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Processes & Impacts
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K. Upadhyayula, V. Gadhamshetty, N. Koratkar and M. Tysklind, Environ. Sci.: Processes Impacts, 2016,
DOI: 10.1039/C6EM00552G.
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Page 1 of 28 Environmental Science: Processes & Impacts
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DOI: 10.1039/C6EM00552G
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Biodiesel is known to promote abiotic corrosion and microbial corrosion of metal components in
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5 storage infrastructure. Industries use polymer liners to protect interior surfaces of biodiesel tanks
6 against corrosion. Further, the biodiesel is dosed with biocides to mitigate microbial corrosion.
Environmental Science: Processes & Impacts Accepted Manuscript

7 Biocides pose environmental and health risks (e.g., tumors of the lungs and skin). The current
8 study evaluates the screening-level, cradle-to-grave, life cycle analysis (LCA) of graphene liners
9 that have been touted to combat microbial corrosion. This LCA study compares the
Published on 22 December 2016. Downloaded by University of Florida Libraries on 27/12/2016 06:45:31.
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environmental impacts of graphene liners with the incumbent system under ten different
12 categories: global warming potential; acidification potential; carcinogenics; non-carcinogenics;
13 respiratory; particulate matter effects; eutrophication; ozone depletion potential; ecotoxicity; and
14 smog and fossil fuel depletion.
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Environmental Science: Processes & Impacts Page 2 of 28
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2 1 Sustainability of Renewable Fuel Infrastructure: A Screening LCA Case Study of Anti-
3 2 Corrosive, Graphene Oxide Epoxy Liners in Steel Tanks for Storage of Biodiesel and its
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3 Blends
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7 5 Govinda Chilkoor1, Venkata K.K. Upadhyayula2*, Venkataramana Gadhamshetty1,4*, Nikhil
8 6 Koratkar3, Mats Tysklind2
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10 8 1
Civil and Environmental Engineering, South Dakota School of Mines and Technology, 501 E. St. Joseph
11 9 Street, Rapid City, SD 57701, USA
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13 10 Department of Chemistry (Environmental Chemistry), Umea University, SE 90187, Umea, Sweden
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14 11 Mechanical and Nuclear Engineering and Material Science and Engineering
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Surface Engineering Research Center, South Dakota School of Mines and Technology, 501 E. St. Joseph
16 13 Street, Rapid City, SD 57701, USA
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21 16 *Corresponding Author1
22 17 V. K. K. Upadhyayula, PhD
23 18 Assistant Professor, Green Technologies and Environmental. Economics Platform
24 19 Department of Chemistry
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20 Umea University, SE 90187
27 21 Umea, Sweden
28 22 Email: krishna.upadhyayula@umu.se
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30 23 *Corresponding Author2
31 24 V. Gadhamshetty, PhD
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33 25 Department of Civil and Environmental Engineering
34 26 South Dakota School of Mines and Technology
35 27 Rapid City, SDA
36 28 Email: Venkata.Gadhamshetty@sdsmt.edu
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2 38 ABSTRACT
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39 Biodiesel is a widely used fuel that meets the renewable fuel standards developed under
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40 Energy Policy Act of 2005. However, biodiesel is known to pose a series of abiotic and biotic
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8 41 corrosion risks to storage tanks. A typical practice (incumbent system) used to protect the tanks
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10 42 from the risks include: (i) coat the interior surface of the tank with solvent free epoxy (SFE)
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12 43 liner, and (ii) add a biocide in the tank. We present a screening-level, life cycle assessment
13 44 study to evaluate and compare the environmental performance of graphene-oxide (GO)-epoxy
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15 45 (GOE) liner with the incumbent system. TRACI is used as an impact assessment tool to model
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17 46 midpoint environmental impacts for the ten categories: global warming potential (GWP, kg
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19 47 CO2 eq.); acidification potential (AP, kg SO2 eq.); potential human health damage impacts due
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48 to carcinogens (HH-CP, CTUh) and non-carcinogens (HH-NCP, CTUh); potential respiratory
22 49 effects (REP, kg PM2.5 eq); eutrophication potential (EP, kg N eq); ozone depletion potential
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24 50 (ODP kg CFC-11 eq); ecotoxicity potential (ETXP, CTUe); smog formation potential (SFP kg
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26 51 O3 eq); and fossil fuel depletion potential (FFDP MJ surplus). The equivalent functional unit of
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28 52 the LCA study is designed to protect the 30 m2 of the interior surface (unalloyed steel sheet) of
29 53 a 10,000 liters biodiesel tank against abiotic and biotic corrosion during its service life of 20
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31 54 years. Overall, this LCA study highlights an improved environmental performance for the GOE
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33 55 liner compared to the incumbent system; GOE-liner system showed: 91% lower ODP impacts;
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35 56 59% smaller for REP; 62% smaller for AP; 67-69% smaller for GWP and HH-CP; 72-76%
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57 smaller for EP, SFP, and FFDP; and 81-83% smaller for ETXP and HH-NCP categories. The
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38 58 scenario analysis study reveals that these potential impacts change by less than 15% when the
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40 59 GOE liners are functionalized with silanized-GO nanosheets or GO-reinforced, polyvinyl
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42 60 carbazole to improve the antimicrobial properties. The results from uncertainty analysis indicate
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61 that the impacts for the incumbent system are more sensitive to changes in key modeling
45 62 parameters compared to that for GOE liner system.
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58 71 KEYWORDS: Biocide, Graphene Oxide, Microbial Induced Corrosion, Epoxy Liners,
59 72 Biodiesel, Life Cycle Assessment
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2 73 1. INTRODUCTION
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74 The Renewable fuel standard (RFS) developed under Energy Policy Act of 2005
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7 75 requires transportation fuel sold in the United States (U.S) to be blended with cellulosic biofuel,
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9 76 biomass-based biofuel, advanced biofuel, or total renewable biofuel1. The biofuel blend was
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12 77 mandated at a minimum of 4 billion gallons in 2006, 7.5 billion gallons in 2012, and 36 billion
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14 78 gallons in 2022.2 Biodiesel is an attractive biofuel3 that is characterized by a high cetane
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16 79 number. It is a biodegradable and non-toxic fuel that can be derived from renewable (e.g.,
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19 80 jatropha oil) or domestic feedstocks (e.g., cooking oil). It is compatible with all the diesel
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21 81 engines4. Further, its combustion results in lower emission of asthma-causing soot, greenhouse
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82 gases, particulate matter and sulfur dioxide4. Despite its advantages, the physical and chemical
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26 83 properties of biodiesel promote corrosion and microbial induced corrosion (MIC) of metal
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28 84 components in storage and transportation infrastructure.
