Pyrogenic Black Carbon Suppresses Microbial Methane Production by Serving as a Terminal Electron Acceptor.

Methane (CH4) is the second most important greenhouse gas, 27 times as potent as CO2 and responsible for >30% of the current anthropogenic warming. Globally, more than half of CH4 is produced microbially through methanogenesis. Pyrogenic black carbon possesses a considerable electron storage capacity (ESC) and can be an electron donor or acceptor for abiotic and microbial redox transformation. Using wood-derived biochar as a model black carbon, we demonstrated that air-oxidized black carbon served as an electron acceptor to support anaerobic oxidation of organic substrates, thereby suppressing CH4 production. Black carbon-respiring bacteria were immediately active and outcompeted methanogens. Significant CH4 did not form until the bioavailable electron-accepting capacity of the biochar was exhausted. An experiment with labeled acetate (13CH3COO-) yielded 1:1 13CH4 and 12CO2 without biochar and predominantly 13CO2 with biochar, indicating that biochar enabled anaerobic acetate oxidation at the expense of methanogenesis. Methanogens were enriched following acetate fermentation but only in the absence of biochar. The electron balance shows that approximately half (∼2.4 mmol/g) of biochar's ESC was utilized by the culture, corresponding to the portion of the ESC > +0.173 V (vs SHE). These results provide a mechanistic basis for quantifying the climate impact of black carbon and developing ESC-based applications to reduce CH4 emissions from biogenic sources.

Abiotic reduction of 3-nitro-1,2,4-triazol-5-one (NTO) and other munitions constituents by wood-derived biochar through its rechargeable electron storage capacity.

The environmental fate of 3-nitro-1,2,4-triazol-5-one (NTO) and other insensitive munitions constituents (MCs) is of significant concern due to their high water solubility and mobility relative to legacy MCs. Plant-based biochars have been shown to possess a considerable electron storage capacity (ESC), which enables them to undergo reversible electron transfer reactions. We hypothesized biochar can act as a rechargeable electron donor to effect abiotic reduction of MCs repeatedly through its ESC. To test this hypothesis, MC reduction experiments were performed using wood-derived biochars that were oxidized with dissolved oxygen or reduced with dithionite. Removal of aqueous NTO, an anion at circumneutral pH, by oxidized biochar was minimal and occurred through reversible adsorption. In contrast, NTO removal by reduced biochar was much more pronounced and occurred predominantly through reduction, with concomitant formation of 3-amino-1,2,4-triazol-5-one (ATO). Mass balance and electron recovery with ferricyanide further showed that (1) the amount of NTO reduced to ATO was relatively constant (85-100 µmol per gram of biochar) at pH 6-10; (2) the fraction of biochar ESC reactive toward NTO was ca. 30% of that toward ferricyanide; (3) the NTO-reactive fraction of the ESC was regenerable over multiple redox cycles. We also evaluated biochar transformation of other MCs, including nitroguanidine (NQ), 2,4-dinitroanisole (DNAN), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). While mass and electron balances could not be established due to sorption, DNAN and RDX reduction by reduced biochar was confirmed via detection of multiple reduction products. In contrast, NQ was not reduced under any of the conditions tested. This study is the first demonstration of organic contaminant degradation through biochar's rechargeable ESC. Our results indicate biochar is a regenerable electron storage medium and sorbent that can remove MCs from water through concurrent reduction and sorption, and is thus potentially useful for pollution control and remediation at military facilities.

Visualizing the distribution of black carbon's electron storage capacity using silver.

We have developed a method that combines chemical reduction, silver tagging, and electron microscopy (EM) for visualizing the electron storage capacity (ESC) of black carbon (BC). ESC is a BC's capacity to store and reversibly exchange electrons with abiotic and microbial agents, processes that are relevant to biochemistry, greenhouse gas production, contaminant fate, and remediation. In addition to the amount of electrons BC can store, the locations and spatial distribution of ESC on and inside biochar are critical for understanding the bioaccessibility of ESC and the kinetics of redox reactions involving BC. To locate the ESC in a BC particle, we fully reduced a BC, removed excess reductant, and applied silver ion (Ag+) as a tagging agent that diffused into BC to react with functional groups where electrons were stored (i.e., ESC) to form silver nanoparticles (nAg). The nAg deposited on and inside BC were then imaged using multiple EM techniques to visualize the locations and distribution of the ESC. The method is a new and potentially useful tool for investigating ESC production and for elucidating BC-mediated redox transformation.•Novel method to probe and assess the distribution of ESC on/within BC.•Visual confirmation of significant ESC both on the surface and in the interior of BC.•A new method to incorporate silver or other redox-sensitive elements into a carbon medium.

