Yolanda Picó1, Damià Barceló2,3. 1. Environmental and Food Safety Research Group-University of Valencia (SAMA-UV), Desertification Research Centre (CIDE), Joint Center CSIC-University of Valencia-Generalitat Valenciana, Moncada Naquera Road km 4.3, 46113 Moncada, Valencia, Spain. 2. Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, C/Jordi Girona 18-26, 08034 Barcelona, Spain. 3. Catalan Institute for Water Research (ICRA), C/Emili Grahit 101, 17003 Girona, Spain.
Abstract
The analysis, prevention, and removal of microplastics (MPs) pollution in water is identified as one major problem the world is currently facing. MPs can be directly released to water or formed by the degradation of bigger plastics. Nowadays, it is estimated that annually between 4 and 12 million tonnes of plastic go into the seas and oceans-with a forecast for them to outweigh the amount of fish in 2050. Based on the existing studies, the characterization of MPs in waters is still one of the remaining challenges because they can be easily confused with organic or other types of matter. Consequently, there is an urgent necessity to establish pathways for the chemical identification of the MP nature. In this perspective, the recent techniques and instrumentation for MP characterization (Raman and Fourier-transform infrared spectroscopies and microscopies, pyrolysis and thermal desorption gas chromatography, imaging techniques, etc.) are discussed including considerations to the multidimensionality of the problem. This perspective also summarizes and provides updated data on the sources and occurrence, transport and fate of MPs in aquatic ecosystems, as well as influencing conditions and factors affecting dispersal. Additionally, how engineering and biotechnological tools, such as advanced water treatments, would help to control, reduce, or even eliminate MP pollution in the near future is outlined.
The analysis, prevention, and removal of microplastics (MPs) pollution in water is identified as one major problem the world is currently facing. MPs can be directly released to water or formed by the degradation of bigger plastics. Nowadays, it is estimated that annually between 4 and 12 million tonnes of plastic go into the seas and oceans-with a forecast for them to outweigh the amount of fish in 2050. Based on the existing studies, the characterization of MPs in waters is still one of the remaining challenges because they can be easily confused with organic or other types of matter. Consequently, there is an urgent necessity to establish pathways for the chemical identification of the MP nature. In this perspective, the recent techniques and instrumentation for MP characterization (Raman and Fourier-transform infrared spectroscopies and microscopies, pyrolysis and thermal desorption gas chromatography, imaging techniques, etc.) are discussed including considerations to the multidimensionality of the problem. This perspective also summarizes and provides updated data on the sources and occurrence, transport and fate of MPs in aquatic ecosystems, as well as influencing conditions and factors affecting dispersal. Additionally, how engineering and biotechnological tools, such as advanced water treatments, would help to control, reduce, or even eliminate MP pollution in the near future is outlined.
The term “microplastic”
(MP) was formally introduced
in 2004 by Thompson et al.,[1] who alerted
to the growing problem of the plastic release to the seas. Since then,
its presence in the environment has gained an increasing attention
among the scientists, authorities, general population, and in the
media.[2] Although neither official definition
or full agreement within the authors exists, MPs are generally defined
as plastic fragments smaller than 5 mm in any dimension with an indeterminate
lower limit. The recent introduction of the term “nanoplastics”
(commonly <100 nm in any of their dimensions) is establishing a
lower limit to these particles.[3] However,
studies showed certain discrepancies on the range of MP sizes as well
as an evolution of the terminology according to their impact (Figure ).[4−11]
Figure 1
Size-based
definition of plastics as proposed by different authors
(Rocha-Santos and Duarte, 2015,[5] Hartmann
et al., 2015,[6] Browne et al., 2007,[7] Ryan et al., 2009,[8] EUCommision, 2011,[9] Claessens et al.,
2013,[10] and Desforges et al., 2014[11]). Reprinted from ref (4) Copyright (2016) with permission from Elsevier.
Size-based
definition of plastics as proposed by different authors
(Rocha-Santos and Duarte, 2015,[5] Hartmann
et al., 2015,[6] Browne et al., 2007,[7] Ryan et al., 2009,[8] EUCommision, 2011,[9] Claessens et al.,
2013,[10] and Desforges et al., 2014[11]). Reprinted from ref (4) Copyright (2016) with permission from Elsevier.MPs are often classified into
two categories: primary and secondary.[12] Primary MPs are those already manufactured with
a microsize, including the microspheres (<500 μm) contained
in some cosmetic products, mixtures used for sandblasting/shotblasting,
and MPs employed as pharmaceuticals vectors and to form 3D printing.[13] Secondary MPs are the products of degradation
of larger plastic materials, from mechanical or photo-oxidative pathways.
