Science of the Total Environment 793 (2021) 148524

Contents lists available at ScienceDirect

Science of the Total Environment

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

Review

A critical analysis of environmental sustainability metrics applied to

green synthesis of nanomaterials and the assessment of environmental
risks associated with the nanotechnology
Angélica García-Quintero, Manuel Palencia ⁎
Research Group in Science with Technological Applications (GI-CAT), Department of Chemistry, Faculty of Natural and Exact Sciences, Universidad del Valle, Cali, Colombia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The designation of a nanosynthesis as

“green” requires a quantitative evalua-
tion.
• Conventional sustainability metrics can
be applied and adapted to nanotechnol-
ogy.
• The LCA emerges as a suitable metric to
assess nanosynthesis sustainability.
• A bio-based nanosynthesis is not per se
a sustainable process.

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

Article history: Nanotechnology is one of the most relevant scientific areas today due to its multiple applications in fields such as
Received 25 March 2021 medicine, environmental remediation, information technology and energy conversion. This importance has led
Received in revised form 3 June 2021 to the need to advance in the development of environmentally sustainable and safe nanomaterials by incorporat-
Accepted 14 June 2021
ing the principles of green chemistry during their synthesis and in their applications. However, this qualitative
Available online xxxx
framework of thought does not offer minimum criteria for the use of the term “green”, and therefore, this adjec-
Editor: Jose Julio Ortega-Calvo tive is commonly used to refer to bio-based or nanotechnological processes without taking into account their net
ecological impact. In this context, environmental sustainability metrics can be applied to nanotechnology to com-
pare, optimize and quantify the environmental sustainability of synthesis procedures. This review provides an
Keywords: overview of green chemistry and its application in nanotechnology, but also an analysis of the use of green chem-
Green nanoscience istry principles in the development of bio-based nanobiotechnology and nanosynthesis, with special emphasis on
Nanobiotechnology the use of sustainability's metrics for the quantitative analysis of nanomaterial synthesis protocols. These include:
Plant-based nano-synthesis Atom Economy, E-factor, Process Mass Intensity, Energy Intensity, and Life Cycle Analysis.
Atom economy
© 2021 Elsevier B.V. All rights reserved.
E-factor
Process mass intensity
Energy intensity
Life Cycle Analysis

⁎ Corresponding author at: Department of Chemistry, Universidad del Valle, Cali, Colombia.
E-mail address: manuel.palencia@correounivalle.edu.co (M. Palencia).

https://doi.org/10.1016/j.scitotenv.2021.148524
0048-9697/© 2021 Elsevier B.V. All rights reserved.
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Green chemistry approach in nanoscience . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Green chemistry: a historical description and fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Green nanoscience . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Green synthesis of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4. Characterization of green nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3. Environmental sustainability metrics applied in green nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1. Atom economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2. E-factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.3. Metrics-based on mass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.4. Metrics based on energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.5. Life Cycle Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4. Remarks and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Declaration of competing interest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

1. Introduction anthropogenic changes. In particular, concern about nanotechnology

Though the first nanomaterials with a practical use were metallic in-
organic nanoparticles, which were synthesized into medieval age to car-
ried out artistic expressions of religious art, specifically, in the stained
glass of churches, it is clear that, while optical properties resulting
from their nanosize were the base for these applications, the conceptu-
alization and understanding of the fundamentals behind these proper-
ties did not happen until much later (Horikoshi and Serpone, 2013).
Since the possibility of manipulating nanometric scale particles for the
development of new technologies arose as a scientific and technique re-
ality, at the end of the 20th century, nanoscience and nanotechnology
have become an area of growing interest in many fields such as medi-
cine, aeronautics, pharmaceutical, food, energy production, materials
industries, among others (Ghosh and Kumar, 2018; Palencia et al.,
2018; Zelić et al., 2018; Sohail et al., 2019). The impact of nanotechnol-
ogy has been of such magnitude that it is considered one of the most in-
fluential research fields for the development of new technologies and an
important precursor of the so-called next industrial revolution (Halada
and Orlov, 2018). The latter claim is based on the unique properties of
nanomaterials arising from nano-sized matter, which differ significantly
from the macroscopic equivalent of a larger size. Thus, many nanoparti-
cles and nanomaterials have biological, antimicrobial, catalytic, optical,
magnetic and electrical properties, which allow them to be used in
different applications such as sensors, bioactive surface, manufacture
of new materials, drug carriers, among others (Fojtů et al., 2017;
Palencia et al., 2017; Halada and Orlov, 2018; Palencia et al., 2019;
Sohail et al., 2019). According to data from the Nanotechnology Con-
sumer Products Inventory and The United States Bureau of Labor Statis-
tics, there are more than 1400 companies in the market focused on the
generation of nanotechnological products, being the nanomaterials
most manufactured those constituted by TiO2, SiO2, FexOy, ZnO, carbon
nanotubes, Ag, Au, and Fe (Skjolding et al., 2016; Fojtů et al., 2017;
Halada and Orlov, 2018; Jensen and Lewinski, 2018; Poynton and
Robinson, 2018; Sohail et al., 2019).
Due to the relevance of nanotechnology in the scientific and com-
mercial field, its development and applications in the real world,
i.e., out-lab, have generated a reasonable concern for knowing the
impact of these substances on planetary health, which is understood
as the correct physical, mental, and social well-being of human civiliza-
tion and the environment (Halada and Orlov, 2018; Jensen and
Lewinski, 2018; Bartolozzi et al., 2019; Sohail et al., 2019). This concern,
resulting from the awareness of the existing risk, is a response that can
be considered normal due to previous experiences and the current rec-
ognition of the fragility of biological systems in the face of uncontrolled
originates from the lack of knowledge of its properties, the conse-
quences of its interaction with biotic and abiotic components of
ecosystems, and the short, medium and long-term effects of the release
of nanotechnological products in the ecosystems. Environment.
Consequently, nanotechnology has been identified as a potential risk
for ecosystems and public health, to the point that its products and de-
rivatives are currently considered part of the so-called emerging pollut-
ants (Mulvihill et al., 2011; Gazsó et al., 2015; Halada and Orlov, 2018;
Xu et al., 2019).
On the other hand, the methods of chemical and physical synthesis
of nanomaterials are characterized by requiring high energy require-
ments, in many cases ecotoxic reagents and a considerable number of
auxiliary reagents are used, but also, in many cases, low material con-
version is achieved (Shah et al., 2015; Nasrollahzadeh et al., 2015;
Sasidharan et al., 2019; Hou and O'Connor, 2020; Rahman et al.,
2020). In addition, the size scale in which nanomaterials are obtained,
i.e., 1–100 nm, allows them to interact easily with biomolecules and cel-
lular components (Palencia et al., 2015); but also, when they are re-
leased into the environment, they can suffer alterations in their
physicochemical characteristics due to processes like agglomeration,
oxidation, aging, biotransformation, degradation, among others
(Devatha and Thala, 2018; Grieger et al., 2018; Sohail et al., 2019;
González-Ballesteros and Rodríguez-Argüelles, 2020). This panorama
has led the academic, industrial, and governmental community to ad-
vance in the development of sustainable synthetic methods, the adop-
tion of systemic thinking, the implementation of standardization and
regulation processes, and the generation of a multi-target approach to
establish relationships among its structure, nature and bioactivity.
These approaches, or goals, can be summarized as the seeking of the im-
plementation of green chemistry principles in the fields of nanoscience
and nanotechnology (Dahl et al., 2007; Poynton and Robinson, 2018;
Soltani and Pouypouy, 2019). In this way, “green nanoscience” has
emerged as a necessity for the ecofriendly development of nanotechnol-
ogy, allowing the use of a holistic approach, in terms of planetary safety,
and with the objective to develop safer and more sustainable products.
This not only makes it possible to reduce ecological impacts, but also to
contribute with new and innovative remediation strategies based on
the removal or elimination of environmental pollution for the restora-
tion of ecosystems (Corsi et al., 2018; Lerma et al., 2018).
The implementation of the green chemistry approach in the area of
nanomaterials and other technologies, both emerging and well
established, can be an intricate process with a considerable degree of
complexity because the principles of this strategy are mainly qualitative,
this means that it does not exist of a universal metric and minimum

2
A. García-Quintero and M. Palencia
designation criteria to apply the concept “green” to a process (Morales
et al., 2011; Tufvesson et al., 2012; Tickner and Becker, 2016;
Constable, 2018). In consequence, the designation as “green” of many
procedures, processes or products becomes subjective and does not
provide specific information, about the implications and impacts, in
terms of environmental sustainability and planetary health risks. The
above has led to the need to adopt and develop quantifiable parameters
that allow quantitatively establishing how green, or sustainable, a pro-
cess is; but also, how much its potential environmental impact is. At
the present, the environmental impact is the most common criterion
taking in consideration in many researches, however, its application
have been scarcely implemented in out-lab studies under non-
controlled conditions; therefore, factors associated with the degree of
material conversion through concepts like the atomic efficiency, the
ratio of residues to the product, the energy efficiency, and the mass pro-
ductivity, as well as holistic approaches focused on life cycle have been
proposed as a first approximation for the quantification of impact and
risks of the processes on environment and human health (Morales
et al., 2011; Mulvihill et al., 2011; Muñoz, 2012; Reid and Reed, 2016;
Sheldon, 2017a, 2017b).
This review comprises two parts, in the first an overview of green
chemistry in the framework of nanomaterials is shown and discussed,
while in the second, a critical analysis of the main approaches for eval-
uating their impact is analyzed. Among the most accepted approaches,
in terms of environmental sustainability, are those associated with
nanobiotechnological and bio-based synthetic pathways (note that eco-
nomic and social sustainability are not part of these review and there-
fore, henceforth the use of the term sustainability refers exclusively to
environmental sustainability). In most cases, in the scientific literature,
these types of nanomaterial synthesis are called “green” methods with-
out the use of any quantitative analysis, or universal criteria, to support
the claim.
The objectives of this review are: (i) to analyze the “green” concept
in the field of nanoscience and nanotechnology, (ii) to provide a precise
vision of the different interpretations that may arise from its use, and
the limitations that these triggers, and (iii) analyze the different types
of existing metrics to quantitatively establish how green a nanomaterial
synthesis process is. In particular, the last two objectives offer a differen-
tiating analysis, considering a combined vision from synthetic chemis-
try, engineering, and the analysis of the existing environmental risk in
all manufacturing processes of new chemical species. In consequence,
in order to contribute to the implementation of quantitative metrics
that allow the objective comparison of the different synthesis methods,
the main “green” evaluation metrics used to evaluate the approxima-
tion of a nanotechnological process are shown and analyzed. These in-
clude: atomic economy, E factor, process mass Intensity analysis,
energy intensity and life cycle.
From a methodological point of view, the information reviewed
here was based mainly on two topics “Green chemistry approach
in nanoscience” and “Sustainability Metrics Applied in Green
Nanomaterials” which was obtained from previously published re-
searches. As strategy for the systematic search of the information a histor-
ical perspective was adopted. In this way, it is intended to illustrate the
evolution of the different approaches adopted around green chemistry
and its application to nanosciences, but also, its evolution from a qualita-
tive approach to quantitative approach strategies is shown.
2. Green chemistry approach in nanoscience
2.1. Green chemistry: a historical description and fundamentals
In recent centuries, humanity has undergone profound social, polit-
ical and economic changes that have led to a modification in the con-
sumption patterns of natural resources, accelerated industrial
production and the generation and release into the environment of dif-
ferent substances, including synthetic plastic materials, fertilizers,
3
Science of the Total Environment 793 (2021) 148524
pesticides, pharmaceuticals, recalcitrant compounds, among others.
This has generated changes in natural ecosystems in terms of their
structure and behavior, leading in some cases to an irreversible alter-
ation of fauna and flora, for example, in the case of aquatic environ-
ments, these have been affected by alterations in the biotic balance,
triggering phenomena such as eutrophication, accumulation of plastic
materials, contamination by heavy metals, and even their complete dis-
appearance. In the case of terrestrial ecosystems, the effects associated
with salinization of their soils, contamination by solid waste and pesti-
cides, and desertification are some examples (Albini and Protti, 2016;
Mehdinia and Mehrabi, 2019; Handojo et al., 2020). It is recognized
that, since the 1960s, these negative facts began to be evident and pro-
moted a social and political consciousness (Paull, 2013; Albini and
Protti, 2016). A chronological description of the main milestones related
to green chemistry and nanotechnology are summarized in Table 1.
Since the EPA's creation, prolific regulations, definitions, institutes,
agencies, and thought models have been generated that represent the
paradigms of ecological awareness (see Table 1). The most representa-
tive milestones that emerged are the concept of sustainable develop-
ment in 1987, the approval of the Pollution Prevention Act in the
American Congress and the implementation of the Life Cycle Analysis
in 1990, and the generation of a fundamental concept based on environ-
mental sustainability for the development of increasingly ecological
technologies and processes, this is Green Chemistry, which is a notion
proposed by chemist Paul Anastas to lay the foundations and objectives
of the Green Chemistry Project (Dicks and Hent, 2015; Upreti et al.,
2015; Albini and Protti, 2016; Coish et al., 2018; Constable and
Jiménez-González, 2018). From this moment on, the development and
interest of the scientific community in the generation of processes
based on green chemistry have led to a transformation in the field of sci-
ence, engineering and industry, in such a way that just two years of the
origin of the term, the first Green Chemistry Symposium was held in
1993 (Albini and Protti, 2016).
On the other hand, the vision of green chemistry underwent a re-
markable conceptual development with the introduction of the qualita-
tive “metrics” proposed by Paul Anastas and John Warner. These
considerations included the materials design process, their molecular
design, synthesis, use, final disposal, and effects on planetary health.
Currently these statements are known as the Twelve Principles of
Green Chemistry (see Fig. 1) (Mulvihill et al., 2011; Dicks and Hent,
2015; Iavicoli et al., 2017; Coish et al., 2018; Soltani and Pouypouy,
2019). These principles are consistent with the standards of ISO
14001, which emerged in 1996 as an international standard for environ-
mental management. In ISO 14001, the use of Life Cycle Analysis is pro-
posed as a holistic approach to evaluate the sustainability of a process by
evaluating the mass and energy flow, final disposal, ecological impact
and potential benefits of the material, being one of the most commonly
used approaches to analysis in the field of green chemistry (Jindal and
Jain, 2018).
It is now widely accepted that green chemistry emerges as a design
philosophy for the development of sustainable processes that allows the
construction of safe technologies in terms of planetary health (Dahl
et al., 2007; Gilbertson et al., 2015; Albini and Protti, 2016; Zhang
et al., 2018). Consequently, green chemistry starts from the researcher's
decision to consider greener alternatives in the design of their process.
In this way, safety and impacts on the environment are a criterion of
equal or greater weight than conventional criteria such as costs, effi-
ciency, yields and logistics involved in the development of the pro-
cesses. This implies that the development of fully sustainable chemical
synthesis is an iterative process that uses the precepts of green chemis-
try as the purpose of innovation (Albini and Protti, 2016). For this rea-
son, in the specialized literature it can be found that a chemical
transformation called green is understood as those that present in
their design a concordance with the twelve principles indicated above.
However, the incorporation of all the principles is a chimerical goal
and therefore only some of these principles are generally satisfactorily
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

Table 1
Historical events related to green chemistry and nanotechnology.