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85 Biodiesel is a hygroscopic substance that develops a water phase in a flow-through (low-
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33 86 velocity pipelines) and stagnant conditions (storage tanks).5-9 Metal surfaces exposed to
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35 87 biodiesel develop metal-water–biodiesel interfaces that provides a labile carbon and sustains
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38 88 growth of microbes (sulfate-reducing bacteria and fungi)10 involved in MIC.11-14 Biodiesel
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40 89 storage and transportation infrastructure is therefore prone to MIC.15
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42 90 MIC results from a genetically diverse set of microbial population that encapsulate
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45 91 themselves in a self-excreted biological film (i.e., biofilm) comprised of complex
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47 92 exopolymers.16 Biofilm accelerates corrosion by altering chemistry of passivation layers on
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93 metal surfaces.16 Considering that 13% of renewable energy in the U.S.17 represent liquid
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52 94 biofuels, the U.S invests significant resources to detect, monitor, prevent, and eradicate biofilm
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54 95 growth. In general, MIC problems account for nearly 40% of the total corrosion costs ($1
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96 trillion) in the U.S.18-20 Post-maintenance techniques (e.g., flushing and thermal treatment) are
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2 97 ineffective against MIC. Infact, they have been reported to aggravate corrosion problems by
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98 dislodging passivation layers from metal surfaces.21
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7 99 Steel industry uses commercial epoxy liners to protect biodiesel tanks and industrial,
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9 100 marine and offshore structures against corrosion. Epoxy liners are characterized by abiotic
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12 101 corrosion resistance, excellent mechanical strength, and they adhere to a variety of metal
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14 102 substrates.22, 23 However, epoxy liners exposed to environments rich in organic carbon (e.g.,
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16 103 biodiesel) are vulnerable to MIC attacks.24-26 Particularly, epoxy-liners used in ship ballast tanks
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19 104 exposed to marine environments have been reported to be vulnerable to MIC for the following
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21 105 reasons.25 Bacteria use organic fraction of plasticizers, fillers and stabilizers in epoxy-liners as
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106 nutrients to sustain biofilm growth. Microbial communities within these biofilms excrete
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26 107 organic acids and attack metal surfaces. They also result in an increased accumulation of
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28 108 chlorides and sulfides and destabilize liners on metal surfaces. Solvent-free epoxy liners such
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109 as Novolac liners have been reported to promote moisture intrusion, osmotic blistering and
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33 110 subsequent failure of liners.25 To inhibit microbial growth and combat MIC problems, biofuel
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35 111 tanks coated with epoxy liners are often dosed with biocides. Biocides when exposed to natural
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38 112 water systems can pose serious health concerns to exposed living beings. For example, triazines
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40 113 are known to cause a litany of health effects, including cancer, birth defects, and disruption of
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42 114 the endocrine (hormone) system.27
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45 115 Typical thickness of epoxy liners (300-500 µm) can disrupt functional properties (e.g.,
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47 116 thermal conductivity) and dimensional tolerances of underlying metals. Numerous studies have
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117 indicated viability of using nano-scale graphene coatings for protecting metals against
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52 118 immersion corrosion, atmospheric corrosion, and microbial corrosion. In our earlier studies, we
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54 119 have observed that graphene coatings minimize MIC of nickel foam exposed to a mixed
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120 microbial population including sulfate-reducing bacteria (e.g., Desulfovibrio spp.), polymer
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59 121 degraders (Stenotrophomonas spp.) and acid producers (Clostridium spp.).28 Our studies have
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2 122 also indicated that graphene provides superior MIC resistance compared to polymer (POLY)
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123 coatings.21 The recent literature also suggests that graphene oxide (GO), reduced GO (rGO) and
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7 124 GO-POLY composites29, 30 can protect a range of metals (nickel, copper, mild steel) against
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9 125 MIC. The motivation to adapt GO liners is evident from the increasing number of relevant
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12 126 publications and patents.31-38
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14 127 GO is a hydrophilic substance that disperses in a wide range of solvents and polymers.39-
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16 128 42
GO is preferred in MIC applications due to its biocidal properties that facilitate a “killing
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19 129 upon contact” mechanism. A series of recent studies suggest that GO acquires antimicrobial
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21 130 property though the following mechanisms: (i) GO disrupts cell membrane with its sharp edges
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131 (physical action); (ii) GO induces cellular oxidative stress (chemical action); (iii) GO facilitates
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26 132 excess release of phospholipids from bacteria and induces its death.43 In another study, Nanda
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28 133 et al.44 have indicated that the antibacterial action of GO is due to the release of biomolecules
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134 such as adenine in the bacterial cultures. A study by Krishnamoorthy et al.45 has demonstrated
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33 135 the biocidal action of GO towards Escherichia coli, Staphylococcus aureus, and Pseudomonas
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35 136 aeruginosa. In another study, GO has been found to inhibit the growth of E-coli biofilm on the
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38 137 Indium tin oxide surfaces by nearly 67%46. Mejías Carpio et al.46 have showed that GO
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40 138 functionalized with polyvinyl-N-carbazole (PVK) presents higher antimicrobial properties
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42 139 compared to pristine GO. They proposed that the PVK-GO encapsulate the bacterial cells,
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45 140 resulting in reduced metabolic activities and subsequent cell death.
