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Hunkeler, Daniel

Nom
Hunkeler, Daniel
Affiliation principale
Fonction
Professeur.e ordinaire
Email
daniel.hunkeler@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/142
_
0000-0003-3525-9736

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  • Publication
    Accès libre
    Documentation of time-scales for onset of natural attenuation in an aquifer treated by a crude-oil recovery system
    (2015-4)
    Ponsin, Violaine
    ;
    Maier, Joachim
    ;
    Guelorget, Yves
    ;
    Hunkeler, Daniel 
    ;
    Bouchard, Daniel 
    ;
    Villavicencio, Hakeline
    ;
    Höhener, Patrick
    A pipeline transporting crude-oil broke in a nature reserve in 2009 and spilled 5100 m3 of oil that partly reached the aquifer and formed progressively a floating oil lens. Groundwater monitoring started immediately after the spill and crude-oil recovery by dual pump-and-skim technology was operated after oil lens formation. This study aimed at documenting the implementation of redox-specific natural attenuation processes in the saturated zone and at assessing whether dissolved compounds were degraded. Seven targeted water sampling campaigns were done during four years in addition to a routine monitoring of hydrocarbon concentrations. Liquid oil reached the aquifer within 2.5 months, and anaerobic processes, from denitrification to reduction of sulfate, were observable after 8 months. Methanogenesis appeared on site after 28 months. Stable carbon isotope analyses after 16 months showed maximum shifts in δ13C of + 4.9 ± 0.22‰ for toluene, + 2.4 ± 0.19‰ for benzene and + 0.9 ± 0.51‰ for ethylbenzene, suggesting anaerobic degradation of these compounds in the source zone. Estimations of fluxes of inorganic carbon produced by biodegradation revealed that, in average, 60% of inorganic carbon production was attributable to sulfate reduction. This percentage tended to decrease with time while the production of carbon attributable to methanogenesis was increasing. Within the investigation time frame, mass balance estimations showed that biodegradation is a more efficient process for control of dissolved concentrations compared to pumping and filtration on an activated charcoal filter.
  • Publication
    Accès libre
    Intrinsic biodegradation potential of aromatic hydrocarbons in an alluvial aquifer - Potentials and limits of signature metabolite analysis and two stable isotope-based techniques
    (2011)
    Morasch, Barbara
    ;
    Hunkeler, Daniel 
    ;
    Zopfi, Jakob 
    ;
    Temime, B
    ;
    Höhener, Patrick
    Three independent techniques were used to assess the biodegradation of monoaromatic hydrocarbons and low-molecular weight polyaromatic hydrocarbons in the alluvial aquifer at the site of a former cokery (Flémalle, Belgium).
    Firstly, a stable carbon isotope-based field method allowed quantifying biodegradation of monoaromatic compounds in situ and confirmed the degradation of naphthalene. No evidence could be deduced from stable isotope shifts for the intrinsic biodegradation of larger molecules such as methylnaphthalenes or acenaphthene. Secondly, using signature metabolite analysis, various intermediates of the anaerobic degradation of (poly-) aromatic and heterocyclic compounds were identified. The discovery of a novel metabolite of acenaphthene in groundwater samples permitted deeper insights into the anaerobic biodegradation of almost persistent environmental contaminants. A third method, microcosm incubations with 13C-labeled compounds under in situ-like conditions, complemented techniques one and two by providing quantitative information on contaminant biodegradation independent of molecule size and sorption properties. Thanks to stable isotope labels, the sensitivity of this method was much higher compared to classical microcosm studies. The 13C-microcosm approach allowed the determination of first-order rate constants for 13C-labeled benzene, naphthalene, or acenaphthene even in cases when degradation activities were only small. The plausibility of the third method was checked by comparing 13C-microcosm-derived rates to field-derived rates of the first approach. Further advantage of the use of 13C-labels in microcosms is that novel metabolites can be linked more easily to specific mother compounds even in complex systems. This was achieved using alluvial sediments where 13C-acenaphthyl methylsuccinate was identified as transformation product of the anaerobic degradation of acenaphthene.
  • Publication
    Accès libre
    Benzene dispersion and natural attenuation in an alluvial aquifer with strong interactions with surface water
    (2009)
    Batlle-Aguilar, Jordi
    ;
    Brouyère, Serge
    ;
    Dassargues, Alain
    ;
    Morasch, Barbara
    ;
    Hunkeler, Daniel 
    ;
    Höhener, Patrick
    ;
    Diels, Ludo
    ;
    Vanbroekhoven, Karolien
    ;
    Seuntjens, Piet
    ;
    Halend, Henri
    Field and laboratory investigations have been conducted at a former coke plant, in order to assess pollutant attenuation in a contaminated alluvial aquifer, discharging to an adjacent river. Various organic (BTEX, PAHs, mineral oils) and inorganic (As, Zn, Cd) compounds were found in the aquifer in concentrations exceeding regulatory values. Due to redox conditions of the aquifer, heavy metals were almost immobile, thus not posing a major risk of dispersion off-site the brownfield. Field and laboratory investigations demonstrated that benzene, among organic pollutants, presented the major worry for off-site dispersion, mainly due to its mobility and high concentration, i.e. up to 750 mg L-1 in the source zone. However, benzene could never be detected near the river which is about 160 m downgradient the main source. Redox conditions together with benzene concentrations determined in the aquifer have suggested that degradation mainly occurred within 100 m distance from the contaminant source under anoxic conditions, and most probably with sulphate as main oxidant. A numerical groundwater flow and transport model, calibrated under transient conditions, was used to simulate benzene attenuation in the alluvial aquifer towards the Meuse River. The mean benzene degradation rate used in the model was quantified in situ along the groundwater flow path using compound-specific carbon isotope analysis (CSIA). The results of the solute transport simulations confirmed that benzene concentrations decreased almost five orders of magnitude 70 m downgradient the source. Simulated concentrations have been found to be below the detection limit in the zone adjacent to the river and consistent with the absence of benzene in downgradient piezometers located close to the river reported in groundwater sampling campaigns. In a transient model scenario including groundwater–surface water dynamics, benzene concentrations were observed to be inversely correlated to the river water levels, leading to the hypothesis that benzene dispersion is mainly controlled by natural attenuation.