Year Historical fact Reference

1959 Potential applications of manipulating objects in nanoscales were suggested at the California Institute of Technology by (Zelić et al., 2018)
physicist Richard Feynman through his work “There's Plenty of Room at the Bottom”.
1962 Rachel Carson published her book Silent Spring about scientific divulgation of the long-term adverse effect of pesticides on (Albini and Protti, 2016)
the environment.
1969 The Coca-Cola Company and the Midwest Research Institute in Kansas City analyzed two different beverage container's (Sheldon, 2017a, 2017b)
environmental releases, being an initial initiative of the Life Cycle Analysis.
1970 The US Environmental Protection Agency (EPA) is founded. (Paull, 2013)
1974 Norio Taniguchi defines the concept ‘Nanotechnology’. (Sohail et al., 2019)
1981 Observation and manipulation of nanostructures with the Scanning Tunneling Microscope of the International Business (Zelić et al., 2018)
Machines Corporation (IBM) were carried out.
1987 The concept ‘Sustainable Development’ was established in the World Commission on Environment and Development (Constable and
(Brundtland Commission). Jiménez-González, 2018)
1988 Office of Pollution Prevention and Toxics at the EPA is founded. (Albini and Protti, 2016)
1990 It is approved the Pollution Prevention Act in the American Congress. (Sheldon, 2017a, 2017b)
1990 Life Cycle Analysis is implemented. (Kralisch, 2008)
1991 “Green Chemistry” is proposed by Paul Anastas in the EPA. (Dicks and Hent, 2015)
1991 Barry Trost proposed the “Atom Economy” metric. (Constable, 2018)
1992 The “Ecological-Factor” or E-factor was proposed by Roger Sheldon. (Sheldon, 2017a, 2017b)
1993 The first Green Chemistry Symposium was held on: “Benign by Design: Alternative Synthetic Design for Pollution (Albini and Protti, 2016)
Prevention”.
1995 The Green Chemistry Challenge Awards were established. (Mulvihill et al., 2011)
1996 The ISO 14001 emerged as an international standard for environmental management. (Jindal and Jain, 2018)
1997 Green Chemistry Institute of American Chemical Society is founded. (Mulvihill et al., 2011)
1998 The 12 principles of green chemistry were established by Paul Anastas and John Warner. (Dicks and Hent, 2015)
1999 It is launched the first publication of the Green Chemistry Journal in the Royal Society of Chemistry. (Dicks and Hent, 2015)
1999 The metric “Effective Mass Yield” is proposed by Tomas Hudlicky. (Hudlicky et al., 1999)
2001 Neil Winterton proposes twelve additional principles of Green Chemistry. (Winterton, 2001)
Early years of the “Green Nano” emerges as working line in the Green Chemistry Institute of the American Chemical Society and the Oregon (Khan, 2020)
21st century Nanoscience and Microtechnologies Institute.
2005 Professor John Andraos established that Atom Economy can encompasses all the chemical substances involved in the (Dicks and Hent, 2015)
synthetic process.

included in the design. In turn, a green synthesis can also be considered
as one that is more sustainable than a less ecological procedure for
obtaining a similar product, regardless of whether this process has
been carried out using green chemistry as a design basis (Albini and
Protti, 2016; Iavicoli et al., 2017; Livingston et al., 2020). In this case,
the adjectival “green” arises as a result of an improvement that contrib-
utes to the desired objective. The above is a resource used many times
for the promotion of research, lines of work and results by many re-
searchers. Therefore, chemical reactions can present minor or major ap-
proaches towards green chemistry, generally determined qualitatively,
without implying that these processes do not represent an environmen-
tal and health risk. An example that illustrates the above is the produc-
tion of polyurethanes. These can be obtained by traditional synthesis
based on the reaction between isocyanate and hydroxyl groups, using
suitable solvents and reaction auxiliaries (Palencia et al., 2016b), but
also, the solvent-free polyurethane synthesis (Lei et al., 2020),
disperse-phase synthesis using water as solvent to obtain waterborne
polyurethanes (Honarkar, 2018), or non-isocyanate polyurethane
from reaction sequences omitting the use of isocyanates as precursor
have been proposed (Asemani and Mannari, 2019) (see Fig. 2).
This situation has led the scientific community to advance in the
development of new principles of green chemistry, such as those pro-
posed by Neil Winterton in 2001 (see Fig. 3). These are aimed at the in-
terrelation of concepts between green chemistry, green engineering
and sustainability, and with them it is intended to advance in the devel-
opment of quantification parameters that allow the processes of com-
parison, control, understanding of the life cycle, the inclusion of
systemic thinking for the optimization of the design, and the incorpora-
tion of quantitative factors associated with the thermodynamic, toxico-
logical and ecotoxic character of the substances. All of the above in order
to generate procedures focused on ecological, economic and social well-
being (Winterton, 2001; Abraham et al., 2008; Dahl et al., 2007;
Gilbertson et al., 2015; Zhang et al., 2018).
In the framework of green chemistry, several considerations allow
progress not only in the implementation and advancement of
sustainable chemistry but also in the implementation of synthetic inno-
vations such as: alternative solvents (e.g., exchangeable solvents and
ionic liquids), application of sources alternative energy sources in syn-
thetic processes (e.g., microwaves, solar energy and ultrasound), and
the development of specific fields such as nanobiotechnology, which is
one of the accepted approaches as more sustainable for the synthesis
of nanomaterials (Upreti et al., 2015; Nasrollahzadeh et al., 2015).
Nanobiotechnology is discussed with greater detail in Section 2.3.
2.2. Green nanoscience
Having established a historical and conceptual framework for green
chemistry, it is appropriate to briefly review the foundations of
nanoscience, nanotechnology, and nanomaterials before to describe
the ideas contained within the “Green Nano” concept. First, nanoscience
is an area of knowledge focused on understanding the fundamental
properties of matter at the nanoscale, in particular those resulting
from its small size. This is mainly due to the prevalence of surface phe-
nomena, quantum confinement and the intimate interaction that occurs
between microscopic components and other components that make up
nanomaterials (Dahl et al., 2007; Kolahalam et al., 2019). On the other
hand, nanotechnology is a concept proposed by scientist Norio
Taniguchi to refer to the design, manufacture, control, characterization
and applications of materials with at least one of their dimensions, ei-
ther internally or externally, on a nanometric scale (Sánchez et al.,
2018; Kolahalam et al., 2019; Sohail et al., 2019; Villalobos et al.,
2019a, 2019b). It is important to clarify that the upper limit of 100
nm, frequently used to define the nanoscale, is a convention whose
use is not generalized and fully accepted by the scientific community;
however, it is very useful to generate an idea of the size of the
nanomaterial being referred to. In this way, any material with at least
one component in the nanoscale size is called a nanomaterial and is
generally classified mainly according to its form of production, size
and nature (Maldonado et al., 2016). Regarding their production,
nanomaterials can be classified as “synthetic” when they are

4
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

Fig. 1. Illustration of the twelve principles of green chemistry proposed by P. Anastas and J. Warner.

intentionally manufactured for research or commercial purposes, “acci-
dental” when they are obtained as by-products, and “natural” when
they are innately found in the environment as product of spontaneous
processes of mechanical, chemical, biological origin, or a combination
of these, such as geochemical or biogeochemical processes (Hochella
et al., 2019). Due to their dimensionality, nanomaterials can be classified
as 0 D when they present all their dimensions at the nanoscale, being
the case of many inorganic nanoparticles such as gold and silver nano-
particles; 1 D when they present one of their dimensions on the macro-
scopic scale, such as nanotubes; 2 D when two of its dimensions are on
the macroscopic scale, like nanoplates; and 3 D when a macroscopic
material has nano-objects in its structure, for example, the presence of
nanopores or the modification of macroscopic materials using nano-
objects (Palencia et al., 2016a; Lerma et al., 2018; Sohail et al., 2019;
Fiorati et al., 2020). Furthermore, nanomaterials can be classified ac-
cording to their composition into organics such as polymers, liposomes
and micelles; inorganics such as ceramic nanomaterials and metallic
nanoparticles; carbon-based nanomaterials such as fullerenes and car-
bon nanotubes; and nanocomposites, in which their constituents have
a different nature, such as exfoliated clays modified with polymers,
and dispersions of nanoparticles within a polymeric phase (Garcés
et al., 2018; Lerma et al., 2018; Sohail et al., 2019).
The structural diversity of nanomaterials has made nanotechnology
a multipurpose area of great scientific and commercial relevance. This
situation implies that the development of nanomaterials must be ana-
lyzed from a total system approach, including their benefit-impact

Fig. 2. Illustration of different strategies for the synthesis of polyurethanes (the use of precursors, reaction auxiliaries, and complementary reactions are emphasized) (adapted from
Palencia et al., 2016b; Honarkar, 2018; Asemani and Mannari, 2019; Lei et al., 2020).

