Waste Management 158 (2023) 76–83

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Nitrogen availability in biochar-based fertilizers depending on activation

treatment and nitrogen source
Raúl Castejón-del Pino *, María L. Cayuela, María Sánchez-García, Miguel A. Sánchez-Monedero
Department of Soil and Water Conservation and Organic Waste Management, CEBAS-CSIC, Campus Universitario de Espinardo, 30100 Murcia, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Different activation and N-doping treatments were used to produce biochar-based fertilizers (BBFs) with
Agricultural waste increased N concentration and slow N release. Pristine biochars were produced by pyrolysis of olive tree pruning
Olive tree pruning feedstock at low and high temperatures (400 and 800 ◦ C). These biochars were activated either by ultra­
N-doped biochar
sonication, or oxidation with hydrogen peroxide (H2O2) or nitric acid (HNO3) to increase their N retention
Available N
Nitrogen use efficiency
potential. Subsequently biochars were enriched with N with either urea or ammonium sulfate. The activation of
Oxidizing treatment low-temperature biochars with HNO3 was the most effective treatment leading to new surface carboxylic groups
that facilitated the later enrichment with N. When treated with urea, BBFs reached 7.0 N%, whereas the H2O2
activation only allowed an increase up to 2.0 N%. The use of urea as the external N source was the most efficient
for incorporating N. Urea treated biochars had a water-soluble fraction that represented up to 14.5 % of the total
N. The hydrolyzable N fraction, composed by amides and simple N heterocycles originated by the N-doping
treatments, and nitro groups generated from HNO3 activation represented up to 60 % of the total N. This study
relates the N chemical forms in the new BBFs to potential N availability in soil. The presence of water-soluble,
hydrolyzable and non-hydrolyzable N implied that these BBFs may supply N that would be progressively
available for plants, acting as slow-release fertilizers.

1. Introduction
Biochar-based fertilizers (BBFs) are a new type of engineered fertil­
izers, where biochar is formulated with mineral fertilizers or beneficial
microorganisms, for precise plant nutrition and the enhancement of soil
properties derived from biochar application (Calabi-Floody et al., 2018;
Rombel et al., 2022). These new BBFs have been proposed as a strategy
to increase nitrogen use efficiency (NUE), to improve soil properties, and
to sequester C in soil simultaneously, in comparison to conventional
mineral fertilizers (Joseph et al., 2021; Melo et al., 2022; Zhou et al.,
2021).
The co-application of biochar and synthetic fertilizers in soil has been
the traditional approach utilized to exploit the benefits of their inter­
action. Biochar applied in combination with mineral N fertilizers has the
potential to increase NUE by reducing N2O emissions and NO–3 leaching,
improving N uptake by plants (Marcińczyk and Oleszczuk, 2022), and
increasing crop yield, as compared to the application of synthetic fer­
tilizer alone (Bai et al., 2022; Melo et al., 2022). One of the most
recognized mechanisms behind this interaction is the adsorption of NH+
on the biochar surface through cation exchange capacity sites, which
regulates the release of N and prevent N losses (Cai et al., 2016).
BBFs represent a new approach to optimize biochar-fertilizer in­
teractions. Different methods have been developed for their production.
The most common strategy is a physical mixture of biochar, synthetic
fertilizer and an adhesive or a coating material (Sim et al., 2021).
Recently, a new promising approach is the production of engineered
biochars, where N is incorporated into the structure of the BBFs, either
by pre- or post-pyrolysis processes (Ndoung et al., 2021).
A variety of methods can be used as pre-pyrolysis treatments: direct
pyrolysis of N-rich feedstock (Piash et al., 2021), using NH3 as the py­
rolysis carrier gas (Yu et al., 2018), or preloading a feedstock with an
exogenous source of N such as ammonium nitrate (Zhu et al., 2018) or
urea (Wang et al., 2019a). These N-doped biochars are typically used for
the removal of contaminants in water or soil (Shakoor et al., 2021; Yu
et al., 2022), but with limited agricultural applications. N-enriched
biochars produced by this strategy usually contain most of the N in a
stable and recalcitrant form that is hardly available for plants. Rasse
4 et al. (2022) also identified the insufficient sorption capacity of biochar

* Corresponding author.
E-mail address: rcastejon@cebas.csic.es (R. Castejón-del Pino).

https://doi.org/10.1016/j.wasman.2023.01.007
Received 13 October 2022; Received in revised form 15 December 2022; Accepted 6 January 2023
Available online 13 January 2023
0956-053X/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
R. Castejón-del Pino et al.
as a limitation for the production of BBFs with enough N concentration
and the capacity to perform as slow release fertilizer.
