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Biotransformation of Furanic and Phenolic Compounds with Hydrogen Gas Production in a Microbial Electrolysis Cell Xiaofei Zeng, Abhijeet P Borole, and Spyros G. Pavlostathis Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.5b02313 • Publication Date (Web): 27 Oct 2015 Downloaded from http://pubs.acs.org on November 1, 2015

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Environmental Science & Technology

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Biotransformation of Furanic and Phenolic Compounds with Hydrogen Gas

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Production in a Microbial Electrolysis Cell

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Xiaofei Zeng1, Abhijeet P. Borole2,3, and Spyros G. Pavlostathis1,*

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School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0512, United States 2 Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States 3 Bredesen Center for Interdisciplinary Research and Education, The University of Tennessee, Knoxville, TN 37996, United States

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*Corresponding author. Phone: 404-894-9367; fax: +404-894-8266; E-mail address: [email protected] (S. G. Pavlostathis)

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ABSTRACT: Furanic and phenolic compounds are problematic byproducts resulting from the

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breakdown of lignocellulosic biomass during biofuel production. The capacity of a microbial

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electrolysis cell (MEC) to produce hydrogen gas (H2) using a mixture of two furanic (furfural,

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FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA;

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and 4-hydroxybenzoic acid, HBA) compounds as the substrate in the bioanode was assessed. The

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rate and extent of biotransformation of the five compounds, efficiency of H2 production, as well

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as the structure of the anode microbial community were investigated. The five compounds were

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completely transformed within 7-day batch runs and their biotransformation rate increased with

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increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the

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mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The

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anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H2

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yield varied from 0.26 to 0.42 g H2-COD/g COD removed in the anode, and the bioanode

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volume-normalized H2 production rate was 0.07-0.1 L/L-d. The biotransformation of the five

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compounds took place via fermentation followed by exoelectrogenesis. The major identified

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fermentation products that did not transform further were catechol and phenol. Acetate was the

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direct substrate for exoelectrogenesis. Current and H2 production were inhibited at an initial

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substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level

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than that measured in other batch runs conducted with a lower initial concentration of the five

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compounds. The anode microbial community consisted of exoelectrogens, putative degraders of

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the five compounds, and syntrophic partners of exoelectrogens. The MEC H2 production

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demonstrated in this study is an alternative to the currently used process of reforming natural gas

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to supply H2 needed to upgrade bio-oils to stable hydrocarbon fuels.

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TOC Art

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INTRODUCTION

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Lignocellulosic biomass is a promising feedstock for the production of biofuels using thermal,

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chemical or biological processes. Breakdown of lignocellulosic biomass, regardless of the

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process used, typically results in furanic and phenolic byproducts, which are inhibitory,

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problematic compounds. For instance, furanic and phenolic compounds in lignocellulosic

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hydrolysates are highly inhibitory to H2 and ethanol producing, fermentative microorganisms,

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which has been a persistent challenge in biofuel production through fermentation processes.1,2 In

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pyrolysis, a thermal process reforming biomass to bio-oil, the presence of polar and oxygen-rich

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compounds (e.g., furan aldehydes and phenolic acids) makes the bio-oil acidic, unstable,

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requiring H2 in the downstream hydrogenation process to upgrade the bio-oil to a stable fuel.3 In

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order to overcome the negative effect of furanic and phenolic compounds, physical and/or

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chemical removal, as well as microbial and enzymatic processes have been explored.4 However,

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these methods have the trade-offs of lowering biofuel yield and do not lessen the challenge of

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downstream wastewater treatment.4 Thus, a process to directly utilize furanic and phenolic

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compounds to produce biofuels would be an improvement over the existing methods.

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Microbial electrolysis cell (MEC) technology is a bioelectrochemical process, which

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produces H2. Exoelectrogenic bacteria in the anode oxidize organic substrates by transferring

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electrons to the electrode and then to the cathode. With a voltage input (> 0.3 V), protons

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transferred from the anode to the cathode via a cation exchange membrane are reduced to H2.5

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Unlike other H2 producing bioprocesses, the MEC produces H2 through an abiotic half-reaction

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in the cathode, with the supply of electrons from the microbially-assisted half-reaction in the

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anode. This feature of MEC eliminates the need for H2-producing bacteria, which are highly

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susceptible to furanic and phenolic compounds.1,6 Thus, the MEC is potentially able to convert



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these problematic compounds to H2, which in turn can be used in the hydrogenation process and

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thus minimize the external H2 supply currently generated by reforming natural gas.

