Journal of Cleaner Production 242 (2020) 118486

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Integral valorization of fruit waste from wine and cider industries

Soria a, Rosa Rodriguez b, Daniela Salvatori a,
Paula Sette a, Anabel Fernandez b, Jose
,*
Germa
n Mazza a

a
n y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas, PROBIEN (CONICET-UNCo), Neuqu

Instituto de Investigacio en, Argentina
b
Instituto de Ingeniería Química - Facultad de Ingeniería (UNSJ) - Grupo Vinculado al PROBIEN (CONICET-UNCo), San Juan, Argentina

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

Article history: Agro-industrial waste disposal is becoming a key issue as a consequence of the increasing number of by-
Received 7 November 2018 products generated. Within this context, this work proposes an integral, effective and sustainable use of
Received in revised form biowaste from regional food industries as a drive towards cleaner production. Apple and grape waste
22 August 2019
from cider and wine industries was valorized by extracting bioactive compounds and pyrolyzing/gasi-
Accepted 17 September 2019
Available online 18 September 2019
fying the residual solid to obtain value-added chemical products, such as biochar. The extraction con-
ditions were as follows: a solvent/fruit ratio of 2/1 (w/w), an extraction temperature of 348 K and an
Handling Editor: Kathleen Aviso extraction time of 1.25 h. The extracts were analysed for soluble solids, sugars, acids, total polyphenol
content, antiradical activity and superficial colour. The grape stalk extract presented the highest poly-
Keywords: phenol content (1,758 ± 24 g gallic acid/100 kg) and antioxidant capacity (156 ± 6 g gallic acid/100 kg).
Agro-industrial waste The liquid fractions can be used to develop functional ingredients. After the extraction process, the
Bioactive compounds recovery remaining solid fraction was subjected to pyrolysis or gasification at low heating rates (10, 15 and 20 K/
Pyrolysis min). The resulting biochars presented low to moderate surface areas (0.9e266 m2/g) and low H/C ratios
Gasification
(high aromaticity). The obtained biochar can be used for the production of activated carbon to be used in
Biochar
fuel applications and as soil structure reinforcement. The proposed methods allowed for the optimization
of waste reclamation with two applications: the development of ingredients for the nutraceutical and
food industries and the production of biochar and renewable energy.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction hazards related to the accumulation of solid residues with high

Increasing concern for environmental pollution related to high
amounts of industrial waste has been noted in recent years. In
addition, the final disposal of this waste has become increasingly
expensive. In particular, in the Northern Patagonia region of
Argentina, fruit production (mainly apples, pears and grapes) is one
of the most developed activities. Fruits that do not meet the re-
quirements for the fresh market are destined to industries gener-
ating approximately 360 kt/y of organic waste, which represents
approximately 60% of total processed fruit. The waste discarded in
juice, cider, wine and sparkling wine production is an important
source of phenolic compounds with antioxidant capacity (Din ~ eiro
García et al., 2009), inhibitors of digestive enzymes and thick-
eners (e.g., pectin, dietary fibre and other antioxidant compounds)
(Llobera and Can ~ ellas, 2007). Considering the environmental
* Corresponding author.
E-mail address: german.mazza@probien.gob.ar (G. Mazza).
organic content, it is appealing to consider the waste of pears, ap-
ples and grapes as potential substrates for obtaining products with
high added value.
Bioactive compounds can be recovered from waste by using
adequate extraction methods. Operational conditions of the
extraction, such as the type of solvent and process duration and
temperature, determine the performance and quality of the com-
pounds obtained (Pinta
c et al., 2018). New technologies have been
explored for more efficient extraction, such as the use of ultra-
sound, microwaves, and pulsed electric fields, which are commonly
expensive, difficult to scale up, or energy intensive (Okolie et al.,
2019) taking into account both the economic and environmental
cost-benefit. Hydrothermal treatment appears as an eco-friendly
technology with several advantages, such as the absence of
organic solvents and related corrosion problems, and the fact that it
is easy to operate and cost effective (Sepúlveda et al., 2018).
Moreover, some studies reported higher bioactive content after
hot-water extractions compared to solvent extraction (Kabir et al.,
2015).

