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Keywords: Biochar generated from thermochemical conversion of biomass reduces greenhouse gas emissions and is useful
Biochar for improving ecological systems in agriculture. However, certain biochars function well in improving soil, and
Returning biochar to soil other biochars do not. Why? Because it is not clear how to prepare the best biochar for soil. There is a disconnect
Systematic analysis of biochar return between biochar preparation and returning the biochar to the soil. To elucidate this relationship, this paper
Physicochemical properties of biochar
reviews (i) technologies for preparing biochar, (ii) how preparation conditions affect biochar properties, and (iii)
Nutrient cycling
the effects on soil physical and chemical properties. In addition to reducing greenhouse gas emissions, biochar
improves the physicochemical and microbial properties of soil and absorbs poisonous and pernicious substances.
Therefore, as biochar is produced by pyrolysis, optimizing processing conditions to improve its properties for
agricultural use is a key issue explored in this article.
⁎
Corresponding author.
E-mail address: tanzx1977@163.com (Z. Tan).
http://dx.doi.org/10.1016/j.apsoil.2017.03.017
Received 21 September 2016; Accepted 22 March 2017
0929-1393/ © 2017 Elsevier B.V. All rights reserved.
Z. Tan et al. Applied Soil Ecology 116 (2017) 1–11
Table 1
Summary of pyrolysis technologies (Wang et al., 2012; Duku et al., 2011; Jones et al., 2011).
Batch preparation Economical Low biomass production rates, causes environmental pollution
Low requirement for equipment
Continuous preparation High biomass production rates High cost, complex equipment
Some of the by-products can be recycled
Easy to operate
Fast pyrolysis Short retention time High required temperature, facility requirements, low carbon yield
Medium-speed pyrolysis Moderate required temperature, retention time and energy consumption Limited carbon yield
Slow pyrolysis Low energy consumption, low temperature, high carbon yield Low rates
pyrolysis include fast pyrolysis, medium-speed pyrolysis and slow of biochar is shown in Fig. 2-1 . The average pore size of biochar
pyrolysis (see Table 1). increases as the residence time increases from 10 to 20 min. When the
residence time is 20 min, the average pore size of biochar is 0.1232 μm,
2.1. Main factors influencing biochar properties corresponding to an 8.45% higher pore size than for 10 min. Increasing
the residence time from 20 to 30 min is associated with a decrease in
The properties of biochar depend on the raw materials (Qin, 2012) the average pore size. The pore size decreases 3.57% between 20 and
and the thermochemical conversion conditions (Zhang et al., 2013) 30 min. The pore structure of biochar is closely connected to its average
including temperature, oxygen level and reaction time (Gundale and pore size and the pore structure is a primary factor affecting its
Deluca, 2006). Biochar ash contains metal alkalinity and thus the pH of adsorption ability. Therefore, pore characteristics are a major contri-
biochar reflects the ash content (Jiang et al., 2013a,b) whereas the butor to the properties of biochar (Ma et al., 1998). The pore structure
cation exchange capacity (CEC) of biochar is related to its surface area, of biochar can be adjusted by controlling the residence time because
the presence of carboxyl functional groups, the raw biomass material there is a critical time for biomass material carbonization.
used and the preparation temperature. The ash content increases with increasing residence time (Figs. 2-2)
because longer residence times drive off more volatile components,
leaving behind ash material. After 60 min, the ash content is 15.7 wt%,
2.1.1. Raw material
which corresponds to an increase in ash content of 128% compared
At a given pyrolysis temperature, the stability of biochar varies with
with 20 min. Therefore, a long residence time is preferred to achieve
the type of biomass (Bridgwater, 2003; Masek et al., 2013; Scheer et al.,
better carbonization. However, as mentioned above, increasing the
2011; Jones et al., 2011) such as soybean straw and peanut straw (Yuan
residence time beyond 20 min decreases the biochar pore size and
et al., 2011).
consequently its adsorption ability. In addition, it may be uneconomical
Fig. 1-1 illustrates the ash content of various types of raw biomass
to run the conversion process for such a long residence time. As biomass
and their biochars. The ash content of biochar is generally related to
carbonization is an endothermic reaction, longer residence times mean
that of the raw material. Among the materials studied, the ash content
more energy consumption and higher operating costs. Therefore,
of biochar prepared from straw is the highest, increasing from 10.4 wt%
selection of an appropriate residence time is important.
