Effective and selective recovery of precious metals by thiourea modified magnetic nanoparticles.

Adsorption of precious metals in acidic aqueous solutions using thiourea modified magnetic magnetite nanoparticle (MNP-Tu) was examined. The MNP-Tu was synthesized, characterized and examined as a reusable adsorbent for the recovery of precious metals. The adsorption kinetics were well fitted with pseudo second-order equation while the adsorption isotherms were fitted with both Langmuir and Freundlich equations. The maximum adsorption capacity of precious metals for MNP-Tu determined by Langmuir model was 43.34, 118.46 and 111.58 mg/g for Pt(IV), Au(III) and Pd(II), respectively at pH 2 and 25 °C. MNP-Tu has high adsorption selectivity towards precious metals even in the presence of competing ions (Cu(II)) at high concentrations. In addition, the MNP-Tu can be regenerated using an aqueous solution containing 0.7 M thiourea and 2% HCl where precious metals can be recovered in a concentrated form. It was found that the MNP-Tu undergoing seven consecutive adsorption-desorption cycles still retained the original adsorption capacity of precious metals. A reductive adsorption resulting in the formation of elemental gold and palladium at the surface of MNP-Tu was observed.

Inactivation of Escherichia coli by dual-functional zerovalent Fe/Al composites in water.

A bimetallic Fe/Al disinfection system was developed to examine the feasibility of inactivation of water borne microorganisms. In this study, the effectiveness and mechanisms of the bimetallic Fe/Al system on the inactivation of model bacteria, Escherichia coli (E. coli), were investigated. Results revealed that the Fe/Al system effectively inactivated E. coli to reach nearly 2 logs (99%) removal within 20 min and 4 logs (99.99%) at 24 h, indicating that the Fe/Al composite was able to sustain a long-term disinfection capacity. The inactivation ability resulted from hydroxyl radicals produced by a Fenton reaction through in-situ self-generated Fe2+ and H2O2 species in the Fe/Al system. In addition to the attack by the radicals, some of E. coli were adsorbed onto the Fe/Al composite (zeta potential of 30-50 mV) as a result of Coulomb interaction. Scanning electron microscope (SEM) images showed that the adsorbed bacteria had damaged pores at the two ends of their rod-like cells. This phenomenon suggested that a micro-electric field between the Fe/Al galvanic couple induced electroporation of the adsorbed E. coli and thus further advanced additional inactivation ability for the bacteria disinfection.

Catalytic hydrodechlorination of 1,2-dichloroethane using copper nanoparticles under reduction conditions of sodium borohydride.

1,2-Dichloroethane (1,2-DCA) is a raw material used for the manufacture of vinyl chloride monomer (VCM) and therefore has very often been detected in the groundwater nearby the VCM manufacturing plant. Zero-valent iron (ZVI) is capable of degrading a wide array of highly chlorinated contaminants; however, the reactivity of ZVI towards 1,2-DCA is very low. In this study, zero-valent copper nanoparticles have been synthesized for effective dechlorination of 1,2-DCA under reduction conditions of sodium borohydride. Copper nanoparticles consisted of mainly metallic copper (Cu(0)) with small amounts of cuprous oxide (Cu(2)O). They have surface areas of about 19.0 m(2) g(-1) and an average diameter of 15 nm. Batch experiments were conducted to test the effectiveness of copper nanoparticles for 1,2-DCA degradation using sodium borohydride as electron donors where the ORP was measured as -1100 mV. More than 80% of 1,2-DCA (30 mg L(-1)) was rapidly degraded within 2 h in the presence of both copper nanoparticles (2.5 g L(-1)) and borohydride (25 mM). No reduction of 1,2-DCA was observed when the system contained either copper nanoparticles alone or borohydride alone. The degradation intermediates included ethane and ethylene accounting for 79% and ∼1.5% of the 1,2-DCA lost, respectively. Potential environmental applications can be achieved by immobilizing copper nanoparticles onto the surface of reducing metals to form a reactive bimetallic structure.

Trimetallic Pd/Fe/Al particles for catalytic dechlorination of chlorinated organic contaminants.