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47 141 GO can therefore be used as a protective pigment that can be blended with epoxy resins to
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142 obtain bifunctional GO-epoxy (GOE) liners (i.e., anticorrosive and antimicrobial liners) in
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52 143 biodiesel tanks. GOE liners can be expected to offer the following advantages: (i) enhance
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54 144 bioavailability and facilitate a greater interaction between antimicrobial GO and bacteria; (ii)
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145 minimize moisture ingress into an underlying metal and reduce MIC risks;23, 29 and (iii) exhibit
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59 146 antimicrobial action against both sessile and planktonic bacteria.30, 46-49 GO manufacturing
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2 147 techniques described in the literature are scalable50 and enables estimation of bulk production
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148 of GO-epoxy. While it is important to embrace GOE liners in biofuel industry, it can be argued
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7 149 that there is limited quantitative information about its environmental impacts through life-cycle
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9 150 assessment (LCA). Similar to other nanomaterials, GOE liners should be evaluated for its LCA
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12 151 impacts in comparison to state-of-the-art liners used in biodiesel industry. The objective of this
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14 152 study is to evaluate environmental performance of a GOE liner as a potential alternative to
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16 153 commercial epoxy liners (Novolac liners) in a biodiesel storage tank.
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19 154 2. LIFE CYCLE ASSESSMENT METHODS
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21 155 2.1 GOE Liner for Biodiesel Storage Tank Interior- Description of Life Cycle Stages
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157 Figure 1 shows an overview of the major processes associated with the life cycle of the
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26 158 GOE liner system. The scope of current LCA study includes the following life cycle stages: (i)
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28 159 the surface preparation (e.g., degreasing) of the tank interior to remove oily impurities and dirt;
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160 (ii) the shot blasting of the clean surface; (iii) the synthesis of the GOE solution; this stage
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33 161 considers a solvent recovery step; (iv) an airless spray of GOE solution on the blasted surface;
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35 162 (v) the thermal curing of the coated surface; and (vi); the storage of biodiesel for 20 years in a
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38 163 steel tank coated with the GOE liner. Synthesis of GOE solution in stage 3 is based on the
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40 164 following procedure suggested in literature.29, 40 Dry GO powder is obtained by using the
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42 165 modified Hummer’s method. A precise quantity of GO powder and bisphenol-A (BPA) epoxy
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45 166 resin are subjected to the high-speed mixing (See Table 2 for details). The resulting mixture is
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47 167 ultrasonicated in presence of NMP and isopropylamine (IPA) to obtain the GOE solution.
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168 The life cycle stages beyond the system boundary (solid red line in Figure 1) are
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52 169 excluded from the scope of the current LCA. The environmental impacts of the excluded stages
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54 170 for the GOE liner system are identical to that for the incumbent system. Therefore, the excluded
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171 stages will not influence the overall conclusions about the LCA performance of the GOE liners.
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43 173 Figure 1. Flow diagram showing the major life cycle stages associated with synthesis of GOE solution
44 174 and its application as the interior liner of a biodiesel storage tank.
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47 177 2.2 Goal and Scope Definition.
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49 178 The work in this study follows the screening-level LCA framework51 and recommended
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52 179 practices of the ISO 14040:2006 and 14044:2006 LCA standards.52 This is characterized as a
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54 180 screening LCA because the life cycle inventory (LCI) of the foreground system, i.e. LCI data
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181 pertaining to the synthesis of the GOE solution is constructed using scale-up assumptions and
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59 182 by replying upon secondary data sources accessible through the academic and patent literature.
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2 183 The lack of primary data reflects the high degree of uncertainty of the proposed LCA model
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184 and associated results, implying that the conclusions presented in this study should be
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7 185 considered as preliminary in nature.
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9 186 The goal of this screening LCA study is to evaluate the environmental performance of
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12 187 a GOE liner system. The GOE liner is used to protect interior surface of a mild steel, biodiesel
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14 188 storage tank against MIC effects. The lifetime of the GOE liner is 20 years. This is based upon
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16 189 a premise that the lifetime of the tanks used to store fuels are limited to 20 years.53, 54 Further,
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19 190 the tank liners are typically designed to match design life of the storage tanks. The geographical
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21 191 boundary of the study is the United States.
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192 The life cycle impact assessment (LCIA) results for the GOE liner is compared with the
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26 193 incumbent system that uses the following “standard practice” (herein referred as incumbent
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28 194 system) to protect the storage tanks against the MIC effects. The standard practice combines
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195 protection from the following two different entities: (i) a thick solvent-free Novolac epoxy
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33 196 (SFE) liner (100% epoxy) is applied on the interior surface of the tank prior to commissioning;
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35 197 (ii) biodiesel is supplemented with a biocide to match the preventive dosage or reactive dosage
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38 198 requirements. A maintenance dosage is added to prevent microbial growth in the biodiesel
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40 199 (preventive maintenance) while a reactive dosage is added only when a first sign of microbial
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42 200 contamination is visible (Post maintenance). This study considers only the preventive dosage.
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45 201 Figure S1 shows the life cycle stages associated with the application of the incumbent system
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47 202 in the storage tank.
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203 2.3 Functional Unit.
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52 204 The equivalent functional unit (FU) is to protect 30 m2 of the interior surface (unalloyed
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54 205 steel sheet) of a 10,000 liters tank storing biodiesel and/or biodiesel blends against abiotic and
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206 biotic corrosion during its lifetime of 20 years. The FU in this study is based on the following
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59 207 specifications for the storage tanks suggested in the commercial literature:55 radius=1.9 m;
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2 208 height=4 m; total surface area =30 m2. The interior surface area to be coated and protected from
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209 MIC (triggered by both, aerobic and anaerobic living organisms) is considered as 30 m2. Figure
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7 210 2 shows the CAD renderings for the two identical storage tanks varying in type of the corrosion
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9 211 protection systems: i) the GOE liner system, and ii) the incumbent Novolac system that includes
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12 212 biocide protection. The tank dimensions shown in Figure 2 are based on the standard
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14 213 specifications established for the fuel oil storage tanks.55 The selected systems are intended to
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16 214 provide the protection throughout the lifespan of 20 years.
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24 Trazine
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53 231 Figure 2. Diagram showing specification of the functional unit chosen for the study
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2 234 2.4 Life Cycle Inventory (LCI) Modeling of GOE liner and Incumbent Systems.