in straw to 34.2 wt% in the corresponding biochar. The ash content of
biochar prepared from walnut shells is 10% higher and the ash content
is approximately 3.5% higher for bamboo sawdust. There are many 2.1.3. Reaction temperature
alkaline ions in the ash and their presence increases the soil pH. The reaction temperature greatly affects biochar properties (Putun
The yields of biochar for different raw materials are shown in Fig.1- et al., 2005). In general, higher temperatures reduce yield with more
2. At 600 °C, the biochar yield of grass stalk is the highest, 16.1 wt%, liquid and gaseous substances produced but they can improve biochar
which is almost the same as that of wood. The biochar yield of rapeseed quality as good biochar has many nutrients (such as N, P, and K),
is the lowest, approximately 8.5 wt% less than that of grass stalk. The abundant pore structure and large surface area (Lehmann et al., 2006).
biochar yield is related to the content of cellulose and lignin in the As shown in Fig. 3-1 , the specific surface area of biochar increases
biomass (Lv et al., 2008). The more lignin and less cellulose in the raw with increasing temperature. The specific surface area of biochar is
biomass material, the higher the biochar yield (Jiang, 2001; Lehmann 0.16 m2/g at 300° C and 110 m2/g at 400 °C, i.e., the specific surface
et al., 2008; Mok et al., 1992). area increases by 109.84 m2/g from 300 °C to 400 °C. With increasing
temperature, the specific surface area increases rapidly from 300 °C to
2.1.2. Reaction time 500 °C and increases relatively slowly above 500 °C. The specific
The residence time affects biochar properties. The average pore size surface area is probably related to the structure of the untreated
Fig. 1. 1-1 Ash content before and after biomass material carbonization. 1–2 Biochar yield of different biomass raw materials.
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Z. Tan et al. Applied Soil Ecology 116 (2017) 1–11
Fig. 2. 2-1 Effect of residence time on average biochar pore size. 2-2 Effect of residence time on the ash content of biochar.
biomass, the distribution and size of the pores, and the density of the 3.1. Biochar microstructure
biochar. In general, biochar with a large specific surface area has a
narrow micro-pore distribution with good pore structure and adsorp- The carbonaceous framework of biochar is illustrated in Fig. 4-1 The
tion ability. The larger the specific surface area, the better the proper- surface of biochar is typically a rectangular pore structure, unlike the
ties of the biochar. It can be seen in Fig. 3-2 that the organic carbon original feedstock (see Fig. 4-2 for a comparison with straw). The
content of biochar decreases gradually with increasing reaction tem- micro-porous structure of biochar plays an important role in improve-
perature. The organic carbon content is 564.02 g/kg at 300 °C, and it ment of the specific surface area and absorption ability (Lin et al.,
decreases by 28.03% at 450 °C and by 54.02% at 600 °C. If biochar is 2009). Large pores can promote soil breathability, increase the water
returned to the soil, the organic carbon in the biochar increases the content of soil and provide space for microbial growth and reproduc-
organic carbon content of the soil, contributing to the mitigation of tion. Small pores can improve the adsorption capacity of biochar (Yuan
greenhouse gas emissions (Cang et al., 2012). Increasing the tempera- and Xu, 2011a, 2011b). Biochar can also absorb poisonous and
ture has a positive effect on the surface area whereas it has a negative pernicious substances in soils through its pores. In addition, the
effect on the organic carbon content and thus it is crucial to choose an abundant pore structures of biochar can affect the infiltration route
appropriate reaction temperature for biochar preparation (Chun et al., and water velocity in the soil and the high moisture content can
2004). enhance fixation of soil nutrients (Wang et al., 2012; Gao et al., 2013).