Zero-valent aluminum based trimetallic particles comprising a combination of catalytically effective amounts (1 wt%) of palladium and zero-valent iron on the aluminum surface were synthesized and tested for the dechlorination of chlorinated methanes in batch reactors. XRD analysis indicated the trimetallic particles present in zero-valent form of all three components. Trimetallic Pd/Fe/Al particles showed a very rapid degradation of carbon tetrachloride leading to a surface normalized rate constant (k(SA)) of approximately 0.03 L/h/m(2), two orders of magnitude higher than that of reported data on zero-valent iron particles under near neutral pH conditions. Hydrocarbons including methane and ethane were the major products that accounted for about 38% and 27% of the carbon tetrachloride lost, respectively. Repetitive addition of carbon tetrachloride showed no loss of activity of Pd/Fe/Al particles for more than 20 cycles. In the absence of palladium, the degradation rate decreased by a factor of 10 suggesting palladium serves as a catalyst. Analysis of anions in the solution revealed that the chloride accounted for 75% of the carbon tetrachloride lost. Metallic ions for aluminum and iron were determined to be about 0.02 and 20 mg/L, respectively at the end of the experiment. No palladium ion was measured.

Bimetallic Fe/Al system: An all-in-one solid-phase Fenton reagent for generation of hydroxyl radicals under oxic conditions.

In the classic Fenton reaction, both H2O2 and ferrous ion (Fe(II)) are required under a narrow low pH range to produce hydroxyl radicals (OH). The modified Fenton processes including heterogeneous Fenton-like reaction, photo-Fenton reaction and electro-Fenton reaction developed to overcome the drawbacks of the homogeneous Fenton reaction have recently received increasing attention. However, all the modifications of the classic Fenton reaction cannot be assembled into one system and require external supply of reagents or energy. We present here, bimetallic Fe/Al, a novel solid-phase Fenton reagent capable of in situ generation of H2O2 and Fe(II) to form OH under near neutral pH conditions without an external energy supply. Aluminum acts as an electron donor to maintain the electron supply and preserve the outer layer of iron at the zero-valence state with enhanced surface areas. The production of OH by bimetallic Fe/Al was quantified and further detected by an electron paramagnetic resonance (EPR) analysis under oxic conditions. Radical scavenging tests were performed by adding isopropanol or 1,4­benzoquinone in the system to investigate the nature of the oxidants produced during the oxidative process. Bimetallic Fe/Al system for the Fenton reaction in water involves both surface-mediated and aqueous-phase reactions. A pilot scale test using a continuous-flow column packed with Fe/Al (9.8 kg) demonstrated the capability of bimetallic Fe/Al for COD removal of acidic dye solutions. The novelty of bimetallic Fe/Al is that it is an all-in-one solid-phase Fenton reagent that can be readily applied to a wide variety of environmental applications.

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.

Zerovalent iron nanoparticles for treatment of ground water contaminated by hexachlorocyclohexanes.

Ground water and aquifer samples from a site contaminated by hexachlorocyclohexanes (HCHs; C(6)H(6)Cl(6)) were exposed to nanoscale iron particles to evaluate the technology as a potential remediation method. The summed concentration of the HCH isomers in ground water was approximately 5.16 micromol L(-1) (1500 microg L(-1)). Batch experiments with 2.2 to 27.0 g L(-1) iron nanoparticles showed that more than 95% of the HCHs were removed from solution within 48 h. Using a pseudo first-order kinetics model, the HCH isomers were removed in accordance with the trend gamma congruent with alpha > beta > delta. This seems to be correlated with the orientation (axial vs. equatorial) of the chlorine atoms lost in the dihaloelimination steps. Although the reactivity of the HCH isomers has been investigated in the classical organic chemistry literature, the present study was the first in the environmental remediation arena. The rate of removal is directly correlated to the number of axial chlorines. The observed rate constant varied from 0.04 to 0.65 h(-1), and the rate constant normalized to the iron surface area concentration ranged from 5.4 x 10(-4) to 8.8 x 10(-4) L m(-2) h(-1). Post-test extractions of the reactor contents detected little HCH remaining in solution or on the iron surfaces, reinforcing the contention that reaction rather than sorption was the operative mechanism for the HCH removal. Together with previously published work on a wide variety of chlorinated organic solvents, this work further demonstrates the potential of zerovalent iron nanoparticles for treatment and remediation of persistent organic pollutants.

