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.     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Halide salts accelerate degradation of high explosives by zerovalent iron

Zerovalent iron (Fe(0), ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe(0) (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24h also restored ZVI reactivity, resulting in complete degradation within 8h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl(-) and Br(-) was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br(-) was present in solution.     

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.     

Performance evaluation of granular iron for removing hexavalent chromium under different geochemical conditions

Long-term column experiments were conducted under different geochemical conditions to estimate the longevity of Fe 0 permeable reactive barriers (PRBs) treating hexavalent chromium (Cr(VI)). Secondary carbonate minerals were precipitated, and their effects on the performance, such as differences in the mechanism for Cr removal and the changes in system hydraulics, were assessed. Sequestration of Cr(VI) occurred primarily by precipitation of Fe(III)-Cr(III) (oxy)hydroxides. Trace amounts of Cr were observed in iron hydroxy carbonate presumably due to substitution of Cr3+ for Fe3+. The formation of Fe(III)-Cr(III) (oxy)hydroxide greatly decreased the reactivity of the Fe 0 and thus resulted in migration of the Cr removal front. Carbonate minerals did not appear to contribute to further passivation with regard to reactivity toward Cr removal; rather, the column receiving high contents of dissolved calcium carbonate showed slightly enhanced Cr removal by means of a higher corrosion rate of Fe 0 and because of sequestration by an iron hydroxy carbonate. Precipitation of carbonates, however, governed other geochemical parameters. The porosity and hydraulic conductivity in the column receiving high contents of dissolved calcium carbonate did not indicate a great loss in system permeability because the accumulation of carbonates declined as the Fe 0 was passivated over time. However, the accumulated carbonates and associated Fe(III)-Cr(III) (oxy)hydroxide could cause problems because the presence of these solids resulted in a decline in flow rate after about 1400 pore volumes of operation.     

Simultaneous removal of arsenite and fluoride via an integrated electro-oxidation and electrocoagulation process

An integrated electro-oxidation and electrocoagulation system was designed and used to remove As(III) and F⁻ ions from water simultaneously. Dimensionally stable anodes (DSA), Fe electrodes, and Al electrodes were combined into an electrochemical system. Two pieces of DSA electrodes were assigned as the outside of the Fe and Al electrodes and were directly connected to the power supply as anode and cathode, respectively. The Fe and Al ions were generated by electro-induced process simultaneously. Subsequently, hydroxides of Fe and Al were formed. Arsenic ions are mainly removed by iron hydroxides and F⁻ ions are mainly removed by the Al oxides. At the initial concentration of 1.0 mg L⁻¹, most of As(III) was transferred into As(V) within 40 min at current density of 4 mA cm⁻², whereas F⁻ ions can be efficiently removed simultaneously. The effect of the ratio of Fe and Al plate electrodes and current density on the removal of As(III) and F⁻ was investigated. With one piece of Fe plate electrode and three pieces of Al plate electrodes, it is observed that As(III) with concentration of 1 mg L⁻¹ and F⁻ with concentration of 4.5 mg L⁻¹ can be removed and their final concentrations were below the values of 10 μg L⁻¹ and 1.0 mg L⁻¹, respectively within 40 min. Removal efficiency of As(III) increases with the increase of solution pH. However, in the pH range of 6-7, removal efficiency of F⁻ is the largest.     

Selective redox degradation of chlorinated aliphatic compounds by Fenton reaction in pyrite suspension

Selective redox degradation of chlorinated aliphatics by Fenton reaction in pyrite suspension was investigated in a closed system. Carbon tetrachloride (CT) was used as a representative target of perchlorinated alkanes and trichloroethylene (TCE) was used as one of highly chlorinated alkenes. Degradation of CT in Fenton reaction was significantly enhanced by pyrite used as an iron source instead of soluble Fe. Pyrite Fenton showed 93% of CT removal in 140 min, while Fenton reaction with soluble Fe(II) showed 52% and that with Fe(III) 15%. Addition of 2-propanol to the pyrite Fenton system significantly inhibited degradation of TCE (99% to 44% of TCE removal), while degradation of CT was slightly improved by the 2-propanol addition (80-91% of CT removal). The result suggests that, unlike oxidative degradation of TCE by hydroxyl radical in pyrite Fenton system, an oxidation by the hydroxyl radical is not a main degradation mechanism for the degradation of CT in pyrite Fenton system but a reductive dechlorination by superoxide can rather be the one for the CT degradation. The degradation kinetics of CT in the pyrite Fenton system was decelerated (0.13-0.03 min⁻¹), as initial suspension pH decreased from 3 to 2. The formation of superoxide during the CT degradation in the pyrite Fenton system was observed by electron spin resonance spectroscopy. The formation at initial pH 3 was greater than that at initial pH 2, which supported that superoxide was a main reductant for degradation of CT in the pyrite Fenton system.     

