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Finding Microplastics in Soils: A Review of Analytical Methods

Julia N. Möller, Martin G. J. Löder, and Christian Laforsch*
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ABSTRACT: Research on microplastics in soils is still un-

common, and the existing publications are often incomparable
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due to the use of different sampling, processing, and analytical

methods. Given the complex nature of soils, a suitable and efficient
method for standardized microplastic analysis in the soil matrix has
yet to be found. This paper proposes a critical review on the
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different published methods for sampling, extraction, purification,

and identification/quantification of microplastics in complex
environmental matrices, with the main focus on their applicability
for soil samples. While large microplastic particles can be manually
sorted out and verified with chemical analysis, sample preparation
for smaller microplastic analysis is usually more difficult. Of the
analytical approaches proposed in the literature, some are
established, whereas others are a proof of principle and have not yet been applied to environmental samples. For the sake of
development, all approaches are discussed and assessed for their potential applicability for soil samples. So far, none of the published
methods seems ideally suitable for the analysis of smaller microplastics in soil samples, but slight modifications and combinations of
methods may prove promising and need to be explored.

1. INTRODUCTION However, considering that the majority of plastic waste is

Microplastics have been defined as “plastic particles smaller generated and emitted on land, it is rather surprising that
than 5 mm”,1 and while this upper size limit is widely accepted, microplastic research has only recently expanded to terrestrial
the lower size limit is still under scientific debate. Some groups, ecosystems, where soils may be a significant long-term sink for
such as the Joint Group of Experts on the Scientific Aspects of microplastic particles.9,10 Especially urban and agricultural soils
Marine Environmental Protection (GESAMP) include “par- are assumed to be prone to microplastic contamination, as they
ticles in the nano-size range”.2 Frias and Nash,3 proposed the are most exposed to human activities and therefore micro-
following definition: “Microplastics are any synthetic solid plastic input pathways.11 Potential pathways are littering and
particle or polymeric matrix, with regular or irregular shape and street runoff,12 often containing tire wear,13 atmospheric
with size ranging from 1 μm to 5 mm, of either primary or deposition,14 irrigation with wastewater, as well as applying
secondary manufacturing origin, which are insoluble in water”. soil amendments such as compost derived from biowaste15 or
This is the definition that is also followed by the authors of this sewage sludge.16 Plastic mulching is also a potentially
critical review. We also distinguish between “large” micro- significant source of microplastic contamination in agricultural
plastics (>500 μm−5 mm) and “small” microplastics (1 μm− soils, where a long-term accumulation of the plastic fragments
500 μm), as some analytical methods perform better when may have severe effects on the soil quality.17,18
searching for larger microplastic particles. It has been stated, that microplastics are likely to be
Research on microplastics has shown that synthetic polymer transported through the soil vertically, for example, due to
particles can be found in all environmental compartments biopores, cracking or plowing, and horizontally, due to soil
worldwide, ranging from the arctic sea ice,4 to the waters of biota or agricultural activities such as harvesting and plowing.19
remote mountain lakes,5 to agricultural soils.6 Initially, De Souza Machado et al.20 suspect that microplastic pollution
microplastic research mainly focused on the marine environ- may be a major stressor on the terrestrial environment, causing
ment, where numerous studies analyzed the occurrence and physicochemical changes to the soil ecosystem by impacting
abundance of microplastic particles in the ocean and along
beaches, while many other studies showed the negative effects Received: July 31, 2019
of microplastics on marine organisms.7 Later, researchers Revised: January 25, 2020
began to examine river and lake systems, which are also Accepted: January 30, 2020
strongly affected by microplastic pollution and are considered Published: January 30, 2020
to be significant microplastic transportation pathways.8

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.est.9b04618

2078 Environ. Sci. Technol. 2020, 54, 2078−2090
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the soil structure and chemical composition (e.g., by leaching one).33 As microplastic particles are particulate and vary
hazardous additives). Shifts in the microbial activity within the strongly in their size, it is likely that the microplastic
soil due to the presence of microplastic could also be distribution within the soil varies significantly as well. To
observed.20,21 Further, introduced plastic particles can be overcome this heterogeneity, using composite samples taken
transferred along the terrestrial food chain.22−24 Although from defined subunits within a sampling site may prove
model studies give a first estimation of the macro- and beneficial to get a more representative image of the extent of
microplastic input into terrestrial and aquatic environments, microplastic contamination, without having to transport, store,
estimating the terrestrial input to be significantly higher than and analyze too many samples. Zhang and Liu18 applied this
the aquatic input,10 the actual extent of terrestrial and method by defining five plots at each sampling site, taking six
microplastic pollution is still unknown.25,26 This is mainly point samples randomly from each plot and combining these
attributed to the lack of customized analytical tools to detect to a single composite sample. Scheurer and Bigalke34 assumed
microplastics in soils. Due to the complexity of the soil matrix, a similar approach, compositing five samples taken along
containing variable proportions of mineral and organic matter parallel transects with differing distances to the river.
in various grain sizes, and the added difficulty of tracing a solid The number of sampling points at each site (single point
analyte in a sample composed of solids, a comprehensive samples or composite samples) could be determined by a
method for the effective microplastic analysis in soils is yet to statistical power analysis. However, the ideal number of
be developed.27,28 replicates and the sample volume is strongly restricted by
The following review aims to give a critical overview over sample processing and subsequent analysis methods, which are
the methods developed and used in scientific literature for still the bottleneck of microplastic quantification in all
sampling, extraction, purification, and detection of micro- environmental compartments.35 Hence, at this point in time,
plastics in complex environmental samples with a special focus no recommendation regarding the minimum amount of
on their applicability for the analysis of soil samples. While sampling points per spatial unit can be given.
