Sorption of pure N 2 O to biochars and other organic and inorganic materials under anhydrous conditions

Abstract

Suppression of nitrous oxide (N 2 O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N 2 O sorption to biochar. The sorption of N 2 O and carbon dioxide (CO 2 ) to four biochars was measured in an anhydrous system with pure N 2 O. The biochar data were compared to those for two activated carbons and other components potentially present in soils—uncharred pine wood and peat—and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities ( Q max ) for N 2 O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17–73 cm 3 g –1 at 20 °C (median 51 cm 3 g –1 ), with Langmuir affinities ( b ) of 2–5 atm –1 (median 3.4 atm –1 ). Both Q max and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [ Q max 1–34 cm 3 g –1 (median 7 cm 3 g –1 ); b 0.4–1.7 atm –1 (median 0.7 atm –1 )]. This indicates that biochar can bind N 2 O more strongly than both mineral and organic soil materials. Q max and b for CO 2 were comparable to those for N 2 O. Modeled sorption coefficients obtained with an independent polyparameter—linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5–24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N 2 O were mostly between −20 and −30 kJ mol –1 , slightly more exothermic than enthalpies of condensation (−16.1 kJ mol –1 ). Q max of N 2 O on biochar (50000–130000 μg g –1 biochar at 20 °C) exceeded the N 2 O emission suppressions observed in the literature (range 0.5–960 μg g –1 biochar; median 16 μg g –1 ) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N 2 O to biochar is a mechanism of N 2 O emission suppression.