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235 The foreground LCI data related to the life cycle stages of the GOE liner system is
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7 236 obtained from the academic and patent literature. The background data for the GOE liner system
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9 237 is obtained from the U.S. LCI secondary database56 built by the National Renewable Energy
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12 238 Laboratory (NREL) and the Ecoinvent database (v.3.2).57 The LCI databases are modified for
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14 239 the U.S. conditions to account for the energy consumption according to the U.S. national energy
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16 240 grid mix.57 LCI data for the incumbent system is built using the industrial literature (section
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19 241 2.5). The SimaPro LCA software package (version 8.0.2)58 was used to build the life cycle
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21 242 model for both the GOE liner system and incumbent system shown in Figure 2.
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243 2.4.1 Key Assumptions Made in Constructing LCI data of GOE liner
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26 244 Table 1 shows the assumptions used to build the LCI for the GOE liner system. Table 2
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28 245 shows the LCI dataset for the foreground system pertaining to the life cycle stages of GOE liner
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246 system, i.e., synthesis of GOE solution, spray coating, thermal curing, and solvent recovery
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33 247 processes.
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35 248 Table 1. Key assumptions for modeling LCI Data of GOE liner system
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38 Life Cycle Stage Major Assumptions Made & Data Sources
39 corresponding to stages
40 shown in Figure 1
41 Surface preparation (Stage 1) • Ecoinvent dataset RER dataset57 for degreasing metal part is
42 used.
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Shot blasting of degreased • Data for shot blasting of steel surface is obtained from Peng et
45 surface (Stage 2) al.59
46 Synthesis of GOE solution • LCI data for preparation of GOE solution is based on the
47 including the solvent recovery academic literature.29, 40
48 step (Stage 3) • LCI data for GO synthesis is based on the modified Hummer’s
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method suggested in Arviddsson et al.60
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51 • Volume of solids (VS) in the GOE solution = 60%. A liter of the
52 solution contains 0.4 liters of NMP solvent (volatile portion)
53 and 0.6 liters of solids (nonvolatile portion).
54 • The solid content of GOE solution is based on 1 wt% of GO, 70
55 wt% bisphenol-A epoxy resin, and 29 wt% of isopropylamine.
56 Mass loadings of the individual components in the GOE
57 solution are shown in Table 2. Relevant calculations are shown
58 in section S2 of the SI.
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2 • Energy for high speed mixing (0.7 KWh/kg) is based on the
3 mixing requirements for viscous materials.61
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• Ultrasonication energy requirements to disperse solid content of
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the coating in NMP solvent is calculated as 0.7 KWh per liter of
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7 solution (i.e., 700 watts per 60 minutes of ultrasonication time).
8 Calculations are shown in section S2 of the SI.
9 • 97% of the solvent is recovered and reused in a closed system.
10 3% of the make-up solvent is considered as a material input in

11 the Stage 3 of Figure 1
12 • 3% of the solvent is lost as VOCs
13 • Processing burden data for the solvent recovery is obtained from
14 industrial literature62 and reported in Table 2.
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Spray coating GOE solution • Airless spray is used to incorporate GOE liner with a transfer
17 on a clean surface of the tank efficiency of 68% (typical value for airless spray).63
18 (Stage 4) • Energy consumption for spray coating is 0.44 KWh/m2 and 210
19 g/m2 of VOCs.64
20 • Dry film thickness (DFT)) of coating is 200µm This assumption is
21 based on the patent literature related to the graphene coatings
22 characterized by anticorrosion and antifouling properties.65
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24 Thermal curing of wet GOE • Wet GOE liner is dried in a hot air oven. Energy requirements for
25 coating (Stage 5) the liner are obtained from industrial literature66 and shown in
26 Table 2
27 Biodiesel storage (use stage) • The lifespan of the GOE liner is 20 years.
28 in steel tank with GOE liner • Additional recoating is not required. Other maintenance action
29 (Stage 6) such as addition of fuel additives is also not required.
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31 249
32 250 Table 2. LCI data of Foreground System for GOE Liner per equivalent functional unit
33 251 (i.e. equivalent amount of coating required for 30 m2 interior surface of the storage tank)
34 252
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Inputs Amount
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37 Materials (kg.)
38 Bisphenol-A epoxy resin 7.22
39 Isopropylamine (Hardener) 2.99
40 GO (Synthesized via Modified Hummer’s method) 0.1
41 NMP solvent (3% of Makeup solvent) 0.186
42 Liquid nitrogen (Processing burdens-solvent recovery) 0.884
43 Deionized water (processing burdens-solvent recovery) 58.8
44
Energy Inputs (KWh)
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46 Energy Consumption for Mixing & Ultrasonication 20.8
47 Processing burdens-solvent recovery-electricity 6.48
48 Processing burdens-solvent recovery-thermal 15.9
49 Emissions (kg)
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VOC compounds 0.19
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2 257 2.4.2 Key Assumptions Made in Construction LCI Data of Incumbent System
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258 The major assumptions in modeling the LCI data of the incumbent system are
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7 259 summarized in Table 2.
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9 260 Table 2. Key assumptions for modeling the LCI Data of the Incumbent system
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261
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12 Coating Life Cycle Stage Major Assumptions Made & Data Sources
13 Surface preparation of the interior • Ecoinvent dataset RER dataset for degreasing a metal part is
14 surface (Stage 1) used.57
15
16
Shot blasting of degreased surface • Data for shot blasting of steel surface is obtained from Peng et
17
(Stage 2) al.59
18 Synthesis of solvent-free epoxy • Following composition for the SFE solution is obtained from
19 (SFE) solution (Stage 3) the industrial literature:62 epoxy resin (50 wt%); amine
20 hardener (25 wt%); benzyl alcohol (20%); and ether
21 components (5 wt.%).
22
23
• Components are mixed thoroughly for 30 mins.
24 • Calculations for estimating amount of coating material
25 required to line the interior surface of the tank is shown in
26 section S1 of the SI.
27 Spray coating SFE solution on the • Airless spray is used to incorporate SFE liner with a transfer
28 clean surface (Stage 4) efficiency of 68% (typical for airless spray).63
29 • Energy consumption for spray coating is 0.44 KWh/m2 and 210
30 g/m2 of VOCs.64
31
32
• DFT of SFE liner ranges from 300-600 µm.67 This study
33 assumes a DFT of 400 µm.
34 Air Drying of the SFE liner • Wet SFE liner is air dried
35 (Stage 5)
36 Biodiesel storage (use stage) • The lifespan of the SFE liner is 20 years.
37 (Stage 6) • Additional recoating is not required. Maintenance action such
38 as addition of fuel additives is also not required.