To give an idea of the magnitude of this contamination in water, it
is estimated that 1.5 million tonnes of primary MPs are released into
water yearly. Plastics mismanaged waste entering into the aquatic
environment, which could form secondary MPs, is higher in almost all
countries with the exception of EEUU (Figure ).[14] MPs can be
also categorized by their form, commonly in fibers, fragments, and
spherical beads, as well as by their chemical composition, for example,
polyethylene (PE), low-density PE (LDPE), PE terephthalate (PET),
polyacrylates (PA), and so on.[13] MPs can
be divided into many groups depending on the characteristics considered,
describing a diversified class of materials that includes a wide range
of polymer types, particle sizes (ranging over 6 orders of magnitude),
shapes (from spheres to fibers), and chemical formulations (thousands
of different types), which are likely to be found in water.[15]
Figure 2
Global release of MPs to the world oceans. Comparison
with plastics
originated from mismanagement of wastes. Reprinted from ref (14) Copyright (2017) with
permission from International Union for Conservation of Nature and
Natural Resources (IUCN).
Global release of MPs to the world oceans. Comparison
with plastics
originated from mismanagement of wastes. Reprinted from ref (14) Copyright (2017) with
permission from International Union for Conservation of Nature and
Natural Resources (IUCN).Nowadays, MPs have already been ubiquitous reported in almost
all
aquatic habitats of the planet, from the open seas to deep oceans,
river, lakes, the water column, and sediments.[14,16] The most pessimistic predictions on the impact of MPs establish
that their amount will overpass that of fish by 2050.[17] It has been demonstrated both in the laboratory and in
nature that animals can take up MPs.[18] Effects
are still largely unknown but are increasingly the subject of scientific
scrutiny, as MP pollution is suspected to rapidly increase in water
in the future.[19] However, one of the gaps
reported almost everywhere is the difficulty to establish the distribution
and to quantify the amount of MPs in waters.[20] This is attributed to the lack of proper and harmonized sampling
and analysis methods. This growing concern is parallel to the increase
of the production linked to the steady demand growth, which reached
49 million tonnes in Europe and 322 in the world in 2015.[17] Plastics and, consequently, MPs are very stable
and therefore stay in the environment a long time after they are discarded
(Table ).[21]
Table 1
Several Characteristics
of the Most
Common Plastics Found in the MPs
In this situation, the need
to find approaches to prevent water
pollution by MPs is imperative. Various strategies have been adopted
to remove MPs from water sources, including biotechnology and engineering
tools.[22] However, removal techniques are
still in its infancy with a number of issues not addressed yet.[20]This perspective summarizes the advances
in the analysis and prevention
of MPs pollution in water in order to perform an overall assessment
of the situation in the aquatic environments. Through this analysis,
several knowledge gaps and research biases in MP pollution and remediation
in water are identified. Finally, a number of explicit proposals to
fill these knowledge gaps are outlined.
Methods
of Sampling and Analysis
A large number of analytical methods
for determining MPs in water
have already been published and several literature reviews compiled
these methods.[12,23−25] The determination
of MPs in water samples involves 5 steps: sampling, separation, clean
up, identification, and confirmation (Figure ).
Figure 3
Scheme of the different steps involved in sampling
and analysis
of MPs in water.
Scheme of the different steps involved in sampling
and analysis
of MPs in water.
Sampling,
Separation, and Clean-Up
The main difficulties in sampling
are representativeness and integrity.
