Trends in Analytical Chemistry 130 (2020) 115993

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Trends in Analytical Chemistry

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

Expanding exploration of dynamic microplastic surface characteristics

and interactions
Stephen D. Burrows a, c, *, Simona Frustaci b, Kevin V. Thomas c, Tamara Galloway a
a
College of Life and Environmental Sciences, University of Exeter, EX4 4QD, Exeter, UK
b
Department of Physics and Astronomy, Living Systems Institute, University of Exeter, EX4 4QD, UK
c
Queensland Alliance for Environmental Health Sciences (QAEHS), The University of Queensland, 20 Cornwall Street, Woolloongabba, QLD, 4102, Australia

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

Article history: Microplastics have been found in all marine ecosystems, raising concern about their potential envi-
Available online 3 August 2020 ronmental impacts. Yet relatively little research has focused on surface characteristics, compared to
polymer type. The aim of this review is to discuss the importance of microplastic surface properties and
Keywords: how expanded characterisation and more detailed quantification can aid in assessing their behaviours in
Microplastics aquatic environments. Concepts including surface roughness, formation of surface ecocoronae and
Ecotoxicology
sorptive behaviours of microplastic surfaces are discussed. To address these concepts, three exemplary
Aquatic
methods are introduced and their application to the study of microplastic surfaces discussed with the
Optical nanosensor
Characterisation
following recommendations; atomic force microscopy should be explored for conducting physical sur-
face characterisation and to examine surface roughness; double-shot Pyrolysis-Gas Chromatography
eMass Spectroscopy should be considered for examining microplastic sorption behaviours in multi-
solute media; and finally, Whispering Gallery Mode nanosensing techniques should be explored as a
potential means to generate data on microplastic sorption kinetics.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction plastics as a resource, with around 50% produced being single-use

Microplastics (generally defined as <5 mm particles of synthetic
polymer) can now be found in every marine ecosystem, regardless of
distance from human populations [1,2]. They have been found from
the Mariana Trench to the polar regions of the Arctic and Antarctica
[3e5]. Their wide distribution and prevalence is mostly due to the
versatility and strength of plastic materials lending themselves well
to technological advancement and economical manufacturing [6].
Since the 1950s, when mass production of plastic began, these
properties of plastic materials have facilitated increased production
[7]. In 1950, 1.7 million tonnes of plastic is estimated to have been
produced, in 2018 production reached 359 million tonnes, >200
times the level of production 68 years previously [7e9]. Significant
resultant pollution has led to a detectable period layer of plastic
material in the depositional record, called the Plasticene [10].
Increased production is not solely to blame for the state of plastic
pollution. A culprit of equal measure would be mismanagement of
* Corresponding author. College of Life and Environmental Sciences, University of
Exeter, EX4 4QD, Exeter, UK.
E-mail address: sb982@exeter.ac.uk (S.D. Burrows).
[11]. A recent publication from the United Nations Environment
Programme estimated that 8.28 million tonnes of plastic is released
into the environment each year [12]. The current throw away cul-
ture enabled by single-use plastic is being challenged through
developing legislation and public awareness, but this has only just
started to develop in recent years [13].
While a significant amount of research has been published on
microplastic pollution, questions remain about their associated risk
to the environment and human health. Microplastics are not a
single entity, but rather represent a hugely complex mixture of
different polymer types, shapes, and sizes of material, many of
which will have aged and weathered in multiple environmental
compartments and under diverse conditions. Significant diversity is
hence found in microplastic surface properties, which is of note, as
these dynamic characteristics affect their behaviour in aquatic
ecosystems [14]. This complexity has rarely been addressed in
detail in publications, and further examination of surface charac-
teristics and interactions are needed to address current arguments
in the literature [14e16].
There is evidence that microplastic physical surface character-
istics, such as surface roughness and surface area, affect the

https://doi.org/10.1016/j.trac.2020.115993
0165-9936/© 2020 Elsevier B.V. All rights reserved.
2 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993
reactivity and potential toxicity of microplastic particles [14,17]. As
such, examining physical surface characteristics is relevant to un-
derstanding microplastic behaviour in the environment (e.g.
sorption). Furthermore, conflicting results in the literature raise the
need for further study. For example, sorption of hydrophobic con-
taminants might be predicted to increase with an increase in sur-
face area, since there is more space available for molecules to bind.
