water

Article
Removal of Microplastics from Waters through
Agglomeration-Fixation Using Organosilanes—Effects of
Polymer Types, Water Composition and Temperature
Michael Toni Sturm 1,2,3 , Harald Horn 3,4 and Katrin Schuhen 1, *

1 Wasser 3.0 gGmbH, Neufeldstr. 17a-19a, 71687 Karlsruhe, Germany; info@wasserdreinull.de

2 abcr GmbH, Im Schlehert 10, 76187 Karlsruhe, Germany
3 Karlsruhe Institute of Technology (KIT), Engler-Bunte-Institut (EBI), Chair of Water Chemistry and
Water Technology, Engler-Bunte-Ring 9a, 76131 Karlsruhe, Germany; harald.horn@kit.edu
4 DVGW Research Laboratories, Water Chemistry and Water Technology, Engler-Bunte-Ring 9a,
76131 Karlsruhe, Germany
* Correspondence: schuhen@wasserdreinull.de; Tel.: +49-721-1565-9593

Abstract: Due to the fact, that microplastics are a global environmental problem, new ways for their
removal from water, soil and air need to be developed. New materials in combination with easy
to implement technologies for microplastic removal come into the focus of scientific studies and
engineering, especially for application in water resources. In our comparative case study, the effects
of water composition and temperature on the agglomeration-fixation reaction of microplastics using
organosilanes were examined. We compared biologically treated municipal wastewater, seawa-
ter and demineralized water at temperatures ranging from 7.5–40 ◦ C. Temperature variations and





 tested water compositions showed no negative effect on microplastic removal. The residues of the
Citation: Sturm, M.T.; Horn, H.;
organosilanes remaining in the water after the fixation process were monitored using ICP-OES and
Schuhen, K. Removal of Microplastics DOC measurements. Only one of the organosilanes tested showed no dissolved residues in the
from Waters through waters. Microplastic encompasses a multitude of different types of polymers with different properties
Agglomeration-Fixation Using and surface chemistries. Therefore, we compared the efficiency of the process for polyethylene,
Organosilanes—Effects of Polymer polypropylene, polyamide, polyester, and polyvinylchloride as examples of common polymer types
Types, Water Composition and with different chemical compositions. A strong effect of the polarity of microplastics and organosi-
Temperature. Water 2021, 13, 675. lanes on removal efficiency was observed. The organic groups of organosilanes can be chemically
https://doi.org/10.3390/w13050675 adapted to different polymer types.

Academic Editor: Bing-Jie Ni

Keywords: microplastic removal; sol-gel chemistry; organosilanes; agglomeration; wastewater;
seawater; water treatment
Received: 26 January 2021
Accepted: 26 February 2021
Published: 2 March 2021

1. Introduction
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
Microplastics are one of the most complex environmental problems today. Since the
published maps and institutional affil- start of mass production in 1950, mismanaged plastic waste has been entering the envi-
iations. ronment [1,2]. Over time, the plastic gets brittle and fragments into smaller and smaller
plastic particles. From a size of 5 mm and smaller, these plastic fragments are defined
as microplastics. Additionally, microplastics can enter the environment directly, e.g., tex-
tile fibers released through washing or tire abrasion [3,4]. Due to their high persistence
Copyright: © 2021 by the authors.
the microplastics degrade very slowly and can spread over long distances. Nowadays
Licensee MDPI, Basel, Switzerland.
microplastics can be found in all parts of the aquatic and terrestrial environment as well as
This article is an open access article
in the air [2,5,6]. Due to continuously increasing plastic consumption and thus release into
distributed under the terms and the environment, the environment will become increasingly contaminated [7,8]. This poses
conditions of the Creative Commons a high risk to the environment and ecosystems as well as to human health [9,10].
Attribution (CC BY) license (https:// Numerous studies identify municipal and industrial wastewater treatment plants as
creativecommons.org/licenses/by/ important point sources for microplastics in the environment [11,12]. Despite reported
4.0/). microplastic removal of 95% to >99% from inflowing wastewater to effluent in tertiary

Water 2021, 13, 675. https://doi.org/10.3390/w13050675 https://www.mdpi.com/journal/water

 

