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B. Nguyen, 2019
B. Nguyen, 2019
S Supporting Information
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Figure 1. Selected density-based and sized-based separation methods. (a) Density separation and (b) dead-end filtration. In (b), it should be noted
that 0.1 μm filtration is done twice. Reproduced from ref 14. Copyright 2017 American Chemical Society. (c) Froth filtration. Reproduced with
permission from ref 10. Copyright 2012 American Society of Limnology and Oceanography. (d) Asymmetric-flow field-flow fractionation.
Reproduced with permission from ref 17. Copyright 2015 Frontiers Media.
However, few data exist on the smallest size fraction of plastic 2.1. Density-Based Approaches
particles in complex matrices, including field-collected Flotation is used to separate plastic from denser sediment.
organisms and wastewater, because of practical and in some Typical density separations for plastics employ salt solutions to
cases fundamental challenges for isolation and analysis. render plastics buoyant. The salt selection balances particle
Consequently, knowledge gaps exist for plastics smaller than recovery, processing cost, and environmental impact.7 Plastics
100 μm. float to the surface passively or assisted by elutriation.8
This Account specifically addresses analysis and separation Alternatively, ethanol can be used as a density separation
of the smallest size fractions of plastics in the most challenging
medium to separate plastics from less dense biological
matrices. Here we outline these challenges to assist researchers
material.9 However, solvents such as ethanol can dissolve or
in pursuing new directions in developing methods to separate
damage some types of plastics, especially in the case of small
and analyze micro- and nanoplastics in environmental samples.
particles.
Flotation can achieve nearly complete separation in the
2. GENERAL APPROACHES FOR PLASTIC millimeter size range. Nevertheless, flotation is seldom used for
SEPARATION plastic particles that are too small to be manually handled
As with any separation process, isolating plastics from complex because of the difficulty of recovery from the air−liquid
matrices (Figure 1) requires leveraging plastic properties that interface. Furthermore, flotation is incompatible with the
differ from their surroundings. Specifically, compared with smallest size fractions of plastic since the buoyant force is low
(wet) environmental matrices, plastics tend to be (1) less and surface fouling can significantly change the particle density.
dense and (2) more hydrophobic. Furthermore, when matrices Another concern is that the attachment of bubbles to
are low in solids content, plastics can be separated by size- nonplastic particles can carry denser particles to the air−liquid
based filtration. interface.
859 DOI: 10.1021/acs.accounts.8b00602
Acc. Chem. Res. 2019, 52, 858−866
Accounts of Chemical Research Article
Figure 2. Overview of the separation methods for microplastics in a variety of field-collected organisms. Chemical: hydrogen peroxide, acids, bases,
and enzymes. Manual: dissection, fixation, and cryosection. Physical: filtration, ultrasonic, and gravity separation. The results were obtained from 45
peer-reviewed articles; the full reference list is given in the Supporting Information.
In our view, density separation techniques common in other “dead-end” filtration, cross-flow filtration followed by asym-
fields are underutilized in plastic pollution research. Specifi- metric-flow field-flow fractionation passes samples through
cally, in biology, density separations are routinely conducted porous sleeves to concentrate small particles and fractionate
via centrifugation. A common approach for density gradient particles by size, respectively.16
centrifugation is to use Percoll (suspended colloidal silica
2.4. Adapting Approaches from Nanoparticle Separation
nanoparticles) as a medium.
2.2. Hydrophobicity-Based Approaches While few techniques have been reported for nanoplastic
separation, adapting methods developed for engineered
Hydrophobic separation of small microplastics from environ- nanoparticles could prove to be effective. These techniques
mental matrices has not been effectively applied. Froth include magnetic field flow fractionation (MFFF), gel
flotation is used to separate minerals by the strength of
electrophoresis, and size-exclusion chromatography (SEC).18
hydrophobic interactions, whereby hydrophobic particles
With MFFF, nanoparticles flowing through a channel are
adhere to the surface of the bubbles which subsequently
carry the particles to the air−liquid interface. However, froth separated by a magnetic field that pulls magnetic particles
flotation may not be suitable for analytical plastic separation tangentially to the direction of flow.19 Adapting MFFF to
because the unpredictability of bubbles can result in high nanoplastic separation will require a method to magnetize
particle losses. Imhof et al.10 recovered only 55% of plastics them, which may be more challenging than with microplastics
from sediments using froth flotation. Crichton et al.11 achieved because magnetic nanoparticles may be too large to effectively
high recovery of relatively large (∼1 mm) microplastics by bind to nanoplastics.
