Journal of Cleaner Production xxx (2016) 1e11

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Journal of Cleaner Production

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Comparative life cycle assessment of different synthesis routes of

magnetic nanoparticles

lez-García a, Y. Moldes-Diz a, C. Vazquez-Vazquez b, G. Feijoo a,
S. Feijoo a, S. Gonza
M.T. Moreira a, *
a
Dept. of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, 15782, Santiago de Compostela, Spain
b
Dept. of Physical Chemistry, Faculty of Chemistry, University of Santiago de Compostela, 15782, Santiago de Compostela, Spain

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

Article history: Nanotechnology is the manufacture and use of functional structures that have at least one characteristic
Received 17 October 2016 dimension measured in nanometers. Among the wide range of applications nanoparticles (NPs) may
Received in revised form present, they can be used as a catalyst or as carrier to immobilize biological catalysts, such as enzymes.
1 December 2016
The use of magnetic nanoparticles (mNPs) presents as main advantage over other alternatives the fact
Accepted 16 December 2016
Available online xxx
that they can be easily separated by the application of a magnetic field, facilitating their recovery from
the reaction medium. In parallel with the increasing interest in the production of nanomaterials, there is
a general consensus about their potential health and environmental risks associated. This paper aims to
Keywords:
Environmental impact
perform the evaluation of different synthesis routes considered for the production of mNPs from a life
LCA cycle assessment (LCA) perspective. Specifically, different approaches of mNPs synthesis were evaluated;
mNPs from simple forms such as sterically-stabilized magnetite and oleic-acid mNPs to production schemes
Nanotechnology that consider the coating of a shell on the preformed nanoparticles such as PEI-coated mNPs and silica-
Synthesis routes coated mNPs for the increased stability of the nanoparticle. When merely assessing the outcomes from
the LCA study, we observed that the manufacturing stage is dominated by the environmental impacts
associated to energy and chemical use, especially relevant for the type of silica-coated mNPs. However,
the selection of the optimal support for enzyme immobilization must comply with additional re-
quirements such high immobilization yield. According to the results, a compromise solution for the
selection of the support is obtained for PEI-coated mNPs, with satisfactory results in the indicators of
enzyme immobilization and limited environmental impact. Moreover, this work highlights two main
challenges currently encountered with the application of LCA to nanoproducts: lack of comparable re-
ports and data availability, both imply uncertainties associated with the estimation of the environmental
impacts of NPs.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction at the surface. Hence, nanoparticles have a greater surface area

Nanomaterials are defined as materials with at least one char-
acteristic dimension in the range of 1 and 100 nm. Nanomaterials
can be natural (e.g., humic and fulvic acids) (Thurman and Malcolm,
1981), incidental to human activity (e.g., diesel emissions, welding
fumes) (Peters et al., 2009), or engineered. Engineered Nano-
materials (ENMs) differ from bulk materials in two main charac-
teristics: relative surface area and quantum effects. Firstly, as
particle size decreases a greater proportion of atoms can be found
* Corresponding author.
E-mail address: maite.moreira@usc.es (M.T. Moreira).
when compared to larger particles and this feature is likely to result
in faster rates of chemical reactions as well as changes in strength
and electrical characteristics. Secondly, the benefit of nano-
materials is attributed to the quantum nature of energy states at the
nanometer scale, which can affect the optical, electrical and mag-
netic behaviour of matter (Royal Society & Royal Academy of
Engineering, 2004). On the contrary, a number of drawbacks are
inherent to the production and use of nanoparticles: the
complexity of their production scheme and their instability as they
can easily undergo transformations. Moreover, their recycling and
disposal may be complicated as there is no definite solution for the
disposal of nanomaterials.
Most ENMs can be divided into two general classes, depending