Accelerated remediation of pesticide-contaminated soil with zerovalent iron

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe0) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe0 for on-site treatment of soil containing > 1000 mg metolachlor, > 55 mg alachlor, > 64 mg atrazine, > 35 mg pendimethalin, and > 10 mg chlorpyrifos kg(-1). While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe0 resulted in > 60% destruction of the five pesticides within 90 d and increased to > 90% when 2% (w/w) Al2(SO4)3 was added to the Fe0. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe0 for ex situ treatment of pesticide-contaminated soil.     

The interaction "light, Fe(III)" as a tool for pollutant removal in aqueous solution: degradation of alcohol ethoxylates

The photoinduced degradation of an alcohol ethoxylate (AE) (Brij 30) by Fe(III) in aqueous solution has been investigated. The study was carried out with the major fraction of ethoxymers having an alkyl chain length of 12 carbon atoms and n ethoxy units E (C12En). The Fe(III) sensitised degradation of this fraction occurs efficiently at 365 nm. The rate of degradation depends on the concentration of Fe(OH)2+, the most photoreactive species in terms of .OH radical formation. Formate ethoxylates were identified as photoproducts and shortening of the ethoxylated chain all along the degradation process was observed. The mechanism of Brij 30 degradation implies a major .OH radicals attack on the polyethoxylated chain. For prolonged irradiations, the total degradation of Brij 30 and of the photoproducts is obtained. Consequently, the degradation photoinduced by iron (III) could be an efficient method of AEs removal in water.     

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).     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron

Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3 d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7 d at 25 °C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions.     

Bimetallic iron-aluminum particles for dechlorination of carbon tetrachloride

Bimetallic iron-aluminum (Fe/Al) particles were synthesized and tested for their reactivity toward carbon tetrachloride using batch reactors and a flow-through column at near neutral pH. Preparation of bimetallic Fe/Al particles was conducted under acidic conditions under which iron was readily deposited onto the aluminum surface. The SEM image showed clusters of iron on the aluminum surface at the measured Fe:Al molar ratio of about 2:3. Results showed that the presence of zero-valent aluminum successfully prevented the formation of a passive layer at the iron surface and maintained the reactivity of iron. The dechlorination of carbon tetrachloride by bimetallic Fe/Al particles produced chloroform (9%), dichloromethane (17%) and methane (38%). Kinetic analysis suggests that bimetallic Fe/Al particles increased the reactivity toward carbon tetrachloride degradation by a factor of 10 compared to zero-valent iron and possessed a comparable reactivity with nano-sized Fe. The effectiveness of bimetallic Fe/Al particles was further confirmed by the continuous flow column study from which an ageing of bimetallic particles was also observed.     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

Fe^0钝化膜的生物还原及其脱氮除磷

微生物的异化Fe（Ⅲ）还原是一种能够利用Fe（III）作为末端电子受体在无氧条件下氧化有机物的产能过程。结合这一特性,考察了在兼性厌氧／严格厌氧条件下Fe^0钝化膜作为Fe（111）源时的生物还原能力以及对N、P等营养元素的去除效果。结果表明,严格厌氧条件下微生物异化Fe（Ⅲ）还原能力较好,富集培养至7d,累计Fe（II）浓度达到最大,最大产生速率为98．69mg／（L·d）,同时TP去除率高达97．1％以上。而体系对NH4-N、TN的去除相对滞后,培养至13d,去除率开始增大,最终分别达到86．6％和76．1％。这为装填有海绵铁＋聚氨酯泡沫载体的SBBR中填料的原位再生问题提供了解决思路。     

Removal of heavy metals and arsenic from contaminated soils using bioremediation and chelant extraction techniques