This conclusion is based on the mechanisms behind sorption
encompassing both absorption and adsorption. Summarised, the
former describes uptake of chemicals into the bulk of a material,
while the latter, uptake onto material surfaces [18]. As such, surface
area is a significant factor in chemical adsorption.
However, in a study by Wang et al. [19], sorption of phenan-
threne decreased with increased roughness of the subject poly-
ethylene (PE) microplastic material at their smaller size fraction
(1 mm), while sorption increased in rougher, larger fibre fractions
(4 mm and 10 mm). This supports our understanding that factors
other than surface area alone are important for sorptive behaviours,
such as curvature of the sorptive surface, or the hydrophobic nature
of the polymer. Guo et al. [20] studied the sorption behaviour of
various hydrophobic organic compounds (phenanthrene, naph-
thalene, lindane, and 1-naphthol) onto polymer surfaces. They
found that polyphenylene oxide, despite its polar chemical struc-
ture which includes significantly more oxygen than polystyrene
(PS) and styreneedivinylbenzene copolymer (these polymers
include oxygen surface content due to sorption from the environ-
ment), was found to sorb significantly more of the solutes than the
latter polymers [20]. This was concluded to be due to the oxygen
moieties of polyphenylene oxide being covered by the surface of
the material, forming a hydrophobic surface, resulting in the higher
uptake [20].
Relating to the influence of curvature, Farrow, et al. [21]
modelled adsorption of oil in a solution onto solid surfaces,
showing an increase in surface coverage with solute is due to the
geometrical effect of increased surface curvature resulting in more
free volume for the solute [21]. Summarised further, the effect of
curvature on sorption results in smaller particle surfaces receiving
significantly greater coverage when compared to the surface of a
larger particle in mutual equilibrium between the solutes and
solvent [21]. Furthermore, issues with standardisation of published
methods (varying results between instruments and difference in
applied terminology e.g. plastic size ranges), such potentially con-
founding variables (such as surface roughness) require attention as
the field progresses [1,22,23].
The sorption behaviour of microplastic pollution has been a
recent source of contention [16]. Despite continuous research, the
potential for microplastics to act as vectors for toxic chemicals and
to transfer them into the tissues of exposed organisms has not been
equivocally proven and the extent to which this occurs in the
natural environment is not clear [16]. Teuten et al. [24] studied
microplastic material exposed to the waters of Tokyo Bay, where
they sorbed PCB content. These microplastics were fed to shear-
water chicks supplemented with a diet of fish, which resulted in a
spike in PCBs from collected preen gland oil [24]. This spike con-
tained lower chlorinated PCBs which was attributed to their ca-
pacity to be metabolised. The fish fed to the shearwater chicks were
also contaminated with PCBs, enough that the content out-
competed that sorbed to the microplastics except initially by the
lower chlorinated fraction [24]. Lower chlorinated PCBs are less
likely biomagnified in ecosystems as they are metabolised more
than those that are more chlorinated [24]. As a result the micro-
plastics transported significantly more of the lower chlorinated
PCBs into the shearwater chicks than the fish in their diet [24].
Furthermore in a study by Scopetani et al. [25], the authors found
that feeding microplastics contaminated with polybrominated
diphenyl ether (PBDE) to Talitrus saltator resulted in transport of the
chemical into the organism tissue. However, the same study also
found evidence that feeding uncontaminated microplastics to
T. saltator contaminated with PBDE resulted in transport of the
chemical from the organism [25]. These studies highlight the more
complicated involvement of microplastics in toxic chemical path-
ways, which requires further research for more certain conclusions
on their environmental significance.
Recent studies have explored other ways in which the sorption
behaviour of microplastics may have environmental impacts.
Dimethyl sulphide (DMS) is formed in the marine environment
from the breakdown of a precursor molecule when zooplankton
graze on phytoplankton and is widely recognised as an infochem-
ical that triggers and controls foraging cascades. Procter et al. [26]
found that the infusing of DMS into microplastic fibres significantly
increased their ingestion by copepods. Considering the sorption
behaviour of microplastics, this study raises the question of how
interactions with environmental chemicals can have other impli-
cations relating to organism chemosensory responses. With the
complexity of sorption in multi-solute environments only starting
to be addressed, a comprehensive understanding of microplastic
sorption behaviour to address such questions more fully is still
lacking [27]. As such, understanding the sorption behaviour and
developed surface layers (ecocoronae) of microplastics in more
detail is urgently needed to address questions about their envi-
ronmental impact.
