Min-Ju Kang

Assessment of mobility and bio-availability of heavy metals in dry depositions of Asian dust and implications for environmental risk.

We assess the potential mobility and bio-availability of selected metals (As, Cd, Co, Cr, Cu, Ni, Mo, Pb, S, Zn, and Zr) in the dry depositions of Asian and non-Asian dust from the city of Daejeon, Korea. For this study, we applied Pb isotopes, total extraction and chemical sequential extraction methods to the dry depositions. In addition, microscopic analysis was performed using X-ray diffraction (XRD) and focused ion beam (FIB)-scanning electron microscopy (SEM-EDS). FIB-SEM cross-section observations and Pb isotope data showed a black carbon is an important carrier of associated heavy metals originating from China. A five-step sequential extraction performed on the dry depositions showed that S and Cd are the most abundant elements in the water-soluble and cation-exchangeable fraction. In addition, Zn and Pb appeared predominantly in the carbonate and reducible fractions. On the other hand, Cu, Mo and, to a lesser degree, As were significantly associated with the organic fraction, while Co, Ni, Cr and Zr were bound to the residual fraction. These results showed that S, Cd, Zn and Pb, which were highly concentrated in potentially mobile fractions, have potential environmental risk because potential changes in redox state and pH may remobilize these metals. In addition, the estimated remobilization concentrations of these metals were significant. Thus, this study shows that frequent and careful monitoring of S, Cd, Z, Pb and, to a lesser degree, Cu, Mo and As is very important for assessing environmental risk in Korea.

Lead chromate detected as a source of atmospheric Pb and Cr (VI) pollution

Spherical black carbon aggregates were frequently observed in dust dry deposition in Daejeon, Korea. They were tens of micrometers in diameter and presented a mixture of black carbon and several mineral phases. Transmission electron microscopy (TEM) observations with energy-dispersive X-ray spectroscopy (EDS) and selected area diffraction pattern (SADP) analyses confirmed that the aggregates were compact and included significant amounts of lead chromate (PbCrO4). The compositions and morphologies of the nanosized lead chromate particles suggest that they probably originated from traffic paint used in roads and were combined as discrete minerals with black carbon. Based on Pb isotope analysis and air-mass backward trajectories, the dust in Daejeon received a considerable input of anthropogenic pollutants from heavily industrialized Chinese cities, which implies that long-range transported aerosols containing PbCrO4 were a possible source of the lead and hexavalent chromium levels in East Asia. Lead chromate should be considered to be a source of global atmospheric Pb and Cr(VI) pollution, especially given its toxicity.

Assessment of Zn pollution sources and apportionment in agricultural soils impacted by a Zn smelter in South Korea

This study was conducted to assess the anthropogenic impact on the metal concentration in agricultural soils in the vicinity of a Zn smelter. We determined Pb isotope ratios to trace source of metals and calculate source apportionment. 19.7% of the agricultural soil samples had Zn concentrations exceeding the Korean worrisome level (WL). The isotopic variation in the contaminated agricultural soils reflected the input of contaminants derived from the Zn smelter. The spatial distribution of Zn concentrations and Pb isotopes suggested that the Zn smelter dust fallout was the major source of heavy metal pollution in the agricultural soils. Lead isotope compositions of soil horizon I was comparable to those of soil horizon II, indicating that smelter-origin Zn had migrated vertically. Binary mixing between Zn concentrates and background soils could explain the variations in Pb isotope ratios in the contaminated agricultural soils. Source apportionment calculations showed that for agricultural soils that were found to exceed the Korean countermeasure standard (CS), the average proportion of smelter-origin Zn was 45.8%-83.3% while for agricultural soils that exceeded the WL but were below the CS, the average proportion of smelter-origin Zn was 36.3%-68.1%. The remainder was derived from a geogenic source.

Characterization of Cr (VI) – containing solid phase particles in dry dust deposition in Daejeon, South Korea

Solid phase speciation of chromium in dry dust deposition and road paint was determined using transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS). Spherical black carbon aggregates in dry dust deposition contained discrete nano-sized lead chromate (PbCrO4) and zinc chromate (ZnCrO4), which likely originated from yellow traffic paint and zinc chromate primer (corrosion resistant pigment), respectively based on their main applications. Road marking paint samples from auto roads included lead chromate particles whose size, shape, composition and crystal structure were similar to those in dry dust deposition. A slight difference was found at the particle boundary. Namely, lead chromate in traffic paint was encapsulated by silica-bearing matrix, while discrete lead chromate in the black carbon of dry deposition was rarely enclosed within silica-bearing matrix. The Cr K edge X-ray absorption near edge structure (XANES) spectrum for dry deposition showed the characteristic pre-edge resonance peak similar to the spectra for the Cr(VI) standard and road paint, but the lower intensity. The amount of Cr(VI) accounted for approximately 45% of the total Cr in the dust sample. The solid phase speciation of Cr observed using TEM and their valence states determined using XANES were consistent with the chemical speciation determined using the sequential extraction. The contribution of this study is that XANES was applied to identify Cr valance states in urban dust deposition and zinc chromate was found as a Cr(VI) phase in dry dust deposition using TEM. These study results provide novel data on Cr speciation and Cr(VI)-containing mineral phases in dry dust deposition and their potential sources. Based on the wide use of lead and zinc chromate, atmospheric contamination with these solid phase speciation of Cr(VI) is expected in other cities in the world.

Temporal and Spatial Variation and Removal Efficiency of Heavy Metals in the Stream Water Affected by Leachate from the Jiknaegol Tailings Impoundment of the Yeonhwa II Mine

This study had been carried out to investigate spatial and temporal variations of the concentrations of trace metals for contaminated surface water in creek affected by leachate from the tailings impoundment of the Yeonhwa II mine for about 2 years. It was also to ascertain the metal removal efficiency for potentially deleterious metals by the artificial and natural attenuation processes such as retention ponds and hydrologic mixing of uncontaminated tributaries. The concentrations of As, Pb, Cd, and Cu for leachate in the rainy season were not detected. On the other hand, the concentrations of Zn, Fe, Mn, Al, and in the rainy season for leachate were 2-66 times higher than those in the dry season, due to the oxidation of the sulfide minerals and the dissolution of the secondary minerals. The concentrations of Zn and Cd for leachate and surface water of the upper creek in the rainy season exceeded the criteria of River Water Quality and Drinking Water Quality but in the dry season, those of analyzed all the metals (As, Pb, Cd, Cu, Zn, Cd, Fe, Mn, and Al) for surface water sampled at the study area were below the criteria of River Water Quality and Drinking Water Quality. In regard of the attenuation efficiency for the concentrations of metals, Fe, Mn, Al, Zn, Cd, As, and Cu were removed highly at retention ponds, while the removal efficiency for major cations and sulfate () were related to mixing of the uncontaminated tributaries. Therefore, the major attenuation processes of the metal and sulfate contents in creek affected by leachate from a tailing dump were precipitation (accompanied by metal co-precipitation and sorption), water dilution, and neutralization.