Akio Enders

Characterization of biochars to evaluate recalcitrance and agronomic performance

Biochars (n=94) were found to have ash contents from 0.4% to 88.2%, volatile matter from 13.2% to 70.0%, and fixed carbon from 0% to 77.4% (w/w). Greater pyrolysis temperature for low-ash biochars increased fixed carbon, but decreased it for biochars with more than 20% ash. Nitrogen recovery varied depending on feedstock used to a greater extent (12-68%) than organic (25-45%) or total C (41-76%) at a pyrolysis temperature of 600 °C. Fixed carbon production ranged from no enrichment in poultry biochar to a 10-fold increase in corn biochar (at 600 °C). Prediction of biochar stability was improved by a combination of volatile matter and H:C ratios corrected for inorganic C. In contrast to stability, agronomic utility of biochars is not an absolute value, as it needs to meet local soil constraints. Woody feedstock demonstrated the greatest versatility with pH values ranging from 4 to 9.

Biochar and denitrification in soils: when, how much and why does biochar reduce N2O emissions?

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.

Adsorption and desorption of ammonium by maple wood biochar as a function of oxidation and pH

The objective of this work was to investigate the retention mechanisms of ammonium in aqueous solution by using progressively oxidized maple wood biochar at different pH values. Hydrogen peroxide was used to oxidize the biochar to pH values ranging from 8.1 to 3.7, with one set being adjusted to a pH of 7 afterwards. Oxidizing the biochars at their lowered pH did not increase their ability to adsorb ammonium. However, neutralizing the oxygen-containing surface functional groups on oxidized biochar to pH 7 increased ammonia adsorption two to three-fold for biochars originally at pH 3.7-6, but did not change adsorption of biochars oxidized to pH 7 and above. The adsorption characteristics of ammonium are well described by the Freundlich equation. Adsorption was not fully reversible in water, and less than 27% ammonium was desorbed in water in two consecutive steps than previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 2M KCl increased from 34% to 99% of ammonium undesorbed by both preceding water extractions with increasing oxidation, largely irrespective of pH adjustment. Unrecovered ammonium in all extractions and residual biochar was negligible at high oxidation, but increased to 39% of initially adsorbed amounts at high pH, likely due to low amounts adsorbed and possible ammonia volatilization losses.

Ecotoxicological characterization of biochars: role of feedstock and pyrolysis temperature.

Seven contrasting feedstocks were subjected to slow pyrolysis at low (300 or 350°C) and high temperature (550 or 600°C), and both biochars and the corresponding feedstocks tested for short-term ecotoxicity using basal soil respiration and collembolan reproduction tests. After a 28-d incubation, soil basal respiration was not inhibited but stimulated by additions of feedstocks and biochars. However, variation in soil respiration was dependent on both feedstock and pyrolysis temperature. In the last case, respiration decreased with pyrolysis temperature (r=-0.78; p<0.0001, n=21) and increased with a higher volatile matter content (r=0.51; p<0.017), these two variables being correlated (r=-0.86, p<0.0001). Collembolan reproduction was generally unaffected by any of the additions, but when inhibited, it was mostly influenced by feedstock, and generally without any influence of charring itself and pyrolysis temperature. Strong inhibition was only observed in uncharred food waste and resulting biochars. Inhibition effects were probably linked to high soluble Na and NH4 concentrations when both feedstocks and biochars were considered, but mostly to soluble Na when only biochars were taken into account. The general lack of toxicity of the set of slow pyrolysis biochars in this study at typical field application rates (≤20 Mg ha(-1)) suggests a low short-term toxicity risk. At higher application rates (20-540 Mg ha(-1)), some biochars affected collembolan reproduction to some extent, but only strongly in the food waste biochars. Such negative impacts were not anticipated by the criteria set in currently available biochar quality standards, pointing out the need to consider ecotoxicological criteria either explicitly or implicitly in biochar characterization schemes or in management recommendations.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

Dynamics of microbial community composition and soil organic carbon mineralization in soil following addition of pyrogenic and fresh organic matter

Pyrogenic organic matter (PyOM) additions to soils can have large impacts on soil organic carbon (SOC) cycling. As the soil microbial community drives SOC fluxes, understanding how PyOM additions affect soil microbes is essential to understanding how PyOM affects SOC. We studied SOC dynamics and surveyed soil bacterial communities after OM additions in a field experiment. We produced and mixed in either 350 °C corn stover PyOM or an equivalent initial amount of dried corn stover to a Typic Fragiudept soil. Stover increased SOC-derived and total CO2 fluxes (up to 6x), and caused rapid and persistent changes in bacterial community composition over 82 days. In contrast, PyOM only temporarily increased total soil CO2 fluxes (up to 2x) and caused fewer changes in bacterial community composition. Of the operational taxonomic units (OTUs) that increased in response to PyOM additions, 70% also responded to stover additions. These OTUs likely thrive on easily mineralizable carbon (C) that is found both in stover and, to a lesser extent, in PyOM. In contrast, we also identified unique PyOM responders, which may respond to substrates such as polyaromatic C. In particular, members of Gemmatimonadetes tended to increase in relative abundance in response to PyOM but not to fresh organic matter. We identify taxa to target for future investigations of the mechanistic underpinnings of ecological phenomena associated with PyOM additions to soil.