Visualizing electron storage capacity distribution in biochar through silver tagging.

Electron storage capacity (ESC) is the capacity of a black carbon to store and reversibly donate and accept electrons in redox processes. Electrochemical and chemical analyses have shown the ESC of black carbon (e.g., plant-based biochars) was on the order of a few mmol/g. However, it remains unknown where ESC is located. The spatial distribution of ESC is important because it controls the bioaccessibility of ESC and the rates of biochar redox reactions. Here we used silver to tag the ESC of a wood-derived biochar. Ag+ was allowed to diffuse into the pores of reduced biochar at a constant pH. Up to 2.49 mmol Ag+/g biochar (corresponding to 62% of its ESC) was reduced to Ago nanoparticles (nAg), which served as an ESC marker and was visualized by electron microscopy. Abundant and dense nAg were observed on the biochar surface. In addition, microtomed samples showed ubiquitous and well-dispersed nAg in the interior of biochar, which explains pore diffusion-limited redox reactions and the partial bioaccessibility of its ESC. In addition to probing ESC distribution in black carbon, this method represents a new, ESC-based approach to incorporate large quantities of Ag and other redox-active elements into carbon media for potential environmental applications.

Methane emissions from landfill: influence of vegetation and weather conditions.

Vegetation plays an important role in CH4 transport and oxidation in landfill cover soil. This study investigated CH4 emission fluxes in two landfills with different surface coverage conditions and it found that the CH4 emission fluxes presented spatial and temporal disparities. A significant discrepancy in CH4 emission flux between day and night in areas covered with Kochia sieversiana indicated that enhanced diffusion induced by rising temperature was the main mechanism for CH4 transport during daytime. A significant increase of CH4 emission flux after the K. sieversiana and Suaeda glauca plants were cut indicated that these plants provide greater contributions to CH4 oxidation than to CH4 transport. Diel CH4 emission flux was found closely correlated with the climatic conditions. Diffusion was determined as the main mechanism for CH4 transport at daytime in bare area, mediated by solar radiation and air temperature. Diffusion and plant-mediated transport by convection was established as the main transport mechanism in areas covered with K. sieversiana. Our results further the understanding of both the CH4 emission mechanism and the impact of vegetation on CH4 oxidation, transport, and emission, which will benefit the development of a reliable model for landfill CH4 emissions.

New methods for assessing electron storage capacity and redox reversibility of biochar.

Black carbon such as biochar has been shown to support microbial redox transformation by accepting and/or donating electrons. Electron storage capacity (ESC) is an important property that determines the capacity of a biochar to mediate redox processes in natural and engineered systems. However, it remained unclear whether a biochar's ESC is constant and reversible and if so to what extent, over what redox potential range ESC is distributed, and what fraction of the ESC is microbially accessible. In this study, we developed chemical methods that employed combinations of reductants and oxidants of different potentials - Ti(III) citrate, ferricyanide, dithionite, and dissolved O2 - to measure the ESC of Soil Reef biochar, a wood-derived biochar that can serve as an electron donor or acceptor for Geobacter metallireducens. For a given oxidant-reductant pair, the ESC obtained over multiple redox cycles was constant and fully reversible, though lower than that of the virgin biochar. Pore diffusion within biochar particles was rate-limiting and controlled the timescale for redox equilibrium. Results suggest that redox-facile functional groups in biochar were distributed over a broad range of potentials. The ESC measured using dithionite indicates approximately 22% of the biochar's reversible ESC was accessible to G. metallireducens. We propose that reversible ESC may be regarded as a constant and quantifiable property of black carbon.

Chemical methods for determining the electron storage capacity of black carbon.