Through a review of biochar preparation technologies, we found
that the biochar preparation technologies corresponding to soil im-
provement are extremely insufficient and that most biochar preparation 3.2. Elemental content
technologies are for biomass energy, not for improving soil. Therefore,
we need to find good working conditions for biochar preparation for Biochar mainly contains C, H, O, N, S and other trace elements
soil improvement, not for producing energy products. (Alexis et al., 2007; Yuan et al., 2011). The elemental composition of
biochar is listed in Table 2. The C content of wood biochar and bamboo
biochar is high, up to 56% higher than in biochars prepared from other
3. Biochar properties materials. For all types of biochar, the N content is less than 3 wt%, the
H content is slightly above that of N, the O content reaches a maximum
The elemental composition and spatial structure of biochar are content of 52.37 wt%, and the S content is lower than 1 wt%. The
related to the raw materials and reaction conditions (section 2; Lu et al., remaining fraction is ash that contains Na, Mg, K, Ca and other mineral
2013). The higher the biochar porosity, the larger the specific surface elements (Liu et al., 2009). Biochar can be aromatic, oxidation state
area (Zhang et al., 2009a,b). Both macro-elements (e.g., N, P and K) and carbon or aliphatic (Abdul et al., 2010; Yuan et al., 2004; Schmidt and
microelements are found in biochar (Cornelissen 2005; Liang et al. Noack, 2000), with more O than N or H. It is important to estimate the
2006; Zwieten et al., 2009). values of H/C and O/C (Sassner et al., 2006). The H/C value reflects the
Fig. 3. 3-1 Influence of temperature on the specific surface area of biochar. 3-2 Influence of temperature on the organic carbon content of biochar.
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Z. Tan et al. Applied Soil Ecology 116 (2017) 1–11
Fig. 4. 4-1 Microscopic surface scan of biochar. 4-2 Microscopic surface scan of straw.
aromatization of organic matter whereas the O/C value reflects the is likely that biochar improves the salt-alkali saturation of soil. The
content of superficial polar functional groups, the hydrophilicity and primary questions are (i) if ions such as Ca2+, K+, or Mg2+ are released
the stability of biochar in soils (Spokas, 2010; Accardi-Dey and after returning biochar to soil; (ii) if the content of exchangeable metal
Gschwend, 2002). elements such as Al, Cu, or Fe decreases; and (iii) if the availability of
The mineral nutrients in biochar increase the nutritional value of plant essential elements such as Ca and Mg is enhanced. Returning
the soil it is applied to, such as the Ca and Mg, which is particularly biochar to soils increases the absorption of nutritive elements by the
good for sterile and sandy soils (He et al., 2011). The microelement plants and reduces the effects of harmful elements such as Cd, Pb, As
content of different types of biochar is listed in Table 3. The Ca content heavy metals (Li et al., 2011). These base-ions can exchange with H+
is slightly higher than those of other elements. The Na content is and Al3+ in soils, lowering their concentrations and further increasing
relatively low (0.008%). Basic ions in biochar directly affect soil pH. It soil pH (Van et al., 2010).
Table 2
Elemental composition of biochar.
Sample name C/wt% N/wt% H/wt% O/wt% S/wt% H/C O/C Reference
Rice straw charcoal−300° 44.99 1.02 3.04 50.263 0.687 0.811 – Lu et al. (2013)
Rice straw charcoal−500° 44.9 0.84 1.982 51.411 0.867 0.530 – Lu et al. (2013)
Rice straw charcoal 61.02 2.29 1.84 34.85 – 0.36 0.43 Ma (2013)
Rice straw charcoal 56.61 1.37 – – 0.57 – – Zhang (2012a,b,c)
Rice straw charcoal 51.3 2.62 2.62 45.0 0.36 0.61 0.66 Liu (2011)
Rice straw charcoal 46.9 2.08 1.34 12.3 0.075 0.34 0.20 Lü et al. (2012)
Rice straw charcoal 63.27 0.62 – 14.89 – – – Jiang et al. (2013a,b)
Rice straw charcoal 72.1 1.55 5.03 21.3 – 0.84 0.22 Wu et al. (2012)
Rice straw charcoal 66.84 1.88 4.22 27.05 – – – Chen et al. (2013)
Rice straw charcoal 51.3 0.01 0.03 – 0.004 0.61 – Dong et al. (2013)
Rice straw charcoal 61.60 0.16 3.42 34.82 – – –
Rice straw charcoal 69.6 1.5 2.1 7.1 – 0.02 0.08 Bruun et al. (2012)
Corn straw charcoal 70.38 1.53 – – 0.65 – – Zhang (2012a,b,c)