Removal of methyl tert-butyl ether (MTBE) with Nafion.

A solid organic polymer, Nafion, is tested for the removal of methyl tert-butyl ether (MTBE) in water. Nafion with perfluorosulfonic acid backbone and terminal sulfonic acid groups has a surface acidity similar to 100% sulfuric acid, and has been commonly used as a strong-acid catalyst in many organic reactions. Sorption and subsequent transformation of MTBE were observed in batch experiments. The transformation of MTBE by porous nanocomposite Nafion SAC-13 to tert-butyl alcohol (TBA), acetone, isobutene and probably methanol was found. Subsequent transformation of TBA to acetone was also observed. Results suggest that transformational pathways may include hydrolysis, dehydrogenation and oxidation. Dissolved oxygen is needed for the oxidation of isobutene to acetone. As Nafion is insoluble in water, chemically stable, and regenerable, its use in packed-bed reactors for MTBE removal looks promising.

Adsorption of precious metals in water by dendrimer modified magnetic nanoparticles.

Magnetic nanoparticles modified by third-generation dendrimers (MNP-G3) and MNP-G3 further modified by ethylenediaminetetraacetic acid (EDTA) (MNP-G3-EDTA) were conducted to investigate their ability for recovery of precious metals (Pd(IV), Au(III), Pd(II) and Ag(I)) in water. Experiments were carried out using batch reactors for the studies of adsorption kinetics, adsorption isotherms, competitive adsorption and regeneration. The pseudo second-order model is the best-fit model among others suggesting that the adsorption of precious metals by MNP-G3 in water is a chemisorption process. Three adsorption isotherms namely Langmuir, Freundlich and Dubinin-Radushkevich isotherm were examined and the results showed the similarities and consistency of both linear and nonlinear analyses. Pd(IV) and Au(III) with higher valence exhibited relatively better adsorption efficiency than Pd(II) and Ag(I) with lower valence suggesting that the adsorption of precious metals by MNP-G3 is a function of valence. In the presence of the competing ion Zn(II), the adsorption efficiency of MNP-G3 for all four precious metals was declined significantly. The use of MNP-G3-EDTA revealed an increase in the adsorption efficiency for all four precious metals. However, the low selectivity of MNP-G3 towards precious metals was not enhanced by the modification of EDTA onto the MNP-G3. The regeneration of metal-laden MNP-G3 can be readily performed by using 1.0% HCl solution as a desorbent solution.

Valorization of aluminum scrap via an acid-washing treatment for reductive removal of toxic bromate from water.

Aluminum scrap (AS) is adopted for the first time as a readily available aluminum source to prepare zero-valent aluminum (ZVAl) for removing bromate from water via a reductive reaction. Since aluminum is easily oxidized to aluminum oxide (Al2O3) on exposure to air, an acid-washing pretreatment on AS is developed to remove the layer of Al2O3. HCl is found as the most effective acid to pretreat AS and the HCl-pretreated or acid-washed AS (AWAS) is able to remove bromate from water and convert it to bromide. Factors, such as temperature, pH, co-existing anions, and particle size, which influence the bromate removal using AWAS are also investigated. The mechanism of bromate removal by AWAS can be attributed to both reduction and adsorption. The elevated temperature also significantly improves bromate removal capacity of AWAS as well as the reaction kinetics. The bromate removal capacity of AWAS is substantially improved under acidic conditions. However, the basic conditions and co-existing anions suppress or interfere with the interaction between bromate and AWAS, leading to much lower removal capacities. The recyclability of AWAS is also evaluated and the acid-washing regeneration is necessary to restore its capacity. However, the mass of AWAS can gradually decrease due to multi-cycle acid-washing regeneration. Through this study, the valorization of AS via acid-washing is demonstrated and optimization of acid-washing parameters is presented. Our findings reveal that the acid-washing is a useful technique to utilize AS as an inexpensive and efficient material for removing bromate from water.

