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Hunkeler, Daniel
Nom
Hunkeler, Daniel
Affiliation principale
Fonction
Professeur.e ordinaire
Email
daniel.hunkeler@unine.ch
Identifiants
Résultat de la recherche
Voici les éléments 1 - 10 sur 14
- PublicationAccès libreInfluence of surface water – groundwater interactions on the spatial distribution of pesticide metabolites in groundwater(2020-4)
; ; In groundwater, pesticidemetabolites tend to occurmore frequently and at higher concentrations than their parent pesticides, due to their highermobility and persistence. These properties might also favor their transfer across surface water – groundwater interfaces. However, the effect of surface water – groundwater interactions on the metabolite occurrence in groundwater and pumpingwells has so far received little attention.Weinvestigated the spatial distribution of metabolites in an unconsolidated aquifer, which interacts with two surface water bodies originating from catchments with contrasting land use. We focused onmetabolites of the herbicide chloridazon, namely desphenyl-chloridazon (DPC) and methyl-desphenyl-chloridazon (MDPC) and characterized surface water – groundwater interactions with various environmental tracers (e.g. electrical conductivity, stable water isotopes,wastewater tracers). In zones influenced by a river fromamountainous area,metabolite concentrations were low(median values ≤0.50 μg L−1 for DPC, ≤0.19 μg L−1 forMDPC). In contrast, high concentrations occurred in areas dominated by recharge fromagricultural fields and/or influenced by a streamfroman adjacent intensely farmed catchment (median values up to 1.9 μg L−1 for DPC and up to 0.75 μg L−1 forMDPC). An endmember analysis using hydro-chemical data suggested that about 20% of the DPC mass in a pumping well originated from the neighboring catchment and on its own would cause a concentration above 0.1 μg L−1 for DPC. Our findings highlight that the mobile metabolites can be imported from zones with intense agriculture outside of the exploited aquifer via surface-water groundwater interactions influencing the metabolite concentration level and longterm dynamics in the aquifer. - PublicationAccès libreInfiltration under snow cover: Modeling approaches and predictive uncertainty(2017)
; ;Moeck, Christian; Groundwater recharge from snowmelt represents a temporal redistribution of precipitation. This is extremely important because the rate and timing of snowpack drainage has substantial consequences to aquifer recharge patterns, which in turn affect groundwater availability throughout the rest of the year. The modeling methods developed to estimate drainage from a snowpack, which typically rely on temporallydense point-measurements or temporally-limited spatially-dispersed calibration data, range in complexity from the simple degree-day method to more complex and physically-based energy balance approaches. While the gamut of snowmelt models are routinely used to aid in water resource management, a comparison of snowmelt models’ predictive uncertainties had previously not been done. Therefore, we established a snowmelt model calibration dataset that is both temporally dense and represents the integrated snowmelt infiltration signal for the Vers Chez le Brandt research catchment, which functions as a rather unique natural lysimeter. We then evaluated the uncertainty associated with the degree-day, a modified degree-day and energy balance snowmelt model predictions using the nullspace Monte Carlo approach. All three melt models underestimate total snowpack drainage, underestimate the rate of early and midwinter drainage and overestimate spring snowmelt rates. The actual rate of snowpack water loss is more constant over the course of the entire winter season than the snowmelt models would imply, indicating that mid-winter melt can contribute as significantly as springtime snowmelt to groundwater recharge in low alpine settings. Further, actual groundwater recharge could be between 2 and 31% greater than snowmelt models suggest, over the total winter season. This study shows that snowmelt model predictions can have considerable uncertainty, which may be reduced by the inclusion of more data that allows for the use of more complex approaches such as the energy balance method. Further, our study demonstrated that an uncertainty analysis of model predictions is easily accomplished due to the low computational demand of the models and efficient calibration software and is absolutely worth the additional investment. Lastly, development of a systematic instrumentation that evaluates the distributed, temporal evolution of snowpack drainage is vital for optimal understanding and management of cold-climate hydrologic systems. - PublicationAccès libreInfiltration under snow cover: Modeling approaches and predictive uncertainty(2016-12)
