No abstract

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.

Natural organic matter (NOM) is a highly active component of soils and sediments, and plays an important role in global C cycling. However, NOM has defied molecular‐level structural characterization, owing to variations along the decomposition continuum and its existence as highly functionalized polyelectrolytes. We conducted a comprehensive systematic overview of spectral signatures and peak positions of major organic molecules that occur as part of NOM using near‐edge x‐ray absorption fine structure (NEXAFS) spectroscopy. The spectra of carbohydrates and amino sugars show resonances between 289.10 and 289.59 eV, attributed to 1s‐3p/σ* transitions of O‐alkyl (C‐OH) moieties. They also exhibited distinct peaks between 288.42 and 288.74 eV, representing C 1s–π*C = O transition from COOH functionalities. Amino acids produced a strong signal around 288.70 eV, which can be identified as a C 1s–π*C=O transition of carboxyl/carbonyl (COOH/COO‐) structures. Spectral features near 285.29 eV were ascribed to C 1s–π*C=C transition of ring structure of aromatic amino acids, while spectra between 287.14 and 287.86 eV were attributed to C 1s–π*C‐H and C 1s–σ*C‐H/3p Rydberg‐like excitations from CH and CH2 groups. Phenols and benzoquinone produced strong resonances between 285.08 and 285.37 eV, attributed to the π* orbital of C (C 1s–π*C=C) atoms connected to either C or H (C–H) in the aromatic ring. The next higher excitation common to both phenols and quinone appeared between 286.05 and 286.35 eV, and could be associated with C 1s–π*C=C transitions of aromatic C bonded to O atom in phenols, and to C 1s–π*C=O transitions from aromatic C connected to O atom (C‐OH) in phenols or to a C=O in p‐benzoquinone and some phenols with carbonyl structures, respectively. Nucleobases exhibited complex spectral features with pronounced resonances between 286.02 and 286.84 eV and between 288.01 and 288.70 eV. Molecular markers for black C (benzenecarboxylic acid and biphenyl‐4,4′‐dicarboxylic acid) exhibit sharp absorption bands between 285.01 and at 285.43 eV, possibly from C 1s–π*C=C transition characteristic of C‐H sites or unsaturated C (C=C) on aromatic ring structures. These aromatic carboxylic acids also exhibit broad peaks between 288.35 and 288.48 eV, reflecting C 1s–π*C=O transition of carboxyl functional groups bonded to unsaturated C. This investigation provides a more comprehensive NEXAFS spectral library of biogeochemically relevant organic C compounds. The spectra of these reference organic compounds reveal distinct spectral features and peak positions at the C K‐edge that are characteristic of the molecular orbitals bonding C atoms. Detailed structural information can be derived from these distinctive spectral features that could be used to build robust peak assignment criteria to exploit the chemical sensitivity of NEXAFS spectroscopy for in situ molecular‐level spatial investigation and fingerprinting of complex organic C compounds in environmental samples.