C H A P T E R T H R E E

Biochar Application to Soil:

Agronomic and Environmental
Benefits and Unintended
Consequences
R. S. Kookana,* A. K. Sarmah,†,1 L. Van Zwieten,‡ E. Krull,* and
B. Singh§

Contents
1. Introduction 104
2. Properties of Biochar as Affected by Feedstock and
Production Technology 107
2.1. Nutrient ratios in biochar 107
2.2. Elemental ratios and aromaticity of biochar 108
2.3. Specific surface area and microporosity of biochars 109
2.4. Cation exchange capacity and charge characteristics 111
3. Biochar as an Effective Sorbent of Agrochemicals 113
3.1. Sorption–desorption of pesticides and other
organic compounds 113
3.2. Retention and release of nutrients and heavy metals 118
4. Agronomic Implications 120
4.1. Herbicide efficacy and development of weed resistance 121
4.2. Nutrient immobilization and release 123
4.3. Soil pH and Al toxicity 124
4.4. Plant germination and seedling growth 125
4.5. Soil biological properties 125
5. Environmental Implications 127
5.1. Biochar as a potential source of toxicants 127
5.2. Mobilization/immobilization of cocontaminants 129

* CSIRO Land and Water, Sustainable Agriculture Research Flagship, Glen Osmond, South Australia,
Australia
{
Soils and Landscape Responses Team, Landcare Research Manaaki Whenua, Hamilton, New Zealand
{
Department of Primary Industries, Wollongbar, New South Wales, Australia
}
Faculty of Agriculture, Food and Natural Resources, The University of Sydney, Sydney, New South Wales,
Australia
1
Current address: Faculty of Engineering, University of Auckland, New Zealand

Advances in Agronomy, Volume 112 # 2011 Elsevier Inc.

ISSN 0065-2113, DOI: 10.1016/B978-0-12-385538-1.00003-2 All rights reserved.

103
104 R. S. Kookana et al.

5.3. Decreased bioavailability and increased

persistence of chemicals 130
5.4. Impact on transport of agrochemicals and
contaminants (including POPs) 131
5.5. Ecotoxicological effect on soil organisms 132
6. Knowledge Gaps and Research Needs 133
Acknowledgments 135
References 135

Abstract
Biochar is increasingly being recognized by scientists and policy makers for its
potential role in carbon sequestration, reducing greenhouse gas emissions,
renewable energy, waste mitigation, and as a soil amendment. The published
reviews on biochar application to soil have so far focused mainly on the
agronomic benefits, and have paid little attention to the potential unintended
effects. The purpose of this chapter is to provide a balanced perspective on the
agronomic and environmental impacts of biochar amendment to soil. The
chapter highlights the physical and chemical characteristics of biochar, which
can impact on the sorption, hence efficacy and biodegradation, of pesticides. As
a consequence, weed control in biochar-amended soils may prove more difficult
as preemergent herbicides may be less effective. Since biochars are often
prepared from a variety of feedstocks (including waste materials), the potential
introduction of contaminants needs to be considered before land application.
Metal contaminants, in particular, have been shown to impact on plant growth,
and soil microbial and faunal communities. Biochar has also been shown to
influence a range of soil chemical properties, and rapid changes to nutrient
availability, pH, and electrical conductivity need to be carefully considered to
avoid unintended consequences for productivity. This chapter highlights some
key areas of research which need to be completed to ensure a safe and
sustainable use of biochar. In particular, understanding characteristics of bio-
chars to avoid ecotoxicological impacts, understanding the effects of biochar on
nutrient and contaminant behavior and transport, the effects of aging and the
influence of feedstock and pyrolysis conditions on key properties are some of
the areas that require attention.

1. Introduction
The carbon-rich byproduct that is produced when biomass (e.g.,
agricultural crop residues, wood, waste, etc.) is heated through the process
of pyrolysis in an oxygen-depleted environment is commonly referred to as
biochar. However, biochar is a fairly loose term without any clear definition
at the moment. According to Lehmann et al. (2006), the term “biochar” is a
relatively recent development and evolved in conjunction with issues such
Biochar Application to Soil: Unintended Consequences 105

as soil management and carbon sequestration. Therefore, biochar is a term

normally associated with plant biomass- or biowaste-derived materials
contained within the black carbon (BC) continuum (Schmidt and Noack,
2000). This definition can include chars and charcoal, but excludes fossil
fuel products or geogenic carbon (Lehmann et al., 2006). Biochar differs
from charcoal in regard to its purpose of use, which is not for fuel, but for
atmospheric carbon capture and storage, and application to soil. Recently,
the European Commission (Verheijen et al., 2010) has defined biochar as
charcoal (biomass that has been pyrolyzed in a zero or low oxygen environ-
ment) for which, owing to its inherent properties, scientific consensus exists
that application to soil at a specific site is expected to sustainably sequester
carbon and concurrently improve soil functions (under current and future
management), while avoiding short- and long-term detrimental effects to
the wider environment as well as human and animal health.
Two types of pyrolysis systems are predominantly used in biochar
production: fast and slow pyrolysis, where the distinction relates to the
heating rate and heating duration. For biochar production, slow pyrolysis
is currently seen as the preferred technology as it maximizes biochar yield
over production of bioenergy (Lehmann and Joseph, 2009; Sohi et al.,
2010). Many forms of organic material can be utilized to produce biochar,
including crop- and forestry-waste products, urban-yard wastes, industrial
biomass by-products, animal manures (i.e., poultry litter, dairy manure),
and municipal sewage sludge.
The use of biochar as a soil additive has been proposed to simultaneously
mitigate anthropogenic climate change while improving soil fertility and
enhancing crop production (e.g., Glaser et al., 2002, 2009; Lehmann et al.,
2006; Ogawa et al., 2006). Indeed, adding charcoal to soil to enhance soil
fertility is an age-old practice in many cultures, perhaps best exemplified by
Terra Preta de Indio soils discovered in Amazonia, associated with native
American settlements. These can be kilometer-sized fertile patches of black
soils, containing charcoal, among less intensely colored and relatively infer-
tile Oxisols (Glaser et al., 2001; Lehmann et al., 2003). However, the true
potential of this practice in terms of both agronomic and environmental
benefits has only been highlighted recently (e.g., Glaser et al., 2009;
Lehmann and Joseph, 2009; Lehmann et al., 2006; Sohi et al., 2010).
Biochar application to the nutrient-poor soils is increasingly being recog-
nized as an attractive option, given the potential agronomical and environ-
mental benefits.
A number of reviews and studies have highlighted the potential benefits
of utilizing biochar as a soil amendment. These have covered issues such as
mitigation of global warming through application of stable C into soil, waste
management, production of bioenergy, soil health, and productivity bene-
fits (Atkinson et al., 2010; Laird, 2008; Lehmann, 2007a,b; Lehmann et al.,
2006; Mathews, 2008; Ogawa et al., 2006; Sohi et al., 2010; Woolf et al.,
106 R. S. Kookana et al.

2010). Consequently, biochar as a soil amendment is also increasingly

attracting the attention of policy makers in the United States, Australia,
Europe, Japan, and some developing countries (e.g., Bracmort, 2009). The
recent modeling and analysis by Woolf et al. (2010) demonstrate that
sustainable biochar production and its soil application have the potential
to make a substantial contribution to mitigating climate change. The use
and functions of biochar in soils have been recently reviewed by Sohi et al.
(2010) and potential mechanisms of achieving agricultural benefits by bio-
char-soil application by Atkinson et al. (2010). However, the hazards, risks,
and other implications associated with biochar technology are yet to be fully
understood (Downie et al., 2011; Kookana, 2010).
The main motivation for this chapter was to provide a balanced per-
spective on the agronomic and environmental impacts of biochar amend-
ments to soil. The primary objective of the chapter is, therefore, to highlight
some of the agronomic and environmental issues that need to be adequately
addressed for this practice to be scientifically sound and sustainable. We
have placed emphasis on (i) the properties of biochars in the context of
production technology and raw material used; (ii) how these properties
influence key physical, chemical, and biological processes in soil; and (iii)
the potential agronomic and environmental implications (Fig. 1) that may

Reduced CO2
emission
Distribution
of POPs in soil
N2O Adding Adding Spraying
emission biochar fertilizer pesticides
Grasshopping
of POP’s

Runoff to
Altered Nutrient rivers and streams
N2O emission release Change in
Enhanced soil pH
nutrient availability
Leaching Increased C
Increased stabilization/
H2O retention Heavy metal Pesticide
sequesteration
nutrient sorption
Chemical sorption/desorption Increased persistence
release/ Bound residue
immobilisation Reduced efficacy
Changes in soil
biological health
Reduced leaching
Interaction with biota
Water table
Groundwater

Figure 1 A schematic diagram representing a range of processes that biochar may

influence in soil and the resultant agronomic and environmental advantages or disad-
vantages. POP stands for persistent organic pollutants (e.g., dioxins).
Biochar Application to Soil: Unintended Consequences 107

arise due to biochars’ unique properties, composition, and production

conditions. In this context, the priority areas of future research have also
been identified.

2. Properties of Biochar as Affected by

Feedstock and Production Technology
Feedstock and pyrolysis conditions are the most important factors
controlling the physical and chemical properties of the resulting biochar.
Structural characteristics of freshly made biochars, as influenced by feed-
stock and processing conditions, have been discussed in detail by Downie
et al. (2009). First, the chemical and structural composition of the biomass
feedstock influences the composition of the resulting biochar and, conse-
quently, its behavior, function, and fate in soils. For instance, when wood-
based feedstocks are pyrolyzed, coarse and resistant biochars are generated
with high carbon contents (up to 80%), as the rigid ligninolytic nature of the
source material is retained in the biochar residue (Winsley, 2007). Second,
the extent of the physical and chemical alterations undergone by the
biomass during pyrolysis (e.g., attrition, cracking, microstructural rearran-
gements) is dependent on the pyrolysis conditions (mainly temperature and
residence times).

2.1. Nutrient ratios in biochar

Combustion of biomass and conversion to biochar is associated with various
changes in the original nutrient content, form of nutrients, and resultant
chemical structure. Maximum heating temperature and heating rate have a
strong influence on the retention of nutrients as does the original composi-
tion of the feedstock. With regard to the former, the different volatilization
temperatures of the different elements play a particular role on the relevant
C/N/P ratios: while C begins to change and certain compounds volatilize
at 100  C, the range of oxidization and transformation products from the
original C is stable over a wide temperature scale and are mainly associated
with decreases in OH and CH3 and increases in aryl C (Baldock and
Smernik, 2002; Krull et al., 2009). Most N and S compounds, however,
volatilize above 200 and 375  C, respectively, while K and P volatilize
between 700 and 800  C (DeLuca et al., 2009). Most biochars are produced
in the temperature range 450–550  C and, as a result, tend to be relatively
depleted in N and S. However, those produced from N-rich feedstocks
(e.g., biosolid biochar) at the lower end of the temperature range (e.g.,
450  C) may retain up to 50% of its original N content and all of its S and, as
108 R. S. Kookana et al.

a result, are comparably richer in these elements than wood-based biochars

produced at higher temperature (Bridle and Pritchard, 2004).
Most wood- and nut-based biochars have extremely high C/P and C/N
ratios. Conversely, manure-, crop-, and food-waste biochars have much
lower ratios with manure-derived biochars being the most nutrient-rich
relative to C, especially in P relative to N. Nutrient-rich and ash-rich
biochars lack the stability that is associated with C-rich and highly aromatic
and condensed wood-derived biochars (e.g., Singh et al., 2010b). Produc-
tion temperature can also alter the extractability of certain nutrients and the
physical and chemical properties of biochars: high-temperature biochars
(800  C) tend to have a higher pH, electrical conductivity (EC), and
extractable NO3 , while low-temperature biochars (350  C) have greater
amounts of extractable P, NH4þ, and phenols (DeLuca et al., 2009). Mg,
Ca, and Mn require even higher temperatures (above 1000  C) and specifi-
cally the relatively high abundance of these alkaline metals (K, Mg, and Ca)
can explain the increase in pH of many biochars. High concentrations of
calcium carbonate (CaCO3) can be found in pulp and paper sludge
(Van Zwieten et al., 2010a) and are retained in the ash fraction of some
biochars.

2.2. Elemental ratios and aromaticity of biochar

H/C and O/C ratios in so-called van Krevelen diagrams (Killops and
Killops, 2005) have been used for geologic organic matter (coal, lignite)
to assess its maturity, which is a function of time and conditions of burial
(temperature and depth/pressure). Applied to biochars, these provide an
indication of their degree of aromaticity (the degree to which aromatic rings
are connected in two- and three dimensions), which is believed to be a
function of temperature. Figure 2 summarizes H/C and O/C ratios from
various feedstocks and common ranges found in coal, BC, natural char,
lignite, protein, carbohydrates, and lipids. However, biochar when applied
to soil undergoes physical and biological oxidation, fragmentation, and
carboxylation, despite its stability relative to other forms of C.
The H/C and O/C ratios decrease with increasing temperature, and it is
assumed that the lower the ratio the greater the degree of aromaticity and
stability. This is confirmed by NMR data suggesting that increasing tem-
perature enhances degree of aromaticity (Baldock and Smernik, 2002;
Smernik et al., 2006). However, the changes are also a function of heating
time. Almendros et al. (1990) heated a peat sample between 60 and 180 s
while keeping the temperature constant at 35  C and found that H/C and
O/C ratios significantly decreased. The data also show that there is a
comparably larger variability in biochars generated at temperatures below
400  C, whereas H/C and O/C values converge above 450  C. Recent
developments in this area show that NMR is relatively insensitive to
Biochar Application to Soil: Unintended Consequences 109

2.0
Lipid
Protein
1.8
Carbohydrate
1.6

1.4
Lignin
1.2
H/C

1.0 Coal

0.8 Low-temperature char

0.6
Char
oxidation
0.4 n
io
s at
0.2 Oxidized den
Fresh Con
BC/soot
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
O/C

Figure 2 A range of biochar products with varying H/C and O/C ratios. Overlain as
circles are typical ratios for BC/soot, char, coal, lignin, carbohydrate, protein, and lipids
(from Preston and Schmidt, 2006), showing the continuum of biochar products ranging
from more lignin-rich to a coal- or soot-like substance. H/C and O/C ratios of biochars
can also change over time within the soil environment as indicated by the squares and
chemical state in italics (after Hammes and Schmidt, 2009) showing the ranges between
fresh, oxidized, and low-temperature biochar.

changes above 400  C. McBeath and Smernik (2009) analyzed 17 heat-

treated materials and confirmed that aromatic condensation increases with
increasing heat-treatment temperature and that activated chars contained
the most highly condensed aromatic structures. This study also highlighted
the importance of starting material and heat-treatment time on aromatic
condensation.

