Lack of knowledge regarding the nature of biochar alkalis has hindered understanding of pH-sensitive biochar-soil interactions. Here we investigate the nature of biochar alkalinity and present a cohesive suite of methods for its quantification. Biochars produced from cellulose, corn stover and wood feedstocks had significant low-pK organic structural (0.03-0.34 meq g), other organic (0-0.92 meq g), carbonate (0.02-1.5 meq g), and other inorganic (0-0.26 meq g) alkalinities. All four categories of biochar alkalinity contributed to total biochar alkalinity and are therefore relevant to pH-sensitive soil processes. Total biochar alkalinity was strongly correlated with base cation concentration, but biochar alkalinity was not a simple function of elemental composition, soluble ash, fixed carbon, or volatile matter content. More research is needed to characterize soluble biochar alkalis other than carbonates and to establish predictive relationships among biochar production parameters and the composition of biochar alkalis.

Biochars are potentially effective sorbents for NH4+ and NO3− in water treatment and soil applications. Here we compare NH4+ and NO3− sorption rates to acid-washed biochars produced from red oak (Quercus rubra) and corn stover (Zea mays) at three pyrolysis temperatures (400, 500 and 600 °C) and a range of solution pHs (3.5–7.5). Additionally, we examined sorption mechanisms by quantification of NH4+ and NO3− sorption, as well as Ca2+ and Cl− displacement for corn stover biochars. Solution pH curves showed that NH4+ sorption was maximized (0.7–0.8 mg N g−1) with low pyrolysis temperature (400 °C) biochar at near neutral pH (7.0–7.5), whereas NO3− sorption was maximized (1.4–1.5 mg N g−1) with high pyrolysis temperatures (600 °C) and low pH (3.5–4). The Langmuir (r2 = 0.90–1.00) and Freundlich (r2 = 0.81–0.97) models were good predictors for both NH4+ (pH 7) and NO3− (pH 3.7) sorption isotherms. Lastly, NH4+ and NO3− displaced Ca2+ and Cl−, respectively, from previously CaCl2-saturated corn stover biochars. Results from the pH curves, Langmuir isotherms, and cation displacement curves all support the predominance of ion exchange mechanisms. Our results demonstrate the importance of solution pH and chemical composition in influencing NH4+ and NO3− sorption capacities of biochar.

The Boehm titration, originally developed to quantify organic functional groups of carbon blacks and activated carbons in discrete pK ranges, has received growing attention for analyzing biochar. However, properties that distinguish biochar from carbon black and activated carbon, including greater carbon solubility and higher ash content, may render the original Boehm titration method unreliable for use with biochars. Here we use seven biochars and one reference carbon black to evaluate three Boehm titration methods that use (i) acidification followed by sparging (sparge method), (ii) centrifugation after treatment with BaCl (barium method), and (iii) a solid-phase extraction cartridge followed by acidification and sparging (cartridge method) to remove carbonates and dissolved organic compounds (DOC) from the Boehm extracts before titration. Our results for the various combinations of Boehm reactants and methods indicate that no one method was free of bias for all three Boehm reactants and that the cartridge method showed evidence of bias for all pK ranges. By process of elimination, we found that a combination of the sparge method for quantifying functional groups in the lowest pK range (∼5 to 6.4), and the barium method for quantifying functional groups in the higher pK ranges (∼6.4 to 10.3 and ∼10.3 to 13) to be free of evidence for bias. We caution, however, that further testing is needed and that all Boehm titration results for biochars should be considered suspect unless efforts were undertaken to remove ash and prevent interference from DOC.

Biochar application to soil has been proposed as a means for reducing soil greenhouse gas emissions and mitigating climate change. The effects, however, of interactions between biochar, moisture and temperature on soil CO2 and N2O emissions, remain poorly understood. Furthermore, the applicability of lab-scale observations to field conditions in diverse agroecosystems remains uncertain. Here we investigate the impact of a mixed wood gasification biochar on CO2 and N2O emissions from loess-derived soils using: (1) controlled laboratory incubations at three moisture (27, 31 and 35%) and three temperature (10, 20 and 30 °C) levels and (2) a field study with four cropping systems (continuous corn, switchgrass, low diversity grass mix and high diversity grass-forb mix). Biochar reduced N2O emissions under specific temperatures and moistures in the laboratory and in the continuous corn cropping system in the field. However, the effect of biochar on N2O emissions was only significant in the field and no effect on cumulative CO2 emissions was observed. Cropping system also had a significant effect in the field study, with soils in grass and grass-forb cropping systems emitting more CO2 and less N2O than corn cropping systems. Observed biochar effects were consistent with previous studies showing that biochar amendments can reduce soil N2O emissions under specific but not all, conditions. The disparity in N2O emission responses at the lab and field scales suggests that laboratory incubation experiments may not reliably predict the impact of biochar at the field scale.

Both soil and biochar properties are known to influence greenhouse gas emissions from biochar-amended soils, but poor understanding of underlying mechanisms challenges prediction and modeling. Here, we examine the effect of six lignocellulosic biochars produced from the pyrolysis of corn stover and wood feedstocks on CO 2 and N 2 O emissions from soils collected from two bioenergy cropping systems. Effects of biochar on total accumulated CO 2 -C emissions were minimal (<0.45 mg C g À1 soil; <10% of biochar C), consistent with mineralization and hydrolysis of small labile organic and inorganic C fractions in the studied biochars. Comparisons of soil CO 2 emissions with emissions from microbially inoculated quartz-biochar mixtures ('quartz controls') provide evidence of soil and biochar-specific negative priming. Five of six biochar amendments suppressed N 2 O emissions from at least one soil, and the magnitude of N 2 O emissions suppression varied with respect to both biochar and soil types. Biochar amendments consistently decreased final soil NO 3 À concentrations, while contrasting effects on pH, NH 4 + , and DOC highlighted the potential for formation of anaerobic microsites in biochar-amended soils and consequential shifts in the soil redox environment. Thus, results implicated both reduced substrate availability and redox shifts as potential factors contributing to N 2 O emission suppression. More research is needed to confirm these mechanisms, but overall our results suggest that soil biochar amendments commonly reduce N 2 O emissions and have little effect on CO 2 emissions beyond the mineralization and/ or hydrolysis of labile biochar C fractions. Considering the large C credit for the biochar C, we conclude that biochar amendments can reduce greenhouse gas emissions and enhance the climate change mitigation potential of bioenergy cropping systems.