https://doi.org/10.1016/j.jclepro.2019.118486
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
Most works concerning the extraction of bioactive compounds
from agri-food residues focus on the extraction process and discard
the remaining solid. This by-product, rich in lignocellulosic com-
pounds, can be used for obtaining fuels and energy using thermo-
chemical treatments, such as pyrolysis and gasification (Di Blasi,
2009). Biowaste can be considered a neutral CO2 source, with low
nitrogen and sulfur contents, resulting in lower sulfur and nitrogen
oxide emissions (Biagini et al., 2008).
Pyrolysis and gasification of biomass produce three main
products: biochar, liquid (tar and water) and non-condensable
gases with yields that depend on the operating conditions and
feedstock properties. Syngas and tar have a high LHV (lower
heating value) and can be used for energy recovery. Tar can also be
further upgraded to renewable transportation fuels. Biochar is a
low-value product that has received increasing attention due to a
wide range of potential applications. It can be used as fuel, pre-
cursor of activated carbons, or as a fertilizer replacement, offering
an advanced option for biological sequestration of carbon (Qian
et al., 2015). The interest of the production of biochar by gasifica-
tion is still relatively novel, but recent reported results are prom-
ising (Fryda and Visser, 2015), particularly since it can be used to
both improve soil characteristics and catalyse hydrogen production.
Therefore, the use of biochar in these valuable applications could
provide economic benefits to biorefinery plants, including those
that use gasification or pyrolysis processes.
The biorefinery approach contributes to a cleaner production,
which is related to the concept of a circular economy (Sousa-Zomer
et al., 2018). Considering that it promotes the systems where ser-
vices and products are traded in cycles (closed loops), the 3R
approach of “reduce, recycle and reuse” is the guiding concept. In
this way, this work proposes an integral, effective and sustainable
use of biowaste from wine and cider industries by applying: 1) an
environmentally friendly extraction to obtain antioxidant-rich in-
gredients and 2) a slow pyrolysis and gasification of waste to pro-
duce chemicals and fuels, particularly biochar generation. This two-
step sequence leads to an almost-zero-waste condition based on
sustainable techniques.
2. Materials and methods
A combination of a selection of techniques and processes for the
integral valorization of fruit waste is comprehensively presented.
Experimental set-up and analytical and statistical methods are
described throughout the following subsections.
2.1. Materials
Fruit waste was collected from industries located in the Río
Negro province (Argentine Patagonia). Humberto Canale winery
located in the city of General Roca provided grape waste (var.
Sauvignon Blanc), and La Flor S.A. cider industry from Cipolletti City
provided green apple waste (var. Granny Smith). Three kinds of
waste were considered: green apple pomace (AP), grape marc
waste (GM) and grape stalk waste (GS) (Fig. 1). After collection, the
biowaste samples were immediately frozen and stored at 251 K
until use.
2.2. Waste characterization
The three biowaste samples (AP, GM and GS) were characterized
according to the Official Methods of Analysis of the Association of
Official Agricultural Chemists (AOAC, 2000): moisture (925.09),
soluble solids (932.12) (Pal e Pocket, ATAGO CO. LTD, Tokyo, Japan),
acidity (945.26), and pH (945.27). Water activity (aw) was deter-
mined using an electronic dew point water activity metre (Aqualab
Series 3 TE, Washington, USA). The methods used for total phenolic
content and antiradical activity determinations are described
below in Section 2.5.
2.3. Extraction process of bioactive compounds
An aqueous extraction process (Fig. 1a) was performed on the
waste samples, following the methodology reported by Garrido
Makinistian et al. (2019) with the optimal temperature-time con-
dition defined by these authors. After the extraction process, two
very different by-products were obtained: 1) liquid extracts con-
taining bioactive compounds and 2) a solid fraction, rich in ligno-
cellulosic material. Both products were characterized to predict
their usefulness.
2.4. Processing of the solid fraction
The residual solid fraction (RSF) obtained after the extraction
process (Fig. 1a) was treated following the steps presented in
Fig. 1b: samples were dried under forced air convection at 333 K
(z10% relative humidity and air speed ¼ 1.5 m/s) using an air
convection oven model Venticell 111- Standard (MMM Medcenter
Einrichtungen GMBH, Munich, Germany). The three sets obtained
after drying (AP, GM, GS) were ground and passed through a sieve
(sieve ASTM-USA, mesh 30). Particulate samples with a 500 mm size
were used for the thermochemical treatments.
2.5. Chemical and functional properties of raw waste and aqueous
extracts
Chemical determinations were performed on methanolic ex-
tracts, which were prepared as follows: 0.001 kg of sample was
homogenized in 25 mL of absolute methanol and constantly mixed
using a magnetic stirrer for 1200 s prior to filtration. Extracts were
prepared by triplicate. A T60 UVeVisible spectrophotometer (PG
Instruments, Leicestershire, United Kingdom) was used for
analytical assessments.
2.5.1. Total phenolic content (TPC)
TPC was determined using the FolineCiocalteu reagent ac-
cording to Sette et al. (2017). A calibration curve was generated
using gallic acid as the standard. The results were expressed as
gallic acid equivalents (GAE) per 100 kg sample (waste or extract)
on a dry basis (d.b.).
2.5.2. Antiradical activity (AA)
AA was evaluated using the bleaching method of the radical 1,1-
diphenyl-2-picrylhydrazyl (DPPH$) according to Sette et al. (2017).
A calibration curve was generated using gallic acid as the standard.
The results were expressed as GAE per 100 kg sample (waste or
extract) on a dry basis (d.b.).
2.5.3. Sugars and acids content
Glucose, fructose, sucrose and organic acids (citric, malic, tar-
taric, succinic, lactic, ascorbic and acetic) were assessed in the three
waste extracts. Twenty microliters of extract was injected in an
Agilent 1260 HPLC (Agilent Technologies, USA) equipped with an
automatic injector (ALS) and two detectors: a refractive index de-
tector (RID, sugar detection at 328.15 K) and a diode array detector
(DAD, organic acid detection). Separation was achieved using a
Hiplex H column (300  7.7 mm, 8 mm particle size, Agilent Tech-
nologies, USA) at 348.15 K, and chromatograms were recorded at
214 nm. The mobile phase was composed of 0.001 M H2SO4 (iso-
cratic) and the flowrate was 0.4 mL/min. Standard compounds were
used to build calibration curves in aqueous solutions with high
 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
Fig. 1. Processing of the fruit waste.
linearity for all standards (r2 > 0.999): D-(þ)-glucose (Sigma
Aldrich), D-()-fructose (Sigma Aldrich), sucrose (Merck), citric
acid (Cicarelli), L-(þ)- tartaric acid (RP ACS), L-malic acid (Sigma
Aldrich), succinic acid (Merck), L-lactic acid (Megazyme), L-ascorbic
acid (Sigma Aldrich), acetic acid (Cicarelli) and glycerol (Sigma
Aldrich).
2.6. Superficial colour of the waste extracts
Superficial colour was determined by photocolorimetry using a
handheld colorimeter (Minolta Co, model CR400, Japan). Colour
functions were calculated for illuminant C at a 2 standard observer
and in the CIELAB uniform colour space. Measurements were per-
formed using glass vials containing enough powder to reach a
height of 1 cm, and ten replicates were used. A white cylindrical cup
was used to cover the vial and standardize the measurements. L*, a*
and b* values were obtained. The L* value represents colour light-
ness (0 ¼ black and 100 ¼ white), the a* scale indicates the chro-
maticity axis from green () to red (þ) and the b* axis ranges from
blue () to yellow (þ).
2.7. Chemical and functional properties of residual solid fraction
(RSF)
Lignin, cellulose and hemicellulose contents, density and par-
ticle morphology of RSFs were evaluated prior to thermal
treatments.
3
2.7.1. Lignin, cellulose and hemicellulose contents
The lignin, cellulose and hemicellulose contents of the different
RSFs were determined according to the American Society for
Testing and Materials standards (ASTM D1106-56, ASTM D1103-60
and ASTM D1103-60).
2.7.2. Density
The absolute density was calculated according to the ISO 13503-
2 (2016) standard using an Accupyc 1330 pycnometer (Micro-
meritics Instruments, Norcross, GA, USA).
2.7.3. Particle morphology
The microstructural characteristics of the dry powders were
analysed by scanning electron microscopy (SEM) using a Zeiss
microscope Supra 40 (Carl Zeiss, Oberkochen, Germany). The
samples were placed in an aluminium support using conductive
carbon double-sided adhesive tape, and then coated with gold
nanoparticles using a sputter coater (Cressington Scientific In-
struments 108). Images were taken with the detector within the
lens, using an acceleration voltage of 3.00 kV.
2.8. Macro-TGA of RSF
The macro-TGA experiments were carried out in a 5 cm ID and
100 cm height stainless steel reactor as described by Fernandez
et al. (2019). Three heating ramps, 10, 15 and 20 K/min, up to final
temperature of 1,173 K, were assayed in this study. A mass of 5 g RSF
with particle sizes ranging from 0.212 to 0.250 mm was used. In the
4 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486