5
A. García-Quintero and M. Palencia
Fig. 3. Illustration of the twelve more principles of green chemistry proposed by Neil Winterton in 2001.
ratio, life cycle cost and life cycle impact (Ciambelli et al., 2019). The lat-
ter is essential to identify and minimize the adverse effects of this tech-
nology on human health and the environment.
From a historical perspective, the foundations of the current mean-
ing of nano green emerged by extrapolating the principles of green
chemistry to this specific area of science and technology (Khan, 2020)
(see Table 1). Thus, the term green nano refers to nanoscience and
nanotechnology with an environmental focus in its design, application
and final disposal; therefore, it is an area of knowledge based on the
generation of sustainable and safe nanomaterials (Eckelman et al.,
2008; Khan, 2020). This sustainability framework implies that the pro-
cess analysis includes the selection of the reagents, the synthetic proce-
dure in terms of mass and energy, the details of the potential
application, the disposal at the end of the useful life and the net environ-
mental consequences throughout the process (Dahl et al., 2007;
Gilbertson et al., 2015). In addition, nanoscience and green nanotech-
nology seek to advance in the development of regulatory frameworks
and procedures to standardize the use, practices and functional and
structural analysis of green nanomaterials for their potential applica-
tions in the environmental field as sensors and repair agents (Iavicoli
et al., 2017; Ciambelli et al., 2019). In this way, the twelve principles
of green chemistry applied in the field of nanotechnology are indicated
below:
• Principle one: Avoiding the production of waste. This principle is based
on the fact that reducing waste production is an easier goal to achieve
than the remediation required as a result of waste released into the
environment (Dicks and Hent, 2015; Coish et al., 2018). In relation
to this point, it is important to note that, in nanotechnology, signifi-
cant advances have been made in the implementation of efficient syn-
theses, capable of obtaining monodisperse and stable nanomaterials,
through the use of natural extracts or nanobiofactories that use a re-
duced number of reagents and avoid the generation of by-products
(Silva et al., 2015). Thereby, biobased or green synthesis has been pro-
posed to be carried out from agro-wastes and biotechnological pro-
cesses (Adelere and Lateef, 2016).
• Principle two: The atom economy is a concept that recognizes the fact
that the synthetic efficiency of a process is not limited only to the yield
of the reaction, but is also closely related to the inclusion of the largest
number of atoms of the reactants in the products (Mulvihill et al.,
2011). This concept has been subject to various interpretations since
6
Science of the Total Environment 793 (2021) 148524
its conceptualization, in such a way that in 2005 it was emphasized
that the concept “atom economy” encompasses all the chemical
substances involved in the synthetic process and not only the main
chemical reaction (Dicks and Hent, 2015). Although nanotechnology
presents multiple limitations in terms of mass production of
nanomaterials; In general, for example, conventional physical synthe-
sis processes are characterized by low material conversion with high
polydispersity of particle size and shape compared to chemical
methods, which are characterized by high waste production and
high usage. of reaction aids such as solvents, stabilizers. Agents, sur-
factants, etc. (Palencia et al., 2014a, 2014b); however, as chemical
synthesis, post-synthesis methods, and bioreactor-based synthesis
advance, the ability to synthesize monodisperse nanoparticles with
homogeneous morphology has continually increased (Palencia et al.,
2014a; Silva et al., 2015; Ciambelli et al., 2019).
• Principle three: Safer synthetic processes. This principle is based on the
premise that the experimental design must consider all the possible
parameters of the process capable of generating adverse effects on
planetary health (Anastas et al., 2018). In nanotechnology, many ad-
vances have been directed at the transmaterialization of dangerous
reagents, such as the replacement of strong reducing agents with
safer alternatives, such as aqueous extracts from biological systems
such as plants, algae and bacteria (Adelere and Lateef, 2016;
Ciambelli et al., 2019; Madanayake et al., 2021). Several review arti-
cles relate to risk of nanomaterial synthesis processes and processes
associated with the release to environment have been published
(Ellenbecker and Tsai, 2011; Hjorth et al., 2017; Bardos et al., 2018;
Fabiano et al., 2019).
• Principle four: Safer products. The use of molecular or intelligent de-
sign, to prevent possible adverse interactions of products with living
beings and the environment, is an excellent strategy to reduce the
risk and danger of products with great potential to be introduced in
the market, and that consequently will be massively produced
(Dicks and Hent, 2015). To achieve this goal, the availability of infor-
mation is an essential aspect that must be easily remedied by all actors
in the field of nanoscience and nanotechnology. Some examples of
strategies are the generation of data libraries and properties related
to the structure-activity relationships on the risks of nanomaterials,
the cooperative work for the creation of data repositories without ac-
cess by web platforms, and the promotion of scientific journals of low-
cost, non-profit open access, funded directly by government entities
A. García-Quintero and M. Palencia
or special projects. However, due to the great variety of
nanomaterials, and the fact that their properties are not only a func-
tion of their composition, but also depend on their shape, size and
coating agent, among others, in the vast majority of cases the available
ones. The information published on many occasions does not allow
generalizations about the environmental fate and the interactions of
nanomaterials with the different components of the environment
(Harper et al., 2008; Li et al., 2018; Poynton and Robinson, 2018;
Ciambelli et al., 2019). In relation to the environmental and health
risk of nanoparticles, several review articles have been published
and offer a comprehensive and broad vision of this topic (Palencia
et al., 2015; Hjorth et al., 2017; Kumar et al., 2017; Bardos et al.,
2018; García-Quintero and Palencia, 2021).
• Principle five: Avoiding the use of auxiliaries. This principle refers to re-
ducing the use of solvents for synthesis and purification, or if it is not
possible, to use those that do not present environmental risk, being
the use of aqueous media always the most appropriate option (Dahl
et al., 2007; Coish et al., 2018). The use of water-soluble precursors
and alternative purification processes such as centrifugation and the
use of green solvents such as ionic liquids or exchangeable solvents
are some examples used in nanotechnology for the implementation
of this point (Khan and Lee, 2015; Silva et al., 2015; Upreti et al.,
2015; Kumar et al., 2017; Bardos et al., 2018).
• Principle six: Energy efficiency. This principle seeks to reduce the use
of conventional energy sources based on fossil fuels, dirty energy
(for example, combustion energy), and any form of energy directly as-
sociated with the generation of greenhouse gases (Livingston et al.,
2020). In accordance with the above, it is intended that nano-
synthesis processes can be carried out at room temperature and atmo-
spheric pressure; In this area, nanotechnology has advanced in the
implementation of alternative energy sources such as microwaves
and ultrasound, allowing reactions to be carried out in less time and
with greater energy efficiency (Upreti et al., 2015). In turn, the use
of biogenic and bio-based synthesis represents a promising alterna-
tive since it allows the majority of synthesis processes to be carried
out under conditions of pressure and room temperature (Dicks and
Hent, 2015; Silva et al., 2015; Pandey, 2018).
• Principle seven: Use of reagents from renewable sources. This principle
is directly represented in the bio-based synthesis through
nanobiotechnology because the use of the natural ability to reduce bio-
molecules and renewable biological systems allows to obtain a wide di-
versity of nanomaterials, with different biological, catalytic and optical
properties (Dicks and Hent, 2015; Khan and Lee, 2015; Upreti et al.,
2015; Adelere and Lateef, 2016; Madanayake et al., 2021).
• Principle eight: Avoiding derivatization and minimizing reaction steps.
Multi-step processes and derivatization result in increased use of chem-
ical reagents and decrease the overall atomic efficiency of the process
(Dicks and Hent, 2015). In this field, nanotechnology has advanced in
processes of synthesis and surface functionalization of nanomaterials
using one-pot strategies, and in the design of synthesis processes of
pure substances or of easy purification. All this in order to avoid
energy-intensive techniques or the use of dangerous reaction auxiliaries
(Dicks and Hent, 2015; Silva et al., 2015).
• Principle nine: Catalysis. This principle is focused on substances with a
high surface area to favor the efficiency and selectivity of chemical reac-
tions (Dicks and Hent, 2015; Erythropel et al., 2018). In this context, due
to the large surface area and chemical reactivity of nanomaterials, they
emerge as ideal catalytic systems. However, processes based on cata-
lytic strategies must avoid the presence of catalyst residues in the final
product and the use of catalysts that by their nature are not highly
toxic should be encouraged, since, although the laboratory quantities
used tend to be very small, after scaling up the processes, the amounts
of catalyst can be significant in terms of toxicity, release frequency and
ecological risk (Dicks and Hent, 2015; Ciambelli et al., 2019).
• Principle ten: Design for final disposal. This principle implies the use of
systemic thinking that allows considering the final disposal of the
7
Science of the Total Environment 793 (2021) 148524
product in such a way that it can be recycled, reused, recovered or
biodegraded (Dahl et al., 2007). In nanotechnology, several advances
have been made in this way, which is why predictive tools for design,
recycling and recovery have been created. These are based on the im-
plementation of computer programs, in order to establish the Life
Cycle Analysis of nanomaterials (Dahl et al., 2007; Dicks and Hent,
2015; Sanjay, 2019).
• Principle eleven: Real-time monitoring. This principle refers to the devel-
opment of analytical tools that allow in situ monitoring of reactions and
processes to avoid the generation of potential contaminants (Dicks and
Hent, 2015; Erythropel et al., 2018). Nanomaterials have been used to
develop more sensitive monitoring tools through the interaction and re-
sponse of the surface plasmon resonance of the nanoparticles. However,
its small size, low concentration and high reactivity, which implies a
rapid change at the moment of being released into the environment,
represent a limitation for its monitoring in uncontrolled environments
(Bhandari, 2018; Ciambelli et al., 2019).
• Principle twelve: Implementation of prevention measures for the devel-
opment of safer processes. This principle is related to accident
prevention through the use of inherently safer substances (Dicks and
Hent, 2015; Khan, 2020). Important advances have been made in the
transmaterialization of solvents and reagents to obtain nanomaterials
with properties analogous to those synthesized by traditional methods;
however, in some cases this is not possible because it is necessary to use
metallic precursors with unsustainable extraction methods and inher-
ent toxicity (Ciambelli et al., 2019; Livingston et al., 2020). In turn, the
incorporation of nanomaterials to macroscopic surfaces or systems
has been implemented. Thus, the direct release of the nanomaterial to
the environment through washing or diffusion processes can be
prevented through the production of nanocomposites, and conse-
quently, through this strategy it is possible to reduce the risk of expo-
sure and improve the mechanical and functional properties of the
phases (Silva et al., 2015; Córdoba and Palencia, 2017; Villalobos et al.,
2019a, 2019b).
2.3. Green synthesis of nanomaterials
Nanomaterial synthesis can be carried out using two main ap-
proaches: bottom-up and top-down. In the Top-Down approach, a mac-
roscopic material is physically or chemically disintegrated until
obtaining nanomaterials, which usually present a high polydispersity
and inhomogeneous morphology, and as a consequence of the above,
its average properties are the result of contributions of particles with
different shapes and sizes, consequently, this approach is associated
with simple and fast methods characterized by low material conversion
(Shah et al., 2015; Devatha and Thala, 2018; Umapathi et al., 2018;
Villalobos et al., 2019a, 2019b; Livingston et al., 2020). In general,
these processes are carried out by physical methods, which require a
high energy intensity that leads to the generation of pollution due to
the production of greenhouse gases; an example of them is the deposi-
tion, grinding and crushing of steam (Shah et al., 2015; López et al.,
2019). Furthermore, to decrease the polydispersity of the nanoparticles,
post-synthesis methods have been proposed, for example, the use of
enhanced membrane filtration with hydrodynamic polymer gels
(Palencia et al., 2019). On the other hand, in the Bottom-Up approach,
nanomaterials are synthesized from atomic and/or molecular entities,
generally using chemical methods (Shah et al., 2015; Pandey, 2018;
Umapathi et al., 2018; Villalobos et al., 2019a, 2019b). In most cases
this strategy involves limited purity and unknown yields, as well as
the use of reagents of a dangerous nature, difficult to handle and elimi-
nate due to their toxic, corrosive, irritating and/or flammable properties.
An example is the synthesis using organic or inorganic solvents in
conjunction with reducing agents such as sodium borohydride, N,N-
dimethyl formamide, and hydrazine, stabilizing agents such as
cetrimonium bromide, polyamidoamine, N-methyl-D-glucamine, citric
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

acid, poly(vinylpyrrolidone), among others (Palencia et al., 2017;
Pandey, 2018; Nasrollahzadeh et al., 2015; Sasidharan et al., 2019;
Hou and O'Connor, 2020; Rahman et al., 2020). Therefore, secondary
pollution events resulting from physical and chemical syntheses make
them harmful to the environment. It is in this area where the philoso-
phy of sustainable design, framed in the principles of green chemistry
and bio-based synthesis strategies such as nanobiotechnology, emerges
as the most appropriate procedure to generate ecological nanomaterials
(Shah et al., 2015; Adelere and Lateef, 2016; Das et al., 2018; Pandey,
2018; Madanayake et al., 2021).
The term “bio-based synthesis” refers to the use of biological entities
and/or biomolecules to carry out synthetic nanomaterial processes
(Shah et al., 2015). In this way, the biobased synthesis of nanostructures
emerges as the most sustainable approach in line with green chemistry
because it is characterized to be a Bottom-Up process, usually carried
out in one-pot systems (principle 8), using renewable and safe raw ma-
terials (principle 3, 7, and 12), under conditions of atmospheric pressure
and ambient temperature, or below 200 °C, in order to avoid the exces-
sive use of non-renewable energy sources (principle 6), and by using
water or alcoholic solutions as the reaction medium (principle 3 and
12) (Kolahalam et al., 2019; Mohammadi et al., 2019). These character-
istics are represented in the generation of procedures with lower costs,
greater safety and an operational simplification compared to traditional
synthesis methods (Adelere and Lateef, 2016; Madanayake et al., 2021).
On the other hand, through nanobiotechnology it is possible to ob-
tain nanostructures with different morphologies, dimensions, surface
charge and functional properties. For this, synthetic in-situ and/or ex-
situ procedures are used, which are based on the use of metabolic path-
ways or biomolecules present in different living entities, which include
microorganisms such as bacteria, yeasts and viruses, and higher organ-
isms such as multicellular algae, mushrooms and plants (Shah et al.,
2015; Bolade et al., 2020; González-Ballesteros and Rodríguez-
Argüelles, 2020; Hou and O'Connor, 2020). Of these biosynthetic alter-
natives, the process based on the use of plant material is the most gen-
eralized and developed synthesis in academia, mainly due to the simple
propagation of plants, and their wide phytochemical and phylogenetic
diversity, the simple extraction capacity of their molecules and compo-
nents through innocuous solvents, and the possibility of using different
tissues, ranging from pulps and peels of fruits, leaves, roots, seeds, to
flowers (see Table 2) (Anastas and Lankey, 2000; Nasrollahzadeh
et al., 2015; Nath, 2015; Shah et al., 2015; Silva et al., 2015; Devatha
and Thala, 2018; Ciambelli et al., 2019; Sebastian et al., 2020). In turn,
small variations in the concentration of the plant extract, the amount
of the precursor nanomaterial, the temperature or the pH conditions
provide the ability to generate nanomaterials with different morphol-
ogy, size and biological properties (Shah et al., 2015). In addition,
plant-based synthesis compared to those using microorganisms tends
to be more efficient in terms of quantity and time, requiring simpler
conditions than those used to maintain adequate nutrition, purity, and
optimal cell culture growth conditions (e.g., lighting, pH, temperature,
aeration, energetic source, among others) (Nasrollahzadeh et al.,
2015; Shah et al., 2015; Devatha and Thala, 2018).
Regarding the versatility of plant synthesis, this is associated with its
varied biochemical composition since plant material has a wide variety

Table 2
Examples of bio-based synthesis of nanomaterials employing diverse plant tissues.