other recent reviews on the topic have already given an As soils are a three-dimensional medium, the sampling depth
overview over the most commonly used analytical methods is of utmost importance and should always be defined and
and their challenges,28,29 this review is more extensive. It documented. If, for instance, the deposition of microplastics on
includes novel innovations to analyze microplastics in other the surface of an undisturbed soil is in the focus of the study,
environmental compartments, that may inspire readers to think bulk sampling of the predefined first few centimeters may be
“out-of-the-box” to find new solutions to the challenging sufficient. If the vertical distribution of microplastics after
problem of finding solid analytes in a complex solid matrix. plowing should be taken into account the sampling depth must
Furthermore, the often-neglected aspects of representative be adapted accordingly. On the other hand, if the
sampling of a nonhomogeneously distributed particulate contamination at varying depths of the soil is to be determined,
contaminant and quality assurance during sample processing core sampling is required. To date, mainly the soil surface
and analysis are also discussed in depth. within the upper 10 cm has been analyzed,6,18,34,36,37 as this is
the range where the bulk of microplastic particles is most
2. SAMPLING probable to be. However, the downward transportation
Arguably, representative sampling is one of the most important mechanisms of microplastic particles of various sizes in
steps during environmental analysis: Nonrepresentative undisturbed soils have not yet been analyzed.38 This should
sampling will lead to unreliable data, independent of the be done before defining a standard depth for soil surface
reliability the subsequent sample processing and analysis.30 analysis.
Naturally, each sampling design must be adapted to the The resulting sample amount (mass/volume) for each
respective research question. Especially when dealing with such sampling point should also be defined and documented. It
an inhomogeneous matrix as soil, in combination with solid should exceed the amount required for the microplastic
analytes such as microplastics, the sampling design must be quantification, allowing for additional aliquots of the sample to
very well planned in order to achieve reliable results.31 This be used (after homogenization) for the determination of water
means the research objective, the sampling area, as well as the content, as backup samples, and samples for recovery analysis
sampling depths must be accurately defined beforehand. The (as a control for the suitability of the method for this specific
history of utilization (e.g agricultural farmland where plastic soil).30 Due to the heterogeneous nature of microplastic
mulching has been applied) and possible discharge from point distribution, larger samples taken in the field are more
sources (e.g., bins, picnic sites, etc.) or diffuse sources such as representative than small amounts and can be reduced to a
nearby roads should be taken into account. Furthermore, smaller laboratory sample by homogenization and splitting.39
potential accumulation zones such as hollows, where micro- In the literature, sampling amounts were chosen arbitrarily,
plastics from surface runoff may be deposited or ridges and ranging from 50 g22 to 4 kg.36 So far, too little is known for us
hedges where wind velocities are decelerated and deposition of to recommend the minimum amount for representative soil
windborne particulate matter increases, should be identified. samples, but it should at least exceed the mass or volume of the
Depending on the research objective, several different sampling reference unit to avoid unjustifiable extrapolation. A sensible
approaches may be used. An overview of possible sampling reference unit would be items per kg(dw), (mean dry weight
approaches is given in Table 1. determined from aliquots of the sample using a standard
After selecting a suitable sampling approach according to the procedure, e.g., ISO 1146540). In this case, the samples taken
respective research objective, the number of sampling points at from the field should exceed 1 kg significantly, taking into
each site must also be addressed. account their water content and additional aliquots that may
Samples can be taken as single point samples, or composite be needed as mentioned above.
samples (several discrete point samples of the same size within The sampling tools can vary, depending on the objective, a
a spatial unit are combined and homogenized to a single stainless-steel spoon, scoop, or shovel can be used for surface
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samples, whereas a core sampler may be used if an analysis of Dried sediment samples are mixed with water and canola oil,
deeper horizons is the objective. All samples should be then agitated thoroughly and left to settle until the oil, water,
transferred into clean and labeled metal or glass containers and mineral fractions are completely separated, any micro-
with (plastic free) lids for transportation and storage. plastic particles coming into contact with the oil should thus be
Generally, measures should be taken to avoid the contami- conveyed into the oil layer, which can easily be transferred
nation of samples with microplastics from tools, clothing, or onto a filter. According to Crichton et al.49 recovery rates range
the ambient air of laboratories and storage facilities. Further from 90−100% for all seven tested pristine polymer types,
information on this topic is given in section 5. For more showing better recovery results than two compared density
information on which sampling methods were used by separation methods with NaI and CaCl2. The procedure is
previous research groups, please refer to the Supporting simple, safe, cheap, and time efficient, but may require an
Information (SI Table S1). additional step to remove organic substances from a sample.49
A recent study conducted by Mani et al.50 tested the oil
3. EXTRACTION extraction method using castor oil to separate microplastics
For an analysis of microplastic particles, it is usually necessary (0.3−1 mm) from four complex environmental matrices:
to remove the bulk of the sample matrix, preferably isolating Fluvial and marine suspended surface solids as well as marine
the microplastic particles from the matrix and removing beach sediments and agricultural soil. The method showed
adhering substances. For inhomogeneous solid samples such as high recovery rates for the four pristine polymers (poly-
soils, microplastic isolation is challengingand becomes even propylene PP, polystyrene PS, poly(methyl methacrylate)
more so with decreasing grain size of the soil matrixand PMMA, and glycol modified polyethylene terephthalate PET-
particle sizes of the microplastic particles.41 Soil particles can G) used in the spiking experiment, with an average recovery
form relatively stable aggregates, which may enclose micro- rate of 99% ± 4% (mean ± SD) and a mean matrix reduction
plastic particles and obscure them from analysis.18,42 Thus, of 95% ± 4% (dry weight). For validation, nonspiked Rhine
finding a method for soil aggregate dispersion without risking river suspended solids underwent the castor oil extraction
the destruction or artificial fragmentation of microplastic protocol. Of 978 microplastic particles found in total in the five
particles is an important first step for the microplastic analysis examined samples, 773 microplastic particles were recovered in
of soils. the upper oil phase, whereas 205 microplastic particles were
3.1. Manual Extraction. The simplest method for recovered from the lower aqueous and solid phase, resulting in
microplastic isolation is sieving and manual sorting, using a a recovery rate of 74% ± 13%. For organic-rich sample
stereo microscope to exclude obviously mineral or biogenic matrices, an additional H2O2 digestion step was required to
matter, for example, particles with visible cell structures.43 This achieve an adequate sample purification.50
method can be combined with the “hot needle test” to further 3.3.2. Density Separation. For the separation of micro-
confine the number of putative microplastic particles. plastics from sediment, density separation protocols are the
However, manual sorting and visual identification is extremely most commonly applied using high density salt solutions as
time and labor intensive, restricted to sizes >500 μm and is extraction media.51 In an early study by Thompson et al.52 a
highly prone to misidentification and bias, rendering a method was devised using a saturated NaCl solution to
subsequent reliable polymer identification indispensable.44−47 separate microplastic from sand. After stirring and sedimenta-
3.2. Electrostatic Separation. A rather novel method- tion the plastic-containing supernatant is sucked into an extra
ology is the electrostatic separation of microplastic particles flask from where it is transferred onto a filtering system.41,52
from solid matter. While experiments conducted by Hidalgo- Losses may occur in the tubing or while decanting, which is
Ruz et al.46 in this direction failed, Felsing et al.48 managed to why more sophisticated devices have been built since.