First, MPs are not homogeneously distributed in the water column but
depending on MPs characteristics (density, shape, size) and environmental
variables (type of water, streams, waves).[12,16] Thus, one identified gap is that MPs profiling will be highly conditioned
by the sampling method and there is no consensus on it. Three approaches—nets,
sieves, or pumps—are commonly used.[12] The sample methods to determine MPs in seas and surface water are
almost the same. The most common is the surface sampling with Neuston
nets because they sampled large water volumes quickly. However, a
study comparing different net-based sampling devices with different
mesh sizes including bongo nets (>500 μm), manta nets (>300
μm), and plankton nets (>200 and >400 μm) to filtration
of grab samples (0.45 μm) established that MP concentrations
using net-based methods were ∼3 orders of magnitude less than
those obtained by filtration of 1 L grab samples.[26] Mesh size is a critical point that determines the minimum
size and the number of MPs detected. Furthermore, synthetic fibers
and particles (as nanoplastics) having dimensions <25 μm
easily bypass these devices.[27] A general
analysis of the studies using different size nets shows that the use
of lower mesh-size nets multiplied by 10 000 the number of
MPs but decrease the resistance to clogging by organic and mineral
suspended matter; so, the volume of water that passes through them
must be reduced with lose reproducibility.[28] Multiplying the number of samples could be a solution to increase
sample representativeness.[29] Alternatively,
the use of filter cascades can reduce the matrix burden of the small
mesh sizes and also result in a size fractionation during the sampling.[27]Sampling in the water column is carried
out by direct filtration of the water with submersible Teflon pumps,
acquisition of batch samples, or plankton or bongo nets[30] but has only been reported occasionally. Sampling
at the wastewater treatment plants (WWTPs) is carried with pump filtration
devices,[31−35] batch samples,[36] or 24 h composite samples.[37] A high-volume homemade sampling device that
fractionated MPs in situ using different mesh sizes has been able
to process large volumes of several types of water (reversed osmosis
samples up to 200 L, primary effluent between 16 and 100 L).[38] Up to the moment, drinking water is grab-sampled
and filtered at the laboratory or directly filtered through 3 μm
stainless steel cartridge filters placed in filter housings. These
samples were always passed through small pore size filters (0.2–3
μm) than those used in other types of samples involving several-step
filtration through descending mesh size to pass the entire sample
volume through the filter without clogging.[39,40]Although some sampling methods are already well-established
and
their advantages and disadvantages have been discussed,[41] there is an absolute lack of standardized method
or guidelines to sampling pan class="Chemical">water for MPs. Particularly, the use of
different mesh sizes makes it difficult to compare the available monitoring
data. Another problem of the MPs analysis, which begins with sampling
but creeps through all remaining processes, is contamination due to
MPs deposition from the atmosphere and through sampling or laboratory
materials or operator clothes. Many studies tackled the problem and
gave recommendations to avoid contamination that cover four aspects:
(i) operators cloth protection, (ii) appropriate cleaning of the material,
(iii) protect samples for the air, and (iv) perform sampling and laboratory
blanks. Although it has been a widely treated topic, there is not
a consensus among the different studies collaborating to make difficult
the comparability.[24]
The MPs isolated
in the nets and sieves are commonly transferred
to glass bottles using water (the so-called reduced sample). The reduced
samples or the grab samples need further treatment to isolate the
MPs.[24,42] First, samples are filtered again using
stain steel sieves or glass fiber filters. In the case of grab samples,
the pore size of the filter is very important because this size determines
the lower limit of the MPs isolated, whereas in the case of reduced
samples, the MP lower limit isolated is already established by the
size of the net.[26] The next step is to
distinguish MPs from other potential interferences, such as organic
matter that could be easily confused with MPs. Thus, the separation
of MPs from natural organic matter (O.M.) minimizes misidentification
or underestimation of MPs. This separation can be carried out by oxidation
of the organic matter and/or by density separation. The detected gap
within these studies is the lack of systematic studies comparing the
efficiency of the different methods and offering guidelines and established
protocols.[3] Many of the studies does not
include information on the validation parameters, such as recovery,
linearity, accuracy or sensitivity, or comparison with other methods.
Neither development of reference materials or consensus on materials
used as analytical standards has been achieved. Only one study, up
to our knowledge, compared density separation methods (using sugar,
olive oil, and ZnCl2), and organic matter degradation methods
(wet hydrogen peroxide oxidation) and BEPP to assess effectiveness,
economical cost, time spent, simplicity, quality, and the total mass
of recovered polymer. The ZnCl2 density separation, wet
peroxide oxidation, BEPP + wet peroxide oxidation, and BEPP are the
more efficient methods (>90%). Among the methods that involved
the
degradation of organic matter, wet peroxide oxidation, and its combination
with a BEPP were more efficient than the BEPP alone.[20] As can be observed to monitor MPs in water, a broad array
of analytical methods can be used. Many more studies comparing the
extraction methods proposed up to the moment are needed to establish
unique protocols and to know their advantages and pitfalls.