This short review aims to discuss the above mentioned topics in
greater detail and critically review three example novel methods
with which to expand chemical and physical characterisation of
microplastic surfaces; atomic force microscopy, double-shot py-
rolysis gas-chromatography mass-spectrometry and Whispering
Gallery Mode optical nanosensors. The application of each of these
exploratory methods is discussed in the context of physical char-
acterisation of microplastic material, exploration of ecocorona
composition in differing multi-solute environments, and the in-
teractions between environmental chemical factors and micro-
plastic surfaces in greater detail. We do not include a
comprehensive review of every method applicable to examine
microplastics and instead the reader is referred to reviews by Fu
et al. [28] and Primpke et al. [29]. Additionally, extensive reviews on
microbiological interactions with microplastics can be found else-
where and are not considered in detail here [30e33].
2. Quantifying surface roughness and potential using atomic
force microscopy
Microplastics come in various shapes and sizes, fibres, nurdles
and fragments. These physical characteristics of microplastics have
significant influence on particle behaviour. For example, properties
such as shape, density and size can influence their transport though
aquatic environments [34]. As described and tested by Ballent et al.
[34], the density of a microplastic particle will significantly affect its
vertical transport though the water column as it physically interacts
with flow and turbulence (dependent on the density difference
between the water and microplastic). Other physical microplastic
properties, such as size and shape will also have a significant
impact on the degree to which the particle is influenced by water
column characteristics such as turbulence. Ballent et al. [34] illus-
trate this in their investigation into the influence of physical
microplastic characteristics on vertical transport, finding larger,
more irregular shaped particles were most drawn down by tur-
bulent flow. Microplastics also vary in their physical surface char-
acteristics. In the environment these properties are altered by
processes such as UV photo-oxidation, in which CeC and CeO
bonds are broken [35], which can affect multiple characteristics
 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993 3

including surface roughness, defined here as the amount and resultant rise and fall of the cantilever is measured by the moni-
extent of deviation of a surface from being perfectly flat [36]. These toring of a laser aimed at the cantilever with a photo detector [44].
changes are of note as there is evidence that physical surface There are three modes of AFM: a contact mode in which the
characteristics, such as roughness, affect how microplastics interact cantilever tip is drawn along the surface of the sample, an
with their environment [36]. intermittent-contact mode in which the tip is tapped at regular
The term “sorption” includes two modes, accumulation on a intervals along the sample, and a non-contact mode in which the
surface (adsorption) and within the bulk of a material (absorption) tip does not come into contact with the sample itself, but with
[18]. The capacity for a material to absorb sorbate is dependent on liquid on its surface from which it measures topography [44].
its free volume, i.e. spaces between polymer chains which allow the Quantitative measurements of the surface roughness of a
sorbate to permeate the sorbent material [37]. As such, the capacity microplastic can be produced using AFM, while producing quali-
of a polymer for absorption is dependent on chemical structure. In tative data in the form of nanoscale resolution images of sample
contrast, as adsorption is a process which occurs on the surface of a surfaces (Fig. 1) [44,47]. Another specific benefit of using AFM is the
sorbent material. Physical surface characteristics (such as curva- scanning resolution in three dimensions, AFM is able to reach
ture) are more significant to the adsorption of sorbate material resolutions
1 nm, dependent on the size of the cantilever tip used
[21,38]. As such, chemical structure and surface characteristics are [48,49]. This high resolution allows for quantified examination of
significant to both a sorbent's capacity for sorption, as well as physical surface structure at a range not yet explored in micro-
which mode of sorption is more dominant. plastics. In addition, the capacity of AFM to scan in three di-
These concepts are explored further by Mao et al. [36] who mensions is not possible at the same resolution in SEM, meaning
found that polystyrene (PS) degraded by UV exposure exhibited AFM is able to detect more detailed changes in surface roughness
increased sorption of heavy metals (Pb, Cu, Cd, Ni and Zn), likely [48].