modify a smaller fair demonstration device of an electrostatic Furthermore, saturated NaCl solution can only achieve a
separation unit commonly used in the recycling industry to maximum density of 1.2 g cm−3, and several synthetic
isolate microplastics from sand and sediment samples. The polymers, such as polyethylene terephthalate (PET) and
method allows a relatively high sample throughput with a mass polyvinylchloride (PVC) have higher densities and are not
reduction of up to 99% and recovery rates of 90−100% for extracted by saturated NaCl solutions. Thus, alternative salt
pristine microplastic particles ranging from 63 μm to 5 mm. solutions such as NaI (ρ = 1.8 g cm−3),41,53 Na6[H2W12O6]
However, to achieve these high recovery rates, the samples (ρ=1.4 g cm−3)54 Zn2Cl (ρ = 1.6−1.7 g cm−3),55,56 and NaBr
underwent the procedure three times, with a temporal effort of (ρ = 1.55 g cm−3)37 were recommended,57 although costs and
3−4 h per 150 g sample. Furthermore the authors claim that hazardousness of these solutions may impose a need for
the method is independent of organic matter content, particle alternatives.
density, shape, age, or biofouling.48 However, the method is Imhof et al.55 developed the Munich Plastic Sediment
not suitable for moist samples,48 and its suitability for cohesive Separator (MPSS), to separate a diverse range of microplastics
soil samples is questionable due to the unavoidable formation from a maximum of 6 L of sediments using a ZnCl2-solution. A
of aggregates. Furthermore, the applicability for very small removable sample chamber equipped with a filter holder allows
particles must be verified, as the adhesive forces to the metal for a direct transfer of the microplastic particles onto a filter,
drum and scraper may be higher than the gravity-force, separating the sample from the density solution. As no
possibly leading to significant losses of the small microplastic decantation or repetitive extraction steps are required, losses
fraction in the final sample. and contamination can be avoided. According to Imhof et al.,55
3.3. Consecutive Matrix Removal, Removal of the recovery rates of 95−100% can be achieved. However, Zobkov
Mineral Fraction. 3.3.1. Oil Extraction. Crichton et al.49 and Esiukova58 evaluated the MPSS and found the recovery
developed the oil extraction protocol, a simple approach for rates of pristine plastics to be similarly high as stated by Imhof
the extraction of microplastic from solid samples, taking et al., but the recovery of aged plastics was significantly lower
advantage of the lipophilic surface properties of most plastics. at only 13−39%. Moreover, ZnCl2 is hazardous and corrosive,
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Table 1. Overview over Possible Sampling Approaches Dependent on the Research Objective30,32,33

has a low pH value, and may react with natural components of small particles get caught on the rough surface and cannot rise
sediment, especially carbonates, resulting in bubbling and a upward, possibly causing significant losses. Coppock et al.59
foam that significantly hampers the procedure.58 It is also saw the need for a cheaper and portable microplastic-sediment
questionable if soil aggregates will be adequately dispersed in separator and devised the Sediment-Microplastic-Isolation unit
the MPSS, or if a previous dispersion is required, especially for consisting of PVC tubes, a PVC ball valve, and zinc chloride
cohesive soils. Furthermore, the large surface area which may agitated by a magnetic stir bar. The principle mirrors that of
corrode due to the nature of the ZnCl2 may be problematic if the MPSS and shows similarly high recovery rates of 92−98%.
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However, PVC must be excluded from the analysis as abrasion Reviewing the above-named publications, no upper or lower
from the PVC tubing may contaminate the samples. This may size limit for the extraction of microplastic particles using
compromise the value of the analytic results, as PVC is a density separation has been established. In general, the
relevant contaminant in environmental samples such as recovery rates of the particles were established for size ranges
sediments and possibly soils, and excluding it from the analysis between 40 μm55 and 5 mm.37,55 The applicability for smaller
poses a significant loss of information. Also inspired by the microplastics and nanoplastics have not yet been analyzed.
