• Energy Research

Artificially stimulated, high-yield microbial production of methane from coal is a challenging problem that continues to generate research interest. Decomposition of organic matter and production of methane from coal are the results of multiple redox reactions carried out by different communities of bacteria and archaea. Recent work by our group (Beckmann et al., 2015) demonstrated that the presence of the redox-mediating molecule neutral red, in its crystalline form on a coal surface, can increase methane production. However, hydrolysis and the acetogenesis of the coal surface are essential precursor steps for methane production by archaea. Acetogenesis is the preparation phase of methanogenesis because methanogens can only assimilate acetate, CO2 and H2 among the products formed during this process. In the present study, the surface chemical analysis of neutral red treated coal using attenuated total reflectance-fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) demonstrate that the acetate production and resulting oxidation of the coal only occurred at few nanometers into the coal surface (at the nanoscale <5 nm). We observed that in the presence of neutral red and groundwater microbes, acetate signals in coal surface chemistry increased. This is the first evidence suggesting that neutral red enhances the biological conversion of coal into acetate. Microscopy demonstrated that neutral red crystals were co-localize with cells at the surface of coal in groundwater. This is consistent with neutral red crystals serving as a redox hub, concentrating and distributing reducing equivalents amongst the microbial community. In this study, the chemical changes of neutral red treated coal indicated that neutral red doubles the concentration of acetate over the control (coal without neutral red), emphasizing the importance of maximizing the fracture surface coverage of this redox mediator. Overall, results suggested that, neutral red not only can benefit acetoclastic methanogens, but also the fermentative and acetogenic bacteria involved in generating acetate.

AbstractControlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic‐core hexagonal‐branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF), as an example for biomass conversion.

Biochar-based compound fertilizers (BCF) and amendments have proven to enhance crop yields and modify soil properties (pH, nutrients, organic matter, structure etc.) and are now in commercial production in China. While there is a good understanding of the changes in soil properties following biochar addition, the interactions within the rhizosphere remain largely unstudied, with benefits to yield observed beyond the changes in soil properties alone. We investigated the rhizosphere interactions following the addition of an activated wheat straw BCF at an application rates of 0.25% (g·g-1 soil), which could potentially explain the increase of plant biomass (by 67%), herbage N (by 40%) and P (by 46%) uptake in the rice plants grown in the BCF-treated soil, compared to the rice plants grown in the soil with conventional fertilizer alone. Examination of the roots revealed that micron and submicron-sized biochar were embedded in the plaque layer. BCF increased soil Eh by 85 mV and increased the potential difference between the rhizosphere soil and the root membrane by 65 mV. This increased potential difference lowered the free energy required for root nutrient accumulation, potentially explaining greater plant nutrient content and biomass. We also demonstrate an increased abundance of plant-growth promoting bacteria and fungi in the rhizosphere. We suggest that the redox properties of the biochar cause major changes in electron status of rhizosphere soils that drive the observed agronomic benefits.

Phenazine crystals enhance methanogenesis by electron delivery to respiratory heterodisulfide reductase enzyme.

Abstract A study has been carried out to test the possibility of measuring detailed quantitative profiles of the abundance of different inorganic elements through exploration cores of coal seams using automated energy-dispersive X-ray fluorescence (ED-XRF) core scanning instrumentation. Such an approach has potential application for rapidly determining the distribution of mineral matter in a coal seam, identifying horizons at which particular elements (such as phosphorus) may be concentrated, evaluating in detail the relationships between different elements in the coal, and maximising the data available to guide broader-scale sampling for conventional analysis programmes. Profiling was carried out on a series of segments from a 60 mm diameter core of the Goonyella Middle seam in the northern Bowen Basin of Queensland, using an Itrax core scanner (Cox Analytical, Sweden). The scanning process included high resolution optical imaging, X-radiography, and ED-XRF spectroscopy covering the principal major elements, with XRF spectra being obtained at intervals of 200 μm along the axis of each core. A series of calibration curves derived from separately-scanned pressed pellets of reference coals was used to determine the concentration of each element for each step in each sample, allowing a set of quantitative element profiles to be created for each core segment. These were evaluated in conjunction with the relevant X-radiographs and optical images to provide an integrated basis for assessing the variations in inorganic element characteristics through the core sections. The results were also compared to conventionally-determined chemical and mineralogical data for a representative core, to confirm the validity of the quantifications developed.

Direct analysis of the colonised surface on coal using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) revealed the nature of bacteria-mediated oxidation at the coal surface. Unique oxidation peaks generated by the presence of Pseudomonas fluorescens on coal was shown through ATR-FTIR measurements, and ATR-FTIR imaging illustrated that this peak was only observed within the region of coal colonised by bacteria. Contact angle measurements and surface free energy of adhesion calculations showed that the adhesion between P. fluorescens and coal was thermodynamically favourable, and scanning electron microscopy (SEM) exhibited individual cell or monolayer cluster attachment on coal. Furthermore, Gaussian peak fitting of peroxidase-treated coal ATR-FTIR spectra revealed that peroxidase or related enzymes produced by P. fluorescens may be responsible for coal oxidation. This study demonstrated the usefulness and practicality of ATR-FTIR for analysing coal oxidation by P. fluorescens and may well be applied to other microbe-driven modifications of coal for its rapidity and reliability.

AbstractThis study describes the first use of concurrent high-precision temperature and drip rate monitoring to explore what controls the temperature of speleothem forming drip water. Two contrasting sites, one with fast transient and one with slow constant dripping, in a temperate semi-arid location (Wellington, NSW, Australia), exhibit drip water temperatures which deviate significantly from the cave air temperature. We confirm the hypothesis that evaporative cooling is the dominant, but so far unattributed, control causing significant disequilibrium between drip water and host rock/air temperatures. The amount of cooling is dependent on the drip rate, relative humidity and ventilation. Our results have implications for the interpretation of temperature-sensitive, speleothem climate proxies such as δ18O, cave microecology and the use of heat as a tracer in karst. Understanding the processes controlling the temperature of speleothem-forming cave drip waters is vital for assessing the reliability of such deposits as archives of climate change.