• Journal of Soil and Groundwater Environment
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• v.21 no.2
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• pp.8-14
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• 2016

We compared the plausible reaction mechanism and quantitative efficiency of highly self-organized TiO₂ nanotube (ntTiO₂) film with TiO₂ powder. Film was fabricated by electrochemical potentiostatic anodization of titanium thin film in an ethylene-glycol electrolyte solution containing 0.3 wt% NH₄F and 2 vol% deionized water. Nanotubes with a pore size of 80-100 nm were formed by anodization at 60 V for 3 h. Humic acid (HA) was degraded through photocatalytic degradation using the ntTiO₂ film. Pseudo first-order rate constants for 0.3 g of ntTiO₂, 0.3 g TiO₂ powder, and 1 g TiO₂ powder were 0.081 min⁻¹, 0.003 min⁻¹, and 0.044 min⁻¹, respectively. HA adsorption on the ntTiO₂ film was minimal while adsorption on the TiO₂ powder was about 20% based on thermogravimetric analysis. Approximately five-fold more normalized OH radicals were generated by the ntTiO₂ film than the TiO₂ powder. These quantitative findings explain why ntTiO₂ film showed superior photocatalytic performance to TiO₂ powder.

• Analytical Science and Technology
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• v.16 no.4
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• pp.292-298
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• 2003

In this study, the photooxidation and ozonation of humic acid (HA) in aqueous solution were conducted and the treated HA samples at different reaction time were analyzed using ultrafiltration techniques to evaluate the change of their molecular size distributions with its DOC removal. Molecular size distribution of untreated HA showed 41.5% in higher molecular size fractions (>30,000 daltons) and 15.2% in much smaller molecular size fraction (<500 daltons). As UV irradiation time was increased, it was observed that the degradation of the large molecules of the fraction of >30,000 daltons into much smaller molecules was increased. In UV system, the HA molecules of the fraction of <500 daltons became significantly more and its percentage was increased from 35.3% (UV only irradiation) to 58.9% ($UV/TiO_2$) and 87.8% ($UV/H_2O_2$) in the presence of the photocatalysis. Otherwise, ozonation of HA produced mainly the fraction of medium molecular size ranging from 3,000 to 30,000 daltons with much lower portion (<~7%) in the fraction of <500 daltons. In ozone only system, the fraction of 30,000~10,000 daltons occupied in 41.5% at 60 min of ozonation time. In $O_3/H_2O_2$ system, the fraction of 30,000~10,000 daltons and 10,000~3,000 daltons occupied in 38.9% and 36.2% respectively. Based on these results, we suggested applicable treatment process which could be combined with $UV/H_2O_2$, $UV/TiO_2$ and $O_3$, $O_3/H_2O_2$ system for more effective removal of humic acid in water treatment.

• Journal of Soil and Groundwater Environment
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• v.14 no.4
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• pp.23-32
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• 2009

The sorption of europium (Eu (III)) onto kaolinite and the influence of humic acids over a range of pH 3 ~ 11 has been studied by batch adsorption experiment (V/m = 250 : 1 mL/g, $C_{Eu(III)}\;=\;1\;{\times}\;10^{-5}\;mol/L$, $C_{HA}\;=\;5{\sim}50\;mg/L$, $P_{CO2}=10^{-3.5}\;atm$). The concentrations of HA and Eu(III) in aqueous phase were measured by UV absorbance at 254nm (e.g., $UV_{254}$) and ICP-MS after microwave digestion for HA removals, respectively. Results showed that the HA sorption onto kaolinite was decreased with increasing pH and their sorption isotherms fit well with the Langmuir adsorption model (except pH 3). Maximum amount ($q_{max}$) for the HA sorption at pH 4 to 11 was ranged from 4.73 to 0.47 mg/g. Europium adsorption onto the kaolinite in the absence of HA was typical, showing an increases with pH and a distinct adsorption edge at pH 3 to 5. However in the presence of HA, Eu adsorption to kaolinite was significantly affected. HA was shown to enhance Eu adsorption in the acidic pH range (pH 3 ~ 4) due to the formation of additional binding sites for Eu coming from HA adsorbed onto kaolinite surface, but reduce Eu adsorption in the intermediate and high pH above 6 due to the formation of aqueous Eu-HA complexes. The results on the ternary interaction of kaolinte-Eu-HA are compared with those on the binary system of kaolinite-HA and kaolinite-Eu and adsorption mechanism with pH was discussed.

