Renewable and Sustainable Energy Reviews 148 (2021) 111268

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Renewable and Sustainable Energy Reviews

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

Inorganics in sugarcane bagasse and straw and their impacts for bioenergy
and biorefining: A review
Djanira R. Negrão a, Adriana Grandis b, Marcos S. Buckeridge b, George J.M. Rocha a,
Manoel Regis L.V. Leal a, Carlos Driemeier a, *
a
Brazilian Biorenewables National Laboratory (LNBR), Brazilian Center for Research in Energy and Materials (CNPEM), 13083-970, Campinas, SP, Brazil
b
Laboratory of Plant Physiological Ecology (Lafieco), Department of Botany, Biosciences Institute, University of São Paulo, Brazil

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

Keywords: Sugarcane is the base of a successful agroindustrial system in several tropical and subtropical regions of the
Herbaceous biomass world. This industry is evolving towards diversification of its product portfolio and valorization of the vast
Biofuel amounts of lignocellulosic feedstocks: bagasse and straw. These trends make the sugarcane industry a learning
Agricultural residue
ground for the utilization of agricultural residues and herbaceous biomass for bioenergy and biorefining. The
Silica
presence of inorganics in sugarcane bagasse and straw, constitutive of the plant as well as originated from
contamination, impacts several of the current and potential uses of the biomass. Although many studies refer
broadly to terms like “inorganics”, “ash”, “silica”, “sand” or “mineral impurity”, there is a lack of a coherent and
nuanced presentation of the inorganics of bagasse and straw: what they are, how variable they can be, and how
they can impact different processes and products in biorefineries. This review article aims at filling this gap.
Bagasse and straw inorganics are discussed considering their agroindustrial context and how they can impact
processes such as combustion, pyrolysis, production of cellulosic ethanol and biomaterials. Prospects for valo­
rization of the biomass inorganics are also discussed, beyond nutrient recycling. In the vision of this review,
inorganics are not a marginal concern for biorefineries, as the percentage of inorganic content in biomass may
seem to suggest. On the contrary, proper understanding and management of inorganics is key for the design of
processes for advanced biorefineries.

1. Introduction presentation focuses on sugarcane lignocellulose, it is key to recognize

Sugarcane is a major crop in tropical and subtropical regions of the
world, with global annual production of about 1.8 billion tonnes (wet
basis) [1], Brazil being the largest global producer [2]. Historically, the
main product from sugarcane has been the sugar obtained from the
sucrose-rich juice [3,4]. However, just about one-third of the
above-ground sugarcane dry mass (and energy content) is in the juice.
The other two-thirds are lignocellulosic matter from plant stalks, tops,
and leaves, which have been recognized as valuable feedstocks for
bioenergy and biorefining [5–9].
The sugarcane industry is evolving to harness this vast lignocellulosic
potential as well as to diversify its product portfolio [6,10–12]. These
two trends are progressively transforming the traditional sugar mills into
modern sugarcane-based biorefineries that can make sizable contribution
to the decarbonization of the global economy [7,13]. As this
that the fibrous residue left after crushing the stalks (i.e., the bagasse) has
always been part of the sugarcane processing landscape [3,4]. On the
other hand, the leafy matter (i.e., the straw) is a relatively recent op­
portunity coming with the substitution of the manual harvest of burnt
cane by the mechanized harvest of green cane [6,9,12,14–17].
While this industry evolution is unfolding, the inorganic constituents
of bagasse and straw have been recognized as key elements for the
introduction of new sugarcane processing technologies. In concise
terms, inorganic contents are main attributes of bagasse and straw
quality [6,9]. The industry tradition, however, is to treat the lignocel­
lulosic biomass as low-value residues, very often with little concern
about their inorganic contents and lacking quality standards. As a result,
inorganics in bagasse and straw are in most cases poorly controlled and
highly variable [6,9,18,19].
The transformation of bagasse and straw from underutilized or low-

* Corresponding author. Brazilian Biorenewables National Laboratory (LNBR), Brazilian Center for Research in Energy and Materials (CNPEM). Rua Giuseppe
Máximo Scolfaro, 10.000 - Zip Code, 13083-970, Campinas, SP, Brazil.
E-mail address: carlos.driemeier@lnbr.cnpem.br (C. Driemeier).