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Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
2 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11
on whether they are carbon-based (e.g., carbon nanotubes and
fullerenes) or metal-containing (e.g., Ag, TiO2, CeO2, Fe) (Heithmar
and Pergantis, 2010). Among the different ENMs, magnetic nano-
particles have received a great deal of attention because of their
potential use in various biomedical applications, including contrast
agents in magnetic resonance imaging (MRI), magnetic separation
and sorting of cells and proteins, immunoassay in pathology labo-
ratories, hyperthermia treatment for cancerous tumors, and tar-
geted delivery of pharmaceuticals and therapeutic genes (Babic
et al., 2008; Tsuzuki, 2013). The potential advantage in the use of
magnetic nanoparticles (mNPs) over other NPs relies on the fact
that they can be easily separated by the application of a magnetic
field.
Regarding the synthesis routes of mNPs, they can be produced
through a variety of processes based on physical, chemical and
biological methods with differing mechanisms, inputs, yields, re-
action conditions and nanoparticle size distributions (Willard et al.,
2004; Tartaj et al., 2006). Chemical coprecipitation is probably the
most common method to prepare magnetic nanoparticles (Laurent
et al., 2008). In this method, it is usually necessary to start from a
mixture of ferrous and ferric salts suspended in an aqueous alkaline
medium that renders into nanoparticles with a broad size distri-
bution (from 4 to 20 nm). Alternatively, other methods are
currently being developed to produce nanoparticles with more
uniform dimensions. In this regard, water-in-oil (w/o) micro-
emulsion can be considered as it consists of nano-sized water
droplets dispersed in an oil phase and stabilized by surfactant
molecules at the water/oil interface (Lo
pez-Quintela et al., 2004).
The surfactant-stabilized nano cavities (typically in the range of
10 nm) provide a confinement effect that limits particle nucleation,
growth and agglomeration.
Beyond the alternatives considered for the production of sta-
bilized magnetic nanoparticles, which can perform the electrostatic
immobilization of proteins, a shell of an appropriate material on the
original nanoparticle such as silica, polyelectrolyte and micelles,
has been applied for a more stable structure (Gupta and Gupta,
2005). The magnetic core ensures a strong magnetic response
and the polymeric shell enables the modification of the surface
with target functional groups. Surface functionalization would
allow the desired molecules such as proteins to be immobilized by
covalent binding on or conjugated to the particles, enabling tar-
geted biological applications such as site-specific markers, bio-
conjugates and sensors (Subbiah et al., 2010). Most enzymes are
covalently attached using their lysine amino groups because of
their frequent presence on the protein surface and high reactivity
(Brady and Jordaan, 2009).
In parallel with the increasing interest in the production of
nanomaterials, extensive research into potential environmental
and health implications of their production and use has been
developed, particularly given the projections for their widespread
incorporation into consumer products. The uncertainty associated
with the potential toxicological effects of nanomaterials is yet to be
assessed in order to develop specific disposal policies (Alagarasi,
2009). Keller et al. (2013) estimates the release of ENMs from
various waste management methods by assuming identical po-
tential of release for all ENMs and applications, due to the absence
of case specific data.
According to Grieger et al. (2012), there is a general consensus
amongst scientists, researchers and regulatory agencies that the
potential health and environmental risks of ENMs should be eval-
uated over their entire life cycle. Application of Life Cycle Assess-
ment (LCA) to nanotechnology would highlight both the positive
and negative impacts of nanotechnology on the environment and it
would have to include all aspects of activities during the life of a
product ‘from cradle to grave’, such as extraction of raw materials
Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
and resources, production process, use of products, and manage-
ment of the product including recycling and disposal at the end-of-
life stage. By doing so, LCA helps to identify the potential risks
associated with nanomaterials in advance to their complete
implementation. However, there are inherent difficulties in per-
forming the LCA of nanomaterials. The major obstacles include the
uncertainty arising from the immature nature of the technology
and markets, the reluctant perspective to provide extensive infor-
mation on the processes under development and the lack of risk-
associated information and characterization factors for LCA
impact assessment (Tsuzuki, 2013).
The available LCA studies of ENMs include nanomaterials such
as CdTe, carbon nanofibres (CNFs) and nanotubes (CNTs), nanoclay
(ONMT, organically modified montmorillonite), nanoscale Pt-group
metals, nanocrystaline-Si, Ag, titanium and titanium oxide
(Hischier and Walser, 2012; Gavankar et al., 2012; Upadhyayula
et al., 2012). The main outcomes from these studies report that
both energy and chemicals use during ENM synthesis contribute a
significant and often dominant share of total life cycle environ-
mental impacts (Walser et al., 2011; Eckelman et al., 2012). How-
ever, the Life Cycle Inventories (LCIs) cannot be classified as
comprehensive as they often lack ENM specific data related to the
outputs of the processes. Moreover, a considerable variability of the
(traditional) inventory items like energy input, material input, etc.
was observed (Hischier and Walser, 2012). Regarding magnetic
nanoparticles (mNPs), no available LCA reports on the different
routes of synthesis were found.
In this paper, different approaches of mNPs synthesis were
considered, from the production of sterically-stabilized magnetite
and oleic-acid stabilized magnetite to production schemes where
the coating of a shell on the preformed nanoparticles is developed
to obtain PEI-coated magnetite and silica-coated magnetic nano-
particles. However, not only is necessary to assess the environ-
mental consequences of the different production alternatives of
magnetic nanoparticles, but also to demonstrate that they can be
used as viable supports for the immobilization of proteins, in this
case, the oxidative enzyme laccase.
2. Materials and methods
2.1. Goal and scope definition
The purpose of this work is to evaluate the environmental
