Manganese biomineral formation in a Superfund treatment system: Implications for environmental remediation

Transcription

1 Manganese biomineral formation in a Superfund treatment system: Implications for environmental remediation Columbia University Superfund Research Program Sp ng 2017 Seminar/Webinar Series Owen W. Duckworth March 20, 2017

2 Mac Jones Reina Diaz Edwin Mitchell Benjamin Uster Megan Andrews Nelson Rivera Leslie Sombers Matt Polizzotto Christian Heath Cara Santelli

3 How do organism interact with the inorganic world? Metals, Microbes, Minerals, Plants Microbes Rhizosphere communication Enzyme function Community composition Nutrient uptake Acid and chelate exudation Soil Solution Soluble ions and complexes Plants Root hormones Acid and chelate exudation Nutrient uptake Organic matter Binding Mineralization Structure Aggregation Minerals New phases Solid solution/isomorphous substitution Surface reactivity Our current major projects focus on biomineralization and bioweathering

4 Solving Problems through Elucidating Fundamental Processes Chemical Structure Spectroscopy (X-ray and infrared), scattering, computational chemistry, microscopy (SEM, TEM, AFM, XRF) Biological Structure Traditional microbiology, mole ular biology, genomic/metageno ic approaches, enzyme assays Gallionella capsiferriformans 98 Gallionella ferruginea OTU Siderooxydans lithotrophicu Leptothrix discophora Leptothrix cholodnii Leptothrix mobilis OTU OTU Leptospirillum ferrooxidans Nitrospira moscoviensis OTU Reactivity Wet chemistry, time resolved spectroscopy Real Problems Process identification, contribution to models, novel technologies, improved management

5 Image: Terra Sea Environmental Image: State of Washington

6 Biomineralization Is Widely Distributed Across the Tree of Life Lanson et al Gonzalez-Contreras, 2012

7 Biomineral Formation May be produced nzymatically (functionally or as a byproduct) or by templatization Biominerals are thought to: Provide structure Provide guidance Collect light Scavenge utrients Sequester toxics and waste products Provide radiation resistance Promote carbon mineralization Or perhaps do nothing at all

8 Biominerals in Remediation Biomineral may be very different from abiotically formed minerals VS. Attractive metal sinks and redox catalysts In-situ generation Cheap synthesis Structure and crystallinity Particle or domain size Morphology and faces expressed Surface charge (organic matter) Association with biofilms Physical arrangement

9 Biogenic Manganese Oxides and Contaminants Models how metals move in the environment require accurate measurements of iron and manganese oxides (biominerals) binding of metals. Cara Santelli Biominerals may a o be used to sequester metals or degrade organic micropollutants in designed remediation systems.

10 Lot 86, Farm Lot Unit #1 Superfund Site

11 Solvent Plume at Lot 86, Farm Lot Unit #1 Superfund Site N chloroform (ug/l) Wade Avenue main highway into Raleigh (population 440,000) Plume is (of course) a complicated multicontaminant waste mixture. EPA, 2008 ( )

12 Pump and Treat Groundwater Remediation System Inlet (groundwater) Activated Carbon Column 1 Activated Carbon Column 2 Ion Exchange Column 1 Ion Exchange Column 2 Process Tank Bag Filter Air Stripper Intermediate Tank Bag Filter Effluent Tank Outlet (surface water)

13 Biogenic Mineral Formation in the Treatment System Scanning electron micrographs and energy dispersive spectra suggests Mn/biomass mixture

14 Structure of Today s Talk 1. Properties and effects of Mn Oxides in the treatment system Inlet (groundwater) Process Tank Bag Filter Air Stripper Intermediate Tank Bag Filter Activated Carbon Column 1 Activated Carbon Column 2 Ion Exchange Column 1 Ion Exchange Column 2 Effluent Tank Outlet (surface water) 2. Products of the treatment system and their prospects for environmental remediation

15 A Geomicrobiological Approach What are the major forms of oxides, what organisms are causing their formation, and what is the effect on the treatment process? Scanning Electron Microscopy/ Energy Dispersive Spectroscopy morphology and composition Culturing Analysis isolation of Mn oxidizers X-ray Diffraction mineralogy 454 pyrosequencing culture-independent community analysis X-ray Absorption Spectroscopy chemical environment around specific elements

