Anett Georgi

Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-Influence of Fe(II)/Fe(III) ratio on catalytic performance.

Nano-sized Fe(II, III) oxides with various Fe(II)/Fe(III) ratios were characterized and tested as catalysts for the oxidative degradation of phenol via Fenton-like reactions at neutral pH. Under conditions typically applied for wet peroxide oxidation, Fe(II) in magnetite is oxidized to Fe(III), successively converting the mineral into maghemite. The residual Fe(II) content in the catalyst core is of only minor benefit for the catalytic activity in phenol oxidation, i.e. magnetite is not superior to maghemite. Achievable reaction rates for phenol degradation appeared to be rather low, e.g. phenol half-life of about 12 h when 3 g L(-1) magnetite and 5 g L(-1) H(2)O(2) were applied. Preceding surface-reduction of maghemite by NaBH(4), leading to an over-stoichiometric Fe(II) content compared to magnetite, only enhanced the non-productive decomposition of H(2)O(2) rather than the rate of phenol degradation. Reaction rates were shown to be relatively insensitive to catalyst concentration in the range of 1-10 g L(-1), probably resulting from a scavenging of reactive species by the catalyst surface, whereby particle agglomeration seems to play a key role. Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH.

Hydrophobic Fe-Zeolites for Removal of MTBE from Water by Combination of Adsorption and Oxidation

Several zeolites were evaluated as adsorbents for the removal of MTBE from water in a screening process. It was observed that the SiO2/Al2O3 molar ratio is a decisive factor for the adsorption properties, at least in the case of ZSM5 zeolites. ZSM5 zeolites with SiO2/Al2O3 ratios >200 were found to provide the best sorption properties for MTBE. To design a combined sorption/reaction method, regeneration of the loaded zeolites by selected advanced oxidation processes (AOP) was studied: (1) Fenton treatment using H2O2 with dissolved iron salts and (2) heterogeneous Fenton-like oxidation with Fe immobilized on the zeolites. The first was ineffective in regenerating loaded zeolites. However, heterogeneous catalysis using Fe species immobilized on the zeolite by liquid ion exchange was markedly more effective. Although these hydrophobic zeolites have a low ion exchange capacity, resulting in iron loadings of ≤ 0.09 wt %, it was possible to obtain sufficiently active catalysts. Hydrophobic Fe-zeolites can therefore be regarded as promising materials for the removal of MTBE from water, since they allow the combination of efficient adsorption and oxidative degradation of MTBE by H2O2. In contrast to the homogeneous catalysis by dissolved iron ions, these heterogeneous catalysts work at near-neutral pH and can be easily reused. Fe-zeolites as adsorbents/catalysts showed a good stability in both batch and column experiments.

Sorption and chemical reactions of PAHs with dissolved humic substances and related model polymers

Sorption coefficients measured for PAHs on dissolved humic substances by SPME and FQT were found to be inevitably different and method-dependent – SPME provides activity-based and FQT concentration-based sorption coefficients. Poly(acrylic acid) esters as well-defined model polymers were used in sorption experiments, leading to the conclusion that short aliphatic chains are more effective in binding PAHs than aromatic moieties. FQT was inappropriate to measure sorption coefficients for the interaction of pyrene with poly(acrylic acid) esters but the experiments revealed a characteristic shift in the fluorescence spectrum. Using pyrene as a probe for the molecular environment in the sorbed state, the observed spectral shift indicated a highly hydrophobic microenvironment. The empirical relationships between lg KDOC and lg KOW were generalized on the basis of a modified Flory-Huggins concept. Introducing only one sorbent-specific parameter, the solubility parameter δDOM, the calculation of sorption coefficients became possible for a wide range of HOCs using fundamental data readily available from the literature. Long-term experiments showed that reactive PAHs (such as acenaphthylene and 9-methylanthracene) are able to react with HAs under strictly abiotic and anoxic conditions, whereas less reactive PAHs (such as naphthalene and dihydroanthracene) do not form bound residues. The HA reveals two functions in the interaction, behaving as a reaction partner and as a protecting ligand. Sorption und chemische Reaktion von PAK mit gelosten Huminstoffen und Modellpolymeren Sorptionskoeffizienten, die mit SPME und FQT bestimmt werden, sind zwangsweise unterschiedlich und methodenabhangig – SPME liefert Sorptionskoeffizienten auf der Basis der Aktivitat und FQT Sorptionskoeffizienten auf Basis der Konzentration. Sorptionsexperimente mit Polyacrylsaureestern als definierten Modellpolymeren fuhrten zu der Schlussfolgerung, dass kurze aliphatische Ketten effektiver PAK binden als aromatische Reste. Die FQT dagegen erwies sich als ungeeignet zur Bestimmung von Sorptionskoeffizienten fur die Wechselwirkung zwischen Pyren und Polyacrylsaureestern. Die Fluoreszenzspektren zeigen eine charakteristische Verschiebung der Fluoreszenzintensitaten. Dabei konnte Pyren als Sonde fur die molekulare Umgebung im sorbierten Zustand dienen, die beobachteten spektralen Verschiebungen weisen auf eine hochhydrophobe Mikroumgebung des Pyrens. Empirische lg KDOC-lg KOW-Beziehungen wurden vereinheitlicht auf der Basis eines modifizierten Flory-Huggins-Konzeptes. Durch das Einfuhren eines einzelnen sorbensspezifischen Parameters, dem Loslichkeitsparameter δDOM, wurde die Berechnung von Sorptionskoeffizienten fur ein weites Spektrum an hydrophoben organischen Verbindungen moglich; alle anderen Parameter liegen in der Literatur tabelliert vor. Langzeitexperimente belegen, dass reaktive PAK (wie Acenaphthylen und 9-Methylanthracen) in der Lage sind, unter strikt abiotischen und anoxischen Bedingungen mit Huminsauren zu reagieren, wohingegen wenig reaktive PAK (wie Naphthalin und Dihydroanthracen) keine gebundenen Reste bilden. Die Huminsaure offenbart zwei Funktionen in der Wechselwirkung – zum einen ist sie Reaktionspartner, zum anderen schutzender Ligand.