due to shifts in the physicochemical characteristics of the micro- Furthermore, AFM is able to image a surface with significantly
plastic material of which surface roughness was considered a sig- less pre-preparation compared to SEM [48]. Due to the risk of a
nificant factor [36]. This would agree with previous studies into the sample's secondary electron signal being interfered with by
influence of surface roughness on sorption. For example, Akkas, external factors, imaging is required in a sealed vacuum, a feature
et al. [39] concluded that surface roughness was as significant to not required by AFM [48]. In addition, changes to the physical
sorption of proteins on polyurethane films as hydrophilicity. surface of a microplastic sample can be caused by the heat gener-
However, due to variation in modes of sorption with different ated by an SEM electron beam, melting the sample [50]. This is
sorbates, this is not applicable to all interactions [18]. A major significant as any processing has the potential to impact the
example difference between groups of polymers would be between
“rubbery” and “glassy” polymers [40]. Referring to physical prop-
erties, glassy polymers are more rigid and brittle while rubbery
polymers are more flexible and have more free volume [18,41]. This
difference in structure (especially the amount of free volume) has
consequences for sorption behaviour [41]. Rubbery polymers have
a heightened capacity for sorption than glassy polymers [18,40].
This difference is primarily due to which mode of sorption is
dominant in the polymer. For example in more rubbery polymers
(with more free volume), generally, absorption is more likely the
dominant mode of sorption [18,40]. This means different polymers
will be affected by surface roughness to a greater or lesser extent
depending on their dominant sorption behaviour. Furthermore,
these variables in sorption behaviour have significant implications
for the strength of bonds between the sorbent and the sorbate,
influencing desorption behaviour [42].
As the involvement of physical surface characteristics is yet to be
fully understood in regards to its influence on microplastic
behaviour (sorption and fate), more extensive surface characteri-
sation is important for a range of related studies (e.g. sorption and
degradation). Characterisation of surface roughness is most often
presented in the form of imaging with scanning electron micro-
scopy (SEM). This method, while practical in producing qualitative
data on microplastic surface structure, is limited in terms of
quantitative analysis [43]. Other methods, such as optical profil-
ometry (OP) and atomic force microscopy (AFM), can enable
quantified analysis of surface structures [43,44]. The former was
applied to microplastic material in a study by Murrell et al. [43], in
which the authors presented the practical application of OP to
quantify the surface roughness of microplastic material as an
improvement from solely qualitative characterisation with SEM.
The potential of the latter method is discussed below.
Atomic force microscopy (AFM) is a physical measurement of
topography down to an atomic resolution [45,46]. It allows for the
measurement of various surface characteristics, including surface
roughness, by physically interacting a cantilever with a specialised Fig. 1. 2D and 3D scans of a virgin PS microplastic nurdle surface generated using an
tip (of nanoscale diameter) with the sample surface [44]. The Asylum Research MFP-3D Cypher S AFM in contact mode.
4 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993
nanoscale surface of a microplastic sample. This change is not
required in AFM and presents the opportunity to measure a more
accurate surface roughness [48].
Quantification of microplastic surface roughness using AFM
provides an avenue to address the issues stated earlier in this
section. However AFM is not limited to quantification of surface
roughness, it has also been used to measure characteristics
including hydrophobicity, adhesiveness (in regards to microbial
interactions) and conductivity [51,52]. Fu and Zhang [51] demon-
strated how measurement of hydrophobicity was possible with
AFM, which was used to measure adhesion forces between the AFM
tip and self-assembly monolayers (SAMs). A linear relationship was
found between the measured adhesion force and water contact
angles (a measurement of hydrophobicity based on the continuum
thermodynamic approach) of the subject nanoparticles (NPs),
which included, CuO, ZnO and TiO2. This relationship enabled
measurement of hydrophobicity with adhesion force measurement
by AFM. It is of note that the accuracy of these measurements
differed depending on the NP material, which is theorised by the
authors to be due to difference in surface roughness and hydration
[51]. Zhang et al. [52] used AFM to calculate the interaction forces
between NPs (haematite and corundum) and bacterial (Escherichia
coli) cells. These interaction forces were used as a measurement of
adhesion between the NPs and the bacteria [52]. This AFM mea-
surement was used by Zhang et al. [52] to investigate the rela-
tionship between NP size and microbe adhesiveness, in which they
found a decrease in adhesion force with increased NP size. This was
presumed due to the effective contact area between the NP and the
cells increasing with decreasing NP size [52].