2.3. Specific surface area and microporosity of biochars

One of the unique properties of the biochars is their high specific surface
area (SSA). While this key property governs most soil–biochar interactions,
SSA itself is affected by the nature of the starting organic material (biomass)
and the conditions under which the biochar is produced (see review by
Downie et al., 2009). Both SSA and microporosity of biochars have been
shown to increase with temperature, as these properties are interlinked.
110 R. S. Kookana et al.

Nevertheless, different biochars produced from the same feedstock or

biomass have very different SSA and microporosities, depending on the
production technology employed (Downie et al., 2009). Chun et al. (2004)
studied a series of biochar samples produced by pyrolyzing a wheat residue
(Triticum aestivum L.) for 6 h at temperatures between 300 and 700  C. They
observed the biochar SSA increased with increasing charring temperatures
(300–600  C); however, the SSA value of char produced at 700  C was
lower than that of char produced at 600  C (Fig. 3). The authors speculated
this to be due to microporous structures which were destroyed at 700  C.
Similarly, Brown et al. (2006) found that regardless of differences in the
ramp rate, maximum SSA was realized at a final temperature of 750  C
(Fig. 3). The chars produced at the lowest final temperature (i.e., 450  C)
had a SSA of <10 m2/g, while those produced at intermediate temperatures
of 600–750  C had SSA of 400 m2/g. They suggested that this is most
likely due to the effect of ramp rate on pore structure (Brown et al., 2006).
Micropores (<2 nm diameter, IUPAC) make a significant contribution
to the increase in surface area of biochars with increasing temperatures. Yu
et al. (2006) and Bornemann et al. (2007) compared biochars produced at
different temperatures (at 250, 450, and 850  C) from air-dried plant
materials from Phalaris grass (Phalaris tuberosa) and red gum-wood (Eucalyp-
tus camadulensis). They noted that SSA markedly increased with production
temperature (from 8 to 600 m2/g—for the wood char) and at any compa-
rable temperature, the SSA of the wood biochar was up to two times greater

500

400
Surface area (m2/g)

300

200 30⬚C/h
350⬚C/h
650⬚C/h
100 1000⬚C/h
Static temp

0
300 400 500 600 700 800 900 1000 1100
Final temperature (⬚C)

Figure 3 The specific surface areas of various biochars produced at different tempera-
ture and using different ramp rates. The legends show the ramp rates ranging from 30 to
1000  C/h. Source: Brown et al., 2006; the solid line is based on the data by Chun et al.,
2004, using static temperature for 1 h.
Biochar Application to Soil: Unintended Consequences 111

than that of the grass biochar. In terms of microporosity, the wood biochar
produced at 450  C had a very low level of microporosity and the peak
maximum of pore size distribution was noted at a pore width of 1.1 nm,
indicating the beginning of micropore formation at 450  C. However,
increasing temperature to 850  C promoted the formation of micropores
with peak maximum occurring at 0.49 nm. At this temperature, essentially
all pores were <1 nm in pore width. Downie et al. (2009) observed that
while elevated temperatures provide the activation energies for reaction
leading to restructuring and ordering of the material, the duration of the
temperature allows the extent of completion of these reactions. They noted
a strong and almost linear relationship between the SSA of biochars (up
to 2000 m2/g) and the micropore volume (0.6 m3/g). Both SSA and
micropores play an important role in sequestration of chemicals by altering
their bioavailability and ecotoxicological impacts on soil organisms (dis-
cussed later).

2.4. Cation exchange capacity and charge characteristics

Biochars can potentially increase the cation exchange capacity (CEC) of
soils especially for highly weathered, nutrient-poor sandy soils; however,
this is dependent on biochar properties and aging of applied biochar in the
soil. The lack of standardized methodology of assessment of CEC in
biochars makes it difficult to compare materials from different feedstocks
and temperatures of production. In some cases, increasing pyrolysis tem-
perature has been shown to decrease CEC of the biochar (Gaskin et al.,
2008), while in other cases, CEC increases with increasing temperature
(Singh et al., 2010b). The lower temperature biochar described by Gaskin
et al. (2008) was shown to have a higher degree of oxygen surface functional
groups, resulting in increased CEC. The published data suggest that bio-
chars from woody materials tend to provide low CEC values, while non-
woody plant materials such as sugarcane trash (leaf) or tree bark tend to have
higher CEC values (Chan et al., 2007; Gaskin et al., 2008; Gundale and
DeLuca, 2006; Major et al., 2009; Singh et al., 2010b; Van Zwieten et al.,
2010b; Yamamoto et al., 2006).
Biochar consists of highly aromatic chemically stable components
(Schmidt and Noack, 2000), and the development of negative charge
from biochar oxidation in soil has been proposed in several studies (e.g.,
Cheng et al., 2006, 2008; Hamer et al., 2004; Liang et al., 2006). In the
Brazilian Amazon, CEC values were found to be up to two times higher in
soils with biomass BC than in the adjacent soils (Liang et al., 2006). The
stability and oxidation of biochar in soils are affected by aging and soil
environmental conditions. Cheng et al. (2006) observed that abiotic pro-
cesses were more important than the biotic processes for the oxidation of
biochar. They reported a more than six-time increase in the potential CEC
112 R. S. Kookana et al.

of a BC-amended soil after incubation for 4 months at 70  C. In an another

study, Cheng et al. (2008) observed that historical BC samples collected
from a number of sites in Canada and the United States have oxidized
substantially after 130 years in soils. The major changes in the historical BC
as compared to the new BC included: (i) decreased C content and increased
O and H contents, (ii) the formation of carboxylic and phenolic functional
groups, and (iii) decreased surface positive charge and increased surface
negative charge. The point of zero charge for the aged BC samples was
significantly lower than the fresh BC; and unlike new biochar (New-
BCHW) that contribute anion exchange capacity, aged biochars (BC30
and BC7) and historical biochar exhibit significant CEC at pH  3
(Fig. 4; Cheng et al., 2008). Biochar stability in soil is also affected by
moisture status; in a 1-year incubation study at 30  C corn biochar miner-
alized significantly faster under unsaturated conditions, while oak wood
biochar lost most carbon under alternate unsaturated and saturated condi-
tions (Nguyen and Lehmann, 2009).
There is limited research on the nature of functional groups on biochars;
however, research on porous and activated carbon shows that acidic and basic
surface sites coexist on carbon surfaces (Barton et al., 1997; Biniak et al., 1997;
Boehm, 2002). The nature and proportion of surface functional groups on
porous carbon can be modified by suitable thermal and chemical treatments.

150 150
Surface charge (mmol/kg C)

BC30
Surface charge (mmol/kg C)

New-BCHW

100 100
Negative charge
Positive charge
150 50

0 0

–50 –50
2 3 4 5 6 7 8 9 10 11 2 3 4 5 6 7 8 9 10 11
pH pH

250 2000
Surface charge (mmol/kg C)
Surface charge (mmol/kg C)

BC70 NY
200 1500
150
1000
100
500
50

0 0

–50 –500
2 3 4 5 6 7 8 9 10 11 2 3 4 5 6 7 8 9 10 11
pH pH

Figure 4 Cation and anion exchange capacities of a new biochar (New-BCHW), aged
biochars (BC30 and BC70), and a historical biochar (NY) as a function of pH (redrawn
from Cheng et al., 2008).
Biochar Application to Soil: Unintended Consequences 113

For example, gas phase oxidation of carbon increased hydroxyl and carbonyl
surface groups, whereas liquid phase oxidation increased carboxylic groups
(Figueiredo et al., 1999), and treatment with ammonia has been used to
introduce nitrogen functional groups such as pyrrole, pyridone, and pyridine
( Jia et al., 2002). Among the basic functional groups, pyrones are considered
to be the most important (Montes-Morán et al., 2004). Biochars produced at
lower temperatures showed higher total surface acidity and lower basicity
than the high-temperature biochars (Singh et al., 2010b). The proportion of
acidic functional groups on biochars, especially carboxylic groups, increased
with aging (Cheng et al., 2006; Nguyen and Lehmann, 2009), and this has
important consequences for the sorption behavior of organic and inorganic
compounds that are discussed in the later sections.
Clearly, biochars are highly carbonaceous materials with unique proper-
ties such as high SSA, micropore volume, and charge characteristics. How-
ever, feedstock and pyrolysis conditions are the most important factors
controlling their physical and chemical properties. Therefore, biochars are
expected to be highly heterogeneous materials with a diverse range of
properties. The physicochemical properties are crucial not only in govern-
ing their biogeochemical interactions in soil environment but also in deter-
mining their agronomic and environmental impacts. These properties also
contribute to the extraordinary ability of biochars to adsorb agrochemicals
in soils, as discussed in some detail in the next section. Therefore, it is
essential to have clear guidelines for biochar production with an under-
standing of feedstocks and pyrolysis parameters (Kwapinski et al., 2010).

3. Biochar as an Effective Sorbent of

Agrochemicals
The ability of biochars to sorb agrochemicals and contaminants is a key
process that has direct bearing on not only the agronomic effectiveness of
agrochemicals (e.g., herbicides, insecticides, and nutrients) but also the
environmental fate and ecotoxicological impacts of contaminants. Usually,
the sorption process is first to occur, as soon as the contact between sorbate
and sorbent is made and in turn affects other processes ranging from chemical
release, transport, bioavailability, uptake, and ecotoxicological impacts.

3.1. Sorption–desorption of pesticides and other

organic compounds
Given the similarities in some of the properties of BC (including char,
charcoals, and biochars) and their similar effects on the fate processes of
agrochemicals or contaminants, the existing body of the literature on BC is
114 R. S. Kookana et al.

highly relevant and can help better understand the likely environmental and
agronomic consequences of biochar amendments on soil. BC and biochars
have been reported to be very effective in sorption of many natural and
anthropogenic organic compounds (i.e., Accardi-dey and Gschwend, 2003;
Allen-King et al., 2002; Cao et al., 2009; Lohmann et al., 2005; Sarmah et al.,
2010; Yu et al., 2006). For example, chars/ashes produced from burning of
wheat and rice residues were reported to be up to 2500 times more effective
than soil in sorbing the herbicide diuron (Yang and Sheng, 2003). A
number of studies have been published in recent years demonstrating similar
observations on a range of herbicides and insecticides and are listed in
Table 1. Such extraordinary sorption ability of biochars arises from their
high SSA, aromaticity, and microporosity. This is also consistent with the
well-known relationships of chemistry of soil organic carbon (SOC) in
relation to sorption of chemicals.
SOC consists of a heterogeneous mix of organic materials often classified
as an amorphous, gel-like “soft or rubbery” matrix or domain and a
condensed, “hard or glassy” matrix or domain (Chiou et al., 1983; Weber
et al., 1992). These two domains have very different sorption efficiencies,
and thus the amount and relative proportion of these materials in SOC
influence the capacity of soil to sorb or sequester organic compounds. The
extent of sorption of pesticides in soils has been found to increase with the
aromaticity of SOC (Abelmann et al., 2005; Ahmad et al., 2001). Ahmad
et al. (2001) noted that among various molecular components of the SOC,
lignin and charcoal contents were highly correlated with the Koc (sorption
coefficient normalized to SOC) values of pesticides. Therefore, it is not
surprising that biochars, being often highly aromatic in nature, are very
effective in sorption of herbicides (Table 1). However, biochars vary widely
in terms of their aromaticity.
The concentration dependency of sorption has also been found to be
markedly affected by the degree of aromaticity of biochars. Sorption iso-
therms on highly carbonaceous sorbents including biochars have been
found to be highly nonlinear (Accardi-dey and Gschwend, 2003; Chun
et al., 2004; Kleineidam et al., 1999; Yu et al., 2006). Kleineidam et al.
(1999) investigated sorption of phenanthrene in geogenic sorbents derived
from sedimentary rocks containing organic materials of different origin and
maturity, including those from marine and terrestrial plant debris, lignite,
coal, and charcoal and found that the Koc values for these materials varied by
several orders of magnitude (Fig. 5). Exceptional high Koc values were
noticed for charcoal and coal, and the sorption isotherms for these materials
were highly nonlinear.
Not only sorption but the desorption or the release behavior of organic
compounds is also strongly affected by the presence of charcoal or biochars
in soil and sediments (Bucheli and Gustafsson, 2003; Jonker et al., 2005; Van
Noort et al., 2003; Yu et al., 2006). Desorption is important because the
Table 1 Selected reports on sorption, bioavailability, and degradation of pesticides in soils amended with ashes and biochars

