Souhail R. Al-Abed

Effect of inorganic, synthetic and naturally occurring chelating agents on Fe(II) mediated advanced oxidation of chlorophenols

This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H2O2) was successfully tested for the degradation of series of chlorophenols (4-CP, 2,4-CP, 2,4,6-CP, 2,3,4,5-CP). The major objective of the present study was to evaluate the effectiveness of three representative chelating agents (citrate, ethylenediaminedisuccinate (EDDS), and pyrophosphate) on Fe(II)-mediated activation of three common peroxide (peroxymonosulfate (PMS), persulfate (PS), and hydrogen peroxide (H2O2)) at neutral pH conditions. Short term (4 h) and long term (7 days) experiments were conducted to evaluate the kinetics and longevity of different oxidative systems for 4-chlorophenol degradation. Results showed that each of the iron-chelating agent couple was superior in activating a particular oxidant and consequently for 4-CP degradation. In case of Fe(II)/PMS system, the inorganic chelating agent pyrophosphate showed effective activation of PMS whereas very fast dissociation of PMS was recorded in the case of EDDS without any apparent 4-CP degradation. In Fe(II)/H2O2 system, EDDS was proven to be the most effective whereas pyrophosphate showed negligible activation of H2O2. Fe(II)/Citrate system showed moderate activation of all three oxidants. PMS was found to be the most universal oxidant, which was activated by all three iron-chelating agent systems and Fe(II)/Citrate was the most universal chelating agent system, which was able to activate all three oxidants to a certain extent.

Effects of pH on dechlorination of trichloroethylene by zero-valent iron

The surface normalized reaction rate constants (k(sa)) of trichloroethylene (TCE) and zero-valent iron (ZVI) were quantified in batch reactors at pH values between 1.7 and 10. The k(sa) of TCE linearly decreased from 0.044 to 0.009l/hm(2) between pH 3.8 and 8.0, whereas the k(sa) at pH 1.7 was more than an order higher than that at pH 3.8. The degradation of TCE was not observed at pH values of 9 and 10. The k(sa) of iron corrosion linearly decreased from 0.092 to 0.018l/hm(2) between pH 4.9 and 9.8, whereas it is significantly higher at pH 1.7 and 3.8. The k(sa) of TCE was 30-300 times higher than those reported in literature. The difference can be attributed to the pH effects and precipitation of iron hydroxide. The k(sa) of TCE degradation and iron corrosion at a head space of 6 and 10ml were about twice of those at zero head space. The effect was attributed to the formation of hydrogen bubbles on ZVI, which hindered the transport the TCE between the solution and reaction sites on ZVI. The optimal TCE degradation rate was achieved at a pH of 4.9. This suggests that lowering solution pH might not expedite the degradation rate of TCE by ZVI as it also caused faster disappearance of ZVI, and hence decreased the ZVI surface concentration.

Arsenic sorption on TiO2 nanoparticles: Size and crystallinity effects

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO(2) was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO(2), solute pH in the range of 4-9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO(2) polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO(2) surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO(2) rather than crystalline TiO(2). The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO(2) at neutral pH.

Chapter 8 TiO2-Based Advanced Oxidation Nanotechnologies for Water Purification and Reuse

Abstract Advanced oxidation technologies (AOTs) produce highly reactive radical species, which readily attack and decompose organic pollutants in water eventually mineralizing them to water, carbon dioxide, and other simple inorganic species. AOTs involve nonselective oxidizing species and are among the most efficient chemical oxidation processes for the treatment of water contaminated with biologically toxic and nondegradable chemicals. Among such technologies, TiO 2 photocatalysis has attracted great attention for the development of efficient water purification and reuse systems due to the effectiveness of TiO 2 to generate the highly oxidizing hydroxyl radicals in the absence of any externally added chemicals in the system. In this chapter, we provide an overview of TiO 2 -based AOTs; from fundamentals to environmental applications. The mechanism of radical generation from TiO 2 /UV systems, principle of photocatalytic water purification, and applications of TiO 2 photocatalysis are described. The chapter also deals with some challenging issues in TiO 2 -based AOTs, including the need for enhancement of photocatalytic activity, challenges in reactor design with immobilized TiO 2 , the concept and multifunction of photocatalytic membranes, aspects on solar energy-based TiO 2 photocatalysis, and catalyst deactivation and fouling problems. Current advances in the technology such as tailor-design of TiO 2 materials at the nanoscale and simultaneous generation of hydroxyl radicals and sulfate radicals are of high interest and are also discussed. Finally, previous and current efforts, point to further development of TiO 2 -based AOTs, and more growth as a competitive process for full-scale applications in the near future are described in the end of this chapter.

Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron

Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0x10(-4) above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC.

