• Applied Biological Chemistry
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• v.12
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• pp.115-118
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• 1969

In a series of studies on the formation processes and chemical properties of humic substances from paddy soils the photoabsorption spectra of hymatomelanic and humic acids were recorded in the visible, ultraviolet and infrared regions. The spectra patterns of both fractions in the visible range were indicative of the decrease in optical density with the rise of wavelength and the UV-spectra showed the maximum peak at $235\;m{\mu}$, the minimum at $395\;m{\mu}$. The IR-spectra indicate a typical pattern showing a few sharp peaks in both fractions. The spectra of both fractions were compared and discussed.

• Korean Journal of Soil Science and Fertilizer
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• v.32 no.4
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• pp.429-439
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• 1999

Potentiometric titration data were collected for some humic acids purified from Korean upland and paddy soils over a range of pH (3.0 - 11.0) with $NaNO_3$ background electrolyte concentrations (0.01, 0.10, 0.50 and 1.00 M). The data were applied to model A and V which included both intrinsic heterogeneity of humic materials and electrostatic interaction influences on binding sites. The elemental analysis were conducted for various type of humic samples. The $E_4/E_6$ ratio proposed negative correlation with the total carboxyl groups ($r^2$= 0.9988). The charge ($cmol_c\;kg^{-1}$) on the humic acids became more negative as the ionic strength increased. In both continuous and batch titrations, the ionic strength effect was greater in Namweon series (pH 6.39) than others at pH 5.00. The effect of ionic strength on surface charge appears to be greater in batch titrations. This could suggest that continuous titrations do not represent an equilibrium state and the effects of electrolyte concentration was not fully realized during the course of titrations. Both models described experimental data obtained from continuous and batch titrations well over a range of ionic strengths. Model A is more simpler than model V but adaptes more fitted parameters. Thus, the observed change in apparent binding constants with surface charge is regarded solely due to electrostatic influences rather than functional group heterogeneity. However, Model V is more mechanistically realistic in a number of discrete ligand binding sites.

• Environmental Engineering Research
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• v.23 no.2
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• pp.181-188
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• 2018

Photocatalytic oxidation in the presence of Fe-doped, Zn-doped or Fe-Zn co-doped $TiO_2$ was used to effectively decompose humic acids (HAs) in water. The highest HAs removal efficiency (65.7%) was achieved in the presence of $500^{\circ}C$ calcined 0.0010% Fe-Zn co-doped $TiO_2$ with the Fe:Zn ratio of 3:2. The initial solution pH value, inorganic cations and anions also affected the catalyst photocatalytic ability. The HAs removal for the initial pH of 2 was the highest, and for the pH of 6 was the lowest. The photocatalytic oxidation of HAs was enhanced with the increase of the $Ca^{2+}$ or $Mg^{2+}$ concentration, and reduced when concentrations of some anions increased. The inhibition order of the anions on $TiO_2$ photocatalytic activities was $CO{_3}^{2-}$ > $HCO_3{^-}$ > $Cl^-$, but a slightly promotion was achieved when $SO{_4}^{2-}$ was added. Total organic carbon (TOC) removal was used to evaluate the actual HAs mineralization degree caused by the $500^{\circ}C$ calcined 0.0010% Fe-Zn (3:2) co-doped $TiO_2$. For tap water added with HAs, the $UV_{254}$ and TOC removal rates were 57.2% and 49.9%, respectively. The $UV_{254}$ removal efficiency was higher than that of TOC because of the generation of intermediates that could significantly reduce the $UV_{254}$, but not the TOC.

• Korean Journal of Soil Science and Fertilizer
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• v.16 no.4
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• pp.347-352
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• 1983

