Oxygen Reduction Reaction with Manganese Oxide Nanospheres in Microbial Fuel Cells.

Operating microbial fuel cells (MFCs) under extreme pH conditions offers a substantial benefit. Acidic conditions suppress the growth of undesirable methanogens and increase redox potential for oxygen reduction reactions (ORRs), and alkaline conditions increase the electrocatalytic activity. However, operating any fuel cells, including MFCs, is difficult under such extreme pH conditions. Here, we demonstrate a pH-universal ORR ink based on hollow nanospheres of manganese oxide (h-Mn3O4) anchored with multiwalled carbon nanotubes (MWCNTs) on planar and porous forms of carbon electrodes in MFCs (pH = 3-11). Nanospheres of h-Mn3O4 (diameter ∼ 31 nm, shell thickness ∼ 7 nm) on a glassy carbon electrode yielded a highly reproducible ORR activity at pH 3 and 10, based on rotating disk electrode (RDE) tests. A phenomenal ORR performance and long-term stability (∼106 days) of the ink were also observed with four different porous cathodes (carbon cloth, carbon nanofoam paper, reticulated vitreous carbon, and graphite felt) in MFCs. The ink reduced the charge transfer resistance (R ct) to the ORR by 100-fold and 45-fold under the alkaline and acidic conditions, respectively. The current study promotes ORR activity and subsequently the MFC operations under a wide range of pH conditions, including acidic and basic conditions.

Corrosion Resistance of Sulfur-Selenium Alloy Coatings.

Despite decades of research, metallic corrosion remains a long-standing challenge in many engineering applications. Specifically, designing a material that can resist corrosion both in abiotic as well as biotic environments remains elusive. Here a lightweight sulfur-selenium (S-Se) alloy is designed with high stiffness and ductility that can serve as an excellent corrosion-resistant coating with protection efficiency of ≈99.9% for steel in a wide range of diverse environments. S-Se coated mild steel shows a corrosion rate that is 6-7 orders of magnitude lower than bare metal in abiotic (simulated seawater and sodium sulfate solution) and biotic (sulfate-reducing bacterial medium) environments. The coating is strongly adhesive, mechanically robust, and demonstrates excellent damage/deformation recovery properties, which provide the added advantage of significantly reducing the probability of a defect being generated and sustained in the coating, thus improving its longevity. The high corrosion resistance of the alloy is attributed in diverse environments to its semicrystalline, nonporous, antimicrobial, and viscoelastic nature with superior mechanical performance, enabling it to successfully block a variety of diffusing species.

Forecasting the dynamics of cumulative COVID-19 cases (confirmed, recovered and deaths) for top-16 countries using statistical machine learning models: Auto-Regressive Integrated Moving Average (ARIMA) and Seasonal Auto-Regressive Integrated Moving Average (SARIMA).

Most countries are reopening or considering lifting the stringent prevention policies such as lockdowns, consequently, daily coronavirus disease (COVID-19) cases (confirmed, recovered and deaths) are increasing significantly. As of July 25th, there are 16.5 million global cumulative confirmed cases, 9.4 million cumulative recovered cases and 0.65 million deaths. There is a tremendous necessity of supervising and estimating future COVID-19 cases to control the spread and help countries prepare their healthcare systems. In this study, time-series models - Auto-Regressive Integrated Moving Average (ARIMA) and Seasonal Auto-Regressive Integrated Moving Average (SARIMA) are used to forecast the epidemiological trends of the COVID-19 pandemic for top-16 countries where 70%-80% of global cumulative cases are located. Initial combinations of the model parameters were selected using the auto-ARIMA model followed by finding the optimized model parameters based on the best fit between the predictions and test data. Analytical tools Auto-Correlation function (ACF), Partial Auto-Correlation Function (PACF), Akaike Information Criterion (AIC) and Bayesian Information Criterion (BIC) were used to assess the reliability of the models. Evaluation metrics Mean Absolute Error (MAE), Mean Square Error (MSE), Root Mean Square Error (RMSE) and Mean Absolute Percent Error (MAPE) were used as criteria for selecting the best model. A case study was presented where the statistical methodology was discussed in detail for model selection and the procedure for forecasting the COVID-19 cases of the USA. Best model parameters of ARIMA and SARIMA for each country are selected manually and the optimized parameters are then used to forecast the COVID-19 cases. Forecasted trends for confirmed and recovered cases showed an exponential rise for countries such as the United States, Brazil, South Africa, Colombia, Bangladesh, India, Mexico and Pakistan. Similarly, trends for cumulative deaths showed an exponential rise for countries Brazil, South Africa, Chile, Colombia, Bangladesh, India, Mexico, Iran, Peru, and Russia. SARIMA model predictions are more realistic than that of the ARIMA model predictions confirming the existence of seasonality in COVID-19 data. The results of this study not only shed light on the future trends of the COVID-19 outbreak in top-16 countries but also guide these countries to prepare their health care policies for the ongoing pandemic. The data used in this work is obtained from publicly available John Hopkins University's COVID-19 database.