performance of different routes for the synthesis of magnetic
nanoparticles. The assessment is based on real data from the pro-
duction schemes of mNPs developed by the NanoMag group at the
University of Santiago de Compostela. Fig. 1 depicts the four pro-
duction schemes or scenarios included within the system bound-
aries of the environmental study. The detailed description of the
four routes is detailed in the next section. Both the amount of waste
streams produced as well as their treatment were considered
identical for the different synthesis routes (i.e. wastewater from
washing steps and re-dispersion activities). Their potential vari-
ability in terms of composition is beyond the scope of the envi-
ronmental analysis since no information about them was supplied.
2.2. Description of the production processes
2.2.1. Preparation of sterically-stabilized magnetite (Scenario 1)
In a typical synthesis, FeCl3.6H2O (9 mmol) and FeSO4.7H2O
(6 mmol, molar ratio Fe3þ/Fe2þ z 1.5) were incubated in 0.01 M HCl
solution with mechanical stirring at 60  C, following the Massart's
method (1981). Ammonium hydroxide solution was added to the
mixture, which led to the immediate formation of black magnetite
nanoparticles, which will be the basis for the different alternatives
 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11
Fig. 1. Block Flow Diagram for different routes of production of magnetic nanoparticles (mNPs).
of production. The type of magnetic nanoparticle referred as
sterically-stabilized magnetite was obtained after the addition of
tetramethylammonium hydroxide (TMAOH; 10%wt) at pH 10
(Berger et al., 1999). According to Jolivet et al. (1983), TMAOH acts
as a surfactant to nanoparticles by absorbing the cationic species at
the surface OH groups; thus, creating an electrostatic repulsion
layer surrounding the particles keeping them apart.
2.2.2. Preparation of polyethylenimine-coated magnetite
nanoparticles (Scenario 2)
Polyethylenimine (PEI) is a branched polymer with a high-
density amine group, (CH2CH2NH)n. Due to the different pKa
values of the primary, secondary and tertiary amino groups, PEI has
the ability to capture protons at different pH conditions, which is
known as the ‘proton sponge’ mechanism. PEI molecules bounded
to particles by electrostatic interaction and the negative charges on
the surface of the particles were converted into positive charges.
Due to its unique properties, PEI appears to be one of the most
appropriate molecules for the surface modification of MNPs for
biological applications. The production process of the poly-
ethylenimine (PEI)-coated magnetite started with the addition of
2 g PEI to the black magnetite nanoparticles obtained previously
after the addition of the ammonia solution. After reaction and
cooling down to room temperature, pH was changed to 4 by adding
HCl. Then, the magnetic nanoparticles were magnetically separated
and washed four times with deionized water and finally redis-
persed in water.
2.2.3. Preparation of oleic-acid magnetite nanoparticles (Scenario
3)
Oleic acid (OA) is a commonly used surfactant to stabilize the
magnetic nanoparticles synthesized by the traditional co-
precipitation method. The chemical bond formed between the car-
boxylic acid and the iron oxide nanoparticles is remarkably strong.
Moreover, OA forms a waterproofing shell around the magnetite
nanoparticles. The procedure to produce oleic-acid-coated Fe3O4
nanoparticles started from the combination of the black magnetite
nanoparticles with the addition of oleic acid. The reaction was
Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
3
allowed to continue for 1 h before being heated on a hot plate until
flocculation occurred. The nanoparticles were washed twice with
deionized water to remove residual concentration of the surfactant
molecules and finally redispersed in cyclohexane.
2.2.4. Preparation of silica-coated magnetic nanoparticles (Scenario
4)
The fourth type of nanoparticles was obtained in a further step
when Fe3O4@SiO2 core-shell nanoparticles were prepared through
a water-in-cyclohexane reverse microemulsion starting from oleic
acid NPs (Fang et al., 2011; Han et al., 2008). The reverse micro-
emulsion method considered to coat magnetic nanoparticles with
silica required neither the use of silane coupling agents as surface
primers nor a polymer stabilizer.
In a typical synthesis, polyoxyethylene(5)nonylphenyl ether
(Igepal CO-520) and cyclohexane were mechanically stirred for
15 min before the addition of oleic-acid magnetite nanoparticles
(0.5% wt in cyclohexane). Finally, ammonium hydroxide solution
and tetraethyl orthosilicate (TEOS) were added consecutively under
stirring to form a transparent red solution of reverse micro-
emulsion until complete reaction after 16 h. The core-shell nano-
particles were precipitated with isopropanol (IPA) to disrupt the
reverse microemulsion and washed four times with IPA and
deionized water. Finally, they were subjected to several cycles of
centrifugation (9000 rpm, 15 min) and washing with deionized
water until no foam was observed. Then, the core-shell nano-
particles were redispersed in deionized water to a concentration ca.
0.5e1% wt (determined by thermogravimetric analysis).
2.2.5. Characterization of the magnetic nanoparticles
For transmission electron microscopy analysis (TEM), a drop
from a diluted sample solution was deposited onto an amorphous
carbon film on 400 mesh copper grids and left to evaporate at room
temperature in an evacuated desiccator. TEM micrographs were
recorded on a transmission electron microscope (JEOL JEM1011)
operating at an accelerating voltage of 100 kV and the particle size
was measured with the software Image J.
The nanoparticles sizes in suspension were determined by
4 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11
dynamic light scattering (DLS) using a Zetasizer Nano ZS instru-
ment (Malvern Instruments Ltd., UK) that allows specific mea-
surements of the z-average diameter (defined as the intensity-
weighted average hydrodynamic diameter of the particles being
measured). An aliquot of a stock suspension of the ground material
in deionized water was prepared and homogenized by ultra-
sonication for 5 min. The z-average diameter was calculated as the
average of six measurements.
2.3. Life cycle inventory, data quality and assumptions
According to the experimental conditions, the amount of mNPs
produced per batch (in mg) was selected as the functional unit (FU).
Hischier and Walser (2012) note that the selection of a weight
based functional unit makes sense when comparing alternative
production processes to produce an equivalent amount of nano-