pyrolysis experiments, the flow rate of nitrogen was set at 100 mL/ Table 1
min. Gasification experiments were carried out under an air/steam Physicochemical and functional properties of the three types of fruit waste: grape
marc (GM), grape stalks (GS) and apple pomace (AP).
atmosphere. The steam flow rate was 0.17 mL/min, setting the
steam/biomass ratio at 2.5 (Fernandez et al., 2019) and the equiv- Properties GM GS AP
alent ratio (ER) at 0.1. aw 0.957 ± 0.007a 0.962 ± 0.003a 0.976 ± 0.004b
Water Content (% w.b.) 61.6 ± 1.2b 59.2 ± 0.3a 85.2 ± 0.6c
pH 4.62 ± 0.12b 4.23 ± 0.12a 4.3 ± 0.7a
2.9. Biochar characterization Acidity (%, d.b.) 3.2 ± 0.4a 3.3 ± 0.3a 3.9 ± 0.2a
TPC (g GAE/100 kg d.b.) 1,140 ± 23b 1,537 ± 31c 650 ± 35a
The elemental analysis was accomplished in a Carlo Erba EA AA (g GAE/100 kg d.b.) 269 ± 12a 971 ± 60b 245 ± 33a
1108 elemental analyser (Carlo Erba Instruments, Milan, Italy), ac- Means within columns with a different lowercase superscript letter are significantly
cording to ASTM D5373. The carbon, hydrogen, nitrogen and sulfur different (p < 0.05).
contents were directly determined, while oxygen was calculated by The values are expressed as the mean ± standard deviation (n ¼ 3).
difference. The ASTM standards (D1102e84 ASTM, 2001; E872 - 82 (d.b. ¼ dry basis; w.b. ¼ wet basis; aw ¼ water activity).