Sorbent and its

production Bioavailability, persistence,
Feedstock temperature Sorbate Sorption/desorption observations and other impacts Source
Wheat (Triticum Ash, temperature Ametryn and Showed up to 2500 times higher Immobilization of diuron Yang and Sheng
aestivum L.) and unknown, open diuron sorption than soil; > 70% led to decreased (2003), Sheng
rice (Oryza air burning herbicide increase in sorption in soil (1%, herbicidal efficacy to et al. (2005),
sativa) residuea wt of biochar) barnyard grass Yang et al.
(2006)
Wheat Ash, temperature Benzonitrile The ash was  2000 times more Biodegradation of Zhang et al.
(T. aestivum L.)a unknown, open herbicide effective per unit mass than benzonitrile was initially (2004, 2005)
air burning soils in sorption of stimulated by the ash
benzonitrile. Amendment with nutrients, followed by
1% ash caused 10-fold increase adsorptive inhibition in
in sorption by soil the presence of the ash
Degradation was substantially
reduced in the presence of the
ash
Eucalyptus spp. 450 and 850  C Diuron Sorption and desorption Degradation and plant Yu et al. (2006,
herbicide; hysteresis of diuron increased uptake of insecticides 2009)
chlorpyrifos with increasing biochar residues decreased with
and carbofuran temperature and content in increased biochar
insecticides soils (to 1%) content
Dairy manure 200 and 350  C Atrazine Partitioning of atrazine is A decrease in the aliphatic Cao et al. (2009)
positively related to biochar phase at 350  C caused a
carbon content at 200 oC reduction in atrazine
sorption despite high
carbon content
(Continued)
Table 1 (Continued)

Sorbent and its

production Bioavailability, persistence,
Feedstock temperature Sorbate Sorption/desorption observations and other impacts Source
Wheat (Triticum Ash, temperature Atrazine Sorption on char alone was 800– The presence of char Loganathan et al.
aestivum L.)a unknown, open 3800 times greater than sorbed reduced mineralization (2009)
air burning by the soils. Successive of atrazine by
desorption experiments Pseudomonas sp. strain.
showed that char-amended ADP and 14CO2
soils contained higher production decreased by
nondesorbable fractions of 11% and 20% in the
atrazine than soils without char char-amended soils and
amendment char, respectively
Mixed sawdust 500  C, fast Atrazine and Low surface area of char noted A decrease in dissipation Spokas et al.
pyrolysis process acetochlor possibly due to bio-oil rates of these herbicides (2009)
deposition. (by a factor of 2–3) was
The addition of biochar (5%, noted in char-amended
w/w) to soil increased the soil (5%, w/w)
sorption of atrazine and
acetochlor compared to non-
amended soils
Greenwaste— Pyrolysis under the Atrazine and Biochar showed high sorption Sorption equilibrium was Zheng et al.
pruning mixture oxygen-limited simazine affinity for the two herbicides. faster on finer fraction of (2010)
of maple, elm, condition for A competitive sorption noted biochars
and oak 60 min at 450  C between these two pesticides
woodchips and on the biochar.
barks Sorption on biochar was
pH-dependent
a
The material was produced by open air burning of wheat residue and therefore may not be a biochar but ash.
Biochar Application to Soil: Unintended Consequences 117

7
Charcoal,
coal, vitrinite
6 Amorphous organic
matter, algae
5
Spores, pollens,
log Koc

wood
4
Humic
3 substances

0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Freundlich exponent

Figure 5 Variations in Koc and Freundlich exponent in sorption of organic compounds

on different types of carbons (after Kleineidam et al., 1999).

bioaccessibility, bioavailability, efficacy, and toxicological impact are

directly linked to the desorption behavior, as the compound needs to be
released back into solution to be effective or have any impact on target or
nontarget organisms. Studies comparing sorption and desorption isotherms
for diuron herbicide and of pyrimethanil fungicide in soils amended with
different biochars have reported relatively flat desorption isotherms (Yu
et al., 2006, 2010) indicating an apparent sorption–desorption hysteresis
(Fig. 6). Specific adsorption, entrapment into micropores and partitioning
into condensed structures of soil organic matter are often the causes for
sequestration of chemicals (e.g., Huang et al., 2003; Weber et al., 1992).
However, our understanding on the various microscale processes
controlling sorption–desorption of organic compounds to biochar particles
in soils and sediments is limited.
Not all biochars are expected to have similar sorption–desorption beha-
viors. However, in most published sorption studies, biochars were pro-
duced from either one fixed biomass or only a small range of temperatures.
A study by James et al. (2005), however, employed a range of different
pyrolysis temperatures for three species of softwood to test sorption of
phenanthrene. They concluded that in addition to surface area, heteroge-
neous surface properties contribute to sorptive ability of biochars. Spokas
et al. (2009), working with a biochar produced from sawdust at 500  C,
noted that, on a mass basis, their biochar was an even less effective organic
sorbent for two herbicides than other forms of SOC. Due to limited
118 R. S. Kookana et al.

800

600 0% BC
0.2% 850BC
Cs (mg/g)

0.5% 850BC
0.8% 850BC
400 1.0% 850BC

200

0
0 5 10 15 20 25
Cw (mg/g)

Figure 6 Sorption–desorption isotherms of diuron herbicide showing an increased

sorption (and its nonlinearity) and sorption–desorption hysteresis with increase in
biochar content of a soil (BC 850 is black carbon produced at 850  C). Cs represents
concentration (mg/kg) on solid phase, and Cw is the solution concentration (mg/L) at
sorption equilibrium (redrawn from Yu et al., 2006).

published work so far, the sorption heterogeneity of biochars and their

potential implications remain largely unexplored.

3.2. Retention and release of nutrients and heavy metals

It is well known that activated carbon-based products are strong adsorbents
of micronutrients and toxic metals (Budinova et al., 1994; Huang, 1978).
However, there is limited research on adsorption of metals on biochars.
Some recent studies indicate that biochars have significant potential for
metal adsorption that varies with the properties of both biochars and metals.
Mohan et al. (2007) studied the adsorption of As, Cd, and Pb on chars
produced by fast pyrolysis at 400 and 450  C from oak bark, pine bark, oak
wood, pine wood, and a commercial activated charcoal. The observed
maximum adsorption of As was noted in 3–4 pH range and that of Pb and
Cd in 4–5 pH range. Among the chars, oak bark char adsorbed maximum
Pb, Cd, and As which was attributed partly to the higher SSA and pore
volume of the char. The authors considered caion exchange as the main
mechanism for the metal adsorption. Adsorption of Cd, Cu, Ni, and Pb was
investigated by Uchimiya et al. (2010b) from a mixture containing these
metals by chars produced by pyrolysis of broiler litter manure at 350 and
700  C and their steam-activated analogues. All the chars adsorbed metals in
the sequence Ni < Cd < Cu < Pb. Significant decrease in solution pH
was observed with heavy metal immobilization that was partly contributed
Biochar Application to Soil: Unintended Consequences 119

to the exchange of protons by divalent cations. However, the total metal

adsorption was 3–4 order of magnitude greater than the amount of proton
released and other mechanisms: (i) complexation of metals by surface groups
(e.g., –O–, ¼ O, and –CHO) that do not release protons, (ii) exchange with
alkali and alkaline cations, and (iii) precipitation of metal hydroxides
(Uchimiya et al., 2010b).
Namgay et al. (2010) investigated the biochar sorption of As, Cd, Cu,
Pb, and Zn and plant availability and uptake of these trace elements from a
sandy soil amended with wood biochar produced at 550  C (Fig. 7). The
sorption sequence of the metal(loid)s on the biochar for initial loadings up
to 200 mM was Pb > Cu > Cd > Zn > As, which is similar with the
sorption behavior of these elements on soil organic matter and activated
carbon. The decrease in equilibrium solution pH with increasing sorption
of metallic cations was suggested due to the exchange of metallic cations
with protons; arsenate sorption increased the solution pH that possibly was
caused by arsenate exchange with OH from biochar surfaces. Biochar
application to soil decreased the concentration of As, Cd, and Cu in
maize shoots from soil which were spiked with 50 mg/kg of these elements;
this was attributed to the sorption of the metal(loid)s by biochar. The effects
of biochar on Pb and Zn availability to plants were inconsistent. The results

500
Pb

Cu
400
Zn
Amount sorbed (mmol/kg)

As
300
Cd

200

100

0
0 5 10 15 20 25
Equilibrium concentration (mmol/L)

Figure 7 Sorption isotherms of As, Cd, Cu, Pb, and Zn onto a wood biochar, initial
solution concentration of the elements 2–800 mmol, initial solution pH 7 and 0.01 M Ca
(NO3)2 background electrolyte. Source: Namgay et al., 2010, reproduced with permis-
sion from CSIRO Publishing, Melbourne, Australia.
120 R. S. Kookana et al.

from the research cited above highlight the need for a thorough under-
standing of the effects of biochar on the bioavailability of metal(loid)s in
agricultural or contaminated soils. The characteristics of biochar and their
interaction in soils need to be understood to determine possible interactions
with metal contaminants.

3.2.1. Effect of “aging” of biochars on sorption

Due to the propensity of biochars to undergo a range of biogeochemical
interactions in soil, their properties are expected to change with time in soil,
a process commonly referred to as “aging.” Sorption of environmental con-
stituents, especially natural organic matter (NOM) and oxidation reactions are
major contributors in aging of biochars (Uchimiya et al., 2010a). It has been
shown that NOM can suppress sorption of organic contaminants on environ-
mental BC by blocking micropores (Pignatello et al., 2006). The presence of
various metallic ions such as copper and silver at environmental relevant
concentrations (50 mg/L) may also alter surface chemistry and/or pore-net-
work structure of the char through complexation (Chen et al., 1997).
In terms of mineral–biochar interactions, it is possible that with time
mineral surfaces may cover the reactive surfaces of biochar and thereby mask
the true sorption capacity of biochars for organic compounds such as
pesticides and other agrochemicals. The studies based on sorption of pesti-
cides before and after removal of paramagnetic materials (e.g., sesquioxides)
from carbon surfaces by hydrofluoric acid treatment (needed for NMR
studies) have shown that sorption on natural charcoal in soils increases by a
factor of 2–3 after such a treatment (e.g., Ahangar et al., 2008; Singh and
Kookana, 2009). This has been attributed to the organomineral interactions
gradually masking sorptive surfaces of aged charcoal in soils.
As highlighted earlier, high specific surface areas, microporosity, and
charge characteristics make biochars very efficient sorbents for a range of
organic chemicals which are of agronomic and environmental importance.
However, such behavior may change with time in soils due to myriad of
biogeochemical interactions biochar is likely to undergo in soils. In the
following sections, we discuss how biochar–chemical interactions may
result in beneficial as well as unintended consequences for crop productiv-
ity, soil health, and the environment.

4. Agronomic Implications
Biochar has the potential to alter a wide range of chemical, physical,
and biological properties of soil (Joseph et al., 2010). Depending on the
feedstock used, biochars can contain significant nutrient content (e.g., Chan
and Xu, 2009; Chan et al., 2008; Singh et al., 2010b; Van Zwieten et al.,
Biochar Application to Soil: Unintended Consequences 121

2010a,b) and offer direct nutritional value. Some biochars can also help
improve nutrient use efficiency (indirectly through nutrient sorption),
particularly in soils where leaching or off-site migration of nutrients is
a concern. Nutrient use efficiency is important both from the water quality
and from the greenhouse gas emissions perspective (Lehmann and
Joseph, 2009).
Several articles have already articulated agronomic benefits that may
potentially be realized from using biochar as a soil amendment (e.g.,
Atkinson et al., 2010; Glaser et al., 2009; Lehmann and Joseph, 2009;
Lehmann et al., 2006; Sohi et al., 2010). Figure 1 summarizes some of the
potential benefits and implications associated with biochar amendments to
soil, but caution is warranted as some potential negative impacts are also
possible. These negative impacts can include binding and deactivation of
agrochemicals (herbicides and nutrients) in soil, release of toxicants that may
be present in biochar (e.g., heavy metals), oversupply of nutrients, increase
in EC and pH, and impacts on germination and soil biological processes.
Here, we explore some of these unintended implications that have not been
fully appreciated in the biochar–soil literature so far.

4.1. Herbicide efficacy and development of weed resistance

Biochar is a particularly interesting material from the standpoint of its ability
to bind agrochemicals and potentially reduce their efficacy. Indeed, the
incorporation of a small amount of some fresh biochars in soil has been
shown to strongly bind organic compounds (e.g., pesticides) and inhibit
their microbial degradation resulting in reduced bioavailability and efficacy
to plants (Yang et al., 2006; Yu et al., 2009; Zhang et al., 2005). Numerous
examples demonstrating increased sorption or reduced bioavailability of
pesticides following biochar application to soil exist in the literature
(Table 1). These observations have direct implications for the effectiveness
of pesticides in controlling target organisms as well as on the label rates
required for pest control.
In Australia, some 35 years ago, Toth and Milham (1975) observed the
effect of combustion materials produced by burning paspalum (Paspalum
dilatatum L.) under a wide range of conditions and noted that these adsorbed
appreciable quantities of diuron from aqueous solution. However, these
were ash materials and not biochars. They noted that one of the two ash-C
products caused a significant reduction in the phytotoxicity of 16 kg
diuron/ha. They subsequently reported markedly reduced efficacy (by
60%) of two preemergent herbicides, thiobencarb (S-eithyl hexahydro-
1,4-azepine-l-thiolcarbamate) and molinate (S-(4-chlorobenzyl)-N.N-
diethylithiolcarbamate), when the herbicides were applied over rice stubble
ash (Toth et al., 1981). Similarly, decreased phytotoxicity of diuron
122 R. S. Kookana et al.

herbicide was noted when applied over the ash of recently burned kangaroo
grass (Themeda australis (R.Br.) Stapf; Toth et al., 1999).
Recent studies have confirmed similar reductions in the efficacy of
pesticides in the presence of biochars in soil. For example, Yang et al.
(2006) reported reduced herbicidal efficacy of diuron, while Xu et al.
(2008) reported reduced efficacy of clomazone to control weeds in soils
amended with so-called wheat and rice straw biochars,1 respectively. The
study by Yang et al. (2006) highlighted that with increasing biochar content
in soil, much higher rates of application of herbicides were needed to get the
desired weed control. Their study showed that even doubling the applica-
tion rate of diuron failed to control the weed growth in the presence of 0.5%
of wheat biochar in soil (as shown in Plate 1). It was noted that even at low
application rate (0.1%), biochar in soil would appreciably reduce the bio-
availability of diuron. It is worth noting that Yang et al. (2006) used
materials produced by open air burning of wheat/rice residues, and thus
these may more appropriately be termed as ash materials (as per some earlier
publications using these materials) rather than biochars. The biochars pro-
duced through pyrolysis of woody materials are likely to be more effective

Wheat char in soil (%)

1.0
0.5
0.1
0.05

0.0

0.0 1.5 3.0 6.0 12

Application rate of diuron (mg/kg)

Plate 1 Weed control of Barnyard grass with diuron herbicide applied at different
application rates to a soil amended with varying rates of wheat straw residue biochar.
Source: Yang et al., 2006, reproduced with permission from Elsevier.