Numerous studies identify municipal and industrial wastewater treatment plants as 
important  point  sources  for  microplastics  in  the  environment  [11,12].  Despite  reported 
Water 2021, 13, 675 2 of 15
microplastic  removal  of  95%  to  >99%  from  inflowing  wastewater  to  effluent  in  tertiary 
wastewater treatment plants, the level of microplastic contamination in the influent has 
such a high level, that the effluent still counts as strongly contaminated. This is especially 
wastewater treatment plants, the level of microplastic contamination in the influent has
noticeable, as monitoring of microplastic contamination in the environment shows higher 
such a high level,
contamination  that the effluent
levels after  still counts
wastewater  as strongly
treatment  plant contaminated. This is especially
effluents. To  prevent  the  release 
noticeable, as monitoring of microplastic contamination in the environment
into  the  environment,  there  is  a  need  for  improved  microplastic  removal  shows higherthe 
during 
contamination levels after wastewater treatment plant effluents. To prevent the release into
wastewater treatment process. 
the environment, there is a need for improved microplastic removal during the wastewater
Additionally, there are several microplastic sensitive seawater using processes. One 
treatment process.
example is membrane‐based seawater desalination, where microplastics pose the risk for 
Additionally, there are several microplastic sensitive seawater using processes. One ex-
membrane  fouling  [11,13].  seawater
ample is membrane-based Near  food  chain  processes, 
desalination, where such  as  sea  salt 
microplastics pose production, 
the risk forcan 
transport the microplastics from the environment to human food and therefore pose a risk 
membrane fouling [11,13]. Near food chain processes, such as sea salt production, can trans-
to human health [9,14,15]. To ensure the functionality of microplastic sensitive water us‐
port the microplastics from the environment to human food and therefore pose a risk to
ing processes there is a need for a method to remove microplastics from water cost effec‐
human health [9,14,15]. To ensure the functionality of microplastic sensitive water using
tively and with low technical effort [11,16,17]. 
processes there is a need for a method to remove microplastics from water cost effectively
andFiltration is a common method for the removal of solids during water treatment and 
with low technical effort [11,16,17].
Filtration is a common method for the removal of solids during water treatment
can also be applied for microplastic removal [11,18]. But the smaller the particles get, the 
and can also be applied for microplastic removal [11,18]. But the smaller the particles
more complex and expensive the filtration process gets. Therefore, processes like mem‐
get, the more complex and expensive the filtration process gets. Therefore, processes like
brane filtration have disadvantages such as high investment costs, high energy consump‐
membrane filtration have disadvantages such as high investment costs, high energy con-
tion and high maintenance, due to, for example, the scaling and fouling of the membranes. 
sumption and high maintenance, due to, for example, the scaling and fouling of the
An easier method could be dissolved air flotation (DAF) [11]. However, different studies 
membranes. An easier method could be dissolved air flotation (DAF) [11]. However,
showed insufficient removal efficiencies of microplastics [19].Even in combination with 
different studies showed insufficient removal efficiencies of microplastics [19].Even in
flocculants and surface modifiers Wang et al. 2020 could only reach values between 68.9% 
combination with flocculants and surface modifiers Wang et al. 2020 could only reach
and 43.8% for microplastic removal using DAF [20]. Microplastics can consist of a multi‐
values between 68.9% and 43.8% for microplastic removal using DAF [20]. Microplastics
tude  of  different 
can consist types  of  polymers 
of a multitude of differentwith 
typesdifferent  properties 
of polymers and  surface 
with different chemistries. 
properties and
These can have a strong influence on the interaction of flocculants and microplastics and 
surface chemistries. These can have a strong influence on the interaction of flocculants
make  finding  suitable 
and microplastics and flocculants 
make finding even  more flocculants
suitable challenging 
even[13,21].Most  commonly 
more challenging used 
[13,21].
flocculants are based on iron or aluminum and therefore have a limited adaptability [21]. 
Most commonly used flocculants are based on iron or aluminum and therefore have a
Polyelectrolyte based flocculants are more adaptable, but due to their solubility they re‐
limited adaptability [21]. Polyelectrolyte based flocculants are more adaptable, but due
main in the water and can cause harm to aquatic organisms and ecosystems [22,23]. 
to their solubility they remain in the water and can cause harm to aquatic organisms
andFacing this challenge, Herbort et al. 2016 developed a new approach to remove mi‐
ecosystems [22,23].
Facing this challenge, Herbort et al. 2016 developed a new approach to remove
croplastics from water using organosilanes (Figure 1) [24–28]. The organosilanes consist 
microplastics from water using organosilanes (Figure 1) [24–28]. The organosilanes consist
of one organic group and three reactive groups. Due to the interaction of the organic group 
of one organic group and three reactive groups. Due to the interaction of the organic
and the surface of the microplastics, the organosilanes attach to the surface of the micro‐
group and the surface of the microplastics, the organosilanes attach to the surface of the
plastic and collect it in agglomerates in the first step of the fixation process [25]. In the 
microplastic and collect it in agglomerates in the first step of the fixation process [25]. In the
second step of the fixation, the three reactive groups form a solid hybrid silica gel that 
second step of the fixation, the three reactive groups form a solid hybrid silica gel that
includes and fixes the microplastics chemically driven by a water induced sol‐gel process. 
includes and fixes the microplastics chemically driven by a water induced sol-gel process.
During this sol‐gel process, the reactive groups are hydrolyzed to highly reactive silanols, 
During this sol-gel process, the reactive groups are hydrolyzed to highly reactive silanols,
which subsequently condensate and form siloxane bonds [27,29]. 
which subsequently condensate and form siloxane bonds [27,29].

 
Figure 1. Agglomeration‐fixation reaction: Removal of microplastics from water using orga‐
Figure 1. Agglomeration-fixation reaction: Removal of microplastics from water using organosilanes.
nosilanes. Organosilanes attach to the surface of microplastics, collect it in large agglomerates and 
Organosilanes attach to the surface of microplastics, collect it in large agglomerates and chemically
chemically fix it by forming a solid hybrid silica in a water induced sol‐gel process. 
fix it by forming a solid hybrid silica in a water induced sol-gel process.

 
Water 2021, 13, 675 3 of 15

The novelty of this process is the combination of a physical agglomeration process

with a water induced chemical fixation process, leading to strong particle growth and stable
agglomerates [25,26]. Hence, the organic groups can be adapted to different polymer types
and surface chemistries. The reactivity of the organosilanes can be adapted to different
water compositions by changes in reactive groups and organic groups [26,27]. The high
diversity and adaptability of organosilanes as chemical substance class gives this relatively
new and little researched approach a high potential for application in water treatment and
microplastic removal.
So far the process has been tested to remove polyethylene and polypropylene based
microplastics on lab scale using demineralized water and on pilot plant scale from tap
water [25,27]. To investigate the transferability to processes in sea water and wastewater, it
is tested how water compositions affect the removal process, as dissolved ions, natural or-
ganic matter or surfactant compounds can affect the sol-gel process and thus the removal
process [28]. Also, the influence of water temperatures is tested, as it can vary depending
on climatic conditions or wastewater origin. As the formation of silanol groups enhances
water solubility, possible organosilane residues remaining dissolved in the water after the
fixation process are monitored. To exclude potential discharge, no organosilanes may remain
dissolved in the water after the process is finished. Additionally, the process was tested for
common polymer types with different properties and surface chemistries, to investigate how
those affect the interaction with the organosilanes and the agglomerate formation. By the
combined investigation of these new and important factors, we want to bring microplastic
removal by organosilanes one step further towards the application transfer.

2. Materials and Methods

2.1. Used Microplastics and Chemicals
Table 1 shows the polymer types, mean size and suppliers of the used microplastics
(Figure S1).

Table 1. Overview of microplastics used in the experiments.

Polymer Type Abbreviation Mean Size [µm] Supplier

Mixture of LyondellBasell, Basell
Polyethylene/Polypropylene PE/PP 318 ± 258 Polyolefine GmbH, Frankfurt,
(1:1) Germany
EMS-Grilltech, Domat/Ems,
Polyamide PA 357 ± 60
Switzerland
EMS-Grilltech, Domat/Ems,
Polyester PES 54 ± 87
Switzerland
Sigma-Adlrich, Taufkirchen,
Polyvinylchloride PVC 110 ± 25
Germany

The organosilanes n-butyltrichlorosilane (CAS 7521-80-4), isooctyltrichlorosilane (CAS

18379-25-4), (3-chloropropyl)trichlorosilane (CAS 2550-06-3) and abcr eco Wasser 3.0 PE-X®
(AB930009), a mixture of organosilanes, were provided by abcr GmbH, Karlsruhe, Germany.
abcr eco Wasser 3.0 PE-X® is abbreviated as PE-X.

2.2. Different Water Types and Temperatures

We compared the removal process in demineralized water, salt water and biologi-
cally treated municipal wastewater (secondary clarifier). The salt water was created by
dissolving 3.5% by weight of untreated Atlantic sea salt (Art. No. 8530, Biova, Wildberg,
Germany) in demineralized water. The biologically treated wastewater was taken from
the sewage treatment plant at Landau i. d. Pfalz, Germany on 2 March 2020 (after several
days of rain). The water parameters can be seen in Table S1. Both water samples were
filtered through a 0.6 µm paper filter (Macherey-Nagel MN 85/70 BF) to remove all solids
Water 2021, 13, 675 4 of 15

contained. To compare the influence of different temperatures, the water samples were
adjusted to 7.5, 20 and 40 ◦ C using ice baths or heating plates.

