A Review of Biochar and Its Use and Function in Soil PDF

C H A P T E R T W O
A Review of Biochar and

Its Use and Function in Soil
S. P. Sohi,*,† E. Krull,} E. Lopez-Capel,‡ and R. Bol§
Contents
1. Introduction 48
1.1. What is biochar? 49
1.2. Policy context 53
1.3. Biochar and the global carbon cycle 54
1.4. Scenarios for the production and deployment of biochar 57
1.5. Trading and acceptability issues for biochar carbon 59
2. Characterization of Biochar 61
2.1. Quantification of char in soil 61
2.2. Chemical composition 63
2.3. Physical characterization 64
3. Biochar Application in Agriculture 64
3.1. Historic usage 64
3.2. Impact on crop productivity 65
3.3. Impact on soil performance and resource implications 67
3.4. Additional impacts on greenhouse gas balance 70
4. Research Priorities and Future Challenges 72
4.1. Mechanistic understanding 72
4.2. Properties, qualities, and environmental risks 74
4.3. Modeling capacity for the soil–biochar system 74
4.4. Barriers and limitations to biochar systems 75
Acknowledgments 76
References 76
* School of GeoSciences, University of Edinburgh, Edinburgh, United Kingdom

{
Department of Soil Science, Rothamsted Research, Harpenden, Herts, United Kingdom
{
The Swan Institute, University of Newcastle, Newcastle upon Tyne, United Kingdom
}
Biogeochemistry of Soils and Water group, North Wyke Research, Okehampton, United Kingdom
}
CSIRO Land and Water, PMB2, Glen Osmond, Australia
Advances in Agronomy, Volume 105 # 2010 Elsevier Inc.

ISSN 0065-2113, DOI: 10.1016/S0065-2113(10)05002-9 All rights reserved.
47
48 S. P. Sohi et al.
Abstract
Agricultural activities and soils release greenhouse gases, and additional emis-
sions occur in the conversion of land from other uses. Unlike natural lands, active
management offers the possibility to increase terrestrial stores of carbon in various
forms in soil. The potential to sequester carbon as thermally stabilized (charred)
biomass using existing organic resource is estimated to be at least 1 Gt yr 1 and
‘‘biochar,’’ defined by its useful application to soil, is expected to provide a benefit
from enduring physical and chemical properties. Studies of charcoal tend to
suggest stability in the order of 1000 years in the natural environment, and various
analytical techniques inform quantification and an understanding of turnover
processes. Other types of biochar, such as those produced under zero-oxygen
conditions have been studied less, but costs associated with logistics and oppor-
tunity costs from diversion from energy or an active form in soil demand certainty
and predictability of the agronomic return, especially until eligibility for carbon
credits has been established. The mechanisms of biochar function in soil, which
appear to be sensitive to the conditions prevailing during its formation or manu-
facture, are also affected by the material from which it is produced. Proposed
mechanisms and some experimental evidence point to added environmental
function in the mitigation of diffuse pollution and emissions of trace gases from
soil; precluding the possibility of contaminants accumulating in soil from the
incorporation of biochar is important to ensure safety and regulatory compliance.
1. Introduction
Agriculture is of relevance to climate change due to emissions in food
production and emissions through land-use change. Collectively, these
account for carbon-equivalent emissions equal, globally, to that of transport
and since agricultural emissions are affected by fertilizer application and the
extent of the livestock sector, emissions are—as for transport—expected to
increase at a faster rate than population growth per se, as a function of wealth
creation and dietary change. However, the fact that agricultural land is actively
managed means that the emissions can potentially be mitigated or reversed.
Agricultural soils contain a relatively small proportion of the global soil carbon
pool, but this quantity is significant relative to the annual atmospheric flux.
Biochar comprises biomass in a deliberately stabilized form, for which the soil
may provide storage on a very large scale. With requisite physical and chemical
properties, these forms of carbon could still offer potential value to crop
productivity through dynamic or reversible interactions with nutrients and
soil mineral particles. Any improvement to the productivity of existing agri-
cultural land has the potential to ease pressure on biodiverse and often carbon-
rich natural ecosystems. It is in this context that biochar has emerged as a
potential win–win strategy for climate change mitigation and food production
at the global scale.
A Review of Biochar and Its Use and Function in Soil 49
1.1. What is biochar?

In the partial or total absence of oxygen the thermal decomposition of plant-
derived biomass (pyrolysis) can be manipulated to yield, and in addition to
CO2 and in variable ratio, combustible gases (chiefly H2, CO, CH4),
volatile oils, tarry vapors, and a solid carbon-rich residue generically referred
to as char. As distinct from char in general, biochar remains ill-defined. It is
generally considered to comprise biomass-derived char intended specifically
for application to soil, that is, according to its purpose. As such, it extends to
related materials produced under more- and less-controlled conditions with
and without total exclusion of oxygen, such as conventional charcoal. A
characteristic of biochar that is common to char in general is that it
comprises mainly stable aromatic forms of organic carbon, and, compared
to the carbon in a pyrolysis feedstock, cannot readily be returned to the
atmosphere as CO2 even under favorable environmental and biological
conditions, such as those that may prevail in the soil.
In a controlled process the energy in gas streams from pyrolysis may be
recovered by combustion, either in gas turbines or gas engines. Separation
of gases may provide feedstock for important chemical conversion processes
such as Fischer–Tropsch (CO as a precursor for diesel) Haber–Bosch (H2 as
a precursor for atmospheric N fixation), etc. Oil and tar fractions have an
energy value as well, though being ‘‘heavy,’’ heterogeneous and acidic they
are currently difficult to refine, and problematic to handle due to their
propensity to condense at relatively high temperature. It is anticipated that
developments in biorefining will change this situation in the near future.
The balance between char and gas, oil and tar products in pyrolysis
depends to a considerable extent upon the rate of heating (Table 1). ‘‘Slow’’
pyrolysis (heating for seconds or minutes) may be deployed as a continuous
process, where purged (oxygen-free) feedstock is transported into and
through an externally heated kiln (gas flow removing volatiles, char
emerging at the other end); ‘‘fast’’ pyrolysis depends on very rapid (ms
to s) transfer of heat, typically to fine biomass particles blown through hot
gases in confined oxygen-free chamber (variants on such equipment have
also been used in slow ‘‘downdraft’’ systems). The character of the char
product is affected by the extent of pyrolysis (peak process temperature), and
its completeness by particle size, kiln residence time. The rate at which
volatiles and gases are drawn from a kiln dictates vapor residence time.
Longer residence times result in secondary reactions, notably the reaction of
tar on char surfaces, and charring of the tar, rather than separate combustion
or processing outside the kiln.
Pyrolysis engineers have traditionally sought to minimize char produc-
tion as it has been viewed as a problematic low-value waste fraction.
Consequently there has been much focus of research effort on fast pyrolysis
which maximizes condensable oil and also gasification (which is a process
Table 1 Fate of initial feedstock mass between products of pyrolysis processes

(IEA, 2007)
Solid Gas
Liquid (biochar) (syngas)
Process (bio-oil) (%) (%)
Fast pyrolysis: Moderate 75% (25% 12 13
temperature (500 C), water)
short hot vapor residence
time (< 2 s)
Intermediate pyrolysis: Low- 50% (50% 25 25
moderate temperature, water)
moderate hot vapor
residence time
Slow pyrolysis: Low- 30% (70% 35 35
moderate temperature, water)
long residence time
Gasification: High temperature 5% tar (5% 10 85
(> 800 C), long vapor water)
residence time
similar to fast pyrolysis, but including a limited supply of oxygen). These