Electron storage capacity (ESC) is a new and important property that determines the capacity of a black carbon to mediate abiotic and microbial electron transfer reactions in natural and engineered systems. It is necessary to develop accurate and reproducible methods to measure black carbon's ESC in order to understand its redox behavior and to predict its capacity to support redox transformation of contaminants in subsurface environments. In this study, we developed chemical methods that employed combinations of reductants and oxidants of different redox potentials - Ti(III) citrate or dithionite as reductant, and ferricyanide or dissolved O2 as oxidant - to measure the ESC of a wood-derived biochar. Pore diffusion within biochar particles was rate-limiting and controlled the timescale for redox equilibrium and ESC measurements. •The new methods can handle sample mass on the order of a gram•Sample pretreatment (e.g., oxidation via aeration) is necessary to produce consistent results•For a given reductant-oxidant pair, colorimetric (or potentiometric) measurements gave constant and reproducible ESC.

A Simulation model for estimating methane oxidation and emission from landfill cover soils.

Quantification of methane (CH4) oxidation and emission from landfill cover soils is important for evaluating measures to mitigate anthropogenic greenhouse gas emissions. In this study, a model that combines the multicomponent diffusive equation and Darcy's law, coupled with the dual Monod kinetic equation, was established to simulate CH4 transport, oxidation and emission in landfill cover soils. Sensitivity analysis was performed to illustrate the influence of model parameters on CH4 transport, oxidation and emission. The model was then applied to predict CH4 emissions from several column experiments. The results of the sensitivity analysis showed that a high CH4 oxidation rate can be obtained with a high Vmax of cover soil, even for a low cover soil thickness, and that oxidation efficiency is constant when the thickness of the cover soil becomes greater than a threshold value. The simulated results fitted well with the measured values, confirming that the new model provides a reliable method for estimating CH4 emissions from landfills.

A simulation model for methane emissions from landfills with interaction of vegetation and cover soil.

Global climate change and ecological problems brought about by greenhouse gas effect have become a severe threat to humanity in the 21st century. Vegetation plays an important role in methane (CH4) transport, oxidation and emissions from municipal solid waste (MSW) landfills as it modifies the physical and chemical properties of the cover soil, and transports CH4 to the atmosphere directly via their conduits, which are mainly aerenchymatous structures. In this study, a novel 2-D simulation CH4 emission model was established, based on an interactive mechanism of cover soil and vegetation, to model CH4 transport, oxidation and emissions in landfill cover soil. Results of the simulation model showed that the distribution of CH4 concentration and emission fluxes displayed a significant difference between vegetated and non-vegetated areas. CH4 emission flux was 1-2 orders of magnitude higher than bare areas in simulation conditions. Vegetation play a negative role in CH4 emissions from landfill cover soil due to the strong CH4 transport capacity even though vegetation also promotes CH4 oxidation via changing properties of cover soil and emitting O2 via root system. The model will be proposed to allow decision makers to reconsider the actual CH4 emission from vegetated and non-vegetated covered landfills.

Site specific diel methane emission mechanisms in landfills: A field validated process based on vegetation and climate factors.

Diel methane emission fluxes from a landfill that was covered by vegetation were investigated to reveal the methane emission mechanisms based on the interaction of vegetation characteristics and climate factors. The methane emissions showed large variation between daytime and nighttime, and the trend of methane emissions exhibited clear bimodal patterns from both Setaria viridis- and Neyraudia reynaudiana-covered areas. Plants play an important role in methane transportation as well as methane oxidation. The notable decrease in methane emissions after plants were cut suggests that methane transportation via plants is the primary way of methane emissions in the vegetated areas of landfill. Within plants, the methane emission fluxes were enhanced due to a convection mechanism. Given that the methane emission flux is highly correlated with the solar radiation during daytime, the convection mechanism could be attributed to the increase in solar radiation. Whereas the methane emission flux is affected by a combined impact of the wind speed and pedosphere characteristics during nighttime. An improved understanding of the methane emission mechanisms in vegetated landfills is expected to develop a reliable model for landfill methane emissions and to attenuate greenhouse gas emissions from landfills.