Physical Activation of Biochar and Its Meaning For Soilfertility and Nutrient Leaching

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SoilUse

and Management
Soil Use and Management, June 2012, 28, 177–184 doi: 10.1111/j.1475-2743.2012.00407.x

Physical activation of biochar and its meaning for soil


fertility and nutrient leaching – a greenhouse experiment

N. Borchard1*, A. Wolf1, V. Laabs1 , R. Aeckersberg2, H. W. Scherer3, A. Moeller4 & W. Amelung1


1
Institute of Crop Science and Resource Conservation, Soil Science and Soil Ecology, University of Bonn, Nussallee 13, Bonn
53115, Germany, 2Formerly Coking, Briquetting and Thermal Waste Treatment Group, RWTH Aachen University, Wüllnerstrasse
2, Aachen 52062, Germany, 3Institute of Crop Science and Resource Conservation, Plant Nutrition, University of Bonn, Karlrobert-
Kreiten-Strasse 13, Bonn 53115, Germany, and 4Department of Groundwater and Soil Science, Federal Institute for Geo-Science
and Natural Resources, Stilleweg 2, Hannover 30655, Germany

Abstract
The slow alteration of the surface of charred biomass (biochar) over time may contribute to an
improved nutrient retention and thus fertility of tropical soils. Here, we investigated soils from
temperate climates and investigated whether a technical steam activation of biochar could accelerate its
positive effects on nutrient retention and uptake by plants relative to nonactivated biochar. To this
aim, we performed microcosm experiments with sandy or silty soil, mixed with 2.0, 7.5 and 15.0 g ⁄ kg
soil of fine (<2 mm) or coarse-sized (2–10 mm) biochar from beech wood (Fagus sp.). After initial
fertilizer (NPK), ashes and excess nutrients were leached with water, and the microcosms were planted
for 142 days with Italian Ryegrass (Lolium multiflorum ssp. italicum). Thereafter, leachate, soil and
plant samples were analysed for their nutrient contents. The results showed that biochar additions of
£15 g ⁄ kg soil left elevated contents of available P and N in the surface soil but reduced their uptake
into the plants. As a result, total biomass production was unchanged. Different particle size and
application amounts influenced these findings only marginally. Nitrate leaching was enhanced in the
sandy soil (+41% for nitrate, but reduced in the silty soil )17%) and P was immobilized. Hence, the
fertility of the temperate soils under study was only marginally affected by pure biochar amendments.
Steam activation, however, almost doubled the positive effects of biochars in all instances, thus being
an interesting option for future biochar applications.

Keywords: Biochar, steam activation, nutrient retention, soil fertility

enhance cation exchange capacity (CEC), nutrient retention


Introduction
and aggregation (Liang et al., 2006; Brodowski et al., 2007;
Biochar (charred biomass) is increasingly discussed as a Steiner et al., 2007). Consequently, it could be more efficient
means to improve soil fertility and contribute to C for the amelioration of soils, if the biochar surfaces are
sequestration (e.g. Sohi et al., 2010; Jeffery et al., 2011). already hydrophilic prior to the adding of biochar to soil.
When applying fresh biochar (plus mineral fertilizers) to This aim, however, cannot be reasonably achieved using
strongly weathered tropical soils, their fertility was improved chemical activation of biochar surfaces, because an exposure
significantly (e.g. Glaser et al., 2002; Steiner et al., 2007), to other chemicals may generate hazardous, unwanted by-
while similar test have rarely been performed for soils of products (Zhang et al., 2004). Such risks are avoided in
temperate climate (Atkinson et al., 2010). It is, however, not physical activation procedures (e.g. Park et al., 2003).
the mere presence of biochar in soils that is needed to Activated carbonaceous materials are widely used for water
enhance its fertility. Predominantly hydrophobic biochar purification, environmental remediation (e.g. Libra et al.,
(Glaser et al., 2002) in soil may be prone to slow surface 2011) and as tissue culture media (Yam et al., 1990). During
alteration, thereby forming hydrophilic surfaces, which activation, the surface area and pore size increases so that the
activated biochars promote the adsorption of nutrients
Correspondence: N. Borchard. E-mail: n.borchard@fz-juelich.de
(Radovic et al., 2001) and possibly also in soils.
Received June 2011; accepted after revision March 2012
*Present address: Forschungszentrum Jülich GmbH, Agrosphere The aim of this study was twofold: (i) First, we wanted to
Institute, 52425 Jülich, Germany. elucidate to which degree the application of biochars may
 
Present address: Gayerstrasse 26, 67346 Speyer, Germany. help to improve nutrient retention (N, P) and biomass

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science 177
178 N. Borchard et al.

production (ryegrass) of temperate soils (neutral sand and

(m2 ⁄ g)
SBET

CEC, potential cation exchange capacity at pH 8.1; PCAL, plant-available P extracted with CAL-method; SBET, surface area; calculation with BET isotherm. aAfter washing with 0.01 m
108
463

466
51
slightly alkaline silt). (ii) Second, we wanted to investigate
whether the positive effects of biochar can be enhanced by

pHCaCl2
steam activation. We tested these questions in a microcosm

(HCla)

6.96
7.10
6.85
6.91
experiment using two soils of different texture and different
amount and size of biochar particles (nonactivated biochar

pHCaCl2
and its steam activated form). The pots were leached

8.00
8.68
8.10
8.58
extensively after initial fertilizer application but prior to
planting of Lolium multiflorum ssp. italicum in order to

(mg ⁄ kg)
minimize the nutrient effects of ashes that are usually

PCAL

2.65

1.49
0.31
n.d.
contained in the biochar particles.