material. The LCI data for the foreground system (i.e. raw materials,
water, chemicals, transport distances, energy consumption) con-
sisted of average data used for the experimental procedure (pri-
mary data). In this case, the different activities carried out
throughout the production chain of each scenario are only aimed to
the production of mNPs and no additional co-products are ob-
tained. Thus, all the environmental burdens derived from each
synthesis route were directly associated with the mNPs and no
allocation procedure was required.
The evaluation of the environmental impacts associated to
mNPs production was based on inventory data from laboratory-
scale experiments, which have been developed at a pilot scale by
the company NANOGAP (Table 1). The background system con-
siders the production of the chemicals and energy used in the
different production stages as well as wastewater treatment, as
summarized in Table 1. In more detail, Ecoinvent® database (2016)
was used to collect background data concerning generation of
electricity (Dones et al., 2007), production of chemicals (Althaus
et al., 2007), transportation (Spielmann et al., 2007) and waste-
water treatment (Doka, 2007). Concerning the production of elec-
tricity, the process included in the database was updated using data
for the average electricity generation and import/export data from
Spain in 2014 (Red Ele
ctrica de Espan
~ a, 2014).
2.4. Environmental impact assessment
The performed LCA is based on a cradle-to-gate approach, from
the production of raw materials to the formulation of the mNPs.
The environmental profile for the different processes was assessed
by performing the classification and characterization stages of the
LCA methodology (ISO 14040, 2006). The characterization factors
reported by the ReCiPe method for Life Cycle Impact Assessment
(LCIA) were used (Goedkoop et al., 2012). The impact potentials
evaluated according to the ReCiPe method were: climate change
(CC), ozone depletion (OD), terrestrial acidification (TA), freshwater
eutrophication (FEU), marine eutrophication (MEU), human
toxicity (HT), photochemical oxidants formation (POF), terrestrial
ecotoxicity (TE), freshwater ecotoxicity (FE), marine ecotoxicity
(ME), water depletion (WD) and fossil fuel depletion (FD). The
software SimaPro 8.2.0.0 was used for the computational imple-
mentation of the inventories (Goedkoop et al., 2012). Firstly, the
environmental burdens of the different scenarios proposed for
analysis were quantified to identify the main hot spots. In addition,
the most relevant stages and parameters were further analyzed by
conducting a sensitivity assessment for alternative scenarios.
3. Results and discussion
Two main purposes are pursued in this work: a) the evaluation
Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
of the environmental performance of different routes for the syn-
thesis of magnetic nanoparticles in order to identify the most
environmentally friendly one; and b) the viability of the use of
magnetic nanoparticles as viable supports for the immobilization of
the oxidative enzyme laccase.
3.1. Technical analysis e viability for enzyme immobilization
The superparamagnetic properties of the different nanoparticles
were evidenced when a magnet was placed under the glass vial.
Then, the particles were accumulated on the bottom of the vial near
the magnet within a few minutes. After removal of the external
magnetic field, the aggregates were rapidly redispersed by gentle
stirring. Moreover, complete characterization of the nanoparticles
was performed for the different processes to assure that the pro-
cesses rendered into viable magnetic nanoparticles.
Transmission electron microscopy of the magnetic nano-
particles was performed to determine the shape, size and unifor-
mity of the particles under optimum conditions. The magnetite
nanoparticles were predominantly spherical, which was confirmed
by field emission scanning electron microscopy. Their average sizes
were 21.5 ± 2.1 nm and 9.9 ± 1.4 nm for the silica-coated and the
sterically-stabilized mNPs. Oleic and PEI coated mNPs have an
average size of 7.8 ± 2.0 nm and 10 ± 2.4 nm, respectively.
When it comes to assessing the viability of the use of mNPs for
enzyme immobilization, the different NPs showed variable results.
The best NPs for laccase immobilization were silica-coated NPs
because they presented an immobilization yield of 103.5 ± 1.3%; the
rationale behind this value is due to the fact that the immobilized
enzyme in silica-mNPs showed higher affinity to ABTS (enzyme
substrate) when measuring its activity. Lower yields of laccase
immobilization were obtained for the other types of NPs: PEI
nanoparticles achieved a yield of enzyme immobilization of
78.3 ± 11.9%, while magnetite NPs attained values below 60% with
reversible leaching from the support when changing the value of
pH. The worst results of immobilization were obtained when oleic
acid NPs were used, around 15%, which was due to the agglomer-
ation of NPs when pH was changed before enzyme immobilization.
The formation of aggregates reduced the available sites of the
support for enzyme immobilization. While the highest yield of
immobilization was achieved for silica-coated mNPs, the selection
of the optimal support should comply with an additional major
requirement: minor environmental impacts.
3.2. Global environmental analysis
From the analysis of the data presented in Table 1 for the
different routes, it is evident that they share a number of stages in
common: mechanical stirring to perform the chemical co-
precipitation of the black magnetite, magnetic separation,
washing and re-dispersion. But they also differ in complexity and
final formulation of the nanoparticle, with distinct stages for oleic
acid, PEI-coated or silica-coated NPs. In the latter option, the pro-
tocol for the preparation of core-shell nanoparticles starts from the
oleic acid NPs; accordingly, more stages are performed in this
protocol because all the previous stages of oleic acid nanoparticles
must be included.
When it comes to analyze the individual inventory data for each
scenario, the two first alternatives (Scenarios 1 and 2) resemble
each other due to the comparable production scheme of nano-
particles, similar use of chemicals and electricity and minor dif-
ferences in the amount of chemicals used to adjust pH, water for
washing stages and wastewater generated. Broadly speaking, the
production of sterically stabilized magnetite and PEI coated nano-
particles will probably have a similar environmental profile.
 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11 5