1
Please note that in these studies and in some others, the crop residues were burnt in an open field. Therefore,
strictly speaking, these are not biochars but ash materials. However, since the authors used the term char or
biochar in some of their publications, the term has been retained in the subsequent discussion on their work.
Biochar Application to Soil: Unintended Consequences 123

in reducing the herbicide efficacy due to their greater sorption affinity to

herbicides than grass biochars (Bornemann et al., 2007; Yu et al., 2006).
It is noteworthy that the reduced efficacy of soil-applied herbicides in
biochar-amended soils may result in a scenario of essentially “underdosing”
(less than the required rate of application) of herbicides, unless applications
are adjusted based on biochar content of soils. Such under-dosing, if persists,
could lead to faster development of weed resistance. Unintended under-
dosing has previously been noted to exacerbate the development of weed
resistance for ryegrass (Lolium rigidum) in Australia (Neve and Powles, 2005;
Powles et al., 1996). The need for increased dose of herbicides (or insecti-
cides) in soils amended with biochars would clearly be an increased cost
burden for growers and thus could be a major disadvantage. It has been well
recognized that the adoption of environmentally attractive practices such as
minimum or zero till has been significantly constrained by the increased cost
of chemical weed control in some areas (D’Emeden and Llewellyn, 2006).
Therefore, serious considerations are warranted to this potential agronomic
and economic disadvantage associated with biochar application to soil.
However, biochar in soils is not expected to affect the efficacy of contact
herbicides directly applied on plants. Further, whether biochars would lose
or retain the capacity to inactivate herbicides with time due to organomin-
eral and biological interactions in soil remains to be seen.

4.2. Nutrient immobilization and release

The potential benefits of biochar to improving soil fertility through nutrient
addition and improvements in fertilizer-use efficiency are well recognized,
as stated above. However, unintentional consequences such as nutrient
sorption, increased leaching of some nutrients, and increased EC need
consideration prior to biochar application to soil.
The changes in N dynamics following biochar application are not fully
understood (Clough et al., 2010; Lehmann, 2007a; Singh et al., 2010a).
However, it has been suggested that weathering of biochar in soil can lead to
immobilization of N (Singh et al., 2010a; Yao et al., 2009). It has been noted
that biochar at high application rates (10% or 20%, w/w) can effectively
reduce NH4þ leaching in contrasting soils (Lehmann et al., 2003). But this
effect depends on biochar type and soil and their contact time (aging). Singh
et al. (2010a) demonstrated that while freshly added biochars had little effect
on NH4þ leaching, upon aging in soil (around 5 months), the wood- and
poultry litter-based biochars produced at 550  C were able to reduce
leaching of NH4þ by 55–65% in an Alfisol. In contrast, however, no effects
were observed with the biochars produced from the same feedstocks at
400  C. The above four biochars (two feedstocks and two temperatures)
significantly reduced NH4þ leaching in a Vertisol, a soil inherently less
prone to NH4þ leaching due to high smectite content in the clay fraction
124 R. S. Kookana et al.

(Singh and Heffernan, 2002). Biochar applications may result in increased

initial leaching of nutrients (e.g., nitrate) from soil, especially when the
biochars have high N content (Singh et al., 2010a).
As biochar alters N dynamics in soil, it can be expected to influence
gaseous losses of N. Loss of N as N2O provides a small, but environmentally
significant route for N loss from soil to the atmosphere. Nitrous oxide is
produced through a range of mechanisms in soil including nitrification,
nitrifier denitrification, and denitrification (Baggs, 2008), and it has been
suggested that biochar can play a significant role in altering these processes
(Singh et al., 2010a; Van Zwieten et al., 2009, 2010b). Incorporation of
biochar into soil has been reported to either stimulate or suppress depending
on initial soil moisture content (Rondon et al., 2007; Singh et al., 2010a;
Yanai et al., 2007) or make no change in N2O emissions (Clough et al.,
2010). Different biochar–soil combinations may show varying results. Fur-
ther studies on biochar application on N dynamics in soils are warranted
(Clough et al., 2010; Lehmann, 2007a).
While the artificial aging of biochar in the presence of humic substances
resulted in immobilization of N (Yao et al., 2009), the availability of other
nutrients, particularly P, Ca, Mg, K increased. Sinclair et al. (2010) noted
increases in plant available P following amendment with animal manure
biochar in a field studies on a ferrosol, a result not observed with greenwaste
biochar. Conversely, high rates of biochar application (4.4% and 11%, w/w)
to a sandy Yellow Earth resulted in a small but statistically significant
reduction in plant available P (Van Zwieten et al., 2010c). It has been
suggested that biochar may increase the EC of leachate, attributed to loss
of Na and K from the biochar–soil matrix (Lehmann et al., 2003; Novak
et al., 2009). It is clear that impacts on nutrients are dependent upon the
properties of both soil and biochar. The wide range of effects on nutrient
dynamics from biochar application to soil is still poorly understood, as
effects can be highly soil and biochar specific.
Given the ability of biochar to immobilize a wide range of organic and
inorganic chemicals, it is conceivable that by applying biochar to soil could
influence the plant uptake of a range of organic compounds or micronu-
trients and their unbalanced uptake may affect even the quality of the
produce. This aspect has not received any attention in the literature so far.

4.3. Soil pH and Al toxicity

Biochars can have a wide range of pH values ranging from slightly acidic to
alkaline (Chan and Xu, 2009). Their ability to provide a liming effect is
once again dependent upon both the feedstock and processing temperature;
increasing pyrolysis temperatures generally led to high pH values of biochars
(Singh et al., 2010b). Biochars produced from papermill wastes have liming
values equivalent to up to 33% that of agricultural lime due to the presence
Biochar Application to Soil: Unintended Consequences 125

of calcite (Singh et al., 2010b; Van Zwieten et al., 2010a). The acid
neutralizing capacity of biochars derived from wood or greenwaste tends
to be smaller than from higher ash feedstocks such as animal manures.
Changes in soil pH can influence the bioavailability of toxic elements
such as Al. Van Zwieten et al. (2010a) demonstrated an increase in soil pH
from 4.2 to between 5.4 and 5.9 with the application of 1% (w/w) papermill
biochar in a ferrosol; resulting in a concomitant reduction in exchangeable
Al from ca. 2 to <0.1 cmol(þ)/kg. Steiner et al. (2007) showed available Al
decreased from 4.7 mg/kg to below detection in an Oxisol. Similar effects
were observed in weathered tropical soils in Indonesia (Yamamoto et al.,
2006). It has been shown that Al toxicity could also decrease due to
its complexation to high-molecular-weight organic compounds (Alleoni
et al., 2010).

4.4. Plant germination and seedling growth

Some research suggests that biochars may contain some phytotoxic com-
pounds (Rogovska et al., 2010) that can impact plant germination, or plant
growth. Conversely, other attributes of biochar, such as sorptive capacity for
allelochemicals (Rogovska et al., 2010), may indeed result in increases in
plant germination. Limited work so far has reported both stimulation and
inhibition of germination, depending on soil type and pyrolysis conditions
associated with the biochars tested. For example, biochars derived from
papermill waste (Van Zwieten et al., 2010a) when applied at 10 t/ha ( 1%
on weight basis) either significantly improved germination or wheat in
Ferrosol, but had no significant effect on other indicator crops including
radish or soybean in either Ferrosol or Calcarosol. In contrast, Kwapinski
et al. (2010) showed that the growth of maize (Zea mays L.) seedlings was
found to be inhibited by soil amendments with a miscanthus (Miscanthus 
giganteus) biochar formed at 400  C for 10 min, but stimulated by the one
produced at 600  C for 60 min. Keller et al. (2010) assessed the phytotoxic
impacts of tar-enriched biochar on Black Seeded Simpson Lettuce (Lactuca
sativa). Their biochar was derived from sorghum feedstock using fast pyrol-
ysis without N2 purge. The authors noted increased germination and
seedling growth of the test plant even with tar-enriched biochar amend-
ment up to 10% in soil.

4.5. Soil biological properties

Published studies so far show that most biochars constitute a medium that
encourages microbial population. For example, Pietikäinen et al. (2000),
Baldock and Smernik (2002), and Hamer et al. (2004) reported enhanced
microbial activity when biochars were inoculated. However, the potential
126 R. S. Kookana et al.

toxic effects on soil microorganisms of residual bio-oils and recondensation

products adsorbed on the surfaces of some biochars have also been reported
in the literature (McClellan et al., 2007).
Biochar surfaces may serve as favorable sites for microorganisms due to
greater concentrations of adsorbed nutrients (Pietikäinen et al., 2000). Their
specific pore size characteristics may also exclude predators such as protozoa
and nematodes and thus favoring the colonization by bacteria and fungi
(Thies and Rilling, 2009; Warnock et al., 2007). It is not clear whether
microbes actively infiltrate biochar particles or colonize the outer surfaces
containing adsorbed nutrients and fresh organic matter (Hammes and
Schmidt, 2009; Lehmann and Joseph, 2009). Enhanced colonization but
decreased respiratory activity of microbes has been observed in biochar-
amended soils (Thies and Rilling, 2009), and Weyers et al. (2010) also found
that soil respiration decreased with increasing application rate of biochar.
Thies and Rilling (2009) noted a shift in the bacterial-to-fungal ratio as
C/N ratios became wider. Increased mycorrhizal colonization has been
observed when soils were amended with some biochars (Solaiman et al.,
2010), apparently indirectly by increasing P solubility in soils (e.g., Gundale
and DeLuca, 2006; Solaiman et al., 2010). In contrast, poultry litter biochars
have been shown to decrease mycorrhizal colonization (Treseder, 1998).
Recently, Steinbeiss et al. (2009) studied the effect of hydrothermally
synthesized biochars from glucose and yeast on the microbial community
when added to soil. Despite not being representative of common feed-
stocks, the study on these biochars showed interesting differences between
the two model components: yeast-derived biochar (seen to be analogous to
easily degradable biochar) showed a strong stimulation of soil microorgan-
isms and particularly fungi, but the glucose-derived biochar did not show
the same effect. They noted that the addition of both biochars increased soil
respiration in the first 12 weeks compared with the control. However, some
other workers have reported an opposite effect of biochar addition to soil
( Jin et al., 2008; Liang, 2008). For example, in the study by Jin et al. (2008),
the total respiration and the respiratory rate (measured over an 8-week
period at the end of the cropping season) were found to decrease
with increasing amount of a corn-derived biochar (at varying rates
0–30 t/ha) in soil.
Due to the relatively short duration of the experiments in the above
studies definitive conclusions cannot be drawn. How microbial commu-
nities change over time in biochar-amended soils is not well studied yet. It is
not clear if microbes could thrive on the nutrients adsorbed on to biochars
(Thies and Rilling, 2009). Clearly, this is an area that deserves much greater
attention in future to establish the long-term effect of biochar application in
soil on soil biological health.
Biochar Application to Soil: Unintended Consequences 127

5. Environmental Implications
Combustion is widely recognized as a process that generally leads to
formation of certain toxic compounds and therefore an obvious question
arises: do biochars contain toxicants associated with their production? The
question becomes even more relevant when feedstock itself may be sourced
from waste materials (e.g., biosolids) containing contaminants or their
precursors. In the following section, we have reviewed research on biochars
either as a source of contaminants or as materials influencing environmental
fate, transport, and potential ecotoxicological impacts of contaminants.

5.1. Biochar as a potential source of toxicants

Presence of combustion-driven toxic organic compounds such as polynu-
clear aromatic hydrocarbons (PAHs), chlorinated hydrocarbons, and diox-
ins is often suspected in biochar products (Chagger et al., 1998). PAHs
consist of fused aromatic rings and generally occur in oil, coal, and tar
deposits, and are by-products of burning of fossil fuel or biomass. They
are of a concern due to the carcinogenic, mutagenic, and teratogenic nature
of some of these compounds. Dioxin is a general term for a large group of
polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated diben-
zofurans (PCDFs). These are part of first 12 persistent organic pollutants
(POPs) covered under the Stockholm Convention (www.pops.int). How-
ever, very little is so far known about the contents of such organic toxicants
in biochars. While the exact mechanisms of formation of these toxicants
during combustion of biomass are unclear, these are speculated to be
synthesized through a catalytic assembly of dioxin structures from C, O2,
and Cl at a temperature window of 300–325  C and other multistep
reaction processes in the post-combustion zone (Chagger et al., 1998),
often catalyzed by copper and iron.
Brown et al. (2006) analyzed different PAH congeners in a range of
synthetic biochars produced from small blocks of pitch pine wood pyro-
lyzed using ramp rates between 30 and 1000  C/h and with maximum
temperatures between 450 and 1000  C. A natural char was also included by
gathering charred pine from a site of a prescribed burn. They found that all
wood chars contained measurable quantities of PAHs and the concentra-
tions were dependent on carbonization temperature and source (natural and
synthetic). A comparison of total PAH contents (the sum of 40 different
PAHs) among the chars produced at different final temperatures (but all
with same ramp temperature of 650  C/h) showed a strong dependence on
the production temperature (16 mg/kg in the 450  C char material,
7 mg/kg in the 525  C char, and only 3 mg/kg for the 1000  C char).
128 R. S. Kookana et al.