(mg ⁄ kg)
NO3-N
Material and methods

2.09
1.05
1.56
0.64
Materials

CEC (HCla)
(cmolc ⁄ kg)
Soil samples were taken from two different soil types in

0.22
0.43
2.75
4.68
Germany, a Haplic Luvisol (silty texture) and sandy textured
Haplic Fluvisol near Bonn. To simulate worst-case soils in
need for amelioration, samples from the topsoil and subsoil

Table 1 Chemical properties and specific surface area of biochar produced from beech wood (475 C, 13–18 h charring)

(cmolc ⁄ kg)
were pooled to adjust for low SOC contents of 7.0 g SOC ⁄ kg

CEC

2.40
6.07
4.53
8.61
(silty soil) and of 3.5 g SOC ⁄ kg (sandy soil). The initial
amounts of nutrients then averaged 25.1 mg NO3-N ⁄ kg,
34.1 mg P ⁄ kg, 44.9 mg K ⁄ kg and 81.5 mg Mg ⁄ kg in the silty

Ash content
soil, and 28.8 mg NO3-N ⁄ kg, 76.3 mg P ⁄ kg, 73.0 mg K ⁄ kg

(mg ⁄ g)

14.5
21.0
14.2
15.7
and 12.2 mg Mg ⁄ kg in the sandy soil. The potential cation
exchange capacity (CECpot) at the start of the experiment was
14.1 cmolc ⁄ kg for the silty and 4.3 cmolc ⁄ kg for the sandy soil,
the pH values (0.01 m CaCl2) were 7.4 and 6.7, respectively.
0.071
0.007
0.065
0.005
O⁄C
Atomic

We used commercial charcoal (biochar) and its steam


ratio

activated form as soil amendment (for selected biochar


H⁄C

0.47
0.18
0.46
0.18
properties, see Table 1). The commercial biochar (proFagus
GmbH, Bodenfelde, Germany) had been produced from 90%
O (mg ⁄ g)

beech (Fagus sp.) and 10% oak (Quercus sp.) wood at 475 C
HCl. bParticle size <2 mm. cParticle size 2–10 mm. n.d., not detectable.
84.1

77.0
9.7

6.0

(±25 C) in the Degussa (Reichert) process (Antal & Grønli,


2003). Depending on initial wood wetness, the feedstock had
been carbonized slowly over a period of 13–18 h in a retort.
N (mg ⁄ g)

14.8
13.6
12.3
7.9

The production quality standards guarantee high content of


fixed C (>83 wt-%), a content of volatile organic matter
(<20 wt-%) and ash (<2 wt-%). The biochar activation was
H (mg ⁄ g)

carried out subsequently at 900 C over a period of 30 min in


34.8
15.0
34.2
15.2

a batch-wise process (Jenkner retort). During this period, hot


water steam was periodically blown into the activation
chamber (heated to 1000 C) for 30 s ⁄ min (Kim & Hong,
C (mg ⁄ g)

1998). We used ambient air (N2 ⁄ O2 gas mixture) and not an


888
975
890
981

inert gas during activation process to ensure surface


oxidation (Shen et al., 2008).
Coarsec and nonactivated
Fineb and nonactivated

Coarse and activated

Pot experiment
Fine and activated

To each soil type, we added one type of biochar in activated


and nonactivated form at a rate of 0, 2.0, 7.5 or 15.0 g ⁄ kg
Sample

soil (for activated biochar only 0, 2.0 and 7.5 g ⁄ kg soil). Each
application was conducted with particle sizes of <2 or

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
Physical activation of biochar 179

