Khalil Hanna

Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils.

In this study, feasibility of magnetite-activated persulfate oxidation (AP) was evaluated for the degradation of polycyclic aromatic hydrocarbons (PAHs) in batch slurry system. Persulfate oxidation activated with soluble Fe(II) (FP) or without activation (SP) was also tested. Kinetic oxidation of PAHs was tracked in spiked sand and in aged PAH contaminated soils at circumneutral pH. Quartz sand was spiked with: (i) single model pollutant (fluorenone) and (ii) organic extract isolated from two PAH contaminated soils (H and NM sampled from ancient coking plants) and was subjected to oxidation. Oxidation was also performed on real H and NM soils with and without an extraction pretreatment. Results indicate that oxidation of fluorenone resulted in its complete degradation by AP while abatement was very low (<20%) by SP or FP. In soil extracts spiked on sand, significant degradation of 16 PAHs was observed by AP (70-80%) in 1 week as compared to only 15% by SP or FP systems. But no PAH abatement was observed in real soils whatever the treatment used (AP, FP or SP). Then soils were subjected to an extraction pretreatment but without isolation of organic extract from soil. Oxidation of this pretreated soil showed significant abatement of PAHs by AP. On the other hand, very low degradation was achieved by FP or SP. Selective degradation of PAHs was observed by AP with lower degradation efficiency towards high molecular weight PAHs. Analyses revealed that no by-products were formed during oxidation. The results of this study demonstrate that magnetite can activate persulfate at circumneutral pH for an effective degradation of PAHs in soils. However, availability of PAHs and soil matrix were found to be the most critical factors for degradation efficiency.

Reactivity of Nanoscale Zero-Valent Iron in Unbuffered Systems: Effect of pH and Fe(II) Dissolution.

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zerovalent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH systems. The reduction rate increased exponentially with respect to the NZVI concentration, and the ratio of dissolved Fe(II)/initial NZVI was related proportionally to the initial pH values, suggesting that lower pH (6-7) with low NZVI loading may slow the 4-NP reduction through acceleration of the dissolution of NZVI particles. Additional experiments using buffered pH systems confirmed that high pH values (8-9) can preserve the NZVI particles against dissolution, thereby enhancing the reduction kinetics of 4-NP. Furthermore, reduction tests using ferrous ion in suspensions of magnetite and maghemite showed that surface-bound Fe(II) on oxide coatings can play an important role in enhancing 4-NP reduction by NZVI at pH 8. These unexpected results highlight the importance of pH and Fe(II) dissolution when NZVI technology is applied to poorly buffered systems, particularly at a low amount of NZVI (i.e., <0.075 g/L).

Sulfate Radical Photogeneration Using Fe-EDDS: Influence of Critical Parameters and Naturally Occurring Scavengers.

In this study, the activation of persulfate induced by Fe(III)-ethylenediamine-N,N′-disuccinic acid (EDDS) under dark and irradiation conditions and the reactivity of the generated sulfate radical (SO4•–) under a wide range of experimental conditions were investigated by means of experimental kinetic analyses and modeling. The Fe(III)-EDDS induced activation of persulfate was found to be efficient across a wide range of pH value (3–7), whereas the second order rate constant of SO4•– with 4-tert-butylphenol (4tBP) kSO4•–,4tBP = (4.21 ± 0.22) × 109 M–1 s–1 was found to be unchanged between pH 2.5 and 8.5. Experimental and theoretical investigations showed clearly that the 4tBP degradation was enhanced in the presence of chloride (10 mM), whereas an almost complete inhibition was observed in the presence of carbonates (10 mM). For the first time, second order rate constants evaluated by laser flash photolysis experiments revealed that SO4•– has a similar reactivity with EDDS (6.21 × 109 M–1 s–1) and 4tBP (4....

Chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soils

Chemical oxidation of hexachlorocyclohexanes (HCHs) was evaluated in (i) artificially spiked sand with HCH isomers (α, β, γ and δ) and (ii) contaminated soil sampled from a former gravel pit backfilled with wastes of lindane (γ-HCH). Following oxidation treatments were employed: hydrogen peroxide alone (HP), hydrogen peroxide with soluble Fe(II) (Fenton-F), sodium persulfate alone (PS), Fe(II) activated persulfate (AP) and permanganate (PM). GC-MS results revealed a significant degradation of all isomers in spiked soil in the order: F>PS>AP>HP>PM. Soluble Fe(II) enhanced the efficiency of H2O2 but decreased the reactivity of persulfate. Similar trend was observed in contaminated soil, but with less degradation probably caused by scavenging effect of organic matter and soil minerals and/or pollutant unavailability. No significant increase in oxidation efficiency was observed after using availability-enhancement agents in contaminated soil. Other limitation factors (oxidant dose, pH, catalyst type etc.) were also addressed. Among all the isomers tested, β-HCH was the most recalcitrant one which could be explained by higher metabolic and chemical stability. No by-products were observed by GC-MS regardless of the oxidant used. For being the premier study reporting chemical oxidation of HCH isomers in contaminated soils, it will serve as a base for in-situ treatments of sites contaminated by HCH isomers and other persistent organic pollutants.

Chemical oxidation of ibuprofen in the presence of iron species at near neutral pH.

The objective of this work was to evaluate the removal of ibuprofen (IBP) using the oxidants hydrogen peroxide (H(2)O(2)) and sodium persulfate (Na(2)S(2)O(8)). The ability of magnetite (Fe(3)O(4)) to activate persulfate (PS) and H(2)O(2) for the oxidation of IBP at near neutral pH was evaluated as well. The use of soluble Fe(2+) to activate H(2)O(2) and Na(2)S(2)O(8) was also investigated. H(2)O(2) and Na(2)S(2)O(8) were inactive during the sixty-minute experiments when used alone. However, activation using Fe(2+) increased the removal to 95% in the presence of H(2)O(2) (Fenton reaction) and 63% in the presence of Na(2)S(2)O(8) at pH 6.6. Chemical oxygen demand (COD) removal was also greater for Fenton oxidation (65%) than for iron-activated PS oxidation (25%). Activation of H(2)O(2) and PS by Fe(3)O(4) was only observed at a high oxidant concentration and over 48 h of reaction time. A second order rate kinetic constant was determined for H(2)O(2) (3.0∗10(-3) M(-1) s(-1)) and Na(2)S(2)O(8) (1.59∗10(-3) M(-1) s(-1)) in the presence of Fe(3)O(4). Finally, several of the degradation products formed during oxidation of IBP in the presence of H(2)O(2) and Na(2)S(2)O(8) (activated by Fe(2+)) were identified. These include oxalic acid, pyruvic acid, formic acid, acetic acid, 4-acetylbenzoic acid, 4-isobutylacetophenone (4-IBAP) and oxo-ibuprofen.

Activation of persulfate by Fe(III) species: Implications for 4-tert-butylphenol degradation

In this study, the activation of persulfate induced by Fe(III) species, including 5 kinds of iron oxhydroxides (IOs) and dissolved Fe3+ under dark condition were investigated. Ferrihydrite (FH) and akaganeite (AK) showed the highest activity in 4-tert-butylphenol (4tBP) removal. The 4tBP degradation rate constant decreased as the solution pH increased from pH 3.2 to 7.8 in FH/S2O82- system. However, the pH value had no significant effect on the 4tBP degradation in AK/S2O82- system. The degradation of 4tBP in Fe3+/S2O82- system was also performed to investigate the role of ferric species in persulfate activation. The pH dependency of 4tBP degradation rate was closely related to the speciation of FeIII, whereas the Fe(H2O)63+ was found to be the most active soluble iron complex form in the activation of S2O82-. 4tBP degradation was mainly due to the SO4- in IOs/S2O82- system, while SO4- and HO2 both had great contribution on 4tBP degradation in Fe3+/S2O82- system. Further investigations showed clearly that 4tBP degradation efficiency was decreased significantly due to the trapping of SO4- by chloride. This finding may have promising implications in developing a new technology for the treatment of contaminated waters and soils, especially where Fe3+ species are naturally occurring.