The natural char had a much higher value with a total PAH concentration of
28 mg/kg. This trend in temperature dependence was also noted for many
individual PAHs. The chars produced at low-temperature contained a higher
concentration of low-molecular-weight/high-vapor-pressure PAHs, whereas
the high-temperature char contained higher concentrations of the higher-
molecular-weight/lower-vapor-pressure PAHs. Recently, Singh et al.
(2010b) analyzed the PAH contents of 11 biochars, made from five feed-
stocks: Eucalyptus saligna wood (at 400 and 550  C both with and without
steam activation), E. saligna leaves (at 400 and 550  C with activation), paper
mill sludge (at 550  C with activation), and poultry litter and cow manure
(each at 400  C without activation and at 550  C with activation). The PAHs
concentrations in all samples were well below <0.5 mg/kg, the Australian
guideline value for PAH concentration in soil (NEPM, 1999). Based on the
few studies above, and considering likely dilutions in soils, the levels of PAHs
in soils introduced through biochars may be acceptable. More work,
however, is needed to confirm this, especially for waste-driven biochars.
Moreover, since highly hydrophobic compounds (e.g., PAHs, dioxins) are
strongly sorbed by biochars, the current extraction procedures may need to
be modified to get a more accurate estimation of the total loads of such
contaminants on biochars (even if these are not readily bioavailable).
Some biochars may be rich in metal contents and may be of concern if
applied to soil without due consideration. For example, Zn contents of
E. saligna wood and poultry litter biochars were found to range from 1312
to 1661 mg/kg, and from 1449 to 1642 mg/kg, respectively (Singh et al.,
2010b). Soil application of these biochars at high rates could build up soil Zn
levels that could be potentially toxic to plants and soil microorganisms. It is
noteworthy that the current Australian guidelines for unrestricted use of
biosolids suggest a range of 200–250 mg Zn/kg on dry weight biosolids
(NRMMC, 2004). Similarly, Cu content of poultry biochars has been
found to be high (805–1034 mg/kg; Gaskin et al., 2008); however, poultry
litter biochar from Australia had a lower Cu concentration of 310 mg/kg
(Van Zwieten et al., 2010b). The levels of toxic metals in biochars depend
on the original content of metals in the feedstocks and processing condi-
tions, and the potential impact on soil would depend on the soil type and
their ability to immobilize and detoxify the contaminants (see Section 3).

5.1.1. Contaminants in biochars from wastes

Waste management is one of the attractive elements associated with the
biochars technology (Lehmann et al., 2006). Therefore, the feedstock
source—especially when biochars are produced from waste material (e.g.,
municipal solid waste—MSW, sewage sludge, or industrial waste)—may
influence the nature and extent of contaminants present in the final biochar
product and/or formed during the production process. MSW is a complex
mixture of varying components, consisting of cellulose- or lignin-derived
Biochar Application to Soil: Unintended Consequences 129

material, polymer-based materials, and inorganic materials. Vassilev and

Braekman-Danheux (1999) studied the trace elements in chars generated
by combustion of MSW. They found that a number of trace elements (Ag,
Cd, Cl, Cr, Cu, Ho, I, Pb, Pr, Re, Sb, Sm, Sn, and Zn) in these chars were
present at concentrations significantly higher (>10 times) than the respective
world-wide averaged values for coals. More recently, Yoshida and Antal
(2009) studied the suitability of sewage sludge as feedstock for the production
of biochar. They produced biochar from a sludge with low heavy metals
content using flash carbonization technique and found that the product was
acceptable for land application according to U.S. EPA regulation 40 CFR
Part 503. Conversely, Van Zwieten et al. (2010b) analyzed biochar from
biosolids produced at 550  C, and found Zn concentrations (890 mg/kg) in
the biochar that exceeds the Grade B biosolids guidelines of New South
Wales (Australia; NSW EPA, 1997). Other metals analyzed including As, Cu,
Cd, Pb, Ni, and Se were suitable for land application (NSW EPA, 2009).
The studies cited above highlight the potential of contaminants to be
present in pyrolysis products and the importance of careful choice of waste
as a feedstock. The makeup of the waste used as a feedstock may contain the
precursors for other toxicants that may be formed during the pyrolysis
process. Currently, little is known of the potential production or transfor-
mation of contaminants (which may be present in waste material used as a
feedstock) during the biochar manufacturing process.

5.2. Mobilization/immobilization of cocontaminants

Organic and inorganic contaminants coexist in soil environments, and
thus the effects of coadsorbed metals on adsorption of organics have been
investigated on charcoals (Cao et al., 2009; Chen et al., 2007). Coadsorption
of Cu2þ decreased the sorption of both polar (2,4-dichlorobenzene) and
nonpolar compounds (dichlorobenzene and naphthalene) between 30% and
60% on wood charcoal (Chen et al., 2007). Chen et al. (2007) assumed that
hydration shells of water are formed in the surface complexation of Cu2þ
which directly competes with the organics for the adsorption sites on the
charcoal. In contrast to Cu2þ, coadsorption of Agþ increased the sorption of
organics by charcoal and this effect contributed to the decreased hydrophi-
licity of charcoal surfaces. Similarly, little competition for sorption was
noted when Pb and atrazine were coadsorbed on a dairy manure biochar
(Cao et al., 2009). This was due to completely different sorption processes,
that is, precipitation for Pb and surface sorption for atrazine were involved
in the sorption of the coadsorbents.
In order to investigate the impact of aging on the effectiveness of
biochars on the immobilization of Cu2þ, Cd2þ, and Ni2þ and release of
S, Uchimiya et al. (2010b) used NOM with known carboxyl contents and
studied the mobilization and immobilization of these elements from a soil.
130 R. S. Kookana et al.

They noted that while biochar amendment generally enhanced the immo-
bilization of heavy metal contaminants (regardless of biomass source and
pyrolysis conditions), the addition of reference Suwannee River NOM or
Elliott soil humic acid (having high carboxyl content) mobilized Cu2þ
otherwise retained by soil. This was possibly due to complex formation
with metal ion-coordinating organic fractions and competition with metal
ions for the sorption sites. Their study suggested that organic fraction of
biochars, and NOM having high carboxyl contents, may mobilize the
native pool of certain heavy metals (e.g., Cu2þ) in soils. Competition for
sorption sites and potential mobilization of cocontaminants or release of
native pool of chemicals is dependent on the nature of biochars, soils, and
chemicals involved.

5.3. Decreased bioavailability and increased

persistence of chemicals
Generally, organic compounds become less bioavailable with time in soils or
sediments (see review by Alexander, 1995; Hunter et al., 2010; Semple et al.,
2003). In this context, the presence of highly microporous hydrophobic
sorbents (such as biochars, BC) may be particularly effective in reducing
their bioavailability with time. Indeed, the physicochemical characteristics
of the sorbent matrix have been shown to have profound effects on the
bioavailability of organic compounds (Luthy et al., 1997). For example, tests
with model sorbents by Nam and Alexander (1998) showed that with glass
and polystyrene beads (with no porosity), phenanthrene was rapidly miner-
alized, whereas with porous polystyrene beads (containing 5 or 300–400 nm
pores), little of the compound was desorbed and only <7% of sorbed
phenanthrene was mineralized. Microporosity of biochar, therefore, is
expected to influence the bioavailability of agrochemicals.
Incorporation of a small amount of biochar in a soil has been shown to
inhibit the microbial degradation of pesticides and thereby to increase their
persistence in the environment (Yu et al., 2009; Zhang et al., 2005; Table 1).
For example, Yu et al. (2009) amended soils with different amounts of
biochars produced at two different temperatures (450 and 850  C) to a
level of 0–1% by weight. Biodegradation and plant uptake of two insecti-
cides (carbofuran and chlorpyrifos with differing hydrophobicities) by
spring onions (Allium cepa) were studied. They noted that the bioavailability
of the two pesticides to microorganisms (biodegradation) as well as for plant
uptake (and efficacy by inference) decreased with increasing biochar con-
tent in soil. This resulted in prolonged persistence of the compounds in
biochar-amended soils. Over 35 days, 86–88% of the pesticides dissipated
from the unamended soil, whereas only 51% of carbofuran and 44% of
chlorpyrifos disappeared from the soil amended with 1.0% biochar pro-
duced at 850  C. Several recent studies have further demonstrated the
Biochar Application to Soil: Unintended Consequences 131

increased persistence of herbicides in soils amended with biochars (Table 1).

Whether the slower degradation of pesticides in biochar-amended soils
would result in buildup of residues and if such (bound) residues have any
environmental relevance, is not clear.

5.4. Impact on transport of agrochemicals and

contaminants (including POPs)
POPs produced and used in industrialized nations are a cause of great
concern globally due to their persistent, bioaccumulative, and toxic nature
as well as their propensity to travel long distances to affect even remote and
uninhabited parts of the globe (Wania, 2006). The partitioning process plays
a crucial role in determining their environmental fate, transport, accumula-
tion, impact on biota, and food safety. Due to their hydrophobic nature,
most POPs have a strong affinity for SOC. Therefore, global surface soils
have been recognized to serve as an important reservoir for POPs, repre-
senting an integration of several processes over a timescale of years to
decades (Sweetman et al., 2005). While the importance of soil biogeochem-
istry and the role of SOC was recognized some 30 years ago (Karickhoff
et al., 1979), it is only in the past decade that organic carbon has been
recognized as the key parameter governing spatial variability of POPs in
soils (Cousins et al., 1999) and partitioning in the marine environment
(Lohmann et al., 2005). It is, therefore, conceivable that biochars in soils,
due to their high sorption capacity (see Section 3), can potentially serve as
sinks for POPs and significantly influence the process of “grasshopping” and
their global distribution (Fig. 1). The work of Meijer et al. (2002) has
highlighted the likelihood of a much retarded transport due to strong
sorption to SOC than what has been taken into account in predictions so
far. In recent years, several workers have called for a greater understanding
and accounting of role of SOC in fluxes, distributions, and long-range
transport of organic contaminants (Koblickova et al., 2008; Lohmann
et al., 2007; Scheringer, 2009). If soil application of biochars becomes a
common practice, the distribution of POPs may be altered even more and
may require understanding of the potential impact of the biochar applica-
tions to soil on the accumulation and distribution of POPs.
Biochar particles can potentially serve as the vehicles for off-site trans-
port of agrochemicals. The importance of colloidal transport as a pathway of
off-site migration of relatively hydrophobic contaminants is well recognized
(McCarthy and Zachara, 1989). It is also known that colloids (being richer
in organic matter and greater sorption affinity) often get enriched in con-
taminants (such as nutrients and pesticides) during their overland transport
(Rose and Dalal, 1988; Sharpley and Menzel, 1987). Soil application of
biochar may facilitate increased off-site migration of agrochemicals through
at least two mechanisms: (i) due to their low specific gravity the freshly
132 R. S. Kookana et al.

produced biochar particles are erosion prone and are likely to get easily
entrained in surface runoff, and (ii) the extraordinary ability of biochars to
sorb chemicals is likely to lead to a greater “enrichment” of residue on the
colloids during their transport. However, whether these contaminants
would remain bioavailable to potentially exert an effect on organisms in
the receiving environment, is not clear.

5.5. Ecotoxicological effect on soil organisms

A variety of organic compound including bio-oils, ash, pyroligneous acids
(Steiner et al., 2008), and volatile matter (McClellan et al., 2007) may remain
on biochar surfaces immediately following pyrolysis. However, the fate of
these compounds with time in soil after biochar application is unknown. It is
expected that the water-soluble components such as acids, alcohols, alde-
hydes, ketones, and sugars that are easily metabolized by soil microbes may
have a positive effect. Whereas the presence of compounds such as PAHs,
cresols, xylenols, formaldehyde, acrolein, and other toxic carbonyl com-
pounds (depending on pyrolysis conditions) may have bactericidal or fungi-
cidal activity (Painter, 2001). Some of the effects of biochar application on
soil microbial changes have already been discussed in Section 5.
Earthworms are useful indicators of soil health (Paoletti et al., 1998), as
they are highly mobile and sensitive to soil contamination (Yeardley et al.,
1996). Several studies have tested the impacts of biochar on earthworms using
either mortality or avoidance behavior studies. For example, Wen et al.
(2009) spiked three soils with pentachlorophenol (PCP) in the laboratory
and included one field-contaminated soil, which was then amended with
2.0% biochar, humic acid, and peat and aged for either 7 or 250 days. They
noted that the bioavailability and the bioaccumulation factor of PCP for
earthworms (Eisenia fetida) were significantly reduced by biochar amendment
to the studied soils. This is consistent with the ability of biochar to sorb
organic contaminants, as discussed above (Section 3). Also, as mentioned
above, Cu contents of some poultry biochars have been found to be as high as
1000 mg/kg (Gaskin et al., 2008). Earthworms can exhibit sublethal toxic
responses at relatively low concentrations (<34 mg/kg) of Cu in soil (Helling
et al., 2000; Van Zwieten et al., 2004), and, therefore, care must be taken in
the soil application to avoid the accumulation of toxic levels of Cu. Biochar
may also indirectly influence the soil environment for earthworms. It has also
been suggested that increasing pH of acid soils through the application of
charcoal can benefit earthworm population (Chan et al., 2008; Topoliantz
and Ponge, 2005; Van Zwieten et al., 2010a). However, alkaline biochars if
applied at high rates can also adversely affect the soil environmental condi-
tions (pH, EC) for earthworms (Liesch et al., 2010). Longer-term studies on a
range of biochars and soil health have already been called for by several
workers (Pietikäinen et al., 2000; Warnock et al., 2007).
Biochar Application to Soil: Unintended Consequences 133

