Biofuels produced via thermochemical conversions of waste biomass could be sustainable alternatives to fossil fuels but currently require costly downstream upgrading to be used in existing infrastructure. In this work, we explore how a low-cost, abundant clay mineral, bentonite, could serve as an in situ heterogeneous catalyst for two different thermochemical conversion processes: pyrolysis and hydrothermal carbonization (HTC). Avocado pits were combined with 20 wt% bentonite clay and were pyrolyzed at 600 °C and hydrothermally carbonized at 250 °C, commonly used conditions across the literature. During pyrolysis, bentonite clay promoted Diels–Alder reactions that transformed furans to aromatic compounds, which decreased the bio-oil oxygen content and produced a fuel closer to being suitable for existing infrastructure. The HTC bio-oil without the clay catalyst contained 100% furans, mainly 5-methylfurfural, but in the presence of the clay, approximately 25% of the bio-oil was transformed to 2-methyl-2-cyclopentenone, thereby adding two hydrogen atoms and removing one oxygen. The use of clay in both processes decreased the relative oxygen content of the bio-oils. Proximate analysis of the resulting chars showed an increase in fixed carbon (FC) and a decrease in volatile matter (VM) with clay inclusion. By containing more FC, the HTC-derived char may be more stable than pyrolysis-derived char for environmental applications. The addition of bentonite clay to both processes did not produce significantly different bio-oil yields, such that by adding a clay catalyst, a more valuable bio-oil was produced without reducing the amount of bio-oil recovered.

Our planet has a natural ecosystem comprised of living organisms and methane hydrates in deep marine environments. This ecosystem was constructed in the present work to examine the influence that subtle temperature fluctuations could have on the dynamic stability of the hydrate deposits. The coupled mass and energy balance equations that describe the microbial bioreactions, their consumption by feather duster worms, and methane hydrate dissociation confirm that the bioreaction kinetics is dominated by endothermic methanogenic metabolism that stabilizes methane hydrates with a fragile tolerance to 0.001 K temperature increases. The feather duster worms also stabilize the hydrates via their selective consumption of methanotrophs that could otherwise overtake the system by their exothermic metabolism. Critical ocean temperature limits exist, beyond which hydrate dissociations would cause underwater eruptions of methane into the sea. Historical ocean temperature records and gas hydrate inventory estimates combined with our model suggest that hydrate deposits as deep as 560 m below sea level could already be at risk, whereas the methane hydrate stability zone will retreat deeper as the ocean temperature rises. Slowing its retreat could avoid the massive release of greenhouse gas.

Our Planet has a natural ecosystem comprised of living organisms and methane hydrates in deep marine environments. This ecosystem was constructed in the present work to examine the influence that subtle temperature fluctuations could have on the dynamic stability of the hydrate deposits. The coupled mass and energy balance equations that describe the microbial bioreactions, their consumption by feather duster worms, and methane hydrate dissociation confirm that the bioreaction kinetics are dominated by endothermic methanogenic metabolism that stabilizes methane hydrates with a fragile tolerance to 0.001K temperature increases. The feather duster worms also stabilize the hydrates via their selective consumption of methanotrophs that could otherwise overtake the system by their exothermic metabolism. Critical ocean temperature limits exist, beyond which hydrate dissociations would cause underwater eruptions of methane into the sea. Historical ocean temperature records and gas hydrate inventory estimates combined with our model suggests that hydrate deposits as deep as 560-meters below sea level could already be at risk, whereas the methane hydrate stability zone will retreat deeper as ocean temperatures rise. Slowing its retreat could avoid the massive release of greenhouse gas.