• Journal of the Korean GEO-environmental Society
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• v.11 no.8
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• pp.41-47
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• 2010

This study was conducted to assess the applicability of pilot scale system and to evaluate the treatment efficiency on operational parameters such as humic acid concentration, initial pH and air flow rate on the ozone/peroxyl radical reaction system. The decolorization of ozone/peroxyl radical system was higher than that of only process. Removal efficiency of ozone/peroxyl radical system was generally increased with the increase of intial concentration of humic acid but decreased over the range of 30mg/L. Treatment efficiency of HA at acid pH was smaller compared to that of neutral or basic pH and increased with increasing the air flow rate from 1L/min to 3L/min. In pilot-scale test, average removal of TOC and $COD_{Cr}$ was about 70% and 60%, respectively and ozone/peroxyl radical reaction system was indicated a potential in water treatment application.

• Korean Journal of Environmental Agriculture
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• v.12 no.1
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• pp.51-57
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• 1993

Objective of this research was to assess the influence of reaction time on the heavy metal-organic ligand complexation by employing kinetic models. Aqueous solutions of humic (HA) or fulvic acid (FA) were reacted with metal solutions with 1:1 ratio to form complexes. Efficiency of organic ligand on metal removal was determined by separating the precipitates from solution using $0.45\;{\mu}m$ filter paper. Complexation between Cu or Pb and HA or FA followed the first- or multiple first order kinetics, largely depending on metal concentration and kind of organic ligand. Amounts of precipitates were increased proportionally with reaction time but reached to quasiequilibrium where rate of precipitate formation was not varied with time. Copper-ligand complexation was, irrespective of ligand, fitted to the single first order kinetics at Cu concentrations lower than $300{\mu}M$, but this was fitted to the multiple first order kinetics at Cu concentrations higher than $300{\mu}M$. As increasing Cu concentrations, the precipitates formed more readily, judging from the increased rate constants (${\kappa}$). In the multiple first order kinetics, ${\kappa}$ was decreased as reaction steps proceeded. Most of Cu-ligand precipitates were formed within 15 min. FA precipitated Cu more rapidly than HA did. ${\kappa}$ for Pb-HA complexation was decreased but that for Pb-FA reaction was increased, as increasing Pb concentration. Most of Pb-organic ligand complexation occurred within 30 min. Afterwards, ${\kappa}$ values were relatively small and not affected much by time. Pb was precipitated by humic acid more readily than Cu when metal concnetrations were $200{\sim}300{\mu}M$. However, when metal concentrations were in the ranges of $400{\sim}500{\mu}M$, a reversed tendency was observed.

• Journal of Environmental Science International
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• v.15 no.8
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• pp.785-797
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• 2006

The formation characteristics of trihalomethanes (THMs) and haloacetic acids (HAAs) were investigated in chlorination of raw water of different organic mallet characteristics. The samples used in this study were hydrophobic (N-HPO) and hydrophilic fraction (N-HPI) (which were concentrated and separated from Nakdong river water), and humic acid (HA) (which is known as a strong hydrophobic acid) as a reference organic matter, the specific UV absorbance (SUVA) of which was 2.19, 1.15 and 7.92, respectively. With increasing chlorine contact time, THMFP and HAAFP (the formation potential of THMs and HAAs) increased, but their increase was different depending on the organic mallet characteristics (i.e., for N-HPI, THMFP was higher than HAAFP, but the inverse result was obtained for N-HPO and HA and the ratio between them was greater for HA), and the mainly formed chemical species were CHCI$_3$ in case of THMs and dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in case of HAAs for N-HPO and HA (and the ratios of CHCI$_3$ to total THMs and DCAA and TCAA to total HAAs for HA were higher than those for N-HPO), but for N-HPI, the ratio of brominated THMs was a little higher than that of CHCI$_3$ and the ratio of DCAA and TCAA to total HAAs was lower than that of N-HPO, although they are main chemical species in case of HAAs. Comparing THMFP and HAAFP with the increase in bromide concentration added with those in not adding it, the former increased greatly and its increase was higher for the organic mallet with stronger hydrophobicity, but the latter was lower for N-HPO and N-HPI and was similar for HA. The main chemical species with increasing bromide concentration were CHBt$_3$ in case of THMs regardless of organic matter characteristics, and dibromoacetic acid (DBAA) for N-HPO and N-HPI, DBAA and tribromoacetic acid (TBAA) for HA in case of HAAs. With increasing reaction temperature and pH, THMFP and HAAFP increased for the former, but for the latter, THMFP increased and HAAFP decreased, although the rate of increase or decrease was different with organic mallet characteristics.

