Journal of Korean Society for Atmospheric Environment
/
v.30
no.5
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pp.434-448
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2014
The aerosol characteristics between haze episode and Asian dust event were identified in January and March, 2013 in Gwang-ju of Korea to investigate the metal elements, ionic concentrations and carbonaceous particles of $PM_{2.5}$ and $PM_{10}$. In the haze episode, the concentrations were increased 1~3.2 times of ionic species and 1.6~2.7 of metal elements. Especially, the concentration of $NO{_3}{^-}$, $SO{_4}{^2-}$ and $NH{_4}{^+}$ consists of 50 percent in ionic species during haze episode that was higher than Asian dust event. This suggests that secondary aerosols from anthropogenic air pollution were mainly contributed by haze episode. During the Asian dust event, increase of metal concentrations was higher than haze episode because of remarkable increase of Ti, K and Fe originated from soil. The concentrations of carbonaceous particles were increased 2.5 times during haze episode, and 2.4 times of OC and 2.1 times of EC during Asian dust event in $PM_{2.5}$. However, these aerosol mass concentration does not affect the OC/EC ratio. The average equivalence ratios of cations/anions in $PM_{2.5}$ were 0.99 in haze episodes and 0.94 during non-event day. The neutralization factor of $NH_3$ was higher than that of $CaCO_3$. Futhermore, $NH{_4}{^+}$ aerosol was aged due to atmospheric stagnation that might be affected by the haze episode.
During a twenty-day period in 2005, a nine-stage Andersen cascade impactor was used to determine the seasonal size distribution of atmospheric particles and its inorganic ion species sampled for 24hr in Iksan city, located southwest of the Korean peninsula. Samples were analyzed for major water-soluble ion species using Dionex-100 ion chromatograph. Average fine and coarse mass concentrations of atmospheric particles were, respectively, 31.4 and $82.6{\mu}g\;m^{-3}$ in spring and 35.8 and $73.4{\mu}g\;m^{-3}$ in fall-winter during the sampling period of 2005, while measurements of 69.8 and 9.9 were obtained in the sampling period of summer, The size distribution of particulate mass concentration during the non-Asian dust period was generally bimodal, whereas the size distribution of particulate mass concentration during the Asian dust period was unimodal due to the significant increase of coarse particles, which originated from long-range transport of soil dust particles from loess regions of the Asian continent. Among ionic species, $SO{_4}^{2-},\;NH{_4}^+,\;K^+$ were mainly distributed in fine particles due to their characteristics of emission sources and gas-to-particle conversion, while $Na^+,\;Mg^{2+}\;and\;Ca^{2+}$ were dominantly in coarse particles. However, $NO_3{^-}\;and\;Cl^-$ were distributed in both coarse particles and fine particles. Although $SO{_4}^{2-}$ was mainly distributed in fine particles, the size distributions of $SO{_4}^{2-}$ in coarse mode were significantly increased during the Asian dust events compared to those during the non-Asian dust period. $Ca^{2+}$ showed the most abundant species in the atmospheric particles during the Asian dust period. $NH{_4}^+$ was found to mainly exist as $(NH_4)_2SO_4$ in fine particles.
According to the bipolar model, ion selectivity of some species in the passive film is important factor to control the passivation. An increase of cation selectivity of outer layer of the passive film can stabilize the film and improves the corrosion resistance. Therefore, the formation and roles of ionic species in the passive film should be elucidated. In this work, two types of solution (hydrochloric or sulfuric acid) were used to test high N and Mo-bearing stainless steels. The objective of this work was to investigate the formation of oxyanions in the passive film and the roles of oxyanions in passivation of stainless steel. Nitrogen exists as atomic nitrogen, nitric oxide, nitro-oxyanions (${NO_x}^-$), and N-H species, not nitride in the passive film. Because of its high mobility, the enriched atomic nitrogen can act as a reservoir. The formation of N-H species buffers the film pH and facilitates the formation of oxyanions in the film. ${NO_x}^-$ species improve the cation selectivity of the film, increasing the oxide content and film density. ${NO_x}^-$ acts similar to a strong inhibitor both in the passive film and at active sites. This facilitates the formation of chromium oxide. Also, ${NO_x}^-$ can make more molybdate and nitric oxide by reacting with Mo. The role of Mo addition on the passivation characteristics of stainless steel may differ with the test environment. Mo exists as metallic molybdenum, molybdenum oxide, and molybdate and the latter facilitates the oxide formation. When nitrogen and molybdenum coexist in stainless steel, corrosion resistance in chloride solutions is drastically increased. This synergistic effect of N and Mo in a chloride solution is mainly due to the formation of nitro-oxyanions and molybdate ion. Oxyanions can be formed by a 'solid state reaction' in the passive film, resulting in the formation of more molybdate and nitric oxide. These oxyanions improve the cation selectivity of the outer layer and form more oxide and increase the amount of chromium oxide and the ratio of $Cr_2O_3/Cr(OH)_3$ and make the film stable and dense.