using oil to capture plastics via oleophilic interaction. However, Gel electrophoresis separates nanoparticles by pulling
this technique requires a potentially plastic-damaging ethanol particles through a gel with an electric field. Since gels are
rinse to remove oil residue. Nevertheless, in other fields nanoporous structures, the speed of a particle is dependent on
hydrophobicity-based separation has successfully been applied its size and charge. Using gel electrophoresis for nanoplastic
down to the molecular scale, where hydrophobic interaction separation will likely present challenges in analysis since the
chromatography is used to separate biomolecules.12 Recently, nanoplastics would be embedded in the gel and electrophoresis
proof-of-concept magnetic separation of 15 μm plastics was is not plastic-specific.
achieved by hydrophobizing iron nanoparticles via silanization SEC is applied to separate particles in a sample by size. The
to cause them to bind to plastic.13 sample is passed through a column of porous beads.20 Smaller
2.3. Size-Based Approaches particles are slowed since they have to pass through the porous
With filtration, we must balance between the ability to capture matrix of the beads while larger particles pass around the
small particles and filter clogging/low sample throughput. beads. Therefore, smaller particles exit the column last.20 SEC
Sequential filtration using increasingly smaller pore sizes can is not plastic-specific.
minimize filter clogging.14 However, this approach confirms Finally, all of these techniques are typically used for
only the presence of nanometer-scale plastics and not their nanoparticles at concentrations much higher than anticipated
total numbers, as a significant fraction of the nanometer-scale environmentally relevant concentrations of nanoplastics. Thus,
particles are likely lost via attachment to filters.15 In contrast to advances in the separation efficiency of these techniques may
860 DOI: 10.1021/acs.accounts.8b00602
Acc. Chem. Res. 2019, 52, 858−866
Accounts of Chemical Research Article
Figure 3. Qualitative chart of matrices in which microplastics and nanoplastics are found. Heterogeneity and biomass content both complicate
separation and analysis.
be required before they can be reliably applied to nanoplastic Fixation and cryosection methods can be useful to investigate
separation. the translocation of microplastics to other tissues (e.g., liver)
prior to examination and quantification.28−30 The physical
3. SEPARATION IN BIOLOGICAL SAMPLES separation techniques discussed above are not typically applied
to biological samples (only 18% of studies) because of the high
Efficient and accurate quantification of plastics in field- biomass content.
collected wildlife is key to advancing the quality of environ- Overall, methods exist for processing of organisms prior to
mental toxicological studies in a risk assessment and manage- plastic quantification, but most are either time-consuming or
ment context. Of 45 peer-reviewed research papers published high-cost, limiting their applicability to large-scale field
between 2012 and 2018, a large portion (90%) studied aquatic investigations. Lengthy separation procedures result in a
organisms, with 35% on fish species, 19% on mussels, 13% on significant risk of contamination.31 The lack of studies on
plankton, and less than 5% on other organisms (Figure 2). In terrestrial organisms means that our understanding of the
contrast, studies on terrestrial organisms were relatively limited distribution and impact of microplastics in terrestrial systems
(10% of studies; Figure 2). Laboratory studies that relied on lags behind that in aquatic systems.32
labeled or dyed plastics at very high concentrations were
excluded from our analysis, as tagging plastics in the
environment prior to exposure is impractical. 4. SEPARATION IN WASTEWATER
Acid or base digestion is frequently used successfully to Plastic transport in wastewater treatment plants (WWTPs) is
isolate microplastics from biological tissues (Figure 1). Nitric poorly understood, largely because of the complexity of
acid (HNO3) (18% of studies), potassium hydroxide (KOH) wastewater itself (Figure 3). Most microplastics (95−99%)
(16% of studies), and hydrogen peroxide (H2O2) (12% of entering a WWTP are estimated to be removed with
studies) are effective and widely applied to destroy or digest biosolids33 or through grease skimming.34 Despite overall
tissue and reduce greasy tissue fractions, leaving behind high removal percentages, the vast quantities of water being
recalcitrant materials. Other strong acids (e.g., hydrochloric treated lead to estimates of 105−108 plastic particles per day
acid) and bases (e.g., sodium hydroxide) can also be used as entering the environment with treated effluent from one
digestants. However, some plastics can be degraded or plant.34−36 Along the treatment process, microplastics may
damaged by these acid/base treatments, particularly at higher become brittle and break down,36 melt or transform,37 or
temperatures (>80 °C), while other plastics such as poly- become biofouled,34 further complicating identification and
ethylene (PE) and polyvinyl chloride (PVC) are resistant to quantification.
these treatments, resulting in inconsistent recoveries.21,22 Separation methods used in recent studies on microplastics
Enzymes (e.g., proteinase K, chitinase, cellulase) have also in wastewater are summarized in Table 1. Method complexity
been successfully applied for more specific digestion of tissue, varies greatly: some scientists report a single sieving step before
either alone or in combination with chemical digestants.23−25 microplastic identification,36,38,39 while others present two to
Dissection (13% of studies) is a traditional method for six steps,34,35,37,40−44 including sieving, homogenization,
assessing plastic uptake in gastrointestinal tracts of larger concentration, digestion, density separation, or staining.