ASTM, 1998) were used to determine the proximate analysis. The

specific surface area was calculated using a multilayer BET
Table 2
adsorption model with N2 at 77 K (Nova 2200, Quantachrome In- Physicochemical properties of waste extracts obtained from apple pomace (AP),
struments, Florida, USA). The biochar characterization also included grape marc (GM) and grape stalks (GS).
the evaluation of typical properties such as recalcitrance potential
Properties GM GS AP
(R50), carbon sequestration potential (CS), persistence in soil (in
aw 0.985 ± 0.002a 0.987 ± 0.001a 0.987 ± 0.001a
terms of the mean residence time, MRT), aromaticity factor (f a Þ,
pH 4.14 ± 0.02b 4.12 ± 0.02b 3.48 ± 0.02a
stable C mass fraction (SCF) and the high heating value (HHV). The Density (g/mL) 1.024 ± 0.004b 1.021 ± 0.003b 1.016 ± 0.002a
calculation of these parameters is described in Section SI-1 of the Brix (%) 5.33 ± 0.06b 7.073 ± 0.064c 4.27 ± 0.12a
Supporting Information, Appendix A. Acidity (%) 0.23 ± 0.02b 0.34 ± 0.02c 0.17 ± 0.02a
Glucose (g/kg) 15.308 ± 0.048c 8.251 ± 0.072b 6.519 ± 0.272a
Fructose (g/kg) 15.137 ± 0.039b 9.063 ± 0.042a 14.165 ± 0.199b
2.10. Assessment of the integral valorization yield (hI) Sucrose (g/kg) nd nd 1.736 ± 0.057
Tartaric acid (g/kg) 1.754 ± 0.032a 1.834 ± 0.044b nd
Aiming to assess the yield of the integral valorization, partial Malic acid (g/kg) 1.14 ± 0.06b 0.865 ± 0.032a 1.313 ± 0.019c
yields on a dry basis for the extraction process (hE) and for the Means within columns with a different lowercase superscript letter are significantly
thermochemical process (hT,G for gasification and hT,P for pyrolysis) different (p < 0.05). The values are expressed as the mean ± standard deviation
were calculated, as well as the yield of the polyphenol compounds (n ¼ 3).
nd: not detected.aw ¼ water activity.
present in the extracts (hTPC,E). Yields were defined as weight
proportions with respect to the initial waste in all cases. Then, the
integral yields for pyrolysis (hI,P) and gasification (hI,G), were Table 3
calculated as follows: Characterization of the RSFs from apple pomace (AP), grape marc (GM) and grape
stalks (GS).
hI;P ¼ hE þ hT;P (1)
Properties GM GS AP

aw 0.222 ± 0.002a 0.214 ± 0.003a 0.287 ± 0.001b

hI;G ¼ hE þ hT;G (2) Water content (%) 3.346 ± 0.005a 4.93 ± 0.05c 4.34 ± 0.02b
Neutral detergent fibre (%) 41.7 ± 0.7b 43.2 ± 0.5b 38.9 ± 1.4a
where, hE ¼ mass of extracts (d.b.)/initial waste mass (d.b.), Acid detergent fibre (%) 36.46 ± 0.18b 37.1 ± 0.3b 28.39 ± 0.6a
Lignin (%) 29.8 ± 0.8c 24.9 ± 0.6b 18.1 ± 0.5a
Hemicellulose (%) 5.2 ± 0.7a 6.1 ± 0.5b 10.6 ± 0.8c
hT,P ¼ mass of char issued from pyrolysis (d.b.)/initial waste Cellulose (%) 6.6 ± 0.5a 12.2 ± 0.4c 10.3 ± 0.4b
mass (d.b.) and Density (g/cm3) 1.4 ± 0.2a 1.41 ± 0.03a 1.47 ± 0.12b
hT,G ¼ mass of char issued from gasification (d.b.)/initial waste Means within columns with a different lowercase superscript letter are significantly
mass (d.b.) different (p < 0.05).
The values are expressed as the mean ± standard deviation (n ¼ 3).
(aw ¼ water activity).