; ; ; Groundwater recharge from snowmelt represents a temporal redistribution of precipitation. This is extremely important because the rate and timing of snowpack drainage has substantial consequences to aquifer recharge patterns, which in turn affect groundwater availability throughout the rest of the year. The modeling methods developed to estimate drainage from a snowpack, which typically rely on temporally-dense point-measurements or temporally-limited spatially-dispersed calibration data, range in complexity from the simple degree-day method to more complex and physically-based energy balance approaches. While the gamut of snowmelt models are routinely used to aid in water resource management, a comparison of snowmelt models’ predictive uncertainties had previously not been done. Therefore, we established a snowmelt model calibration dataset that is both temporally dense and represents the integrated snowmelt infiltration signal for the Vers Chez le Brandt research catchment, which functions as a rather unique natural lysimeter. We then evaluated the uncertainty associated with the degree-day, a modified degree-day and energy balance snowmelt model predictions using the null-space Monte Carlo approach. All three melt models underestimate total snowpack drainage, underestimate the rate of early and midwinter drainage and overestimate spring snowmelt rates. The actual rate of snowpack water loss is more constant over the course of the entire winter season than the snowmelt models would imply, indicating that mid-winter melt can contribute as significantly as springtime snowmelt to groundwater recharge in low alpine settings. Further, actual groundwater recharge could be between 2 and 31% greater than snowmelt models suggest, over the total winter season. This study shows that snowmelt model predictions can have considerable uncertainty, which may be reduced by the inclusion of more data that allows for the use of more complex approaches such as the energy balance method. Further, our study demonstrated that an uncertainty analysis of model predictions is easily accomplished due to the low computational demand of the models and efficient calibration software and is absolutely worth the additional investment. Lastly, development of a systematic instrumentation that evaluates the distributed, temporal evolution of snowpack drainage is vital for optimal understanding and management of cold-climate hydrologic systems. - PublicationAccès libreStable carbon isotope analysis to distinguish biotic and abiotic degradation of 1,1,1-trichloroethane in groundwater sediments(2014)
;Broholm, M.M; ;Tuxen, N ;Jeannottat, SScheutz, CThe fate and treatability of 1,1,1-TCA by natural and enhanced reductive dechlorination was studied in laboratory microcosms. The study shows that compound-specific isotope analysis (CSIA) identified an alternative 1,1,1-TCA degradation pathway that cannot be explained by assuming biotic reductive dechlorination. In all biotic microcosms 1,1,1-TCA was degraded with no apparent increase in the biotic degradation product 1,1-DCA. 1,1,1-TCA degradation was documented by a clear enrichment in 13C in all biotic microcosms, but not in the abiotic control, which suggests biotic or biotically mediated degradation. Biotic degradation by reductive dechlorination of 1,1-DCA to CA only occurred in bioaugmented microcosms and in donor stimulated microcosms with low initial 1,1,1-TCA or after significant decrease in 1,1,1-TCA concentration (after ˜day 200). Hence, the primary degradation pathway for 1,1,1-TCA does not appear to be reductive dechlorination via 1,1-DCA. In the biotic microcosms, the degradation of 1,1,1-TCA occurred under iron and sulfate reducing conditions. Biotic reduction of iron and sulfate likely resulted in formation of FeS, which can abiotically degrade 1,1,1-TCA. Hence, abiotic degradation of 1,1,1-TCA mediated by biotic FeS formation constitute an explanation for the observed 1,1,1-TCA degradation. This is supported by a high 1,1,1-TCA 13C enrichment factor consistent with abiotic degradation in biotic microcosms. 1,1-DCA carbon isotope field data suggest that this abiotic degradation of 1,1,1-TCA is a relevant process also at the field site. - PublicationAccès libreAssessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon–chlorine isotope analysis and quantitative PCR(Elsevier, 2011)
; ;Abe, Y. ;Broholm, M.M. ;Jeannotat, S ;Westgaard, C ;Jacobsen, C.S ;Aravena, RBjerg, P.LThe fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (qPCR) methods targeting Dehaloccocides sp. and vcrA genes. Redox conditions were characterized as well based on concentrations of dissolved redox sensitive compounds and sulfur isotopes in SO24 ¯.
In the first 400 m downgradient of the source, the plume was confined to the upper 20m of the aquifer. Further downgradient it widened in vertical direction due to diverging groundwater flow reaching a depth of up to 50 m. As the plume dipped downward and moved away from the source, O2 and NO¯3 decreased to below detection levels, while dissolved Fe2+ and SO24¯ increased above detectable concentrations, likely due to pyrite oxidation as confirmed by the depleted sulfur isotope signature of SO24¯. In the same zone, PCE and trichloroethene (TCE) disappeared and cis-1,2-dichloroethene (cDCE) became the dominant chlorinated ethene. PCE and TCE were likely transformed by reductive dechlorination rather than abiotic reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of 13C in the daughter products followed by an enrichment of 13C as degradation proceeded. At 1000 m downgradient of the source, cDCE was the dominant chlorinated ethene and had reached the source δ13C value confirming that cDCE was not affected by abiotic or biotic degradation.