https://doi.org/10.1016/j.rser.2021.111268
Received 15 September 2020; Received in revised form 17 May 2021; Accepted 25 May 2021
Available online 1 June 2021
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
D.R. Negrão et al.
value residues into valuable biorefinery feedstocks is requiring scientific
and technical knowledge to support the design of the biorefineries. With
this vision, this review presents bagasse and straw inorganics answering
questions such as: What are they? Where do they come from? How
variable can they be? How can they impact processes in bioenergy and
biorefining? Although this review is mainly based on Brazilian experi­
ences, the presentation aims at touching general facts, practices, and
trends of the global sugarcane industry. It aims at helping scientists and
engineers in the timely mission of designing novel concepts and pro­
cesses for the advancement of biorefineries. In addition, looking to the
broader context of biomass utilization for bioenergy and biorefining, the
sugarcane industry is positioned as a learning ground for processing of
herbaceous biomass, which encompasses agricultural residues and en­
ergy crops [20]. Therefore, investigations of other types of herbaceous
biomass may also benefit from the presentation given in this review.
2. Agroindustrial context of sugarcane bagasse and straw
2.1. The sugarcane plant and its potential
Sugarcane is a semi-perennial monocotyledon hybrid that belongs to
the Saccharum genus of the grass family Poaceae [21]. Modern sugarcane
cultivars are complex hybrids derived from two species: Saccharum
officinarum L. and S. spontaneum. Breeding based on the classical genetic
approach resulted in plants with higher levels of sugar, productivity, and
resistance to pathogens [22,23]. Additional species (S. sinense, S. barberi
and S. robustum) can contribute to breeding for the development of new
sugarcane varieties [24].
Sugarcane is cultivated in various tropical and subtropical regions of
the world. Crop yield is typically between 60 and 100 tonnes per hectare
per year, reported in wet stalk basis. Traditionally the plant was used to
produce sugar from the sucrose-rich juice contained in the plant stalks
(Fig. 1). The contents of sucrose, reducing sugars and minerals in the
juice depends on a range of variables including plant genetics, soil,
climate, agronomic management, and plant maturity [8].
Besides the sugars in the juice, the above-ground sugarcane mass
comprises substantial lignocellulosic matter in stalks, tops, and leaves
(Fig. 1). The mass and energy contents of the sugarcane components
varies according to the cultivars [25]. Table 1 presents their typical
Fig. 1. Representation of the sugarcane plant showing the above-ground frac­
tions: the stalk rich in juice, the top, the green and the dry leaves.
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Renewable and Sustainable Energy Reviews 148 (2021) 111268
Table 1
Mass and primary energy of sugarcane components adapted from the compila­
tion by Leal et al. [5].
Component Mass (kgdry/tc)a Energy (MJ/tc)b
Sugars: juice 150 2500
Lignocellulose from stalk: bagasse 135 2400
Lignocellulose from tops and leaves: straw 140 2500
Total 425 7400
a
tc = tonne of cane = tonne of clean stalk.
b
energy calculated for higher heating value (HHV).
potential as compiled by Leal et al. [5], having tops and leaves grouped
under the denomination of straw. As one can notice, the proportions are
approximately 1/3 for each component, in either dry mass or energy
basis. With global annual production of sugarcane of about 1.8 billion
tonnes of cane (tc) [1], one can use the summation of stalks and leaves
from Table 1 to calculate a lignocellulose potential of 495 million tonnes
(dry basis), or 9 EJ in energy basis. This is a sizable share of the current
global supply of bioenergy (~63 EJ per year) [26], which highlights the
potential of sugarcane lignocellulose (bagasse and straw) and its
importance as a renewable resource.
It is important to mention definitions and nomenclatures that can be
found in the literature, which sometimes present variations. “Trash” is
sometimes used as synonym for “straw”. Sugarcane leaves are discrim­
inated in two groups: green and dry leaves. Green leaves are attached to
the upper part of the stalk and are living tissues exposed to sunlight and
contributing to photosynthesis. The dry leaves are attached to lower
nodes of the stalk and already reached the senescent stage (Fig. 1). The
so-called tops are the piece of cane starting at the last node of the stalk.
Depending on methodology, tops can be counted as a separate entity [6]
or included together with green leaves [16].
In terms of dry matter content, the mass of dry leaves per hectare
tends to be slightly higher than the green leaves (with tops included),
whereas most nutrients are more abundant in green leaves. This is
shown in Table 2 based on the assessment by Menandro et al. [16],
which quantified chemical elements using plant nutrition protocols
based on sample digestion followed by atomic emission spectrometry
[27]. Higher nutrient content in green leaves is a result of nutrient
remobilization taking place during leaf senescence, which increases
nutrient use efficiency by the plants [28–30]. Changing nutrient levels in
sugarcane leaves were studied by Martins et al. [31]. They observed
intense remobilization of N, P, K, B, Cu, Fe, and Zn at the same time
other elements such as Ca, S, Mg, Mn and Al accumulates in the senesced
leaves. These processes are dynamic and dependent on specific locations
in the leaves. Noteworthy, a significant share of the leaves should be left
on the field for soil protection from erosion and water losses. The rec­
ommended amount of leaves on the ground is site-specific [9], but a
general prescription is to prioritize the green leaves on the soil for
Table 2
Range of nutrient contents in 312 samples of sugarcane leaves compiled by
Menandro et al. [16]. Green leaves include cane tops. Data for each chemical
element is reported in dry matter basis and presented as
minimum-median-maximum.
Chemical element Green leaves (g/kg) Dry leaves (g/kg)
N 4.7-8.6-11.7 1.8–3.3-6.3
P 0.6–1.1-2.2 0-0.2-0.5
K 4.3-12.0-19.9 0.2-2.0-9.2
Ca 1.3–2.8-6.7 1.4–3.7-7.0
Mg 0.5–1.2-2.8 0.6–1.1-2.5
S 0.3–1.0-3.1 0.4–0.7-3.0
Zn 0.01–0.02-0.05 0.003–0.01-0.03
Cl 1.9–5.3-7.8 0.1-1.9-5.3
B 0.003–0.005-0.015 0.003–0.006-0.013
Mn 0.02–0.06-0.17 0.02–0.09-0.24
Cu 0.001–0.004-0.011 0.001–0.002-0.008
D.R. Negrão et al.
nutrient recycling [16,32–34]. From a practical standpoint, with current
technology this prescription can be partly implemented using the
detopper of the cane harvester, which cut the cane tops that fall on the
ground, recycling the nutrients from cane tops.
As mentioned in the introduction section, sugarcane is positioned as
a learning ground for processing of herbaceous biomass, which en­
compasses agricultural residues and energy crops [20]. It is therefore
instructive to compare Table 2 with studies that analyzed nutrients in
other types of herbaceous biomass from crops such as sweet sorghum
[35], corn and wheat [36], and energy crops such as miscanthus, giant
reed and switchgrass [37]. From this comparison, it is possible to learn
that variability is substantial, which is indeed represented by the ranges
reported in Table 2. Nevertheless, the orders of magnitude of nutrient
content in different species of grasses are comparable, suggesting that
lessons learned from sugarcane inorganics can indeed serve as basis for
investigations of other types of herbaceous biomass.
2.2. The trend towards mechanized harvest
The traditional harvest of sugarcane has been done by manual labor,
collecting the stalks after burning the leaves at the sugarcane field. This
traditional practice is intensive in low-cost labor, loses about 1/3 of the
sugarcane energy potential (i.e., the straw) [5], and causes the emission
of soot (particulate matter) into the atmosphere, which has been
correlated with the prevalence of respiratory diseases [38–40]. In this
context, the combination of shortage of labor, recognition of the value of
the straw and environmental law is creating, in several countries, a
no-return tendency for mechanized harvest of green (i.e., unburned)
sugarcane [41].
In mechanized harvest, the machine cuts the stalks at the base.
Leaves are stripped off from the stalks and are blown onto to the field
(Fig. 2). The fan speed can be regulated to tune the fraction of leaves left
on the field or deposited together with the stalks in the truck load [42,
43]. Moreover, stalks are cut into segments, called billets. Billeted stalks
mixed with tops, leaves, and additional vegetal impurities are trans­
ported and delivered to the mills. Mechanized harvest is known to in­
crease the mineral impurities harvested with the sugarcane [44]. This
Fig. 2. Sketch of the sugarcane agroindustrial system, showing the three main sugarcane fractions in the biorefinery (juice, bagasse, and straw) and the two
alternative pathways for straw collection: baling (bottom truck) and integral harvest (top truck).
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Renewable and Sustainable Energy Reviews 148 (2021) 111268
contamination can happen by several mechanisms. First, the base cutter
is usually regulated to cut the stalks as close as possible to the soil sur­
face to collect most of the stalk. The base cutter occasionally contacts
and revolves the soil, and thus bring soil together with the harvested
cane. In addition, stalks may be occasionally pulled of the ground
without effective cutting at the base. In such cases stalks come associ­
ated to roots and adhered chunks of soil. In addition, the heavy ma­
chinery moving on the field creates dirt (in dry terrain) and mud (in wet
terrain), which will also add soil fragments collected with the biomass.
Stalks with such contaminants are delivered to the sugarcane mill where
the sugarcane is processed.
2.3. Industrial processing of stalks
There are significant advantages to process clean sugarcane stalks.
This is widely recognized and several technologies for cane cleaning are
described in cane engineering books [3,4]. In addition to separating
vegetal impurities, cleaning systems aim at removing soil, stones, pieces
of machinery, and other extraneous matter eventually delivered
together with sugarcane (Fig. 2). Traditional manual harvest of burnt
cane used to deliver to the mill the whole stalks. In this system, wet
cleaning technologies (i.e., using liquid water) were the standard prac­
tice. However, with billeted stalks from mechanized harvest, wet
cleaning became troublesome due to losses of sugar leaching from the
edges of the billeted stalks. Dry-cleaning systems then became the
preferred choice to associate with the mechanized harvest of sugarcane.
After cleaning, stalks are shredded aiming at rupturing the cells that
contain the sucrose-rich juice. The sugars in the shredded stalks are
extracted, either in a tandem of roller mills or in a diffuser. Most of the
juice is contained in fragile parenchyma cells that are easily ruptured to
release the juice, but most of the more robust thick-walled fiber cells
remain intact and still contains liquid after extraction [45]. With current
technologies, industrial extraction efficiencies are in the range of
94–98%. The extracted juice is further treated for production of sugar
and ethanol [46]. The fibrous by product, the bagasse, is a heteroge­
neous particulate [47] with particles having a porous system resulting
from the cells and tissues of the plant combined with the structural
D.R. Negrão et al. Renewable and Sustainable Energy Reviews 148 (2021) 111268