produce predominantly heavy oil or gas, yielding only small proportions of
char. The development of integrated systems that produce energy and char at
high efficiency by slow pyrolysis is still, therefore, mainly on the research
scale, with technology commercially deployed only at a handful of locations.
The energy content of biochar depends on its feedstock, but may reach 30
and 35 MJ kg-1 (Ryu et al., 2007). Therefore char is conventionally used to
provide the heat driving the primary pyrolysis through burning or gasifica-
tion (Demirbas et al., 2006), or to dry incoming feedstock. Maximizing
biochar is therefore at the expense of usable energy in gaseous and liquid
forms (Demirbas, 2006) and has an opportunity cost. Although a mitigation
strategy for the abatement of greenhouse gases may favor maximization of
biochar production (Gaunt and Lehmann, 2008), the realistic balance is a
function of market and engineering constraints. Process parameters funda-
mentally affect the properties of the biochar product, modifying its possible
value in agriculture, and in the sequestration of carbon. Temperature and
residence (heating) time are particularly important, but the feedstock and its
interaction with temperature may be equally significant.
Human society in general has extensive experience of pyrolysis in the
specific context of producing charcoal, mainly as a clean-burning fuel.
Currently produced in rural areas for urban markets and industrial smelting
of iron (where carbon credits can be obtained for emissions offset
from coke), traditional methods of charcoal production predominate and
represent the most widely practiced form of pyrolysis at the current time. In
charcoal production process heat is generated within the kiln by initiating
combustion of some of the feedstock in air, prior to restricting air flow.
Although no fuel is required for external heating, the combustion phase and
incomplete exclusion of air lowers conversion rates from biomass to char-
coal (about 20% in traditional kilns). This type of production is typically
small scale and a ‘‘batch’’ process where the full cycle of heating and cooling
is applied to a confined and stationary charge. In addition to being energeti-
cally inefficient and time-consuming, these processes are highly polluting:
potentially useful gases are emitted, together with aerosol (smoke) from
partially combusted oil and tar. Unfortunately, in addition to the emission of
CO2 and potent trace greenhouse gases in these streams, traditional charcoal
manufacture is also implicated in depletion of forest and wood fuel
resources, and wasteful in terms of utilization of biomass carbon as such a
large fraction is lost back to the atmosphere. Nonetheless, the current
definition of biochar does encompass charcoal, ostensibly to recognize its
historic value in soil management, and to acknowledge the accessibility and
universality of technology used to produce it. Much evidence drawn upon
to assess biochar function rests on studies made using charcoal.
The difference in the proportion of feedstock carbon retained is the key
difference between traditional production of charcoal and slow pyrolysis, by
which typically 30–40% of feedstock mass is recovered as char. Although
optimised for char production it is thought that 50% retention might be
achievable. It is also possible that additional carbon retained in slow pyroly-
sis is not chemically or physically consistent with traditional charcoal con-
taining, for example, a greater concentration of hydrogen and oxygen (due
to less complete pyrolysis), deposited oils and tars, and possibly thermal
alteration of these. The formation of secondary char increases with vapor
residence time, which is in turn a function of the rate at which gas flows or is
propelled from the reactor. The current position of pyrolysis in the context
of a range of other biomass conversion processes is shown in Fig. 1.
Although feedstock is important in determining the function of biochar
in soil, there is no consensus as to optimal feedstock in terms of both soil use
and energy production, mainly because commercial pyrolysis plants are
scarce, and those that exist are associated with the processing of specific
waste streams. A limited amount of research-scale pyrolysis has been con-
ducted using a wider range of feedstock (Gaunt and Lehmann, 2008; Das
et al., 2008; Day et al., 2005). Feedstock currently used at commercial and
research facilities includes wood chip and wood pellets, tree bark; crop
residues including straw, nut shells, and rice hulls; switch grass; organic
wastes including paper sludge, sugarcane bagasse, distillers grain, olive waste
(Yaman, 2004); chicken litter (Das et al., 2008), dairy manure, and sewage
sludge (Shinogi et al., 2002). Research- and pilot-scale pyrolysis has been
undertaken at a rate of 28–300 kg h-1 (dry feedstock mass basis), which is
Feedstocks Process Product Uses and applications
Biomass energy Fast pyrolysis Synthesis gas – Heat

crops (corn, (anhydrous) Bio-oil liquid – Fuel (combusted to generate electricity
cereals, wood Biochar solid or converted to syngas)
pellets, palm oil, – High value bio-chemicals used as food
oilseed rape) Slow pyrolysis
additives or pharmaceuticals
(low temp. 450– Syngas
– Soil conditioners/fertilisers
550 °C, O2-free,
Bioenergy residues some-times steam)
“cake” Biochar – Soil amendment (neutral/alkaline pH,
porosity retains water, cation exchange
Slow pyrolysis capacity: robust benefits to plant growth
Agricultural waste Activated
(high temp. 600– compared to high-temp char)
(wheat straw, biochar
900 °C, O2-free) – Fuel (cooking and heat)
hazelnut and
peanut shells, Combustible
waste wood, etc.) Gasification (high ethane, – Extreme porosity and surface area
temp., fast heating methane – Water filtration and adsorption of
Compost (green rate., O2 present) contaminants (gas, liquid, or solid)
waste)
Char
– Fuel (low yield, high reactivity)
Fermentation, – Contamination of some feedstocks
Manure/animal
anaerobic digestion, Ethanol (e.g., metal and plastic in kitchen waste)
waste (chicken)
and mechanical may preclude use of sludge/char in soil
bio-treatment
Kitchen waste Methane and
– Fuel (for electricity or cooking)
plastic, food, etc. sludge
Carbonization – Bi-products (wood spirits, wood tar)
(‘brown’ at 300 °C, – Substitute for coal-derived coke in
Sewage sludge ‘black’ at 380 °C) Charcoal metal smelting
Figure 1 Biochar and other products of thermal conversion of biomass according to available technologies and feedstocks.
about one-tenth of commercial plants (2–3 t h-1). Comparing the efficiency

of pyrolysis plants is difficult as the fate and the quantitative balance for solid,
liquid, and gaseous products are rarely fully quantified in individual studies,
yet vary considerably. The composition and hence heating value of syngas
also varies, particularly with respect to feedstock quality and moisture
content.
In production of oil from biomass, the feedstock ratio in carbon, oxygen,
and hydrogen is considered an indicator of quality (Friedl et al., 2005). Low-
mineral and N contents provided by wood and biomass crops include short-
rotation willow, high productivity grasses such as Miscanthus spp., and a
range of other herbaceous plants. However, abundant and available agricul-
tural by-products, particularly cereal straw, may be suitable. Proportions of
hemicellulose, cellulose, and lignin content appear to influence the ratio of
volatile carbon in oil and gas and the proportion of carbon stabilized in
biochar. Feedstocks with high lignin content generate high yields of biochar
when pyrolyzed at temperatures of approximately 500 C (Demirbas et al.,
2006; Fushimi et al., 2003). More knowledge is required for feedstock to be
selected or processed to achieve a specified balance between all three classes
of pyrolysis products (i.e., gas, oil, and char). However, the basic conversion
technology—slow pyrolysis or a related process—is the most critical factor.
This review concerns biochar produced from the utilization of biomass
with simultaneous energy capture. However, much of the current evidence
for the impacts on soil properties and soil carbon rests on research using char
produced experimentally by more traditional methods.
1.2. Policy context

The biochar concept has a strong global context, as it is positioned strongly
in the context of climate change (carbon abatement), but intrinsically linked
to renewable energy capture (biomass pyrolysis), and food production and
land-use change (food and feed production), further extending to the
enhancement of environmental quality (control of diffuse pollution) and
management of organic wastes (stabilization and use), through management
of soil nutrients.
Climate change and food production are causally linked as 13.5% of
radiative forcing is attributable to greenhouse gases emitted through agri-
cultural activity (Barker et al., 2007). The carbon release associated with
switching land previously under natural or unmanaged vegetation to crop
production releases typically large amounts of carbon from standing bio-
mass, and also from the soil. The conversion of land use at current rates
accounts for another 17.4% of radiative forcing (Barker et al., 2007) mainly
through the loss of biomass carbon as CO2, and workable technologies to
enhance the productivity of agriculture may be important in stemming
these sources as land pressure is a significant factor. Climate change is linked
to energy use by the remaining 70% of radiative forcing that results from use
of fossil fuels. However, energy and land-use change are also linked.
Although the use of replenishable biomass in energy production is consid-
ered carbon neutral (and to offset fossil fuel emissions), it is clear that
dedicated energy crops produced at a scale that is significant in terms of
global energy supply would lead to direct and indirect pressure on natural
ecosystems, and a net emission of CO2 in conversion. Losses documented
for some existing conversions are extremely large (Fargione et al., 2008),
and although the benefit of a long-term annual offset of fossil carbon
emissions is important, short-term losses from conversion of natural eco-
systems do not favor, even in carbon terms alone, land-use change. This is
because the pace of climate change is rapid compared to the timescale for
delivery of net benefit from bioenergy crops after conversion.
Assessments of the realistic potential for biochar in carbon abatement
have converged on a figure of about 1 GtC yr 1 (Lehmann, 2007), which
presents a potential ‘‘wedge’’ for climate change mitigation; Pacala and
Socolow (2004) proposed that a portfolio of such wedges is required to
avert the threat of catastrophic climate change. Currently, abatement poten-
tial is the most quantifiable and certain of the many characteristics of
biochar. However, at the moment simple stabilization of biomass carbon
is not eligible for trading under the Clean Development Mechanism
(CDM), the international scheme designed to achieve carbon abatement
under the Kyoto protocol. In the absence of eligibility for carbon credits, or
simply to supplement a future income stream from carbon stabilization, it is
likely that biochar addition to soil will proceed only where sufficient
improvements in soil performance and productivity are perceived or
assured.
In addition to the avoidance of CO2 and methane emissions during
normal decomposition of feedstock, a suppression of nitrous oxide and
methane emissions from otherwise normally managed soils is frequently
claimed. Since the global warming potential (GWP) of these gases is high
and the main source globally agricultural, this effect is of potential signifi-
cance, although the evidence base is still very limited.
A role for biochar in control of diffuse pollution from agriculture,
including sorption of agrichemicals, has also been proposed, and available
evidence is reviewed later in this study.
1.3. Biochar and the global carbon cycle