Table 1
Global inventory of the production processes.

Type of mNPs Inventory Amount Unit

Sterically-stabilized magnetite nanoparticles Inputs from Technosphere

Mechanical stirring
FeCl3$6H2O (99% wt) 12.2 g
FeSO4$7H2O (99% wt) 8.4 g
HCl (37% wt) 98.5 mg
NH4OH (28% wt) 30.0 mL
Electricity from agitation 441 kJ
Electricity from heating 4095 kJ
Washing
Deionized water 0.30 L
Re-dispersion
TMAOH (10% wt) 10.0 mL
Deionized water 0.10 L
Outputs to Technosphere
Sterically-stabilized magnetite nanoparticles 6.8 g
Emissions to treatment facility
Wastewater 0.40 L
PEI coated nanoparticles Inputs from Technosphere
Mechanical stirring
FeCl3$6H2O (99% wt) 12.2 g
FeSO4$7H2O (99% wt) 8.4 g
HCl (37% wt) 98.5 mg
NH4OH (28% wt) 30.0 mL
Electricity from agitation 441 kJ
Electricity from heating 4095 kJ
PEI 2.0 g
Cooling
HCl (9% wt) 35.0 mL
Washing
Deionized water 0.40 L
Re-dispersion
Deionized water 0.10 L
Outputs to Technosphere
PEI coated nanoparticles 7e7.5 g
Emissions to treatment facility
Wastewater 0.50 L
Oleic acid coated nanoparticles Inputs from Technosphere
Mechanical stirring
FeCl3$6H2O (99% wt) 2.4 g
FeSO4$7H2O (99% wt) 1.7 g
HCl (37% wt) 19.7 mg
NH4OH (28% wt) 6.0 mL
Electricity from agitation 441 kJ
Electricity from heating 4095 kJ
Oleic acid 0.45 mL
Heating
Electricity 2340 kJ
Washing
Deionized water 0.15 L
Re-dispersion
Cyclohexane 100 mL
Outputs to Technosphere
Oleic acid coated nanoparticles 2.5e3.0 g
Emissions to treatment facility
Wastewater 0.24 L
Fe3O4@SiO2 coated nanoparticles Inputs from Technosphere
Reactor
Oleic acid coated nanoparticles 0.10 g
Igepal CO-520 15.0 g
Cyclohexane 180 g
NH4OH (28% wt) 2.1 mL
TEOS 2.4 mL
Electricity from agitation 189 kJ
Electricity from mechanical agitation 4032 kJ
Precipitation
IPA 100 mL
Electricity 42.0 kJ
Washing
Deionized water 0.40 L
IPA 0.40 L
Electricity from agitation 168 kJ
Electricity from ultrasonic bath 192 kJ
Re-dispersion
(continued on next page)

Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
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Table 1 (continued )

Type of mNPs Inventory Amount Unit

Deionized water 0.10 L

Outputs to Technosphere
Fe3O4@SiO2 coated nanoparticles 0.50 g
Emissions to treatment facility
Wastewater 0.79 L

Regarding the production of oleic acid nanoparticles (Scenario alternatives.