Furthermore, the development of hybrid AFM techniques (AFM-
Raman and AFM-infrared spectroscopy (AFM-IR) have extended the
minimum size range threshold of chemical characterisation tech-
niques into the nanoscale [53,54]. In these advances there is sig-
nificant evidence that AFM can contribute more to the
development of characterisation in microplastic research. AFM-IR is
a method which combines the chemical characterisation of infrared
(IR) spectroscopy with the resolution of AFM [53,55]. The method
exposes a sample to an IR laser, which causes photothermal
expansion, the degree of which is dependent on the IR absorbance
properties of the sample material [53]. This expansion is monitored
by measuring the oscillation of an AFM tip in contact with the
sample as a wavelength, and this wavelength is converted into an IR
absorbance spectra [55]. This development has expanded IR spec-
troscopic chemical characterisation into the nanoscale resolution,
previously not possible with methods such as FT-IR [55]. As plastic
research expands into nanoplastic pollution, development of such
methods may become increasingly important to the field.
While the potential benefit in using AFM is significant, there are
considerations which need to be taken into account in regards to its
use. Physical contact in AFM has the potential to cause damage to
the surface of samples potentially affecting results and preventing
accurate and reliable physical characterisation of the sample [56].
This contact can be minimised by using intermittent-contact or
non-contact AFM, however this can be a trade off with the reso-
lution of the acquired image [56].
Further needed consideration when using AFM comes from its
limited depth of field [48]. Compared to SEM, AFM has a signifi-
cantly shorter depth of field, where SEM can show a depth of field at
a magnitude of mm, AFM is limited to that of mm [48]. In the context
of imaging a surface, if a surface is particularly rough in regards to
height differences in a given area, then AFM will be limited in the
vertical information it is able to collect [48]. This has implications
for the scan size used to measure the surface roughness of a
microplastic particle, significant due to the effect scan size has on
measured surface roughness [57]. This is illustrated by Mwema
et al. [57] whose found that surface roughness of aluminium films
was increased by increasing the scan size used (1 mm2, 3 mm2,
30 mm2). These limitations being considered, developing use of
AFM holds significant potential to expand microplastic physical
surface characterization and to contribute to the development of
characterisation techniques regarding other microplastic
properties.
3. Exploring sorption in multi-solute media with double-shot
pyrolysis-gas chromatographyemass spectrometry
As microplastics are exposed to the environment they sorb
various chemical and biological factors, eventually forming a sur-
face layer called an ecocorona [11]. The composition of these eco-
coronae is dependent on the nature of the particle, the
environment the particle has been exposed to and potential to
interact with the surrounding ecosystem [58]. Such interactions
can range from influencing organism behaviour to increasing or
decreasing the toxicity of sorbed chemicals [26,59].
There are in addition questions to be addressed around the ef-
fects of polymer degradation and multi-solute media on sorption
behaviour, for which the exploration of microplastic surface layers
is imperative [18,26,27,60]. Ho and Leung [27] studied the sorption
to microplastics (LDPE and PS) of UV filters (benzophenone-3 (BP-
3), 4-methylbenzylidene camphor (4-MBC) in a multi-solute envi-
ronment containing ethylhexyl methoxycinnamate (EHMC) and
octocrylene (OC). They found that although most interactions be-
tween co-solutes appeared antagonistic, sorption of 4-MBC by PS
increased in the presence of the other UV filters [27]. Laterally
attractive interactions between the adsorbed co-solute UV filters
(BP-3, EHMC and OC) and the 4-MBC were proposed to explain the
subsequent increase in adsorption by the PS [27]. The study high-
lights the complexity of sorption behaviours concerning micro-
plastics in multi-solute environments.
Wang et al. [60] exposed microplastic polyethylene tere-
phthalate (PET) material to 313 nm wavelength UV light (from
50 W/m2 lamps) for up to 500 h, finding an increased sorption
capacity for metal ions Cu2þ and Zn2þ. The authors conclude that
the increased sorption with UV degradation was likely due to
increased surface area with microplastic material becoming more
irregular in shape (which was highlighted by changes in surface
structure shown by SEM images), in addition to the increased
number of oxygen groups on the PET surface caused by photooxi-
dation [60]. Furthermore, both increases in temperature and pH are
noted as being significant to the sorption rate, the former due the
endothermic characteristic of adsorption of the metal ions by PET,
and the latter due to resultant increased charged sites on the
microplastic surface and the positive charge of the subject ions [60].
This highlights the complexity brought by variation in conditions
such as pH and temperature, as well as the physical degradation of
the microplastic material, which all have consequences for subse-
quent sorption behaviours.