Identification, Quantification, and Confirmation
Interestingly,
Renner et al.[43] worked
through more than 170 peer reviewed research papers published between
2015 and 2017 and dealt with MPs analysis to figure out how identification
of MPs is currently performed. The detection, identification, sizing,
and quantification of MPs is in 79% of the studied carried out by
visualization (naked-eye or using a microscope). MPs are identified
by their unnatural coloration (e.g., bright blue and multicolored)
and/or unnatural shape (e.g., fragments with sharp edges, perfectly
spherical)[44] (Figure ). However, even though clean-up to eliminate
organic matter has been performed, MPs can easily be mistaken for
other spherical anthropogenic particles (fly-ash, particles in road
paint, metal fume, fish scales, ceramic flakes, etc.). Several physicochemical
tests can help in the visual inspection (i.e., staining of natural
and nonplastics particles),[38] heating MPs
at >100 °C,[45] hot needle point
for
fibers.[46] There has also been an evolution
of the MPs visualization techniques to see lower size MPs parallel
to the use of smaller net sizes. Visual counting with a stereomicroscope
or an optical microscope is time-consuming and prone to human error
but is the most well-established technique for quantifying MP.
Figure 4
Typical appearance
of different polymers detected in different
stages of the WWTP and recipient lake and identified by micro-FTIR
and/or micro-Raman. (A–E) Polyester, (F–I) PE, (J–K)
polyamide and (L) polypropylene. Reprinted from ref (27) Copyright (2018) with
permission from Elsevier.
Typical appearance
of different polymers detected in different
stages of the WWTP and recipient lake and identified by micro-FTIR
and/or micro-Raman. (A–E) Polyester, (F–I) PE, (J–K)
polyamide and (L) polypropylene. Reprinted from ref (27) Copyright (2018) with
permission from Elsevier.Visual inspection alone is not adequate to characterize MPs,
physical
analysis is generally a more reliable way.[32,47] Vibrational techniques—Fourier-transform infrared spectroscopy
(FT-IR) and Raman spectroscopy, their microscopy versions (μFT-IR
or μRaman) and their recently developed imaging version—have
been the most widely applied techniques (28 and 14% of the studies,
respectively, according to Renner et al.[43]). These techniques offer available libraries that help in the identification.
The attenuated total reflection technique is preferred in FT-IR because
its more efficient for thick samples as MPs but its inconveniences
are the lack of sensitivity and that is not so efficient to detect
low-size MPs.[24] Apart from different IR
absorption or Raman scattering properties,[48] pyrolysis-gas chromatography/mass spectrometry (Pyr-GC-MS)[49,50] or thermogravimetry coupled to differential scanning calorimetry[51] is increasingly used to characterize MPs; we
have still little examples of their applications (<10% of the studies
according to Renner et al.[43]). Both techniques
are based on the preliminary thermal decomposition of MPs in their
monomers and additives. Although there is no enough information yet
to establish their advantages and disadvantages to chemically identify
MPs, it is exciting to speculate on the prospects that these new techniques
could open within the field.
Transport,
Distribution, and Fate
Runoff from urban, agricultural, and
recreational activities, indiscriminate
disposal (plastic bottles, packaging, and shipping), industrial release
(including fisheries and cosmetics), atmospheric fallout, and WWTP
effluents are among the multiple plastic and MPs sources to the environment.[4,52,53] Limited data exist that describe
the processes and mechanisms removing plastic debris from the surface
water. These processes include sedimentation, shore deposition, fragmentation,
and ingestion (Figure ).[53,54] Combined with physical abrasion and/or microbial
populations, exposure of plastic to solar UV radiation would result
in photodegradation, break, and fragmentation.[35,55,56] Aquatic organisms ingest MPs that accumulate
through the food chain more readily than larger plastics. Their bioaccumulation
potential increases with decreasing size.[57,58] These studies have raised concern about detrimental effects of MPs
in marine and freshwater ecosystems.[59] Although
the currently available information is somehow contradictory,[76,77] plastics can absorb surrounding organic contaminants and serve as
attachment media for pathogens acting as vectors to organisms for
these chemical and microbial contaminants. More relevant is that once
the MPs have been degraded enough, they release not only monomers
but also toxic additives contained in almost all plastic materials
since levels are much higher.[60] It is demonstrated
that ingestion of MPs by aquatic biota increases the bioaccumulation
of plastic additives. In the environment, MPs and NPs may undergo
various transformations commonly associated with natural or anthropogenic
colloids, namely, homo- and heteroaggregation, interactions with microorganisms
and macromolecules (e.g., adsorption of proteins, natural organic
matter), and biodegradation.[61,62] Few studies have examined
the transformations and transport of natural colloids and how these
environmental processes and conditions affect different types of MPs.