2–10 mm. Each treatment was performed in quadruplicate. The dried biochar and soil samples (35 C) were then
To avoid nutrient limitations for grass growth, the soils were characterized by the measurement of pH (0.01 m CaCl2) and
fertilized with Ca(H2PO4)2*H2O, NH4NO3 and K2SO4 potential cation exchange capacity (CEC), using a modified
at rates corresponding to 18 mg P ⁄ kg, 190 mg N ⁄ kg and Mehlich-250 method (Schlichting et al., 1995). The amounts
178 mg K ⁄ kg in the sandy soil, and to 29 mg P ⁄ kg, of plant-available P were extracted by the CAL-method
190 mg N ⁄ kg, and 180 mg K ⁄ kg in the silty soil, according (0.05 m Ca-lactate, 0.05 m Ca-acetate, acetic acid, pH 4.1,
to good agricultural practice. In total, 72 Kick-Brauckmann 1:20 w ⁄ v) and quantified photometrically using the
pots were filled with 8 kg of soil mixtures each and installed molybdenum blue method (Schlichting et al., 1995) and a
in a greenhouse. Specord 205 photometer (Analytik Jena AG, Germany) at
Prior to the start of experiment, the water content was 578 nm. The contents of plant-available NO3-N were
adjusted to 60% of the maximum water-holding capacity estimated after extraction with 0.01 m CaCl2 (1:10 w ⁄ v),
(WHC) and the soils were equilibrated for 5 days. (Soper & Huang, 1963) centrifugation of extracts for 10 min
Afterwards, soils were saturated bottom up with water and at 266 g (Heraeus Multifuge 3SR; Thermo Fisher Scientific
leaching of ashes and excess nutrients was induced by Inc., USA), filtration (paper filter 589 ⁄ 2; Schleicher &
percolating 1 L tap water each day for seven consecutive Schuell, Germany) and quantification with a Specord 205
days. At each of these 7 days, three 100 mL aliquots of the photometer (Analytik Jena AG) at 210 nm. Ammonium
percolated water were filled into PET-flasks, preserved with analyses are not reliable after sample drying and were not
chloroform and stored at 4 C for £7 days until chemical performed. The maximal WHC was calculated as difference
analyses. from wet weight (water saturation for about 30 min and with
After a further 5 days of letting soils dry to 60% subsequent drainage for about 2 h) and dry weight. The
WHC, 0.55 g Ryegrass (L. multiflorum ssp. italicum) seeds contents of total C and N in soil and biomass were measured
(corresponding to ca. 230 seeds per pot) were sown. The after dry combustion using a C ⁄ N analyzer (NA 2000; Fisons
WHC was kept constant through daily gravimetric control of Instruments, UK).
the zero biochar treatment pots as a reference and rewetting Contents of P in biomass were analysed after incineration
with 200–700 mL of deionized water per day. Ryegrass was (at 550 C for about 4 h) and dissolution of the ash in hot
harvested 23, 37, 71 and 125 days after sowing (at growth 5.0 m HCl. It was measured with inductively coupled plasma
heights of about 30 cm), dried at 60 C and ground prior to optical emission spectrometry (Jobin Yvon 70 Plus
analyses. spectrometer; Horiba Jobin Yvon Inc., USA).
At day 142 [5 (equilibration) + 7 (leaching experiment)
+ 5 (drying) + 125 (incubation experiment) days], the
Statistical analysis
experiment was stopped and composite soil samples were
taken at five positions from each pot with a stainless steel To evaluate whether biochar type, size or amount changed
auger (Ø 1.5 cm), dried at 40 C and passed through a sieve leaching, soil and biomass properties multiple group
(<2 mm); coarse biochar particles were softly passed through comparisons were carried out using Kruskal–Wallis H-test.
the sieve. Comparisons between nonactivated and activated biochar
were performed using Mann–Whitney U-test. Nonparametric
methods were chosen instead of analysis of variance because
Analyses of biochar, soil and plant material
data distribution was non-normal and ⁄ or variances of groups
Biochar samples were analysed using the BET method for its were not homogenous, tested by Shapiro–Wilks test and
specific surface area with nitrogen sorption at )196 C Levene’s test. Statistical analysis was performed using
(ASAP 2010-Accelerated Surface Area and Porosimetry Statistica 8 for Windows.
System; Micromeritics Instrument Corporation, USA). Prior
to the measurements, the samples were degassed at 35 C in
Results and discussion
high vacuum. The element contents of C, H and N were
measured from carbonate-free biochar with a CHN-2000- Characterization
Analyzer (LECO Corporation, USA) and S was measured
The element contents of the activated and nonactivated
using a SC-144DR-Analyzer (LECO Corporation). The
materials are comparable with biochars produced at similar
O-content (dry ash-free weight; daf) was calculated
temperatures (Table 1; Keiluweit et al., 2010). Yet, steam
accordingly: O [% daf] = 100 ) C [% daf] ) H [% daf] ) N
activation increased the C-content of the biochar by about
[% daf]. The ash contents were analysed by incineration at
10% (w ⁄ w) and reduced its H and O contents by 55 and 90%
815 C until weight stability. Carbonates were removed with
(w ⁄ w), respectively, relative to nonactivated biochar. This
0.01 m HCl and excess chlorine was washed out with 500 mL
result has been somewhat surprising, as a higher degree of
Millipore water.
oxidations (and thus O-content) was expected to result from

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
180 N. Borchard et al.