Studies into the sorption behaviour of microplastics in single
solute media, in which one chemical contaminant in solution is
studied at a time, are numerous in the literature. Despite the use of
such studies to understand sorption behaviour and the different
affinities for sorption with varying sorbates, in the environment
microplastics are exposed to chemically diverse media [18,27]. This
is significant, as sorption in multi-solute media involves factors
such as competitive sorption, which would affect the composition
of microplastic surface layers [27,61]. Therefore, in looking to
address how microplastic surface layers form in different envi-
ronments, analysis of the sorbed contents of microplastics in multi-
solute experimental media, with quantification of the formed
ecocorona composition, would be effective.
 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993
Such analysis of the sorbed content of microplastics has been
achieved with a number of different methods in the literature, with
numerous variations in liquid and gas-chromatography mass-
spectrometry [19,62]. However, we focus here on one method in
particular; based on recent advances in microplastics quantification
in pyrolysis-gas chromatographyemass spectrometry (Py-GCMS).
In Py-GCMS, materials are thermally degraded, and the volatile
products that are produced are subsequently identified through
mass spectrometry [63]. To achieve this, samples are raised to be-
tween 500 and 1400 C in an inert gas, transforming the sample into
a volatile product [64]. This volatile product is chromatographically
separated and identified through mass spectrometry based on
reference spectra libraries [64].
This method has been modified in a number of ways to analyse
both microplastic material and their additives [2,65]. Sequential Py-
GCMS is an example, where the temperature is raised at intervals,
which has been used to separate additives (e.g. organic plastic
additives: diethylhexyl phthalate, dibutyl phthalate and dimethyl
phthalate) from microplastics (e.g. PE, polypropylene and PS) for
analysis [65]. Thermo-extraction and desorption with GCMS (TED-
GCMS) would be another example [2]. This technique combines
thermogravimetric analysis with desorption GCMS for practical
chemical analysis of relatively high quantities of microplastic ma-
terial [2]. Progress in Py-GCMS has now enabled the separation of
microplastics from environmental material (such as biosolids) for
subsequent analysis [66]. Okoffo et al. [66] described a so-called
double-shot technique, where interfering environmental material
is thermally desorbed from the sample before pyrolysis of the
microplastic content. The authors apply this method to process
biosolid material, with a combined use of solid phase extraction
and double-shot Py-GCMS resulting in separation of microplastic
material from biosolid samples [66]. However, in using Py-GCMS to
look at the associated chemical content, as previously published by
Fries et al. [65] sequential Py-GCMS to quantify organic plastic
additives, such a method may be used to quantify sorbed content.
Applying the concept of double-shot Py-GCMS from Okoffo et al.
[66] to isolate the sorbed material from the sample, but for sub-
sequent quantification rather than disposal (Fig. 2). This could
provide a method to address the aforementioned questions relating
to microplastic sorption behaviour in more detail.
It is possible that this method could be used to expand exami-
nation of accumulated biological factors; Py-GCMS has been used to
this end previously. Zhu et al. [67] used Py-GCMS to quantify mi-
crobial biomass through the detection of specific “microbial sig-
nals” (including benzyl nitrile, pyrrole and indole). The study used
five pyrolysis products (including those mentioned above) as a
“fingerprint” of microbial presence to measure the biomass in
Fig. 2. Simplified illustrated flow diagram of a proposed method based on the Py-GCMS technique of Okoffo et al. [66].
5
marine sediment samples [67]. Using the proposed double-shot Py-
CGMS method to examine the relationship between biofilm for-
mation and microplastic characteristics, could facilitate further
developing our understanding of microplastic ecocoronae.
Various plastic additives are commonly used to manipulate the
properties of plastics. Pigments are added for colour, antioxidants
are added for age resistance and UV stabilisers are added for light
resistance [65]. As microplastics are weathered by the environment
these additives are progressively lost through the process of
leaching [68]. The loss of these additives results in significant
changes to microplastic properties and their chemical composition
[69]. Py-GCMS has been shown to be a suitable method of quan-
tification for these additives, as Fries et al. [65] quantified organic
plastic additives (including diethylhexyl phthalate, dibutyl phtha-
late and dimethyl phthalate) with sequential Py-GCMS. Further-
more, the leaching of additives could influence sorption behaviour,
and as shown in the previously mentioned study by Ho and Leung
[27], where co-solutes had either antagonistic and enhancing ef-
fects on sorption behaviours depending on the primary solute and
the sorbent material (see earlier in this section). As such, potentially
an adapted double-shot Py-GCMS method could be used to quan-
tify the relationship between the sorption rate of different sorbates
and the successive leaching of different plastic additives.
