Silane grafted chitosan for the efficient remediation of aquatic environment contaminated with arsenic(V).

HYPOTHESIS: Chitosan, naturally abundant biomaterial showed an insignificant affinity toward arsenate. The incorporation of organosilane could improve the physical and chemical properties of chitosan for the efficient removal of arsenate from aquatic environment. EXPERIMENT: The hybrid materials were obtained by grafting the natural biopolymer chitosan with 3-mercaptopropyl trimethoxysilane (CHMS) and trimethoxy-octylsilane (CHTS). The hybrid materials along with bare chitosan were characterized with SEM-EDX, FT-IR and BET specific surface area analyses and the solid materials were further employed in the efficient remediation of aqueous solutions contaminated with As(V) under batch and column reactor operations. FINDINGS: The hybrid materials showed an extremely high percentage of As(V) removal compared to bare chitosan within a wide range of pH. As(V) was aggregated rapidly onto the solid surfaces and relatively high percent removal of As(V) was achieved in a wide range of As(V) initial concentrations. Moreover, As(V) was bound with, relatively, weaker forces and forming an 'outer sphere complexes' at the surface of solids. The presence of co-existing ions could not significantly affect the removal of As(V) from aqueous solutions. Furthermore, breakthrough data confirmed that these two hybrid materials possessed significantly high loading capacity of As(V) even under dynamic conditions.

Degradation of multi-DNAPLs by a UV/persulphate/ethanol system with the additional injection of a base solution.

This study was conducted to investigate the inhibited influences on and solution to the degradation of four types of dense non-aqueous phase liquids (DNAPLs) (i.e. perchloroethylene [PCE], trichloroethylene [TCE], chloroform [CF], and carbon tetrachloride [CT]) all at the same instance in groundwater (GW). Degradations of DNAPLs in de-ionized water (DW) and GW were carried out by applying an ultraviolet radiation-activated persulphate (UV/PS) system. PCE and TCE were degraded by over 90% and CT was only degraded by 25% in both DW and GW. However, CF was degraded by over 90% in DW, while it was only degraded by 50% in GW. First of all, degradations with an inorganic anion (either Cl- or HCO3-) indicated that the lower degradation of CF in GW was caused by the existence of the chloride ion. Moreover, the low CF degradation in GW was overcome by the additional injection of a base solution (sodium hydroxide [NaOH]) into the UV/PS system. The results showed that PCE, TCE, and CF were degraded by over 90%, respectively, when a molar ratio of [base]0:[PS]0 was larger than 0.5:1, but CT was still not effectively degraded in the UV/PS system. To achieve effective CT degradation, UV/PS with the ethanol (EtOH) system was evaluated and it was found that it degraded CT over 90%. However, at this time, CF was not effectively degraded in the UV/PS/EtOH system. Finally, degradations of DNAPLs in the UV/PS/EtOH system with the additional injection of a base solution were conducted and it showed that multi-DNAPLs were degraded by over 90%, respectively, when the molar ratio of [PS]0:[EtOH]0:[base]0 was 1:1:3.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2.

The oxidation of toluene sorbed on activated carbon in the presence of H(2)O(2) and manganese oxide.

We investigated the oxidation of toluene sorbed on activated carbon (AC) in the presence of hydrogen peroxide (H(2)O(2)) and pyrolusite (MnO(2)). Sorbed toluene was prepared by reacting a toluene-saturated solution and AC. The amounts of sorbed toluene (mg of toluene/g of AC) decreased as the amounts of AC were increased. The reaction was conducted in a gas-purging (GP) reactor and the gas flow at the outlet of a GP reactor was carefully maintained. As a result, the percentage of toluene captured by ORBO tube was 28% in the control system with pure water. When H(2)O(2) was catalyzed by AC (i.e. this forms a hydroxyl radical by electron transfer), approximately 17% of the desorbed toluene was oxidized and 68% of toluene remained on AC which was similar to the control system. However, when pyrolusite (650 mg/L) was added together with H(2)O(2) (10,000 mg/L), only 5% of toluene was captured by the ORBO tube and 55% of toluene remained on AC, which indicated that both desorbed and sorbed toluene was oxidized. Moreover, toluene oxidation increased when concentrations of pyrolusite and H(2)O(2) were increased. It was suggested that superoxide anion, which is generated by the reaction of H(2)O(2) and pyrolusite, might stimulate toluene desorption and then toluene in the aqueous phase could be oxidized by hydroxyl radical.

Synthesis of iron composites on nano-pore substrates: identification and its application to removal of cyanide.

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III)=1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe(2)O(3)) and iron silicate composite ((Mg, Fe)SiO(3)) existed on Fe-WR, while clinoferrosilite (FeSiO(3)) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H(2)O(2) system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k(obs)) for cyanide removal were 0.49 (± 0.081) h(-1). Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H(2)O(2).