This missing information together with the need to enlarge knowledge
on MPs effects are important gaps to fill within the field.
Figure 5
Physical, chemical,
and biological processes affecting MPs in the
aquatic environment.
Physical, chemical,
and biological processes affecting MPs in the
aquatic environment.Up to now, the majority of research conducted on plastic
pollution
(all size fractions) has focused on marine ecosystems.[52,63−65] The frequency of occurrence of plastic debris in
the surface samples of the open ocean was considerably high (88%; Figure ).[66] Plastic debris has accumulated in the ocean surface because
its density is generally less than that of seawater.[67] Oceanic circulation models predict possible regions of
accumulation in the five subtropical oceanic gyres associated with
the confluence of surface currents. In addition, the high concentrations
of floating plastic debris that have accumulated in the North Atlantic
may be due to the higher presence of densely populated coastal areas.[68] Results of these models were further confirmed
by the distribution pattern of plastic debris in the ocean surface
that agreed with those predicted.[14,66]
Figure 6
Concentrations
of plastic debris in surface waters of the global
ocean. Colored circles indicate mass concentrations (legend on top
right). The map shows average concentrations in 442 sites (1127 surface
net tows). Gray areas indicate the accumulation zones predicted by
a global surface circulation model (6). Dark and light gray represent
inner and outer accumulation zones, respectively, white areas are
predicted as non-accumulation zones. Reprinted from ref (66) Copyright (2014), with
permission from National Academy of Sciences.
Concentrations
of plastic debris in surface waters of the global
ocean. Colored circles indicate mass concentrations (legend on top
right). The map shows average concentrations in 442 sites (1127 surface
net tows). Gray areas indicate the accumulation zones predicted by
a global surface circulation model (6). Dark and light gray represent
inner and outer accumulation zones, respectively, white areas are
predicted as non-accumulation zones. Reprinted from ref (66) Copyright (2014), with
permission from National Academy of Sciences.MP concentrations have been also reported in rivers, lakes,
wetlands
estuaries, and even on WWTPs.[12,69] However, the comprehensive
examination of this freshwater plastics literature shows that it is
still scarce and fragmented, owing to the numerous differences between
freshwater studies (including studied species and habitats, geographical
locations, social and economic contexts, the type of data obtained,
and also the broad range of purposes). This highlights the lack of
a holistic view and indicates several information gaps and inconsistencies
of MP pollution research within freshwater ecosystems.[70]One of the topics still little exploited
is the presence of MPs
in drinking water, even though it is of growing concern as one of
the potential routes of exposure to humans.[71] The presence of anthropogenic particles were reported in the 81%
of 159 samples of globally sourced tap water. The majority of these
particles were fibers (98.3%) between 0.1 and 5 mm in length. The
range was 0–61 MPs L–1, with important differences
according to the country (Figure ).[72] Pivokonsky et al. investigated
MPs (size up to <1 μm) in raw and treated water of three
water treatment plants supplied by reservoirs or river waters. The
average abundance ranged from 1473 to 3605 particles L–1 in raw water and from 338 to 628 particles L–1 in treated water mostly with size <10 μm.[40] Contrarily, Mintenig et al.[39] analyzed ground water and drinking water for the presence of MPs
(>20 μm). Concentrations ranged from 0 to 7 × 10–3 MPs L–1 raw water or drinking water
with an overall
mean of 0.7 × 10–3 MPs L–1. The difference could be explaining taking into account the different
water supplies, surface waters in the former and groundwater in the
latter, as well as the different MPs size covered. More global toxicological
study is needed, together with further epidemiological evidence, for
a comprehensive assessment of the possible risks resulting from the
ubiquitous exposure to MPs.
Figure 7
Percentage of tap water samples containing MPs
according to the
country (Guardian graphic/Source: Orb media).
Percentage of tap water samples containing MPs
according to the
country (Guardian graphic/Source: Orb media).