While there is significant potential in the use of double-shot Py-
GCMS to explore the above stated research avenues, it is of note Py-
GCMS does also result in sample destruction [64]. Due to this, no
further observations or measurements can be made on the sample
after the technique has been used. As Py-GCMS only produces data
relating to the chemical composition of the sample, other charac-
teristics such as colour, shape and size are lost if not measured
before the process [2]. Despite this drawback, the potential for the
double-shot Py-GCMS concept to be applied to the sorbed content
of microplastics shows significant potential to facilitate our un-
derstanding of microplastic sorption behaviour in greater detail.
Such possible analyses are supported by the extensive review by
Pico
and Barcelo
[70] regarding the use of Py-GCMS on micro-
plastics and associated environmental material.
4. Examining surface interactions with whispering gallery
mode optical nanosensors
Understanding sorption kinetics of microplastics in greater
detail is of fundamental importance for interpreting studies of their
interactions in the aquatic environment. More detailed data
collection on sorption kinetics will facilitate the development of
more accurate sorption kinetics models to mass balance models
[59,71]. This will in turn result in more accurate estimation of the
6 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993
effects of microplastics on the fate, transport and bioavailability of
sorbed chemicals [59,71]. Sorption kinetics have been measured
using ICPeMS, liquid and gas-chromatography MS to good effect
[18,19,72]. Here, we describe a novel technique, with potential to
contribute to examining sorption kinetics in greater detail.
Whispering Gallery Mode (WGM) optical nanosensors utilise
the “whispering gallery mode” recirculation of photons involving
the internal reflection of light within microcavities [73] (Fig. 3). This
accumulation of photons generates an evanescent field which en-
ables significantly sensitive nanosensors [73] (Fig. 3). The “Whis-
pering gallery mode” name comes from the phenomenon
described by Lord Rayleigh in 1910 in which a whisper can be heard
from one end of the gallery of St Paul's Cathedral, London, UK to the
other (32 m apart) [74,75]. This is caused by the acoustic waves
being guided along the walls of the circular room [75]. These WGM
optical nanosensors harness a similar movement of waves but that
of light rather than sound [75]. Light is accumulated inside a
resonator (which can be formed of various materials and shapes,
glass to silica, spheres to toroids) through the internal reflection of
light [73] (Fig. 3). The longer the light is able to circulate within the
specific resonator, the higher the sensitivity of the measurement (Q
factor) [73]. As such, the Q factor is important when considering
what materials are suitable for constructing the microsphere
resonator component.
To date the application of WGM to environmentally relevant
micro/nanoplastics has not been reported. However, previous ex-
periments have provided potential insights into how WGM may be
applied to the study of nanoscale surface interactions on micro-
plastic surfaces. Constructing a microsphere resonator with plastic
would be of interest. This has been found to be possible with plastic
materials using entirely plastic structures and silica microspheres
coated in plastic material [76,77]. In a paper by Dong et al. [76],
researchers coated silica microspheres with polymethyl methac-
rylate (PMMA) using a dip coating technique. The study found that
the coating improved the Q factor of the microsphere resonator for
WGM [76]. Furthermore, Lutti, et al. [77] demonstrated the suit-
ability of polystyrene microspheres as WGM resonators thanks to a
satisfactory Q factor when prepared in the described manner.
The advantage of analysing microplastic surface structures using
WGM optical nanosensors is that it would allow for the measure-
ment of the number and duration of interactions with the resonator
surface within a specific time resolution [73]. Simplified, an inter-
action between a resonating WGM evanescent field and a single
molecule is detected by the resonance shift the molecule causes at
the surface of the resonator [73]. Looking at a plastic surface, this
Fig. 3. Simplified illustrated diagram of the main components to a WGM nanosensor (A) and its ability to detect interactions on the surface of the resonator though measured
changes in the light signal detected (B).
could provide a wealth of information about the dynamism of in-
teractions between single chemical factors and microplastics.
The sorption of chemical factors is a dynamic process of sorption
and desorption which reaches a state of equilibrium once concen-
trations in the solid phase (microplastic) and the liquid phase
remain constant [59]. The detailed information WGM could pro-
duce from examining these interactions would provide more ac-
curate data to improve sorption kinetics models and mass balance
models [59,71]. Ultimately, this would result in a more accurate
examination of the effects of microplastic sorption behaviour on
chemical transport in the context of the environment.