3), the lower use of chemicals also renders into reduced production
of nanoparticles. In addition, this protocol suffers from the
remarkable volume of cyclohexane required for re-dispersion,
which will probably have a detrimental effect on the impact. The
fourth scheme designed for the production of silica-coated nano-
particle (Scenario 4) is foreseen to present the largest impacts as it
comprises not only the stages of oleic acid nanoparticles but also
four additional stages, with important requirements of chemicals in
the reactor.
Beyond the analysis of inventory data, the environmental im-
pacts are determined from the characterization stage (results pre-
sented in Table 2 and Fig. 2), which split the results into the stages
and processes depicted previously in Fig. 1. As expected, silica
coated nanoparticles clearly present the highest environmental
impacts. Sterically-stabilized magnetite NPs, PEI coated NPs and
oleic acid NPs show lower and similar contributions, which will be
further examined.
Although the outcomes of the analysis for a number of impact
categories were obtained, special emphasis was paid to
greenhouse-gas emissions and energy-related impacts and in-
dicators, e.g., primary energy, as they are the most widely used ones
in the LCA studies and their evaluation methods are globally
accepted, which allows us to compare impacts across technology
types and maturity levels. Results show that, for the different
synthesis routes, the impacts associated with the consumption of
energy are dominant for nearly every impact category, contributing
to over 90% of life cycle burdens in some cases (Fig. 3).
Nevertheless, chemicals also contribute up to 60% in some sce-
narios (Fig. 4). Therefore, their possible replacement has encour-
aged the proposal of other options (Figs. 5e7). The environmental
analysis of alternative scenarios for the ones considered under
study is reported below.
3.3. Proposal of alternative solutions to the environmental hotspots
In the production of sterically-stabilized magnetite nano-
particles (Scenario 1), FeCl3, NH4OH and TMAOH contribute to most
of the impact share, about one third each (Fig. 4a). Since TMAOH is
only used after the washing step to adjust pH at 10, it is one of the
target compounds that have been compared with other
In this case, the impact of using equivalent amounts of NH3 and
NaOH were modeled as their suitability has been demonstrated
experimentally. The relative impact in each category from using
such chemicals is shown in Fig. 5. From this plot, it can be assumed
that the impact associated to TMAOH is not higher than for other
alkaline solutions; therefore, the suggested change does not render
into any significant improvement.
In the case of PEI coated nanoparticles (Scenario 2), HCl con-
tributes with more than 60% of the impact associated to the
chemicals in most categories (Fig. 4b). As in the case of sterically-
stabilized magnetite nanoparticles, HCl is used to adjust pH to 4.
Hence, the use of another type of acid solution could be used to
perform the same task. Equivalent amounts of HNO3, H2SO4, acetic
acid and formic acid in substitution of HCl have been tested
experimentally and the results of comparing their environmental
effects are presented in Fig. 6. Among the different chemicals,
H2SO4 has proved to be the most environmentally friendly acid and
additionally, it is an affordable commercial compound.
During the production of oleic acid coated nanoparticles and
silica-coated nanoparticles (Scenario 3 and 4, respectively), cyclo-
hexane is used in the re-dispersion stage and in the reaction stage,
respectively. Cyclohexane accounts for more than 90% of the
chemicals impact in the manufacturing of oleic acid coated nano-
particles and for more than 25% for the silica-coating (Fig. 4c and d,
respectively). When modeling the use of similar organic solvents
(N-heptane and 1,1-dimethylcyclopentane), cyclohexane presents
the lowest impact in most categories, so the use of the other al-
ternatives would not be advisable (Fig. 7a and b, respectively for
Scenario 3 and 4).
3.4. Environmental analysis per unit immobilization yield
As previously reported, the environmental profiles for the
different synthesis routes of mNPs have been displayed considering
one production batch as functional unit. However, the production
yields of mNPs are different between scenario (Table 1) as well as
the viability for enzyme immobilization. If laccase is considered for
immobilization, silica-coated nanoparticles should be preferred
due to their high immobilization yield (i.e. 103.5 ± 1.3%) while oleic
acid NPs would be rejected due to the low immobilization yield

Table 2
Environmental impacts in the production of nanoparticles.

Impact category Unit Sterically-stabilized magnetite NPs PEI coated magnetite NPs Oleic acid NPs Silica coated NPs

Climate change kg CO2 eq 9.94$102 9.60$102 4.15$101 3.73

Ozone depletion kg CFC-11 eq 7.97$109 1.23$108 2.32$108 1.73$107
Terrestrial acidification kg SO2 eq 8.08$104 7.74$104 3.12$103 1.96$102
Freshwater eutrophication kg P eq 4.45$105 4.63$105 1.57$104 9.01$104
Marine eutrophication kg N eq 3.54$105 3.76$105 1.06$104 8.94$104
Human toxicity kg 1,4-DB eq 3.89$102 4.36$102 1.25$101 9.03$101
Photochemical oxidant formation kg NMVOC 3.93$104 3.74$104 1.62$103 1.46$102
Terrestrial ecotoxicity kg 1,4-DB eq 2.97$106 5.61$106 1.12$105 1.06$104
Freshwater ecotoxicity kg 1,4-DB eq 8.23$104 8.69$104 2.83$103 1.92$102
Marine ecotoxicity kg 1,4-DB eq 8.21$104 8.86$104 2.84$103 1.95$102
Water depletion m3 4.55$103 4.62$103 1.85$102 1.55$101
Fossil depletion kg oil eq 2.89$102 2.70$102 1.44$101 2.07

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 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11 7

2000

CharacterizaƟon results (unit eq substance/FU)

1500

1000

500

0
CC OD TA FEU MEU HT POF TE FE ME WD FD
Sterically-stabilised magneƟte nanoparƟcles PEI coated magneƟte nanoparƟcles
Oleic acid coated nanoparƟcles Silica coated nanoparƟcles

Fig. 2. Total environmental impact for the different types of nanoparticles. Acronyms: CC e Climate Change (kg CO2 eq$102), OD e Ozone Depletion (kg CFC-11 eq$1010), TA e
Terrestrial Acidification (kg SO2 eq$105), FEU e Freshwater Eutrophication (kg P eq$106), MEU e Marine Eutrophication (kg N eq$106), HT e Human Toxicity (kg 1,4-DB eq$103), POF
e Photochemical Oxidant Formation (kg NMVOC$105), TE e Terrestrial ecotoxicity (kg 1,4-DB eq$107), FE e Freshwater Ecotoxicity (kg 1,4-DB eq$105), ME e Marine Ecotoxicity (kg
1,4-DB eq$105), WD e Water Depletion (m3$104), FD e Fossil Depletion (kg oil eq$103).

