Remediation of DDT-contaminated water and soil by using pretreated iron byproducts from the automotive industry

The objective of this study was to quantify the effectiveness of different pretreated iron byproducts from the automotive industry to degrade DDT [(1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in aqueous solutions and soil slurry. Iron byproducts from automotive manufacturing were pretreated by three different methods (heating, solvent and 0.5N HCl acid washing) prior to experimentation. All pretreated irons were used at 5% (wt v-1) to treat 0.014 mM (5 mgL-1) of DDT in aqueous solution. Among the pretreated irons, acid pretreated iron results in the fastest destruction rates, with a pseudo first-order degradation rate of 0.364 d-1. By lowering the pH of the DDT aqueous solution from 9 to 3, destruction kinetic rates increase more than 20%. In addition, when DDT-contaminated soil slurry (3.54 mg kg-1) was incubated with 5% (wt v-1) acid-pretreated iron, more than 90% destruction of DDT was observed within 8 weeks. Moreover, DDT destruction kinetics were enhanced when Fe(II), Fe(III) or Al(III) sulfate salts were added to the soil slurry, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. These results provide proof-of concept that inexpensive iron byproducts of the automotive industry can be used to remediate DDT-contaminated water and soil.     

The reductive degradation of 1,1,1-trichloroethane by Fe(0) in a soil slurry system

Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl^?, HCO₃ ^?, SO₄ ^2?, and NO₃ ^? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L^?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl^? and SO₄ ^2? anions had negligible effects. HCO₃ ^? anions had a accelerative effect on 1,1,1-TCA removal, and both NO₃ ^? and HA had inhibitory effects. A Cl^? mass balance showed that the amount of Cl^? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10^{? 3} h^{? 1} to 7.0 × 10^{? 3} h^{? 1}. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Selection of surfactant in remediation of DDT-contaminated soil by comparison of surfactant effectiveness

With an aim to select the most appropriate surfactant for remediation of DDT-contaminated soil, the performance of nonionic surfactants Tween80, TX-100, and Brij35 and one anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in enhancement of DDT water solubility and desorption of DDT from contaminated soil and their adsorption onto soil and ecotoxicities were investigated in this study. Tween80 had the highest solubilizing and soil-washing ability for DDT among the four experimental surfactants. The adsorption loss of surfactants onto soil followed the order of TX-100 > Tween80 > Brij35 > SDBS. The ecotoxicity of Tween80 to ryegrass (Lolium perenne L.) was lowest. The overall performance considering about the above four aspects suggested that Tween80 should be selected for the remediation of DDT-contaminated soil, because Tween80 had the greatest solubilizing and soil-washing ability for DDT, less adsorption loss onto soil, and the lowest ecotoxicity in this experiment.     

Enhanced Fenton's destruction of non-aqueous phase perchloroethylene in soil systems

The Fenton's system is applied to the destruction of perchloroethylene (PCE) present as a dense non-aqueous phase liquid (DNAPL) in soil slurry systems; the initial concentration of PCE was 45 times higher than its aqueous solubility. Studies were conducted in two matrices: Ottawa sand and soil from Warsaw, IN. In Ottawa sand, a 60-62% decrease in PCE concentration was observed, and Cl(-) recovery was 47-58%, whereas in Warsaw soil, a 44-49% decrease in PCE concentration and a Cl(-) recovery of 40-42% were observed after the addition of 600 mM H(2)O(2) and 10 mM dissolved iron. Significantly enhanced destruction resulted during application of N-(2-hydroxyethyl) iminodiacetic acid (HEIDA) to Warsaw soil. For example, in the absence of HEIDA in Warsaw soil, 36% PCE loss and 33% Cl(-) release were observed at 600 mM H(2)O(2) and 5 mM Fe(III), while 74% PCE loss and 63% Cl(-) release were achieved at 600 mM H(2)O(2) and 5 mM Fe(III)-HEIDA. For both soils, the catalytic activities of Fe(II) and Fe(III) were nearly equivalent. These findings clearly demonstrate that system design can be optimized with regard to process variables in Fenton's treatment of DNAPL in soils.     

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics,transformation products,and toxicity evolvement

The aqueous photodegradation of fluopyram was investigated under UV light (λ?≥?200 nm) and simulated sunlight irradiation (λ?≥?290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO₃ ^?), Fe (III) ions, and titanium dioxide (TiO₂) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO₃ ^?, Fe (III), and TiO₂ slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L^?1 Fe (III) and 500 mg L^?1 TiO₂ were about 7-fold and 13-fold faster than that without Fe (III) and TiO₂ under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.     