Limitations in using WGM come from method development.
One example would be the time resolution of measurements, being
dependent on the “cavity lifetime” (t) (t ¼ Q/u, where Q ¼ Q factor
and u ¼ the light's angular frequency) [78]. This limits the time
resolution of WGM measurements to durations in the order of
nanoseconds, potentially missing more transient interactions [78].
While improvements to WGM sensors are planned to surpass this
threshold time resolution, currently they are limited by this “cavity
lifetime”. Another example relating to method development would
be the considerations needed for more complex samples such as
may be generated in complex aquatic environments [79]. The more
complex a sample is, the more likely non-specific interaction events
are to occur, creating signal noise [79]. For example, if a sample was
being analysed for interaction with a specific UV filter but included
two more co-solute molecules, which readily interact with the
resonator surface, these co-solutes would generate non-specific
interaction events. These non-relevant signals can be mitigated in
various ways, from quantifying the difference in signal between all
the sample constituents, to using labels to amplify the desired
signal (enzymes and antibodies have been previously used in WGM
biosensing) [79]. These noise mitigation methods, while effective,
take time to develop, and as such can be seen as a limitation to the
method.
5. Summary and recommendations
The continued progress of microplastic chemical and physical
characterisation is important to develop more accurate and in
depth understanding of their impacts on the environment. We
know microplastics are found throughout the environment, we
now need to understand in what form and how they interact. The
physical characteristics of microplastics can have implications for
their reactivity and so their behaviour in the environment [19]. As
such, examining the relationship between physical characteristics
 S.D. Burrows et al. / Trends in Analytical Chemistry 130 (2020) 115993
(such as surface roughness) and sorption behaviour of different
sorbates is important to understand microplastic behaviour.
High resolution imaging of a sample surface can be provided by
AFM while producing quantified information about surface
roughness [44,47]. AFM could be applied to microplastics research
in studies investigating sorption, UV degradation and characteri-
sation of surface roughness. This would facilitate more in depth
examination of the relationship between physical characteristics
and sorption, and help expand microplastic characterisation in the
literature.
Recent advances in double-shot Py-GCMS show potential to
provide a novel method to quantify sorbed microplastic content
[66]. The technique could be used to examine sorption rates of
multi-solute media through analysis of accumulated surface layers.
This would provide more in depth data concerning microplastic
sorption behaviour and so their potential for environmental
impact.
Furthermore, more detailed data collection on microplastic
sorption kinetics would facilitate the development of accurate
models to estimate the environmental impact of microplastic
pollution [59,71]. This is in terms of the transport and bioavail-
ability of sorbed chemical factors [59]. Therefore, it would be
beneficial to develop methods which measure microplastic surface
interactions with greater precision.
The WGM technique shows significant potential to reveal more
about how microplastics interact with chemicals in the environ-
ment. Based on the knowledge that WGM techniques enable the
measurement of interactions between a chemical factor and the
surface of a microsphere resonator, that WGM resonators have
been formed of plastic, and that WGM can be coated in plastic; it is
possible WGM could be used to examine microplastic surfaces in-
teractions [73,76,77].
Quantifying these interactions will lead to a more detailed grasp
of the environmental impact of microplastic pollution. This could
go some way to addressing the concerns of Connors et al. [80] that
greater physical and chemical characterisation is a necessary
development to microplastic research.
Funding
SB was funded through the QUEX Institute, a partnership be-
tween the University of Exeter and The University of Queensland.
TG was funded by the Natural Environment Research Council: grant
NE/N006178/1.
Declaration of competing interest
The authors declare no conflict of interest.
Acknowledgements
Thanks to Professor Mike Allen, Christopher Evans (Plymouth
Marine Laboratory) and Dimitris Samaras (University of Bristol) for
providing guidance and advice on atomic force microscopy. Thanks
to Sivaraman Subramanian and Professor Frank Vollmer from the
University of Exeter for comments and guidance on whispering
gallery mode optical nanosensors. Thanks to Katherine Colvin,
Rebekah Boreham and Dr Corey Holt from the University of Exeter
for proofreading. This work was performed in part at the Queens-
land node of the Australian National Fabrication Facility. A company
established under the National Collaborative Research Infrastruc-
ture Strategy to provide nano and microfabrication facilities for
Australia's researchers.
7
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