2.3. Determination of Removal Efficiency

The removal efficiency was determined gravimetrically according to Sturm et al.
2020 [27]. 1 L of water was filled into a 2 L beaker, the microplastic was added and the
suspension was stirred using a magnetic stirrer for 5 min at the highest speed. Subsequently,
the stirrer was set to 500 rpm, the organosilane was added and the mixture was stirred
for 20 min to perform the agglomeration process. After 20 min, the contents of the beaker
were filtered through an analysis sieve (stainless steel, mesh size 1 mm, diameter 20 cm).
Therefore, agglomerates larger than 1 mm remained in the sieve and were classified as
removed. The filtrate with the remaining free microplastic was repeatedly filtered through
a filter crucible (porosity 4, max. pore size 16 µm) and rinsed with isopropanol to remove
possible attached organosilane residues. After drying the sample at 105 ◦ C for 24 h,
the weight of the free microplastic could be determined.
Unless otherwise stated, the organosilane dosage was 100 µL/L and microplastic
concentration was 100 mg/L. Performing lab scale experiments using 1 L water, 100 mg
microplastics per liter was the lowest concentration possible to achieve reliable and repro-
ducible results. An organosilane dosage of 100 µL/L was chosen, as in previous studies
it turned out to be the lowest concentration to remove 100 mg PE/PP efficiently (>95%)
from water on laboratory scale. The size limit for the agglomerates to be classified as
removed was set to 1 mm, as from this size the agglomerates proved to be easy to remove
in pilot plant experiments. Microplastics that stick to the wall or the bottom of the beaker
and cannot be removed by rinsing thoroughly with the wash bottle are also considered
as removed.

2.4. Determination of the Organosilane Residues Dissolved in Water

To measure the dissolved organosilane residues, the standardized removal process was
conducted using 100 mg/L of a PE/PP mixture (1:1) as microplastics. After 20 min stirring
time, a water sample was taken and filtered through a 0.45 µm syringe filter. The silicon
concentration of the sample was measured using an ICP-OES spectrometer (Inductive
Coupled Plasma Optical Emission Spectroscopy) (Agilent Technologies, ICP-OES 5110,
Waldbronn, Germany). The DOC concentration (dissolved organic carbon) was measured
with the Sievers TOC Analyzer 820. Blank values from the respective water samples were
subtracted from the measured values.

2.5. Additional Analytics

To determine the mean size, 20 microplastic particles respectively ten agglomerates
were photographed with the stereomicroscope SMT4 from ASKANIA Mikroskop Technik
Rathenow GmbH, Rathenow, Germany coupled with a Canon EOS 600D digital camera
and subsequently measured.
IR spectra (4000–300 cm−1 , resolution 1 cm−1 ) of the aggregates and hybrid silica
gels, which had been dried previously for 24 h at 105 ◦ C, were taken with the ATR-FTIR
spectrometer Vertex 70, Bruker, Ettlingen, Germany.
Thermogravimetric analysis (TGA) was conducted using a Q5000 IR from TA Instru-
ments using a platinum crucible. Starting temperature was 45 ◦ C, purge gas 1: nitrogen 5.0;
25 mL/min with a heating rate of 20 ◦ C/min. The gas switching temperature was at
600 ◦ C, purge gas 2: oxygen 5.0; 0.25 mL/min with a heating rate of 20 ◦ C/min and final
temperature of 950 ◦ C.

3. Results and Discussion

3.1. Different Water Types and Temperatures
The comparison of the removal efficiencies at different temperatures (Figure 2) shows
no negative impacts of high or low temperatures on the removal process. Also, no sig-
Water 2021, 13, x FOR PEER REVIEW  5 of 15
 
Water 2021, 13, 675 5 of 15
Water 2021, 13, x FOR PEER REVIEW  5 of 15
  be  applicable  without  problems  at  high  temperatures,  which  can  occur  in  industrial
wastewaters and at low temperatures, which can occur in the winter months in natural
nificant differences can be seen among the different organosilanes. All values are within
waters or different wastewaters [30,31]. 
theapplicable 
be  standard deviations
without respectively
problems  measurement fluctuations.which 
at  high  temperatures,  The process shouldin 
can  occur  there-
industrial
fore be applicable without problems at high temperatures, which can occur in industrial
wastewaters and at low temperatures, which can occur in the winter months in natural
wastewaters and at low temperatures, which can occur in the winter months in natural
waters or different wastewaters [30,31]. 
waters or different wastewaters [30,31].

 
Figure 2. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized water at 
different temperatures using 100 μL organosilane (A = PE‐X; B = n‐Butyltrichlorosilane; C = Iso‐
octyltrichlorosilane). 
 
Figure 2. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized wa-
Figure 2. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized water at 
ter at different temperatures using 100 µL organosilane (A = PE-X; B = n-Butyltrichlorosilane;
different temperatures using 100 μL organosilane (A = PE‐X; B = n‐Butyltrichlorosilane; C = Iso‐
This could be shown analogously for different water types. The three different water
C = Isooctyltrichlorosilane).
octyltrichlorosilane). 
types show no significant differences regarding the removal process (Figure 3). Measure‐
ment fluctuations caused the lower removal efficiency using isooctyltrichlorosilane in salt
This could be shown analogously for different water types. The three different water
This could be shown analogously for different water types. The three different water
water, which is also expressed in the higher standard deviation. Due to turbulent flow
types show no significant differences regarding the removal process (Figure 3). Measure-
types show no significant differences regarding the removal process (Figure 3). Measure‐
ment fluctuations caused the lower removal efficiency using isooctyltrichlorosilane in salt
conditions in the experimental setup, inducing random movement of agglomerates and
ment fluctuations caused the lower removal efficiency using isooctyltrichlorosilane in salt
water, which is also expressed in the higher standard deviation. Due to turbulent flow
microplastics, such fluctuations can occur [14]. On pilot plant scale the flow conditions
water, which is also expressed in the higher standard deviation. Due to turbulent flow
conditions in the experimental
and  fluctuations  setup, inducing
can  be  controlled  random
better  due  movement
to  advanced  of agglomerates
steering  and mecha‐
and  mixing 
conditions in the experimental setup, inducing random movement of agglomerates and
microplastics, such fluctuations can occur [14]. On pilot plant scale the flow conditions and
nisms.   
fluctuations can be controlled better due to advanced steering and mixing mechanisms.
microplastics, such fluctuations can occur [14]. On pilot plant scale the flow conditions
and  fluctuations  can  be  controlled  better  due  to  advanced  steering  and  mixing  mecha‐
nisms.   

 
Figure 3. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized water (DW),
Figure 3. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized water 
salt water (SW) or biologically treated wastewater (WW) using 100 µL organosilane (A = PE-X;
(DW), salt water (SW) or biologically treated wastewater (WW) using 100 μL organosilane (A = 
B = n-Butyltrichlorosilane; C = Isooctyltrichlorosilane).
PE‐X; B = n‐Butyltrichlorosilane; C = Isooctyltrichlorosilane). 
 
