From organic matter to pyrogenic char to ash: the role of smouldering combustion

Guillermo Rein Rory Hadden School of Engineering University of Edinburgh Claudio Zaccone Agro-Environmental Sciences University of Foggia

Context
Smouldering combustion of natural organic soils like peatlands leads to the largest fires on Earth Poses a positive feedback mechanism to climate change

1. Fate of organic matter during smouldering 2. A missing mechanism in biochar stability/degradation

2008 - The Evans Road fire, NC - burned for 7 months

Smouldering wildlfires propagate slowly during several months consuming organic matter and threatening to release ancient carbon stored deep in the soil
During worst drought on record 16,500 ha burned (2x annual avg.) 1 m deep into the soil Stopped by flooding and excavation

100

km

This plume is no larger than those from flaming fires in California, Greece, Australia, National Geographic 2008/ AP Photo/MODIS etc, but it remained active for ~30 times longer than any flaming fire

Burning of natural organic soils

Organic soils, Italy

Moscow fires the summer of 2010

Organic soils, Mali

Rothiemurchus, Scotland

Feedback Mechanism in the Earth System

Permafrost thaw are already resulting in large smouldering artic fires (e.g., Alaska 2010).

topics I work on

smouldering fire

Mega-fires
The oldest continuously burning fire on Earth is a smouldering coal seam in Australia ignited >6,000 years old

& mt (t ) = mt dt =
0

0S d S l2t 3
Recent figures at the global scale estimate average greenhouse gas emissions from smouldering peat is equivalent to >15% of manmade emissions

In-depth spread over thick peat layers consumes biomass in the order of 100 kg/m^2, this is 50 to 100 times larger than flaming fires

Smouldering Combustion

R Hadden, UoE

Flameless Low peak temperature ~600C Low heat of combustion ~5 kJ/g Creeping propagation ~1 mm/min Incomplete combustion
heat

Heterogeneous combustion on fuel surface (pores) Fuels: peat, coal, duff, organic soils Two-step combustion reaction:

Peat char + (volatiles ,CH 4,PAH )

Char + O 2 heat + ash + CO 2 + CO + H 2O

Smouldering spread
30x30 cm tray setup with 5 cm layer of peat
Top view, Visual camera Top view, Infrared camera

video speeded up 600 times 1 s video = 10 min experiment

tim e

igniter

fate of organic matter

leading edge

Sd
in-depth

igniter
Sl undisturbed peat

h0
trailing edge

residual layer of char and ash

St

Char is simultaneously product and reactant in pyrolysis and oxidation reactions, which initially results in net char production and later become net char consumption.
Hadden et al, Proceedings of the Combustion Institute, 2012

Carbon Balance

Ash

Carbon fraction in char is ~1.5 times higher than peat Carbon fraction of ash is ~20 times lower than peat Carbon gaseous emissions mostly as CO2 and CO, but also CH4 and PAH

Hadden et al, Proceedings of the Combustion Institute, 2012

Chemical Analysis of smouldering residue

Location of last combustion front in peat

Depth from front (mm)

The chemical analysis of the solid residue shows it is a mixture of ash and char with a strong increases of pH, higher C/H and lower C/N ratios relative to the virgin peat
Zaccone et al., EGU2012-4795, SSS10.2 Poster XY648

Combustion Dynamics:

As the intensity of the fire increases (proxy via increasing oxygen concentration), the fraction of residual char rapidly decreases to zero.

Biochar degradation via fire

1. Wildfires 2. Self-heating = Accidental Release
Self-heating refers to the tendency of certain reactive solids in oxidative atmospheres to spontaneous exothermic reactions at low or ambient temperatures. Initially, small amounts of heat are released and accumulate during longer times when heat losses are low. This results in a sustained increase of temperature and leads to thermal run away, and smouldering fire.
& ql
& q

2 Heat

T c = 123 4 t 4 Rate Change

& qg

1 TC Stockpile Temperature T

A hT (T T0 ) V 4 3 Self heating 14 244 generation Heat losses

H 2 & 13

Conclusions

El Mundo

Smouldering are the largest and longest fires on Earth 100 times higher fuel consumption than flaming fires Consume organic matter and threat to release ancient carbon stored deep in the soil Smouldering combustion involves the simultaneous production and consumption of pyrogenic char (at different rates) Topic of global interest linked to ecosystem perturbation, carbon sequestration and climate change Smouldering illuminates the role of wildfires in pyrogenic char Fire is the fastest biochar degradation mechanism, not considered in the literature (?)

Thanks
Zaccone et al., EGU2012-4795, SSS10.2 Poster XY648 Belcher et al, PNAS 2011 Rein, Int Review Chemical Engineering 2009 Hadden, PhD Thesis 2011 Rein et al., Proc Combustion Institute 2009 Rein et al, Catena 2008

Very long-term sequestration of solid carbon

In order to minimize and avoid the risk of an accidental release associated with biochar storage, a new type of large facilities for stable and very-long-term storage should be built. Facilitates can be designed to store on surface, marine or mining sites. The methods for designing these facilities would use technological concepts borrowed from infrastructure fire protection. These facilities should be self-sufficient and passive (no input of energy required). Technologies for designing these facilities would drawn concepts from:

Stockpile size: As the size of the pile is made smaller, heat losses increase and the risk of self-heating is reduced. The maximum safe stockpile size is given by the ambient temperature. Ventilation: Design features enhancing natural ventilation and cooling Sealing: Storage in sealed compartments with low O2 (or inert) atmospheres. It is known that smouldering fires cannot propagate at [O2]<17%. Wetting: Material with large water contents (>125% dry base) do not ignite. Inertation: Reducing reactivity by mixing biochar with inert material

New Concept: Inertation

to reduce reactivity by mixing biochar with inert material, has been proven for the first time in a series of experiments on samples of char/sand (ratios 1 to 3). The reactivity of the mixtures was measured for different basket sizes and oven temperatures. Kamenetskis theory allows then to obtain the maximum safe stockpile sizes for different temperatures. Inertation allows for 200 to 600% larger stockpile sizes, even for hot countries.

Maximum safe stockpile sizes for the range of ambient temperatures found in hot to mild climates

Geo-Engineering facilities for biochar storage

The Royal Society defined in 2009 Geo-Engineering as: deliberate large-scale intervention in the Earths climate system, in order to moderate global warming The author thinks that designing and building facilities for very long-term sequestration of solid carbon would represent a engineering task at the Earthscale and thus a Geo-Engineering topic, but with a lower level of geo-intervention compared to other proposal put forward.