Remediation Strategies
Strategies to solve
the problem of MPs pollution should focus on
(i) source control commonly achieved by legislation and awareness
programs and (ii) remediation and clean up (to eliminate the MPs already
present in water).There are some legislative measures already
in force in order to
decrease MP release. Since 2017, US already banned the used MP beads
in the cosmetics products. Many other countries including Australia,
Canada, or European Union (EU) are also thinking in implementing effective
measures in the same sense. The MPs used in cosmetics is the most
important source of primary MPs to the environment. Regarding plastic
(potential source of secondary MPs), there are also important effort
to restrict the sale and consumption of single-use plastics, with
a focus on plastic straws and plastic bags.[73] Many countries have established restrictions to the use of single-use
plastic bags.[74] As an example, the EU in
a recent press release has proposed a Europe-wide strategy on plastics,
as a part of the transition toward a more circular economy. Under
the new plans, all plastic packaging on the EU market will be recyclable
by 2030, the consumption of single use plastics will be reduced, and
the intentional use of MPs will be restricted.[75] These legislative measures needs of the public enrolment
to be effective. The combined approach of the levy and a restriction
on plastic bag use applied in the program is an attempt to educate
the public and increase their awareness on the environmental hazards
of using plastic bags.This restriction in the production and
use of MPs is going in parallel
to large-scale clean-up of plastics in the oceans and the increase
application remediation technologies to reduce plastic pollution of
water ecosystems.[76−78] The former is based on floating systems that intercept
and capture plastics. It is expected that this can remove half of
the plastic in the Great Pacific Garbage Patch within five years’
time.[79] Remediation technologies can be
divided in (i) engineering tools, (ii) use of biobased or biodegradable
polymers, and (iii) biotechnological tools. The first comprises advanced
wastewater and drinking water treatment technology. The latter involves
the application of bacteria to biodegrade the plastics already present
in the environment. The EU press release also highlights the need
to drive investment and innovation in these fields in order to ensure
a reduction of MP contamination.[75]
Engineering Tools
WWTPs are a source
input of microliter and MPs to the environment. Then, these plants
provide an opportunity to develop and implement novel technologies
to manage MP pollution. Several studies evaluated the caal">pacity of
conventional and innovative WWTP technologies to remove plastics.[27,80,81] These studies show that conventional
WWTP treatments eliminate a high percentage of the MPs present in
the influents (between 90 and 98%).[27,82] Despite this,
effluents are a source of microliter and MPs into the aquatic environment
due to the large volume of effluent discharged constantly.[80] The advanced wastewater technologies more frequently
used are membranes, electrodeposition, and coagulation. The membrane
bioreactor (MBR)—the combination of a membrane process like
microfiltration or ultrafiltration with a biological wastewater treatment—is
one of the most promising. This technique showed better removal efficiency
of MPs (99.4%) compared to the overall conventional activated sludge-based
process (98.3%).[81] The efficiency of an
MBR system that finishes treatment with microfiltration in removing
MPs was also compared to that of WWTPs employing either secondary
treatment (activated sludge) or tertiary treatment (granular sand
filtration) as a final step.[71] The MBR
system provides the highest removal rate (99.4%) discharging 0.5 MPs
L–1 (Figure ).
Figure 8
Removal efficiency of different conventional secondary and tertiary
treatments and MBRs as well as MPs L–1 quantified
in the effluent. Reprinted from ref (82) Published by The Royal Society of Chemistry
under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
Removal efficiency of different conventional secondary and tertiary
treatments and MBRs as well as MPs L–1 quantified
in the effluent. Reprinted from ref (82) Published by The Royal Society of Chemistry
under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.MBRs have also been compared to
other innovative tertiary treatments,
such as rapid gravity sand filters and dissolved air flotation that
provide removal rates of MPs >95% from primary and secondary effluents.