Figure 3. Removal efficiency for 100 mg mixture of PE/PP (1:1) from 1 L demineralized water 
Possible positive impacts of sea- or wastewater could not be examined with the ap-
(DW), salt water (SW) or biologically treated wastewater (WW) using 100 μL organosilane (A = 
pliedPossible positive impacts of sea‐ or wastewater could not be examined with the ap‐
parameters, since the combination of 100 mg of microplastics in one liter of water
PE‐X; B = n‐Butyltrichlorosilane; C = Isooctyltrichlorosilane). 
plied parameters, since the combination of 100 mg of microplastics in one liter of water
with 100 µL of organosilane was selected in such a way that it had achieved optimum
with 100 μL of organosilane was selected in such a way that it had achieved optimum
removal (>95%) with demineralized water as a reference, which leaves no room for mea-
Possible positive impacts of sea‐ or wastewater could not be examined with the ap‐
surable improvements.
removal (>95%) with demineralized water as a reference, which leaves no room for meas‐
plied parameters, since the combination of 100 mg of microplastics in one liter of water
urable improvements. 
with 100 μL of organosilane was selected in such a way that it had achieved optimum
In general, wastewater shows temporal variations on the chemical composition and
removal (>95%) with demineralized water as a reference, which leaves no room for meas‐
particle load but also variations depending on the catchment area [32]. In our experiments,
urable improvements. 
 we decided to test municipal wastewater, taken during a rainy period, as it con
microplastic washed from the roads by surface runoff (e.g., tire wear) and po
Water 2021, 13, 675
the biggest point sources for microplastics into the environment 6[33,34]. of 15
Be
wastewater is diluted with rainwater and usually contains less nutrients and ot
icals as surfactants. On the day of sampling, the inflow amounted to 38 million
whereas the average
In general, wastewaterinflow
showson dry days
temporal amounts
variations on the to 11 million
chemical L perand
composition day. Alt
particle load but also variations depending on the catchment area
could not find any negative effect in the wastewater used in our studies, furth [32]. In our experi-
ments, we decided to test municipal wastewater, taken during a rainy period, as it contains
gations should focus on the variations of wastewater compositions. Especially
more microplastic washed from the roads by surface runoff (e.g., tire wear) and poses
wastewater can show
one of the biggest strongfor
point sources variations depending
microplastics on the type
into the environment of industry
[33,34]. Besides, [35]
theFor salt water,
wastewater oceans
is diluted withshow spatial
rainwater and temporal
and usually variations
contains less for the
nutrients and othersalt con
chemicals as surfactants. On the day of sampling, the inflow amounted to 38 million Liter
and composition [36]. The salt concentration usually varies between 3.2–3.8%
(L), whereas the average inflow on dry days amounts to 11 million L per day. Although we
average
could notoffind
3.5%,
anywhich
negativewe chose
effect in theas the concentration
wastewater for thefurther
used in our studies, experiments.
investi- As
difference between
gations should focus ondemineralized
the variations of water andcompositions.
wastewater 3.5% salt water, theindustrial
Especially fluctuations o
wastewater can show strong variations depending on the type of industry
centrations in the oceans should be negligible. Only saline lakes, which can ea [35].
For salt water, oceans show spatial and temporal variations for the salt concentration
saltand
concentrations
composition [36].>10% and
The salt are oftenusually
concentration used varies
for salt extraction,
between 3.2–3.8%,could
with anaffect t
[37]. Nevertheless,
average of 3.5%, which theweremoval process
chose as the should
concentration forbe
thetransferable
experiments. As to there
municipal
is w
no difference between demineralized water and 3.5% salt water, the
and sea water. The functionality of the process in drinking water could already fluctuations of salt
concentrations in the oceans should be negligible. Only saline lakes, which can easily reach
in salt
a previous study [25].
concentrations > 10% and are often used for salt extraction, could affect the process [37].
Nevertheless, the removal process should be transferable to municipal wastewater and
3.2.seaComparison of PolymerofTypes
water. The functionality the process in drinking water could already be proven in
a previous study [25].
Comparing the efficiency of the removal process with different types of
3.2. differences
clear Comparison of Polymer
betweenTypesthe types of polymers and the organosilanes used co
Comparing the efficiency of
termined (Figure 4). During the removal the removal process with the
process, different typesgroups
organic of polymers,
of the org
clear differences between the types of polymers and the organosilanes used could be
needs to attach
determined to 4).
(Figure theDuring
surface of the process,
the removal microplastic particles
the organic groups ofto collect
the them in agg
organosilanes
Therefore, these
needs to attach differences
to the are
surface of the caused by
microplastic the varying
particles interactions
to collect them of the orga
in agglomerates.
andTherefore, these differences
the surface are caused
of the different by the varying
polymer typesinteractions
[27]. of the organic groups
and the surface of the different polymer types [27].

Figure 4. Removal efficiency for 100 mg microplastics from 1 L demineralized water us-
Figure 4. Removal efficiency for 100 mg microplastics from 1 L demineralized water us
ing 100 µL organosilane (A = PE-X; B = n-Butyltrichlorosilane; C = Isooctyltrichlorosilane;
organosilane (A = PE-X; B = n-Butyltrichlorosilane; C = Isooctyltrichlorosilane; D = (3-Ch
D = (3-Chloropropyl)trichlorosilane).
pyl)trichlorosilane).
PE and PP consist of pure alkyl chains, have no heteroatoms and are, therefore, non-
polar. PA has nitrogen and oxygen and PES oxygen as heteroatoms, which is why they
arePE
moreand PP However,
polar. consist of pure
since thealkyl chains, have
C–H component no heteroatoms
predominates, there and are,
they are classified
polar. PA has nitrogen and oxygen and PES oxygen as heteroatoms, which is
are more polar. However, since the C–H component predominates, they are
with medium polarity. PVC results from the crosslinking of vinyl chloride (C2H3
Water 2021, 13, 675 7 of 15