Chemical assessment of soil pollution with heavy metals was made by analyzing the changes in pH, ionic strength, cationic concentration and chemical species in the soil solution. Saturated pastes of the unpolluted soils were made by adding solutions containing Cu or Cd and the final Cu or Cd concentrations were in the range of 0 to 400 mg/kg. After equilibrating for 24 hours at $25^{\circ}C$, the soil solution was extracted from the saturated pastes by the vacuum extraction method and analyzed for pH, electrical conductivity, Cu, Cd, cations and inorganic ligands. Chemical species in soil solution were calculated by the GEOCHEM-PC program employing the input variables of pH, ionic strength(${\mu}$), molar concentrations of cations and ligands. Increasing Cu or Cd additions lowered pH of the soil solution but increased concentrations of Ca, Mg and K resulting in increases of ${\mu}$ of the soil solution. Effects of Cu on lowering pH and increasing ${\mu}$ were greater than those of Cd. Concentrations of Cu or Cd in soil solution were relatively very low as compared to those of additions, but increased linearly with increasing additions representing that concentrations of Cu were higher than those of Cd. At 400 mg/kg additions, concentrations of Cu were in the range of 0.51 to 11.70 mg/L but those of Cd were 34.4 to 88.5 mg/L. Major species of Ca, Mg and K were free ions and these species were equivalent to greater than 95 molar % of the existing respective molar concentrations. These cationic species were not changed by Cu or Cd additions. Major species of Cu in lower pH soils such as SiCL and SL were free $Cu^{2+}$ (>95 molar %), but those in LS having a higher pH were free $Cu^{2-}$ and Cu-hydroxide complex. At 100 mg Cu/kg treatment, $Cu^{2+}$ and Cu-hydroxide complex were equivalent to 73 and 22.4 molar %, respectively. These respective percentages were decreased and increased correspondingly with increasing Cu treatments. Major species of Cd in soil solution were free $Cd^{2+}$ and Cd-chloride complex, representing 79 to 85 molar % for $Cd^{2+}$ and 13 to 20% for Cd-chloride complex at 10 mg Cd/kg treatment. With increasing Cd additions to 400 mg/kg, $Cd^{2+}$ species decreased to $40{\sim}47%$ but Cd-chloride complexes increased to $53{\sim}60$ molar %. These results demonstrated that soil contamination with heavy metals caused an adverse effect on the plant nutritional aspects of soil solution by lowering pH, increasing cations temporarily, and increasing free metal concentrations and species enough to be phytotoxic.
Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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v.4
no.3
/
pp.235-243
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2006
In this study, an experimental study on the sorption properties of uranium(VI) onto a bentonite colloid generated from Gyeongju bentonite which is a potential buffer material in a high-level radioactive waste repository was performed as a function of the pH and the ionic strength. The bentonite colloid prepared by separating a colloidal fraction was mainly composed of montmorillonite. The concentration and the size fraction of the prepared bentonite colloid measured using a gravitational filtration method was about 5100 ppm and 200-450 nm in diameter, respectively. The amount of uranium removed by the sorption reaction bottle walls, by precipitation, and by ultrafiltration was analyzed by carrying out some blank tests. The removed amount of uranium was found not to be significant except the case of ultrafiltration at 0.001 M $NaClO_4$. The ultrafiltration was significant in the lower ionic strength of 0.001 M $NaClO_4$ due to the cationic sorption onto the ultrafilter by a surface charge reversion. The distribution coefficient $K_d$ (or pseudo-colloid formation constant) of uranium(VI) for the bentonite colloid was about $10^4{\sim}10^7mL/g$ depending upon pH and ionic strength of $NaClO_4$ and the $K_d$ was highest in the neutral pH around 6.5. It is noted that the sorption of uranium(VI) onto the bentonite colloid is closely related with aqueous species of uranium depending upon geochemical parameters such as pH, ionic strength, and carbonate concentration. As a consequence, the bentonite colloids generated from a bentonite buffer can mobilize the uranium(VI) as a colloidal form through geological media due to their high sorption capacity.