Corn straw charcoal 63.5 0.71 3.77 21.62 0.44 0.64 0.26 Herath and Hedley (2013)
Corn straw charcoal 29.5 0.6 1.6 7.9 0.02 – – Catherine et al. (2011)
Corn straw charcoal 41.6 0.4 1.5 8.1 – – 1.43 Hale et al. (2011)
Corn Straw charcoal 55.6 1.2 5.1 38.0 – 1.1 0.51 Zhou et al. (2011)
Bamboo charcoal 83.2 2.28 2.28 13.9 0.05 0.33 0.13
Bamboo charcoal 62.61 0.75 0.02 16.91 0.75 – – Gao et al. (2013)
Bamboo charcoal 63.19 0.56 4.86 30.04 – – – Wang et al. (2010)
Bamboo charcoal 83.2 0.006 0.023 – 0.0005 – – Dong et al. (2013)
Wheat straw charcoal 69.1 – 3.1 26.5 – 0.54 0.29 Wu et al. (2007)
Wheat straw charcoal 57.52 0.47 – 14.26 – – – Jiang et al. (2013a,b)
Wheat straw charcoal 45.2 – 0.047 33.2 0.01 – – Bruun et al. (2011)
Cotton stalk charcoal 47.46 0.86 3.18 39.97 0.40 – – Xiong et al. (2013)
Cotton straw charcoal 54.86 1.39 4.47 39.28 – – – Li et al. (2013)
Wood charcoal 70.65 0.2 3.37 21.3 – – – Herath and Hedley (2013)
Wood charcoal 85.6 – 1.3 7.8 – – – Jablonowski et al. (2013)
Wood charcoal 81.13 0.69 2.36 13.15 0.69 – – Gao et al. (2013)
Wood charcoal 70.65 0.20 3.37 21.3 – 0.57 0.23 Zhang et al. (2009a,b)
Bagasse charcoal 76.45 0.79 2.93 19.83 – – – Liu et al. (2009)
Willow branch charcoal 37.5 0.5 2.2 8.9 0.16 – – Catherine et al. (2011)
Rapeseed plant straw charcoal 71.34 1.43 3.93 10.84 0.24 0.66 0.11 Karaosmanoglu et al. (2000)
Organic waste charcoal 41.38 2.92 1.72 52.37 0.41 0.499 0.949 Zhang (2012a,b,c)
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Table 3
Metal content in biochar.
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Z. Tan et al. Applied Soil Ecology 116 (2017) 1–11
Fig. 8. 8-1 Influence of biochar ratio on soil particle density. 8-2 Influence of biochar on soil bulk density.
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Fig. 10. Influence of pyrolysis temperature on the C, N, AP, and P content of soil.
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Fig. 13. 13-1 Effect of biochar quantities on soil organic matter content. 13-2 Influence of different treatments on the active soil organic matter content.
Fig. 15. Removal rate of PAHS from soil using different treatments.
Fig. 16. The effect of greenhouse gas emissions using different treatments.
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Unfortunately, CO2 emission data are not available for each treatment. the accumulation of organic pollutants in plants. Biochar can also
If the CO2 emissions are considered, returning biochar to fields will improve the activity of soil microbes, inducing increased degrada-
more obviously show the benefit of biochar use for the reduction of tion of pollutants; and (v) Carbon in biochar is in a complicated and
greenhouse gas emissions. stable form. Biochar can reduce carbon emissions for a long time. It
fixes carbon and reduces the emission of the greenhouse gases CH4,
4.6. Future research on retuning biochar to soil N2O and CO2.
Regarding the return of biochar to soil, some biochars function to Although many biochar studies have been conducted, we found that
improve the soil (e.g., adjusting the pH, reducing greenhouse gas there is a disconnect between biochar preparation and returning
emissions) but other biochars do not have good function for soil. biochar to soil. In the future, biochar researchers must systematically
Why? Because there is a disconnect between the function of returning consider the research of returning biochar from biochar preparation to
biochar and biochar preparation. The reason for this is the knowledge the function on the soil. Only in doing so can biochar research really
structure problem of biochar researchers. Agronomists who study solve some soil problems.
returning biochar use the biochar products and know little about the
thermochemical process of biochar preparation. Other researchers of Acknowledgements
biochar preparation from the biomass energy field only focus on
producing energy products and few pay attention to the function of This work was supported by the National Natural Science
returning biochar to soil. Thus, researchers of biochar return to soil Foundation of China (No. 41571283).
must systematically consider the directional function of returning
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