Feasibility study on an oxidant-injected permeable reactive barrier to treat BTEX contamination: adsorptive and catalytic characteristics of waste-reclaimed adsorbent.

The adsorptive and catalytic characteristics of waste-reclaimed adsorbent (WR), which is a calcined mixture of bottom-ash and dredged-soil, was investigated for its application to treating BTEX contamination. BTEX adsorption in WR was 54%, 64%, 62%, and 65%, respectively, for a 72 h reaction time. Moreover, the catalytic characteristics of WR were observed when three types of oxidation systems (i.e., H(2)O(2), persulfate (PS), and H(2)O(2)/Fe(III)/oxalate) were tested, and these catalytic roles of WR could be due to iron oxide on its surface. In PS/WR system, large amounts of metal ions from WR were released because of large drops of solution pH, and the surface area of WR was also greatly reduced. Moreover, the BTEX that was removed per consumed oxidant (ΔC(rem)/ΔOx) increased with increasing PS. In H(2)O(2)/Fe(III)/oxalate with WR system, the highest BTEX degradation rate constants (k(deg)) were calculated as 0.338, 0.365, 0.500 and 0.716 h(-1), respectively, when 500 mM of H(2)O(2) was used, and the sorbed BTEX on the surface of WR was also degraded, which suggests the regeneration of WR. Therefore, the oxidant-injected permeable reactive barrier filled in WR could be an alternative to treating BTEX with both adsorption and catalytic degradation.

Effect of metal oxides on the reactivity of persulfate/Fe(II) in the remediation of diesel-contaminated soil and sand.

The effect of metal oxides on the ability of persulfate (PS) with Fe(II) to remediate diesel-contaminated soil was investigated. In both natural soil and purchased sand, the highest diesel degradation occurred at pH 3 and the optimum molar ratio of PS/Fe(II) was 100:1 (i.e. 500 mM PS to 5 mM Fe(II)). Moreover, adding Fe(II) increased PS reactivity more in soil than it did in sand, indicating the involvement of metal oxides in the soil matrix. Evaluating the effects of metal oxides (i.e. goethite, hematite, magnetite, and manganese oxide) on the reactivity of PS with/without Fe(II) in a system containing diesel-contaminated sand revealed that manganese oxide increased PS activity the most and that the highest diesel degradation by PS occurred when both manganese oxide and Fe(II) were used as activators. XRD did not show the transformation of manganese oxide in the presence of Fe(II). SEM-EDS showed the association of Fe(II) on the surface of manganese oxide, and ICP analysis revealed that almost all the added Fe(II) adsorbed to manganese oxide but almost none adsorbed to iron oxides under acidic conditions. Therefore, the high reactivity of PS could be due to the high density of Fe(II) over the surface of manganese oxide.

Application of a peroxymonosulfate/cobalt (PMS/Co(II)) system to treat diesel-contaminated soil.

We investigated the feasibility of using peroxymonosulfate (PMS) with transition metals (PMS/M(+) system) for remediation of diesel-contaminated soils. To the best of our knowledge, this is the first attempt to apply a PMS/M(+) system for the treatment of diesel-contaminated soils. Two well-known transition metals, Fe(II) and Co(II), used to activate PMS including the effect of co-existence of counter anions (Cl(-) and SO(4)(2-)) were tested and it revealed that the most effective degradation of diesel was achieved with cobalt chloride. The effect of PMS (i.e. 0-500 mM) indicated that the increasing the molar ratio of PMS/diesel increased degradation of diesel on soils. The effect of Co(II) (i.e. 0-4mM) showed that at least 2mM of Co(II) was needed to degrade above 30% of diesel. Moreover, a maximum diesel degradation of 47% was achieved at a single injection of PMS/Co(II) (i.e. 500 mM/2mM). Assessments of system pH showed that diesel degradation was higher under acidic conditions (pH 3) possibly due to the dissolution of metal ions from soils that are not possible at other pHs (pH 6 and 9). Sequential injections of both PMS and Co(II) were employed to improve the level of remediation (approximately 90% degradation). The degradation of diesel increased as much as 88% when PMS/Co(II) was sequentially injected. This indicates that PMS/Co(II) systems are applicable for remediation of soil contaminated with diesel fuel as an aspect of in situ chemical oxidation.

PCE DNAPL degradation using ferrous iron solid mixture (ISM).