2.11. Statistical analysis

With the exception of superficial colour, the determinations
involved three replicates (n ¼ 3), and the results were expressed in
terms of the mean and standard deviation of the mean (SD).
Analysis of variance (ANOVA) was accomplished to establish the
presence or absence of significant differences. Multiple compari-
sons were performed using the Tukey test to establish significant
differences between means at a significance level set at p < 0.05
(letters used as superscripts in Tables 1e3). All statistical analyses
were carried out using the data analysis software system STATIS-
TICA 8.0 (StatSoft, Inc., Tulsa, OK, USA).
3. Results and discussion
This section is divided into three parts to present the results
obtained: 1) physicochemical characterization of the as-received
residues samples, 2) analysis of the extraction process stage, and
3) analysis of the thermochemical treatments of the remaining
solid waste.
3.1. Waste characterization
Table 1 shows properties that are relevant to usage of extracts
from wastes, such as polyphenol content and antioxidant capacity,
as well as other parameters often used to characterize materials
from vegetable sources including water content, water activity and
acidity, among others.
Regarding the bioactive compounds, the GS stands out from the
rest of the biowaste samples, since significantly higher values of
polyphenol and antioxidant capacity were recorded for this sample.
These results are in accordance with those obtained for the
 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
polyphenol content of stalks (Alonso et al., 2002) and pomace
(Llobera and Can ~ ellas, 2007) from the winemaking process. The TPC
values obtained in the AP samples fit the data values reported by
Din~ eiro García et al. (2009). The AP sample also had a high hu-
midity, similar to that of the parenchymatic tissue of fresh apples
(var. Granny Smith) (Salvatori et al., 1998).
3.2. Extraction of bioactive compounds
Cebulj et al. (2017) observed that the apple skins of different
varieties presented higher contents of sugars, organic acids and
phenolic compounds compared to flesh. Peixoto et al. (2018) also
observed in grapes that seed, skin and pomace contained the
highest phenolic content. During industrial pressing, only a fraction
of these compounds will transfer into the juice, while the rest will
be retained in the biowaste (Oszmianski et al., 2011).
Characterization in terms of sugar content and organic acids
(Table 2) showed that sugar-rich extracts, containing mainly fruc-
tose and glucose and with a considerable amount of acids, were
obtained. As expected, malic acid was detected in all cases, and
tartaric acid was present in the extracts from the grape waste
samples.
In GS extracts, the presence of a certain amount of sugars is due
to the impregnation of the material by grape juice during the
destemming operation (Spigno et al., 2013) (Table 2). GM extract
presented the highest content of glucose and fructose because this
fruit is richer in sugars and because the marc from white wine
making processes did not undergo fermentation preserving resid-
ual sugars. Although both grape and apple fruits are composed of
sucrose, it was only detected in AP extracts, probably as a conse-
quence of hydrolysis during processing.
Samples containing the highest phenolic content, such as GS
extracts (Fig. 2a), also showed the highest antiradical activity
(Fig. 2b). AP extract exhibited the lowest antiradical activity (AA)
Fig. 2. Total phenolic content (TPC) (a) and Antiradical Activity (AA) (b) of the extracts
obtained from the different fruit waste. Apple pomace (AP), grape marc (GM) and
grape stalks (GS). (w.b. ¼ wet basis).
5
value (24.2 ± 4 g GAE/100 kg) among all the samples, in line with
this extract exhibiting very low TPC content (6.5 ± 0.7 g GAE/
100 kg). The absence of a clear correlation between the phenolic
content of GM and the AA value suggests that factors other than
polyphenol compounds are involved in the antioxidant potency in
terms of the ability to reduce free radicals. Indeed, the degradation
products of phenolic compounds can also have AA that is some-
times higher than that of the initial phenolic compounds
(Murakami et al., 2004). Additionally, polyphenols have been found
to be synergists; that is, the antioxidant effect is enhanced when
they are combined (Phan et al., 2017). Regarding the significant
level of phenolic content and AA detected in extracts from grape
stalks, some studies have demonstrated that leaves and stems of
grapevine represent an ideal biomass feedstock to obtain phenolic
compounds (Eftekhari et al., 2017).
Grape extracts presented a particularly high polyphenol level
and AA (Fig. 2) compared to the corresponding initial biowaste
(Table 1); only the AP extract exhibited a lower TPC value. The
observed increase could be due to the release of phenolic and
antioxidant compounds as a consequence of the operating condi-
tions of the extraction process. All soluble phenolic compounds are
accumulated in the cell vacuole. Free compounds are easy to
extract, but when phenolic acids and several other components
exist as insoluble bound complexes, they are not as easy to extract,
since they are coupled to cell wall polymers through ester and
glycosidic links. Therefore, the total polyphenol content deter-
mined in waste samples would not account for the phenolic acids
bound to the cell wall of the fruit tissue. However, when the
extraction process is applied, the integrity of cell walls can be
affected and make the phenolic compounds in waste fruits more
accessible for extraction. This phenomenon could explain the
higher polyphenol amount observed in the extracts compared to
that in both grape waste samples.
From a nutritional standpoint, it can be concluded that
compared with commercial fruit juice as a polyphenol source, the
intake through biowaste extracts would be similar, if not higher.
The consumption of commercial apple juice provides approxi-
mately 15e60 g of polyphenols/100 kg (Ignat et al., 2011), while
commercial grape juice provides between 111.2 and 343.3 g TPC/
100 kg of juice (Yuan and Baduge, 2018). The GM and GS extracts
obtained in this work had a TPC higher than 250 g/100 kg extract
(Fig. 2), indicating the high potential of these products as a source