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Given the advantage of the MEC technology, recent studies have investigated the

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potential of integrating MEC in biofuel production platforms. Lignocellulosic effluent, refinery

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wastewater and switchgrass-derived bio-oil aqueous phase have been treated in MECs with

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simultaneous H2 production.7,8,9 However, the fate and effect of furanic and phenolic

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compounds, which are the problematic components of the above-mentioned feedstocks, remain

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unknown. This study investigated a MEC for H2 production from two furanic and three phenolic

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compounds. This is the first attempt to understand the fate of specific inhibitory compounds and

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their potential to produce H2 in a MEC. The most commonly used substrates in MECs are acetate

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and wastewater.10-12 However, acetate is a favorable organic substrate for exoelectrogens,13,14

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whereas, furanic and phenolic compounds are less biodegradable and have not been reported as

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direct substrates for exoelectrogens. On the other hand, wastewater streams generally include

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easily biodegradable components, which may be the major contributors to H2 production. Two

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previous studies used furanic and phenolic compounds as the substrate in the anode of a

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microbial fuel cell (MFC), but had mixed results. Catal et al. reported that, with the exception of

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HMF, use of nine individual furanic and phenolic compounds (2-furaldehyde, syringaldehyde,

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vanillin, trans-cinnamic acid, trans-4-hydroxy-3-methoxy-cinnamic acid, 4-hydroxy-cinnamic

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acid, 3,5-dimethoxy-4-hydroxy-cinnamic acids, benzyl alcohol and acetophenone) did not

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generate voltage.15 In contrast, Borole et al. demonstrated that an anode microbial consortium

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was able to convert furfural, HMF, 4-hydroxybezaldehyde, hydroxyacetophenone, and vanillic

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acid to electricity.16 Thus, the question remains whether a MEC anode microbial community can


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use furanic and phenolic compounds as the sole carbon and energy source to produce H2 in the

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cathode.

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The overall goal of this study is to produce H2 through the biotransformation of specific

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furanic and phenolic compounds using MEC technology. The specific objective of the work

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presented here was to enrich a microbial community, assess its capacity to biotransform two

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furanic and three phenolic compounds, and produce H2 in a batch-fed MEC. Biotransformation

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of the selected furanic and phenolic compounds, formation of metabolites, production of current

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and H2, as well as the structure of the anode microbial community were investigated.

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MATERIALS AND METHODS

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Chemicals. Furfural (FF, 99%), 5-hydroxymethyl furfural (HMF, ≥ 99%), syringic acid

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(SA, ≥ 95%) and 4-hydroxybenzoic acid (HBA, ≥ 99%) were purchased from Sigma-Aldrich (St.

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Louis, MO). Vanillic acid (VA, ≥ 99%) was purchased from Alfa Aesar (Ward Hill, MA). The

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five compounds are soluble in water (1.5-364 g/L at 25oC), not volatile (Henry’s law constant =

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10-14 - 10-6 atm-m3/mol), and have a low hydrophobicity (log Kow = -0.09 to 1.58)(Table S1;

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Supporting Information). The standard potential at pH 7.0 (E ) of the five compounds is from -

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0.388 to -0.303 V (Table S2) compared to the E value of -0.414 V for proton reduction to H2.

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Inoculum. The bioanode inoculum was a piece of biofilm-attached carbon felt from a

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MFC anode developed at the Oak Ridge National Laboratory (Oak Ridge, TN), which over time

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had been fed with a mixture of furanic/phenolic compounds, corn stover hydrolysates, and

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switchgrass pyrolysis aqueous stream.9,16,17 The original inoculum of this MFC was a sample

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collected from a municipal anaerobic digester. The bioanode inoculum was further enriched in

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the present study in a different MFC anode, fed with the mixture of the two furanic and three

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phenolic compounds, prior to being transferred to a MEC anode. 5 ACS Paragon Plus Environment


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MFC Setup and Operation. An air-cathode MFC was set up to enrich the inoculum.