16 Fundamentals of X-Ray Absorption Spectroscopy XANES X-ray Absorption Near Edge Spectroscopy Probes: Properties of absorbing atom (e.g., oxidation state) EXAFS Extended X-ray Absorption Fine Structure Spectroscopy Probes: Local Coordination Environment Constructive Interference Normalized Absorption Enegry (ev) Destructive Interference

17 Interpretation of X-Ray Absorption Spectra Interference k 3 χ(k) EXAFS k (Å -1 ) FT Magnitude Fourier Transform Radial Distribution Function R (Å) k 3 χ(k) k (Å -1 ) FT Magnitude R (Å)

18 Manganese Oxides in Biofilm are Dominantly Layer-Type H + -birnessite H + -birnessite 2 Air Stripper 2 Carbon Cap Ion Select. Res. todorokite k 3 (k) P. putida 2 IC todorokite P. putida 2 IC FT magnitude Layer structure is dominant (60-80%) Similar to bacterial Mn oxides Large sorbtion capacity and redox reactivity CC CC AS AS k(å -1 ) R+ R (Å) Tunnel structure is smaller component (20-40%) Gen ally less reactive

19 Metals Bind to Biofilm Similarly to Biogenic Mn Oxides Zn on synthetic Mn oxide Co on biomass Zn on bacteriogenic Mn Oxide 1 Co on bacteriogenic Mn oxide 100% Zn on ferrihydrite 25-10% Zn on bacteriogenic Mn oxide 2 ~75-90%

20 Metals Sorption to Mn Oxide Biofilm Chemical analysis indicated abundant trace metals associated with Mn K-edge X-ray absorption spectroscopy of Ba, Zn, and Co suggests that Ba and Zn are predominantly adsorbed at defect sites and Co is incorporated into the oxide layer (similar to laboratory biominerals). Manganese = purple Cobalt = blue Zinc, Barium = yellow Oxygen = red

21 Isolation of Mn Oxidizing Organisms A culture-based assay of Mn(II) oxidizers from different locations yielded 95% fungi and only 5% bacteria. Based on ITS analysis, we isolated 6 different genera of Mn(II) oxidizing fungi belonging to two phyla. Fungi (occurrences) Phylum Isolation location Fusarium sp. (1) Ascomycota Air stripper Phoma sp. (9) Ascomycota Air stripper Coprinellus sp. (2) Basidiomycota Activated carbon column Paraconiothyrium sp. (1) Ascomycota Air stripper Paecilomyces sp. (1) Ascomycota Ion exchange column Coniothyrium sp. (1) Ascomycota Air stripper The organisms were isolates from contaminated environments and may be useful for the development of myconanotechnologies for environmental remediation. Gardner et al., Advanced Preparation A

22 Morphologies of Mn Oxidizing Fungi Coprinellus sp. Fusarium sp. Coniothyrium sp. Phoma sp. Paraconiothyrium sp.

23 The Next Steps: Evaluate Fungal Cultures for Remediation todorokite (tunnel) -MnO 2 (layer) birnessite (layer) Fusarium solani Coniothyrium sp. Paecilomyces sp. Coprinellus sp. Relative heights of peaks measure ordering (and perhaps metal binding capacity and redox reactivity) We see a range of structures in isolates from the treatment system, which may reflect how they bind metals. Do we see differences in metal binding and redox reactivity? Coprinellus sp. Phoma sp. Phoma sp. Phoma sp. Because the organisms can grow in harsh environments, can we exploit their reactivity in remediation systems or water treatment systems? Phoma sp. Phoma sp. Paraconiothyrium sp. Phoma sp. Paraconiothyrium sp.

24 Fungi Chosen for Further Investigation Fungi were chosen based on morphology and ability to grow in liquid medium. Synthetic Oxides Paraconiothyrium sp. AMON = 3.4 c-disordered birnessite AMON = 3.81 Coprinellus sp. AMON = 3.5 -MnO 2 AMON = 4.0 Coniothyrium sp. AMON = 3.4

25 Structure of Today s Talk 1. Properties and effects of Mn Oxides in the treatment system Inlet (groundwater) Process Tank Bag Filter Air Stripper Intermediate Tank Bag Filter Activated Carbon Column 1 Activated Carbon Column 2 Ion Exchange Column 1 Ion Exchange Column 2 Effluent Tank Outlet (surface water) 2. Products of the treatment system and their prospects for environmental remediation