The ionic compositions of atmospheric aerosols were investigated and characterized in coastal and mountainous sites of Jeju Island, which were Gosan and Mt. Halla-1100 sites respectively. It was found that the concentrations of nss-$SO_4^{2-}$ (non-sea salt sulfate) and $NH_4^+$ at two measurement sites were almost similar and they showed high concentrations in June at the same time. The concentration of soil-originated nss-$Ca^{2+}$ (non-sea salt calcium) was generally associated with that of anthropogenic $NO_3^-$ and its concentration was increased during spring season. From the comparison of time-series variation and regression analysis of ionic species between two measurement sites, TSP (total suspended particulate) in Gosan site was directly influenced by sea salt particles and the concentration levels of nss-$SO_4^{2-}$, $NH_4^+$, nss-$Ca^{2+}$, $K^+$, and $NO_3^-$ were mainly related with long-range transported air pollutants rather than local pollution sources.
The objectives of the study were to analyze chemical water quality and fish community structures in the downstreams of Geum River during 2004~2005. Water quality parameters showed that ionic dilution was evident during July~August due to a rainfall and river runoff by Asian monsoon. Mean concentrations of BOD showed a seasonal variation and were greater in the downstream than in the midstream. The total number of fish species observed was 34 (11 families) and 30.3% of them was Korean endemic species. The dominant species with > 20% of the total were Zacco platypus (25.9%) and Microphysogobio jeoni (21.5%) in the river. Exotic species observed was only one species, Carassius cuvieri with relative abundance of 1.8%. According to the structure analysis of fish community, species richness index was highest (3.714) in S6 and lowest in S4 (1.961), while species diversity index was highest in S2 (1.01) and lowest in S5 (0.507). Tolerant species dominated the fish community (49%), and the sensitive species were rare (4.4%), indicating a biological degradation of ecosystem. In the mean time, omnivore species was composed of 49% in the fish community and insectivore species was nearly same with the proportion of the omnivores.
Journal of Korean Society for Atmospheric Environment
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v.31
no.3
/
pp.269-286
/
2015
24-hr integrated $PM_{2.5}$ measurements were performed between December 2013 and October 2014 at an urban site in Gwangju and the collected samples were analyzed for organic carbon (OC), elemental carbon (EC), ionic species, and elemental species. Objectives of this study were to identify $PM_{2.5}$ pollution episodes, to characterize their chemical components, and to examine their probable origins. Over the course of the study period, average $PM_{2.5}$ concentration was $37.7{\pm}23.6$$(6.0{\sim}121.5){\mu}g/m^3$. Concentrations of secondary ionic species; $NH_4{^+}$, $NO_3{^-}$, and $SO_4{^{2-}}$ was on average $5.54{\mu}g/m^3$ (0.28~ 20.86), $7.60{\mu}g/m^3$ (0.45~ 33.53), and $9.05{\mu}g/m^3$ (0.50~ 34.98), accounting for 13.7% (4.6~ 22.7), 18.6% (2.9~ 44.8), and 22.9% (4.9~ 55.1) of the $PM_{2.5}$ concentration, respectively. Average OC and EC concentrations were $5.22{\mu}g/m^3$ and $1.54{\mu}g/m^3$, taking possession of 4.6 and 22.2% (as organic mass) of the $PM_{2.5}$, respectively. Frequencies at which 24-hr averaged $PM_{2.5}$ exceeded a 24-hr averaged Korean $PM_{2.5}$ standard of $50{\mu}g/m^3$ (termed as an "episode" in this study) were 30, accounting for 21.3% of total 141 measurements. These pollution episodes were mostly associated with haze phenomenon and weak surface wind speed. It is suggested that secondary formation of aerosol was one important formation mechanism of the episodes. The episodes were associated with enhancements of organic mass, $NO_3{^-}$ and $SO_4{^{2-}}$ in winter, of $NO_3{^-}$ and $SO_4{^{2-}}$ in spring, and of $SO_4{^{2-}}$ in summer. Potential source contribution function results indicate also that $PM_{2.5}$ episodes were likely attributed to local and regional haze pollution transported from northeastern China in winter, to atmospheric processing of local emissions rather than long-range transport of air pollutants in spring, and to the $SO_4{^{2-}}$ driven by photochemistry of $SO_2$ in summer.