100 100
RelaƟve contribuƟon (%)

80 80
60 60
40 40
20 20
00 00
HT
MEU

HT
MEU
FEU
OD

POF

WD
TE

OD

FEU

POF
TE

WD
FE
ME

FD

CC

FE
ME

FD
CC

TA

TA

Chemicals Deionized water Chemicals Deionized water

Energy Wastewater Energy Wastewater

(a) (b)

100 100
RelaƟve contribuƟon (%)

80 80
60 60
40 40
20 20
00 00
FE
HT

ME
CC

FEU
MEU
OD
TA

POF
TE

WD
FD

CC

MEU
TA
FEU

WD
OD

HT
POF

FD
FE
ME
TE

Chemicals Deionized water Chemicals Deionized water

Energy Wastewater Energy Wastewater
Oleic nanoparƟcles
(c) (d)

Fig. 3. Environmental impact distribution for discrete amounts of different types of nanoparticles produced: (a) sterically-stabilized magnetite, (b) PEI-coated, (c) oleic acid, (d)
silica-coated nanoparticles. Acronyms: CC e Climate Change, OD e Ozone Depletion, TA e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine Eutrophication,
HT e Human Toxicity, POF e Photochemical Oxidant Formation, TE e Terrestrial ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e Water Depletion, FD e
Fossil Depletion.

(15%). If the mNPs production yield is assessed, 0.50 g and 2.75 g PEI coated and sterically-stabilized mNPs the ones with the highest
should be obtained per batch respectively in both scenaria, being production yields. Therefore, an additional functional unit has been

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8 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11

RelaƟve contribuƟon (%)

100 100
80 80
60 60
40 40
20 20
0 0

HT

FE
ME
CC

MEU
OD
TA
FEU

POF

WD
TE

FD
HT

ME
CC

MEU
OD
TA
FEU

POF
TE

WD
FE

FD
FeCl3 FeSO4 HCl FeCl3 FeSO4 HCl

TMAOH NH4OH NH4OH PEI

(a) (b)
RelaƟve contribuƟon (%)

100 100
80 80
60 60
40 40
20 20
0 0
CC

MEU
OD
TA
FEU

POF

WD
HT

ME

FD
TE
FE

HT
MEU
OD

FEU

POF

WD
TE
FE
ME

FD
CC

TA
FeCl3 FeSO4 HCl C6H12 Igepal NH4OH
C6H12 NH4OH Oleic acid TEOS IPA

(c) (d)

Fig. 4. Chemical impact distribution for discrete amounts of different types of nanoparticles produced: (a) sterically-stabilized magnetite, (b) PEI-coated, (c) oleic acid, (d) silica-
coated nanoparticles. Acronyms: CC e Climate Change, OD e Ozone Depletion, TA e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine Eutrophication, HT e
Human Toxicity, POF e Photochemical Oxidant Formation, TE e Terrestrial ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e Water Depletion, FD e Fossil
Depletion.

100
90
RelaƟve contribuƟon (%)

80
70
60
50
40
30
20
10
0
CC OD TA FEU MEU HT POF TE FE ME WD FD

TMAOH NaOH NH3

Fig. 5. Comparison between the use of TMAOH, NaOH and NH3 in the production of sterically-stabilized nanoparticles. Acronyms: CC e Climate Change, OD e Ozone Depletion, TA
e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine Eutrophication, HT e Human Toxicity, POF e Photochemical Oxidant Formation, TE e Terrestrial
ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e Water Depletion, FD e Fossil Depletion.

proposed for assessment considering both the mNPs production again the worst option regardless the impact category considered
yield and the enzyme unit immobilization yield. Thus, the envi- for assessment. However, Scenario 2 (PEI coated mNPs) should be
ronmental profiles have been reported per unit of enzyme immo- preferred since reductions of around ~99.5% could be obtained with
bilized (Fig. 8). respect to Scenario 4. Thus, this type of mNPs could be considered
According to the experimental results, 0.15, 1.54, 0.20 and 2.66 as an optimal option from technical and environmental indicators.
units of enzyme are immobilized per mg of mNP in Scenario 1, 2, 3
and 4, respectively, which are equivalent to 1020, 11165, 550 y 1330 4. Conclusions
units of enzyme immobilized per batch. Taking into account the
environmental profiles displayed in Fig. 8, Scenario 4 should be This work provides the first detailed life cycle inventory and

Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11 9

120

100

RelaƟve contribuƟon (%)

80

60

40

20

00
CC OD TA FEU MEU HT POF TE FE ME WD FD

HCl HNO3 H2SO4 AceƟc acid Formic acid

Fig. 6. Comparison between the use of HCl, HNO3, H2SO4, acetic acid and formic acid in the production of PEI coated nanoparticles. Acronyms: CC e Climate Change, OD e Ozone
Depletion, TA e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine Eutrophication, HT e Human Toxicity, POF e Photochemical Oxidant Formation, TE e
Terrestrial ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e Water Depletion, FD e Fossil Depletion.

