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 Applied Energy 169 (2016) 652–662

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Toward a functional integration of anaerobic digestion and pyrolysis

for a sustainable resource management. Comparison between
solid-digestate and its derived pyrochar as soil amendment
F. Monlau a, M. Francavilla a, C. Sambusiti a, N. Antoniou c, A. Solhy b, A. Libutti a, A. Zabaniotou a,c,
A. Barakat d, M. Monteleone a,⇑
a
Star*AgroEnergy Research Unit, Department of Agriculture, Food and Environment, University of Foggia, Via Napoli, 25, 71122 Foggia, Italy
b
Centre for Advanced Material, Mohammed VI Polytechnic University, Lot 660 – Hay Moulay Rachid, 43150 Ben Guerir, Morocco
c
Biomass Group, Chemical Engineering Department, Aristotle University of Thessaloniki, Un. Box 455, 54124 Thessaloniki, Greece
d
INRA, UMR 1208 Ingénierie des Agropolymères et Technologies Emergentes 2, Place Pierre Viala, F-34060 Montpellier, France

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Coupling anaerobic digestion and

Biogas Energy
pyrolysis is technologically efficient. Syngas
CH4/CO2

This technology integration is Animal slurries H2/CO
environmentally sound and boosts and manure
circular economy.
ANAEROBIC

Digestate and pyrochar are soil Screw separator Dryer
DIGESTION

PYROLYSIS
amendments with different but
Bio-oil
complementary properties. Digestate

While pyrochar sequesters carbon,
Feed and
digestate could contribute to soil energy crops,
microbiological processes. crop residues
Separated solid digestate Pyrochar

Their characteristics are fully
consistent with those of agricultural
Proximate and ultimate analysis, chemical and physical properties.
soil amendments. Macro and micro-nutrients, heavy metals, pH, porosity, water
holding capacity, carbon stability and sequestration.
SOIL
AMENDMENT

a r t i c l e i n f o a b s t r a c t

Article history: The integration of different technologies acts as a leverage in boosting ‘‘circular economy” and improving
Received 24 October 2015 resource use efficiency. In this respect, the coupling of anaerobic digestion with pyrolysis was the focus of
Received in revised form 9 February 2016 this work. Solid-digestate obtained from anaerobic digestion was addressed to supply pyrolysis thus
Accepted 14 February 2016
increasing the net energy gains and obtaining ‘‘biochar” (called ‘‘pyrochar” in our case) to be used as soil
amendment alternatively to solid-digestate. The current interest on biochar is linked to its long-term soil
carbon sequestration, thus contributing to global warming mitigation.
Keywords:
A parallel detailed screening of the physical and chemical properties of both solid-digestate and pyro-
Anaerobic digestion
Digestate
char was performed, inferring their effects on soil quality. Results showed that while P and K are enriched
Pyrolysis in pyrochar, total N showed no significant differences. Heavy metals revealed higher concentrations in
Biochar pyrochar, but always largely below the biochar quality thresholds. Pyrochar exhibited a higher surface
Soil quality area (49–88 m2 g1), a greater water holding capacity (352–366%), and a more recalcitrant carbon struc-
Carbon sequestration ture. Both solid-digestate and pyrochar showed good soil amendments properties but with complemen-
tary effects. Although starting from the same biomass, being the original feedstock processed differently,

⇑ Corresponding author.
E-mail address: massimo.monteleone@unifg.it (M. Monteleone).