organisms (e.g., whale, shark, fish) or whole bodies of smaller There is no standardized procedure for digestion of
organisms (e.g., mussels and barnacles). Dissection is wastewater samples. In the recent literature, researchers used
inexpensive and accurate for visual identification of >500 μm Fenton’s reagent (peroxide with iron), 41,42 peroxide
microplastics in gastrointestinal tracts. However, smaller alone,35,40,44 enzymatic digestion followed by Fenton’s
microplastics can translocate to other tissues and organs.26,27 reagent,43 3% NaOCl,34 or no digestion.34,36−39 Digestion
861 DOI: 10.1021/acs.accounts.8b00602
Acc. Chem. Res. 2019, 52, 858−866
Accounts of Chemical Research Article
Figure 4. Overview of microplastics and nanoplastics separation and analysis methods in simple and complex matrices.
Raman spectra of microplastics exposed to UV degradation are spectrometry. Interlab reproducibility is challenging with Py-
not significantly altered.60 The spatial resolution of Raman GC-MS, as results are highly dependent on sample
microscopy is approximately 1 μm,56 and particle shape and preparation, pyrolysis type, and pyrolysate transfer.67 In
thickness do not influence the measurement. These advantages electrically heated filament pyrolysis, the sample is inserted
make Raman microscopy a potentially more sensitive tool to into a quartz tube that is then placed inside a resistively heated
identify microplastics compared with FTIR.61 However, some coil.68 In furnace pyrolysis, the solid sample is inserted into a
materials exhibit fluorescence, masking the vibrational preheated furnace, and a carrier gas transports the pyrolysate
information. The Raman signal is heavily influenced by into the gas chromatography column.68 In Curie point
dyes60 and microbiological,62 organic,56 and inorganic pyrolysis, the solid sample is placed inside a ferromagnetic
substances.56 foil, which is later placed in the induction pyrolyzer.67,69 In all
5.2.2. Mass Spectrometry Methods. In mass-spectrom- cases, the temperature increase is performed under a controlled
etry-based methods, the sample is analyzed in bulk. This trades atmosphere. In filament and Curie point pyrolysis, the
the spatial resolution of vibrational spectroscopy for potentially disposable sample substrate is the main advantage, as
increased sensitivity, which can allow detection of nanoplastics. suspensions with microplastics and nanoplastics can be dried
The detection signal depends on the total mass analyzed. and further pyrolyzed. This is impossible in furnace pyrolysis,
These methods are suitable to qualitatively identify a mixture as fused quartz sample containers must be reused. The main
of plastic particles, and certain configurations also allow for advantage of Curie point pyrolysis is that the composition of
quantification, albeit in relative quantities rather than discrete the pyrolysate does not change in the range of 480−980 °C,
particle counts. whereas it is temperature-dependent in furnace and coil
5.2.2.1. Thermal Desorption Coupled with Gas Chroma- pyrolysis.70 Additionally, Curie point pyrolysis is faster and
tography−Mass Spectrometry (TDS-GC-MS). TDS-GC-MS more precise, and quantification is possible since the
involves placing a sample onto a thermogravimetric balance temperature is high enough to avoid unpyrolyzed residue.
and heating it to temperatures up to 1000 °C.63 Degradation With filament pyrolysis, some of the pyrolysate will condense
products are adsorbed onto a solid phase, which is then to form a residue in the quartz tube.
transferred to a thermal desorption unit. The degradation In comparison to TDS-GC-MS, py-GC-MS offers greater
products are then desorbed by increasing the temperature, sensitivity, making it more appealing for identification of small
separated with a chromatography column, and analyzed by masses of nanoplastics (down to ∼50 μg).68 This can be
mass spectrometry. TDS-GC-MS is a technique suited for relevant in simple matrices such as drinking water, where
samples with relatively high mass (up to 100 mg) but is limited separation is straightforward. However, in environmental
to qualitative analysis.64−66 samples, where the nanoplastics are likely to be embedded
5.2.2.2. Pyrolysis Coupled with Gas Chromatography− or attached to other materials, sensitivity may still be a barrier.
Mass Spectrometry (py-GC-MS). Py-GC-MS involves decom- Furthermore, the amount of sample that can be injected is
position of a sample at high temperatures, separation of the restricted by the size of the pyrolyzer, leaving room for
products via gas chromatography, and analysis by mass improvement.