MPSS is the so-called Bauta-separator developed by the However, according to the Stokes equation, small particles
Norwegian Technical Institute. Instead of a metal cone, a glass have very low settling velocities, that are further reduced by
cylinder constricted at the top and fitted with a ball valve and high drag coefficients which are dependent on the particle
separation chamber is used. The separation medium is a mixed shape, thus, an in-depth empirical study of the minimum size
solution of ZnCl2 and CaCl2, and the stated recovery rate was of various microplastic particles in common density separation
between 82% for fibers and 100% for pellets.60 The fluids is called for.
applicability of these methods for terrestrial soils has not yet 3.3.3. Froth Flotation. Another method, which is not only
been tested but may face similar constrictions as mentioned for dependent on the density of the matter, but also on the
the MPSS, especially concerning the dispersion of soil hydrophobicity of its surface, is froth flotation, commonly used
aggregates. in the recycling industry.62−64 Air bubbles will selectively
Claessens et al.53 developed an elutriation step with water attach to the more hydrophobic particles and carry them
after the principle of Barnett’s fluidized sand bath61 to reduce upward, thus separating them from the less hydrophobic
the sample bulk before density separation. The sediment matrix. According to Imhof et al.55 however, the mean
sample is aerated and fluidized while an upward stream of efficiency of the froth flotation to separate microplastic from
water transports small and light particles toward the top, where sediment is quite low (55 ± 28%), with high differences
they overflow and are retained on a 35 μm filter. Subsequently between polymer types.
the reduced sample undergoes a density separation with a NaI 3.3.4. Magnetic Extraction. Another method relying on the
solution. The extraction efficiency is stated to be higher than hydrophobic nature of microplastic surfaces is the method
98%.53 However, for the fluidization method, loose sand is introduced by Grbic et al.65 By functionalizing iron nano-
necessary, thus this protocol may be unsuitable for most soil particles with hydrophobic hydrocarbon tails (using hexadecyl-
samples. trimethoxysilane (HDTMS)), the iron nanoparticles will bind
Recently, Liu et al.37 developed a device specifically designed to the microplastic surfaces, and allow extraction with a
magnet. In addition to water samples, the method was tested
for the extraction of microplastics from soil samples, using an
for sieved (mesh size 45 μm) benthic sediment spiked with
acrylic glass cylinder constructed with an aeration disc at the
microplastics (200 μm to 1 mm; PP, PVC, PU, PS, and PE).
bottom and two rows of holes (diameter 5 mm) at the top. A
The recovery rates ranged from 49% (PP) to 90% (PE), albeit
circumjacent tray with an inclination collects the floating
with high standard deviations within trials. This method is a
particles and transports them toward a tube leading to a
proof of concept, that still has a few disadvantages: Lipophilic
vacuum filtration system. Here, the particulate matter is
substances, that may very well be present in soil organic matter
retained and the liquid is recycled via a circulation pump back may result in nonspecific binding, reducing the effectiveness of
to the separator cylinder, in order to retain the constant the method. The authors suggest using the method for
overflow. The soil samples (50−200 g) are mixed with the sediment samples after density separation or digestion, after
separation medium and stirred manually for 5 min and then which perhaps a further extraction method would no more be
left to subsequently settle for 2 h. After settling, the aeration necessary. Furthermore, brittle microplastic particles were
disc is turned on and separation medium continuously added shown to fragment during the procedure. In environmental
until the system overflows into the tray leading to the samples, where aged microplastics may be more brittle than
collection filter. A NaBr solution (1.55 g cm −3) was pristine particles, this could distort the results significantly.
determined as the most suitable separation medium, due to Grbic et al.65 propose that limiting microplastic contact with
its relatively high density and low viscosity. Recovery rates of the magnet may reduce fragmentation. However, the question
over 90% were reported for 10 types of microplastics (PA, PC, of the iron interfering with possible subsequent analytical
PP, ABS, PE, PS, PMMA, POM, PET, and PVC). PE particles characterization methods is not addressed, and should be
of different size ranges (100−500 μm, 500−1000 μm, 100− further examined. While the authors describe that sonicating
3000 μm) and shapes (particle, fiber, film) were tested with the the magnet in a surfactant or acid solution can remove the iron
device. The recovery rates only differed marginally for the nanoparticles from the microplastic surfaces, this method may
different sizes, whereas the shape of “particles”, that is, lead to further fragmentation of microplastic particles,45 and is
fragments, showed the highest recovery rate (98.3%), opposed thus undesirable.
to films, with the lowest recovery rate (85%). 3.3.5. Vertical Density Gradient Separation. A new
This method appears promising for soil sample analysis for methodology for density separation developed for the recycling
microplastic particles >100 μm, and although particles down to industry uses a liquid containing colloidal ferromagnetic
32 μm were found in soil samples, the recovery rate (i.e., particles. A magnetic field around the liquid creates a vertical
reliability) of the device for smaller particles (e.g., 1−100 μm) density gradient, with the highest density being at the bottom
must first be systematically determined. One severe drawback and the lowest density being at the top of the liquid container,
of the described system is that the separation cylinder is made thus a separation of a sample into different strata of various
of Plexiglas (i.e., PMMA). Abrasion caused by the stirring of densities can be achieved.66 This method may have potential
coarse soils may lead to overestimation of the PMMA concerning the isolation of microplastics from environmental
contamination in the samples, thus, a nonplastic material samples; however, no research in this field has been conducted
should be used, or PMMA excluded from the analysis. yet, and the costs may be unjustifiably high.
