Marco C. Mangayayam

University of Copenhagen

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Dominique J. Tobler

University of Copenhagen

Knud Dideriksen

University of Copenhagen

Virginia Alonso-de-Linaje

Universidad de Salamanca

Liane G. Benning

Helmholtz Centre Potsdam - GFZ German Research Centre for Geosciences

Simon H. J. Eiby

University of Copenhagen

Jeffrey Paulo H. Perez

Universidade Federal do ABC

Laura Voigt

Technical University of Denmark

Cathrine Frandsen

Technical University of Denmark

S. L. S. Stipp

Technical University of Denmark

Case M. van Genuchten

Geological Survey of Denmark and Greenland

Cooperative Institutions

University of Copenhagen

École Polytechnique Fédérale de Lausanne

University of Lausanne

Karlsruhe Institute of Technology

Helmholtz Centre Potsdam - GFZ German Research Centre for Geosciences

Charles Humbert 8

Technical University of Denmark

Geological Survey of Denmark and Greenland

University of California, Berkeley

University of Leeds

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BoneChar Mediated Dechlorination of Trichloroethyleneby Green Rust

Figshare (2020)

Jing Ai Hui Ma Dominique J. Tobler Marco C. Mangayayam Changyong Lu

Biochars function as electron transfer mediators and thus catalyze redox transformations of environmental pollutants. A previous study has shown that bone char (BC) has high catalytic activity for reduction of chlorinated ethylenes using layered Fe(II)–Fe(III) hydroxide (green rust) as reductant. In the present study, we studied the rate of trichloroethylene (TCE) reduction by green rust in the presence of BCs obtained at pyrolysis temperatures (PTs) from 450 to 1050 °C. The reactivity increased with PT, yielding a maximum pseudo-first-order rate constant (k) of 2.0 h–1 in the presence of BC pyrolyzed at 950 °C, while no reaction was seen for BC pyrolyzed at 450 °C. TCE sorption, specific surface area, extent of graphitization, carbon content, and aromaticity of the BCs also increased with PT. The electron-accepting capacity (EAC) of BC peaked at PT of 850 °C, and EAC was linearly correlated with the sum of concentrations of quinoid, quaternary N, and pyridine-N-oxide groups measured by XPS. Moreover, no TCE reduction was seen with graphene nanoparticles and graphitized carbon black, which have high degrees of graphitization but low EAC values. Further analyses showed that TCE reduction rates are well correlated with the EAC and the C/H ratio (proxy of electrical conductivity) of the BCs, strongly indicating that both electron-accepting functional groups and electron-conducting domains are crucial for the BC catalytic reactivity. The present study delineates conditions for designing redox-reactive biochars to be used for remediation of sites contaminated with chlorinated solvents.

Reactivity

10.1021/acs.est.9b07069.s001

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Order and Disorder in Layered Double Hydroxides: Lessons Learned from the Green Rust Sulphate - Nikischerite Series.

Knud Dideriksen Laura Voigt Marco C. Mangayayam Simon H. J. Eiby Case M. van Genuchten

Layered double hydroxides (LDHs) occur naturally and are synthesised for catalysis, drugdelivery and contaminant remediation. They consist of Me(II)-Me(III) hydroxide sheetsseparated by hydrated interlayers and weakly held anions. Often, LDHs are nanocrystalline andsheet stacking and Me(II)-Me(III) arrangement can be disordered, which influence reactivity andcomplicate structural characterisation. We have used pair distribution function (PDF) analysis, toprovide detailed information about local and medium range order (< 9 nm), to determine thestructure of synthetic Fe(II)-Fe(III)/Al(III) LDH. The data are consistent with ordered Me(II)and Me(III) in hydroxide sheets, where structural coherence along the c axis decreases with increasing Al content. The PDF for Fe(II)-Al(III) LDH (nikischerite) is best matched by apattern for a single metal hydroxide sheet. Parallel to decreased structural coherence betweenlayers, coherence within layers decreased to ~6 nm for synthetic nikischerite. Thus, disorderdeveloped within and between the sheets, resulting in mosaic crystals with coherent scatteringdomains decreasing in all directions. The high density of grain boundary terminations wouldaffect reactivity. Based on classical nucleation theory and the Kossel crystal growth model, wepropose that loss of structural coherence stems from increased supersaturation and the presenceof Al-hydroxides during formation of the Al-rich LDH

Layered double hydroxides

10.26434/chemrxiv.11925507.v1

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Effects of common groundwater ions on the transformation and reactivity of sulfidized nanoscale zerovalent iron

Chemosphere (2020)

Marco C. Mangayayam Virginia Alonso-de-Linaje Knud Dideriksen Dominique J. Tobler