Water soluble organic and inorganic species are important components in atmospheric aerosol particles and may act as cloud condensation nuclei to indirectly affect the climate. To characterize organic and elemental carbon(OC and EC), water-soluble organic carbon(WSOC) and inorganic ionic species contents, daily $PM_{2.5}$ measurements were made during the wintertime at an urban site of Gwangju. Average concentrations of WSOC, $NO_3^-$, $SO_4^{2-}$ and $NH_4^+$, which are major components in the water-soluble fraction in PM2.5, are 2.11, 5.73, 3.51 and $3.31{\mu}g/m^3$, respectively, representing 12.0(2.9~23.9%), 21.0(12.9~37.6%), 11.6(2.5~25.9%) and 11.7%(3.8~18.6%) of the $PM_{2.5}$, respectively. Abundance of water soluble organic compounds ranged from 5.4 to 35.9% of total water soluble organic and inorganic components with a mean of 17.6%. Even though the sampling was performed during the winter, the average contributions of secondary OC and WSOC, as deduced from primary OC/EC(or WSOC/EC) ratio, were relatively high, accounting for 17.9%(0~44.4%) of the total OC and 11.2%(0.0~51.4%) of the total WSOC, respectively. During the sampling period, low $SO_4^{2-}/(SO_4^{2-}+SO_2$) ratio of 0.14(0.03~0.32) and relative humidity condition in the winter time suggest an possibility of impact of long-range transport and/or aqueous transformation processes such as metal catalyzed oxidation of sulfur, in-cloud processes, etc.
This study was conducted to know that if ionic liquids can be applicable as control agents of harmful algae in water-ecosystem and to find out problems caused by ionic liquid application. Firstly, the differential selectivity of various fresh-water algal species to several 1-alkyl-3-methylimidazolium chloride ionic liquids was investigated. There was a distinct differential response between alkyl chain lengths from butyl to dodecyl and towards the algal organisms : Generally algicidal activity was increased with increase of chain length and among the algae used in this study, Stephanodiscus hantzschii f. tenuis, Oscillatoria tenuis and Spirulina pratensis were most sensitive to 1-dodecyl-3-methylimidazolium chloride (MAIC12), next was Microcystis aeruginosa, and the others were relatively less sensitive to the chemical. The selectivity degree was about ten to twenty times based on the $EC_{80}$ (Effective concentration required for 80% growth inhibition). Secondly, an activity persistence of ionic liquids was investigated in natural mimic condition (using water bottle containing soil-sediments under the greenhouse condition). At the application of $1.0{\mu}g\;mL^{-1}$ of 1-octyl-3-methylimidazolium chloride (MAIC8), the algal growth did not occur at all until 6 days after treatment(DAT) and observed a only little growth at 9 DAT. But the algae grew rapidly after 9 DAT. So at 20 DAT, total chlorophylls was $264.4{\mu}g\;L^{-1}$ and the growth was inhibited by 58.2% compared to untreatment. On the other hand, MAIC12 also had a similar persistence pattern to MAIC8, showing nearly 5 times more activity than MAIC8. At 20 days after $0.2{\mu}g\;mL^{-1}$ application of MAIC12, that is, total chlorophylls was $251.2{\mu}g\;L^{-1}$ and the growth was inhibited by 55.2% compared to untreatment. In summary, 1-alkyl-3-methylimidazolium chloride ionic liquids is likely to be applicable for selective control of harmful algae as potent compounds having long lasting activity. However, the difficulty of degradation seems to be a limiting factor in an eco-friendly application of the compounds.
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