Post-pyrolysis treatments to produce N-rich biochars are heteroge­
neous, and produce different end materials with slow-release perfor­
mance (Marcińczyk and Oleszczuk, 2022). In order to optimize N
incorporation, a previous activation step is recommended (Rasse et al.,
2022). The activation treatments can be separated between physical and
chemical (Jellali et al., 2022): i) physical modification is related to the
increase in the specific surface area and the total pore volume by ball-
milling, ultrasonication, and CO2 or steam activation, ii) chemical
modification by acidic, salt and alkaline solutions, or a mixture of
chemicals, to increase the number of functional groups. Oxygenated
functional groups facilitate surface chemical interactions, notably
increasing the active binding sites (Yang et al., 2019). Either acid,
alkaline or oxidizing modifications enhance the formation of O-func­
tional groups such as carboxylic, lactonic, phenolic, and carbonyl
groups, which can interact with N (Wang and Wang, 2019). The complex
mechanisms behind the retention of N into biochar represent an op­
portunity to produce controlled N-release fertilizers with different N
bioavailability (Bakshi et al., 2021).
In this work, we propose the production of a new type of engineered
fertilizers by the chemical incorporation of mineral N fertilizers on the
activated surface of biochar and we relate the chemical characterization
of the incorporated N forms in biochar with their bioavailability. To
achieve this aim, we produced BBFs through the post-pyrolysis treat­
ments of biochars, which were pyrolyzed at two highest treatment
temperatures (HTT) of 400 and 800 ◦ C. The surface of these biochars
was activated to maximize their N retention capacity either by soni­
cation or by oxidation with hydrogen peroxide or nitric acid. Urea and
ammonium sulfate were used as N sources to enrich the biochars. We
postulated that (i) the physicochemical activation influences the N
enrichment of the BBFs and (ii) the N chemical forms incorporated with
the added N sources may define the N bioavailability in BBFs.
2. Materials and methods
2.1. Biochar production
Olive tree pruning was selected as feedstock for the production of
biochar. Pruning consisted of tree branches with a diameter of 5–15 mm,
which were separated from leaves. Feedstock was collected in an olive
orchard located in the South-East of Spain. Prior to biomass pyrolysis,
the feedstock was air-dried to a moisture content below 10 % and milled
to a particle size of <6 mm. Dried and milled feedstock was slow-
pyrolyzed (a temperature ramp of 5 ◦ C min− 1 and 2 h of residence
time) in a rotatory tube furnace (RSR-B 80/500/11, Nabertherm, Ger­
many) at two HTT of 400 and 800 ◦ C (B-400 and B-800, respectively) in
an oxygen-free environment, maintained with an Ar flux. Further in­
formation on the pyrolysis conditions and the physicochemical proper­
ties of feedstock and biochars was provided in a previous study by
Sánchez-García et al. (2019). Pristine biochars were washed twice by
stirring for 10 min with deionized water (1:10 w/w), dried at 105 ◦ C,
milled and sieved (<1 mm).
2.2. Synthesis of the BBFs
Three activation treatments were applied to biochars prepared at
both temperatures: ultrasonication (treatment 1) and oxidation either
with hydrogen peroxide (treatment 2) or nitric acid (treatment 3).
Treatment 1: Ultrasonic treatment at room temperature for 0.5 h using a
1:10 mass ratio of biochar:deionized water in an ultrasonic device set at
80 W and 50 Hz (LT − 80 PRO, TQTECH., Spain). Treatment 2: 5 % H2O2
treatment following a methodology modified from Mia et al. (2017).
This treatment was performed at 80 ◦ C for 1.5 h, and shaken at 80 rpm
(1:25 w/v) in a water bath (WNB 14, Memmbert, Germany). Treatment
3: 40 % HNO3 treatment following a methodology modified from Güzel
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Waste Management 158 (2023) 76–83
et al. (2017). This treatment was performed at 80 ◦ C for 1 h and shaken
at 50 rpm (1:25 w/v) in a water bath (WNB 14, Memmbert, Germany).
After the activation treatments, samples were washed with deionized
water three times and dried at 105 ◦ C until a constant weight was
obtained.
Eventually, the activated biochars were supplemented with N either
as urea (U) or ammonium sulfate (AS). Biochars were submerged (1:10
w/v) in a 2 M urea or ammonium sulfate solution at 80 ◦ C for 1.5 h in a
thermoreactor (ECO 16, Velp Scientifica, Italy). After the N-doping
treatments, samples were washed with deionized water three times and
dried at 80 ◦ C until a constant weight was obtained. The complete
description of the different biochar-based fertilizers and the identifica­
tion codes are summarized in the Supplementary Material in Table S1.
2.3. Characterization of BBFs
An automatic elemental analyzer (CHNS-932, LECO, USA) was used
to measure the elemental content of carbon (C), hydrogen (H) and ni­
trogen (N) in the samples. The sulfur concentration was below the limit
of detection (0.2 %). Before analysis, the samples were ball-milled to
<0.5 mm. Ash content was analyzed according to ASTM D1762-84
(2021) following the next equation: Ash (%) = (calcined material (g) /
dried material (g)) × 100. Oxygen (O) concentration was determined by
subtraction (O (%) = 100 – C (%) – H (%) – N (%) – ash (%)). Electrical
conductivity (EC) and pH were determined in a 1:20 (w/v) water-
soluble extract after the sample was shaken for 2 h, centrifuged for
20 min at 4000 rpm, and paper-filtered.