Globally, photosynthesis by plants draws 120 Gt CO2–C from the atmo-
sphere into energy-rich carbohydrate carbon each year (Schlesinger, 1995).
Half of this is rapidly returned to the atmosphere through plant respiration,
but about 60 Gt CO2–C yr 1 is invested in new plant growth (carbon
comprising 45% of plant biomass). After accounting for approximately
2.2 Gt CO2–C yr 1 loss through land-use change (Houghton, 2003), and

some ‘‘fertilization’’ from increasing atmospheric CO2 concentration, the
amount of carbon in living plant biomass (560 GtC; Schlesinger, 1995)
appears to be broadly constant. This confirms that the magnitude of crop-
ping and harvest, as well as the deposition of litter and exudates by plants and
plant roots into soil, is broadly equal to annual net primary productivity.
The pathways by which much of this carbon is returned to the atmosphere
are varied and complex, but in a particular year the gross flux to the
atmosphere—the product of the progressive degradation of all cohorts of
previous plant production—approximates to the amount that is fixed over
the same period. Human intervention in the management of forests and
agroecosystems means that 20–40% of net primary productivity is in some
way associated with active management (Vitousek et al., 1986).
A strategy to deploy biochar on a large scale would divert a portion of the
existing global carbon flux that resides within managed ecosystems, or to
intercept enhanced net primary productivity production in the form of
increased harvest or waste biomass. This material would be pyrolyzed and
replaced in soil in a stabilized rather than a degradable form, in this way
returning much less carbon to the atmosphere from sites of decomposition
(soil, landfill, etc.), and simultaneously decreasing associated emission of other
greenhouse gases (notably methane). The net anthropogenic addition of car-
bon to the atmosphere (6.3 GtCO2–C yr 1; Houghton, 2003) is small relative
to the scale of the natural atmosphere–plant–soil–atmosphere cycle. If the net
primary productivity of managed agricultural and forest ecosystems is between
12 and 24 GtC yr 1, the interception and stabilization of 1 GtC does not appear
an extraordinary goal. Assuming that the carbon in biochar is stable, diversion
of organic resources and wastes to pyrolysis would result in a permanent offset
against future atmospheric CO2, which could be extended on an annual basis,
according to other priorities and circumstances for use of biomass.
A strategy based around biochar thus differs from the more established
proposition for sequestration of carbon in soil, where the objective is to
increase the equilibrium level of active soil organic matter, which broadly
requires that rate at which carbon—in the form of organic resource or
wastes—is forced through the soil system to be permanently increased to a
higher rate. Despite the large size of the global soil carbon pool (1500 GtC)
the potential for this strategy to accumulate carbon per unit area is limited in
absolute quantitative terms. This is because intensively managed lands
account for a small part of the global soil carbon pool, and incremental
enhancements account for trivial amounts of carbon, and because the
capacity for any soil to stabilize labile carbon has fundamental limits. In
addition, storage is delivered over a lengthy period of time (usually decades),
and this annual rate diminishes as equilibrium is approached. The increased
flow of carbon into the soil must be maintained after equilibration to avoid
reversal of soil storage, making the diversion of resource into the soil a
permanent commitment. Increasing the quantity and turnover of carbon in

soil, in the form of organic matter, seems certain to provide crop-related
benefits ( Janzen, 2006; Lal et al., 2004). This is therefore a desirable strategy
where sufficient organic resource exists, but should be weighed against a
more efficient strategy where adopted explicitly for carbon sequestration,
especially in fertile soils.
The cycling of black carbon produced during wildfire provides a natural
analog for a biospheric intervention based on biochar. Wildfire is currently the
largest source of black carbon globally, a small proportion of above-ground
biomass (about 1%) being incompletely combusted and returned to the soil as
char of various forms. The extent and frequency of wildfire in many systems
means that this pathway may already provide a terrestrial net sink for about
0.05–0.2 Gt yr 1 atmospheric CO2–C (Kuhlbush, 1998). Increasing recogni-
tion for the global significance of this flux arises in part, from development of
measurements that discriminate black carbon from other soil carbon. These
seem to indicate much larger amounts of black carbon in soil than has been
assumed in global stock estimates, or than has been allowed for in soil models.
This may affect, among other things, the response of the global soil pool to
climate change, black carbon being much more stable than the typical com-
ponents of soil carbon (Lehmann et al., 2008). Interpretation of black carbon
measurements is, however, complicated by some uncertainty over their effi-
cacy and also their capacity to discriminate charcoal from other forms of black
carbon, specifically those arising from anthropogenic activity—deliberate
vegetation burning, wood fuel, combustion of coal and oil.
The possible indirect effects of biomass stabilization on radiative forcing
have to be considered. Soot from biomass burning is implicated in an
acceleration of polar ice melt, but conversely in facilitating cloud formation
and ‘‘global dimming’’ (McConnell et al., 2007; Ramanathan and
Carmichael, 2008). The production of biochar under controlled conditions
should be clean, but the means to control methods of production are
unclear. Biochar in soil also visibly darkens soil color, especially in soils
that are already low in organic matter, and a relationship between soil color
and occurrence of low temperature wildfire has been demonstrated
(Ketterings and Bigham, 2000; Oguntunde et al., 2008). As dark soils absorb
more solar energy they may, depending on water content and plant cover,
display higher soil temperatures (Krull et al., 2004). This would potentially
accelerate cycling of nutrients and beneficially extend growing season in
temperate regions, and in Japan it is a traditional farming practice to apply
charcoal to accelerate snow melt. The study of Oguntunde et al. (2008)
showed a one-third reduction in soil albedo in char-enriched soils from
historic charcoal making sites. On a large spatial scale, the application of
biochar could potentially reduce the albedo of the Earth’s surface, whereas
increasing surface albedo has been proposed as a possible mitigation measure

for climate forcing (Crutzen, 2006).
1.4. Scenarios for the production and deployment of biochar

Producing charcoal using traditional kilns liberates greenhouse gases,
particularly methane and nitrous oxide, and conserves relatively small pro-
positions of carbon in the feedstock (FAO, 1985) and wastes the heat energy
product. Apart from being associated with deforestation, sequestration of
carbon into charcoal using unmodified, traditional methods may therefore
not, depending on the source and ordinary fate of feedstock, provide
climate change mitigation.
Controlled pyrolysis stabilizes some carbon in solid form but also cap-
tures energy-rich liquids and gases which can be used to drive the pyrolysis
reactions or used elsewhere. Although energy is retained in solid char the
amount of energy liberated from the pyrolyzed feedstock may be higher,
per mass of feedstock carbon, than in combustion. Pyrolysis could therefore
be more efficient in terms of carbon emissions (CO2 MJ 1), and production
of biochar carry greater abatement potential than biomass combustion,
provided there is an overall adequate supply of feedstock, and storage for
the biochar product is available.
Although it has previously been proposed that entire valleys might be
dedicated to provide storage for carbon stabilized as biochar (Seifritz, 1993),
applying biochar to agricultural soil is proposed for three reasons: (1) only
the soil seems to have a capacity sufficient to accommodate biochar at the
scale relevant to the long-term mitigation of climate change, (2) there is
potential for biochar to enhance soil function for agricultural productivity
and thus offset the opportunity cost associated with its residual energy value,
and (3) the possible suppression of methane and nitrous oxide release would
increase the value of biochar as a means to offset agricultural greenhouse gas
emissions. The impact of biochar on existing and future levels of non-
biochar soil carbon should also be considered in this context.
Ideally biochar will provide reliable agronomic benefits and command a
value in crop production that precludes combustion for energy, with or
without a value placed on sequestration of the carbon that it contains. In this
evaluation of value, allowance has to be made for the cost of acquisition and
incorporation of biochar into soil. A value can also be assigned by producers
and upstream food processors to the marketing potential of low-carbon or
‘‘carbon-neutral’’ food products produced in systems that deploy biochar. It
is expected that a growing understanding of the relationship between
feedstock, the manipulation of the pyrolysis process, and the function of
biochar in soil will ultimately enable biochar to be ‘‘engineered’’ to provide
the balance of benefits most appropriate to a particular system. The value of

the energy captured in pyrolysis must also exceed the price for the alter-
native use of the feedstock, unless it is genuinely a waste, in which case the
normal cost of disposal can be added to the value of the energy. It should be
recognized that the price of feedstock depends on demand, however, and
from a market perspective wastes may cease to be wastes once demand as
novel feedstock exceeds their rate of production within a relevant catch-
ment area.
In a closed-loop biochar system, the biochar product is returned to the
same land that provided the feedstock. There are opportunity costs in
diverting straw to pyrolysis, and there is an additional direct cost of applying
biochar. There are also possible non-monetary costs associated with the
collection of straw for pyrolysis, in terms of disruption of schedules and soil
disturbance. Currently, there are no socioeconomic studies that have
addressed such matters. A key advantage of a biochar strategy is that,
assuming that the provision of key functions is limited only by the longevity
of the biochar, its stability would dictate that the application frequency
required to deliver benefits is single or occasional, rather than annual.
Scenarios using non-waste feedstock for co-production of energy and
biochar may impact commodity prices and feedback into feedstock costs.
The proximity of a pyrolysis facility to an adequate catchment for feedstock
must be economically and logistically viable, and can potentially affect the
CO2-equivalent savings. This is the case for biomass and bioenergy facilities
generally. However, for biochar the proximity of suitable locations for
biochar application to soil is important as well. If the gathering of feedstock
and the distribution of biochar occur over the same area the logistical and
cost impacts may not be greatly affected.
Possible off-farm sources of pyrolysis feedstock include municipal green
waste (from gardens and parks), composted urban waste, digested sewage
sludge and mixed municipal waste. In addition, in the future, by-products
of other bioenergy or biofuel systems are likely to become available.
Utilizing off-farm wastes is attractive in cost terms where it results in
avoided landfill and other disposal costs. In addition, compared to typical
or existing disposal methods, there may be a lower emission of CH4 and
N2O greenhouse gases than placement in soil, enhancing the net gain in
carbon equivalents through avoided emissions of gases with much higher
GWP. However, many such wastes have a high water content which will
incur increased emissions (and cost) associated with higher requirement for
process energy in pyrolysis.
In the ‘‘closed-loop’’ scenario, biochar is incorporated into the same
land, the same enterprise, or groups of enterprises from which the pyrolysis
feedstock originates. A typical scenario would involve the use of cereal crop
straw that, in intensive arable areas, is often available at a relatively low cost.
Although there is no published laboratory work to support the use of
biochar produced from wheat straw, there is limited existing information on

