation of DMDTAV. To this end, the HPLC–ICPMS system equipped with the reversed-phase C18 column was used to determine DMDTAV. Simulated landfill leachates (SLLs) were prepared to cover a mature landfill condition with the addition of sodium sulfate and sulfide at varying concentrations in the presence of dimethylarsinic acid (DMAV). The concentration of sodium sulfide added in the SLLs generally exhibited a strong positive correlation with the concentration of DMDTAV. As such, the formation of DMDTAV in the SLLs is demonstrated to be controlled by the interactive relationship between DMAV and the HS−.

A Review on the Analytical Techniques for the Determination of Fluorine Contents in Soil and Solid Phase Samples

Current status of soil contamination with fluorine and its source were investigated. The basic principles and procedures of various techniques for the analysis of fluorine contents in soil and solid phase samples were summarized in this review. Analysis of fluorine in solid matrices can be achieved by two types of techniques: (i) UV/Vis spectrophotometer or ion selective electrode (ISE) analysis after performing appropriate extraction steps and (ii) direct solid analysis. As the former cases, the standard method of Korean ministry of environment, alkali fusion-ISE method, pyrohydrolysis, oxygen bomb combustion, aqua regia digestion-automatic analysis, and sequential extraction-ISE method were introduced. In addition, direct analysis methods (i.e., X-ray fluorescence spectrometry and proton induced gamma-ray emission spectrometry) and atomic spectrometry combining with the equipment for introducing solid phase sample were also reviewed. Fluorine analysis techniques can be reasonably selected through site-specific information such as matrix condition, contamination level, the amount of samples and the principles of various methods for the analysis of fluorine presented in this review.

Determination of fluorine contents in plant samples by means of facilitated extraction with enzyme.

In this study, facilitated extraction with enzyme was employed for the first time to extract fluorine (F) from plants. Feasibility of the proposed method for F analysis was assessed by comparing with the alkali fusion-ion selective electrode (ISE) method. In the extraction procedure, 30 mg of a protease and 0.1 g of a plant sample were added in 10 mL of deionized water. In the absence of sonication, the solution was mechanically shaken for 10 s. A variety of parameters (i.e., the amounts of enzymes used, physical treatment conditions applied, extraction time, temperature, and pH) were optimized to enhance the extraction efficiency of the proposed method. The suitability of the proposed method for various plant samples (i.e., grass, perilla, peanut, hot pepper, and eggplant) was also evaluated. The proposed method involves decreased operation time, simplified extraction procedures, and minimal consumption of hazardous reagents and solvents in comparison with other existing methods. Experimental results demonstrated that facilitated extraction with enzyme is appropriate for the rapid determination of F content in plant samples.

Assessment of Risk Based Pollution Level of Pb and Cd in Metal Contaminated Soils Using Biotic Ligand Model

Risk based pollution level of Pb and Cd in metal contaminated soils depending on physicochemical properties of soil in a target site was assessed using biotic ligand model. Heavy metal activity in soil solution defined as exposure activity (EA) was assumed to be toxic to Vibrio fischeri and soil organisms. Predicted effective activity (PEA) determined by biotic ligand model was compared to EA value to calculate risk quotient. Field contaminated soils (n