An X-ray Photoelectron Spectrometer (XPS) analysis was performed
to obtain the surface functional group distribution and atomic elemental
composition of the BBFs, using an XPS system (K-Alpha, Thermo Sci­
entific, UK) with a monochromatic Al Kα radiation source. The quanti­
tative analysis of the XPS results was performed by calculating the
integral of each peak, where baselines were adjusted following the
Shirley method. The peaks were detected in Lorentzian-Gaussian type
curves. The XPS data were processed with the available software
XPSPEAK 4.1. Before XPS analysis, samples were ball-milled < 0.5 mm.
Fourier Transform Infrared (FTIR) spectroscopy was performed with
a Perkin-Elmer 1430 spectrophotometer to evaluate the surface func­
tional groups. The KBr pellet method was used for this. Briefly, 1–2 mg
of the sample were mixed with 200 mg of dried KBr and compressed to
form pellets. 10 scans were recorded per sample. Before the IR analysis,
the samples were ball-milled < 0.5 mm.
Three N fractions were defined depending on its bioavailability, as
referred to the grade of N availability to plants: water-soluble N (shortly
available N for plants), hydrolyzable N (gradually available N) and non-
hydrolyzable N (hardly available N). Water-soluble N was determined in
a deionized water extraction, which was shaken for 2 h (1:20 w/v),
centrifuged for 15 min at 4000 rpm, filtered (<0.45 μm), and measured
by an aqueous elemental analyzer (multi N/C 3100, Analytik Jena,
Germany). Hydrolyzable and non-hydrolyzable N fractions were
analyzed following an acid digestion according to Wang et al. (2012).
This procedure allows us to separate the bio-reactive N pool from the
chemically stable N of the BBFs. Briefly, a 0.5 g sample of biochar was
treated with 25 mL of 6 M HCl and 0.1 % phenol plus 2 drops of octyl
alcohol in a 100 mL Pyrex cation digestion tube. The 1:50 mixture was
blended with a vortex mixer, covered with a reflux funnel, and placed on
an Al digestion block (Bloc Digest 12, J.P. Selecta, Spain) for 24 h at
105 ◦ C. Non-hydrolyzable N was determined by elemental analysis in
the biochar after the acid-digestion, whereas hydrolyzable N was esti­
mated as follows:
Hydrolyzable N = Total N – non-hydrolyzable N – water-soluble N.
Additionally, mineral N-fractions were determined as follows: NO–3
and NO–2 were analyzed by ion chromatography (ICS 2100, Dionex, USA)
in the same water extract used for water-soluble N. NH+
4 was extracted
R. Castejón-del Pino et al. Waste Management 158 (2023) 76–83

by shaking the samples for 2 h (1:20 w/v) with 2 M KCl, centrifuging for
15 min at 4000 rpm, and filtering (<0.45 μm). NH+ 4 was measured by a
colorimetric method based on Bethelot’s reaction (Sommer et al., 1992).
Two replicates were performed in each analysis to calculate the
means and the standard deviations.
3. Results
3.1. Elemental and physicochemical characterization of BBFs
Biochar-based fertilizers were prepared from olive tree pruning
biochars (B-400 and B-800), which were characterized by a rich organic
composition, and low N and ash concentrations (Table 1). Nitric acid
oxidation was the most effective treatment for incorporating N into the
biochar structure. The oxidation with HNO3, without any additional
source of N, increased N concentration from 0.68 to 4.31 % in B3-400
and from 0.81 to 1.97 % in B3-800. The addition of either urea or
ammonium sulfate further increased N concentrations up to 7.02 % and
5.39 % in B3U-400 and B3AS-400, respectively. The addition of extra N
was less effective in biochars prepared at 800 ◦ C, where the N concen­
tration slightly increased up to 2.79 % and 1.62 % in B3U-800 and B3AS-
800, respectively. At both HTT, the use of urea as an added N source was
more effective than ammonium sulfate in incorporating N into the BBF
structure.
The activation with H2O2 slightly facilitated the incorporation of the
added N in biochars produced at 400 ◦ C (B2U-400 and B2AS-400), in
comparison to the non-activated biochar (BU-400). The incorporation of
N in H2O2-treated biochar was even less effective in biochars prepared at
800 ◦ C. The sonication treatment did not show any significant effect
neither in 400 nor in 800 ◦ C biochars.
The Van Krevelen diagram can group biochars according to their
degree of aromaticity and the content of O-functional groups
(Figure S1). For all modified biochars, molar H/C ratios were under the
0.7 limit established by the IBI Biochar Standard (2015). BBFs were
grouped according to pyrolysis HTT. The aromaticity of the biochars was
mostly affected by the pyrolysis temperature, regardless of the activa­
tion treatment, except for the HNO3 treatment, which caused a signifi­
cant decrease in the H concentrations in the biochars. BBFs made at
800 ◦ C were grouped between 0.1 and 0.2H/C ratios, whereas those at
400 ◦ C were found between 0.5 and 0.6. Similarly, molar O/C ratios
were also grouped according to pyrolysis temperature in the 0.05–0.20
range in biochars made from B-800, and 0.20–0.45 in biochars derived
from B-400. Surface activating treatments also had a strong impact on
the O/C molar ratios of the BBFs, which was more evident in biochars
made at 400 ◦ C. Furthermore, the biochars activated with HNO3 showed
the highest molar O/C ratio at both HTT, caused by the increase in O and
the decrease in C concentrations. The source of N did not affect the
molar ratios.