the relative stability of biochar from rice husk, sugarcane bagasse, and straw
from maize.
Using literature evidence Gaunt and Lehmann (2008) compared the
carbon-equivalent gain to be derived from pyrolysis of maize straw versus a
dedicated biomass crop. Biochar produced in the latter scenario has implica-
tions for land use as indicated earlier, and it was assumed that biochar was
incorporated into different land from that producing the feedstock offering
greater potential for agronomic gain. In general, the defined spatial boundaries
are important and indirect as well as direct land-use impacts should be consid-
ered in establishing the overall net greenhouse gas benefit (Searchinger et al.,
2008).
In the combined energy and bio-oil case study considered by Ogawa
et al. (2006), biochar was returned as a by-product to adjacent arable land.
Most scenarios considered to date have focused on conventionally managed
arable land, where biochar could be added to soil as part of an existing tillage
regime. Biochar could be incorporated during conversion of land to no-till,
but strategic integration of application into no-till and grazed grassland
systems has not been widely considered, although amendment of slurry
and manure already spread presents clear opportunities.
1.5. Trading and acceptability issues for biochar carbon

Biochar products used in soil will ultimately have specified agronomic
value, and if associated with a carbon credit for the storage of a fraction of
the carbon that they contain, a high and predictable level of stability. The
ability to verify actual rates of degradation at a research level is important
(Matthews, 2008; Ogawa et al., 2006), and identifying the specific char-
acteristics that govern stability will enable such properties to be quantified
and optimized, and to adapt production process accordingly.
Until research provides the tools required to optimize the agronomic
function of biochar, the viability of biochar-based soil management may
depend on a claim for carbon credits. However, knowledge and awareness
of bioenergy and carbon markets is lacking, and in the absence of markets
where credit for carbon stabilized in biochar can be claimed, it is not
possible for management of carbon to influence decision making of indi-
vidual land users. The absence of robust figures for the costs and benefits to
crop production arising from the use of biochar in soil is a major barrier to
deployment. The economic case for pyrolysis of biomass rather than com-
plete combustion is sensitive to the prevailing value of heat and power
generated using other fuels, as well as the value of biochar in soil. It can be
further affected by subsidy for renewable energy, which may have the effect
of further inflating the value of the energy in biochar, as a renewable source.
Compared to schemes intended to store carbon by increasing standing

plant biomass or stocks of soil organic matter, accounting for the impact of
biochar should be relatively straightforward. However, a framework within
which biochar carbon could be certified as an offset has not yet been
established and, moreover, land-based offsets are not allowed under the
CDM. Methodologies do exist for estimating the avoided emission of
methane in the pyrolytic stabilization of crop residues (UNFCCC, 2007),
as well as for carbon storage enhanced by adoption of no-tillage in the
Voluntary Carbon Market which currently trades carbon worth USD
30 bn yr 1.
Rather than dealing with carbon stabilized into biochar, a suitable
accounting methodology might deal with CO2 avoided in decomposition,
based on an assumption of the proportion of feedstock carbon released as
CO2 during pyrolysis, and the proportion of the residual char that is entirely
stable. Key elements of a suitable system based on this principle would be
limited to: (1) documentation showing delivery of crop-derived feedstock
to a pyrolysis facility, (2) a guarantee from the processor for the stability of
the pyrolyzed product, and (3) a simple system to verify the presence of
biochar in amended soils. Establishing the total carbon-equivalent gain from
applications of biochar to soil, taking into account the avoidance of any
non-CO2 greenhouse gases is more complex, and unlikely to emerge for
some time. The mechanisms for these effects are not understood or proven,
and the timescales over which they occur is much more uncertain.
At the current time, a number of Annex II nations are seeking inclusion
of biochar into the successor to the Kyoto Protocol, through the United
Nations Convention to Combat Desertification (UNCCD), which tackles
the productivity of dryland as well as desertified and desertifying areas. The
CDM specifies the offsets by Annex II nations (broadly, developing and
newly industrialized countries) that are available to Annex I nations
(broadly, industrialized countries). Various governments have implemented
national carbon-trading schemes to meet their emission reduction commit-
ments under the Kyoto protocol. In Europe this has led to the EU Green-
house Gas Emission Trading Scheme, and subsidiary schemes such as the
UK Emissions Trading Scheme. More recently, Australia has announced
plans for a Carbon Pollution Reduction Scheme (Anon, 2007). The inclu-
sion of biochar into some national trading schemes is anticipated.
In terms of potential risk to human health posed by biochar, attention
has focused on two classes of toxic compounds associated with combustion
processes, namely PAHs and dioxins. Dioxins predominantly form at tem-
peratures in excess of 1000 C, but there are no published studies to confirm
their absence in biochar (Garcia-Perez, 2008). The proliferation of PAH in
secondary pyrolytic reactions above 700 C is well established (Ledesma
et al., 2002), but may form at low concentration in the operating tempera-
ture range of pyrolysis reactors (Garcia-Perez, 2008), and PAH profiles have
even been considered to provide a reliable thermal history for environmen-

tal samples (Brown et al., 2006).
Unpublished analyses of several biochar samples found PAH content
similar to those of rural UK soils (Manning, pers. comm, 2009); a single
published study examined the full PAH profile (40 individual PAH com-
pounds) in a number of synthetic char samples, manufactured at relatively
high heating rates (Brown et al., 2006). In the latter study, total PAH
concentration was 3–16 mg g 1 depending on peak temperature, compared
to 28 mg g 1 in char from a prescribed burn in pine forest. However,
empirical relationships to relate these results to process parameters—and
which could then be used to predict their formation—have not been
established. It has been noted by Ahmed et al. (1989) that while biochar
comprises entire systems of PAH molecules, the existing evidence suggests
no leachable PAH are present. Thus although the timescale over which
PAH from biochar are altered in the soil, and most importantly, the rate at
which they become bioavailable, it appears that degradation predominates.
In one study in temperate soils, a mean residence time for PAH has been
estimated at less than ten years (Paterson et al., 2003), which is low relative
to most estimates for the stability of biochar.
2. Characterization of Biochar
The key challenge in quantification is to distinguish biochar from soil
organic matter and from other forms of black carbon present in bulk soil
samples. A variable and unpredictable level of interference from the mineral
matrix in soil presents a major challenge in the application of many potential
techniques, and many of the techniques depend on spectroscopic character-
istics rather than physical separation or isolation. Some of the techniques
that most effectively distinguish different types of biochar can also be used to
characterize individual biochar fragments (or collections of fragments)
recovered from soil. Examination of pure samples removes the matrix
effects, but where function of a recalcitrant substrate depends on its surface
characteristics or those of accessible pores, separation of active and inactive
components presents a significant challenge.
2.1. Quantification of char in soil

The categorization of soil organic carbon in general presents a major
challenge. Quantifying black carbon is particularly difficult on account of
its chemical complexity and diversity, yet inherently unreactive nature. Due
to its recalcitrance, biochar cannot meaningfully be extracted from soil using
chemicals, though potential biomarkers may be. Results from studies using
the physical location of char within a soil matrix (Brodowski et al., 2006;
Glaser et al., 2000; Liang et al., 2009a; Murage et al., 2007; Shindo et al.,
2004) suggest that efficacy of physical separations using density or means
other than hand picking (which is limited to very small samples) are sensitive
to site factors.
Until recently, the most practical approaches have sought to remove
non-black carbon fractions (i.e., soil organic matter and mineral carbonates)
with subsequent evaluation of the residue. However, for quantifying bio-
char specifically this type of quantification may be affected by the presence
of the more recalcitrant black carbon forms, as well as by the presence of
highly resistant organic compounds—such as those stabilized on clay—not
incompletely removed, and which in some cases are estimated separately.
Different techniques discriminate components of increasing minimum
stability: partially charred biomass, char, charcoal, soot, and graphitic black
carbon. Leading methods in this category include removal of non-black carbon
by oxidation—chemically (e.g., sodium chlorite, potassium dichromate), using
ultraviolet radiation, or by a thermal approach (De la Rosa et al., 2008).
Hydrogen pyrolysis (HyPy) is alternative approach to removal of non-black
carbon (Ascough et al., 2009), while evolved gas analysis seeks to infer source
from the character of the diverse gaseous products of thermal decomposition.
A combined chemothermal oxidation method, with a temperature threshold
of 375 C (Gustafsson et al., 2001), forms the basis of a standard procedure for
the determination of fixed carbon, which comprised the most stable fraction of
black carbon, and has the more stable component of biochar.
Virtual separations have traditionally relied on spectroscopic techniques
in combination with pretreatment (or other allowance) for mineral inter-
ference, for example using hydrofluoric acid (Simpson and Hatcher,
2004)—pyrolysis gas chromatography mass spectroscopy (PyCG/MS), and
solid-state 13C nuclear magnetic resonance (NMR) spectroscopy with
cross-polarization, Bloch decay, and combined with magic angle spinning
(MAS) (Skjemstad et al., 1999; Smernik et al., 2002)—or chemically
extracted and purified biomarkers, particularly benzene polycarboxylic
acids (BPCA) (Brodowski et al., 2005), and levoglucosan (Kuo et al.,
2008). A further approach considered in this category is matrix-assisted
laser desorption ionization (MALDI–TOF) (Bourke et al., 2007).
The applicability of these methods depends on the purpose of the
analysis and the specific nature of the target fraction, so although all have
been evaluated for a set of 12 environmental and black carbon samples in a
ring trial (Hammes et al., 2007, 2008), there remains relatively little consen-
sus as to a universal standard. Since most depend on progressive exclusion
based on increasing recalcitrance, the methods cannot readily exclude both
recalcitrant soil organic matter and graphitic and soot fractions, and directly
reveal the content of relatively less condensed (stable) charcoal or char
fractions. Nonetheless, UV or chemical oxidation with elemental and 13C
NMR analysis of residues, thermal analysis (De la Rosa et al., 2008;