39
• Triazine biocide is dosed at a concentration of 125 ppm (i.e.
40
41
1.25 kg for 10,000 liters of biodiesel) to provide biocidal action
42 and minimize microbial growth in the storage tank.68, 69
43 • Biodiesel has a holding time of 6 months. This implies that
44 10,000 liters of biodiesel is emptied and the corresponding
45 amount is refilled every 6 months. Thus, 2.5 kg of triazine is
46 required annually which corresponds to a 50 kg requirement
47 during the 20 years lifespan. This scenario simulates the long
48 term biofuel storage conditions in the field.70
49 262
50
51
52 263 2.5 Impact Assessment Methodology.
53
54 264 The Tool for the Reduction and Assessment of Chemical and other environmental
55
56
57
265 Impacts (TRACI 2.1)71, 72
was used to assess the ten midpoint impact categories: global
58
59 266 warming potential (GWP, kg CO2 eq.); acidification potential (AP, kg SO2 eq.); potential
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2 267 human health damage impacts due to carcinogens (HH-CP, CTUh) and non-carcinogens (HH-
3
4
5
268 NCP, CTUh); potential respiratory effects (REP, kg PM2.5 eq); eutrophication potential (EP, kg
6

7 269 N eq); ozone depletion potential (ODP kg CFC-11 eq); ecotoxicity potential (ETXP CTUe);
8
9 270 smog formation potential (SFP kg O3 eq); and fossil fuel depletion potential (FFDP MJ surplus).
10
11
12 271 TRACI is a North American mid-point impact assessment method developed by the U.S.
13
14 272 Environmental Protection Agency (EPA)71 and is tailored to the US conditions. TRACI 2.1
15
16 273 incorporates the USEtox environmental model for characterizing human health and ecotoxicity
17
18
19 274 impacts.73, 74
20
21 275 2.6. Scenario Analysis
22
23
276 A recent body of the scientific literature confirms that the hybrid silane coatings
24
25
26 277 reinforced with silanized GO (SGO) nanosheets are characterized by anti-fouling and anti-
27
28 278 corrosive properties.75-77 SGO in hybrid silane coatings provides a physical barrier to foulants
29
30
31
279 (microorganisms and slimy proteins), resulting in their detachment from the underlying metal
32
33 280 surface. A series of recent studies have also confirmed that GO can be reinforced in polymers
34
35 281 such as polyvinyl-carbazole (PVK) to obtain GO-PVK coatings with enhanced anti-microbial
36
37
38 282 action46, 49, 78
against sessile and film-forming bacteria. The GO-PVK coatings have been
39
40 283 reported to exhibit the contact-upon-killing mechanism to inhibit microbial growth.46 Based on
41
42 284 the above background, we carried out a scenario-based sensitivity analysis to study the effects
43
44
45 285 of changes in the key modeling parameters on the potential environmental impacts of the GOE
46
47 286 liner systems. The following two scenarios considered in this study are expected to enhance the
48
49
287 corrosion resistance of the GO liners in the biodiesel tanks: (i) a silanized-GO (SGO) is spray
50
51
52 288 coated and thermally cured to obtain a DFT of 20 µm (Volume solids =20%) on the top of the
53
54 289 GOE-lined-surface; the modified GOE-lined surface is expected to be characterized by
55
56
57
290 antifouling properties; (ii) a GO-PVK is spray coated and thermally cured to obtain a DFT of
58
59 291 20 µm on the top of the GOE-lined-surface. The synthesis procedures and the LCI data related
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2 292 to the SGO coating and GO-PVK coating is reported in the section S3 of the SI. In both the
3
4
5
293 scenarios, the GO composition is fixed at 1 wt%.
6

7 294 2.6.1. Uncertainty Analysis of GOE Liner System
8
9 295 It may be fair to argue that there is an inadequate evidence to prove that GOE liner
10
11
12 296 system is capable of protecting the storage tanks against abiotic and biotic corrosion, especially
13
14 297 for lifetime periods as long as 20 years proposed in this study. To the best of the authors
15
16 298 knowledge, there is no peer-reviewed literature that confirms success or failure of the GOE
17
18
19 299 liners against corrosive and MIC effects of biodiesel. Majority of the corrosion studies that
20
21 300 evaluated graphene, GO, rGO, GOE, and other GO composites are based on the short-term
22
23
301 immersion studies that range from six days to six months. Specifically, the GOE evaluated in
24
25
26 302 the current LCA study has never been tested as the liner in biodiesel tanks under the field
27
28 303 conditions, especially under time scale as long as 20 years. Further, the superior LCA
29
30
31
304 performance results for the GOE liner system may become invalid under the following
32
33 305 circumstances: (i) the exposed GOE liner is delaminated due to the aggressive physico-chemical
34
35 306 characteristics of biodiesel; and (ii) the corrosion protection of the GOE liners fails before the
36
37
38 307 lifetime of 20 years. These conditions introduce uncertainty in the modeling parameters
39
40 308 considered in the baseline study. Figure 5 suggests the reasons for the underperformance and
41
42 309 failure of GOE liners and the measures required to mitigate these effects. For example, GO
43
44
45 310 liners can be functionalized with amine groups to promote its adherence to the underlying steel
46
47 311 surface.40, 42, 79-81 GOE liners have been reported to work effectively when they are covalently
48
49
312 attached to the metals40, 79, 80. This process can reduce the ingress of moisture and gases to the
50
51
52 313 liner surface.40, 79, 80 Functionalization techniques can also be used to enhance surface area of
53
54 314 GOE liners and promote the interaction between GO and microorganisms (both sessile and film-
55
56
57
315 forming microbes)82 present in the biodiesel. As mentioned earlier, cellular membrane of
58
59 316 microbes exposed to the sharp edges of GO nanosheets will undergo a lysis process.82
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2
3
4
5
6

7
8
9
10
11
12
13
14
15
16
17
18 317 Figure 5. Rationale for selecting Uncertainty Analysis for the proposed GOE Liner System
19
20
21 318 Uncertainty in the results can arise due to the modeling parameters associated with the
22
23 319 thermal curing and solvent recovery stages of the GOE life cycle. For example, the thermal
24
25 320 curing process used to obtain the GOE liner in the baseline study can be replaced with an
26
27
28 321 energy-efficient UV curing. Further, the LCI data used to quantify processing burdens for the
29
30 322 solvent recovery has also been reported to vary to a larger extent.62, 83.