Sulfidized nanoscale zerovalent iron (S-nZVI) is an Fe-based reactant widely studied for its potential use for groundwater remediation. S-nZVI reactivity has been widely investigated testing various contaminants in various water matrices, but studies on S-nZVI corrosion behaviour and reactivity upon exposure to complex groundwater chemistries are limited. Here, we show that anoxic aging of S-nZVI for 7 days in the absence and presence of key groundwater solutes (i.e., Cl−, SO42−, Mg2+, Ca2+, HCO3−, CO32−, NO3−, or HPO42−) impacts Fe0 corrosion extent, corrosion product and reduction rates with trichloroethene (TCE). White rust was the dominant corrosion product in ultrapure water and in SO42−, Cl−, Mg2+ or Ca2+ solutions; green rust and/or chukanovite formed in HCO3− and CO32− solutions; magnetite, formed in NO3− solutions and vivianite in HPO42− solutions. The aged S-nZVI materials expectedly showed lower reactivities with TCE compared to unaged S-nZVI, with reaction rates mainly controlled by ion concentration, Fe0 corrosion extent, type(s) of corrosion product, and solution pH. Comparison of these results to observations in two types of groundwaters, one from a carbonate-rich aquifer and one from a marine intruded aquifer, showed that S-nZVI corrosion products are likely controlled by the dominant GW solutes, while reactivity with TCE is generally lower than expected, due to the multitude of ion effects. Overall, these results highlight that S-nZVI corrosion behaviour in GW can be manifold, with varied impact on its reactivity. Thus, testing of S-nZVI stability and reactivity under expected field conditions is key to understand its longevity in remediation applications.

Zerovalent iron

Reactivity

Carbonate Ion

Groundwater Remediation

Mackinawite

10.1016/j.chemosphere.2020.126137

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Citations (38)

Bone Char Mediated Dechlorination of Trichloroethylene by Green Rust

Environmental Science & Technology (2020)

Jing Ai Hui Ma Dominique J. Tobler Marco C. Mangayayam Changyong Lu

Reactivity

10.1021/acs.est.9b07069

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Citations (61)

FeOx magnetization enhancing E. coli inactivation by orders of magnitude on Ag-TiO2 nanotubes under sunlight

Applied Catalysis B Environment and Energy (2016)

Marco C. Mangayayam J. Kiwi Stefanos Giannakis C. Pulgarín Ivica Z̆ivković

10.1016/j.apcatb.2016.09.064

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Citations (63)

Effects of metal cation substitution on hexavalent chromium reduction by green rust

Geochemical Transactions (2020)

Andrew N. Thomas Elisabeth Eiche Jörg Göttlicher Ralph Steininger Liane G. Benning

Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust's layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42-) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic δ-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by δ-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.

Hexavalent Chromium

Rust (programming language)

Substitution (logic)

10.1186/s12932-020-00066-8

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Citations (16)

The Structure of Sulfidized Zero-Valent Iron by One-Pot Synthesis: Impact on Contaminant Selectivity and Long-Term Performance

Environmental Science & Technology (2019)

Marco C. Mangayayam Knud Dideriksen Marcel Ceccato Dominique J. Tobler

Sulfidized zerovalent iron (sZVI) is widely studied because of its remarkable reactivity with a number of groundwater contaminants. Nonetheless, its nanoscale structure is not well understood. As such, there is an uncertainty on how sZVI structure controls its reactivity and fate in the subsurface environment. Using pair distribution function analyses, we show that sZVI made from one-pot synthesis using dithionite as sulfur precursor consists of an Fe0 core with a shell composed dominantly of short-range ordered Fe(OH)2 and FeS having coherent scattering domains of less than 8 Å. Reactivity experiments show that increasing shell material significantly decreases rate for cis-dichloroethene (cis-DCE) reduction, whereas the opposite is observed for trichloroethene (TCE). The results are consistent with a conceptual model wherein cis-DCE reduction requires active Fe0 sites, which become largely inaccessible when shell material is abundant. Conversely, an increase in FeS shell volume led to faster TCE reduction via direct electron transfer. Aging experiments showed that sZVI retained >50% of its TCE removal efficiency after 30-day exposure to artificial groundwaters. The decline in sZVI reactivity due to long-term exposure to groundwater, is attributed to Fe0 oxidation from water reduction coupled by reorganization and recrystallization of the poorly ordered shell material, which in turn reduced access to reactive FeS sites.