Hammes et al., 2007), and HyPy (Ascough et al., 2009) were identified as
the most promising techniques.
A relatively new development in the quantification of black carbon has
been the application of correlative techniques based on mid-infrared (MIR)
spectroscopy. Initially evaluated for the estimation of organic carbon con-
tent of bulk soil samples, among other key properties, algorithms have been
developed for relating the MIR response spectrum to black carbon, using a
calibration set assessed using a UV-oxidation method ( Janik et al., 2007).
The method has been applied to evaluate charcoal content in regional
evaluation using archived soils (Lehmann et al., 2008) and holds potential
for similar assessments in the global context provided the algorithms can be
shown to hold for soils of contrasting organic carbon contents.
2.2. Chemical composition

Some of the quantification techniques may also be relevant to the characteri-
zation and comparison of various samples of pure biochar, that is, ex situ. The
purpose here is to assess variation in properties of black carbon between
samples, and to document the process of aging in contrasting soils and envir-
onments. Elemental ratios of O:C, O:H, and C:H have been found to provide
a reliable measure of both the extent of pyrolysis and the level of oxidative
alteration of biochar in the soil, and are relatively straightforward to determine.
Diffuse reflectance infrared Fourier transform spectroscopy (FTIR), X–ray
photoelectron spectroscopy (XPS), energy dispersive X–ray spectroscopy
(EDX), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy
(Baldock and Smernik, 2002; Fernandes and Brooks, 2003; Lehmann et al.,
2006) have been used to examine surface chemistry of biochar in more detail.
These analyses provide qualitative information that may enable the mechan-
isms behind aging and functionalization of biochar to be elucidated.
Biogeochemical characterization may also help understand the agro-
nomic function of biochar products at the soil process level and facilitate
production of biochar that offers specified benefits. To develop the predic-
tive capacity for the longevity and interaction of biochar in soil, determin-
ing its value as a carbon sink and soil conditioner, the nature of its
interventions in typical soil processes must be established. From a practical
point of view it is important that the devised methods enable biochar
characteristics to be determined sufficiently rapidly and inexpensively as to
permit widespread application and use.
A preliminary set of seven key properties for the evaluation of biochar
have been defined: pH, content of volatile compounds, content of ash,
water-holding capacity, bulk density, pore volume, and specific surface area
(Okimori, et al., 2003). Feedstock is a key factor governing the status of such
physicochemical properties. Pyrolysis temperature is the most significant
process parameter, carbon content of biochar inversely related to biochar

yield, increasing from 56% to 93% between 300 and 800 C in one study,
while yield of biochar decreased from 67% to 26% (Okimori, et al., 2003).
Beyond a certain temperature threshold, biochar yield may continue to
decrease with no further increase in the concentration of carbon within it.
However, since ash is broadly conserved, the ash content of biochar
increases with temperature. In the study described earlier, the ash content
of remaining biochar rose from 0.67% to 1.26% as peak formation temper-
ature was increased from 300 to 800 C
2.3. Physical characterization

Scanning electron microscopy (SEM) is often used to describe the physical
structure of biochar. The macroporous structure (pores of approximately
1 mm diameter) of biochar produced from cellulosic plant material inherits
the architecture of the feedstock, and is potentially important to water-
holding and adsorption capacity of soil (Day et al., 2005; Ogawa et al., 2006;
Yu et al., 2006). Surface area measured by gas adsorption, however, is
influenced by micropores (nm scale) that are not relevant to plant roots,
microbes, or to the mobile soil solution. Process temperature is the main
factor governing surface area, increasing in one study from 120 m2 g 1 at
400 C to 460 m2 g 1 at 900 C (Day et al., 2005). The importance of
temperature leads to the suggestion that biochar created at low temperature
may be suitable for controlling release of fertilizer nutrients (Day et al.,
2005), while high temperatures would lead to a material analogous to
activated carbon (Ogawa et al., 2006). It is also noted that the surfaces of
low temperature biochar can be hydrophobic, and this may limit the
capacity to store water in soil. The form and size of the feedstock and
pyrolysis product may affect the quality and potential uses of biochar.
Initially, the ratio of exposed to total surface area of biochar will be affected
by its particle size. However, although low temperature biochar is stronger
than high temperature products, it is brittle and prone to abrade into fine
fractions once incorporated into the mineral soil. It may be proposed that
the surface area over the long term, that is, of weathered biochar, is not
greatly affected by this parameter.
3. Biochar Application in Agriculture

3.1. Historic usage
The fertile terra preta of the central Amazon are anthropogenic dark earths,
in a landscape characterized by soils of generally low fertility. Archaeological
evidence and carbon dating indicates that these soils were created over a
period of millennia from about 9000 ybp, through the activity of dispersed
but relatively large and settled communities eliminated, presumably, by
western disease, approximately 1000 ybp. These soils subsequently recolo-
nized by natural forest were uncovered relatively recently, and are locally
popular for the production of cash crops such as papaya and mango, which
anecdotal evidence suggests grow three times faster on this land compared
to the surrounding soil. The terra preta are distributed patchily in areas of
historic habitation, averaging 20 ha in area, but with individual sites of up to
350 ha reported so far (Smith et al., 2009). The fertility of terra preta has been
attributed to a high char content (Glaser et al., 2001), which largely deter-
mines their dark color. The source of char is considered to have been
incompletely combusted biomass from both domestic fires and burning
in-field, but the extent of the deposits suggests that the applications were
increasingly deliberate, presumably as a management strategy to address low
soil fertility. Residually, terra preta display elevated soil organic matter
content, and enhanced nitrogen, phosphorus, potassium, and calcium status.
Similar soils have been documented elsewhere within the region,
namely Ecuador and Peru, in West Africa (Benin, Liberia), and the savanna
of South Africa (Lehmann et al., 2003). Use of charring in traditional soil
management in the past (Young, 1804) or at the current time (Lehmann and
Joseph, 2009) has also been reported in other countries. It seems probable
that these practices have been ubiquitous globally through history and that
further examples will emerge in the future. Currently, Japan has the largest
commercial production of charcoal for soil application, with approximately
15,000 t traded annually (Okimori et al., 2003). Growing recognition for
the potential of the terra preta as a model for modern management of soil
fertility using biproducts of bioenergy is now well established, and has
spurred a slew of research effort, published outputs of which are reviewed
later. A larger number of current experiments are yielding data, which are
not yet in press.
3.2. Impact on crop productivity