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In general, density separation may be useful to remove the while differences in the PA particles are attributed to variations
mineral fraction of soil samples, but methods developed for of the nylon fragment stock rather than the effect of Fenton’s
aquatic sediments must be adjusted to the new matrix reagent.78 However, the effect on weathered plastics was not
“terrestrial soil” which can be extremely heterogeneous as tested here, and may show different results than when using
stated above. Special care must be taken here that no pristine particles. Hurley et al.,79 conducted a test series for the
microplastic losses occur due to enclosure in soil aggregates. removal of organic matter from complex, organic-rich
Also, soil organic matter has a similar density (ρ = 1−1.4 g environmental matrices with 30% H2O2 at 60 and 70 °C,
cm−3)42 to most plastics and needs to be removed separately, with Fenton’s reagent at room temperature and 1 M NaOH as
as organic compounds can impede microplastic analysis. well as 10 M NaOH at 60 °C and 10% KOH at 60 °C. They
3.4. Consecutive Matrix Removal, Removal of the found that oxidization with Fenton’s reagent at room
Organic Fraction. 3.4.1. Acidic and Alkaline Digestion. temperature has the highest organic removal rate for soils
Acidic and alkaline digestion methods are frequently reported and sewage sludge while having no effects on any of the tested
in literature to remove the organic fraction of the sample microplastic granules. They also tested the effect of the order
matrix. Due to the fact that also soils contain organic matter, a of digestion procedure combined with density separation by
digestive step is imperative for an undisturbed analysis. water and NaI: Organic matter removal followed by density
Claessens et al.53 determined, that the most efficient chemical separation or density separation followed by organic matter
digestion of mussel tissue was obtained by treating the sample removal, and found the order to have no significant effect on
with 22.5 M HNO3. Also the ICES (international council for the recovery rate.79 To exclude any effects of the highly
the exploration of the sea) recommends an acid blend of reactive H2O2 on weathered microplastics on environmental
HNO3:HClO4 (4:1) to digest marine animal tissue for samples, it may be advisible to test weathered microplastics
microplastic analysis.67 However, several studies state that instead of pristine granules. Furthermore, care should be taken
certain strong acids may destroy specific polymers such as that organic-rich samples treated with Fenton’s reagent do not
polystyrene and polyamide.68−71 Alkaline digestion is similarly exceed temperatures above 60 °C due to the strong exothermal
discussed, especially for the digestion of animal tissue. reaction to avoid thermal degradation.80 Hurley et al.79
However, treatment with NaOH was found to destroy recommend not to let reaction temperatures exceed 40 °C.
polyamide and polyethylene (PE) fibers while leading to Frei et al.81 successfully used Fenton’s reagent for the removal
melding or discoloration of other polymers.72,73 Foekema et of organic matter in sediment samples from the hyporheic zone
al.74 digested fish intestines with 10% KOH solution at room of rivers.
temperature for 2−3 weeks. While apparently successful and Hurley et al.79 show that Fenton’s reagent can effectively
nondestructive to synthetic polymers, the procedure is time- reduce organic matter from soil samples, as this method is
consuming and may not be applicable for plant material or relatively cost and time-efficient, it shows potential to become
stabilized soil organic matter.42,73 Generally, purification of an important step in the microplastic analysis of terrestrial
samples with strong acidic or alkaline solutions will lead to samples. However, certain biogenic matter will not be
uncontrolled bias in the resulting microplastic composition of removed, thus a complementary organic removal step may
the sample.75 be necessary (personal observation).
3.4.2. Oxidisation with Hydrogen Peroxide. Oxidization 3.4.3. Enzymatic Digestion. Organic matter within soils is
treatment with boiling hydrogen peroxide (30% H2O2) is one of the most difficult fractions to remove without
commonly used in soil analysis to remove soil organic matter.76 destroying the microplastic particles. Thus, an adapted
It has also been used, at lower temperatures, to destroy organic enzymatic digestion may be beneficial; however, most reports
matter in the context of microplastic isolation from organic on enzymatic digestion procedures were developed for aquatic
rich sediment matrices: Nuelle et al. (2014)69 allowed samples samples. Cole et al.72 developed one of the first enzymatic
to remain in 30% H2O2 for 7 days. Around 50% of the biogenic digestion protocols using Proteinase-K for plankton-rich
matter was dissolved completely, but polyamide (PA), seawater samples, resulting in digestion efficiencies >97% by
polycarbonate (PC), and polypropylene (PP) pellets showed weight. The enzymatic method was then compared to
visible signs of degradation such as discoloration and size digestion protocols using HCl and NaOH and proved to
reduction. Liebezeit and Dubaish56 claim that a 30% H2O2 have the highest efficiency with the additional benefit of not
treatment overnight does not affect plastic particles;56 degrading the plastic particles. Other groups further developed
however, it is not stated if pristine or weathered plastic the enzymatic digestion protocols for mussel tissue71,82,83 and
polymers were used, which can affect results. Zhao et al.77 fish guts,72 reporting good matrix removal rates and very high
observed in a study concerning microplastics in marine snow, microplastic recovery rates, with no degradation of the polymer
that 30% hydrogen peroxide treatment of organic-rich samples particles. However, all the above-named enzymatic protocols
often results in the formation of a dense foam, which may are aimed at removing animal soft tissue, and exclusively use
suspend a significant portion of the sample above the proteolytic enzymes, that will not be able to remove the
reagent.77 They therefore propose using 15% H2O2 at 75 °C stabilized plant organic matter contained in soils. Thus, a more
for 24 h, instead, which is claimed to be just as effective as 30% promising approach was derived by Löder et al.:75 A sequential
H2O2; however, temperature sensitive polymers may be altered enzymatic digestion coupled with short-term reactions with
at such high temperatures. Instead of reducing the concen- H2O2. The used enzymes target specific organic compounds
tration in order to avoid the alteration of microplastic samples, and using different enzymes may result in better digestion
Tagg et al.78 propose reducing the exposure time. Fenton’s efficiencies than, for example, a single oxidization step using
reagent uses ferrous cations to catalyze the oxidization of H2O2. The presented protocol by Löder et al.75 is adequate for
organic components with H2O2. It was successfully used in the complex aquatic samples, but the removal of terrestrial plant
isolation of microplastic particles in wastewater and shows no matter and stabilized soil organic matter will probably require a
alteration of the surface of PE, PP, and PVC microplastics, different set of enzymes; thus, an adaptation of this protocol
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may be necessary for terrestrial samples. In the authors’ requires an extensive sample cleanup for matrix-rich samples,
experience, (unpublished results) and as proposed by Löder et making it rather unsuitable for bulk analysis. Additionally it is
al.75 a sequential combination of Fenton’s reagent, SDS and prone to contaminations or even blockages.104 To overcome
specific enzymes can enhance the purification of soil organic these shortcomings, Dümichen et al.104 developed the thermal