31
32 323 For the incumbent system, the uncertainty can arise in the model due to the variation of
33
34
35 324 values for the following two key modeling parameters: (a) the thickness of the SFE liner, and
36
37 325 (b) the concentration of triazine in the biodiesel. An uncertainty analysis is conducted by
38
39
40
326 incorporating the above said uncertainties into the respective life cycles of GOE and incumbent
41
42 327 systems. Table 3 shows the ranges established for these key parameters during uncertainty
43
44 328 analysis. The uncertainty analysis was conducted within SimaPro using Monte Carlo simulation
45
46
47 329 with 5000 steps and a 95% level of confidence.
48
49 330
50
51 331
52
53
54 332
55
56 333
57
58
59
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2 334 Table 3 Variation of Key Modeling Parameters for Uncertainty Analysis of GOE Liner and
3 335 Incumbent Systems.
4
336
5
6 GOE Liner system Incumbent System

7
8 • Amine-functionalized GO as an alternative to • Thickness of coating of SFE liner is varied
9 GO filler in order to facilitate adhesion from 300-500µm (The minimum and
10 • Coating thickness (DFT) varied from 50-400 maximum coating thicknesses of SFE liner as
11 µm. suggested by commercial literature).22, 67
12 • Energy consumption for shot blasting is • Consumption of triazine biocide is varied
13
varied from 0.995 KWh to 3 KWh/m2. A from 125 ppm to 250 ppm.
14
15 typical value of energy consumption for sand • Energy consumption of shot blasting is varied
16 blasting is 3 KWh/m2.84 from 0.995 KWh to 3 KWh/m2 (3 KWH/m2
17 • Energy consumption of curing is varied from being typical consumption of sand blasting).84
18 0.126-0.1488 KWh/m2 (electrical energy) and
19 0-0.6901 KWh/m2(thermal energy) to
20 accommodate for the differences between
21 thermal curing and UV curing
22 337
23
24
25 338 3. RESULTS AND DISCUSSION
26
27 339 3.1. Contribution Analysis of GOE Liner System
28
29
340 The environmental performance of the GOE liner system is analyzed using
30
31
32 341 contribution analysis and the relative contributions of the individual life cycle stages (i.e.,
33
34 342 surface preparation, shot blasting, GOE synthesis, spray coating, and thermal curing)
35
36
37
343 towards its total life cycle impact under the ten categories (Figure 3). The total scores for
38
39 344 each impact category are shown on the top of the graph. This contribution analysis can
40
41 345 be used to identify hotspots for potential stage improvements.
42
43
44 346 Among the five life cycle stages of the GOE liner system shown in Figure 3, the
45
46 347 stage involving preparation of the GOE solution accounted for 45% of the total impact
47
48 348 in the REP category; 50-55% of impacts in the GWP, AP and EP categories; 61-65% in
49
50
51 349 the SFP, ETXP and HH-NCP categories; and 70-76% in the HH-CP, ODP and FFDP
52
53 350 impact categories. Figure S2 shows the potential environmental impacts for synthesizing
54
55
56
351 GOE solution required to coat 30 m2 of the interior surface area. These results indicate
57
58 352 that the type of resin used as a binder influences the overall environmental performance
59
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2 353 of the GOE liner system. For example, BPA epoxy resin contributes to at least 40% of
3
4
5
354 the total impact due to the GOE solution in seven out of the ten categories. The impacts
6

7 355 of the hots spots identified during the preparation of GOE solution can be lowered by
8
9 356 replacing BPA epoxy resin with alkyd, polyester or urea-formaldehyde resins.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35 357
36 358 Figure 3. Contribution Analysis of GOE Liner Using Internally Normalized Impact Scores
37 359
38 360
39 361 The impacts due to the solvent recovery step are primarily attributed to processing
40
41
42 362 burdens (electrical energy and thermal energy incurred) in recovering the NMP solvent.
43
44 363 The potential impact contributions for the solvent recovery step are attributed to the
45
46 364 energy requirements for mixing and ultrasonication processes. Mass production of the
47
48
49 365 GOE solution can likely reduce the overall energy requirements and associated impacts
50
51 366 due to the ultrasonication and mixing processes. The results also show that the shot
52
53
54
367 blasting stage is the second largest contributor to the total environmental impacts of the
55
56 368 GOE liner system (Figure 3). The domination of shot blasting stage on the overall
57
58 369 impacts of the GOE liner system is primarily due to the energy requirements (0.99 KWh
59
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2 370 per m2 of surface).59 Further, the impacts due to the spray coating stage can be reduced
3
4
5
371 by considering alternate options such as a brush-coating process.
6

7 372 3.2. Baseline Comparison of GOE Liner Results with the Incumbent System
8
9 373 Figure 4 compares the internally normalized impact scores for the GOE liner
10
11
12 374 system with the incumbent system, i.e. SFE liner and Triazine biocide (with the highest
13
14 375 scores in each impact category listed on the top of the graph).
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 376 Figure 4. Comparison of Life Cycle Impact Assessment Results for GOE liner system
43
377 and the Incumbent System (refers to Standard Corrosion Protection Practice: Solvent Free
44
45
378 Novolac Epoxy Liner (400 µm thick) + 125 ppm of Triazine Biocide)
379
46
47 380 The results indicate that the environmental impacts due to the GOE liner system are
48
49 381 lower than the incumbent system in all the ten impact categories. The impacts for GOE liner
50
51 382 system are 59% smaller for the REP category; 62% smaller for AP; 67-69% smaller for GWP
52
53
54 383 and HH-CP; 72-76% smaller for EP, SFP, and FFDP; 81-83% smaller for ETXP and HH-NCP:
55
56 384 and 91% smaller for ODP impact categories. The larger environmental impacts for the
57
58
59
385 incumbent system are attributed to the use of biocide (i.e., triazine). Figure S2 shows breakdown
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2 386 of the impact contributions from the solvent-free epoxy and biocide in the incumbent system.