26 Understanding Structure and Reactivity What are the structures of mycogenic Mn oxides and how does metal binding affect them? How does structure and metal binding affect electron structure and redox chemistry? Scanning Electron Microscopy/ Energy Dispersive Spectroscopy morphology and composition Compuational Chemistry electron structure X-ray Diffraction and X-ray Absorption Spectroscopy structure and mineralogy Chemical Reduction Kinetics and Voltammetry redox reactivity Sorption Isotherms binding capacity of surfaces X-ray Absorption Spectroscopy chemical environment around specific elements

27 Mn Oxides and Quinones M HQ ~2000 M Mn (as -MnO 2 ) OH [Mn] [HQ] control O. O -e -, -H + -e -, -H + 60 OH OH O um Time (sec)

28 Determination of Electron Transfer Rates via Voltammetry drop-cast oxides onto carbon electrodes reoxidation Potential (V) reduction Vary scan rates Electron transfer rates for internal comparison between different minerals and bewteen metal doped minerals, and with chemcial reduction rates Ep-E o log( )

29 Voltammetry and Chemical Electron Transfer Rates 80 Loose correlation between reaction rates? MnO 2 electron transfer rate (cm s -1 ) Second order MnO 2 -HQ rate coefficient (M -1 s -1 )

30 Sorption of Zinc to Synthetic and Mycoge ic Oxides

31 Zinc Binding to Mn Oxides and Biomass Chalcophanite (octahedral) Toner's biogenic Mn oxide (tetraherdal) 60 Corresponding biomass (Coprinellus sp.) Paraconiothyrium sp. high Zn Coprinellus sp. high Zn Coprinellus sp. low Zn Coniothyrium sp. high Zn Coniothyrium sp. low Zn 50 (k) k Fits Mn oxide vacancies <10% octahedral 10-50% tetrahedral Fungal biomass 30-80% biomass (P) k (Å -1 )

32 Sorption of As(V) to Synthetic and Mycogenic Oxides Sorbed As concentration (mg As kg Mn -1 ) Synthe c -MnO 2 Coprinellus sp. Paraconiothyrium sp. Coniothyrium sp Dissolved As concentration (mg As L -1 )

33 Metals Sorption to Synthetic and Mycogenic Mn Oxides Zn sorbs to a larger extent than As (a though some Zn sorbs to biofilm) Differ nt Mn oxides have differ nt relative affinities for Zn and As EXAFS suggest that Zn sorbs to vacancies and As sorbs to edge sites (As data not shown) Does the sorption of metals affect rates of redox reactions? Sample e - transfer rate -MnO 2 21 ± 9 -MnO 2 + Zn 1.2 ± 0.8 -MnO 2 +As 5 ±3 C-diss. birnessite 40 ± 20 C-diss. birnessite + Zn 0.7 ± 0.5 C-diss. birnessite + As 11 ± 5 N.B. Still need to conduct chemical reactivity experiments

34 Implications for Remediation Phenols Cl compounds Antibacterial Dyes Chelators Pesticides Surfactants Oxidation Products Phenols Cl compounds Antibacterial Dyes Chelators Pesticides Surfactants Phenols Cl compounds Antibacterial Dyes Chelators Pesticides Surfactants x Remucal and Ginder-Vogel, 2014 But metal are more stabilized!

35 Conclusions Fungi isolated from a Superfund remediation system produce layer-type Mn oxides with a variety of morphologies and properties. Because they grow in the treatment system, they may be able to produce oxides in other waste streams. Mycogenic Mn oxides have sorption and redox reactivities in the range of synthetic minerals. Zn and As sorption to Mn oxides may inhibit redox reactivity. There may be trade off between ability of oxides to degrade organics via redox reactions and to sequester metals. However, bec use metals sorption reduces redox reactivity, sorption may enhance long term sorbent stability. ACKNOWLEDGEMENTS

36 Acknowledgements This work is supported by National Science Foundation grants EAR (REU), CHE , a NCSU Research Innovation and Seed Funding grant, and NCSU undergraduate research grants. This research was carried out in part at the Stanford Synchrotron Radiation Lighta national user facility operated by Stanford University on behalf of the U.S. DOE, Office of Basic Energy Sciences. We thank Brandy Toner, Jackie Pena, Audrey Matteson, Ryan Davis, John Bargar, and Kim Hutchinson