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The anode electrode was porous carbon felt (5 stripes, 1 cm × 1 cm × 10 cm each; Alfa Aesar,

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Ward Hill, MA) tied to a stainless steel rod. The anode chamber was a modified square glass

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bottle with an open channel on one side. The empty bed volume was 250 mL, and the liquid

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volume was 200 mL due to electrode displacement. The cathode was a membrane-electrode

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assembly with a surface area of 5.7 cm2 purchased from Fuel Cells Etc (College Station, TX),

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which was made of a cation exchange membrane and carbon cloth containing 0.5 mg/cm2 Pt.

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The cathode was clamped to the side channel extended from the anode chamber and exposed to

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air on one side.

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A piece of biofilm-attached carbon felt (approximately 1 cm ×1cm × 3 cm) was placed in

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the center of the anode carbon felt electrode. The anode medium consisted of (in g/L): NH4Cl,

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0.31; KCl, 0.13; NaH2PO4·H2O, 2.45; Na2HPO4, 4.58, along with trace metals and vitamins.18

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The pH of the medium was 7.0. The anolyte was deoxygenated by bubbling N2 through the

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liquid phase prior to use, and was continuously mixed magnetically. The MFC was maintained at

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room temperature (20-22°C). A mixture of the five compounds at equal electron equivalents

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(each at 62.5 mg COD/L) and a total concentration of 200 mg/L (312 mg COD/L) was fed to the

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MFC anode once a week (7-day fed-batch). During the first ten feeding cycles (~70 days),

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glucose (200 mg/L) was fed along with the five compounds to enhance microbial growth. A

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variable resistor was placed between the anode and cathode, and its resistance was gradually

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reduced from 500 to 250 and then to 100 Ω, in order to promote the growth of exoelectrogenic

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bacteria. The voltage was recorded by a potentiostat (Interface 1000TM, Gamry Instruments,

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Warminster, PA); culture enrichment lasted for 6 months. The MFC activity stabilized with a


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mean maximum current of 1.25 mA, soluble COD (sCOD) removal of 50-60% and coulombic

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efficiency (CE) of 40-60%, measured over the last 20 feeding cycles.

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MEC Setup and Operation. An H-type MEC was developed with two square glass

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bottles separated by a cation exchange membrane (Nafion 117, 5.7 cm2; Dupont, Wilmington,

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DE) and maintained at room temperature (20-22oC). Both chambers and the anode electrode had

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the same configuration as the above-described MFC anode. The cathode electrode was a carbon

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cloth containing 0.5 mg/cm2 of Pt (5 cm × 6 cm; Fuel Cell Etc, College Station, TX). A gas

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collection burette using displacement of an acid brine solution (10% NaCl w/v, 2% H2SO4 v/v)

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was connected to each chamber headspace for gas volume measurement (Figure S1; Supporting

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Information).

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The inoculation procedure and anolyte of the MEC were the same as for the above-

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described MFC. The MEC catholyte was a 100 mM phosphate buffer (pH 7.0), deoxygenated by

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bubbling N2 prior to use. Both the anolyte and catholyte were replaced at the beginning of each

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feeding cycle. During the startup, the anode chamber was amended with 200 mg/L of the five

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compounds mixture (same composition as the MFC feed). After the startup, which lasted for 9

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weeks, the total initial concentration of the substrate mixture was increased from 200 to 400,

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800, and then to 1,200 mg/L. A voltage of +0.6 V was set to the MEC anode relative to the

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cathode, and the current was recorded every 4 hours by the potentiostat. The duration of each

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feeding cycle was 6-7 days until the current dropped below 0.2 mA. The anolyte and catholyte

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were continuously mixed magnetically and the anode and cathode headspaces were initially

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filled with N2.

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Two controls were evaluated. Control 1 was used to investigate the stability of the five compounds in the presence of the porous carbon felt and anolyte. Four serum bottles, each



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containing 100 mL anolyte and 200 mg/L compound mixture, were kept under N2 headspaces.

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Two of the bottles contained carbon felt with equivalent quantity (v/v) as in the MEC anode. The

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concentration of the five compounds was monitored for 7 days. Control 2, setup with a biomass-

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free anode electrode in the MEC, was used to evaluate the potential contribution of the applied

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voltage on current production and transformation of the five compounds in the absence of

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microbial activity.