6. Knowledge Gaps and Research Needs

The review of the literature, especially dealing with agronomic and
environmental implications of biochar application to soils, has highlighted
several benefits as well as potentially negative implications, such as (i)
reduced efficacy and increased agro-input costs, (ii) release and increased
persistence of agrochemicals, (iii) accumulation and transport of contami-
nants, and (iv) potential ecotoxicological impacts on soil flora and fauna.
Several knowledge gaps have emerged, as listed below. These are, by no
means, intended to cover all aspects of future research on biochar applica-
tions to soils, instead highlight key gaps that need to be addressed especially
to avoid potential unintended consequences identified in this chapter.
 Biochar properties are a function of type of feedstock and pyrolytic
conditions employed in its production. Given the variety of feedstock
being used and different production technologies employed, high het-
erogeneity in biochar properties has been observed. Studies on limited
ranges of biochars prepared at different temperatures have shown marked
differences in their properties and ability to supply nutrients, immobilize,
or interact with chemicals such as herbicides and heavy metals. Despite
the increasing research effort in recent years in this area, a sound under-
standing of the relationship between desired biochar characteristics and
production conditions/feedstock is still lacking. Further work is needed,
especially to identify what combination of feedstock and pyrolysis con-
ditions would provide the most appropriate properties for biochar as a soil
amendment.
 Due to the extraordinary ability of biochars to sorb organic chemicals,
one of the major unintended consequences of biochar application to soil
identified in this chapter is the likely compromised efficacy of pesticides.
Owing to the direct and indirect agronomic and economic implications
associated with this finding, it is imperative that a thorough understanding
is developed about the nature and extent of such effects of different types
of biochars in soils. Perhaps the most important questions here are as
follows: (i) Over time will biochar in soil retain or lose its ability to
deactivate herbicides? (ii) Could biochars production be customized, or
be pretreated before application or are applied to soil in a manner to avoid
such adverse effects (e.g., by incorporation, banding, or subsurface
placement)?
 Once applied to soil, biochars undergo numerous biogeochemical inter-
actions that are likely to affect their properties over time. Most studies in
the literature are on freshly prepared biochars. The understanding of
organomineral interactions of biochar in soils and consequences of aged
biochars for pesticide, nutrient, and microbiological interactions is
extremely limited. This aspect deserves urgent scientific attention.
134 R. S. Kookana et al.

 The questions commonly asked by regulators and community about

biochars as a source of contaminants and their long-term impact on
natural resources have not been answered yet. Limited published/unpub-
lished work on biochars sourced from plant biomass or crop residue so far
indicates that contaminants such as PAHs, dioxins may not be a major
issue (in relation to existing guidelines on soil contaminants). However,
some biochars have been noted to contain elevated levels of heavy metals
and may also contain precursors of toxicants that may be created during
biochar production. Currently, there is no comprehensive study available
in the literature that can address the above questions adequately, espe-
cially for biochars produced from wastes.
 This chapter has shown that effects of biochar on soil flora and fauna are
poorly understood. Given that residues of some of the potentially tox-
icants (e.g., heavy metals, PAHs, cresols, xylenols, formaldehyde, acro-
lein, and other toxic carbonyl compounds) may remain on biochars
(depending on pyrolysis conditions), their ecotoxicological impact on
plants, microorganisms, and other indicators of soil health (e.g., earth-
worms) need to be established. The little work cited above clearly calls for
further investigations in this area.
 Particles of freshly made biochars, being relatively lighter than other soil
particles, are likely to be easily transported in surface runoff water. Better
understanding is needed of the role of biochar-assisted transport and off-
site migration of pesticides and other contaminants. Moreover, any
environmental effects of biochar-sorbed contaminants on nontarget
organisms in receiving environments need to be assessed. If biochar
addition to soil becomes as a widely adopted agronomic practice, the
potential impact this may have on accumulation of POPs in soils and their
long-range transport would need to be evaluated.
 As the use of biochar in soils becomes common, the potential impact on
quality of produce may also become important, especially those targeting
a particular market niche. To the best of our knowledge, currently, no
work is available in the literature on this topic.
Undoubtedly, biochar application to soil has major potential benefits in
relation to carbon sequestration, bioenergy, enhanced soil fertility, and
waste management (as discussed above and reviewed previously by several
workers). However, prior to recommendation of this agronomic practice at
a large scale, a complete analysis of potential agronomic and environmental
implications is prudent. This chapter has highlighted that while the body of
the literature on biochar interactions in soil and environment is growing
rapidly, some of the potential unintended consequences have not been fully
appreciated or addressed as yet. A better understanding of long-term agro-
nomic and environmental impact of biochar application to soils is essential
for the realization of full potential and sustainability of the biochar
technology.
Biochar Application to Soil: Unintended Consequences 135

ACKNOWLEDGMENTS
The authors thank CSIRO’s Sustainable Agriculture Research Flagship for the financial
support and the two internal reviewers (Drs. Michael Warne and Mark Farrell) for their
comments on the chapter.

REFERENCES
Abelmann, K., Kleineidam, S., Knicker, H., Grathwohl, P., and Kögel-Knabner, I. (2005).
Sorption of HOC in soils with carbonaceous contamination: Influence of organic-matter
composition. J. Plant Nutr. Soil Sci. 168, 1–14.
Accardi-Dey, A., and Gschwend, P. M. (2003). Reinterpreting literature sorption data
considering both absorption into organic carbon and adsorption onto black carbon.
Environ. Sci. Technol. 37, 99–106.
Ahangar, A. G., Smernik, R. J., Kookana, R. S., and Chittleborough, D. J. (2008).
Separating the effects of organic matter-mineral interactions and organic matter chemis-
try on the sorption of diuron and phenanthrene. Chemosphere 72, 886–890.
Ahmad, R., Kookana, R. S., Alston, A. M., and Skjemstad, J. O. (2001). The nature of soil
organic matter affects the sorption of pesticides. 1. Relationship with carbon chemistry as
determined by 13C CPMAS NMR spectroscopy. Environ. Sci. Technol. 35, 878–884.
Alexander, M. (1995). How toxic are toxic chemicals in soil? Environ. Sci. Technol. 29, 2713–
2717.
Allen-King, R. M., Grathwohl, P., and Ball, W. P. (2002). New modeling paradigms for the
sorption of hydrophobic organic chemicals to heterogeneous carbonaceous matter in
soils, sediments and rocks. Adv. Water Resour. 25, 985–1016.
Alleoni, L. R. F., Cambri, M. A., Caires, E. F., and Garbuio, F. J. (2010). Acidity and
aluminum speciation as affected by surface liming in tropical no-till soils. Soil Sci. Soc.
Am. J. 74, 1010–1017.
Almendros, G., González-Vila, F. J., and Martin, F. (1990). Fire-induced transformation of
soil organic matter from an oak forest. An experimental approach to the effects of fire on
humic substances. Soil Sci. 149, 158–168.
Atkinson, C. J., Fitzgerald, J. D., and Hipps, N. A. (2010). Potential mechanisms for
achieving agricultural benefits from biochar application to temperate soils: A review.
Plant Soil 337, 1–18.
Baggs, E. M. (2008). A review of stable isotope techniques for N2O source partitioning in
soils: Recent progress, remaining challenges and future considerations. Rapid Commun.
Mass Spectrom. 22, 1664–1672.
Baldock, J. A., and Smernik, R. J. (2002). Chemical composition and bioavailability of
thermally altered Pinus resinosa (red pine) wood. Org. Geochem. 33, 1093–1109.
Barton, S. S., Evans, M. J. B., Halliop, E., and MacDonald, J. A. F. (1997). Acidic and basic
sites on the surface of porous carbon. Carbon 35, 1361–1366.
Biniak, S., Szymanski, G., Siedlewski, J., and Swiatkowski, A. (1997). The characterization
of activated carbons with oxygen and nitrogen surface groups. Carbon 35, 1799–1810.
Boehm, H. P. (2002). Surface oxides on carbon and their analysis: A critical assessment.
Carbon 40, 145–149.
Bornemann, L. C., Kookana, R. S., and Welp, G. (2007). Differential sorption behaviour of
aromatic hydrocarbons on charcoals prepared at different temperatures from grass and
wood. Chemosphere 67, 1033–1042.
136 R. S. Kookana et al.

Bracmort, K. S. (2009). Biochar: Examination of an emerging concept to mitigate climate

change., http://ncseonline.org/NLE/CRs/abstract.cfm?NLEid¼2216, Congressional
Research Service, 7–5700, CRS report no. R40186.
Bridle, T. R., and Pritchard, D. (2004). Energy and nutrient recovery from sewage sludge
via pyrolysis. Water Sci. Technol. 50, 169–175.
Brown, R. A., Kercher, A. K., Nguyen, T. H., Nagle, D. C., and Ball, W. P. (2006).
Production and characterization of synthetic wood chars for use as surrogates for natural
sorbents. Org. Geochem. 37, 321–333.
Bucheli, T. D., and Gustafsson, O. (2003). Soot sorption of non-ortho and ortho substituted
PCBs. Chemosphere 53, 515–522.
Budinova, T. K., Gergova, K. M., Petrov, N. V., and Minkova, V. N. (1994). Removal of
metal ions from aqueous solution by activated carbons obtained from different raw
materials. J. Chem. Technol. Biotechnol. 60, 177–182.
Cao, X., Ma, L., Gao, B., and Harris, W. (2009). Dairy-manure derived biochar effectively
sorbs lead and atrazine. Environ. Sci. Technol. 43, 3285–3291.
Chagger, H. K., Kendall, A., McDonald, A., Pourkashanian, M., and Williams, A. (1998).
Formation of dioxins and other semi-volatile compounds in biomass combustion. Appl.
Energy 60, 101–114.
Chan, K. Y., and Xu, K. (2009). Biochar: Nutrient properties and their enhancement.
In “Biochar for Environmental Management. Science and Technology” ( J. Lehmann
and S. Joseph, Eds.), pp. 13–323. Earthscan, London.
Chan, K. Y., Van Zwieten, L., Meszaros, I., Downie, A., and Joseph, S. (2007). Agronomic
values of greenwaste biochar as a soil amendment. Aust. J. Soil Res. 45, 629–634.
Chan, K. Y., Van Zwieten, L., Meszaros, I., Downie, A., and Joseph, S. (2008). Using
poultry litter biochars as soil amendments. Aust. J. Soil Res. 46, 437–444.
Chen, G., Yu, Q., and Sjostrom, K. (1997). Reactivity of char from pyrolysis of birchwood.
J. Anal. Appl. Pyrolysis 40–41, 491–499.
Chen, J., Zhu, D., and Sun, C. (2007). Effect of heavy metals on the sorption of hydropho-
bic organic compounds to wood charcoal. Environ. Sci. Technol. 41, 2536–3541.
Cheng, C. H., Lehmann, J., Thies, J. E., Burton, S. D., and Engelhard, M. H. (2006).
Oxidation of black carbon by biotic and abiotic processes. Org. Geochem. 37, 1477–1488.
Cheng, C. H., Lehmann, J., and Engelhard, M. H. (2008). Natural oxidation of black carbon
in soils: Changes in molecular form and surface charge along a climosequence. Geochim.
Cosmochim. Acta 72, 1598–1610.
Chiou, C. T., Porter, P. E., and Schmeddling, D. W. (1983). Partition equilibria of nonionic
organic compounds between soil organic matter and water. Environ. Sci. Technol. 17,
227–231.
Chun, Y., Sheng, G. Y., Chiou, C. T., and Xing, B. S. (2004). Compositions and sorptive
properties of crop residue-derived chars. Environ. Sci. Technol. 38, 4649–4655.
Clough, T. J., Bertram, J. E., Ray, J. L., Condron, L. M., O’Callaghan, M., Sherlock, R. R.,
and Wells, N. S. (2010). Unweathered wood biochar impact on nitrous oxide emissions
from a bovine-urine amended pasture soil. Soil Sci. Soc. Am. J. 74, 852–860.
Cousins, I. T., Gevao, B., and Jones, K. C. (1999). Measuring and modelling the vertical
distribution of semivolatile organic compounds in soils. I: PCB and PAH soil core data.
Chemosphere 39, 2507–2518.
D’Emeden, F. H., and Llewellyn, R. S. (2006). No-tillage adoption decisions in southern
Australian cropping and the role of weed management. Aust. J. Exp. Agric. 46, 563–569.
DeLuca, T. H., MacKenzie, M. D., and Gundale, M. J. (2009). Biochar effects on soil
nutrient transformations. In “Biochar for Environmental Management: Science and
Technology” ( J. Lehmann and S. Joseph, Eds.), Earthscan, London.
Biochar Application to Soil: Unintended Consequences 137