Anaerobic wastewater treatment and reuse enabled by thermophilic bioprocessing integrated with a bioelectrochemical/ultrafiltration module.

The current study aimed to develop an anaerobic wastewater treatment and reuse module enabled by thermophilic bioprocessing, a microbial fuel cell (MFC) and ultrafiltration (UF) treatment. A previously unexplored consortium based on Thermoanaerobacterium thermosaccharolyticum and Arcobacter sp. was used to remove ~73% of chemical oxygen demand (COD) from wastewater under anaerobic conditions (CODi = 200 mg/L). The subsequent MFC and UF treatment removed the COD remnants to meet the secondary treatment standards and reuse criteria. The energy efficiency of polyethersulfone UF membranes was improved by modifying their surfaces with coatings based on self-polymerized dopamine, mixtures of dopamine and poly(2-dimethylamino) ethyl methacrylate methyl, and dopamine analog norepinephrine. The resulting hydrophilic, anti-fouling layers were found to reduce interactions between rejected species and the membrane surface. Finally, this study presents a comparative treatment performance and energy efficiency of the wastewater treatment and reuse modules arranged in six different configurations.

Valorization of methane from environmental engineering applications: A critical review.

Wastewater and waste management sectors alone account for 18% of the anthropogenic methane (CH4) emissions. This study presents a critical overview of methanotrophs ("methane oxidizing microorganisms") for valorizing typically discarded CH4 from environmental engineering applications, focusing on wastewater treatment plants. Methanotrophs can convert CH4 into valuable bioproducts including chemicals, biodiesel, DC electricity, polymers, and S-layers, all under ambient conditions. As discarded CH4 and its oxidation products can also be used as a carbon source in nitrification and annamox processes. Here we discuss modes of CH4 assimilation by methanotrophs in both natural and engineered systems. We also highlight the technical challenges and technological breakthroughs needed to enable targeted CH4 oxidation in wastewater treatment plants.

Vitamin-C-enabled reduced graphene oxide chemistry for tuning biofilm phenotypes of methylotrophs on nickel electrodes in microbial fuel cells.

This study reports the use of multi-layered reduced graphene oxide (rGO) coating on porous nickel foam (NF) electrodes for enhancing biofilm growth of Rhodobacter Sphaeroides spp fed with methanol in microbial fuel cells (CH3OH-MFCs). Electrochemical methods were used to assess the methylotrophic activity on rGO/NF electrodes. The power density and current density offered by rGO/NF (1200 mW m-2 and 680 mA m-2) were 220-fold and 540-fold higher compared to bare NF (5.50 mW m-2 and 1.26 mA m-2), respectively. Electrochemical impedance spectroscopy results show that rGO/NF suppresses charge transfer resistance to CH3OH oxidation by 40-fold compared to the control. This improved performance is due to the ability of rGO coatings to decrease the wetting contact angle (improve the hydrophilicity) of NF from 1280 to 00. A preliminary cost analysis was carried out to assess the viability of rGO/NF electrodes via vitamin-C-enabled graphene oxide chemistry for CH3OH-MFCs applications.