http://dx.doi.org/10.1016/j.apenergy.2016.02.084
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.
 F. Monlau et al. / Applied Energy 169 (2016) 652–662
their ability to improve the physical and chemical soil properties has proved to be different. While several
other soil improvers of organic origin can substitute digestate, the important role played by biochar
appears not-replaceable considering its precious ‘‘carbon negative” action.
1. Introduction
Our globalized society urgently needs ensuring food supply and
energy to a growing population without further exploiting our lat-
est fossil energy resources or causing environmental burdens and
damages [1]. In this respect, biomass could supply a large amount
of renewable energy but, on the counterpart, land use changes
(from food/feed to bioenergy crops) might generate food scarcity,
food prize volatility and a higher intensification in agricultural
management, thus jeopardizing soil fertility and crop yield [2–4].
At the same time, a continuing increase in food supply, keeping
the pace with population growth at planetary level, is leading to
higher fossil energy consumptions due to higher cultivation inputs,
thus eroding an already scarce non-renewable resource as well as
worsening global warming.
The options for reducing fossil fuel dependency and greenhouse
gases emissions (GHG), as well as benefitting of the social and eco-
nomic advantages that might result from biomass energy, are great
challenges on condition that these biomass resources are used
effectively and sustainably.
For this purpose, new strategic approaches are required and
new productive concepts are gaining momentum. The transition
to a bio-based industry is taking place, among others, by means of:
(1) A progressive integration (‘‘industrial symbiosis”) of differ-
ent conversion technologies, establishing functional connec-
tions and links across different processes according to a
‘‘systemic” view [5,6].
(2) The development of new value-chains implementing the
‘‘cascading” biomass utilization scheme, where the output
of one process becomes the input of the following one (thus
also targeting the ‘‘zero-waste” goal) with biomass progress-
ing through a series of material flows and energy conver-
sions [7].
(3) Processing biomasses in compliance with the ‘‘closed-loop”
principle, i.e. favoring the returning of plant nutrients into
the soil, thus making the farming system more ecologically
sustainable and preserving soil quality, its fertility and
organic matter (the latter to be also intended as an influen-
tial ‘‘carbon stock”).
This multi-functional, cascading and closed-loop arrangement
of new designed bioenergy systems is also offering significant effi-
ciency gains, maximizing the value extracted from a given amount
of biomass by fulfilling both material and energy needs from the
same feedstock [8].
In a previous work from the same team [9], the opportunity of
coupling two different energy conversion processes, anaerobic
digestion (AD) and pyrolysis (PY), respectively, was investigated.
While AD is a biological degradation process producing biogas (that
consists mainly of CH4 and CO2), PY is a thermochemical decompo-
sition of biomass occurring in the absence of oxygen [10,11],
producing syngas (a mixture mainly formed by H2 and CO2) and
bio-oil. In any case, both are energy conversion processes.
By applying this integrated approach, the solid-digestate result-
ing from a previous AD biological conversion, formerly treated
through solid–liquid separation and a drying process, becomes
653
Ó 2016 Elsevier Ltd. All rights reserved.
the entering feedstock of the subsequent PY thermochemical
conversion.
Very recently, other researchers have also proposed this pecu-
liar approach. The ‘‘Supergen” Bioenergy Hub is currently working
out a project developing a synergy between biological (AD) and
thermal (PY) conversion processes in which the overall net energy
yield can be significantly improved [12]. Differently from our
approach, PY precedes AD thus allowing access within the biomass
to lignin-bound components that are otherwise unavailable for
anaerobic biological conversion. Although considering different
technical operations, Shen et al. [13] proposed a similar integrated
approach by adding biochar into the AD digester. An in situ biogas
upgrading system was thus obtained with a significant increase in
the methane yield, biomethanation rate constant and maximum
methane production rate. In addition to the thermochemical con-
version of digestate, the integrated AD + PY also allowed the bio-
conversion of the aqueous phase of pyrolysis liquor, the one
derived from the pyrolysis of solid digestate [14]. Biochar, indeed,
has the ability to catalyze AD by mitigating mild ammonia inhibi-
tion, supporting archaeal growth and the methanization of the bio-
char labile carbon [15]. Therefore, this option of coupling AD with
PY could open up new interesting pathways for the integration of
biological and thermochemical processes [16].
The AD + PY functional coupling is of great potential interest not
only because the resulting energy gain is higher than the AD pro-
cess individually considered (positive interaction or synergic
effect), but also because relevant side-effects are generated [9,17].
Indeed, during the AD process, approximately 50–70% of the
organic matter is decomposed, while the residual organic matter,
more recalcitrant to degradation, generates the so-called ‘‘diges-
tate” [18]. Digestate is generally characterized by high biological
stability, a relative high content of organic molecules [19] and
nutrients, such as nitrogen and phosphorus [20]. After the mechan-
ical solid–liquid separation (by centrifugal screw, rotary or press
separator), solid digestate can be utilized to replace soil organic
amendments and synthetic fertilizers [21]. Indeed, from the con-
centrated solid fraction an organic amendment is obtained
[22,23], while the remaining liquid fraction, being particularly rich
in ammonia, is analogous to a mineral N fertilizer [20].
In recent years, a rapid growth in newly installed anaerobic
digestion plants is observed and huge amounts of digestates are
increasingly available. The use of liquid and solid manure for bio-
gas production is becoming popular in many EU countries, together
with the use (in co-digestion) of crop residues and dedicated
energy crops (previously used as animal feed) to increase the
energy yield of the process. Concerning these large amounts of
digestate as crop fertilizer and soil amendment, there are relevant
economic and environmental concerns that are constraining their
extensive application, today, on cropland [24,25]. The high spatial
density of the AD-facilities (for instance, a very high number of AD
plants within a small geographic area is currently observed in the
‘‘Po Valley” in northern Italy) and the consequent limited cropland
available for spreading, is leading to overcharge nearby fields with
digestate. Therefore, excessive nitrogen loads may have negative
effects on soil tilth properties, plant growth and grain yield, even
significantly contributing to threaten water quality due to higher
risks of nitrate leaching and groundwater contamination. Improper
654 F. Monlau et al. / Applied Energy 169 (2016) 652–662
land application practices can lead to large ammonia volatilization
and nitrous oxide emissions, as well as nutrient runoff, thus spark-
ing considerable debate about the environmental sustainability of
this practice [23]. Apart nutrient overload and losses, several addi-
tional concerns could be addressed to an intensive use and irre-
sponsible management of digestate in agriculture, including
pathogen exposure and long distance transport costs to allow a
proper digestate spreading over cropland [26].
To improve economic and environmental sustainability in the
management of the AD effluent, alternative methods are therefore
required [25–27]. Addressing digestate to PY, and obtaining
‘‘biochar” besides extra-energy, might be considered a viable alter-
native. From PY, indeed, a residual ‘‘charred” organic matter is
derived. When specifically utilized as a soil amendment, this form
of ‘‘black carbon” biomass is defined ‘‘biochar” (called ‘‘pyrochar”
in our case). The current interest related to the use of biochar, how-
ever, is connected to its ability to act as a carbon sink, promoting a
long-term carbon sequestration into the soil, thus contributing to
global warming mitigation. For this reason, ‘‘biochar” is also
defined as a ‘‘carbon negative” technology [28]. Biochar is com-
posed of a large amount of highly stable carbon and, consequently,
this stability is the major determinant of its long-term C-
sequestration capacity [29].
In the previous work by Monlau et al. [9], solid-digestate (still
containing about 30–50% of organic carbon, on dry basis), was fur-
ther treated by means of pyrolysis in order to yield an extra
amount of energy in parallel to biochar. It was clearly demon-
strated that the integrated strategy of AD + PY led to a net 42%
increase in electricity production. While the objective of the previ-
ous work was to assess the energy advantage of coupling AD with
PY, the interest of the present work (as a follow-up of the same
approach) was focused on the possible benefit of transforming
the solid-digestate into pyrochar and its effects on agricultural soil
quality and health.
The purpose is to use ‘‘pyrochar” instead of ‘‘digestate” as soil
amendment, as a means for potential carbon sequestration and
the recovery of valuable nutrients (N, P). In the perspective of
applying the integrated technology combining AD + PY, as sug-
gested by Monlau et al. [9], the present work aimed to investigate
whether pyrochar can replace solid digestate, obtaining even bet-
ter or at least similar effects on soil quality. Alternatively, their
joint or sequential application may be suggested. Although much
research has been carried out individually on both solid digestate
and its derived pyrochar, studies on the direct comparison of their
properties as soil amendment are few. [30,31]. Up to date, only Ste-
faniuk and Oleszczuk [27] have studied the physicochemical
parameters of solid digestate and its derived pyrochar thus data
are clearly missing in literature. More schematically, the aims of
this study were the following:

Determining and comparing the main physicochemical proper-
ties of solid digestate (DG) and its derived pyrochar (PC).