3
4
5
387 As shown in Figure S3, the use of triazine accounts for at least 58% of its total environmental
6

7 388 impact in SFP; 67% in REP and at least 75% in the other impact categories. It is noteworthy to
8
9 389 observe that the incumbent system results in the higher environmental impacts in spite of
10
11
12 390 considering a conservative estimate of 125 ppm for the triazine concentration (compared to the
13
14 391 typical dosage rates of 350-1000 ppm reported in the literature).27, 85
15
16 392 3.3. Scenario Analysis- Antifouling/Antimicrobial Top Coat on the GOE Liner
17
393
18
19 394 We carried out the scenario analysis and compare the environmental impacts of the
20
21 395 incumbent system with the following two modified GOE liner systems: (i) the GOE liner coated
22
23
396 with an anti-fouling, silane-functionalized GO (SGO) (50µm SGO topcoat + 200µm GOE
24
25
26 397 undercoat); and (ii) the GOE liner coated with an antimicrobial GO-PVK (50µm GO-PVK
27
28 398 topcoat + 200 µm GOE undercoat).
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 399
56
400 Figure 5. Comparison of Life Cycle Impact Assessment Results for Incumbent System (Referring to
57
401 Standard Corrosion Protection Practice- Solvent Free Novolac Epoxy Liner (400 µm thick) + 125 ppm
58
59 402 of Triazine Biocide) and the GOE Liners modified with SGO antifoulant and Antimicrobial GO-PVK .
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2 403 The results presented in Figure 5 shows that the impacts for the modified GOE liners
3
4
5
404 were slightly higher than the GOE liners in the baseline study (Figure 5). However, the
6

7 405 environmental impacts of the modified GOE liners are lower than the incumbent system in the
8
9 406 ten impact categories. Compared to the incumbent system, the environmental impacts of the
10
11
12 407 two layered liner system with enhanced antifouling functionality (i.e. SGO-silane topcoat plus
13
14 408 GOE undercoat) are 48% smaller for REP impact category; 52% smaller for AP; 61% smaller
15
16 409 for HH-CP and GWP; 66% smaller for FFDP; 68-70% smaller for EP and SFP; 76-78% smaller
17
18
19 410 for ETXP and HH-NCP; 84% smaller for ODP impact categories. A similar study86 is
20
21 411 performed recently where authors compared the environmental performance of an antifouling
22
23
412 paint loaded with marine biocide with conventional copper based paint for marine applications.
24
25
26 413 In this study the authors compared two systems based on 1 m2 of functional surface area and
27
28 414 with a lifetime of a paint as 3 years. Translating their results to the equivalent functional unit
29
30
31
415 considered in our LCA, the GWP and FFDP impacts of SGO-silane antifouling coating alone
32
33 416 (without taking GOE undercoat into consideration) are smaller then the antifoulant system
34
35 417 proposed by them. On the other hand, the two layered coating with enhanced antimicrobial
36
37
38 418 functionality (i.e. GO-PVK top coating on GOE undercoat) has 45% smaller impact in REP
39
40 419 category; 46% smaller for AP; 58-50% smaller for HH-CP and GWP; 65% smaller for FFDP;
41
42 420 67-68% smaller for EP and SFP; 75-77% smaller for ETXP and HH-NCP; 87% smaller for
43
44
45 421 ODP impact categories.
46
47 422 3.4. Uncertainty Analysis
48 423
49
424 Figure 6 compares the uncertainty analysis results for the incumbent system and the
50
51
52 425 modified GOE liner systems after accounting for the variations of key modeling parameters
53
54 426 shown in Table 3. The error bars correspond to 95% confidence intervals and + 1 Standard
55
56
57
427 deviation (SD) around the mean.
58
59
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2 428
3
4
5
6

7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 429
30
31 430 Figure 6. Comparison of Uncertainty Analysis Results for Incumbent System (Referring to Standard
32 431 Corrosion Protection Practice- Solvent Free Novolac Epoxy Liner (400 µm thick) + 125 ppm of Triazine
33 432 Biocide), and amino functionalized-GOE liner.
34 433
35 434
36 435 The results show that nine out of the ten impacts for the modified GOE liner
37
38
39 436 system vary by only 15% when the key parameters are changed. The HH-C impacts of
40
41 437 modified GOE liner systems show a variation of 60%, which is mainly when the coating
42
43
438 thickness is varied between 50-300 µm. Variation in coating thickness will influent the
44
45
46 439 GO consumption, which in turn effects the consumption of sulfuric acid and phosphoric
47
48 440 acids, used during the modified Hummer’s method. The mists of inorganic acids (e.g.,
49
50
51
441 H2SO4) produced during GO production are carcinogenic in nature. For the incumbent
52
53 442 system, the impacts of GWP, AP, REP, SFP and FFDP varied by less than 20%; ODP by
54
55 443 26%; EP by 42%; ETXP by 52%; HH-NCP by 85% and HH-CP by 179%. The variation
56
57
58 444 seen in EP and ETXP categories are attributed to the increase in consumption of trazine
59
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2 445 from 125 to 250 ppm. A large variation in impacts of HH-CP and HH-NCP impacts is
3
4
5
446 also attributed to the increase in the trazine consumption, and also due to the increase in
6

7 447 the SFE thickness (i.e., from 300 to 500 µm). The phenolic components of the Novolac
8
9 448 resin used in the incumbent liner are known to cause cancer and other health effects,87
10
11
12 449 which is a primary reason for the huge variation in the impacts under these categories.