Downie, A., Crosky, A., and Munroe, P. (2009). Physical properties of biochar. In “Biochar
for Environmental Management: Science and Technology” (J. Lehmann and S. Joseph,
Eds.), Earthscan, London.
Downie, A., Munroe, P., Cowie, A., Van Zwieten, L., and Lau, D. M. S. (2011). Biochar as
a Geo-Engineering climate solution: Hazard identification and risk management. Crit.
Rev. Environ. Sci. Technol.10.1080/10643389.2010.507980, (in press).
Figueiredo, J. L., Pereira, M. F. R., Freitas, M. M. A., and Órfão, J. J. M. (1999).
Modification of the surface chemistry of activated carbons. Carbon 37, 1379–1389.
Gaskin, J. W., Steiner, C., Harris, K., Das, K. C., and Bibens, B. (2008). Effect of low
temperature pyrolysis conditions on biochars for agricultural use. Trans. ASABE 51,
2061–2069.
Glaser, B., Haumaier, L., Guggenberger, G., and Zech, W. (2001). The ’Terra Preta’
phenomenon: A model for sustainable agriculture in the humid tropics. Naturwissenschaf-
ten 88, 37–41.
Glaser, B., Lehmann, J., and Zech, W. (2002). Ameliorating physical and chemical proper-
ties of highly weathered soils in the tropics with charcoal: A review. Biol. Fertil. Soils 35,
219–230.
Glaser, B., Parr, M., Braun, C., and Kopolo, G. (2009). Biochar is carbon negative. Nat.
Geosci. 2(1), 2.
Gundale, M. J., and DeLuca, T. H. (2006). Temperature and source material influence
ecological attributes of ponderosa pine and Douglas fir charcoal. For. Ecol. Manage. 231,
86–93.
Hamer, U., Marschner, B., Brodowski, S., and Amelung, W. (2004). Interactive priming of
black carbon and glucose mineralisation. Org. Geochem. 35, 823–830.
Hammes, K., and Schmidt, M. W. I. (2009). Changes of biochar in soil. In “Biochar for
Environmental Management: Science and Technology” (J. Lehmann and S. Joseph,
Eds.), Earthscan, London.
Helling, B., Reinecke, S. A., and Reinecke, A. J. (2000). Effects of the fungicide copper
oxychloride on the growth and reproduction of Eisenia fetida (Oligochaeta). Ecotoxicol.
Environ. Safe. 46, 108–116.
Huang, C. P. (1978). Chemical interactions between inorganic and activated carbon.
In “Carbon Adsorption Handbook” (P. N. Cheremisinoff and F. Ellerbursch, Eds.),
pp. 281–330. Ann Arbor Science, New York.
Huang, W. L., Peng, P. A., Yu, Z. Q., and Fu, J. M. (2003). Effects of organic matter
heterogeneity on sorption and desorption of organic contaminants by soils and sediments.
Appl. Geochem. 18, 955–972.
Hunter, W. H., Gan, J., and Kookana, R. S. (2010). Bioavailability of hydrophobic organic
contaminants in soils and sediments. In “Biophysico-Chemical Processes of Anthropo-
genic Organic Compounds in Environmental Systems” (P. M. Huang and N. Senesi,
Eds.), John Wiley & Sons, Hoboken, NJ, (in press).
James, G., Sabatini, D. A., Chiou, C. T., Rutherford, D., Scott, A. C., and
Karapanagioti, H. K. (2005). Evaluating phenanthrene sorption on various wood chars.
Water Res. 39, 549–558.
Jia, Y. T., Xiao, B., and Thomas, K. M. (2002). Adsorption of metal ions on nitrogen surface
functional groups in activated carbon. Langmuir 18, 470–478.
Jin, H., Lehmann, J., and Thies, J. E. (2008). Soil microbial community response to
amending corn soils with corn stover charcoal. In “Proceedings of the 2008 Conference
of International Biochar Initiative,” 8–10 September 2008, Newcastle, UK.
Jonker, M. T. O., Hawthorne, S. B., and Koelmans, A. A. (2005). Extremely slowly
desorbing polycyclic aromatic hydrocarbons from soot and soot-like materials: Evidence
by supercritical fluid extraction. Environ. Sci. Technol. 39, 7889–7895.
138 R. S. Kookana et al.

Joseph, S. D., Camps-Arbestain, M., Lin, Y., Munroe, P., Chia, C. H., Hook, J.,
Van Zwieten, L., Kimber, S., Cowie, A., Singh, B. P., Lehmann, J., and Foidl, N.
(2010). An investigation into the reactions of biochar in soil. Aust. J. Soil Res. 48, 501–515.
Karickhoff, S. W., Brown, D. S., and Scott, T. A. (1979). Sorption of hydrophobic
pollutants on natural sediments. Water Res. 13, 241–248.
Keller, M. L., Masiello, C. A., Dugan, B., Rudgers, J. A., and Capareda, S. C. (2010).
Phytotoxicity and plant productivity analysis of tar-enriched biochars. In “American
Geophysical Union, Fall Meeting 2008, abstract #B23D-0481,” http://adsabs.harvard.
edu/abs/2008AGUFM.B23D0481K, (accessed October 5, 2010).
Killops, S. D., and Killops, V. J. (2005). An Introduction to Organic Geochemistry.2nd edn.
Blackwell Publishing, Malden.
Kleineidam, S., Rügner, H., and Grathwohl, P. (1999). Impact of grain scale heterogeneity
on slow sorption kinetics. Environ. Toxicol. Chem. 18, 1673–1678.
Koblickova, M., Ruzickova, P., Cupr, P., Komprda, J., Holoubek, I., and Klanova, J.
(2008). Soil burdens of persistent organic pollutants: Their levels, fate, and risks. Part
IV. Quantification of volatilization fluxes of organochlorine pesticides and polychlori-
nated biphenyls from contaminated soil surfaces. Environ. Sci. Technol. 43, 3588–3595.
Kookana, R. S. (2010). The role of biochar in modifying the environmental fate, bioavail-
ability, and efficacy of pesticides in soils: A review. Aust. J. Soil Res. 48, 627–637.
Krull, E. S., Baldock, J. A., Skjemstad, J. O., and Smernik, R. S. (2009). Characteristics of
biochar: Organo-chemical properties. In “Biochar for Environmental Management:
Science and Technology” ( J. Lehmann and S. Joseph, Eds.), Earthscan, London.
Kwapinski, W., Byrne, C. M. P., Kryachko, E., Wolfram, P., Adley, C., Leahy, J. J.,
Novotny, E. H., and Hayes, M. H. B. (2010). Biochar from biomass and waste. Waste
Biomass Valorization 1, 177–189.
Laird, A. D. (2008). The charcoal vision. A win-win-win scenario for simultaneously
producing bioenergy, permanently sequestering carbon, while improving soil and
water quality. Agron. J. 100, 178–181.
Lehmann, J. (2007a). Bio-energy in the black. Front. Ecol. Environ. 5, 381–387.
Lehmann, J. (2007b). A handful of carbon. Nature 447, 143–144.
Lehmann, J., and Joseph, S. (2009). Biochar for environmental management: An introduc-
tion. In “Biochar for Environmental Management: Science and Technology”
( J. Lehmann and S. Joseph, Eds.), Earthscan, London.
Lehmann, J., da Silva, J. P. Jr., Steiner, C., Nehls, T., Zech, W., and Glaser, B. (2003). Nutrient
availability and leaching in an archaeological Anthrosol and a Ferralsol in the Central
Amazon basin: Fertiliser, manure and charcoal amendments. Plant Soil 249, 343–357.
Lehmann, J., Gaunt, J., and Rondon, M. (2006). Bio-char sequestration in terrestrial
ecosystems—A review. Mitig. Adapt. Strateg. Glob. Change 11(2), 403–427.
Liang, B. (2008). The Biogeochemistry of Black Carbon in Soils. PhD thesis, Cornell
University, Ithaca, NY.
Liang, B., Lehmann, J., Solomon, D., Kinyangi, J., Grossman, J., O’Neill, B.,
Skjemstad, J. O., Thies, J., Luizaö, F. J., Petersen, J., and Neves, E. G. (2006). Black
carbon increases cation exchange capacity in soils. Soil Sci. Soc. Am. J. 70, 1719–1730.
Liesch, A. M., Weyers, S. L., Gaskin, J. W., and Das, K. C. (2010). Impact of two different
biochars on earthworm growth and survival. Ann. Environ. Sci. 4, 1–9.
Loganathan, V. A., Feng, Y., Sheng, G. D., and Clement, T. P. (2009). Crop-residue-
derived char influences sorption, desorption and bioavailability of atrazine in soils. Soil
Sci. Soc. Am. J. 73, 967–974.
Lohmann, R., Mac Farlane, J. K., and Gschwend, P. M. (2005). Importance of black carbon
to sorption of native PAHs, PCBs, and PCDDs in Boston and New York harbour
sediments. Environ. Sci. Technol. 39, 141–148.
Biochar Application to Soil: Unintended Consequences 139

Lohmann, R., Breivik, K., Dachs, J., and Muir, D. (2007). Global fate of POPs: Current and
future research directions. Environ. Pollut. 150, 150–165.
Luthy, R. G., Aiken, G. R., Brusseau, M. L., Cunningham, S. D., Gschwend, P. M.,
Pignatello, J. J., Reinhard, M., Traina, S. J., Weber, W. J., and Westall, J. C. (1997).
Sequestration of hydrophobic organic contaminants by geosorbents. Environ. Sci. Technol.
31, 3341–3347.
Major, J., Lehmann, J., Rondon, M., and Goodale, C. (2009). Fate of soil applied black
carbon: Downward migration, leaching and soil respiration. Glob. Change Biol. 16, 1366–
1379.
Mathews, J. A. (2008). Viewpoint: Carbon-negative biofuels. Energy Policy 36(3), 940–945.
McBeath, A. V., and Smernik, R. J. (2009). Variation in the degree of aromatic condensa-
tion of chars. Org. Geochem. 40, 1161–1168.
McCarthy, J. F., and Zachara, J. M. (1989). Subsurface transport of contaminants. Environ.
Sci. Technol. 23, 496–502.
McClellan, A. T., Deenik, J., G., and Antal, M. (2007). Effects of flash carbonized macada-
mia nutshell charcoal on plant growth and soil chemical properties.American Society of
Agronomy Abstracts, 3–7 November, New Orleans, LA.
Meijer, S. N., Steinnes, E., Ockenden, W. A., and Jones, K. C. (2002). Influence of
environmental variables on the spatial distribution of PCBs in Norwegian and U.K.
soils: Implications for global cycling. Environ. Sci. Technol. 36, 2146–2153.
Mohan, D., Pittman, C. U. Jr., Brcika, M., Smith, F., Yancey, B., Mohammad, J.,
Steele, P. H., Alexandre-Franco, M. F., Gómez-Serrano, V., and Gong, H. (2007).
Sorption of arsenic, cadmium and lead by chars produced from fast pyrolysis of wood and
bark during bio-oil production. J. Colloid Interface Sci. 310, 57–73.
Montes-Morán, M. A., Suárez, D., Menéndez, J. A., and Fuente, E. (2004). On the nature
of basic sites on carbon surfaces: An overview. Carbon 42, 1219–1225.
Nam, K., and Alexander, M. (1998). Role of nanoporosity and hydrophobicity in seques-
tration and bioavailability: Tests with model solids. Environ. Sci. Technol. 32, 71–74.
Namgay, T., Singh, B., and Singh, B. P. (2010). Influence of biochar application to soil on
the availability of As, Cd, Cu, Pb, and Zn to maize (Zea mays L.). Aust. J. Soil Res. 48,
638–647.
NEPM. (1999). National Environment Protection (Assessment of Site Contamination)
Measure 1999. National Environment Protection Council, Adelaide, South Australia.
Neve, P., and Powles, S. B. (2005). Recurrent selection with reduced herbicide rates results
in the rapid evolution of herbicide resistance in Lolium rigidum. Theor. Appl. Genet. 110,
1154–1166.
Nguyen, B. T., and Lehmann, J. (2009). Black carbon decomposition under varying water
regimes. Org. Geochem. 35, 823–830.
Novak, J. M., Busscher, W. J., Laird, D. L., Ahmedna, M., Watts, D. W., and
Niandou, M. A. S. (2009). Impact of biochar amendment on fertility of a Southeastern
Coastal Plain. Soil Sci. 174, 105–112.
NRMMC. (2004). Guidelines for Sewerage Systems—Biosolids Management.National
Water Quality Management Strategy Paper No 13, National Resource Management
Ministers Council, Canberra, Australia, p. 45.
NSW EPA. (1997). Guidelines for the Use and Disposal of Biosolids Products New South
Wales Environment Protection Authority, Sydney.
NSW EPA. (1997). EPA Compost Guidelines (Public Consultation) New South Wales
Environment Protection Authority, Sydney.
Ogawa, M., Okimori, Y., and Takahashi, F. (2006). Carbon sequestration by carbonization
of biomass and forestation: Three case studies. Mitig. Adapt. Strateg. Glob. Change 11,
429–444.
140 R. S. Kookana et al.