ruptures due to shredding and crushing [48].
2.4. Straw collection pathways
There are two main pathways to bring straw as an additional biomass
to the sugarcane biorefinery: i) baling and ii) integral harvest [6,9,41,49,
50]. There is a third pathway based on hay harvester, but it has serious
limitations due to low density of the straw load [41]. In the baling
pathway, after harvesting the stalks the straw is left on the field for about
two weeks to decrease its water content by natural drying. Then straw is
windrowed, baled, and transported to the industry [51], as depicted in
Fig. 2. Soil contacts the biomass while it is on the ground (Fig. 3) and
during windrowing and baling, which are additional sources of mineral
impurities [9]. In the integral harvest pathway, cane cleaning by air
blowing in the harvester is tuned to reduce the leafy material left on the
field and increase the fraction of the leaves that is collected with the
stalks. This cane is received at the mill and processed in dry cleaning
systems that reduce the amount of mineral impurities as well as leafy
plant matter and other vegetal impurities mixed with the cane stalks [9,
52].
3. Inorganics in bagasse and straw
3.1. Scheme for classification of inorganics
There are multiple possible ways to classify biomass inorganics. In
this review, inorganics in bagasse and straw are classified as in Fig. 4,
which follows a sugarcane industry tradition to first discriminate the
intrinsic (constitutive of the sugarcane plant) from the extrinsic in­
organics (originated from biomass contamination). For a more complete

Fig. 3. Panel of inorganics in sugarcane biomass. (top-left) Pictures exemplifying soil contacts with biomass on the field. (top-right) Pictures of coarse contaminants
separated from bagasse in the LNBR/CNPEM Pilot Plant pneumatic dry-cleaning system. (bottom-left) Evidence of microscopic particulate debris in bagasse and
straw. A piece of straw after wiping with wet swab, showing reddish soil adhered to the cotton ball. X-ray microtomography cross-section showing high-contrast
bodies assigned to soil aggregates on the surface of a straw particle and 3D renderization of a bagasse particle and mineral bodies detected within. (bottom-
right) Scanning electron micrographs and associated Si maps from energy dispersive X-ray spectroscopy (SEM-EDS) showing epidermal Si distributed in the tissues as
well as localized in phytoliths.

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D.R. Negrão et al. Renewable and Sustainable Energy Reviews 148 (2021) 111268

Fig. 4. Scheme for classification of inorganics in sugarcane bagasse and straw.

and rigorous classification scheme, the reader is directed to the work of

Vassilev et al. [53]. Table 3
Examples of elemental composition of bagasse ashes after efficient and ineffi­
The intrinsic inorganics can be further classified considering whether
cient juice extraction. Data adapted from Ref. [3]. Bold numbers indicate higher
they are leachable in water or not. This approach is motivated by
presence of the constituent in the comparison between efficient and inefficient
practical purposes: in the industrial extraction of juice from sugarcane extractions.
stalks, most of the leachable inorganics end up in the juice. Due to in­
Constituent Ash constituent (wt%)
efficiency in extraction, residues of the juice remain in bagasse, together
with the structural (i.e., non-leachable) inorganics. An analogous after efficient after inefficient
juice extraction juice extraction
rationale is applicable to straw, although there is no consolidated pro­
cess for industrial extraction of the juice of straw. Concerning the SiO2 92.80 54.40
extrinsic inorganics of bagasse and straw, they are primarily particulate Al2O3 3.00 1.70
Fe2O3 0.50 1.70
debris, which can be further classified considering their main origins: TiO2 0.01 0.00
either machinery or soil. P2O5 0.27 5.02
CaO 0.40 9.10
MgO 0.70 4.40
Na2O 0.01 0.01
3.2. Leachable inorganics
K2O 0.70 13.09
SO3 0.50 8.00
After industrial juice extraction at sugarcane mills, most of the MnO2 0.02 0.04
leachable inorganics of stalks end up in the juice. Sugarcane juice con­
tains about 80 wt% water and 20 wt% total dissolved solids [54]. The
major fraction of the dissolved solids is sucrose and other organic be reduced by factors of 10–20 after leaching [59].
compounds, but dissolved inorganic salts are also present. For instance,
Walford [55] compiled juice composition including cations K 3.3. Structural inorganics
(0.77–1.31), Na (0.01–0.04), Ca (0.24–0.48), Mg (0.10–0.39), Fe
(0.006–0.04), Al (0.005–0.17), Si (0.02–0.10) and anions Cl Part of plant inorganics become integrated into the plant structure
(0.16–0.27), P (0.14–0.40), and S (0.17–0.52), where the numeric in­ and are non-leachable according to the classification scheme of Fig. 4.
tervals represent wt% within the dissolved solids (reported as %Brix, Although Si is considered a non-essential element for plants [60,61], it is
where ◦ Brix is the common industrial method to determine sugar con­ by far the most abundant structural inorganic element incorporated in
tent in aqueous solution). Inefficiency in industrial extraction increases grasses like rice, sorghum, wheat, maize, and sugarcane [62,63]. The Si
the contents in bagasse of the characteristic inorganic elements from the concentration in the plants is variable in a range between 1 and 16 wt%
juice. This is shown in Table 3, which compares the elemental compo­ (dry matter basis) that depends on the species and environment. Si
sition of ashes from bagasse obtained with variable extraction accumulation mechanisms start by the uptake of monosilicic acid Si
efficiencies. (OH)4 by plant roots and subsequent deposit by polymerization within
As for sugarcane straw, it is key to remind that this is a new feedstock plant tissues. Silicon stocks in sugarcane are found all over leaves and
in sugarcane biorefineries, and its processing is not yet technologically stalks (Fig. 1) with variable concentrations in epidermis, cuticle, hairs,
mature. Therefore, the discussion cannot be made in terms of a stomata and cell walls of certain tissues [63–69].
consolidated industrial process like the extraction of juice from the The main mechanism of Si accumulation is the formation of micro-
stalks. Nevertheless, an analogy with the extraction of juice from the sized silica deposits known as phytoliths. Phytoliths have amorphous
stalks is helpful. Straw contains a similar range of soluble chemical el­ structure (classified as biogenic opal) and variable size and shape
ements that take part of the plant metabolism. These chemical elements [70–73]. In sugarcane, for example, their size varies roughly between 15
include K, Na, Ca, Mg, Fe, Cl, P, and S and are usually more abundant in and 30 μm. Phytoliths are relatively hard bodies that cause wear on the
green leaves (tops included) than in dry leaves (Table 2). If water teeth of animals [74,75]. They contribute to plant mechanical strength
extraction is applied, such soluble inorganics can be leached [56–58]. and resistance to abiotic and biotic stresses [60,61] such as attacks from
For example, in a laboratory study and assessment of the potential of the sugarcane borer [65]. As the biomineralization takes place within
water extraction from sugarcane straw, K and Cl contents were shown to cells, a fraction of carbon is occluded inside silica phytoliths. This

