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    Topics 2017 Isotope Lab

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    Topics 2017 Isotope Lab

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    Topics 2017 Isotope Lab

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    © All Rights Reserved
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    of 2

    Master Thesis Topics in Environmental Chemistry

    Major in Biogeochemistry and Pollutant Dynamics, ETH Zürich

    Supervised by PD Dr. Thomas B. Hofstetter


    Eawag, Department of Environmental Chemistry
    [email protected]

    Topic 1: Assessing the biodegrada- in Scheme 1 for lindane (γ-HCH). The ini-
    tion of hexachlorocyclohexane iso- tial steps of for aerobic transformation
    mers in contaminated soil is the HCl-elimination (β-elimination) and
    LinA stands for a dehydrochlorinase en-
    Hexachlorocyclohexanes (HCH), such as zyme.
    the insecticidal γ-HCH isomer, belong to Students will learn (1) how to purify
    the class of largely banned persistent or- and work with LinA and LinB enzymes
    ganic pollutants (POP). Because HCHs that are capable of transforming HCH iso-
    only degrade over time-scales of decades mers into less chlorinated compounds as
    and more, they are still found to contam- well as (2) how to carry out compound-
    inate soils at former production sites. 1 specific stable isotope analysis of H and
    Cl Cl C using gas chromatographs coupled to
    H H isotope ratio mass spectrometers.
    H H
    Cl Cl
    Cl Cl Collaboration with Eawag Dept of Environmental
    H H Microbiology, Dr. Hans-Peter Kohler
    γ-HCH

    LinA
    Cl Topic 2: Tracking the degradation
    H
    H Cl Cl of insecticides and industrial chem-
    Cl Cl
    H LinA spont. icals in contaminated groundwaters
    H Cl Cl
    H Cl
    γ-PCCH 1,2,4-TCB
    In collaboration with environmental con-
    sultants and the chemical industry, we
    Figure 1 Initial steps of lindane (γ-HCH) bio- evaluate efforts to mitigate the pollution
    transformation to a pentachloro-cyclohexene iso- of groundwaters with organic chemicals.
    mer (γ-PCCH). LinA catalyzes further dehy-
    NH 2
    drochlorination, which can lead to the formation N
    CH3
    of equally problematic trichlorobenzene (TCB).
    N ?
    In our research, we develop new ap- CH3
    proaches to track biodegradation pro- ... Cl
    cesses based on the stable isotope frac-
    ...
    tionation that can be measured in the Cl
    remaining pollutant. 2 In this project, we
    aim at understanding the C and H isotope Figure 2 Unknown chemical transformation
    effects pertinent to the different enzy- routes of the insecticide chlorodimeform to
    matic dechlorination mechanisms of sev- chloromethylaniline
    eral HCH isomers. An example of the In this project, we study the abi-
    most frequent reaction pathway is shown otic transformation of an insecticide

    Master Thesis Topics 2017 | Environmental Chemistry | 1


    chlorodimeform to a toxic products such approaches to derive thermodynamic pa-
    as substituted anilines as well as the bi- rameters of such mineral phases. 4–6
    ological degradation of the latter 3 (Figure Mediated Electrochemical Reduction SWy-2 SWa-1 NAu-1 NAu-2
    e-
    2). Recent evidence from laboratory ex- 2.3% Fe 12.6% Fe 21.2% Fe 19.2% Fe

    electrode
    periments, however, suggest a reversible Fe3+

    Fe2+/FeTotal
    first reaction, which implies that the orig-
    inal insecticide may be formed (!) in the

    electrode
    environment. This study in environmen- Fe2+

    tal forensics involves the elucidation of


    e- Reducing EH Oxidizing
    reaction mechanisms with laboratory ex- Mediated Electrochemical Oxidation
    periments as well as the use of modern
    stable isotope tools to track such pro- Figure 3 Mediated electrochemical analysis offers
    cesses in contaminated groundwaters. new avenues to quantify thermodynamics proper-
    ties of redox active Fe in clay minerals. 5
    Topic 3: Bioavailability of struc- In this work, we explore whether the
    tural iron in smectites activity of iron-reducing bacteria (She-
    wanella and Geobacter species) is con-
    Iron-bearing clay minerals are important
    trolled by the thermodynamic properties
    redox buffers in the subsurface that can
    of the mineral specimen. Students will
    affect the biogeochemical cycling of ele-
    have the opportunity to combine their
    ments and the fate, transport, and tox-
    knowledge on biogeochemistry and ther-
    icity of pollutants. To assess the role
    modynamics with new experience in elec-
    that structural Fe in clay minerals plays
    trochemical analyses.
    in redox reactions in pristine and con-
    taminated environments, we have re- Collaboration with Environmental Chemistry ETH
    cently developed electrochemistry-based Zürich, Dr. Michael Sander

    Suggested reading
    (links to publications are highlighted)

    nol., vol. 46, no. 21, pp. 11844–11853, 2012


    doi:10.1021/es03043t.
    [1] R. Lal, G. Pandey, P. Sharma, K. Ku-
    mari, S. Malhotra, R. Pandey, V. Raina, [4] M. Sander, T. B. Hofstetter, and C. A.
    H. P. E. Kohler, C. Holliger, C. Jackson, Gorski, “Electrochemical analyses of redox-
    and J. G. Oakeshott, “Biochemistry of micro- active iron minerals: a review of nonmediated
    bial degradation of hexachlorocyclohexane and and mediated approaches.,” Environ. Sci. Tech-
    prospects for bioremediation,” Microbiol. Mol. nol., vol. 49, no. 10, pp. 5862–5878, 2015
    Biol. Rev., vol. 74, no. 1, pp. 58–80, 2010 doi:10.1021/acs.est.5b00006.
    doi:10.1128/Mmbr.00029-09.
    [5] C. A. Gorski, L. E. Klüpfel, A. Voegelin,
    M. Sander, and T. B. Hofstetter, “Redox
    [2] T. B. Hofstetter, J. Bolotin, S. G. Pati, properties of structural Fe in clay miner-
    M. Skarpeli-Liati, S. Spahr, and R. S. als: 3. Relationships between smectite redox
    Wijker, “Isotope effects as new prox- and structural properties.,” Environ. Sci. Tech-
    ies for organic pollutant transformation,” nol., vol. 47, no. 23, pp. 13477–13485, 2013
    CHIMIA, vol. 68, no. 11, pp. 788–792, 2014 10.1021/es403824x.
    doi:10.2533/chimia.2014.788.
    [6] C. A. Gorski, R. Edwards, M. Sander, T. B.
    [3] S. G. Pati, K. A. Shin, M. Skarpeli-Liati, Hofstetter, and S. M. Stewart, “Thermody-
    J. Bolotin, S. N. Eustis, J. C. Spain, and T. B. namic characterization of iron oxide-aqueous
    Hofstetter, “Carbon and nitrogen isotope ef- Fe2+ redox couples.,” Environ. Sci. Tech-
    fects associated with the dioxygenation of ani- nol., vol. 50, no. 16, pp. 8538–8547, 2016
    line and diphenylamine,” Environ. Sci. Tech- 10.1021/acs.est.6b02661.

    Master Thesis Topics 2017 | Environmental Chemistry | 2

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