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Abstract Extracellular enzymes play a key role in microbe‐mediated organic matter decomposition in soils, and the efficiency of these enzymes in substrate decomposition depends on their mobility and specific activity in soils. In this work, we explored the influence of biochar adsorption on extracellular enzyme activity across a spectrum of environmental conditions, from simple to complex. Batch adsorption results showed that biochar adsorption of two hydrolytic enzymes—α‐amylase and amyloglucosidase (AMG)—similarly decreases with pH and follows the Langmuir isotherm, suggesting electrostatic interaction between them. Activity of AMG and alkaline phosphatase (ALP), which belong to carbon and phosphorus cycling enzymes, was measured using a novel calorimetric method. The technique demonstrated advantages over conventional enzyme assays, such as in situ real‐time measurement of reaction rate and the ability to identify potential interferences. The technique enabled the measurement of specific activity of biochar‐adsorbed AMG, which ranged from 10% to 90% of that of free AMG. The effect of substrate adsorption on activity measurement was demonstrated through the examination of two substrates for ALP, which suggested the use of effective substrate concentration (instead of nominal concentration) in calculating enzyme activity kinetics. Soil column experiments showed that biochar amendment can affect the activity of AMG in starch hydrolysis through changing the mobility of AMG (and accessibility to substrate) and its specific activity. Results from this work improve our understanding of the effects of biochar adsorption on enzyme activity and suggest the need to appropriately interpret enzyme activity data and account for confounding processes. 

Background Vegetation fire may change Phosphorus (P) cycling in terrestrial ecosystems through converting biomass into fire residues. Aim The aim of this study was to understand the chemistry and mobility of P in fire residues to help reveal P thermochemistry during biomass burning and post-fire P cycling. Methods A combination of sequential extraction, liquid 31P NMR and P K-edge XANES was used to obtain quantitative P speciation and explain P solubilisation behaviours of charcoal. Key results Despite varying diverse P species existing in raw biomass, only two P structural moieties – orthophosphate and pyrophosphate – were identified in charcoal. However, relative abundance of pyrophosphate differs greatly among charcoal samples from different biomass types, ranging between 0 and 40% of total extractable P. Although P K-edge XANES data indicates abundant soluble phosphate minerals, most P (70–90%) is likely occluded physically in the charcoal. The bicarbonate-extractable P (the Olsen-P) varies significantly and cannot be explained by surface P concentration or elemental stoichiometry alone. Conclusion and implications The results suggest the importance of starting biomass P speciation (i.e. molecular structure and complexation environment) and thermal conditions in controlling P speciation and availability in charcoal. The different P chemistry between charcoal and ash suggests the importance of fire types and severity in disturbing the P cycle.