Hexagonal Boron Nitride: The Thinnest Insulating Barrier to Microbial Corrosion.

We report the use of a single layer of two-dimensional hexagonal boron nitride (SL-hBN) as the thinnest insulating barrier to microbial corrosion induced by the sulfate-reducing bacteria Desulfovibrio alaskensis G20. We used electrochemical methods to assess the corrosion resistance of SL-hBN on copper against the effects of both the planktonic and sessile forms of the sulfate-reducing bacteria. Cyclic voltammetry results show that SL-hBN-Cu is effective in suppressing corrosion effects of the planktonic cells at potentials as high as 0.2 V ( vs Ag/AgCl). The peak anodic current for the SL-hBN coatings is ∼36 times lower than that of bare Cu. Linear polarization resistance tests confirm that the SL-hBN coatings serve as a barrier against corrosive effects of the G20 biofilm when compared to bare Cu. The SL-hBN serves as an impermeable barrier to aggressive metabolites and offers ∼91% corrosion inhibition efficiency, which is comparable to much thicker commercial coatings such as polyaniline. In addition to impermeability, the insulating nature of SL-hBN suppresses galvanic effects and improves its ability to combat microbial corrosion.

Extremophiles for microbial-electrochemistry applications: A critical review.

Extremophiles, notably archaea and bacteria, offer a good platform for treating industrial waste streams that were previously perceived as hostile to the model organisms in microbial electrochemical systems (MESs). Here we present a critical overview of the fundamental and applied biology aspects of halophiles and thermophiles in MESs. The current study suggests that extremophiles enable the MES operations under a seemingly harsh conditions imposed by the physical (pressure, radiation, and temperature) and geochemical extremes (oxygen levels, pH, and salinity). We highlight a need to identify the underpinning mechanisms that define the exceptional electrocatalytic performance of extremophiles in MESs.

Comparative performances of microbial capacitive deionization cell and microbial fuel cell fed with produced water from the Bakken shale.

This study evaluates and compares the performance of microbial fuel cells (MFCs) and microbial capacitive deionization cells (MCDCs) fed with wastewater produced from the Bakken shale. The produced water was characterized by high levels of dissolved solids and chemical oxygen demand (COD). Two-compartment MFCs and three-compartment MCDCs were evaluated under batch-fed mode using mixed microbial consortia in the anode, ferricyanide in the cathode, and produced water as the electrolyte in the anode and capacitive deionization units. COD removal in the MFCs was 88%, while that in the MCDCs was limited to 76%. The lower performance of the MCDCs was due to the large impedance (6600 Ω cm2) compared with the MFCs (870 Ω cm2). However, the MCDCs achieved two-fold higher removal of dissolved solids. Both the MFCs and MCDCs suffered from a higher impedance induced by fouling in the latter stages of the operation.

Integrated membrane and microbial fuel cell technologies for enabling energy-efficient effluent Re-use in power plants.

Municipal wastewater is an attractive alternative to freshwater sources to meet the cooling water needs of thermal power plants. Here we offer an energy-efficient integrated microbial fuel cell (MFC)/ultrafiltration (UF) process to purify primary clarifier effluent from a municipal wastewater treatment plant for use as cooling water. The microbial fuel cell was shown to significantly reduce chemical oxygen demand (COD) in the primary settled wastewater effluent upstream of the UF module, while eliminating the energy demand required to deliver dissolved oxygen in conventional aerobic treatment. We investigated surface modification of the UF membranes to control fouling. Two promising hydrophilic monomers were identified in a high-throughput search: zwitterion (2-(Methacryloyloxy)-ethyl-dimethyl-(3-sulfopropyl ammoniumhydroxide, abbreviated BET SO3-), and amine (2-(Methacryloyloxy) ethyl trimethylammonium chloride, abbreviated N(CH3)3+). Monomers were grafted using UV-induced polymerization on commercial poly (ether sulfone) membranes. Filtration of MFC effluent by membranes modified with BET SO3- and N(CH3)3+ exhibited a lower rate of resistance increase and lower energy consumption than the commercially available membrane. The MFC/UF process produced high quality cooling water that meets the Electrical Power Research Institute (EPRI) recommendations for COD, a suite of metals (Fe, Al, Cu, Zn, Si, Mn, S, Ca and Mg), and offered extremely low corrosion rates (<0.05 mm/yr). A series of AC and DC diagnostic tests were used to evaluate the MFC performance.