with medium polarity. PVC results from the crosslinking of vinyl chloride (C2 H3 Cl),
which means that it has an extremely high proportion of chlorine atoms and the highest
polarity in the polymer series shown.
Among the organosilanes, PE-X, n-butyltrichlorosilane and isooctyltrichlorosilane
have non-polar organic groups made of pure hydrocarbons. In the tests with microplastics
based on PE and PP, satisfactory removal efficiencies between 97 and 98.3% were consis-
tently reached. However, with increasing polarity of the microplastics, the effectiveness
decreased, as much smaller agglomerates are formed which partially do not reach the size
limit of 1 mm (Figure 6). With very polar PVC values between 30–55% can be achieved. An-
other influence factor could the higher density of the polar polymer types, as it can hinder
the accumulation of the microplastics and smaller agglomerates in the vortex by sinking.
In comparison Lapointe et al. 2020 tested aluminum and polyacrylamide based floc-
culants towards weathered and unweathered PE and could show that the introduction of
polar hydroxyl and carboxylic acid groups by weathering could improve the interaction of
the flocculants and microplastics leading to improved removal [21]. This result shows that
coagulants with polar sorption sites can lead to enhanced flocculation of polar microplas-
tics.
Therefore, (3-chloropropyl)trichlorosilane was added to the tested organosilanes,
which has a higher polarity due to a chlorine substitution at the end of the organic propyl
group. This creates an improved interaction with the surface polar polymers. For the
highly polar PVC a clear improvement of the removal efficiency is reached. In the case
of polymers of medium polarity (PES and PA), which have both polar and non-polar
structural units, no clear improvement could be achieved by the chlorine substitution.
Using PE/PP, no agglomerate formation was observed, since there was no interaction
between the non-polar surface and the polar chloropropyl group. These results prove the
strong interaction between the organic group of the organosilanes and the surface of the
microplastics depending on the polymer type.
Because chlorinated hydrocarbons are generally both ecotoxicologically hazardous
and harmful to health, the use of (3-Chloropropyl)trichlorosilane in actual application
is unlikely [38]. Due to the good results achieved by the chemical modification of the
organic group, future studies should focus on environmentally friendly alternatives for
organosilanes with polar organic groups. For this adaption however, it must also be taken
into account that the organic groups can have a strong influence on the reactivity of the
organosilanes and thus can negatively influence the fixation process [27]. Therefore, not all
organic groups are suitable for this adaptation.
Additionally, a higher dosage or combination of organosilanes was tested for the re-
moval of PVC (Figure 5). An increase in the dosage to 300 µL n-butyltrichlorosilane (84.0%)
and the combination of 100 µL PE-X with an additional 100 µL isooctyltrichlorosilane
(79.6%) respectively 100 µL n-butyltrichlorosilane (77.6%) show an increase in efficiency
comparable to (3-chloropropyl)trichlorosilane (80.7%). This shows the potential of the
combination of organosilanes for microplastic removal and that there is still potential for
further improvement of PE-X. Using a dosage of 1 mL n-butyltrichlorosilane, an almost
complete removal could be achieved reaching 98.1%. Studies using aluminum, iron or poly-
acrylamide based flocculants also showed increased effectivity of higher dosages [13,21].
The mean size of the microplastics and the agglomerates is shown in Figure 6. It can
be seen, that the size composition of the virgin microplastics differs significantly among
the polymer types and mixtures. CoPA (Ø 357 µm) and PE/PP (Ø 318 µm) have a larger
starting size than PVC (Ø 110 µm) and CoPES (Ø 54 µm). Additionally, the standard
deviations show that PVC and PA particles have a more even size while the size of PES
and PE/PP particles show large deviations. It is currently unclear whether the initial size
of the microplastics has an influence on the final size of the agglomerates, as data shows
strong particle growth during the agglomeration process for all polymer types. In previous
studies testing flocculation of microplastics with different size compositions using iron,
 Water 2021, 13, x FOR PEER REVIEW 8 of 15

Water 2021, 13, 675 8 of 15

2021, 13, x FOR PEER REVIEW

aluminum and polyacrylamide based flocculants, larger microplastic particles showed
worse flocculation as they are more difficult to incorporate into the flocks [13,21].

Figure 5. Removal efficiency for 100 mg PVC from 1 L demineralized water using 100 µL orga-
nosilane at different dosages and combinations (A = PE-X; B = n-Butyltrichlorosilane; C = Isooctyl-
trichlorosilane; D = (3-Chloropropyl)trichlorosilane).

The mean size of the microplastics and the agglomerates is shown in Figure 6. It can
be seen, that the size composition of the virgin microplastics differs significantly among
the polymer types and mixtures. CoPA (Ø 357 µm) and PE/PP (Ø 318 µm) have a larger
starting size than PVC (Ø 110 µm) and CoPES (Ø 54 µm). Additionally, the standard de-
viations show that PVC and PA particles have a more even size while the size of PES and
PE/PP particles show large deviations. It is currently unclear whether the initial size of the
microplastics has an influence on the final size of the agglomerates, as data shows strong
particle growth during efficiency
Removal the agglomeration
for 100 mgprocess for1all polymer types. In previous stud-
Figure
Figure 5.5.Removal efficiency for PVC
100 from
mg L demineralized
PVC from 1 Lwater using 100
demineralized µL organosilane
water using 10
ies testing flocculation of microplastics with different size compositions using iron, alu-
at different dosages and combinations (A = PE-X; B = n-Butyltrichlorosilane; C = Isooctyltrichlorosi-
nosilane
minum and
lane; D=
at different dosages
polyacrylamide and combinations
based flocculants,
(3-Chloropropyl)trichlorosilane). larger microplastic(Aparticles
= PE-X; B = n-Butyltrichlorosilane
showed worse
trichlorosilane; D = (3-Chloropropyl)trichlorosilane).
flocculation as they are more difficult to incorporate into the flocks [13,21].

The mean size of the microplastics and the agglomerates is shown in F

be seen, that the size composition of the virgin microplastics differs signifi
the polymer types and mixtures. CoPA (Ø 357 µm) and PE/PP (Ø 318 µm)
starting size than PVC (Ø 110 µm) and CoPES (Ø 54 µm). Additionally, the
viations show that PVC and PA particles have a more even size while the si
PE/PP particles show large deviations. It is currently unclear whether the ini
microplastics has an influence on the final size of the agglomerates, as data
particle growth during the agglomeration process for all polymer types. In p
ies testing flocculation of microplastics with different size compositions us
minum and polyacrylamide based flocculants, larger microplastic particles s
flocculation as they are more difficult to incorporate into the flocks [13,21].

Figure 6. Mean
Figure Mean
6. size size of microplastics
of microplastics and agglomerates.
and agglomerates. The dashed
The dashed black black
line marks the 1line
mmmarks the 1 mm
limit limit
from which the microplastics
from which are assessed
the microplastics as removed.
are assessed (A = PE-X; (A
as removed. B ==n-Butyltrichlorosilane;
PE-X; B = n-Butyltrichlorosilane;
C = Isooctyltrichlorosilane; D = (3-Chloropropyl) trichlorosilane).
C = Isooctyltrichlorosilane; D = (3-Chloropropyl) trichlorosilane).
Ma etMa
al. 2019
et al.reported flock sizes
2019 reported of 258.6
flock sizes±of
20.8 µm ±
258.6 using
20.8aluminium-based floccu-
µm using aluminium-based floc-
lants and 474.8 ± 25.6 for iron-based flocculants for the removal of PE. Lapointe et al. 2020
culants and 474.8 ± 25.6 for iron-based flocculants for the removal of PE. Lapointe et al.
reported flock diameters of 977 ± 36 µm for the removal of PE < 140 µm and of 504 ± 18
2020 reported flock diameters of 977 ± 36 µm for the removal of PE < 140 µm and of
504 ± 18 µm for PE > 140 µm applying polyacrylamide-based flocculants. Compared to
this, using organosilanes higher agglomerate sizes could be reached for the removal of
PE/PP with up to 13,130 µm using PE-X. Also it is notable that on pilot plant scale much
higher agglomerate sizes could be achieved [25]. This is a big advantage of this method,
as larger agglomerates can be removed more easily.
 Water 2021, 13, x FOR PEER REVIEW 9 of 15