Investigation of the removal mechanism of Cr(VI) in groundwater using activated carbon and cast iron combined system

Zero-valent iron (Fe⁰) has been widely used for Cr(VI) removal; however, the removal mechanisms of Cr(VI) from aqueous solution under complex hydrogeochemical conditions were poorly understood. In this research, the mixed materials containing cast iron and activated carbon were packed in columns for the treatment of aqueous Cr(VI)-Cr(III) in groundwater with high concentration of Ca²⁺, Mg²⁺, HCO₃ ⁻, NO₃ ⁻, and SO₄ ²⁻. We investigate the influences of those ions on Cr(VI) removal, especially emphasizing on the reaction mechanisms and associated precipitations which may lead to porosity loss by using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) techniques. The results show that the precipitations accumulated on the material surface were (Fe/Cr) (oxy)hydroxide, mixed Fe(III)-Cr(III) (oxy)hydroxides, Fe₂O₃, CaCO₃, and MgCO₃. During these reactions, the Cr(VI) was reduced to Cr(III) coupled with the oxidated Fe⁰ to Fe(II) through the galvanic corrosion formed by the Fe⁰-C and/or the direct electron transfer between Fe⁰ and Cr(VI). In addition, Cr(VI) could be reduced by aqueous Fe(II), which dominated the whole removal efficiency. The primary aqueous Cr(III) was completely removed together with Cr(III) reduced from Cr(VI) even when Cr(VI) was detected in the effluent, which meant that the aqueous Cr(III) could occupy the adsorption sites. In general, the combined system was useful for the Cr(VI)-Cr(III) treatment based on galvanic corrosion, and the hardness ions had a negative effect on Cr(VI) removal by forming the carbonates which might promote the passivation of materials and decrease the removal capacity of the system.

     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

Kinetics and mechanism for omethoate degradation by catalytic ozonation with Fe(III)-loaded activated carbon in water

The kinetics and mechanism for degradation of omethoate (OMT) by catalytic ozonation with Fe(III)-loaded activated carbon (Fe@AC) were investigated in this study with focus on identification of degradation byproducts. The rate constants of OMT reacting with ozone and hydroxyl radical (OH) were determined to be 0.04 and 5.3 × 10⁸ M^?1 s^?1 at pH 7.5 and 20 °C, respectively. OMT was predominantly degraded by OH in the catalytic ozonation with Fe@AC. The high-molecular-weight degradation byproducts identified were O,O,O-trimethyl phosphoric ester (TMP), pyrrolidin-2-one, N-methyl-2-sulfanylacetamide, 2-(methylthio)acetamide, O,O,S-trimethylthiophosphate (STMP), and N-methyl-2-(methylthio)acetamide. Besides, low-molecular-weight organic acids and inorganic anions were also detected and quantified, including formic, acetic and oxalic acids as well as nitrate, sulfate and phosphate ions. In the catalytic ozonation, TMP and phosphate were two major P-containing byproducts resulting from OMT degradation. The toxicity of OMT solution gradually decreased during the catalytic ozonation, indicating that Fe@AC is a safe catalyst for OMT removal by ozone in water.     

Ferric iron amendment increases Fe(III)-reducing microbial diversity and carbon oxidation in on-site wastewater systems

Onsite wastewater systems, or septic tanks, serve approximately 25% of the United States population; they are therefore a critical component of the total carbon balance for natural water bodies. Septic tanks operate under strictly anaerobic conditions, and fermentation is the dominant process driving carbon transformation. Nitrate, Fe(III), and sulfate reduction may be operating to a limited extent in any given septic tank. Electron acceptor amendments will increase carbon oxidation, but nitrate is toxic and sulfate generates corrosive sulfides, which may damage septic system infrastructure. Fe(III) reducing microorganisms transform all major classes of organic carbon that are dominant in septic wastewater: low molecular weight organic acids, carbohydrate monomers and polymers, and lipids. Fe(III) is not toxic, and the reduction product Fe(II) is minimally disruptive if the starting Fe(III) is added at 50–150 mg L^?1. We used ¹⁴C radiolabeled acetate, lactate, propionate, butyrate, glucose, starch, and oleic acid to demonstrate that short and long-term carbon oxidation is increased when different forms of Fe(III) are amended to septic wastewater. The rates of carbon mineralization to ¹⁴CO₂ increased 2–5 times (relative to unamended systems) in the presence of Fe(III). The extent of mineralization reached 90% for some carbon compounds when Fe(III) was present, compared to levels of 50–60% in the absence of Fe(III). ¹⁴CH₄ was not generated when Fe(III) was added, demonstrating that this strategy can limit methane emissions from septic systems. Amplified 16S rDNA restriction analysis indicated that unique Fe(III)-reducing microbial communities increased significantly in Fe(III)-amended incubations, with Fe(III)-reducers becoming the dominant microbial community in several incubations. The form of Fe(III) added had a significant impact on the rate and extent of mineralization; ferrihydrite and lepidocrocite were favored as solid phase Fe(III) and chelated Fe(III) (with nitrilotriacetic acid or EDTA) as soluble Fe(III) forms.     