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D.R. Negrão et al.
organic matrix-mediated biomineralization is known as phytolith
occluded carbon (PhyOC). Besides Si, O and C, traces of many other
elements, like K, Al, Fe, Mg, Ti, can also be incorporated to silica phy­
toliths [76].
3.4. Debris from machinery and soil
Machinery and soils are the main sources of extrinsic inorganics in
sugarcane bagasse and straw (Fig. 4). Pieces of machinery from agri­
culture and industry eventually brake and end up mixed with the
biomass. Since they are coarse ferrous particles, they are relatively easy
to separate in the industry using electromagnets [3,4]. Nevertheless,
practical experience in biomass processing shows that machinery pieces
and stones are commonly found mixed with industrial bagasse, as
exemplified in Fig. 3.
Soil contamination is a more nuanced contribution. Several ways by
which soil gets into contact with the biomass were described in section 2
and represented in Fig. 3. Here, it is worth adding that, when the soil is
wet, soil fragments become stickier and it is known to the agroindustrial
practice that contents of mineral impurities increase when harvesting on
wet terrain. Moreover, soil contamination in straw bales may be
aggravated by the direct contact of the straw with the ground, notably
during windrowing [9].
To understand soil contamination in biomass, it is important to
consider that soils have a multiscale structure, and the size of the soil
particles determine how they interact with the biomass. Soil texture
classifies soil particles in terms of their size. Following the ABNT clas­
sification and terminology [77], one has clay (<0.002 mm), silt
(0.002–0.06 mm), sand (0.06–2 mm) and gravel (2–60 mm) fractions.
Soil fragments rich in clay tend to be sticky, especially if wet, while
coarse sand grains and gravel will hardly adhere to biomass surfaces but
may be found as particles trapped to the biomass irregular morphology
or dispersed in the bulk of biomass loads. Moreover, the mineralogy of
the soil particles depends on particle size and soil type [78,79]. If
biomass is shredded (like bagasse), the smaller soil fragments, especially
in the clay and silt scales, are small enough to penetrate the ruptured
biomass tissues [80]. A comparison of the characteristic length scales of
the biomass structure and soil particles is given in Fig. 5. Noteworthy,
microscopic observations using X-ray microtomography and micro­
fluorescence indicated that particle size and mineralogy of the soil
together with the wetness and the tissue ruptures are key to understand
Fig. 5. Comparison of characteristic length scales from biomass structure and soil particles. Cross-section microtomographic image of a bagasse particle showing the
cellular structure with trapped mineral particles (high contrast bodies in green rectangles) and tissue cracks (pointed by green arrows). Examples of clay (yellow dots
inside yellow rectangle), silt (orange circle) and sand (red circle) particles scaled for comparison with the size of the biomass features.
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Renewable and Sustainable Energy Reviews 148 (2021) 111268
the interaction of soil debris with bagasse and straw [81]. Understand­
ing these diverse mechanisms of soil contamination is key to rationalize
the variability of inorganics in bagasse and straw as well as to design
technology and management to reduce the content of mineral impurities
in the biomass.
3.5. Variability
Several studies explored the variability of inorganics in different
types of biomass [37,53] and in particular in sugarcane bagasse and
straw [6,9,18,19]. All these studies show significant variability in ash
contents and elemental compositions. The purpose here is not to report
all the variations in the obtained numbers. Instead, the purpose is to
rationalize the origins of the variability in bagasse and straw inorganics. As
can be learned from the classification scheme (Fig. 4), variability of
inorganic contents in bagasse and straw is a combination of (1) the
intrinsic structural inorganics; (2) the intrinsic leachable inorganics; and
(3) the extrinsic contaminants. Since the contaminants and the leachable
inorganics can be reduced industrially through cleaning and leaching,
respectively, it is instructive to start understanding the remaining factor
(i.e., the structural inorganics), which provides a baseline for inorganic
contents in sugarcane biomass. More specifically, it is key to understand
the variability in biogenic silica that dominates the content of structural
inorganics.
Table 4 summarizes data from several Si accumulation studies in the
sugarcane literature. Most studies investigate the effect of Si fertilization
on the agronomic performance of sugarcane. Adding Si as a fertilizer
cause Si accumulation in stalks and leaves, bringing several potential
benefits, including prevention of Al and Mn toxicities, improved
photosynthesis, water use efficiency, P nutrition and protection from
pest and fungal disease [82–85]. Evaluation of the Si ranges in Table 4
should take into account that most of the presented data is obtained from
agronomic experiments of Si fertilization and, therefore, the maxima of
the ranges is often unrealistically high if compared to commercial
practices in sugarcane fields. With this remark in mind, it is noteworthy
that Si accumulation is higher in leaves compared to stalks, a
well-known fact in sugarcane [63] and other grasses [37]. In SiO2 basis,
which would be comparable to measurements of biomass wt% of ashes,
stalks often have <2 wt% SiO2, compared to <4 wt% SiO2 in leaves
(Table 4).
In comparison to the accumulation of structural SiO2 in sugarcane
D.R. Negrão et al. Renewable and Sustainable Energy Reviews 148 (2021) 111268