To characterize humus fractions in soil, visible, ultraviolet and infrared absorption spectra of humic acids in alkaline solutions and hymatomelanic acids in ethanol solutions extracted by Stevenson's method from paddy rice soils, peats, and volcanic ash soils were analyzed. The spectra patterns of both fractions in visible and ultraviolet ranges did not have any peak and the absorbance decreased as the wavelength increased. Visible and ultraviolet spectra of the solutions from all the peats, volcanic ash soils and paddy rice soil were very similar each other but absorbances were slowly declined in the order of volcanic ash soils, peats and mineral paddy soils. The infrared spectra of the two solutions appeared in a typical pattern, showing a few broad peaks. The main absorption bands were in the regions of $3400cm^{-1}$ (hydrogen bonded OH), near $2900cm^{-1}$ (aliphatic CH), $1720cm^{-1}$ (C=O of COOH, C=O of carbonyl), $1625cm^{-1}$ (aromatic C-C conjugated with C=O and/or COO-), $1400-1450cm^{-1}$ (CH stretch), $1200-1250cm^{-1}$ (CaO stretch of phenolic OH or OH-deformation of COOH) and $1050cm^{-1}$. The hymatomelanic acid fractions, however, had spectra that were characterized especially by very distinct absorption at $2900cm^{-1}$ and $1720cm^{-1}$, for aliphatic CH and carbonyl stretching vibration respectively in addition to the weaker bands for COO- or aromatic CH vibration at $1625cm^{-1}$, as compared to humic acid. No differences were noted in the general patterns of the spectograms of both fractions extracted. Analyses of the functional groups revealed little differences between peats and paddy soils, although total acidity and the content of carboxyl groups were decreased in the order of volcanic ash soils, peats and mineral paddy soils.

• Journal of Soil and Groundwater Environment
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• v.20 no.7
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• pp.70-79
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• 2015

A sample of soil humic acid (HA) was divided by ultrafiltration (UF) into five fractions of different molecular size (UF₁: > 300, UF₂: 100~300, UF₃: 30~100, UF₄: 10~30, UF₅: 1~10 kilodaltons). Apparent average molecular weight (M_w) of the HA fractions were measured using high performance size exclusion chromatography (HPSEC), and the chemical and structural properties of the five HA fractions were characterized by elemental compositions (H/C, O/C and w ((2O + 3NH)/ C)) and ultraviolet-visible absorption ratios (SUVA, A_4/6). The organic carbon normalized-sorption coefficients (Koc) for the binding of phenanthrene to the HA fractions were determined by fluorescence quenching and relationship between the sorption coefficients and structural characteristics of the HA fractions were investigated. The elemental analysis and UV-vis spectral data indicated that the HA fractions with higher molecular weights have grater aliphatic character and lower contents of oxygen, while the HA fractions with lower molecular size have greater aromatic character and molecular polarity that correspond to greater SUVA and internal oxidation values (w). The log Koc values (L/kg C) were gradual increased from 4.45 for UF₅ to 4.87 for UF1. The correlation study between the structural descriptors of the HA fractions and log Koc values of phenanthrene show that the magnitude of Koc values positively correlated with $M_w$ and H/C, while negatively correlated with the independent descriptors of the O/C, w, SUVA and A_4/6.

• Asian Journal of Atmospheric Environment
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• v.12 no.2
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• pp.153-164
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• 2018

We measured $^1H$ and $^{13}C$ nuclear magnetic resonance (NMR) spectra of Humic-like substances (HULIS) in urban atmospheric aerosols isolated by diethylaminoethyl (DEAE) and hydrophilic-lipophilic balance (HLB) resin to characterize their chemical structure. HULIS isolated by DEAE resin were characterized by relatively high contents of aromatic protons and relatively low contents of aliphatic protons in comparison with HULIS isolated by HLB resin, while the contents of protons bound to oxygenated aliphatic carbon atoms were similar. These results were consistent with the results of the $^{13}C$ NMR analysis and indicate that hydrophobic components were more selectively adsorbed onto HLB, while DEAE resins selectively retained aromatic carboxylic acids. Furthermore, we demonstrated that the chemical structural features of HULIS were significantly different between spring and summer samples and that these disparities were reflective of their different sources. The estimated concentrations of HULIS in spring were found to be regulated by vehicle emissions and pollen dispersion, while the behavior of HULIS in summer was similar to photochemical oxidant and nitrogen dioxide concentrations. The proportion of aliphatic protons for summer samples was higher than that for spring samples, while the proportion of aromatic protons for summer samples was lower than that for spring samples. These seasonal changes of the chemical structure may also involve in their functional expression in the atmosphere.