13
14 450 4. CONCLUSIONS
15
16 451 This study highlights the environmental benefits of using the GOE liner in the biodiesel
17
18
19 452 infrastructure. The results suggest that the GOE liner obviates the need to use biocides in
20
21 453 biodiesel storage tanks. However, the concept of using the GOE liners for protection tanks
22
23
454 against corrosive effects of biodiesel is still at its infancy. GOE coatings may fail to offer
24
25
26 455 corrosion protection under two different circumstances: (a) a premature failure of the GOE
27
28 456 liners due to peeling and delamination effects; and (b) a gradual decrease in corrosion resistance
29
30
31
457 of the GOE liners and its failure prior to 20 years; for example, the percentage antimicrobial
32
33 458 efficiency can decrease over time. The long-term performance of the GOE liner can be
34
35 459 increased by using functionalized GO (fGO) pigment in place of GO in order to improve the
36
37
38 460 adherence characteristics. The antifouling and antimicrobial characteristics of the GOE liner
39
40 461 can be enhanced by adapting a bi-layered liner with the SGO/GO-PVK top coat and the GOE
41
42 462 undercoat. The LCA results suggest than GOE liners have an improved environmental
43
44
45 463 performance compared to the incumbent system in all the following three conditions: (i) when
46
47 464 a single coating of GOE liner is adequate for mitigating abiotic and biotic corrosion; (ii) the bi-
48
49
465 layered liner is used; and (iii) the fGO pigment is used in the GOE liner. Further, the
50
51
52 466 environmental benefits are warranted covering a broad spectrum of GOE liner thickness.
53
54 467 However, the findings related to the GOE liners should be considered with care until
55
56
57
468 performance of the GOE liners has been established for an extended period of duration (~20
58
59 469 years) in the field conditions. A series of experimental investigations are necessary to evaluate
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2 470 if the GOE liner can remain attached to the tank surface and does escape into the environmental
3
4
5
471 subsystems. Further, the antimicrobial/antifoulant efficacy of the GOE liners should be tested
6

7 472 with indigenous microbial population that may typically thrive in biodiesel. Studies are also
8
9 473 required to develop a deeper understanding on toxic effects of the GOE material on living
10
11
12 474 beings and aquatic species.
13
14 475 According to a recent LCA study88 on biodiesel, the fuel storage and distribution stage
15
16 476 contributes to 12.8% of total biodiesel’s GWP impact.88 While this is modestly minimal, the
17
18
19 477 impacts of biodiesel storage tank to entire fuel storage and distribution stage can be even smaller
20
21 478 and the storage tank liner impacts can be even minuscule considering the whole life cycle of
22
23
479 biodiesel. However, an important inference from this study is that graphene liners may have the
24
25
26 480 ability to internalize environmental externalities by reducing the biocide usage in biofuel
27
28 481 infrastructure and thereby reduce environmental impacts of trace air pollutants that can be
29
30
31
482 potentially generated during combustion of biodiesel loaded with biocides. At this point, it is
32
33 483 uncertain if the biocides used in the biodiesel will reach the internal combustion (IC) engines
34
35 484 of automobiles to undergo subsequent combustion and influence the air pollution profiles in
36
37
38 485 affected regions. A recent study suggests that combustion of an additive package containing
39
40 486 biocide will not result in an increased exhaust emissions.89 However, it does not mean that the
41
42 487 combustion will not emit known and unknown pollutants into atmosphere. The biocide usage
43
44
45 488 in the biofuel infrastructure will contribute to the use-stage environmental externalities that are
46
47 489 not easily detected by the LCA study. Currently, there is also a need to develop new methods
48
49
490 that quantify the presence or absence of the air pollution due to combustion of GO nanoparticles
50
51
52 491 in IC engines. If GOE liners were to be implemented in near future, it is certain that a well-
53
54 492 engineered biofuel infrastructure is necessary to restrict the GOE materials from reaching filling
55
56
57
493 stations and fuel docks.
58
59
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2 494 Finally, this LCA serves as a case study for other applications where the negative
3
4
5
495 environmental externalities of using toxic chemicals (e.g. wood preservatives) can be
6

7 496 internalized by rationalizing material selection process.
8
9 497
10
11
12 498 5. ACKNOWLEDGEMENTS
13
14 499 Gadhamshetty acknowledges the funding support from National Science Foundation
15
16 500 CAREER Award (#1454102); NASA (NNX16AQ98A); and the South Dakota Board of
17
18
19 501 Regents under the auspices of the Surface Engineering Research Center (SERC). We are
20
21 502 thankful to Namita Shrestha for providing the CAD renderings.
22
23
503
24
25
26 504 6. REFERENCES
27
28 505 1. USEPA Program overview for renewable fuel standard program. https://www.epa.gov/renewable-fuel-
29 506 standard-program/program-overview-renewable-fuel-standard-program (September 27),
30 507 2. Buss, J. Biodiesel: Fat to fuel. https://www3.epa.gov/region9/waste/biodiesel/ (September 27),
31 508 3. Eryilmaz, T.; Yesilyurt, M. K.; Cesur, C.; Gokdogan, O., Biodiesel production potential from oil seeds
32 509 in Turkey. Renewable and Sustainable Energy Reviews 2016, 58, 842-851.
33 510 4. NBB Biodiesel and the U.S. diesel vehicle market -V1; National Biodiesel Board: Jefferson City, MO,
34 511 USA, 2016; pp 1-24.
35 512 5. Sørensen, G.; Pedersen, D. V.; Nørgaard, A. K.; Sørensen, K. B.; Nygaard, S. D., Microbial growth
36 513 studies in biodiesel blends. Bioresource technology 2011, 102, (8), 5259-5264.
37 514 6. Azam, M. M.; Waris, A.; Nahar, N., Prospects and potential of fatty acid methyl esters of some non-
38 515 traditional seed oils for use as biodiesel in India. Biomass and bioenergy 2005, 29, (4), 293-302.
39 516 7. He, B.; Thompson, J.; Routt, D.; Van Gerpen, J., Moisture absorption in biodiesel and its petro-diesel
40 517 blends. Applied engineering in agriculture 2007, 23, (1), 71-76.
41 518 8. Luque, R.; Herrero-Davila, L.; Campelo, J. M.; Clark, J. H.; Hidalgo, J. M.; Luna, D.; Marinas, J. M.;
42 519 Romero, A. A., Biofuels: a technological perspective. Energy & Environmental Science 2008, 1, (5), 542-564.
43 520 9. Junior, J. S.; Mariano, A. P.; de Angelis, D., Biodegradation of biodiesel/diesel blends by Candida
44 521 viswanathii. African Journal of Biotechnology 2009, 8, (12).
45 522 10. Dodos, G.; Konstantakos, T.; Longinos, S.; Zannikos, F., Effects of microbiological contamination in the
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