Water 2021, 13, 675 9 of 15

µm for PE > 140 µm applying polyacrylamide-based flocculants. Compared to this, using

organosilanes higher agglomerate sizes could be reached for the removal of PE/PP with
up to 13,130 µm using PE-X. Also it is notable that on pilot plant scale much higher ag-
For the determination
glomerate of the [25].
sizes could be achieved removal
This isefficiency, the limit
a big advantage formethod,
of this agglomerates
as larger classified
as removed was set at 1 mm, since
agglomerates can be removed more easily. those could easily be removed in pilot plant tests in a
2 m3 test Forreactor system [27].
the determination Considering
of the the mean
removal efficiency, sizefor
the limit and standard classified
agglomerates deviations of the
as removed was
agglomerates, set atPES
for PA, 1 mm,
and since
PVC those could easilyof
a proportion bethe
removed in pilot plant
agglomerates testsreach
do not in a the size
of 12mm
m3 test
andreactor system
therefore [27].
are Considering
classified the microplastics
as free mean size and standard
despite deviations of the growth
a strong particle
agglomerates,
compared to thefor PA, PES
initial andThus,
size. PVC abyproportion of thethe
optimizing agglomerates
agglomeratedo not reach theon
removal size
pilot plant
of 1 mm and therefore are classified as free microplastics despite a strong particle growth
scale and therefore lowering the size limit for the removal, a strong increase in removal
compared to the initial size. Thus, by optimizing the agglomerate removal on pilot plant
efficiency
scale and can be expected.
therefore lowering the size limit for the removal, a strong increase in removal
efficiency can be expected.
3.3. Organosilanes Residues Dissolved in Water
3.3.
TheOrganosilanes
examination Residues Dissolved
of the in Water residues dissolved in water (Figure 7) shows
organosilane
that for The examination of the organosilane
isooctyltrichlorosilane residues dissolved inbetween
and n-butyltrichlorosilane, water (Figure
76.47)and
shows
46.3% of the
that for isooctyltrichlorosilane and n-butyltrichlorosilane, between
added organosilane (calculated based on the Si content) remains in solution. This 76.4 and 46.3% of the happens
added organosilane (calculated based on the Si content) remains in solution. This happens
as the silanols formed during the hydrolysis of the chlorine groups increase the water
as the silanols formed during the hydrolysis of the chlorine groups increase the water
solubility of the organosilanes [39]. During the sol-gel process formed oligomers or dimers
solubility of the organosilanes [39]. During the sol-gel process formed oligomers or dimers
withwith remainingsilanol
remaining groupscan
silanol groups canremain
remain in solution
in solution andreact
and not notcompletely
react completely
to solid to solid
hybrid-silica
hybrid-silicagels.
gels.This posesa aproblem
This poses problem for for a technical
a technical application
application of theprocess.
of the fixation fixation process.
However,
However, this
thiseffect
effect cannot
cannot bebeseen
seen with
with PE-X,
PE-X, as noasresidues
no residues
could becould be detected
detected in the in the
water.
water. Therefore,PE-X
Therefore, PE-X is
is suitable
suitableforforthethe
application.
application.

Figure
Figure 7. 7. Percentage
Percentage of organosilane residues
of organosilane residues ininthethe
water calculated
water from the
calculated Si content
from the Si(a)content
and DOC (a)content (b) after
and DOC content (b) Commented
adding 100 mg PE/PP (50:50) in 1 L water, subsequently adding 100 µL organosilane and stirring for 20 min. (DW = de-
after adding 100 mg PE/PP (50:50) in 1 L water, subsequently adding 100 µL organosilane and stirring for 20 min. to round brac
mineralized Water; SW = salt water; WW = biological treated wastewater; A = PE-X; B = n-butyltrichlorosilane; C = iso-
(DW = demineralized Water;
octyltrichlorosilane). For SW
DOC=100%
salt water; WW
correspond to=Abiological
= 58.7 mg/L,treated
B = 29.1wastewater;
mg/L and C = A = mg/L.
41.8 PE-X; For
B =Sin-butyltrichlorosilane;
content 100%
corresponds to A = 17.2 For
C = isooctyltrichlorosilane). mg/L,
DOCB = 17
100%mg/L A = 58.7 mg/L, B = 29.1 mg/L and C = 41.8 mg/L. For Si content Commented
and C = 12.1tomg/L.
correspond
100% corresponds to A = 17.2 mg/L, B = 17 mg/L and C = 12.1 mg/L.
Comparing the results of the DOC and Silica concentrations, it is noticeable that the
residues measured with the ICP-OES (Si content) are always slightly higher than the val-
Comparing the results of the DOC and Silica concentrations, it is noticeable that the
ues measured by DOC. At the start of the DOC measurement, highly concentrated phos-
residues measured with the ICP-OES (Si content) are always slightly higher than the values
phoric acid is added to the sample in order to remove the contained inorganic carbon.
measured
This acidby DOC. At
catalyzes thethe start
sol-gel of thewhich
process, DOCmeans
measurement, highly
that dissolved concentrated
dimers and oligomersphosphoric
acidcontained
is addedintothe sample can condense, precipitate and deposit on tubes [29]. This effect is This acid
the sample in order to remove the contained inorganic carbon.
catalyzes the sol-gel
particularly process,
noticeable in salt which means
water, as that dissolved
the combination dimers
of acid and oligomers
and dissolved salt addi-contained
tionally
in the intensifies
sample the condensation
can condense, of theand
precipitate oligomers.
deposit on tubes [29]. This effect is particularly
noticeable in salt water, as the combination of acid and dissolved salt additionally intensifies
the condensation of the oligomers.
In general, ICP-OES delivers more accurate and reliable measured values, due to
the short distance from the intake to the plasma torch and the general robustness of the
measuring method. DOC is a good alternative for process control, as it is a cheap and easy
to handle method.

3.4. Additional Analytics

3.4.1. Microscope Images
The microscope images (Figure 8 and Figure S1) show the formation of stable agglom-
erates, where the microplastics are held together by the organosilane. As the organosilane
forms a thin, transparent to slightly white hybrid silica layer on the microplastics during
 handle method. 