Pristine biochars produced at 400 ◦ C and 800 ◦ C had a basic pH of
8.32 and 10.69, respectively (Table 1). Both oxidizing treatments, HNO3
and H2O2, decreased the pH values, especially in biochars modified with
HNO3, reaching 3.40 for B3-400 and 4.53 for B3-800. Generally, urea-
treated biochars showed higher pH values (between 5.46 and 8.99)
than ammonium sulfate-enriched biochars (between 4.65 and 7.0).
Although most BBFs had a circumneutral pH, B3U-400 and B3AS-400
were moderately acidic, with a pH of 5.46 and 4.65, respectively. The
electrical conductivity (EC) of pristine biochars was low for both B-400
and B-800, with a similar value of 0.73 and 0.59 dS/cm, respectively
(Table S2). The biochar’s EC increased with the N content, especially
when ammonium sulfate was used.
3.2. Surface functionalization of BBFs
The surface functionalization of the BBFs was assessed by both XPS
and FTIR spectroscopy. The FTIR spectra of pristine biochar (B-400)
were dominated by the presence of two main bands at 3430 and 1600
cm− 1 (Fig. 1), corresponding to the stretching vibrations of O–H and
aromatic C–– C/C–C bonds, respectively (Johnston, 2017). In the case of
B-800, these bands were less intense, especially the one at 1600 cm− 1
(Figure S2). The oxidation treatments enhanced the O–H band, espe­
cially HNO3 treatments. Furthermore, the FTIR spectra of the HNO3-
treated biochars (B3-400, B3U-400 and B3AS-400) were characterized
by three peaks at 1720, 1532 and 1385 cm− 1, corresponding to C– –O
stretching vibration from carboxylic acid groups (Li et al., 2014),
asymmetric –NO2 and symmetric –NO2, respectively (Fan et al., 2018;
Qian and Chen, 2014) (Fig. 1). In contrast, the sonication treatments did
not change the spectra as compared to the non-activated biochars.
The differences observed in the FTIR spectra of the BBFs were driven
by the oxidation treatments rather than the added N source, since
ammonium sulfate and urea-enriched biochars had similar FTIR spectra.

Table 1
Elemental content (C, H, O and N in %), ash (%) and pH of the pristine biochars produced at 400 and 800 ◦ C, the HNO3-activated biochars without subsequent N
addition (treatment 3) and the sixteen final materials doped with urea (U) or ammonium sulfate (AS) after ultrasonic (1), H2O2 (2) or HNO3 (3) treatments.
%C %H %O %N %Ash pH

Pristine biochars
B-400 73.2 ± 0.7 3.86 ± 0.63 17.6 ± 1.4 0.68 ± 0.07 4.6 ± 0.0 8.32 ± 0.06
B-800 82.0 ± 0.4 1.04 ± 0.11 12.0 ± 0.1 0.81 ± 0.03 4.1 ± 0.2 10.7 ± 0.12
Only treated with HNO3
B3-400 57.9 ± 0.5 2.51 ± 0.27 31.3 ± 0.94 4.31 ± 0.03 3.9 ± 0.1 3.40 ± 0.07
B3-800 76.2 ± 0.7 0.88 ± 0.14 18.0 ± 1.16 1.97 ± 0.07 3.0 ± 0.5 4.53 ± 0.17
Urea
BU-400 69.0 ± 0.7 3.16 ± 0.07 20.3 ± 0.6 1.51 ± 0.00 6.0 ± 0.0 8.05 ± 0.01
B1U-400 69.5 ± 0.0 3.54 ± 0.07 18.3 ± 0.6 1.61 ± 0.04 7.0 ± 0.7 7.82 ± 0.08
B2U-400 68.2 ± 2.0 3.51 ± 0.07 23.9 ± 2.3 2.04 ± 0.02 2.3 ± 0.2 6.98 ± 0.13
B3U-400 56.8 ± 1.0 2.68 ± 0.19 32.4 ± 0.5 7.02 ± 0.02 1.1 ± 0.3 5.46 ± 0.06
BU-800 84.7 ± 0.7 0.93 ± 0.08 9.3 ± 0.4 1.53 ± 0.04 3.6 ± 0.1 8.62 ± 0.18
B1U-800 83.1 ± 0.1 1.28 ± 0.30 10.5 ± 1.1 1.73 ± 0.67 3.3 ± 0.2 8.99 ± 0.11
B2U-800 80.4 ± 0.8 0.88 ± 0.01 14.1 ± 2.1 1.33 ± 0.01 3.3 ± 1.2 8.29 ± 0.05
B3U-800 76.9 ± 0.8 1.09 ± 0.07 17.3 ± 0.2 2.79 ± 0.02 1.9 ± 0.7 7.18 ± 0.01
Ammonium sulfate
BAS-400 68.4 ± 1.6 3.07 ± 0.07 25.7 ± 1.4 0.88 ± 0.07 2.0 ± 0.3 6.90 ± 0.15
B1AS-400 66.5 ± 1.1 3.24 ± 0.07 28.1 ± 1.0 0.98 ± 0.02 1.2 ± 0.0 6.64 ± 0.02
B2AS-400 70.5 ± 0.6 2.97 ± 0.03 23.9 ± 0.9 1.03 ± 0.02 1.5 ± 0.3 6.04 ± 0.18
B3AS-400 57.5 ± 0.5 2.67 ± 0.21 34.0 ± 0.5 5.39 ± 0.02 0.2 ± 0.3 4.56 ± 0.01
BAS-800 86.3 ± 0.2 0.92 ± 0.09 7.7 ± 0.0 0.90 ± 0.06 4.2 ± 0.3 7.00 ± 0.07
B1AS-800 84.1 ± 1.4 0.89 ± 0.09 9.3 ± 0.6 0.97 ± 0.03 4.6 ± 0.7 7.01 ± 0.04