Assessing the DG and PC use as soil conditioners, their effects on
agricultural soil properties and quality.
2. Materials and methods
2.1. Feedstock materials
Two solid-digestates (DG1 and DG2) were obtained from two
different mesophilic full-scale biogas production plants, located
in the Apulia region (Southern Italy), whose main characteristics
are reported in Table 1.
The first plant (AD1) was a two-stage plant where the hydroly-
sis–acidogenesis phases and the subsequent methanogenesis
Table 1
Main characteristics of the two anaerobic digestion plants.
Anaerobic digester parameters AD1 AD2
Digester volume (m ) 3
3720 5840
Feeding (t FM/day) 56 120
HRT (days) 62 53
pH 7.5–7.8 7.5–7.8
Temperature (°C) 45 45
Daily solid digestate production (t DM/day) 7.1 6.7
phase have been physically separated in two consecutive digesters.
AD1 was daily supplied with a mixture of 9% groats, 29% olive oil
cake, 57% silage of triticale and 5% chicken manure. The main
AD1 characteristics were: digester volume of 3720 m3, an organic
loading rate (OLR) of 56 t FM d1, and a hydrolytic retention time
(HRT) of 62 days.
The second considered plant (AD2) was a one-stage plant with a
conventional configuration (a first digester followed by a post-
digester). AD2 was daily supplied with a mixture of 43% animal
sewage, 20% cow manure, 25% maize and triticale silages and
12% cereal bran. The main AD2 characteristics were: volume of
5,840 m3, OLR of 120 t FM d1, and HRT of 53 days.
After mechanical screw separation performed on farm, a daily
production of 7.1 and 6.7 t DM d1 of solid-digestate was obtained
for AD1 and AD2, respectively. Prior to any analysis, the two sam-
ples were oven dried overnight at 105 °C in our laboratory.
2.2. Pyrolysis procedure
A quartz rotary kiln reactor was used to carry out pyrolysis
experiments. The pyrolysis flow sheet has been already reported
elsewhere [9,32]. Prior to each experimental trial, the reactor
was purged with N2 for 30 min to ensure an oxygen free environ-
ment. The experiments were carried out at 600 °C, applying a heat-
ing rate of approximately 20 °C min1 at atmospheric pressure and
inert atmosphere, while the residence time at the maximum tem-
perature was 10 min. The initial feedstock weight was set at 10 g of
dry solid anaerobic digestate. The collected pyrolysis products
were char, liquid and non-condensable gas. Char was weighted
after collection. The produced pyrolysis gas was analyzed offline
in a gas chromatography (Model 6890N. Agilent Technologies) fit-
ted with two columns: HP-Plot Q and HP-Molsive type [10]. The
obtained yield of the liquid fraction was calculated by subtraction
from the mass balance equation, as follows:
W liquid ¼ W dry digestate  W gas  W biochar ð1Þ
2.3. Analytical determinations
A complete set of chemical analyses was conducted on the two
solid digestates (DG1 and DG2) and the two corresponding pyro-
chars (PC1 and PC2).. All analysis were performed in duplicate.
Proximate analysis determined the relative content in total solid
(TS), volatile solid (VS), ash (AS) and fixed carbon (FC). For pyro-
chars, the analyses were performed by using a TGA analyser
(LECO-TGA701) and the ASTM D7582 method, while digestate
samples were analyzed according to the APHA methods [33].
The pH determination was carried out by adding de-ionized
water in a mass ratio 1:20. The solution was then hand shaken
and allowed to stand for 5 min before measuring pH using a Basic
Crison 20Ò pH meter.
Structural-carbohydrates from cellulose and hemicelluloses
together with ‘‘klason lignin” were measured using a strong acid
 F. Monlau et al. / Applied Energy 169 (2016) 652–662
hydrolysis method previously described by Monlau et al. [9]. All
monosaccharides (i.e. glucose, xylose, arabinose) were analyzed
by HPLC (AgilentÒ 1260) coupled to refractometric detection. The
analysis was carried out with a Hi-PLex H column at 50 °C. The elu-
ent corresponded to 5 mM H2SO4 under a flow rate of
0.3 mL min1. A refractive index detector was used to quantify
the carbohydrates. The system was calibrated with glucose, xylose
and arabinose standards (SigmaAldrichÒ). Thereafter, cellulose
and hemicelluloses contents were estimated as follows:
Cellulose ð%TSÞ ¼ Glucose ð%TSÞ=1:11
Hemicelluloses ð%TSÞ ¼ ½Xylose ð%TSÞ þ Arabinose ð%TSÞ=1:13 ð3Þ
where 1.11 is the conversion factor for glucose-based polymers
(glucose) to monomers and 1.13 is the conversion factor for
xylose-based polymers (arabinose and xylose) to monomers.
A TGA analyser was also used to obtain the ‘‘differential ther-
mogravimetric curve” (dM/dT) were the rates of mass loss are
recorded with respect to increasing temperature values according
to a specific ‘‘temperature-programmed oxidation” (TPO). Experi-
ments were performed in a TGA Instrument ‘‘Q500 apparatus”,
with a 10 °C/min ramp between 25 and 1000 °C. Samples of
approximately 20 mg were progressively heated from room tem-
perature to 980 °C, under a heating rate of 10 °C min1 and a con-
stant air flow (20 mL min1). The resulting thermograms were
corrected for moisture and ash content.
To evaluate the carbon sequestration potential of both
digestates and pyrochars, the R50 coefficient was calculated.
According to Harvey et al. [34], the R50 is a useful index for
quantifying pyrochar recalcitrance and screening pyrochars with
respect to their carbon sequestration potential. The R50 uses the
energy required for thermal oxidation of the pyrochars (normal-
ized to that needed for the oxidation of graphite) as a measure
of recalcitrance. The R50 recalcitrance index was calculated
according to the following:
R50PC ¼ T 50PC =T 50GRAPH
where T50PC and T50GRAPH are the temperature values corre-
sponding to 50% oxidation/volatilization of pyrochars (PC) and gra-
phite, respectively. Values for R50PC are obtained directly from TG
thermograms appropriately corrected for water and ash content.
T50GRAPH was assumed to be 886 °C [34]. The R50 was interpreted
considering the following recalcitrance/carbon sequestration
classes: Class A (R50 P 0.70), Class B (0.50 6 R50 < 0.70), or Class
C (R50 < 0.50).
Ultimate analysis (C, H, N) was performed using an ‘‘Elementar
Vario Macro Cube” analyser. S content was determined with an ele-
mental analyser CHNS-LECO 680 using the method LECO- ASTM-D
5291.
Elemental analysis (micro- and macro-elements) was per-
formed by digesting 0.15 g of sample in 5 mL of HNO3 in a closed
vessel microwave digester (CEM-Mars6) for 20 min at 220 °C. The
metals in the solution were analyzed by inductively coupling
plasma spectrometry-optical emission spectroscopy (ICP-OES
Agilent 720).
2.4. Physical analytical procedure
The water holding capacity (WHC) was determined applying an
adapted protocol from Ang [35]. Accessible surface was deter-
mined by N2 adsorptiondesorption method that was performed
on a Micromeritics ASAP 2010 volumetric apparatus at 77 K. Prior
to adsorption measurements, samples (0.50.3 g) were outgassed
at 373 K under vacuum for 72 h. Specific surface area of the sam-
655
ples was evaluated using the BrunauerEmmettTeller (BET)
method.
3. Results
3.1. Pyrolysis product yields
The relative weights of pyrolysis products (bio-oil, syngas, and
biochar) are presented in Fig. 1. The biochar reached 34 wt%, both
in DG1 and DG2, respectively. Such results are in accordance with
ð2Þ other literature data [36,37]. Yao et al. [37] reported a biochar yield
of 45.5 wt% after pyrolysis at 600 °C from digested of sugar beet
tailings. Inyang et al. [36] reported a lower biochar yield of 18 wt
% after pyrolysis at 600 °C of digested sugarcane bagasse.
The relative amount of recovered bio-oil (51% and 56% for
DG1 and DG2, respectively) was significantly higher with
respect to syngas (15% and 10%, respectively). The produced
bio-oils were characterized by a high water content correspond-
ing to 45 wt%. Literature findings prove that pyrolysis oil could
be effectively used as fuel in CHP engines, either solely or in
blends with liquid fossil fuels or biodiesel, if its water content
is below 30 wt% [38,39]. In the current study, the high water
content of bio-oil (>30 wt%) prevents its direct utilization in
combustion engines and, therefore, upgrading processes (mild
hydrodeoxygenation or reactive distillation) are required.
According to the concept of farm biorefinery, both syngas and
bio-oil produced by PY (the latter only after an upgrading treat-
ment) can be converted into heat and electricity through a CHP
system, thus significantly improving the renewable energy gain
and the sustainability of the coupled system, compared to the
single AD process [9,40].
3.2. Chemical characteristics: proximate and ultimate analysis
The proximate and ultimate analysis, together with pH, of both
digetates and pyrochars are reported in Table 2.
ð4Þ The digestate showed an alkaline pH, with values between 8.6
(DG2) and 9.1 (DG1). Digestate alkalinity is commonly observed
and it is mainly due to the degradation of VFAs and the production
of ammonia during the AD process. The AD management operation
to control pH and improve buffer capacity frequently involves the
addition of basic compounds or carbonates into the digester [19],
that could explain the resulting high pH. Higher pH values were
found for pyrochars (11.1 for PC1 and 11.4 for PC2) with respect
to solid digestate. Inyang et al. [36] reported pH value of 10.9 for
pyrochar obtained after pyrolysis at 600 °C of anaerobically
15,0
DG 1
34,2
10,2
DG 2 55,8
34,0
Syngas Yield (%) Bio-oil Yield (%) Biochar yield (%)
Fig. 1. Products distribution (pyrochar, bio-oil and syngas) after pyrolysis at 600 °C
of DG1 and DG2, respectively. Bio-oil yields refer to raw bio-oil, including its
aqueous phase at 45 wt.%.
656 F. Monlau et al. / Applied Energy 169 (2016) 652–662