  • Publication
    Accès libre
    Carbon Isotope Fractionation during Diffusion and Biodegradation of Petroleum Hydrocarbons in the Unsaturated Zone: Field Experiment at Værløse Airbase, Denmark, and Modeling
    (2008)
    Bouchard, Daniel 
    ;
    Hunkeler, Daniel 
    ;
    Gaganis, Petros
    ;
    Aravena, Ramon
    ;
    Höhener, Patrick
    ;
    Broholm, Mette M.
    A field experiment was conducted in Denmark in order to evaluate the fate of 13 volatile organic compounds (VOCs) that were buried as an artificial fuel source in the unsaturated zone. Compound-specific isotope analysis showed distinct phases in the 13C/12C ratio evolution in VOC vapors within 3 m from the source over 114 days. At day 3 and to a lesser extent at day 6, the compounds were depleted in 13C by up to −5.7‰ with increasing distance from the source compared to the initial source values. This trend can be explained by faster outward diffusion of the molecules with 12C only compared to molecules with a 13C. Then, the isotope profile leveled out, and several compounds started to become enriched in 13C by up to 9.5‰ with increasing distance from the source, due to preferential removal of the molecules with 12C only, through biodegradation. Finally, as the amount of a compound diminished in the source, a 13C enrichment was also observed close to the source. The magnitude of isotope fractionation tended to be larger the smaller the mass of the molecule was. This study demonstrates that, in the unsaturated zone, carbon isotope ratios of hydrocarbons are affected by gas-phase diffusion in addition to biodegradation, which was confirmed using a numerical model. Gas-phase diffusion led to shifts in δ13C >1‰ during the initial days after the spill, and again during the final stages of source volatilization after >75% of a compound had been removed. In between, diffusion has less of an effect, and thus isotope data can be used as an indicator for hydrocarbon biodegradation.
  • Publication
    Accès libre
    Carbon Isotope Fractionation During Volatilization of Petroleum Hydrocarbons and Diffusion Across a Porous Medium: A Column Experiment
    (2008)
    Bouchard, Daniel 
    ;
    Höhener, Patrick
    ;
    Hunkeler, Daniel 
    The study focuses on the effect of volatilization, diffusion, and biodegradation on the isotope evolution of volatile organic compounds (VOCs) in a 1.06 m long column filled with alluvial sand. A liquid mixture of 10 VOCs was placed at one end of the column, and measurements of VOC vapor concentrations and compound-specific isotope ratios (δ13C) were performed at the source and along the column. Initially, the compounds became depleted in 13C by up to −4.8‰ along the column axis, until at 26 h, uniform isotope profiles were observed for most compounds, which is expected for steady-state diffusion. Subsequently, several compounds (n-pentane, benzene, n-hexane) became enriched in 13C throughout the column. For the same compounds, a significant decrease in the source vapor concentration and a gradual enrichment of 13C by up to 5.3‰ at the source over a period of 336 h was observed. This trend can be explained by a larger diffusive mass flux for molecules with light isotopes compared to those with a heavy isotope, which leads to a depletion of light isotopes in the source. The isotope evolution of the source followed closely a Rayleigh trend and the obtained isotope enrichment factor corresponded well to the ratio between the diffusion coefficients for heavy and light molecules as expected based on theory. In contrast to diffusion, biodegradation had generally only a small effect on the isotope profiles, which is expected because in a diffusion-controlled system the isotope shift per decrease of mass flux is smaller than in an advection-controlled system. These findings open interesting perspectives for monitoring source depletion with isotope and have implications for assessing biodegradation and source variability in the unsaturated zone based on isotopes.
  • Publication
    Métadonnées seulement
    Evidence for in situ degradation of mono-and polyaromatic hydrocarbons in alluvial sediments based on microcosm experiments with 13C-labeled contaminants
    (2007-4-29)
    Morasch, Barbara
    ;
    Höhener, Patrick
    ;
    Hunkeler, Daniel 
    A microcosm study was conducted to investigate the degradation of mono- and polyaromatic hydrocarbons under in situ-like conditions using alluvial sediments from the site of a former cokery. Benzene, naphthalene, or acenaphthene were added to the sediments as C-13-labeled substrates. Based on the evolution of C-13-CO2 determined by gas chromatography isotope-ratio mass spectrometry (GC-IRMS) it was possible to prove mineralization of the compound of interest in the presence of other unknown organic substances of the sediment material. This new approach was suitable to give evidence for the intrinsic biodegradation of benzene, naphthalene, and acenaphthene under oxic and also under anoxic conditions, due to the high sensitivity and reproducibility of C-13/C-12 stable isotope analysis. This semi-quantitative method can be used to screen for biodegradation of any slowly degrading, strongly sorbing compound in long-term experiments. (c) 2007 Elsevier Ltd. All rights reserved.
  • Publication
    Métadonnées seulement
    One method may not be enough: evaluation of intrinsic contaminant degradation
    (Venice: INCA, 2005)
    Morasch, Barbara
    ;
    Höhener, Patrick
    ;
    Hunkeler, Daniel 
    ;
    Canepa, P.
    ;
    Fava, F.