A combined chemical and biological treatment scheme was evaluated in this study aiming at obtaining the simultaneous removal of metalloid arsenic and cationic heavy metals from contaminated soils. The treatment involved the use of the iron reducing microorganism Desulfuromonas palmitatis, whose activity was combined with the chelating strength of EDTA. Taking into consideration that soil iron oxides are the main scavengers of As, treatment with iron reducing microorganisms aimed at inducing the reductive dissolution of soil oxides and thus obtaining the release of the retained As. The main objective of using EDTA was the removal of metal contaminants, such as Pb and Zn, through the formation of soluble metal chelates. Experimental results however indicated that EDTA was also indispensable for the biological reduction of Fe(III) oxides. The bacterial activity was found to have a pronounced positive effect on the removal of arsenic, which increased from the value of 35% obtained during the pure chemical treatment up to 90% in the presence of D. palmitatis. In the case of Pb, the major part, i.e. approximately 85%, was removed from soil with purely chemical mechanisms, whereas the biological activity slightly improved the extraction, increasing the final removal up to 90%. Co-treatment had negative effect only for Zn, whose removal was reduced from 80% under abiotic condition to approximately 50% in the presence of bacteria.     

Evaluation of accelerated dechlorination of p,p'-DDT in acidic paddy soil

The reductive dechlorination and behavior of p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was investigated in a paddy soil. Treatment with 5% (w/w) metallic iron (Fe(0)) resulted in sharp decrease of p,p'-DDT, whereas there was no extra effect when 2% (w/w) aluminum sulfate (Al(2)(SO(4))(3)) was added to the Fe(0) treatment. These results suggest that Fe(0) could effectively promote the reductive dechlorination of p,p'-DDT and its metabolites while Al(2)(SO(4))(3) did not show any effect on those processes. Furthermore, p,p'-DDT and its daughter compounds inhibited holistic soil respiration greatly at first but could be metabolized by certain species of indigenous microorganisms after a period of adaptation time in the soil. When treated with Fe(0), the polluted soil produced much less CO(2) while the addition of Al(2)(SO(4))(3) counteracted its negative effect to much extent.     

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.     

Effects of Mn(II) and Fe(II) on microbial removal of arsenic (III)

Goal, scope, and background  Arsenic contamination in groundwater creates severe health problems in the world. There are many physiochemical and biological methods available for remediation of arsenic from groundwater. Among them, microbial remediation could be taken as one of the least expensive methods, though it takes longer treatment time. The main objective of this research was to study the improvement on remediation by addition of some essential ion salts such as Mn and Fe. Materials and methods   Staphylococcus aureus, Bacillus subtilis, Klebsiella oxytoca, and Escherichia coli were taken as model microbes from Dhulikhel, 30 km east from Kathmandu, Nepal. Results and discussion  Microbes used in this study showed different abilities in their removal of As(III) with and without addition of Mn and Fe salts. The trend of remediation increased with time. S. aureus was found to be the best among the microbes used. It showed almost 100% removal after 48-h culture, both with and without Fe and Mn salts. Rate of removal of As increased with addition of Fe and Mn for all microbes. Removal efficiency was found to increase by about 32% on average after addition of salts in 24-h cultures of S. aureus.     

An in situ study of the role of surface films on granular iron in the permeable iron wall technology

Permeable walls of granular iron are a new technology developed for the treatment of groundwater contaminated with dissolved chlorinated solvents. Degradation ofthe chlorinated solvents involves a charge transfer process in which they are reductively dechlorinated, and the iron is oxidized. The iron used in the walls is an impure commercial material that is covered with a passive layer of Fe2O3, formed as a result of a high-temperature oxidation process used in the production of iron. Understanding the behaviour of this layer upon contact with solution is important, because Fe2O3 inhibits mechanisms involved in contaminant reduction, including electron transfer and catalytic hydrogenation. Using a glass column specially designed to allow for in situ Raman spectroscopic and open circuit potential measurements, the passive layer of Fe2O3 was observed to be largely removed from the commercial product, Connelly iron, upon contact with Millipore water and with a solution of Millipore water containing 1.5 mg/l trichloroethylene (TCE). It has been previously shown that Fe2O3 is removed from iron surfaces upon contact with solution by an autoreduction reaction; however, prior to this work, the reaction has not been shown to occur on the impure commercial iron products used in permeable granular iron walls. The rate of removal was sufficiently rapid such that the initial presence of Fe2O3 at the iron surface would have no consequence with respect to the performance of an in situ wall. Subsequent to the removal of Fe2O3 layer, magnetite and green rust formed at the iron surface as a result of corrosion in both the Millipore water and the solution containing TCE. The formation of these two species, rather than higher valency iron oxides and oxyhydroxides, is significant for the technology. The former can interfere with contaminant degradation because they inhibit electron transfer and catalytic hydrogenation. Magnetite and green rust, in contrast, will not inhibit the mechanisms involved in contaminant reduction, and hence their formation is beneficial to the long-term performance of the iron material.