Glaser et al., 2001 reviewed a number of early studies conducted during the
1980s and 1990s. These tended to show marked impacts of low charcoal
additions (0.5 t ha 1) on various crop species, but inhibition at higher rates.
Since then, data have been published only for approximate field experi-
ments (Asai et al., 2009; Blackwell et al., 2007; Kimetu et al., 2008; Rondon
et al., 2007; Steiner et al., 2007, 2008a; Yamato et al., 2006), where the
short-term response of staple grain crops to biochar application, in terms of
plant biomass or crop yield, has been assessed.
Universally, these studies have used charcoal, produced commercially,
traditionally, or under conditions designed to simulate wildfire and in all
cases from wood, one from short-rotation forestry crops (Blackwell et al.,
2007). An additional two studies have examined the agronomic value of

biochar produced under zero-oxygen conditions, although these also used
contrasting feedstock—poultry litter (Chan et al., 2008) and ‘‘green waste’’
(Chan et al., 2007)—and indicator plants (radish) in pot experiments making
comparisons against the function of the charcoal difficult. Seven of the eight
studies in total have tested moderate rates of addition, broadly 5–15 t ha 1
(or up to 0.5% by soil mass). Four included rate of addition as a test variable,
either to high (60–300 t ha 1, or 2–10% by mass), or even higher rates (in
pot experiments). The charcoal in these experiments was produced either at
a documented lower temperature (approximately 350–450 C) or at a likely
similar range of temperature in a traditional kiln, and was generally alkaline.
Biochar in these experiments was added to acidic, tropical soils, though
collectively encompassed a textural range. The mean duration for the
experiments was less than eight months with measurements—in addition
to yield—related in some way to nutrient dynamics. The precise regime of
nutrient management was the most common second variable included in
these studies.
Positive yield effects from biochar addition were reported by Kimetu
et al. (2008), who were able to establish that the impact were in part due to
non-nutrient improvement to soil function. Improved fertilizer use effi-
ciency was pin-pointed as an explanation for biochar maintaining crop
yields after forest clearance in Amazonia, in essentially a recreation of terra
preta (Steiner et al., 2008a). Biochar-amended plots receiving NPK sustained
higher crop yield compared to control plots where yield declined rapidly.
Results from semi-arid soils in Australia have shown positive response to
biochar in combination with fertilizer in pot trials (Chan et al., 2007), and in
Indonesia maize and peanut yields were enhanced where bark charcoal was
applied in combination with N fertilizer in the field (Yamato et al., 2006).
The view that nutrient management and pre-existing soil nutrient status
determine crop response to biochar was supported by a study in rice (Asai
et al., 2009), where statistically higher first-season yield was observed only
when biochar (at a low rate) was applied together with fertilizer N and in a
low-yielding crop variety; yield was lower than the control in an equivalent
treatment using a high-yielding (and thus N-demanding) variety. However,
some studies show no significant yield response, for example at low rates of
application in an Australian study in wheat (Blackwell et al., 2007). A pot
study of maize showed higher biological nitrogen fixation with biochar
addition due to nutrient effects (Rondon et al., 2007); higher yield and
N uptake reported in pot trials using radish (Chan et al., 2007, 2008).
A key consideration highlighted in several studies is the potential for biochar
to immobilize previously plant available N. This could be from the
mineralization of labile, high C–to–N fractions of biochar drawing N into
microbial biomass, sorption of ammonium, or sequestration of soil solution
into fine pores.
The mechanisms of crop response are covered later and in the absence of
long-term data (other than terra preta), development of predictive certainty
for the longevity and durability of yield and other effects, particularly in
relation to specific crop and soil types, is critical to guide selection of
feedstock, production method, and application rate. Predictability and
certainty are required to assign a financial value to the agronomic value of
biochar and to open the possibility for large-scale deployment.
3.3. Impact on soil performance and resource implications

Both the mineral and the organic components of soil influence water-
holding capacity. Although higher levels of soil organic matter increase
water-holding capacity and can be deliberately managed, changes will be
temporary unless a regime is maintained. Glaser et al. (2002) reported that
water retention in terra preta was 18% higher than in adjacent soils where
charcoal was low or absent, and likely a combined consequence of higher
biochar content and higher levels of organic matter that appear to be
associated with charcoal in these soils. As biochar is broadly stable in soil,
it has potential to provide a direct and long-term modification to soil water-
holding capacity through its often macroporous nature (predominantly mm-
sized pores), reflecting cellular structures in the feedstock from which it is
typically produced. The direct impact of particle size distribution in biochar
added to the soil may have a direct impact on soil texture at the macroscale,
but this effect must be short-lived as physically biochar appears to divide
rapidly in soil to particles of silt size or less (Brodowski et al., 2007),
presumably by abrasion and the effects of shrink–swell or freeze-thaw, etc.
This suggests that in the longer term the effect of biochar on available
moisture will be positive in sandy soils ordinarily dominated by much larger
pores than present in biochar, rather neutral in medium-textured soils, and
potentially detrimental to moisture retention in clay soils—though since
preferential flow is important in cracking clays, the impact of biochar on the
nature of soil cracking might be important. The usual measure for pore size
distribution in soil is the moisture release curve, which shows how quickly
moisture is drawn from a soil under increasing tension. Although this
method is well suited to discriminating soils of contrasting texture, it is
not well able to discriminate the effects of subtle differences in soil manage-
ment at a particular location: levels of replication have not been sufficient to
attach statistical significance to differences in mean characteristics of
amended and non-amended soils. In recent work, moisture release curves
were determined for a loamy sand field soil to which up to 88 t ha 1 biochar
had been applied (Gaskin et al., 2007). For soils where biochar has been
added at rates up to 22 t ha 1 there was no difference compared to non-
amended soil, but at the highest rate there was a significant effect at water
potentials in the range 0.01–0.20 MPa. At the highest potential the
volumetric water content was double that of soil without biochar added.
Soils of lower bulk density are generally associated with higher soil organic
matter, and bulk density provides a crude indicator for how organic matter
modifies soil structure and pore-size distribution. Many studies where the
effect of biochar on crop yield has been assessed have cited moisture
retention as a key factor in the results. Soil temperature, soil cover, evapo-
ration, and evapotranspiration affect soil water availability, so comparison of
volumetric water content between biochar-amended and control soils in
field experiments may be confounded by indirect effects, that is, on plant
growth and soil thermal properties. In addition to the chemical stabilization
of nutrients, modification of the physical structure of the bulk soil may result
in biochar not simply increasing the capacity of soil to retain water, but also
nutrients in soil solution.
There are several reasons why biochar might be expected to decrease the
potential for nutrient leaching in soils, and thus enhance nutrient cycling
and also protect against leaching loss. In field studies where positive yield
response to biochar application has been observed, enhanced nutrient
dynamics has been frequently cited as an explanation. However, the under-
lying processes have not been demonstrated directly, and no empirical or
mechanistic description has been established. In general, both mineral and
organic fractions of soil contribute to cation exchange capacity (CEC) in
soil, although not in a summative manner. The CEC largely controls the
flush of positively charged ammonium ions after fertilizer or manure appli-
cation, and rapid mineralization of soil organic matter under favorable
environmental conditions. These relatively loose associations do not auto-
matically preclude acquisition by the plant, but have an important effect on
mitigating losses of nitrate by leaching, and consequently on agronomy and
avoided eutrophication of aquatic and marine environments. Only certain
inorganic components of the soil contribute significant CEC due to miner-
alogy, abundance, and particle size and surface area, with certain types of
clay being most important. On a mass basis the exchange capacity of soil
organic matter is up to 50 times greater than for any mineral, but is a small
proportion of soil mass in most agricultural situations, particularly under
tropical conditions. In heavy textured soils in climates favoring organic
matter about one-third of total CEC may derive from organic matter
(Stevenson, 1982). Since the mineralization of organic matter is also a
major source of ammonium in soil, increasing organic matter inputs to
increase soil organic matter can potentially increase rather than decrease
leaching losses. Available evidence suggests that the specific CEC of biochar
is consistently higher than that of whole soil, clay minerals, or soil organic
matter and analogy can be drawn to the very high CEC associated with
activated carbon that defines its function as a sorption medium for decolor-
izing and purifying solutions. Since secondary thermal treatment of charcoal
is one method for activating charcoal substrate, it is expected that of the
process parameters that appear to affect the CEC of biochar, temperature

should be the most critical (Gaskin et al., 2007). This function of biochar
arises from specific surface area, which increases with temperature through
the formation of micropores (Bird et al., 2008), and the abundance of
carboxyl groups on those surfaces. The apparent proliferation of carboxyl
groups on char surfaces over time, within or outside the soil environment,
suggests either partial oxidation of accessible surfaces by biotic and abiotic
processes (Cheng et al., 2006) or, alternatively, chemisorption. To develop
understanding of this process and the rate at which it proceeds, it may be
necessary to perfect methods for recovery of larger samples of intact and
increasingly aged biochar from field soils. Although information on the
CEC of fresh pyrolysis products relates to limited feedstock and production
conditions, and it appears that CEC can substantially develop prior to
biochar application to soil. The inherent stability of biochar creates a
distinction between the CEC that it provides, and CEC associated with
soil organic matter. Importantly, there is no obvious constraint on the level
of benefit that that could be attained with repeated addition, by incremental
enhancement of CEC. Provided that biochar is biologically stable, the
benefits of higher CEC could be achieved but without causing seasonal
flushes of nitrate. It is possible that if biochar were proven to significantly
impact retention of nutrients and benefit water dynamics at application rates
feasible for strategic deployment in vulnerable catchments, it could assist in
the mitigation of diffuse pollution from agriculture. It could also be possible
to utilize its sorptive capacity to remove contamination in water treatment
processes. Studies that demonstrate the capacity for biochar to remove
nitrate (Mizuta et al., 2004) and phosphate (Beaton et al., 1960) have been
cited in this context.
However, although biochar may loosely hold nutrient elements in a
plant-available form, it also has an affinity for organic compounds and may
sorb toxic by-products from the wastewater treatment process (Yu et al.,
2006). Using post-treatment biochar products on land would be subject to
regulation, and the economic and overall carbon and environmental gain
achieved from centralized rather than distributed production has not been
assessed. A centralized system using activated carbon for the removal of
chlorine and organic chemicals such as phenols, polychlorinated biphenyls,
trihalomethanes, pesticides and halogenated hydrocarbons, heavy metals,
and organic contaminants (Boateng, 2007) has been discussed. However, it
is not clear whether the use of biochar derived from agricultural crop wastes
would provide qualitative of quantitative differences in efficacy through
contrasting surface area and sorptive capacity (Zanzi et al., 2002).
Indirect effects of biochar on soil chemistry appear to arise from modifi-
cation of soil pH, although no dynamic studies of biochar in agronomic
trials have controlled for this effect. Intensively studied terra preta sites are
higher in pH than surrounding soils, as well as exhibiting higher phosphorus
status. Biochar also contains ash which may be in a soluble or a more