Zerovalent iron

Reactivity

Permeable reactive barrier

10.1021/acs.est.8b06480

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Citations (117)

Intercalation of aromatic sulfonates in ‘green rust’ via ion exchange

Energy Procedia (2018)

Jeffrey Paulo H. Perez Marco C. Mangayayam Sandra Navaz Rubio Helen M. Freeman Dominique J. Tobler

'Green rust' intercalated with aromatic sulfonates can potentially be effective materials for the treatment of soil and groundwater polluted with chlorinated benzenes. We investigated the potential intercalation of benzene sulfonate (BzS) and 1,3-benzene disulfonate (BzDS) into green rust sulfate (GRSO4) via ion exchange. The GRSO4 reacted with various concentrations of sulfonates were characterized by X-ray diffraction, X-ray scattering and transmission electron microscopy. GR interacted with BzDS did not result in intercalation due to stearic hindrance and electrostatic repulsion. For BzS, mixtures of GRSO4 and GR-BzS (d001 = 14.3 Å) were obtained at molar equivalents of ion exchange capacity >5. The intercalation of BzS in the GR structure is limited (~18% intercalation) since BzS cannot fully replace SO42-. The BzS molecules are likely arranged in the interlayer as a dehydrated monolayer with the –SO3 groups facing away in alternate directions.

Birnessite

10.1016/j.egypro.2018.07.023

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Hematite Crystallization in the Presence of Organic Matter: Impact on Crystal Properties and Bacterial Dissolution

ACS Earth and Space Chemistry (2019)

Svend H. C. Weihe Marco C. Mangayayam Karina K. Sand Dominique J. Tobler

Microbial dissimilatory iron reduction (DIR) is a widespread process in oxygen-poor sediments and waters, where it regulates Fe and C cycling and contributes to nutrient and trace metal distribution. This process is fairly well-studied in terms of iron substrate, microbial DIR strain, and water chemistry. However, far less is known about DIR rates and yields of iron substrates that are tightly associated with organic matter, even though most iron substrates that form in nature are partially or completely covered by organic matter. Here, we assessed the impact of alginate on hematite crystallization and subsequently assessed the stability of thus formed alginate–hematite precipitates in DIR experiments with Shewanella oneidensis MR-1. We found that during hematite synthesis via forced hydrolysis, the presence of alginate reduces hematite crystal and particle sizes and induces the formation of closely associated alginate–hematite composites. This is explained by alginate molecules acting as nucleation sites. Upon exposure of these composites to S. oneidensis MR-1, a ∼30–50% decrease (dependent upon the alginate content of composites) in the initial hematite reduction rate is observed in comparison to alginate-free, pure hematite. However, while DIR rates ceased after 48 h in the pure hematite system, reduction steadily progressed in the presence of the alginate–hematite composites, overall leading to a slightly higher DIR yield after 8 days. These trends are explained by alginate physically hindering direct contact between bacterial cells and hematite surfaces, thus lowering initial DIR rates. In turn, this lower rate potentially reduces quick passivation of cell and/or mineral surfaces by Fe(II) adsorption and/or surface precipitates as observed in the pure hematite system, thus enabling prolonged DIR reaction in the presence of alginate. Overall, this study highlights that a common natural organic molecule, such as alginate, can largely impact hematite formation in natural settings, leading to composites that show very different stabilities toward DIR compared to pure hematite. These are important considerations for predicting DIR processes and any associated element cycles in natural settings as well as for potential use of DIR for biotechnical applications.

Shewanella oneidensis

Crystal (programming language)

10.1021/acsearthspacechem.8b00166

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Citations (18)

Order and Disorder in Layered Double Hydroxides: Lessons Learned from the Green Rust Sulphate - Nikischerite Series.

Knud Dideriksen Laura Voigt Marco C. Mangayayam Simon H. J. Eiby Case M. van Genuchten

<div>Layered double hydroxides (LDHs) occur naturally and are synthesised for catalysis, drug</div><div>delivery and contaminant remediation. They consist of Me(II)-Me(III) hydroxide sheets</div><div>separated by hydrated interlayers and weakly held anions. Often, LDHs are nanocrystalline and</div><div>sheet stacking and Me(II)-Me(III) arrangement can be disordered, which influence reactivity and</div><div>complicate structural characterisation. We have used pair distribution function (PDF) analysis, to</div><div>provide detailed information about local and medium range order (< 9 nm), to determine the</div><div>structure of synthetic Fe(II)-Fe(III)/Al(III) LDH. The data are consistent with ordered Me(II)</div><div>and Me(III) in hydroxide sheets, where structural coherence along the c axis decreases with </div><div>increasing Al content. The PDF for Fe(II)-Al(III) LDH (nikischerite) is best matched by a</div><div>pattern for a single metal hydroxide sheet. Parallel to decreased structural coherence between</div><div>layers, coherence within layers decreased to ~6 nm for synthetic nikischerite. Thus, disorder</div><div>developed within and between the sheets, resulting in mosaic crystals with coherent scattering</div><div>domains decreasing in all directions. The high density of grain boundary terminations would</div><div>affect reactivity. Based on classical nucleation theory and the Kossel crystal growth model, we</div><div>propose that loss of structural coherence stems from increased supersaturation and the presence</div><div>of Al-hydroxides during formation of the Al-rich LDH</div>

Nanocrystalline material

10.26434/chemrxiv.11925507

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