Hsing-Lung Lien

Treatment of chlorinated organic contaminants with nanoscale bimetallic particles

Abstract Nanoscale bimetallic particles (Pd/Fe, Pd/Zn, Pt/Fe, Ni/Fe) have been synthesized in the laboratory for treatment of chlorinated organic pollutants. Specific surface areas of the nanoscale particles are tens of times larger than those of commercially available microscale metal particles. Rapid and complete dechlorination of several chlorinated organic solvents and chlorinated aromatic compounds was achieved by using the nanoscale bimetallic particles. Evidence observed suggests that within the bimetallic complex, one metal (Fe, Zn) serves primarily as electron donor while the other as catalyst (Pd, Pt). Surface-area-normalized reactivity constants are about 100 times higher than those of microscale iron particles. Production of chlorinated byproducts, frequently reported in studies with iron particles, is notably reduced due to the presence of catalyst. The nano-particle technology offers great opportunities for both fundamental research and technological applications in environmental engineering and science.

Nanoscale iron particles for complete reduction of chlorinated ethenes

Abstract This paper examines the potential for using laboratory synthesized nanoscale Pd/Fe bimetallic particles to reduce chlorinated ethenes. Rapid and complete dechlorination was achieved for six chlorinated ethenes: tetrachloroethene (PCE, C 2 Cl 4 ), trichloroethene (TCE, C 2 HCl 3 ), 1,1-dichloroethene (1,1-DCE, C 2 H 2 Cl 2 ), cis - and trans -1,2-dichloroethene (c-DCE, t-DCE, C 2 H 2 Cl 2 ), and vinyl chloride (VC, C 2 H 3 Cl). The chlorinated ethenes (20 mg l −1 ) were completely reduced within 90 min at a metal loading of 5 g l −1 . Ethane was the primary product from these reactions, amount to 60–90% of the total carbon. Ethene (3–20%) was produced during the transformation of TCE, DCEs and VC. No chlorinated intermediates or final products were detected above the method detection limit ( −1 ). The remarkable performance of the nanoscale particles can be attributed to: (1) High specific surface area of the nanoscale metal particles, approximately 35 m 2 g −1 , tens to hundreds of times higher than commercial grade micro- or milli-scale iron particles; (2) Increased reactivity per unit metal surface area, largely due to the presence of the noble metal (Pd) on the surface. Values of the surface-area-normalized rate coefficients ( k SA ) were two orders of magnitude higher than those reported in the literature for larger iron particles. Due to their small particle size and high reactivity, the nanoscale bimetallic particles may be useful in a wide array of environmental applications including subsurface injection for groundwater treatment.

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.

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.

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.

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.

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.

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.

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.