Professional Education


  • Doctor of Science, Eidgenossische Technische Hochschule (ETH Zurich), Environmental Sciences (2019)
  • Master of Science, Eidgenossische Technische Hochschule (ETH Zurich), Environmental Sciences (2015)
  • Bachelor of Science, Eidgenossische Technische Hochschule (ETH Zurich), Environmental Sciences (2012)

Stanford Advisors


All Publications


  • Decreases in Iron Oxide Reducibility during Microbial Reductive Dissolution and Transformation of Ferrihydrite ENVIRONMENTAL SCIENCE & TECHNOLOGY Aeppli, M., Vranic, S., Kaegi, R., Kretzschmar, R., Brown, A. R., Voegelin, A., Hofstetter, T. B., Sander, M. 2019; 53 (15): 8736–46

    Abstract

    Ferrous iron formed during microbial ferric iron reduction induces phase transformations of poorly crystalline into more crystalline and thermodynamically more stable iron (oxyhydr)oxides. Yet, characterizing the resulting decreases in the reactivity of the remaining oxide ferric iron toward reduction (i.e., its reducibility) has been challenging. Here, we used the reduction of six-line ferrihydrite by Shewanella oneidensis MR-1 as a model system to demonstrate that mediated electrochemical reduction (MER) allows directly following decreases in oxide ferric iron reducibility during the transformation of ferrihydrite into goethite and magnetite which we characterized by X-ray diffraction analysis and transmission electron microscopy imaging. Ferrihydrite was fully reducible in MER at both pHMER of 5.0 and 7.5. Decreases in iron oxide reducibility associated with ferrihydrite transformation into magnetite were accessible at both pHMER because the formed magnetite was not reducible under either of these conditions. Conversely, decreases in iron oxide reducibility associated with goethite formation were apparent only at the highest tested pHMER of 7.5 and thus the thermodynamically least favorable conditions for iron oxide reductive dissolution. The unique capability to adjust the thermodynamic boundary conditions in MER to the specific reducibilities of individual iron (oxyhydr)oxides makes this electrochemical approach broadly applicable for studying changes in iron oxide reducibility in heterogeneous environmental samples such as soils and sediments.

    View details for DOI 10.1021/acs.est.9b01299

    View details for Web of Science ID 000480370600028

    View details for PubMedID 31339302

  • Electrochemical Analysis of Changes in Iron Oxide Reducibility during Abiotic Ferrihydrite Transformation into Goethite and Magnetite ENVIRONMENTAL SCIENCE & TECHNOLOGY Aeppli, M., Kaegi, R., Kretzschmar, R., Voegelin, A., Hofstetter, T. B., Sander, M. 2019; 53 (7): 3568–78

    Abstract

    Electron transfer to ferric iron in (oxyhydr-)oxides (hereafter iron oxides) is a critical step in many processes that are central to the biogeochemical cycling of elements and to pollutant dynamics. Understanding these processes requires analytical approaches that allow for characterizing the reactivity of iron oxides toward reduction under controlled thermodynamic boundary conditions. Here, we used mediated electrochemical reduction (MER) to follow changes in iron oxide reduction extents and rates during abiotic ferrous iron-induced transformation of six-line ferrihydrite. Transformation experiments (10 mM ferrihydrite-FeIII) were conducted over a range of solution conditions (pHtrans = 6.50 to 7.50 at 5 mM Fe2+ and for pHtrans = 7.00 also at 1 mM Fe2+) that resulted in the transformation of ferrihydrite into thermodynamically more stable goethite or magnetite. The changes in iron oxide mineralogy during the transformations were quantified using X-ray diffraction analysis. MER measurements on iron oxide suspension aliquots collected during the transformations were performed over a range of pHMER at constant applied reduction potential. The extents and rates of iron oxide reduction in MER decreased with decreasing reaction driving force resulting from both increasing pHMER and increasing transformation of ferrihydrite into thermodynamically more stable iron oxides. We show that the decreases in iron oxide reduction extents and rates during ferrihydrite transformations can be linked to the concurrent changes in iron oxide mineralogy.

    View details for DOI 10.1021/acs.est.8b07190

    View details for Web of Science ID 000463679600024

    View details for PubMedID 30758207

  • Mediated Electrochemical Reduction of Iron (Oxyhydr-)Oxides under Defined Thermodynamic Boundary Conditions ENVIRONMENTAL SCIENCE & TECHNOLOGY Aeppli, M., Voegelin, A., Gorski, C. A., Hofstetter, T. B., Sander, M. 2018; 52 (2): 560–70

    Abstract

    Iron (oxyhydr-)oxide reduction has been extensively studied because of its importance in pollutant redox dynamics and biogeochemical processes. Yet, experimental studies linking oxide reduction kinetics to thermodynamics remain scarce. Here, we used mediated electrochemical reduction (MER) to directly quantify the extents and rates of ferrihydrite, goethite, and hematite reduction over a range of negative reaction free energies, ΔrG, that were obtained by systematically varying pH (5.0 to 8.0), applied reduction potentials (-0.53 to -0.17 V vs SHE), and Fe2+ concentrations (up to 40 μM). Ferrihydrite reduction was complete and fast at all tested ΔrG values, consistent with its comparatively low thermodynamic stability. Reduction of the thermodynamically more stable goethite and hematite changed from complete and fast to incomplete and slow as ΔrG values became less negative. Reductions at intermediate ΔrG values showed negative linear correlations between the natural logarithm of the reduction rate constants and ΔrG. These correlations imply that thermodynamics controlled goethite and hematite reduction rates. Beyond allowing to study iron oxide reduction under defined thermodynamic conditions, MER can also be used to capture changes in iron oxide reducibility during phase transformations, as shown for Fe2+-facilitated transformation of ferrihydrite to goethite.