3.4. Additional Analytics 
3.4.1. Microscope Images 
Water 2021, 13, 675 10 of 15
The microscope images (Figures 8 and S1) show the formation of stable agglomerates, 
where the microplastics are held together by the organosilane. As the organosilane forms 
a  thin,  transparent  to  slightly  white  hybrid  silica  layer  on  the  microplastics  during  the 
the formation process, the single microplastics particles can still be recognized. The texture
formation process, the single microplastics particles can still be recognized. The texture of 
of the agglomerate is tough and viscoelastic, which is typical for hydrogels [40]. In addition,
the agglomerate is tough and viscoelastic, which is typical for hydrogels [40]. In addition, 
the agglomerates are very sticky and attach to glass, metal, and plastic surfaces.
the agglomerates are very sticky and attach to glass, metal, and plastic surfaces. 

 
Figure 8. Microscope images of wet agglomerates formed during the removal of 100 mg microplastics from 1 L demin, 
Figure 8. Microscope images of wet agglomerates formed during the removal of 100 mg microplastics from 1 L demin, wa-
water  using 
ter using 100 
100 µLμL  organosilane. 
organosilane. (A) =(A) 
PE-X=  PE‐X  and  PE/PP 
and PE/PP (1:1), 
(1:1), (B) (B)  =  n‐Butyltrichlorosilane 
= n-Butyltrichlorosilane and PA, (C)and  PA,  (C)  =  Isooctyltri‐
= Isooctyltrichlorosilane
chlorosilane and PES, (D) = (3‐Chloropropyl)trichlorosilane and PVC. 
and PES, (D) = (3-Chloropropyl)trichlorosilane and PVC.

3.4.2. IR‐Spectra 
3.4.2. IR-Spectra
Figures S2–S7 show the IR spectra of the different polymers, the hybrid silica result‐
Figures
ing  from  the S2–S7 show the
respective  IR spectra of
organosilane  the different
after  polymers,
20  min  water  the hybrid
contact  silica
and  the  resulting
agglomerates 
from the respective organosilane after 20 min water contact and the agglomerates formed
formed during the removal process. The IR spectra of the hybrid silica gels show small 
during the removal process. The IR spectra −1of the hybrid silica gels show small peaks −1
peaks for the siloxane bonds at 1200–1240 cm  (υasSi–O–Si), a wide peak of 1100–1000 cm  
for the siloxane bonds at 1200–1240 cm−1 (υas Si–O–Si), a wide peak of 1100–1000 cm−1
(υasSi–O–Si) and a peak at 390‐460 cm−1− (δO–Si–O) [25,41]. The deformation oscillations of 
1
(υas Si–O–Si) and a peak at 390–460 cm (δO–Si–O) [25,41]. The deformation oscillations
the alkyl groups (δ
of the alkyl groupsSC–H, δ
(δS C–H,asC–H, δ–CH2–) can be seen in the range of 1260–1470 cm−1−
δas C–H, δ–CH2–) can be seen in the range of 1260–1470 cm . The  1.
stretching vibrations of the alkyl groups (υ asC–H, υsC–H) can be found in the range 2850–
The stretching vibrations of the alkyl groups (υas C–H, υs C–H) can be found in the range
2970 cm −1. 
2850–2970 cm−1 .
These peaks for the alkyl groups can also be found in the spectra of the microplastic 
These peaks for the alkyl groups can also be found in the spectra of the microplastic
samples. Therefore, the agglomerates show stronger peaks of the alkyl groups compared 
samples. Therefore, the agglomerates show stronger peaks of the alkyl groups compared to
to pure silica, caused by the included microplastics. The presence of PVC in the agglom‐
pure silica, caused by the included microplastics. The presence of PVC in the agglomerate
can be confirmed by the peak at 600–650 cm−1 (δC–Cl)
erate can be confirmed by the peak at 600–650 cm [42,43]. PA shows additional peaks
−1 (δC–Cl) [42,43]. PA shows additional 

at 3290 cm −1 (υN–H), 1630 cm −1 (δC=O), 1540 cm −1 (δC–N, υN–H) and 680 cm−1 (υN–H;
peaks at 3290 cm  (υN–H), 1630 cm  (δC=O), 1540 cm−1 (δC–N, υN–H) and 680 cm
−1 −1 −1 (υN–

υC=O). Typical PES peaks are visible at 1710 cm−1 (υC=O), 1230 cm−1 (υC-O), 1100 cm−1
(υC–O), 725 cm−1 (ωγ,δ C–H of aromatic compounds). In addition, the Si–O–Si peaks of
the hybrid silica are clearly visible in the agglomerates, which confirms the inclusion of the
  microplastic in a hybrid silica gel during the fixation process.

3.4.3. TGA
For the TGA measurements, the removal experiments were additionally conducted
with mixtures of different polymer types. The data (Figure 9 and Figures S8–S10) show that
 microplastic in a hybrid silica gel during the fixation process.

3.4.3. TGA
Water 2021, 13, 675 For the TGA measurements, the removal experiments were additionally 11 of 15conduc
with mixtures of different polymer types. The data (Figures 9 and S8–S10) show that
agglomerates include the different polymers and the organosilane based hybrid sil
formed during the
the agglomerates fixation
include process.
the different Thus, the
polymers and fixation processbased
the organosilane is also suitable
hybrid silica to remo
mixtures
formed duringof different polymers.
the fixation process.The peak
Thus, the at 414 °C
fixation can beisassigned
process to PES,
also suitable the peak at 4
to remove
mixtures of different polymers. The peak at 414 ◦ C can be assigned to PES, the peak at
°C results from the overlapping PE, PP and PA peaks and the first peak of the hybrid sil
◦ C results from the overlapping PE, PP and PA peaks and the first peak of the hybrid
475515
at °C. The peak at 610 °C and the continuing weight loss after 505 °C, where the po
silica at 515 ◦ C. The peak at 610 ◦ C and the continuing weight loss after 505 ◦ C, where the
mers show no weight loss anymore, confirm the presence of the hybrid silica in the
polymers show no weight loss anymore, confirm the presence of the hybrid silica in the
glomerate.
agglomerate.Due Duetotothetheoverlapping
overlapping ofofthe
theTGA
TGApeaks,
peaks, a quantitative
a quantitative analysis
analysis of theof the co
position of the agglomerate was not possible.
composition of the agglomerate was not possible.