of natural phenolic compounds.
For applications in foods such as beverages, jelly or concen-
trates, it is also important to consider the colour of the extracts
evaluated through the chromatic parameters (Fig. 3). Positive a*
and b* parameters were obtained in all cases, with the extracts
generated from AP having the highest b* value and the lowest a*
value, consistent with the more yellowish tone also illustrated in
Fig. 3c. Regarding luminosity, these samples were also the lightest.
These chromatic characteristics make it possible to use AP extracts,
for example, for the development of light preparations. Grape ex-
tracts exhibited darker colours (<L*, > a*), thus being suitable for
polyphenol enrichment of dark beverages or other foods without
changing the colour to a great extent.
Considering the presence of natural carbohydrates and organic
acids (Table 2), the extracts could also be considered for the prep-
aration of natural syrups with antioxidant potential. For example,
for their application in nutraceutical tablets or medicinal capsules,
the extracts must be purified and dried and further combined with
other compounds according to the requirements for these products.
If a powdered product is developed for use in composite food
development, such as cereal, fruit bars or candies with antioxi-
dants, no purification of the extracts would be needed prior to the
drying process.
6 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
Fig. 3. CIELAB coordinates b* versus a* (a) and lightness (L*) (b) of AP extract (:), GM extract (-) and GS extract (C) (c) Images of the obtained extracts from grape marc (GM),
grape stalks (GS) and apple pomace (AP).
3.3. Use of RSF for pyrolysis and gasification
The chemical composition of the three RSFs of the present study
is an important topic to be considered when the thermal treatment
is to be selected, but it also determines the type of fuel or energy
by-product that will be primarily generated. From Table 3, it can be
observed that the highest hemicellulose and lignin contents were
present in AP and GM, respectively, while GS had the highest cel-
lulose content (12.19%). The contents of cellulose, hemicellulose
and lignin of AP, GS and GM were similar to those reported by Saffe
et al. (2019).
A preliminary qualitative observation of the particle size and
shape, as well as surface features from micrographs obtained by
SEM (Fig. 4), allows comparing the three RSF samples to antici-
pate the potential applicability of these solids. In Fig. 4a, it can be
observed that the solid AP presented a more homogeneous par-
ticle size. The particles were smaller than those of GM and GS
(Fig. 4c and e), which exhibited more irregular structures. Thus,
the apple pomace RSF looked adequate for mixing dry in-
gredients or for thermochemical treatments in fluidized bed
units.
3.3.1. Pyrolysis
Fig. 5 shows the weight loss and the weight loss rate (DTG)
curves obtained during the pyrolysis process. Thermal decompo-
sition occurred in three stages. During the first step, the average
weight loss was approximately 12% for GM (Figs. 5a), 10% for GS
(Figs. 5b) and 14% for AP (Fig. 5c). It is related to water evaporation
and free sugar decomposition or volatilization, taking place in the
temperatures range of 300e520 K for GM, and up to 540 and 560 K
for GS and AP, respectively (Nolasco and Massaguer, 2006). The
greatest weight loss was observed in the second stage achieving
37% for GM, 42% for GS and 54% for AP. It is most likely due to the
degradation of some low-molecular-weight components, such as
hemicellulose and cellulose (Volker and Rieckman, 2009) and it
occurred in the range 560e750 K for GM, 540e830 K for GS and
520e800 K for AP. The AP exhibited the highest mass loss, which
could be a consequence of the higher fraction of cellulose and
hemicellulose. The weight loss and corresponding temperature
ranges for the third stage were 27% (750e1,173 K) for GM, 33%
(830e1,173 K) for GS and 26% (800e1,173 K) for AP. It can be
attributed to the decomposition of substances with more complex
structures, such as lignin. Lignin decomposition can also take place
throughout a wider range of temperatures, as reported by Yang
et al. (2007). The additional peaks observed for GS (Fig. 5b) at
approximately 998 K could indicate triglyceride decomposition, as
stated by Casazza et al. (2016).
The highest total mass loss (94%) during pyrolysis corresponded
to AP (Fig. 6a). Such a behaviour can be explained by the higher
contents of cellulose and hemicellulose and the lower lignin frac-
tion compared with GM and GS (Table 3) as reported by Wang et al.
(2018). When performing TGA experiments on cellulose, hemicel-
lulose and lignin samples, the authors found that the highest
weight loss occurred for cellulose. Additionally, the heating rate
had a significant influence on the biochar yield, although no
defined trend was observed (Fig. 6a), which is in agreement with
the observations reported by Zhao et al. (2018).
A comparison with unextracted GM and GS samples (Fernandez
et al., 2016) was performed. The authors found that the maximum
weight loss at 10 and 15 K/min occurred at lower temperatures
(500e600 K) when compared to the results obtained in this work. A
lower weight loss was observed during the first stage of pyrolysis
for the RSFs from GM and GS, which may be due to the removal of
compounds other than polyphenols, such as a certain fraction
polysaccharides in the waste matrix (Casazza et al., 2016). More-
over, the biochar yields obtained for the RSF samples were higher
than those obtained from the as-received samples (Casazza et al.,
2016).
3.3.2. Gasification
Three stages were also observed for gasification (Fig. 7). The first
stage, also related to water evaporation and free sugar volatiliza-
tion, produced a 14% weight loss for GM (Figs. 7a), 13% for GS
(Figs. 7b) and 14% for AP (Fig. 7c). It occurred between 300 and
620 K (GM), 300 and 630 K (GS) and 300 and 580 K (AP). Greater
weight loss (40% for GM, 40% for GS, and 60% for AP) took place in
the second stage between 610 and 900 K for GM, 590 and 830 K for
GS and 520 and 770 K for AP. The last weight loss observed was
related to the decomposition of more complex compounds and
occurred between 800 and 1,173 K for GM, 700 and 1,173 K for GS
 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486 7