• Journal of Korean Society on Water Environment
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• v.32 no.1
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• pp.98-107
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• 2016

This study examined the effects of environmental conditions and the presence of refractory organic matter on oxidation rates of total organic carbon (TOC) measurements based on high temperature combustion and ultraviolet-sulfate methods. Spectroscopic indices for prediction of oxidation rates were also explored using the UV spectra and fluorescence excitation-emission matrix (EEM) of humic acids. Furthermore, optimum TOC instrument conditions were suggested by comparing oxidation rates of a standard TOC material under various conditions. Environmental conditions included salts, reduced ions, and suspended solids. Salts had the greatest influence on oxidation rates in the UV-sulfate method. However, no effect was detected in the high temperature combustion method. The UV-sulfate method showed lower humic substance oxidation rates, refractory natural organic matter, compared to the other methods. TOC oxidation rates for the UV-sulfate method were negatively correlated with higher specific-UV absorbance, humification index, and humic-like EEM peak intensities, suggesting that these spectroscopic indices could be used to predict TOC oxidation rates. TOC signals from instruments using the UV-sulfate method increased with increasing chamber temperature and increasing UV exposure durations. Signals were more sensitive to the former condition, suggesting that chamber temperature is important for improving the TOC oxidation rates of refractory organic matter.

• Journal of Korean Society on Water Environment
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• v.21 no.2
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• pp.125-131
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• 2005

Natural organic matter(NOM) is defined as the complex matrix of organic material and abundant in natural waters. It affects the performance of unit operations for water purification. Several kinds of analytical indicators such as DOC, specific ultraviolet absorbance(SUVA), apparent molecular weight (AMW), fractionation and high performance size exclusive chromatography(HPSEC) have been used to understand characteristics and variations of NOM. This study aims to evaluate the characteristics of NOM in the Geum River system comprising with stream flows and reservoirs. It was identified that SUVA denoting the portion of humic substance in water ranged within 1.60~3.36. Using resin adsorbents, dissolved organic carbon(DOC) was fractionated into three classes: hydrophobic bases(HOB), hydrophobic acids(HOA) and hydrophilic substances(HI). HI dominates in all samples, collectively accounting for more than 62% of the DOC. HOA was the second dominated fraction and it varied considerably but accounted for about 30% of the DOC. The distribution of high molecular weight(HMW) measured by HPSEC being used to determine the molecular weight distribution of aquatic humic substances was 40.1% and 38.7% in reservoir and stream flow, respectively. The distribution of low molecular weight(LMW) in stream flow was 13.2% higher than that in reservoir. And apparent molecular weight less than 1KDa, which include the molecular weight of hydrophilic organic matter, occupied with 69.2% and 68.2% in stream flow and reservoir, respectively. While the molecular weight of 1 to 100 KDa including humic substances ranged with 18.6% and 21.6% in stream flow and reservoir, respectively. Seasonal variation of refractory dissolved organic carbon was similar to that of SUVA.

• Journal of Environmental Science International
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• v.14 no.10
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• pp.965-972
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• 2005

This research studied the effect of factors that are able to form disinfection by-products (DBPs) of chlorination, including natural organic matter (NOM) with sewage, bromide ions, pH and contact time. Trihalomethane (THMs) yield of $0.95{\mu}mol/mg$ was higher than other DBPs yield for the chlorinated humic acid samples. THMs yield of sewage sample was $0.14{\mu}mol/mg$ and haloacetonitriles (HANs) yield in the sewage samples were $0.13{\mu}mol/mg$ but only $0.02{\mu}mol/mg$ for the humic acid samples. As the concentration of bromide ions increased, brominated DBPs increased while chlorinated DBPs decreased, because bromide ions produce brominated DBPs. THMs were highest $(55.55{\mu}g/L)$ at a pH of 7.9 and haloacetic acids (HAAs) were highest $(34.98{\mu}g/L)$ at a pH of 5. Also THMs increased with increasing pH while HAAs decreased with increasing pH. After chlorination, the rate of THMs and HAA formation are faster at initial contact time and then reaches a nearly constant value after 24 hours. This study considers ways to reduce DBP formation by chlorination.

• Environmental Engineering Research
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• v.11 no.4
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• pp.181-193
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• 2006

The hydrophilic or hydrophobic characteristics of dissolved organic matter (DOM) from different origins in lake and river waters were investigated using spectrometric and chromatographic analyses of water samples. DOM in a deep, mesotrophic lake (Lake Unmun) was fractionated using three types of ion exchange resins and classified into aquatic humic substances (AHS), hydrophobic neutrals (HoN), hydrophilic acids (HiA), hydrophilic neutrals (HiN), and bases (BaS). The DOM fractionation provided insight into the understanding of the nature of heterogeneous DOM molecules present in different water sources. The UV/DOC ratios were determined for samples from the influent river and lake waters during DOM fractionation and incubation. AHS prevailed over DOM in the lake and river waters. After biodegradation, the relative contribution of AHS in the total DOM became more significant. It indicates that the AHS fraction would increase while water stay long time in the lake.