Table 2
Proximate and ultimate analysis of the two samples of digestate (DG) pyrochar (PC).

Parameters (Units) DG 1 DG 2 PC 1 PC 2
pH 9.05 (±0.08) 8.6 (±0.04) 11.1 (±0.03) 11.4 (±0.01)
VS (%TS) 91.0 (±2.1) 89.5 (±0.1) 69.5 (±1.1) 55.3 (±0.9)
Ash (%TS) 7.7 (±0.8) 9.5 (±0.1) 22.8 (±0.7) 32.1 (±0.4)
FC (%TS) 1.3 (±0.7) 1.0 (±0.5) 7.7 (±0.4) 12.6 (±0.8)
C (g 100 g1 TS) 42.5 (±0.24) 43.0 (±0.07) 62.2 (±1.57) 57.3 (±0.53)
H (g 100 g1 TS) 6.1 (±0.03) 6.2 (±0.03) 2.0 (±0.02) 2.0 (±0.02)
N (g 100 g1 TS) 1.4 (±0.12) 1.3 (±0.03) 1.5 (±0.02) 1.4 (±0.00)
S (g 100 g1 TS) 0.14 (±0.03) 0.14 (±0.05) 0.04 (±0.02) 0.07 (±0.02)
O (g 100 g1 TS)a 42.1 39.5 11.4 7.2
FC/C (%) 3 2.3 12.4 22.1
H/Corg ratio 1.72 1.73 0.39 0.42
O/Corg ratio 0.65 0.68 0.14 0.10
Cellulose (g 100 g1 TS) 17.0 (±0.8) 17.0 (±0.9) 5.5 (±0.2) 6.8 (±0.1)
Hemicellulose (g 100 g1 TS) 10.1 (±1.4) 12.2 (±1.7) 0 0
Lignin-Like (g 100 g1 TS) 31.9 (±1.8) 34.0 (±1.2) 50.3 (±0.9) 40.5 (±0.9)
a
Determined by difference O = 100–C–H–N–S–Ash.