matter compared to the use of Fenton’s reagent alone. extraction desorption gas chromatography mass spectrometry
(TED GC-MS) for microplastic detection. Each run can
4. IDENTIFICATION AND QUANTIFICATION accommodate up to 100 mg of sample, which requires no
Since microplastic occurrence in the environment has become pretreatment other than grinding and mixing in an attempt to
a scientific issue, a surprising amount of methods has been homogenize the samples. The processing time requires 2−3 h,
developed for the qualitative, quantitative, or combined which is less than most of the current spectroscopic methods
analysis of microplastics in environmental samples. Some of available.104 This new analytical method may still need some
these methods may be well applicable for soil samples, if the refinement, but seems suitable for the fast analysis of many
preceding sample purification is adequate. different environmental sample types, including soils. Eisen-
4.1. Methods That Are Based on Visual Identification. traut et al.,105 confirmed the possibility of identifying tire wear
The earliest and simplest mode of microplastic analysis was in environmental samples using TED GC-MS, an achievement
visual identification under a light microscope,84,85 which that is very important to monitor the massive input of
however, is extremely prone to bias with error rates ranging microplastic particles into the environment by traffic. However,
from 20%86 to 70%.46 To reduce the shortcomings of the if sample grinding is necessary, quality controls should take
purely visual distinction between plastic and natural particles, place, ensuring that the risk of microplastic losses and
some publications recommend the “hot needle test” which contamination remain at a minimum. One significant drawback
makes use of the thermoplastic properties of many synthetic of TED GC-MS isas with all extraction-chromatography
polymers.67,87−91 Zhang et al.92 further developed this methodsthat it is destructive. Hence, information on the
principle for a simple identification of low-density polymers number, size, and morphology of the plastic particles cannot be
in soils: After a density separation with water the residue in the obtained, although this information may be crucial in the
supernatant is analyzed by comparing microscope-images context of assessing the effects of microplastics on organisms
taken prior and after heating the sample at 130 °C for 3−5 and eco-systems: The bioavailability of polymer particles is
s. Melted particles are then identified as thermoplastic dependent on its size and form and the environmental impact
polymers. While simple and feasible in most field laboratories, is most probably dependent on the concentration of
this form of identification neglects high density and bioavailable particles in the ecosystem. In addition, the
thermosetting plastics, does not consider that some natural morphology of the microplastics may also be important in
substances such as wax also melt at certain temperatures, is the context of their influence on the soil structure and
destructive and lacks the possibility of identifying the exact function.20
type of polymer. 4.3. Thermogravimetric Analysis. A different thermal
Similarly indiscriminate, but nondestructive is the use of analysis method is the thermogravimetric analysis (TGA).
polarized light microscopy under which certain synthetic Majewsky et al.106 coupled TGA with differential scanning
particles appear vibrantly illuminated.16,93,94 Maes et al.95 calorimetry (DSC) for the microplastic analysis of wastewater.
proposed the use of Nile Reda lipophilic fluorescent dye However, in that study, only polyethylene (PE) and
to specifically stain microplastic particles in environmental polypropylene (PP) could clearly be identified. David et
samples and make them fluoresce under a microscope by al.107 attempted coupling TGA with mass spectrometry (MS)
applying blue light and an orange filter.95 This method has, to quantitatively analyze polyethylene terephthalate (PET) in
however, not yet been tested for soil samples containing soil samples without sample pretreatment. While successful,
organic matter, where it may be possible that the dye the method still requires further development and is, to the
unselectively adsorbs to other lipophilic compounds in the best of the author’s knowledge, still restricted to the analysis of
surrounding matrix. PET only.
4.2. Chromatography. More sophisticated methods, Thermogravimetric analysis and chromatography bear
which allow the qualitative and quantitative identification of several promising approaches for fast mass-quantitative
individual polymer types include various extraction methods identification of microplastics in soils and other complex
coupled to a chromatographic unit. Suggested developments in matrices.108 However, they are limited insofar that subsequent
the literature include high temperature gel-permeation analyses are impossible due to the destructive nature of the
chromatography (HT-GPC) for the identification of poly- methods and number, size and form of the particles remain
olefins in cosmetics,96 liquid extraction with size-exclusion unknown, resulting in the drawbacks mentioned above in the
chromatography (SEC) for the identification and quantifica- chromatography section.
tion of polystyrene (PS) and polyethylene terephthalate (PET) 4.4. Vibrational Spectroscopy. Vibrational spectroscopy,
in soil samples,97 and pyrolysis gas chromatography mass such as Raman or Fourier transform infrared (FTIR)
spectrometry (Pyr GC-MS). Pyr GC-MS is a sensitive and spectroscopy are the most commonly used state of the art
well-established method for the characterization and mass- analytical methods in microplastic research, because they
quantification of many polymer types and their organic enable the precise identification of polymer types, their
additives.69,98−102 Together with μ-ATR-FTIR spectroscopy, abundance, shape, and size. Raman microspectroscopy allows
Pyr GC-MS has been shown to be well suitable for the chemical imaging of samples down to a pixel resolution of 500
detection of microplastics in environmental samples.103 nm,109 while focal plane array (FPA) based micro-FTIR
However, it also has several drawbacks. The size of the spectroscopy allows the identification of particles in a size
pyrolysis capsule and accordingly the sample amount per run is range from 10 to 500 μm.110 Larger particles (>500 μm) can
exceedingly small, 1.5 mm99 and 0.5 mg,104 respectively, which be analyzed by attenuated total reflectance (ATR)- FTIR
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spectroscopy.111 For further information on the function and dissolved in the corresponding deuterated solvent: Deuterated
application modes of FTIR and Raman spectroscopy, please toluene for PE, deuterated chloroform for PS, and deuterated
refer to Renner et al.111 and Käppler et al.112 Information on chloroform with trifluoracetic acid for PET, and subsequently
the automatic software recognition of microplastics in samples measured with an NMR spectrometer. Polymer mixtures were
measured with a micro-FTIR spectrometer can be found in the not tested. Although the method is described as cost-efficient
publications by Hufnagl et al.113 and Primpke et al.114 Raman- and fast (approximately 1 min per measurement), there is the
and FTIR-based chemical imaging complement each other and severe drawback of having to completely remove any organic
should be chosen in accordance with the specific research matter from the environmental sample to avoid signal
questions: The Raman imaging run time is significantly higher overlays.117 As a 100% removal of organic matter from soil
than FTIR imaging,112 but is independent of the shape, size, or samples without destroying the plastic as well is not possible at
thickness of the measured particles, which can influence the this point in time, the 1H NMR method is deemed unsuitable
results in micro-FTIR imaging. Black particles often result in for microplastic detection in soil samples.