Effects of water chemistry on the destabilization and sedimentation of commercial TiO2 nanoparticles: Role of double-layer compression and charge neutralization.

Nanomaterials are considered to be emerging contaminants because their release into the environment could cause a threat to our ecosystem and human health. This study aims to evaluate the effects of pH, ions, and humic acid on the destabilization and sedimentation of commercial stabilized TiO2 nanoparticles (NPs) in aquatic environments. The average hydrodynamic size of TiO2 NPs was determined to be 52 ± 19 nm by dynamic light scattering. The zero point charge (ZPC) of the commercial TiO2 NPs was found to occur at pH 6. The stability of commercial TiO2 NPs is independent of its concentration in the range of 50-200 mg/L. In the absence of NaCl, the commercial TiO2 NPs rapidly settled down near pHzpc when the aggregated nanoparticle size surpassed 1 µm. However, when the commercial TiO2 NPs aggregated with the increase of NaCl concentrations, the large aggregates (>1 µm) were found to remain suspended. For example, even at the critical aggregation concentration of NaCl (100 meq/L), TiO2 NP aggregates suspended for 45 min and then slowly deposited. This implies an increase in the exposure risk of NPs. In the presence of Suwannee river humic acid (SRHA), the commercial TiO2 NPs did not settle down until the SRHA concentration increased to 20 mg/L, and were seen to restabilize at SRHA concentrations of 50 mg/L. The uncommon behaviors of the commercial TiO2 NPs we observed may be attributed to the different destabilization mechanisms caused by different species (i.e., NaCl and SRHA) in water.

High-level arsenite removal from groundwater by zero-valent iron.

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.

Enhanced dehalogenation of halogenated methanes by bimetallic Cu/Al.

A low-cost and high effective copper/aluminum (Cu/Al) bimetal has been developed for treatments of halogenated methanes, including dichloromethane, in near neutral and high pH aqueous systems. Bimetallic Cu/Al was prepared by a simple two-step synthetic method where Cu was deposited onto the Al surface. The presence of Cu on Al significantly enhanced rates of degradation of halogenated methanes and reduced toxic halogenated intermediates. The stability of Cu/Al was preliminarily studied by a multi-spiking batch experiment where complete degradation of carbon tetrachloride was achieved for seven times although the Cu/Al aging was found. Roles of Cu may involve protecting Al against an undesirable oxidation with water, enhancing reaction rates through the galvanic corrosion, and increasing the selectivity to a benign compound (i.e., methane). Kinetic analyses indicated that the activity of bimetallic Cu/Al was comparable to that of iron-based bimetals (e.g., palladized iron) and zero-valent metals. Bimetallic Cu/Al could be a promising reactive reagent for remediation of halogenated solvents-contaminated groundwater associated with high pH problems.

Iron nanoparticles for environmental clean-up: recent developments and future outlook.

Nanoscale zero-valent iron (nZVI) is one of the most extensively applied nanomaterials for groundwater and hazardous waste treatment. In the past fifteen years, progress made in several key areas has deepened our understanding of the merits and uncertainties of nZVI-based remediation applications. These areas include the materials chemistry of nZVI in its simple and modified forms, the nZVI reactivity with a wide spectrum of contaminants in addition to the well-documented chlorinated solvents, methods to enhance the colloidal stability and transport properties of nZVI in porous media, and the effects of nZVI amendment on the biogeochemical environment. This review aims to provide an up-to-date account of advancement in these areas as well as insights gained through field experience.

Biodegradable surfactant stabilized nanoscale zero-valent iron for in situ treatment of vinyl chloride and 1,2-dichloroethane.