Nanoparticles Plant tissue Remarks Reference

FeO Avicennia marina The extract was obtained using an aqueous system boiled for 5 min. A FeCl3 solution was added to the extract (Karpagavinayagam
(30–100 nm) flower to obtain cubic morphology nanoparticles. and Vedhi, 2018)
ZnO Bougainvillea flowerThe extract was obtained using a zinc acetate solution at room temperature. Nanomaterials with antibacterial (Ahmar Rauf et al.,
(~ 40 nm) activity against E. coli, P. aeruginosa, S. aureus, and anticancer activity against the MCF-7 cell line were 2019)
obtained.
Ag Nigella sativa seed Seeds were macerated and dissolved in an aqueous medium, boiled for 20 min, cooled, and filtered. AgNO3 (Chand et al., 2021)
(10–12 nm) 1 Mm was added, and the system was heated at 80 °C for 2 h. Silver nanoparticles with catalytic activity in the
degradation of the Congo Red dye were obtained.
Ferula persica root Roots were collected, dried and macerated. Double-distilled water was added. and system was heated at 100 (Nasiri et al., 2018)
°C for 15 min. Later, AgNO3 was added to obtain Ag nanoparticles. Nanoparticles showed lower phytotoxicity
on the germination of Matricaria chamomilla and Ocimum basilicum compared to Ag nanoparticles obtained by
traditional methods.
Allium cepa peels Peels were sanitized, segmented, placed in an aqueous medium, boiled for 10–15 min, and filtered. AgNO3 was (Santhosh et al., 2020)
added to the extract for the obtaining of nanoparticles that showed antibacterial activity against Salmonella
typhimurium and S. aureus.
ZnO Eriobutria japonica Seeds were dried at 50 °C for 24 h, macerated, placed in an aqueous medium, and heated at 40 °C for 1 h. (Shabaani et al., 2020)
(< 50 nm) seed Supernatant was mixed with a solution of zinc acetate and heated at 60 °C for 2 h, at this time the system was
centrifuged and ZnO nanoparticles obtained were washed with ethanol. These nanomaterials showed
antibacterial activity against S. aureus.
SnO2 Green papaya Leaf extract was obtained by refluxing at 120 °C for 45 min, filtering, and addition of SnCl4·5H2O (0.1 M) and (Jadhav and Kokate,
(~ 7.10 nm) leaves hydrazine hydrate (0.01 M). Nanomaterial was collected after to heating and centrifugation. 2020)
Fe3O4 Persicaria bistorta Fe3O4 nanoparticles were coprecipitated using FeCl2·4H2O which was added dropwise to the aqueous extract (Azadi et al., 2018)
(~ 45.5 nm) root of the roots. Mixture was alkalinized at room temperature and under stirring to obtain nanoparticles with a
maximum magnetization of 62.5 emu/g.
Co3O4 Trigonella Leaves were collected, sanitized, dried at room temperature, and macerated. Extract was obtained using an (Akhlaghi et al., 2020)
(~ 13.2 nm) foenumgraceum ethanolic medium at 30 °C for 12 h. The extract was filtered, and CoCl2·6H2O (0.1 M) was added, in an alkaline
leaves medium, the system was heated at 80 °C, centrifuged, subjected to heating at 500 °C for 2 h, and dried at 100
°C, for finally to obtain the nanomaterial.
S Ocimum basilicum Leaves were collected, sanitized, placed in distilled water, and subjected to stirring. A solution of Na2S2O3 was (Ragab and Saad-Allah,
(~ 23 nm) leaves added to extract. At room temperature, extract was acidified for the obtaining a precipitate of yellow hue 2020)
corresponding to the nanomaterial, which shows an ability to increased tolerance of the sunflower species to
Mn toxicity.
Spherical Ni/Fe Punica granatum Peel was dried at 60 °C for 40 h, and extract was obtained using an ethanolic medium and refrigerated. FeCl3, (Ravikumar et al.,
(~ 129 nm) peels NiSO4, and carboxymethyl cellulose were added to the solution to obtain nanomaterials. These were applied 2018)
for the removal of tetracycline.
Blue Carica papaya waste The extract was obtained by heating of aqueous system at 100 °C. Later, it was pyrolyzed and dissolved in (Pooja et al., 2019)
luminescent water for the obtaining of luminescent nanomaterials with a quantum yield of 54%.
C-dots
(< 10 nm)