• Journal of Korean Society of Environmental Engineers
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• v.37 no.2
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• pp.73-80
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• 2015

An investigation on the removals of tetracycline (TTC), which is a family of antibiotics widely founded in the environment, from the aqueous solution by birnessite(${\delta}-MnO_2$)-mediated oxidative transformation was described. This study also examined the potential effect of the naturally occurring substances, humic acid (HA) on the oxidative transformation. The experiment was carried out in various conditions (reaction time, Mn oxide loadings, pH) and in the presence of HA as a batch test. The removals of TTC followed pseudo-first order reactions, and rate constants (k, $hr^{-1}$) for the removals of TTC were constantly increased with decreasing pH from 0.98 (pH 9) to 2.97 (pH 3). The rate constants also increased about 1.3 times when the birnessite loading increased from 1 to 2 g/L. Presence of HA (5 mg-C/L, at $pH{\geq}6$) caused some enhancement in the removals of TTC as compared to the control, and also showed the removal efficiencies of TTC in the birnessite mediated systems (TTC=0.25 mM, ${\delta}-MnO_2=2.0g/L$, pH 6) increased with increasing HA concentrations (1~10 mg-C/L). The results obtained from the oxidative transformation of TTC and the effect of HA were discussed in terms of reaction characteristics and mechanism.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.375-381
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• 2006

In this sturdy, spherical activated carbon(SPAC) contained $TiO_2$ was made by ion-exchanged treatment and heat treatment for applying fluidizing bed system. The ion-exchange resin was treated by $TiCl_3$ aqueous solution. The treated resin and raw resin were heat-treated under nitrogen condition to convert into Ti-SPAC. During the heat-treatment, burn-off weight amounts and the element were measured by means of TGA and TGA/MS, individually. The physicochemical properties of Ti-SPAC was characterized by means of XRD, SEM, EDS, BET, EPMA, ESR, intensity and titanium content. The Ti-SPAC had spherical shape with diameter size about $350{\mu}m{\sim}400{\mu}m$ and $617m^2/g$ specific surface area. Structure of $TiO_2$ in Ti-SPAC was anatase and rutile form. Also, $TiO_2$ on SPAC were found that the $TiO_2$ were uniformly distributed through EPMA analysis. Moreover, the Ti-SPAC showed indirect photocatalyst activity estimation through ESR analysis, characteristics of photocatalyst potentially. Over all results, Ti-SPAC was used in fluidizing bed UV/photocatalyst system to remove HA(Humic Acid). That results were HA removal efficiency was about 70％ and Ti-SPAC intensity was preserved during reaction. Ti-SPAC showed practical possibility as photocatalyst in fluidizing bed system.

• Journal of Korean Society of Water and Wastewater
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• v.11 no.4
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• pp.118-125
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• 1997

Conventional sedimentation method has some limitations for turbidity removal in water treatment because drinking water sources are getting polluted. Removal rates of turbidity using DAF and sedimentation process were compared for various water conditions to know whether DAF is effective to improve sedimentation process. Water samples were clay(gravity 2.65) water 100mg/l, H raw water, mixed water of H raw water and clay 100mg/l, and mixed water of HA(Humic Acid) 5mg/l and clay 100mg/l. Other parameters were temperature, coagulants(Alum, $FeCl_3$), and treatment time. Water temperature greatly affected in removal rates of turbidity for sedimentation and DAF. Generally DAF was more effective in removal rates of turbidity than sedimentation at the same experimental condition. Removal rates of $UV_{254}$ were high to over 90%, and independent of temperature and coagulant.

• Membrane Journal
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• v.22 no.6
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• pp.441-449
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• 2012

Effect of humic acid (HA) with periodic nitrogen back-flushing was investigated in hybrid process of alumina microfiltration and photocatalyst for drinking water treatment. It was compared and investigated with the previous results of microfiltration water back-flushing or ultrafiltration nitrogen back-flushing in viewpoints of membrane fouling resistance ($R_f$), permeate flux (J), and total permeate volume ($V_T$). As results, the trends of membrane fouling were different depending on nitrogen or water back-flushing, and depending on ultrafiltration or microfiltration made with the same material. Also, the nitrogen back-flushing using microfiltration was more effective membrane fouling inhibition than ultrafiltration, and the nitrogen back-flushing was more effective than water back-flushing using the same microfiltration membrane. Turbidity treatment efficiencies were almost constant independent of HA concentration, but HA treatment efficiency was the maximum at HA 10 mg/L. From this results, it was shown that the treated water HA quality increased as increasing HA concentration, but HA could be removed the most effectively by photocatalyst beads adsorption and photo-oxidation at HA 10 mg/L.