digested sugarcane bagasse. Pyrolysis led to higher pH because of uted to dehydration and depolymerisation reactions forming sol-
the ashes content of digestate and their increasing concentration uble lignin as well as to the condensation of cellulose forming
in the course of the thermochemical treatment. Indeed, the accu- graphitic structures [47].
mulation of these basic cations increased the pH values of the pyr-
ochar samples; the higher the ash content, the higher the pH.
3.3. Physical characteristics of final products
[41,42].
The VS content (Table 2) showed significant differences
The main physical properties of digestates and pyrochars are
between pyrolyzed and non-pyrolyzed feedstock. The organic con-
presented in Table 3. Interestingly, after pyrolysis, the obtained
tent of both pyrochars ranged from 55.3% to 69.5 wt% of the total
PC samples exhibited a higher accessible surface area than DG
solid content, a quite remarkable value. The ash content almost
samples (1.4 m2 g1). In our study, surface areas of 49 and
tripled considering the conversion of DG into PC. Fixed carbon
88 m2 g1 were found for PC1 and PC2, respectively. Inyang et al.
(FC) ranged from 1 to 1.3 wt% in DG and from 7.7 to 12.6 wt% in
[48] reported values of accessible surface area ranging from 49 to
PC. As expected, the two pyrochars exhibited higher total Carbon
161 m2 g1 on biochar produced from pyrolysis of agricultural
content (Table 2) with 50% increase compared to the correspond-
anaerobic digestate at 600 °C. The pyrochars obtained from our
ing digestates. Finally, a significant increase in the FC/C ratio was
experiments exhibited low values of N2 specific surface area, not
detected after pyrolysis, with values of 2.3–3% for DG to 12.4–
exceeding 150 m2 g1, thus not fulfilling the requested EBC thresh-
22.1% for PC samples.
old. Generally, high surface areas is a desired characteristic for soil
According to the ‘‘Guidelines for a Sustainable Production” of
amendment [47]. Considering this parameters, mild activation
biochar [43], the Carbon content must be higher than 50% (in dry
with steam, at temperatures higher than those of pyrolysis, or
mass) so that the char could be considered as ‘‘biochar”. Biochar
chemical activation could be proposed [49]. The significant
material is assigned to a ‘‘class” accordingly to its percentage
increase of surface area after pyrolysis is the result of thermal
content of organic C (Class 1: Corg P60%; Class 2: Corg P30%
decomposition of the organic material through which volatiles
and <60%; Class 3: Corg P10% and <30%). Considering this
are driven off; the remaining structure being comprised of highly
classification, PC1 belongs to biochar Class 1, while PC2 to biochar
concentrated carbon chains. Such a significantly increase of acces-
Class 2.
sible surface area and porosity was also confirmed by the MEP
Moreover, carbon stability could be indirectly evaluated by the
microscopy analysis presented in Fig. 2.
molar ratio of hydrogen to organic carbon (H/Corg) as well as the
Finally, water holding capacity (WHC) was determined for the
ratio of oxygen to organic carbon (O/Corg). Lower values of these
various samples. WHC is an important agronomic soil property
ratios are correlated with greater carbon stability. H/Corg values
since the higher the WHC the higher is the moisture retention of
fluctuate dependently on the biomass and process used, although
the soil and, therefore, the capacity to hold nutrients and avoid
values exceeding 0.7 are an indication of non-pyrolytic chars or
leaching losses. In our case, an increase of 42% and 57% in the
pyrolysis deficiencies [44]. In this study, H/Corg ratios of PC1 and
WHC for the two pyrochar was estimated compared to solid-
PC2 were 0.39 and 0.42, respectively. In both cases, the require-
digestate. Such an increase in WHC for pyrochars could be
ment of EBC criteria for H/Corg ratio <0.7 was fully complied. In
explained by the increase of both accessible surface area and
addition, the O/Corg ratio is also a relevant index for characterizing
porosity that occurred during the pyrolysis process.
biochar stability and differentiating it from other carbonization
products [44]. An O/Corg ratio less than 0.2 should ensure a mini-
mum half-life of 1,000 years [45]. This property provides indica- Table 3
tions of a long-term stability and persistence of biochar in the Main physical characteristics of solid anaerobic digestate and pyrochar.
soil, contributing to carbon sequestration [46]. In our study, the DG 1 DG 2 PC 1 PC 2
O/Corg ratios for PC1 and PC2 were 0.14 and 0.10, respectively,
CrI (%) 76.4 53.8 – –
showing this material suitable for soil amendment operations with SA (m2 g1 TS) 1.4 1.4 49.0 88.0
an effect of increased C stability [45]. Lastly, the sharp decrease in WHC (%) 327 (±1) 428 (±0.3) 515 (±0.2) 608 (±0.8)
the values of the H/Corg and O/Corg molar ratios observed in the two T50 (°C) 317 298 352 366
pyrochars indicates an increase of aromaticity, which can be attrib- R50 (–) 0.36 0.34 0.40 0.41
 F. Monlau et al. / Applied Energy 169 (2016) 652–662 657

Fig. 2. SEM images of DG1 (a), DG2 (b), PC1 (c), and PC2 (d).