Nanoscale zero-valent iron (NZVI) stabilized with dispersants is a promising technology for the remediation of contaminated groundwater. In this study, we demonstrated the use of biodegradable surfactant stabilized NZVI slurry for successful treatment of vinyl chloride (VC) and 1,2-dichloroethane (1,2-DCA) in a contaminated site in Taiwan. The biodegradable surfactant stabilized NZVI was coated with palladium and synthesized on-site. From monitoring the iron concentration breakthrough and distribution, it was found that the stabilized NZVI is capable of transporting in the aquifer at the test plot (200 m(2)). VC was effectively degraded by NZVI while the 1,2-DCA degradation was relatively sluggish during the 3-month field test. Nevertheless, as 1,2-DCA is known to resist abiotic reduction by NZVI, the observation of 1,2-DCA degradation and hydrocarbon production suggested a bioremediation took place. ORP and pH results revealed that a reducing condition was achieved at the testing area facilitating the biodegradation of chlorinated organic hydrocarbons. The bioremediation may be attributed to the production of hydrogen gas as electron donor from the corrosion of NZVI in the presence of water or the added biodegradable surfactant serving as the carbon source as well as electron donor to stimulate microbial growth.

Perchlorate removal by acidified zero-valent aluminum and aluminum hydroxide.

Removal of perchlorate using either acid-washed zero-valent aluminum or aluminum hydroxide was studied in batch reactors under ambient temperature and pressure. Approximately 90-95% of perchlorate was removed within 24h in the presence of 35 g L(-1) aluminum at acidic pH (4.5+/-0.2). Although aluminum is a strong reductant, this study indicated no explicit evidence to support perchlorate reduction while it was found that an adsorption process is involved in the perchlorate removal. The adsorbed perchlorate ions were desorbed effectively using a 1.0 N MgSO(4) solution. The effective composition for the perchlorate adsorption is confirmed as aluminum hydroxide (bayerite), which is a product of the aluminum corrosion. Rapid adsorption of perchlorate was observed in the presence of aluminum hydroxide. The perchlorate adsorption by aluminum hydroxide is dependent on the solution pH. The removal mechanism can be attributed to the ion-pair formation at the aluminum hydroxide surface.

Influence of nanoscale zero-valent iron on geochemical properties of groundwater and vinyl chloride degradation: A field case study.

A 200m(2) pilot-scale field test successfully demonstrated the use of nanoscale zero-valent iron (NZVI) for effective remediation of groundwater contaminated with chlorinated organic compounds in Taiwan within six months. Both commercially available and on-site synthesized NZVI were used. A well-defined monitoring program allowing to collect three-dimensional spatial data from 13 nested multi-level monitoring wells was conducted to monitor geochemical parameters in groundwater. The degradation efficiency of vinyl chloride (VC) determined at most of monitoring wells was 50-99%. It was found that the injection of NZVI caused a significant change in total iron, total solid (TS) and suspended solid (SS) concentrations in groundwater. Total iron concentration showed a moderate and weak correlation with SS and TS, respectively, suggesting that SS may be used to indicate the NZVI distribution in groundwater. A decrease in oxidation-reduction potential (ORP) values from about -100 to -400mV after NZVI injection was observed. This revealed that NZVI is an effective means of achieving highly reducing conditions in the subsurface environment. Both VC degradation efficiency and ORP showed a correlative tendency as an increase in VC degradation efficiency corresponded to a decrease of ORP. This is in agreement with the previous studies suggesting that ORP can serve as an indicator for the NZVI reactivity.

Reductive activation of dioxygen for degradation of methyl tert-butyl ether by bifunctional aluminum.

Bifunctional aluminum is prepared by sulfating aluminum metal with sulfuric acid. The use of bifunctional aluminum to degrade methyl tert-butyl ether (MTBE) in the presence of dioxygen has been examined using batch systems. Primary degradation products were tert-butyl alcohol, tert-butyl formate, acetone, and methyl acetate. The initial rate of MTBE degradation exhibited pseudo-first-order behavior, and the half-life of reaction was less than 6 h. XPS analysis indicates the formation of sulfate at the surface of bifunctional aluminum. The concentration of surface sulfate varies linearly with increasing strength of the sulfuric acid used during bifunctional aluminum preparation. The rate of MTBE degradation is a function of the concentration of the surface sulfate. MTBE degradation rates increased by a factor of 2 as surface sulfate concentrations increased from 233 to 641 micromol/m2. This relationship implies that sulfate at the surface of bifunctional aluminum acts as a reactive site.