Critical evaluation of the 2D-CSIA scheme for distinguishing fuel oxygenate degradation reaction mechanisms.

Although the uniform initial hydroxylation of methyl tert-butyl ether (MTBE) and other oxygenates during aerobic biodegradation has already been proven by molecular tools, variations in carbon and hydrogen enrichment factors (ε(C) and ε(H)) have still been associated with different reaction mechanisms (McKelvie et al. Environ. Sci. Technol. 2009, 43, 2793-2799). Here, we present new laboratory-derived ε(C) and ε(H) data on the initial degradation mechanisms of MTBE, ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME) by chemical oxidation (permanganate, Fenton reagents), acid hydrolysis, and aerobic bacteria cultures (species of Aquincola, Methylibium, Gordonia, Mycobacterium, Pseudomonas, and Rhodococcus). Plotting of Δδ(2)H/ Δδ(13)C data from chemical oxidation and hydrolysis of ethers resulted in slopes (Λ values) of 22 ± 4 and between 6 and 12, respectively. With A. tertiaricarbonis L108, R. zopfii IFP 2005, and Gordonia sp. IFP 2009, ε(C) was low (<|-1|‰) and ε(H) was insignificant. Fractionation obtained with P. putida GPo1 was similar to acid hydrolysis and M. austroafricanum JOB5 and R. ruber DSM 7511 displayed Λ values previously only ascribed to anaerobic attack. The fractionation patterns rather correlate with the employment of different P450, AlkB, and other monooxygenases, likely catalyzing ether hydroxylation via different transition states. Our data questions the value of 2D-CSIA for a simple distinguishing of oxygenate biotransformation mechanisms, therefore caution and complementary tools are needed for proper interpretation of groundwater plumes at field sites.

A field investigation on transport of carbon-supported nanoscale zero-valent iron (nZVI) in groundwater.

The application of nanoscale zero-valent iron (nZVI) for subsurface remediation of groundwater contaminants is a promising new technology, which can be understood as alternative to the permeable reactive barrier technique using granular iron. Dechlorination of organic contaminants by zero-valent iron seems promising. Currently, one limitation to widespread deployment is the fast agglomeration and sedimentation of nZVI in colloidal suspensions, even more so when in soils and sediments, which limits the applicability for the treatment of sources and plumes of contamination. Colloid-supported nZVI shows promising characteristics to overcome these limitations. Mobility of Carbo-Iron Colloids (CIC) - a newly developed composite material based on finely ground activated carbon as a carrier for nZVI - was tested in a field application: In this study, a horizontal dipole flow field was established between two wells separated by 5.3m in a confined, natural aquifer. The injection/extraction rate was 500L/h. Approximately 1.2kg of CIC was suspended with the polyanionic stabilizer carboxymethyl cellulose. The suspension was introduced into the aquifer at the injection well. Breakthrough of CIC was observed visually and based on total particle and iron concentrations detected in samples from the extraction well. Filtration of water samples revealed a particle breakthrough of about 12% of the amount introduced. This demonstrates high mobility of CIC particles and we suggest that nZVI carried on CIC can be used for contaminant plume remediation by in-situ formation of reactive barriers.

Kinetics of desorption of organic compounds from dissolved organic matter.