the hot steam activation of biochar surfaces (Shen et al., >150 g biochar ⁄ kg soil, smaller biochar particle sizes than
2008). Seemingly, the main effect of the activation process those taken by Karhu et al. (2011) <10 mm, and biochars
was the removal of low-volatile tar constituents, which with lower contents of ashes, which may potentially rise
showed a higher O-content than the solid biochar matrix, WHC (Stoof et al., 2010), than those used by Libra et al.
thereby lowering the overall O-content of the remaining (2011) and Brockhoff et al. (2010). With unchanged WHC,
biochar. There was no difference in element contents between we assume that water fluxes were unaffected by biochar
the coarse and fine materials after activation, as reported for additions during the experiments. Some soil chemical
charred material from high-temperature pyrolysis (Demirbas, properties, however, were altered significantly. There was an
2002). elevated pH of the biochar-amended soils (Table 2), because
The pH values of both biochars were higher than 8.0 of the alkaline effect of the added ash (Rondon et al., 2007).
(Table 1), indicating remaining alkaline, carbonate containing Intriguingly, also total N contents were elevated in the
ash, with quite common contents ranging between 14 and biochar-soils (Table 3), probably due to added biochar-N
21 mg ⁄ g biochar. The contents of available NO3-N and P (Table 1) or caused by a positive feedback loop: that is,
were low in the used biochar variants (Table 1), which is in elevated nutrient contents enabled plants to provide microbes
accordance with nutrient contents of biochars reviewed by with carbohydrates in exchange for nutrients (Chapin et al.,
Chan & Xu (2009). A process-specific variability of nutrient 2011). Such nutrient allocation may in principle comprise
contents in biochars is mostly influenced by the type of both labile and stable nutrient forms (Atkinson et al., 2010;
feedstock and pyrolysis conditions (Joseph et al., 2010). The Chapin et al., 2011).
activation of biochar reduced contents of available NO3-N The contents of available soil nitrate and P tended to be
and P on average by 55 and 90% (w ⁄ w) (Table 1). The loss elevated relative to the control (Table 2). However, increasing
of available nitrogen is likely to have resulted from the escape amounts of biochar did not affect contents of available NO3-
of volatile nitrogen-containing compounds during biochar N and P in soils (Table 2). For nitrate, the finding is
activation at 1000 C (Leppälahti & Koljonen, 1995; Zhou consistent with Rondon et al. (2007), who investigated
et al., 2000) and from net transfer of labile nitrogen into biochar additions even at rates up to 90 g ⁄ kg soil for 80 days.
heterocyclic N forms (Knicker et al., 1996). Martin et al. For P, biochar effects appear to be less consistent with earlier
(1999) described that P was retained in the gasification system reports: Chan et al. (2007) did not find any effects on
completely, but that available P decreased strongly. available P contents (6 g biochar ⁄ kg soil; 42 days of
After activation, there was an average 6.7-fold increase in incubation), they were only elevated after addition of 35 and
the specific surface area (SBET) and an average 2.2-fold rise in 60 g biochar ⁄ kg (corresponding to an application rate of ca.
CEC (Table 1), which is in line with Zhang et al. (2004) and 50 and 100 t ⁄ ha, respectively). Novak et al. (2009) found
Singh et al. (2010). With the gain of SBET, the physical basis elevated contents of extractable P even at biochar additions
for CEC increased (Sohi et al., 2010). Arriagada et al. (1994) £15.0 g ⁄ kg soil to acidic, sandy soils (67 days of incubation),
found that steam activation removes highly acidic functional while Rondon et al. (2007) observed reduced contents of
groups (e.g. carboxylic, lactonic) and enlarges weakly acidic extractable P. In any case, our data confirmed that in arable
groups (e.g. phenolic). Hence, the rise in CEC was less soils from temperate zone neither the concentration of nitrate
pronounced than indicated by the gain in SBET. nor those of inorganic P were significantly affected by
biochar additions (Jones et al., 2012).
Intriguingly, the N uptake into plant biomass was reduced
Effects of biochar amendments on soil properties and
by up to 24% (w ⁄ w), particularly at the highest biochar
biomass yield
application rate of 15.0 g ⁄ kg soil (Table 2). As the biochars
During our study, the CEC of the soils did not change after exhibits a wide C ⁄ N ratio, the addition of 15.0 g biochar ⁄ kg
application of £15 g biochar ⁄ kg soil (Table 2). It is likely that soil increased the soil C ⁄ N ratio from 11.4 up to 29.2
the addition of CEC with the biochars was not strong enough (Table 2). This value exceeds favourable C ⁄ N ratios of <25,
to be detectable in the complete soil matrix. Also no effects above which soil microbes are increasingly forced to
on CEC were observed by Steiner et al. (2007), Novak et al. immobilize plant-available nitrogen to meet their own N
(2009) and van Zwieten et al. (2010) after addition of even up demand (Chapin et al., 2011). As a result, the N uptake of
to 150 g biochar ⁄ kg soil. These results do not comply with the plants was reduced, resulting in lower N contents at
Tryon (1948), who reported an elevated CEC after addition similar amounts of total dry mass (Table 2). If the rise in soil
of >150 g hardwood biochar ⁄ kg soil, which, however, is far C ⁄ N ratio was lower than 21, however, no reduced uptake of
above realistic application scenarios for larger areas. N was found (Table 2). Plant uptake of P did not change
In contrast to earlier studies, the WHC did not change significantly, as also reported for the first vegetation season
after biochar application in our soils. However, we have to by Major et al. (2010).
consider that we used much lower biochar application rates The influence of biochar particle size on nutrient contents
than Tryon’s (1948) and Kishimoto & Sugiura’s (1985) in soil and biomass was relatively small. The uptake rates of

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
Table 2 Nutrient leaching at beginning of microcosm (pot) experiment, soil nutrient stocks after 142 days of experimental time, and nutrient contents in biomass and harvested dry
mass (average for silty and sandy soil, standard deviation in parenthesis)

Dry mass and nutrient


Nutrient leaching Soil nutrient concentrations after 142 days stocks in biomassa

Available nutrients

NO3-N NO3-N CEC WHC%


(mg ⁄ kgb) P (mg ⁄ kgb) pHc (mg ⁄ kg) P (mg ⁄ kg) (cmolc ⁄ kg) (w ⁄ w) C⁄N Ntot (mg ⁄ kg) DM (g) Ntot (mgd) Ptot (mgd)