Further downgradient (up to 1900 m), cDCE became enriched in 13C by up to 8‰ demonstrating its further transformation while vinylchloride (VC) concentrations remained low (<1 µg/L) and ethene was not observed. The correlated shift of carbon and chlorine isotope ratios of cDCE by 8 and 3.9‰, respectively, the detection of Dehaloccocides sp genes, and strongly reducing conditions in this zone provide strong evidence for reductive dechlorination of cDCE. The significant enrichment of 13C in VC indicates that VC was transformed further, although the mechanism could not be determined. The transformation of cDCE was the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon–chlorine isotope analysis and qPCR combined with traditional approaches can be used to gain detailed insight into the processes that control the fate of chlorinated ethenes in large scale plumes. - PublicationAccès libreGroundwater–surface water interaction and its role on TCE groundwater plume attenuation(2007)
;Chapman, Steven W. ;Parker, Beth L. ;Cherry, John A. ;Aravena, RamonA field investigation of a TCE plume in a surficial sand aquifer shows that groundwater–surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of μg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of μg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water–air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone. - PublicationAccès libreBacteriophage transport through a fining-upwards sedimentary sequence : laboratory experiments and simulationA column containing four concentric layers of progressively finer-grained glass beads (graded column) was used to study the transport of the bacteriophage T7 in water flowing parallel to layering through a fining-upwards (FU) sedimentary structure. By passing a pulse of T7, and a conservative solute tracer upwards through a column packed with a single bead size (uniform column), the capacity of each bead type to attenuate the bacteriophage was determined. Solute and bacteriophage responses were modelled using an analytical solution to the advection–dispersion equation, with first-order kinetic deposition simulating bacteriophage attenuation. Resulting deposition constants for different flow velocities indicated that filtration theory-determined values differed from experimentally determined values by less than 10%. In contrast, the responses of solute and bacteriophage tracers passing upwards through graded columns could not be reproduced with a single analytical solution. However, a flux-weighted summation of four one-dimensional advective–dispersive analytical terms approximated solute breakthrough curves. The prolonged tailing observed in the resulting curve resembled that typically generated from field-based tracer test data, reflecting the potential importance of textural heterogeneity in the transport of dissolved substances in groundwater. Moreover, bacteriophage deposition terms, determined from filtration theory, reproduced the T7 breakthrough curve once desorption and inactivation on grain surfaces were incorporated. To evaluate the effect of FU sequences on mass transport processes in more detail, bacteriophage passage through sequences resembling those sampled from a FU bed in a fluvioglacial gravel pit were carried out using an analogous approach to that employed in the laboratory. Both solute and bacteriophage breakthrough responses resembled those generated from field-based test data and in the graded column experiments. Comparisons with the results of simulations using averaged hydraulic conductivities show that simulations employing averaged parameters overestimate bacteriophage travel times and underestimate masses recovered and peak concentrations.
- PublicationAccès libreEffect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers(2004)
; ;Chollet, N ;Pittet, X. ;Aravena, R ;Cherry, J. A.Parker, B. L.Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26‰), which is consistent with field observations. At most sampling points, the δ13C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a 13C enrichment of up to 2.4‰ was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with 12C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the δ13C values varied substantially from −24.3‰ to −33.6‰. Comparison of the δ13C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in δ13C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network. - PublicationAccès libreGeochemical influences on H40/1 bacteriophage inactivation in glaciofluvial sands(2004)
;Flynn, Raymond; ;Guerin, Christine ;Burn, Christine ;Rossi, PierreGeochemical heterogeneities may cause spatial variations in virus inactivation rates resulting from interactions with minerals leading to differences in natural disinfection capacity within an aquifer. Column studies investigating the interaction of the bacteriophage H40/1 with natural sands sampled from the Kappelen test site (Kappelen), Bern, Switzerland indicated that inactivation rates are higher for adsorbed bacteriophages than for those suspended in groundwater. Moreover, breakthrough curves obtained from field-based tracer tests at Kappelen indicated that the adsorbed H40/1 is inactivated in-situ at comparable rates. Statistical analyses of mineralogical data failed to demonstrate significant spatial variations in aquifer composition either across the site or with depth. In contrast hydrochemical analyses of groundwater samples collected at Kappelen demonstrated that iron-reducing groundwater occurs below aerobic waters. Tracer breakthrough curves indicate that H40/1 survival is not affected by variable redox conditions. Investigation results suggest that spatial geochemical variability does not significantly affect H40/1s inactivation rate at Kappelen. - PublicationAccès libreEngineered and subsequent intrinsic in situ bioremediation of a diesel fuel contaminated aquifer(2002)
; ;Höhener, PZeyer, JA diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO24‾ and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.