8
A. García-Quintero and M. Palencia
Fig. 4. Plant's bioactive compounds associated to nanobiosynthesis.
of chemical compounds, including lipids, polysaccharides, proteins, vi-
tamins, nucleic acids, aglycones, polyols, pigments, steroids, flavonoids,
terpenoids, alkaloids, saponins, polyphenols, peptides, resins, proteins,
phytohormones, among others (see Fig. 4) (Nagajyothi and Tvm,
2015; Nasrollahzadeh et al., 2015; Razavi et al., 2015; Shah et al.,
2015; Silva et al., 2015; Srivastava et al., 2015; Pandey et al., 2019;
López-Valdez et al., 2018; Kolahalam et al., 2019). These compounds
contain functional groups such as aldehyde, ketone, alcohol, unsatu-
rated segments and/or thiols in their structure, allowing chemical reac-
tions of nanoparticle reduction-oxidation and/or stabilization processes
to be carried out during synthesis reactions (Nagajyothi and Tvm, 2015;
Nasrollahzadeh et al., 2015; Razavi et al., 2015; Silva et al., 2015;
Kolahalam et al., 2019; Pandey et al., 2019). However, the concentration
of phytochemicals in plant material is characterized by a wide natural
variability because its concentration is conditioned by nutrition, light-
ing, phylogenetics, the growth stage in which the plant is found
(e.g., Seedling, flowering, senescence, etc.), climate, geographical
conditions, impurities, interactions with the environment (for example,
physical or biological stressors, allelochemicals, plant-rhizosphere
interaction, among others). Furthermore, there is the difficulty of estab-
lishing the exact nature of the biomolecules that act in the stabilization
process of nanomaterials; therefore, these situations make plant syn-
thesis a process of limited reproducibility and difficulty in obtaining
nanomaterials with a defined stabilizing agent (Pati et al., 2014; Silva
et al., 2015; Bolade et al., 2020). These aspects make it difficult to
build stoichiometric relationships between reactants, making it impos-
sible in most cases to define a molecular formula or net yield; therefore,
this is a generalized difficulty for the application of sustainability met-
rics, mainly those based on mass and molar efficiency (Pati et al.,
2014; Silva et al., 2015; Bolade et al., 2020). Another well-known ap-
proach consists of using a purified biomolecule, which allows to have
control over the nanomaterial's capping agent and to carry out an ade-
quate structure-activity relationship, but also allows to advance in the
establishment of stoichiometric coefficients. However, in environmen-
tal terms, this strategy involves purification and isolation processes, lim-
iting the sustainability of the synthetic process due to waste generation
9
Science of the Total Environment 793 (2021) 148524
and energy consumption (Shah et al., 2015; Bolade et al., 2020;
González-Ballesteros and Rodríguez-Argüelles, 2020).
Although plant-based synthesis is a known alternative to achieve the
goals of green nanoparticle synthesis, the fact that most scientific publi-
cations do not use quantitative parameters to establish its net ecological
effect, and the limited information on the total energy consumption and
performance in the conversion of raw materials, makes the conclusions
derived from these investigations regarding their real benefit in terms of
their ecological impact are not very useful (Pati et al., 2014; Gilbertson
et al., 2015; Devatha and Thala, 2018; Khan, 2020). In this way, in the
scientific literature, reactions denominated to be green can be found
where nanobiosynthesis is based on the principle seven of green chem-
istry; however, these do not involve the other principles, nor consider
the life cycle analysis of the nanomaterial, and even in some cases,
toxic reagents are used into stages of purification or a high energy inten-
sity is used during process of purification, heating, or calcination (Dicks
and Hent, 2015; Singh et al., 2018; Akhlaghi et al., 2020). Therefore, it is
pertinent to establish that not all processes that use nanobiotechnology
or bio-based synthesis are consistent with the principles of green chem-
istry. This is because the use of renewable raw materials does not guar-
antee that the ecological impact of the process is less than that produced
by classical procedures. From this perspective, it follows that, since
there are no minimum criteria to classify a synthesis procedure as a
green process, the naming of a synthesis using this label can be impre-
cise and even arbitrary. Consequently, it is clear that there is an inherent
difficulty in objectively comparing how sustainable a nanobium-based
process is compared to a conventional synthesis. Therefore, this situa-
tion shows the need to apply sustainability metrics in nanosynthesis
processes to have objective comparison tools (Pati et al., 2014; Dicks
and Hent, 2015; Albini and Protti, 2016).
2.4. Characterization of green nanomaterials
Nanomaterials synthesized by green chemistry are characterized
identically to those obtained by classical methodologies; however,
there are no standardized protocols for this process (Bolade et al.,
A. García-Quintero and M. Palencia
2020). However, the main characterizations are carried out to establish
the surface composition of the nanomaterial, its morphology, average
size, structure and depending on the application, a wide set of functional
properties are of interest, which include antibacterial, anticancer, cyto-
toxic and hemolytic activity, photocatalytic, magnetic and adsorptive
properties, among other characteristics (Palencia et al., 2016a; Salouti
and Derakhshan, 2019; Sánchez et al., 2019). In the field of green
nanomaterials, the determination of their structural and functional
properties is of special relevance because it allows progressively to ad-
vance in the development of structure-activity libraries; thus, through
databases it is possible to correlate and predict the relationships be-
tween the composition of nanomaterials, their size and their behavior
under natural conditions and their effects on living beings (Gilbertson
et al., 2015; Li et al., 2018; Poynton and Robinson, 2018; Ciambelli
et al., 2019).
In the case of colloidal dispersions, one of the first signs of their for-
mation is the change in the tonality of the solution and the presence of
dispersion properties such as the Tyndall effect (Shah et al., 2015). Usu-
ally, before carrying out the purification of the nanomaterial,
ultraviolet-visible spectroscopy (UV–Vis) is used to analyze the disper-
sion. This technique makes it possible to identify in some cases the res-
onance band of the surface plasmon, which is generated due to the
interaction of the surface electrons with the radiation when they enter
into resonance with them; in turn, since the maximum resonance wave-
length is related to the nature of the metal, the polydispersity of the par-
ticle size and the slight displacements of the maximum with size, this
band offers qualitative information on the characteristics of the particle
(Sánchez et al., 2018). On the other hand, when nanomaterials are puri-
fied, analyzes are carried out to establish the functional groups and mol-
ecules existing in them, for which techniques such as infrared
spectroscopy and Raman spectroscopy are usually used (Shah et al.,
2015; Umapathi et al., 2018).
A fundamental aspect in the functionality of nanomaterials is the de-
termination of their dimensions since their nanometric properties are
strongly related with their size; for this, several techniques have been
used such as Atomic Force Microscopy (AFM), Scanning Electron
Microscopy (SEM), Transmission Electron Microscopy (TEM), X-Ray
Diffraction (XRD), and Dynamic Light Scattering (DLS) (Shah et al.,
2015). The high-resolution microscopy techniques are based on elec-
tron's interaction with the matter (e.g., SEM and TEM) or in small inter-
molecular interactions (e.g., AFM), they allow to obtain an amplified
image of the sample, making possible the determining of the
nanomaterial morphology and size (Palencia et al., 2015; Sánchez
et al., 2018). However, a small amount of the sample is used in these
techniques and therefore, strictly speaking, their results are representa-
tive only when a great number of samples are analyzed. Furthermore, in
SEM and TEM, the sample is altered during the analysis, producing ag-
gregation phenomena that, in the case of not being considered in the
size descriptors, erroneous interpretations and incorrect generalizations
can be obtained (Palencia et al., 2015; Sánchez et al., 2018). In the case
of XRD, by the use of X-rays is possible establish the crystalline phases of
the nanomaterial, determining its approximated size through Scherrer
equation, and obtaining the corresponding diffraction pattern;
however, it presents drawbacks similar to those present in the atomic
microscopy (Bethi and Sonawane, 2018). By DLS is possible determine
the size of particles in dispersion using the equivalent hydrodynamic
radius as size descriptor. This technique is based on the scattering of
light and the Stokes-Einstein equation. However, DLS is blind to particle
shape and is influenced by aggregation phenomena of dispersed parti-
cles (Sánchez et al., 2018).
It is important to highlight that one of the great challenges of the
characterization of nanomaterials is the reproducibility and accuracy
of the results due to their inherent variability, which is often a function
of the manufacturing technique, but also, it depends on small variations
of protocols, purity of reagents, working volumes, etc. (Baer, 2018;
Mülhopt et al., 2018).
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Science of the Total Environment 793 (2021) 148524
3. Environmental sustainability metrics applied in green
nanomaterials
The importance to quantitatively describe the sustainability of a
chemical process is an aspect that has been discussed in the field of
green chemistry since the first publication of the Green Chemistry Jour-
nal in 1999 (Dicks and Hent, 2015). It is evident that there is no consen-
sus on how to transform the principles of green chemistry into
quantifiable metrics able to compare processes and quantitatively iden-
tify the aspects to optimize in a synthesis process (Muñoz, 2012;
Constable, 2018). This difficulty to objectively define a process as
green makes necessary the use of metrics based on scientifically-
rigorous arguments, covering the aspects of the processes in material,
energy, and environmental terms, in order to allows the academic, in-
dustrial, and government communities can establish the environmental
implications of regulation and consumption when a product or process
is denominated as “green” (Mulvihill et al., 2011; Gilbertson et al.,
2015). In this way, different types of metrics have been developed and
adapted to evaluate the approximation of synthesis to sustainability
and green chemistry principles, these mainly are focused on aspects of
mass, energy, molar efficiency, and environmental and ecotoxic impact
(Andraos, 2008; Constable, 2018; Zhang et al., 2018). At present, there is
a wide diversity of metrics that can be applied to evaluate particular as-
pects of the green chemistry principles in different types of procedures,
the best-known are: Atom Economy, E-Factor, Process Mass intensity,
Effective Mass Yield, Material Recovery, Energy Efficiency, and Life
Cycle Analysis, being the last a tool with a context-dependent multivar-
iate perspective (Manley et al., 2008; Albini and Protti, 2016; Reid and
Reed, 2016; Constable, 2018). Despite this variety of approaches, there
is a considerable difficulty in standardizing of the evaluation for a syn-
thetic procedure because there is no universal green metric that can
be applied to all processes (Constable et al., 2008; Reid and Reed,
2016). Parameters associated to green metrics have been mainly ap-
plied in synthetic organic and analytical chemistry, due to nature of in-
herent procedures carried out in these disciplines characterized for the
use of a great amount of auxiliary reagents, experimental stages, and di-
rected towards the obtaining of homogeneous or pure substances. In
contrast, when the same parameters are evaluated in the synthesis of
nanomaterials, they are not applicable in an ideal way due to the
inherent polydispersity of nanomaterial, their inherent heterogeneity,
the difficulty for the establishing stoichiometric relationships among
their components, the unknowledge of nanomaterial concentration
in the natural and urban world, and the lack of understanding of
nanomaterial-environment interactions (Constable et al., 2008; Reid
and Reed, 2016). In addition, the absence of the necessary information
in most scientific articles is frequent, so that the conclusions that can
be obtained around the application of the twelve principles of green
chemistry through prospective studies or meta-analysis are not always
feasible due to limited data availability. Therefore, the use of metrics is
not a common practice within many research teams. The analysis of
the results usually focuses on the characteristics and properties of the
product, the methodology in terms of its effectiveness to achieve a syn-
thetic purpose, and the use of “green” in a large number of publications
is synonymous with bio-based or nanobiotechnological synthesis. Con-
sequently, it is clear that there is still a significant way forward to bring
the concepts of sustainability and green chemistry from academia and
reflective discourse to real practice in research and technological devel-
opment activities. Other aspects that hinder the application of metrics in
nanomaterials are the lack of standardization of synthesis procedures,
characterizations, toxicity evaluation and environmental impacts in
the field of nanotechnology (Gilbertson et al., 2015; DeVierno Kreuder
et al., 2017). Undoubtedly, this panorama has led the scientific commu-
nity to seek to optimize and adopt known metrics of green chemistry in
order to apply them to the manufacture of nanomaterials. The most
used metrics are: atomic economy, E factor, energy intensity, process
mass intensity and life cycle analysis (Gilbertson et al., 2015; Reid and
A. García-Quintero and M. Palencia
Reed, 2016; DeVierno Kreuder et al., 2017). These metrics will be
discussed below.
3.1. Atom economy
The atom economy is a metric proposed in 1991 by the chemist
Barry Trost from Stanford University (Dicks and Hent, 2015;
Constable, 2018). This metrics is directly related to second principle of
green chemistry, which establishes that in a chemical synthesis must
be ensured that the greatest number of atoms from reactants are in-
cluded in the target product (Anastas, 2008; Erythropel et al., 2018).
In this way, atom economy is defined as the quotient of the molar
mass ratio between the product and its corresponding precursors in a
balanced chemical reaction (Dicks and Hent, 2015). Mathematically
this relationship is determined by Eq. (1).
SCP  MWP
AE ¼ ð1Þ
∑ðSCR  MWRÞ
where AE denotes atom economy, SCP and SCR are the respective stoi-
chiometric coefficients of products and reactants, in that order, and
MWP and MWR are the molecular weight of corresponding product
and reactant, respectively. From Eq. (1), it can be established that AE an-
alyzes a reaction by using exact stoichiometric quantities and implicitly
assumes a 100% yield; therefore, this value is essentially theoretical and
obviates the importance of other aspects of the reaction such as energy
consumption, the use of solvents and catalysts, and even the effect on
planetary health of reactants, products, and by-products (Albini and
Protti, 2016; Sheldon, 2017a, 2017b). But also, it is influenced by the na-
ture of the substances in terms of atomic number of atoms forming the
products, for example, for the neutralization of acetic acid using a hy-
droxide, the nature of cation contained in the hydroxide molecule influ-
ences the value of AE due to atomic number and not due to the danger,
toxicity, or reactivity of the cation. In addition, AE does not consider the
context, for example, for 2 H2 (g) + O2 (g) ➔ 2 H2O (g) (reaction-1) and
2 H2O (g) ➔ 2 H2 (g) + O2 (g) (reaction-2) is possible conclude that AE
for reaction-1 is larger than AE for reaction-2 since in the first case H2
and O2 are included in the molecule of water; however, gaseous water
is a greenhouse gas, and consequently, it is not the same that said reac-
tion occurred in the laboratory than in the upper border, from the
earth's surface, of the stratosphere. In addition, it is a parameter de-
pending strongly on stoichiometry and therefore it is not useful for
non-stoichiometric systems which are very usual in the chemical syn-
thesis of nanoparticles. For example, the amount of capping agent of in-
organic nanoparticles is not defined by the stoichiometric ratios.
Consequently, it has been used in the synthesis of nanomaterials as a
“qualitative” descriptor since to carry out optimal processes for the gen-
eration of nanostructures usually require an excess of the reagents act-
ing as reducing or stabilizing substances. However, this parameter is
easy to calculate, and it can be used as an exploratory factor to evaluate
whether the proposed synthesis could be optimized in terms of molar
efficiency, therefore, AE is a practical metric but short-range, adequate
for the design and theoretical analysis (Sheldon, 2017a, 2017b). Atom
economy allows comparing the molar efficiency of synthesis with an
analogous target nanomaterial. Such is the case of the research carried
out by Green et al. (2012) who analyzed a single-source precursor
synthesis of CdS quantum dots based on cadmium perchlorate and N-
(dithiocarboxy)-N-methyl-D-glucamine sodium salt as a source of
sulfur. They established that this approximation presents an atom
economy of 22.0%, 5.0% lower than that exhibited by a process carried
out with the precursor diethyldithiocarbamate of zinc as a source of
sulfur (Green et al., 2012). Therefore, atom economy allows establish-
ing, through a simple calculation, the most efficient alternative from
the material point of view for the obtaining of CdS quantum dots. In this
particular case, the establishing of the product's molecular mass and its
stoichiometric relationship with the reactants constitutes a feasible
11
Science of the Total Environment 793 (2021) 148524
aspect due to the known formula of the product, and the fact that the
single-source precursor synthesis presents a fixed element stoichiome-
try. For the case of the precursor derived from N-methyl-D-glucamine, it
is established that the relationship between a Cd2+ cation and N-
(dithiocarboxy)-N-methyl-D-glucamine is one and two, respectively
(Green et al., 2012). Nevertheless, most of the reactions of nanomaterial
synthesis does not present a fixed element stoichiometry, so in the field
of nanomaterials, the application of atom economy is in some cases a
complex parameter hardly calculable. Some strategies have been used
to define an approximate molecular formula based on the results of
structural characterization by XRD, morphology and dimension using
TEM, stability analysis by thermogravimetric studies, and analysis of
proportions in the reaction system (Reid and Reed, 2016). An example
of this is the research carried out by Reid and Reed, who established a
possible molecular formula of gold nanoparticles obtained using
dodecanethiol and HAuCl4. For this, the researchers used a weighted av-
erage formula related with the size distribution of the gold nanoparti-
cles obtained through a TEM histogram (Reid and Reed, 2016). Thus,
the number of gold atoms was estimated by Liu's method, which calcu-
lates the relationship between the density of gold atoms in fcc crystal
packing, the molecular mass, and the nanomaterial diameter with
spherical modeling. Through thermogravimetric analysis was deter-
mined the number of thiols and the diameter of the nanoparticle using
a second-order polynomial correlation (Reid and Reed, 2016). From the
results of the number of thiols and the gold atoms, Reid and Reed were
able to define a molecular mass for the nanoparticles based on their size
and behavior; establishing that for a range of sizes between 1 and 4 nm
the possible molecular formula corresponds to Au286(C12H25S)95, be-
tween 1 and 3 nm to Au247(C12H25S)86, and between 1 and 2 nm to
Au127(C12H25S)56. Using the previous molecular formulas and the molar
mass of products and reagents, it was determined the atom economy for
each range of nanoparticle sizes: 65.15% for 1 to 4 nm, 65.47% for 1 to 3
nm, and 66.43% for 1 at 2 nm (Reid and Reed, 2016). The importance of
evaluating the nanomaterial's polydispersity in the determination of
atom economy has been evidenced. Besides, it is clear that polydisper-
sity is a characteristic of great importance because, as it was mentioned
in previous sections, nanostructure's properties are dependent on their
dimensions. Additionally, it is important to remember that the results
obtained are influenced by the uncertainty in the histogram generated
by TEM, which may not be representative of system under study
(Sánchez et al., 2018). In turn, it must be considered that the data are in-
fluenced by the approximations made in the Liu's method, as well as by
the uncertainty of the second-order correlation used to define the pro-
portion of dodecanethiol molecules in the nanomaterial, for the size of
the sample, the sampling used for the collection of the samples, and
for the reproducibility of experimental conditions and their effect on
the product.
On the other hand, the previous approach was used for Reid and
Reed (2016) to compare different syntheses of gold nanoparticles
with thiolated capping agents and an average size of 2 nm (Reid and
Reed, 2016). The compared methods were: (i) the synthesis based on
HAuCl4 and 2-phenylethanethiol for the obtaining of nanoparticles
with the formula Au144 (C6H5CH2CH2S)60 and 1.6 nm in diameter; (ii)
the synthesis based on HAuCl4 and hexanethiol for the obtaining of
nanoparticles of formula Au75(CH3(CH2)5S)40 with 1.4 nm in diameter;
and (iii) the previous synthesis for the obtaining of nanoparticles of for-
mula Au127(C12H25S)56 with 1 to 2 nm in diameter. They were able to
establish that the first method has an atom economy of 63.96%, whereas
the second and third methods have values of 61.08%, and 66.43%, re-
spectively. In consequence, from the perspective of atom economy,
the third method was proposed to be the most efficient (Reid and
Reed, 2016).
As it has been established, the concept of atom economy is limited,
and not includes aspects as the functionality of the material. Freund
et al. (2018) extended the principles of atom economy concept to multi-
functional nanomaterials and generated a metric called Multifunctional
A. García-Quintero and M. Palencia
Efficiency (MFE). This metric is focused on the design of nanomaterials
with the highest incorporation of functional units and the minimum of in-
active components (Freund et al., 2018). For this, authors defined a func-
tional unit (FU) as a characteristic building block of the nanomaterial
providing the specific functionality; being the functionality ratio (FR),
the quotient between the number of functional units and the total num-
ber of building blocks of the nanomaterial; in addition, they included
the process efficiency (PE) which is defined as the quotient between the
number of functional units and the number of steps to obtain the incorpo-
ration of the functionality in the nanostructure (Freund et al., 2018).
Based on these parameters, the MFE was defined as the product between
the FR and PE, generating a metric consistent with AE and applicable to
aspects of nanomaterial functionality (Freund et al., 2018). MFE has
been used to establish the multifunctional efficiency during nanocarrier's
synthesis for the drug delivery. In this way, for example, researchers have
been able to establish that material with high multifunctionality for drug
delivery applications is one that can be synthesized in one process provid-
ing 3 FU and 3 MFE, this is the case of the nanospheres based on Fe3O4 in a
monodisperse zeolitic imid-azolate framework-8 core-shell for drug en-
capsulation (Zhuang et al., 2014; Freund et al., 2018).
Concerning the so-called “green” syntheses, in the context of
biobased synthesis carried out without prior purification of a specific
biomolecule, it is difficult to establish the molecule's identity interacting
closely with the nanomaterial to achieve stabilization. Therefore, it is a
challenging to obtain a stoichiometric factor between the reactants dur-
ing of synthesis of nanomaterials, which is why applying the atom econ-
omy metric is a task involving great difficulty, consequently, this metric
is an important concept from theoretical approach but, in practice, it is
an unfeasible characterization parameter.
3.2. E-factor
The Ecological-Factor, commonly known as E-factor, is a metric pro-
posed in 1992 by Roger Sheldon, which allows to quantify the first prin-
ciple of green chemistry. But also, it is associated with principle two of
atom economy since the E-factor is based on the relationship between
the mass of waste generated in the synthetic process respect to the
product mass. This quotient is described by Eq. (2) and allows to estab-
lish a partial and global perspective about the production of waste
in one-step and multi-step synthetic processes. Unlike atom economy,
E-Factor considers the real performance of the reaction and the inclu-
sion of solvents, being even possible to incorporate an energy aspect
into the analysis by considering the generation of CO2 as waste from
fossil fuels used as source of energy (Dicks and Hent, 2015; Sheldon,
2017a, 2017b; Constable, 2018).
Mass of waste ðkg Þ
E−Factor ¼ ð2Þ
Mass of product ðkgÞ
In the field of nanomaterials, unlike Atom Economy, the E-factor can
be easily used because it does not require establishing a molecular for-
mula. For this reason, E-factor has been used in the field of nanomaterials
to establish a correlation between the amount of waste generated respect
to different classes of materials (Eckelman et al., 2008; Goulas and van
Ommen, 2014). By instance, it has been able to establish ranges of values
between different productive sectors during 2007–2008, such as, oil refin-
ing industry (E-Factor = 0.1), bulk chemicals (E-Factor = 1.0 and 5.0),
fine chemicals (E-Factor = 25.0 to 100.0), and in nanosynthesis (E-Factor
= 100.0 and 100,000.0) (Goulas and van Ommen, 2014). In consequence,
although nanomaterials represent the principle of dematerialization,
i.e., the reduction of the amount of raw materials and energy for the mak-
ing or achievement of any product or service, their processes of obtaining
involves a significant amount of waste (Reid and Reed, 2016). Neverthe-
less, over the years, nanosynthesis processes have been optimized and, at
present, some syntheses of nanomaterials are characterized by E-Factor
values lower than 20. Such is the case of the catalyst made by a gas-
12
Science of the Total Environment 793 (2021) 148524
phase coating using fluidized titanium dioxide nanoparticles under atmo-
spheric pressure conditions, by atomic layer deposition, and obtaining an
E-factor of the process between 6 and 7 (Goulas and van Ommen, 2014).
In addition, an E-factor = 15 was obtained for the nanosynthesis reaction
of a fibrous nanosilica obtained by the hydrolysis-polycondensation
method; this low value of E-factor is directly associated with the material
recovery of a large part of the reagents used in the process, such as 70% of
the xylene used as the solvent, 88% of the CTAB surfactant, and 92% of the
ethanol used in washing and extraction protocol (Maity and Polshettiwar,
2018). From another perspective, the E-factor has been used to compare
different nanomaterial synthesis processes, including those carried out
through biobased approaches. By instance, Eckelman et al. (2008) deter-
mined the E-factor of various syntheses of purified nanomaterials (see
Table 3). It is possible to observe from values in Table 3 that the nanotech-
nological method, based on starch-glucose synthesis, presents one of the
highest E-factor values (29600). That is, for each kilogram of gold nano-
particles obtained by this method, 29,600 kg of waste are generated,
which it would make this synthesis a process that is not in concordance
with principles 1 and 2 of green chemistry, therefore, under this perspec-
tive, to denominate this process a “green” nanosynthesis because it based
on biomolecules results clearly inappropriate.
In contrast, according to Table 3, the synthesis of gold nanoparticles
carried out using the bioreactor presents the lowest value of E-factor;
from this perspective, biogenic synthesis method is more sustainable
than the other methodologies to obtain gold analog materials in term of
residues production, however, result should be carefully analyzed and
generalization should be avoided, because E-Factor must be calculated
for each methodology and interpreted according its context with an ob-
jectively delimited scope. The above reinforces the fact that bio-based
nanotechnology is not per se a “green process” following the principles
proposed by Anastas and Warner in 1998. In contrast, it is interesting to
note that the second-lowest value of E-factor corresponds to a method
such as chemical vapor deposition, which has been considered not very
eco-friendly due to its energy intensity, which usually implies the gener-
ation of secondary pollutants (i.e., greenhouse gases and unsafe wastes),
therefore, a limitation of E-factor is evidenced, i.e., this metric no including
the dangerous of wastes being independent of the nature of them. It is
well-known that a small amount of wastes should not be understood as
low dangerous since some wastes are highly toxic and eco-toxic at low
concentrations. In conclusion, the E-factor does not consider the ecologi-
cal impact of the generated waste, and the determination of similar values
of E-factor in a synthesis does not allow to establish which is the most en-
vironmentally friendly process because it ignores the nature of the waste
(Anastas, 2008; Mulvihill et al., 2011; Dicks and Hent, 2015). In order to
eliminate this limitation, an environmental impact factor (EQ-Factor)
has been introduced, this is the result of the multiplication of E-factor
and Q-factor, which is a value assigned to the environmentally hazardous
of the waste, analogously to environmental dangerous of chemical
substances manufactured and released to environment (e.g., pesticides).
Informatics tools as EATOS, or Environmental Assessment Tool for
Organic Syntheses, has been developed from this approximation
(Van Aken et al., 2006; Tufvesson et al., 2012; Sheldon, 2017a, 2017b).
The Q-factor has been widely used to determine the impact of pesti-
cides, and it considers three components including each one two types
of effects associated with different toxicity grades (see Table 4). Values
of Q-Factor for some usual pesticides have been published (Kovach
et al., 1992; Kniss and Coburn, 2015), also, values are available in web
page of Cornell Turfgrass Program (Cornell CALS, 2021). However,
two limitations emerge from the use of this factor in conjunction
with E-Factor: (i) Information required to calculate Q-Factor for
nanomaterials is lack, and (ii) its definition to be used in conjunction
with E-Factor implies the loss of information as a result of multiplication
of two independent amounts (i.e., Q-Factor becomes an amplification
factor of E-Factor or vice versa, since they are not interdependent a
low value resulting of product of factors not permits distinguish
between individual contributions of each parameter).
A. García-Quintero and M. Palencia
Table 3
E-factor for several syntheses of nanomaterials (Eckelman et al., 2008; Pini et al., 2014; Maity and Polshettiwar, 2018; Patwardhan et al., 2018).
Type Nanomaterial
Metal NP Gold NP
Metal oxide TiO2 nanoparticles
Nanosilica fibers
Mesoporous silica
Carbon-based NPs Carbon nanotubes
Fullerenes
NP: nanoparticle; Ch-Red: chemical reduction.
For nanomaterials, the determination of Q-Factor is complex and its
magnitude contains information related directly with the nature of sub-
stances, whereas E-factor is determined from the knowledge of the syn-
thesis product and its corresponding wastes (in terms of mass). For a
process described by a + b ➔ x + y + z, where a and b denote raw ma-
terials, x is the target product whereas y and z denote wastes and
byproducts in any order. Note that E-factor is given by a single value
with a specific interpretation. However, Q-Factor can be partitioned
in individual contributions of target product and each waste or
byproduct (q x , q y , and q z , respectively). Thus, Q-Factor = q x + q y
+ q z , and since minimum value of q i is zero (i = x, y, and z), and
the contribution of each term is additive, Q-Factor increases with
the number of wastes, but also, it increases with the specific magni-
tude associated with the nature of target product and wastes pro-
duced (i.e., Q-factor is zero only when target product is 100%
ecofriendly in the specific context, for example, in any process usu-
ally occurring in the nature without a negative impact on ecosys-
tem). For nanomaterials Q-Factor can be standardized considering
a specific system including Q-Factor for organic substances and as-
pects directly related with the nanometric nature (see Table 5).
However, we proposed the use of one more specific and complex
descriptor formed by two or three dimensions instead of EQ-Factor:
ε ¼ ðQ − FactorÞ þ ðE − FactorÞe
where ε is the resulting of two individual contributions, being Q-Factor
a dimensionless parameter whereas E-Factor has units of mass of resi-
dues per mass of product in kilograms (denoted as e for simplicity).
Note that, environmental impact is described as a vector whose compo-
nents are E-Factor and Q-Factor, or what is the same, ε is a linear com-
bination of two independent terms. In a second paper we will studied
Table 4
Individual factors considered in the Q-Factor of pesticides (adapted from diagram described by Kovach et al. (1992).
Components Effects
Farm worker component Application effects
Picker effects
Consumer component Consumer effects
Groundwater effects
Ecological component Aquatic effects
Terrestrial effects
Science of the Total Environment 793 (2021) 148524
Synthesis strategy E-factor
Ch-Red and stabilizing with thiols and ionic liquids 99,400
Reduction with the starch and glucose biomolecules 29,600
Ch-Red and stabilization with phosphines 19,200
Chemical reduction and stabilization with thiols 3320
Use of Medicago sativa as a biological reactor 163
Synthesis by hydrolysis-calcination 7200
Hydrolysis-polycondensation method 15
Making using triblock copolymers 3400
Making using ionic and neutral-surfactant template 250
Making using liquid-crystal templates 90
Synthesis by chemical vapor deposition 170
By benzene‑oxygen flame 17,800
Titanium isopropoxide and water 7.2
and analyzed the scope and applicability of this proposal, but it is clear
that the knowledge of one component is only a partial description of en-
vironmental impact, and a descriptor based on two or three terms (since
an energetic component could be included) is easily interpreted and
computed.
On the other hand, the E-factor can be established by two different
approximations, the first one is a simplified approach, in which the
use of solvents or water is not considered as a residue, this factor is
known as sEF; while the second perspective considers these parameters
in the analysis and is known as the complete E-Factor (cEF) (Albini and
Protti, 2016; Sheldon, 2017a, 2017b). Clearly the sEF is lower than cEF
and hides the real impact of synthesis process, since several stages are
strongly associated with the use of solvents including pre-treatment,
dissolution of reagents, and purification. However, auxiliary operations
such as cleaning or transport stages should not be included because they
are not directly associated with the synthesis process, but rather with
the operating conditions of the workplace and process design at the
production plant level, which is useful for the characterization of a spe-
cific industry within environmental improvement programs, but not
the transformation associated with the synthesis itself. E-Factor has
been used to establish a comparison between the synthesis of gold
nanoparticles stabilized with sulfur agents through the methods based
on 2-phenylethanethiol (A), hexanethiol (B), and dodecanethiol (C), es-
ð3Þ tablishing that in the case of synthesis A, sEF = 14 and cEF = 3327; for
B, sEF = 607 and cEF = 3447, and for synthesis C, sEF = 94 and cEF =
2060 (Reid and Reed, 2016). The above evidence the E-factor discrepan-
cies resulting to include or not include aspects such as the use of sol-
vents in the nanomaterial synthesis analysis. In addition, it is possible
to establish that under the sEF analysis, the synthesis with the lowest
residue production is the method A, whereas from cEF the most appro-
priate synthesis is that described by method C. Therefore, it is strongly
Evaluated aspects
• Chronic toxicity (reproductive, teratogenic, mutagenic, oncogenic).
• Acute toxicity (dermal toxicity)
• Chronic toxicity (reproductive, teratogenic, mutagenic, oncogenic).
• Acute toxicity (dermal toxicity).
• Plant surface half-life.
• Chronic toxicity (reproductive, teratogenic, mutagenic, oncogenic).
• Sistemicity.
• Soil half-life and plant half-life.
• Leaching potential (Water half-life, solubility, adsorption coefficient, soil properties).
• Surface loss potential (water half-life, solubility, adsorption coefficient, soil properties).
• Fish toxicity.
• Bird effects (bird toxicity, soil half-life, plant-surface half-life).
• Bee effects (bee toxicity, plant-surface half-life).
• Arthropod effects (arthropod toxicity, plant surface, half-life).
13
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