Figure 9. TGA curves of (a) agglomerate formed in removal process 100 mg of PE/PP/PA/PES
Figure 9. TGA curves of (a) agglomerate formed in removal process 100 mg of PE/PP/PA/PES
(1:1:1:1) from 1 L demineralized water using 100 µL n-Butyltrichlorosilane; (b) hybrid silica formed
(1:1:1:1) from 1 L demineralized water using 100 µL n-Butyltrichlorosilane; (b) hybrid silica
by adding 100 µL n-Butyltrichlorosilane in 1 L demineralized water and different polymer types
formed by adding 100 µL n-Butyltrichlorosilane in 1 L demineralized water and different polym
used in experiments. Grey dashed line = weight in %; black line = derived weight in %/◦ C.
types used in experiments. Grey dashed line = weight in %; black line = derived weight in %/°C
4. Conclusions
In summary, this study showed that the novel method of microplastic removal using
organosilanes has a huge potential to be applied for microplastic removal on technical scale.
Temperature and water type, here salt water and biologically treated municipal wastewater,
show no negative effect on microplastic removal with organosilanes, which shows the
robustness of the method and should make it easily transferable to processes as advanced
Water 2021, 13, 675 12 of 15

wastewater treatment or sea water using processes. As wastewater composition can vary
strongly depending on the catchment area, weather and climatic conditions, further investi-
gations are needed to ensure the applicability in different wastewaters. Also, application in
highly saline lakes could pose a challenge to the process.
It was also shown that the chemical composition and surface chemistry of microplas-
tics have a strong influence on the removal process and physical interaction with the
organosilanes. The removal efficiency of microplastics based on different polymer types de-
creases with the increasing polarity of the polymer. Highly polar polymers can be removed
more efficiently by increasing the polarity of the organic group. However, this leads to a
reduced effectiveness towards non-polar polymers. These results show that the organosi-
lanes can be adapted specifically to improve the removal of certain polymer types by
adjusting the organic group to the surface chemistry of the polymer. The high variability
and modifiability of organosilanes makes them a very promising substance class for this
challenge. Another alternative to increase the efficiency is using higher concentrations of
organosilanes. Further studies should focus on the combination of different organosilanes
for an effective removal of mixtures of polar and non-polar polymers, as they occur in the
environment. Also, the effect of biofilm coverage, weathering and natural organic matter
adsorption can be taken into consideration.
The analysis of the size composition of the microplastics and agglomerates shows a
strong increase in size during the agglomeration process for all polymer types. However,
the limit of 1 mm for the agglomerates for efficient removal on pilot plant scale is often not
achieved. An improved removal process for the agglomerates with a lower size limit is
therefore expected to lead to strongly improved microplastic removal on technical scale.
From the tested organosilanes n-butyltrichlorosilane and isooctyltrichlorosilane both
show high quantities of residues dissolved in water after the removal process, ranging from
76.4 to 46.3%. PE-X shows no dissolved residues and therefore is perfectly suited for the
application on technical scale without posing any risk of the introduction of organosilanes
into the environment or technical processes, which is a big advantage of this specific
organosilane. The tested water compositions show no significant differences on the amount
of residues. To control dissolved organosilanes residues, ICP-OES showed more precise
and reliable results than DOC measurements. But as a cheaper and faster method, DOC is
still suitable for an efficient process control in possible technical applications.
Microscope images, IR-spectra and TGA curves confirm the inclusion of the microplas-
tics in a hybrid silica formed by a water induced sol-gel process during the fixation process
The TGA curves can additionally show that it is possible to fix mixtures of different poly-
mers simultaneously in the agglomerates. Therefore, these methods are well suited to
investigate the composition of agglomerates and later on to control the process during
continuous application.
Due to the limitations of the laboratory scale test setup, 100 mg/L could be selected
here as the smallest concentration of microplastics. However, environmental concentrations
are usually far below that concentration. Therefore, further pilot-plant studies will focus on
a reduction of the microplastics concentrations as well as the function in real applications
without microplastic spiking. Also, a broader variety of water compositions is going to
be tested. Due to the adaptability of this process to different polymer types and the low
technical effort for the application on technical scale, we see a high potential for this process
to be a cost-effective and easily applicable alternative for standard flocculants.

Supplementary Materials: The following are available online at https://www.mdpi.com/2073-4

441/13/5/675/s1, Figure S1: Stereomicroscope images of raw microplastics used for the fixation
experiments. Table S1: Water parameters of a 24 h composite sample taken on 2nd March 2020 at the
effluent of the sewage treatment plant Landau i. d. Pfalz, Germany. Figure S2: FTIR-Spectra of the
microplastics used in the fixation experiments. Figure S3: FTIR-Spectra of the hybrid silica formed
by adding the respective organosilane to water and stirring for 20 min. Figure S4: FTIR-Spectra of
the agglomerates formed during the fixation process using PE-X and different polymers. Figure S5:
FTIR-Spectra of the agglomerates formed during the fixation process using n-butyltrichlorosilane and
Water 2021, 13, 675 13 of 15

different polymers. Figure S6: FTIR-Spectra of the agglomerates formed during the fixation process
using isooctyltrichlorosilane and different polymers. Figure S7: FTIR-Spectra of the agglomerates
formed during the fixation process using (3-chloropropyl)trichlorosilane and different polymers.
Note: Using (3-chloropropyl)trichlorosilane and PE/PP, no agglomerates were formed during the
fixation experiments. Figure S8: TGA curves of (a) agglomerate formed in removal process 100 mg of
PVC from 1 L demin. water using 100 µL PE-X; (b) hybrid silica formed by adding 100 µL PE-X in
1 L demin. water and of the different polymer types used in experiments. Figure S9: TGA curves
of (a) agglomerate formed in removal process 100 mg of PES from 1 L demin. water using 100 µL
Isooctyltrichlorosilane; (b) hybrid silica formed by adding 100 µL Isooctyltrichlorosilane in 1 L demin.
water and of PES. Figure S10: TGA curves of (a) agglomerate formed in removal process 100 mg of
PE/PA (1:1) from 1 L demin. water using 100 µL PE-X; (b) hybrid silica formed by adding 100 µL
PE-X in 1 L demin. water and of the polymer types used in experiments.
Author Contributions: Conceptualization, M.T.S. and K.S.; methodology, M.T.S., K.S. and H.H.;
formal analysis, M.T.S.; investigation, M.T.S.; resources, H.H. and K.S.; data curation, M.T.S.; writing—
original draft preparation, M.T.S. and K.S.; writing—review and editing, M.T.S.; visualization, M.T.S.;
supervision, K.S. and H.H.; project administration, K.S. and H.H.; funding acquisition, K.S. and H.H.
All authors have read and agreed to the published version of the manuscript.
Funding: This study was not part of a special funded project.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study is available in the current manuscript,
raw data is available on request from the corresponding author.
Acknowledgments: The research projects of Wasser 3.0 (www.wasserdreinull.de, accessed on 2
March 2020) are conducted by sponsors and donors. Wasser 3.0 gGmbH is a non-profit company with
strong focus on responsible research, education, and communication. The enterprise abcr GmbH
(www.abcr.de, accessed on 2 March 2020) from Karlsruhe (GERMANY) is directly involved in the
project as an industrial partner. The authors acknowledge special support from abcr service lab
and Dennis Schober from EW Landau for the fruitful discussion about the microplastic removal.
Michael Sturm additionally thanks the ‘Deutsche Bundesstiftung Umwelt’ (DBU) for the grant of
a PhD scholarship (Az. 20018/549).
Conflicts of Interest: The authors declare no conflict of interest.

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