B2AS-800 82.6 ± 0.2 1.02 ± 0.07 12.4 ± 0.1 0.73 ± 0.04 3.3 ± 0.2 6.77 ± 0.02
B3AS-800 75.4 ± 0.0 1.25 ± 0.03 19.4 ± 0.1 1.62 ± 0.02 2.4 ± 0.2 6.16 ± 0.08

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R. Castejón-del Pino et al. Waste Management 158 (2023) 76–83

Fig. 1. a) Region between 4000 and 750 cm− 1 of infrared spectra of pristine biochar made at 400 ◦ C (B-400), biochar only treated with HNO3 (B3-400) and non-
treated biochar or activated with treatments 1, 2 and 3 (ultrasonic, H2O2 and HNO3, respectively) with final N-enrichment with urea (BU-400, B1U-400, B2U-400 and
B3U-400). b) FTIR spectra of B-400, B3-400 and BBFs made at 400 ◦ C treated with ammonium sulfate.

The only difference was the peak at 1590–1600 cm− 1, which showed a
rise after the urea treatments, due to the formation of amide or amine
groups (Bamdad et al., 2021; Shi et al., 2020). Only minor differences
were found in BBFs produced with B-800 due to their high recalcitrant
structure (Figure S2). The only difference was observed in the HNO3-
treated biochars, which exhibited a peak at 1385 cm− 1, corresponding to
N–O stretching vibration from –NO2 groups.
XPS was used to describe the surface chemical composition of C, O
and N content by studying the binding energies of C1s, O1s and N1s
photoelectrons of the carbonaceous materials (Table S3). C1s were

Fig. 2. N1s XPS over the binding energy range 410–395 eV of pristine biochar made at 400 ◦ C (B-400), B-400 with urea treatment (BU-400), B-400 with HNO3
treatment (B3-400) and B-400 with HNO3 and urea treatments (B3U-400).

79
R. Castejón-del Pino et al.
decomposed into three peaks at 284.5 eV (aromatic and aliphatic C–C/
C–H bonds), 286.1–286.3 eV (C–O) and 288.2–288.5 eV (C– – O)
(Zhang et al., 2021). The total C1s concentration did not change
significantly between treatments. In all cases, the XPS results were
dominated by the C– – C/C–C signal (aromatic and aliphatic C), which
represented up to 80 % of the total C concentration. However, after the
HNO3 and H2O2 treatments, the C– – C/C–C relative percentage
decreased due to the oxidizing effect, while the peaks corresponding to
functionalized C, such as C–O and C– – O, increased. This effect was
clearly observed in HNO3-treated biochars, B3-400 and B3-800. The
functionalization of surface was also observed in the O1s spectra, which
presented three peaks at 531.1–531.3 eV (C– – O bonds), 532.5–532.7 eV
(O–C– – O) and 533.7 eV (C–O) (Zhang et al., 2020) (Table S3). In
general, the relative percentage of O functional groups only showed
minor differences between the samples. Nitric acid treatments (B3-400
and B3-800) produced an increase in O–C– – O and C–O stretching vi­
bration in comparison to pristine biochars. BBFs prepared with urea,
presented a higher percentage of C– – O, which increased gradually with
the abundance of N in the samples, as compared with those prepared
with ammonium sulfate.
In the N1s spectra (Fig. 2), three peaks were detected in all the
samples at 398.7 (pyridinic N bonds), 399.9–400.1 (amides, amines and
pyrrolic N) and 401.2–401.5 eV (graphitic N) (Leng et al., 2020; Wang
et al., 2019b). In the case of HNO3-treated biochars, an additional peak
associated to the bonding stretching of –NO2 was observed at 405.5 eV
in BBFs made with biochar at 400 ◦ C (Fig. 2, Table S3), and at 406.5 eV
in samples made with biochar at 800 ◦ C. Fig. 2 also shows that amide
and pyrrolic N increased after both HNO3 and urea treatments. The
pyridinic N peak slightly increased after HNO3 treatment, but increased
more strongly after the urea treatment. The graphitic N peak hardly
changed by the treatments, and lastly, the presence of ammonium was
not proven (Fig. 2).