C 60 ± 42 2.7 ± 2.9 6.17 ± 0.12 0.8 ± 0.6 62 ± 12 7.1 ± 4.8 32.0 ± 9.6 11.4 ± 1.5 489 ± 210 3.4 ± 1.0 514 ± 102 2.9 ± 0.7
BCN 56 ± 26 2.1 ± 2.2 6.31 ± 0.12** 2.0 ± 2.2 66 ± 13 7.4 ± 4.9 30.8 ± 8.7 21.0 ± 8.5*** 526 ± 206 3.1 ± 0.6 390 ± 62* 3.0 ± 0.3
BCA 53 ± 17 1.8 ± 1.9 6.33 ± 0.13** 3.0 ± 3.0 66 ± 11 7.7 ± 4.7 28.9 ± 9.7 17.0 ± 6.4** 536 ± 192 3.8 ± 1.1 502 ± 57 2.9 ± 1.1
BCF 57 ± 25 2.0 ± 2.0 6.36 ± 0.12*** 2.8 ± 2.9 66 ± 13 7.7 ± 4.9 30.1 ± 8.7 22.2 ± 8.7*** 538 ± 192 3.5 ± 1.0 454 ± 51 3.1 ± 0.9
BCC 52 ± 20 2.0 ± 2.1 6.28 ± 0.12 2.0 ± 2.2 66 ± 11 7.3 ± 4.7 30.0 ± 9.6 16.5 ± 6.0** 521 ± 209 3.4 ± 0.9 440 ± 106 2.9 ± 0.7
BC2 54 ± 24 2.1 ± 2.1 6.26 ± 0.12 2.1 ± 2.3 66 ± 11 7.6 ± 4.8 28.4 ± 8.5 13.5 ± 2.5 524 ± 198 ND ND ND
BC7.5 54 ± 22 1.9 ± 2.0 6.35 ± 0.12** 2.5 ± 2.9 65 ± 13 7.2 ± 4.7 30.9 ± 9.3 20.3 ± 6.1*** 533 ± 204 3.8 ± 1.1 502 ± 57 2.9 ± 1.1
BC15 57 ± 25 2.0 ± 2.1 6.37 ± 0.11** 2.6 ± 2.7 68 ± 12 7.3 ± 5.1 31.6 ± 10.9 29.2 ± 8.0*** 534 ± 208 3.1 ± 0.6 391 ± 62* 3.0 ± 0.3
BC 55 ± 25 2.1 ± 2.1 6.31 ± 0.13** 2.2 ± 2.5 66 ± 12 7.5 ± 4.8 30.2 ± 8.8 18.6 ± 7.9** 526 ± 200 3.5 ± 1.0 460 ± 88 3.0 ± 0.8

CEC, Potential cation exchange capacity at pH 8.1; WHC, Water-holding capacity; DM, Dry mass; C, Control with no biochar amendment; BCN, Treatment with nonactivated
biochar; BCA, Treatment with activated biochar; BCF, Treatment with biochar – particle size smaller than 2 mm; BCC, Treatment with biochar – particle size from 2 to 10 mm; BC2,
Treatment with 2 g biochar ⁄ kg; BC7.5, Treatment with 7.5 g biochar ⁄ kg; BC15, Treatment with 15 g biochar ⁄ kg; BC, All treatments; ND, not determined. Data are means and standard
deviations. a2nd harvest; bCalculated as nutrient loss per kg soil; cSignificance calculated with de-logarithmized pH values; dCalculated as nutrient contents in biomass (mg ⁄ kg) per kg
soil; Significance at the *P < 0.05, **P < 0.01 and ***P < 0.001 level (Kruskal–Wallis H-test).
Physical activation of biochar 181

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
182 N. Borchard et al.

Table 3 Biochar affected P and NO3-N leaching, soil contents of P, NO3-N and total N and uptake of P and N through plants

Nutrient stocks
Nutrient leaching Soil nutrient content after 142 days in biomass

Treatment P (mg ⁄ kga) NO3-N (mg ⁄ kga) P (mg ⁄ kg) NO3-N (mg ⁄ kg) Nt (mg ⁄ kg) P (mgb) N (mgb)

Sandy soil
Control 5.3a 23a 72a 0.23a 293a 2.3a 595a
Nonactivated biochar 4.2ab 32ab 78b 0.30a 324ab 2.8a 397b
Activated biochar 3.6b 38b 75ab 0.41a 348b 1.9a 532a
Silty soil
Control 0.03a 97a 52a 1.35a 685a 3.6a 432a
Nonactivated biochar 0.02a 81a 54a 3.64a 728b 3.2a 386a
Activated biochar 0.02a 67b 56a 5.54b 724b 4.0a 472a
a
Calculated as nutrient loss per kg soil; bCalculated as nutrient contents in biomass (mg ⁄ kg) per kg soil; homogenous groups are indicated with
same letter (P < 0.05; Kruskal–Wallis H-test).