Ferrous iron solid mixture (ISM) containing Fe(II), Fe(III), and Cl was synthesized for degradation of tetrachloroethene (PCE) as a dense non-aqueous phase liquid (DNAPL), and an extraction procedure was developed to measure concentrations of PCE in both the aqueous and non-aqueous phases. This procedure included adding methanol along with hexane in order to achieve the high extraction efficiency, particularly when solids were present. When PCE was present as DNAPL, dechlorination of PCE was observed to decrease linearly with respect to the total PCE concentration (aqueous and non-aqueous phases) and the concentration of PCE in the aqueous phase was observed to be approximately constant. In the absence of DNAPL, the rate of PCE degradation was observed to be the first-order with respect to the concentration in the aqueous phase. A kinetic model was developed to describe these observations and it was able to fit experimental data well. Increasing the concentration of Fe(II) in ISM increased the values of rate constants, while increasing the concentration of PCE DNAPL did not affect the value of the rate constant. The reactivity of ISM for PCE dechlorination might be close to that of Friedel's salt, and the accumulation of trichloroethylene (TCE) might imply the lower reactivity of ISM for degradation of TCE or the necessity of large amount of Fe(II) in ISM. TCE (the major chlorinated intermediate), ethene (the major non-chlorinated compound), acetylene and ethane were detected, which implied that both hydrogenolysis and beta-elimination were pathways of PCE DNAPL degradation on ISM.

Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism.

The objective of this study is the kinetic interpretation of hydrogen peroxide decomposition on manganese oxide (pyrolusite) and the explanation of the reaction mechanism including the hydroperoxide/superoxide anion. The decomposition of hydrogen peroxide on manganese oxide at pH 7 was represented by a pseudo first-order model. The maximum value of the observed first-order rates constants (k(obs)) was 0.741 min(-1) at 11.8 of [H(2)O(2)]/[triple bond MnO(2)] when [H(2)O(2)]/[triple bond MnO(2)] were ranged from 58.8 to 3.92. The pseudo first-order rate constants (kMnO(2)) approximated as the average value of 0.025 (min mM)(-1) with a standard deviation of 0.003 at [H(2)O(2)]/[triple bond MnO(2)] ranged from 39.2 to 11.8. When [H(2)O(2)]/[triple bond MnO(2)] was 3.92, the rate constants (kMnO(2)) was 0.061 (min mM)(-1) as maximum. Oxygen production showed that the initial rates increased with decreasing [H(2)O(2)]/[triple bond MnO(2)] and the total amounts of oxygen was slightly less than the stoichiometric value (0.5) in most experiments. However, oxygen was produced at more than 0.5 in low [H(2)O(2)]/[triple bond MnO(2)] (i.e. 3.92 and 9.79). The relative production of hydroperoxide/superoxide anion implied that the production increased with low [H(2)O(2)]/[triple bond MnO(2)], and the existence of anions suggested that the mechanism includes propagation reactions with intermediates such as hydroperoxide/superoxide anion in solution. In addition, both [H(2)O(2)] decomposition and the production of anion were accelerated in alkaline solution. Manganese ion dissolved into solution was negligible in neutral and alkaline conditions, but it greatly increased in acidic conditions.

Kinetics of BTEX biodegradation by a coculture of Pseudomonas putida and Pseudomonas fluorescens under hypoxic conditions.

Pseudomonas putida and Pseudomonas fluorescens present as a coculture were studied for their abilities to degrade benzene, toluene, ethylbenzene, and xylenes (collectively known as BTEX) under various growth conditions. The coculture effectively degraded various concentrations of BTEX as sole carbon sources. However, all BTEX compounds showed substrate inhibition to the bacteria, in terms of specific growth, degradation rate, and cell net yield. Cell growth was completely inhibited at 500 mg l(-1) of benzene, 600 mg l(-1) of o-xylene, and 1000 mg l(-1) of toluene. Without aeration, aerobic biodegradation of BTEX required additional oxygen provided as hydrogen peroxide in the medium. Under hypoxic conditions, however, nitrate could be used as an alternative electron acceptor for BTEX biodegradation when oxygen was limited and denitrification took place in the culture. The carbon mass balance study confirmed that benzene and toluene were completely mineralized to CO2 and H2O without producing any identifiable intermediate metabolites.

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash.

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.

Analysis of trihalomethanes in drinking water using headspace-SPME technique with gas chromatography.

In many drinking water treatment plants, the chlorination process is one of the main techniques used for the disinfection of water. This disinfecting treatment leads to the formation of trihalomethanes (THMs) such as chloroform, dichlorobromomethane, chlorodibromomethane and bromoform. In this study, headspace-solid-phase microextraction (HS-SPME, 85 microm carboxen/polydimethylsiloxane fiber) technique was applied for the analysis of THMs in drinking water. The effects of experimental parameters such as kinds of SPME fiber, the volume ratio of sample to headspace, the addition of salts, magnetic stirring, extraction temperature, extraction time and desorption time on the analysis were investigated. Analytical parameters such as linearity, repeatability and limit of detection were also evaluated. The results of THMs from the survey of Seongnam (Korea) drinking water samples showed that the highest total trihalomethane and chloroform were 24.03 and 13.34 microg/l, which were well within the Korean drinking water quality standard of 100 and 80 microg/l, respectively.