accessible form in biochar than in the unpyrolyzed feedstock. The indirect
effect of biochar on soil phosphorus availability, plus the accessibility of
mineral ash (containing phosphorus, potassium and other potentially impor-
tant trace elements) in the biochar matrix may be important in explaining
some short-term impacts of biochar on crop growth, especially since phos-
phorus availability cannot, unlike ammonium, be improved simply by
increasing soil organic matter status (Lehmann, 2007; Steiner et al., 2007).
However, there has been no systematic work published to show the relative
availability of mineral nutrients in biochar under different process para-
meters, and appropriate extraction protocols are not yet defined.
Much speculation concerns the effects of biochar on microbial activity in
soil, which in the context of terra preta has been reviewed in detail by Steiner
et al. (2003). Assuming that plant inputs and hence microbial substrate are not
changed by biochar, enhanced microbial activity will diminish soil organic
matter. However, this is contrary to the observation in terra preta that non-
black carbon is generally higher than surrounding soil (Liang et al., 2006) and
that the rate of stabilization of substrates seems to be increased (Liang et al.,
2009b). It is possible that the contrasting balance in microbial activity
between different functional groups impacts crop nutrition, specifically
enhancement of mycorrhizal fungi (Ishii and Kadoya, 1994), with soil organic
matter maintained through a positive feedback from increased net primary
productivity of plants and hence carbon input to the soil. There is relatively
extensive literature documenting stimulation of indigenous arbuscular
mycorrhizal fungi by biochar, and this has been associated with enhanced
plant growth (e.g., Nishio, 1996; Rondon et al., 2007). This literature has
been reviewed in some detail by Warnock et al. (2007) who proposed four
mechanistic explanations of which combined effects on nutrient availability,
water storage, and CEC were considered most probable. Assessing the impact
of fresh biochar addition to soils that previously contained negligible quan-
tities is a different proposition to evaluation of terra preta soils where biochar is
abundant but heavily aged and appears to contain a distinct microbial com-
munity structure (Kim et al., 2007). Microbial communities may respond in
the short term to labile components of biochar when added to the soil,
especially at higher rates, and traces of pyrolysis condensates seem to promote
microbial activity (Steiner et al., 2008b).
3.4. Additional impacts on greenhouse gas balance

There may be additional and potentially important affects of biochar addi-
tion on the emission of other greenhouse gases from soil and on indirect
emissions. Key indirect emissions savings would include those associated
with manufacture of fertilizer not required to produce equivalent crop yield
where positive effects on crop nutrient use efficiency have been achieved.
This extends to avoided emissions of N2O during the manufacture of the

fertilizer and from the use of the fertilizer via the soil. It is estimated that
currently the production and use of 1 t of fertilizer nitrogen results in a
carbon-equivalent emission of 1.9 CO2 by these pathways (Mortimer et al.,
2003). More speculatively, emission of carbon from above- and below-
ground stocks may be avoided if agricultural productivity is enhanced to a
level where reduced pressure on natural ecosystems avoided conversion of
forest or savannah land to agriculture (Searchinger et al., 2008). Reduced
irrigation costs from improved water-holding capacity could be important
in certain cropping systems, and potentially reduced energy requirement in
tillage in soil physical properties are significantly altered. Surprisingly little
information has been collected on the impact of biochar on such para-
meters, though in a tropical environment topsoil bulk density was found to
be approx. 10% lower at old kiln sites due to the presence of aged biochar
than in nearby soils (Oguntunde et al., 2008).
Observations of the terra preta suggest that biochar in soil can lead to a net
stabilization of other organic matter (Liang et al., 2009b). If this were proven
in soils of modern agroecosystems, the overall net carbon gain from bio-
char-based soil management strategies would be considerably enhanced.
This is a particularly important prospect, since it would provide a means to
benefit from higher soil organic matter without depending on the capacity
of clay surfaces which is finite and fixed for a particular soil (Verheijen et al.,
2005). In addition to representing a carbon store of its own, biochar would
enhance the intrinsic soil organic carbon storage capacity of soil itself, by
affecting the turnover of indigenous carbon. However, apparently contra-
dictory data have been published (Wardle et al., 2008) which suggested
accelerated decomposition of organic matter by charcoal. This appeared to
be a short-term effect, possibly resulting from the perturbation of nutrient
and pH status of essentially plant litter (Lehmann and Sohi, 2008). The
mechanisms and predictive description for these effects remain to be deter-
mined and defined.
Although no peer-reviewed studies document suppression of nitrous
oxide or methane emission in the field from biochar application in the field,
data have been presented in conference proceedings suggesting drastic
reduction of these fluxes (Renner, 2007), and some limited laboratory
evidence is published (Yanai et al., 2007). Nitrous oxide has a GWP of
310 (IPCC, 1996) and is emitted mainly by heterotrophic denitrifying
bacteria, which under anaerobic conditions reduce nitrate rather than
oxygen (NO3 to N2O via nitrite and nitric oxide). More continuous,
low-rate production of N2O may occur at aerobic as well as anaerobic
positions in the soil, from the activity of the chemotrophic bacteria that
convert ammonium from mineralization processes to soluble nitrate
(Bateman and Baggs, 2005). Higher soil organic matter is associated with
greater nitrification rates, but the greatest immediate impact on soil nitrate
concentrations and hence denitrification rate is the application of inorganic

nitrogen fertilizers and also manure or slurry. Elimination of reduction of
trace gas fluxes from soil would significantly impact carbon-equivalent
impacts of agriculture (Gaunt and Lehmann, 2008). Proposed mechanisms
for the suppression of N2O from biochar revolve around modification of
soil water dynamics, that is, drawing soil solution (and dissolved nitrate) into
pores inaccessible by microbes and maintaining aerobic conditions inside
inhabited pore space. Increase of soil pH which under anaerobic conditions
also favors completion of nitrate reduction to N2 (from N2O) or the
adsorption of ammonium that prevents nitrification and denitrification.
The effect of water addition cannot be evaluated completely under constant
conditions, but increasing water filled pore space from partial to near-
complete saturation has been seen to reverse 90% suppression in small
laboratory incubations with biowaste charcoal, at a high rate equivalent to
180 t ha 1(Yanai et al., 2007). Application of ash separately from charcoal in
the same experiment did not equally suppress emission, suggesting that pH
was not a factor in the result, though simultaneous monitoring of N2 would
be required to confirm N2O reduction. In conference proceedings, research
has shown nitrate to accumulate where N2O has been suppressed.
4. Research Priorities and Future Challenges

4.1. Mechanistic understanding
The fundamental mechanisms by which biochar affects the function of soil
and the wider agroecosystem are poorly defined and consequently current
capacity to predict the effects on biochar are inadequate. In short-term
experiments of months to a few years biochar may be seen to generally
enhance plant growth and soil nutrient status, and decrease N2O emissions.
However, the explanation for these benefits is not fully described, and
neither the quantitative variability in response nor the durability of the
effects is specified. Consequently soil–biochar dynamics need to be strate-
gically investigated to deliver understanding in several areas.
Functional interaction with soil microbial communities. Biochar may modify
symbiotic relationships between plants and microbes in close proximity to
the root (the rhizosphere). At the moment the net effect of physical
protection provided to microbial colonies, and evidence for adequate access
of those same colonies to labile and soluble carbon substrates has not been
established. The component of biochar stability provided by association of
individual biochar particles and fine mineral particles has not been estab-
lished, and the role of microbial and rhizosphere secretions in promoting
them will be important. Fundamentally, the apparent conflict between high
stability, soil organic matter accumulation, and apparent enhancement of
soil microbial activity needs to be resolved. Useful methods will separate

indirect effects of increased water-holding capacity or altered water release
characteristics, pH effects, and allow for their potentially transient nature.
Surface interactions. It seems that the CEC of biochar surfaces develops
over time, but the role of feedstock and production parameters in deter-
mining initial and ultimate activity of surfaces needs to be established, as
well as the trajectory of development. Once the relative importance of
biotic and abiotic processes is known as is the net effect of simultaneous
change in the relative abundance of external and internal surface area
following physical disintegration with soil movement, the effect of climate
might become predictable. The nature of interactions between biochar and
nutrient anions, most importantly phosphate, needs to be established and
the extent to which nutrient effects are derived from finite supply of mineral
ash within the biochar matrix, or supplied from the wider soil, must be
determined.
Nutrient use efficiency. Understanding the link between biochar function
and its interactions with nutrients and crop roots may enable fertilizer use
efficiency to be improved, with concomitant benefit to diffuse pollution in
watercourses and wetlands.
Soil physical effects. Quantitative description for the function of biochar
with respect to water infiltration, water retention, macroaggregation, and
soil stability would enable prediction of beneficial properties, and selection
of biochar with particular properties for use in specific environmental and
agricultural contexts. Methods for spreading and incorporation of biochar in
soil are required to mitigate lateral movement, and the potential for surface
flow and loss at depth need to be specified.
Fate of biochar. The stability of biochar carbon is intrinsic to fulfilling its
role as a significant CO2 sink, but to perform an agronomic role it must also
remain within the soil to which it is applied. The environmental role or
impact of biochar once it has moved through a soil profile, or into water-
courses, is yet to be assessed. Information on the extent to which physical
breakdown of biochar changes the balance in its properties, particularly with
respect to soil water dynamics, exchange capacity and soil micro- and
macroaggregation is lacking. Methods are urgently required to assess the
long-term biological stability of specific biochar samples, possibly extrapo-
lating from the dynamics of atypically high initial rates of loss in soil.
Impacts on soil nitrous oxide and methane emission. Published data for the
effect on trace gas emission are extremely limited, but this could have an
important effect in determining the net greenhouse gas balance, especially
over longer timeframes if the suppression is continuous. It is unlikely that
these effects will be tradable in carbon accounting for biochar projects
without a predictive model, and at the moment a clear underlying explana-
tion for the effect is lacking.
Impact on physiological plant response. Given that biochar seems to have

some complex effects on plant growth beyond simple supply of nutrients, this
is an area of fundamental research that needs to be targeted for future work.
4.2. Properties, qualities, and environmental risks