Fenton oxidation to remediate PAHs in contaminated soils: A critical review of major limitations and counter-strategies

Fenton oxidation constitutes a viable remediation strategy to remove polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. This review is intended to illustrate major limitations associated with this process like acidification, PAH unavailability, and deterioration of soil quality along with associated factors, followed by a critical description of various developments to overcome these constraints. Considering the limitation that its optimal pH is around 3, traditional Fenton treatment could be costly, impractical in soil due to the high buffering capacity of soils and associated hazardous effects. Use of various chelating agents (organic or inorganic) allowed oxidation at circumneutral pH but factors like higher oxidant demand, cost and toxicity should be considered. Another alternative is the use of iron minerals that can catalyze Fenton-like oxidation over a wide range of pH, but mobility of these particles in soils (i.e. saturated and unsaturated zones) should be investigated prior to in-situ applications. The PAH-unavailability is the crucial limitation hindering their effective degradation. Research data is compiled describing various strategies to address this issue like the use of availability enhancement agents, extraction or thermal pretreatment. Last section of this review is devoted to describe the effects of various developments in Fenton treatment onto soil quality and native microbiota. Finally, research gaps are discussed to suggest future directions in context of applying Fenton oxidation to remediate contaminated soils.

Sorption of Two Naphthoic Acids to Goethite Surface under Flow through Conditions

While the transport of low molecular weight organic acids was widely investigated, little is known about the mobility of the carboxylated aromatic compounds containing double rings in natural porous media. This study combines macroscopic (batch and column), microscopic (vibration spectroscopy), and surface complexation modeling to evaluate the mobility of two PAH degradation products: naphthoic acid (1-naphthoic acid (NA) and 1-hydroxy-2-naphthoic acid (HNA)), in porous media consisting of goethite-coated sand. The loss of ligands from aqueous solution was attributed to (1) a hydrogen-bonded surface complex present over the entire 3-10 pH range as well as protonated (2) surface and (3) bulk precipitates below pH 5. Mobility in column experiments was strongly affected by ligand functionality. Adsorption breakthrough predictions that make use of surface complexation parameters accurately predicted NA mobility. Those for HNA however predicted much less adsorption reactions than in the batch sorption experiments. Additional breakthrough experiments and test calculations confirmed that these differences were not related to sorption kinetics. HNA adsorption breakthrough data could only be predicted by lowering intrinsic complexation constant of the formation of hydrogen-bonded species, thereby suggesting modifications of the diffuse layer properties under flow conditions. These findings have strong implications in the assessment and prediction of contaminant transport and environmental remediation.

Kinetics and Mechanisms of Ciprofloxacin Oxidation on Hematite Surfaces

Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment.

Magnetite and Green Rust: Synthesis, Properties, and Environmental Applications of Mixed-Valent Iron Minerals

Mixed-valent iron [Fe(II)-Fe(III)] minerals such as magnetite and green rust have received a significant amount of attention over recent decades, especially in the environmental sciences. These mineral phases are intrinsic and essential parts of biogeochemical cycling of metals and organic carbon and play an important role regarding the mobility, toxicity, and redox transformation of organic and inorganic pollutants. The formation pathways, mineral properties, and applications of magnetite and green rust are currently active areas of research in geochemistry, environmental mineralogy, geomicrobiology, material sciences, environmental engineering, and environmental remediation. These aspects ultimately dictate the reactivity of magnetite and green rust in the environment, which has important consequences for the application of these mineral phases, for example in remediation strategies. In this review we discuss the properties, occurrence, formation by biotic as well as abiotic pathways, characterization techniques, and environmental applications of magnetite and green rust in the environment. The aim is to present a detailed overview of the key aspects related to these mineral phases which can be used as an important resource for researchers working in a diverse range of fields dealing with mixed-valent iron minerals.