3.3. N availability in BBFs
N in the BBFs was separated into three different fractions according
to its availability: water-soluble N, hydrolyzable N, and non-
hydrolyzable N (Fig. 3). N in pristine biochars was mostly non-
hydrolyzable. Modified biochars not only presented a high percentage
of N, but also exhibited an enhanced proportion of bioavailable N,
especially those prepared with HNO3 and/or urea. Ultrasonic-treated
biochars showed a high proportion of non-hydrolyzable N, similar to
pristine biochars. The oxidation with H2O2 increased the concentration
Fig. 3. Water-soluble N, hydrolyzable N and non-hydrolyzable N of pristine biochars, biochars treated with HNO3, and the sixteen BBFs, expressed in N g kg− 1. U and
AS represent urea and ammonium sulfate treatments, respectively. 1, 2, and 3 correspond to ultrasonic, H2O2 and HNO3 activations, respectively. 400 ◦ C and 800 ◦ C
are the pyrolysis HTT of the biochars.
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Waste Management 158 (2023) 76–83
of hydrolyzable N in B2U-400, as compared to BU-400 and B1U-400.
BBFs with the HNO3 treatment showed the highest content of poten­
tially bioavailable N (water-soluble and hydrolyzable N), especially
those produced from biochar made at 400 ◦ C, which reached 39.3 and
24.4 N g kg− 1 of potentially bioavailable N in B3U-400 and B3AS-400,
respectively.
The added N source highly influenced hydrolyzable N, as urea was
more efficient for incorporating N than ammonium sulfate, and espe­
cially for incorporating hydrolyzable N forms. N in ammonium sulfate
samples was basically non-hydrolyzable, except with nitric acid acti­
vation and subsequent ammonium sulfate treatment. In urea-treated
biochars, the concentration of water-soluble N was higher than the
sum of the inorganic soluble N. For instance, the water-soluble N of B3U-
400 was 10.19 N g kg− 1, whereas the sum of NO–3-N and NH+ 4 -N only
reached 1.49 N g kg− 1 (Table S2), meaning that other soluble N sources
apart from the mineral forms, dominated the water-soluble fraction.
Pyrolysis HTT affected N availability of the BBFs, as those made with
B-800 showed not only lower total N concentrations, but also lower
water-soluble and hydrolyzable N than those produced with B-400. Only
BBFs treated with nitric acid showed a relevant bioavailable N fraction
in the BBFs produced with B-800, with the ammonium sulfate treatment
being unsuccessful in increasing N concentration in biochar produced at
high pyrolysis temperatures.
4. Discussion
4.1. Influence of activation treatments on the N enrichment of BBFs
In agreement with our first hypothesis, the activation of biochar
before the addition of an external source of N was a suitable strategy for
enhancing N retention. Whereas the addition of N source to non-
activated biochars achieved N concentrations of up to 1.5 %, the com­
bination of the oxidation with HNO3 and the addition of N sources
produced BBFs with up to 7.0 % N. Activation with H2O2, and especially
HNO3, are known to increase biochar surface functional acid groups. Li
and Li (2019) described that HNO3 treatment produced carboxyl,
carbonyl and hydroxyl groups, as a consequence of the oxidation of
aromatic and aliphatic C on the biochar surface. In our case, an
enhancement of –COOH and –OH groups were observed in the FTIR
spectra of biochar oxidized with either HNO3 (B3-400) or H2O2 (B2-400)
(Figure S3). In addition, the XPS analysis confirmed an increase in these
functional groups in B3-400. The degree of oxidation was unequal for
both oxidizing treatments, as HNO3 oxidation was stronger than H2O2,
R. Castejón-del Pino et al.
as reflected by the increase in the intensity of the –COOH peak observed
in the FTIR spectra of B3-400 compared with B2-400 (Figure S3). The
increase in surface acidic functional groups in the oxidized biochars
improved its reactivity, favoring chemical and electrostatic interactions
with the added N sources to produce the enriched BBFs, in accordance
with Wang et al. (2020). Figure S4 was included in Supplementary
Material summarizing the main chemical reactions produced by the
activation treatments and the added N source.
The addition of urea led to the formation of amides, which represents
one of the largest N fractions incorporated into the BBFs’ surface, as
reflected in the enhancement in the amide/pyrrolic peak observed in the
XPS analysis (Fig. 2), and in the FTIR peak at 1590–1600 cm− 1 (Fig. 1).
The interaction between the carboxylic acid groups of the biochar with
amine-N compounds to form amides has already been described for
ethylenediamine (Zahedifar et al., 2021) and urea (Chhatwal et al.,
2020). Amine-N may interact either by a nucleophilic reaction with a
carbonyl group, or by a condensation reaction with carboxyls, forming
amides in both cases (Li and Li, 2019). Another fact that demonstrates
the formation of amides after urea treatment was the perceptible
carboxyl peak in B2-400 and B2AS-400, and its inexistence in B2U-400
(Fig. 1). This information suggested the conversion of carboxyl to an
amide peak in the urea samples and not in the ammonium sulfate ones.
The urea treatment also increased pyridinic N concentration as
observed in the XPS analysis (Fig. 2). O-containing functional groups can
react with amines through Maillard reactions, producing pyridinic and
other heterocyclic N groups (Chen et al., 2018). The formation of pyr­
idinic N after the urea treatment was previously reported to occur at
high temperatures during pyrolysis (Hulicova-Jurcakova et al., 2009),
with the highest pyridinic N formation observed at 600 ◦ C (Wang et al.,
2019b). In our study, we obtained a large proportion of pyridinic N, in
the range between 21.4 and 47.9 %, in BBFs treated with urea, even at
relatively low temperatures (80 ◦ C).