Table 5
Tentative parameters proposed by authors for the determination of Q-Factor of nanomaterials.

Effects and aspects to evaluate Type of Associated to Chemical entity

nanomaterial

For all cases should be evaluated: Application effects, user effects, Inorganic nanoparticles Nanomaterial Metal core.
consumer effects, groundwater effects, effects on terrestrial and aquatic ecosystems. Metal oxide core.
No-metal core.
Stabilizing agent.
Process Byproducts, additives, solvent.
Wastes Liquid, solid, or gaseous wastes.
Organic nanoparticles Nanomaterial Organic component.
Process Byproducts, additives, solvent.
Wastes Liquid, solid, or gaseous wastes.
Nanocomposites Nanomaterial Inorganic component.
Organic component.
Interface additives.
Process Byproducts, additives, solvent.
Wastes Liquid, solid, or gaseous wastes.

recommended the use of cEF or the adequate description of approxima-
tion used in order to avoid errors.
3.3. Metrics-based on mass
In the context of green chemistry, mass-based metrics are primarily
related to the evaluation of the principles establishing that chemical re-
actions must be designed to reduce the amount of waste from the pro-
cess (principle 1), including the higher quantities of atoms of the
reactants into the target product (principle 2), avoiding the use of aux-
iliaries, solvents, and derivatization stages (principles 5 and 8); and as
much as possible the use catalysts favoring material conversion in the
processes (principle 9) (Sheldon, 2017a, 2017b). This type of sustain-
ability metrics is commonly used in the analysis of industrial and
laboratory-scale processes since they are simple parameters to calculate
and interpret in term of the efficiency of the material conversion for a
specific procedure. Currently several mass metrics have been proposed,
being the most recognized: Reaction Mass Efficiency (RME), Process
Mass Intensity (PMI) and Effective Mass Yield (EMY) (Dicks and Hent,
2015).
RME is a mass-based metric defined by the mass quotient between
products and reactants (see Eq. (4)), where the reactants are all chem-
ical species contributing to balanced chemical reaction (Sheldon, 2017a,
2017b; Andraos and Hent, 2018).
Mass of products ðkgÞ
RME ¼
Mass of reagents ðkgÞ
RME also can be described by Eq. (5) and allows the incorporating of
EMY and the value of the Atom Economy, yield, and the Stoichiometric
Factor (SF) which is used to analyze the use of an excess of reagents in a
real process during chemical synthesis (Dicks and Hent, 2015).
EMY x AE
RME ¼
SF
material efficiency according to the size distribution of the synthesized
nanostructure (Reid and Reed, 2016).
In contrast, PMI is a mass-based metric allowing to include the mass
of all the substances used in the synthetic and during the purification
stage, and the real yield of the chemical reaction, see Eq. (7) (Dicks
and Hent, 2015; Constable, 2018). As can be established from Eq. (8),
PMI includes the E-factor in its definition, which allows, through a sim-
ple equation, to establish aspects related with material efficiency, use of
resources, and generation of waste (Dicks and Hent, 2015; Sheldon,
2017a, 2017b).
Mass of chemicals used in the process ðkgÞ
PMI ¼ ð7Þ
Mass of product ðkgÞ
or being the same,
Mass of waste ðkg Þ þ mass of product ðkg Þ
PMI ¼ ¼ E − factor þ 1 ð8Þ
Mass of product ðkgÞ
PMI has been used in nanomaterials to evaluate the material effi-
ciency in the synthesis of gold nanoparticles using thiolated compounds
as stabilizing agents. Being able to establish a value of PMI = 3328 when
it is assumed that all the synthesized nanoparticles correspond to the
objective product (Reid and Reed, 2016). However, when size criteria
are used, the PMI is affected by the polydispersity increasing its value,
ð4Þ
in consequence, system's polydispersity and the functionality are im-
portant criteria which should be considered (Reid and Reed, 2016).
On the other hand, the EMY is a metric relating the mass of products
and non-benign reactants in its analysis, mathematically it is defined by
Eq. (9) (Hudlicky et al., 1999).
Mass of products x 100
EMY ¼ ð9Þ
ð5Þ Mass of non − benign reagents