Painter, T. J. (2001). Carbohydrate polymers in food preservation: An integrated view of the

Maillard reaction with special reference to discoveries of preserved foods in Sphagnum
dominated peat bogs. Carbohydr. Polym. 36, 335–347.
Paoletti, M. G., Sommaggio, D., Favretto, M. R., Petruzzelli, G., Pezzarossa, B., and
Barbafieri, M. (1998). Earthworms as useful bioindicators of agroecosystem sustainability
in orchards and vineyards with different inputs. Appl. Soil Ecol. 10, 137–150.
Pietikäinen, J., Kiikkilä, O., and Fritze, H. (2000). Charcoal as a habitat for microbes and its
effect on the microbial community of the underlying humus. Oikos 89, 231–242.
Pignatello, J. J., Kwon, S., and Lu, Y. F. (2006). Effect of natural organic substances on the
surface and adsorptive properties of environmental black carbon (char): attenuation of
surface activity by humic and fulvic acids. Environ. Sci. Technol. 40, 7757–7763.
Powles, S. B., Preston, C., Bryan, I. B., and Jutsum, A. R. (1996). Herbicide resistance:
Impact and Management. Adv. Agron. 58, 57–93.
Preston, C. M., and Schmidt, M. W. I. (2006). Black (pyrogenic) carbon: A synthesis of
current knowledge and uncertainties with special consideration of boreal regions. Bio-
geosciences 3, 397–420.
Rogovska, N., Laird, D., Cruse, R., and Heaton, E. (2010). Evaluation of biochar quality utilizing
standard germination test. In “Proceedings of the ASA, CSSA and SSSA 2010 International
Annual Meeting, Long Beach, CA, October 31–November 4. Presentation No. 166–4,”
http://a-c-s.confex.com/crops/2010am/webprogram/Paper57931.htmlAccessed October 5,
2010.
Rondon, M. A., Lehmann, J., Ramı́rez, J., and Hurtado, M. (2007). Biological nitrogen
fixation by common beans (Phaseolus vulgaris L.) increases with bio-char additions. Biol.
Fertil. Soils 43, 699–708.
Rose, C. W., and Dalal, R. C. (1988). Erosion and runoff of nitrogen. In “Advances in
Nitrogen Cycling in Agricultural Ecosystems” ( J. R. Wilson, Ed.). CAB International,
Wallingford.
Sarmah, A. K., Srinivasan, P., Smernik, R. J., Manley-Harris, M., Antal, M. J. Jr.,
Downie, A., and Van Zwieten, L. (2010). Retention capacity of biochar-amended
New Zealand dairy farm soil for an estrogenic steroid hormone and its primary metabo-
lite. Aust. J. Soil Res. 48, 648–658.
Scheringer, M. (2009). Long-range transport of organic chemicals in the environment.
Environ. Toxicol. Chem. 28, 677–690.
Schmidt, M. W. I., and Noack, A. G. (2000). Black carbon in soils and sediments: Analysis,
distribution, implications and current challenges. Glob. Biogeochem. Cycle 14, 777–793.
Semple, K. T., Morriss, A. W. J., and Paton, G. I. (2003). Bioavailability of hydrophobic
organic contaminants in soils: Fundamental concepts and techniques for analysis. Eur.
J. Soil Sci. 54, 809–818.
Sharpley, A. N., and Menzel, R. G. (1987). The impact of soil and fertilizer phosphorus on
the environment. Adv. Agron. 41, 297–324.
Sheng, G. Y., Yang, Y. N., Huang, M. S., and Yang, K. (2005). Influence of pH on pesticide
sorption by soil containing wheat residue-derived char. Environ. Pollut. 134, 457–463.
Sinclair, K., Slavich, P., Morris, S., Kimber, S., Downie, A., and Van Zwieten, L. (2010).
Influence of biochar on soil fertility, carbon storage and biomass in subtropical pasture:
Results from a 3 year field study. In “Proceedings of the 3rd International Biochar
Conference, Rio de Janeiro, Brazil, 12–15 September 2010,” pp. 169–170.
Singh, B., and Heffernan, S. (2002). Layer charge characteristics of smectites from Vertosols
(Vertisols) of New South Wales. Aust. J. Soil Res. 40, 1159–1170.
Singh, N., and Kookana, R. S. (2009). Organo-mineral interactions mask the true sorption
potential of biochars in soils. J. Environ. Sci. Health B 44, 214–219.
Biochar Application to Soil: Unintended Consequences 141

Singh, B. P., Hatton, B. J., Singh, B., Cowie, A. L., and Kathuria, A. (2010a). Influence of
biochars on nitrous oxide emission and nitrogen leaching from two contrasting soils.
J. Environ. Qual. 39(4), 1224–1235.
Singh, B., Singh, B. P., and Cowie, A. L. (2010b). Characterisation and evaluation of
biochars for their application as a soil amendment. Aust. J. Soil Res. 48, 516–525.
Smernik, R. J., Kookana, R. S., and Skjemstad, J. O. (2006). NMR characterization of 13C-
Benzene sorbed to natural and prepared charcoals. Environ. Sci. Technol. 40, 1764–1769.
Sohi, S. P., Krull, E., Lopez-Capel, E., and Bol, R. (2010). A review of biochar and its use
and function in soil. Adv. Agron. 105, 47–82.
Solaiman, Z. M., Blackwell, P., Abbott, L. K., and Storer, P. (2010). Direct and residual
effect of biochar application on mycorrhizal root colonisation, growth and nutrition of
wheat. Aust. J. Soil Res. 48, 546–554.
Spokas, K. A., Koskinen, W. C., Baker, J. M., and Reicosky, D. C. (2009). Impacts of
woodchip biochar additions on greenhouse gas production and sorption/degradation of
two herbicides on Minnesota soil. Chemosphere 77, 574–581.
Steinbeiss, S., Gleixner, G., and Antonietti, M. (2009). Effect of biochar amendment on soil
carbon balance and soil microbial activity. Soil Biol. Biochem. 41, 1301–1310.
Steiner, C., Teixeira, W. G., Lehmann, J., Nehls, T., de Macedo, J. L. V., Blum, W. E. H.,
and Zech, W. (2007). Long term effects of manure, charcoal and mineral fertilization on
crop production and fertility on a highly weathered Central Amazonian upland soil. Plant
Soil 291, 275–290.
Steiner, C., Das, K. C., Garcia, M., Forster, B., and Zech, W. (2008). Charcoal and smoke
extract stimulate the soil microbial community in a highly weathered xanthic Ferralsol.
Pedobiologia 51, 359–366.
Sweetman, A. J., Valle, M. D., Prevedouros, K., and Jones, K. C. (2005). The role of soil
organic carbon in the global cycling of persistent organic pollutants (POPs): Interpreting
and modelling field data. Chemosphere 60, 959–972.
Thies, E., and Rilling, M. C. (2009). Characteristics of biochar: Biological properties.
In “Biochar for Environmental Management. Science and Technology” ( J. Lehmann
and S. Joseph, Eds.), Earthscan, London.
Topoliantz, S., and Ponge, J. F. (2005). Charcoal consumption and casting activity by
Pontoscolex corethrurus (Glossoscolecidae). Appl. Soil Ecol. 28, 217–224.
Toth, J., and Milham, P. J. (1975). Activated-carbon and ash-carbon effects on the adsorp-
tion and phytotoxicity of diuron. Weed Res. 15, 171–176.
Toth, J., Milham, P. J., and Raison, J. M. (1981). Ash from rice stubble inactivates
thiobencarb and molinate. Weed Res. 21, 113–117.
Toth, J., Milham, P. J., and Kaldor, C. J. (1999). Decreased phytotoxicity of diuron applied
over ash of recently burned kangaroo grass (Themeda australis (R.Br.) Stapf). Plant Prot.
Quart. 14, 151–154.
Treseder, K. K. (1998). A meta-analysis of mycorrhizal responses to nitrogen, phosphorus,
and atmospheric CO2 in field studies. Commun. Soil Sci. Plant Anal. 29, 1779–1784.
Uchimiya, M., Lima, I. M., Klasson, K. T., and Wartelle, L. H. (2010a). Contaminant
immobilization and nutrient release by biochar soil amendment: Roles of natural organic
matter. Chemosphere 80, 935–940.
Uchimiya, M., Lima, I. M., Klasson, K. T., Chang, S., Wartelle, L. H., and Rodgers, J. E.
(2010b). Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler
litter-derived biochars in water and soil. J. Agric. Food Chem. 58, 5538–5544.
Van Noort, P. C. M., Cornelissen, G., ten Hulscher, T. E. M., Vrind, B. A., Rigterink, H.,
and Belfroid, A. C. (2003). Slow and very slow desorption of organic compounds from
sediment: Influence of sorbate planarity. Water Res. 37, 317–2322.
142 R. S. Kookana et al.

Van Zwieten, L., Rust, J., Kingston, T., Merrington, G., and Morris, S. (2004). Influence of
copper fungicide residues on occurrence of earthworms in avocado orchard soils. Sci.
Total Environ. 329, 29–41.
Van Zwieten, L., Singh, B. P., Joseph, S., Kimber, S., Cowie, A., and Chan, K. Y. (2009).
Biochar reduces emissions of non-CO2 GHG from soil. In “Biochar for Environmental
Management” (J. Lehmann and S. Joseph, Eds.), Earthscan, London.
Van Zwieten, L., Kimber, S., Morris, S., Chan, Y. K., Downie, A., Rust, J., Joseph, S., and
Cowie, A. (2010a). Effects of biochar from slow pyrolysis of papermill waste on agro-
nomic performance and soil fertility. Plant Soil 327, 235–246.
Van Zwieten, L., Kimber, S., Morris, S., Downie, A., Berger, E., Rust, J., and Scheer, C.
(2010b). Influence of biochars on flux of N2O and CO2 from Ferrosol. Aust. J. Soil Res.
48, 555–568.
Van Zwieten, L., Kimber, S., Downie, A., Morris, S., Rust, J., and Chan, K. Y. (2010c). A
glasshouse study on the interaction of low mineral ash biochar with nitrogen in a sandy
soil. Aust. J. Soil Res. 48, 569–576.
Vassilev, S. V., and Braekman-Danheux, C. (1999). Characterization of refuse-derived char
from municipal solid waste. 2. Occurrence, abundance and source of trace elements. Fuel
Process. Technol. 59, 135–161.
Verheijen, F., Jeffery, S., Bastos, A. C., van der Velde, M., and Diafas, F. (2010). Biochar
application to soils. A critical scientific review of effects on soil properties, processes, and
functions.EUR 24099 EN Office for the Official Publications of the European Com-
munities, Luxembourgp. 149.
Wania, F. (2006). Potential of degradable organic chemicals for absolute and relative
enrichment in the Arctic. Environ. Sci. Technol. 40, 569–577.
Warnock, D. D., Lehmann, J., Kuyper, T. W., and Rillig, M. C. (2007). Mycorrhizal
responses to biochar in soil—Concepts and mechanisms. Plant Soil 300, 9–20.
Weber, W. J. Jr., Mcglnley, P. M., and Katz, L. E. (1992). A distributed reactivity model for
sorption by soils and sediments. 1. Conceptual basis and equilibrium assessment. Environ.
Sci. Technol. 26, 1955–1962.
Wen, B., Li, R. J., Zhang, S., Shan, X. Q., Fang, J., Xiao, K., and Khan, S. U. (2009).
Immobilization of pentachlorophenol in soil using carbonaceous material amendments.
Environ. Pollut. 157, 968–974.
Weyers, S. L., Gaskin, J., Liesch, A. M., and Das, K. C. (2010). Earthworms, microbes and
the release of c and n in biochar amended soil. In “Proceedings of the 2010 U.S. Biochar
Initiative Conference, June 27–30, 2010, Ames, Iowa” .
Winsley, P. (2007). Biochar and bioenergy production for climate change mitigation. N. Z.
Sci. Rev. 64, 5–10.
Woolf, D., Amonette, J. E., Street-Perrott, F. A., Lehmann, J., and Joseph, S. (2010).
Sustainable biochar to mitigate global climate change. Nat. Commun. 1(56), 1–9.
Xu, C., Liu, W., and Sheng, G. D. (2008). Burned rice straw reduces the availability of
clomazone to barnyardgrass. Sci. Total Environ. 392, 284–289.
Yamamoto, M., Okimori, Y., Wibowo, I. F., Anshori, S., and Ogawa, M. (2006). Effects of
the application of charred bark of Acacia mangium on the yield of maize, cowpea and
peanut, and soil chemical properties in South Sumatra, Indonesia. Soil Sci. Plant Nutr. 52,
489–495.
Yanai, Y., Toyota, K., and Okazaki, M. (2007). Effects of charcoal addition on N2O
emissions from soil resulting from rewetting air-dried soil in short-term laboratory
experiments. Soil Sci. Plant Nutr. 53, 181–188.
Yang, Y. N., and Sheng, G. Y. (2003). Enhanced pesticide sorption by soils containing
particulate matter from crop residue burns. Environ. Sci. Technol. 37, 3635–3639.
Yang, Y. N., Sheng, G. Y., and Huang, M. (2006). Bioavailability of diuron in soil
containing wheat- straw-derived char. Sci. Total Environ. 354, 170–178.
Biochar Application to Soil: Unintended Consequences 143

Yao, F. X., Arbestain, M. C., Virgel, S., Blanco, F., Arostegui, J., Macia-Agullo, J. A., and
Macias, F. (2009). Simulated geochemical weathering of a mineral ash-rich biochar in a
modified Soxhlet reactor. Chemosphere 80, 724–732.
Yeardley, R. B., Lazorchak, J. M., and Gast, L. C. (1996). The potential of an earthworm
avoidance test for evaluation of hazardous waste sites. Environ. Toxicol. Chem. 15, 1532–
1537.
Yoshida, T., and Antal, M. J. Jr. (2009). Sewage sludge carbonization for terra preta
applications. Energy Fuels 23, 5454–5459.
Yu, X. Y., Ying, G. G., and Kookana, R. S. (2006). Sorption and desorption behaviors of
diuron in soils amended with charcoal. J. Agric. Food Chem. 54, 8545–8550.
Yu, X. Y., Ying, G. G., and Kookana, R. S. (2009). Reduced plant uptake of pesticides with
biochar additions to soil. Chemosphere 76, 665–671.
Yu, X. Y., Pan, L. G., Ying, G. G., and Kookana, R. S. (2010). Enhanced and irreversible
sorption of pesticide pyrimethanil by soil amended with biochars. J. Environ. Sci. 22, 615–620.
Zhang, P., Sheng, G., Wolf, D. C., and Feng, Y. (2004). Reduced biodegradation of
benzonitrile in soil containing wheat residue-derived ash. J. Environ. Qual. 33, 868–872.
Zhang, P., Sheng, G. G., Feng, Y., and Miller, D. M. (2005). Role of wheat-residue-derived
char in the biodegradation of benzonitrile in soil: Nutritional stimulation versus adsorp-
tive inhibition. Environ. Sci. Technol. 39, 5442–5448.
Zheng, W., Guo, M., Chow, T., Bennett, D. N., and Rajagopalan, N. (2010). Sorption
properties of greenwaste biochar for two triazine pesticides. J. Hazard. Mater. 181, 121–126.