Table 4
Ranges of Si contents reported in the literature for sugarcane stalks, leaves (or a single leaf), and the whole above-ground fraction of the plant. All contents are
expressed in dry matter basis and the Si and SiO2 weight percentages are related by stoichiometry.
Cane fraction Si (wt%) SiO2 (wt%) Reference Number of Figure/ Comment
Table in the Original
Reference

stalk 0.1–0.2 0.2–0.5 [86] Tables 4 and 5 Control experiment (minimum Si%) and fertilized with calcium silicate slag
stalk 0.5–1.0 1.1–2.1 [83] – Introduction statement
stalk 0.1–0.5 0.1–1.1 [84] Table 5 Control experiments and fertilized with Ca–Mg silicate
leaves 0.3–0.7 0.7–1.5 [86] Tables 4 and 5 Control experiment (minimum Si%) and fertilized with calcium silicate slag
leaves 1.0–2.0 2.1–4.3 [83] – Introduction statement
leaves 0.3–0.6 0.6–1.4 [84] Table 5 Control experiments and fertilized with Ca–Mg silicate
leaf 0.03–1.2 0.1–2.7 [82] Table 3 TVD leaf, control experiment (minimum Si%) and fertilized with silicic acid
leaf 0.3–2.4 0.6–5.1 [82] Table 8 Control experiment (minimum Si%) and fertilized with silicic acid
leaf 0.3–1.3 0.6–2.8 [82] Fig. 2 Control experiment (minimum Si%) and fertilized with silicic acid
leaf 0.1–1.5 0.2–3.2 [85] Fig. 1b Third leaf, control experiment (minimum Si%) and application of various Si
fertilizers
whole 0.7–1.9 1.5–4.1 [87] Table 7.3 Control experiment (minimum Si%) and fertilized Si
sugarcane
whole 0.5–1.1 1.1–2.4 [88] Table 1 Measured mass of extracted phytolith corrected for carbon content
sugarcane

significant, but clearly improvable [9]. Moreover, significant share of

Table 5 mineral impurities are sticky clayey soil fractions that adhere to the
Ranges of ash contents (wt%, dry basis) reported for bagasse and straw collected surface of leafy matter [81] and wet washing of the separated leaves is
at industrial sites. an attractive alternative for cleaning such adhered impurities [9].
Lignocellulosic Ash (wt Reference Number of Table in the Original
fraction %) Reference 4. Roles of inorganics in different uses of the sugarcane biomass
bagasse 1.1–6.0 [19] Table 1
bagasse 2.0–5.1 [18] Table 5 4.1. Nutrients for food, feed, bioprocesses, and soils
bagasse 2.2–6.5 [6] Tables 6 and 42
straw 4.0–9.4 [14] Table 1
straw 7.5 [18] Table 5
The sugarcane inorganics leachable in water (Fig. 4) are mainly
straw 4.2–29.1 [6] Tables 43 and 44 nutrients of the plant. As such, they also serve as nutrients in food and
feed as well as for microorganisms used in bioprocesses or back to plants
if the minerals are recycled to the soil. Although this review is focused
plants (Table 4), bagasse and straw collected at industrial sites shows on the inorganics of the lignocellulosic fractions (bagasse and straw),
higher contents of total ash (Table 5). In extreme cases, ash contents can this section discusses the inorganics of the sugarcane juice. Such juice
exceed 10 wt%. This demonstrates that, in industrial reality, the inorganics are already managed in current sugarcane mills and provide
leachable inorganics and the extrinsic contaminants make a sizable simple examples on the roles of inorganics in nutrition as well as po­
share of the total inorganics in bagasse and straw. Indeed, the extrinsic tential environmental impacts.
contaminants are often majoritarian, being factors that could in princi­ By processing the juice of sugarcane stalk into sugar, juice inorganics
ple be managed by cleaning technologies in the sugarcane biorefineries, will be summed up to minerals added in sugar production (e.g., Mg in
as discussed in the next section. clarification, Ca in carbonation and liming, and P in phosphating).
Furthermore, these inorganics mainly end up in the residues of sugar
3.6. Prospects for reducing inorganic contents production, the molasses. Molasses can be used as food and feed in­
gredients, where the inorganics are valuable as mineral nutrients. Most
Reaching baseline levels of inorganic contents in bagasse and straw Brazilian sugarcane biorefineries uses molasses mixed with sugarcane
requires cleaning (to remove extrinsic contaminants) and leaching (to juice for fermentation into ethanol fuel [46]. The yeast (Saccharomyces
remove the intrinsic leachable inorganics). Cleaning and leaching are cerevisiae) used in fermentation requires minerals in growth media,
critically affected by biomass shredding. Shredding is beneficial for including macronutrients (C, N, S, P, K, and Mg, in millimolar concen­
leaching, because it opens the plant cells and thus eases the extraction of tration) and micronutrients (Ca, Cu, Fe, Mn and Zn, in micromolar
intracellular components [3,4,56,59]. On the other hand, shredding is concentration) [89]. Cane juice and molasses provide these nutrients,
detrimental for cleaning particulate impurities, because shredding dis­ often in appropriate amounts. Moreover, these minerals incorporated by
rupts the biomass tissues and creates a sponge-like material with plenty the microorganisms can be further valorized by directing dried yeast
of irregular surfaces, tissue cracks and access points to the interior of the from the ethanol process to be used as feed ingredient [90].
biomass. All these features increase the potential for trapping of spurious Inorganics in the fermentation media that are not incorporated by
particles [80,81]. the yeast end up in the ethanol distillation residue, the vinasse [46].
Therefore, a general prescription for reducing inorganic contents in Vinasse is a potential source of nutrients (highlight to K) and energy
bagasse and straw is to perform the following sequence of operations: (due to its organic content), but inappropriate usage of vinasse can also
cleaning-shredding-leaching. Following this principle, one would pre­ be an environmental liability [91]. Current practice in Brazilian mills is
scribe, as an example, cleaning of sugarcane stalks instead of cleaning to return vinasse to soils, which has been dubbed fertirrigation because
bagasse that has already been shredded. Industrial dry-cleaning systems, it supplies both water and nutrients. Recycling minerals to soils, through
which aim at separating mineral impurities and leafy matter from bil­ vinasse, filter cake, ashes (see section 4.6 Valorization of combustion
leted stalks delivered to the industry, are crucial to advance in this di­ ashes) or any other means, is certainly interesting within a circular
rection [9,52]. In a recent assessment of industrial efficiencies of economy framework, but it is not free of challenges. Vinasse is produced
dry-cleaning systems in Brazilian mills, efficiencies in the separation in large volumes (10–15 L of vinasse per liter of ethanol) [46,91].
of leafy matter (17–49%) and mineral impurities (18–76%) were