unidentifiable FTIR-spectra, due to the high absorption of 4.6. In-Situ Identification. An approach for an in situ
infrared radiation. Additionally, Raman is insensitive to water methodology was developed by Paul et al.,118 who attempted
and atmospheric CO2. However, background fluorescence of to combine near-infrared (NIR) spectroscopy (opposed to the
organic matter or pigments in the polymers may strongly mid-infrared range used in conventional FTIR spectroscopy)
interfere with the desired spectra, making them unidentifi- with chemometrics to identify microplastics in soils. Near-
able.112 This may be especially problematic when dealing with infrared radiation can penetrate deeper than mid-infrared
soil samples with a high soil organic matter content. For both radiation, enabling analysis of particles even when coated with
vibrational spectroscopy methods, a thorough sample a thick biofilm, and the method is generally not sensitive to
purification is needed prior to the concentration on the filter water.118 Paul et al.118 were not able to achieve a sensitive
surface on which the analysis takes place.75 For solid samples, quantification of the plastic content in soil samples. However,
this fact significantly reduces the amount of sample that can Corradini et al.119 developed a method to “rapidly assess
realistically be processed. Thus, the need for an easy high- microplastic concentrations in soils without extraction”119
throughput technique for a representative amount of solid using a portable visible NIR spectroscope. Here the micro-
samples, such as soils, has been recognized and solutions have plastic concentration is to be estimated directly on the field,
been proposed. without time- and labor-consuming extraction and detection
Fuller and Gautam115 used pressurized fluid extraction procedures. LDPE, PET, and PVC (0.5−1 mm) particles in
(PFE) to dissolve specific microplastics from a soil matrix, let artificially polluted soil samples were successfully detected,
the polymer-solvent-extract evaporate and measured the solid with an accuracy of 10 g kg−1 and a detection limit of around
residue with ATR-FTIR spectroscopy.115 This method is fast, 15 g kg−1 in the predictive model. Current limitations to this
as it does not require sample purification and it is independent method are the low accuracy and high detection limit (which
of particle size. However, similar to the chromatographic may be much higher than realistic concentrations in natural
methods, it is also a destructive method and only allows mass- soils) as well as the need for a training set to accurately predict
quantitative analysis, not providing information on number, the polymer concentrations, which has to be adapted to
size, and shape of the polymer particles. Additionally, multiple different soil types. Additionally, only the concentration is
polymer types in one sample produce complex absorption given, while no information is obtained on the size or shape of
spectra that may hamper identification. the polymer particles. As the method is nondestructive though,
A similar, novel method was introduced by Schmidt et al.116 where necessary subsamples for plastic extraction and analysis
who used short-wave infrared (SWIR) imaging spectroscopy to could be taken after the NIR assessment.
analyze surface water samples taken from the Teltow Canal in Shan et al.120 also addressed a method for in situ
Berlin (Germany). The purified (using H2O2) samples were microplastic analysis on soil surfaces by hyperspectral imaging.
filtered onto several glass fiber filters each (diameter 47 mm) Like FTIR or Raman spectroscopy, hyperspectral imaging is a
and scanned with a SWIR imaging spectrometer, measurement nonbiased, nondestructive identification method, giving
speed: 52 048 mm2 per hour, resulting in the measurement of information on the spatial position, size, and specific
10 filters within 20 min. The lower detection limit is for reflectance spectrum of objects. However, the method is
particles of a size of 560 μm by 280 μm (2 pixels). The limited by the particle size and can only be applied to the soil
evaluation of the spectroscopic images was done automatically surface, whereas polymer particles situated in deeper soil strata
by the “PlaMAPP” algorithm, yielding a 75% true detection are neglected.120 Hyperspectral imaging or visible NIR
efficiency. To achieve more reliable results, additional manual spectroscopy for microplastic analysis in environmental
checking was required.116 While the SWIR imaging spectros- samples are methods in development and have the potential
copy can process many sample filters in comparatively little for rapid automated identification methods in soil samples in
time, its drawbacks are the rather large lower size limit and the the future.119,121,122
need for improvement for correct particle detection in the
automated analysis algorithm.
