Effect of environmental exposure on charcoal density and porosity in a boreal forest.

Although charcoal's density and porosity shape its environmental roles (e.g. controlling its landscape movement and determining the internal pore space available as microbial habitat), the rate of change of these properties in the environment remains largely unknown. With time, charcoal pores may fill or charcoal particles may shatter, altering the ecosystem services delivered. In this study we examined the effects of environmental exposure on the density and porosity of charcoals pyrolyzed at two different temperatures (350 and 520°C). Fresh charcoal made from the dominant local tree (Pinus sylvestris) was returned in litter incubations to Norwegian boreal forest soils for 20months in three different placements: (i) aboveground, (ii) in the humus layer, and (iii) under the humus layer in contact with the mineral subsoil. By varying soil horizon placement we were able to separate the effects of infill from the effects of environmental disturbance on charcoal density and porosity. Environmental exposure changed charcoal density and porosity, and the response varied with environmental placement. Charcoal placed in soil layers increased in porosity by ~1-2% after 20months' incubation. This is likely because open indentations on the charcoal surface became partially occluded, creating more detectable pore space. In contrast, the porosity of charcoal incubated aboveground decreased slightly (~1-2% over 20months). Because there were no minerals or humic substances to infill the aboveground charcoal samples, this porosity reduction was likely caused by breakage of particles induced by weathering. When charcoal particles cleave through pores, internal pore space is destroyed. The small changes observed here indicate that environmental exposure did not trigger rapid shifts in charcoal density and porosity. In addition, these physical properties appear not to have reached equilibrium after 20months incubation, suggesting that the effect of environmental exposure on charcoal's physical properties occurs on the timescale of years to decades.

Chemical and Isotopic Thresholds in Charring: Implications for the Interpretation of Charcoal Mass and Isotopic Data.

Charcoal plays a significant role in the long-term carbon cycle, and its use as a soil amendment is promoted as a C sequestration strategy (biochar). One challenge in this research area is understanding the heterogeneity of charcoal properties. Although the maximum reaction temperature is often used as a gauge of pyrolysis conditions, pyrolysis duration also changes charcoal physicochemical qualities. Here, we introduce a formal definition of charring intensity (CI) to more accurately characterize pyrolysis, and we document variation in charcoal chemical properties with variation in CI. We find two types of responses to CI: either linear or threshold relationships. Mass yield decreases linearly with CI, while a threshold exists across which % C, % N, and δ(15)N exhibit large changes. This CI threshold co-occurs with an increase in charcoal aromaticity. C isotopes do not change from original biomass values, supporting the use of charcoal δ(13)C signatures to infer paleoecological conditions. Fractionation of N isotopes indicates that fire may be enriching soils in (15)N through pyrolytic N isotope fractionation. This influx of "black N" could have a significant impact on soil N isotopes, which we show theoretically using a simple mass-balance model.

Toward a "molecular thermometer" to estimate the charring temperature of wildland charcoals derived from different biomass sources.

The maximum temperature experienced by biomass during combustion has a strong effect on chemical properties of the resulting charcoal, such as sorption capacity (water and nonpolar materials) and microbial degradability. However, information about the formation temperature of natural charcoal can be difficult to obtain in ecosystems that are not instrumented prior to fires. Benzene polycarboxylic acids (BPCA) are molecular markers specific for pyrogenic carbon (PyC) which can provide information on the degree of aromatic condensation in charcoals. Here we apply the BPCA molecular marker method to a set of 10 charcoals produced during an experimental fire in a Pitch pine-scrub oak forest from litter and bark of pitch pine and inkberry plants in the Pinelands National Reserve in New Jersey, USA. We deployed temperature-sensitive crayons throughout the burn site, which recorded the maximum air temperature and made comparisons to the degree of thermal alteration recorded by BPCA molecular markers. Our results show an increase of the degree of aromatic condensation with monitored temperatures for bark biomass, while for needles no clear trend could be observed. For leaf-derived charcoals at increasing monitored fire temperatures, decreasing degree of aromatic condensation was obtained. This suggests that molecular markers can be used to roughly estimate the maximum fire temperatures experienced by bark and wood materials, but not based on leaf- and needle-derived materials. Possible applications include verifying declared pyrolysis temperatures of biochars and evaluating ecosystem fire temperature postburn.