title: Sorption of pure N2O to biochars and other organic and inorganic materials under anhydrous conditions.
abstract: Suppression of nitrous oxide (N2O) 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 N2O sorption to biochar. The sorption of N2O and carbon dioxide (CO2) to four biochars was measured in an anhydrous system with pure N2O. 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 (Qmax) for N2O 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 Qmax and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [Qmax 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 N2O more strongly than both mineral and organic soil materials. Qmax and b for CO2 were comparable to those for N2O. 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 N2O were mostly between -20 and -30 kJ mol(-1), slightly more exothermic than enthalpies of condensation (-16.1 kJ mol(-1)). Qmax of N2O on biochar (50000-130000 μg g(-1) biochar at 20 °C) exceeded the N2O 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 N2O to biochar is a mechanism of N2O emission suppression.
authors.affiliation: U.S. Geological Survey , Denver, Colorado 80225, USA. gco@ngi.no
authors.forename: Gerard
authors.initials: G
authors.lastname: Cornelissen
authors.forename: David W
authors.initials: DW
authors.lastname: Rutherford
authors.forename: Hans Peter H
authors.initials: HP
authors.lastname: Arp
authors.forename: Peter
authors.initials: P
authors.lastname: Dörsch
authors.forename: Charlene N
authors.initials: CN
authors.lastname: Kelly
authors.forename: Colleen E
authors.initials: CE
authors.lastname: Rostad
mesh_terms: D002606:Charcoal; D007287:Inorganic Chemicals / Q000737:chemistry*; D008962:Models, Theoretical; D009609:Nitrous Oxide / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*; D014934:Wood / Q000737:chemistry
chemical_list: D007287:Inorganic Chemicals; D009930:Organic Chemicals; C540010:biochar; D014867:Water; D002606:Charcoal; D009609:Nitrous Oxide