The biologically active filter (BAF) process (filter that allow the
growth of contaminant degrading microorganism in it) showed also high
efficiency to remove MPs.[81] The removal
of microliter from wastewater during different treatment steps of
mechanical, chemical, and biological treatments (activated sludge)
followed by BAF in a large (population equivalent 800 000)
advanced WWTP showed an overall retention capacity over 99%.[80] MBR and MAF are already implemented in many
WWTP showing their industrial viability, even though they are more
expensive than other tertiary conventional treatment.Furthermore,
the efficacy of electrocoagulation (EC), a well-known
and established process for MP removal from wastewater streams, has
also been studied using artificial wastewater containing PE microbeads
at different concentrations. Microbead removal efficiencies >90%
were
observed in different conditions (initial pH, NaCl concentration,
and current density), thus suggesting that EC is an effective method
of removing MPs from wastewater streams. The optimum removal efficiency
of 99.24% was found at a pH of 7.5.[44] This
technique has been tested in a bench-scale stirred-tank batch reactor
(1 L) and could be viable at the large scale using an industrial EC
cell with a two-stage, continuous EC reactor/settler unit.Some
of the technologies applied to wastewater have possibilities
to be extended to other freshwater systems, such as the pH-induced
agglomeration and subsequent removal of particles from water.[83] This two-step-based process includes first a
localization and second an aggregation of MP particles (250–350
μM) in a physicochemical process. This process is based on the
strong increase in the particle size independent of pH of the aquatic
milieu induced by the addition of trichlorosilane-substituted Si derivatives.
The resulting Si-based MP aggregates (particle size after aggregation
is 2–3 cm) could be easily removed by the use of, for example,
sand traps. This process proved to be transferable and reproducible
from the laboratory scale to the industrial scale.Effluents
of washing machine are one of the major sources of MPs
and fibers in municial">pal and surface water. The impact of these effluents
could be alleviated treating them before their discharge into the
sewer system[84] by electro-oxidation (EO)
in an electrochemical flow reactor using active (Ti/Pt) or non-active
(boron doped diamond (BDD)) anodes and Ti cathode. The BDD anode showed
a well-defined trend as well as higher removal efficiency at all current
densities studied when compared to Ti/Pt. Besides, faster and higher
COD decay was attained by adding Na2SO4 to the
effluent compared to as-received effluent regardless of the anode
material used. Active chlorine species were also electrochemically
produced at both anodes from the Cl– ions in the
real effluent, contributing to the elimination of the fibers and MPs.
Based on the reported results, EO could became an efficient and effective
treatment approach for the remediation of MPs and other pollutants
in washing machine effluents especially with the BDD anode. These
results up to the moment only establish the applicability of prepilot
electrochemical plants.
As MPs have been gradually detected
in freshwaters, understanding
how MPs, with their small particle size and low density, will behave
during current drinking water treatment processes is urgently needed.
However, up to the moment, only the PE removal behavior with commonly
used coagulants and ultrafiltration membranes was systematically investigated.[41] Results showed that Al-based saltsperformed
better in PE removal efficiency than Fe-based salts. The smaller the
PE particle size, the higher the removal efficiency. Polyacrylamide
(PAM) addition played an important role in removing PE, especially
anionic PAM addition, because of the positively charged Al-based flocks
it generates under neutral conditions. For ultrafiltration, although
PE particles can be completely rejected, slight membrane fouling was
induced after coagulation with conventional Al-based salts. Based
on this study, coagulation and ultrafiltration processes have potential
application in drinking water treatment to eliminate MPs. However,
the study was performed only at the laboratory scale but both techniques
are viable at the large scale.This information altogether pinpointed
how advanced final-stage
water treatment technologies can substantially reduce the MP pollution
discharged from WWTPs into the aquatic environments as well as help
to remove these contaminants from freshwater ecosystems and drinking
water.