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Microbial Community Analysis. Microbial community analysis of the MEC anode was

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performed after 9 weeks (9 feedings) from the startup. A piece of anode electrode with attached

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biofilm (approximately 1 cm ×1cm × 3 cm) was washed several times with the anolyte and then

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cut into small pieces (< 0.5 cm). The genomic DNA was extracted with the PowerSoil DNA

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isolation Kit (MO BIO Laboratories, Carlsbad, CA), according to the manufacturer’s

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instructions. The concentration and purity of the DNA sample were determined with a ND-1000

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spectrophotometer (NanoDrop Technologies, Wilmington, DE). The 16S rRNA gene was

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sequenced using an Illumina MiSeq system (LC Science, Houston, TX). Bacterial primers 319F

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(5'-ACTCCTACGGGAGGCAGCAG-3') and 806R (5'-GGACTACHVGGGTWTCTAAT-3')

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were used to amplify the V3-V4 hypervariable regions of the 16S rRNA gene. The obtained

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sequences were clustered into Operational Taxonomic Units (OTUs) with 97% similarity. The

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longest read in each OTU was chosen as the representative sequence for taxonomic classification

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using the RDP classifier Version 2.7. The sequence-based phylogenetic tree of the abundant

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bacteria (>1% abundance) was constructed by applying the neighbor-joining algorithm using the

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program MEGA 6.06. The tree topology was evaluated by bootstrap resampling analysis of 1000

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data sets. The representative sequences of the abundant species have been deposited to GenBank,


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National Center for Biotechnology Information (NCBI; www.ncbi.nlm.nih.gov/) with sequence

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accession numbers from KT124613 to KT124626.

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Analytical Methods. The furanic and phenolic compounds were quantified using a high

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performance liquid chromatography (HPLC) unit equipped with a UV-Vis detector (Agilent

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1100, Santa Clara, CA). A HPX-87H column (BioRad, Hercules, CA) was used with an eluent of

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15% acetonitrile in 5 mM H2SO4 (v/v) at a flow rate of 0.6 mL/min.16 The wavelength of 280 nm

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and 210 nm was used for the furanic and phenolic compounds, respectively. Acetate and other

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volatile fatty acids were quantified by the same HPLC method at the wavelength of 210 nm,

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except that the eluent was 5 mM H2SO4 without any organic solvent. Metabolites of the five

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compounds were identified using an LC/MS/MS unit (Agilent 1260 Infinity LC system, 6410

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Triple Quad MSD) equipped with a Kinetex biphenyl column (3×150 mm, 5 µm; Phenomenex,

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Torrance, CA). The eluent consisted of (A) 5 mM ammonium acetate with 0.5% acetic acid in

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acetonitrile (v/v) and (B) 5 mM ammonium acetate in 0.5% acetic acid (v/v) at a flow rate of 0.5

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mL/min, using gradient elution as follows: eluent A was increased from 2% to 30% in 2.3 min

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and to 90% in 1.2 min, and then was maintained at 90% for 2.5 min. The MS/MS was operated

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in both positive and negative modes at 100 eV in an m/z range of 50-250. The product ions of the

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same molecular weight as hypothesized metabolites were fragmented, and the fragmentation

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patterns were compared with those of purchased pure chemicals. Soluble chemical oxygen

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demand (sCOD) and pH were measured following procedures outlined in Standard Methods.19

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Total gas production was measured by the acid brine solution displacement in the burettes,

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equilibrated to 1 atm. Headspace gas composition (i.e., H2, CO2, and CH4) was determined with

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a gas chromatography unit equipped with two columns and two thermal conductivity detectors.20

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Calculations. Coulombic efficiency and H2 yield were calculated as previously



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described.21 Current density was normalized to either the empty bed volume of the anode

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chamber (250 mL) for comparison with single-chamber MECs, or the projected surface area of

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the Nafion membrane (5.7 cm2), assuming the membrane surface area was limiting, due to the

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narrow channel of the H-type reactor.22

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RESULTS AND DISCUSSION

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MEC Startup. During the MEC startup period, fed-batch addition of 200 mg/L

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compound mixture was conducted in repetitive 7-day feeding cycles. Stable maximum current

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and H2 production was observed by day 28 (Figure S2) and the startup period continued for

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another 35 days (5 feeding cycles) to confirm stable performance. During the MEC operation,

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the anolyte and catholyte pH was in the range of 6.7-7.0 and 7.0-7.3, respectively. The maximum