60

50
RelaƟve contribuƟon (%)

40

30

20

10

0
CC OD TA FEU MEU HT POF TE FE ME WD FD

Cyclohexane N-heptane 1,1-dimethylcyclopentane

(a)

60

50
RelaƟve contribuƟon (%)

40

30

20

10

00
CC OD TA FEU MEU HT POF TE FE ME WD FD

Cyclohexane N-heptane 1,1-dimethylcyclopentane

(b)

Fig. 7. Comparison between the use of cyclohexane, N-heptane and 1,1-dimethylcyclopentane in the production of oleic acid coated nanoparticles (a) and silica coated nanoparticles
(b). Acronyms of Figure A and B respectively: CC e Climate Change, OD e Ozone Depletion, TA e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine
Eutrophication, HT e Human Toxicity, POF e Photochemical Oxidant Formation, TE e Terrestrial ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e Water
Depletion, FD e Fossil Depletion.

Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
10 S. Feijoo et al. / Journal of Cleaner Production xxx (2016) 1e11
100
80
ComparaƟve profile (%)
60
40
20
0 Berger, P., Adelman, N.B., Beckman, K.J., et al., 1999. Preparation and properties of an
CC OD TA FEU MEU HT POF TE FE ME WD FD
Scenario 1 Scenario 2 Scenario 3 Scenario 4
Fig. 8. Comparative environmental profiles for the different scenarios considering 1
unit of enzyme immobilizated. Acronyms: CC e Climate Change, OD e Ozone Deple-
tion, TA e Terrestrial Acidification, FEU e Freshwater Eutrophication, MEU e Marine
Eutrophication, HT e Human Toxicity, POF e Photochemical Oxidant Formation, TE e
Terrestrial ecotoxicity, FE e Freshwater Ecotoxicity, ME e Marine Ecotoxicity, WD e
Water Depletion, FD e Fossil Depletion. Scenario 1 - Sterically-stabilized mNPs; Sce-
nario 2 - PEI coated mNPs; Scenario 3 - Oleic acid coated mNPs; Scenario 4 -
Fe3O4@SiO2 coated mNPs.
environmental assessment for the different production alternatives
of magnetic nanoparticles. The routes of production of the mag-
netic nanoparticles exposed in this paper are innovative processes
whose environmental impact had not been analyzed so far.
From the mere analysis of technical feasibility, silica-coated
mNPs are the most reliable option over the other supports. How-
ever, the environmental impacts associated to its production hinder
its selection as the most suitable synthesis route. The decision-
making criteria must consider the balance between the perfor-
mance of the nanoparticles as supports for enzyme immobilization
and the environmental indicators, specially related to the re-
quirements for chemicals and energy in each synthesis route. PEI
coated nanoparticles methods were generally preferred among the
different alternatives because this choice combines a satisfactory
yield of laccase immobilization and reduced environmental impact.
The use of sterically-stabilized magnetite NPs and oleic acid
magnetite are options that present limited immobilization effi-
ciency as the major limitation. With the aim of reducing the envi-
ronmental impact, we considered alternative scenarios with
changes proposed for the hotspots; however, limited variations of
the environmental profile with respect to the baseline scenario
were found.
Other available LCA studies on synthesis routes for gold (Pati
et al., 2013) and silver nanoparticles (Pourzahedi and Eckelman,
2015) indicated that the hotspot of the process is the upstream
production of the metal. This is largely due to the industrial activ-
ities involved in the mining, refining and transport operations. It
should be highlighted that the methodology used and the synthesis
routes differ considerably between the abovementioned reports
and this work. Accordingly, no relationship can be established be-
tween these types of nanoparticles.
Acknowledgements
This work was financially supported by the Spanish Ministry of
Economy and Competitiveness (CTQ2013-44762-R). The authors
(SF, SG-G, YM-D, GF, MTM) belong to the Galician Competitive
Research Group GRC 2013-032 as well as to CRETUS (AGRUP2015/
Please cite this article in press as: Feijoo, S., et al., Comparative life cycle assessment of different synthesis routes of magnetic nanoparticles,
Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/j.jclepro.2016.12.079
02) and the author CV-V belongs to GRC 2013-044, programs fun-
ded by FEDER and Xunta de Galicia. Dr. S. Gonz
alez-García would
like to express her gratitude to the Spanish Ministry of Economy
and Competitivity (Grant reference RYC-2014-14984) for financial
support.
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