N and P from the coarse-sized biochar were not significantly pots with activated biochar after an experimental time of
different from the fine particle amendments (Table 2). 142 days compared to pots with nonactivated biochar
So far, all described effects of biochar on soil fertility and (Table 2). This finding confirms results of van Zwieten et al.
nutrient acquisition were relatively consistent for both soil (2010), who reported that nitrate may be produced after
textures. The picture changes if leaching of nutrients is adding low-mineral ash biochars to an acidic sandy soil.
considered prior to the ryegrass pot experiment: In the silty However, NH4-N contents remained unchanged. Probably,
soil, the biochar additions tended to reduce the nitrate changed soil pH conditions mediated nitrification (Barnard
content in soil leachates, despite higher contents of total N et al., 2005), which has an optimum at moderate pH values
and, in tendency, also of nitrate, in the bulk soil (Table 3; (Table 2). Furthermore, the higher CEC of activated biochars
Figure 1). In the sandy soil with larger pore volume and thus may promote retention of ammonium (e.g. Ding et al., 2010),
likely faster water flux, the amount of biochar applied failed which later can be nitrified (Atkinson et al., 2010). Also the
to retain nitrate; and significantly elevated nitrate contents lower C ⁄ N ratio of the activated biochar may result in lower
were found in the leachate water (Table 3; Figure 1). nitrate immobilization by soil microbes (Table 2).
Compared with coarser biochar particles, leaching of NO3-N Notably, only in silty textured soil, the NO3-N was
was elevated by finer particles (Table 2), which may retained and available NO3-N was significantly enriched after
additionally clog pores. For soil phosphates, the low addition of the activated biochar (Table 3), possibly because
additions of biochar (£15 g ⁄ kg soil) were sufficient to retain P the rates of ammonium adsorption or nitrate diffusion into
significantly in sandy soil, but not in silty soil (Table 3). the biochar particles was not fast enough to compensate for
Yet, no significant effect on plant yields were observed, rapid nitrate leaching in the sandy soil. Also uptakes of N
thus contrasting with results reported for some coarse and P by plants grown on the silty soil were promoted by the
textured tropical soils (Jeffery et al., 2011). It should be noted activation of biochar, whereas the effect of nonactivated
that in our study biochar-inherent ashes were removed prior biochar had been negative (Figure 1). Rapid nitrate losses
to the start of plant growth, which in field studies may act as from the sandy soils likely prevented an efficient N use by the
short-term fertilizers. However, Jones et al. (2012) did also plants compared with the silty soil. Furthermore, the
not find increased biomass yields for a temperate soil after activation processes reduced the risk of microbial N
application of nonwashed biochar. immobilization due of lower C ⁄ N ratios.
Overall, the activation of the biochar reduced the
concentrations of NO3-N in the leachate by 5% (w ⁄ w) and
Effects of biochar activation
that of P by 14% (w ⁄ w) compared with nonactivated biochar
Limited effects on soil fertility and leaching prevention lead treatments (Table 2). The activation of biochar doubled the
to question whether more positive effects can be achieved retention of NO3-N in silty soil and in the sandy soil P
when the biochar is activated. Here, we used a hot steam retention was 55% (w ⁄ w) higher than in the pots with
activation of the biochar. Indeed, almost all biochar effects nonactivated biochar (Figure 1). Yet, in the sandy soil, even
could be enhanced by its activation, such as nutrient the elevated SBET in the activated biochar treatment did not
retention, availability and plant uptake (Table 3, Figure 1): prevent the soils from losing more N with the leachate water
The contents of available NO3-N increased by 50% (w ⁄ w) in than the control. Possibly, this N was simply washed out too

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
Physical activation of biochar 183

Phosphorus Nitrogen also of N. However, because of the observed variability, this


500 b finding should be further investigated using more extensive
testing schemes. The hot steam activation of biochar enhanced
400 the positive effects of biochar on nutrient availability,
a
Silty soil

300 retention and plant uptake by up to a factor of 2, though


Biochar induced changes in N and P [% of control]

also failed to reduce nitrate leaching from the sandy soil.


200
Further improving biochar properties through physical
b (steam) activation may thus be a potential option for its
0 combined use as soil amendment and for environmental
protection purposes (e.g. prevention of water pollution with
a a
b nitrate and phosphate).

–100 References
Antal, M.J. & Grønli, M. 2003. The art, science, and technology of
100 charcoal production. Industrial & Engineering Chemistry Research,
42, 1619–1640.
a Arriagada, R., Garcı́a, R. & Reyes, P. 1994. Steam and carbon
Sandy soil