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current density (Imax) was 0.16 ± 0.04 mA/cm2 or 3.6 ± 0.9 A/m3, cumulative H2 production was

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19.3 ± 1.2 mL (20°C, 1 atm), and coulombic efficiency was 44 ± 12% over the last 5 feeding

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cycles. The five compounds were completely transformed, with sCOD removal of 57 ± 10%

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during each feeding cycle. An abiotic control assay (Control 2), conducted under the same MEC

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conditions, with the exception that the anode was not inoculated, resulted in negligible current

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(1% abundance)

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detected in the MEC bioanode are shown in Figure S8. The detected species in the bioanode are

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mainly related to exoelectrogens, putative degraders of the furanic and phenolic compounds, and

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potential syntrophic partners with exoelectrogens. Desulfovibrio desulfuricans is a sulfate-

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reducing bacterium, which is able to perform exoelectrogenesis through cytochrome c.40 In

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addition, the major known degraders of furfural and 5-HMF under anaerobic conditions belong

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to Desulfovibrio genus.41 Geobacter spp. are well studied exoelectrogens, using acetate and H2 as

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primary electron donors.34,42 Eubacterium limosum is known to grow on methoxylated aromatic

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compounds, such as syringic acid and vanillic acid.43 E. limosum is also a homoacetogen, which

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could consume H2 formed during fermentation and produce acetate for exoelectrogens.44

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Pelobacter propionicus is not known to perform exoelectrogenesis or to use acetate as the

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electron donor, but is thought to be involved in syntrophic interactions with exoelectrogens

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fermenting initial substrates to acetate.14,45 Clostridium populeti and Clostridium

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aminobutyricum are known mixed-acids fermenters, and the latter has been found in acetate- and

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glucose-fed MFC anodes.46,47 Phascolarctobacterium faecium can convert succinate to

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propionate.48 Therefore, E. limosum, P. propionicus, P. faecium and Clostridium spp. could be

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syntrophic partners with exoelectrogens by converting the furanic and phenolic compounds or

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their biotransformation products to readily available substrate (e.g., acetate) for

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exoelectrogenesis. Several detected species in the present study are closely related to bacteria,

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such as Dysgonomonas spp.,17 Pleomorphomonas oryzae, 49 and the uncultured bacterium clones

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(JX462549.1 and GU083415.1)45,50 previously found in bioelectrochemical systems, but their

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functions are unknown. Other phylotypes related to the OTUs detected in the present study are

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Cloacibacillus evryensis, an amino-acid degrading bacterium found in anaerobic digesters,51 and



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a bacterial species found in cellulose and xylan-pectin enrichments of cow feces.52 These species

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may have been carried over from the original inoculum, which came from a municipal anaerobic

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digester.

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The present study demonstrated the capacity of MEC to convert furanic and phenolic

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compounds to H2, which strengthens the promise of integrating MEC technology in biorefinery

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platforms. Furanic and phenolic inhibitors, which are a great challenge in dark fermentation of

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lignocellulosic hydrolysates, were productively utilized in the MEC to produce H2, which can

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then be used for the hydrogenation of bio-oils, thus eliminating the need to reform natural gas to

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H2. Moreover, the biotransformation fate of furanic and phenolic compounds shown in the

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present study provides mechanistic insights into bioprocesses taking place in MEC and

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fermentation systems which use complex, lignocellulose-derived feedstocks. The relatively low

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H2 production rate and inhibition of exoelectrogenesis at 1,200 mg/L observed in the present

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study, need to be addressed. On-going research is investigating continuous-flow MEC operation

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to find the means to mitigate the observed inhibitory effect during the batch MEC operation, as

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well as increase the H2 production rate and yield.

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ASSOCIATED CONTENT

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Supporting Information

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Tables S1-S3, and Figures S1-S8 are available free of charge via the Internet at

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http://pubs.acs.org.

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ACKNOWLEDGEMENT

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We acknowledge funding for this work from the U.S. Department of Energy, BioEnergy

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Technologies Office under the Carbon, Hydrogen and Separations Efficiency (CHASE) in Bio-

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Oil Conversion Pathways program, DE-FOA-0000812. The manuscript has been co-authored by 20 ACS Paragon Plus Environment

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UT-Battelle, LLC, under Contract No. DEAC05-00OR22725 with the U.S. Department of

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Energy.