BBFs obtained with ammonium sulfate as the external N source
showed similar FTIR and XPS peaks than those treated with urea, but the
amount of the N forms differed as compared with urea-treated BBFs. The
XPS analysis of biochars treated with ammonium sulfate showed lower
amide/pyrrolic peaks than urea-treated biochars, suggesting a minor
formation of amides in ammonium sulfate BBFs. In the case of B3U-400,
which had the highest concentration of carboxylic acid groups, it
showed a higher amide/pyrrolic peak than B3AS-400, confirming that it
did not form a significant amount of amide groups (Table S3).
Biochar has traditionally been considered to adsorb NH+ 4 mainly
through H-bonding and electrostatic interactions (Cai et al., 2016),
however, the XPS analysis demonstrated the absence of NH+ 4 in both
urea and ammonium sulfate treatments, evidencing that biochar cation
exchange capacity was not an important mechanism for N retention in
our case. KCl extracts further demonstrated the absence of significant
concentrations of NH+ 4 in cation exchange sites (Table S2), which con­
tradicts the traditional view. Other less-studied mechanisms, involving
the retention of NH+ 4 with O-functional groups, may be relevant as
suggested by Takaya et al. (2016) for hydrochar and low temperature
biochars.
Apart from the interaction of the added N with carboxylic groups, the
incorporation of nitro groups in the modified biochars represented up to
50 % of the N functional groups in B3-400 and B3-800, as measured in
the XPS analysis (Table S3). The nitration of the aromatic rings to form
nitro groups represents another N retention mechanism derived from the
oxidation with nitric acid, as reported by Sajjadi et al. (2018). In
concentrated nitric acid solution, nitro-aromatic compounds are formed
between NO–2 and aromatic C rings by electrophilic aromatic substitution
(Yang et al., 2019). The oxidation with HNO3 also originated an increase
in pyrrolic and pyridinic N, as observed in the N1s spectra (Fig. 2). The
increase in heterocyclic N alongside the formation of nitro groups has
been previously reported (Lu et al., 2021; Zheng et al., 2020). Li and Li
(2019), in a biochar pre-treated with H3PO4, found graphitic N enrich­
ment with increasing the concentration of HNO3 treatment up to 25 %,
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Waste Management 158 (2023) 76–83
but, in our case, even using higher HNO3 concentration, we did not find
any significant increase.
BBFs treated with urea showed a remarkable amount of water-
soluble N, with inorganic N being a minor fraction of the total water-
soluble N (Fig. 3, Table S2). This result suggested the availability of
organic N in urea form. Sajjadi et al. (2019) noted H-bonding between
carboxyl and hydroxyl groups and urea. Aside from the chemical
bonding of N, activated biochars may retain N by other physicochemical
mechanisms. Otieno et al. (2021) found that the surface area and porous
structure of biochar can contribute in retaining ammonium in solution,
but in our case, the XPS and FTIR spectra rejected significant NH+ 4
concentrations. In fact, neither NO–3 nor NH+ 4 were the main water-
soluble N forms in urea-treated biochars, suggesting that a consider­
able amount of urea was trapped in the biochar pores. Liu et al. (2019)
described how the specific surface area diminished after the urea
application, suggesting that urea particles filled the micro and meso­
pores of the biochar. Nevertheless, HNO3-BBFs, which showed the
highest water-soluble N contents, are characterized by decreasing both
surface area and total pore volume (Chacón et al., 2020; Yang et al.,
2019), and the transformation of the micro- and mesopores to macro­
pores (Güzel et al., 2017; Vu et al., 2017). These macropores may have
been responsible for the physical retention of urea, as previously re­
ported by Liu et al. (2019).
The ultrasonic treatment was less effective for incorporating N than
the oxidation treatments. Sonication has been previously used to clean
the biochar surface, increasing its porosity (Sajjadi et al., 2019). These
authors used sonication as a pretreatment for the activation of biochar
with urea as a strategy to increase its adsorption capacity. The final N
concentration of biochars were in the 1.80 and 2.23 % range, which is in
line with the N concentrations of the sonicated BBFs in our study (be­
tween 0.97 and 1.73 %).
Pyrolysis HTT also influenced N enrichment, as lower temperatures
of biochar production led to higher N retention. Condensed aromatic C is
the most common structure found in biochars produced at a high py­
rolysis temperature, in which aliphatic structures and functional groups
(such as carbonyls, carboxyls, ketones and esters) are almost absent
(Hassan et al., 2020). Due to the high chemical stability of high tem­
perature biochars, oxidizing treatments were more effective in low
pyrolysis-temperature biochars. Our results are in agreement with Singh
et al. (2020), who found, in a study comparing urea sorption in biochars
made at different temperatures, the highest values for biochar made at
450 ◦ C, associated to the optimum equilibrium between functionality,
porosity and cation exchange capacity. Nevertheless, the application of
activation treatments is essential for biochar produced at a high tem­
perature, where the combination of HNO3 and urea treatments showed a
remarkable hydrolyzable N concentration despite the highly stable C
structure.