Sustainability of renewable fuel infrastructure: a screening LCA case study of anticorrosive graphene oxide epoxy liners in steel tanks for the storage of biodiesel and its blends.

Biodiesel is a widely used fuel that meets the renewable fuel standards developed under the Energy Policy Act of 2005. However, biodiesel is known to pose a series of abiotic and biotic corrosion risks to storage tanks. A typical practice (incumbent system) used to protect the tanks from these risks include (i) coating the interior surface of the tank with a solvent-free epoxy (SFE) liner, and (ii) adding a biocide to the tank. Herein, we present a screening-level life-cycle assessment study to compare the environmental performance of a graphene oxide (GO)-epoxy (GOE) liner with the incumbent system. TRACI was used as an impact assessment tool to model the midpoint environmental impacts in ten categories: global warming potential (GWP, kg CO2 eq.); acidification potential (AP, kg SO2 eq.); potential human health damage impacts due to carcinogens (HH-CP, CTUh) and non-carcinogens (HH-NCP, CTUh); potential respiratory effects (REP, kg PM2.5 eq.); eutrophication potential (EP, kg N eq.); ozone depletion potential (ODP kg CFC-11 eq.); ecotoxicity potential (ETXP, CTUe); smog formation potential (SFP kg O3 eq.) and fossil fuel depletion potential (FFDP MJ surplus). The equivalent functional unit of the LCA study was designed to protect 30 m2 of the interior surface (unalloyed steel sheet) of a 10 000 liter biodiesel tank against abiotic and biotic corrosion during its service life of 20 years. Overall, this LCA study highlights the improved environmental performance for the GOE liner compared to the incumbent system, whereby the GOE liner showed 91% lower impacts in ODP impact category, 59% smaller in REP, 62% smaller in AP, 67-69% smaller in GWP and HH-CP, 72-76% smaller in EP, SFP, and FFDP, and 81-83% smaller ETXP and HH-NCP category results. The scenario analysis study revealed that these potential impacts change by less than 15% when the GOE liners are functionalized with silanized-GO nanosheets or GO-reinforced polyvinyl carbazole to improve the antimicrobial properties. The results from an uncertainty analysis indicated that the impacts for the incumbent system were more sensitive to changes in the key modeling parameters compared to that for the GOE liner system.

Potential water resource impacts of hydraulic fracturing from unconventional oil production in the Bakken shale.

Modern drilling techniques, notably horizontal drilling and hydraulic fracturing, have enabled unconventional oil production (UOP) from the previously inaccessible Bakken Shale Formation located throughout Montana, North Dakota (ND) and the Canadian province of Saskatchewan. The majority of UOP from the Bakken shale occurs in ND, strengthening its oil industry and businesses, job market, and its gross domestic product. However, similar to UOP from other low-permeability shales, UOP from the Bakken shale can result in environmental and human health effects. For example, UOP from the ND Bakken shale generates a voluminous amount of saline wastewater including produced and flowback water that are characterized by unusual levels of total dissolved solids (350 g/L) and elevated levels of toxic and radioactive substances. Currently, 95% of the saline wastewater is piped or trucked onsite prior to disposal into Class II injection wells. Oil and gas wastewater (OGW) spills that occur during transport to injection sites can potentially result in drinking water resource contamination. This study presents a critical review of potential water resource impacts due to deterministic (freshwater withdrawals and produced water management) and probabilistic events (spills due to leaking pipelines and truck accidents) related to UOP from the Bakken shale in ND.