Fig. 3. TGA curves of DG1 (a), DG2 (b), PC1 (c), and PC2 (d).
658 F. Monlau et al. / Applied Energy 169 (2016) 652–662

3.4. Thermogravimetric results 3.5. Nutrients and heavy metals in the final products

The chemical composition changes that occurred during the
pyrolysis process were also investigated by TGA analysis. The ther-
mogravimetric and its derivative mass losses curves are showed in
Fig. 3. For all the samples, the mass loss due to dehydration
occurred at temperature lower than until 105 °C° [50].
Considering the two digestates, when the temperature
increased from 200 to 400 °C, a steady mass decrease was
observed, resulting in a major weight loss that exceeded 65 wt%.
A first peak of weight loss was observed at temperature of 271
and 282 °C for DG1 and DG2, respectively. This peak corresponds
to the degradation of materials such as hemicellulose and cellulose
fibers [51]. Additionally, the thermograms of both digestates
revealed other peaks at higher temperatures (one at 423 °C for
DG1, other two peaks for DG2 at 427 and 436 °C, respectively).
These peaks can be the consequence of the decomposition of
organic polymers (including lignin) already present in the original
material or the generation of complex aromatic structures result-
ing from the breakdown of cellulose and hemicewllose [52]. Once
the temperature of 600 °C was reached, both digestates had lost
more than 90 wt% of their initial mass.
For pyrochars samples, the temperature peaks at 270–280 °C,
the ones mostly associated to hemicelluloses, were not observed.
Since hemicelluloses are not any more a pyrochar constituent
(Table 2), due to complete degradation in the pyrolysis process,
the corresponding peak was not detected.
Finally, the recalcitrance index (R50) was calculated from T50
values using the obtained thermogravimetric curves corrected
for moisture and ash content. R50 values of 0.34 and 0.36 were
determined for DG2 and DG1, respectively, while R50 values of
0.40 and 0.41 were detected for PC1 and PC2, respectively
(Table 3). Such results confirmed the more recalcitrant structure
of PC than DG samples and thus their better ability in carbon
sequestration. Considering these R50 values, the obtained pyro-
chars should be ranked in the third class (see Section 2.3). A lower
stability was observed comparing the obtained results with those
of biochars from pyrolysis of manure and residues of agricultural
crops [34,47,53].
The chemical composition of digestates and pyrochars were
very similar to data reported by other authors for similar feedstock,
in terms of macro and microelements [54,55]. Results from Tables
2 and 4 showed that both pyrochars have interesting N–P–K fertil-
izer ratios which were 1.5/1.5/5.9% and 1.4/2.2/3.8%, in PC1 and
PC2, respectively. The N content was similar in both pyrochars
(1.5% and 1.4%). P and K were found more concentrated in pyrochar
than in their original solid-digestate, with an average enrichment
coefficient (EC) of 3.5 (Table 4). Similarly, Wang et al. [56] found
that pyrolysis elevated the total P content from 13.7 g kg1 in
raw poultry litter to 27.1 g kg1 in poultry litter-derived pyrochar.
However, these ratios were calculated based on the total contents
of the elements in the pyrochars and do not necessarily reflect the
real availability of nutrients to plants. Indeed, Jassal et al. [57]
recently reported that very small amount of adsorbed N in biochar
was released, indicating that the retained N was strongly held in
complex bonds within the biochar pores. The results reported by
Wang et al. [56] for phosphorous are in the same line. They showed
that pyrolysis reduced the water-soluble P from 2.95 g kg1 in
poultry litter to 0.17 g kg1 in their derived biochar. The thermal
treatment was supposed to transform labile P in raw poultry litter
into putatively Mg/Ca phosphate minerals in biochar, this latter
being water-unextractable. Finally, a decrease in S content was
observed in PC compared to DG samples, which is in agreement
with a previous work from Stefaniuk and Oleszczuk [27]. Indeed,
during pyrolysis process, there is probably a decomposition of
the sulfur containing compounds to volatile SO2 [27].
Excessive levels of contaminants such as heavy metals should
be carefully detected in case of application on agricultural soils
[58]. This is particularly true for waste where inorganic toxicants
(e.g. As, Cd, Cu, etc.) can be present [59]. Therefore, some authors
strongly recommend checking that soil amendments do not affect
soil health without causing any environmental impact [55,58].
Most of the products used in agriculture comply with specific
regulation standards thus ensuring they can be safely used in soil
application [55,60]. Several biochar quality guidelines have been
recently proposed, such as the IBI Biochar Standard [61], the

Table 4
Concentrations (mg kg1 TS) and enrichment coefficients (EC) of nutrients and heavy metals sources in the two samples of digestate (DG) and pyrochar (PC). Bold fonts refer to
macro-nutrients relevant in plant nutrition.

Element Units DG 1 DG 2 PC 1 PC 2 EC 1 EC 2
Al mg kg1 TS 327.8 356.2 1,083.2 2,458.9 3.3 6.9
As mg kg1 TS 1.0 1.0 6.2 2.6 6.2 2.6
Ba mg kg1 TS 12.3 17.7 32.3 46.0 2.6 2.6
Ca mg kg1 TS 14,528.1 10,814.4 24,569.8 39,692.0 1.7 3.7
Cd mg kg1 TS nd nd nd nd – –
Co mg kg1 TS nd nd nd nd – –
Cr mg kg1 TS 0.4 0.5 23.2 112.5 58.0 225.0
Cu mg kg1 TS 10.9 10.7 32.9 29.3 3.0 2.7
Fe mg kg1 TS 415.5 629.9 1716.9 3913.1 4.1 6.2
K mg kg1 TS 16,739.1 11,966.3 58,933.4 38,466.4 3.5 3.2
Mg mg kg1 TS 4842.2 3688.6 9082.5 15,643.3 1.9 4.2
Mn mg kg1 TS 68.3 96.5 188.7 286.4 2.8 3.0
Na mg kg1 TS 5232.4 1885.6 6535.9 4062.6 1.2 2.2
Ni mg kg1 TS 0.7 1.2 3.8 5.8 5.4 4.8
P mg kg1 TS 5020.3 5288.6 14,988.3 22,375.5 3.0 4.2
Pb mg kg1 TS nd nd nd nd – –
Se mg kg1 TS nd nd 1.0 4.1 – –
Si mg kg1 TS 27.3 33.5 52.1 100.8 1.9 3.0
Sr mg kg1 TS 35.9 33.2 91.2 94.5 2.5 2.8
Ti mg kg1 TS nd nd nd nd – –
V mg kg1 TS 0.6 1.6 2.4 5.3 4.0 3.3
Zn mg kg1 TS 31.1 34.9 94.0 121.3 3.0 3.5

n.d.: Not Detected because under detection limits.