Distribution of potentially toxic elements (PTEs) in tailings,soils, and plants around Gol-E-Gohar iron mine,a case study in Iran

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg^?1 for As (with a mean of 25.39 mg kg^?1 for tailings), 7.9 and 261.5 mg kg^?1 (mean 189.83 mg kg^?1 for tailings) for Co, 17.7 and 885.03 mg kg^?1 (mean 472.77 mg kg^?1 for tailings) for Cu, 12,500 and 400,000 mg kg^?1 (mean 120,642.86 mg kg^?1 for tailings) for Fe, and 28.1 and 278.1 mg kg^?1 (mean 150.29 mg kg^?1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

Fenton (H2O2/Fe) reaction involved in Penicillium sp. culture for DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation

The purpose of this work was to demonstrate that a Fenton (H₂O₂/Fe) reaction was involved in DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation in a culture of Penicillium sp. spiked with FeSO₄. A commercial DDT mixture (10% DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], 30% o,p-DDT and 60% of p,p′ -DDT) of 10 mg L^{? 1} was used. Hydrogen peroxide (H₂O₂), tartaric acid and oxalic acid were identified at 18 h in culture media, with and without added DDT; this correlated positively with lowering of pH from 5.8 to 2.7. Lower concentrations of oxalic acid and H₂O₂ (7.9 and 52.6 mg L^{? 1}, respectively) occurred in media with DDT at 30 h, in comparison to that one without DDT mixture (27.9 and 65.3 mg L^{? 1}, respectively), at this time there was maximum degradation (87.7, 91.7 and 94.2%) for DDE, o,p-DDT and p,p′-DDT, respectively. We propose that the degradation of the DDT mixture by Penicillium sp. was through a Fenton reaction (H₂O₂/Fe) under acidic conditions produced in situ during the fungal culture amended with FeSO₄.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Chemical amendment of pig slurry: control of runoff related risks due to episodic rainfall events up to 48 h after application

Losses of phosphorus (P) from soil and slurry during episodic rainfall events can contribute to eutrophication of surface water. However, chemical amendments have the potential to decrease P and suspended solids (SS) losses from land application of slurry. Current legislation attempts to avoid losses to a water body by prohibiting slurry spreading when heavy rainfall is forecast within 48 h. Therefore, in some climatic regions, slurry spreading opportunities may be limited. The current study examined the impact of three time intervals (TIs; 12, 24 and 48 h) between pig slurry application and simulated rainfall with an intensity of 11.0?±?0.59 mm h^?1. Intact grassed soil samples, 1 m long, 0.225 m wide and 0.05 m deep, were placed in runoff boxes and pig slurry or amended pig slurry was applied to the soil surface. The amendments examined were: (1) commercial-grade liquid alum (8 % Al₂O₃) applied at a rate of 0.88:1 [Al/ total phosphorus (TP)], (2) commercial-grade liquid ferric chloride (38 % FeCl₃) applied at a rate of 0.89:1 [Fe/TP] and (3) commercial-grade liquid poly-aluminium chloride (10 % Al₂O₃) applied at a rate of 0.72:1 [Al/TP]. Results showed that an increased TI between slurry application and rainfall led to decreased P and SS losses in runoff, confirming that the prohibition of land-spreading slurry if heavy rain is forecast in the next 48 h is justified. Averaged over the three TIs, the addition of amendment reduced all types of P losses to concentrations significantly different (p?<?0.05) to those from unamended slurry, with no significant difference between treatments. Losses from amended slurry with a TI of 12 h were less than from unamended slurry with a TI of 48 h, indicating that chemical amendment of slurry may be more effective at ameliorating P loss in runoff than current TI-based legislation. Due to the high cost of amendments, their incorporation into existing management practices can only be justified on a targeted basis where inherent soil characteristics deem their usage suitable to receive amended slurry.     

Use of waste iron metal for removal of Cr(VI) from water

Cr(VI) removal from water was evaluated using waste iron particles in batch experimental mode. The reaction rates were inversely proportional to the initial Cr(VI) concentrations, and the reaction rates of Cr(VI) removal with the waste iron metal were faster than those with Peerless iron, a commercial zero-valent iron. The loss in iron reactivity due to the oxidation, from Fe(0) to Fe(II), ultimately to Fe(III), could be recovered by adding iron-reducing consortium (IRC) to the oxidized iron. Bacterial reduction of Cr(VI) also helped to decrease the aqueous concentration of Cr(VI), but the reduction of oxidized iron by IRC and the consequent reduction of Cr(VI) to Cr(III) by the reduced iron was more significant. Thus, reusing waste iron metal for Cr(VI) removal can reduce the cost of reactive media. Furthermore, the addition of IRC to the waste iron metal can accelerate the removal rate of Cr(VI), and can recover the reactivity of irons which were oxidized by Cr(VI).     

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-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) 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/H₂O₂ 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 H₂O₂.     

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-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) 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/H₂O₂ 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 H₂O₂.     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.