7
D.R. Negrão et al.
Because of that, the viability of vinasse fertirrigation in areas sur­
rounding the biorefinery is limited by a so-called economic radius.
Therefore, inorganics are recycled to an area that is small compared to
the area of sugarcane harvesting. Such concentrated application of in­
organics to soils can lead to overloads and caution is recommended due
to risks of soil salinization and presence in vinasse of phytotoxic ele­
ments (such as Al and Fe, concentrations between 2 and 15 mg/L) and
priority pollutants (such as Cu, Cr, Ni, Pb and Zn, concentrations below
mg/L) [92,93].
Vinasse biodigestion has been considered a major alternative for
production of energy (biogas) with the concomitant benefits of reducing
the organic load of the waste stream [94]. While biodigestion maintains
the mineral value of vinasse, co-digestion with other
inorganic-containing residues such as food waste and mill filter cake
may be beneficial to the biodigestion process [95,96]. Nevertheless,
added Na-based alkalizing compounds in biodigestion plants appears as
a potential concern for soil sodification [93]. This serves as an example
on how inorganics added in bioprocessing can interfere with the pros­
pects for nutrient recycling back to soils.
4.2. Combustion
Bagasse is traditionally used as boiler fuel to provide heat and power
to the sugarcane mills [3,4,46]. More recently, straw has been intro­
duced as an additional fuel to expand the production of electricity by the
mill [6,9,97]. However, although bagasse used to be considered a benign
fuel [3], higher ash contents in bagasse (due to contaminants brought by
the mechanized harvest) and the addition of straw are bringing new
challenges for the combustion of sugarcane biomass.
In the combustion of different types of biomass, extrinsic inorganics
coming mainly from soil (Fig. 4) are known to increase the formation of
ashes, predominantly in the SiO2, Al2O3, Fe2O3, and TiO2 components
[53,58]. The increasing amounts of ash cause a range of problems to the
combustion system including slagging, fouling, vitrification, agglomer­
ation, corrosion and the need for appropriate disposal of the ashes [98].
The presence of alkali, mainly K and Na, are related to low ash melting
temperatures causing slagging and fouling. In addition, alkali combi­
nation with Cl and S is a cause of corrosion [18,98]. Moving to the
specifics of bagasse and straw, chemical elements such as K, Cl, and S
may be present in bagasse, but usually in relatively minor and harmless
amounts due to juice extraction (Table 3). In the case of straw, these
critical elements are present in much higher amounts (Table 2), being a
major concern for the use of straw as boiler fuel [9]. Fortunately, the
contents of these elements can be substantially reduced if leaching is
applied to straw prior to combustion [9,56–59].
It is also instructive to consider the role of inorganics in case bagasse
and straw are densified as pellets to be combusted elsewhere [99,100].
Pellet specifications restrict the contents of total ash (<1.5% in most
specifications) and the contents of specific elements such as N, S, and Cl
and the temperature of ash deformation (>1100 ◦ C, lowered by alkali
such as Na and K) may be restricted as well [101,102]. Stricter specifi­
cations may additionally impose limits to trace pollutants such as As, Cd,
Cr, Cu, Pb, Hg, Ni and Zn [101,102]. Therefore, because of the usual
high ash contents in bagasse and straw (Table 5), proper management of
inorganics is key for the access of sugarcane bagasse and straw into the
pellets market [103].
A major driver to increase biomass combustion worldwide is the
substitution of coal to mitigate its greenhouse gas emissions that cause
global warming [100,104]. Besides this environmental motivation, such
fuel substitution may be economically attractive because it uses existing
assets and does not require risky investments in novel facilities. Never­
theless, either complete fuel substitution or co-firing biomass and coal
comes with technical challenges because biomass and coal differ in their
fuel properties [105,106]. In particular, biomass and coal differ in their
composition of inorganics with highlight to biomass water-soluble in­
organics (e.g., Cl, S, K, Na, N, and P) that cause critical technological
8
Renewable and Sustainable Energy Reviews 148 (2021) 111268
phenomena such as the aforementioned slagging, fouling and corrosion.
These biomass inorganics also bring environmental concerns due to
volatilization of hazardous compounds and increased fine particulate
emissions from combustion systems [58], exemplifying that biomass
combustion brings its own environmental challenges.
4.3. Pyrolysis
Pyrolysis is the thermochemical decomposition of organic material
at elevated temperatures in absence of oxygen. This thermochemical
process has been investigated as a possible use for bagasse and straw
[107–109]. Pyrolysis of lignocelluloses fractionates the biomass into
solid (biochar), liquid (bio-oil), and gas fractions [110–112]. The three
fractions can be used as fuels, while biochar can also be added to soils for
amendment and carbon sequestration [113]. The bio-oil can be upgra­
ded into advanced liquid biofuels such as green diesel and bio-jet fuel as
well as biochemicals such as phenols [110,114]. A common target in
pyrolysis is to maximize the more valuable bio-oil fraction and this has
been achieved by the processes of fast pyrolysis performed at
400–600 ◦ C for less than 5 s [110,111].
The presence of inorganics in the biomass catalyzes chemical re­
actions and affects pyrolysis performance. Presence of alkali and alka­
line earth metallic (AAEM; Na, Mg, K, Ca and others) components are
detrimental to bio-oil yield and quality, while increasing the generation
of biochar [110,111]. In addition, solid metal oxides such as SiO2, Al2O3,
Fe2O3 and TiO2 can also act as catalysts [111]. Such oxides are abundant
in soils and, therefore, one can speculate soil debris in the biomass may
act as unintentional catalysts.
Recent studies have investigated the leaching of AAEM from biomass
prior to pyrolysis as well as the mechanisms of AAEM interference on
pyrolytic reactions. Chen et al. [115] investigated the leaching of AAEM
from rice straw, cotton stalk and fir sawdust using aqueous solutions of
variable pH, including the acidic aqueous phase of pyrolysis bio-oil.
Lower pH increased the leaching of AAEM and synergy with
non-acidic components of bio-oil (phenols, ethylene glycol, furfural, and
others) was identified. Li et al. [116] investigated the role of AAEM on
the pyrolysis of pine wood through assessment of reaction activation
energies and the role of AAEM was observed to vary with the extent of
conversion. Wang et al. [117] investigated the role of AAEM loading on
lignin pyrolysis. The AAEM promoted improved char porous structure
and changes in bio-oil composition. Moreover, several studies
[118–122] used quantum mechanical calculations (Density Functional
Theory, DFT) to learn the mechanisms of AAEM interference with py­
rolysis of cellulose and lignin model compounds. Roles of AAEM elec­
tronegativity on bond lengths and energies were identified, revealing
catalytic effects of AAEM on pyrolytic decomposition of lignin and
saccharides.
As pyrolysis of sugarcane bagasse and straw is concerned, the pres­
ence of AAEM in bagasse is much reduced due to juice extraction (Fig. 2
and Table 3). Nevertheless, acidic leaching pretreatment applied to
bagasse was beneficial for production of pyrolytic levoglucosan due to