This study presents a new experimental technique for measuring rates of desorption of organic compounds from dissolved organic matter (DOM) such as humic substances. The method is based on a fast solid-phase extraction of the freely dissolved fraction of a solute when the solution is flushed through a polymer-coated capillary. The extraction interferes with the solute-DOM sorption equilibrium and drives the desorption process. Solutes which remain sorbed to DOM pass through the extraction capillary and can be analyzed afterward. This technique allows a time resolution for the desorption kinetics from subseconds up to minutes. It is applicable to the study of interaction kinetics between a wide variety of hydrophobic solutes and polyelectrolytes. Due to its simplicity it is accessible for many environmental laboratories. The time-resolved in-tube solid-phase microextraction (TR-IT-SPME) was applied to two humic acids and a surfactant as sorbents together with pyrene, phenanthrene and 1,2-dimethylcyclohexane as solutes. The results give evidence for a two-phase desorption kinetics: a fast desorption step with a half-life of less than 1 s and a slow desorption step with a half-life of more than 1 min. For aliphatic solutes, the fast-desorbing fraction largely dominates, whereas for polycyclic aromatic hydrocarbons such as pyrene, the slowly desorbing, stronger-bound fraction is also important.

Accelerated Catalytic Fenton Reaction with Traces of Iron: An Fe–Pd-Multicatalysis Approach

An accelerated catalytic Fenton (ACF) reaction was developed based upon a multicatalysis approach, facilitating efficient contaminant oxidation at trace levels of dissolved iron. Beside the Fe(II)/H2O2 catalyst/oxidant pair for production of OH-radicals, the ACF system contains Pd/H2 as catalyst/reductant pair for fast reduction of Fe(III) back to Fe(II) which accelerates the Fenton cycle and leads to faster contaminant degradation. By this means, the concentration of the dissolved iron catalyst can be reduced to trace levels (1 mg L(-1)) below common discharge limits, thus eliminating the need for iron sludge removal, which is one of the major drawbacks of conventional Fenton processes. ACF provides fast degradation of the model contaminant methyl tert-butyl ether (MTBE, C0 = 0.17 mM) with a half-life of 11 min with 1 mg L(-1) dissolved iron, 500 mg L(-1) H2O2, 5 mg L(-1) Pd (as suspended Pd/Al2O3 catalyst) and 0.1 MPa H2, pH 3. The effects of pH, H2 partial pressure and H2O2 concentration on MTBE degradation rates were studied. Results on kinetic deuterium isotope effect and quenching studies are in conformity with OH-radicals as main oxidant. The heterogeneous Pd/Al2O3 catalyst was reused within six cycles without significant loss in activity.

Fe-Zeolites as Catalysts for Wet Peroxide Oxidation of Organic Groundwater Contaminants: Mechanistic Studies and Applicability Tests

Two types of iron-containing zeolites, Fe-ZSM5 and Fe-Beta, were tested as catalysts for wet peroxide oxidation of organic groundwater contaminants such as trichloroethene (TCE) and methyl tert-butyl ether (MTBE) at nearly neutral pH. Adsorption of TCE is more favorable on the ZSM5 zeolite whereas MTBE is effectively adsorbed on Beta zeolite. Batch experiments showed that the efficiency of utilization of H2O2 for contaminant degradation is more favorable for the catalyst with the higher adsorptive enrichment of the respective contaminant. Laboratory-scale column experiments, including the use of contaminated groundwater, were conducted in order to test the stability of the Fe-zeolites under flow-through conditions.

Water solubility enhancement of pyrene in the presence of humic substances, by S. Tanaka et al.: comments

Abstract The ability of the anionic surfactant sodium dodecylbenzene sulfonate to significantly enhance the solubility of pyrene in aqueous solution when added at a concentration below the cmc was not confirmed. Possible reasons for the discrepancy are revealed.

Colloidal activated carbon for in-situ groundwater remediation — Transport characteristics and adsorption of organic compounds in water-saturated sediment columns

Colloidal activated carbon can be considered as a versatile adsorbent and carrier material for in-situ groundwater remediation. In analogy to other nanoremediation approaches, activated carbon colloids (ACC) can be injected into the subsurface as aqueous suspensions. Deposition of ACC on the sediment creates a sorption barrier against further spreading of hydrophobic pollutants. This study deals with the optimization of ACC and their suspensions with a focus on suspension stability, ACC mobility in saturated porous media and sorption efficiency towards organic contaminants. ACC with an appropriate particle size range (d50=0.8μm) were obtained from a commercial powdered activated carbon product by means of wet-grinding. Among the various methods tested for stabilization of ACC suspensions, addition of humic acid (HA) and carboxymethyl cellulose (CMC) showed the best results. Due to electrosteric stabilization by adsorption of CMC, suspensions remained stable even at high ACC concentrations (11gL(-1)) and conditions typical of very hard water (5mM divalent cations). Furthermore, CMC-stabilized ACC showed high mobility in a water-saturated sandy sediment column (filter coefficient λ=0.2m(-1)). Such mobility is a pre-requisite for in-situ installation of sorption or reaction barriers by simple injection-well or direct-push application of ACC suspensions. Column experiments with organic model compounds proved the efficacy of ACC deposits on sediment for contaminant adsorption and retardation under flow-through conditions.