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The effects of biochar properties on crop growth are little understood. Therefore, biochar was produced from eight feedstocks and pyrolyzed at four temperatures (300°C, 400°C, 500°C, 600°C) using slow pyrolysis. Corn was grown for 46 days in a greenhouse pot trial on a temperate and moderately fertile Alfisol amended with the biochar at application rates of 0.0%, 0.2%, 0.5%, 2.0%, and 7.0% (w/w) (equivalent to 0.0, 2.6, 6.5, 26, and 91 t biochar ha −1 ) and full recommended fertilization. Animal manure biochars increased biomass by up to 43% and corn stover biochar by up to 30%, while food waste biochar decreased biomass by up to 92% in relation to similarly fertilized controls (all P<0.05). Increasing the pyrolysis temperature from 300°C to 600°C decreased the negative effect of food waste as well as paper sludge biochars. On average, plant growth was the highest with additions of biochar produced at a pyrolysis temperature of 500°C (P < 0.05), but feedstock type caused eight times more variation in growth than pyrolysis temperature. Biochar application rates above 2.0% (w/w) (equivalent to 26 t ha −1 ) did generally not improve corn growth and rather decreased growth when biochars produced from dairy manure, paper sludge, or food waste were applied. Crop N uptake was 15% greater than the fully fertilized control (P<0.05, average at 300°C) at a biochar application rate of 0.2% but decreased with greater application to 16% below the N uptake of the control at an application rate of 7%. Volatile matter or ash content in biochar did not correlate with crop growth or N uptake (P>0.05), and greater pH had only a weak positive relationship with growth at intermediate application rates. Greater nutrient contents (N, P, K, Mg) improved growth at low application rates of 0.2% and 0.5%, but Na reduced growth at high application rates of 2.0% and 7.0% in the studied fertile Alfisol.

Agricultural soils represent the main source of anthropogenic N2O emissions. Recently, interactions of black carbon with the nitrogen cycle have been recognized and the use of biochar is being investigated as a means to reduce N2O emissions. However, the mechanisms of reduction remain unclear. Here we demonstrate the significant impact of biochar on denitrification, with a consistent decrease in N2O emissions by 10–90% in 14 different agricultural soils. Using the 15N gas-flux method we observed a consistent reduction of the N2O/(N2 + N2O) ratio, which demonstrates that biochar facilitates the last step of denitrification. Biochar acid buffer capacity was identified as an important aspect for mitigation that was not primarily caused by a pH shift in soil. We propose the function of biochar as an “electron shuttle” that facilitates the transfer of electrons to soil denitrifying microorganisms, which together with its liming effect would promote the reduction of N2O to N2.

Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria–carbon–mineral conductive network.

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The objective of this work was to investigate the retention mechanisms of ammonium in aqueous solution by using progressively oxidized maple wood biochar at different pH values. Hydrogen peroxide was used to oxidize the biochar to pH values ranging from 8.1 to 3.7, with one set being adjusted to a pH of 7 afterwards. Oxidizing the biochars at their lowered pH did not increase their ability to adsorb ammonium. However, neutralizing the oxygen-containing surface functional groups on oxidized biochar to pH 7 increased ammonia adsorption two to three-fold for biochars originally at pH 3.7-6, but did not change adsorption of biochars oxidized to pH 7 and above. The adsorption characteristics of ammonium are well described by the Freundlich equation. Adsorption was not fully reversible in water, and less than 27% ammonium was desorbed in water in two consecutive steps than previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 2M KCl increased from 34% to 99% of ammonium undesorbed by both preceding water extractions with increasing oxidation, largely irrespective of pH adjustment. Unrecovered ammonium in all extractions and residual biochar was negligible at high oxidation, but increased to 39% of initially adsorbed amounts at high pH, likely due to low amounts adsorbed and possible ammonia volatilization losses.

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo–mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo–organic interfaces in contrast to exclusively organo–mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo–organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo–mineral interface, 88% (72–92%) and 33% (16–53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo–organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.