Fig. 4. Scanning electron microscope micrographs of the solid waste powders: (a, b) AP; (c, d) GM; (e, f) GS.

and 720 and 1,173 K for AP, with weight loss values of 22%, 17% and the steam/air atmosphere, may produce complex chemical reaction
24% for GM, GS and AP, respectively. mechanisms, which impact in biochar yield.
Comparing the pyrolysis and gasification results, more signifi-
cant weight loss took place during the latter process. The second
3.4. Biochar characterization
stage of gasification began at higher temperatures than those for
pyrolysis, probably due to the highly complex chemical reaction
The composition of biochar produced at different heating rates
mechanisms exhibited in gasification (Jarosz and Małecki, 2014).
during both pyrolysis and gasification processes of the three re-
Even if the reaction of char with steam commonly produces
sidual solid fractions is presented in Table S1 (Appendix A, in the
higher weight loss than that corresponding to the third stage of
Supporting Information). The three biochars exhibited different
pyrolysis, the mass loss observed in our experiments was quite
behaviours, illustrating the heterogeneous nature of the material. It
similar for both pyrolysis and gasification. This may be caused by
can be noted that char from AP contained the highest carbon
the pretreatment step (extraction).
content (>74 wt%) as well as hydrogen content, followed by GM,
The biochar yields did not seem to follow the same trend, when
while GS displayed the lowest content of carbon (<65 wt%). In
increasing heating rate, as that of pyrolysis (Fig. 6b). The lignin-
contrast, biochar from GS presented the highest oxygen content,
cellulose-hemicellulose interactions, along with the influence of
regardless of the heating rate and thermochemical process. The
8 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486

Fig. 5. Weight loss and derivatives curves for (a) grape marc, (b) grape stalk and (c) apple pomace at different heating rates (pyrolysis).

Fig. 6. Residual biochar (%) after the pyrolysis (a) and gasification (b) for apple pomace (AP), grape marc (GM) and grape stalk (GS) at different heating rates.
 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
Fig. 7. Weight loss and derivatives curves for (a) grape marc, (b) grape stalk and (c) apple pomace at different heating rates (gasification).
nitrogen for the three biochar samples was in the range of 1e1.95%,
which is similar to chars obtained from vegetables. Moreover, sulfur
was not detected since it was eliminated during pyrolysis. On this
basis, the biochar could be suitable as a fuel and for the production
of activated carbons.
The results of Table S1 indicate that an increase in the heating
rate enhanced the carbon content for the three biochars. In
contrast, the presence of the oxygen decreased by using higher
heating rate. Onay (2007) reported a similar trend for the pyrolysis
of safflower seed. The effect of the heating rate on oxygen content
can be attributed to CO and CO2 generation (Ayala-Corte
s et al.,
2019). Moreover, it was observed that the effect of heating rate
on elemental composition was more important in GS than in GM or
AP.
No significant changes were detected when pyrolyzing or gasi-
fying the AP or the GM. Nevertheless, the pyrolyzed grape stalk
biochar had a lower content of carbon than the corresponding
gasified RSF, in agreement with observations from Qian et al.
(2013).
9
Based on the theoretical concepts presented by Xiao et al.
(2016), the H/C and O/C ratios were calculated to first estimate
the degree of aromaticity and stability of the biochar samples. It is
found that the three biochar samples presented a low H/C ratio
which indicates a high aromaticity (Ronsse et al., 2013). The low
values of the H/C ratio derive from the cleavage of weak bonds
inside the biochar matrix at high temperatures (Demirbas, 2004).
The influence of the heating rate was not significant, and the H/C
ratio seemed to be more dependent on the type of RSF than on
other factors. In addition, the thermochemical process did not
considerably influence the H/C ratio.
The effect of the heating rate on the O/C ratio was not significant
for the biochar derived from pyrolysis/gasification of AP and GM
but it has a remarkable effect on the material derived from GS.
Additionally, it is worth noting that the biochar from GM and AP
had the lowest O/C ratio, enhancing the stability in comparison to
the GS biochar.
Table S2 summarizes the main parameters for the character-
ization of the biochar, as mentioned in Section 2.9. The R50 values of
10 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486

Table 4
Yields of the extraction (hE) and thermochemical (hT,P,hT,G) steps and overall yield (hI,P,hI,G) obtained with apple pomace (AP), grape marc (GM) and grape stalks (GS).

Yield AP GM GS

hE (%) 43.60 14.40 41.00

hTPC,E(%) 9.52 58.67 317.9
xRSF ¼ wtRSF/wtdry raw waste 0.56 0.86 0.59
10 K/min 3.96 7.78 9.90
hT,P (%) 15 K/min 2.03 18.36 5.43
20 K/min 5.32 25.31 14.25
10 K/min 1.85 23.79 7.41
hT,G (%) 15 K/min 0.41 8.32 17.94
20 K/min 0.13 26.81 23.06
10 K/min 47.56 22.18 50.90
hI,P (%) 15 K/min 45.63 32.76 46.43
20 K/min 48.92 39.71 55.25
10 K/min 45.45 38.19 48.41
hI,G (%) 15 K/min 44.01 22.72 58.94
20 K/min 43.73 41.21 64.06