The role of biochar in mitigation of climate change hinges on the stability of
the bulk of the carbon that it contains. Transferable methods for rapid
assessment of relative long-term levels of stability for specific biochar sam-
ples in soil are required, rather than relying on direct linear extrapolations
from short-term losses.
A critical, experimental analysis of the risks arising from deployment of
biochar is required, particularly in the context of pyrolysis bioenergy, since
most charcoal used in traditional ways is also produced using traditional
kilns. This assessment would consider exposure to solid, liquid, and gaseous
products of pyrolysis at all stages of production, in distribution, and in the
physical application of biochar to soil, as well as the impacts on the health of
the soil and plants grown on it. This assessment is critical as biochar is
irretrievable once added to soil, and given its apparent permanency, the
scale and speed at which it would have to be added in order to address
climate change is large and rapid. In addition, the position regarding
responsibility and liability around large-scale deployment of biochar will
become much clearer through such assessment. Moreover, deriving mini-
mum standards will remove a key impediment to those seeking to invest
biochar in soil that is also used for producing food.
Although the economic case may be otherwise favorable, producing
biochar from sewage sludge and municipal waste streams requires different
assessments of risk, as considering only the contaminants that might form
during pyrolysis is insufficient. In these cases it is important to consider
whether contaminants present in the pyrolysis feedstock are eliminated, or
modified to become more or less available in the biochar product. The
environmental impact and function of biochar in subsoil and in water-
courses needs to be assessed.
Methodologies for validation and audit of biochar deployment will
emerge, and it will be necessary to be able to retrospectively determine
the source of biochar applied at a particular location. Databases should play
an important role in enabling optimal biochar products to be selected for use
at a particular location.
4.3. Modeling capacity for the soil–biochar system

Two types of carbon modeling are required: static spreadsheet models
to compare alternative scenarios for their relative carbon-equivalent
gain, and mechanistic soil simulation models that capture information
from short-term experiments to predict longer-term impacts on soil func-

tion. In addition, socioeconomic models that incorporate a spatial dimen-
sion are required to assess the workability of particular scenarios. So far only
generic, theoretical analyses have been published. Full assessment spread-
sheet models based on improved experimental evidence are required to
conduct scenario comparisons for strategies based around specific feedstock
streams and pyrolysis technologies, taking the spatial dimension of feedstock
supply and biochar use into account. Economic models must define care-
fully selected conceptual and geographic boundaries, and account for the
entire supply chain. Socioeconomic constraints relevant to the application
of biochar must be recognized.
Simulation modeling for the carbon and nitrogen cycles in soil with and
without biochar is essential to understanding the functional behavior of
biochar, and the impact on soil-based greenhouse gas emissions. Modeling
of soil carbon currently relies on conceptual pools and essentially ignores
black carbon from a mechanistic perspective. Progress in this area is dependent
on improved quantification methods for biochar in soil. Development cor-
relative techniques based on spectral analysis may lead to an approach that is
both rapid and low cost, relying on the MIR wavelength ( Janik et al., 2007).
It is likely that sites used for parameterization of soil models contain
atypically low levels of char. Adjustments have previously been required to
simulate plots with documented history of burning (Coleman et al., 1997),
and reallocating carbon between soil pools according to direct measurement
can benefit model prediction (Skjemstad et al., 2004). In the absence of
long-term experiments using biochar, modeling will be central to attempts
to predict long-term fate. Globally it appears that char in soil may be more
abundant than previously assumed (Preston and Schmidt, 2006; Schmidt
et al., 1999), and that greater amounts of stable carbon will lessen the rate at
which soil carbon is lost in feedback effects from climate change (Lehmann
et al., 2008).
4.4. Barriers and limitations to biochar systems

A market for carbon credits in which land managers can engage in deploy-
ing biochar does not exist. In general, there also remains a lack of know-
ledge and awareness of bioenergy and carbon markets, how to access these
markets, and particularly a way to accurately evaluate costs and benefits
associated with the use of biochar in soil. Crucially, as well as being
multiple, the relevant markets are interdependent, extending to the supply
of feedstock for pyrolysis. However, no framework exists within which the
carbon sequestered in biochar can be certified as a tradable commodity, and
this extends beyond trading under the CDM to the voluntary carbon
markets. To date the methodology required to recognize the stabilization
of degradable organic matter as an avoided CO2 emission has not been

presented.
There are significant organizational and institutional obstacles to the use
of biochar in soil. Since biochar could be used on a large scale and cannot be
removed from soil once applied, there is a need to carefully assess the
potentially negative impacts on occupational health, environmental pollu-
tion, water quality, and food safety. This requires a concerted effort to
evaluate potential products, and ideally define product standards. Support
for the use of biochar in meeting policy objectives will draw upon life-cycle
analysis with full greenhouse accounting, backed by a body of experimental
data. Where biochar is designated as a regulated waste material, pending
defined standards land users in many countries may be subject to a complex
and expensive approval process.
The lack of mechanistic understanding as to the function of biochar, and
its interaction with already complex soil processes, means predicting the
return to an investment in biochar between locations in terms of extent,
predictability, and durability of benefits does not yet exist. Providing a
measure of certainty to the many possible benefits is a key challenge to be
addressed by further research.
ACKNOWLEDGMENTS
This original review on which this work is based was undertaken with support from CSIRO
Land and Water in Australia (Sohi et al., 2009). The contributions of Peter Brownsort
(University of Edinburgh) and Keith Goulding (Rothamsted Research) to the preparation
of this manuscript is a acknowledged. Rothamsted Research is an institute of the UK
Biotechnology and Biological Sciences Research Council in the UK.
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C H A P T E R T W O

A Review of Biochar and

* School of GeoSciences, University of Edinburgh, Edinburgh, United Kingdom

Advances in Agronomy, Volume 105 # 2010 Elsevier Inc.

1.1. What is biochar?

Table 1 Fate of initial feedstock mass between products of pyrolysis processes

similar to fast pyrolysis, but including a limited supply of oxygen). These

Biomass energy Fast pyrolysis Synthesis gas – Heat

about one-tenth of commercial plants (2–3 t h-1). Comparing the efficiency

1.2. Policy context

1.3. Biochar and the global carbon cycle

2.2 Gt CO2–C yr 1 loss through land-use change (Houghton, 2003), and

permanent commitment. Increasing the quantity and turnover of carbon in

increasing surface albedo has been proposed as a possible mitigation measure

1.4. Scenarios for the production and deployment of biochar

the balance of benefits most appropriate to a particular system. The value of

biochar produced from wheat straw, there is limited existing information on

1.5. Trading and acceptability issues for biochar carbon

Compared to schemes intended to store carbon by increasing standing

even been considered to provide a reliable thermal history for environmen-

2.1. Quantification of char in soil

NMR analysis of residues, thermal analysis (De la Rosa et al., 2008;

2.2. Chemical composition

process parameter, carbon content of biochar inversely related to biochar

2.3. Physical characterization

3. Biochar Application in Agriculture

3.2. Impact on crop productivity

2007). An additional two studies have examined the agronomic value of

3.3. Impact on soil performance and resource implications

process parameters that appear to affect the CEC of biochar, temperature

status. Biochar also contains ash which may be in a soluble or a more

3.4. Additional impacts on greenhouse gas balance

This extends to avoided emissions of N2O during the manufacture of the

concentrations and hence denitrification rate is the application of inorganic

4. Research Priorities and Future Challenges

soil microbial activity needs to be resolved. Useful methods will separate

Impact on physiological plant response. Given that biochar seems to have

4.2. Properties, qualities, and environmental risks

4.3. Modeling capacity for the soil–biochar system

from short-term experiments to predict longer-term impacts on soil func-

4.4. Barriers and limitations to biochar systems

of degradable organic matter as an avoided CO2 emission has not been

fourth assessment. In ‘‘Report of the Intergovernmental Panel on Climate Change’’

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