dioxide activation of Eucalyptus globulus charcoal. Journal of


0
Chemical Technology & Biotechnology, 60, 427–433.
b b Atkinson, C., Fitzgerald, J. & Hipps, N. 2010. Potential mechanisms
a for achieving agricultural benefits from biochar application to
–100 Nt soil temperate soils: a review. Plant and Soil, 337, 1–18.
PCAL in soil NO3-N soil Barnard, R., Leadley, P.W. & Hungate, B.A. 2005. Global change,
Ptot in biomass Nt biomass nitrification, and denitrification: a review. Global Biogeochemical
Cycles, 19, GB1007.
PMo-blue in leachate NO3-N leachate
–200 Brockhoff, S.R., Christians, N.E., Killorn, R.J., Horton, R. &
Nonactivated Activated Nonactivated Activated Davis, D.D. 2010. Physical and mineral-nutrition properties of
biochar biochar biochar biochar
sand-based turfgrass root zones amended with biochar. Agronomy
Journal, 102, 1627–1631.
Figure 1 Biochar induced changes of N- and P-pools in the soils
Brodowski, S., Amelung, W., Haumaier, L. & Zech, W. 2007. Black
relative
h to the biochar-free controli soil. The calculation
carbon contribution to stable humus in German arable soils.
Change ð%Þ ¼ Treatment  Control  100 is based on averages of
Control Geoderma, 139, 220–228.
all treatments with different biochar sizes and amounts, but
Chan, K.Y., Van Zwieten, L., Meszaros, I., Downie, A. & Joseph, S.
separated for activated and nonactivated biochar. Significant
2008. Agronomic values of green waste biochar as a soil
differences between properties of nonactivated biochar and activated
amendment. Australian Journal of Soil Research, 45, 629–634.
biochar treatments are indicated with different letters (P < 0.05,
Chan, K.Y. & Xu, Z. 2009. Biochar: nutrient properties and their
Mann–Whitney U-test). PCAL, mg available P ⁄ kg soil; Ptot in
enhancement. In: Biochar for environmental management – science
biomass, P content in biomass (mg ⁄ kg) and soil (kg); PMo-blue in
and technology (eds J. Lehmann & S. Jospeh), pp. 67–84.
leachate, calculated as mg Pleachate ⁄ kg soil; Ntot in soil, mg N ⁄ kg
Earthscan, London.
soil; NO3-N in soil, mg available NO3-N ⁄ kg soil; Ntot in biomass, N
Chapin, I., Stuart, F., Matson, P.A. & Vitousek, P.M. 2011.
content in biomass (mg ⁄ kg) and soil (kg); NO3-N in leachate,
Principles of terrestrial ecosystem ecology. Springer, New York,
calculated as mg Nleachate ⁄ kg soil).
Dordrecht, Heidelberg, London.
Demirbas, A. 2002. Gaseous products from biomass by pyrolysis
fast. In summary, our results obtained from greenhouse
and gasification: effects of catalyst on hydrogen yield. Energy
studies show that additions of activated biochar affect N and
Conversion and Management, 43, 897–909.
P in soil–plant system, but it should be mentioned that the Ding, Y., Liu, Y.-X., Wu, W.-X., Shi, D.-Z., Yang, M. & Zhong,
intensity of these effects depend on soil texture. Z.-K. 2010. Evaluation of biochar effects on nitrogen retention
and leaching in multi-layered soil columns. Water, Air, & Soil
Pollution, 213, 47–55.
Conclusion
Glaser, B., Lehmann, J. & Zech, W. 2002. Ameliorating physical and
The application of activated and nonactivated biochar from chemical properties of highly weathered soils in the tropics with
wood in rates up to 1.5% of soil dry weight revealed that charcoal – a review. Biology and Fertility of Soils, 35, 219–230.
both biochar types enhanced the concentrations of available Jeffery, S., Verheijen, F.G.A., van der Velde, M. & Bastos, A.C.
2011. A quantitative review of the effects of biochar application to
nutrients in the two temperate soils. However, there were no
soils on crop productivity using meta-analysis. Agriculture,
significant effects on plant yields. Yet, biochar amendment to
Ecosystems & Environment, 144, 175–187.
soil reduced leaching losses of inorganic P and, in silty soil

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184
184 N. Borchard et al.