    View details for DOI 10.1021/acs.est.7b04411

    View details for Web of Science ID 000423012200020

    View details for PubMedID 29200267

  • Viruses at Solid Water Interfaces: A Systematic Assessment of Interactions Driving Adsorption ENVIRONMENTAL SCIENCE & TECHNOLOGY Armanious, A., Aeppli, M., Jacak, R., Refardt, D., Sigstam, T., Kohn, T., Sander, M. 2016; 50 (2): 732–43

    Abstract

    Adsorption to solid-water interfaces is a major process governing the fate of waterborne viruses in natural and engineered systems. The relative contributions of different interaction forces to adsorption and their dependence on the physicochemical properties of the viruses remain, however, only poorly understood. Herein, we systematically studied the adsorption of four bacteriophages (MS2, fr, GA, and Qβ) to five model surfaces with varying surface chemistries and to three dissolved organic matter adlayers, as a function of solution pH and ionic strength, using quartz crystal microbalance with dissipation monitoring. The viruses were selected to have similar sizes and shapes but different surface charges, polarities, and topographies, as identified by modeling the distributions of amino acids in the virus capsids. Virus-sorbent interactions were governed by long-ranged electrostatics and favorable contributions from the hydrophobic effect, and shorter-ranged van der Waals interactions were of secondary importance. Steric effects depended on the topographic irregularities on both the virus and sorbent surfaces. Differences in the adsorption characteristics of the tested viruses were successfully linked to differences in their capsid surface properties. Besides identifying the major interaction forces, this work highlights the potential of computable virus surface charge and polarity descriptors to predict virus adsorption to solid-water interfaces.

    View details for DOI 10.1021/acs.est5b04644

    View details for Web of Science ID 000368563400024

    View details for PubMedID 26636722

  • Methane dynamics in an alpine fen: a field-based study on methanogenic and methanotrophic microbial communities FEMS MICROBIOLOGY ECOLOGY Franchini, A. G., Henneberger, R., Aeppli, M., Zeyer, J. 2015; 91 (3)

    Abstract

    Wetlands are important sources of the greenhouse gas methane (CH4). We provide an in situ study of CH4 dynamics in the permanently submerged soil of a Swiss alpine fen. Physico-chemical pore water analyses were combined with structural and microbiological analyses of soil cores at high vertical resolution down to 50 cm depth. Methanotrophs and methanogens were active throughout the depth profile, and highest abundance of active methanotrophs and methanogens [6.1 × 10(5) and 1.1 × 10(7) pmoA and mcrA transcripts (g soil)(-1), respectively] was detected in the uppermost 2 cm of the soil. Active methanotrophic communities in the near-surface zone, dominated by viable mosses, varied from the communities in the deeper zones, but further changes with depth were not pronounced. Apart from a distinct active methanogenic community in the uppermost sample, a decrease of acetoclastic Methanosaetaceae with depth was observed in concomitance with decreasing root surface area. Overall, root surface area correlated with mcrA transcript abundance and CH4 pore water concentrations, which peaked (137.1 μM) at 10 to 15 cm depth. Our results suggest that stimulation of methanogenesis by root exudates of vascular plants had a stronger influence on CH4 dynamics than stimulation of CH4 oxidation by O2 input.

    View details for DOI 10.1093/femsec/fiu032

    View details for Web of Science ID 000352781700016

    View details for PubMedID 25789997

  • Dissolved Organic Matter Adsorption to Model Surfaces: Adlayer Formation, Properties, and Dynamics at the Nanoscale ENVIRONMENTAL SCIENCE & TECHNOLOGY Armanious, A., Aeppli, M., Sander, M. 2014; 48 (16): 9420–29

    Abstract

    Adlayers of dissolved organic matter (DOM) form on many surfaces in natural and engineered systems and affect a number of important processes in these systems. Yet, the nanoscalar properties and dynamics of DOM adlayers remain poorly investigated. This work provides a systematic analysis of the properties and dynamics of adlayers formed from a diverse set of eight humic and fulvic acids, used as DOM models, on surfaces of self-assembled monolayers (SAMs) of different alkylthiols covalently bound to gold supports. DOM adsorption to positively charged amine-terminated SAMs resulted in the formation of water-rich adlayers with nanometer thicknesses that were relatively rigid, irreversibly adsorbed, and collapsed upon air drying, as demonstrated by combined quartz crystal microbalance and ellipsometry measurements. DOM adlayer thicknesses varied only slightly with solution pH from 5 to 8 but increased markedly with increasing ionic strength. Contact angle measurements revealed that the DOM adlayers were relatively polar, likely due to the high water contents of the adlayers. Comparing DOM adsorption to SAM-coated sensors that systematically differed in surface charge and polarity characteristics showed that electrostatics dominated DOM-surface interactions. Laccase adsorption to DOM adlayers on amine-terminated SAMs served to demonstrate the applicability of the presented experimental approach to study the interactions of (bio)macromolecules and (nano)particles with DOM.

    View details for DOI 10.1021/es5026917

    View details for Web of Science ID 000340701800058

    View details for PubMedID 25024044