4.2. N Bioavailability in BBFs
N-doping of biochar through surface functionalization with N com­
pounds has been mostly used as a strategy to remove pollutants from the
environment (Yang et al., 2019). The adsorption properties of N-doped
biochars rely on the presence of amines, pyrrolic and pyridinic N, that
contain free electrons that can interact with organic and inorganic
pollutants (Wang and Wang, 2019).
In the case of BBFs, the added N needs to be plant-available to behave
as a slow or controlled N release fertilizer. For this reason, a different
approach is needed to reduce the recalcitrance of the added N and in­
crease its bioavailability. In this study, we hypothesized that the added
N source may influence the availability of the N in BBFs. The urea
treatments showed a high amount of hydrolyzable N, while ammonium
sulfate BBFs only reached a relevant N concentration when HNO3 was
used as the activation treatment. Approximately two thirds of the N in
urea BBFs were potentially bioavailable in the soil. In the case of the
most efficient BBFs (B3U-400), about 15 % of the total N was soluble in
R. Castejón-del Pino et al.
water, mostly in organic forms, as the inorganic N available for plants
represented 2.1 % of the N. This indicates that urea was either trapped in
pores as found by Liu et al. (2019); or retained by hydrogen bonding
interaction in accordance with Sajjadi et al. (2019) and Chen et al.
(2020). Our results suggest that a small amount of NO–3-N and NH+ 4 -N
would be plant-available at first, and the hydrolysis of the trapped urea
could start some days later in the short term (Sigurdarson et al., 2018).
A large proportion of the added N could be slowly available for
plants, since about 50 % of N in B3U-400 was hydrolyzable in acid,
which is considered a fraction that could be mineralized over time in soil
(Otto et al., 2013). Amides and nitro groups found on the biochar’s
surface may be the most relevant functional groups included in the N
hydrolyzable fractions of BBFs. Piash et al. (2021) described that in a soil
incubation experiment with an amide-rich biochar, most of the amide
content was released after the first 120 days, being available for plant
use in a reasonable crop growing period. We found that acid digestion
degraded most nitro groups, as confirmed by FTIR, where the peaks
associated to nitro groups (1385 and 1532 cm− 1) reduced their intensity
after hydrolysis (Figure S5). Accordingly, Marvin-Sikkema and de Bont
(1994) previously reported that microorganism degrade numerous
nitro-aromatic compounds in soil. The aromatic N contained in biochar
is generally considered unavailable (Jassal et al., 2015). However, our
results suggest that a small fraction of the heterocyclic N of BBFs,
especially low molecular weight pyrrols and pyridines, may also be
included in the hydrolyzable N fraction. Even though aromatic N in
biochar is generally considered to be mostly recalcitrant (Jassal et al.,
2015), Wang et al. (2012) reported that low molecular weight hetero­
cyclic N can decompose in soil.
The non-hydrolyzable N fraction represented about one third of the
total N in urea BBFs. This remaining N, composed of graphitic and the
non-hydrolyzable fraction of pyridinic and pyrrolic N, can be considered
to be recalcitrant. Aromatic N is mostly classified as a stable form,
although some authors revealed that aging, weathering and microbial
activity could mineralize it, being available for plant nutrition (Williams
et al., 2019). The biochar structure protects aromatic heterocyclic N, and
it only becomes available when the biochar structure starts to degrade in
soil. Mineralization of heterocyclic N may be possible on longer periods;
however, the C ring could be opened by hydroxylation, producing
aliphatic N compounds available for microbial use (Torres-Rojas et al.,
2020).
5. Conclusions
This study provided several modified biochars obtained from olive
tree pruning with a potential use as slow-release N fertilizers. The
biochar-based fertilizers contain heterogeneous chemical N forms,
which may regulate the N release. In general, oxidation treatments
enhanced the incorporation of N from the added N source, as compared
to sonicated and non-activated biochar. Biochars treated with nitric acid
showed the highest concentration of O-functional groups, which were
responsible for an important part of N retention. Aside from the incor­
poration of external sources of N, the oxidation with HNO3 increased N
content by itself, forming nitro groups and pyrrolic N. The combination
of HNO3 and urea led to the highest N enrichment in the biochar-based
fertilizers (BBFs). About two thirds of the N of the BBFs treated with urea
would be potentially available for plants with different release rates. The
water-soluble N, mostly in the form of trapped urea that would be firstly
available, represented a fraction of 14.5 %. Hydrolyzable N groups, as
amides, nitro groups and low weight molecular N that would be slowly
released in soils for plants nutrition, represented approximately 50 % of
the total N. These findings provide new insights to design future field
experiments to evaluate the slow-release performance, the efficient use
of the N of these engineered BBFs and their economic feasibility.
82
Waste Management 158 (2023) 76–83
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
We gratefully acknowledge the financial support of the projects
RTI2018-099417-BI00 and PID2021-128896OB-I00 from the Spanish
Ministry of Science, Innovation and Universities, co-funded with EU
FEDER funds. The authors are very grateful to Mr. Mario Fon for editing
the final version of the manuscript.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.wasman.2023.01.007.
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