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597

Page 28 of 33

Table 1. Efficiency parameters of the MEC fed with the mixture of the five compounds. Initial substrate concentration (mg/L)

Parameter

200

400

800

2.9 ± 0.2 e

2.5 ± 0.2

1.7 ± 0.03

(%) b

38 ± 0.2

42 ± 7

26 ± 0.4

sCOD removal (%)

49 ± 0.1

49 ± 8

61 ± 4

58 ± 1

69 ± 8

44 ± 0.1

0.07 ± 0.0004

0.10 ± 0.002

0.10 ± 0.001

H2 yield (mol/mol) a

CE (%) c H2 production rate (L/L-d) d 598 599 600 601 602 603 604 605

a

Moles of H2 collected per mole of the compound mixture transformed

b

H2-COD per COD removed during each batch run

c

Electrons recovered as electrical current per electron equivalent of COD removal during

each batch run d

Maximum production rate, observed on day 1 during each feeding cycle (20ºC and 1

atm) normalized to the empty bed volume of the anode chamber (0.25 L) e

Mean ± standard deviation; n = 3


Page 29 of 33


606

Table 2. Possible fermentation of the identified transformation products to acetate and other

607

products (∆ ; Gibbs free energy at pH 7 and 298 K).

∆ (kJ/mol)

Compound

Reaction

Catechola

C H + 4H O = 3CH COO + H + 3H

-69.12

Phenola

C H O + 5H O = 3CH COO + 2H + 3H

+8.46

FAb

9 11 2 C H O + 6 H O ⇌ HCO + CH COO + H 2 2

-763.66

HMF-OHb

C H O + 3 H O ⇌ 3CH COO + H + 3 H

-215.76

diHBAb

2 C H O + 8 H O ⇌ HCO +

13 15 CH COO + H 2 2

608 609 610

a

! value from Yaws, 2003 53

b

! value calculated based on the group contribution method 54


-257.66


611

LIST OF FIGURES

612

Figure 1. Current and cumulative H2 production during four batch assays conducted at increased

613

initial substrate concentrations in the MEC anode (A, 200 mg/L; B, 400 mg/L; C, 800 mg/L; D,

614

1,200 mg/L). Error bars represent mean values ± one standard deviation, n = 3.

615

Figure 2. Normalized concentration profiles of the five compounds fed to the MEC anode at

616

various initial total concentrations (200 to 1,200 mg/L).

617

Figure 3. Biotransformation products detected during the four batch assays at increased initial

618

substrate concentrations in the MEC anode (200-1,200 mg/L).


Page 30 of 33

Page 31 of 33


2.5

A

Current H2

2.0 1.5 1.0 0.5 0.0 2.5

B

2.0 1.5

Current (mA)

1.0 0.5 0.0 2.5

C

2.0 1.5 1.0 0.5 0.0 2.5

D

2.0 1.5 1.0 0.5 0.0 0

1

2

3

4

5

6

Time (d)

31

ACS Paragon Plus Environment

7

70 60 50 40 30 20 10 0 70 60 50 40 30 20 10 0 70 60 50 40 30 20 10 0 70 60 50 40 30 20 10 0

Cumulative H2 (mL at 20oC, 1 atm)

Figure 1


Page 32 of 33

Figure 2

FF

HMF

1.0

Initial concentration (mg/L):

Normalized Concentration (C/C0)

0.8

200 (biomass-free) 200 400 800 1200

0.6 0.4 0.2 0.0

SA

1.0

HBA

VA

0.8 0.6 0.4 0.2 0.0 0

1

2

3

4

5

6

7

0

1

2

3

4

5

6

7

Time (d)

32


0

1

2

3

4

5

6

7

Page 33 of 33


Figure 3

120

120

Phenol

Catechol 100

100

Initial concentration (mg/L):

80

80

200 (biomass-free)

60

60

400

40

40

800

20

20

0

0

Concentration (mg/L)

200

1200

6

180

diHBA

60

HMF-OH

FA

150

5

50

120

4

40

90

3

30

60

2

20

30

1

10

0

0 0

1

2

3

4

5

6

7

0 0

1

2

3

4

5

6

7

0

Time (d)

33


1

2

3

4

5

6

7

Biotransformation of Furanic and Phenolic ... - ACS Publications

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