Use of Biobased and/or Biodegradable Polymers
Other strategy to solve the problem of the presence of plastics,
MPs, and NPs is to use more biodegradable materials.[22] Bioplastics are made of renewable starting materials, such
as starch, cellulose, lignin, and bioethanol. Currently, bioplastics
represent about 0.5% of the about 335 million tonnes of plastic produced
annually, which is expected to increase to approximately 2.62 million
tonnes in 2023.[85] Bioplastics can be classified
in three groups:Biobased
or partially biobased non-biodegradable such as, biobased
PE, PP, or PET (so-called drop-ins) and biobased
technical performance polymers, such as polytrimethylene terephthalate
or thermoplastic polyester elastomers. These polymers are made of
biological sources but as persistent as petroleum-based one.Simultaneously biobased and biodegradable, such as polylactic acid and polyhydroxyalkanoates or polybutylene
succinate. These help to solve the urgent problem of pollution.Based on fossil resources and biodegradable, such as polybutylene adipate terephthalate or polycaprolactone
diol. These also help to solve the problem of pollution but not the
dependence of fossil resources.Biodegradable
plastics are capable of undergoing biological
anaerobic or aerobic degradation. A major problem with these plastics
is that they have the potential to be biodegraded, but this process
requires suitable conditions and microorganisms that are not always
reliable in environmental conditions. However, one study on the chemical
modifications in the surface of commercial PCLD (average molecular
weight of 1250 Da) incubated under aerobic and denitrifying conditions
showed chemical modifications in the sample surface after 7 days allowing
to be optimistic on this MP elimination in the WWTPs.[86] This also pointed out the importance to specify the environment
where biodegradation is intended to take place.Some biodegradable
bioplastics are also compostable that can be
broken down by microorganisms into nutrient-rich biomass in as little
as 3 months and leave behind no toxins or residue. Compost has many
beneficial uses including improving and fertilizing soil. The European
Standard EN 13432 lays down criteria for what can or cannot be described
as compostable and what can be called biodegradable. The US Standard
ASTM D6400-99, Canadian BNQ 9011-911/2007, and Jaal">panese JBPA/2011,
set out similar standards. The term compostable is nowadays preferred
to that of biodegradable because it can be defined based on evidence.[85]
Bioengineering-Based Solutions
The
other bioengineering-based solution is to search new biodegradation
routes for classical plastics, like different types of bacteria and
fungi or isolate the involved enzymes to ensure the enzymatic hydrolysis
of plastics. Biodegradable polyesters can be hydrolyzed by extracellular
carboxylesterases.[76] Plastics can be degraded
by specialized bacteria, for example PET can be breakdown by Ideonella sakaiensis(77) and PE by the marine fungus Zalerion maritimum.[87] Despite the alternatives that seem
promising, the remediation of macro and MPs is in its infancy at the
laboratory scale. It is crucial to develop strategies for in situ
biodegradation of MPs by addition of microorganisms or by enhanced
natural attenuation using native microflora. However, the present
and future importance of the bioengineering-based solutions needs
considerable further research and development to make it suitable
for large scale application. It is clearly needed to move toward a
more sustainable and circular plastic economy, and biotechnology-based
strategies are the interesting approaches to apply in order to palliate
what may be the most worrying environmental issue of our time.
Conclusions
In this perspective paper, the main analytical
advances to identify,
characterize, and quantify MPs have been summarized. With the latest
advances in analytical technologies, most MPs can now be sampled,
isolated, and extensively characterized. However, several needs, such
as standardization/homogenization of the methods to facilitate comparison
of the results obtained in different studies, establishment of guidelines
to validate analytical methods, development of reference materials,
and interlaboratory exercises, are identified. We believe that further
exploration and gap analysis are of great importance for determining
priorities in implementing solutions and developing new approaches
important in the future.Much progress has been made in the
past few years in understanding
the sources, transport, fate, and biological effects of MPs in aquatic
ecosystems. The first important pillar is the evidence of the occurrence
and accumulation of MPs in any aquatic environment. However, there
is still little knowledge on the effect in different species as well
as the effects of several types of plastics with different chemical
compositions and different forms. Recent findings of MPs in drinking
water have raised concern on human exposure to these particles (with
food and air as additional sources of exposure). At present, although
there is no reason to be an alarmist about the health effects, more
research is needed to establish the hazard of these particles to humans.
Nevertheless, since MPs have proven to be an environmental threat,
measures addressed to reduce the release of plastics and primary MPs
and to eliminate the already existing MPs have become crucial.Governments are dealing with the problem of MPs and we will see
in the next coming years more measures in the direction of pollution
prevention, like restricted use of plastic bags, plastic bottles,
other plastic materials, and so on. In this respect, the European
Union indicated in a recent press release that in the year 2030, all
plastic packaging on the EU market would be recyclable. These legislative
decisions must be supported by the development of smarter and more
recyclable plastics materials, making recycling processes more efficient
by the study and isolation of degrading microorganisms, and tracing
and removing MPs through advanced wastewater treatments. Suitable
combinations of these processes may modulate and reduce MP pollution
in water. Furthermore, continuous press releases and information to
the public in general from governments, nongovernmental organizations,
and scientists are needed in order to reduce the use of plastic. These
measures together with additional recycling/remediation/removal technologies
will help to reduce plastic and litter pollution in our planet.
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