 F. Monlau et al. / Applied Energy 169 (2016) 652–662
European Biochar Certificate [43] or the UK Biochar Quality Man-
date [62]. In these standards, environmental risks are accounted
for by the establishment of threshold values for pollutants such
as heavy metals, dioxins/furans, PAHs, PCBs or BTEX.
In our studies, the content of heavy metals both for DG and PC
samples was investigated (Table 4). Results showed that both PC
samples contained heavy metals, with concentrations ranging from
not detectable amount for Cd, Co and Pb to amounts as high as
286.4 mg kg1 for Mn in PC2. In general, the concentrations of all
heavy metals in the two investigated pyrochars were higher than
in raw digestate from which they were obtained, with enrichment
coefficients that ranged between 2.6 for As and 225 for Cr (Table 4).
Nonetheless, it is important to notice that none of the pyrochars
exceeded the total heavy metal threshold values set in the IBI,
EBC and BQM guidelines [63] for the so-called ‘‘basic” biochar qual-
ity grade, suggesting their possible use in agricultural practise
(with the only exception for Cr in PC2).
4. Comparative agronomic properties of digestate and pyrochar
Apart from bioenergy utilization, particular interest is focused
on pyrochar systems as a long-term solution to improve soil qual-
ity, given that many European soils are largely degraded, and to
mitigate climate change. Solid-digestate is considered already a
good candidate to replace commercial organic soil amendments
(such as compost, peat, manure, worm casting, and stabilized bio-
solids). It still contains a large fraction of organic Carbon (about
30–50%, on dry basis) and, as proposed in this work, it could be fur-
ther processed by means of pyrolysis to obtain extra-energy but
also an alternative by-product: the ‘‘pyrochar”, precisely. If the
solid-digestate is converted into pyrochar, both deemed soil
amendments, the question is whether the latter should be consid-
ered a good alternative to the former in terms of improving soil
tilth properties, thus conferring higher and better crop
productions.
Soil amendments improve soil structure. Soils tend to become
compacted over time, thus hindering root expansion and the
uptake of water and nutrients by the plants. Soil compaction is also
at the origin of water surface run-off and the consequent soil
erosion. Structuring ability is typically performed by the organic
CARBON EMISSIONS SAVED
Indirect Fossil
Displacement
ATMOSPHERIC
CARBON
Organic Carbon
Synthesis
PLANT Plant ORGANIC
NUTRIENTS Uptake FEEDSTOCK
SOM
Mineralizaon
SOIL ORGANIC
MATTER Labile-C
SOM
Mineralizaon
Fig. 4. Conceptual framework and diagram of the material transformations and consequent energy conversions of organic feedstock through the sequence ‘‘Anaerobic
Digestion” and ‘‘Pyrolysis” and the final closing loop with the return of the organic and mineral by-products to the agricultural soil (as soil amendment and/or fertilizer). The
soil is acting as a carbon sink allowing the stock of carbon in organic form. Direct and indirect fossil displacements allow energy savings and a decrease in the CO2 equivalent
emissions.
659
fraction of the applied conditioner; organic matter, indeed, strongly
favors the aggregation of soil particles and the long-lasting
stabilization of these aggregates. Solid-digestate is still rich of a
large organic fraction (both labile and partially stabilized) while
pyrochar is mainly characterized by a fixed C component (Fig. 4).
The organic matter of digestate, therefore, is directly performing
such structuring function. Differently, pyrochar only indirectly
improves soil structure through stimulating soil colonization by
microorganisms.
Concerning soil physical properties, the addition of pyrochar
decreases the bulk density and increases the water holding capac-
ity of the soil due to its highly porous structure [64]. An increase in
the water holding capacity (approx. 10–15% depending on the soil
original hydraulic properties) is generally detected soon after its
application [65–67]. Differently, the positive effect of digestate is
the indirect result of a better soil structuring.
Considering the main chemical features of a good quality soil
amendment, biochar and solid-digestate display approximately
the same properties. Pyrochar porosity and covalent interaction
on a large surface area can significantly contribute to nutrient
retention. Amended soil with pyrochar showed an increased soil
cation exchange capacity (in the range 4–17%, according to soil
conditions) and the negative charge concentration on its surfaces
increases with age [68]. Charring is also coupled to a reduction of
nutrient leaching from soil profile and cumulative NO 3 leaching
significantly decreases with pyrochar application under temperate
climatic conditions (according to [66], by 75% over the control).
Pyrochar application, moreover, could be a management option
to reduce the risk of contaminant dispersion. The risk of Cu, Ni
and Zn leaching was lower in soils treated with biochar obtained
from sewage sludge than directly using the same raw sludge from
wastewater treatment [69]. As previously reported (Section 3.5),
macro- and micro-nutrients solubility and availability to plants is
strongly affected by the retention bonds distinguishing the pyro-
char surface area. In general, a higher concentration of nutrients
(as well as heavy metals) is observed on soils treated with pyro-
char. The same properties are attributed to the organic colloidal
fraction of the solid-digestate. This enrichment does not necessar-
ily correspond to an increased availability, this being a positive fac-
tor in the case of soil contaminants, but negative if soil nutrients
are concerned. The slightly high pH values of both digestate and
Direct Fossil
Displacement
ENERGY ENERGY ENERGY
OUTPUT OUTPUT OUTPUT
SOLID
PYROCHAR
DIGESTATE
Anaerobic Pyrolysis Combuson
Digeson
ASHES
Stable-C Recalcitrant-C
Organic Soil Amendment
Soil Ferlizaon with Minerals
660 F. Monlau et al. / Applied Energy 169 (2016) 652–662
biochar (higher in the latter than in the former) points out the
interesting liming effect of the two soil amendments. These
amendments partially neutralize soil acidity due to their mineral
content; at the same time, their great buffer capacity do not modify
significantly the pH of the soil circulating water solution, so that
also neutral or somewhat basic soils could benefit from biochar
and digestate applications.
Particular care, moreover, should also be assigned to a possible
higher concentration of heavy metals or other specific soil contam-
inants that accumulate in the residues resulting from AD and PY,
thus jeopardizing the long-term soil agricultural productivity
[23,70,71]. Only through a direct assessment, the agronomic use of
such soil amendments can be optimized and properly managed [70].