Jones, D.L., Rousk, J., Edwards-Jones, G., DeLuca, T.H. & Park, S.-J., Jang, Y.-S., Shim, J.-W. & Ryu, S.-K. 2003. Studies on
Murphy, D.V. 2012. Biochar-mediated changes in soil quality and pore structures and surface functional groups of pitch-based
plant growth in a three year field trial. Soil Biology and activated carbon fibers. Journal of Colloid and Interface Science,
Biochemistry, 45, 113–124. 260, 259–264.
Joseph, S.D., Camps-Arbestain, M., Lin, Y., Munroe, P., Chia, Radovic, L.R., Moreno-Castilla, C. & Rivera-Utrilla, J. 2001.
C.H., Hook, J., van Zwieten, L., Kimber, S., Cowie, A., Singh, Carbon materials as adsorbents in aqueous solutions. In:
B.P., Lehmann, J., Foidl, N., Smernik, R.J. & Amonette, J.E. Chemistry and physics of carbon, Vol. 27 (ed. L.R. Radovic), pp.
2010. An investigation into the reactions of biochar in soil. 227–405. CRC Press, New York.
Australian Journal of Soil Research, 48, 501–515. Rondon, M., Lehmann, J., Ramı́rez, J. & Hurtado, M. 2007.
Karhu, K., Mattila, T., Bergström, I. & Regina, K. 2011. Biochar Biological nitrogen fixation by common beans (Phaseolus vulgaris
addition to agricultural soil increased CH4 uptake and water L.) increases with bio-char additions. Biology and Fertility of Soils,
holding capacity – Results from a short-term pilot field study. 43, 699–708.
Agriculture, Ecosystems & Environment, 140, 309–313. Schlichting, E., Blume, H.-P. & Stahr, K. 1995. Bodenkundliches
Keiluweit, M., Nico, P.S., Johnson, M.G. & Kleber, M. 2010. Praktikum. Eine Einführung in pedologisches Arbeiten für Ökologen,
Dynamic molecular structure of plant biomass-derived black insbesondere Land- und Forstwirte, und für Geowissenschaftler.
carbon (biochar). Environmental Science & Technology, 44, 1247– Blackwell, Berlin.
1253. Shen, W., Li, Z. & Liu, Y. 2008. Surface chemical functional groups
Kim, S.C. & Hong, I.K. 1998. Pore development of the activated modification of porous carbon. Recent Patents on Chemical
carbon prepared by steam activation process. Journal of Industrial Engineering, 1, 27–40.
and Engineering Chemistry, 4, 177–184. Singh, B., Singh, B.P. & Cowie, A.L. 2010. Characterisation and
Kishimoto, S. & Sugiura, G. 1985. Charcoal as a soil conditioner. evaluation of biochars for their application as a soil amendment.
Symposium on Forest Products Research International Australian Journal of Soil Research, 48, 516–525.
Achievements and the Future, CSIR Conference Centre: Pretorai, Sohi, S.P., Krull, E., Lopez-Capel, E. & Bol, R. 2010. A review of
National Timber Research Institute, South African Council for biochar and its use and function in soil. Advances in Agronomy,
Scientific and Industrial Research. 105, 47–82.
Knicker, H., Almendros, G., Gonzalez-Vila, F.J., Martin, F. & Soper, R.J. & Huang, P.M. 1963. The effect of nitrate nitrogen in
Ludemann, H.D. 1996. 13C- and 15N-NMR spectroscopic the soil profile on the response of barley to fertilizer nitrogen.
examination of the transformation of organic nitrogen in plant Canadian Journal of Soil Science, 43, 350–358.
biomass during thermal treatment. Soil Biology and Biochemistry, Steiner, C., Blum, W.E.H., Zech, W., de Macedo, J.L.V., Teixeira,
28, 1053–1060. W.G., Lehmann, J. & Nehls, T. 2007. Long term effects of
Leppälahti, J. & Koljonen, T. 1995. Nitrogen evolution from coal, manure, charcoal and mineral fertilization on crop production and
peat and wood during gasification: literature review. Fuel fertility on a highly weathered Central Amazonian upland soil.
Processing Technology, 43, 1–45. Plant and Soil, 291, 275–290.
Liang, B., Lehmann, J., Solomon, D., Kinyangi, J., Grossman, J., Stoof, C.R., Wesseling, J.G. & Ritsema, C.J. 2010. Effects of fire
O’Neill, B., Skjemstad, J.O., Thies, J., Luizão, F.J., Petersen, J. & and ash on soil water retention. Geoderma, 159, 276–285.
Neves, E.G. 2006. Black carbon increases cation exchange Tryon, E.H. 1948. Effect of charcoal on certain physical, chemical,
capacity in soils. Soil Science Society of America Journal, 70, and biological properties of forest soils. Ecological Monographs,
1719–1730. 18, 81–115.
Libra, J.A., Ro, K.S., Kammann, C., Funke, A., Berge, N.D., Yam, T.W., Ernst, R., Arditt, J., Nair, H. & Weatherhead, M.A.
Neubauer, Y., Titirici, M.-M., Fühner, C., Bens, O., Kern, J. & 1990. Charcoal in orchid seed germination and tissue culture
Emmerich, K.-H. 2011. Hydrothermal carbonization of biomass media: a review. Lindleyana, 5, 256–265.
residuals: a comparative review of the chemistry, processes and Zhang, T., Walawender, W.P., Fan, L.T., Fan, M., Daugaard, D. &
applications of wet and dry pyrolysis. Biofuels, 2, 71–106. Brown, R.C. 2004. Preparation of activated carbon from forest
Major, J., Rondon, M., Molina, D., Riha, S. & Lehmann, J. 2010. and agricultural residues through CO2 activation. Chemical
Maize yield and nutrition during 4 years after biochar application Engineering Journal, 105, 53–59.
to a Colombian savanna Oxisol. Plant and Soil, 333, 117–128. Zhou, J., Masutani, S.M., Ishimura, D.M., Turn, S.Q. & Kinoshita,
Martin, R.S., Manahan, S.E., Morris, J.S. & Larsen, D.W. 1999. C.M. 2000. Release of fuel-bound nitrogen during biomass
The destruction of chemical warfare surrogates and subsequent gasification. Industrial & Engineering Chemistry Research, 39, 626–
phosphorus distribution during gasification. Journal of 634.
Environmental Science and Health, Part A Toxic ⁄ Hazardous van Zwieten, L., Kimber, S., Downie, A., Morris, S., Petty, S., Rust,
Substances and Environmental Engineering, 34, 241–261. J. & Chan, K.Y. 2010. A glasshouse study on the interaction of
Novak, J.M., Busscher, W.J., Laird, D.L., Ahmedna, M., Watts, low mineral ash biochar with nitrogen in a sandy soil. Soil
D.W. & Niandou, M.A.S. 2009. Impact of biochar amendment on Research, 48, 569–576.
fertility of a southeastern coastal plain soil. Soil Science, 174, 105–
112.

ª 2012 The Authors. Journal compilation ª 2012 British Society of Soil Science, Soil Use and Management, 28, 177–184

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