A feasibility study on Pd/Mg application in historically contaminated sediments and PCB spiked substrates.

A vast majority of literature on bimetals deals with aqueous contaminants, very little being on organics strongly adsorbed on sediments and hence very challenging to remediate. Having previously reported materials, mechanistic and parametric aspects of PCB dechlorination with Pd/Mg bimetals, here we evaluate their ability to dechlorinate (i) PCBs spiked in clean clays and sediments and (ii) historically contaminated aged sediments (Waukegan Harbor, WHS). It was determined that while water, as a medium, dechlorinated low surface area clays it was ineffective with high surface area clays and sediments. Dechlorination was governed by desorption of PCBs, hence addition of 10-25% ethanol improved dechlorination performance. Triton X-100, a surfactant, effectively desorbed PCBs from WHS but their dechlorination was not observed. Investigating possible causes, we found that while (i) Pd/Mg completely dechlorinated multi-component commercial PCB mixtures (i.e. complex PCB distribution in WHS did not limit Pd/Mg effectiveness) and (ii) active components in extraction media did not inhibit dechlorination, sulfide in WHS was poisoning Pd, compromising its activity.

PCB congener sorption to carbonaceous sediment components: macroscopic comparison and characterization of sorption kinetics and mechanism.

Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K(F) (Lkg(-1)) spanned several orders of magnitude, ranging from logK(F) of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

Feasibility of electrokinetic soil remediation in horizontal Lasagna™ cells ☆

An integrated soil remediation technology called Lasagna has been developed that combines electrokinetics with treatment zones for use in low permeability soils where the rates of hydraulic and electrokinetic transport are too low to be useful for remediation of contaminants. The technology was developed by two groups, one involving industrial partners and the DOE and another involving US EPA and the University of Cincinnati, who pursued different electrode geometries. The Industry/DOE group has demonstrated the technology using electrodes and treatment zones installed vertically from the soil surface. We have demonstrated the feasibility of installing horizontal electrodes and treatment zones in subsurface soils by hydraulic fracturing, a process that we adapted from petroleum industry practices. When horizontal electrodes were connected to a dc power supply, uniform electrical potential gradients of 10-40 V/m were created in soil between the electrodes, inducing electroosmotic flow that facilitated movement of water and contaminants into treatment zones between the electrodes.

Chronic TiO2 nanoparticle exposure to a benthic organism, Hyalella azteca: impact of solar UV radiation and material surface coatings on toxicity

There is limited information on the chronic effects of nanomaterials to benthic organisms, as well as environmental mitigating factors that might influence this toxicity. The present study aimed to fill these data gaps by examining various growth endpoints (weight gain, instantaneous growth rate, and total protein content) for up to a 21 d sediment exposure of TiO2 nanoparticles (nano-TiO2) to a representative benthic species, Hyalella azteca. An uncoated standard, P25, and an Al(OH)3 coated nano-TiO2 used in commercial products were added to sediment at 20 mg/L or 100 mg/L Under test conditions, UV exposure alone was shown to be a greater cause of toxicity than even these high levels of nano-TiO2 exposure, indicating that different hazards need to be addressed in toxicity testing scenarios. In addition, this study showed the effectiveness of a surface coating on the decreased photoactivity of the material, as the addition of an Al(OH)3 coating showed a dramatic decrease in reactive oxygen species (ROS) production. However, this reduced photoactivity was found to be partially restored when the coating had been degraded, leading to the need for future toxicity tests which examine the implications of weathering events on particle surface coatings.

Statistical validation of sulfate quantification methods used for analysis of acid mine drainage

Turbidimetric method (TM), ion chromatography (IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES) with and without acid digestion have been compared and validated for the determination of sulfate in mining wastewater. Analytical methods were chosen to compare the performance of a portable field turbidimetric instrument and to validate the underlying assumption utilized in conversion of total sulfur to sulfate during ICP-AES analysis. Accuracy and precision of analytical techniques were compared to one another using control and field samples collected from a mine site using the Bonferroni multiple comparison test. Effects of sample dilution, filter pore size and acidification on sulfate quantification were also studied. The results showed that IC and ICP-AES with and without acid digestion provided excellent recoveries in the case of control samples (within 90-110%). These analytical methods also showed lower relative standard deviation for both control and field samples. On the other hand, performance of the turbidimetric method was severely affected by sample dilution and acidification, and also revealed poor sulfate recoveries for control samples ranging from 0 to 83.5%. Analysis of variance (ANOVA) was used to evaluate the response (sulfate concentration) obtained from factorial design. Analytical method had significant effect (P<0.0001) on the sulfate quantification. The interaction between determination method and sample dilution was more significant than other two-way interactions.