4.5. Proton Nuclear Magnetic Resonance Spectros- 5. QUALITY ASSURANCE/QUALITY CONTROL
copy (1H NMR). A completely new approach for size- Synthetic polymers are ubiquitous, and the risk of contami-
independent microplastic analysis was recently described by nation of environmental samples during sampling, sample
Peez et al.117 Using quantitative 1H NMR spectroscopy, model processing, and analysis for microplastics is very high, for
samples of polyethylene (PE) particles, polystyrene (PS) example, by contamination with abraded particles from plastic
beads, and polyethylene terephthalate (PET) fibers could equipment, synthetic fibers from clothes, or airborne polymer
successfully be qualitatively and quantitatively analyzed with a particles and fibers.45 Thus, precautions must be taken during
calibration curve method. Each analyte was separately each processing step: Generally, plastic material should be
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avoided and replaced wherever possible by alternative matrix becomes, as many small polymer particles tend to stick
materials like metal or glass. to walls, forceps or other equipment,125 so counting and
Woodall et al.123 comprehensively describe using a forensic manually transferring them into the sample is near impossible
science approach to minimize sample contamination. Recom- for sizes smaller than 100 μm. Emulsifying an exact mass of
mended steps are all equipment and material should be particles for transfer is possible, but only applicable for mass-
thoroughly cleaned with prefiltered (0.2 μm) deionized water quantification analysis (e.g., Pyr GC-MS or TED GC-MS) as
and 35% ethanol.6,75 Samples should be taken with clean metal long as the losses during transfer are negligible (which may not
tools and stored in clean glass or metal containers with a lid. be the case, depending on the adhering forces of the particles
While handling the samples or being in the laboratory, only in the pipet). However, for number-quantification analysis
clothing made of natural fibers should be worn and covered by (e.g., vibrational spectroscopy) determining the exact number
a 100% cotton lab coat. To avoid cross contamination, all tools of particles within any volume before transferring it completely
have to be thoroughly cleaned before coming into contact with to the sample may prove difficult. One possibility, (unpub-
the next sample. To control if the cleaning steps are sufficient, lished data) would be to emulsify a defined amount of
regular equipment (rinsate) blanks should be taken after microplastics in a liquid that hardens upon drying and is
“decontamination”, by rinsing the equipment with filtered resoluble in water (e.g., gelatin), allowing the exact
water and collecting the rinsate for subsequent analysis. Any determination of particle number in each hardened gelatin
certified precleaned labware obtained from third parties should platelet under a microscope before transferring it (loss free) to
previously be tested for contamination. Furthermore, taking the sample, where it can be redissolved and homogenized in a
field blanks to assess the extent of unavoidable contamination mixture of soil and water, which can subsequently be dried
on site is imperative. A field blank is prepared, treated, and again. This procedure not only allows the addition of an
kept with the actual samples throughout the sampling event to exactly defined number of very small standard particles to the
identify any ambient contamination of the samples during the sample, but also allows the particles to be incorporated into
sampling process. Thus the empty field blank jars are opened, soil aggregates formed by the drying of moist soil, making the
rinsed, and if possible filled with, for example, sand that was validation more representative of environmental soil samples.79
previously treated in a muffle kiln at 550 °C to remove all During the research for this critical review, it has become
plastics or any other microplastic-free particular matrix similar apparent, that not only a standardized analytical process has to
to the sample matrix before being closed, sealed, and be found, but that beforehand, a consensus on how to validate
transported the same way as the soil samples.124 any given analytical process for each environmental matrix
Processing in the laboratory should take place under a must be determined.
laminar flow box/clean box/clean lab to prevent airborne
contamination. Furthermore, restricting access to the labo- 6. PERSPECTIVES AND OUTLOOK
ratory to a minimum of employees and covering vents with As with all analytical processes there is a trade-off between
natural-fiber dustfilters will also help reduce ambient time- and effort reduction for sample preparation and analysis
contamination.123 All lab-equipment should be plastic-free; on one hand and on information quality of the generated data
where this is not possible a polymer that seldom occurs in on the other hand. This also holds especially true with respect
environmental samples should be used and characterized, for to the new research field of microplastic analysis in soil
example, Teflon, which will be excluded from the analyte list. samples. Thus, researchers as well as readers should be
To monitor possible sample contaminations, it is essential to cautious of large extrapolation factors when normalizing data
apply blank samples that undergo the same treatment as the to larger units (e.g., kg) as a consequence of the small sample
environmental samples,67 as well as monitoring used liquids amounts currently processable in microplastic analysis of soils.
and the ambient air (e.g., by laying out wet filter papers for a Authors of publications based on such data should be aware of
defined amount of time.123 Finally, prior to and after working the potential uncertainties related to such extrapolation and
in a workspace all surfaces should be wiped clean. call attention of the readers.
Apart from reducing and monitoring any sample contami- Nevertheless, the research conducted in the frame of this
nation, other QA/QC procedures have been widely lacking in critical review has shown, that several different analytical
past microplastic research, not only for soils, but also for the methods can be validly used for microplastic detection and
analysis of samples from other environmental compartments: quantification, depending on the research question at hand. In
The comprehensive validation of procedures and interlabor- order to enhance the methods toward a standard protocol for
atory comparisons of protocols, even among similar analytical soil-microplastic monitoring, several aspects need to be
methods, are severely lacking in frequency and quality.125 addressed in the near future:
Regular internal quality control and external proficiency tests (1) Developing a framework of sampling procedures, in
have never, to the best of the authors’ knowledge, been order to harmonize sample taking and to render projects
conducted. This is mainly due to a lack of certified reference with similar research questions comparable.
materials,91 that are urgently needed for such procedures.
(2) Automating currently labor-intensive purification proto-
Hence, research efforts are currently being made on this topic
cols, to reduce bias and promote parallel processing of
on a national and international level. Validation processes must
several samples at once.
address standardized microplastic particles of different polymer
types, sizes and forms. Also “aged” particles vs “pristine” (3) Promoting in situ microplastic detection methods.
particles is a factor that should be considered. This is a major (4) Establishing standard validation processes for micro-
task that has, to date, not been addressed appropriately. But plastic detection methods and develop appropriate
not only the spiking material is lacking, but also a standard reference materials.
procedure for spiking with very small microplastic particles. (5) Developing methods that are capable of identifying
The smaller the particle size, the more difficult the spiking of a nanoplastic particles in soil samples.
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pubs.acs.org/est Critical Review

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