removal of AAEM interference, demonstrating that bagasse pyrolysis
can indeed be affected by AAEM residues [123]. The concern for AAEM
interference is much more severe for straw that is rich in nutrients
(Table 2) and is not leached in current sugarcane industry (Fig. 2).
Oudenhoven et al. [124] assessed the techno-economic viability of
bagasse and straw acid leaching prior to pyrolysis, revealing circum­
stances of scale, co-products and process integration under which the
leaching pretreatment could be feasible.
4.4. Cellulosic ethanol
Bagasse and straw are composed mainly of cellulose, hemicelluloses
and lignin. About 65–70% of the mass corresponds to cellulose and
hemicelluloses, which can be hydrolyzed to the monomeric glucose
(mostly from cellulose) and xylose (from hemicelluloses). These
D.R. Negrão et al.
monomeric sugars can be fermented into ethanol, the so-called second
generation (2G) or cellulosic ethanol [125–127]. Since ethanol pro­
duction from sugarcane juice and molasses is already deployed in large
scale [3,8,46], expanding mill capability to produce cellulosic ethanol is
an attractive technological alternative being pursued at pilot, demon­
stration, and pioneer commercial facilities [126,128,129].
In the cellulosic ethanol production process, the first conversion step
is the so-called pretreatment aiming at disrupting biomass structure and
solubilizing part of its chemical constituents. For pretreatments per­
formed at low pH, mineral acid (e.g., H2SO4) is added to reaction media
and biomass cations (e.g., K, Ca, Mg, Na, Mn) can partly neutralize the
added acid through ion exchange reactions between the inorganic cat­
ions and hydronium ions [130,131]. More acid is required to compen­
sate for this neutralization. This is an issue for straw that has not been
water-leached of its inorganics, contrary to bagasse that has lower
mineral cation content due to leaching in juice extraction. In the next
process step, pretreated biomass is directed to enzymatic hydrolysis.
Although some metal ions may interfere with enzymatic hydrolysis
[132,133], at the reaction conditions this is usually not a matter of
concern. Concerning nutrients for fermentation and vinasse biodigestion
as discussed in previous section (4.1 Nutrients for food, feed, bio­
processes, and soils), it is noteworthy that soluble inorganics from
cellulosic ethanol process can serve as nutrients as well, but concen­
tration of mineral nutrients is lower than in juice and molasses [95].
In cellulosic ethanol processes wear of industrial equipment has been
a top concern and minerals in the biomass have been blamed. The main
problems have been observed in the feeder and discharge of pressurized
thermochemical pretreatment reactors used to hydrolyze and disrupt the
biomass structure [134,135]. Biogenic silica as well as machinery and
soil contaminants in the biomass may be responsible for the observed
biomass abrasiveness [81,134,136]. The nature of biomass abrasiveness
is a matter of debate. For instance, there is still dispute on the cause of
abrasion to the teeth of grass-eating animals, concerning the relative
contributions from biogenic silica and soil fragments [137,138]. In the
Mohs scale of materials hardness, amorphous silica from biogenic phy­
toliths has hardness of 5.5–6.5 [74,75]. This is comparable to the
hardness of common soil mineral such as hematite (5.0–6.0), goethite
(5.0–5.5) and anatase (5.5–6.0) [139]. Highlight should be given to the
higher hardness of quartz (7.0), which in relatively large (>60 μm) and
faceted grains of sand could make a disproportionate contribution to
abrasion. Therefore, considering the variable ash contents in industrial
bagasse and straw (Table 5), biomass abrasiveness should be thought as
a variable characteristic, often (but not always) dominated by mineral
impurities, with a highlight to the presence of sand grains.
4.5. Cellulosic biomaterials
Sugarcane bagasse has been used for a long time as a feedstock for
production of pulp and paper, competing in the global market with pulp
and paper obtained from wood [3,140]. Like in cellulosic ethanol,
mineral impurities have been blamed for equipment wear out. Never­
theless, the fact that bagasse pulp and paper have been operating at
industrial scale for several decades serves as a demonstration that sug­
arcane biomass can be used for production of biomaterials. New families
of biomaterials are currently under investigation with highlight to cel­
lulose nanomaterials: cellulose nanocrystals and nanofibrils [141,142].
Production of such materials from sugarcane biomass has been
demonstrated in laboratory scale [143,144]. Furthermore, these mate­
rials were proposed to be coproduced with cellulosic ethanol [145,146].
Chemical fractionation to isolate cellulose is a first step for the pro­
duction of cellulose nanocrystals and nanofibrils [141,142]. In this
sense, inorganics in bagasse and straw can perturb the chemical process
along the lines mentioned in previous sections of this review: e.g., acid
neutralization by biomass cations [130,131] or abrasion of pressurized
thermochemical reactors and other equipment [134–136,140]. For the
energy-intensive mechanical fibrillation of cellulose [141], the problem
9
Renewable and Sustainable Energy Reviews 148 (2021) 111268
of abrasiveness may be a major concern for non-wood feedstocks such as
sugarcane bagasse or straw [147]. Nevertheless, this type of process
with sugarcane biomass has not yet achieved industrial scale and
currently these industrial impacts are only presumed, but not yet
demonstrated.
4.6. Valorization of combustion ashes
The industrial combustion of bagasse and straw generates ashes. The
most common industrial practice is to return sugarcane ashes to soils as a
mean to recycle nutrients. Nevertheless, other applications of ashes such
as use in construction materials and adsorbents have been considered for
a long time [148]. More recently, using ashes from agricultural residues
in construction materials have attracted significant attention and this
research field is presented in two recent review articles [149,150]. A
major driver for this use of ashes is the reduction of carbon dioxide
emission from conventional production of cement. For instance, Jamora
et al. investigated the potential in Philippines for greenhouse gas re­
ductions by the utilization of sugarcane ashes as partial cement
replacement in mortar and concrete, estimating potential reduction of
273 ktonnes CO2e yr− 1 [151]. In this context, sugarcane bagasse ash
characterization and upgrading for improved properties as cementitious
material has been investigated to transform the ashes into sustainable
building materials [152–158].
Besides construction materials, bagasse ashes were investigated as
feedstock for a diverse set of products such as adsorbents based on
activated carbon [159], silica nanoparticles [160] and catalysts [161].
Noteworthy, in the development of a process or a product using biomass
ashes as the feedstock, one should consider the sources of variability in
biomass inorganic contents, as detailed in section “3.5 Variability”.
Otherwise, there is significant risk that variability in ash characteristics
will compromise attempts to generate products with consistent proper­
ties and quality.
4.7. Valorization of biogenic silica
Another approach for valorizing bagasse and straw inorganics is to
design process that isolate and valorize the biogenic silica phytoliths,
without the combustion that transforms biogenic silica into a fraction of