From an ecosystem perspective, functions carried out by the
two soil amendments (digestate and pyrochar, respectively) are
very different (Fig. 4). While digestate is rich of degradable organic
matter that will be slowly decomposed by soil microbes (the so
called ‘‘pabulum”), pyrochar has a very poor easily degradable
organic matter and its chemical form is particularly stable over
time. Digestate gradually releases plant nutrients under microbial
mineralization and its degradable organic matter is the primary
source to start up the so called ecological ‘‘debris chain”. Con-
versely, pyrochar plays a role in carbon capturing and its long-
term sequestration into the soil, thus contributing to climate
change mitigation.
An almost perfect complementarity, therefore, may be sug-
gested so that the two soil amending practices (applying digestate
and pyrochar) should be done in combination (within the same
treatment or alternately) in order to promote a comprehensive soil
fertility.
5. Discussion on the optimization of the overall bioenergy
system
A comprehensive conceptual framework that oversees to the
transformation of the organic feedstock into digestate, first, and
into pyrochar, then, is clearly described in Fig. 4. A closed loop sys-
tem is achieved since the organic by-products obtained from the
energy conversion processes (AD and PY, respectively) are then
addressed to restore soil fertility.
The shorter is this loop (eg. SOM > Feedstock > SOM; or
SOM > Feedstock > Digestate > SOM) the greater is the amount of
organic carbon recycled but, in parallel, the easier and faster is
its mineralization, thus converting this organic C back to CO2. Con-
versely, the obtainable bioenergy is of limited amount and the con-
sequent direct fossil displacement is quite low.
When a longer transformation loop is considered (eg.
SOM > Feedstock > Digestate > Pyrochar > SOM) the organic carbon
recycled is lower but much higher its stability over time (the min-
eralization process is very slow or even stopped due to the pyro-
char recalcitrant carbon structure). At the same time, the
renewable energy obtained is of considerable amount and the abil-
ity to directly displace fossil energy is also significant.
If the longest transformation loop is applied (eg. SOM > Feed-
stock > Digestate > Pyrochar > Ashes > SOM), the energy conversion
of feedstock is moved to its extreme level, resulting in the com-
plete thermochemical degradation of biomass (e.g. by combus-
tion). In such a case, the recovery of organic carbon is no more
possible and only the mineral content of feedstock returns to the
soil. On the other hand, the energy generation capabilities of the
system are maximized and, therefore, its direct fossil displacement
potential is the highest.
The application of organic by-products from energy conversion
processes to arable land ensures that crops receive the majority of
the essential nutrients required for growth, i.e. soil fertility is
conserved and the soil structure and humus balance is improved,
thus promoting the closure of the natural nutrient cycles [24]. In
contrast, application of inorganic fertilizers to crop fields is an
additional component to the natural nutrient cycle, resulting in
an increased production of synthetic fertilizers requiring signifi-
cant fossil energy inputs. Therefore, the use of organic residues
(DG or PC) as an alternative to chemical fertilizers should not only
close the nutrient cycle, but also indirectly reduce greenhouse gas
emissions to the atmosphere through a decreased need for chem-
ical fertilizers. This specific interpretive aspect of the general
framework can be clearly observed in Fig. 4.
According to Janzen [72], sequestering C in soils not only
removes excess CO2 from the atmosphere, but also improves soils
by augmenting organic matter, an energy and nutrient source for
biota. However, organic matter is most useful, biologically, when
it decays. Again, Janzen [72] stated that the benefits of organic
matter arise not from its accumulation, but from its decay, being
the fuel for soil’s biological machinery. This being so, we face a
dilemma: can we both conserve organic matter and profit from
its decay? There is a way out of this paradox, Janzen [72] said,
increasing the amount of C entering the soil. We should also ask
whether it is possible to encourage some organic fraction to retain
Carbon while others are available to microbial communities and
their biological demand for energy and nutrients.
This evident trade-off [73] between carbon accrual and decay,
nutrient availability and carbon sequestration, direct and indirect
fossil displacement (Fig. 4) could be optimize just considering
the AD + PY model. This model, indeed, is the one that maximize
the total environmental benefit of the integrated energy system,
considering the sum of direct and indirect fossil displacements
and the consequent total GHG balance (that should be negative
and minimized).
Significant differences between pyrolyzed and non-pyrolyzed
digestate as soil amendments were highlighted. Both digestate
and pyrochar showed good soil amendments properties but with
complementary effects. Their ability to improve physical and
chemical soil properties is different, although they have derived
from the same initial feedstock; this is because they have been pro-
cessed differently. While several other soil improvers of organic
origin can substitute digestate, the important role played by pyro-
char appears not-replaceable considering its peculiar ‘‘carbon neg-
ative” action.
6. Conclusions
The AD + PY integrated bioenergy system should be regarded as
an innovative model, based on a multi-functional, cascading and
closed-loop arrangement of the two AD and PY energy conversion
processes. A multiple-win solution was carefully tuned to optimize
the trade-off between bioenergy generation and carbon sequestra-
tion, to achieve significant efficiency gains, maximizing the value
extracted from a given amount of biomass, both in term of energy
and environmental services (such as a negative GHG balance to
mitigate global warming).
This integrated, synergic dual-system proved to show manifold
advantages. It can generate several bioenergy carriers (both biogas
or biomethane from AD and bio-oil and syngas from pyrolysis),
thus increasing the net renewable energy gain. Furthermore, due
to its soil amending properties, pyrochar improves soil fertility,
enhancing agriculture productivity, avoiding nutrient leaching,
preserving water quality, reducing soil erosion, and substituting
(at least partially) the use of inorganic fertilizers, further contribut-
ing to GHG savings. Its ability to sequester carbon into agricultural
soil provides an effective strategy to mitigate global climate
changes.
 F. Monlau et al. / Applied Energy 169 (2016) 652–662 661

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