Rapid electron transfer by the carbon matrix in natural pyrogenic carbon

Surface functional groups constitute major electroactive components in pyrogenic carbon. However, the electrochemical properties of pyrogenic carbon matrices and the kinetic preference of functional groups or carbon matrices for electron transfer remain unknown. Here we show that environmentally relevant pyrogenic carbon with average H/C and O/C ratios of less than 0.35 and 0.09 can directly transfer electrons more than three times faster than the charging and discharging cycles of surface functional groups and have a 1.5 V potential range for biogeochemical reactions that invoke electron transfer processes. Surface functional groups contribute to the overall electron flux of pyrogenic carbon to a lesser extent with greater pyrolysis temperature due to lower charging and discharging capacities, although the charging and discharging kinetics remain unchanged. This study could spur the development of a new generation of biogeochemical electron flux models that focus on the bacteria–carbon–mineral conductive network.

Terrestrial pyrogenic carbon export to fluvial ecosystems: lessons learned from the White Nile watershed of East Africa

Pyrogenic carbon (PyC) is important because of its role in the global organic C (OC) cycle and in modifying soil properties. However, our understanding of PyC movement from terrestrial to fluvial ecosystems is not robust. This study examined (i) whether erosion or subsurface transport was more important for PyC export from headwaters, (ii) whether PyC was exported preferentially to total OC (TOC), and (iii) whether the movement of PyC from terrestrial to aquatic ecosystems provides an explanation for the coupling of PyC and non-PyC observed in rivers at a global scale. In the Guineo-Congolian highland forest region of western Kenya, duplicate catchments with sizes of 1–12 ha were equipped with stream gauges in primary forest and adjacent mixed agricultural landscapes that were cleared by fire 10, 16, or 62 years before. Stream water samples were taken weekly throughout 1 year and compared with runoff to assess PyC movement. Additional stream samples were taken from all major tributaries of the White Nile watershed of Lake Victoria. PyC was not found to be preferentially eroded relative to TOC or non-PyC, as topsoil (0–0.15 m) PyC concentrations (6.3 ± 0.3% of TOC; means and standard errors) were greater than runoff sediment (1.9 ± 0.4%) and dissolved PyC concentrations (2.0 ± 0.4%, n = 252). In addition, PyC proportions in eroded sediment were lower than and uncorrelated (r2 = 0.04; P = 0.14) with topsoil PyC. An enrichment of PyC was found with depth in the soil, from 6.3 ± 0.3% of TOC in the topsoil (0–0.15 m) to 12.3 ± 0.3% of TOC at 1–2 m. Base flow PyC proportions of TOC correlated well with subsoil PyC (r2 = 0.57; P   0.05). Similar PyC proportions were found in the studied headwater streams (2.7 ± 0.2%), their downstream inflow into Lake Victoria (3.7%), the other nine major rivers into Lake Victoria (4.9 ± 0.8%), and its outflow into the White Nile (1.1%). A strong positive correlation between dissolved PyC and non-PyC (r2 = 0.91; P < 0.0001) in the headwater streams reflect relationships previously seen for a range of globally important rivers, and contrasts with a negative relationship for suspended sediments (r2 = −0.5; P < 0.0001). The estimated PyC export from the Lake Victoria watershed of 11 Gg yr−1 may therefore originate to a large extent from subsoil pathways in dissolved form that appeared to be an important source of PyC in aquatic environments and may explain the coupling of PyC and non-PyC at a global scale.

Ammonium retention by oxidized biochars produced at different pyrolysis temperatures and residence times

In order to investigate the effects of pyrolysis conditions and oxidation on the retention potential of ammonium by biochar in aqueous solution, biochars were produced from mixed maple wood at different pyrolysis temperatures (300, 400, 500, 600, 700 °C) and residence times (5, 60, 120, 400, 800 min) and adsorption and desorption was determined. Hydrogen peroxide was used to oxidize the biochars with pH values ranging from 7.6 to 2.7, with one set being adjusted to a pH of 7 afterwards. Without oxidation, varying either pyrolysis temperatures or residence times did not have a relevant effect on ammonium adsorption. When oxidized, however, ammonium adsorption was up to 3.6 and 1.6 times greater at lower higher pyrolysis temperatures and shorter longer residence times, respectively. Neutralizing the oxygen-containing surface functional groups on oxidized biochar to pH 7 further increased ammonium adsorption three to four-fold for biochars originally at a temperature of 500 °C and residence time of 5 min, but did not change adsorption of biochars pyrolyzed at 600 °C and above and residence times at 400 min and above. Adjusting the pH of unoxidized biochars had no effect on ammonium adsorption. Both pyrolysis temperature and residence time significantly influence the way oxidation changes the charge properties with respect to ammonium adsorption by woody biochar.

Simultaneous Quantification of Electron Transfer by Carbon Matrices and Functional Groups in Pyrogenic Carbon

Pyrogenic carbon contains redox-active functional groups and polyaromatic carbon matrices that are both capable of transferring electrons. Several techniques have been explored to characterize the individual electron transfer process of either functional groups or carbon matrices individually. However, simultaneous analysis of both processes remains challenging. Using an approach that employs a four-electrode configuration and dual-interface electron transfer detection, we distinguished the electron transfer by functional groups from the electron transfer by carbon matrices and simultaneously quantified their relative contribution to the total electron transfer to and from pyrogenic carbon. Results show that at low to intermediate pyrolysis temperatures (400-500 °C), redox cycling of functional groups is the major mechanism with a contribution of 100-78% to the total electron transfer; whereas at high temperatures (650-800 °C), direct electron transfer of carbon matrices dominates electron transfer with a contribution of 87-100%. Spectroscopic and diffraction analyses of pyrogenic carbon support the electrochemical measurements by showing a molecular-level structural transition from an enrichment in functional groups to an enrichment in nanosized graphene domains with increasing pyrolysis temperatures. The method described in this study provides a new analytical approach to separately quantify the relative importance of different electron transfer pathways in natural pyrogenic carbon and has potential applications for engineered carbon materials such as graphene oxides.