863 DOI: 10.1021/acs.accounts.8b00602
Acc. Chem. Res. 2019, 52, 858−866
Accounts of Chemical Research Article
■
With all of these spectroscopic/spectrometric techniques, the
spectra are interpreted to obtain useful information. While AUTHOR INFORMATION
developing new libraries and applying existing libraries are
Corresponding Author
important to optimize identification, a thorough understanding
of the fundamental chemical implications of the spectra is *Phone: (514) 398-2999. Fax: (514) 398-6678. E-mail:
invaluable to decoding the signal. [email protected].
ORCID
6. BLANK AND SPIKE CONTROLS
Nathalie Tufenkji: 0000-0002-1546-3441
Quality controls, including blanks, spike recovery, and Author Contributions
contamination assessment, are critical aspects of microplastic §
and nanoplastic analysis. Blanks undergoing some or all B.N. and D.C.-M. contributed equally.
extraction steps are often analyzed.38,40,41,43 Background levels Notes
can represent a significant portion of the signal in low- The authors declare no competing financial interest.
concentration samples.40 Positive controls (spiked samples)
were used for both solid and liquid samples,34,35,40,42−44 with Biographies
recoveries between 70 and 95% in most studies, though Brian Nguyen completed his Ph.D. at the University of Toronto in
comparison between biota studies is still hampered by 2018. He developed methods for studying the prevalence and
variation in recovery rate across size fractions and processing ecotoxicology of microplastics. His current research interest is
methods.31 Spikes are generally limited to only a few types of developing techniques to study the smallest size fractions of plastic
particles, with polystyrene most commonly employed. Spike pollution.
particles are typically 100−500 μm in size.37,40,44 While
satisfactory recovery was sometimes reported using spikes as Dominique Claveau-Mallet completed her Ph.D. at Polytechnique
small as 10−45 μm,34 studies using nanometer-sized spike Montreal in 2017. She developed technology for domestic wastewater
controls are lacking. Few35 studies spike samples with fibers. treatment in small-scale applications. She is now a postdoctoral
Frequently, recoveries for positive controls are solely analyzed researcher working on cotransport of contaminants with micro-
visually, but ideally, chemical analysis should be conducted to plastics.
identify transformations due to processing. Airborne contam- Laura M. Hernandez is a Ph.D. student working on sources and fate
ination controls using clean Petri dishes or filters have been of nanoplastics and developing new methods to separate and
employed, leading researchers to count fibers depending on characterize nanoplastics. She completed her Master’s degree at the
color.35,71 Using laminar flow hoods, clean environments, and/ Universidad de los Andes in 2015. She worked with anisotropic
or natural fiber clothing can limit microfiber contamination.36 particles and surfaces for manipulation of transport phenomena
Contamination is especially problematic in nanoplastic properties.
detection with mass spectrometry methods because of the Elvis Genbo Xu obtained his Ph.D. from the University of Hong
bulk nature of the analysis.
■
Kong in 2015. He worked on the integrated risk assessment of
endocrine-disrupting chemicals in marine protected areas. He
CONCLUSIONS
completed a postdoc at the University of California. His recent
In this Account, we have reviewed recent developments in research focuses on ecotoxicity of micro- and nanoplastics and
microplastic and nanoplastic separation and analysis, focusing developing detection methods in biological samples.
on particular challenges with small plastic particles and
Jeffrey M. Farner received his Ph.D. from Duke University in 2016.
processing of complex samples, including field-sampled
He studied the role of aggregation and surface interactions on
organisms and wastewater (Figures 3 and 4). A common
nanoparticle photoreactivity. He is currently a postdoctoral researcher
theme in our Account is that new techniques are required to
and focuses on the environmental fate and transport of nanoparticles
answer key questions in the field of microplastic and
and nanoplastics originating from consumer products.
nanoplastic research. To this end, we recommend combining
different techniques to leverage the unique advantages of each Nathalie Tufenkji is a Professor at McGill University. She holds a
technique. For example, the chemical specificity of spectro- Tier 1 Canada Research Chair in Biocolloids and Surfaces. She has
scopic techniques could be combined with the high resolution extensive expertise in nanoscience, colloid chemistry, microbiology,
of electron microscopy using correlative microscopy techni- and environmental engineering. She earned her Ph.D. from Yale
ques. In the development of methods employing combined University.
techniques, looking to other fields could prove helpful. For
example, micro- and nanoscale separations and analysis are
routinely employed in fields such as cellular and molecular
■ ACKNOWLEDGMENTS
The authors acknowledge the financial support of the Canada
biology. Borrowing methodological principles from these fields Research Chairs program, the Natural Sciences and Engineer-
could help in the development of new techniques to answer ing Research Council of Canada, and the Canada Foundation
outstanding questions in microplastic and nanoplastic research.
■
for Innovation. D.C.M. was supported by an NSERC Banting
Fellowship and L.M.H. was supported by a McGill University
ASSOCIATED CONTENT MEDA Scholarship.
■
* Supporting Information
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