the boiler ashes. Biomasses such as pineapple peals [162], rice husks
[163], sorghum husk [164] and sugarcane bagasse [165,166] have been
recently investigated as potential sources of biogenic silica particles.
Methods for isolation of biogenic silica from sugarcane biomass have
been recently proposed, including microwave-assisted ashing [167] and
combination of thermal and chemical steps [168]. Potential applications
of biogenic silica phytoliths have also been investigated. Proposed ap­
plications include use in ceramics and glasses [168], harnessing phyto­
liths optical and encapsulation properties [73,169] and production of Si
anode material for Li-ion batteries [167,170].
Furthermore, phytoliths have gained attention as an opportunity for
carbon sequestration in soils taking advantage of the long-term (century
to millennia) stability of the occluded carbon, PhyOC [88,171]. Carbon
sequestration in soils has been recognized by the International Panel on
Climate Change (IPCC) as one important pathway for mitigation of
global climate change [113], but the potential contribution of PhyOC is
still elusive. In pioneer work, the potential of carbon sequestration in
sugarcane phytoliths was investigated in the context of Australia, where
the bio-sequestration potential was estimated to be between 0.12 and
0.36 tonnes CO2e ha− 1 yr− 1 [88]. However, these numbers are still a
matter of controversy and research is ongoing to establish the true po­
tential of carbon sequestration in phytoliths [172].
5. Concluding remarks and prospects
Bioenergy and biorefining have a key role for a sustainable XXI
century, delivering renewable electricity, fuels, chemicals, and
D.R. Negrão et al.
materials, often integrated to the production of food and feed, enhancing
rural economies, and contributing to carbon sequestration and climate
change mitigation. Lignocellulosic biomass from grasses stands at the
core of this vision, considering the residues from major food crops
(wheat, maize, rice, sugarcane, and others) as well as dedicated high-
yield energy cultivars. Sugarcane is in a special position because it is
already deployed in large scale for bioenergy and biorefining and
therefore serves as a learning ground for new technologies. The practice
with sugarcane lignocellulosic fractions — bagasse and straw — is
showing that proper understanding and management of the biomass
inorganics is critical for the advancement of bioenergy and biorefining.
Looking into the future of research and development, it is important
to highlight the need for reducing the amounts of mineral impurities in
the biomass. Current agroindustrial practices bring high loads of mineral
impurities with bagasse and straw and these impurities, mostly debris
from soil, impede all sorts of biomass valorization processes. Most
notably, mineral impurities increase biomass abrasiveness and ash for­
mation, which impairs industrial equipment efficiency and utilization.
Reducing biomass contamination is mainly a task for the agroindustrial
sector, improving management practices and deploying biomass clean­
ing technology at the biorefineries. Nevertheless, research and devel­
opment are still needed to improve biomass cleaning technology. For
instance, in section 3.6 Prospects for reducing inorganic contents, a
technological principle was prescribed: cleaning before shredding. This
prescription came from the observation that ruptured tissues offer
plenty of sites for trapping of particulate impurities, thus hampering
attempts for downstream (after shredding) biomass cleaning. As simple
as it sounds, this concept would direct efforts for cleaning intact tissues
such as sugarcane stalks and contradict efforts for cleaning disintegrated
tissues such as bagasse.
Concerning the natural inorganic components of the biomass,
including leachable nutrients as well as biogenic structural silica, there
are many opportunities for novel research and development. As dis­
cussed in chapter 4, these inorganics can be either valuable or delete­
rious, depending on how they are integrated in the conceptual design of
biorefineries. Obviously, it is wise to maximize the value and minimize
the burden, but unfortunately the biomass inorganics are often over­
looked. It is therefore recommended that research in the areas of process
design and sustainability assessment (which provide holistic under­
standing of mass-energy flows and sustainability indicators [173–175])
includes biomass inorganics in the analyses to illuminate the pathways
with most synergies.
For the plant inorganics leachable in water, a main synergy is clearly
delineated. These inorganics are valuable as nutrients in food, feed,
bioprocesses and soils, whereas they are detrimental for thermochem­
ical conversions such as combustion or pyrolysis. In the processing of
sugarcane stalks in traditional sugarcane mills, this synergy is largely
harnessed, because the nutrients are mostly extracted with the juice
while the stalk fibers (bagasse) are used as a relatively benign fuel for the
mill boilers. However, research is needed to identify suitable pathways
for valorization of sugarcane straw. There is no sugar-rich juice to be
economically extracted from straw, but straw is rich in inorganic nu­
trients (Table 2). Therefore, conversion pathways for the valorization of
straw must indicate how these inorganics will be managed in the bio­
refinery to provide the most benefit for the agroindustrial system.
A final point to consider is the need for research on sugarcane
biogenic silica, mostly present in micrometric bodies, the phytoliths.
Biogenic silica is detrimental to biorefineries mainly due to its abra­
siveness and contribution to ash deposits. Therefore, it would be bene­
ficial to remove silica from the biomass as early as possible in the
process. Furthermore, the potential for valorization of silica-based
products would be synergistic with such removal of the silica bodies.
However, there is currently a very limited understanding on how sug­
arcane biorefineries could be modified to economically isolate and
valorize the biogenic silica phytoliths. For comparison, valorization of
ashes (formed partly by the biogenic phytoliths) is a more
10
Renewable and Sustainable Energy Reviews 148 (2021) 111268
straightforward approach, but relatively unambitious if one considers
that ashes have contributions from all sorts of biomass contaminants
and, therefore, there are inherent challenges to reach higher-value ap­
plications. Transforming valorization of ashes into valorization of
biogenic phytoliths is a research direction for the longer term, which
perhaps finds synergy with novel processes being developed for sugar­
cane biorefineries.
To conclude, this review provided an organized presentation of the
multifaceted topic of sugarcane biomass inorganics and their impor­
tance for bioenergy and biorefining. This work aims at contributing to
the advancement not only of the sugarcane industry, but also to the
broader context of bioenergy and biorefining based on a wide range of
agricultural residues and dedicated bioenergy grasses.
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.
Acknowledgements
DN, AG, MB and CD acknowledge funding from INCT Bioetanol and
Fundação de Amparo à Pesquisa do Estado de São Paulo - FAPESP
(grants 14/50884–5, 18/07033–5 and 19/13936–0). ML acknowledges
funding from the Global Environment Facility (GEF) for the project,
BRA/10/G31—“Sugarcane Renewable Electricity - SUCRE”—and
United Nations Development Programme (UNDP) for management.
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