the biochars were lower than 0.50, which is similar to uncharred the initial waste (Table 4). The same trend was observed when
plant biomass. Additionally, there were no significant differences analysing the overall yields. As the heating rate increased, the
between the R50 values for the biochar from pyrolysis and from overall yield was the highest for GS samples. Thus, GS waste seems
gasification. Low values of CS were obtained, regardless of the to be the most convenient for the integral valorization processes
thermochemical process, although the highest value of CS corre- proposed in this work.
sponded to biochar from gasification of the grape marc RSF. Addi-
tionally, no significant differences were observed for the MRT
values, which were between 1253 and 1701 years. The aromaticity
4. Conclusions
(fa) varied between 0.87 and 0.98 and between 0.74 and 0.88 for
biochar from pyrolysis and gasification, respectively. The obtained
In this work, the combination of an aqueous extraction of
SCF values ranged between 0.81 and 0.86 for pyrolysis and between
phenolic compounds, as a pretreatment, followed by thermo-
0.77 and 0.85 for gasification. The low H/C ratio and high aroma-
chemical processes has been proposed for the valorization of grape
ticity values resulting from the high thermal processes (>500  C),
and pomace waste from regional industries.
would indicate that these biochars could not be suitable for the
It was found that aqueous extracts, especially those obtained
removal of inorganic pollutants. On the contrary, the obtained
from grape stalks usually not considered in extractive processes,
biochars would be adequate for the remediation of organic com-
presented high polyphenolic content and antioxidant capacity.
pounds from water and soil (Oliveira et al., 2017). On the other
They even surpass those of commercial fruit juice, suggesting their
hand, the high stability of the biochars suggests their potential to
potential as functional ingredients in foods or for nutraceutical
reinforce soil structure. Finally, it should be noted that the HHV
development.
values of biochar derived from pyrolysis and gasification of the
The TGA results indicated that the pretreatment caused the
three RSFs were higher than those of biochars generated from
maximum weight loss to occur at higher operating temperatures,
unextracted biomass (Fernandez et al., 2016).
producing a slight decrease in the solid biochar yield. Based on the
The influence of the heating rate and RSF type on the biochar
low nitrogen and sulfur contents along with the small surface areas
surface area (SA) is presented in Fig. S1a and S1b for pyrolysis and
of the biochars, they can be used as fuel for energy purposes as well
gasification, respectively. As the heating rate increased from 10 to
as a raw material for the production of activated carbons. Addi-
20 K/min, the SA decreased. It is believed that the volatiles are
tionally, the high stability of the biochar enables their consideration
produced faster, which may lead to an intra- and inter-particle
as an agent to reinforce soil structure.
accumulation of volatiles, thus increasing the chance of pore
Finally, the overall yield analysis revealed grape stalk waste as
blockage by carbon deposits (Angın, 2013). A decrease in SA with
the most promising waste for the valorization approach proposed
heating rate was also reported previously (Mui et al., 2010). The
in this work.
highest surface area was obtained for biochar from the apple
This work provides a strategy to achieve a high valorization of
pomace RSF for both pyrolysis and gasification processes. However,
fruit residues, promoting the development of combined sustainable
the biochar SA for the gasified RSF was considerably lower than the
processes while minimizing waste disposal. This approach could
value obtained during pyrolysis. The gasification tends to provoke
have a positive economic and environmental impact, contributing
the breakage of the biochar structure and it may cause carbon soot
to cleaner production in line with the concept of a circular
deposition which partially obstructs the voids. Both processes
economy.
contribute to the decrease in SA. Compared with activated carbons,
Future work can focus on the use of new green extraction
the biochars exhibited much lower SA, which may limit their use as
technologies in order to improve the antioxidant potential of the
sorbents for removing contaminants.
extracts. Additionally, bearing in mind that this work dealt with the
biochar production, a further study on operating conditions to
3.5. Yield of the integral valorization
upgrade gas and tar fractions is envisaged.

Although GS and AP wastes presented higher yield values

regarding the extraction process (hE) compared to GM waste, the
effective ingredient yield in terms of polyphenols was significant in Declarations of interest
both grape extracts. In particular, the extraction method applied to
the GS samples succeeded in recovering polyphenol compounds of The authors have no conflicts of interest to report.
 P. Sette et al. / Journal of Cleaner Production 242 (2020) 118486
Acknowledgements
The authors appreciate the support of the following Argentine
institutions: Universidad Nacional del COMAHUE, Argentina (PIN
No. 04/I223 and 04/L007); CONICET (National Scientific and Tech-
nical Research Council, Argentina) PUE PROBIEN 22920150100067;
ANPCyT (National Agency for Scientific and Technological Promo-
tion, Argentina) e MINCyT (PICT No. 2014e2078); and CONICET and
SECITI e San Juan (PIOeNo. 15020150100042CO).
Anabel Fernandez has a Doctoral Fellowship from CONICET.
Paula Sette has a Post-doctoral Fellowship from ANPCyT. Germ
an
Mazza, Daniela Salvatori and Jose
Soria are Research Members of
CONICET. The authors also thank L. Bajda, M. Amaro and R. C.
Maturano (PROBIEN, CONICET-UNCo) for their technical assistance
in the HPLC analysis and waste physicochemical characterization.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.118486.
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