where
∑mass of excess reagents
SF ¼ 1 þ
∑mass of stoichiometric reagents
In turn, Eq. (5) allows the incorporation of substances used as sol-
vents, catalysts, purification reagents, and extraction by multiplying of
RME value by the Material Recovery Parameter (MRP), which also con-
siders whether these auxiliaries are recovered from the reaction system
(Andraos, 2008; Dicks and Hent, 2015; Andraos and Hent, 2018). Al-
though the use of these metrics is not generalized, it should be noted
that they can be easily applied to the synthesis of nanomaterials, in ad-
dition, they have the advantage that can be adapted to establish the
The importance of this metric in green chemistry lies in the fact that
it includes considerations about hazard of the reagents used, allowing
an approach to green chemistry principles in term of a greater safety
ð6Þ
of synthetic processes (principles 4 and 12). Nevertheless, in this metric
there is no minimum factor or criteria to designate a reactant as non-
benign, being a subjective assignment performed by the researcher,
thus, depending on the perspective and context, the results of EMY
can be different for identical processes, based on considerations of re-
agent hazard and the probability of exposure or release to the environ-
ment (Anastas, 2008; Constable, 2018). In consequence, its use is not
recommended for comparison of processes without a prior determina-
tion of the objective criteria for the classification of reagents as non-
benign. In addition, its use in the field of nanomaterials is not common.

14
A. García-Quintero and M. Palencia
3.4. Metrics based on energy
Energy efficiency is a fundamental aspect in the framework of envi-
ronmental sustainability, as it is evidenced from the sixth principle of
green chemistry (Mulvihill et al., 2011). In this sense, to establish the
energy demand of a synthetic method is an interesting goal because,
under this perspective, a process using safer reagents could present a
high-energy demand and to be associated to some type of secondary
pollution. This approach to energy efficiency has promoted the use of al-
ternative of no-conventional heating such as those based on the use of
microwave energy and ultrasound. Consequently, several types of met-
rics have been used to define the energy consumption of a process, in-
cluding Energy Efficiency (EE), Specific Productivity (SP), and Energy
Intensity (EI) (Mulvihill et al., 2011; Albini and Protti, 2016).
Energy Efficiency is a metric which can be easily calculated and es-
tablishes a relationship between the mass of the target product and
the energy consumption for its production (Eq. (10)) (Albini and
Protti, 2016),
Mass of product ðkg Þ
EE ¼ ð10Þ
Energy consumption ðkJÞ
Similarly, SP defines a correlation between the number of moles of
the product and the electrical work necessary to obtain it (Eq. (11))
(Albini and Protti, 2016),
Mol of product ðmolÞ
SP ¼ ð11Þ
Electric work ðkWhÞ
while the EI relates the total energy of the process concerning the mass
of the target product (Eq. (12)) (Albini and Protti, 2016).
Total process energy ðMJ Þ
EI ¼ ð12Þ
Mass of the final product ðkgÞ
The EI has been used to determine the energy usage during the
nanomaterial's obtaining, including their synthesis and purification pro-
cess. For example, it has been possible to characterize the synthesis of
CdSe quantum dots obtained using a roll-to-roll deposition by an EI of
70,000 MJ/kg (Kim and Fthenakis, 2012), but also, to compare different
methods of synthesis of nanomaterials, by instance, the obtaining of
TiO2 nanoparticles employing a hydrochloride-based process showed
an EI of 116 MJ/kg whereas TiO2 nanoparticles obtained by sulfates
showed a EI = 32 MJ/kg and, those obtained by chlorides showed EI
= 19 MJ/kg. On the other hand, also it has been possible to compare
carbon-based nanomaterials synthesis, which is recognized as a high-
energy intensity methodology, and establishing that for single-walled
nanotubes obtained by laser ablation, by the arc method, by fluidized
bed reactors-chemical vapor deposition, and by high-pressure carbon
monoxide their values of EI are 32,000, 7600, 2400, and 1900, respec-
tively (Kim and Fthenakis, 2012). However, EI evaluates only a small
part of green chemistry omitting aspects related with material conver-
sion and potential environmental risk.
Regarding the evaluation of the energy demand of biobased synthe-
sis methods, the synthesis of Au nanoparticles obtained from plant bio-
mass has been analyzed, taking into consideration aspects as the energy
consumed for the obtaining the gold salt, the generation of deionized
water, the stirring, and heating. For example, under laboratory condi-
tions, analysis of the energy demand of traditional bottom-up methods
based on citrate, hydrazine, and sodium borohydride have been per-
formed, concluding that these are not statistically different when
grape pomace is used as a reducing and stabilizing agent (see Fig. 5)
(Pati et al., 2014).
On the other hand, a comparative analysis of the cumulative energy
demand for synthesis processes based on plant biomass and biomole-
cules, such as coriander, mushroom, ginseng, vitamin B, D-glucose,
among others, permitted establishing that the energy demand of these
15
Science of the Total Environment 793 (2021) 148524
Fig. 5. Cumulative energy demands for gold nanoparticles synthesis methods (adapted
from Pati et al., 2014). The blue bars present an assumption of a 100% yield, the red bars
to a yield of 80% for grape pomace and 94% for cypress leaf extract. The error bars
represent 95% confidence interval. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)
procedures does not result in an energy statistically significant different.
However, the environmental impact of the cumulative energy demand
of coriander-based synthesis, assuming a yield of up to 100%, was iden-
tified to be statistically higher than the use of traditional chemical re-
agents such as borohydride, citrate, and hydrazine (see Fig. 5 (Pati
et al., 2014). Therefore, in energy terms, the use of cypress leaf extract
and coriander to obtain gold nanostructures does not justify the trend
existing to call a “green” process only for the usage of reagents obtained
from renewable sources.
3.5. Life Cycle Analysis
Life Cycle Analysis (LCA) seeks to identify the parameters to optimize
the generation of processes with a minimum amount of waste, material
efficiency, and low impact on public and environmental health (Meyer
and Upadhyayula, 2014; Jiménez-González, 2018; Jindal and Jain, 2018).
This metric emerges as a quantitative parameter of ecological impacts
that holistically covers the processes, from a systematic and iterative ap-
proach that fundamentally consists of four axes described below:
(i) Goal and scope: This first step consist of defining of target sub-
stance or product in a functional area (functional unit) and the
analysis framework around the LCA scope. It implies to define
LCA type suitable to be applied in the process under study. In
other words, LCA should be defined as: cradle-to-grave (obtain-
ment raw materials until final disposal), cradle-to-gate (obtaining
the raw materials and manufacturing), gate-to-gate (manufactur-
ing), gate-to-grave (manufacturing and final disposal), or cradle-
to-cradle (for circular production processes) (see Fig. 6) (Olsen
and Jørgensen, 2005; Tufvesson et al., 2012; Dicks and Hent,
2015; Sheldon, 2017a, 2017b; Livingston et al., 2020).
(ii) Life Cycle Inventory (LCI): This axis is focused on collecting, validat-
ing, and quantifying of necessary information in terms of energy
and materials from the phases established in the first stage. This
implies the knowing of relevant aspects associated with the goal
and scope involved in the process under study, ranging from pre-
cursors, synthesis process, waste generation, considerations of
the product and its use, its potential destination, and the environ-
mental emissions associated with each stage. There are different
databases that allow the acquisition and comparison of these
data, such as EcoInvent, SimaPro, Umberto, and GABI (Anastas
and Lankey, 2000; Sheldon, 2017a, 2017b).
A. García-Quintero and M. Palencia
Fig. 6. Illustration of stage of Life Cycle Analysis (LCA) for any general process and its correlation with the nanomaterial synthesis (adapted from Jiménez-González, 2018 and Bartolozzi
et al., 2019).
(iii) Life Cycle Impact Assessment (LCIA): In this stage, the analysis
framework and the environmental indicators are defined, selected
from relevance into the process, and quantified, allowing the use
of equivalences and comparisons of results against reference com-
pounds in the next step. A wide variety of environmental impact
indicators have been defined, being the most relevant: Global
Warming (GW), Photochemical Smog (PS), Land Use (LU), Abiotic
Resource Depletion (ADP), Eutrophication (EU), Acidification
(AC), Photochemical Ozone Creation (POCP), Ozone Depletion
(OD), Human Toxicity (HH), Eco-toxicity (EC), Respiratory Effects
(RE), Fossil Fuel Depletion (FF), and Cumulative Energy Demand
(CED) (Anastas and Lankey, 2000; Kralisch, 2008; Sheldon,
2017a, 2017b).
(iv) Life Cycle Interpretation: In this stage, the results obtained in LCIA
are interpreted according to the goal and scope; thus, aspects as
the uncertainty in the data are considered, as well as the relevance
of the results, and the definitions in which both impacts and pro-
cess are comparable. It is relevant to note that the criterion of rel-
evance between environmental impact categories is usually an
aspect depending on contexts like geographic area, type of indus-
try, cultural and temporal conceptions (Sheldon, 2017a, 2017b).
Even though the LCA has been accepted as the complete tool for
evaluating the sustainability of a process, it is considered an improper
approach for evaluating emerging technologies that do not have robust
data for the construction of the LCIA, being this the case of nanotechnol-
ogy products (Muñoz, 2012; Bartolozzi et al., 2019), at present, the LCA
16
Science of the Total Environment 793 (2021) 148524
is accepted as the most suitable metric for the analysis of the integral
ecological impact of nanomaterials (Seager and Linkov, 2009;
Mulvihill et al., 2011; Gilbertson et al., 2015; Mortimer and Holden,
2019). In the context of nanomaterials, LCA has been widely applied in
the study of sustainability of metallic nanoparticles, nanocomposites,
and carbon-based nanomaterials (Miseljic and Olsen, 2014). From anal-
ysis of nanomaterial LCAs can be concluded that the majority of studies
use a cradle-to-grave or cradle-to-gate approach, which has demon-
strated the high energy intensity and low material conversion efficiency
of some of these technologies, and consequently, it given a view about
their environmental impacts in terms of greenhouse gases emissions,
eco-toxicity associated with the release of metals, and in the case of me-
tallic nanostructures, considerable environmental effects associated
with obtaining raw materials through unsustainable extraction
methods (Bartolozzi et al., 2019; Livingston et al., 2020).
In the framework of this review, the focus is directed towards the
metrics used in nanomaterials based on nanobiotechnology principles,
biobased strategies, or the called “green” methods. Thus, although the
LCA is a standardized tool since 1996, two years before the formulation
of the 12 principles of green chemistry, it is widely accepted that the LCA
can be used for the evaluation of any product or process; however, since
LCA is not based on the green chemistry framework, it does not consider
fundamental aspects of this approach, such as worker safety, a funda-
mental aspect of principle 12 of green chemistry (DeVierno Kreuder
et al., 2017; Jindal and Jain, 2018). Despite this, numerous authors
have accepted the LCA in the field of green chemistry as the most appro-
priate tool to analyze a procedure from an integral point of view,
A. García-Quintero and M. Palencia
establish its potential impact on planetary health, and identify key as-
pects to optimize (Muñoz, 2012).
An example of “prospective” LCA for optimization in the field of
emerging biomass-based nanotechnologies is the research carried out
by Bartolozzi et al. (2019). They used the LCA cradle-to-gate as an eco-
design tool to optimize sustainability in production, both at the
laboratory-scale and in a simulated larger production scale, of
nanoporous sponges based on recycled cellulose pulp, as an approxima-
tion to principle 7 of green chemistry, in the context of activities of envi-
ronmental nanoremediation. Nanoporous sponges were obtained in an
initial approach by means of the partial oxidation of the hydroxyl group
of carbon 6 of cellulose mediated by TEMPO/NaClO/KBr and precipitation
with HCl, solubilization in NaOH, and defibrillation to obtain cellulose
nanofibers by sonication and subsequent acidification with HCl, followed
of crosslinking with poly(ethyleneimine) and sonification, frozen, and
freeze-dried, and subsequent heat treatment for the generation of
nano-porosity, and the subsequent purification with methanol. Using
the LCA with a functional unit of 1 kg of material production, the ILCD
2011 Midpoint + method, recommended by the European Commission
in the product environmental footprint methodology, and the databases
Ecoinvent 3.1 and SimaPro 8.3 researchers achieved to identify the eco-
logical impact aspects to optimize the process. These impacts were pri-
marily associated with the use of water-refrigerant, an aspect that
makes a large contribution to water and fossil resource depletion;
methanol purification and energy consumption associated with the
freeze-drying and thermal treatment-oven process, which contribute to
the ecological impact of climate change, ozone depletion, human toxicity,
particulate matter, ionizing radiation, ozone formation, eutrophication,
land use, and acidification. Finally, this panorama allowed optimizing
the ecological aspect of the purification process, which constituted 80%
of the water resource depletion (53 m3 water eq.), 90% of CO2 eq. to
climate change (2964 kg), and 95% to acidification (16.8 molc H+ eq.).
On the other hand, ecological impact was reduced employing trans-
materialization principles based on the use of water instead of methanol
for the purification, reducing the heating temperature of the solvent
during the washing steps, which decreases energy consumption and
the use of water as a cooler. It was estimated that the impact on climate
change decreased from 38 to 4.3 kg of CO2 whereas the decreasing in
temperature was from 2759 to 2461 kg of CO2 (Bartolozzi et al., 2019).
However, it is important to indicate that, although this protocol is based
on the use of renewable and recycled raw materials, a wide variety of
dangerous substances and energy are used to obtain the nanoporous
material, so using the LCA allows to reduce the ecological impacts
generating a greener process, however, its design is not framed into the
twelve principles of green chemistry.
On the other hand, LCA in the field of green nanomaterials has been
used to compare the net sustainability of synthesis processes of nano-
structures with similar chemical composition through different meth-
odologies, including conventional physical and chemical synthesis and
those based in plants, biomolecules, and bioreactors. In this context,
Pourzahedi and Eckelman performed a cradle-to-gate LCA with a func-
tional unit of 1 kg of nanomaterial, for the synthesis of silver nanoparti-
cles, and using several tools such as SimaPro software 8.1, US EPA's Tool
for the Reduction and Assessment of Chemical and Other Environmen-
tal Impacts (TRACI) and US-Ecoinvent 3.1 database. The synthesis
methods by chemical reduction included the use of sodium citrate
(CR-TSC), sodium borohydride (CR-SB), ethylene glycol (CR-EG), and
starch (CR-Starch), whereas physical methods were flame spray pyrol-
ysis (FSP), arc plasma (AP), and reactive magnetron sputtering in
Ar\\N2 (RMS-AR-N). Results showed that the flame spray pyrolysis
method is a synthesis method with the most significant environmental
impact in all categories, except fossil fuel depletion, where the ethylene
glycol-based method is the most harmful. In addition, Results allow
determining that the synthesis based on starch presents a lower ecolog-
ical impact compared to the flame spray pyrolysis method in all aspects
and contributions of less than 50% in terms of global warming,
17
Science of the Total Environment 793 (2021) 148524
photochemical smog, acidification, eutrophication, and human health
impact (See Fig. 7) (Pourzahedi and Eckelman, 2015). However, it is rel-
evant to note that the biomass-based method presents higher values for
all categories regarding the arc plasma method, which is expected to
have a more significant environmental impact due to its energy inten-
sity. In this way, it was possible to establish that the parameters that
allow defining a synthesis as eco-friendlier are relative and depend on
the strategies used to carried out their comparison (Pourzahedi and
Eckelman, 2015).
An analogous situation was observed by Wu et al. (2019). They
identified a dependence of eco-friendly grade in function of the compar-
ison criteria in the cradle-to-gate LCA. In this case, they used SimaPro
software 8.5, Ecoinvent, USLCI (US Life Cycle Inventory Database), and
TRACI 2.1 to compare different routes for the obtaining of TiO2 nanopar-
ticles (Wu et al., 2019). Synthesis methods: were sol-gel, hydrothermal,
microemulsion, solvothermal, flame spray pyrolysis, radio frequent ther-
mal plasma (RF-Thermal), and Lactobacillus sp. as a bioreactor. Re-
searchers established that the biological method is more sustainable
compared with RF-Thermal since it has a lower ecological impact, except
for the noncarcinogenic effects on health, global warming, eutrophica-
tion, and acidification aspect (see Fig. 8). However, when they compared
the ecological impacts of the synthesis carried out by the bioreactor with
the sol-gel, hydrothermal, solvothermal and microemulsion methods,
these presented a lower ecological impact in all categories (Wu et al.,
2019). In the previously mentioned investigations, nanobiotechnological
processes have presented an ecological impact superior to some of the
conventional nano-synthesis techniques which could be called “non-
green” synthesis. However, it is important don't forget that these results
are based on aspects related to the nanomaterial composition, the origin
of the reagents, reaction conditions, and reference framework, conse-
quently, depending on each procedure, their specifications, and their ref-
erence process, a nanobiotechnological synthesis can or cannot be a more
sustainable process.
Compared with the previous examples, the research carried out by
Marimón-Bolívar and González on synthesis based on biomolecules
showed a more sustainable approach in all the ecological impacts eval-
uated (Marimón-Bolívar and González, 2018). This analysis was carried
out through a cradle-to-gate LCA, using the GABI software, and the
Ecoinvent database. Methodologies compared were: (i) the synthesis
of magnetite using glutathione as a reducing agent and, (ii) a conven-
tional co-precipitation approach. Results allowed to establish that the
biological method presented one or more orders of magnitude lower
than the conventional methodology in terms of its impact on climate
change, global warming, fossil and water depletion (Marimón-Bolívar
and González, 2018). Thus, the biobased alternative emerged as the
most sustainable method in this reference framework, which justifies
by quantitative aspects that the authors denominate this method as a
green synthesis.
On the other hand, it is widely accepted that LCA allows contrasting
the ecological impacts of a process, evaluating the aspects to be opti-
mized, and comparing different methodologies to obtain analogous
compounds. However, it should be taken in consideration that the LCA
is a quantitative tool subject to qualitative aspects regarding the defini-
tion of the goal and scope, therefore, LCA is not a universal descriptor of
environmental impact or sustainability; besides, LCA presents a notable
disadvantage in the evaluation of emerging technologies in terms of
limited access to data and differences between them depending on
the source of information consulted, and therefore, assumptions or
using averages of a general material for a particular process are usually
required (Tufvesson et al., 2012; Romero-Franco et al., 2017; Anastas
et al., 2018). Thus, the fact that the fate-exposure-effect models are
established from the quantities released into the environment, the
need to introduce assumptions, the strong limitation of the information
available for making comparisons, together with the unavailability of
standardized systems for the recording of initial information, and the
tendency in the field of nanotechnology to focus on potential
A. García-Quintero and M. Palencia Science of the Total Environment 793 (2021) 148524

Fig. 7. Ecological impact of seven different Ag nanoparticles synthesis. OD refers to ozone depletion, GW to global warming potential, AC to acidification, EU to eutrophication, HH to human
carcinogenic health, HHNC to human non carcinogenic health, EC to eco-toxicity, FD to fossil fuel depletion (adapted from Pourzahedi and Eckelman, 2015).

applications in a race to develop new technologies, slow down the ad- green chemistry (Olsen and Jørgensen, 2005; Dhingra et al., 2010;
vance of metrics for the description of the environmental impact of dif- Tufvesson et al., 2012; Gilbertson et al., 2015; Poynton and Robinson,
ferent methods of nanomaterial production, in particular, the 2018; Rajasekhar and Kanchi, 2018; Bartolozzi et al., 2019; Ciambelli
adaptation of the LCA and its harmonization with the principles of et al., 2019; Mortimer and Holden, 2019). However, LCA has been

Fig. 8. (A) Relative environmental impacts of the TiO2 nanoparticles synthesis based on 1 kg functional unit (adapted from Wu et al., 2019) and (B) Fe3O4 nanoparticles synthesis obtained
by glutathione and co-precipitation method's (adapted from Marimón-Bolívar and González, 2018). Ozone depletion (OD), global warming potential (GW), acidification (AC),
eutrophication (EU), human carcinogenic health (HH), human non carcinogenic health (HHNC), eco-toxicity (EC), fossil fuel depletion (FD), flame spray pyrolysis (FSP), climate
change (CC), global warming potential (GW), terrestrial acidification (TA), marine eutrophication (ME), photochemical oxidant formation (PO), particulate matter formation (PM),
water depletion (WD), and terrestrial eutrophication (TE).

18
A. García-Quintero and M. Palencia
directed to continue advancing and being implemented within the sci-
entific and productive culture, in such a way that LCA tools focused on
the analysis of nanomaterials have been developed. By instance, the
simulation tools RedNano and LearNano. The first one uses the
MendNano modeling platform of nanomaterial's environmental con-
centration based on climatic conditions and size distribution, whereas
the second one is focused on the estimating of the release of
nanomaterials across the life cycle. Other example is Nano LCRA consid-
ering the LCA of the nanomaterial, the potential risks of its cradle-to-
gave process, the possible release of the nanomaterial in these stages,
and analyzes the ecotoxic risks of exposure (Dhingra et al., 2010; Liu
et al., 2015; Walker et al., 2015; Gallagher et al., 2017; Ciambelli et al.,
2019). In addition, results evident that problems to face are much,
even in the cases of greater eco-friendly projection, for example, in
nanobiotechnology and biobased synthesis, the performing of LCA of
raw materials obtained from plants is intricate because the agricultural
industry is dependent on geography and time, decentralized and related
to production techniques; but also, since the ecological impact must be
considered not only in terms of the land usage but rather in the applica-
tion of pesticides, usage of water, and greenhouse gas emissions of NO2,
result is evident that quantitatively establishing the net impact on the
ecosystem is intricate for processes using plant material in the synthesis
of nanomaterials (Tufvesson et al., 2012; DeVierno Kreuder et al., 2017;
Seager et al., 2017).
4. Remarks and conclusions
The historical description of green chemistry is presented as an illus-
trative tool to show the growing importance of eco-friendly and sus-
tainable approaches that today accompany the different advances in
science and technology, but also, it is an illustration of the evolution of
chemistry “green” and its progressive introduction into new fields of
scientific and technological interest. From the perspective of green
chemistry, “green” nanomaterials are those structures that have been
developed to reduce their environmental and public health risk from
their design, synthesis, application, and final disposal, though from a
practical and scientific point of view, “green” nanomaterials are those
that are obtained by synthesis that present a lower ecological impact.
However, it is evidenced that according as these concepts are qualita-
tive, they are subject to temporal, geographical, commercial, and per-
ceptual conceptions, and therefore, the label “green” is not usually an
adequate synonym for sustainability, and even, “green” is frequently
used as an analog of nanobiotechnological or bio-based synthesis. The
above makes it necessary to apply metrics or minimum criteria to des-
ignate a process as green, which includes conventional sustainability
metrics based on molecular, mass, or energy efficiency that lack the gen-
eral framework of green chemistry and does not consider essential fac-
tors for a nanomaterial such as its morphology, size distribution, and
properties. However, these metric's application provides an overview
of some of the principles of green chemistry, allowing, through simple
calculations, to establish the aspects of the process requiring to be opti-
mized to achieve a greater sustainability. In this context, LCA has been
proposed as the most appropriate tool to carry out a general approach
to the sustainability of a nano-synthesis, considering different environ-
mental impacts and quantifying them based on the context of the pro-
cess, allowing, in particular, to establish that nanobiotechnological or
bio-based synthesis is not eco-friendly per se when they are compared
with conventional syntheses. However, it is not appropriate to define
if a synthetic methodology is green without prior analysis of its ecolog-
ical impacts.
It is concluded that, given that the sustainability metrics are based
on a simple calculation, they allow a quick addressing and easy interpre-
tation of the methodologies for the obtaining of nanomaterial, however,
they are only valid for controlled conditions at the laboratory level or
pilot studies. In this direction, these metrics are very valuable tools for
the design stages in the early levels of the development of a technology
19
Science of the Total Environment 793 (2021) 148524
(i.e., if the Technology Readiness Level, or TRL, developed by NASA dur-
ing the 1970s, is taken as a reference framework, then these metrics are
tools for TRL ranged among 1 and 5). On the other hand, when technol-
ogy advances to higher values of TRL, for example, evaluation in a rele-
vant environment, scaling, and commercialization, these metrics lack
practical usefulness since technical and practical situations for which
they are not suitable emerges, thus, their main limitations are directed
towards the appearing of new factors affecting the processes. In con-
trast, LCA, as a methodology for assessing environmental impacts re-
lated to all the stages of the life cycle beyond laboratory or controlled
working conditions, implies a high-relatively complexity for its imple-
mentation, and therefore, it is a meaningless strategy in the research
and design stages of nanomaterials. For its adaptation to this context, as-
sumptions, models, and specific information are required. The above
makes that inferences obtained in stages where the processes are
changing, no-standardized, and far away to the real productive environ-
ment are poor approximations with lack or null validity. However, LCA
emerges with great force in situations where its full potential can be
exploited. This is the case of evaluations in a relevant environment, en-
gineering studies aimed at scaling up, and in situations where nanotech-
nology products are already on the market, used in specific applications,
discarded, and released to environment. Therefore, for values of TRL
greater than 5, LCA acquires prominence and becomes a very useful
tool. Finally, as a summary, the metrics should be considered as comple-
mentary tools depending on the degree of development of a technology.
In particular, in the field of nanomaterials, these must be directed to-
wards the standardization of their parameters in order to allow compar-
isons and decision-making, but also, they must include key aspects that
define to nanomaterials and their processes, such as the size of particle,
their polydispersity of sizes and shapes, their nanometric properties,
among others.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
Authors thank the Universidad del Valle (Colombia) for the re-
sources received in the framework of the projects (C.I. 71210 and C.I.
71259).
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